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In this work, the analysis of alkylphenols, bisphenols and alkylphenol ethoxylates in bottled waters, kombuchas and water kefir was performed through a vortex-assisted dispersive liquid–liquid microextraction method based on a natural hydrophobic eutectic solvent. For this purpose, mixtures of monoterpenes and fatty acids were employed. Different factors affecting extraction were optimized and the method was validated in terms of matrix effect, linearity, limits of detection and recovery. Recovery values varied between 70.0 and 124.3% (except for 4-tert-butylphenol: 67.0% and 4-n-nonylphenol: 60.8% in water kefir) and limits of detection were in the range 0.10 ng/L – 2.99 µg/L. Finally, 8 bottled waters, 8 kombuchas and 4 water kefirs were analyzed and 4-tert-octylphenol monoethoxylate was detected in water (20.28 ± 0.99 – 62.08 ± 3.63 µg/L). This is the first application analyzing xenobiotic contaminants in kombucha and water kefir and the first time in which the three types of compounds are simultaneously extracted by dispersive liquid–liquid microextraction.

Alkyl and alkoxy phenols are desirable products from the catalytic depolymerisation of lignin. In this work, ex-situ catalytic pyrolysis of Etek lignin in presence of Na, Ce, NiCe, MgCe, Fe and FePd on ZrO2 was studied. The largest combined yield of monomeric phenolics and alkylphenols was produced by Na/ZrO2 catalysts. A parametric study of the most promising Na/ZrO2 then resulted in using a catalyst:lignin ratio of 3:1 at 500 degrees C as the best option, enhancing at 17.5 wt% the recovery of total phenolics including 6 wt% alkyl phenols, which is equivalent to 27.8 wt% and 9.5 wt% of the starting lignin in Etek lignin waste. The study of the catalyst basicity indicates that the mild basicity of Na/ZrO2 was mostly responsible for the enhanced mono phenols recovery. Due to formation of thermally stable Na2CO3 during pyrolysis, successful Na/ZrO2 regeneration requires temperature of 900 degrees C or higher.

The distribution of per- and polyfluoroalkyl substances (PFAS), alkylphenols, organotin compounds, phthalates, alkylated polycyclic aromatic hydrocarbons, current-use pesticides (CUPs) and personal care products (PCPs) was characterized in 29 surface sediments from two Spanish Iberian continental shelf areas (14 on the Atlantic and 15 on the Mediterranean coasts). Concretely, 115 organic contaminants were determined and a specific methodology was used for each contaminant group, including contaminants of emerging concern (CECs) and traditional ones, such as polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs) and organochlorinated pesticides (OCPs). PAHs, alkylated PAHs, alkylphenols and phthalates were found in all samples, showing mean concentrations per group higher than 20 ng/g (16-4974 ng/g d.w.) in the subregions under consideration (Galician, Cantabrian, Levantine-Balearic and Strait-Alboran). CUPs and PCPs were found in the majority of samples at very low concentrations of ng/g (1.4-46.8 ng/g d.w.), whereas organotins and PFAS were found principally in sediments from the Mediterranean subregions (2.5-3.9 ng/g d.w.). Different distribution patterns were observed for the contaminant groups and subregions under consideration as a consequence of the diverse predominant sources (industrial, urban, transport and agricultural activities) and environmental behavior (mainly hydrophobicity and persistence). Risk assessment confirmed the impact of phthalates, alkylphenols, PAHs and PCBs on Atlantic ecosystems and of alkylphenols, chlorpyrifos, phthalates, TBT, PAHs, OCPs and PCBs on the Mediterranean ones. Furthermore, the presence of CUPs, PCPs and PFAS in sediments from the Spanish continental shelf located between 2 and 31 km from the coast suggested that those contaminants may also provoke adverse effects on coastal marine ecosystems between their sources and their depositional areas. CAPSULE: Alkylphenols, phthalates and organotins may provoke

The spatial and temporal distribution of selected endocrine disrupting compounds (4-tert-octylphenol, 4-n-octylphenol, 4-n-nonylphenol, nonylphenol, and bisphenol A) in two coastal areas of the Iberian Peninsula (Ria de Vigo and Mar Menor lagoon) were evaluated for the first time. Seawater and sediment samples collected during spring and autumn of 2015 were analysed using greener extraction techniques and liquid chromatography-tandem mass spectrometry. The presence of branched isomers (4-tert-octylphenol and nonylphenol) and bisphenol A in almost all seawater and sediment samples demonstrated their importance as pollutants in the frame of water policy, while no concentrations of linear isomers (4-n-octylphenol and 4-n-nonylphenol) were found. Higher seawater levels were observed in Mar Menor lagoon, especially in spring, associated with wastewater treatment plant effluents and nautical, agricultural and industrial activities. Similar sediment concentrations were measured in both studied areas, being nonylphenol levels five times higher than those measured for the other EDCs. Experimental sediment–water partition coefficients showed a moderate sorption of target compounds to sediments. Risk quotients for water compartment evidenced a moderate risk posed by nonylphenol, considering the worst-case scenario. For sediments, moderate risk related to 4-tert-octylphenol and high risk to nonylphenol were estimated.

Alkylphenols (APs) are a diverse class of chemicals that can cross the placental barrier and interfere with embryonic and fetal development. This work investigates the comparative toxicity, ability to inhibit aromatase activity, and to alter the lipid composition of 10 alkylphenols in the human placenta choriocarcinoma cell line JEG-3. Among the selected APs, 4-dodecylphenol (DP), 4-heptylphenol (HP), and 4-cumylphenol (CP) showed the highest cytotoxicity (EC50: 18-65 µM). Aromatase inhibition was closely related to the hydrophobicity of APs. HP significantly induced the generation of reactive oxygen species (ROS) (43-fold), inhibited placental aromatase activity (IC50: 41 µM), and induced a general dose-dependent depletion of polyunsaturated lipids (10-20 µM), which were attributed to high levels of oxidative stress. In contrast, 2,4,6-tri-tert-butylphenol (TTBP) significantly induced the intracellular accumulation of triacylglycerides (TGs), whereas DP increased the synthesis of phosphatidylcholines (PCs) and TGs at the expense of diacylglycerides (DGs). Overall, this study evidences the different modes of action of alkylphenols in human placental JEG-3 cells, describes differential lipidomic fingerprints, and highlights DP, HP, CP, and TTBP as the ones that caused the most harmful effects.

L’étude ECUME était une opération destinée à tester localement dans les eaux côtières du littoral normand, des outils développés nationalement lors de nombreux travaux, et pressentis pour être utilisés lors des prochaines campagnes d’évaluation de la qualité chimique des masses d’eau littorales pour la DCE. Ceci afin de déterminer la méthode la plus adaptée et opérationnelle de les déployer, et comparer leurs résultats entre eux et par rapport aux connaissances actuelles des niveaux de contamination. Trois sites ont été choisis : Chausey, baie des Veys et estuaire de Seine. Les résultats des analyses chimiques dans l’eau de mer grâce aux DGT, POCIS, SBSE, et dans les moules ont permis de confirmer le contraste du niveau de contamination en éléments traces métalliques et en polluants organiques entre les trois sites de l’étude, avec une contamination croissante de Chausey, à la baie des Veys, à l’estuaire de Seine dans l’eau, les moules, et grâce aux biomarqueurs. Parmi les trois biomarqueurs testés, la stabilité lysosomale et le dénombrement des micronoyaux se sont avérés les plus intéressants. Enfin, un bilan opérationnel ainsi qu’une synthèse des travaux en cours à l’échelle nationale sont présentés. Ce premier reste mitigé avec la nécessité de revoir notamment la méthode de mouillage dans les eaux littorales normandes.

The enantioselective oxyfunctionalisation of C−H bonds is a highly interesting reaction, as it provides access to chiral alcohols that are important pharmaceutical building blocks. However, it is hard to achieve using traditional methods. One way in which it can be achieved is through the action of oxidative enzymes. Although many reports of the oxyfunctionalisation capabilities of enzymes at an analytical scale have been published, reports on the use of enzymes to achieve oxyfunctionalisation on a synthetically relevant scale are fewer. Here, we describe the scale-up of the conversion of 4-ethylphenol to (R)-1-(4′-hydroxyphenyl)ethanol using the flavin-dependent enzyme vanillyl alcohol oxidase. The process was optimised by testing different reaction media and substrate and enzyme concentrations and by performing it under an oxygen atmosphere. Under optimised reaction conditions, 4.10 g (R)-1-(4′-hydroxyphenyl)ethanol at 97% ee was obtained from 10 g 4-ethylphenol (isolated yield 36%). These results highlight some of the challenges that can be encountered during scale-up of an enzymatic oxyfunctionalisation process to a synthetically relevant scale and will be of use for the development of enzymatic processes for the synthesis of industrially relevant compounds. (Figure presented.).

Endocrine-disrupting chemicals (EDCs) generate reproductive dysfunctions affecting the biosynthesis of steroid hormones and genes of the steroidogenic pathway. EDCs effects are mainly reported as a result of exposure to single compounds. However, humans are environmentally exposed to a mixture of EDCs. Herein, we assess chronic exposure to single alkylphenols and phthalates versus a mixture in mouse testes histology and steroidogenesis. Pregnant mice were exposed through drinking water to: 0.3 mg/Kg-body weight (BW)/day of each phthalate (DEHP, DBP, BBP), 0.05 mg/Kg-BW/day of each alkylphenol (NP, OP), or their mixture, covering from 0.5 post-coital day to weaning, continuing in the male offspring each exposure until adulthood (60 days old). Body and relative testis weight were increased in mixture-exposed mice along with histological alterations. Intratesticular testosterone (T) changed only in mice exposed to DBP, whereas estradiol (E2) levels were altered in all groups (except BBP). mRNA levels of genes encoding hormones of the steroid pathway (Cyp11a1, Hsd3b1, Cyp17a1 and Cyp19a1), cholesterol transporters (Star), and transcriptional factors (Sp1) showed that mice exposed to single or mixed compounds had alterations in at least two transcripts. However, none of the different types of exposure induced changes in all transcripts. In addition, changes at the mRNA or protein levels with single compounds were not always the same as those with a mixture. In conclusion, the effects of a chronic exposure to a mixture of EDCs on the expression of genes and proteins of the steroidogenic pathway and hormonal status were different from those exposed to single EDC.

The objective of this study was to isolate a new bacterium and investigate its ability for degradation of various toxic organic compounds. Based on 16S rRNA gene sequence and phylogenetic analysis, the isolated strain was identified as Bacillus sp. CYR2. Degradation of various toxic compounds and growth of CYR2 strain were evaluated with 2 and 4% inoculum sizes. All the experiments were conducted for 6 days, flasks were incubated at 30oC under 180 rpm. Among the 2 and 4% inoculum sizes, bacteria showed highest growth and toxic compounds degradation at 4% inoculum size. Especially, compared to 2% inoculum size, growth of the strain CYR2 at 4% inoculum size was increased by 15.1 folds with 4-secondarybutylphenol, 9.1 folds with phenol, and 5.4 folds with 4-tertiary-butylphenol. Strain CYR2 at 4% inoculum size showed highest removal of phenol (84 ± 5%), followed by 4-tertiary-butylphenol (66 ± 3%), 4-secondary-butylphenol (63 ± 5%) and 4-nonylphenol (57 ± 6%). Compared with 2% inoculum size, degradation ability of strain CYR2 with 4% inoculum size was enhanced by 3.45 times with 4-tertiary-octylphenol, and 2.53 times with 4-tertiarybutylphenol. Our results indicated that the newly isolated Bacillus sp. CYR2 can be used for in situ bioremediation of phenol and alkylphenols contaminated water.

In the present study five different types of alkylphenols, each of the two different types of mono and poly-aromatic hydrocarbons were selected for degradation, and conversion into poly-3-hydroxybutyrate (PHB) using the Bacillus sp. CYR1. Strain CYR1 showed growth with various toxic organic compounds. Degradation pattern of all the organic compounds at 100 mg/l concentration with or without addition of tween-80 were analyzed using high pressure liquid chromatography (HPLC). Strain CYR1 showed good removal of compounds in the presence of tween-80 within 3 days, but it took 6 days without addition of tween-80. Strain CYR1 showed highest PHB production with phenol (51 ± 5%), naphthalene (42 ± 4%), 4-chlorophenol (32 ± 3%) and 4-nonylphenol (29 ± 3%). The functional groups, structure, and thermal properties of the produced PHB were analyzed. These results denoted that the strain Bacillus sp. CYR1 can be used for conversion of different toxic compounds persistent in wastewaters into useable biological polyesters.

136 p. ; ill. ; 30 cm, Phenols and s-triazines are two great chemical classes to which 2, 4,6-tri-substituted-sym-triazines belong. They are compounds endowed of antioxidizing and thermo-stabilizing properties, whose one finds applications very varied in the fields as well agronomic, petrochemical that medical. The 2,6-di-tert-butyl-4-methylphenol (BHT) and 2,6- di-tert-butylphenol (2,6-DTBPH) used as raw materials for the synthesise of these molecules, are known to terminate the oxidation radical chains by reacting with peroxyls radicals. Hindered phenolics play an important role when used alone or in synergistic mixtures in very small quantities, they are pound to protect effectively certain polymers from action of light and exhibit good antioxidative properties in stabilization of fuels and lubricants. However, the efficiency of such antioxidants decreases sharply at high temperatures because of their insufficient thermal stability…

We report here on the removal of alkylphenols (phenol, 4-n-propylphenol, 4-n-heptylphenol and 4-nonylphenol) dissolved in water using the composite particles of nanocrystalline titania and alkyltrimethylammonium bromide (CnH2n+1N(CH3)(3)Br, C(n)TAB; n = 12, 14, 16 and 18) (named as TiO2/C(n)TAB Nanoskeleton) as adsorbents and photocatalysts. In particular, the adsorption of alkylphenols onto TiO2/C(n)TAB Nanoskeleton in water was investigated in terms of hydrophobic interaction between alkylphenols and C(n)TAB, surface area, pore structure and crystal size of TiO2/C(n)TAB Nanoskeleton. We revealed that C(n)TAB incorporated in the TiO2/C(n)TAB Nanoskeleton promotes the adsorption of alkylphenols onto TiO2/C(n)TAB Nanoskeleton due to the hydrophobic interaction between alkylphenols and C(n)TAB. On the other hand, the surface area, pore structure and crystal size of TiO2/C(n)TAB Nanoskeleton did not affect the adsorption of allcylphenols onto TiO2/C(n)TAB Nanoskeleton. We also found that the alkylphenols dissolved in water were completely removed by the combination of adsorption and photocatalytic degradation by the TiO2/C(n)TAB Nanoskeleton under UV irradiation. These results prove that the TiO2/C(n)TAB Nanoskeleton acts as in tandem an adsorbent and a photocatalyst for removal of alkylphenols dissolved in water.

Author Posting. © National Shellfisheries Association, 2012. This article is posted here by permission of National Shellfisheries Association for personal use, not for redistribution. The definitive version was published in Journal of Shellfish Research 31 (2012): 555-562, doi:10.2983/035.031.0215., Alkylphenols, anthropogenic estrogenic endocrine disruptors in vertebrates, have been found in lobsters (Homarus americanus) in New England sites. We hypothesize that alkylphenols interfere in the shell hardening during molting. We used an in vitro cuticle bioassay to investigate the effects of 2 alkylphenolic compounds—2,4-bis-(dimethylbenzyl) phenol (compound 3) and bisphenol A (BPA; 4,4′-dihydroxy-2,2-diphenylpropane (also referred to as 4,4′-(propan-2-ylidene) diphenol)) on tyrosine incorporation during the hardening of new cuticle following lobster molting. During sclerotization, both alkylphenols and cold tyrosine competed with C14-tyrosine incorporation in a concentration-dependent manner. This process was also phenoloxidase dependent, as treatment with phenylthiourea (PTU; a phenoloxidase inhibitor) significantly decreased C14-tyrosine incorporation. We also found that incorporation of C14-2,4-bis-(dimethylbenzyl) phenol during the shell hardening process was inhibited by cold alkylphenol, cold tyrosine, or PTU, and competition was concentration dependent. Furthermore, incorporation of tyrosine and derivatives into new cuticle decreased with time after molting from 27% incorporation 1 day after a molt to 6% by 4 days after a molt. In nonmolting cuticles, there was no incorporation of alkylphenol or tyrosine derivatives. When lobsters were injected with 2,4-bis-(dimethylbenzyl) phenol during the premolt stage, it took the shells 12 ± 1 days to harden sufficiently to resist deflection by 5 lb pressure exerted by a pressure gauge, compared with 7 ± 1 days for control shells. Thus, shell hardening is delayed significantly by the presence of 2,4-bis-(dimethylbenzyl) phenol. The effects of this compound on shell hardening may result in lobsters' susceptibility to microbial invasion and, therefore, may contribute to the onset of shell disease., This research was supported by the National Marine Fisheries Service as the New England Lobster Research Initiative: Lobster Shell Disease under NOAA grant NA06NMF4720100 to the University of Rhode Island Fisheries Center.

Two rapid methods were evaluated for the simultaneous extraction of seven parabens and two alkylphenols from soil based on matrix solid-phase dispersion (MSPD) and microwave-assisted extraction (MAE). Soil extracts were derivatized with N,O-bis(trimethylsilyl)trifluoroacetamide and analyzed by gas chromatography with mass spectrometry. Extraction and clean-up of samples were carried out by both methods in a single step. A glass sample holder, inside the microwave cell, was used in MAE to allow the simultaneous extraction and clean-up of samples and shorten the MAE procedure. The detection limits achieved by MSPD were lower than those obtained by MAE because the presence of matrix interferences increased with this extraction method. The extraction yields obtained by MSPD and MAE for three different types of soils were compared. Both procedures showed good recoveries and sensitivity for the determination of parabens and alkylphenols in two of the soils assayed, however, only MSPD yielded good recoveries with the other soil. Finally, MSPD was applied to the analysis of soils collected in different sites of Spain. In most of the samples analyzed, methylparaben and butylparaben were detected at levels ranging from 1.21 to 8.04 ng g -1 dry weight and 0.48 to 1.02 ng g -1 dry weight, respectively. © 2011 Springer-Verlag.

The paper expresses an attempt to tackle the problem due to the presence of micropollutants in wastewater which may be able to disrupt the endocrine system of some organisms. These kinds of compounds are ubiquitously present in municipal wastewater treatment plant (WWTP) effluents. The aim of this paper is to compare the fate of the alkylphenols-APs (4-(tert-octyl)) phenol, t-nonylphenol and 4-p-nonylphenol and the hormones (estrone, 17ß-estradiol and 17¿-ethinylestradiol) in a submerged anaerobic membrane bioreactor (SAMBR) pilot plant and in a conventional activated sludge wastewater treatment plant (CTP). The obtained results are also compared with the results obtained in a previous study carried out in an aerobic MBR pilot plant. The results showed that the APs soluble concentrations in the SAMBR effluent were always significantly higher than the CTP ones. Moreover, the analyses of the suspended fraction revealed that the AP concentrations in the SAMBR reactor were usually higher than in the CTP reactor, indicating that under anaerobic conditions the APs were accumulated in the digested sludge. The aerobic conditions maintained both in the CTP system and in the aerobic MBR favoured the APs and hormones degradation, and gave rise to lower concentrations in the effluent and in the reactor of these systems. Furthermore, the results also indicated that the degradation of APs under aerobic conditions was enhanced working at high solid retention time (SRT) and hydraulic retention time (HRT) values. © IWA Publishing 2012.

This paper reports the first results on alkylphenol pollution in edible bivalves from the Spanish coast. Two sampling campaigns (July 2006 and July 2007) were carried out to determine the concentration of nonylphenol (NP), octylphenol (OP), and eight polycyclic aromatic hydrocarbons (PAHs) in wild mussels (Mytilus galloprovincialys) and clams (Donax trunculus) at 14 sampling sites along the eastern Mediterranean Spanish coast. The results show that NP is the predominant alkylphenol, being the port of Valencia the most polluted area (up to 147 mu g/kg wet weight in clams). Moving away from the ports the concentration of NP in bivalves decreased. OP concentration was below its detection limit in most of the studied areas and its maximum concentration (6 mu g/kg w/w) was measured in clams from the port of Sagunto. The presence of low levels of PAHs was observed in most of the studied areas. The total PAHs concentration (i.e., sum of the eight measured PAHs) achieved a maximum value of 10.09 mu g/kg w/w in the north coast of Valencia city. The distribution pattern of the individual PAHs showed that both pollution sources petrogenic and pyrolytic were present in the sampled areas. Fluoranthene was the most abundant PAH in mussels while benzo(b)fluoranthene in clams. The maximum concentration of 10 mu g/kg w/w for benzo(a)pyrene established by the European Commission was never reached, indeed sampled bivalves showed concentrations 10 times lower than this reference value. Thus, they can be considered safe for human consumption. Despite the low contamination levels, the results show an overall pollution of bivalves by alkylphenol and PAHs as well as an increment in the number of polluted areas from 2006 to 2007. Thus, periodical sampling campaigns should be carried out to monitor the long-term tendency of these toxic and persistent pollutants. © 2010 Springer Science+Business Media B.V.

Immersion and field surveys were conducted in the northwestern part of Kyushu, to investigate the estrogenic activity in male Japanese common goby. Serum vitellogenin (Vg) concentration and total estrogenic activity in male common goby, based on microanalysis of natural estrogens (E1, E2, E3) and estrogenic compounds (NP, BPA, OP), were measured. The immersion survey in Ariake Sound suggested the possibility of the progress of environmental estrogen pollution. Field surveys in Ohmura Bay and Ariake Sound also detected estrogenic activity. An extremely high ratio of Vg-positive males were recorded in Ohmuta River Estuary, and total estrogenic activity in environmental water in this site were also higher than that recorded in other sites. The main causative substance of the estrogenic activity was not alkylphenols, but natural estrogens (E2), probably due to a high population density and a low sewage diffusion rate., Nagasaki University Major Research Project: Restoration of Marine Environment and Resources in East Asia, Coastal Environmental and Ecosystem Issues of the East China Sea ,pp.205-213; 2010

Sediments can function as secondary source for water pollution of aerobically biodegradable non-halogenated organic compounds, which are persistent in anaerobic sediments. The mass transfer of compounds from sediment to bulk water depends on hydraulic conditions. In this study, desorption, mass transfer and biodegradation are investigated under settled and resuspended sediment conditions for branched nonylphenol (NP), which was used as model compound for aerobically biodegradable and anaerobic persistent compounds. Continuous flow through reactor experiments were performed in duplicate with aged NP polluted sediment under sterile and non-sterile conditions to investigate the mass transfer and combined mass transfer and biodegradation. The mass transfer of NP from the sediment bed to the bulk water decreased from 5.1 +/- 0.6 mu g d(-1) to a stable value of 0.3 +/- 0.02 mu g d(-1). The desorbed NP in the non-sterile reactors was biodegraded in the first 20 days of the experiment. At the end of the settled sediment conditions, the biodegradation became very limited, and the mass transfer was comparable to the mass transfer under sterile conditions. Upon resuspension, the NP concentration in the bulk water increased instantaneously in all reactors with a factor of 100. This immediate, increased mass transfer of NP from the sediment was larger than the amount that can be biodegraded under optimal conditions. Under non-sterile conditions, a second increase in the mass transfer was observed. However, the amount of desorbing NP during this second increase in mass transfer can be biodegraded under optimal environmental conditions. NP desorbs continuously at low concentrations from the sediment bed into the bulk water, which can almost be completely biodegraded. Resuspension of NP-polluted sediment initially led to an increase in the desorbing NP concentrations and can be followed by a subsequent reduction of the concentrations due to biodegradation under environmental condit

Urdaibai was declared a Biosphere’s Reserve by UNESCO in 1984. Because we observed a high prevalence of hermaphroditism in mussels sampled in Urdaibai in March 2004, we started the present research work in order to determine the presence of endocrine disruptors (EDs) in sediments and to study possible EDs effects on mussels and oysters using gonad index and vitellogenin (VTG)-like protein levels as biomarkers. Samples were collected at five localities in April 2007 and 2008, and in October 2007. Estrogenic hormones were not detected in sediments and levels of bisphenol A and organotin compounds were very low. Alkylphenols were found at moderate levels and showed a time-dependent decrease. Phthalates were found at levels up to 8000 ng/g. High prevalence of oocyte atresia and necrosis occurred in mussels sampled in April. Retarded gametogenesis was observed in an oyster population from a shipyard. Hermaphrodites or alterations in VTG-like protein levels were not found but the high prevalence of histopathological alterations in oocytes is of concern.

This paper is a review with more than 100 references discussing the immunochemical methods reported in the literature for the most important man-made chemicals with suspected endocrine disrupting activity. Details regarding immunizing hapten design, antibody production, and the features (limit of detection, dynamic range, specificity) of the most important immunochemical methods developed (ELISA, FIIA, immunosorbents, immunosensors, etc.) are presented for important environmental pollutants such as bisphenol A, phthalates, alkylphenol polyethoxylates, alkylphenols, polychlorinated biphenyl compounds, and dioxins. Availability of commercial reagents and methods is reported.

The EC Water framework directive priority substances were analysed in surface sediments from urban, suburban and coastal areas in Stockholm and the Baltic Sea. The results are discussed in terms of spatial trends, local impact and ecological risk, The EC Water framework directive priority substances were analysed in surface sediments from urban, suburban and coastal areas in Stockholm and the Baltic Sea. The results are discussed in terms of spatial trends, local impact and ecological risk

Among the various compounds considered as emerging pollutants, alkylphenolic surfactants, steroid sex hormones, and pharmaceuticals are of particular concern, both because of the volume of these substances used and because of their activity as endocrine disruptors or as causative agents of bacterial resistance, as is the case of antibiotics. Today, the technique of choice for analysis of these groups of substances is liquid-chromatography coupled to mass spectrometry (LC–MS) and tandem mass spectrometry (LC–MS–MS). In the last decades, this technique has experienced an impressive progress that has made possible the analysis of many environmental pollutants in a faster, more convenient, and more sensitive way, and, in some cases, the analysis of compounds that could not be determined before. This article reviews the LC–MS and LC–MS–MS methods published so far for the determination of alkylphenolic surfactants, steroid sex hormones and drugs in the aquatic environment. Practical considerations with regards to the analysis of these groups of substances by using different mass spectrometers (single quadrupole, ion trap and triple quadrupole instruments, etc.), interfaces and ionization and monitoring modes, are presented. Sample preparation aspects, with special focus on the application of advanced techniques, such as immunosorbents, restricted access materials and molecular imprinted materials, for extraction/purification of aquatic environmental samples and extracts are also discussed.

Two categories of chemicals were determined within this project: (i) alkylphenolsrepresented by 4-nonylphenols (technical mixture), 4-tert-octylphenol and 4-tert-butylphenol; (ii) musk compounds: polycyclic musks – celestolide (ADBI), phantolide (AHDI), traseolide :(ATII), galaxolide (HHCB), tonalide (AHTN) and nitro musks – musk xylene (MX) and musk ketone (MK).

General Alkylphenols are mainly used as raw material in the production of a variety of industrial products such as surfactants, detergents, phenolic resins, polymer additives and lubricants. Private and commercial use of alkylphenols does not occur. Current world demand is estimated at approximately 400,000 tonnes/y, with nonylphenol as the most widely used compound (market share: 80- 90%). Octyl-, dibutyl-, decyl- and dodecylphenols are produced in total quantities of 60,000 tonnes/year. Nonylphenol production in Western Europe amounts to 75,000- 80,000 tonnes/year. Octylphenol production is estimated at approx. 7,000 tonnes/year. In the Netherlands, there are no production sites for alkylphenols. Nonylphenol demand in The Netherlands is estimated at 1300- 1400 tonnes/year. For the next few years, world demand will grow 1-2 % per year. Alkylphenol ethoxylates are primarily used as surfactants, detergents and emulsifiers in a wide range of applications in the industry (auxiliaries) and as commercial product (cleaning agents, wetting agents, dispersants, lubricants, etc) in many end use sectors. Current world demand is estimated at 600,000 tonnes/y, with nonylphenol (85%) and octylphenol ethoxylates (15%) as most widely used compounds. World demand growth is estimated at 2-3 %/year. In the EU, due to voluntary and regulatory initiatives, the use of these substances is to be limited in order to minimise alkylphenol emissions to the environment. In Western Europe, nonylphenol ethoxylates production is about 120,000 tonnes/year. Demand in the EU varies from 65,000 to 80,000 tonnes, while export amounts to 35,000- 45,000 tonnes/year. In the Netherlands, there is no production of alkylphenol ethoxylates. Annual nonylphenol ethoxylates demand in 1997 was estimated at approx. 1,500 tonnes, coming down from 4,900 tonnes/year in 1986. Sources and emissions Nonylphenol emissions due to use in the chemical and polymer industry in the Netherlands (<15 kg/ year) are negligible co

In recent years, it has been demonstrated that endocrine systems of living beings can be altered by many chemical substances of anthropogenic origin, designated as endocrine disrupters. There are growing concerns about the number of these endocrine disrupters. It has not been possible to define a single chemical structure that allows the classification of a chemical compound as a mimic of female sex hormones, so that chemical structures similar to natural estrogens, based on cyclopentanoperhydrophenanthrene, share their hormonal effect with stilbenes, bisphenols, alkylphenols, dioxins, furans and parabenes. The recognition of estrogenic activity in different biological models has been used to update the list of xenoestrogens and reveal sources of human exposure that were previously unknown. New previously unsuspected chemical compounds have been added to the list, as well as their precursors, metabolites and degradation products, whose effects are only now beginning to be recognised., En los últimos años se ha puesto en evidencia que muchas sustancias químicas de origen antropogénico son capaces de alterar el sistema endocrino de los seres vivos y se ha acuñado el nombre de disruptores endocrinos para definirlas. El número de disruptores endocrinos es una preocupación creciente si se añade a la inclusión de nuevos compuestos químicos, hasta ahora insospechados, la información generada sobre sus precursores, metabolitos y productos de degradación que tan solo ahora empiezan a conocerse. No se ha podido definir una estructura química única que permita clasificar a un compuesto químico como mimetizador de las hormonas sexuales femeninas, de tal manera que estructuras químicas similares a los estrógenos naturales, basados en el ciclopentanoperhidrofenantreno, comparten con los estilbenos, bisfenoles, bifenilos, alquilfenoles, dioxinas, furanos y parabenes su efecto hormonal estrogénico. El reconocimiento de la actividad estrogénica en diferentes modelos biológicos se ha utilizado para actualizar el censo de xenoestrógenos y poner de manifiesto fuentes de exposición humana hasta el momento insospechadas.

Analytical procedures have been developed for the quantitative analysis of phenols in crude oils and sedimentary rock pyrolysates and extracts. The procedures involve isolation of the phenolic components of the sedimentary organic matter by extraction with alkaline aqueous methanol, followed by the removal of carboxylic acids using a back extraction step. Co-extracted non-polar components are removed from the alkaline extract by liquid chromatography or by extracting it with hexane. The phenol isolates thus obtained were analysed by capillary GC, GC-MS and GC-FTIR. Recoveries of 70-95% were measured for C(subscript)0-C(subscript)3 alkylphenol compounds using these procedures.Crude oil samples (45) representing a range of locations, ages, depositional environments, maturities, source types, and biodegradation levels have been analysed for their phenol contents. A range of C(subscript)0-C(subscript)5 alkylphenols (approximately 40) were identified in crude oils using co-chromatography on up to three different stationary phases and by comparison of their retention times, mass spectral and infrared spectral properties with reference compounds. Isopropylmethylphenols (six) and sec-butylmethylphenols (nine) were synthesised for use in the identification of these compounds. A range of C(subscript)0-C(subscript)4 alkylphenols (24) were quantified using a dimethyl siloxane column (BP 1 or DB 1) and found to occur at concentrations ranging from 190x10(subscript)3 ng/g down to the limit of detection of 10 ng/g (ppb).The crude oil samples were classified into six groups based on their C(subscript)0-C(subscript)5 alkylphenol compositions. Group 1 crude oils have at least one isomer class in which the relative proportions of the alkylphenol isomers reflect their relative thermodynamic stabilities. The vast majority of samples, however, do not contain relative proportions of phenols which reflect their stabilities, and these differences have been used to group the remaining crude