Polyfluoroalkyl compounds in the aquatic environment: a review of their occurrence and fate

The occurrence and fate of polyfluoroalkyl compounds (PFCs) in the aquatic environment has been recognized as one of the emerging issues in environmental chemistry. PFCs comprise a diverse group of chemicals that are widely used as processing additives during fluoropolymer production and as surfactants in consumer applications for over 50 years. PFCs are known to be persistent, bioaccumulative and have possible adverse effects on humans and wildlife. As a result, perfluorooctane sulfonate (PFOS) has been added to the persistent organic pollutants (POPs) list of the Stockholm Convention in May 2009. However, their homologues, neutral precursor compounds and new PFCs classes continue to be produced. In general, several PFCs from different classes have been detected ubiquitously in the aqueous environment while the concentrations usually range between pg and ng per litre for individual compounds. Sources of PFCs into the aqueous environment are both point sources (e.g., wastewater treatment plant effluents) and nonpoint sources (e.g., surface runoff). The detected congener composition in environmental samples depends on their physicochemical characteristics and may provide information to their sources and transport pathways. However, the dominant transport pathways of individual PFCs to remote regions have not been conclusively characterised to date. The objective of this article is to give an overview on existing knowledge of the occurrence, fate and processes of PFCs in the aquatic environment. Finally, this article identifies knowledge gaps, presents conclusions and recommendations for future work.     

Pyrethroid insecticides in bed sediments from urban and agricultural streams across the United States

Pyrethroid insecticides are hydrophobic compounds that partition to streambed sediments and have been shown to cause toxicity to non-target organisms; their occurrence is well documented in parts of California, but there have been limited studies in other urban and agricultural areas across the United States. To broaden geographic understanding of pyrethroid distributions, bed sediment samples were collected and analyzed from 36 streams in 25 states, with about 2/3 of the sites in urban areas and 1/3 in agricultural areas. At least one pyrethroid (of the 14 included in the analysis) was detected in 78% of samples. Seven pyrethroids were detected in one or more samples. Bifenthrin was the most frequently detected (58% of samples), followed by permethrin (31%), resmethrin (17%), and cyfluthrin (14%). The other three detected pyrethroids (cyhalothrin, cypermethrin and delta/tralomethrin) were found in two or fewer of the samples. Concentrations ranged from 0.3 to 180 ng g(-1) dry weight. The number of pyrethroids detected were higher in the urban samples than in the agricultural samples, but the highest concentrations of individual pyrethroids were split between urban and agricultural sites. The pyrethroids detected in the agricultural areas generally followed use patterns. Predicted toxicity was greater for urban areas and attributed to bifenthrin, cyfluthrin and cypermethrin, while in agricultural areas the toxicity was mainly attributed to bifenthrin.     

Pesticide burden on some insects of economic importance in Lucknow (India)

Some insects of economic importance from Lucknow (India) have been investigated for their pesticide burden. Chlorinated pesticide residues of DDT, BHC and aldrin along with their metabolites and isomers have been detected in crop pollinating insects, honeybees (Apis indica) and butterflies (Danais chrysippus and Eurema sp.) and predators, dragonfly (Platythemis sp.) and wasps (Polistes herebreus). DDT and their metabolites were present in concentrations which varied from 231–796 ng g^–1, followed by BHC (10–60 ng g^–1), and aldrin (0.26–6.68 ng g^–1). This finding is likely to stimulate newer interest in the area of pesticide research and start meaningful investigation to find if bioaccumulated pesticides would have adverse impact on otherwise beneficial potentials of such insects in our ecosystems.     

Detection of polybrominated diphenyl ethers in tilapia (Oreochromis mossambicus) from O'ahu, Hawai;i

Polybrominated diphenyl ethers (PBDEs) have been detected for the first time at a range from 231.58 to 685.61 ng g(-1) lipid weight in the muscles of tilapia (Oreochromis mossambicus) collected from O'ahu, an island of the geographically isolated Hawaiian archipelago.     

Evaluation of soil contamination in intensive agricultural areas by pesticides and organic pollutants: south-eastern Spain as a case study

A comprehensive survey of the occurrence and fate of pesticides and organic contaminants in soils from an intensive agricultural area devoted to horticultural production in plastic-based greenhouses has been performed to determine if the operation under integrated pest management practices has contributed to reduce the levels of these compounds. Almería province (south-eastern Spain) was selected for the case study. 38 agricultural soil samples (each sample corresponds to an independent private greenhouse) of areas working under integrated pest management (IPM) programs have been analyzed in order to evaluate their contamination fate. Sampling was designed to cover an area of about 400 km(2). Pesticides, polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), phenolic compounds and di-(2-ethylhexyl)phthalate (DEHP) were monitored. The obtained results were compared to other studies reported in Spain and Europe. Among relevant persistent pesticides, DDTs and endosulfans were mainly found and the results indicated historical application, although recent application of endosulfan was rarely detected. PAHs were also found but to a lesser extent and derived from pyrogenic sources. DEHP levels were considerably higher in comparison to the other monitored analytes. The evaluation revealed that despite the use of IPM programs, pesticide and organic contaminants are still being detected in this type of agricultural soil, although at relatively low concentration levels. In general, the contamination rate was similar or lower in comparison to other agricultural areas from nearby regions or countries. However, further monitoring studies should be carried out to establish the possible reduction in contamination by the selected compounds.     

九洲江沉积物多环芳烃和抗生素的分布特征与风险评价

利用液相色谱-三重四级杆质谱法(HPLC-MS/MS)以及超高压液相色谱法(HPLC),于2018年1月对九洲江沉积物样品中31种抗生素和16种多环芳烃(PAHs)的分布特征进行研究并评价其生态风险。结果表明,九洲江沉积物检出20种抗生素,其中四环素类(TCs)抗生素质量分数最高,或因其在养殖业用量最大且易被沉积物吸附;滩面镇（S3点位）抗生素的总质量分数（52 ng/g）最高,与附近的滩面镇生猪养殖业发达,也与S3点位正好位于污水处理厂排口下游不远处有关;沉积物中共检出15种PAHs,温泉镇（S1点位）沉积物中PAHs的质量分数最高。沉积物中,4环PAHs占比最高,说明九洲江流域PAHs主要来源于煤和木柴的燃烧。生态风险评价结果表明,TCs抗生素处于高风险水平,且高风险点集中出现在滩面镇河段（S3点位）,需要采取措施减少TCs抗生素的使用;所有点位的PAHs的生态风险均为低风险,但有部分无安全剂量的PAHs组分被检出,对九洲江生态环境存在潜在威胁。     

Bioluminescent yeast estrogen assay (BLYES) as a sensitive tool to monitor surface and drinking water for estrogenicity

Estrogenic Endocrine Disrupting Chemicals (EDCs) are a concern due to their ubiquity and recognized adverse effects to humans and wildlife. Methods to assess exposure to and associated risks of their presence in aquatic environment are still under development. The aim of this work is to assess estrogenicity of raw and treated waters with different degrees of pollution. Chemical analyses of selected EDCs were performed by liquid chromatography-tandem mass spectrometry, and estrogenic activity was evaluated using in vitro bioluminescent yeast estrogen assay (BLYES). Most raw water samples (18/20) presented at least one EDC and 16 rendered positive in BLYES. When EDCs were detected, the bioassay usually provided a positive response, except when only bisphenol A was detected at low concentrations. The highest values of estrogenic activity were detected in the most polluted sites. The maximum estrogenic activity observed was 8.7 ng equiv. of E2 L(-1). We compared potencies observed in the bioassay to the relative potency of target compounds and their concentrations failed to fully explain the biological response. This indicates that bioassay is more sensitive than the chemical approach either detecting estrogenic target compounds at lower concentrations, other non-target compounds or even synergistic effects, which should be considered on further investigations. We have not detected either estrogenic activity or estrogenic compounds in drinking water. BLYES showed good sensitivity with a detection limit of 0.1 ng equiv. E2 L(-1) and it seems to be a suitable tool for water monitoring.     

Aerobic biodegradation of linear alkylbenzene sulfonates and sulfophenylcarboxylic acids for different salinity values by means of continuous assays

Aerobic biodegradation of linear alkylbenzene sulfonates (LAS) and sulfophenylcarboxylic acids (SPCs) in water, at different salinity values, has been studied. Three experiments have been carried out employing a staircase model system with continuous dosage of LAS to the system and using concentrations of LAS of the same order as those detected in littoral waters receiving urban wastewater discharges. LAS biodegradation was observed to be almost complete (showing a great extent), and in all cases exceeds 98.4%. At the very low concentration values of LAS utilized in the experiments, no significant variations in the biodegradation of LAS due to the effect of the different salinity values assayed were observed. The biodegradation intermediates detected for all the cases were sulfophenylcarboxylic acids with carboxylic chains of between five and 13 carbon atoms. The detection of C13-SPC (which is only produced by C13-LAS) confirms the existence of ω-oxidation. The total disappearance of SPCs in all cases indicates that mineralization of LAS at the concentrations tested was complete.     

The environmental behaviour of polychlorinated phenols and its relevance to cork forest ecosystems: a review

Pentachlorophenol (PCP) has been used as a herbicide, biocide and preservative worldwide since the 1930s and as a result, extensive and prolonged contamination exists. The environmental impact increases when its many degradation products are taken into consideration. A number of chloroanisols and their related chlorophenols have been found in cork slabs collected from Portuguese oak tree forests before stopper manufacturing, and contamination by PCP and polychlorinated anisole (PCA) has been detected in Canadian forests. It is suggested that the use of polychlorinated phenols, in particular PCP, is thought to be a cause of the cork taint problem in wine, a major socio-economic impact not only for industry but on sensitive and highly biodiverse ecosystems. It also highlights particular issues relating to the regional regulation of potentially toxic chemicals and global economics world wide. To fully understand the impact of contamination sources, the mechanisms responsible for the fate and transport of PCP and its degradation products and assessment of their environmental behaviour is required. This review looks at the current state of knowledge of soil sorption, fate and bioavailability and identifies the challenges of degradation product identification and the contradictory evidence from field and laboratory observations. The need for a systematic evaluation of PCP contamination in relation to cork forest ecosystems and transfer of PCP between trophic levels is emphasised by discrepancies in bioaccumulation and toxicity. This is essential to enable long term management of not only transboundary contaminants, but also the sustainable management of socially and economically important forest ecosystems.     

Determination of Polycyclic Aromatic Hydrocarbons in Rougan, a Traditional Chinese Barbecued Food, by Capillary Gas Chromatography

Several polycyclic aromatic hydrocarbons (PAHs), including those which are carcinogenic, have been detected in rougan, a traditional Chinese barbecued pork dish. The food samples were cleaned up by caustic digestion, solvent extraction, liquid-liquid partition, and column chromatography. The determination was carried out using capillary gas-chromatography with a flame ionization detector. A 25-m HP-1 capillary column was used. Fluorene, phenanthrene, anthracene, benzo[a]anthracene, chrysene and benzo[k]fluoranthene were detected in three of the five samples within the range of 3-17 ng/g. Fluoranthene and pyrene were detected in only two of the samples at similar levels. Two potent carcinogenic compounds, benzo[a]pyrene and benzo[b,j,k]fluoranthene, were not detected in any of the samples. No detectable PAHs have been found in meat cooked without the direct contact of food with flame and smoke. In barbecuing over an open charcoal fire, animal fat and juices dripping onto the open fire probably enhanced the formation of PAHs.     

环境中新型阻燃剂检测技术研究进展

新型阻燃剂(NFRs)是传统阻燃剂受到严格管控后的推广替代品,主要包括新型溴代阻燃剂(NBFRs)、新型氯代阻燃剂(NCFRs)和有机磷酸酯阻燃剂(OPFRs)等。NFRs是一类新污染物,大多属于持久性有机污染物。目前,已有多种NFRs在世界各地被检出,引起各国的普遍关注,环境中NFRs的来源及迁移转化规律也由此成为新的研究热点。通过综述环境样品中NFRs检测技术在提取、净化和仪器检测等方面的国内外研究现状,讨论了各种分析技术的特点,分析了NFRs分析过程的质量控制与质量保证问题,展望了该领域未来的发展趋势。     

A positive chemical ionization GC/MS method for the determination of airborne ethylene glycol and propylene glycols in non-occupational environments

An analytical method for ethylene glycol and propylene glycols has been developed for measuring airborne levels of these chemicals in non-occupational environments such as residences and office buildings. The analytes were collected on charcoal tubes, solvent extracted, and analyzed by gas chromatography-mass spectrometry using a positive chemical ionization technique. The method had a method detection limit of 0.07 microg m(-3) for ethylene glycol and 0.03 microg m(-3) for 1,2- and 1,3-propylene glycols, respectively, based on a 1.44 m3 sampling volume. Indoor air samples of several residential homes and other indoor environments have been analyzed. The median concentrations of ethylene glycol and 1,2-propylene glycol in nine residential indoor air samples were 53 microg m(-3) and 13 microg m(-3) respectively with maximum values of 223 microg m(-3) and 25 microg m(-3) detected for ethylene glycol and 1,2-propylene glycol respectively. The concentrations of these two chemicals in one office and two laboratories were at low microg m(-3) levels. The maximum concentration of 1,3-propylene glycol detected in indoor air was 0.1 microg m(-3).     

Occurrence and fate of pharmaceuticals and personal care products in drinking water in southern China

Occurrence and fate of pharmaceuticals and personal care products (PPCPs) in drinking water was investigated in southern China. Fifteen and twelve PPCPs were detected with concentrations of 0-36 ng L(-1) in source water and of 0-20 ng L(-1) in treated water, respectively. Four PPCPs were detected with concentrations of approximately 1 ng L(-1) in drinking water of distribution network. Conventional water treatment processes removed the types and average concentrations of PPCPs by 30% and above 50%, respectively. Advanced water treatment processes were more efficient in the removal of most PPCPs, with the types and concentrations reduced by 50% and approximately 90%, respectively. Molecular properties of PPCPs had an important influence on their behaviors during water treatment. pK(a) (acidity coefficient) and K(oc) (organic carbon partition coefficient) of PPCPs appeared to have a combined effect on PPCPs removal during coagulation and oxidation. Adsorption and biodegradation were two possible mechanisms responsible for PPCPs removal during sand filtration.     

Spatial distribution and temporal trends of polycyclic aromatic hydrocarbons in Mytilus galloprovincialis from the Iberian Mediterranean coast

Polycyclic aromatic hydrocarbons (PAHs) have been determined in blue mussels (Mytilus galloprovincialis) from several Iberian Mediterranean coastal areas through the implementation of a monitoring programme from Spain in the framework of the Mediterranean Pollution Programme (MED POL). The selected areas correspond to sites with differing degrees of exposure to the main pollution sources (hot spots, coastal and reference areas). The sampling campaigns were performed from 2004 to 2009, with samples being taken from May to June, the non-spawning period for mussels in this area. Thirteen PAHs were determined by high-performance liquid chromatography with specific fluorescence detection. In general, total PAHs concentration was lower than 50 μg kg^?1 d.w., except in areas close to the principal ports and cities (Barcelona, Tarragona, Valencia and Algeciras) where it varies from 75 to 390 μg kg^?1 d.w. Background concentrations have been proposed for PAHs in mussels (23.8 μg kg^?1 d.w.) from Western Mediterranean area. Temporal trends were not statistically significant for PAHs concentrations from 2004 to 2009. Longer monitoring periods would be required to detect a continuous tendency, especially for PAHs because although the efficiency of combustion engines has reduced PAHs emissions, their increasing use could alter this potential reduction. The predominant PAHs were three and four ring congeners in all cases, with the predominance of phenanthrene in mussels sited far from the main PAHs sources. The phenanthrene/anthracene (lower than 10) and fluoranthene/pyrene (higher than 1) ratios indicate that PAHs detected in Spanish Mediterranean coastal mussels are mainly of pyrolytic origin.     

垃圾填埋场不同区域挥发性有机污染物季节变化特点

通过对北京某垃圾填埋场大气中不同区域挥发性有机污染物(VOCs)的定性和定量分析,研究了其中部分VOCs的季节性特点和浓度分布规律。结果表明,夏、冬2季分别检测出98种和86种化合物,有12种美国环保署(USEPA)优先控制污染物在夏、冬季样品中均有检出。夏季样品中VOCs的浓度大多比冬季高,有的甚至高1个数量级以上。采用不同卫生填埋技术的各代表性区域的臭气浓度也呈现出规律性变化。为加强科学管理,减少扩散,降低风险提供参考。     

Chromatium species: an emerging bioindicator of crude oil pollution of tidal mud flats in the Niger Delta mangrove ecosystem, Nigeria

Establishing microbiological indices for the monitoring of environmental decay by crude oil pollution in the Niger Delta region has been a major concern of our current researches. Chromatium species, a purple, Gram positive pleomorphic, motile, microaerophlic sulfur bacterium offers a good potential for use in the assessment of the short term effects of oil pollution of tidal mud flats in the Niger Delta mangrove ecosystem. Its response to the November 22, 2003 spillage at the Qua Iboe Estuary and the adjoining Cross River Estuary was investigated. Our results have revealed that the sulphur bacterium is easily identified and widely distributed in the epipellic sediment of the mangrove ecosystem but very sensitive to hydrocarbon pollution. The bacterium was readily detected in the tidal mud flats containing as much as 2.0 mg kg(-1) but not detected in sediment with THC level of 3.65 mg kg(-1) and above. It is thus, suggestive that the threshold and lethal limits of effect of hydrocarbons against the sulfur bacterium lies between 2.04 and 3.65 mg kg(-1). These imply that in any case of crude oil pollution that Chromatium is not detected during monitoring the THC levels of the sediment may have been raised to a level close to or above 3.65 mg kg(-1). Statistical analysis of the relationship between THC level and density of Chromatium in sediment revealed a significant (p < 0.05) negative relationship (r = -0.85) in Qua Iboe mangrove ecosystem as against an insignificant (p > 0.05) relationship (r = -0.41) recorded for the Cross River mangrove ecosystem which served as the control. The result indicates that oil pollution affect the homeostatic status of Chromatium in tidal mud flats despite its even distribution (R2 = 71.4%). The finding though not definitive may contribute to the hierarchical process of oil pollution assessment in the Niger Delta region of Nigeria. However, its effective utilization will require not only the development of a selective medium for enumeration and isolation of the bacterium but also the establishment of a defined dose-response relationship under controlled conditions which requires further research.     

化工废水中邻苯二甲酸酯的研究

对北京市五个化工厂的废水中8种邻苯二甲酸酯类环境激素进行分析和调查研究.在化工废水中普遍检出的邻苯二甲酸酯有邻苯二甲酸二丁酯(DBP)、邻苯二甲酸二(2-乙基己基)酯(DEHP)、邻苯二甲酸丁基苄基酯(BBP)、邻苯二甲酸二环己酯(DCHP),其中邻苯二甲酸二乙酯(DEP)、邻苯二甲酸二正丙酯(DPrP)、邻苯二甲酸二戊酯(DAP)和邻苯二甲酸二正己酯(DHP)4种物质未检出.废水中DEHP和DBP的浓度均低于排放标准.     

WATER AND WASTEWATER QUALITY MONITORING, MCMURDO STATION, ANTARCTICA

McMurdo Station is the largest research station in Antarctica and has a population that ranges from 250 to 1200 people. Wastewater from the Station is macerated, was sometimes mixed with waste brine from the desalinization plant and is discharged to McMurdo Sound. Effluent water quality has been routinely monitored since 1989, and a special ambient water quality study was conducted by Idaho National Engineering Laboratory (INEL) personnel in 1992. Results of the effluent monitoring efforts show that low concentrations of a few organic contaminants have been detected, while concentrations of metals, particularly copper, are considerably higher. Ambient water quality and sea ice monitoring detected very few contaminants, all at very low levels. Only minor and variable dissolved oxygen depression was detected near the outfall. Diatom communities near the outfall differ in relative abundance, cell counts, and chlorophyll a content compared to control sites. For the purpose of evaluating the impact of McMurdo`s effluent on ambient water quality, improved effluent monitoring and sediment quality monitoring are recommended instead of frequent monitoring of ambient water quality.