AQUA-GAPS/MONET-Derived Concentrations and Trends of PAHs and Polycyclic Musks across Global Waters.

Polycyclic aromatic hydrocarbons (PAHs), released from petrogenic, pyrogenic or diagenetic sources (degradation of wood materials), are of global concern due to their adverse effects, and potential for long-range transport. While dissolved PAHs have been frequently reported in the literature, there has been no consistent approach of sampling across water bodies. Passive samplers from the AQUA/GAPS-MONET initiative were deployed at 46 sites (28 marine and 18 freshwater), and analyzed for 28 PAHs and six polycyclic musks (PCMs) centrally. Freely dissolved PAH concentrations were dominated by phenanthrene (mean concentration 1500 pg L-1; median 530 pg L-1) and other low molecular weight compounds. Greatest concentrations of phenanthrene, fluoranthene, and pyrene were typically from the same sites, mostly in Europe and North America. Of the PCMs, only galaxolide (72% of samples) and tonalide (61%) were regularly detected, and were significantly cross-correlated. Benchmarking of PAHs relative to penta- and hexachlorobenzene confirmed that the most remote sites (Arctic, Antarctic, and mountain lakes) displayed below average PAH concentrations. Concentrations of 11 of 28 PAHs, galaxolide and tonalide were positively correlated (P < 0.05) with population density within a radius of 5 km of the sampling site. Characteristic PAH ratios gave conflicting results, likely reflecting multiple PAH sources and postemission changes.

Occurrence, Spatial Distribution, and Bioaccumulation of Dissolved Synthetic Musks in Freshwaters across China.

Commercial chemicals, such as synthetic musks, are of global concern, but data on their occurrence and spatial distribution in aquatic environments of large scale are scarce. Two sampling campaigns were conducted in the present study to measure freely dissolved synthetic musks in freshwaters across China using passive samplers, along with biological coexposure at selected sites. Polycyclic musks (PCMs) dominated synthetic musks, with a detection frequency of 95%. Higher concentrations of PCMs were observed in densely populated Mid, East, and South China compared to less populated regions, indicating the significance of anthropogenic activities for synthetic musks in water. The concentration ratios of galaxolide (HHCB)/tonalide (AHTN) were significantly higher in low-latitude areas than in high-latitude areas from June to September, suggesting that solar radiation played an important role in the degradation of HHCB/AHTN. Significant correlations were found between dissolved concentrations of HHCB and AHTN and their lipid-normalized concentrations in coexposed fish and clam. The estimated hazard quotients for HHCB and AHTN in freshwater fish consumed by humans were less than 0.01 at all sampling sites except the Yangtze River Basin. These results help to understand the environmental fate and ecological risks of synthetic musks on a large geographical scale.

Binding Mechanism of Nitro Musks to Human Lactoferrin: Multispectral Approach, Docking and Molecular Dynamics Simulation.

Nitro musks are highly bioaccumulative and potentially carcinogenic, commonly used as additives in fabric softeners, detergents, and other household products. Furthermore, these substances have been detected in breast milk and human adipose tissue, posing a risk of direct exposure to pregnant women and infants. Human lactoferrin (HLF) is abundant in colostrum, and plays an important role in the non-specific immune system of the human body. In this study, the mechanisms of action of two nitro musk compounds, typical examples of synthetic musks, with HLF were investigated using molecular docking, dynamics simulation and multispectral methods. The fluorescence findings demonstrated that nitro musks quenched the intrinsic fluorescence of human lactoferrin through static quenching. Thermodynamic analysis of the binding parameters suggested that hydrophobic interactions acted synergistically in the formation of the complex. Moreover, analyses utilizing multispectral techniques, such as Fourier transform infrared (FTIR) spectroscopy, validated that the microenvironment and structure of HLF were altered in the presence of nitro musks. Finally, molecular docking and molecular dynamics simulations were employed to explore the specific binding mode of nitro musks with HLF and to assess the stability of the complex. These findings may provide a reference for assessing health risks to pregnant women and infants.

Dermal exposure to synthetic musks: Human health risk assessment, mechanism, and control strategy.

Synthetic musks (SMs) have been widely used as odor additives in personal care products (PCPs). Dermal exposure to SMs is the main pathway of the accumulation of these chemicals in human kerateins and poses potential health risks. In this study, in silico methods were established to reduce the human health risk of SMs from dermal exposure by investigating the risk mechanisms, designing lower bioaccumulation ability SMs and suggesting proper PCP ingredients using molecular docking, molecular dynamics simulation, and quantitative structure-activity relationship (QSAR) models. The binding energy, a parameter reflecting the binding ability of SMs and human keratin protein (4ZRY), was used as the indicator to assess the human health risk of SMs. According to the mechanism analysis, total energy was found as the most influential molecular structural feature influencing the bioaccumulation ability of a SM, and as one of the main factors influencing the function (i.e., odor sensitivity) of an SM. The 3D-QSAR models were constructed to control the human health risk of SMs by designing lower-risk SMs derivatives. The phantolide (PHAN)- 58 was determined to be the optimum SM derivative with lower bioaccumulation ability (reduced 17.25%) and improved odor sensitivity (increased 7.91%). A further reduction of bioaccumulation ability of PHAN-58 was found when adding proper body wash ingredients (i.e., alkyl ethoxylate sulfate (AES), dimethyloldimethyl (DMDM), EDTA-Na4, ethylene glycol distearate (EGDS), hydroxyethyl cellulose (HEC), lemon yellow and octyl glucose), leading to a significant reduction of the bioaccumulation ability (42.27%) compared with that of PHAN. Results demonstrated that the proposed theoretical mechanism and control strategies could effectively reduce the human health risk of SMs from dermal exposure.

Derivation of predicted no effect concentration and ecological risk assessment of polycyclic musks tonalide and galaxolide in sediment.

Polycyclic musks (PMs) have drawn increased attention in recent years because of their persistence, bioaccumulation and toxicity. As two typical PMs contaminants, tonalide (AHTN) and galaxolide (HHCB) are widely detected in sediment worldwide. Acute and chronic toxicity data of AHTN and HHCB to freshwater and seawater organisms in water and sediments are collected and screened. The predicted no effect concentrations (PNECsediment) for AHTN and HHCB is derived according to the equilibrium partitioning method recommended by the EU technical guidance document (TGD) and the species sensitivity distribution (SSD) method based on the measured sediment toxicity data. The concentration levels of AHTN and HHCB are investigated and evaluated in freshwater and seawater sediments. Results show the difference between native and non-native freshwater species is not statistically significant. AHTN is more toxic to freshwater and seawater organisms than HHCB, and seawater organisms are more sensitive to 2 musks than freshwater organisms. The chronic PNECsediment values of AHTN and HHCB are 194.48 and 416.47 ng/g in freshwater sediment, 88.93 and 128.34 ng/g in seawater sediment respectively. The AHTN and HHCB linear correlation analysis exhibited a strong positive linear correlation in both domestic (R2=0.9054) and foreign (R2 = 0.9645) sediment. Preliminary risk assessment shows that the risks posed by AHTN and HHCB in sediment based on individual or combined concentrations of two musks are at medium to high levels in some regions. Further risk assessment results indicate that, for HHCB, 1.72% of foreign freshwater sediment may pose an ecological risk to 5% species; for AHTN, 8.06% of foreign freshwater sediment and 1.02% of domestic freshwater sediment may pose an ecological risk to 5% species, and 5.86% of seawater sediment may pose an ecological risk to 5% species. The above results indicate that there are some negligible risks in domestic and foreign sediments posed by these two musks, we should continue to pay attention to the toxic effects and pollution level of both musks in environment.

Novel Bayesian Method to Derive Final Adjusted Values of Physicochemical Properties: Application to 74 Compounds.

Accurate values of physicochemical properties are essential for screening semivolatile organic compounds for human and environmental hazard and risk. In silico approaches for estimation are widely used, but the accuracy of these and measured values can be difficult to ascertain. Final adjusted values (FAVs) harmonize literature-reported measurements to ensure consistency and minimize uncertainty. We propose a workflow, including a novel Bayesian approach, for estimating FAVs that combines measurements using direct and indirect methods and in silico values. The workflow was applied to 74 compounds across nine classes to generate recommended FAVs (FAVRs). Estimates generated by in silico methods (OPERA, COSMOtherm, EPI Suite, SPARC, and polyparameter linear free energy relationships (pp-LFER) models) differed by orders of magnitude for some properties and compounds and performed systematically worse for larger, more polar compounds. COSMOtherm and OPERA generally performed well with low bias although no single in silico method performed best across all compound classes and properties. Indirect measurement methods produced highly accurate and precise estimates compared with direct measurement methods. Our Bayesian method harmonized measured and in silico estimated physicochemical properties without introducing observable biases. We thus recommend use of the FAVRs presented here and that the proposed Bayesian workflow be used to generate FAVRs for SVOCs beyond those in this study.

Modified dispersive solid-phase extraction and cleanup followed by GC-MS/MS analysis to quantify ultraviolet filters and synthetic musk compounds in soil samples.

A simple method for the analysis of 13 synthetic musk compounds and six ultraviolet filters in soil samples was developed using a modified dispersive solid-phase methodology known as "Quick, Easy, Cheap, Effective, Rugged and Safe," followed by gas chromatography-triple quadrupole mass spectrometry. The methodology was validated by assessing linearity ranges, detection limits, precision, and accuracy. The method detection limit ranged between 0.01 and 10.00 ng/g dry weight and accuracy from 81 to 122%. A good precision was achieved, with relative standard deviation <10%. The applicability of the methodology was tested using different types of soils. Both synthetic musks and ultraviolet filters were detected in all soil samples. The most frequently detected compounds were benzophenone, octocrylene, 2-ethylhexyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-methoxycinnamate, and galaxolide. Higher levels were detected for benzophenone (maximum value of 158 ng/g dry weight) and octocrylene (137 ng/g dry weight). In comparison with conventional techniques, this method uses lower amounts of solvents and sorbents, producing less waste ("greener" technique) and comparable performances. In addition, it presents as main advantages the simplicity, speed (short extraction/cleaning time), low cost, and minimum handling of extracts, which can minimize the possibility of samples cross-contamination.

Facile preparation of stainless steel microextraction fiber via in situ growth of metal-organic framework UiO-66 and its application to sensitive analysis of polycyclic musks.

A functional stainless steel microextraction fiber easily prepared by in situ growing metal-organic framework UiO-66 was presented and used for high-performance analysis of polycyclic musks. Via the robust Ag-SH bonding reaction, mercaptoacetic acid was easily anchored on Ag film to provide carboxyl group on the stainless steel fiber, then in situ grown UiO-66 was fulfilled via the coordination reaction between Zr4+ and carboxyl group. Good characteristics including large surface area, high thermal stability, and good adsorption property were achieved. Sensitive detection limits (0.015-0.040 ng/L) were achieved for polycyclic musks by coupling with gas chromatography with mass spectrometry, and it could be stable enough for 150 extraction cycles without a significant loss of extraction efficiency. Compared with the classical commercial fibers, 2.2-11.4 times higher enhancement factors were shown. Applied to the analysis of fortified river water samples, five typical polycyclic musks were well detected with the recoveries of 90.2-101.8%, respectively. It showed a facile approach for preparing stainless steel microextraction fiber via chemically bonding in situ grown metal-organic framework for high-performance enrichment.

Levels and distribution of synthetic musks in farmland soils from the Three Northeast Provinces of China.

The levels and distribution of synthetic musks (ADBI, AHMI, ATII, HHCB, AHTN, MX and MK) were investigated in farmland soils from the Three Northeast Provinces of China. The total concentrations of SMs ranged from 2.40 ng/g to 12.2 ng/g (dry weight). HHCB and AHTN were the main pollutants that were detected in all samples, accounting for 99.35% of the total SMs. The hazard quotients were 0.0700 and 0.102 for AHTN and HHCB, respectively. Although the results indicate there is no serious environmental impact, the detection frequency of SMs in the farmland soil is high, which demonstrated that SMs are widely used in the Three Northeast Provinces of China. Therefore, more attention should be given to synthetic musks during environment monitoring and risk assessments for their bioaccumulation, lipophilicity and persistence.

Synthetic Musks: A Class of Commercial Fragrance Additives in Personal Care Products (PCPs) Causing Concern as Emerging Contaminants.

Synthetic musks (SMs) are promising fragrance additives used in personal care products (PCPs). The widespread presence of SMs in environmental media remains a serious risk because of their harmful effects. Recently, the environmental hazards of SMs have been widely reported in various environmental samples including those from coastal and marine regions. This paper provides a systematic review of SMs, including their classification, synthetic routes, analysis and occurrence in environmental samples, fate and toxicity in the environment, as well as the associated risk assessment and pollution control. Research gaps and future opportunities were also identified with the hope of raising interest in this topic.

Simple method for the determination of personal care product ingredients in lettuce by ultrasound-assisted extraction combined with solid-phase microextraction followed by GC-MS.

A simple method for the simultaneous determination of personal care product ingredients: galaxolide, tonalide, oxybenzone, 4-methylbenzyliden camphor, padimate-o, 2-ethylhexyl methoxycinnamate, octocrylene, triclosan, and methyl triclosan in lettuce by ultrasound-assisted extraction combined with solid-phase microextraction followed by gas chromatography with mass spectrometry was developed. Lettuce was directly extracted by ultrasound-assisted extraction with methanol, this extract was combined with water, extracted by solid-phase microextraction in immersion mode, and analyzed by gas chromatography with mass spectrometry. Good linear relationships (25-250 ng/g, R2  > 0.9702) and low detection limits (1.0-25 ng/g) were obtained for analytes along with acceptable precision for almost all analytes (RSDs < 20%). The validated method was applied for the determination of personal care product ingredients in commercial lettuce and lettuces grown in soil and irrigated with the analytes, identifying the target analytes in leaves and roots of the latter. This procedure is a miniaturized and environmentally friendly proposal which can be a useful tool for quality analysis in lettuce.

Occurrence, distribution and ecological risks of organophosphate esters and synthetic musks in sediments from the Hun River.

The Hun River is an important main tributary of the Liao River system. It is located in northeast China, and provides water resources for agriculture and industry. A man made reservoir (Dahuofang Reservoir, DHF) has been constructed mid-stream in the Hun River, supplying drinking water to surrounding cities. Pollution from organic contaminants is of great concern. In the present study, 40 sediment samples were collected and analyzed for the occurrence and distribution of two groups of emerging organic pollutants; namely, organophosphate esters (OPs) and synthetic musks (SMs). In all samples taken from upstream of the Hun River (UHR), downstream of the Hun River (DHR), and from DHF, the following concentrations were recorded: 0.141-4.39, 1.21-245, and 0.117-0.726 µg/kg galaxolide (HHCB), and 0.098-3.82, 2.79-213, 0.430-0.956 µg/kg tonalide (AHTN), respectively. For OPs, seven target analytes were detected in most of the sediment samples, with chlorinated OPs Tris-(2-chloroethyl) phosphate and Tris(2-chloro-isopropyl) phosphate being the dominant components, at levels varied in the range of LOD-0.810, ND-49.6, and 0.532-3.18 µg/kg, and LOD-0.786, ND-60.1, and 0.352-1.32 µg/kg from UHR, DHR and DHF, respectively. The elevated levels of these target compounds were detected in DHR, including its two main tributaries, Xi River and Pu River, which drain through cities with industrial development and dense populations. Our results indicate that domestic and industrial wastewater contributed to OPs and SMs sediment pollution, posing low to medium ecological risks to sediment dwelling organisms.

Graphene-Derivatized Silica Composite as Solid-Phase Extraction Sorbent Combined with GC-MS/MS for the Determination of Polycyclic Musks in Aqueous Samples.

Polycyclic musks (PCMs) have recently received growing attention as emerging contaminants because of their bioaccumulation and potential ecotoxicological effects. Herein, an effective method for the determination of five PCMs in aqueous samples is presented. Reduced graphene oxide-derivatized silica (rGO@silica) particles were prepared from graphene oxide and aminosilica microparticles and characterized by scanning electron microscopy, Fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy. PCMs were preconcentrated using rGO@silica as the solid-phase extraction sorbent and quantified by gas chromatography-tandem mass spectrometry. Several experimental parameters, such as eluent, elution volume, sorbent amount, pH, and sample volume were optimized. The correlation coefficient (R) ranged from 0.9958 to 0.9992, while the limits of detection and quantitation for the five PCMs were 0.3-0.8 ng/L and 1.1-2.1 ng/L, respectively. Satisfactory recoveries were obtained for tap water (86.6-105.9%) and river water samples (82.9-107.1%), with relative standard deviations <10% under optimal conditions. The developed method was applied to analyze PCMs in tap and river water samples from Beijing, China. Galaxolide (HHCB) and tonalide (AHTN) were the main PCM components detected in one river water sample at concentrations of 18.7 for HHCB, and 11.7 ng/L for AHTN.

Amine-functionalized MIL-53(Al)-coated stainless steel fiber for efficient solid-phase microextraction of synthetic musks and organochlorine pesticides in water samples.

The fiber coating is the key part of the solid-phase microextraction (SPME) technique, and it determines the sensitivity, selectivity, and repeatability of the analytical method. In this work, amine (NH2)-functionalized material of Institute Lavoisier (MIL)-53(Al) nanoparticles were successfully synthesized, characterized, and applied as the SPME fiber coating for efficient sample pretreatment owing to their unique structures and excellent adsorption properties. Under optimized conditions, the NH2-MIL-53(Al)-coated fiber showed good precision, low limits of detection (LODs) [0.025-0.83 ng L-1 for synthetic musks (SMs) and 0.051-0.97 ng L-1 for organochlorine pesticides (OCPs)], and good linearity. Experimental results showed that the NH2-MIL-53(Al) SPME coating was solvent resistant and thermostable. In addition, the extraction efficiencies of the NH2-MIL-53(Al) coating for SMs and OCPs were higher than those of commercially available SPME fiber coatings such as polydimethylsiloxane, polydimethylsiloxane-divinylbenzene, and polyacrylate. The reasons may be that the analytes are adsorbed on NH2-MIL-53(Al) primarily through π-π interactions, electron donor-electron acceptor interactions, and hydrogen bonds between the analytes and organic linkers of the material. Direct immersion (DI) SPME-gas chromatography-mass spectrometry methods based on NH2-MIL-53(Al) were successfully applied for the analysis of tap and river water samples. The recoveries were 80.3-115% for SMs and 77.4-117% for OCPs. These results indicate that the NH2-MIL-53(Al) coating may be a promising alternative to SPME coatings for the enrichment of SMs and OCPs.

Volatile and semi-volatile organic compounds of respiratory health relevance in French dwellings.

Over the last decades, the prevalence of childhood respiratory conditions has dramatically increased worldwide. Considering the time spent in enclosed spaces, indoor air pollutants are of major interest to explain part of this increase. This study aimed to measure the concentrations of pollutants known or suspected to affect respiratory health that are present in dwellings in order to assess children's exposure. Measurements were taken in 150 homes with at least one child, in Brittany (western France), to assess the concentrations of 18 volatile organic compounds (among which four aldehydes and four trihalomethanes) and nine semi-volatile organic compounds (seven phthalates and two synthetic musks). In addition to descriptive statistics, a principal component analysis (PCA) was used to investigate grouping of contaminants. Formaldehyde was highly present and above 30 µg/m(3) in 40% of the homes. Diethyl phthalate, diisobutyl phthalate, and dimethylphthalate were quantified in all dwellings, as well as Galaxolide and Tonalide. For each chemical family, the groups appearing in the PCA could be interpreted in term of sources. The high prevalence and the levels of these compounds, with known or suspected respiratory toxicity, should question regulatory agencies to trigger prevention and mitigation actions.

Determination of Synthetic Musks in Surface Sediment from the Bizerte Lagoon by QuEChERS Extraction Followed by GC-MS.

A new analytical method for the simultaneous determination of eight synthetic musks compounds (SMs) including five polycyclic musks (PCMs) and three nitro musks (NMs) was validated for sediment samples based on a simple QuEChERS (Quick, Easy, Cheap, Effective, Rugged and Safe) sample preparation procedure followed by gas chromatography-mass spectrometry (GC-MS). Good analytical performances were obtained for all the target compounds. For the validation of the method, internal calibration (IC) and internal calibration with QuEChERS (ICQ) were compared. Good linearity was obtained for both calibration methods with determination coefficients (R2) ranging between 0.990 for Musk Xylene (MX) and 0.999 for Tonalide (AHTN) with IC and between 0.991 for Musk Ketone (MK) and 0.999 for Traseolide (ATII) with ICQ. The repeatability ranges were 0.1 %-1.9 % with the IC and 0.1 %-2.6 % with the ICQ. The apparent recoveries obtained for SMs in the standard reference sediment (SRM1944) varied in the range of 70 %-98 % and 75 %-103 % in the sediment from the Bizerte Lagoon (Tunisia). The absolute recoveries ranged between 61 % and 92 % for the SRM1944 and between 61 % and 89 % in the sediment from the Bizerte Lagoon. The limits of detection (LOD) calculated for the two main compounds, Galaxolide (HHCB) and Tonalide (AHTN) were 0.3 and 0.1 ng g-1 respectively. The LODs obtained for ADBI (Celestolide), AHMI (Phantolide), ATII (Traseolide), MM (Muks mosken), MK (Musk Ketone) and MX (Musk Xylene) were 0.08, 0.12, 0.03, 0.34, 0.11, 0.08, 0.10 and 0.15 ng g-1 respectively. The levels of ∑SMs in surface sediments from the Bizerte Lagoon ranged from 1.4 to 4.5 ng g-1, which are 1000 times lower that the predicted no effect concentration (PNEC) for marine organisms.

Determination of Synthetic Musks in Sediments of Yellow River Delta Wetland, China.

In this study, seven kinds of synthetic musks were characterized in sediment samples of Yellow River Delta wetland, including celestolide, phantolide, traseolide, galaxolide, tonalide, musk xylene, and musk ketone. They were analyzed using gas chromatography-mass spectrometry (GC-MS), with recoveries of 91.85 %-105.35 % and the relative standard deviation (% RSD) were 3.30 %-8.11 % for all analytes. Galaxolide and tonalide were the main musk contaminants which were detected in sediment samples. The total concentrations of galaxolide ranged from 1.42 to 8.60 ng/g (mean 2.92 ng/g) (dry weight, dw); the total concentrations of tonalide ranged from the detection limit (LOD) to 3.63 ng/g (mean 1.69 ng/g, dw). The one reason of the higher level of SM pollutants was the domestic wastewater dumped by the local residents in some sites. And there was no significant correlation between SMs and TOC in sediment samples of Yellow River Delta wetland (p > 0.05).

Exposure of the population of Catalonia (Spain) to musk fragrances through seafood consumption: Risk assessment.

The occurrence of ten synthetic musks in samples of 10 widely consumed fish and shellfish species from Tarragona (Catalonia, Spain) was determined. The most used nitro and polycyclic musks, as well as a well-known transformation product in tissues, were analyzed. Furthermore, the human health risks derived from the musk exposure through seafood consumption were characterized. None of the nitro musks were detected in any of the analyzed samples. In contrast, most of the polycyclic musks were found, being galaxolide (HHCB) and tonalide (AHTN) present in all the samples. HHCB was the greatest contributor, with maximum levels in sardine and mackerel (367 and 304 ng g(-1) (d.w.) (dry weight), respectively). The highest exposure to individual musks was estimated for HHCB and HHCB-Lactone, with average values of 19.7 and 6.8 ng kg(-1)bw day(-1), respectively, in adults. A notably lower mean exposure was calculated for AHTN, cashmeran (DPMI) and traseolide (ATII), being ranged between 1.1 and 3.7 ng kg(-1)bw day(-1). The current concentrations of musks in fish and shellfish should not mean human health risks for the adult population living in Tarragona. However, a continuous monitoring would be desirable to assure that the exposure does not follow increasing temporal trends.

Octyl-modified magnetic graphene as a sorbent for the extraction and simultaneous determination of fragrance allergens, musks, and phthalates in aqueous samples by gas chromatography with mass spectrometry.

An effective, simple, and low-cost sample preparation method based on dispersive SPE followed by GC with MS is developed for the multianalyte determination of fragrance allergens, musks, and phthalates, at sub-ppb levels. The extraction procedure is based on a novel magnetic graphene sorbent, which is functionalized with octylamine, taking advantage of the functionalization's hydrophobic properties and π-π interactions with the analytes. Two alkyl amines, the octylamine and octadecylamine are studied to introduce alkyl chains in the basal plane of graphene. Magnetic graphene- octadecylamine is proved to be highly hydrophobic to such a degree that is hard to disperse in the bulk aqueous matrixes. Because of this behavior, its extraction efficiency for the target analytes is low. The synthesis and applicability of the magnetic graphene-octylamine as more favored sorbent are optimized in terms of the most determining experimental conditions. The detection and quantification limits, which are calculated based on S/N ratio of 3 and 10, respectively, ranged from 0.29 to 3.2 ng L(-1) and from 0.89 to 9.6, respectively. The dispersive SPE is successfully applied to routine analysis for the determination of the target analytes in samples from municipal treatment plant of Ioannina (Greece), from Pamvotis Lake and baby bathwater. The reproducibility of the spiked biological treatment plant water sample is evaluated and the relative standard deviation values range between 2.1 and 9.4%.

Evaluation of preconcentration methods in the analysis of synthetic musks in whole-water samples.

According to the European Water Framework Directive, environmental assessment of organic compounds should be made in whole-water samples, but due to their hydrophobicity and strong attraction to organic content these compounds can be found bound to suspended particle matter or in the dissolved fraction. In this work, the extraction of musk compounds was studied in whole-water samples exhibiting different amounts of dissolved organic carbon and suspended particulate matter using polyethersulfone preconcentration technique. Matrix effects in estuarine and wastewater (both influent and effluent) were evaluated for filtered and unfiltered samples. For unfiltered samples, estuarine water exhibited matrix effects <20%, while for effluent it was up to 48% and for influent ranged from 85 to 99%. To compensate matrix effects and determine total concentrations in unfiltered samples, different quantification approaches were tested: the use of deuterated analogues and standard additions. Standard additions provided the best results for unfiltered samples. Finally, filtered and unfiltered samples were analyzed using both polyethersulfone preconcentration and membrane-assisted solvent extraction and results showed a good agreement between the two methods. In both cases unfiltered samples provided concentrations 1.5-2.6 times higher than filtered samples.