Nitro Musks Research Articles

Ligand Specificity and Evolution of Mammalian Musk Odor Receptors: Effect of Single Receptor Deletion on Odor Detection.

The long-sought musk odor receptor family in mammals was discovered and found to be well conserved and narrowly tuned to musk odors. In mice, deletion of the most sensitive musk receptor resulted in drastic reduction in sensitivity to muscone, demonstrating a strong link between receptor and odor perception. In humans, we found one musk receptor that recognized both macrocyclic and nitro musks that had distinct chemical structures. The structure-activity relationships were in a good agreement with human sensory perception and therefore may be used to develop novel musk aroma in fragrance fields. Finally, identification of a natural ligand(s) for musk receptors in mammals other than musk deer would reveal an evolutionarily pivotal role in each species in the future.

Synthetic musk in seafood products from south Europe using a quick, easy, cheap, effective, rugged and safe extraction method

This study aims at developing a method for the determination of 9 synthetic musk compounds in seafood products by combining the quick, easy, cheap, effective, rugged, and safe (QuEChERS) method and determination by gas chromatography mass spectrometry (GC–EI–MS). Method detection limits (MDL) ranging between 0.001 and 1.94ngg−1 were obtained. The linearity is higher than 0.9899 in the range MDL – 100ngg−1 with precision below 18% and recoveries between 46% and 120% were obtained. The method was applied to quantify musk compounds in seafood products from the European southwest coast (oysters, mussels, salmon organs, glass eels). Galaxolide and Tonalide exhibited the highest concentration levels ranging between MDL – 96.4ngg−1 and MDL – 6.85ngg−1, respectively. Contamination levels observed for the two nitro musks (musk xylene and musk ketone) are significantly lower ranging between MDL – 0.6ngg−1 and MDL – 0.09ngg−1, respectively. Analysis of different organs of salmons showed higher concentrations in liver and gonad than in muscle tissues.

Environmental fates of synthetic musks in animal and plant: An in vivo study

As emerging contaminants, synthetic musks (SMs) cause worldwide concern due to their bioaccumulation in biota. However, the environmental fates of SMs in biota are poorly understood. Here, for the first time, the uptake and elimination behaviors, as well as the transferable capacities, of SMs in living edible biota (fish and aloe) were revealed. Fish muscle was approximately 100–2000 times more efficient in accumulating SMs than was aloe leaf, and nitro musks showed a higher bioaccumulation potential than did polycyclic musks in biota. In addition, the transferable capabilities of SMs by root uptake in aloe were poor. This investigation also showed that both nitro musks and polycyclic musks that accumulated in biota exhibited excellent elimination rates in clean water, and the elimination rates were greater than 78% and 80% in fish (3d) and aloe (2d), respectively. Furthermore, the calculated results suggest that SMs might act as chemosensitizers and enhance the accumulation of normally excluded toxicants in biota in a real aquatic environment.

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 304ngg−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 6.8ngkg−1bwday−1, respectively, in adults. A notably lower mean exposure was calculated for AHTN, cashmeran (DPMI) and traseolide (ATII), being ranged between 1.1 and 3.7ngkg−1bwday−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.

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.

Macrocyclic-, polycyclic-, and nitro musks in cosmetics, household commodities and indoor dusts collected from Japan: Implications for their human exposure

This paper reported the occurrence and concentrations of macrocyclic-, polycyclic- and nitro musks in cosmetics and household commodities collected from Japan. The high concentrations and detection frequencies of Musk T, habanolide, and exaltolides were found in commercial products, suggesting their large amounts of production and usage in Japan. Polycyclic musks, HHCB and OTNE, also showed high concentrations in cosmetics and products. The estimated dairy intakes of Musk T and HHCB by the dermal exposure to commercial products were 7.8 and 7.9μg/kg/day in human, respectively, and perfume and body lotion are dominant exposure sources. We also analyzed synthetic musks in house dusts. Polycyclic musks, HHCB and OTNE, showed high concentrations in samples, but macrocyclic musks were detected only in a few samples, although these types of musks were highly detected in commercial products. This is probably due to easy-degradation of macrocyclic musks in indoor environment. The dairy intakes of HHCB by dust ingestions were 0.22ng/kg/day in human, which were approximately five orders of magnitudes lower than those of dermal absorption from commercial household commodities.

On-line coupling of solid-phase extraction to gas chromatography–mass spectrometry to determine musk fragrances in wastewater

An on-line coupling solid-phase extraction (SPE) has been developed for the first time to preconcentrate trace amounts of 17 musk fragrances extensively used in personal care products (6 polycyclic musks, 3 nitro musks, 7 macrocyclic musks and 1 polycyclic musk degradation product) from wastewater samples, prior to analysis by gas chromatography and mass spectrometry through an on-column interface. A 10mm×2mm I.D. precolumn packed with Oasis HLB (60μm) or C18 (60μm) was compared for the optimization of the solid-phase extraction process. The parameters affecting the transfer of the analytes from the precolumn to the GC system (e.g. flow-rate, temperature and solvent vapor exit time) as well as SPE parameters (e.g. sample flow, sample volume, elution solvent, etc.) were optimized. An organic modifier such as methanol was added to the sample before the extraction process to avoid adsorption problems. The use of the MS detector under selected ion monitoring acquisition enabled the analytes to be quantified at low ngL−1 levels, preconcentrating only 10mL of sample, and the limits of detection were between 1 and 30ngL−1. The method was applied for the determination of musk fragrances in wastewater samples from three urban wastewater treatment plants (WWTPs). The analysis of influent urban wastewater revealed that galaxolide, tonalide and ambrettolide were the most abundant musk compounds with concentrations ranging between 18ngL−1 and 45,091ngL−1, 852ngL−1 and 49,904ngL−1 and 507ngL−1 and 21,528ngL−1 respectively. The remaining musks were present at lower concentrations and two of the macrocyclic musk studied (musk MC4 and civetone) were not detected. The analysis of effluent wastewater showed a decrease in the concentrations of all of the compounds present in influent samples, with the decrease being more significantly in the case of polycyclic and nitro musks than for macrocyclic musks. Only HHCB-lactone remained constant or increased its concentration.

Sorbent-packed needle microextraction trap for synthetic musks determination in wastewater samples

A needle trap (NT) device filled with HF Bondesil-C18 as a sorbent material was evaluated for the dynamic headspace analysis of a family of nine synthetic musks compounds that include two nitro musks, six polycyclic musks (with galaxolide and tonalide as the most widespread used polycyclic musks) and the degradation product of galaxolide (galaxolidone) in wastewater samples. Different parameters affecting the adsorption capacity of the sorbent were studied (e.g. extraction mode, extraction temperature, salt concentration, preincubation time fill and ejection speed or fill volume). Furthermore, injection parameters used with the NT device (e.g. desorption mode, desorption temperature and time) were evaluated to optimize the desorption and transfer of the target compounds into the GC column. Method detection limits obtained with gas chromatography–tandem mass spectrometry (GC–MS/MS) detection were found in the low ngL−1 range, between 2.5 and 10ngL−1, depending on the target compounds. Moreover, under optimized conditions, the method gave good levels of intra-day and inter-day repeatabilities in wastewater samples with relative standard deviations (n=5, 100ngL−1) less than 11 and 17%, respectively. The developed method was satisfactorily applied to the analysis of aqueous samples obtained from three wastewater treatment plants. All the polycyclic musks studied were detected in influent samples with cashmeran, galaxolide and tonalide as the most representative compounds. The analysis of effluent wastewater showed a decrease in the concentrations of all of the polycyclic musk detected in influent samples and an increase in the concentration of galaxolidone until a maximum value of 820ngL−1.

Headspace stir bar sorptive extraction followed by thermal desorption and gas chromatography with mass spectrometry to determine musk fragrances in sludge samples without sample pretreatment

A direct, simple and solvent-free method based on headspace stir bar sorptive extraction and thermal desorption gas chromatography with mass spectroscopy was developed to determine 13 musk fragrances (six polycyclic musks, three nitro musks and four macrocyclic musks) in sludge without sample treatment. The optimal headspace stir bar sorptive extraction conditions were achieved when a polydimethylsiloxane stir bar was exposed for 45 min in the headspace of a 10 mL vial filled with 100 mg of sludge mixed with 0.2 mL of water stirred at 750 rpm at 80°C. The stir bar was then desorbed in the thermal desorption gas chromatography and mass spectrometry system, obtaining limits of detection between 5 and 30 ng/g. The method applicability was tested with sewage sludge from two urban wastewater treatment plants and from a potable water treatment plant. Results showed galaxolide and tonalide to be the most abundant musk fragrances found in wastewater treatment plants with maximal concentrations of 9240 and 7500 ng/g, respectively. Maximum concentration levels between 35 and 635 ng/g were found for musk ketone, musk moskene, traseolide, phantolide and celestolide in this kind of samples. Concentrations below the limits of quantitation of phantolide, galaxolide, tonalide and musk ketone were found in sludge from a potable water treatment plant.

Human exposure to nitro musks and the evaluation of their potential toxicity: an overview.

Synthetic nitro musks are fragrant chemicals found in household and personal care products. The use of these products leads to direct exposures via dermal absorption, as well as inhalation of contaminated dust and volatilized fragrances. Evidence also suggests that humans are exposed to low doses of these chemicals through oral absorption of contaminated liquids and foods. As these compounds are lipophilic, they and their metabolites, have been found not only in blood, but also breast milk and adipose tissue. After personal use, these environmentally persistent pollutants then pass through sewage treatment plants through their effluent into the environment.Little is known about the biological effects in humans after such a prolonged low dose exposure to these chemicals. While epidemiologic studies evaluating the effects of nitro musk exposures are lacking, there is limited evidence that suggest blood levels of nitro musks are inversely related to luteal hormone levels. This is supported by animal models and laboratory studies that have shown that nitro musks are weakly estrogenic. Nitro musks exposure has been associated with an increased risk of tumor formation in mice. The evidence suggests that while nitro musks by themselves are not genotoxic, they may increase the genotoxicity of other chemicals. However, animal models for nitro musk exposure have proven to be problematic since certain outcomes are species specific. This may explain why evidence for developmental effects in animals is conflicting and inconclusive. Given that animal models and cell-line experiments are suggestive of adverse outcomes, further epidemiologic studies are warranted.

Organochlorine compounds, nitro musks and perfluorinated substances in breast milk – Results from Bavarian Monitoring of Breast Milk 2007/8

The aim of the Bavarian Monitoring of Breast Milk (BAMBI) project was to examine 10 organochlorine pesticides (OPs), 3 nitro musks, 6 indicator polychlorinated biphenyls (PCBs), 7 polychlorinated dibenzo-p-dioxins (PCDDs), 10 polychlorinated dibenzofurans (PCDFs), 12 dioxin-like PCBs (dl-PCBs) and several perfluorinated alkyl compounds in breast milk samples. A total of 516 breast milk samples were collected from seven regions in Bavaria and were analyzed by means of GC/ECD, GC/HRMS, and LC/MS-MS.Concerning the OPs, only hexachlorobenzene and a metabolite of DDT, 1,1-dichloro-2,2-bis(4-chlorophenyl) ethylene (p,p′-DDE), could be quantified in all samples (median: 16ngg−1 lipid and 63ngg−1 lipid, respectively). Median concentrations of 150ngg−1 lipid (range: 3–1900ngg−1 lipid) were found for the sum of the indicator PCBs. The concentrations of the PCDDs/PCDFs and the dl-PCBs ranged from 0.8 to 15.1 (median 5.7) pg WHO-TEQ1998g−1 lipid and from 1.5 to 18.9pg (median 6.4) WHO-TEQ1998g−1 lipid, respectively. The median perfluorooctane sulfonate concentration was 0.05μgL−1 (range: <0.02–0.26μgL), while the other PFCs were observed only in a subset of samples.On the basis of the median and 95th percentile concentration, “medium” and “high” intake levels were estimated for a 3-month-old exclusively breastfed infant. In particular, “medium” and “high” intake levels were calculated of 69 and 133pg WHO1998 TEQkg−1 b.w. for PCDDs/PCDFs, 8 and 21ngkg−1 b.w. for dl-PCBs, and 6 and 25ngkg−1 b.w. for perfluorooctane sulfonate, respectively.The calculated intake for perfluorinated substances is clearly below the tolerable daily intake (TDI), while the established TDI values are still clearly exceeded for PCDDs/PCDFs and dl-PCBs.

Occupational exposure to synthetic musks in barbershops, compared with the common exposure in the dormitories and households

Synthetic musks (SMs) have been widely used as fragrance ingredients in personal care and sanitary commodities. Due to their high volatility and particle-binding affinity, the indoor dust is a major reservoir of SMs, and dust ingestion could be an important exposure way to special populations, such as hairdressers. In spite of the known toxicity of SMs, there is no information regarding the occurrence of SMs in barbershop dusts and the exposure of hairdressers through indoor dust ingestion. In the present study, the levels of two nitro musks and five polycyclic musks were measured from indoor dust samples collected from barbershops, and some other indoor dust samples were also collected from dormitories, bathhouses and households for comparison. The concentrations of ∑SMs in barbershop dusts were 10–100 times higher than those from the other three indoor microenvironments. Polycyclic musks accounted for 89.4% of ∑SMs on average in all samples, of which two compounds, HHCB and AHTN jointly dominated 97.9% of polycyclic musks. The levels of HHCB and AHTN varied from 12.2 to 8.39×105 and from 13.2 to 3.49×105ngg−1, respectively. The daily intakes (DIs) of ∑SMs through house dust ingestion were estimated using the model of high dust ingestion and worst-case exposure (P95), and the corresponding exposure rates were 2791, 135 and 727ngd−1 for the hairdressers, general population and toddlers. SMs were also detected in blood samples collected from the hairdressers and normal adults (n=50 and 10, respectively). There was no significant difference between these two groups. Despite the absence of higher SM concentrations in hairdresser’s blood, we should not overlook the potential occupational health risks due to their high SMs ingestion rate.

Determination of polycyclic and nitro musks in environmental water samples by means of microextraction by packed sorbents coupled to large volume injection-gas chromatography–mass spectrometry analysis

In this work the development and validation of a new procedure for the simultaneous determination of 9 nitro and polycyclic musk compounds: musk ambrette (MA), musk ketone (MK), musk mosken (MM), celestolide (ADBI), phantolide (AHMI), tonalide (AHTN), traseolide (ATII), cashmeran (DPMI) and galaxolide (HHCB) in environmental water samples (estuarine and wastewater) using microextraction by packed sorbent (MEPS) followed by large volume injection-gas chromatography–mass spectrometry (LVI-GC–MS) was carried out. Apart from the optimization of the different variables affecting MEPS (i.e., nature of the sorbent, nature of the solvent elution, sample load, and elution/injection volume) extraction recovery was also evaluated, not only for water samples but also for environmental water matrices such as estuarine and waste water. The use of two deuterated analogs ([2H3]-AHTN and [2H15]-MX) was successfully evaluated in order to correct matrix effect in complex environmental matrices such as influent samples from wastewater treatment plants. Method detection limits (MDLs) ranged from 5 to 25ngL−1, 7 to 39ngL−1 and 8 to 84ngL−1 for influent, effluent and estuarine samples, respectively. Apparent recoveries were higher than 75% for all target compounds in all the matrices studied (estuarine water and wastewater) and the precision of the method, calculated as relative standard deviation (RSD), was below 13.2% at 200ngL−1 concentration level and below 14.9% at low level (20ngL−1 for all the target analytes, except for AHTN which was set at 40ngL−1 and HHCB at 90ngL−1, due to the higher MDL values presented by those target compounds). Finally, this MEPS procedure was applied to the determination of the target analytes in water samples, including estuarine and wastewater, from two estuaries, Urdaibai (Spain) and Adour (France) and an established stir-bar sorptive extraction-liquid desorption/large volume injection-gas chromatography–mass spectrometry (SBSE-LD/LVI-GC–MS) method was performed in parallel for comparison. Results were in good agreement for all the analytes determined, except for DPMI.

Development of a selective solid phase extraction method for nitro musk compounds in environmental waters using a molecularly imprinted sorbent

A powerful analytical method for the determination of the family of the nitro musk compounds at trace level in environmental waters—river, sea, and water from a treatment plant—is presented. The method is based on the use of molecularly imprinted silica (MIS) as sorbent for solid phase extraction (SPE) used for the clean-up and the concentration step of the target analytes previous to their determination by gas chromatography–mass spectrometry. The optimized extraction procedure allowed extraction recoveries between 61% and 87% using the MIS. The comparison with a non-imprinted silica (NIS) sorbent, for which extraction recoveries between 8% and 26% were obtained, showed the high selectivity of the MIS for the nitro musks. Moreover, high enrichment factors, ranging between 580 and 827, were achieved. The imprinted sorbent was compared to a conventional polymeric SPE sorbent for the extraction of the target compounds from environmental waters, showing high selectivity of the MIS and its clean-up potential. For the first time, the five nitro musk compounds were selectively extracted with an imprinted material.

Determination of Henry's Law Constant Using Diffusion in Air and Water Boundary Layers

A simple and precise method for determining the Henry’s law constant for hydrophobic organic chemicals was developed. Henry’s law constants were obtained as air–water partition coefficients in a dilute solution from the two partition coefficients between polydimethylsiloxane (PDMS) and air (KPDMSa) and between PDMS and water (KPDMSw). Measurements of the low concentrations in air or water at phase equilibrium were avoided. Instead, the KPDMSa and KPDMSw values were obtained by measuring the mass transfer rate constants in a boundary layer and relating them with KPDMSa and KPDMSw using a film diffusion model. Twenty hydrophobic chemicals (11 polycyclic aromatic hydrocarbons, 5 chlorinated benzenes, 2 phthalate esters, and 2 aromatic nitro musks) with literature values of the Henry’s law constant ranging from 10–2 to 102 Pa·m3·mol–1 were chosen to evaluate the method. The Henry’s law constants derived in this study agreed very well with the experimentally determined values from the literature. Because the proposed method provides a fast and simple method for measuring the Henry’s law constant within three days, it is a very promising method for generating the Henry’s law constants widely used in the assessment of the environmental fate of hydrophobic chemicals.

Determination of musk fragrances in sewage sludge by pressurized liquid extraction coupled to automated ionic liquid‐based headspace single‐drop microextraction followed by GC‐MS/MS

A method for the quantitative determination of ten musk fragrances extensively used in personal care products from sewage sludge was developed by using a pressurized liquid extraction (PLE) followed by an automated ionic liquid-based headspace single-drop microextraction and gas chromatography-tandem mass spectrometry. The influence of main factors on the efficiency of PLE was studied. For all musks, the highest recovery values were achieved using 1 g of pretreated sewage sludge, H(2) O/methanol (1:1) as an extraction solvent, a temperature of 80°C, a pressure of 1500 psi, an extraction time of 5 min, 2 cycles, a 100% flush volume, a purge time of 120 s, and 1 g Florisil as in-cell clean-up extraction sorbent. The use and optimization of an in-cell clean-up sorbent was necessary to remove fatty interferents of the PLE extract that make the subsequent ionic liquid-based headspace single-drop microextraction difficult. Validation parameters, namely LODs and LOQs, ranged from 0.5-1.5 to 2.5-5 ng/g, respectively. Good levels of intra- and interday repeatabilities were obtained analyzing sewage sludge samples spiked at 10 ng/g (n = 3, RSDs < 10%). The method applicability was tested with sewage sludge from different wastewater treatment plants. The analysis revealed the presence of all the polycyclic musks studied at concentrations higher than the LOQs, ranging from 6 to 530 ng/g. However, the nitro musk concentrations were below the LOQs or, in the case of musk xylene, was not detected.

Musks and organochlorine pesticides in breast milk from Shanghai, China: Levels, temporal trends and exposure assessment

The concentrations of musks (polycyclic musks and nitro musks) and traditional organochlorine pesticides (OCPs), including dichlorodiphenyltrichloroethane and its metabolites (DDT, DDE, DDD, and total DDTs), hexachlorobenzene (HCB), and hexachlorocyclohexanes (HCHs) in breast milk collected in Shanghai, China during the period 2006–2010, were determined. The total concentrations ranged from 4.7 to 276.2 (median: 58.4) ng/glipid weight (lw) for musks and from 88.3 to 2532.9 (median: 1003.8)ng/glw for OCPs. 4,4′-DDE (median: 655.4ng/glw) was the predominant OCP, followed by β-HCH (median: 172.5ng/g lw), and HHCB (1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethylcyclopenta[γ]-2-benzopyran) (median: 17.7ng/g lw) was the dominant musk. There was no statistical correlation between total musk concentrations, and HCB, HCHs, DDTs or total OCP concentrations, indicating their different exposure routes and metabolism in humans (p=0.182–0.325). Clear reductions in temporal trends in the levels of DDTs and HCB, especially HCHs (p<0.01) were observed during the sampling period, and the high DDE/DDT ratios in the samples indicated past exposure to DDTs. The relatively high median concentrations of HHCB and HHCB-lactone in 2010 suggested a probably increasing tendency. There were statistically significant influences regarding maternal age and parity on OCP accumulation (p=0.001–0.002), but no significant effect on musks was found (p=0.542–0.919). Musk exposure in neonates via breast milk was 2–3 orders of magnitude lower than suggested provisional tolerable daily intakes (PTDI). The estimated daily intakes for HCB and DDTs were below the PTDI in Canada, however, 56% of those for HCHs exceeded the Canadian PTDI. OCP contamination of breast milk requires further attention.

Tissue concentrations, bioaccumulation, and biomagnification of synthetic musks in freshwater fish from Taihu Lake, China

Synthetic musks are ubiquitous pollutants in aquatic environments. As hydrophobic chemicals, they can accumulate in terrestrial and aquatic organisms. Investigations into the bioaccumulation of these chemicals in aquatic ecosystem have, however, been limited, and previous results were inconsistent among species and ecosystem. Studies on this topic have been carried out in European countries, the USA, and Japan, but very few are known of the situation in China. The aim of this study was to investigate contaminant levels of musks in fish from Taihu Lake, the second largest freshwater lake in China, as well as bioaccumulation and biomagnification of the pollutants in the freshwater food chain. Five polycyclic musks and two nitro musks were determined in 24 fish species and nine surface sediment samples from Taihu Lake. HHCB (1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethylcyclopenta[γ]-2-benzopyran) and AHTN (7-acetyl-1,1,3,4,4,6-hexamethyl-1,2,3,4-tetrahydronaphthalene) were the predominant contaminants in the fish samples, with concentrations ranging from below the limit of detection (LOD) to 52.9 and from <LOD to 7.5 ng/g lipid weight, respectively. Other contaminants were at low detection frequencies. The results indicated low concentrations of musks yet widespread occurrence of these contaminants in fish from Taihu Lake. Species-specific and lipid-related bioaccumulation characteristics were suggested, but no significant region-specific differences were observed. Normalized biota-sediment accumulation factors for HHCB and AHTN were noted to increase with trophic levels in fish. Trophic magnification factors were estimated at 1.12 for HHCB and 0.74 for AHTN. A biomagnification for HHCB, and probably biodilution for AHTN, in the freshwater food chain are indicated, when trophic magnification factors were concerned. However, the correlations between logarithmic concentrations of the chemicals and trophic levels were not statistically significant. Further study using long food chains in this lake is still needed.

Fully automated ionic liquid-based headspace single drop microextraction coupled to GC–MS/MS to determine musk fragrances in environmental water samples

A fully automated ionic liquid-based headspace single drop microextraction (IL-HS-SDME) procedure has been developed for the first time to preconcentrate trace amounts of ten musk fragrances extensively used in personal care products (six polycyclic musks, three nitro musks and one polycyclic musk degradation product) from wastewater samples prior to analysis by gas chromatography and ion trap tandem mass spectrometry (GC–IT-MS/MS). Due to the low volatility of the ILs, a large internal diameter liner (3.4mm i.d.) was used to improve the ILs evaporation. Furthermore, a piece of glass wool was introduced into the liner to avoid the entrance of the ILs in the GC column and a guard column was used to prevent analytical column damages. The main factors influencing the IL-HS-SDME were optimized. For all species, the highest enrichments factors were achieved using 1μL of 1-octyl-3-methylimidazolium hexafluorophosphate ([OMIM][PF6]) ionic liquid exposed in the headspace of 10mL water samples containing 300gL−1 of NaCl and stirred at 750rpm and 60°C for 45min. All compounds were determined by direct injection GC–IT-MS/MS with a chromatographic time of 19min. Method detection limits were found in the low ngmL−1 range between 0.010ngmL−1 and 0.030ngmL−1 depending on the target analytes. Also, under optimized conditions, the method gave good levels of intra-day and inter-day repeatabilities in wastewater samples with relative standard deviations varying between 3% and 6% and 5% and 11%, respectively (n=3, 1ngmL−1). The applicability of the method was tested with different wastewater samples from influent and effluent urban wastewater treatment plants (WWTPs) and one potable treatment plant (PTP). The analysis of influent urban wastewater revealed the presence of galaxolide and tonalide at concentrations of between 2.10ngmL−1 and 0.29ngmL−1 and 0.32ngmL−1 and <MQL (Method Quantification Limit), respectively; while the remaining polycyclic musks concentrations were below the method quantification limits and two of the nitro musks (musk xylene and musk moskene) were not detected. The analysis of effluent urban wastewater showed a decrease in galaxolide and tonalide concentrations while the other target analytes were not detected. In waters from PTP only galaxolide was found at a concentration higher than MQL.

Determination of synthetic musk compounds in indoor house dust by gas chromatography–ion trap mass spectrometry

A new method for the simultaneous determination of 11 synthetic musks and one fragrance compound in house dust was developed. The nitro musks included musk ketone (MK, 4-tert-butyl-3,5-dinitro-2,6-dimethylacetophenone), musk xylene (MX, 1-tert-butyl-3,5-dimethyl-2,4,6-trinitrobenzene), musk ambrette (1-tert-butyl-2-methoxy-4-methyl-3,5-dinitrobenzene) and musk moskene (1,1,3,3,5-pentamethyl-4,6-dinitroindane). The polycyclic musk compounds were 1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethylcyclopenta-(γ)-2-benzopyran (HHCB), 7-acetyl-1,1,3,4,4,6-hexamethyl-1,2,3,4-tetrahydronaphthalene (AHTN), 4-acetyl-1,1-dimethyl-6-tert-butylindane, 6-acetyl-1,1,2,3,3,5-hexamethylindane, 5-acetyl-1,1,2,6-tetramethyl-3-isopropylindane, 6,7-dihydro-1,1,2,3,3-pentamethyl-4(5H)-indanon. The one macrocyclic musk was 1,4-dioxacycloheptadecane-5,17-dione. The bicyclic hydrocarbon fragrance compound (1,2,3,4,5,6,7,8-octahydro-2,3,8,8-tetramethylnaphthalen-2yl)ethan-1-one (OTNE) and HHCB-lactone (4,6,6,7,8,8-hexamethyl-1H,3H,4H,6H,7H, 8H-indeno[5,6-c]pyran-1-one), a degradation product of HHCB, were also analysed. NIST SRM 2781 (domestic sludge) and SRM 2585 (organic contaminants in house dust) were analysed for these target compounds. The method was applied for the analysis of 49 paired samples collected using two vacuum sampling methods: a sample of fresh or "active" dust (FD) collected using a Pullman-Holt vacuum sampler, and a household dust (HD) sample taken from the participants' vacuum cleaners. Method detection limits and recoveries ranged from 12 to 48ng/g and 54 to 117%, respectively. AHTN, HHCB, OTNE and HHCB-lactone were detected in all samples, with median concentrations of 552, 676, 252 and 453ng/g for FD samples, respectively; and 405, 992, 212 and 492ng/g for HD samples, respectively. MX and MK were detected with high frequencies but with much lower concentrations. The two sampling methods produced comparable results for the target analytes. Widely scattered concentration levels were observed for target analytes from this set of 49 house dust samples, suggesting a wide variability in Canadian household exposure to synthetic musks.