Synthetic musk fragrances in Lake Michigan

Synthetic musk fragrances are added to a wide variety of personal care and household products and are present in treated wastewater effluent. Here we report for the first time ambient air and water measurements of six polycyclic musks (AHTN, HHCB, ATII, ADBI, AHMI, and DPMI) and two nitro musks (musk xylene and musk ketone) in North America. The compounds were measured in the air and water of Lake Michigan and in the air of urban Milwaukee, WI. All of the compounds except DPMI were detected. HHCB and AHTN were found in the highest concentrations in all samples. Airborne concentrations of HHCB and AHTN average 4.6 and 2.9 ng/m3, respectively, in Milwaukee and 1.1 and 0.49 ng/m3 over the lake. The average water concentration of HHCB and AHTN in Lake Michigan was 4.7 and 1.0 ng/L, respectively. A lake-wide annual mass budget shows that wastewater treatment plant discharge is the major source (3470 kg/yr) of the synthetic musks while atmospheric deposition contributes less than 1%. Volatilization and outflow through the Straits of Mackinac are major loss mechanisms (2085 and 516 kg/yr for volatilization and outflow, respectively). Concentrations of HHCB are about one-half the predicted steady-state water concentrations in Lake Michigan.     

Synthetic musk fragrances in human milk from the United States

Synthetic musk compounds are used as additives in many consumer products, including perfumes, deodorants, and detergents. Earlier studies have reported the occurrence of synthetic musks in environmental and wildlife samples collected in the United States. In this study, human breast milk samples collected from Massachusetts, were analyzed for the determination of concentrations of synthetic musks such as musk xylene (1-tert-butyl-3,5-dimethyl-2,4,6-trinitrobenzene), musk ketone (4-tert-butyl-2,6-dimethyl-3,5-dinitroacetophenone), HHCB (1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethylcyclopenta[gamma]-2-benzopyran), AHTN (7-acetyl-1,1,3,4,4,6-hexamethyl-1,2,3,4-tetrahydronaphthalene), and HHCB-lactone, the oxidation product of HHCB. In addition, we estimated the daily intake of synthetic musks by infants based on the ingestion rate of breast milk. Synthetic musks were found in most of the samples analyzed, and the concentrations ranged from < 2 to 150 ng musk xylene/g, < 2 to 238 ng musk ketone/ g, < 5 to 917 ng HHCB/g, < 5 to 144 ng AHTN/g, and < 10 to 88.0 ng HHCB-lactone/g, on a lipid weight basis. The concentrations of HHCB were higher than the concentrations of other synthetic musks in breast milk samples. The mean concentration of HHCB (220 ng/g, lipid weight) was 5 times greater than the concentrations reported 10 years ago for breast milk samples collected in Germany and Denmark. Maternal age was not correlated with the concentrations of musk xylene, musk ketone, HHCB, or AHTN. There was a trend of decreasing concentrations of musk xylene, musk ketone, HHCB, and AHTN, with the number of children previously breast-fed, although the correlation was not significant. Based on average daily ingestion rate of breast milk, an infant is estimated to ingest 297 +/- 229 ng musk xylene, 780 +/- 805 ng musk ketone, 1830 +/- 1170 ng HHCB, 565 +/- 614 ng AHTN, and 649 +/- 598 ng HHCB-lactone per day. The ingestion rate of synthetic musks by infants in the United States is lower than that estimated for persistent organic pollutants (POPs) such as polychlorinated biphenyls (PCBs). Based on the residue patterns and accumulation features, it can be concluded that the exposure characteristics for synthetic musks are different from those of POPs, and that the major source of exposure to synthetic musks is probably via dermal absorption or inhalation.     

Occurrence of synthetic musk fragrances in marine mammals and sharks from Japanese coastal waters

In this study, the occurrence of the polycyclic musk fragrances HHCB (1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethylcyclopenta[g]-2-benzopyran) and AHTN (7-acetyl-1,1,3,4,4,6-hexamethyltetrahydeonaphthalene) in marine mammals and sharks collected from Japanese coastal waters is reported. HHCB was present in the blubbers of all finless porpoises (Neophocaena phocaenoides) analyzed (n = 8), at levels ranging from 13 to 149 ng/g on a wet weight basis. A fetus sample of finless porpoise contained a notable concentration of HHCB (26 ng/g wet wt), suggesting transplacental transfer of this compound. Among 12 tissues and organs of a finless porpoise analyzed, the highest HHCB concentration was found in blubber, followed by kidney. This indicates that HHCB accumulates in lipid-rich tissues in marine mammals, which is similar to the accumulation profiles of persistent organochlorines, such as PCBs and DDTs. In general, the residue levels of AHTN and nitro musks were low or below the detection limits in finless porpoises, implying either less usage in Japan or high metabolic capacity of these compounds in this animal. HHCB was also found in the livers of five hammerhead sharks (Sphrna lewini) from Japanese coastal waters, at concentrations ranging from 16 to 48 ng/g wet wt. Occurrence of HHCB in higher trophic organisms strongly suggests that it is less degradable in the environment and accumulates in the top predators of marine food chains. This is the first report on the accumulation of synthetic musk fragrances in marine mammals and sharks.     

Synthetic musk fragrances in Lake Erie and Lake Ontario sediment cores

Two sediment cores collected from Lake Ontario and Lake Erie were sectioned, dated, and analyzed for five polycyclic musk fragrances and two nitro musk fragrances. The polycyclic musk fragrances were HHCB (Galaxolide), AHTN (Tonalide), ATII (Traseolide), ADBI (Celestolide), and AHMI (Phantolide). The nitro musk fragrances were musk ketone and musk xylene. Chemical analysis was performed by gas chromatography/mass spectrometry (GC/MS), and results from Lake Erie were confirmed using gas chromatography/triple-quadrupole mass spectrometry (GC/MS/MS). The chemical signals observed at the two sampling locations were different from each other primarily because of large differences in the sedimentation rates at the two sampling locations. HHCB was detected in the Lake Erie core whereas six compounds were detected in the Lake Ontario core. Using measured fragrance and 210Pb activity, the burden of synthetic musk fragrances estimated from these sediment cores is 1900 kg in Lake Erie and 18 000 kg in Lake Ontario. The input of these compounds to the lakes is increasing. The HHCB accumulation rates in Lake Erie for 1979-2003 and 1990-2003 correspond to doubling times of 16 +/- 4 and 8 +/- 2 years, respectively. The results reflect current U.S. production trends for the sum of all fragrance compounds.     

Polycyclic aromatic hydrocarbons in smoked fish

Summary The levels of polycyclic aromatic hydrocarbons (PAH) were determined in 70 samples of smoked fish and fish products. By application of capillary gas chromatography with flame ionization detection 13 PAH components were determined simultaneously.In 19 of 46 samples of commercially smoked fish, mainly from traditional kilns, the concentration of benzo[a]pyrene (BaP) exceeded 1 g/kg. The BaP levels in the samples from kilns with external smoke generation were without exception lower than 1 g/kg.Four of 16 canned smoked fish samples contained more than 1 g/kg of BaP. A sample of home-smoked herring from a home-made bricked kiln showed the highest level of BaP and total PAH in this study, 11.3 and 1,100 g/kg, respectively.

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Polycyclische aromatische Kohlenwasserstoffe in geräuchertem Fisch

Zusammenfassung Die Gehalte an polycyclischen aromatischen Kohlenwasserstoffen (PAH) wurden in 70 Räucherfischproben bestimmt. Bei Anwendung von Capillargaschromatographie mit Flammenionisationsnachweis wurden gleichzeitig 13 PAH bestimmt.In 19 von 46 Proben von kommerziell geräucherten Fischen, hauptsächlich aus herkömmlichen Öfen, überstieg der Gehalt an Benz(a)pyren (BaP) 1 g/kg. Die BaP-Gehalte in den Proben aus Rauchanlagen mit externer Raucherzeugung lagen ausnahmlos unter 1 g/kg.Von 16 untersuchten Räucherfisch-Konserven enthielten 4 Proben mehr als 1 g BaP/kg. Eine Probe eines hausgeräucherten Herings aus einem selbstge mauerten Räucherofen wies den höchsten Gehalt an BaP und totalen PAH dieser Untersuchung mit 11,3 und 1 100 g/kg auf.

     

Photoallergic potential in the guinea-pig of the nitromusk perfume ingredients musk ambrette, musk moskene, musk xylene, musk ketone, and musk tibetene

The nitromusk perfume ingredient, musk abrette, has been reported to cause photoallergic reactions in man. The potential of alternative, chemically related, nitromusks to cause photoallergy has been studied using the Colworth guinea-pig photoallergy test.
The results showed that, compared with musk ambrette, musk moskene had a weak potential for inducing photoallergy, and that the musks xylene, ketone and tibetene had only very weak potentials. A study of photo-crossreaction to musk ambrette showed that musk moskene was active, musk xylene was weakly active, while the musks ketone and tibetene were inactive.
We conclude that musk moskene is likely to be less hazardous for man than musk ambrette, but caution should be used in selection of concentrations for use on sun-exposed skin. The musks xylene, ketone and tibetene are likely, photobiologically, to be acceptable alternatives to musk ambrette. The photoallergic potential of the nitromusks can, probably, be related to chemical structure.     

Polycyclic aromatic hydrocarbons in food samples collected in Barcelona, Spain

This study reports on the concentrations of eight polycyclic aromatic hydrocarbons (PAHs) in food samples collected in the city of Barcelona (Catalonia, Spain) from 2003 to 2004. Food samples included meat products, fish (fresh and smoked), other seafood (cephalopods, crustaceans, and bivalves), vegetable oil, and tea. Concentrations of benz[a]anthracene, benzo[b]fluoranthene, benzo[k]fluoranthene, benzo[g,h,i]perylene, benzo[alpha]pyrene, benzo[e]pyrene, dibenz[a,h]anthracene, and indeno[1,2,3-c,d]pyrene were determined by reversed-phase high-performance liquid chromatography with fluorescence detection. PAHs were detected in most tea samples (94%), which had the highest concentration of total PAHs (mean concentration of 59 microg/kg). Other food groups with a high presence of PAHs were bivalves (present in 34% of the samples; mean value of 2.7 microg/kg) and meat products (present in 13% of the samples; mean value of 1.7 microg/kg). The PAHs detected most frequently were benzo[e]pyrene and benzo[b]fluoranthene. No sample had levels above current regulation standards. Nevertheless, the frequent presence of PAHs in bivalves, tea samples, and meat products, together with the fact that dietary sources are the main exposure to these carcinogenic compounds, suggests the need for some monitoring scheme to follow up on these trends.     

Levels, tissue distribution, and age-related accumulation of synthetic musk fragrances in Chinese sturgeon (Acipenser sinensis): comparison to organochlorines

Chinese sturgeon (Acipenser sinensis) was listed as a Grade I protected animal in China in 1989, and the observed intersexual phenomenon and sex ratio deviation have suggested that chemicals have posed a risk as environment pollutants. This study analyzed seven musk fragrances in liver, muscle, heart, gonad, stomach, intestines, adipose, gill, pancreas, kidney, gallbladder, and roe from 13 female Chinese sturgeons, and the toxicokinetic behavior of musks were studied and compared with some organochlorines. Of the seven musks, HHCB, AHTN, and musk xylene were detected, and the highest concentrations were observed in adipose tissue: from 33.7 to 62.1 ng/g wet weight (ww), from 1.0 to 5.4 ng/g ww, and from 1.1 to 13 ng/g ww, respectively. Similar to the tissue distribution of DDTs and HCB, musks were detected frequently in high lipid content tissues such as roe, adipose, and liver, suggesting that tissue distribution of musks is controlled by the affinity to lipids. The concentration ratios based on lipid weight between roe and adipose were estimated to be 0.47 for HHCB, 0.58 for AHTN, and 0.51 for musk xylene, and those for the total DDTs and HCB were 0.27 and 0.61, which were relatively low compared with mammals. Relatively high concentrations of p,p'-DDE (68.4-449 ng/g ww) were detected in 10 of total 11 samples, which would cause the feminization of Chinese sturgeons during embryonic development. It was found that lipid-corrected concentrations of HHCB, AHTN, p,p'-DDE, and p,p'-DDD increased with age in female sturgeon, of which the trends were similar to those in fishes and different from those in mammals.     

Total and inorganic arsenic in fish samples from Norwegian waters

The contents of total arsenic and inorganic arsenic were determined in fillet samples of Northeast Artic cod, herring, mackerel, Greenland halibut, tusk, saithe and Atlantic halibut. In total, 923 individual fish samples were analysed. The fish were mostly caught in the open sea off the coast of Norway, from 40 positions. The determination of total arsenic was carried out by inductively coupled plasma mass spectrometry following microwave-assisted wet digestion. The determination of inorganic arsenic was carried out by high-performance liquid chromatography–ICP-MS following microwave-assisted dissolution of the samples. The concentrations found for total arsenic varied greatly between fish species, and ranged from 0.3 to 110?mg?kg^–1 wet weight. For inorganic arsenic, the concentrations found were very low (<0.006?mg?kg^–1) in all cases. The obtained results question the assumptions made by the European Food Safety Authority (EFSA) on the inorganic arsenic level in fish used in the recent EFSA opinion on arsenic in food.     

Development of an ultrasensitive PCR assay for polycyclic musk determination in fish

Polycyclic musks (PCMs) in the aquatic environment and organisms have become an emerging environmental issue because of their potential risk. The most used method for polycyclic musk determination is gas chromatography-mass spectrometry (GC-MS) with different sample extractions, which are somewhat expensive to operate, complex and laborious. In this study, a novel and ultrasensitive real-time polymerase chain reaction (PCR) assay with multiple signal amplification of carboxylic-DNA by gold nanoparticle-polyamidoamine conjugation (Au-PAMAM) was developed for determining polycyclic musks in fish. Hapten and immunogen were specially prepared. Polyclonal antibodies were produced based on the optimal immunisation, and the antibodies were characterised. Due to PAMAM’s unique nanostructure of numerous functional amino groups, polyclonal antibody and carboxylic-DNA were immobilised by Au-PAMAM conjugation to develop the antibody-Au-PAMAM-DNA probes, which were used as a signal DNA amplifier in the PCR system. Compared with real-time immuno-PCR, this biological probe-amplified immuno-PCR (BPAI-PCR) assay had higher sensitivity due to the probes’ higher ratio of signal DNA. Finally, the BPAI-PCR assay was applied to analyse AHTN (7-acetyl-1,1,3,4,4,6-hexamethyl-1,2,3,4-tetrahydronaphthalene,Tonalide) concentrations in fish samples in the range from 1 pg/L to 10 ng/L, giving an of LOD 0.61 pg/L. In general, due to the specificity of the antibody and novel nanoprobe design, this BPAI-PCR assay provided a potential way for trace analysis of AHTN in the aquatic organisms. The high concentrations of AHTN found in cultivated fish should encourage further toxicological studies.     

Polycyclic aromatic hydrocarbons in smoked fish – a critical review

Among hundreds of components, wood smoke also contains at least 100 polycyclic aromatic hydrocarbons (PAH) and their alkylated derivatives. Many of them are carcinogenic. Benzo[α]pyrene (BaP) is regarded as a marker of the carcinogenic PAH in smoke and smoked fish, although in olive residual oil the maximum level of 2 μg/kg for each of the eight most carcinogenic PAHs, including BaP, has been set. Contemporary analytical procedures based on extraction of the hydrocarbons from the matrix, clean-up procedure, separation by gas chromatography (GC) or high performance liquid chromatography (HPLC), followed by detection and quantification by mass spectrometry (MS) or fluorescence detectors (FLD), respectively, make it possible to determine individual PAH in smoked foods at concentrations of the order of 0.1 μg/kg or even 0.01 μg/kg. Heavily smoked fish from traditional kilns, especially their outer parts, may contain up to about 50 μg BaP/kg wet weight, while the meat of mild hot-smoked fish, from smokehouses supplied with conditioned wood smoke from external generators, contains only about 0.1 μg/kg, or even less. Some older data on the contents of BaP in smoked fish should be treated with caution, if the analytical procedures used did not guarantee unequivocal separation and identification of the individual PAH.     

Polychlorinated dibenzo-p-dioxins, dibenzofurans, and polychlorinated biphenyls in human tissues, meat, fish, and wildlife samples from India

Concentrations of polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs), and non- and mono-ortho-substituted polychlorinated biphenyls (dioxin-like PCBs) were measured in tissues of humans, fishes, chicken, lamb, goat, predatory birds, and Ganges River dolphins collected from various locations in India. PCDDs/DFs were found in most of the samples analyzed with the liver of spotted owlet containing the highest concentration of 3,300 pg/g, fat wt. 2,3,7,8-Substituted PCDDs and PCDFs were found in human fattissues at concentrations ranging from 170 to 1,300 pg/g, fat wt. Concentrations of PCDDs were generally greaterthan those of PCDFs in human tissues, fishes, animal fat, and dolphin. Among fishes, meat, and wildlife samples analyzed, concentrations of PCDDs/DFs were found in the following order: country chicken < goat/lamb fat < fishes < river dolphins < predatory birds. Hepta-CDDs and OCDD were the major PCDD homologues found in humans, fishes, meat products, and dolphins. 2,3,7,8-Tetrachlorodibenzo-p-dioxin equivalents of PCDDs/DFs were greater than those of PCBs in selected fish, dolphin, and human samples. To our knowledge, this is the first report of PCDDs and PCDFs in human tissues, fishes, meat, and wildlife collected from India.     

Zinc and copper content in marine fish samples collected from the eastern Mediterranean Sea

Zinc and copper contents in the edible parts (muscle, fillet) of 49 commercially used fish species from the eastern Mediterranean Sea (Izmir Outer Bay, Homa Lagoon/Izmir and Mersin Bay) were determined by differential pulse stripping anodic voltammetry. In the sample preparation step, all frozen fish samples were lyophilized, milled in a ball mill and finally decomposed in an oxygen plasma ashing chamber. Among the three sampling locations, the highest zinc concentration was found in Mediterranean shad (Alosa fallax nilotica) from Izmir Outer Bay with 9.73 mg/kg wet weight and the highest copper content was found in derbio (Trachinotus ovatus) from Homa Lagoon with 1.14 mg/kg wet weight. The accuracy of the concentrations determined in this study was checked by the measurements of certified reference material no. 422 cod muscle from the Commission of the European Communities, Community Bureau of Reference. All zinc and copper concentrations observed in species of the eastern Mediterranean Sea showed that fish from this area are good sources of these essential elements.     

In vitro cytotoxicity of melanoidins isolated from cooked meat and fish samples

A study has been undertaken to investigate the biological activity of melanoidins isolated from meat samples baked according to Kuntscheva (electro-baking oven, 200-300 degrees C, 60-210 min) and from semi-finished meat products baked in swimming fat (200 degrees C, 3 X 50 min, repeated use of the oil) as well as from semi-finished fish products (190 degrees C, 60 min). A weak toxicity of the melanoidins formed within a longer thermal treatment, but no mutagenic effect was stated. The cytotoxic alterations showed no specific character.     

Plasma biomarkers in fish provide evidence for endocrine modulation in the Elbe River,Germany

Blood plasma samples were collected from wild bream (Abramis brama L.) in the Elbe River, Germany, and analyzed for the yolk protein precursor vitellogenin (VTG), a biomarker for estrogen exposure, and the sex steroids 11-ketotestosterone (11KT), testosterone (T), and 17beta-estradiol (E2) to investigate for evidence of endocrine modulation. In addition, the gonadal status and the prominence of spawning tubercles were investigated. Nine riverine sites were investigated on the Elbe that were influenced by different sources of endocrine-active substances. Bream were collected from a lake that received no domestic or industrial discharges as a control. Plasma VTG concentrations were significantly higher in male bream from the Czech border to the middle Elbe, with the highest concentrations in fish sampled at the locations near Magdeburg and downstream of Dresden (between 20 and 100 times higher than in the controls), regions that are characterized by high levels of effluent discharges into the river. Following the Elbe from this site to the sea, the concentrations of plasma VTG in males were lower than at Meissen but were still elevated above the controls. 11KT and E2 titers showed suppressions in their normal concentrations at some locations (those receiving the greatest industrial discharges). There were reciprocal relationships between inhibitory effects on gonadal growth, maturation, and plasma sex steroids and exposure to pollutants, such as organotins, pesticides, or metals. However, there was no single chemical that alone could explain the observed inhibitory effects on sexual development. The results indicate that the endocrine system in wild bream is disrupted in stretches of the Elbe River.     

Prevalence of clinically relevant antibiotic resistance genes in surface water samples collected from Germany and australia

The prevalence and proliferation of antibiotic resistant bacteria is profoundly important to human health, but the extent to which aquatic environments contribute toward the dissemination of antibiotic resistant genes (ARGs) is poorly understood. The prevalence of 24 ARGs active against eight antibiotic classes (β-lactams, aminoglycosides, glycopeptides, chloramphenicols, tetracycline, macrolides, trimethoprim, and sulfonamides) was evaluated in surface water samples collected from Germany and Australia with culture independent methods. The ARGs most frequently detected both in Germany and Australia were sulI, sulII (77-100%), and dfrA1 (43-55%) which code for resistance to sulfonamide and trimethoprim. Macrolides resistance gene ermB was relatively more prevalent in the surface water from Germany (68%) than Australia (18%). In contrast, the chloramphenicol resistance gene catII was more frequently detected in Australia (64%) than Germany (9%). Similarly, β-lactams resistance gene ampC was more prevalent in the samples from Australia (36%) than Germany (19%). This study highlights wide distribution of ARGs for sulfonamide, trimethoprim, macroline, β-lactams and chloramphenicol in the aquatic ecosystems. Aquatic ecosystems can therefore be reservoirs of ARGs genes which could potentially be transferred from commensal microorganisms to human pathogens.