Fragrances in the Environment: Pleasant odours for nature? (9 pp)

Goal, Scope and Background Fragrance preparations or perfumes are used in an increasing variety of applications, as for example washing, cleansing, personal care products, consumer goods or in applications to modify indoor air. However, up to now, little is known to the general or scientific public about their chemical identity and the use pattern of single substances, not even for high production volume chemicals. Some toxicological data are published for a comparatively small number of substances with a focus on sensitisation and dermal effects, while other effects are neglected. Information on ecotoxicity and environmental fate are rare, especially for long-term exposure. Data for a detailed hazard and risk analysis are available in exceptional cases only. According to the current legal situation, fragrance industry is self-regulated, which means that pre-market risk evaluation is not required for most fragrances. Odour and the ability to smell play a major role for wildlife for all taxonomic groups. Reproductive and social behaviour, defence, communication and orientation depend on volatile compounds which can be identical to those used in fragrance preparations. Our interdisciplinary approach leads to the question of whether and, if so, to what extent anthropogenic fragrances may influence life and reproduction of organisms in the environment. Main Features Information from literature on use, exposure and biological effects was combined to analyse the state of knowledge. Following an overview of the amounts of fragrances used in different consumer products and their release into the environment, the roles of odours in nature are shown for a selection of compounds. Existing regulation was analysed to describe the data basis for environmental risk evaluation. Finally, recommendations for further action are derived from these findings. Results Three main results were elaborated: First, fragrance substances are continuously discharged in large amounts into the environment, especially via the waste water. Second, there are some indications of negative effects on human health or the environment, although the data basis is very thin due to the self regulation of the fragrance industry and the regulatory situation of fragrance substances. Third, many odoriferous substances used by man are identical to those which are signal substances of environmental organisms at very low concentrations, thus giving rise to specific mode of actions in the ecosystem. Recommendations For the adequate risk assessments of fragrances, test results on their unspecific as well as their specific effects as signal substances are needed. This would imply prioritisation methods and development of useful test methods for specific endpoints for appropriate risk assessments. Before a comprehensive testing and evaluation of results has been finished, a minimization of exposure should be envisaged. Eco-labelling of products containing acceptable fragrance ingredients could be a first step and provide consumers with the respective information. Transparency concerning the fragrance ingredients used and their biological potency will help to build up confidence between producers and consumers. Conclusions and Perspectives The interdisciplinary approach, bringing together chemical, biological, toxicological and ecotoxicological data with information provided by manufacturers and with legal and consumer aspects, offers new insights into the field of fragrance substances used in consumer products. The amounts and application fields of fragrance substances increases while fate and effects in the environment are hardly known. The current legal situation is not suited to elucidate the effects of fragrances on human health and the environment sufficiently, especially as it was shown that fragrances may play a considerable role in the ecosystem on the behaviour of organisms. According to the precautionary principle, the lack of knowledge should best be tackled by reducing exposure, especially for compounds such as fragrance substances where no ethical reasons object a substitution by less hazardous chemicals. ESS-Submission Editor: Dr. Thomas Knacker (th-knacker@ect.de)     

Principles and perspectives

BACKGROUND, AIM AND SCOPE: With respect to the enormous increase of chemical production in the last decades and the tens of thousands of individual chemicals on the market, the permanent improvement of chemical management is a permanent target to achieve the goals of sustainable consumption and production set by the WSSD in Johannesburg 2002. MAIN FEATURES: Several approaches exist to describe sustainability of chemistry. However, commonly agreed criteria are still missing. There is no doubt that products of modern chemistry help to achieve important goals of sustainability and that significant improvements have occurred regarding direct releases from production sites, but several facts demonstrate that chemistry is far from being sustainable. Still too many chemicals exhibit hazardous characteristics and pose a risk to health and environment. Too many resources are needed to produce chemicals and finished products. RESULTS AND CONCLUSION: Therefore, a strategy for sustainability of chemistry should be developed which comprises the following main elements: 1. Sustainable chemicals: sustainable chemical management includes a regulatory framework which makes no difference between new and existing chemicals, contains efficient information flow through the supply chain which allows users to handle chemicals safely and offers an authorisation procedure and/or an efficient restriction procedure for substances of high concern. This regulatory scheme should promote the development of inherently safe chemicals. 2. Sustainable chemical production: Sustainable chemical production needs the development and implementation of emerging alternative techniques like selective catalysis, biotechnology in order to release less CO2 and less toxic by-products, to save energy and to achieve higher yields. Information exchange on best available techniques (BAT) and best environmental practices (BEP) may help to promote changes towards more sustainability. 3. Sustainable products: An integrated product policy which provides a framework for sustainable products promotes the development of products with a long-term use phase, low resource demand in production and use, low emission of hazardous substances and properties suitable for reuse and recycling. This may be promoted by eco-labelling, chemical leasing concepts and extended information measures to enhance the demand of consumers and various actors in the supply chain for sustainable products. RECOMMENDATION AND PERSPECTIVE: Important tools for the promotion of sustainable chemistry are the abolition of barriers for innovation in legislation and within the chemical industry, more transparency for all users of chemical products, a new focus on sustainability in education and research, and a new way of thinking in terms of sustainability.     

A review of personal care products in the aquatic environment: environmental concentrations and toxicity

Considerable research has been conducted examining occurrence and effects of human use pharmaceuticals in the aquatic environment; however, relatively little research has been conducted examining personal care products although they are found more often and in higher concentrations than pharmaceuticals. Personal care products are continually released into the aquatic environment and are biologically active and persistent. This article examines the acute and chronic toxicity data available for personal care products and highlights areas of concern. Toxicity and environmental data were synergized to develop a preliminary hazard assessment in which only triclosan and triclocarban presented any hazard. However, numerous PCPs including triclosan, paraben preservatives, and UV filters have evidence suggesting endocrine effects in aquatic organisms and thus need to be investigated and incorporated in definitive risk assessments. Additional data pertaining to environmental concentrations of UV filters and parabens, in vivo toxicity data for parabens, and potential for bioaccumulation of PCPs needs to obtained to develop definitive aquatic risk assessments.     

Including degradation products of persistent organic pollutants in a global multi-media box model

GOAL, SCOPE AND BACKGROUND: Global multi-media box models are used to calculate the fate of persistent organic chemicals in a global environment and assess long-range transport or arctic contamination. Currently, such models assume substances to degrade in one single step. In reality, however, intermediate degradation products are formed. If those degradation products have a high persistence, bioaccumulation potential and / or toxicity, they should be included in environmental fate models. The goal of this project was to gain an overview of the general importance of degradation products for environmental fate models, and to expand existing, exposure-based hazard indicators to take degradation products into account. METHODS: The environmental fate model CliMoChem was modified to simultaneously calculate a parent compound and several degradation products. The three established hazard indicators of persistence, spatial range and arctic contamination potential were extended to include degradation products. Five well-known pesticides were selected as example chemicals. For those substances, degradation pathways were calculated with CATABOL, and partition coefficients and half-lives were compiled from literature. RESULTS: Including degradation products yields a joint persistence value that is significantly higher than the persistence of the parent compound alone: in the case of heptachlor an increase of the persistence by a factor of 58 can be observed. For other substances, the increase is much smaller (4% for alpha-HCH). The spatial range and the arctic contamination potential (ACP) can increase significantly, too: for 2,4-D and heptachlor, an increase by a factor of 2.4 and 3.5 is seen for the spatial range. However, an important increase of the persistence does not always lead to a corresponding increase in the spatial range: the spatial range of aldrin increases by less than 50%, although the persistence increases by a factor of 20 if the degradation products are included in the assessment. Finally, the arctic contamination potential can increase by a factor of more than 100 in some cases. DISCUSSION: Influences of parent compounds and degradation products on persistence, spatial range and ACP are discussed. Joint persistence and joint ACP reflect similar characteristics of the total environmental exposure of a substance family (i.e., parent compound and all its degradation products). CONCLUSIONS: The present work emphasizes the importance of degradation products for exposure-based hazard indicators. It shows that the hazard of some substances is underestimated if the degradation products of these substances are not included in the assessment. The selected hazard indicators are useful to assess the importance of degradation products. RECOMMENDATIONS AND PERSPECTIVES: It is suggested that degradation products be included in hazard assessments to gain a more accurate insight into the environmental hazard of chemicals. The findings of this project could also be combined with information on the toxicity of degradation products. This would provide further insight into the importance of degradation products for environmental risk assessments.     

Occurrence of PPCPs in the marine environment: a review

Little research has been conducted on the occurrence of pharmaceuticals and personal care products (PPCPs) in the marine environment despite being increasingly impacted by these contaminants. This article reviews data on the occurrence of PPCPs in seawater, sediment, and organisms in the marine environment. Data pertaining to 196 pharmaceuticals and 37 personal care products reported from more than 50 marine sites are analyzed while taking sampling strategies and analytical methods into account. Particular attention is focused on the most frequently detected substances at highest concentrations. A snapshot of the most impacted marine sites is provided by comparing the highest concentrations reported for quantified substances. The present review reveals that: (i) PPCPs are widespread in seawater, particularly at sites impacted by anthropogenic activities, and (ii) the most frequently investigated and detected molecules in seawater and sediments are antibiotics, such as erythromycin. Moreover, this review points out other PPCPs of concern, such as ultraviolet filters, and underlines the scarcity of data on those substances despite recent evidence on their occurrence in marine organisms. The exposure of marine organisms in regard to these insufficient data is discussed.     

Oxidative transformation of polybrominated diphenyl ether congeners (PBDEs) and of hydroxylated PBDEs (OH-PBDEs)

BACKGROUND, AIM, AND SCOPE: The historical and widespread use of polybrominated diphenyl ethers (PBDEs) as flame retardants in consumer products worldwide has caused PBDEs to now be regarded as pervasive environmental contaminants. Most recently, hydroxylated PBDEs (OH-PBDEs) and methoxylated PBDEs (MeO-PBDEs) have emerged as environmentally relevant due to reports of their natural production and metabolism. An important parameter for assessing the environmental impact of a chemical substance is persistence. By formulating the concept that persistence is the result of the substance's physicochemical properties and chemical reactivity, Green and Bergman have proposed a new methodology to determine the inherent persistence of a chemical. If persistence could be predicted by straightforward methods, substances with this quality could be screened out before large-scale production/manufacturing begins. To provide data to implement this concept, we have developed new methodologies to study chemical transformations through photolysis; hydrolysis, substitution, and elimination; and via oxidation. This study has focused on adapting an oxidative reaction method to be applicable to non-water soluble organic pollutants. MATERIALS AND METHODS: PBDEs and one MeO-PBDE were dissolved in tetrahydrofuran/methanol and then diluted in alkaline water. The OH-PBDEs were dissolved in alkaline water prior to reaction. The oxidation degradation reaction was performed at 50 degrees C using potassium permanganate as described elsewhere. The pH was maintained at 7.6 with disodium hydrogen phosphate and barium hydrogen phosphate, the latter also serving as a trapping agent for manganate ions. The oxidation reactions were monitored by high-performance liquid chromatography and reaction rates were calculated. RESULTS: The OH-PBDEs have very fast oxidative transformation rates compared to the PBDEs. The reaction rates seem to be primarily dependent on substitution pattern of the pi-electron-donating bromine substituents and of bromine content. There are indications that further reactions of OH-PBDEs, e.g., methylation to the MeO-PBDEs, decrease the oxidation rates, and thereby generate more persistent substances. DISCUSSION: The resistance of PBDEs to oxidation, a major degradation pathway in air, should be further investigated, since these compounds do undergo long range transport. With slight modifications, the original method has been adapted to include a larger variety of chemical substances, and preliminary data are now available on the oxidative transformation rates for PBDEs and of OH-PBDEs. CONCLUSIONS: The original oxidation degradation method can now include non-water soluble compounds. This modification, using low concentrations of test chemicals, allows us to measure oxidative transformation rates, for some of the lower brominated DEs, data that can be used to assess their persistence in future model calculations. Oxidative transformation rates for PBDEs are slow compared to those for the OH-PBDEs. This suggests that OH-PBDEs, when released into the environment, undergo faster oxidative metabolism and excretion than the PBDEs. RECOMMENDATIONS AND PERSPECTIVES: To evaluate the modified method, more degradation reactions with non-water soluble compounds should be investigated. Recent studies show that OH-PBDEs are present in rats and in humans and, because of their activity as endocrine disruptors, determining their subsequent environmental fate is of importance. The resistance of PBDEs to oxidative degradation should be acknowledged as of possible future concern. Several other compound classes (such as polychlorinated biphenyls (PCBs), hydroxylated polychlorinated biphenyls (OH-PCBs), and pharmaceuticals) need to be subjected to this screening method to increase the database of transformation rates that can be used with this model.     

Aerobic biodegradability of the calcium channel antagonist verapamil and identification of a microbial dead-end transformation product studied by LC-MS/MS

In recent years pharmaceuticals and personal care products have been detected in increasing concentrations in hospital effluents, sewage treatment plants (STP) as well as in different environmental compartments such as surface water, groundwater and soil. Little is known about the elimination of these substances during sewage treatment or about the formation of potential metabolites in the environment caused by bacterial biotransformation. To assess the biodegradability of the popular cardiovascular drug verapamil and the possible formation of potential microbial degradation products, two tests from the OECD series were used in the present study: the widely used Closed Bottle test (OECD 301 D) and the modified Zahn-Wellens test (OECD 302 B). In the Closed Bottle test, a screening test that simulates the conditions of an environmental surface water compartment, no biological degradation was observed for verapamil at concentrations of 2.33mgl(-1). In the Zahn-Wellens test, a test for inherent biodegradability which allows evaluation of aerobic degradation at high bacterial density, only a partial biological degradation was found. Analysis of test samples by high performance liquid chromatography coupled to multiple stage mass spectrometry (HPLC-MSn) revealed 2-(3,4-dimethoxyphenyl)-2-isopropyl-5-(methylamino)pentane nitrile, already known as D617 (Knoll nomenclature), a metabolite of mammalian metabolism, which is the major degradation product and dead-end transformation product of aerobic degradation of verapamil.     

Modelling concentrations of decamethylcyclopentasiloxane in two UK rivers using LF2000-WQX

Current regulatory environmental exposure assessments for decamethylcyclopentasiloxane (D₅), used in a range of personal care products, are based on a number of erroneous assumptions. Using an estimated D₅ flux to waste water of 11.6 mg cap⁻¹ d⁻¹, a 95.2% removal rate in Sewage Treatment Plants (STP) and a dilution factor of 10 results in modelled surface water concentrations that are up to an order of magnitude higher than concentrations observed downstream of STPs in two UK rivers. A GIS-based water quality model (LF2000-WQX) was used to predict concentrations of D₅ in two UK rivers. Assuming the STP removal rate is reasonable, a waste water flux of 2.4 mg cap⁻¹ d⁻¹ is needed in order to obtain a reasonable match between predicted and observed in-river concentrations. This flux is consistent with measured effluent concentrations. The results highlight major uncertainties in estimating chemical emission rates for volatile chemicals used in personal care products and suggest that measured concentrations in waste water are needed to refine exposure assessments.     

Pharmaceuticals and personal care products (PPCPs) in Arctic environments: indicator contaminants for assessing local and remote anthropogenic sources in a pristine ecosystem in change

A first review on occurrence and distribution of pharmaceuticals and personal care products (PPCPs) is presented. The literature survey conducted here was initiated by the current Assessment of the Arctic Monitoring and Assessment Programme (AMAP). This first review on the occurrence and environmental profile of PPCPs in the Arctic identified the presence of 110 related substances in the Arctic environment based on the reports from scientific publications, national and regional assessments and surveys, as well as academic research studies (i.e., PhD theses). PPCP residues were reported in virtually all environmental compartments from coastal seawater to high trophic level biota. For Arctic environments, domestic and municipal wastes as well as sewage are identified as primary release sources. However, the absence of modern waste water treatment plants (WWTPs), even in larger settlements in the Arctic, is resulting in relatively high release rates for selected PPCPs into the receiving Arctic (mainly) aquatic environment. Pharmaceuticals are designed with specific biochemical functions as a part of an integrated therapeutically procedure. This biochemical effect may cause unwanted environmental toxicological effects on non-target organisms when the compound is released into the environment. In the Arctic environments, pharmaceutical residues are released into low to very low ambient temperatures mainly into aqueous environments. Low biodegradability and, thus, prolonged residence time must be expected for the majority of the pharmaceuticals entering the aquatic system. The environmental toxicological consequence of the continuous PPCP release is, thus, expected to be different in the Arctic compared to the temperate regions of the globe. Exposure risks for Arctic human populations due to consumption of contaminated local fish and invertebrates or through exposure to resistant microbial communities cannot be excluded. However, the scientific results reported and summarized here, published in 23 relevant papers and reports (see Table S1 and following references), must still be considered as indication only. Comprehensive environmental studies on the fate, environmental toxicology, and distribution profiles of pharmaceuticals applied in high volumes and released into the Nordic environment under cold Northern climate conditions should be given high priority by national and international authorities.     

Simulated use and wash-off release of decamethylcyclopentasiloxane used in anti-perspirants

The cyclic volatile methylsiloxane, decamethylcyclopentasiloxane (D₅) is used in a large variety of personal care products. Based on the physical–chemical properties of D₅, it is likely that losses due to volatilisation may strongly influence the levels entering the aquatic environment. The aim of this study was to quantify the amount of D₅ in waste wash water, after typical application and use in a range of deodorant and anti-perspirant (AP) products. Results implied significant losses after a 24 h period (>99.9%), and suggest that the use of D₅ in leave-on products, such as deodorants/AP is not likely to contribute a significant down-the-drain emission source. An illustrative example is presented, based on data reporting the use of D₅ in a range of personal care products (both wash-off and leave-on), which suggests that the contribution of D₅ used in wash-off products to the aquatic environment may be considerably more significant. Limitations associated with our understanding of the actual D₅ inclusion levels in the products, the market share of the products containing D₅, and the variability of consumer habits, are identified as data gaps that need to be addressed in order to better refine down-the-drain emission estimates.     

Aqueous photolysis of the iron (III) complexes of NTA, EDTA and DTPA

The rate of photolysis of iron complexes with three common complexing agents, NTA, EDTA and DTPA was analysed. Aqueous solutions of each complex were illuminated in a Xenotest 1200. Using a sun spectrum from 60°N (Stockholm latitude), environmentally related half lifetimes were calculated.

The half lifetimes were 43, 11 and 8 min for the three 1:1 complexes, resp., dissolved in the top layer of a water system and illuminated at the yearly maximum of sun light in the specified area. In the environment several factors operate to reduce this rate. However, photolytic degradation pathways seem to be an important environmental fate of these substances.     

Perfluoroalkyl and polyfluoroalkyl substances (PFASs) in consumer products in Norway - a pilot study

Perfluoroalkyl and polyfluoroalkyl substances (PFAS) are used in numerous industrial and consumer products because of their special chemical properties, for instance the ability to repel both water and oil. A broad variety of PFAS have been introduced into the Norwegian market through industrial use (e.g. via fire fighting foams and paints) as well as in treated customer products such as textiles and coated paper. Our present knowledge of the exact chemical PFAS compositions in preparations using perfluorinated compounds is limited. This lack of knowledge means that it is difficult to provide an accurate assessment of human exposure to these compounds or to the amount of waste that may contain treated products. It is a growing concern that these potentially harmful compounds can now be found throughout the global environment.Samples of consumer products and preparations were collected in Norway, with supplemental samples from Sweden. In 27 of the 30 analyzed consumer products and preparations a number of polyfluorinated substances that were analyzed were detected but this does not exclude the occurrence of unknown PFAS. Notable was that perfluorooctanesulphonate (PFOS), which has been strictly regulated in Norway since 2007, was found in amounts close to or exceeding the EU regulatory level in 4 of the 30 analyzed products, all within the leather or carpet product groups. High amounts of fluorotelomer alcohols (FTOHs) were found in waterproofing agents, carpets and textiles, consistent with earlier findings by Fiedler et al. (2010). The presence of PFAS in a broad range of consumer products can give rise to a constant diffuse human exposure that might eventually result in harm to humans.     

Occurrence and toxicity of antimicrobial triclosan and by-products in the environment

Introduction and aims  

A review was undertaken on the occurrence, toxicity, and degradation of triclosan (TCS; 5-chloro-2,4-dichlorophenoxy)phenol) in the environment. TCS is a synthetic, broad-spectrum antibacterial agent incorporated in a wide variety of household and personal care products such as hand soap, toothpaste, and deodorants but also in textile fibers used in a range of other consumer products (e.g., toys, undergarments and cutting boards among other things).     

Photochemical behaviour of musk tibetene

BACKGROUND: Synthetic musk compounds are widely used as additives in personal care and household products. The photochemical degradation of musk tibetene in aqueous solutions or in acetonitrile/water mixtures under different conditions was studied in order to assess its environmental fate. METHODS: Musk tibetene dissolved (or suspended) in water and/or acetonitrile/water mixtures was irradiated at different times by UV-light and by solar light. The irradiation mixtures were analyzed by NMR and TLC. The photoproducts formed were identified by GC-MS and NMR data. RESULTS: The experimental results indicated that musk tibetene was photodegradable in water or acetonitrile/water mixtures with half-life reaction times close to 20 minutes. The irradiation mixtures were separated by chromatographic techniques yielding three photoproducts (3,3,5,6,7-pentamethyl-4-nitro-3H-indole, 3,3,5,6,7-pentamethyl-4-nitro-1H-indoline and 3,3,5,6,7-pentamethyl-4-nitro-3H-indolinone) identified by means of spectroscopic analysis. DISCUSSION: The numerical modelling of the photodegradation concentration-time profiles gave (8.13 +/- 0.15) x 10(-2) and (1.34 +/- 0.04) x 10(-2) mol/E for the overall primary quantum yield of direct photolysis for musk tibetene and the major intermediate (3,3,5,6,7-pentamethyl-4-nitro-3H-indolinone), respectively, in the wavelength range 305-366 nm. The half-life times of photodegradation of the both substances varied from 1-1.5 hours at 20 degrees N during the summer season to 6-10 hours for highest latitudes in winter. CONCLUSIONS: Under solar light, musk tibetene was photolabile in acetonitrile and acetonitrile/water 1/1, while it was slowly degraded when suspended in water. In all media, musk tibetene was photodegraded into three photoproducts. By using a kinetic model, the overall primary quantum yields of direct photolysis of musk tibetene and its main photoproduct, in the wavelength range 305-366 nm, were estimated, indicating that the photodegradation rate for musk tibetene is faster than the photolysis rate of the major by-product. RECOMMENDATIONS AND PERSPECTIVES: The results indicate that, in order to assess the environmental impact of musk tibetene on the aquatic ecosystem, great attention should be focused on the major photoproduct which is proved to be more persistent than the parent compound under light irradiation. The predicted half-life times of direct photolysis for both substances ranged from 1-1.5 hours at 20 degrees N during the summer season to about 6-10 hours for highest latitudes in winter, indicating that, from a photochemical point of view, the environmental persistence of these substances increases by increasing the latitudes and during the cold seasons, making more realistic an intake of these xenobiotic molecules into the food chain of aquatic living organisms. Tanabe reports in his Editorial (Tanabe 2005) that "It is necessary to have knowledge of the global picture of synthetic musk pathways. So, it is conceivable that now is the time to study the transport, persistency, distribution, bioaccumulation and toxic potential of this new environmental menace on a global scale, especially in developing countries". Therefore, the future environmental analysis and investigations on the eco-toxicity of nitro musk compounds should take into account not only the presence of the parent compounds but also their photochemical intermediates or end-by-products.     

环境介质中药物和个人护理品的潜在风险研究进展

药物和个人护理品(PPCPs)在环境介质中的残留物作为一种新型污染物在环境介质中的转归,逐渐成为环境工作者和公众密切关注的焦点.这些物质特殊的物化特性及其被大量使用的现状,给生态环境和人类健康带来一定的潜在风险.由PPCPs使用所引发的风险问题正在成为当前学术界所面临的研究方向之一.欧洲和美国已经开始了对PPCPs的风险评估研究,中国研究者仅对某些药物的分析检测方法进行了初步探索,对PPCPs的潜在风险研究还呈空白.从PPCPs的物化特性及其对环境介质的影响入手,对其潜在风险进行了分析,并介绍了目前国外PPCPs风险研究进展,以期为中国开展PPCPs的风险评估提供参考.     

Phyto-products may be essential for sustainability and implementation of phytoremediation

Interest in selenium pollution and remediation technology has escalated during the past two decades. Although not known to be essential for plants, selenium is essential but could be toxic for humans and animals, depending on its concentration. A major selenium controversy in the 1980's emerged in California when the general public and scientific community became aware of selenium's potential as an environmental contaminant. After extensive research on several strategies to reduce loads of mobile Se for entering the agricultural ecosystem a plant-based technology, defined as 'phytoremediation' received increasing recognition, as a low-cost environmentally friendly approach for managing soluble Se in the soil and water environment. Successful long-term field remediation of Se by plants is, however, dependent upon acceptance and widespread use by growers, who are also concerned about potential commercial value from using the plant-based technology. Obtaining products with economic value from plants used in the cleanup of soil would certainly be an additional benefit to phytoremediation, which could help sustain its long-term use.     

Occurrence of phthalates in aquatic environment and their removal during wastewater treatment processes: a review

Phthalates are plasticizers and are concerned environmental endocrine-disrupting compounds. Due to their extensive usage in plastic manufacturing and personal care products as well as the potential to leach out from these products, phthalates have been detected in various aquatic environments including drinking water, groundwater, surface water, and wastewater. The primary source of their environmental occurrence is the discharge of phthalate-laden wastewater and sludge. This review focuses on recent knowledge on the occurrence of phthalate in different aquatic environments and their fate in conventional and advanced wastewater treatment processes. This review also summarizes recent advances in biological removal and degradation mechanisms of phthalates, identifies knowledge gaps, and suggests future research directions.     

Sensitized photooxygenation of the fungicide furalaxyl

BACKGROUND: The photolysis of pesticides is of high current interest since light is one of the most important abiotic factors which are responsible for the environmental fate of these substances and may induce their conversion into noxious products. The action of light can also be mediated by oxygen and synthetic or naturally occurring substances which act as sensitizers. Our objective in this study was to investigate the photochemical behaviour of the systemic fungicide furalaxyl in the presence of oxygen and various sensitizers, and to compare the toxicity of the main photoproduct(s) to that of the parent compound. Previous reports on the direct photolysis of the pesticide demonstrated a very slow degradation and the only identified photoproducts were N-2,6-xylyl-D,L-alaninare and 2,6-dimethylaniline. METHODS: Solutions of furalaxyl in CH3CN were photooxygenate using a 500W high-pressure mercury lamp (through a Pyrex glass filter, lambda>300 nm) or a 650W halogen lamp or sunlight and the proper sensitizer. When sunlight was used, aqueous solutions were employed. The photodegradation was checked by NMR and/or GC-MS. The photoproducts were spectroscopically evidenced and, when possible, isolated chromatographically. Acute toxicity tests were performed on the rotifer Brachionus calyciflorus, the crustacean cladoceran Daphnia magna and the anostracan Thamnocephalus platyurus, while chronic toxicity tests (sublethal endpoints) comprised a producer, the alga Pseudokirchneriella subcapitata and the crustacean Ceriodaphnia dubia, as a consumer. RESULTS AND DISCUSSION: In the presence of both oxygen and sensitizer, furalaxyl underwent rapid photochemical transformations mainly to N-disubstituted formamide, maleic anhydride and a 2(5H)-furanone derivative. The formation of these products was rationalized in terms of a furan endoperoxide intermediate derived from the reaction of furalaxyl with active dioxygenated species (singlet oxygen, superoxide anion or ground state oxygen). The 2(5H)-furanone exhibited a higher toxicity than the parent compound. CONCLUSION: This work reports the first data on the photosensitized oxygenation of furalaxyl with evidence of the high tendency of the pesticide to undergo photodegradation under these conditions leading, among other things, to a 2(5H)-furanone, which is more toxic than the starting furalaxyl towards aquatic organisms. RECOMMENDATIONS AND OUTLOOK: Investigation highlights that the photolytic fate of a pesticide, although quite stable to direct photoreaction due to its low absorption of solar radiation at ground level, can be significantly influenced in the environment by the presence of substances with energy or electron-transfer properties as natural dyes, e.g. chlorophyll, or synthetic pollutants, e.g. polycyclic aromatic hydrocarbons (PAH).     

Application of a novel modeling tool with multistressor functionality to support management of organic contaminants in the Baltic Sea

Organic contaminants constitute one of many stressors that deteriorate the ecological status of the Baltic Sea. When managing environmental problems in this marine environment, it may be necessary to consider the interactions between various stressors to ensure that averting one problem does not exacerbate another. A novel modeling tool, BALTSEM-POP, is presented here that simulates interactions between climate forcing, hydrodynamic conditions, and water exchange, biogeochemical cycling, and organic contaminant transport and fate in the Baltic Sea. We discuss opportunities to use the model to support different aspects of chemicals management. We exemplify these opportunities with a case study where two emission-reduction strategies for a chemical used in personal care products (decamethylcyclopentasiloxane) are evaluated, and where the confounding influence of future climate change and eutrophication on the impact of the emission-reduction strategies are assessed.