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The effect of adding a plug-in air freshener into 60 houses was hard to detect due to pre-existing VOCs from other sources; in homes with low ventilation rates however small increases in monoterpenes were seen, consistent with emission rates.

The speciation of volatile organic compounds (VOCs) emitted from personal care products (PCPs) is complex and contributes to poor air quality and health risks to users via the inhalation exposure pathway. Detailed VOC emission profiles were generated for 26 sunscreen products; consequently, variability was observed between products, even though they were all designed for the same purpose. Some were found to contain fragrance compounds not labelled on their ingredients list. Five contaminant VOCs were identified (benzene, toluene, ethylbenzene, o-xylene, and p-xylene); headspace sampling of an additional 18 randomly selected products indicated that ethanol originating from fossil petroleum was a potential source. The gas phase emission rates of the VOCs were quantified for 15 of the most commonly emitted species using SIFT-MS. A wide range of emission rates were observed between the products. Usage estimates were made based on the recommended dose per body surface area, for which the total mass of VOCs emitted from one full-body application dose was in the range of 1.49 × 103–4.52 × 103 mg and 1.35 × 102–4.11 × 102 mg for facial application (men aged 16+; children aged 2–4). Depending on age and sex, an estimated 9.8–30 mg of ethanol is inhaled from one facial application of sunscreen.

Systematic measurements of atmospheric methane (CH4) mole fractions at the northern high latitudes only began in the early 1980s. Although CH4 measurements from Greenland ice cores consistently covered the period before ∼ 1900, no reliable observational record is available for the intermediate period. We newly report a data set of trace gases from the air trapped in firn (an intermediate stage between snow and glacial ice formation) collected at the NGRIP (North Greenland Ice Core Project) site in 2001. We also use a set of published firn air data at the NEEM (North Greenland Eemian ice Drilling) site. The two Arctic firn air data sets are analysed with a firn air transport model, which translates historical variations to depth profiles of trace gases in firn. We examine a variety of possible firn diffusivity profiles, using a suite of measured trace gases, and reconstruct the CH4 mole fraction by an iterative dating method. Although the reconstructions of the Arctic CH4 mole fraction before the mid-1970s still has large uncertainties (> 30 ppb – parts per billion), we find a relatively narrow range of atmospheric CH4 history that is consistent with both depth profiles of NGRIP and NEEM. The atmospheric CH4 history inferred by this study is more consistent with the atmospheric CH4 scenario prepared for the NEEM firn modelling than that for the CMIP6 (Climate Model Intercomparison Project Phase 6) experiments. Our study shows that the atmospheric CH4 scenario used for the NEEM firn modelling is considered to be the current best choice for the Arctic CH4 history, but it should not be used to tune firn air transport models until being verified by further measurements from sources such as the Arctic ice cores. Given the current difficulty in reconstructing the CH4 history with low uncertainty from the firn air data sets from Greenland, future sampling and measurements of ice cores at a high-accumulation site may be the only way to accurately reconstruct the atmospheric CH4 trend over the 20th century.

The largest inorganic, gas-phase reservoir of chlorine atoms in the atmosphere is hydrogen chloride (HCl), but challenges in quantitative sampling of this compound cause difficulties for obtaining high-quality, high-frequency measurements. In this work, tunable infrared laser direct absorption spectroscopy (TILDAS) was demonstrated to be a superior optical method for sensitive, in situ detection of HCl at the 2925.89645 cm−1 absorption line using a 3 µm inter-band cascade laser. The instrument has an effective path length of 204 m, 1 Hz precision of 7–8 pptv, and 3σ limit of detection ranging from 21 to 24 pptv. For longer averaging times, the highest precision obtained was 0.5 pptv with a 3σ limit of detection of 1.6 pptv at 2.4 min. HCl-TILDAS was also shown to have high accuracy when compared with a certified gas cylinder, yielding a linear slope within the expected 5 % tolerance of the reported cylinder concentration (slope = 0.964 ± 0.008). The use of heated inlet lines and active chemical passivation greatly improve the instrument response times to changes in HCl mixing ratios, with minimum 90 % response times ranging from 1.2 to 4.4 s depending on inlet flow rate. However, these response times lengthened at relative humidities >50 %, conditions under which HCl concentration standards were found to elicit a significantly lower response (−5.8 %). The addition of high concentrations of gas-phase nitric acid (>3.0 ppbv) were found to increase HCl signal ( %), likely due to acid displacement with HCl or particulate chloride adsorbed to inlet surfaces. The equilibrium model ISORROPIA suggested a potential of particulate chloride partitioning into HCl gas within the heated inlet system if allowed to thermally equilibrate, but field results did not demonstrate a clear relationship between particulate chloride and HCl signal obtained with a denuder installed on the inlet.

The largest inorganic, gas phase reservoir of chlorine atoms in the atmosphere is hydrogen chloride (HCl), but the challenges in quantitative sampling of this compound cause difficulties for obtaining high-quality, high-frequency measurements. In this work, tunable infrared laser direct absorption spectroscopy (TILDAS) was demonstrated to be a superior optical method for sensitive, in situ detection of HCl at the 2925.89645 cm-1 absorption line using a 3 𝜇m interband cascade laser. The instrument has an effective path length of 204 m, 1 Hz precision of 7–8 pptv, and 3𝜎 limit of detection ranging from 21–24 pptv. For longer averaging times, the highest precision obtained was 0.5 pptv and 3𝜎 limit of detection of 1.6 pptv at 2.4 minutes. HCl TILDAS was also shown to have high accuracy when compared with a certified gas cylinder, yielding a linear slope within the expected 5 % tolerance of the reported cylinder concentration (slope = 0.964 ± 0.008). The use of heated inlet lines and active chemical passivation greatly improve the instrument response times to changes in HCl mixing ratios, with minimum 90 % response times ranging from 1.2–4.4 s, depending on inlet flow rate. However, these response times lengthened at relative humidities > 50 %, conditions under which HCl concentration standards were found to elicit a significantly lower response (-5.8 %). The addition of high concentrations of gas phase nitric acid (> 4.0 ppbv) were found to increase HCl signal (< 10 %), likely due to acid displacement with HCl or particulate chloride adsorbed to inlet surfaces. The equilibrium model ISORROPIA suggested a potential of particulate chloride partitioning into HCl gas within the heated inlet system if allowed to thermally equilibrate, but field results did not demonstrate a clear relationship between particulate chloride and HCl signal obtained with a denuder installed on the inlet.

Tropospheric ozone (O3) negatively impacts human health and is also a greenhouse gas. It is formed photochemically by reactions of nitrogen oxides (NOx) and volatile organic compounds (VOCs), of which wildfires are an important source. This study presents data from research flights sampling wildfires in West and Central African savannah regions, both close to the fires and after the emissions had been transported several days over the tropical North Atlantic Ocean. Emission factors (EFs) in g kg−1 for NOx (as NO), six VOCs and formaldehyde were calculated from enhancement to mole fractions in data taken close to the fires. For NOx, the emission factor was calculated as 2.05 ± 0.43 g kg−1 for Senegal and 1.20 ± 0.28 g kg−1 for Uganda, both higher than the average value of 1.13 ± 0.6 g kg−1 for previous studies of African savannah regions. For most VOCs (except acetylene), EFs in Uganda were lower by factors of 20–50% compared to Senegal, with almost all the values below those in the literature. O3 enhancement in the fire plumes was investigated by examining the ΔO3/ΔCO enhancement ratio, with values ranging from 0.07–0.14 close to the fires up to 0.25 for measurements taken over the Atlantic Ocean up to 200 hours downwind. In addition, measurements of O3 and its precursors were compared to the output of a global chemistry transport model (GEOS-CF) for the flights over the Atlantic Ocean. Normalised mean bias (NMB) comparison between the measured and modelled data was good outside of the fire plumes, with CO showing a model under-prediction of 4.6% and O3 a slight over-prediction of 0.7% (both within the standard deviation of the data). For NOx the agreement was poorer, with an under-prediction of 9.9% across all flights. Inside the fire plumes the agreement between modelled and measured values is worse, with the model being biased significantly lower for all three species. In total across all flights, there was an under-prediction of 29.4%, 16.5% and 37.5% for CO, O3 and NOx respectively. Finally, the measured ΔO3/ΔCO enhancement ratios were compared to those in the model for the equivalent flight data, with the model showing a lower value of 0.17 ± 0.03 compared to an observed value of 0.29 ± 0.05. The results detailed here show that the O3 burden to the North Atlantic Ocean from African wildfires may be underestimated and that further study is required to better study the O3 precursor emissions and chemistry.

Volatile organic compound (VOC) emissions from personal care products (PCPs) contribute to poor indoor air quality. Exposure to indoor VOCs is typically determined through ambient concentration measurements; however, for some PCPs the proximity of use to the nose and mouth may lead to disproportionately large inhaled doses. In this paper, we quantify emission factors for six common PCP ingredient VOCs (ethanol, 2-propanol, benzyl alcohol, 1,3-butanediol, t-butyl alcohol, and the grouping of monoterpenes as limonene) from 16 facial day-moisturizers using headspace analysis and selected ion flow-tube mass spectrometry. A wide range of emissions rates were observed across the range of products tested (e.g., ethanol 3.3-6.9 × 102 µg s-1 g[product]-1 , limonene 1.3 × 10-1 -4.1 × 10-1 µg s-1 g[product]-1 ). We use a mannequin head with reconstructed nose and mouth airways to sample VOCs from facial application at typical respiration volumes. A single facial application of moisturizer can lead to a much larger inhaled VOC dose than would be inhaled from typical indoor ambient air over 24 h (e.g., limonene up to ~×16 greater via facial application, ethanol up to ~×300). Emissions from facially applied PCPs typically decayed to background concentrations over periods ranging from 5 to 150 min.

Systematic measurements of atmospheric methane (CH4) mole fractions at the northern high latitudes only began in the early 1980s, and whilst CH4 measurements from Greenland ice cores covered the period before ~1900, no reliable observational record is available for the intermediate period. In this study, we reconstruct the atmospheric CH4 for that period, when the mole fraction started to increase rapidly. We use a set of trace gas data measured from firn (an intermediate stage between snow and glacial ice formation) air samples collected at the NGRIP (North Greenland Ice Core Project) site in 2001, in combination with a firn air transport model whose performance is validated by using a set of published firn air data at the NEEM (North Greenland Eemian ice Drilling) site. We examine a variety of possible firn diffusivity profiles using a suite of measured trace gases, and reconstruct the CH4 mole fraction by an iterative dating method. We find that, given the currently available firn air data sets from Greenland, reliable reconstruction of the Arctic CH4 mole fraction is possible only back to the mid 1970s. For the earlier period, it is difficult to identify the atmospheric CH4 history that consistently reproduce the depth profiles of CH4 in firn at both NGRIP and NEEM sites. Therefore, the currently proposed Arctic CH4 history should still be considered preliminary and uncertain, and should not be treated as the known history for constraining firn-air transport models.

Dichloromethane (CH2Cl2) and perchloroethylene (C2Cl4) are chlorinated very short lived substances (Cl-VSLS) with anthropogenic sources. Recent studies highlight the increasing influence of such compounds, particularly CH2Cl2, on the stratospheric chlorine budget and therefore on ozone depletion. Here, a multiyear global-scale synthesis inversion was performed to optimize CH2Cl2 (2006–2017) and C2Cl4 (2007–2017) emissions. The approach combines long-term surface observations from global monitoring networks, output from a three-dimensional chemical transport model (TOMCAT), and novel bottom-up information on prior industry emissions. Our posterior results show an increase in global CH2Cl2 emissions from 637 ± 36 Gg yr−1 in 2006 to 1,171 ± 45 Gg yr−1 in 2017, with Asian emissions accounting for 68% and 89% of these totals, respectively. In absolute terms, Asian CH2Cl2 emissions increased annually by 51 Gg yr−1 over the study period, while European and North American emissions declined, indicating a continental-scale shift in emission distribution since the mid-2000s. For C2Cl4, we estimate a decrease in global emissions from 141 ± 14 Gg yr−1 in 2007 to 106 ± 12 Gg yr−1 in 2017. The time-varying posterior emissions offer significant improvements over the prior. Utilizing the posterior emissions leads to modeled tropospheric CH2Cl2 and C2Cl4 abundances and trends in good agreement to those observed (including independent observations to the inversion). A shorter C2Cl4 lifetime, from including an uncertain Cl sink, leads to larger global C2Cl4 emissions by a factor of ~1.5, which in some places improves model-measurement agreement. The sensitivity of our findings to assumptions in the inversion procedure, including CH2Cl2 oceanic emissions, is discussed.

The effectiveness of transport of short-lived halocarbons to the upper troposphere and lower stratosphere remains an important uncertainty in quantifying the supply of ozone-depleting substances to the stratosphere. In early 2014, a major field campaign in Guam in the western Pacific, involving UK and US research aircraft, sampled the tropical troposphere and lower stratosphere. The resulting measurements of CH3I, CHBr3 and CH2Br2 are compared here with calculations from a Lagrangian model. This methodology benefits from an updated convection scheme that improves simulation of the effect of deep convective motions on particle distribution within the tropical troposphere. We find that the observed CH3I, CHBr3 and CH2Br2 mixing ratios in the tropical tropopause layer (TTL) are consistent with those in the boundary layer when the new convection scheme is used to account for convective transport. More specifically, comparisons between modelled estimates and observations of short-lived CH3I indicate that the updated convection scheme is realistic up to the lower TTL but is less good at reproducing the small number of extreme convective events in the upper TTL. This study consolidates our understanding of the transport of short-lived halocarbons to the upper troposphere and lower stratosphere by using improved model calculations to confirm consistency between observations in the boundary layer, observations in the TTL and atmospheric transport processes. Our results support recent estimates of the contribution of short-lived bromocarbons to the stratospheric bromine budget.

This study explores key features of bromine and iodine metabolism in the filamentous brown alga and genomics model Ectocarpus siliculosus. Both elements are accumulated in Ectocarpus, albeit at much lower concentration factors (2-3 orders of magnitude for iodine, and

Bromine chemistry, particularly in the tropics, has been suggested to play an important role in tropospheric ozone loss (Theys et al., 2011) although a lack of measurements of active bromine species impedes a quantitative understanding of its impacts. Recent modelling and measurements of bromine monoxide (BrO) by Wang et al. (2015) have shown current models under predict BrO concentrations over the Pacific Ocean and allude to a missing source of BrO. Here, we present the first simultaneous aircraft measurements of atmospheric bromine monoxide, BrO (a radical that along with atomic Br catalytically destroys ozone) and the inorganic Br precursor compounds HOBr, BrCl and Br2 over the Western Pacific Ocean from 0.5 to 7 km. The presence of 0.17-€“1.64 pptv BrO and 3.6-8 pptv total inorganic Br from these four species throughout the troposphere causes 10-20% of total ozone loss, and confirms the importance of bromine chemistry in the tropical troposphere; contributing to a 6 ppb decrease in ozone levels due to halogen chemistry. Observations are compared with a global chemical transport model and find that the observed high levels of BrO, BrCl and HOBr can be reconciled by active multiphase oxidation of halide (Br- and Cl-ˆ’) by HOBr and ozone in cloud droplets and aerosols. Measurements indicate that 99% of the instantaneous free Br in the troposphere up to 8 km originates from inorganic halogen photolysis rather than from photolysis of organobromine species.

The main field activities of the Coordinated Airborne Studies in the Tropics (CAST) campaign took place in the west Pacific during January–February 2014. The field campaign was based in Guam (13.5°N, 144.8°E), using the U.K. Facility for Airborne Atmospheric Measurements (FAAM) BAe-146 atmospheric research aircraft, and was coordinated with the Airborne Tropical Tropopause Experiment (ATTREX) project with an unmanned Global Hawk and the Convective Transport of Active Species in the Tropics (CONTRAST) campaign with a Gulfstream V aircraft. Together, the three aircraft were able to make detailed measurements of atmospheric structure and composition from the ocean surface to 20 km. These measurements are providing new information about the processes influencing halogen and ozone levels in the tropical west Pacific, as well as the importance of trace-gas transport in convection for the upper troposphere and stratosphere. The FAAM aircraft made a total of 25 flights in the region between 1°S and 14°N and 130° and 155°E. It was used to sample at altitudes below 8 km, with much of the time spent in the marine boundary layer. It measured a range of chemical species and sampled extensively within the region of main inflow into the strong west Pacific convection. The CAST team also made ground-based measurements of a number of species (including daily ozonesondes) at the Atmospheric Radiation Measurement Program site on Manus Island, Papua New Guinea (2.1°S, 147.4°E). This article presents an overview of the CAST project, focusing on the design and operation of the west Pacific experiment. It additionally discusses some new developments in CAST, including flights of new instruments on board the Global Hawk in February–March 2015.

We infer surface fluxes of bromoform (CHBr3) and dibromoform (CH2Br2) from aircraft observations over the western Pacific using a tagged version of the GEOS-Chem global 3-D atmospheric chemistry model and a maximum a posteriori inverse model. Using GEOS-Chem (GC) as an intermediary, we find that the distribution of a priori ocean emissions of these gases are reasonably consistent with observed atmospheric mole fractions of CHBr3 (r=0.62) and CH2Br2 (r=0.38). These a priori emissions result in a positive model bias in CHBr3 peaking in the marine boundary layer, but reproduce observed values of CH2Br2 with no significant bias by virtue of its longer atmospheric lifetime. Using GEOS-Chem, we find that observed variations in atmospheric CHBr3 are determined equally by sources over the western Pacific and those outside the study region, but observed variations in CH2Br2 are determined mainly by sources outside the western Pacific. Numerical closed-loop experiments show that the spatial and temporal distribution of boundary layer aircraft data have the potential to substantially improve current knowledge of these fluxes, with improvements related to data density. Using the aircraft data, we estimate aggregated regional fluxes of 3.6±0.3×108 and 0.7±0.1×108 g month−1 for CHBr3 and CH2Br2 over 130–155∘E and 0–12∘ N, respectively, which represent reductions of 20 %–40 % of the prior inventories by Ordóñez et al. (2012) and substantial spatial deviations from different a priori inventories. We find no evidence to support a robust linear relationship between CHBr3 and CH2Br2 oceanic emissions, as used by previous studies. We find that over regions with dense observation coverage, our choice of a priori inventory does not significantly impact our reported a posteriori flux estimates.

We provide new estimates of the air‐sea flux of CCl4 using simulations from a global ocean biogeochemistry model (NEMO‐PlankTOM) in combination with depth‐resolved CCl4 observations from global oceanic databases. Estimates of global oceanic CCl4 uptake are derived from a range of model analyses, including prescribed parameterizations using reported values on hydrolysis and degradation, and analyses optimized using the global observational databases. We evaluate the sensitivity of our results to uncertainties in air‐sea gas exchange parameterization, estimation period, and circulation processes. Our best constrained estimate of ocean CCl4 uptake for the period 1996–2000 is 20.1 Gg/year (range 16.6–22.7), corresponding to estimates of the partial atmospheric lifetime with respect to ocean uptake of 124 (110–150) years. This new oceanic lifetime implies higher emissions of CCl4 than currently estimated and therefore a larger missing atmospheric source of CCl4.

Ozonesondes reaching the tropical tropopause layer (TTL) over the west Pacific have occasionally measured layers of very low ozone concentrations - less than 15 ppbv - raising the question of how prevalent such layers are and how they are formed. In this paper, we examine aircraft measurements from the Airborne Tropical Tropopause Experiment (ATTREX), the Coordinated Airborne Studies in the Tropics (CAST) and the Convective Transport of Active Species in the Tropics (CONTRAST) experiment campaigns based in Guam in January-March 2014 for evidence of very low ozone concentrations and their relation to deep convection. The study builds on results from the ozonesonde campaign conducted from Manus Island, Papua New Guinea, as part of CAST, where ozone concentrations as low as 12 ppbv were observed between 100 and 150 hPa downwind of a deep convective complex. TTL measurements from the Global Hawk unmanned aircraft show a marked contrast between the hemispheres, with mean ozone concentrations in profiles in the Southern Hemisphere between 100 and 150 hPa of between 10.7 and 15.2 ppbv. By contrast, the mean ozone concentrations in profiles in the Northern Hemisphere were always above 15.4 ppbv and normally above 20 ppbv at these altitudes. The CAST and CONTRAST aircraft sampled the atmosphere between the surface and 120 hPa, finding very low ozone concentrations only between the surface and 700 hPa; mixing ratios as low as 7 ppbv were regularly measured in the boundary layer, whereas in the free troposphere above 200 hPa concentrations were generally well in excess of 15 ppbv. These results are consistent with uplift of almost-unmixed boundary-layer air to the TTL in deep convection. An interhemispheric difference was found in the TTL ozone concentrations, with values < 15 ppbv measured extensively in the Southern Hemisphere but seldom in the Northern Hemisphere. This is consistent with a similar contrast in the low-level ozone between the two hemispheres found by previous measurement campaigns. Further evidence of a boundary-layer origin for the uplifted air is provided by the anticorrelation between ozone and halogenated hydrocarbons of marine origin observed by the three aircraft.

The oceans are a key source of a number of atmospherically important volatile gases. The accurate and robust determination of trace gases in seawater is a significant analytical challenge, requiring reproducible and ideally automated sample handling, a high efficiency of seawater–air transfer, removal of water vapour from the sample stream, and high sensitivity and selectivity of the analysis. Here we describe a system that was developed for the fully automated analysis of dissolved very short-lived halogenated species (VSLS) sampled from an under-way seawater supply. The system can also be used for semi-automated batch sampling from Niskin bottles filled during CTD (conductivity, temperature, depth) profiles. The essential components comprise a bespoke, automated purge and trap (AutoP & T) unit coupled to a commercial thermal desorption and gas chromatograph mass spectrometer (TD-GC-MS). The AutoP & T system has completed five research cruises, from the tropics to the poles, and collected over 2500 oceanic samples to date. It is able to quantify >25 species over a boiling point range of 34–180 °C with Henry's law coefficients of 0.018 and greater (CH22l, kHcc dimensionless gas/aqueous) and has been used to measure organic sulfurs, hydrocarbons, halocarbons and terpenes. In the eastern tropical Pacific, the high sensitivity and sampling frequency provided new information regarding the distribution of VSLS, including novel measurements of a photolytically driven diurnal cycle of CH22l within the surface ocean water.

This study investigates the impact of halogens on atmospheric chemistry in the tropical troposphere and explores the sensitivity of this to uncertainties in the fluxes of halogens to the atmosphere and the chemical processing. To do this the regional chemistry transport model WRF-Chem has been extended, for the first time, to include halogen chemistry (bromine, chlorine and iodine chemistry), including heterogeneous recycling reactions involving sea-salt aerosol and other particles, reactions of Br with volatile organic compounds (VOCs), along with oceanic emissions of halocarbons, VOCs and inorganic iodine. The study focuses on the tropical East Pacific using field observations from the TORERO campaign (January–February 2012) to evaluate the model performance. Including all the new processes, the model does a reasonable job reproducing the observed mixing ratios of BrO and IO, albeit with some discrepancies, some of which can be attributed to difficulties in the model's ability to reproduce the observed halocarbons. This is somewhat expected given the large uncertainties in the air-sea fluxes of the halocarbons in a region where there are few observations of seawater concentrations. We see a considerable impact on the Bry partitioning when heterogeneous chemistry is included, with a greater proportion of the Bry in active forms such as BrO, HOBr and dihalogens. Including debromination of sea-salt increases BrO slightly throughout the free troposphere, but in the tropical marine boundary layer, where the sea-salt particles are plentiful and relatively acidic, debromination leads to overestimation of the observed BrO. However, it should be noted that the modelled BrO was extremely sensitive to the inclusion of reactions between Br and the VOCs, which convert Br to HBr, a far less reactive form of Bry. Excluding these reactions leads to modelled BrO mixing ratios greater than observed. The reactions between Br and aldehydes were found to be particularly important, despite the model underestimating the amount of aldehydes observed in the atmosphere. There are only small changes to Iy partitioning and IO when the heterogeneous reactions, primarly on sea-salt, are included. Our model results show that the tropospheric Ox loss due to halogens is 31 %. This loss is mostly due to I (16 %) and Br (14 %) and it is in good agreement with other estimates from state-of-the-art atmospheric chemistry models.

We report novel in situ speciated observations of monoterpenes (α- and β-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

Ocean emissions of inorganic and organic iodine compounds drive the biogeochemical cycle of iodine and produce reactive ozone-destroying iodine radicals that influence the oxidizing capacity of the atmosphere. Di-iodomethane (CHI) and chloro-iodomethane (CHICl) are the two most important organic iodine precursors in the marine boundary layer. Ship-borne measurements made during the TORERO (Tropical Ocean tRoposphere Exchange of Reactive halogens and Oxygenated VOC) field campaign in the east tropical Pacific Ocean in January/February 2012 revealed strong diurnal cycles of CHI and CHICl in air and of CHI in seawater. Both compounds are known to undergo rapid photolysis during the day, but models assume no night-time atmospheric losses. Surprisingly, the diurnal cycle of CHI was lower in amplitude than that of CHICl, despite its faster photolysis rate. We speculate that night-time loss of CHI occurs due to reaction with NO radicals. Indirect results from a laboratory study under ambient atmospheric boundary layer conditions indicate a k of ≤4 × 10 cm molecule s; a previous kinetic study carried out at ≤100 Torr found k of 4 × 10 cm molecule s. Using the 1-dimensional atmospheric THAMO model driven by sea-air fluxes calculated from the seawater and air measurements (averaging 1.8 +/− 0.8 nmol m d for CHI and 3.7 +/− 0.8 nmol m d for CHICl), we show that the model overestimates night-time CHI by >60 % but reaches good agreement with the measurements when the CHI + NO reaction is included at 2–4 × 10 cm molecule s. We conclude that the reaction has a significant effect on CHI and helps reconcile observed and modeled concentrations. We recommend further direct measurements of this reaction under atmospheric conditions, including of product branching ratios.

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Study Objective To measure the safety culture in the robotics surgery operating room before and after implementation of the Robotic Operating Room Computerized Checklist (RORCC). Design Prospective study. Subjects Gynecology surgical staff (n = 32). Setting An urban community hospital. Interventions The Safety Attitudes Questionnaire domains examined were teamwork, safety, job satisfaction, stress recognition, perceptions of management, and working conditions. Questions and domains were described using percent agreement and the Cronbach alpha. Paired t -tests were used to describe differences before and after implementation of the checklist. Measurements and Main Results Mean (SD) staff age was 46.7 (9.5) years, and most were women (78%) and worked full-time (97%). Twenty respondents (83% of nurses, 80% of surgeons, 66% of surgical technicians, and 33% of certified registered nurse anesthetists) completed the Safety Attitudes Questionnaire; 6 were excluded because of non-matching identifiers. Before RORCC implementation, the highest quality of communication and collaboration was reported by surgeons and surgical technicians (100%). Certified registered nurse anesthetists reported only adequate levels of communication and collaboration with other positions. Most staff reported positive responses for teamwork (48%; α = 0.81), safety (47%; α = 0.75), working conditions (37%; α = 0.55), stress recognition (26%; α = 0.71), and perceptions of management (32%; α = 0.52). No differences were observed after RORCC implementation. Conclusion Quality of communication and collaboration in the gynecology robotics operating room is high between most positions; however, safety attitude responses are low overall. No differences after RORCC implementation and low response rates may highlight lack of staff support.

We describe the design and execution of the BORTAS (Quantifying the impact of BOReal forest fires on Tropospheric oxidants using Aircraft and Satellites) experiment, which has the overarching objective of understanding the chemical aging of airmasses that contain the emission products from seasonal boreal wildfires and how these airmasses subsequently impact downwind atmospheric composition. The central focus of the experiment was a two-week deployment of the UK BAe-146-301 Atmospheric Research Aircraft (ARA) over eastern Canada. The planned July 2010 deployment of the ARA was postponed by 12 months because of activities related to the dispersal of material emitted by the Eyjafjallajökull volcano. However, most other planned model and measurement activities, including ground-based measurements at the Dalhousie University Ground Station (DGS), enhanced ozonesonde launches, and measurements at the Pico Atmospheric Observatory in the Azores, went ahead and constituted phase A of the experiment. Phase B of BORTAS in July 2011 included the same measurements, but included the ARA, special satellite observations and a more comprehensive measurement suite at the DGS. The high-frequency aircraft data provided a comprehensive snapshot of the pyrogenic plumes from wildfires. The coordinated ground-based and sonde data provided detailed but spatially-limited information that put the aircraft data into context of the longer burning season. We coordinated aircraft vertical profiles and overpasses of the NASA Tropospheric Emission Spectrometer and the Canadian Atmospheric Chemistry Experiment. These space-borne data, while less precise than other data, helped to relate the two-week measurement campaign to larger geographical and longer temporal scales. We interpret these data using a range of chemistry models: from a near-explicit gas-phase chemical mechanism, which tests out understanding of the underlying chemical mechanism, to regional and global 3-D models of atmospheric transport and lumped chemistry, which helps to assess the performance of the simplified chemical mechanism and effectively act as intermediaries between different measurement types. We also present an overview of some of the new science that has originated from this project from the mission planning and execution to the analysis of the ground-based, aircraft, and space-borne data.

[1] Atmospheric mixing ratios of C2H5I, CH2ClI, CH2Br2, and CHBr3 were quantified from whole air samples collected aboard the FAAM BAe 146-301 atmospheric research aircraft during flights over the tropical Atlantic Ocean (30°N to 10°S) as part of the Trade Wind Ozone Photochemistry Experiment (TROMPEX) in September 2009. Mixing ratios of C2H5I and CH2ClI increased with decreasing latitude, and concentrations of all measured halocarbons were elevated with increasing proximity to the oceanic upwelling along the coast of Mauritania. Vertical profiles highlighted the rapid photolytic degradation of these compounds within the tropical troposphere, with CH2ClI concentrations reduced by 50% at the top of the boundary layer. The spatial distributions of CH2ClI indicated an open ocean source.

Forests fires are a significant source of chemicals to the atmosphere including numerous non-methane organic compounds (NMOCs). We report airborne measurement of hydrocarbons, acetone and methanol from >500 whole air samples collected over Eastern Canada, including interceptions of several different boreal biomass burning plumes. From these and concurrent measurements of carbon monoxide (CO) we derive fire emission ratios for 29 different organic species relative to the emission of CO. These range from 8.9 ± 3.2 ppt ppb−1 CO for methanol to 0.007 ± 0.004 ppt ppb−1 CO for cyclopentane. The ratios are in good to excellent agreement with literature values. Using the GEOS-Chem global 3-D chemical transport model (CTM) we show the influence of biomass burning on the global distributions of benzene, toluene, ethene and propene (species which are controlled for air quality purposes and sometimes used as indicative tracers of anthropogenic activity). Using our observationally derived emission ratios and the GEOS-Chem CTM, we show that biomass burning can be the largest fractional contributor to observed benzene, toluene, ethene and propene levels in many global locations. The widespread biomass burning contribution to atmospheric benzene, a heavily regulated air pollutant, suggests that pragmatic approaches are needed when setting air quality targets as tailpipe and solvent emissions decline in developed countries. We subsequently determine the extent to which the 28 global-status World Meteorological Organisation – Global Atmosphere Watch stations worldwide are influenced by biomass burning sourced benzene, toluene, ethene and propene as compared to their exposure to anthropogenic emissions.

We describe the development of a compact comprehensive two-dimensional gas chromatograph suitable for the measurement of biogenic VOCs in the atmosphere at part per billion mixing ratios. The design seeks to minimise instrument size and power consumption and maximise portability and autonomy. The instrument concept is to achieve high analyte selectivity for complex VOC mixture analysis using comprehensive two-dimensional GC (GC×GC), rather than hyphenation with larger more expensive detectors such as MS. Key features of the analytical approach are a custom-built miniature thermal desorption trap to collect and concentrate VOCs from the sample gas stream, a copper conducting direct column heating system and a valve-modulated interface to enable GC×GC. The high power and large form-factor turbulent GC oven is replaced by direct column heating (and cooling below ambient) by thermal transfer from copper bobbin holders with heating and cooling input from Peltier devices. The combination of two independent copper bobbins allows for independent control of the two columns needed for comprehensive GC. A heated two position 1/16′′ diaphragm valve is used to enable flow modulation between two columns, with analyte detection at the outlet of the second column using a miniaturised low cost photo-ionisation detector. The instrument sub-components are controlled by a Compact RIO computer (National Instruments) and purpose designed software written in LabVIEW allowing autonomous measurements. The complete system weighs 15 kg, is around the size of a desktop computer and has a mean power demand of 112 W when battery powered. Results on the sensitivity and linearity for isoprene collection and analysis of standard gas mixtures are presented along with a discussion of limiting factors that hinder field device performance.

We present a comparison of aircraft measurements of halogenated very short-lived substances (VSLS) and dimethyl sulphide (DMS, C2H6S) from a co-ordinated campaign in Jan/Feb 2014 in the Tropical West Pacific. Measurements were made on the NASA Global Hawk, NCAR GV HIAPER and FAAM BAe146 using four separate GC-MS instruments operated by the University of Miami (UoM), the National Centre for Atmospheric Research (NCAR) and two from the University of York (UoY), respectively. The instruments were inter-calibrated during the campaign period using two gas standards on separate scales; a NOAA SX-3581 standard representative of clean low-hydrocarbon air, and an Essex canister prepared by UoM representative of coastal air, which was higher in VSLS and hydrocarbon content. UoY and NCAR use the NOAA scale/standard for VSLS calibration and UoM use a scale based on dilutions of primary standards calibrated by GC with FID and AED (atomic emission) detection. Analysis of the NOAA SX-3581 standard resulted in good agreement for CH2Cl2, CHCl3, CHBr3, CH2Br2, CH2BrCl, CHBrCl2, CHBr2Cl, CH3I CH2ICl and CH2I2 (average RSD

Ocean emissions of inorganic and organic iodine compounds drive the biogeochemical cycle of iodine and produce reactive ozone-destroying iodine radicals that influence the oxidizing capacity of the atmosphere. Di-iodomethane (CH2I2) and chloro-iodomethane (CH2ICl) are the two most important organic iodine precursors in the marine boundary layer. Ship-borne measurements made during the TORERO (Tropical Ocean tRoposphere Exchange of Reactive halogens and Oxygenated VOC) field campaign in the east tropical Pacific Ocean in January/February 2012 revealed strong diurnal cycles of CH2I2 and CH2ICl in air and of CH2I2 in seawater. Both compounds are known to undergo rapid photolysis during the day, but models assume no night-time atmospheric losses. Surprisingly, the diurnal cycle of CH2I2 was lower in amplitude than that of CH2ICl, despite its faster photolysis rate. We speculate that night-time loss of CH2I2 occurs due to reaction with NO3 radicals. Indirect results from a laboratory study under ambient atmospheric boundary layer conditions indicate a k CH2I2+NO3 of ≤4 × 10−13 cm3 molecule−1 s−1; a previous kinetic study carried out at ≤100 Torr found k CH2I2+NO3 of 4 × 10−13 cm3 molecule−1 s−1. Using the 1-dimensional atmospheric THAMO model driven by sea-air fluxes calculated from the seawater and air measurements (averaging 1.8 +/− 0.8 nmol m−2 d−1 for CH2I2 and 3.7 +/− 0.8 nmol m−2 d−1 for CH2ICl), we show that the model overestimates night-time CH2I2 by >60 % but reaches good agreement with the measurements when the CH2I2 + NO3 reaction is included at 2–4 × 10−13 cm3 molecule−1 s−1. We conclude that the reaction has a significant effect on CH2I2 and helps reconcile observed and modeled concentrations. We recommend further direct measurements of this reaction under atmospheric conditions, including of product branching ratios.

Objective. To compare the survival, morbidity, and cost of treating women with intermediate risk endometrial cancer with postoperative vaginal cuff brachytherapy versus observation followed by treatment for vaginal recurrence. Methods. A cost-effectiveness analysis was performed comparing two treatment strategies for intermediate risk endometrial cancer (Stage IC, IG3, II—tumors limited to the uterus with greater than 50% myometrial invasion or poor differentiation or cervical metastasis). All patients undergo hysterectomy, oophorectomy, and lymphadenectomy: strategy 1—postoperative vaginal cuff brachytherapy, strategy 2—observation. Strategy 2 patients who develop vaginal recurrence undergo diagnostic work-up followed by teletherapy and brachytherapy. All six principles of cost-effectiveness analysis were employed. Importantly, actual payer costs were evaluated, not charges. Results. Although the treatment for vaginal cuff recurrence is expensive, since only 8% of patients develop a vaginal recurrence, there was a 31% decreased cost by not treating patients with postoperative low-dose rate brachytherapy (strategy 2). Also, although the complication rate for teletherapy is greater than brachytherapy, since only 8% of patients develop a vaginal recurrence and require teletherapy, projected complication rates for the two strategies are similar. Survival would be decreased 3% by withholding postoperative brachytherapy (strategy 2). With postoperative high-dose rate brachytherapy (strategy 1), the cost per life saved would be $38764. Conclusion. Using a cost-effectiveness analysis, we have shown that withholding postoperative brachytherapy for patients with intermediate risk endometrial cancer results in a 31% decrease in cost, has a similar radiation complication rate, and results in a 3% decrease in survival.

Postoperative gastrointestinal care after major gynecologic surgery has evolved considerably over the last decade. According to evidence-based scientific medicine, the following conclusions can be drawn: (1) Postoperative colonic stasis occurs after major abdominal surgery and persists for approximately 3 days (classes I and IIA). (2) Elective postoperative nasogastric decompression after major abdominal surgery is unnecessary (class I). (3) Early feeding after major gynecologic surgery results in emesis but does not increase the incidence of aspiration pneumonia, dehiscence, or intestinal leaks and decreases hospital stay (class I). (4) Slow advancement of postoperative diet after major gynecologic surgery is probably unnecessary (class III). (5) After major abdominal gynecologic surgery, there appear to be minimal medical benefits (decreased infection rate) of early postoperative feeding (class III). (6) After radical hysterectomy, postoperative bowel stimulation decreases length of hospital stay (class IIA). (Am J Obstet Gynecol 2001;185:1-4.)

Objectives. Abstraction of data from National Cancer Data Base (NCDB)/Surveillance Epidemiology and End Results (SEER) for reasons other than incidence, mortality, and patterns of care has risen. A potential problem with these data is that insensitive-measure bias can exist because of possible inaccuracies in hospital tumor registry staging. The purpose of this study is to assess the accuracy of tumor registry staging from six community hospitals. Methods. Staging of 103 consecutive cancers operated on by a gynecologic oncologist (one of the authors) as a surgical consultant to a gynecologist or surgeon was reviewed. Hospital tumor registry staging forms were arbitrarily assigned to be completed by the nongynecologic oncologist versus the gynecologic oncologist by the medical records department. The authors reassessed cancer staging by medical chart review. The tumor registry staging was compared with the actual staging as determined by the authors. Major staging violations were defined as errors that would significantly change stage enough to alter prognosis or change recommended adjuvant treatment. All other violations were defined as minor. Results. Twenty-eight (27%) cancers were staged by the gynecologic oncologist and 75 (73%) by nongynecologic oncologists. Eighty (78%) cancers were endometrial and 14 (13%) ovarian. Eighty-three (81%) tumors were stage I or II. Major staging violations occurred in 0% of cancers staged by the gynecologic oncologist and 22% (16/75) by a nongynecologic oncologist ( P = 0.002). Minor staging violations occurred in 14% (4/28) of cancers staged by the gynecologic oncologist and 42% (32/75) by a nongynecologic oncologist ( P = 0.005). Minor violations were due to omission of histologic subtype and/or grade. Conclusion. The 22% major staging violation rate represents significant insensitive-measure bias. If additional studies produce similar results, abstraction of data from NCDB/SEER for reasons other than incidence, mortality, and patterns of care cannot be accepted as evidence-based scientific medicine.

The Mesoproterozoic Upper McNamara Group forms the uppermost division of the Lawn Hill platform in the western Mount Isa block. Several zinc and lead occurrences, including the Century deposit, are hosted by clastic and carbonate sediments within this interval. The Upper McNamara Group is subdivided into four formations: the Shady Bore Quartzite, Riversleigh Siltstone, Termite Range Formation, and Lawn Hill Formation.The Shady Bore Quartzite comprises up to 460 m of sandstone and dolomitic siltstone, deposited in a marginal to shallow subaqueous environment. The Riversleigh Siltstone is up to 2,900 m thick in the southern Lawn Hill region, where four members, R 1 to R 4 , are recognized. Member R 1 to R 3 sandstone, carbonate, and shale were mostly deposited in mid- and outer-shelf environments, indicating a regional transgression above the Shady Bore Quartzite. Sediment transport during the R 1 to R 3 interval was mostly from the south. Member R 4 shale and sandstone represent deeper subaqueous deposits. Riversleigh Siltstone sedimentation focused on a depocenter in the southern Lawn Hill region. All members display an abrupt decrease in thickness and facies changes to the north of the Termite Range and Barramundi faults, which are interpreted as active structures during deposition.The Termite Range Formation is up to 1,300 m thick and comprises two fining upward sequences, T 1 and T 2 , both dominated by sandstone in the lower part and by shale in the upper part. The Termite Range Formation is sandiest in the north and thins to the south and east. Sandstone beds are interpreted as high-concentration turbidites, deposited in a deep subaqueous environment. T 1 and T 2 are interpreted as two major episodes of turbidite fan sedimentation, sourced from the northwest. Fault activity to the west of the Lawn Hill region at about 1640 Ma is inferred to account for deposition of sandstone and the major shift in provenance from the south to the northwest.The Lawn Hill Formation is 2,200 m thick in the southern Lawn Hill region where six members, H 1 to H 6 , are recognized. Member H 1 shale and sandstone were deposited in outer shelf and deeper environments. Member H 2 and H 3 tuffaceous sediments were deposited in a mid-shelf environment, indicating a regional regression. Member H 1 to H 3 sediments were sourced from the west. Member H 4 shale and siltstone were deposited at outer shelf and greater depths, indicating a regional transgression above member H 3 . Member H 5 sandstone beds are interpreted as high-concentration turbidites, deposited in prograding turbidite fans. Member H 1 to H 3 sedimentation occurred throughout the Lawn Hill region, but a major depocenter was located in the northeast at this time. Member H 1 H 2 , and H 3 sediments rapidly thicken to the north of the Termite Range fault, which is interpreted as an active structure during deposition of this interval. The northward shift of the depocenter with respect to the Riversleigh Siltstone can be attributed to a reversal in movement along the Termite Range fault. Member H 5 sandstone beds are widespread throughout the northern Lawn Hill platform, and their deposition indicates another significant change in the distribution and style of sedimentation. Deposition in response to uplift in the south can be interpreted by the age of the sandstone (1595 Ma), which may coincide with the onset of the D 1 phase of the Isan orogeny.This study provides a framework for the identification of prospective areas for base metal mineralization within the Upper McNamara Group, based on a knowledge of sediment architectures and their controls.

Purpose of review As the number of gynecologic cancer survivors grows, there is an increased awareness and need for effective therapy for late side-effects caused by cancer treatments. Several treatment modalities are used to treat gynecologic malignancies, including surgery, radiotherapy, and chemotherapy. Each modality can be responsible for causing late-term side-effects. Recent findings There has been an increased awareness of the late detrimental side-effects of cancer treatment, mostly by the use of patient-generated surveys. Effective ways to treat and ameliorate the late side-effects have lagged behind the ability to describe and categorize these effects on patient's quality of life. Summary This review will highlight the recent studies to help the clinician caring for gynecologic cancer survivors in recognizing and treating the late effects of cancer therapy.

Boreal forest fires are a significant source of chemicals to the atmosphere including numerous non-methane hydrocarbons (NMHCs). We report airborne measurements of NMHCs, acetone and methanol from > 500 whole air samples collected over Eastern Canada, including interception of several different boreal biomass burning plumes. From these and concurrent measurements of carbon monoxide (CO) we derive fire emission ratios for 29 different species relative to the emission of CO. These range from 8.9 ± 3.2 ppt ppb−1 CO for methanol to 0.007 ± 0.004 ppt ppb−1 CO for cyclopentane. The ratios are in good to excellent agreement with recent literature values. Using the GEOS-Chem global 3-D chemical transport model (CTM) we show the influence of biomass burning on the global distributions of benzene, toluene, ethene and propene (species considered generally as indicative tracers of anthropogenic activity). Using our derived emission ratios and the GEOS-Chem CTM, we show that biomass burning can be the largest fractional contributor to observed benzene, toluene, ethene and propene in many global locations. The widespread biomass burning contribution to atmospheric benzene, a heavily regulated air pollutant, suggests that pragmatic approaches are needed when setting air quality targets as tailpipe and solvent emissions continue to decline. We subsequently determine the extent to which the 28 Global WMO-GAW stations worldwide are influenced by biomass burning sourced benzene, toluene, ethene and propene when compared to their exposure to anthropogenic emissions.

Very short-lived halocarbons (VSLH) such as CH3I, CH2Br2 and CHBr3 provide an important source of reactive halogens to the atmosphere, however high spatial and seasonal variability in their ambient mixing ratios and sea-air fluxes gives rise to considerable uncertainty in global scale emission estimates. One solution to improve global flux estimates is to combine the multitude of individually published datasets to produce a database of collated global halocarbon observations. Some progress towards this has already been achieved through the HalOcAt (Halocarbons in the Ocean and Atmosphere) database initiative, but the absence of a common calibration scale for very short-lived halocarbons makes it difficult to distinguish true environmental variations from artefacts arising from differences between calibration methodologies. As such, the lack of inter-calibrations for both air and seawater measurements of very short-lived halocarbons has been identified as a major limitation to current estimations of the global scale impact of these reactive trace gases. Here we present the key findings from the first national UK inter-laboratory comparison for calibrations of the halocarbons CH3I, CH2Br2 and CHBr3. The aim of this inter-calibration was to provide transparency between halocarbon calibrations from major UK research institutions, an important step towards enabling all measurements from these institutions to be treated as one coherent integrated dataset for global source term parameterisations.

Topotecan at a dose of 1.5 mg/m(2) on days 1 to 5 of a 21-day cycle is an approved therapy for recurrent ovarian cancer. However, heavily pretreated patients may be predisposed to hematologic adverse events. This prospective study, therefore, investigates the safety and efficacy of an alternate weekly schedule of topotecan in patients with recurrent ovarian or peritoneal cancer.Patients with potentially platinum-sensitive recurrent ovarian or peritoneal cancer were treated with 4.0 mg/m(2) weekly topotecan as tolerated until disease progression. Antitumor response and safety were assessed. Dose reductions, delays, or omissions were implemented for grades 3-4 adverse events.Of the 41 enrolled patients (median age, 62 years; range, 42 to 82 years), 39 patients had ovarian cancer, and 2 patients had peritoneal cancer. The median platinum-free interval was 11.7 months. A median of 9 topotecan cycles (range, 1 to 45 doses) was administered. Weekly topotecan was well tolerated: 7 (17%) patients had grades 3-4 neutropenia, and 9 (22%) had grades 3-4 fatigue. No grade 4 thrombocytopenia or anemia was reported. Of 38 response-evaluable patients, 1 (3%) had a complete response, 8 (21%) had a partial response, 16 (42%) had stable disease, and 13 (34%) had progressive disease.Weekly topotecan was well tolerated in patients with platinum-sensitive ovarian or peritoneal cancer at first relapse, with a hematologic profile that compared favorably with that of the 5-day topotecan regimen. Moreover, antitumor activity was similar to that reported for the 5-day regimen.