Synthetic Musk Fragrances Research Articles

Behaviour of synthetic musk fragrances in freshwaters: occurrence, relations with environmental parameters, and preliminary risk assessment

The aims of this study were to investigate the presence, possible sources, and potential ecological risks of synthetic musk fragrances in freshwaters and sediments of the main tributaries of a deep subalpine lake in Northern Italy. The total musk concentrations ranged from few ng L−1 up to values > 500 ng L−1, depending on river characteristics: water flow and the presence of wastewater effluents proved to be the main factors affecting fragrance concentrations. The water flow may indeed dilute fragrance input mainly deriving from treated wastewaters. Good correlations (determination coefficients > 0.60) between synthetic fragrances concentrations and parameters related to anthropogenic impacts confirmed this hypothesis: synthetic fragrances were mainly detected in most polluted rivers crossing urbanized areas. Sediment analysis highlighted accumulation of fragrances in this matrix. Concentrations of synthetic fragrances up to 329 ng g−1 organic carbon were measured in sediments of the most contaminated rivers Boesio and Bardello, which also show the highest nutrient content. The preliminary environmental risk assessment revealed that present levels of synthetic musk fragrances do not pose any risk to the studied environmental compartments. However, a probable medium risk level was evidenced during the dry season in the most contaminated rivers Boesio and Bardello. For these reasons, small rivers draining urbanized watersheds and affected by wastewater effluents should be considered synthetic musk contamination hotspots that warrant further research.

Uptake and translocation of synthetic musk fragrances by pea plant grown in sewage sludge-amended soils

Sewage sludges are rich in organic matter and several essential nutrients for plant growth, making them very appealing for application in agricultural soils. However, they may also contain a wide range of emerging pollutants, which has raised concerns about the potential risks of this practice to crops, the environment, and public health - accumulation in soils and/or plant uptake and translocation of contaminants. Therefore, there is a need to study plant-soil interactions and assess the uptake potential of these contaminants by food crops to better understand these risks. The main aim of this work was to assess the possible drawbacks of sludge application to cropland, by observing the impact on the growth and yield of a model crop (pea plant - Pisum sativum) grown over an 86-day greenhouse experiment and by assessing the uptake potential of synthetic musk fragrances. Different sewage sludge application rates (4–30-ton ha−1) and initial concentrations of contaminants were tested. The application of sludge yielded benefits to the cultivated plants, finding improved crop productivity with an application rate of 30-ton ha−1. At the end of the experiment, soil samples and plants separated into sections were analysed using a QuEChERS extraction methodology followed by gas chromatography-mass spectrometry (GC-MS) quantification. Galaxolide (HHCB) and tonalide (AHTN) underwent uptake by the plant roots, having been detected in concentrations up to 346 ng g−1 on a dry weight basis (dw), but only HHCB was detected in above ground tissues. At the end, a decrease in the levels of synthetic musks in the amended soils (>80% in several instances) was observed. Assuming the worst-case scenario, no risk to human health was observed from the ingestion of peas grown on sewage sludge-amended soils. However, a soil hazard quotient analysis yielded worryingly high quotient values for AHTN in nearly all tested conditions.

Synthetic Musk Fragrances in Water Systems and Their Impact on Microbial Communities

The presence of emerging contaminants in aquatic systems and their potential effects on ecosystems have sparked the interest of the scientific community with a consequent increase in their report. Moreover, the presence of emerging contaminants in the environment should be assessed through the “One-Health” approach since all the living organisms are exposed to those contaminants at some point and several works already reported their impact on ecological interactions. There are a wide variety of concerning emerging contaminants in water sources, such as pharmaceuticals, personal care products, house-care products, nanomaterials, fire-retardants, and all the vast number of different compounds of indispensable use in routine tasks. Synthetic musks are examples of fragrances used in the formulation of personal and/or house-care products, which may potentially cause significant ecotoxicological concerns. However, there is little-to-no information regarding the effect of synthetic musks on microbial communities. This study reviews the presence of musk fragrances in drinking water and their impact on aquatic microbial communities, with a focus on the role of biofilms in aquatic systems. Moreover, this review highlights the research needed for a better understating of the impact of non-pharmaceutical contaminants in microbial populations and public health.

Occurrence and Sources of Synthetic Musk Fragrances in the Sewage Treatment Plants and the Han River, Korea

Levels of synthetic musk fragrances (SMFs) and various personal care products (PCPs) were measured in the Han River and its tributaries in Seoul, Korea. The most abundant SMF in all river and PCP samples was 4,6,6,7,8,8-hexamethyl-1,3,4,7-tetrahydrocyclopenta(g)sochromene (HHCB), followed by 1-(3,5,5,6,8,8-hexamethyl-6,7-dihydronaphthalen-2-yl)ethanone (AHTN), musk ketone (MK), and 1,1,2,3,3-pentamethyl-2,5,6,7-tetrahydroinden-4-one (DPMI). The most abundant SMF in both PCPs and the Han River samples was HHCB, followed by AHTN. Moving from upstream to downstream in the Han River, the median SMF concentration was 6.756, 2.945, 0.304, and 0.141 μg/L in the sewage treatment plant (STP) influents, effluents, tributaries, and mainstream, respectively, implying that effective SMF removal was achieved during the sewage treatment process, followed by dilution in the receiving water. Four STPs using advanced biological treatment processes had removal efficiencies of 58.5%, 56.8%, and 38.1% for HHCB, AHTN, and MK, respectively. The highest SMF concentrations in the tributaries were observed at locations close to the STPs. Our study confirmed that the main source of SMFs in the receiving water were sewage effluents containing untreated SMFs, which largely originate from household PCPs, especially hair care products (e.g., shampoo) and perfumes.

Synthetic musk fragrances in sediments from a subtropical river-lake system in eastern China: occurrences, profiles, and ecological risks.

Synthetic musk fragrances (SMFs) in aquatic environments have been of increasing concern because of their potential characteristic of persistent, bioaccumulated, and ecological harm. However, little is known about the distribution of SMFs in river-lake systems. In this study, the occurrence and risks of six SMFs measured in sediments from Lake Chaohu (eastern China) and the rivers flowing into it were investigated. The total sedimentary SMF concentrations ranged from 2.43 to 15.5 ng/g in Lake Chaohu (median = 5.17 ng/g), and 2.34-104 ng/g in the rivers (median = 10.6 ng/g). Overall, moderate levels of SMFs were found in comparison with previous results from other areas. Galaxolide and tonalide dominated in the rivers whereas cashmeran was dominant in Lake Chaohu. A source assessment indicated that the discharge from industries contributed importantly to the pollution of SMFs in the studied waters, in addition to the inputs from domestic sewage. Our estimates suggested that the current sedimentary SMF concentrations were likely to pose extremely low ecological risk to aquatic organisms. However, more studies are needed to focus on the spatial and temporal trends in distribution as well as the ecotoxicological implications of SMFs in the Lake Chaohu area because there is a general lack of relevant information.

The in situ treatment of synthetic musk fragrances in groundwater

AbstractSynthetic musk fragrances (SMFs) have been shown to be micropollutants in various aquatic and groundwater systems, often occurring at microgram per liter concentrations. Studies have shown that the most commonly detected SMFs in water are nitro musks and polycyclic musks. The SMFs are typically introduced into the environment in continuous streams such as from wastewater and land application of wastewater or sludge generated during wastewater treatment. Various studies for the treatment of SMFs have been undertaken for wastewater but studies for the treatment of SMFs in groundwater are limited, especially for in situ treatment. A pilot‐scale test was conducted to determine if the use of colloidal activated carbon (CAC) could effectively reduce dissolved concentrations of nitro and polycyclic synthetic musk compounds including musk xylene, musk ketone, galaxolide, and tonalide. The pilot test was carried out downgradient of a septic system in Central Canada where a series of nitrification and denitrification reactions are occurring in an unconfined aquifer. A 10‐weight percent CAC solution was injected into a series of temporary direct push injection points to target the synthetic musk plume. The plume contained galaxolide and tonalide concentrations up to 687 and 187 nanograms per liter (ng/L), respectively, while the concentrations of musk ketone and musk xylene were below the method detection limit (20 ng/L). A total of 13,950 liters of CAC solution was injected during one injection event. The pilot test results indicated that the CAC was effectively delivered to the target injection zone resulting in an increase in total organic carbon concentrations within the saturated soil greater than two orders of magnitude compared to the background concentrations. Analyses of the groundwater chemistry before and post‐injection indicated that the CAC had no detrimental impact on the groundwater quality while reducing the concentration of dissolved galaxolide and tonalide within the plume to below the method detection limits within 51 days of injection with the exception of two of the 14 wells monitored which had galaxolide and tonalide concentrations up to 78 and 35 ng/L. Within 6 months of application, the concentrations of galaxolide and tonalide had decreased to below the method detection limits. Subsequent monitoring of the groundwater quality over a one‐year period failed to detect galaxolide and tonalide, suggesting that the CAC was effective in attenuating the galaxolide and tonalide.

Partitioning and Bioaccumulation of Legacy and Emerging Hydrophobic Organic Chemicals in Mangrove Ecosystems.

Knowledge regarding partitioning behavior and bioaccumulation potential of environmental contaminants is important for ecological and human health risk assessment. While a range of models are available to describe bioaccumulation potential of hydrophobic organic chemicals (HOCs) in temperate aquatic food webs, their applicability to tropical systems still needs to be validated. The present study involved field investigations to assess the occurrence, partitioning, and bioaccumulation behavior of several legacy and emerging HOCs in mangrove ecosystems in Singapore. Concentrations of synthetic musk fragrance compounds, methyl triclosan (MTCS), polychlorinated biphenyls, organochlorine pesticides, and polycyclic aromatic hydrocarbons were measured in mangrove sediments, clams, and caged mussels. Freely dissolved concentrations of the HOCs in water were determined using silicone rubber passive samplers. Results showed that polycyclic musks and MTCS are present in mangrove ecosystems and can accumulate in the tissues of mollusks. The generated HOC concentration data for mangrove water, sediments, and biota samples was further utilized to evaluate water-sediment partitioning (e.g., Koc values) and bioaccumulation behavior (e.g., BAF and BSAF values). Overall, the empirical models fit reasonably well with the data obtained for this ecosystem, supporting the concept that general models are applicable to predict the behavior of legacy and emerging HOCs in mangrove ecosystems.

Solid phase microextraction Arrow for the determination of synthetic musk fragrances in fish samples

A novel solid phase microextraction Arrow (SPME Arrow) system has been applied for the first time to determine synthetic musk fragrances in fish samples. The lack of regulation concerning the concentration of musk fragrances in fish along with the risk associated to these compounds has led to an increased development of analytical methods on this topic. This study applies SPME Arrow followed by gas chromatography coupled to tandem mass spectrometry (ion trap) to determine nine musk fragrances and compares this novel technique with its predecessor (SPME). Parameters such as type of coating, extraction time and temperature as well as water addition were optimized to achieve higher sensitivity. Results show that detection limits ranging between 0.5 ng g−1 (for cashmeran, celestolide, phantolide, tonalide and musk ketone) and 2.5 ng g−1 (dry weight) (for musk xylene) when SPME Arrow is used instead of a conventional fibre, with an up to ten-fold increase in sensitivity. Moreover, commercial fish samples were analysed using the method developed and galaxolideand tonalidewere quantified at concentrations ranging from 6.5 ng g−1 to 17.5 ng g−1 (d.w.) and 2.9 ng g−1 and 5.1 ng g−1 (d.w.) in all the species analysed.

Use of full-scale hybrid horizontal tubular photobioreactors to process agricultural runoff

Diffuse pollution in rural areas due to agricultural runoff is a widespread and difficult problem to address due to the large areas affected. Drainage channels receive polluted water, but its introduction into conventional treatment network is often unfeasible. Within this context, microalgae-based treatment systems could be used as alternative treatment plants. A new design of semi-closed (hybrid) tubular horizontal photobioreactor (HTH-PBR) with low energy requirements has been evaluated for microalgae cultivation at full-scale (8.5 m3), using agricultural runoff as feedstock. This novel system was tested in batch and continuous mode over 4 and 135 d. Considering a full-scale application in an agricultural context, a batch test was carried out to evaluate the performance of the system. An increase of 22% in the biomass concentration in 4 d was registered, and all nutrients were consumed during the first two days. In the continuous experiment carried out over winter (December–April), productivity was between 2 and 14 g g [TSS] m−3 d, but values up to 76.4 g [TSS] m−3 d were reached at the end of the study in spring, despite the low nutrients concentration in the feedstock. Elimination of emerging contaminants was also evaluated, obtaining the highest removals for the synthetic musk fragrances tonalide and galaxolide (73% and 68%), and the anti-inflammatory drug diclofenac (61%).

Biomonitoring levels and trends of PAHs and synthetic musks associated with land use in urban environments

Polycyclic aromatic hydrocarbons (PAHs) are some of the most studied organic compounds in urban environments, due to their known adverse effects on human health and persistence in environmental matrices. During the last decade, new groups of organic compounds with an intensive use worldwide such as synthetic musks have been raising the interest of the scientific community given their toxicity and health effects. However, literature is still scarce in studies dealing with their concentration in the environment, especially in developing countries, where they are even more rare or non-existing at all. We employed leaves of Ligustrum lucidum to assess the concentrations of PAHs and synthetic musks in different land use areas in Cordoba city, therefore contributing with environmental information in Argentina. We found higher levels of PAHs in urban and industrial areas than in the peri-urban sampling sites, naphthalene being one of the dominant PAHs in all sampling areas. Regarding synthetic musk fragrances, polycyclic musks were the most contributing compounds and the highest levels found in industrial areas as well. A high environmental risk could be expected due to the frequent occurrence of galaxolide in addition to the high hazardous potential of phantolide, which was present in 50% of the samples. The results of the present study indicate that leaves of an urban ubiquitous tree can be used to assess the spatial behavior of both “classic” and “emerging” organic pollutants, allowing an assessment of urban air quality in areas where common air sampling devices are unavailable.

Chemical contamination assessment in mangrove-lined Caribbean coastal systems using the oyster Crassostrea rhizophorae as biomonitor species.

This paper aims to contribute to the use of mangrove cupped oyster, Crassostrea rhizophorae, as a biomonitor species for chemical contamination assessment in mangrove-lined Caribbean coastal systems. Sampling was carried out in eight localities (three in Nicaragua and five in Colombia) with different types and levels of contamination. Oysters were collected during the rainy and dry seasons of 2012-2013 and the tissue concentrations of metals, polycyclic aromatic hydrocarbons (PAHs), and persistent organic pollutants (POPs) were determined. Low tissue concentrations of metals (except Hg) and PAHs; moderate-to-high tissue concentrations of Hg, hexachlorocyclohexanes (HCHs), and dichlorodiphenyl-trichloroethanes (DDTs); detectable levels of chlorpyrifos, polychlorinated biphenyls (PCBs) (mainly CB28, CB118, CB138 and CB 153) and brominated diphenyl ethers 85 (BDE85); and negligible levels of musks were recorded in Nicaraguan oysters. A distinct profile of POPs was identified in Colombia, where the tissue concentrations of PCBs and synthetic musk fragrances were low to moderate, and Ag, As, Cd, Pb, and PAHs ranged from moderate to extremely high. Overall, the values recorded for HCHs, DDTs and PCBs in Nicaraguan mangrove cupped oysters greatly exceeded the reference values in tissues of C. rhizophorae from the Wider Caribbean Region, whereas only the levels of PCBs were occasionally surpassed in Colombia. Different contaminant profiles were distinguished between oysters from Nicaragua and Colombia in radar plots constructed using the main groups of contaminants (metals, PAHs, musks, PCBs, and organochlorine pesticides (OCPs)). Likewise, integrated pollution indices revealed differences in the levels of contaminants. Moreover, the profiles and levels in oyster tissues also varied with season. Thus, principal component analysis clearly discriminated Nicaraguan and Colombian localities and, especially in Colombia, seasonal trends in chemical contamination and differences amongst localities were evidenced. The geographical and environmental disparity of the studied scenarios may represent to a large extent the diversity of mangrove-lined Caribbean coastal systems and therefore the present results support the use of C. rhizophorae as suitable biomonitor species at Caribbean regional scale, where seasonal variability is a major factor controlling pollutant mobility and bioavailability.

Tetraphasic polar organic chemical integrative sampler for the determination of a wide polarity range organic pollutants in water. The use of performance reference compounds and in-situ calibration

In the present work, a homemade polar organic chemical integrative sampler (POCIS) was studied for the determination of 16 target analytes. The suitability of the combination of triphasic mixture (used in so called pesticides-POCIS) and octadecyl-functionalized silica gel (C18) as sorbent for POCIS was evaluated for the determination of alkylphenols (APs), several hormones, bisphenol-A (BPA), synthetic musk fragrances and herbicides such as trifluralin (Tri) and alachlor (Ala).With this purpose, POCIS laboratory calibration study, using a continuous-flow calibration system, was carried out in order to determine the uptake behavior and sampling rate (Rs) values for each target analyte. While the most hydrophobic compounds, (synthetic musk fragrances, some APs and Tri), showed poor linearity and low accumulation, a linear accumulation was observed for compounds whose logarithmic octanol-water partition coefficient (log Kow) ranged from 5.3 (4-tert-octylphenol, 4t-OP) to 3.1 (cis-androsterone, ADT). The Rs values obtained ranged from 0.190Lday−1 (4t-OP) to 0.042Lday−1 (BPA and equilin, EQ). The addition of C18 to the commonly used triphasic mixture increased the applicability of the POCIS sampler to compounds slightly more non-polar, such as 4t-OP. As far as we know, this is the first time that a combination of tetraphasic sorbent composed by the commercially available triphasic sorbent (Isolute ENV+polystyrene divinylbenzene and Ambersorb 1500 carbon dispersed on S-X3 Biobeads) and C18 was evaluated for passive sampling of the target analytes.The developed POCIS samplers were applied in field experiments from Halle (Germany) wastewater treatment plant (WWTP) effluent. Concerning the calculation of Rs values, the time weighted average (TWA) water concentration CWTWA values were determined considering three different approaches: (i) Rs from laboratory calibration (ii) Rs from laboratory calibration corrected with the use of performance reference compounds (PRCs) and (iii) Rs derived from field experiments or in-situ calibration. Several deuterated compounds such as, [2H3]-17β-estradiol ([2H3]-E2), [2H4]-nonylphenol ([2H4]-NP), [2H4]-equilin ([2H4]-EQ), [2H3]-tonalide ([2H3]-AHTN) and [2H15]-musk xylene ([2H15]-MX) were also studied for their applicability as PRCs. Finally, a reasonable agreement between grab sampling and CWTWA was found when results from in-situ calibration were considered, but not when PRCs were used for correction.

Group raises stink about a fragrance

An environmental group last week called on U.S. consumer product makers to halt use of a synthetic musk fragrance sold under the trade name Galaxolide. Women’s Voices for the Earth says published studies show 1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethylcyclopenta-γ-2-benzopyran (HHCB), which is used in laundry products, air fresheners, personal care products, and perfumes, is increasingly found in the Great Lakes. The group pointed to an assessment it commissioned of HHCB that concluded the chemical is persistent, accumulates in the environment, and is toxic to aquatic life. The assessment was done with GreenScreen for Safer Chemicals, a proprietary tool used to examine a compound’s hazards and compare it against alternative substances. SC Johnson, a company the activists are targeting for using HHCB, has cried foul. The company says the chemical “is present at very low concentrations that are hundreds to thousands of times lower than levels deemed safe by worldwide regulatory agencies.” EPA last year

Ultrasound-assisted dispersive liquid–liquid microextraction for the determination of synthetic musk fragrances in aqueous matrices by gas chromatography–mass spectrometry

A rapid and simple method for the simultaneous determination of twelve synthetic musks in water samples, using ultrasound-assisted dispersive liquid–liquid microextraction (UA-DLLME) coupled with gas chromatography–mass spectrometry (GC–MS) was successfully developed.The influence of seven factors (volume of the extraction solvent and disperser solvent, sample volume, extraction time, ionic strength, type of extraction and disperser solvent) affecting the UA-DLLME extraction efficiency was investigated using a screening design. The significant factors were selected and optimised employing a central composite design: 80μL of chloroform, 880μL of acetonitrile, 6mL of sample volume, 3.5% (wt) of NaCl and 2min of extraction time.Under the optimised conditions, this methodology was successfully validated for the analysis of 12 synthetic musk compounds in different aqueous samples (tap, sea and river water, effluent and influent wastewater). The proposed method showed enrichment factors between 101 and 115 depending on the analyte, limits of detection in the range of 0.004–54ngL−1 and good repeatability (most relative standard deviation values below 10%). No significant matrix effects were found, since recoveries ranged between 71% and 118%. Finally, the method was satisfactorily applied to the analysis of five different aqueous samples. Results demonstrated the existence of a larger amount of synthetic musks in wastewaters than in other water samples (average concentrations of 2800ngL−1 in influent and 850ngL−1 in effluent). Galaxolide, tonalide and exaltolide were the compounds most detected.

Scented traces – Dermal exposure of synthetic musk fragrances in personal care products and environmental input assessment

Synthetic musks are organic compounds used as fragrance and fixative additives in several personal care products. Until now, little is known about their occurrence and distribution in these household commodities. However, this information is essential to perform a human dermal exposure assessment. Therefore, this study gives an overview on the levels of 12 synthetic musks in 140 personal care products from 7 different categories (body and hair wash, toilet soaps, shaving products, dentifrice products, deodorants/antiperspirants, moisturizers and perfumes). They were analysed by QuEChERS extraction followed by gas chromatography–mass spectrometry. Detection limits were found between 0.01ngg−1 (galaxolide) and 5.00ngg−1 (musk xylene). Higher average concentrations of total synthetic musks were detected in perfumes (5245.05μgg−1) and shampoos (487.67μgg−1) for adults. Galaxolide, exaltolide and cashmeran were the most detected compounds. Combining these results with the daily usage amounts, an average daily dermal exposure of 75.69μgkgbw−1day−1 for adults and 15.54μgkgbw−1day−1 for babies/children was achieved. The main contributors for adult and babies/children dermal exposure were perfumes and lotions, respectively. About 40% of the adult daily dermal exposure is related to exaltolide, 30% galaxolide, and 15% tonalide, while for babies/children 96% occurs due to exaltolide.An estimate of the amount of musks discharged “down-the-drain” into the wastewater treatment systems through the use of toiletries was also performed. An average emission per capita of 6.7mgday−1 was determined and galaxolide and exaltolide were the predominant musks in the effluents.

Determinants of exposure to fragranced product chemical mixtures in a sample of twins.

Fragranced product chemical mixtures may be relevant for environmental health, but little is known about exposure. We analyzed results from an olfactory challenge with the synthetic musk fragrance 1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethyl-cyclopento-γ-2-benzopyran (HHCB), and a questionnaire about attitudes toward chemical safety and use of fragranced products, in a sample of 140 white and 17 black twin pairs attending a festival in Ohio. Data for each product were analyzed using robust ordered logistic regressions with random intercepts for “twin pair” and “sharing address with twin”, and fixed effects for sex, age, education, and “ever being bothered by fragrances”. Due to the small number of black participants, models were restricted to white participants except when examining racial differences. Overall patterns of association were summarized across product-types through random-effects meta-analysis. Principal components analysis was used to summarize clustering of product use. The dominant axis of variability in fragranced product use was “more vs. less”, followed by a distinction between household cleaning products and personal care products. Overall, males used fragranced products less frequently than females (adjusted proportionate odds ratio 0.55, 95% confidence interval 0.33, 0.93). This disparity was driven by personal care products (0.42, 95% CI: 0.19, 0.96), rather than household cleaning products (0.79, 95% CI: 0.49, 1.25) and was particularly evident for body lotion (0.12, 95% CI: 0.05, 0.27). Overall usage differed by age (0.64, 95% CI: 0.43, 0.95) but only hand soap and shampoo products differed significantly. “Ever being bothered by fragrance” had no overall association (0.92, 95% CI: 0.65, 1.30) but was associated with laundry detergent use (0.46, 95% CI: 0.23, 0.93). Similarly, black vs. white differences on average were not significant (1.34, 95% CI: 0.55, 3.28) but there were apparent differences in use of shampoo (0.01, 95% CI: 0.00, 0.69), body lotion (4.67, 95% CI: 1.18, 18.47), and perfume (6.22, 95% CI:1.08, 35.89). There was no overall association with thinking about product risks (0.90, 95% CI: 0.79, 1.02), nor with inability to smell HHCB (0.84, 95% CI: 0.63, 1.12). Exposure to fragranced products may differ demographically. The relevance for health disparities should be studied.

Influence of pre-treatment process on matrix effect for the determination of musk fragrances in fish and mussel

Musk compounds are widely used as fragrances in personal care products. On account of their widespread use and their low biodegradation, they can be found in environmental samples. In our study two extraction methodologies were compared and different clean-up strategies were also studied in order to develop a reliable analytical method, with minimum matrix effect and good detection limits, to determine synthetic musk fragrances- six polycyclic musks, three nitro musks and the degradation product of one polycyclic musk- in fish and mussel samples. The first extraction technique involves a QuEChERS extraction, a consolidate extraction methodology in the field of food analysis of growing interest over recent years, followed by a dispersive solid-phase extraction (dSPE) as clean-up strategy. The second extraction technique consists of a conventional pressurised liquid extraction (PLE) with dichloromethane and an in-cell clean-up to decrease the matrix effect and remove the undesired components⁎present in PLE extracts. Large volume injection (LVI) followed by gas chromatography-ion trap-tandem mass spectrometry (GC-IT-MS/MS) was chosen as the separation and detection technique. Validation parameters, such as method detection limits and method quantification limits were found at ng g−1 levels for both fish and mussel matrices. Good levels of intra-day and inter-day repeatabilities were obtained analysing fish and mussel samples spiked at 50ng g−1 (d.w.) (n=5, RSDs<17%). The developed PLE/GC-IT-MS/MS method was successfully applied to determine the target musk fragrances present in fish and mussel samples from the local market in Tarragona and fish samples from the Ebro River. The results showed the presence of galaxolide (2.97–18.04ng g−1 (d.w.)) and tonalide (1.17–8.42ng g−1 (d.w.)) in all the samples analysed, while the remaining polycyclic musks such as cashmeran, celestolide and phantolide, were only detected in some of the fish samples analysed. None of the samples analysed contained detectable traces of the nitro musks studied.

Occurrence and fate of synthetic musk fragrances in a small German river

The polycyclic musks tonalide® (acetyl hexamethyltetraline=1-(3,5,5,6,8,8-hexamethyl-6,7-dihydronaphthalen-2-yl)ethanone, AHTN), galaxolide® (1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethylcyclopenta(g)-2-benzopyrane, HHCB) and the degradation product HHCB-lactone were determined in water samples and brown trouts (Salmo trutta fario) of the river Ammer, a small catchment in the state of Baden-Württemberg, south-west Germany. The Ammer receives the effluent discharge of two municipal wastewater treatment plants (WWTPs) with 90,000 population equivalents. The wastewater contributes 14% of the total discharge of the river (average 1.0m3/s). Water samples were collected monthly at 12 sampling points from June 2010 to May 2011. Downstream the WWTPs the median concentrations of HHCB, AHTN and HHCB-lactone were 0.26μg/L, 0.06μg/L and 1.0μg/L, respectively. The effluent of the WWTPs was identified as main source of the synthetic musks in the surface water. The ratio of HHCB-lactone/HHCB showed significant seasonal variations indicating the influence of the water temperature on the degradation of HHCB in the surface water.A total of 251 trout was caught in two campaigns in October 2010 at 12 sampling points. The median concentrations of HHCB and AHTN in the trouts downstream the WWTPs significantly increased to 10.8μg/g lipid weight (LW) and 3.7μg/g LW, respectively.

Expanding the Applications of the Ionic Liquids as GC Stationary Phases: Plasticizers and Synthetic Musks Fragrances

The exceptional properties of the ILs make them ideal for gas chromatography stationary phases. New stationary phases exhibiting good separation selectivity, high efficiency, and high thermal stability are in high demand. Recently, several gas chromatographic capillary columns containing IL stationary phases of various polarities have been introduced on the market. The aim of this work is to extend the applications of the ILs as GC column coatings. The effectiveness of five different commercial IL columns (SLB™-IL59, SLB™-IL76, SLB™-IL82, SLB™-IL100 and SLB™-IL111) for the analysis of two different families of emerging contaminants of environmental concern (plasticizers and synthetic musk fragrances) has been explored. The results obtained for these two families of compounds are compared with the ones obtained when using a (5 %-phenyl)-methylpolysiloxane column. For three of these IL columns, applications have not yet been described. Good resolution for the most of the studied emerging pollutants belonging to five different analytical groups (adipates, phthalates, macrocyclic musks, nitromusks and polycyclic musks) was achieved in all the IL columns.

Membrane assisted solvent extraction coupled to large volume injection-gas chromatography–mass spectrometry for trace analysis of synthetic musks in environmental water samples

This work describes the optimisation, validation and application of membrane assisted solvent extraction (MASE) together with a large volume injection (LVI) in a programmable temperature vaporisation (PTV) injector coupled to gas chromatography–mass spectrometry (GC–MS) for the quantification of ten synthetic musk fragrances (musks) in surface and wastewater samples. Regarding the MASE, musks were extracted from 150mL of aqueous samples to 200μL of n-hexane hold in home-made low density polyethylene (LDPE) bags. The extraction took 240min and the performance of the method made possible the direct analysis of the extracts by LVI-PTV-GC–MS without needing any further treatment and avoiding losses of analytes. During the optimisation of LVI-PTV set-up, the response surfaces of every analyte signal against the cryo-focussing temperature, injection speed and vent time were built. Finally, the figures of merit of the whole procedure allowed the analysis of most of the musks owing to the low method detection limits (between 4 and 25ngL−1) and good precisions (<20%). In fact, this method was successfully applied to the analysis of musks in surface and wastewater samples. Galaxolide and tonalide are the main two synthetic musks observed in most of the analysed environmental water samples.