Polycyclic Musks Research Articles

Development of aquatic life criteria for tonalide (AHTN) and the ecological risk assessment.

AHTN (tonalide) is a polycyclic musk that is widely used as fragrance additive in numerous consumer products. AHTN is of great worldwide concern owing to its adverse effects on aquatic organisms and frequent detection in both domestic and foreign aquatic environments. Therefore, derivation of the aquatic life criteria for AHTN exposure is urgently needed. In this work, AHTN toxicity data for eight Chinese native freshwater organisms were used to derive a criterion maximum concentration of 59.39μg/L and a criterion continuous concentration of 22.43μg/L using United States Environmental Protection Agency guidelines. Toxicity tests showed that the annelid L. hoffmeisteri and the amphibian R. nigromaculata were the least and most sensitive species to AHTN, respectively. The sensitivity of the planktonic crustacean D. magna to AHTN obviously differed from that of the benthic crustacean M. nipponense. The AHTN and HHCB correlation analysis exhibited a strong positive linear correlation (R2=0.8622) in water. The ecological risk assessment showed that AHTN and HHCB posed a higher risk in foreign surface waters than Chinese waters, but a lower risk in foreign wastewater treatment plant effluent than in China. The ecological risks of AHTN and HHCB in most surveyed water bodies of various countries were at acceptable levels, with a few exceptions.

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.

Deriving aquatic life criteria for galaxolide (HHCB) and ecological risk assessment

The polycyclic musk galaxolide (HHCB) is widely used as fragrances in personal care products (PCPs) and has been detected in various environmental media. There is an urgent need to derive aquatic life criteria (ALC) of HHCB for the protection of aquatic organisms. Toxicity tests with 8 Chinese resident aquatic organisms from 3 phyla and 8 families were conducted, and three methods were used for deriving the ALC. A criterion maximum concentration (CMC) of 8.33 μg/L and a criterion continuous concentration (CCC) of 2.20 μg/L were derived according to the USEPA guidelines. The acute predicted no effect concentrations (PNECs) values derived by log-normal species sensitivity distribution (SSD) and log-logistic SSD method were 77.41 and 66.47 μg/L, respectively. In addition, a significant sensitivity difference was observed between the planktonic crustacean and benthic crustacean, and there was no significant difference (p > 0.05) among SSDs based on resident and non-resident species. A comparison of chronic SSDs between HHCB, tonalide (AHTN) and musk ketone (MK) showed that nitro musk (MK) was more toxic to aquatic organisms than polycyclic musks (HHCB and AHTN). Finally, an assessment of risk to aquatic organisms in surface waters and effluents of wastewater treatment plants (WWTPs) worldwide showed that potential risk may exist at several locations. HHCB concentrations in 4.08 and 46.17% of the WWTP effluents in China and 1.71 and 16.13% of the WWTP effluents in other countries exceed the hazard concentration for 5% and 1% aquatic species.

Enantiomeric analysis of polycyclic musks AHTN and HHCB and HHCB-lactone in sewage sludge by gas chromatography/tandem mass spectrometry.

Enantioselective analysis of chiral compounds is an interesting and challenging technique used to elucidate the degradation/transformation mechanisms of these compounds or understand their environmental processes. In this study, we have developed an effective separation and detection approach for the enantiomeric analysis of AHTN and HHCB, as well as a transformation product of HHCB (HHCB-lactone), in sludge samples. The analytical method was developed using a cyclodextrin-based enantioselective gas chromatography column combined with tandem mass spectrometry (GC/MS/MS). The GC oven temperature gradients, the linear velocity of the helium carrier gas, as well as the MS/MS parameters, including quantitative and qualitative ion pairs, dwell times, and collision energies, were optimized to achieve good separation and high sensitivity for all target enantiomers. Baseline separations of all target enantiomers were observed. Limits of quantification (LOQs) for all enantiomers ranged from 0.010 to 0.045 μg/L, and calibration linearity for all single enantiomers was higher than 0.99. The intra-day and inter-day precisions for all single enantiomers of AHTN, HHCB, and HHCB-lactone ranged from 0.8 to 3.8% and from 4.2 to 8.3%, respectively. The developed method was fully validated through enantioselective analyses of AHTN, HHCB, and HHCB-lactone in sludge samples collected from 17 WWTPs. The enantiomeric fractions (EFs) of HHCB and HHCB-lactone in sludge samples distinctly deviated from 0.50, indicating a significant enantioselective transformation of HHCB with preferential degradation of the 4S enantiomers. Significant positive correlations were found between the EF values of cis-HHCB enantiomers and cis-HHCB-lactone enantiomers in the sludge samples, implying that further efforts are still needed to clarify the degradation/transformation mechanism from HHCB to HHCB-lactone.

Degradation of Aqueous Polycyclic Musk Tonalide by Ultraviolet-Activated Free Chlorine

Chlorine-incorporating ultraviolet (UV) provides a multiple barrier for drinking water disinfection. Meanwhile, post-UV employment can promote the degradation of micropollutants by radical production from chlorine residual photolysis. This work studied the degradation of one such chemical, tonalide (AHTN), by low-pressure UV-activated free chlorine (FC) under typical UV disinfection dosage of <200 mJ·cm−2 and water matrix of filtered tank effluent. AHTN was rapidly degraded by UV/FC in accordance with pseudo-first-order kinetics. The reaction rate constants of AHTN with reactive chlorine species and hydroxyl radical (HO•) were estimated. Mechanistic exploration evidenced that under UV/FC, AHTN degradation was attributable to direct photolysis, ClO•, and HO•. The carbonyl side chain of AHTN served as an important attack site for radicals. Water matrices, such as natural organic matter (NOM), HCO 3 − , Cu 2 + , PO 4 3 − , and Fe 2 + , showed noticeable influence on the UV/FC process with an order of NOM > HCO 3 − > Cu 2 + > PO 4 3 − > Fe 2 + . Reaction product analysis showed ignorable formation of chlorinated intermediates and disinfection byproducts.

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.

Urban sources of synthetic musk compounds to the environment.

The occurrence and potential sources of synthetic musk compounds (SMCs) in the urban and surrounding environment were investigated. We analyzed air, soils and surface waters from a wide array of land-use types and urban densities including air from wastewater treatment plants (WWTPs), indoor, urban, rural, and remote Arctic sites; surface waters from urban and rural tributaries; and effluents of three WWTPs. In air, the median sum concentration of six selected polycyclic musks (Σ6PCMs) (i.e., galaxolide, tonalide, cashmeran, celestolide, phantolide, traseolide) were the highest from WWTP on-site > indoor > urban > WWTP off-site > rural. SMCs were not found in remote Arctic air indicating low potential for long-range atmospheric transport. SMCs were not found in soils, likely because of their high volatility and fast biodegradation rate. Galaxolide (HHCB) and tonalide (AHTN) were the two most abundant SMCs in air, tributaries and WWTP effluents. Σ6PCM concentrations in air taken along urban-rural transects and in tributary water were positively correlated with population density. In WWTP on-site air, trace levels of the toxic nitro-musks, namely musk xylene and musk ketone were detected and macrocyclic musks accounted for ∼10% of the total SMCs measured. In WWTP effluents, the concentrations of Σ6PCMs were proportional to the population served. We conclude that sources of SMCs to the outdoor urban environment and hence the surrounding region, originate from releases from indoor air, and temperature-dependent volatilization from WWTPs during treatment.

Identifying Organic Toxicants in Sediment Using Effect-Directed Analysis: A Combination of Bioaccessibility-Based Extraction and High-Throughput Midge Toxicity Testing.

Toxicity identification evaluation (TIE) and effect-directed analysis (EDA) were integrated to diagnose toxicity drivers in a complex system, such as sediment. In TIE manipulation, XAD resin was utilized as an amending agent for characterizing organic toxicants, which also facilitate a large-volume bioaccessibility-based extraction for EDA purposes. Both raw sediments in TIE and extract fractions in EDA were tested with Chironomus dilutus for toxicity using whole-sediment testing and a high-throughput microplate assay. This allowed for a direct link between whole-sediment TIE and EDA, which strongly strengthened the characterization and identification of toxicants. Sediments amended with XAD resin, as part of the TIE, significantly reduced midge mortality compared with unamended sediments, suggesting that organics were one class of main toxicants. On the basis of bioaccessible concentrations in sediment measured by XAD extraction, a group of previously unidentified contaminants, synthetic polycyclic musks (versalide, tonalide, and galaxolide), were found to explain 32-73% of the observed toxicity in test sediments. Meanwhile, three pyrethroids contributed to an additional 17-35% of toxicity. Surprisingly, the toxicity contribution of musks and pyrethroids reached 58-442 and 56-1625%, respectively, based on total sediment concentrations measured by exhaustive extraction. This suggested that total sediment concentrations significantly overestimated toxicity and that bioavailability should be considered in toxicity identification. Identifying nontarget toxicants sheds a light on application of the integrated TIE and EDA method in defining causality in a complex environment.

Fate and effects of sediment-associated polycyclic musk HHCB in subtropical freshwater microcosms

Galaxolide (HHCB) is used as a fragrance ingredient in household and personal care products, and has been ubiquitously detected in the environment. Here we investigated the fate of HHCB in subtropical freshwater microcosms, and evaluated effects of sediment-associated HHCB on a biological community consisting of algae, Daphnia, benthic macroinvertebrates and bacteria. The concentrations of sediment-associated HHCB did not change significantly during a 28 days exposure period, but HHCB accumulated in worms with biota-sediment accumulation-factor (BSAF) values in the range of 0.29–0.66 for Branchiura sowerbyi and 0.94–2.11 for Limnodrilus hoffmeisteri. There was no significant effects of HHCB (30 μg/g dry weight (dw) sediment) on chlorophyll-a content, sediment bacterial community composition, and survival and growth of benthic macroinvertebrates. However, the presence of benthic macroinvertebrates altered the sediment bacterial community structure relative to microcosms without introduced organisms. The findings of this study suggest that a single high-dose of HHCB, over 28 days, at environmentally relevant concentrations would not impose direct toxicological risks to aquatic organisms such as benthic macroinvertebrates.

Elimination of typical polycyclic musks in a full-scale membrane bioreactor combined with anaerobic-anoxic-oxic process in municipal wastewater treatment plant.

The objective of this study was to investigate the removal of 11 synthetic polycyclic musks in a municipal wastewater treatment plant located in Jilin, China, by using a membrane bioreactor combined with anaerobic-anoxic-oxic process. The analysis of synthetic polycyclic musks was conducted with gas chromatography/mass spectrometry after solid-phase extraction. The removal efficiency of 11 synthetic polycyclic musks ranged from 65.9% (3-methylcyclopentadecanone) to 84.6% (Galoxolide) in the influent. Along the treatment process, it was observed that the anaerobic tank could remove the synthetic polycyclic musks effectively whereas the role of the membrane was to the musks, which could be ascribed to the relatively strong hydrophobic property of the musks. The sludge-water distribution coefficients (Kd values) as indicator of adsorption propensity for the sludge from anaerobic, anoxic, oxic and membrane tanks were measured. The high value of Kd, above 5.0 litres per gram of suspended solids, showed most of the musks could be removed by sludge through the adsorption process; thus the removal rate from the water phase caused by adsorption in the wastewater treatment plant can be predicted.

Emerging Compounds in Standard Reference Material 2585 Organic Contaminants in House Dust

Standard Reference Materials (SRMs) are homogeneous, well-characterized materials that are used to validate measurements and improve the quality of analytical data (www.nist.gov/srm). Originally issued in 2005, SRM 2585 Organic Contaminants in House Dust was intended for use in evaluating analytical methods for legacy organic pollutants (including polycyclic aromatic hydrocarbons, polychlorinated biphenyls, and chlorinated pesticides) in house dust and similar matrices. This SRM, while intended for analysis of legacy compounds, became an important matrix for the measurement of emerging organic chemicals (polyborminated diphenyl ethers, synthetic musks, per- and polyfluorinated compounds (PFAS), and newer use flame retardants) because interlaboratory studies of these compounds showed considerable disagreements. NIST has been measuring these emerging chemicals in SRM 2585 with the goal of assigning values on the Certificate of Analysis. In late 2017 NIST finished measurements and updated SRM 2585 with the addition of polycyclic musks, PFAS, and selected flame retardants. This presentation will highlight the methods for adding analytes to an existing SRM and provide values for emerging compounds in SRM 2585.

Ultrasound-assisted emulsification microextraction for rapid determination of unmetabolized synthetic polycyclic and nitro-aromatic musks in human urine

An effective method to rapidly determine the presence of seven unmetabolized synthetic musks in human urine samples is developed. The target musks are five synthetic polycyclic musks (i.e., celestolide (ADBI), phantolide (AHMI), traseolide (ATII), galaxolide (HHCB), tonalide (AHTN)), and two nitro-aromatic musks (i.e., musk xylene (MX) and musk ketone (MK)). The method involved an ultrasound-assisted emulsification microextraction (USAEME) coupled with gas chromatography–mass spectrometry (GC–MS). The factors that affect USAEME efficiency were optimized in detail, and the optimized procedure involved the rapid injection of 50 μL of carbon tetrachloride into 1.0 mL of urine sample (contained 0.1-g of sodium chloride) in a conical bottom glass tube. After 1.0 min ultrasonication and 3 min centrifugation (at 7000 rpm), the sedimented extract 10 μL was directly injected into the GC–MS system. The limits of quantitation (LOQs) varied from 0.1 to 0.5 ng/mL. The precisions for both repeatability and reproducibility were <8%. The trueness varied from 79 to 96% with the RSD ranging from 2 to 8%. The total concentrations of the seven unmetabolized target musks in collected human urine samples were in the range from 0.93 to 3.74 ng/mL. HHCB and AHTN were detected in all the collected samples, and the daily excretion doses were evaluated.

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

ABSTRACTPolycyclic 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.

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

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

Occurrence and distribution of organophosphorus flame retardants/plasticizers and synthetic musks in sediments from source water in the Pearl River Delta, China.

The Pearl River (China) and its tributaries receive discharges of treated/untreated domestic sewage and industrial wastewater throughout the entire drainage basin. The river provides source water for many local inhabitants, and there is great concern over its pollution status. Fifteen sediment samples were collected from source water areas in the Pearl River Delta, and analyzed for the occurrence and distribution of 2 classes of emerging pollutants, organophosphorus flame retardants (OPs) and synthetic musks. In most sediments, 5 polycyclic musks and 2 nitro musks were detected, and galaxolide (1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethylcyclopenta (g)-2-benzopyran [HHCB]) and tonalide (7-acetyl-1,1,3,4,4,6-hexamethyl-1,2,3,4-tetrahydronaphthalene [AHTN]) were the predominant components, with concentrations of 0.030 to 547 and 4.31 to 439 ng/g, respectively. Seven widely used OPs were found in most sediments, at varying total concentrations from 1.79 to 143 ng/g, with tris(2-butoxyethyl) phosphate (TBEOP), tris(2-chloro-isopropyl) phosphate (TCIPP), and triphenyl phosphate (TPHP) being the main components. The results indicated that industrial discharge and domestic sewage played important roles for synthetic musk and OP distribution in sediments in the study area. In general, higher levels of OPs and synthetic musks were found in Guangzhou, Foshan, and Dongguan, suggesting a significant impact from industrial discharges and the dense population of these regions. Environ Toxicol Chem 2018;37:975-982. © 2017 SETAC.

A carbon nanotube-enhanced real-time immuno-PCR for ultrasensitive detection of AHTN in water

Polycyclic musks (PCMs) in the aquatic environment have become an emerging environmental issue because of their potential risk. The most commonly used method for analysis of PCMs is gas chromatography-mass spectrometer (GC-MS) with different sample extractions, which are somewhat expensive to operate, laborious and complex. In this paper, a carbon nanotube-enhanced real time immuno-PCR was developed for ultrasensitive detection of AHTN in water for the first time. The SWCNTs were used to immobilize numerous amino-DNA and polyclonal antibody to form polyclonal antibody-CNTs-DNA conjugates, which were used as a signal-amplifier in the proposed immunoassay system. This proposed carbon nanotube enhanced real time immuno-PCR assay was used to determine AHTN in water samples ranging from 5 pg/L-0.1 ng/L; using sample size as low as 10 μL. This proposed carbon nanotube enhanced real time immuno-PCR is the most ultrasensitive one for determination of AHTN in water without pre-concentration or extractions; and it provide a potential way for ultra-trace AHTN detection in the aquatic environment.

Multibiomarker Responses of Juvenile Stages of Zebrafish (Danio rerio) to Subchronic Exposure to Polycyclic Musk Tonalide.

Synthetic polycyclic musks, widely used as additives in personal care products, are present in both biotic and abiotic matrices of the aquatic environment at concentrations of ng/l to µg/l. Although they are determined at comparatively low concentrations, these levels are biologically relevant and pose a significant growing risk as stressors to aquatic organisms. The purpose of our study was to evaluate the effects of 28-day-long exposure to polycyclic musk tonalide in zebrafish juvenile stages (Danio rerio) using selected biomarkers. Environmentally relevant concentrations of tonalide caused significant changes in selected enzyme activities in the experimental groups exposed to the highest concentrations. The activity of glutathione S-transferase and lipid peroxidation increased significantly (p<0.05) after exposure to the highest concentration (50,000ng/l) compared with the control. A similar trend was observed in catalase activity; there was a significant increase (p<0.05) after exposure to two highest concentrations of tonalide (5000 and 50,000ng/l). In addition, a statistically significant decrease (p<0.05) in glutathione reductase activity was found in the lowest test concentration of tonalide (50ng/l). None of the tested concentrations resulted in histopathological changes in liver, kidney, skin, or gill. Furthermore, no effects on body weight, body length, specific growth rate, and behavior were observed. Our results showed that tonalide exposure induced profound changes in the activities of antioxidant and detoxifying enzymes, such changes representing an adaptive response of the fish organism to tonalide toxicity.

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.

Occurrence of Chiral Bioactive Compounds in the Aquatic Environment: A Review

In recent decades, the presence of micropollutants in the environment has been extensively studied due to their high frequency of occurrence, persistence and possible adverse effects to exposed organisms. Concerning chiral micropollutants in the environment, enantiomers are frequently ignored and enantiomeric composition often neglected. However, enantioselective toxicity is well recognized, highlighting the need to include enantioselectivity in environmental risk assessment. Additionally, the information about enantiomeric fraction (EF) is crucial since it gives insights about: (i) environmental fate (i.e., occurrence, distribution, removal processes and (bio)degradation); (ii) illicit discharges; (iii) consumption pattern (e.g., illicit drugs, pharmaceuticals used as recreational drugs, illicit use of pesticides); and (iv) enantioselective toxicological effects. Thus, the purpose of this paper is to provide a comprehensive review about the enantioselective occurrence of chiral bioactive compounds in aquatic environmental matrices. These include pharmaceuticals, illicit drugs, pesticides, polychlorinated biphenyls (PCBs) and polycyclic musks (PCMs). Most frequently analytical methods used for separation of enantiomers were liquid chromatography and gas chromatography methodologies using both indirect (enantiomerically pure derivatizing reagents) and direct methods (chiral stationary phases). The occurrence of these chiral micropollutants in the environment is reviewed and future challenges are outlined.

Bioconcentration of polycyclic musks in fathead minnows caged in a wastewater effluent plume

The synthetic polycyclic musks HHCB (Galaxolide®) and AHTN (Tonalide®) were monitored in fathead minnows (FHMs) caged for a month at various locations in the North Saskatchewan River (NSR), upstream and downstream of the Gold Bar wastewater treatment plant that serves the city of Edmonton, AB, Canada. In addition, the distribution of these musk compounds in the river was predicted using the fugacity-based Quantitative Water Air Sediment Interface (QWASI) model. In FHMs caged 0.15 km downstream of the wastewater outfall, mean concentrations of HHCB and AHTN were 7.4 and 0.4 μg g−1 wet weight, respectively. These are among the highest reported concentrations of these musk compounds in fish exposed to treated wastewater. The musk concentrations in FHMs were significantly lower further downstream of the outfall. High bioconcentration factors (BCFs) in FHMs that exceeded 104 higher than estimated concentrations in water indicated that there were low rates of biotransformation of the musks in the fish. In the FHMs caged at the site closest to the wastewater outfall, HHCB concentrations in FHMs were comparable to the body burdens that have been reported to moderate expression of vitellogenin in female rainbow trout, indicating that fish in the NSR downstream of the wastewater outfall may be at risk of anti-estrogenic effects. The QWASI model applied to six individual river sections of the NSR predicted that the largest fluxes of HHCB and AHTN would be for downstream transport in water, which explains why FHMs accumulated elevated concentrations of the musks at the furthest downstream site, 9.9 km from the wastewater discharge.