Occurrence and seasonal variations of organophosphate flame retardants in air and dust from college microenvironments at Qingdao, China: Implications for student's exposure and risk assessment.

Organophosphate flame retardants (OPFRs) are widely used as alternatives to brominated flame retardants in a variety of consumer products and their consumption has continuously increased in recent years. However, their concentrations and human exposures in indoor microenvironments, particularly in a university environment, have received limited attention. In this study, the concentrations and seasonal variations of 15 OPFRs were assessed in typical microenvironments of two universities, including dormitories, offices, public microenvironments (PMEs: classroom, dining hall, gymnasium and library), and laboratories on the northern coast of China. Analysis of the OPFRs in both air and dust samples indicated widespread distribution in college campuses. The average concentration of ∑15OPFRs in the winter (12,774.4 ng/g and 5.3 ng/m3 for dust and air, respectively) was higher than in the summer (2460.4 ng/g and 4.6 ng/m3 for dust and air, respectively). The dust and air samples collected from PMEs and laboratories exhibited higher concentrations of OPFRs, followed by offices and dormitories. An equilibrium was reached between dust and air in all collected microenvironments. The daily intakes of OPFRs were significantly lower than the reference dose. Dust ingestion was the primary intake pathway in the winter, while inhalation and dust ingestion were the main intake pathways in the summer. The non-carcinogenic hazard quotients fell within the range of 10-7-10-3 in both the summer and winter, which are below the theoretical risk threshold. For the carcinogenic risk, the LCR values ranged from 10-10 to 10-8, indicating no elevated carcinogenic risk due to TnBP, TCEP, and TDCP in indoor dust and air.

Concentrations of PCDD/Fs and dl-PCBs in ambient air in Hanoi, Vietnam, between 2017 and 2021, and health risk assessments.

The concentrations and seasonal and temporal variations in polychlorodibenzo-p-dioxins/polychlorodibenzofurans (PCDD/Fs) and dioxin-like polychlorobiphenyls (dl-PCBs) in ambient air from November 2017 to September 2021 were investigated via passive air samplers containing polyurethane foam (PUF) discs in three residential areas: the Cau Giay (CG) urban, Quang Minh (QM) industrial-suburban, and Ba Vi (BV) rural areas, Hanoi, Vietnam. The average total toxic equivalents (TEQs) of PCDD/Fs and dl-PCBs (∑TEQs), using WHO2005-TEFs, were highest in the QM area (506 fg WHO-TEQ/PUF day) and ranged from 317 to 752 fg WHO-TEQ/PUF day. Compared to that in the QM area, the average ∑TEQs were lower in the CG area, ranging between 372 and 615 fg WHO-TEQ/PUF day with an average value of 482 fg WHO-TEQ/PUF day. The average ∑TEQs were lowest in the BV area, ranging from 121 to 414 fg WHO-TEQ/PUF day with an average of 231 fg WHO-TEQ/PUF day. PCDD/F and dl-PCB air pollution increased during spring and winter. The highest seasonal average ∑TEQs in the CG area was 534 fg WHO-TEQ/PUF day in winter. The highest average ∑TEQs in the QM and BV areas were 653 and 280 fg WHO-TEQ/PUF day in spring, respectively. The average daily dose (ADD) values of PCDD/Fs and dl-PCBs through inhalation for adults in the three areas were minimal (9.9-96.2 fg WHO-TEQ/kg body weight (BW)/day) and below the 10% threshold of the tolerable daily intake (TDI) value recommended by the WHO (100-400 fg WHO-TEQ/kg BW/day). For children, the ADD values (15.1-244 fg WHO-TEQ/kg BW/day) were less than and within 10% of the recommended TDI value.

Preliminary results from the Tunisian monitoring program on POPs in air under the Stockholm Convention.

Persistent organic pollutants (POPs) have been measured using passive air samplers (PASs) over two years (2017-2018) in the city of Tunis within the framework of the UNEP/GEF GMP2 projects to support Stockholm Convention implementation. Several POPs, although banned for a long time from Tunisia, were registered in relatively high amounts in the atmospheric compartment. The most unexpected compound is hexachlorobenzene (HCB), with concentrations ranging from 5.2 ng/PUF to 16 ng/PUF. Furthermore, the current results seem to confirm the presence of dichlorodiphenyltrichloroethane (DDT) and its transformation products and hexachlorocyclohexanes (HCHs) at relatively high concentrations (4.6 ng/PUF to 9.4 ng/PUF and 2.7 ng/PUF to 5.1 ng/PUF, respectively), followed by hexabromocyclododecane (HCBD), which varies from 1.5 ng/PUF to 7.7 ng/PUF. Nondioxin-like PCB (ndl-PCB) concentrations in Tunis were very high (62.0 ng/PUF to 419.3 ng/PUF), higher than those in other African countries participating in this project. Uncontrolled combustion seems to be one of the most important sources of the emanation of dioxin compounds dl-PCBs and Polychlorinated dibenzodioxins PCDD/polychlorinated dibenzofurans PCDF. Toxic equivalents (TEQs) ranged from 4.1 pg WHO-TEQ/PUF to 6.4 pg WHO-TEQ/PUF. The perfluorinated compounds (PFAS) and congeners of polybrominated diphenyl ethers (PBDEs) show relatively low amounts that remain below the African continent average. The PFAS pattern suggests a local source rather than long-range transport. These results constitute the first exhaustive work capable of providing an overview of the levels of POPs in the air in Tunis. As a result, it will be possible to set up an adequate monitoring program with specific investigations and experimental studies.

Persistent organic pollutants in air from Asia, Africa, Latin America, and the Pacific.

In support of the United Nations Environment Programme (UNEP) global monitoring plan under the Stockholm Convention concentrations of persistent organic pollutants (POPs) were determined during two years in air from 42 countries in Asia, Africa, Latin America, and the Pacific by using polyurethane foams installed in passive samplers. The compounds included were polychlorinated biphenyls (PCBs), organochlorine pesticides (OCPs), polybrominated diphenylethers (PBDEs), one polybrominated biphenyl and hexabromocyclododecane (HBCD) diastereomers. Total-DDT and PCBs were the highest in concentrations in about 50% of the samples, which shows their high persistency. Total DDT in air from the Solomon Islands ranged from 200 to 600 ng/polyurethane foam disk (PUF). However, at most locations, a decreasing trend is observed for PCBs, DDT and most other OCPs. Patterns varied per country with e.g. elevated dieldrin in air from Barbados and chlordane in air from the Philippines. A number of OCPs, such as heptachlor and its epoxides, some other chlordanes, mirex and toxaphene have decreased down to almost undetectable levels. PBB153 was hardly found and penta and octa--mix related PBDEs were also relatively low at most locations. HBCD and the decabromodiphenylether were more prominent at many locations and may even still increase. To draw more holistic conclusions more colder climate countries should be included in this program.

Preliminary trends over ten years of persistent organic pollutants in air - Comparison of two sets of data in the same countries.

In two series of ambient air measurement campaigns to support the implementation of the global monitoring plan (GMP) component of the Stockholm Convention on Persistent Organic Pollutants (POPs), passive air samplers (PAS) using polyurethane foams were implemented by the United Nations Environment Programme (UNEP). With the same laboratories responsible for the chemical analyses of the different groups of POPs, a total of 423 PUFs were analyzed for organochlorine pesticides (OCPs) including hexachlorobenzene (HCB) and polychlorinated biphenyls (PCB); 242 for dioxin-like POPs. For trend analysis, to compare amounts of POPs in the PUFs during the first phase in 2010/2011 and the second phase from 2017 to 2019, only results were assessed that were generated in the same country and for the same POP in both campaigns. Finally, there were 194 PUFs available for OCPs (GMP1 = 67 and GMP2 = 127), 297 for PCB (GMP1 = 103, GMP2 = 194), 158 for polychlorinated dibenzodioxins and polychlorinated dibenzofurans (PCDD, PCDF) (GMP1 = 39, GMP2 = 119), and 153 for dl-PCB (GMP1 = 34, GMP2 = 119). Indicator PCB and dioxin-like POPs were quantified in all countries at all times; decreases of about 30% based on median values were determined. A 50% increase was found for HCB. By scale, DDT remained with the highest values, although more than 60% decrease was found; mainly due to smaller values in the Pacific Islands region. Our assessment showed that on relative scale - per PUF - trend analysis was achieved and that such approach should be undertaken at regular intervals, not necessarily on an annual basis.

Mapping the Contribution of Biomass Burning to Persistent Organic Pollutants in the Air of the Indo-China Peninsula Based on a Passive Air Monitoring Network.

Biomass burning (BB) is an important source of atmospheric persistent organic pollutants (POPs) across the world. However, there are few field-based regional studies regarding the POPs released from BB. Due to the current limitations of emission factors and satellites, the contribution of BB to airborne POPs is still not well understood. In this study, with the simultaneous monitoring of BB biomarkers and POPs based on polyurethane foam-based passive air sampling technique, we mapped the contribution of BB to polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs) in the Indo-China Peninsula. Spearman correlations between levoglucosan and 16 PCBs (rs = 0.264-0.767, p < 0.05) and 2 OCPs (rs = 0.250-0.328, p < 0.05) confirmed that BB may facilitate POP emissions. Source apportionment indicated that BB contributed 9.3% to the total PCB and OCP mass. The high contribution of positive matrix factorization-resolved BB to PCBs and OCPs was almost consistent with their concentration distributions in the open BB season but not completely consistent with those in the pre-monsoon and/or monsoon seasons. Their contribution distributions may reflect the use history and geographic distribution in secondary sources of POPs. The field-based contribution dataset of BB to POPs is significant in improving regional BB emission inventories and model prediction.

The impact of three related emission industries on regional atmospheric chlorinated paraffins pollution.

Identifying the contributions of various chlorinated paraffins (CPs) sources in the environment plays an important practical role in the prevention and control of the CPs contamination. However, little is known about how main CP-related emission industries affect the regional atmospheric characteristics of CPs, including CP products industry, metal working industry, and polyvinyl chloride (PVC) industry. In this study, 60 passive air samples were collected from five typical cities in Henan Province, China, which had serious CP pollution and different structures of CP-related emission industry. Short chain CPs (SCCPs) and medium chain CPs (MCCPs) were detected in all samples in concentrations ranging of 2.6-7.7 × 102 and 2.1-4.3 × 102 ng m-3, respectively, which were higher than those in most reports. Moreover, Luoyang (LY) is different from other cities, showing a relatively severe MCCP contaminations. The CP pollution characteristics between different cities are obviously affected by the proportion of local CP-related industries. According to the results of cluster heatmaps, the local CP-related emission industrial structure had a greater impact on MCCPs pollution than SCCPs. Additionally, the contribution of metal working industry was beyond that of PVC production industry and CP products industry.

Novel eco-friendly methodology to determine polycyclic aromatic hydrocarbons in polyurethane foam for air monitoring: Application to spatial and temporal distribution survey.

This study aimed at developing a new method for the extraction of polycyclic aromatic hydrocarbons (PAHs) in polyurethane foam (PUF). In the field of PAH monitoring, passive samplers using PUF disks are widely used. However, current extraction methods are time and solvent consuming. This new method employs 3 times a sixteenth of the PUF disk, with method detection limits (MDL) values below 5 and 13 ng/sampler for 3- and 4-rings PAHs, respectively. The use of only parts of the disk allows extraction by ultrasounds using exclusively 120 mL of ethanol, making it environmentally friendly. Ethanolic extracts are then purified and concentrated using microextraction by packed sorbent (MEPS) before GC-MS analyses. This method was applied for an environmental survey in a French urban area with an oceanic climate. Variations in PAH concentrations were observed depending on the site studied (urban, traffic, periurban and rural), as well as temporal variations.

Seasonal occurrence, concentrations, and occupational exposure to VMSs in different environments of a WWTP.

In the present study, indoor and outdoor environments of a wastewater treatment plant (WWTP) were monitored by passive air samplers to assess the presence and seasonal trends of three linear (L3-L5) and four cyclic (D3-D6) volatile methylsiloxanes (VMSs). Furthermore, passive sampling rates (PSRs) were estimated from literature values to calculate VMSs air concentrations and occupational exposure to potentially toxic (D4-D6) congeners. Results showed a seasonal pattern of VMSs in outdoor locations (especially in the aeration tank and preliminary treatment), being the highest levels of total VMSs reached in Summer and the lowest in Spring, caused by the confluence of changing weather conditions and VMSs consumption patterns. This seasonality was not found in indoor sites. The congener profiles of VMSs were consistent throughout the year, showing a prevalence of D5 outdoors, and of D3 and D4 in strictly indoor environments. Different sources of VMSs, together with an air filtering system installed in the sampled buildings explain these differences. Estimated PSRs yielded lower values indoors (0.16-0.21 m3/day) than outdoors (0.32-0.49 m3/day), due to different wind speeds. Overall, outdoor locations showed higher VMSs concentrations in air than indoors. However, the values detected in both environments (∑VMSs between 8.00 and 2000 ng/m3) were within the ranges described in the literature for these locations. The occupational exposure to D4-D6 estimated for three different activities in the WWTP showed the highest values for Maintenance Technicians (8010 ± 722 ng/(kg·year)) and the lowest for Laboratory Technicians (5410 ± 874 ng/(kg·year)), in direct correlation with the higher amount of time spent outdoors by the former. In any case, the exposure was below the inhalation threshold of 150 µg/(kg·day) proposed as safe by other authors.

Air monitoring of tire-derived chemicals in global megacities using passive samplers.

Pollution from vehicle tires has received world-wide research attention due to its ubiquity and toxicity. In this study, we measured various tire-derived contaminants semi-quantitatively in archived extracts of passive air samplers deployed in 18 major cities that comprise the Global Atmospheric Passive Sampling (GAPS) Network (GAPS-Megacities). Analysis was done on archived samples, which represent one-time weighted passive air samples from each of the 18 monitoring sites. The target analytes included cyclic amines, benzotriazoles, benzothiazoles, and p-phenylenediamine (PPD) derivatives. Of the analyzed tire-derived contaminants, diphenylguanidine was the most frequently detected analyte across the globe, with estimated concentrations ranging from 45.0 pg/m3 in Beijing, China to 199 pg/m3 in Kolkata, India. The estimated concentrations of 6PPD-quinone and total benzothiazoles (including benzothiazole, 2-methylthio-benzothiazole, 2-methyl-benzothiazole, 2-hydroxy-benzothiazole) peaked in the Latin American and the Caribbean region at 1 pg/m3 and 100 pg/m3, respectively. In addition, other known tire-derived compounds, such as hexa(methoxymethyl)melamine, phenylguanidine, and various transformation products of 6PPD, were also monitored and characterized semi-quantitatively or qualitatively. This study presents some of the earliest data on airborne concentrations of chemicals associated with tire-wear and shows that passive sampling is a viable techniquefor monitoring airborne tire-wear contamination. Due to the presence of many tire-derived contaminants in urban air across the globe as highlighted by this study, there is a need to determine the associated exposure and toxicity of these chemicals to humans.

Occurrence and distribution of persistent organic pollutants (POPs) in the atmosphere of the Andean city of Medellin, Colombia.

Passive air sampling (PAS) was used to evaluate organochlorine pesticides, polychlorinated biphenyls, polybrominated diphenyl ethers, polybrominated biphenyl, hexabromocyclododecane, polychlorinated dibenzo-p-dioxins, polychlorinated dibenzofurans, and perfluoroalkane substances in the atmosphere of Medellin, Colombia. PAS was carried out for three months (four quarters per year) over two consecutive years (2017 and 2018). This study allowed establishing the baseline of some pollutants in the city against which future temporal trends can be assessed. Furthermore, monitoring results suggested releases of DDT in the city or surrounding areas despite this pollutant was banned many years ago in the country. Moreover, this study evidenced the limited scope of the national laboratories to analyze persistent organic pollutants, specially brominated and fluorinated contaminants. However, there is an installed capacity to analyze organochlorine pesticide and indicator PCB in future national monitoring plans. Therefore, it is essential to realize efforts to improve the analytical capacity and increase the scope of the national laboratories. Furthermore, the PAS strategy was valuable for monitoring these pollutants in air. Finally, the results provide an overall view of persistent organic pollutants levels and represent an initial attempt to monitor and surveillance the releases of these pollutants in the city.

POPs monitoring in Mongolia - Core matrices.

Persistent organic pollutants (POPs) are of global concern due to their negative effects on humans and the environment, and globally are regulated in the Stockholm Convention on POPs. The present study had Mongolia as a partner in a multinational project funded and coordinated by the United Nations Environment Programme with the aim to monitor POPs in core media, including air (with passive samplers), water, and a pooled human milk sample. Project implementation and all sampling were undertaken by the Institute of Chemistry and Chemical Technology whereas POPs analysis was performed in laboratories abroad. Brominated and chlorinated POPs were analyzed by gas chromatography/mass spectrometry, perfluorinated compounds (PFAS) and isomers of hexabromocyclododecane (HBCD) by liquid chromatography/mass spectrometry. The monitoring results found very low concentrations of PFAS in river water. Toxic equivalents (TEQs) for PCDD/PCDF were low in air and in human samples but had a relatively higher presence of TEQ from dioxin-like PCB than in other countries. With respect to chlorinated POPs, drins, chlordanes, DDTs, heptachlors, and mirex were very low in air and human milk. Elevated levels were found for polychlorinated biphenyls (PCB), hexachlorobenzene (HCB), hexachlorocyclohexanes (HCHs), pentachlorobenzene (PeCBz), and HBCD in air with extreme values for hexachlorobutadiene. The abundance of HCHs and HCB was confirmed in the human milk sample but not for PCB, PeCBz or HBCD. Short-chain chlorinated paraffins (170 ng/g lipid) were the highest among all human milk pools. It is recommended to continue POPs monitoring in the future, especially for those where high concentrations were found.

Changes and distribution of gas-phase polycyclic aromatic hydrocarbons and organochlorine compounds in a high-mountain gradient over a three-year period (Pyrenees, 2017-2020).

The atmospheric gas-phase concentrations of several polychlorinated biphenyls (PCBs), polycyclic aromatic hydrocarbons (PAHs), hexachlorobenzene (HCB), and pentachlorobenzene (PeCB) were measured in six high-mountain sites in the Pyrenees (1619-2453 m). Polyurethane foam passive air samplers were used for this purpose, providing continuous records spanning over three years (2017-2020). The mean concentrations of ∑PCBs, HCB, and PeCB, 13 ± 4 pg m-3, 44 ± 18 pg m-3, and 23 ± 20 pg m-3, respectively, were of the order of those reported in other mountain sites and similar to those measured 20 years ago in the same area, evidencing the persistence of these compounds despite the international regulatory actions. The mean concentration of ∑PAHs was 631 ± 238 pg m-3, representing between two- and three-times lower values than 20 years ago in the same area, but still in the range of other mountain regions. Statistically significant increases in gas-phase concentrations at higher temperatures were observed for most compounds. The experimental phase-change pseudo-enthalpies calculated from the slopes of the regressions between the natural logarithm of the concentrations and the reciprocal of temperature were lower than the reference values for nearly all compounds. This difference suggested a main contribution of long-range atmospheric transport of the gas-phase PAH and organochlorine concentrations in this mountain area. However, the less volatile compounds such as benz[a]anthracene, PCB138, and PCB180 showed a closer similarity between experimental and laboratory enthalpies, indicating that a significant portion of the variations in concentration of these compounds originated from temperature-dependent diffusive exchange by re-volatilization from local surfaces. The concentrations found in these sentinel ecosystems demonstrate that long-range transport of organic pollutants remains a risk in remote continental environments.

Occurrence and temperature dependence of atmospheric gas-phase organophosphate esters in high-mountain areas (Pyrenees).

The air concentrations of organophosphate esters (OPEs) were studied in a network of six remote high-mountain areas of the Pyrenees located along an altitudinal profile between 1619 m and 2453 m above sea level on a restricted planar surface to assess their vertical distribution based on long-range atmospheric transport and temperature gradients. Polyurethane foam passive samplers were used in five periods spanning over three years (September 2017-October 2020). The sum of concentrations of five OPEs were between 5.3 and 100 pg m-3, averaging 16-53 pg m-3 across campaigns at the different locations. These concentrations were much lower than those observed in areas under anthropogenic influence but also than those found in low altitude remote continental sites. A significant progressive change in predominant compounds was observed along the altitudinal gradient, with prevalence of tris(1-chloro-2-propyl) phosphate (TCIPP) or tris(2-chloroethyl) phosphate (TCEP) below or above 2300 m above sea level, respectively. This trend was consistent with the higher volatility of TCEP, which was retained at greater extent at lower environmental temperatures (higher altitude). A significant temperature dependence of the gas phase concentrations was observed for TCEP, TCIPP and triphenyl phosphate (TPHP), which could be explained by retention in the cold periods, predominantly adsorbed in snow, and their release to the atmosphere during snowmelt. This mechanism was consistent with the good agreement found between the vaporization enthalpies measured under laboratory conditions and the experimental values obtained from the slopes of the significant linear regressions when representing the vertical gradients.

Evaluation of effects of essential oil vapors on the bacterial count in bioaerosols.

Background: The aerosols generated during dental treatments contain bacteria and other microorganisms that penetrate the body through the respiratory system of dental surgeons and cause infectious diseases. Several studies have been done to reduce these hazards. The aim of the present study is to evaluate the effects of the plant extract essential oil (EO) vapors of Neem, Clove, Cinnamon bark, Thyme, Lemon Grass, and Eucalyptus on the bacterial count in bioaerosols near dental units. Materials and Methods: Sampling was taken on nutrient blood agar plates by placing them open near dental units using passive air sampling method, before commencement of treatment for 1 h, during treatments for 2 h, and after introducing EO vapors for 2 h. The collected samples were taken for incubation at 37°C for 48 h. The colonies formed were counted in colony-forming units per cubic meter and taken for statistical analysis. Results: After comparing the obtained results, it was found that there was a significant reduction (P < 0.05) in the bacterial count for about 43% near the dental units after the introduction of the EO vapours. Conclusion: It is concluded that natural extracts like EOs can reduce bacterial contamination near dental units in the vapourized state, thereby reducing the health hazards in Dental Health Professionals.

Seasonal variations in air concentrations of 27 organochlorine pesticides (OCPs) and 25 current-use pesticides (CUPs) across three agricultural areas of South Africa.

For decades pesticides have been used in agriculture, however, the occurrence of legacy organochlorine pesticides (OCPs) and current-use pesticides (CUPs) is poorly understood in Africa. This study investigates air concentrations of OCPs and CUPs in three South African agricultural areas, their spatial/seasonal variations and mixture profiles. Between 2017 and 2018, 54 polyurethane foam-disks passive air-samplers (PUF-PAS) were positioned in three agricultural areas of the Western Cape, producing mainly apples, table grapes and wheat. Within areas, 25 CUPs were measured at two sites (farm and village), and 27 OCPs at one site (farm). Kruskal-Wallis tests investigated area differences in OCPs concentrations, and linear mixed-effect models studied differences in CUPs concentrations between areas, sites and sampling rounds. In total, 20 OCPs and 16 CUPs were detected. A median of 16 OCPs and 10 CUPs were detected per sample, making a total of 11 OCPs and 24 CUPs combinations. Eight OCPs (trans-chlordane, o,p'-/p,p'-dichlorodiphenyldichloroethylene (DDE)/dichlorodiphenyltrichloroethane (DDT), endosulfan sulfate, γ-hexachlorocyclohexane and mirex) and two CUPs (carbaryl and chlorpyrifos) were quantified in all samples. p,p'-DDE (median 0.14 ng/m3) and chlorpyrifos (median 0.70 ng/m3) showed the highest concentrations throughout the study. Several OCPs and CUPs showed different concentrations between areas and seasons, although CUPs concentrations did not differ between sites. OCPs ratios suggest ongoing chlordane use in the region, while DDT and endosulfan contamination result from past-use. Our study revealed spatial and seasonal variations of different OCPs and CUPs combinations detected in air. Further studies are needed to investigate the potential cumulative or synergistic risks of the detected pesticides.

Spatial trends of chlorinated paraffins and dechloranes in air and soil in a tropical urban, suburban, and rural environment.

There are large knowledge gaps concerning environmental levels and fate of many organic pollutants, particularly for chemicals of emerging concern in tropical regions of the Global South. In this study, we investigated the levels of chlorinated paraffins (CPs) and dechloranes in air and soil in rural, suburban, and urban regions in and around Dar es Salaam, Tanzania. Samples were also collected near the city's main municipal waste dumpsite and an electronic waste (e-waste) handling facility. In passive air samples, short chain CPs (SCCPs) dominated, with an average estimated concentration of 22 ng/m3, while medium chain CPs (MCCPs) had an average estimated concentration of 9 ng/m3. The average estimated air concentration of ∑dechloranes (Dechlorane Plus (DP) + Dechlorane 602 + Dechlorane 603) was three to four orders of magnitudes lower, 2 pg/m3. In soil samples, MCCPs dominated with an average concentration of 640 ng/g dw, followed by SCCPs with an average concentration of 330 ng/g dw, and ∑dechloranes with an average concentration of 0.9 ng/g dw. In both air and soil, DP was the dominating dechlorane compound. Urban pulses were observed for CPs and dechloranes in air and soil. CPs were in addition found in elevated levels at the municipal waste dumpsite and the e-waste handling facility, while DPs were found in elevated levels at the e-waste handling facility. This suggests that waste handling sites represent important emission sources for these pollutants. Investigations into seasonal trends and environmental fate of CPs and dechloranes showed that monsoonal rain patterns play a major role in governing air concentrations and mobility, particularly for the less volatile MCCPs and dechloranes. This study is the first to report levels of CPs in air from sub-Saharan Africa, and DP, Dechlorane 602, and Dechlorane 603 in soil from sub-Saharan Africa.

Field comparison of passive polyurethane foam and active air sampling techniques for analysis of gas-phase semi-volatile organic compounds at a remote high-mountain site.

Polyurethane foam passive air samplers (PUF-PAS) are good candidates for the determination of gas-phase semi-volatile organic compound (SVOC) air concentrations in high-mountain areas over long periods because they do not require an energy supply. However, the harsh meteorological conditions present in such locations can increase the uncertainties inherently associated to PAS sampling rates due to the many variables involved in their calculation and to the assumptions made regarding PUF diffusive uptake mechanics, which can considerably bias the resulting concentrations. Therefore, we studied the performance of PUF-PASs in a remote location in the Pyrenees mountain range for the analysis of several SVOCs in air, including polychlorobiphenyls (PCBs), hexachlorobenzene, pentachlorobenzene, polycyclic aromatic hydrocarbons (PAHs), and the less studied emerging organophosphate flame retardants (OPFRs). An in-situ PUF-PAS calibration using Performance Reference Compounds (PRCs) provided compound- and sampler-specific sampling rates, showing mean experimental errors (12%) that adequately conformed to an estimate of their expanded theoretical uncertainties (15%). This showcases the suitability of this calibration strategy in an area with conditions beyond those typically considered in calibration efforts available to date. Moreover, gas-phase concentrations of the studied pollutants from PUF-PAS samples showed very good agreement (R2 up to 0.91, p < 0.01) when compared to those obtained using a conventional high-volume active air sampler (PUF-AAS), with some minor deviations observed for PAHs caused by the seasonality in their atmospheric concentrations. No relevant levels of pollutants preferentially bound to the particle phase were detected in the PUF-PASs, the particle infiltration efficiency of the sampler configuration used was found to be low, and compounds typically distributed between the gas and particle phases of AAS samples revealed profiles consistent with their vapor pressures, except for some OPFRs.

Cytotoxic and Transcriptomic Effects in Avian Hepatocytes Exposed to a Complex Mixture from Air Samples, and Their Relation to the Organic Flame Retardant Signature.

Assessing complex environmental mixtures and their effects is challenging. In this study, we evaluate the utility of an avian in vitro screening approach to determine the effects of passive air sampler extracts collected from different global megacities on cytotoxicity and gene expression. Concentrations of a suite of organic flame retardants (OFRs) were quantified in extracts from a total of 19 megacities/major cities in an earlier study, and levels were highly variable across sites. Chicken embryonic hepatocytes were exposed to serial dilutions of extracts from the 19 cities for 24 h. Cell viability results indicate a high level of variability in cytotoxicity, with extracts from Toronto, Canada, having the lowest LC50 value. Partial least squares (PLS) regression analysis was used to estimate LC50 values from OFR concentrations. PLS modeling of OFRs was moderately predictive of LC50 (p-value = 0.0003, r2 = 0.66, slope = 0.76, when comparing predicted LC50 to actual values), although only after one outlier city was removed from the analysis. A chicken ToxChip PCR array, comprising 43 target genes, was used to determine effects on gene expression, and similar to results for cell viability, gene expression profiles were highly variable among the megacities. PLS modeling was used to determine if gene expression was related to the OFR profiles of the extracts. Weak relationships to the ToxChip expression profiles could be detected for only three of the 35 OFRs (indicated by regression slopes between 0.6 and 0.5 when comparing predicted to actual OFR concentrations). While this in vitro approach shows promise in terms of evaluating effects of complex mixtures, we also identified several limitations that, if addressed in future studies, might improve its performance.

Global intercomparison of polyurethane foam passive air samplers evaluating sources of variability in SVOC measurements.

Polyurethane foam passive air samplers (PUF-PAS) are the most common type of passive air sampler used for a range of semi-volatile organic compounds (SVOCs), including regulated persistent organic pollutants (POPs) and polycyclic aromatic hydrocarbons (PAHs), and emerging contaminants (e.g., novel flame retardants, phthalates, current-use pesticides). Data from PUF-PAS are key indicators of effectiveness of global regulatory actions on SVOCs, such as the Global Monitoring Plan of the Stockholm Convention on Persistent Organic Pollutants. While most PUF-PAS use similar double-dome metal shielding, there is no standardized dome size, shape, or deployment configuration, with many different PUF-PAS designs used in regional and global monitoring. Yet, no information is available on the comparability of data from studies using different PUF-PAS designs. We brought together 12 types of PUF-PAS used by different research groups around the world and deployed them in a multi-part intercomparison to evaluate the variability in reported concentrations introduced by different elements of PAS monitoring. PUF-PAS were deployed for 3 months in outdoor air in Kjeller, Norway in 2015-2016 in three phases to capture (1) the influence of sampler design on data comparability, (2) the influence of analytical variability when samplers are analyzed at different laboratories, and (3) the overall variability in global monitoring data introduced by differences in sampler configurations and analytical methods. Results indicate that while differences in sampler design (in particular, the spacing between the upper and lower sampler bowls) account for up to 50 % differences in masses collected by samplers, the variability introduced by analysis in different laboratories far exceeds this amount, resulting in differences spanning orders of magnitude for POPs and PAHs. The high level of variability due to analysis in different laboratories indicates that current SVOC air sampling data (i.e., not just for PUF-PAS but likely also for active air sampling) are not directly comparable between laboratories/monitoring programs. To support on-going efforts to mobilize more SVOC data to contribute to effectiveness evaluation, intercalibration exercises to account for uncertainties in air sampling, repeated at regular intervals, must be established to ensure analytical comparability and avoid biases in global-scale assessments of SVOCs in air caused by differences in laboratory performance.