Polycyclic Musk Compounds Research Articles

Long-term exposure to polycyclic musk tonalide - A potential threat to juvenile zebrafish (Danio rerio)?

Polycyclic musk compounds are commonly used in personal care products to replace expensive natural fragrances. Due to their huge consumption, they have become a part of the aquatic environment. Inthe present study, atwo-month exposure effect oftonalide onjuvenile zebrafish (Danio rerio) was investigated. Wedetermined thevitellogenin concentration todefine the potential endocrine-disrupting effect oftonalide and also analysedselected indices toevaluate the induction ofoxidative stress. The environmentally relevant concentration oftonalide (i.e., 500ng/l) caused asignificant decrease inthe catalase activity (P<0.05) and asignificant increase (P<0.05) inthe lipid peroxidation. Anincreasing lipid peroxidation was also recorded for the highest concentration group tested (i.e., 50000ng/l). Onthe other hand, nosignificant changes were recorded invitellogenin inall theexposed groups. Thus, based onthese results, wehave not demonstrated the endocrine-disrupting activity oftonalide inzebrafish. The results ofthe oxidative stress indices showed asignificant impairment oftheantioxidant defence after the two-month tonalide exposure, which could indicate part ofthe adaptive response tothetonalide toxicity.

Occurrence of synthetic polycyclic and nitro musk compounds in sewage sludge from municipal wastewater treatment plants

Synthetic musk compounds (SMCs) are widely used as fragrances that can be released from different sources and through the sewer system, finally reaching wastewater treatment plants (WWTPs). In this study, 6 synthetic polycyclic and 5 nitro musk compounds were screened in 55 sewage sludge (SS) samples from 43 different WWTPs in the Czech Republic, and the effect of WWTP technology parameters on SMC content in SS was assessed. Galaxolide and Tonalide were predominant synthetic polycyclic musk compounds (SPMCs) detected in all SS tested and accounted for 99.5% of the average content of sludge SMCs (5518 μg/kg dw). The amount of synthetic nitro musk compounds (SNMCs) in SS samples was negligible. The Tonalide content in SS correlated significantly with the WWTP design capacity (r = 0.32, P < 0.05). The significant correlation between chemical oxygen demand (COD) removal efficiency and SMCs (r = −0.37, P < 0.05) partly suggests the recalcitrance of SMCs, mainly of Celestolide, Galaxolide and Tonalide, to biodegradation in WWTPs. A statistically lower SNMC content was found in anaerobically digested sludges than in aerobic ones. There was no significant difference (P > 0.05) between the digestion technology as well as the temperature of anaerobic digestion on the SPMC content in sewage sludge. The wastewater (WW) load percentage or WW hydraulic retention time had no influence on the SMC content in the resulting SS. Musk compounds did not change over time when the SS samples were analysed with a gap of two years, suggesting that sewage sludge for soil applications only needs to be analysed for musk compounds once a year. Our study indicates that the currently common WWTP technologies have only very limited potential to affect the accumulation of musk compounds in sewage sludge.

Photodegradation of fragrance materials and triclosan in water: Direct photolysis and photosensitized degradation

The present study aims to assess the photodegradation of three polycyclic musk compounds (OTNE, HHCB, and AHTN) and one disinfectant (triclosan) under simulated sunlight irradiation using a halogen lamp in pH-adjusted DI water, natural waters, and humic acid solution. The degradation induced by hydroxyl radical was examined with the addition of 2-propanol. The targeted compounds were considerably decreased in several days under irradiation, except for triclosan for blank water, with the pseudo-first-order rate constants in the order of one per day at the maximum. They were degraded with the paths of both direct and indirect photosensitized processes, with the hydroxyl radical and others. The main findings were that OTNE direct photolysis was possibly influenced by pH. HHCB photosensitized pathway was more eminent than that of AHTN, and triclosan was degraded mostly by the photosensitized process. The major influential factors were found to differ with the compounds and solution conditions, which intensifies the importance of the consideration of key factors for predicting the degree of photodegradation in water environments. • Direct photolysis and photosensitized degradation were evaluated simultaneously. • Triclosan was mostly degraded by photosensitized pathway, not by direct photolysis. • ONTE direct photolysis was influenced by pH.

Galaxolide and tonalide modulate neuroendocrine activity in marine species from two taxonomic groups

Galaxolide (HHCB) and tonalide (AHTN) are polycyclic musk compounds (PMCs) used in household and personal care products that have been included on the list as emerging contaminants of environmental concern due to their ubiquity in aquatic and terrestrial environments. There still exists a dearth of information on the neurotoxicity and endocrine disrupting effects of these contaminants, especially for marine and estuarine species. Here, we assessed the neuroendocrine effects of HHCB and AHTN using adult clams, Ruditapes philippinarum, and yolk-sac larvae of sheepshead minnow, Cyprinodon variegatus. The clams were treated with concentrations (0.005–50 μg/L) of each compound for 21 days. Meanwhile, sheepshead minnow larvae were exposed to 0.5, 5 and 50 μg/L of HHCB and AHTN for 3 days. Enzyme activities related to neurotoxicity (acetylcholinesterase - AChE), neuroendocrine function (cyclooxygenase - COX), and energy reserves (total lipids - TL) were assessed in R. philippinarum. Gene expression levels of cyp19 and vtg1 were measured in C. variegatus using qPCR. Our results indicated induction of AChE and COX in the clams exposed to HHCB while AHTN exposure significantly inhibited AChE and COX. Gene expression of cyp19 and vtg1 in yolk-sac C. variegatus larvae exposed to 50 μg/L AHTN was significantly downregulated versus the control. The results of this study demonstrate that HHCB and AHTN might pose neurotoxic and endocrine disrupting effects in coastal ecosystems.

Effects and Risk Assessment of the Polycyclic Musk Compounds Galaxolide® and Tonalide® on Marine Microalgae, Invertebrates, and Fish

The current research investigated the potential environmental risk of the polycyclic musk compounds, Galaxolide® (HHCB) and Tonalide® (AHTN), in the marine environments. These substances are lipophilic, bioaccumulated, and potentially biomagnified in aquatic organisms. To understand the toxicity of HHCB and AHTN, acute toxicity tests were performed by exposing marine microalgae (Phaeodactylum tricornutum, Tretraselmis chuii, and Isochrysis galbana), crustaceans (Artemia franciscana), echinoderms (Paracentrotus lividus), bivalves (Mytilus galloprovincialis), fish (Sparus aurata), and a candidate freshwater microalga (Raphidocelis subcapitata) to environmentally relevant concentrations (0.005–5 µg/L) following standardized protocols (US EPA, Environment Canada and OECD). P. tricornutum and I. galbana were sensitive to both substances and for P. tricornutum exposed to HHCB and AHTN, the IC10 values (the inhibition concentration at which 10% microalgae growth inhibition was observed) were 0.127 and 0.002 µg/L, respectively, while IC10 values calculated for I. galbana were 5.22 µg/L (a little higher than the highest concentration) and 0.328 µg/L, for HHCB and AHTN, respectively. Significant (p &lt; 0.01) concentration dependent responses were measured in P. lividus and M. galloprovincialis larvae developments, as well as S. aurata mortality tested with HHCB. The effect of HHCB on P. lividus larvae development was the most sensitive endpoint recorded, producing an EC50 value (the effect concentration at which 50% effect was observed) of 4.063 µg/L. Considering the risk quotients both substances seem to represent high environmental risk to P. tricornutum and M. galloprovincialis in marine environments.

Potential of environmental concentrations of the musks galaxolide and tonalide to induce oxidative stress and genotoxicity in the marine environment

Polycyclic musk compounds have been identified in environmental matrices (water, sediment and air) and in biological tissues in the last decade, yet only minimal attention has been paid to their chronic toxicity in the marine environment. In the present research, the clams Ruditapes philippinarum were exposed to 0.005, 0.05, 0.5, 5 and 50 μg/L of the fragrances Galaxolide® (HHCB) and Tonalide® (AHTN) for 21 days. A battery of biomarkers related with xenobiotics biotransformation (EROD and GST), oxidative stress (GPx, GR and LPO) and genotoxicity (DNA damage) were measured in digestive gland tissues. HHCB and AHTN significantly (p < 0.05) induced EROD and GST enzymatic activities at environmental concentrations. Both fragrances also induced GPx activity. All concentrations of both compounds induced an increase of LPO and DNA damage on day 21. Although these substances have been reported as not acutely toxic, this study shows that they might induce oxidative stress and genotoxicity in marine organisms.

The removing and discharge of the synthetic polycyclic musk compounds in sewage treatment plant

The removing and discharge of the synthetic polycyclic musk compounds in sewage treatment plant

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.

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.

Occurrence of synthetic musk fragrances in effluent and non-effluent impacted environments

Synthetic musk fragrances (SMFs) are considered micropollutants and can be found in various environmental matrices near wastewater discharge areas. These emerging contaminants are often detected in wastewater at low concentrations; they are continuously present and constitute a constant exposure source. Objectives of this study were to investigate the environmental fate, transport, and transformation of SMFs. Occurrence of six polycyclic musk compounds (galaxolide, tonalide, celestolide, phantolide, traseolide, cashmeran) and two nitro musk compounds (musk xylene and musk ketone) was monitored in wastewater, various surface waters and their sediments, as well as groundwater, soil cores, and plants from a treated wastewater land application site. Specifically, samples were collected quarterly from (1) a wastewater treatment plant to determine initial concentrations in wastewater effluent, (2) a storage reservoir at a land application site to determine possible photolysis before land application, (3) soil cores to determine the amount of sorption after land application and groundwater recharge to assess lack thereof, (4) a lake system and its sediment to assess degradation, and (5) non-effluent impacted local playa lakes and sediments to assess potential sources of these compounds. All samples were analyzed using gas chromatography coupled with mass spectrometry (GC–MS). Data indicated that occurrence of SMFs in effluent-impacted environments was detectable at ng/L and ng/g concentrations, which decreased during transport throughout wastewater treatment and land application. However, unexpected concentrations, ng/L and ng/g, were also detected in playa lakes not receiving treated effluent. Additionally, soil cores from land application sites had ng/g concentrations, and SMFs were detected in plant samples at trace levels. Galaxolide and tonalide were consistently found in all environments. Information on occurrence is critical to assessing exposure to these potential endocrine disrupting compounds. Such information could provide a scientific framework for establishing the need for environmental regulations.

Municipal landfill leachates: A significant source for new and emerging pollutants

Landfills have historically remained the most common methods of organized waste disposal and still remain so in many regions of the world. Thus, they may contain wastes resulting from several decades of disposal and decomposition with subsequent release of organic compounds that may have environmental, wildlife and human health consequences. Products containing different types of additives with unique beneficial improvement properties are in daily use. However, when these products are decomposed, additives are release into the environment, some of which have been shown to have negative environmental impacts, resulting in the ban or at least restricted application of some chemicals. New and emerging compounds are continuously discovered in the environment. Herein, we report qualitative and quantitative data on the occurrence of new and emerging compounds with increasing environmental and public health concern in water- and particle phase of landfill leachates. Under normal environmental conditions, several of these chemicals are persistent high-volume products. Identified chemicals in the leachates at nanogram (ng) or microgram (μg) per liter levels include — chlorinated alkylphosphates such as tris(1-chloro-2-propyl) phosphate (TCPP), N-butyl benzensulfonamide (NBBS), the insect repellent diethyl toluamide (DEET) and personal care products such as the non-steroidal anti-inflammatory drug ibuprofen and polycyclic musk compounds. Among new and emerging contaminants, perfluorinated compounds (PFCs) were measured in the water phase at concentrations up to 6231 ng/L. Compared with the other chemicals, PFCs were primarily distributed in water phase. An effective removal method for PFCs and other polar and persistent compounds from landfill leachates has been a major challenge, since commonly used treatment technologies are based on aeration and sedimentation. Thus, the present study has shown that municipal landfill leachates may represent a significant source of concern for legacy, new and emerging chemicals in groundwater.

At-line microextraction by packed sorbent-gas chromatography–mass spectrometry for the determination of UV filter and polycyclic musk compounds in water samples

An at-line analysis protocol is presented that allows the determination of four UV filters, two polycyclic musk compounds and caffeine in water at concentration level of ng L −1. The fully automated method includes analytes enrichment by Microextraction by packed sorbent (MEPS) coupled directly to large volume injection-gas chromatography–mass spectrometry. Two common SPE phases, C8 and C18, were examined for their suitability to extract the target substances by MEPS. The analytes were extracted from small sample volumes of 800 μL with recoveries ranging from 46 to 114% for the C8-sorbent and 65–109% for the C18-sorbent. Limits of detection between 34 and 96 ng L −1 enable the determination of the analytes at common environmental concentration levels. Both sorbents showed linear calibration curves for most of the analytes up to a concentration level of 20 ng mL −1. Carryover was minimized by washing the sorbents 10 times with 100 μL methanol. After this thorough cleaning, the MEPS are re-used and up to 70 analyses can be performed with the same sorbent. The fully automated microextraction GC–MS protocol was evaluated for the influence of matrix substances typical for wastewater. Dilution of samples prior to MEPS is recommended when the polar caffeine is present at high concentration. Real water samples were analyzed by the MEPS-GC–MS method and compared to standard SPE.

Partitioning of polycyclic musk compounds in soil and aquatic environment—experimental determination of KDOC

Purpose Polycyclic musk compounds (PMC) are used as fragrances in cosmetics and detergents and enter rivers via domestic wastewater and sewage treatment plants. Soils can be contaminated by PMC through application of sewage sludge. Accumulation of PMC occurs in sediments and biota due to their persistence and lipophilicity. Dissolved organic matter (DOM) is of special relevance for their transport and behavior in the environment as it acts as solubilizer and carrier in aquatic and terrestrial systems. With the distribution coefficient KDOC, one can predict their affinity to DOM. Different approaches exist to determine KDOC, resulting in a range of coefficients for a number of organic pollutants. The objective of this study was to determine KDOC values for PMC using solid-phase microextraction (SPME).

Synthetic musks in blood of healthy young adults: Relationship to cosmetics use

Production of polycyclic musk compounds is increasing accompanied by a decline in nitro musk production. Although it can be assumed that due to this reduction nitro musks are less prevalent in human body fluids, there are no data available from the last decade. This study examined the concentrations of five nitro musks and six polycyclic musks in blood samples from young healthy volunteers. Blood was taken from 100 healthy students of the Medical University of Vienna. The lipophilic fraction was extracted and after purification analyzed by GC–MS. Study participants also completed a questionnaire on the use of cosmetics, about nutrition and other life-style aspects. Highest percentages of synthetic musks in blood plasma samples were found for galaxolide (91%, median 420 ng L − 1 ) and musk xylene (79%, median 11 ng L − 1 ). Both musk ketone and tonalide were found in 17%. In two cases musk ambrette was detected. In a multivariate approach only younger age, use of lotion and perfumes did significantly predict blood concentrations of polycyclic musks. For nitro musks except body surface area no significant predictor could be found. High percentage of the population is still exposed to nitro musk compounds although blood concentrations of nitro musks are generally lower than those of polycyclic musks. Compared to earlier investigations performed in the 1990s nitro musks were detected in lower percentages and concentrations. There seems to be no dominant source of nitro musk uptake although relationship to body surface area indicates cosmetic products applied to the skin as the likely origin of plasma concentrations.

Personal care compounds in a reed bed sludge treatment system

Sewage sludge (also referred to as biosolids) has long been used as fertilizer on agricultural land. The usage of sludge as fertilizer is controversial because of possible high concentration of xenobiotic compounds, heavy metals as well as pathogens. In this study, the fate of the xenobiotic compounds triclosan (5-chloro-2-(2,4-dichlorophenoxy)phenol), OTNE (1-(2,3,8,8-tetramethyl-1,2,3,4,5,6,7,8-octahydro-naphthalen-2-yl)ethan-1-one), HHCB (1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethylcyclopenta-(g)-2-benzopyran), HHCB-lactone, AHTN (7-acetyl-1,1,3,4,4,6 hexamethyl-1,2,3,4 tetrahydronaphthalene), and DEHP (bis(2-ethylhexyl)phthalate) in advanced biological treatment of sludge was determined. During 13 months of field-incubation of the sludge in reed beds, the xenobiotic compounds were analysed. The bactericide triclosan was reduced to 60%, 45%, and 32% of its original concentration in the top, middle, and bottom layer. The fragrance OTNE was decreased to 42% in the top layer, 53% in the middle layer, and 70% in the bottom layer, respectively. For DEHP a reduction of 70%, 71%, and 40% was observed in the top, middle, and bottom layer, respectively. The polycyclic musk compounds HHCB, AHTN, and the primary metabolite of HHCB, i.e., HHCB-lactone showed no degradation in 13 months during the experimental period in this installation. Tentative half-lives of degradation of triclosan, OTNE and DEHP were estimated to be 315–770 d, 237–630 d, and 289–578 d, respectively.

Polycyclic musks in green-lipped mussels ( Perna viridis) from Hong Kong

Six polycyclic musk compounds [Cashmeran (DPMI), Celestolide (ADBI), Phantolide (AHMI), Traseolide (ATII), Tonalide (AHTN), and Galaxolide (HHCB)] were analysed in marine green-lipped mussels ( Perna viridis) from Hong Kong. ADBI, HHCB and AHTN were detected in almost all samples, while AHMI, ATII and DPMI were not detected. Concentrations of ADBI, HHCB and AHTN in mussels ranged from below detection limit–0.0743 (mean: 0.0246), 0.247–6.08 (mean: 1.15) and 0.0591–0.738 (mean: 0.190) mg/kg lipid weight, respectively. Mussels from two sampling sites in central Victoria Harbour contained the highest total polycyclic musk levels, suggesting that these waters are heavily influenced by domestic sewage. Concentrations of HHCB and AHTN detected in the mussel samples were the second highest and the highest levels, respectively, compared to global concentrations. A preliminary risk assessment indicated that HHCB and AHTN in mussels pose little or no threat to the health of shellfish consumers. Nevertheless, more comprehensive studies are required to further assess the ecological and human health risks associated with polycyclic musks.

SPE/SPME–GC/MS approach for measuring musk compounds in serum and breast milk

Musks can be used to provide distinctive odor or scent in many personal care products. Musk compounds have received growing attention in recent years by environmental scientists and regulatory agencies because of their increasing production volume and widespread environmental presence. A combined separation approach using solid phase extraction (SPE) and solid phase micro extraction (SPME) coupled to detection by gas chromatography mass spectrometry was developed for measuring four polycyclic musk compounds (Galactoside ®, Tonalide ®, Muskene ®, Celestolide ®) in serum and milk. The SPE and SPME separation steps were fully automated and required minimal sample handling. The method, which requires only 1 mL serum or breast milk to achieve limits of detection of 0.03–0.3 ng/mL, is applicable in biomonitoring studies for human internal dose measurement of polycyclic musk compounds.

Preliminary study on the occurrence and distribution of polycyclic musks in a wastewater treatment plant in Guandong, China

The occurrence and distributions of six polycyclic musks were studied in influent, primary and effluent waters from a municipal wastewater treatment plant (WWTP) in Guangdong. Five polycyclic musk compounds, 1,2,3,5,6,7-hexahydro-1,1,2,3,3-pentamethyl-4 H-inden-4-one (DPMI), 4-acetyl-1,1-dimethyl-6- tert-butylindan (ADBI), 6-acetyl-1,1,2,3,3,5-hexamethylindan (AHMI), 1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethylcyclopenta( g)-2-benzopyran (HHCB) and 7-acetyl-1,1,3,4,4,6-hexamethyl-1,2,3,4-tetrahydronaphthalene (AHTN) were found in wastewater in the WWTP. DPMI, HHCB and AHTN were measured at 0.38–0.69, 11.5–146, 0.89–3.47 μg/l, respectively, in influents. Meanwhile 0.06–0.10 μg/l DPMI, 0.95–2.05 μg/l HHCB, 0.10–0.14 μg/l AHTN were detected in effluents, ADBI and AHMI were also detected in some primary waters and effluents. The results suggested that wastewater from cosmetic plants cause high loadings of polycyclic musks to this WWTP. Under the currently applied treatment technology, the removal efficiencies achieved were 61–75% for DPMI, 86–97% for HHCB and 87–96% for AHTN by transfer to sludge as the main removal route.

Occurrence of Polycyclic Musks in Sewage Sludge and their Behaviour in Soils and Plants. Part 2: Investigation of Polycyclic Musks in Soils and Plants (9 pp)

Part 2: Investigation of Polycyclic Musks in Soils and Plants Part 1: Behaviour of Polycyclic Musks in Sewage Sludge of Different Treatment Plants in Summer and Winter Preamble. In Part 1 of the study, screening tests were performed to investigate the occurrence of PCM in sewage sludges. For a preliminary risk assessment, further information is needed about their behaviour in the terrestrial environment. Hence Part 2 examined the adsorption of PCMs to soil, their dissipation and leaching in soil and their uptake in plants. Polycyclic Musks (PCMs) enter the terrestrial environment via the use of sewage sludge as fertilizer. After entry into soil, they can be taken up by plants or move into the groundwater body. However, until now no overall risk assessment for polycyclic musks is available. For a preliminary risk assessment further information is needed about their behaviour in the soil environment. Therefore, Part 2 of the study (Part 1, see J Soils Sediments, OnlineFirst ) examined the adsorption of PCMs to soil, their dissipation and leaching in soil and their uptake by plants. Analytical methods for the determination of HHCB and AHTN in soil and plant samples were developed and applied. The adsorption/desorption studies were performed according to OECD guideline 106 and draft guideline 121 using three soils. Dissipation (aerobic degradation) was examined according to BBA guideline 4-1 in three soils over a test period of 37 weeks under controlled conditions. Leaching experiments in soil columns were performed using columns of 14 cm O and 30 cm filling height for a test period of 48 hours. Finally the uptake of PCMs by lettuce and carrots was studied in laboratory and outdoor experiments. The adsorption/desorption studies resulted in Koc values between 4200 and 7900 for HHCB and between 4800 and 13600 for AHTN showing strong sorption to the soils investigated. The dissipation of the PCMs occurred very slowly with elimination rates after 37 weeks of approx. 50% and 25% for HHCB and AHTN, respectively. The leaching experiments showed leaching rates of < 0.001% for HHCB and AHTN during a test period of 48 hours. The slight leaching is presumably due to ‘preferential flow'. The transfer factors (ratio of concentrations in the plant to concentrations in the soil ) for HHCB in lettuce and carrot leaves determined in plant uptake experiments were as low as 0.003. For HHCB in carrot roots however high transfer factors of 0.095 for a humic and 0.48 for a loamy soil were obtained. The high uptake may be caused by partitioning of the HHCB into the essential oil cells of the carrot roots. The polycyclic musk compounds HHCB and AHTN showed high adsorption to soil. A desorption phenomenon occurred after three desorption steps. High adsorption influences the slow degradation kinetic. Comparable investigations into the degradation behaviour show the same results, whereas other authors observed a faster degradation. We assume a dependency on microbial consortia, which can vary as a function of the substrate and adaptation of the microbial population. Leaching tests were carried out in our study, but not by other studies. The results reflect the adsorption into the soil matrix. The results show that PCMs are widespread contaminants in sewage sludge and should be considered in a risk assessment as potential contaminants of sewage sludge destined for agricultural use. When applied to soil they may remain in the upper soil layers due to their high sorption, low degradability and low leaching behaviour. Uptake by some plants like carrot roots may be relevant. . This study examined the adsorption of PCMs to soil, their dissipation and leaching in soil and their uptake into plants. For a qualitative risk assessment more data on adsorption /desorption, and degradation in soils under different soil conditions needs to be generated. Also, further studies have to be carried out to gain a better understanding of plant uptake of PCMs, especially HHCB and AHTN.

Membrane-assisted liquid–liquid extraction coupled with gas chromatography–mass spectrometry for determination of selected polycyclic musk compounds and drugs in water samples

Selected polycyclic musk compounds and drugs were extracted from water samples by membrane-assisted micro liquid–liquid extraction. The two-phase extraction system consisted of polyethylene membrane bags filled with an organic solvent. Chloroform proved to be most suited as acceptor phase to extract caffeine, Galaxolide, Tonalide, phenazone and carbamazepine from aqueous samples. The compounds were enriched from 50 mL sample into a volume of 500 μL of chloroform. Gas chromatography–mass spectrometry (GC–MS) was applied for analysis. The extraction procedure was optimised in regard to membrane material, extraction time and temperature. The evaluation of the entire analysis protocol found limits of detection that ranged from 20 to 200 ng/L. The linear range of calibration covered one magnitude with standard deviations between 4 and 12%. Method comparison with standard analysis techniques such as solid-phase extraction (SPE) combined with GC–MS as well as LC–MS–MS confirmed this method as an easy and reliable protocol, even for the monitoring of matrix-loaded wastewater. The analysis of real samples established the feasibility of the technique.