Polycyclic aromatic hydrocarbons inside and outside of apartments in an urban area

In the context of environmental monitoring in Berlin polycyclic aromatic hydrocarbon (PAH) concentrations in air and household dust were measured inside 123 residences (and simultaneously in a sub group in the air outside the windows). The aim of this study was to determine exposure to PAHs in the environment influencing by several factors, for instance, motor vehicle traffic in a populous urban area. Indoor air samplings were carried out in two periods (winter and spring/summer) in smokers and non-smokers apartments. Benzo(a)pyrene (BaP) median values were 0.65 ng m(-3) (winter) and 0.27 ng m(-3) (spring/summer) in smokers' apartments and 0.25 ng m(-3) (winter) and 0.09 ng m(-3) (spring/summer) in the apartments of non-smokers. The median BaP content in ambient air was 0.10 ng m(-3) (maximum: 1.1 ng/m(-3)) with an indoor-outdoor mean concentration ratio of 0.9 in non-smoker households and 5.4 in smoker apartments. In household dust we obtained median values of 0.3 mg kg(-1) (range: 0.1-1.4 mg kg(-1)). We found a significant relation between indoor and outdoor values. Approximately 75% of the variance of indoor air values was caused by the corresponding BaP concentrations in the air outside the apartment windows. Otherwise a significant correlation between indoor air and household dust values cannot be found. Therefore, according to our results, it is suggested that the indoor PAH concentration in non-smoker apartments could be attributed mainly to vehicular emissions.     

Organophosphate and phthalate esters in settled dust from apartment buildings in Stockholm

In this study, the occurrence of nine phthalate diesters (phthalates) and 14 organophosphorus flame retardants (PFRs) was investigated in 62 house dust samples collected from 19 buildings in Stockholm area during the year 2008. Eight phthalates were detected in almost all samples, with median concentrations ranging from 0.47 μg/g to 449 μg/g with di(2‐ethylhexyl) phthalate being the most abundant compound. Twelve PFRs were detected with median concentrations ranging from 0.19 μg/g to 11 μg/g. Within this class of compounds, the most abundant were tris(2‐chloroisopropyl) and tris(2‐butoxyethyl) phosphate. Both classes of compounds were also measured in the air of the apartments, but no correlation between air and dust concentrations could be found. Based on these measurements, exposure, via house dust ingestion and air inhalation, was calculated for adults and toddlers, and compared to published limit values in order to estimate potential health risks. In an extreme exposure scenario for toddlers, di(2‐ethylhexyl) phthalate, tris(2‐chloroethyl) phosphate, tris(2‐butoxyethyl) phosphate, and tributyl phosphate were close to the reference dose for chronic oral exposure or the tolerable daily intake. Standard Reference Material SRM 2585 was used as a quality control sample, and the levels of diisononyl and diisodecyl phthalates were determined in this material.     

Fate of synthetic musks in a domestic wastewater treatment plant and in an agricultural field amended with biosolids

Synthetic musks are widely used as fragrance ingredients in personal care products, and they enter domestic wastewater treatment plants (WWTPs) through discharges into municipal sewage systems. Samples of aqueous sewage and biosolids collected from the Peterborough Wastewater Treatment Plant (WWTP), Ontario, Canada were analyzed for 11 synthetic musk compounds using GC/MS. The results showed that 1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethyl-cyclopenta[g]-2-benzopyrane (HHCB, 173.1+/-43.4 ng/L) and 7-acetyl-1,1,3,4,4,6-hexamethyl-tetrahydronaphthalene (AHTN, 41.6+/-15.8 ng/L) were the dominant fragrances in sewage, but other polycyclic musks and nitro musks were present at lower concentrations. The concentrations of HHCB and AHTN in the aqueous phase of the sewage were highly correlated with both BOD5 and TOC. The overall removal efficiency of synthetic musks from the aqueous sewage in the WWTP ranged from 43.3% to 56.9%, but removal occurred mainly by partitioning into the biosolids. Based on a mass balance model, the daily input and output of HHCB and AHTN in the Peterborough WWTP were 47 g and 46 g, respectively. In an agricultural field amended with biosolids from the Peterborough WWTP, HHCB and AHTN were detected in soil immediately after application at mean concentrations of 1.0 and 1.3 mug/kg, respectively, but concentrations declined relatively rapidly over the next 6 weeks, post-application.     

Polycyclic and nitro musks in indoor air: a primary school classroom and a women's sport center

Indoor air gas and particulate-phase samples (PM(2.5) ) were collected from a primary school classroom and a women's sport center because children are one of the sensitive population subgroups and women are frequent users of personal care products in addition to the high level of activity in this specific microenvironment. PM(2.5) was collected with a Harvard impactor, and polyurethane foam was used for the gas phase. Samples were ultrasonically extracted, concentrated, and analyzed with a GC-MS. The mean gas-phase concentrations in the classroom ranged from 0.12 ± 0.2 ng/m(3) for MK to 267 ± 56?ng/m(3) for HHCB, while it was from 0.08 ± 0.10 ng/m(3) for AHMI to 144 ± 61 ng/m(3) for HHCB in the sports center. Particulate-phase average concentrations in the sports center ranged from 0.22 ± 0.11 ng/m(3) for ATII to 1.34 ± 071 ng/m(3) for AHTN, while it ranged from 0.05 ± 0.02 ng/m(3) (musk xylene) to 2.50 ± 0.94 ng/m(3) (HHCB) in the classroom. Exposure-risk assessment showed that inhalation route is most probably far less significant than the dermal route; however, it should be noted that the exposure duration covered in this study was not the larger fraction of the day. PRACTICAL IMPLICATIONS: Synthetic musk compounds (SMCs) are found everywhere because their use in household and personal care products (laundry detergents, carpet cleaners, cleaning agents, fabric softener soaps, shampoos, cosmetics, etc.) has been increasing. These compounds are semi-volatiles that may result in direct and indirect exposures through inhalation route. Although SMCs were found to be dominant in the gas phase, exposure via inhalable particles may be important as we found several compounds in the particulate phase (PM(2.5)).     

Phthalates in indoor dust in Kuwait: implications for non‐dietary human exposure

Phthalates are semivolatile organic compounds with a ubiquitous environmental distribution. Their presence in indoor environments is linked to their use in a variety of consumer products such as children's toys, cosmetics, food packaging, flexible PVC flooring among others. The goal of this study was to investigate the occurrence and concentration of phthalates in dust from homes in Kuwait and to assess non‐dietary human exposure to these phthalates. Dust samples were randomly collected from 21 homes and analyzed for eight phthalates. The concentrations of total phthalates were log normally distributed and ranged from 470 to 7800 μg/g. Five phthalates [Di(2‐ethylhexyl) phthalate (DEHP), Di‐n‐octyl phthalate (DnOP), Di‐n‐butyl phthalate (DBP), Benzyl butyl phthalate (BzBP), and Dicyclohexyl phthalate (DcHP)] were routinely detected. The major phthalate compound was DEHP at a geometric mean concentration of 1704 μg/g (median, 2256 μg/g) accounting for 92% of the total phthalates measured. Using the measured concentrations and estimates of dust ingestion rates for children and adults, estimated human non‐dietary exposure based on median phthalate concentrations ranged from 938 ng/kg‐bd/day for adults to 13362 ng/kg‐bd/day for toddlers. The difference in exposure estimates between children and adults in this study supports previous reports that children are at greater risk from pollutants that accumulate indoors.     

Indoor phthalate exposure and contributions to total intake among pregnant women in the SELMA study

Phthalates are widely used in consumer products. Exposure to phthalates can lead to adverse health effects in humans, with early-life exposure being of particular concern. Phthalate exposure occurs mainly through ingestion, inhalation, and dermal absorption. However, our understanding of the relative importance of different exposure routes is incomplete. This study estimated the intake of five phthalates from the residential indoor environment for 455 Swedish pregnant women in the SELMA study using phthalate mass fraction in indoor dust and compares these to total daily phthalate intakes back-calculated from phthalate metabolite concentrations in the women's urine. Steady-state models were used to estimate indoor air phthalate concentrations from dust measurements. Intakes from residential dust and air made meaningful contributions to total daily intakes of more volatile di-ethyl phthalate (DEP), di-n-butyl phthalate (DnBP), and di-iso-butyl phthalate (DiBP) (11% of total DEP intake and 28% of total DnBP and DiBP intake combined). Dermal absorption from air was the dominant pathway contributing to the indoor environmental exposure. Residential exposure to less volatile phthalates made minor contributions to total intake. These results suggest that reducing the presence of low molecular weight phthalates in the residential indoor environment can meaningfully reduce phthalate intake among pregnant women.     

A rapid method to measure the solid-water distribution coefficient (Kd) for pharmaceuticals and musk fragrances in sewage sludge

Pharmaceuticals and personal care products are omnipresent in wastewater world-wide. In order to predict their sorption quantities onto sludge in wastewater treatment plants (WWTPs), the solid-water distribution coefficients (Kd values) of selected pharmaceuticals (antiphlogistics, estrogens, lipid regulators, anti-epileptic and cytostatic agents) and polycyclic musk fragrances (HHCB, AHTN) were determined in primary and secondary sludges taken from a German municipal WWTP. For the Kd determination, batches of primary and secondary sludge slurries were spiked with the respective target compounds and slowly stirred under defined conditions (e.g. an argon atmosphere). Finally, the water and solid sludge phases were analysed. The Kd values of pharmaceuticals ranged from <1 to 500 L kg(-1), while those for the polycyclic musk fragrances AHTN and HHCB proved to be up to 5300 and 4900 L kg(-1), respectively. The primary and secondary sludge showed significant differences for some pharmaceuticals such as Diclofenac and Cyclophosphamide due to the different pH and composition of the two sludges. The removal rate from the water phase caused by sorption in a WWTP can be reasonably predicted on the basis of the Kd values.     

Semi‐volatile organic compounds in the air and dust of 30 French schools: a pilot study

The contamination of indoor environments with chemical compounds released by materials and furniture, such as semi‐volatile organic compounds (SVOCs), is less documented in schools than in dwellings—yet children spend 16% of their time in schools, where they can also be exposed. This study is one of the first to describe the contamination of the air and dust of 90 classrooms from 30 nursery and primary schools by 55 SVOCs, including pesticides, phosphoric esters, musks, polycyclic aromatic hydrocarbons (PAHs), polychlorobiphenyls (PCBs), phthalates, and polybromodiphenylethers (PBDEs). Air samples were collected using an active sampling method, and dust samples were collected via two sampling methods (wiping and vacuum cleaning). In air, the highest concentrations (median >100 ng/m³) were measured for diisobutyl phthalate (DiBP), dibutyl phthalate (DBP), diethyl phthalate (DEP), bis(2‐ethylhexyl) phthalate (DEHP), and galaxolide. In dust, the highest concentrations (median >30 μg/g) were found for DEHP, diisononyl phthalate (DiNP), DiBP, and DBP. An attempt to compare two floor dust sampling methods using a single unit (ng/m²) was carried out. SVOC concentrations were higher in wiped dust, but frequencies of quantification were greater in vacuumed dust.     

Occurrence of synthetic musks in Korean sewage sludges

Six polycyclic musks (PCMs) and five nitro musks (NMs) were analyzed in dewatered sludge samples from 13 municipal, 4 livestock and 1 pharmaceutical wastewater treatment plants (WWTPs) in South Korea. 1,3,4,6,7,8-Hexahydro-4,6,6,7,8,8-hexamethylcyclopenta-(g)-2-benzopyran (HHCB; Galaxolide^®, Abbalide^®), and 7-acetyl-1,1,3,4,4,6-hexamethyl-1,2,3,4-tetrahydronaphthalene (AHTN; Tonalide^®, Fixolide^®) were the two predominant PCMs in the sludge samples, at concentrations ranging from 0.52 to 82.0 mg/kg dry weight (dw) and 0.12 to 28.8 mg/kg (dw), respectively, suggesting the extensive use of these two PCMs in South Korea. Hierarchical cluster analysis (HCA) revealed the different usage patterns of PCMs between livestock cultivating farm and household. The levels of HHCB and AHTN in the effluent discharged from the WWTPs were lower than the threshold effect levels derived for fish, suggesting low potential risks to aquatic organisms. Nevertheless, the calculated discharge of synthetic musks (SMs) from sludge in each target WWTP ranged from 36 to 10,961 g/d. These results indicate the necessity of conducting monitoring studies in marine ecosystems due to ocean disposal of sludge, particularly focused on the two prevailing PCMs.     

Analysis of selected phthalates in Canadian indoor dust collected using household vacuum and standardized sampling techniques

Phthalates have been used extensively as plasticizers to improve the flexibility of polymers, and they also have found many industrial applications. They are ubiquitous in the environment and have been detected in a variety of environmental and biological matrices. The goal of this study was to develop a method for the determination of 17 phthalate esters in house dust. This method involved sonication extraction, sample cleanup using solid phase extraction, and isotope dilution GC/MS/MS analysis. Method detection limits (MDLs) and recoveries ranged from 0.04 to 2.93 μg/g and from 84 to 117%, respectively. The method was applied to the analysis of phthalates in 38 paired household vacuum samples (HD) and fresh dust (FD) samples. HD and FD samples compared well for the majority of phthalates detected in house dust. Data obtained from 126 household dust samples confirmed the historical widespread use of bis(2‐ethylhexyl) phthalate (DEHP), with a concentration range of 36 μg/g to 3840 μg/g. Dibutyl phthalate (DBP), benzyl butyl phthalate (BzBP), diisononyl phthalate (DINP), and diisodecyl phthalate (DIDP) were also found in most samples at relatively high concentrations. Another important phthalate, diisobutyl phthalate (DIBP), was detected at a frequency of 98.4% with concentrations ranging from below its MDL of 0.51 μg/g to 69 μg/g.     

Polycyclic musk fragrances in different environmental compartments in Berlin (Germany)

The aim of this study was to obtain data about the contamination of different environmental compartments (102 surface water samples, 59 sediment samples and 165 eel samples) by polycyclic musks (HHCB, AHTN, ADBI, AHMI, and ATII) within the framework of an exposure monitoring program. Results for HHCB (Galaxolide) gave the following mean values in areas strongly polluted with sewage: surface water 1.59 micrograms l-1; sediment 0.92 mg kg-1 d.w. and eel 1513 micrograms kg-1 f.w. (in the edible portion) (6471 micrograms kg-1 lipid). The following average concentrations were found in waters hardly contaminated with sewage: surface water 0.07 microgram l-1, sediment < 0.02 mg kg-1 and eel 52 micrograms kg-1 f.w. (445 micrograms kg-1 lipid). Mean concentrations of 6.85 micrograms l-1 (maximum: 13.3 micrograms/l) could be measured at sewage treatment plants' outlets. It could be shown that these polycyclics are highly suited to use as indicators of the degree of contamination of waters with organic substances originating from sewage. A mean bioconcentration factor (BCF) on wet weight of 862 (HHCB) and 1069 (AHTN) for the transfer from water to eel under natural conditions could be calculated. The corresponding BCF-values based on the lipid content of eel were 3504 (HHCB) and 5017 (AHTN).     

Elemental carbon and respirable particulate matter in the indoor air of apartments and nursery schools and ambient air in Berlin (Germany)

This study was performed to examine exposure to typical carcinogenic traffic air pollutants in the city center of an urban area. In all, 123 apartments and 74 nursery schools were analyzed with and without tobacco smoke interference and the households in two measuring periods. Simultaneously, the air outside 61 apartment windows as well as the average daily traffic volume were measured. Elemental carbon (EC), the marker for particulate diesel exhaust and respirable particulate matter (RPM) were determined. The thermographic EC analysis was conducted with and without prior solvent extraction of the soluble carbon fraction. Comparison of these two thermographic EC measurements clearly showed that method-related differences in the results, especially for indoor measurements, when high background loads of organic material were present (e.g. tobacco smoke), existed. Solvent extraction prior to EC determination was therefore appropriate. For the first winter measuring period, the EC concentration levels without solvent extraction in the indoor air were about 50% higher than those measured in the spring/summer period. In the second measuring period (i.e. spring/summer), the median EC concentrations after solvent extraction were 1.9 microg/m3 for smokers' apartments and 2.1 microg/m3 for non-smokers' apartments, with RPM concentrations of 57 and 27 microg/m3, respectively. Nursery schools showed high concentrations with median values of 53 microg/m3 for RPM and 2.9 microg/m3 for EC after solvent extraction. A significant correlation between the fine dust and EC concentrations (after solvent extraction) in the indoor and ambient air was determined. Outdoor EC values were also correlated with the average daily traffic volume. The EC ratios between indoor and ambient concentration showed a median of 0.8 (range: 0.3-4.2) in non-smoker households and 0.9 (range: 0.4-1.5) in smoker apartments. Furthermore, the EC/RPM ratio in indoor and ambient air was 0.01-0.15 (median 0.06) and 0.04-0.37 (median 0.09), respectively. PRACTICAL IMPLICATIONS: In the absence of indoor sources a significant correlation with regard to respirable particulate matter (RPM) and elemental carbon concentrations between the indoor and ambient air of apartments was observed. The high degree of certainty resulting from this correlation underscores the importance of ambient air concentrations for indoor air quality. In nursery schools we found higher concentrations of RPM. An explanation of these results could be the high number of occupants in the room, their activity and the cleaning intensity.     

Semi‐volatile organic compounds in heating,ventilation, and air‐conditioning filter dust in retail stores

Retail stores contain a wide range of products that can emit a variety of indoor pollutants. Among these chemicals, phthalate esters and polybrominated diphenyl ethers (PBDEs) are two important categories of semi‐volatile organic compounds (SVOCs). Filters in heating, ventilation, and air‐conditioning (HVAC) system collect particles from large volumes of air and thus potentially provide spatially and temporally integrated SVOC concentrations. This study measured six phthalate and 14 PBDE compounds in HVAC filter dust in 14 retail stores in Texas and Pennsylvania, United States. Phthalates and PBDEs were widely found in the HVAC filter dust in retail environment, indicating that they are ubiquitous indoor pollutants. The potential co‐occurrence of phthalates and PBDEs was not strong, suggesting that their indoor sources are diverse. The levels of phthalates and PBDEs measured in HVAC filter dust are comparable to concentrations found in previous investigations of settled dust in residential buildings. Significant correlations between indoor air and filter dust concentrations were found for diethyl phthalate, di‐n‐butyl phthalate, and benzyl butyl phthalate. Reasonable agreement between measurements and an equilibrium model to describe SVOC partitioning between dust and gas‐phase is achieved.     

Synthetic musk emissions from wastewater aeration basins

Wastewater aeration basins at publicly owned treatment works (POTWs) can be emission sources for gaseous or aerosolized sewage material. In the present study, particle and gas phase emissions of synthetic musks from covered and uncovered aeration basins were measured. Galaxolide (HHCB), tonalide (AHTN), and celestolide (ADBI) were the most abundant, ranging from 6704 to 344,306 ng m⁻³, 45-3816 ng m⁻³, and 2-148 ng m⁻³ in the gas phase with particle phase concentrations 3 orders of magnitude lower. The musk species were not significantly removed from the exhaust air by an odor control system, yielding substantial daily emission fluxes (∼200 g d⁻¹ for HHCB) into the atmosphere. However, simple dispersion modeling showed that the treatment plants are unlikely to be a major contributor to ambient air concentrations of these species. Emission of synthetic musk species during wastewater treatment is a substantial fate process; more than 14% of the influent HHCB is emitted to the atmosphere in a POTW as opposed to the <1% predicted by an octanol-water partition coefficient and fugacity-based US EPA fate model. The substantial atmospheric emission of these compounds is most likely due to active stripping that occurs in the aeration basins by bubbling air through the sludge.     

Determining source strength of semivolatile organic compounds using measured concentrations in indoor dust

Consumer products and building materials emit a number of semivolatile organic compounds (SVOCs) in the indoor environment. Because indoor SVOCs accumulate in dust, we explore the use of dust to determine source strength and report here on analysis of dust samples collected in 30 US homes for six phthalates, four personal care product ingredients, and five flame retardants. We then use a fugacity‐based indoor mass balance model to estimate the whole‐house emission rates of SVOCs that would account for the measured dust concentrations. Di‐2‐ethylhexyl phthalate (DEHP) and di‐iso‐nonyl phthalate (DiNP) were the most abundant compounds in these dust samples. On the other hand, the estimated emission rate of diethyl phthalate is the largest among phthalates, although its dust concentration is over two orders of magnitude smaller than DEHP and DiNP. The magnitude of the estimated emission rate that corresponds to the measured dust concentration is found to be inversely correlated with the vapor pressure of the compound, indicating that dust concentrations alone cannot be used to determine which compounds have the greatest emission rates. The combined dust‐assay modeling approach shows promise for estimating indoor emission rates for SVOCs.     

Occurrence of endocrine-disrupting chemicals in indoor dust

Human exposure to indoor dust enriched with endocrine-disrupting chemicals released from numerous indoor sources has been a focus of increasing concern. Longer residence times and elevated contaminant concentrations in the indoor environment may increase chances of exposure to these contaminants by 1000-fold compared to outdoor exposure. To investigate the occurrence of semi-volatile endocrine-disrupting chemicals, including PBDEs (polybrominated diphenyl ethers), PCBs (polychlorinated biphenyls), phthalates, pyrethroids, DDT (dichlorodiphenyltrichloroethane) and its metabolites, and chlordanes, indoor dust samples were collected from household vacuum cleaner bags provided by 10 apartments and 1 community hall in Davis, California, USA. Chemical analyses show that all indoor dust samples are highly contaminated by target analytes measured in the present study. Di-(2-ethylhexyl)phthalate was the most abundant (104-7630 microg/g) in all samples and higher than other target analytes by 2 to 6 orders of magnitude. PBDEs were also found at high concentrations (1780-25,200 ng/g). Although the use of PCBs has been banned or restricted for decades, some samples had PCBs at levels that are considered to be concerns for human health, indicating that the potential risk posed by PCBs still remains high in the indoor environment, probably due to a lack of dissipation processes and continuous release from the sources. Although the use of some PBDEs is being phased out in some parts of the U.S., this trend may apply to PBDEs as well. We can anticipate that exposure to PBDEs will continue as long as the general public keeps using existing household items such as sofas, mattresses, and carpets that contain PBDEs. This study provides additional information that indoor dust is highly contaminated by persistent and endocrine-disrupting chemicals.     

Quantification of Muramic Acid,a Marker for Bacterial Peptidoglycan,in Dust Collected from Hospital and Home Air-Conditioning Filters using Gas Chromatography — Mass Spectrometry

The development of standardized non-culture-based approaches capable of assessing microbial contarnination of airborne dust is sorely needed. Direct chemical analysis has previously been successfully used for measuring components unique to Gram-negative bacteria. In the present study, dust from primary filters of hospital air-conditioning intake systems (which filter incoming outdoor and recirculated air) and dust from secondary room filters (filtering primarily indoor air) were analyzed. Dust from home air-condition-ing filters (which also filter outdoor air, with recirculation) were also analyzed. Muramic acid is an aminosugar present in Gram-positive and Gram-negative bacterial cell walls and can serve as a measure of bacterial contamination in dust. Samples were analyzed by gas chromatography-mass spectrometry after hydrolysis and conversion of released sugars (including muramic acid) to alditol acetates. Primary hospital filters contained 26.3 ± 10.0 ng of muramic acid/mg dust while secondary filters contained 5.3 ± 5.4 ng/mg. The level of inuramic acid in home air-conditioner dust was 31.7 ± 13.4 ng/mg. This study of dust collected from air-conditioners demonstrates the feasibility of chemical assessment of the microbial contamination of indoor air.     

Fate and removal of polycyclic musks, UV filters and biocides during wastewater treatment

The fate of polycyclic musks (PCMs) (HHCB, AHTN, ADBI, AHDI, ATII, DPMI), UV filters (3-(4-methylbenzylidene) camphor, 4-MBC; octyl-methoxycinnamate, OMC; octocrylene, OC; octyl-triazone, OT) and biocides (permethrin, carbendazim) during wastewater treatment was studied on a full-scale plant. Average influent concentrations of OMC, HHCB, OC, AHTN, 4-MBC and OT were at 20070, 4420, 1680, 1430, 960 and 720 ng L(-1), respectively. The other PCMs, permethrin and carbendazim ranged between < limits of quantification and 670 ng L(-1). Concentrations in the water line decreased significantly for most compounds. Removal rates for PCMs ranged from 72% to 86%, for UV filters from 92% to >99% and were at 92% and 37% for permethrin and carbendazim, respectively. Removal during wastewater treatment was mainly driven by sorption onto solids and biodegradation. For anaerobic sludge digestion, elimination of PCMs, OMC and the biocides was observed.     

Occurrence and reductions of pharmaceuticals and personal care products and estrogens by municipal wastewater treatment plants in Ontario, Canada

Over the last ten years there have been reports of pharmaceuticals and personal care product (PPCP) residuals in municipal wastewater treatment plant (WWTP) effluents. The principle goal of this study was specifically to expand and in some cases establish a Canadian database for the presence of selected acidic drugs, triclosan, polycyclic musks, and selected estrogens in MWWTP influent and effluent. The impact of treatment configuration (e.g. lagoons, conventional activated sludge (CAS), and CAS followed by media filtration (CAS+filtration)) was also examined. For CAS systems, the most prevalent treatment type, the effect of operating temperature and SRT was evaluated. Selected PPCPs included ten acidic pharmaceuticals (i.e. a group of pharmaceuticals that are extractable at a pH of 2 or less), triclosan, five polycyclic musks and two estrogens. The pharmaceuticals and musks were selected on the basis of levels of use in Canada; reported aquatic toxicity effects; and the ability to analyze for the compounds at low levels. Twelve MWWTPs discharging into the Thames River, the second largest river in southwestern Ontario, were surveyed. The only common characteristic of acidic drugs is their extraction pH as they differ in their intended biological function and chemical structure. Many organics degraded by WWTP processes benefit from warm temperatures and long SRTs so the impact of these variables warranted additional attention. Influent concentrations and reductions for acidic drugs reported by this study were compared to other Canadian studies, when available, and European investigations. The data of this study seems consistent with other reports. Ten acidic drugs were considered by this study. Three were consistently present at non-quantifiable levels (e.g. CLF, FNP and FNF). Additionally, one analyte, SYL, presented results that were so inconsistent that the values were not analysed. The remaining six acidic pharmaceuticals were placed into three categories. IBU and NPX members of the first category had consistently high reductions. At the level of reduction achieved (i.e. median reduction of greater than 93%) and any effect of treatment type or operating characteristics would be subtle and non-discernable given the analytical noise. In the second group are KTP and IND, and definitive comments are difficult to make on the impact of treatment type and operational considerations due to a sparse data set (i.e. many influent values were at non-quantifiable concentrations). Median reductions were in the 23% to 44% range. In the last category are GMF and DCF which have median reductions of 66% and -34%, respectively. Several negative reduction values in the data set (i.e. twelve of twenty six sampling events) suggest that DCF may be deconjugated under certain conditions. This warrants further evaluation when analytical methods for measuring human metabolites of DCF are available. For both GMF and DCF, reduction does not appear to be strongly influenced by SRTs up to 15 days, while SRTs over 30 days were associated with more frequent non-quantifiable effluent levels of DCF. This would suggest that better treatment would be provided by lagoons and CAS systems with extended aeration. Preliminary data suggests that temperature does not play a strong role in the reduction of these compounds. Triclosan (TCL) was detected at concentrations of 0.01-4.01 microg/L in influent samples and 0.01-0.324 microg/L in effluent samples. Reduction of TCL ranged from 74% to 98%. Lagoon treatment seems to be the best TCL reduction as it was present in the influent and effluent at quantifiable and non-quantifiable concentrations, respectively, on nine of nine sampling occasions. Influent and reduction values of five polycyclic musks (e.g. ADBI, AHMI, ATII, HHCB, and AHTN) were examined over the course of this study. AHMI was predominantly present at non-quantifiable concentrations. HHCB and AHTN were present at the highest concentrations. A comparison between Canadian values and those of European studies indicate that in general polycyclic musk concentrations in Canadian MWWTP effluents are 5-10 times lower. More extensive European and Canadian databases would be useful in confirming this initial observation. Median reductions for the five remaining musks range between 37% and 65% in CAS systems. CAS+filtration systems would be expected to have higher reductions if musks were bound to the effluent solids. This trend is not apparent but this may be due to the small size of the data set. In lagoon systems, musk reduction for HHCB and AHTN are approximately 98-99%. For ADBI and ATII musk, there are no numerical reduction values as most often the effluent concentration was non-quantifiable. In some instances, both the influent and effluent concentrations were non-quantifiable. The hormones 17-beta-estradiol (E2) and estrone (E1) were detected at concentrations of 0.006 to 0.014 and 0.016 to 0.049 microg/L, respectively. E2 was not detected in any effluent samples (<0.005 microg/L) whereas E1 was detected in effluent samples from CAS treatment plants (median of 0.008 microg/L), and in one sample from lagoons. These data demonstrate that there are detectable levels of PPCPs entering Canadian waterways at trace levels, and that only some of these compounds are being reduced in a significant proportion by municipal wastewater treatment processes.     

Determination of the solid-water distribution coefficient (Kd) for pharmaceuticals, estrogens and musk fragrances in digested sludge

This work determined the solid-water distribution coefficient (K(d)) and the organic carbon normalized distribution coefficient (K(oc)) of several pharmaceuticals (carbamazepine, ibuprofen, naproxen, diclofenac, iopromide, sulfamethoxazole and roxithromycin), three estrogens (estrone, 17beta-estradiol and 17alpha-ethinylestradiol) and two musk fragrances (HHCB and AHTN) in digested sludge. These sorption coefficients can be used to evaluate the fate of these substances during sludge treatment, thus avoiding the expensive and time-consuming analysis in the sludge phase. For determining the K(d) and K(oc) values of the target compounds in digested sludge, their concentrations were measured in the aqueous and solid phase of the effluent of an anaerobic digestion pilot plant run at several operational conditions. The results obtained were compared with the values modelled by using simple K(ow) approaches. The resulting log K(d) values ranged between 3.5 and 4.4 for the two musk fragrances (log K(oc) of 4.5-6.0), between 2.1 and 2.9 for estrogens (log K(oc) of 2.9-4.2) and between 0.8 and 1.9 for the remaining pharmaceuticals (log K(oc) of 1.8-3.5). These values are in the same range as those reported in the literature for primary and secondary sludge and no significant influence of the anaerobic digestion operational conditions was observed. For most compounds, the modelled K(oc) were close or within the lower range of the experimentally determined K(oc). Major deviations of the modelled K(oc) values were found for iopromide, sulfamethoxazole and roxithromycin, which were 1-3 orders of magnitude lower than the measured values.