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1.
Indoor Air ; 30(3): 459-472, 2020 May.
Artigo em Inglês | MEDLINE | ID: mdl-32034823

RESUMO

Volatile organic compounds (VOCs) emitted from personal care products (PCPs) can affect indoor air quality and outdoor air quality when ventilated. In this paper, we determine a set of simplified VOC species profiles and emission rates for a range of non-aerosol PCPs. These have been constructed from individual vapor analysis from 36 products available in the UK, using equilibrium headspace analysis with selected-ion flow-tube mass spectrometry (SIFT-MS). A simplified speciation profile is created based on the observations, comprising four alcohols, two cyclic volatile siloxanes, and monoterpenes (grouped as limonene). Estimates are made for individual unit-of-activity VOC emissions for dose-usage of shampoos, shower gel, conditioner, liquid foundation, and moisturizer. We use these values as inputs to the INdoor air Detailed Chemical Model (INDCM) and compare results against real-world case-study experimental data. Activity-based emissions are then scaled based on plausible usage patterns to estimate the potential scale of annual per-person emissions for each product type (eg, 2 g limonene person-1  yr-1 from shower gels). Annual emissions from non-aerosol PCPs for the UK are then calculated (decamethylcyclopentasiloxane 0.25 ktonne yr-1 and limonene 0.15 ktonne yr-1 ) and these compared with the UK National Atmospheric Emissions Inventory estimates for non-aerosol cosmetics and toiletries.

3.
Sci Total Environ ; 684: 1-13, 2019 Sep 20.
Artigo em Inglês | MEDLINE | ID: mdl-31150871

RESUMO

We report a 24-month statistical baseline climatology for continuously-measured atmospheric carbon dioxide (CO2) and methane (CH4) mixing ratios linked to surface meteorology as part of a wider environmental baselining project tasked with understanding pre-existing local environmental conditions prior to shale gas exploration in the United Kingdom. The baseline was designed to statistically characterise high-precision measurements of atmospheric composition gathered over two full years (between February 1st 2016 and January 31st 2018) at fixed ground-based measurement stations on, or near to, two UK sites being developed for shale gas exploration involving hydraulic fracturing. The sites, near Blackpool (Lancashire) and Kirby Misperton (North Yorkshire), were the first sites approved in the UK for shale gas exploration since a moratorium was lifted in England. The sites are operated by Cuadrilla Resources Ltd. and Third Energy Ltd., respectively. A statistical climatology of greenhouse gas mixing ratios linked to prevailing local surface meteorology is presented. This study diagnoses and interprets diurnal, day-of-week, and seasonal trends in measured mixing ratios and the contributory role of local, regional and long-range emission sources. The baseline provides a set of contextual statistical quantities against which the incremental impacts of new activities (in this case, future shale gas exploration) can be quantitatively assessed. The dataset may also serve to inform the design of future case studies, as well as direct baseline monitoring design at other potential shale gas and industrial sites. In addition, it provides a quantitative reference for future analyses of the impact, and efficacy, of specific policy interventions or mitigating practices. For example, statistically significant excursions in measured concentrations from this baseline (e.g. >99th percentile) observed during phases of operational extraction may be used to trigger further examination in order to diagnose the source(s) of emission and links to on-site activities at the time, which may be of importance to regulators, site operators and public health stakeholders. A guideline algorithm for identifying these statistically significant excursions, or "baseline deviation events", from the expected baseline conditions is presented and tested. Gaussian plume modelling is used to further these analyses, by simulating approximate upper-limits of CH4 fluxes which could be expected to give observable enhancements at the monitoring stations under defined meteorological conditions.

4.
Sci Total Environ ; 673: 445-454, 2019 Jul 10.
Artigo em Inglês | MEDLINE | ID: mdl-30991334

RESUMO

Rural observations of air quality and meteorological parameters (NOx, O3, NMHCs, SO2, PM) were made over a 2.5-year period (2016-2018) before, during and after preparations for hydraulic fracturing (fracking) at a shale gas exploration site near Kirby Misperton, North Yorkshire, England. As one of the first sites to apply for permits to carry out hydraulic fracturing, it has been subject to extensive regulatory and public scrutiny, as well as the focus for a major programme of long-term environmental monitoring. A baseline period of air quality monitoring (starting 2016) established the annual climatology of atmospheric composition against which a 20-week period of intensive activity on the site in preparation for hydraulic fracturing could be compared. During this 'pre-operational phase' of work in late 2017, the most significant effect was an increase in ambient NO (3-fold) and NOx (2-fold), arising from a combination of increased vehicle activity and operation of equipment on site. Although ambient NOx increased, air quality limit values for NO2 were not exceeded, even close to the well-site. Local ozone concentrations during the pre-operational period were slightly lower than the baseline phase due to titration with primary emitted NO. The activity on site did not lead to significant changes in airborne particulate matter or non-methane hydrocarbons. Hydraulic fracturing of the well did not subsequently take place and the on-site equipment was decommissioned and removed. Air quality parameters then returned to the original (baseline) climatological conditions. This work highlights the need to characterise the full annual climatology of air quality parameters against which short-term local activity changes can be compared. Based on this study, changes to ambient NOx appear to be the most significant air quality ahead of hydraulic fracturing. However, in rural locations, concentrations at individual sites are expected to be below ambient air quality limit thresholds.

5.
Sci Total Environ ; 664: 771-779, 2019 May 10.
Artigo em Inglês | MEDLINE | ID: mdl-30763857

RESUMO

Conventional volatile organic compound (VOC) monitoring based on thermal desorption - gas chromatography-mass spectrometry (TD-GC-MS) or gas chromatography-flame ionization detector (TD-GC-FID) is relatively cumbersome and expensive. In this study commercial off the shelf low-cost and low-power photo-ionization detector (PID) sensors are used as simple detectors in VOC analysis systems based on GC, including a miniaturised GC × GC device with portable, low-cost, and low-energy-consumption features. PID sensors produce a voltage signal positively proportional to VOC concentration, which when incorporated into a TD-GC system gave limit of detection of 0.02 ppbV for isoprene. To test PID performance in real-world applications, PID sensors were deployed as (i) a second alternative detector in a GC-Quadruple Time Of Flight Mass spectrometry (GC-Q-TOF-MS), and (ii) the main detector in a compact two-dimensional gas chromatograph (GC × GC). PID sensors with 10.6 eV and 11.7 eV lamps were used to measure eight toxic chemicals including organic sulfide and organic phosphonates via GC; two species were ionized by a 10.6 eV lamp and four species by the 11.7 eV lamp. Commercially available low-cost PIDs designed for standalone could be straightforwardly and effectively re-used as detectors in compact GC × GC systems, in this work showing excellent VOC sensitivity, fast response and low operational demands compared to comparable field instruments based on GC-FID or MS.

9.
Environ Sci Technol ; 51(18): 10449-10458, 2017 Sep 19.
Artigo em Inglês | MEDLINE | ID: mdl-28752764

RESUMO

We report novel in situ speciated observations of monoterpenes (α- and ß-pinene, myrcene, δ3-carene, ocimene, limonene) in seawater and air during three cruises in the Arctic and Atlantic Oceans, in/over generally oligotrophic waters. Oceanic concentrations of the individual monoterpenes ranged from below the detection limit of <1 pmol L-1 to 5 pmol L-1, with average concentrations of between 0.5 and 2.9 pmol L-1. After careful filtering for contamination, atmospheric mixing ratios varied from below the detection limit (<1 pptv) to 5 pptv, with averages of 0.05-5 pptv; these levels are up to 2 orders of magnitude lower than those reported previously. This could be at least partly due to sampling over waters with much lower biological activity than in previous studies. Unlike in previous studies, no clear relationships of the monoterpenes with biological variables were found. Based on our measured seawater concentrations and a global model simulation, we estimate total global marine monoterpene emissions of 0.16 Tg C yr-1, similar to a previous bottom-up estimate based on laboratory monoculture studies but 2 orders of magnitude lower than a previous top-down estimate of 29.5 Tg C yr-1.


Assuntos
Monoterpenos/análise , Regiões Árticas , Oceano Atlântico , Compostos Bicíclicos com Pontes , Monitoramento Ambiental
10.
Faraday Discuss ; 200: 599-620, 2017 08 24.
Artigo em Inglês | MEDLINE | ID: mdl-28580967

RESUMO

Volatile organic compounds (VOCs) originate from a variety of sources, and play an intrinsic role in influencing air quality. Some VOCs, including benzene, are carcinogens and so directly affect human health, while others, such as isoprene, are very reactive in the atmosphere and play an important role in the formation of secondary pollutants such as ozone and particles. Here we report spatially-resolved measurements of the surface-to-atmosphere fluxes of VOCs across London and SE England made in 2013 and 2014. High-frequency 3-D wind velocities and VOC volume mixing ratios (made by proton transfer reaction - mass spectrometry) were obtained from a low-flying aircraft and used to calculate fluxes using the technique of eddy covariance. A footprint model was then used to quantify the flux contribution from the ground surface at spatial resolution of 100 m, averaged to 1 km. Measured fluxes of benzene over Greater London showed positive agreement with the UK's National Atmospheric Emissions Inventory, with the highest fluxes originating from central London. Comparison of MTBE and toluene fluxes suggest that petroleum evaporation is an important emission source of toluene in central London. Outside London, increased isoprene emissions were observed over wooded areas, at rates greater than those predicted by a UK regional application of the European Monitoring and Evaluation Programme model (EMEP4UK). This work demonstrates the applicability of the airborne eddy covariance method to the determination of anthropogenic and biogenic VOC fluxes and the possibility of validating emission inventories through measurements.

11.
Faraday Discuss ; 200: 621-637, 2017 08 24.
Artigo em Inglês | MEDLINE | ID: mdl-28608899

RESUMO

Low cost air pollution sensors have substantial potential for atmospheric research and for the applied control of pollution in the urban environment, including more localized warnings to the public. The current generation of single-chemical gas sensors experience degrees of interference from other co-pollutants and have sensitivity to environmental factors such as temperature, wind speed and supply voltage. There are uncertainties introduced also because of sensor-to-sensor response variability, although this is less well reported. The sensitivity of Metal Oxide Sensors (MOS) to volatile organic compounds (VOCs) changed with relative humidity (RH) by up to a factor of five over the range of 19-90% RH and with an uncertainty in the correction of a factor of two at any given RH. The short-term (second to minute) stabilities of MOS and electrochemical CO sensor responses were reasonable. During more extended use, inter-sensor quantitative comparability was degraded due to unpredictable variability in individual sensor responses (to either measurand or interference or both) drifting over timescales of several hours to days. For timescales longer than a week identical sensors showed slow, often downwards, drifts in their responses which diverged across six CO sensors by up to 30% after two weeks. The measurement derived from the median sensor within clusters of 6, 8 and up to 21 sensors was evaluated against individual sensor performance and external reference values. The clustered approach maintained the cost competitiveness of a sensor device, but the median concentration from the ensemble of sensor signals largely eliminated the randomised hour-to-day response drift seen in individual sensors and excluded the effects of small numbers of poorly performing sensors that drifted significantly over longer time periods. The results demonstrate that for individual sensors to be optimally comparable to one another, and to reference instruments, they would likely require frequent calibration. The use of a cluster median value eliminates unpredictable medium term response changes, and other longer term outlier behaviours, extending the likely period needed between calibration and making a linear interpolation between calibrations more appropriate. Through the use of sensor clusters rather than individual sensors, existing low cost technologies could deliver significantly improved quality of observations.

12.
Environ Sci Process Impacts ; 19(4): 528-537, 2017 Apr 19.
Artigo em Inglês | MEDLINE | ID: mdl-28224154

RESUMO

The abundance of volatile organic compounds (VOCs) found in homes depends on many factors such as emissions, ventilation and the oxidative environment and these are evolving over time, reflecting changes in chemical use, behaviour and building design/materials. The concentrations of VOCs in 25 UK homes of varying ages, design and occupancy were quantified using continuous indoor air sampling over five days. Air was collected through low flow (1 mL min-1) constant flow restrictors into evacuated 6 L internally silica-treated canisters until the canisters reached atmospheric pressure. This was followed by thermal desorption-gas chromatography and high mass accuracy time-of-flight mass spectrometry (TD-GC-TOF/MS). A fully quantitative analysis was performed on the eight most abundant hydrocarbon-based VOCs found. Despite differences in building characteristics and occupant numbers 94% of the homes had d-limonene or α-pinene as the most abundant VOCs. The variability seen across the 25 homes in concentrations of monoterpenes indoors was considerably greater than that of species such as isoprene, benzene, toluene and xylenes. The variance in VOCs indoors appeared to be strongly influenced by occupant activities such as cleaning with 5-day average concentrations of d-limonene ranging from 18 µg m-3 to over 1400 µg m-3, a peak domestic value that is possibly the highest yet reported in the literature.


Assuntos
Poluentes Atmosféricos/análise , Poluição do Ar em Ambientes Fechados/análise , Monoterpenos/análise , Compostos Orgânicos Voláteis/análise , Monitoramento Ambiental , Cromatografia Gasosa-Espectrometria de Massas , Reino Unido
13.
J Sep Sci ; 40(3): 753-766, 2017 02.
Artigo em Inglês | MEDLINE | ID: mdl-27928898

RESUMO

Stir bar sorptive extraction is a powerful technique for the extraction and analysis of organic compounds in aqueous matrices. Carbonyl compounds are ubiquitous components in rainwater, however, it is a major challenge to accurately identify and sensitively quantify carbonyls from rainwater due to the complex matrix. A stir bar sorptive extraction technique was developed to efficiently extract carbonyls from aqueous samples following chemical derivatization by O-(2,3,4,5,6-pentafluorobenzyl) hydroxylamine hydrochloride. Several commercial stir bars in two sizes were used to simultaneously measure 29 carbonyls in aqueous samples with detection by gas chromatography with mass spectrometry. A 100 mL aqueous sample was extracted by stir bars and the analytes on stir bars were desorbed into a 2 mL solvent solution in an ultrasonic bath. The preconcentration Coefficient for different carbonyls varied between 30 and 45 times. The limits of detection of stir bar sorptive extraction with gas chromatography mass spectrometry for carbonyls (10-30 ng/L) were improved by ten times compared with other methods such as gas chromatography with electron capture detection and stir bar sorptive extraction with high-performance liquid chromatography and mass spectrometry. The technique was used to determine carbonyls in rainwater samples collected in York, UK, and 20 carbonyl species were quantified including glyoxal, methylglyoxal, isobutenal, 2-hydroxy ethanal.


Assuntos
Monitoramento Ambiental/métodos , Cromatografia Gasosa-Espectrometria de Massas , Compostos Orgânicos/análise , Chuva/química , Limite de Detecção , Reprodutibilidade dos Testes , Poluentes Químicos da Água/análise
16.
Faraday Discuss ; 189: 85-103, 2016 07 18.
Artigo em Inglês | MEDLINE | ID: mdl-27104223

RESUMO

Low cost pollution sensors have been widely publicized, in principle offering increased information on the distribution of air pollution and a democratization of air quality measurements to amateur users. We report a laboratory study of commonly-used electrochemical sensors and quantify a number of cross-interferences with other atmospheric chemicals, some of which become significant at typical suburban air pollution concentrations. We highlight that artefact signals from co-sampled pollutants such as CO2 can be greater than the electrochemical sensor signal generated by the measurand. We subsequently tested in ambient air, over a period of three weeks, twenty identical commercial sensor packages alongside standard measurements and report on the degree of agreement between references and sensors. We then explore potential experimental approaches to improve sensor performance, enhancing outputs from qualitative to quantitative, focusing on low cost VOC photoionization sensors. Careful signal handling, for example, was seen to improve limits of detection by one order of magnitude. The quantity, magnitude and complexity of analytical interferences that must be characterised to convert a signal into a quantitative observation, with known uncertainties, make standard individual parameter regression inappropriate. We show that one potential solution to this problem is the application of supervised machine learning approaches such as boosted regression trees and Gaussian processes emulation.

17.
Faraday Discuss ; 189: 105-20, 2016 Jul 18.
Artigo em Inglês | MEDLINE | ID: mdl-27092375

RESUMO

There is growing global consumption of non-fossil fuels such as ethanol made from renewable biomass. Previous studies have shown that one of the main air quality disadvantages of using ethanol blended fuels is a significant increase in the production of acetaldehyde, an unregulated and toxic pollutant. Most studies on the impacts of ethanol blended gasoline have been carried out in the US and Brazil, with much less focus on the UK and Europe. We report time resolved measurements of ethanol in London during the winter and summer of 2012. In both seasons the mean mixing ratio of ethanol was around 5 ppb, with maximum values over 30 ppb, making ethanol currently the most abundant VOC in London air. We identify a road transport related source, with 'rush-hour' peaks observed. Ethanol is strongly correlated with other road transport-related emissions, such as small aromatics and light alkanes, and has no relationship to summer biogenic emissions. To determine the impact of road transport-related ethanol emission on secondary species (i.e. acetaldehyde and ozone), we use both a chemically detailed box model (incorporating the Master Chemical Mechanism, MCM) and a global and nested regional scale chemical transport model (GEOS-Chem), on various processing time scales. Using the MCM model, only 16% of the modelled acetaldehyde was formed from ethanol oxidation. However, the model significantly underpredicts the total levels of acetaldehyde, indicating a missing primary emission source, that appears to be traffic-related. Further support for a primary emission source comes from the regional scale model simulations, where the observed concentrations of ethanol and acetaldehyde can only be reconciled with the inclusion of large primary emissions. Although only constrained by one set of observations, the regional modelling suggests a European ethanol source similar in magnitude to that of ethane (∼60 Gg per year) and greater than that of acetaldehyde (∼10 Gg per year). The increased concentrations of ethanol and acetaldehyde from primary emissions impacts both radical and NOx cycling over Europe, resulting in significant regional impacts on NOy speciation and O3 concentrations, with potential changes to human exposure to air pollutants.


Assuntos
Poluição do Ar/análise , Etanol/análise , Acetaldeído/análise , Cromatografia Gasosa , Etanol/química , Modelos Lineares , Londres , Óxidos de Nitrogênio/análise , Oxirredução , Ozônio/análise , Estações do Ano
18.
Faraday Discuss ; 189: 455-72, 2016 Jul 18.
Artigo em Inglês | MEDLINE | ID: mdl-27098421

RESUMO

To date, direct validation of city-wide emissions inventories for air pollutants has been difficult or impossible. However, recent technological innovations now allow direct measurement of pollutant fluxes from cities, for comparison with emissions inventories, which are themselves commonly used for prediction of current and future air quality and to help guide abatement strategies. Fluxes of NOx were measured using the eddy-covariance technique from an aircraft flying at low altitude over London. The highest fluxes were observed over central London, with lower fluxes measured in suburban areas. A footprint model was used to estimate the spatial area from which the measured emissions occurred. This allowed comparison of the flux measurements to the UK's National Atmospheric Emissions Inventory (NAEI) for NOx, with scaling factors used to account for the actual time of day, day of week and month of year of the measurement. The comparison suggests significant underestimation of NOx emissions in London by the NAEI, mainly due to its under-representation of real world road traffic emissions. A comparison was also carried out with an enhanced version of the inventory using real world driving emission factors and road measurement data taken from the London Atmospheric Emissions Inventory (LAEI). The measurement to inventory agreement was substantially improved using the enhanced version, showing the importance of fully accounting for road traffic, which is the dominant NOx emission source in London. In central London there was still an underestimation by the inventory of 30-40% compared with flux measurements, suggesting significant improvements are still required in the NOx emissions inventory.

19.
J Chromatogr A ; 1426: 191-200, 2015 Dec 24.
Artigo em Inglês | MEDLINE | ID: mdl-26684592

RESUMO

Thirdhand tobacco smoke (THS) constitutes a poorly understood pathway of exposure of non-smokers, especially toddlers, to tobacco-related carcinogens. However, to date most of the carcinogens present in tobacco smoke have not been detected in THS and, therefore, the significance of THS health risk is still unknown. In this study, we have compared the performance of two analytical methods - one based on gas chromatography coupled to ion trap mass spectrometry detection (GC-IT-MS) and the other on comprehensive two-dimensional gas chromatography coupled to a nitrogen chemiluminescence detector (GC×GC-NCD) - for simultaneously determining, in settled house dust, the presence of 16 organic nitrogen carcinogens already detected in tobacco smoke. The target compounds included four aromatic amines, two nitrocompounds, eight N-nitrosamines and two tobacco-specific nitrosamines, as well as nicotine as a tobacco marker. Dust samples were extracted using in-cell clean up pressurized liquid extraction with silica as clean up sorbent and ethyl acetate as the organic solvent, with average recovery of 89%. Although GC-IT-MS, using chemical ionization with methanol and tandem MS, performed well, the optimized GC×GC-NCD gave lower limits of detection (from 4 to 22ngg(-1)) and better repeatability and reproducibility a low concentration levels (%RSD<8%) and, therefore, was applicable for determining these different groups of carcinogens without the need for derivatization prior to the GC analysis. The performance of the optimized PLE/GC×GC-NCD method was tested by quantifying the target compounds in house dust samples from smokers' and non-smokers' homes. The median carcinogen compounds detected was 3.8µgg(-1) and 1.1µgg(-1) in smokers' and non-smokers' house dust, respectively. In this study, we have detected highly carcinogenic aromatic amines and nitro compounds for the first time in settled house dust complementing the state of knowledge of THS composition and providing fresh evidence about THS health risks.


Assuntos
Carcinógenos/análise , Nitrocompostos/análise , Fumaça/análise , Tabaco/química , Aminas/análise , Cromatografia Gasosa/métodos , Poeira/análise , Luminescência , Nicotina/análise , Nitrogênio/análise , Nitrosaminas/análise , Reprodutibilidade dos Testes , Espectrometria de Massas em Tandem/métodos
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