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Volatile methylsiloxanes (VMS) have been identified as contaminants of emerging concern in aquatic systems. Here, we report on the presence of VMS in sediment and wastewater from Arctic regions in 2014 to 2016 and model their persistence in Adventfjorden in Longyearbyen, Svalbard. Total concentrations of VMS in sediment were dominated by D4 and D5 and ranged from 0.0024 to 1.7 ng g-1 at Svalbard (Longyearbyen), from 4.0 to 43 ng g-1 in Greenland (Nuuk) and from 0.19 to 21 ng g-1 in the Canadian Archipelago. Concentrations in wastewater samples from Svalbard ranged from 12 to 156 ng L-1. Large variability in reported values of the partition ratio between organic carbon and water (KOC) and enthalpy of sorption (ΔHOC; often estimated from enthalpy of phase change between octanol and water, ΔHOW) of VMS has resulted in high uncertainty in evaluating persistence in aquatic systems. We evaluated previously reported KOC and ΔHOC values from the literature in predicting measured VMS concentrations in sediment and wastewater in scenarios using a fugacity-based multimedia model for VMS concentrations in Svalbard. We tested two different model scenarios: (1) KOC and ΔHOW measurements for three cyclic VMS previously reported by Kozerski et al. (Environ. Toxicol. Chem., 2014, 33, 1937-1945) and Xu and Kropscott (Environ. Chem., 2014, 33, 2702-2710) and (2) the KOC and ΔHOC measurements from Panagopoulos et al. (Environ. Sci. Technol., 2015, 49, 12161-12168 and Environ. Sci. Technol. Lett., 2017, 4(6), 240-245). Concentrations of VMS in sediment predicted from concentrations in wastewater in scenario 2 were in good agreement with measured concentrations, whereas in scenario 1, predicted concentrations were 2 to 4 orders of magnitude lower. Such large discrepancies indicate that the differences in the predicted concentrations are more likely to be attributed to KOC and ΔHOC than to uncertainty in environmental parameters or emission rates.

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.

The long-term time trends of atmospheric pollutants at eight Arctic monitoring stations are reported. The work was conducted under the Arctic Monitoring and Assessment Programme (AMAP) of the Arctic Council. The monitoring stations were: Alert, Canada; Zeppelin, Svalbard; Stórhöfði, Iceland; Pallas, Finland; Andøya, Norway; Villum Research Station, Greenland; Tiksi and Amderma, Russia. Persistent organic pollutants (POPs) such as α- and γ-hexachlorocyclohexane (HCH), polychlorinated biphenyls (PCBs), α-endosulfan, chlordane, dichlorodiphenyltrichloroethane (DDT) and polybrominated diphenyl ethers (PBDEs) showed declining trends in air at all stations. However, hexachlorobenzene (HCB), one of the initial twelve POPs listed in the Stockholm Convention in 2004, showed either increasing or non-changing trends at the stations. Many POPs demonstrated seasonality but the patterns were not consistent among the chemicals and stations. Some chemicals showed winter minimum and summer maximum concentrations at one station but not another, and vice versa. The ratios of chlordane isomers and DDT species showed that they were aged residues. Time trends of perfluorooctanoic acid (PFOA) and perfluorooctane sulfonic acid (PFOS) were showing decreasing concentrations at Alert, Zeppelin and Andøya. The Chemicals of Emerging Arctic Concern (CEAC) were either showing stable or increasing trends. These include methoxychlor, perfluorohexane sulfonic acid (PFHxS), 6:2 fluorotelomer alcohol, and C9-C11 perfluorocarboxylic acids (PFCAs). We have demonstrated the importance of monitoring CEAC before they are being regulated because model calculations to predict their transport mechanisms and fate cannot be made due to the lack of emission inventories. We should maintain long-term monitoring programmes with consistent data quality in order to evaluate the effectiveness of chemical control efforts taken by countries worldwide.

Long-term Arctic air monitoring of per- and polyfluoroalkyl substances (PFASs) is essential in assessing their long-range transport and for evaluating the effectiveness of chemical control initiatives. We report for the first time temporal trends of neutral and ionic PFASs in air from three arctic stations: Alert (Canada, 2006–2014); Zeppelin (Svalbard, Norway, 2006–2014) and Andoya (Norway, 2010–2014). The most abundant PFASs were the perfluorooctanoic acid (PFOA), perfluorooctane sulfonic acid (PFOS), perfluorobutanoic acid (PFBA), and fluorotelomer alcohols (FTOHs). All of these chemicals exhibited increasing trends at Alert with doubling times (t2) of 3.7 years (y) for PFOA, 2.9 y for PFOS, 2.5 y for PFBA, 5.0 y for 8:2 FTOH and 7.0 y for 10:2 FTOH. In contrast, declining or non-changing trends, were observed for PFOA and PFOS at Zeppelin (PFOA, half-life, t1/2 = 7.2 y; PFOS t1/2 = 67 y), and Andoya (PFOA t1/2 = 1.9 y; PFOS t1/2 = 11 y). The differences in air concentrations and in time trends between the three sites may reflect the differences in regional regulations and source regions. We investigate the source region for particle associated compounds using the Lagrangian particle dispersion model FLEXPART. Model results showed that PFOA and PFOS are impacted by air masses originating from the ocean or land. For instance, PFOA at Alert and PFOS at Zeppelin were dominated by oceanic air masses whereas, PFOS at Alert and PFOA at Zeppelin were influenced by air masses transported from land.

The concentrations of organic flame retardants (FRs) and dioxin-like activities in dust collected from five countries were investigated. The correlations between the concentrations of the different groups of FRs and dioxin-like activities were examined. Chlorinated paraffins (CPs, C 9 to C 31 ) were found in the highest concentration (median ∑CP 700 μg/g, range 280–4750 μg/g), followed by organophosphate esters (median ∑ 13 OPEs 56 μg/g, range 21–110 μg/g), halogenated flame retardants (median ∑ 17 HFRs 3.3 μg/g, range 0.87–14 μg/g) and polybrominated diphenyl ethers (median ∑ 17 PBDEs 2.8 μg/g, range 0.46–11 μg/g). There were no significant differences in concentrations of the FRs among the countries but differences in PBDE and CP congener profiles were found. BDE209 predominated in dust from Australia, the UK, Sweden and China, ranging from 50 to 70% of total PBDEs. The lowest percentage of BDE209 was found in the dust from Canada, representing only 20% of total PBDEs. For CPs in dust from Sweden, the long-chain CPs (especially C 18 congeners) predominated, while for other countries, medium-chain CPs (especially C 14 congeners) predominated. The dioxin-activities of the dusts ranged from 58 to 590 pg CALUX-TEQ/g, and had a median of 200 pg CALUX-TEQ/g. There were significant positive correlations between concentrations of PBDEs and CPs with dioxin-like activities. The dioxin-like activity may be due to the presence of polychlorinated or polybrominated dioxin/furans (PBDD/DFs) or polychlorinated naphthalenes (PCNs) in the dust. The PBDD/DFs are known impurities and degradation product of the penta-BDE mixture, and PCNs are known impurities of CPs which exhibit dioxin-like activities.

We investigated the concentrations and temporal variability of organophospate esters (OPEs), halogenated flame retardants (HFRs) and polybrominated diphenyl ethers (PBDEs) in indoor and outdoor urban air in Stockholm, Sweden over one year (2014–2015) period. The median concentrations of the three target chemical groups (OPEs, HFRs, PBDEs) were 1–2 orders of magnitude higher in indoor air than outdoor urban air. OPEs were the most abundant target FRs with median concentrations in indoor (Σ10OPE = 340 000 pg/m3) and outdoor urban (Σ10OPEs = 3100 pg/m3) air, being 3 orders of magnitude greater than for HFRs in indoor (Σ15HFRs = 120 pg/m3) and outdoor urban (Σ15HFRs = 1.6 pg/m3) air. In indoor air, PBDE concentrations (Σ17PBDEs = 33 pg/m3) were lower than for the HFRs, but in outdoor urban air, concentrations (Σ17PBDEs = 1.1 pg/m3) were similar to HFRs. The most abundant OPEs in both the indoor and outdoor urban air were tris(2-butoxyethyl)phosphate (TBOEP), tris(chloroisopropyl)phosphate (TCIPP), tris(2-chloroethyl)phosphate (TCEP), tri-n-butyl-phosphate (TnBP), triphenyl phosphate (TPhP) and tris(1,3-dichloroisopropyl)phosphate (TDCIPP). TCIPP in indoor air was found in the highest concentrations and showed the greatest temporal variability, which ranged from 85 000 to 1 900 000 pg/m3 during the one-year sampling period. We speculate that activities in the building, e.g. floor cleaning, polishing, construction, introduction of new electronics and changes in ventilation rate could explain its variation. Some OPEs (TnBP, TCEP, TCIPP, TDCIPP and TPhP), HFRs/PBDEs (pentabromotoluene, 2, 3-dibromopropyl 2, 4, 6-tribromophenyl ether, hexabromobenzene, BDE-28, -47, and -99) in outdoor urban air showed seasonality, with increased concentrations during the warm period (p

The Arctic has been contaminated by legacy organochlorine pesticides (OCPs) and currently used pesticides (CUPs) through atmospheric transport and oceanic currents. Here we report the time trends and air−water exchange of OCPs and CUPs from research expeditions conducted between 1993 and 2013. Compounds determined in both air and water were trans- and cis-chlordanes (TC, CC), trans- and cis-nonachlors (TN, CN), heptachlor exo-epoxide (HEPX), dieldrin (DIEL), chlorobornanes (ΣCHBs and toxaphene), dacthal (DAC), endosulfans and metabolite endosulfan sulfate (ENDO-I, ENDO-II, and ENDO SUL), chlorothalonil (CHT), chlorpyrifos (CPF), and trifluralin (TFN). Pentachloronitrobenzene (PCNB and quintozene) and its soil metabolite pentachlorothianisole (PCTA) were also found in air. Concentrations of most OCPs declined in surface water, whereas some CUPs increased (ENDO-I, CHT, and TFN) or showed no significant change (CPF and DAC), and most compounds declined in air. Chlordane compound fractions TC/(TC + CC) and TC/(TC + CC + TN) decreased in water and air, while CC/(TC + CC + TN) increased. TN/(TC + CC + TN) also increased in air and slightly, but not significantly, in water. These changes suggest selective removal of more labile TC and/or a shift in chlordane sources. Water−air fugacity ratios indicated net volatilization (FR > 1.0) or near equilibrium (FR not significantly different from 1.0) for most OCPs but net deposition (FR < 1.0) for ΣCHBs. Net deposition was shown for ENDO-I on all expeditions, while the net exchange direction of other CUPs varied. Understanding the processes and current state of air−surface exchange helps to interpret environmental exposure and evaluate the effectiveness of international protocols and provides insights for the environmental fate of new and emerging chemicals. Funding agencies: Environment Canada; Arctic Net; Northern Contaminants Program (Aboriginal Affairs and Northern Development Canada); Centre for Global Science, University of Toronto; Northern Science Training Program, Aboriginal Affairs and Northern Development Canada

Quantifying the competing rates of intake and elimination of persistent organic pollutants (POPs) in the human body is necessary to understand the levels and trends of POPs at a population level. In this paper we reconstruct the historical intake and elimination of ten polychlorinated biphenyls (PCBs) and five organochlorine pesticides (OCPs) from Australian biomonitoring data by fitting a population-level pharmacokinetic (PK) model. Our analysis exploits two sets of cross-sectional biomonitoring data for PCBs and OCPs in pooled blood serum samples from the Australian population that were collected in 2003 and 2009. The modeled adult reference intakes in 1975 for PCB congeners ranged from 0.89 to 24.5 ng/kg bw/day, lower than the daily intakes of OCPs ranging from 73 to 970 ng/kg bw/day. Modeled intake rates are declining with half-times from 1.1 to 1.3 years for PCB congeners and 0.83 to 0.97 years for OCPs. The shortest modeled intrinsic human elimination half-life among the compounds studied here is 6.4 years for hexachlorobenzene, and the longest is 30 years for PCB-74. Our results indicate that it is feasible to reconstruct intakes and to estimate intrinsic human elimination half-lives using the population-level PK model and biomonitoring data only. Our modeled intrinsic human elimination half-lives are in good agreement with values from a similar study carried out for the population of the United Kingdom, and are generally longer than reported values from other industrialized countries in the Northern Hemisphere. Keywords: PCBs, OCPs, Pharmacokinetics, Modeling, Elimination, Intake

The mechanistic details of many polyketide synthases (PKSs) remain elusive due to the instability of transient intermediates that are not accessible via conventional methods. Here we report an atom replacement strategy that enables the rapid preparation of polyketone surrogates by selective atom replacement, thereby providing key substrate mimetics for detailed mechanistic evaluations. Polyketone mimetics are positioned on the actinorhodin acyl carrier protein (actACP) to probe the underpinnings of substrate association upon nascent chain elongation and processivity. Protein NMR is used to visualize substrate interaction with the actACP, where a tetraketide substrate is shown not to bind within the protein, while heptaketide and octaketide substrates show strong association between helix II and IV. To examine the later cyclization stages, we extended this strategy to prepare stabilized cyclic intermediates and evaluate their binding by the actACP. Elongated monocyclic mimics show much longer residence time within actACP than shortened analogs. Taken together, these observations suggest ACP-substrate association occurs both before and after ketoreductase action upon the fully elongated polyketone, indicating a key role played by the ACP within PKS timing and processivity. These atom replacement mimetics offer new tools to study protein and substrate interactions and are applicable to a wide variety of PKSs.

Human biomonitoring studies have shown that concentrations of perfluorooctane sulfonic acid (PFOS) in men are higher than in women. We investigate sex differences in elimination of PFOS by fitting a population-based pharmacokinetic model to six cross-sectional data sets from 1999 to 2012 from the US National Health and Nutrition Examination Survey (NHANES) and derive human first-order elimination rate constants (kE) and corresponding elimination half-lives (t1/2) for PFOS, where t1/2 = ln 2/kE. We use a modified version of the Ritter population-based pharmacokinetic model and derive elimination rate constants separately for men and women. The model accounts for population-average lifetime changes in PFOS intake, body weight, and menstruation rate. We compare the model-derived elimination rate constant for hypothetical nonmenstruating women to the elimination rate constant for men and women when menstruation is included as a loss process to evaluate the hypothesis that loss of PFOS by menstruation is an important process for women. The modeled elimination half-life for men is 4.7 years, and the modeled elimination half-life for women when excluding losses from menstruation is 3.7 years. The elimination half-life for women when menstruation is included in the model is 4.0 years. Thus, menstruation accounts for 30% of the discrepancy in elimination of PFOS between men and women. The remaining discrepancy is likely due to other sex-specific elimination routes that are not considered in our modeling.

We examine the balance between intake, intrinsic elimination half-lives and human body burdens measured in biomonitoring for polybrominated diphenyl ethers (PBDEs) in the North American population using the population-level pharmacokinetic model developed by Ritter et al. (2011). Empirical data are collected from two studies that made total intake estimates for the North American population for the years 2004 and 2005, and eight biomonitoring studies for the years 1992 to 2009. We assume intake of PBDEs increased exponentially to a peak in 2004, and has since exponentially declined. The model is fitted to the empirical PBDE intake and biomonitoring data on PBDE body burden using a least-square optimization method by adjusting the intake in 2004 and 2038, and the intrinsic elimination rate constants, which can be expressed as equivalent half-lives. We fit the model in two types of scenarios using different combinations of PBDE intake estimates and biomonitoring data. Our modeling results indicate that there is an inconsistency between the PBDE intake estimates and the biomonitoring data, and that the inconsistency is likely due to underestimation of population-level intake. More efforts are needed to better characterize intake rates and identify potentially-unrecognized exposure pathways. Additional age-stratified biomonitoring data, and time trends of PBDE intakes would better constrain the model and provide an improved estimation of the intrinsic elimination half-lives. Keywords: PBDE, Exposure, Intake, Biomonitoring, Intrinsic elimination half-lives, Pharmacokinetic modeling

Fourteen organophosphate esters (OPEs) were measured in the filter fraction of 117 active air samples from yearly ship-based sampling campaigns (2007-2013) and two land-based stations in the Canadian Arctic, to assess trends and long-range transport potential of OPEs. Four OPEs were detected in up to 97% of the samples, seven in 50% or less of the samples, and three were not detected. Median concentrations of ∑OPEs were 237 and 50 pg m(-3) for ship- and land-based samples, respectively. Individual median concentrations ranged from below detection to 119 pg m(-3) for ethanol, 2-chloro-, phosphate (3:1) (TCEP). High concentrations of up to 2340 pg m(-3) were observed for Tri-n-butyl phosphate (TnBP) at a land-based sampling location in Resolute Bay from 2012, whereas it was only detected in one ship-based sample at a concentration below 100 pg m(-3). Concentrations of halogenated OPEs seemed to be driven by river discharge from the Nelson and Churchill Rivers (Manitoba) and Churchill River and Lake Melville (Newfoundland and Labrador). In contrast, nonhalogenated OPE concentrations appeared to have diffuse sources or local sources close to the land-based sampling stations. Triphenyl phosphate (TPhP) showed an apparent temporal trend with a doubling-time of 11 months (p = 0.044). The results emphasize the increasing relevance of halogenated and nonhalogenated OPEs as contaminants in the Arctic.

The air-sea gas exchange of alpha-hexachlorocyclohexane (α-HCH) in the Canadian Arctic was estimated using a micrometeorological approach and the commonly used Whitman two-film model. Concurrent shipboard measurements of α-HCH in air at two heights (1 and 15 m) and in surface seawater were conducted during the Circumpolar Flaw Lead study in 2008. Sampling was carried out during eight events in the early summer time when open water was encountered. The micrometeorological technique employed the vertical gradient in air concentration and the wind speed to estimate the flux; results were corrected for atmospheric stability using the Monin-Obukhov stability parameter. The Whitman two-film model used the concentrations of α-HCH in surface seawater, in bulk air at 1 and 15 m above the surface, and the Henry's law constant adjusted for temperature and salinity to derive the flux. Both approaches showed that the overall net flux of α-HCH was from water to air. Mean fluxes calculated using the micrometeorological technique ranged from -3.5 to 18 ng m(-2) day(-1) (mean 7.4), compared to 3.5 to 14 ng m(-2) day(-1) (mean 7.5) using the Whitman two-film model. Flux estimates for individual events agreed in direction and within a factor of two in magnitude for six of eight events. For two events, fluxes estimated by micrometeorology were zero or negative, while fluxes estimated with the two-film model were positive, and the reasons for these discrepancies are unclear. Improvements are needed to shorten air sampling times to ensure that stationarity of meteorological conditions is not compromised over the measurement periods. The micrometeorological technique could be particularly useful to estimate fluxes of organic chemicals over water in situations where no water samples are available.

An organic rich muck soil which is highly contaminated with native organochlorine pesticide (OCs) was spiked with known amounts of (13)C-labeled OCs and nonlabeled polychlorinated biphenyls (PCBs). Spiked soils were aged under indoor, outdoor, and sterile conditions and the change in volatility, surrogate bioaccessibility, and degradation of chemicals was monitored periodically over 730 d. Volatility was measured using a fugacity meter to characterize the soil-air partition coefficient (K(SA) = C(SOIL)/C(AIR)). The fraction of bioaccessible residues was estimated by comparing recoveries of chemical with a mild extractant, hydroxylpropyl-β-cyclodextrin (HPCD) vs a harsh extractant, DCM. K(SA) of the spiked OCs in the nonsterile (Indoor, Outdoor) soils were initially lower and approached the K(SA) of native OCs over time, showing reduction of volatility upon aging. HPCD extractability of spiked OCs and PCBs were negatively correlated with K(SA), which suggests that volatility can be used as a surrogate for bioaccessibility. Degradation of endosulfans, PCB 8 and 28 was observed in the nonsterile soils, and (13)C(6)-α-HCH showed selective degradation of the (+) enantiomer. Enantiomer fractions (EF) in air and HPCD extracts were lower than in nonsterile soils, suggesting greater sequestering of the (+) enantiomer in the soil during microbial degradation.

Shipboard measurements of organohalogen compounds in air and surface seawater were conducted in the Canadian Arctic in 2007-2008. Study areas included the Labrador Sea, Hudson Bay, and the southern Beaufort Sea. High volume air samples were collected at deck level (6 m), while low volume samples were taken at 1 and 15 m above the water or ice surface. Water samples were taken within 7 m. Water concentration ranges (pg L(-1)) were as follows: α-hexachlorocyclohexane (α-HCH) 465-1013, γ-HCH 150-254, hexachlorobenzene (HCB) 4.0-6.4, 2,4-dibromoanisole (DBA) 8.5-38, and 2,4,6-tribromoanisole (TBA) 4.7-163. Air concentration ranges (pg m(-3)) were as follows: α-HCH 7.5-48, γ-HCH 2.1-7.7, HCB 48-71, DBA 4.8-25, and TBA 6.4 - 39. Fugacity gradients predicted net deposition of HCB in all areas, while exchange directions varied for the other chemicals by season and locations. Net evasion of α-HCH from Hudson Bay and the Beaufort Sea during open water conditions was shown by air concentrations that averaged 14% higher at 1 m than 15 m. No significant difference between the two heights was found over ice cover. The α-HCH in air over the Beaufort Sea was racemic in winter (mean enantiomer fraction, EF = 0.504 ± 0.008) and nonracemic in late spring-early summer (mean EF = 0.476 ± 0.010). This decrease in EF was accompanied by a rise in air concentrations due to volatilization of nonracemic α-HCH from surface water (EF = 0.457 ± 0.019). Fluxes of chemicals during the southern Beaufort Sea open water season (i.e., Leg 9) were estimated using the Whitman two-film model, where volatilization fluxes are positive and deposition fluxes are negative. The means ± SD (and ranges) of net fluxes (ng m(-2) d(-1)) were as follows: α-HCH 6.8 ± 3.2 (2.7-13), γ-HCH 0.76 ± 0.40 (0.26-1.4), HCB -9.6 ± 2.7 (-6.1 to -15), DBA 1.2 ± 0.69 (0.04-2.0), and TBA 0.46 ± 1.1 ng m(-2) d(-1) (-1.6 to 2.0).

Hydroxypropyl-beta-cyclodextrin (HPCD) was used as a non-exhaustive extractant for organochlorine pesticides (OCs) and polychlorinated biphenyls (PCBs) in muck soil. An optimized extraction method was developed which involved using a HPCD to soil mass ratio of 5.8 with a single extraction period of 20 h. An aging experiment was performed by spiking a muck soil with (13)C-labeled OCs and non-labeled PCBs. The soil was extracted with the optimized HPCD method and Soxhlet apparatus with dichloromethane over 550 d periodically. The HPCD extractability of the spiked OCs was greater than of the native OCs. A decreased in HPCD extractability was observed for the spiked OCs after 550 d of aging and their extractability approached those of the natives. The partition coefficient between HPCD and soil (logK(CD-Soil)) was negatively correlated with the octanol-water partition coefficient (logK(OW)) with r(2)=0.67 and p

The spatial distribution of organochlorine pesticides (OCs) in soils and their potential for soil–air exchange was examined. The most prominent OCs were the DDTs (Geometric Mean, GM = 1.6 ng g−1), endosulfans (0.16 ng g−1), and toxaphenes (0.64 ng g−1). DDTs in soils of southern Mexico showed fresher signatures with higher FDDTe = p,p′-DDT/(p,p′-DDT + p,p′-DDE) and more racemic o,p′-DDT, while the signatures in the central and northern part of Mexico were more indicative of aged residues. Soil–air fugacity fractions showed that some soils are net recipients of DDTs from the atmosphere, while other soils are net sources. Toxaphene profiles in soils and air showed depletion of Parlar 39 and 42 which suggests that soil is the source to the atmosphere. Endosulfan was undergoing net deposition at most sites as it is a currently used pesticide. Other OCs showed wide variability in fugacity, suggesting a mix of net deposition and volatilization.

It is estimated that nearly 1 million people contract a sexually transmitted infection (STI) every day worldwide (1). In Western Europe, 17 million new cases of curable STIs occur annually (2). In the European Union (EU), the most common STIs are chlamydial genital infections, gonorrhea, hepatitis, and syphilis (3). Addressing more than 30 other bacterial, viral, and parasitic pathogens causing STIs has re-emerged as a major public health issue in Europe, starting in 1999 and building on the 2003 global health sector strategy that focused on HIV/AIDS (4-6). At the 59th World Health Assembly, in May 2006, the World Health Organization approved the Global Strategy for the Prevention and Control of Sexually Transmitted Infections: 2006-2015. This strategy makes strong arguments for why preventing STIs is important not only for maintaining general health, but also for ensuring safe pregnancies and preventing HIV transmission. STIs are transmitted through sexual contact, including vaginal, oral, and anal sex. Some STIs can also be transmitted through childbirth or breastfeeding, as well as through sharing needles during injecting drug use. Transmission patterns have changed over time and often differ greatly among and within EU member states. In some settings, HIV coinfection with other STIs is common, while in others, they appear independently. In Europe, the populations most at risk for HIV and for other STIs are often – but not always – the same: men who have sex with men (MSM), injecting drug users and their sexual partners, and heterosexual migrants from outside of the EU. Some STIs, like Chlamydia, are more prevalent among young people (7), and interventions frequently target this group to prevent the spread of STIs, both in and out of school. Various theories, including the health belief model, the theory of reasoned action, the trans-theoretical model and social cognitive theory, have been employed to promote behavior change (8). They are utilized in various ways in concrete interventions to reach young people and reduce their risk of contracting STIs. Unfortunately, the lack of age-disaggregated data on sexual and reproductive health and varying definitions of “young” make it difficult to assess the situation and provide a common evidence base for designing these interventions (9). Inspired by an EU call to action (10), we undertook this systematic review to examine the effectiveness of STI interventions for young people in the EU in the decade after the International Conference on Population and Development, held in Cairo in 1994, which put a focus on them. In doing so, it gathers a variety of approaches, such as the major implementation models – being peer-, teacher- and health professional-led – for reaching young people with sexual and reproductive health information and services, to inform and advance future policy development.

Surface soils and sediments were collected in Toronto, Canada to investigate the concentrations and enantiomeric signatures of urban versus rural locations. Samples were analyzed for polychlorinated biphenyls (PCBs), polyaromatic hydrocarbons (PAHs) and organochlorine pesticides (OCs). In soils, the sum of 10 PCB congeners (Sigma PCB 28, 52, 95, 101, 118, 136, 138, 149, 153, 180) and 15 PAHs (Sigma PAHs) ranged from 0.76-58 to 58-3200 ng g(-1), respectively. The most abundant OCs detected were DDTs, followed by chlordanes and endosulfans. Sigma PAHs exhibited an urban-rural gradient of up to 60 times but a gradient was not observed for Sigma PCBs and OCs which may reflect local sources of these chemicals. In sediments, Sigma PCBs and Sigma PAHs ranged from 0.03-23 ng g(-1) to 42-3300 ng g(-1), respectively. Sigma PCBs, Sigma PAHs, chlordanes and DDTs exhibited weak urban-rural gradients. Chiral signatures of PCB 95, 136, 149, trans-chlordane (TC), cis-chlordane (CC) and o,p-DDT were characterized to study the enantiomeric degradation in urban versus rural areas and its relation to contaminant levels. Supplementary to these data, we also report on the chiral signatures of PCBs in UK lake sediments from a variety of urban and rural locations. The extent of enantiomeric degradation was expressed as the enantiomeric excess (EE%) which is defined as 100x(E1-E2)/(E1+E2), where E1 is always the most abundant enantiomer and E2 is the least abundant enantiomer. The EE% of PCB 149 in the UK sediments was negatively correlated (p0.05) with Sigma PAHs suggesting either more recent emissions of this PCB congener in the more contaminated urban locations and hence a more racemic signature or less enantiomeric degradation of the congener in more contaminated urban soils. However, no significant correlation was observed between EE% of any of the chiral chemicals and contaminant levels in the Toronto soils.

Air samples were collected in southern Mexico in 2002–2004 to determine the extent of contamination with organochlorine (OC) pesticides and polychlorinated biphenyls (PCBs). The ΣDDTs ranged from 239 to 2360 pg m−3. Other prominent OC pesticides were endosulfans, toxaphene and lindane. Pesticides detected in lower concentrations include chlordanes, dieldrin, and heptachlor. Proportions of DDT compounds suggested fresh use of DDT in some locations and a mix of fresh and aged residues at others. Ratios of trans-chlordane/cis-chlordane were consistent with fresh chlordane usage or emission of residues from former termiticide applications. The ΣPCBs was relatively low at all sites. Concentrations of OC pesticides measured with passive samplers agreed well with those measured using high-volume samplers. Air back trajectory analysis suggests a complex pattern of regional atmospheric transport.

Chlordane was used as an insecticide for half a century until its withdrawal from the world market in 1997. Trans- and cis-chlordane (TC, CC) are racemic in the technical product, but undergo enantio selective degradation in soil to leave nonracemic residues. In most cases, the (+) enantiomer of TC and the (-) enantiomer of CC are depleted, leading to enantiomer fractions, EF = (+)/[(+) + (-)], that are 0.500 for CC. Nonracemic EFs of TC and CC, showing the same degradation preference as soils, were found in 1998-2001 air samples from stations in Arctic Canada and Finland, and on the west coast of Sweden. Environmental samples representing different time periods of chlordane history were also examined in: (a) archived atmospheric deposition samples collected in Sweden, Slovakia and Iceland in 1971-1973, (b) soils from southern Sweden sampled in 2001 and (c) a laminated lake sediment core from the Canadian Arctic representing similar to50 years of accumulation. TC and CC were racemic or nearly so in the historical atmospheric deposition samples and nonracemic in the Swedish soils. The EF of TC in the dated take sediment core decreased from nearly racemic in the past to nonracemic in recent times. These observations suggest that sources of chlordane to the atmosphere have changed over time and are now influenced to a greater extent by emission from soils. (Less)

For decades sea ice has been perceived as a physical barrier for the loading of contaminants to the Arctic Ocean. We show that sea ice, in fact, facilitates the delivery of organic contaminants to the Arctic marine food web through processes that: 1) are independent of contaminant physical–chemical properties (e.g. 2–3-fold increase in exposure to brine-associated biota), and 2) depend on physical–chemical properties and, therefore, differentiate between contaminants (e.g. atmospheric loading of contaminants to melt ponds over the summer, andtheir subsequent leakage to the ocean). We estimate the concentrations of legacy organochlorine pesticides (OCPs) and current-use pesticides (CUPs) in melt pond water in the Beaufort Sea, Canadian High Arctic, in 2008, at near-gas exchange equilibriumbased on Henry's lawconstants (HLCs), air concentrations and exchange dynamics. CUPs currently present the highest risk of increased exposures through melt pond loading and drainage due to the high ratio of melt pond water to seawater concentration (Melt pond Enrichment Factor, MEF),which ranges from 2 for dacthal to 10 for endosulfan I. Melt pond contaminant enrichment can be perceived as a hypothetical ‘pump’ delivering contaminants from the atmosphere to the ocean under ice-covered conditions, with 2–10% of CUPs annually entering the Beaufort Sea via this input route compared to the standing stock in the Polar Mixed Layer of the ocean. The abovementioned processes are strongly favored in first-year ice compared to multi-year ice and, therefore, the dynamic balance between contaminant inventories and contaminant deposition to the surface ocean is being widely affected by the large-scale icescape transition taking place in the Arctic.

A new decay station has been built for the ISAC facility at TRIUMF for the rapid and reliable characterization of radioactive ion beam (RIB) compositions and intensities with the capability of simultaneously collecting α, β, and γ decay data from RIB with intensities between a few and ≈10(11) ions per second. It features user-friendly control, data acquisition, and analysis software. The analysis of individual decay time structures allows the unambiguous assignment of α and γ lines even with substantial isobaric contamination present. The capability for accurate half-life measurements is demonstrated with the example of (46)K. The coupling of the yield station to the laser ion source, TRILIS, allows the correlation of radiometric data with automated laser frequency scans. First results of in-source laser spectroscopy measurements on astatine are discussed.

To date, research delving into the narratives of persons living with dementia is limited. Taking part in usual mealtime activities such as preparing food can sustain the identity of persons living with dementia. Yet if capacity for mealtime activities changes, this can put a strain or demand on the family, which must adjust and adapt to these changes. The aim of this study was to develop an in-depth story of resilience in one family living with dementia that was experiencing mealtime changes. Thematic narrative analysis following the elements of Clandinin and Connelly's (2000) 3D narrative inquiry space was used. One family's dementia journey was highlighted using the metaphor of a baking recipe to reflect their story of resilience. Developing positive strategies and continuing to learn and adapt were the two approaches used by this resilient family. Reminiscing, incorporating humour, having hope and optimism, and establishing social support were specific strategies. This family continued to learn and adapt by focusing on their positive gains and personal growth, accumulating life experiences, and balancing past pleasures while adapting to the new normal. Future work needs to further conceptualise resilience and how it can be supported in families living with dementia.

Response to Comment on Enhanced Elimination of Perfluorooctane Sulfonic Acid by Menstruating Women : Evidence from Population-based Pharmacokinetic Modeling

Background:Facility-based and context-specific interventions to promote physical activity (PA) among pregnant women from economically underprivileged communities remain sparse and undocumented in South Africa. This study aimed to generate information about pregnant women’s views and experiences of PA during pregnancy, which will later be used to inform the development of a PA-based intervention targeting this group.Methods:Qualitative methods were used and framed on the Theory of Planned Behavior (TPB). Five focus group discussions were conducted at a Community Health Centre in Cape Town, each comprising a stratified random sample of between 8 and 6 pregnant women living in eight low socioeconomic status communities close to the facility. The participants included primi- and multigravida black and mixed racial ancestry women at different stages of pregnancy. Data were analyzed using a Framework approach.Results:PA was considered important for self and the baby for most participants. However, they reported a number of barriers for translating intentions into action including the lack of supportive environment, fear of hurting oneself and the growing baby, lack of time due to work and family responsibilities, and not knowing which and how much PA is safe to do. Some of the incentives to engage in PA included establishing community-based group exercise clubs, initiating antenatal PA education and PA sessions during antenatal visits.Conclusion:Based on our findings the need for an intervention to promote PA in pregnancy is evident. Such an intervention should, however, aim at addressing barriers reported in this study, particularly those related to the behavioral context.

Elimination of persistent organic pollutants (POPs) under national and international regulations reduces “primary” emissions, but “secondary” emissions continue from residues deposited in soil, water, ice and vegetation during former years of usage. In a future, secondary source controlled world, POPs will follow the carbon cycle and biogeochemical processes will determine their transport, accumulation and fate. Climate change is likely to affect mobilisation of POPs through e.g., increased temperature, altered precipitation and wind patterns, flooding, loss of ice cover in polar regions, melting glaciers, and changes in soil and water microbiology which affect degradation and transformation. Chiral compounds offer advantages for following transport and fate pathways because of their ability to distinguish racemic (newly released or protected from microbial attack) and nonracemic (microbially degraded) sources. This paper discusses the rationale for this approach and suggests applications where chiral POPs could aid investigation of climate-mediated exchange and degradation processes. Multiyear measurements of two chiral POPs, trans-chlordane and α-HCH, at a Canadian Arctic air monitoring station show enantiomer compositions which cycle seasonally, suggesting varying source contributions which may be under climatic control. Large-scale shifts in the enantioselective metabolism of chiral POPs in soil and water might influence the enantiomer composition of atmospheric residues, and it would be advantageous to include enantiospecific analysis in POPs monitoring programs.

Assessing the behaviour of organic chemicals in soil is a complex task as it is governed by the physical chemical properties of the chemicals, the characteristics of the soil as well as the ambient conditions of the environment. The chemical partitioning space, defined by the air-water partition coefficient (K(AW)) and the soil organic carbon-water partition coefficient (K(OC)), was employed to visualize the equilibrium distribution of organic contaminants between the air-filled pores, the pore water and the solid phases of the bulk soil and the relative importance of the three transport processes removing contaminants from soil (evaporation, leaching and particle erosion). The partitioning properties of twenty neutral organic chemicals (i.e. herbicides, pharmaceuticals, polychlorinated biphenyls and volatile chemicals) were estimated using poly-parameter linear free energy relationships and superimposed onto these maps. This allows instantaneous estimation of the equilibrium phase distribution and mobility of neutral organic chemicals in soil. Although there is a link between the major phase and the dominant transport process, such that chemicals found in air-filled pore space are subject to evaporation, those in water-filled pore space undergo leaching and those in the sorbed phase are associated with particle erosion, the partitioning coefficient thresholds for distribution and mobility can often deviate by many orders of magnitude. In particular, even a small fraction of chemical in pore water or pore air allows for evaporation and leaching to dominate over solid phase transport. Multiple maps that represent soils that differ in the amount and type of soil organic matter, water saturation, temperature, depth of surface soil horizon, and mineral matters were evaluated.

Background: Novel efforts and accompanying tools are needed to tackle the global burden of chronic disease. This paper presents an approach to describe the environments in which people live, work, and play. Community Health Environment Scan Survey (CHESS) is an empirical assessment tool that measures the availability and accessibility, of healthy lifestyle options. CHESS reveals existing community assets as well as opportunities for change, shaping community intervention planning efforts by focusing on communityrelevant opportunities to address the three key risk factors for chronic disease (i.e. unhealthy diet, physical inactivity, and tobacco use). Methods: The CHESS tool was developed following a review of existing auditing tools and in consultation with experts. It is based on the social-ecological model and is adaptable to diverse settings in developed and developing countries throughout the world. Results: For illustrative purposes, baseline results from the Community Interventions for Health (CIH) Mexico site are used, where the CHESS tool assessed 583 food stores and 168 restaurants. Comparisons between individual-level survey data from schools and community-level CHESS data are made to demonstrate the utility of the tool in strategically guiding intervention activities. Conclusion: The environments where people live, work, and play are key factors in determining their diet, levels of physical activity, and tobacco use. CHESS is the first tool of its kind that systematically and simultaneously examines how built environments encourage/discourage healthy eating, physical activity, and tobacco use. CHESS can help to design community interventions to prevent chronic disease and guide healthy urban planning. Keywords: physical activity; nutrition; tobacco use; chronic disease; environmental assessment; built environment (Published: 7 March 2011) Citation: Global Health Action 2011, 4 : 5276 - DOI: 10.3402/gha.v4i0.5276

[1] A flow-through sampler was deployed to record the seasonal variability of the atmospheric concentrations of semivolatile organic compounds (SOCs) at a remote research station located close to Nam Co Lake on the Tibetan plateau. Between October 2006 and February 2008, fifteen consecutive one month-long samples, with air volumes ranging from 4,500 to 16,000 m3, were taken and analyzed for polychlorinated biphenyls (PCBs), polycyclic aromatic hydrocarbons (PAHs) and organochlorine pesticides (OCPs). Separate analysis of three polyurethane plugs in series in combination with frontal chromatographic theory allows for the correction of the break-through observed for the most volatile SOCs. The concentrations of Σ56PCB in air range from 0.10 to 2.6 pg·m−3 and are among the lowest values ever reported. Levels of OCPs at Nam Co are generally also very low, particularly during wintertime. The concentrations of hexachlorocyclohexanes (HCHs), endosulfans, and various dichlorodiphenyltrichloroethane (DDT) related substances display a distinct seasonal variability consistent with the monsoon. Back-trajectory analysis reveals that higher OCP levels during summer correlate with air mass origin south of the Himalayas. A high α/γ-HCH ratio and a non-racemic composition of α-HCH during July/August suggest that evaporation from Nam Co Lake contributes to the relatively high concentrations of α-HCH (averaging ca. 91 pg·m−3) recorded in the summertime atmosphere.

The spatial and temporal variation of organochlorine pesticides (OCs) in air across Mexico was investigated by deploying passive samplers at eleven stations across the country during 2005-2006. Integrated samples were taken over three-month periods and quantified for DDT compounds, endosulfans, toxaphenes, components of technical chlordane, hexachlorocyclohexanes (HCHs), and dieldrin. Enantiomers of chiral chlordanes and o,p'-DDT were determined on chiral stationary phase columns as an indicator of source and age. Results are discussed in combination with pumped air samples taken at four other stations in southern Mexico during 2002-2004. DDT and its metabolites, endosulfan and toxaphene were the most abundant OCs detected in all sampling sites. Atmospheric concentrations of SigmaDDT (p,p'-DDT + o,p'-DDT + p,p'-DDE + o,p'-DDE + p,p'-DDD + o,p'-DDD) ranged from 15 to 2360 pg m(-3) with the highest concentrations found in southern Mexico and the lowest found in northern and central Mexico. A fresher DDT residue was observed at sites with greater DDT use and in the southern part of the country, as shown from the higher FDDTe = p,p'-DDT/(p,p'-DDT + p,p'-DDE) and nearly racemic o,p'-DDT. This agrees with the former heavy use of DDT in the endemic malarious area of the country. A local hotspot of endosulfan was identified at an agricultural area in Mazatlan, Sinaloa, with a annual mean concentration of SigmaENDO (endosulfans I + II + endosulfan sulfate) = 26,800 pg m(-3). At this site, higher concentrations of SigmaENDO were recorded during the winter (November to February) and spring (February to May) periods. From back trajectory analysis, this coincides with a shift in the air mass coming from the Pacific Ocean (May to November) to the inland agricultural area (November to May). The elevated SigmaENDO observed is likely due to the local agricultural usage. HCHs, chlordanes, transnonachlors, and dieldrin were more evenly distributed across the country likely due to them being aged residues and more diffuse in the environment. In contrast, hotspots of endosulfans, DDTs, and toxaphenes were observed as they were heavily used in localized agricultural or malarious regions of Mexico.

Spatial and temporal variation in the atmospheric deposition of PAHs to soil was examined by deploying experimental soils for approximately 165 days and conducting a survey of forest soils at several sites along an urban-rural transect extending from downtown Toronto to approximately 80 km north of the city. PAH concentrations decreased with distance from the urban centre-by a factor of 2 and 60 for the experimental and forest soils respectively. The large gradient for the forest soils is generally consistent with air concentrations of PAHs measured using high volume and passive air samplers. The smaller gradient for the experimental soils was due to kinetic limitations of PAH accumulation and the relatively short deployment period of approximately 165 days. Mean effective deposition velocities (gas+particle) for the full range of PAHs for the experimental soils at the urban, suburban, and the rural sites were 2, 31 and 26 cm s(-1), respectively. These were incorporated into a dynamic model that was used to assess the long-term uptake of PAHs in forest soils. Model results indicate that lower molecular weight PAHs may achieve equilibrium and become involved in soil-air exchange whereas higher molecular weight PAHs are accumulated for much longer time periods.