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Volatile organic compounds (VOCs) and particulate matter (PM) are major constituents of smog. Delhi experiences severe smog during the post-monsoon season, but a quantitative understanding of VOCs and PM sources is still lacking. Here, we conduct a source apportionment study for VOCs and PM using a recent (2022), high-quality dataset of 111 VOCs, PM2.5, and PM10 in a positive matrix factorization (PMF) model. Contrasts between clean monsoon air and polluted post-monsoon air, VOC source fingerprints, and molecular tracers enabled us to differentiate paddy residue burning from other biomass-burning sources, which had previously been impossible. Burning of fresh paddy residue, as well as residential heating and waste burning, contributed the most to observed PM10 levels (25 % and 23 %, respectively) and PM2.5 levels (23 % and 24 %, respectively), followed by heavy-duty vehicles fuelled by compressed natural gas (CNG), with a PM10 contribution of 15 % and a PM2.5 contribution of 11 %. For ambient VOCs, ozone formation potential, and secondary-organic-aerosol (SOA) formation potential, the top sources were petrol four-wheelers (20 %, 25 %, and 30 %, respectively), petrol two-wheelers (14 %, 12 %, and 20 %, respectively), industrial emissions (12 %, 14 %, and 15 %, respectively), solid-fuel-based cooking (10 %, 10 %, and 8 %, respectively), and road construction (8 %, 6 %, and 9 %, respectively). Emission inventories tended to overestimate residential biofuel emissions at least by a factor of 2 relative to the PMF output. The major source of PM pollution was regional biomass burning, while traffic and industries governed VOC emissions and secondary-pollutant formation. Our novel source apportionment method even quantitatively resolved similar biomass and fossil fuel sources, offering insights into both VOC and PM sources affecting extreme pollution events. This approach represents a notable advancement compared to current source apportionment approaches, and it could be of great relevance for future studies in other polluted cities and regions of the world with complex source mixtures.

Winter fog and severe aerosol loading in the boundary layer over northern India, particularly in the Indo-Gangetic Plain (IGP), disrupt the daily lives of millions of people in the region. To better understand the role of aerosol–radiation (AR) feedback on the occurrence, spatial extent, and persistence of winter fog, as well as the associated aqueous chemistry in fog in the IGP, several model simulations have been performed using the Weather Research and Forecasting model coupled with Chemistry (WRF-Chem). While WRF-Chem was able to represent the fog formation for the 23–24 December 2017 fog event over the central IGP in comparison to station and satellite observations, the model underestimated PM2.5 concentrations compared to the Central Pollution Control Board (CPCB) of India monitoring network. While evaluating aerosol composition for fog events in the IGP, we found that the WRF-Chem aerosol composition was quite different from measurements obtained during the Winter Fog Experiment (WiFEX) in Delhi, with secondary aerosols, particularly the chloride aerosol fraction, being strongly underpredicted (∼ 66.6 %). Missing emission sources (e.g., industry and residential burning of cow dung and trash) and aerosol and chemistry processes need to be investigated to improve model–observation agreement. By investigating a fog event on 23–24 December 2017 over the central IGP, we found that the aerosol–radiation feedback weakens turbulence, lowers the boundary layer height, and increases PM2.5 concentrations and relative humidity (RH) within the boundary layer. Factors affecting the feedback include loss of aerosols through deposition of cloud droplets and internal mixing of absorbing and scattering aerosols. Aqueous-phase chemistry increases the PM2.5 concentrations, which subsequently affect the aerosol–radiation feedback by both increased mass concentrations and aerosol sizes. With aerosol–radiation interaction and aqueous-phase chemistry, fog formation began 1–2 h earlier and caused a longer fog duration than when these processes were not included in the WRF-Chem simulation. The increase in RH in both experiments was found to be important for fog formation as it promoted the growth of aerosol size through water uptake, increasing the fog water content over the IGP. The results from this study suggest that the aerosol–radiation feedback and secondary aerosol formation play an important role in the air quality and the intensity and lifetime of fog over the IGP, yet other feedbacks, such as aerosol–cloud interactions, need to be quantified.

Devising effective national-level climate action plans requires a more detailed understanding of the regional distribution of sources and sinks of greenhouse gases. Due to insufficient observations and modelling capabilities, India's current carbon source–sink estimates are uncertain. This study uses a high-resolution Lagrangian transport model to examine the potential of available CO2 observations over India for inverse estimation of regional carbon fluxes. We use four different sites in India that vary in the measurement technique, frequency and spatial representation. These observations exhibit substantial seasonal (7.5 to 9.2 ppm) and intra-seasonal (2 to 12 ppm) variability. Our modelling framework, a high-resolution Weather Research and Forecasting Model combined with the Stochastic Time-Inverted Lagrangian Transport model (WRF–STILT), performs better in simulating seasonal (R2=0.50 to 0.96) and diurnal (R2=0.96) variability (for the Mohali station) of observed CO2 than the current-generation global models (CarboScope, CarbonTracker and ECMWF EGG4). The seasonal CO2 concentration variability in Mohali, associated with crop residue burning, is largely underestimated by the models. WRF–STILT captures the seasonal biospheric variability over Nainital better than the global models but underestimates the strength of the CO2 uptake by crops. The choice of emission inventory in the modelling framework alone leads to significant biases in simulations (5 to 10 ppm), endorsing the need for accounting for emission fluxes, especially for non-background sites. Our study highlights the possibility of using the CO2 observations from these Indian stations for deducing carbon flux information at regional (Nainital) and suburban to urban (Mohali, Shadnagar and Nagpur) scales with the help of a high-resolution model. On accounting for observed variability in CO2, the global carbon data assimilation system can benefit from the measurements from the Indian subcontinent.

The Winter Fog Experiment (WiFEX) was an intensive field campaign conducted at Indira Gandhi International Airport (IGIA) Delhi, India, in the Indo-Gangetic Plain (IGP) during the winter of 2017–2018. Here, we report the first comparison in South Asia of high-temporal-resolution simulation of ammonia (NH3) along with ammonium (NH4+) and total NHx (i.e., NH3+ NH4+) using the Weather Research and Forecasting model coupled with chemistry (WRF-Chem) and measurements made using the Monitor for AeRosols and Gases in Ambient Air (MARGA) at the WiFEX research site. In the present study, we incorporated the Model for Simulating Aerosol Interactions and Chemistry (MOSAIC) aerosol scheme into WRF-Chem. Despite simulated total NHx values and variability often agreeing well with the observations, the model frequently simulated higher NH3 and lower NH4+ concentrations than the observations. Under the winter conditions of high relative humidity (RH) in Delhi, hydrogen chloride (HCl) was found to promote the increase in the particle fraction of NH4+ (which accounted for 49.5 % of the resolved aerosol in equivalent units), with chloride (Cl−) (29.7 %) as the primary anion. By contrast, the absence of chloride (HCl / Cl−) chemistry in the standard WRF-Chem model results in the prediction of sulfate (SO42-) as the dominant inorganic aerosol anion. To understand the mismatch associated with the fraction of NHx in the particulate phase (NH4+ / NHx), we added HCl / Cl− to the model and evaluated the influence of its chemistry by conducting three sensitivity experiments using the model: no HCl, base case HCl (using a published waste burning inventory), and 3 × base HCl run. We found that 3 × base HCl increased the simulated average NH4+ by 13.1 µg m−3 and NHx by 9.8 µg m−3 concentration while reducing the average NH3 by 3.2 µg m−3, which is more in accord with the measurements. Thus HCl / Cl− chemistry in the model increases total NHx concentration, which was further demonstrated by reducing NH3 emissions by a factor of 3 (−3 × NH3_EMI) in the 3 × base HCl simulation. Reducing NH3 emissions in the 3 × base HCl simulation successfully addressed the discrepancy between measured and modeled total NHx. We conclude that modeling the fate of NH3 in Delhi requires a correct chemistry mechanism accounting for chloride dynamics with accurate inventories of both NH3 and HCl emissions.

We present the first global glyoxal (CHOCHO) tropospheric column product derived from the TROPOspheric Monitoring Instrument (TROPOMI) on board the Sentinel-5 Precursor satellite. Atmospheric glyoxal results from the oxidation of other non-methane volatile organic compounds (NMVOCs) and from direct emissions caused by combustion processes. Therefore, this product is a useful indicator of VOC emissions. It is generated with an improved version of the BIRA-IASB scientific retrieval algorithm relying on the differential optical absorption spectroscopy (DOAS) approach. Among the algorithmic updates, the DOAS fit now includes corrections to mitigate the impact of spectral misfits caused by scene brightness inhomogeneity and strong NO2 absorption. The product comes along with a full error characterization, which allows for providing random and systematic error estimates for every observation. Systematic errors are typically in the range of 1 ×1014–3 ×1014 molec. cm−2 (∼30 %–70 % in emission regimes) and originate mostly from a priori data uncertainties and spectral interferences with other absorbing species. The latter may be at the origin, at least partly, of an enhanced glyoxal signal over equatorial oceans, and further investigation is needed to mitigate them. Random errors are large (>6×1014 molec. cm−2) but can be reduced by averaging observations in space and/or time. Benefiting from a high signal-to-noise ratio and a large number of small-size observations, TROPOMI provides glyoxal tropospheric column fields with an unprecedented level of detail. Using the same retrieval algorithmic baseline, glyoxal column data sets are also generated from the Ozone Monitoring Instrument (OMI) on Aura and from the Global Ozone Monitoring Experiment-2 (GOME-2) on board Metop-A and Metop-B. Those four data sets are intercompared over large-scale regions worldwide and show a high level of consistency. The satellite glyoxal columns are also compared to glyoxal columns retrieved from ground-based Multi-AXis DOAS (MAX-DOAS) instruments at nine stations in Asia and Europe. In general, the satellite and MAX-DOAS instruments provide consistent glyoxal columns both in terms of absolute values and variability. Correlation coefficients between TROPOMI and MAX-DOAS glyoxal columns range between 0.61 and 0.87. The correlation is only poorer at one mid-latitude station, where satellite data appear to be biased low during wintertime. The mean absolute glyoxal columns from satellite and MAX-DOAS generally agree well for low/moderate columns with differences of less than 1×1014 molec. cm−2. A larger bias is identified at two sites where the MAX-DOAS columns are very large. Despite this systematic bias, the consistency of the satellite and MAX-DOAS glyoxal seasonal variability is high.

The TROPOspheric Monitoring Instrument (TROPOMI), launched in October 2017 on board the Sentinel-5 Precursor (S5P) satellite, monitors the composition of the Earth's atmosphere at an unprecedented horizontal resolution as fine as 3.5 × 5.5 km2. This paper assesses the performances of the TROPOMI formaldehyde (HCHO) operational product compared to its predecessor, the OMI (Ozone Monitoring Instrument) HCHO QA4ECV product, at different spatial and temporal scales. The parallel development of the two algorithms favoured the consistency of the products, which facilitates the production of long-term combined time series. The main difference between the two satellite products is related to the use of different cloud algorithms, leading to a positive bias of OMI compared to TROPOMI of up to 30 % in tropical regions. We show that after switching off the explicit correction for cloud effects, the two datasets come into an excellent agreement. For medium to large HCHO vertical columns (larger than 5 × 1015 molec. cm−2) the median bias between OMI and TROPOMI HCHO columns is not larger than 10 % (< 0.4 × 1015 molec. cm−2). For lower columns, OMI observations present a remaining positive bias of about 20 % (< 0.8 × 1015 molec. cm−2) compared to TROPOMI in midlatitude regions. Here, we also use a global network of 18 MAX-DOAS (multi-axis differential optical absorption spectroscopy) instruments to validate both satellite sensors for a large range of HCHO columns. This work complements the study by Vigouroux et al. (2020), where a global FTIR (Fourier transform infrared) network is used to validate the TROPOMI HCHO operational product. Consistent with the FTIR validation study, we find that for elevated HCHO columns, TROPOMI data are systematically low (−25 % for HCHO columns larger than 8 × 1015 molec. cm−2), while no significant bias is found for medium-range column values. We further show that OMI and TROPOMI data present equivalent biases for large HCHO levels. However, TROPOMI significantly improves the precision of the HCHO observations at short temporal scales and for low HCHO columns. We show that compared to OMI, the precision of the TROPOMI HCHO columns is improved by 25 % for individual pixels and by up to a factor of 3 when considering daily averages in 20 km radius circles. The validation precision obtained with daily TROPOMI observations is comparable to the one obtained with monthly OMI observations. To illustrate the improved performances of TROPOMI in capturing weak HCHO signals, we present clear detection of HCHO column enhancements related to shipping emissions in the Indian Ocean. This is achieved by averaging data over a much shorter period (3 months) than required with previous sensors (5 years) and opens new perspectives to study shipping emissions of VOCs (volatile organic compounds) and related atmospheric chemical interactions.

The comparative reactivity method (CRM) was developed more than a decade to measure OH reactivity (i.e., OH loss frequency) in both laboratory and field studies. However, accurate OH reactivity quantification remains challenging under real ambient conditions, especially for OH reactivity measurements in high-NOx (e.g., > 10 ppbv) environments, as ambient NO enhances the regeneration of OH radicals in the CRM reactor. To solve this problem, we design a new and improved CRM reactor (ICRM) and add NO into the system continuously so that the HO2 radical concentration is suppressed. We confirmed the appropriate level of NO by determining the maximum decrease in the pyrrole level caused by regenerated OH radicals from NO + HO2. RO2 radicals induced by volatile organic compounds (VOCs) in the ICRM reactor were also found to react with NO, which led to the regeneration of OH radicals and thus the underestimation of OH reactivity. This effect was quantified by the calibration of representative VOC species at different NO levels, and the correction coefficients obtained were used to correct the measured OH reactivity. All these efforts resulted in reducing the uncertainty of the NO-artifact correction by at least an order of magnitude compared to the original CRM system. Additionally, these technological improvements also considerably reduced the systematic errors from pyrrole photolysis in the original system. A new operation mode was proposed for the ICRM, which is able to avoid the interference resulting from OH radicals produced by photolysis of residual humidity and save time for ambient measurement. The ICRM system was employed in a field campaign to measure OH reactivity and performed well with ambient NO levels ranging from 0 to 50 ppbv, which are typically observed in the urban and suburban atmosphere.

We present comprehensive long-term ground-based multi-axis differential optical absorption spectroscopy (MAX-DOAS) measurements of aerosols, nitrogen dioxide (NO2), and formaldehyde (HCHO) from Mohali (30.667∘ N, 76.739∘ E; ∼310 m above mean sea level), located in the densely populated Indo-Gangetic Plain (IGP) of India. We investigate the temporal variation in tropospheric columns, surface volume mixing ratio (VMR), and vertical profiles of aerosols, NO2, and HCHO and identify factors driving their ambient levels and distributions for the period from January 2013 to June 2017. We observed mean aerosol optical depth (AOD) at 360 nm, tropospheric NO2 vertical column density (VCD), and tropospheric HCHO VCD for the measurement period to be 0.63 ± 0.51, (6.7 ± 4.1) × 1015, and (12.1 ± 7.5) × 1015 molecules cm−2, respectively. Concerning the tropospheric NO2 VCDs, Mohali was found to be less polluted than urban and suburban locations of China and western countries, but comparable HCHO VCDs were observed. For the more than 4 years of measurements during which the region around the measurement location underwent significant urban development, we did not observe obvious annual trends in AOD, NO2, and HCHO. High tropospheric NO2 VCDs were observed in periods with enhanced biomass and biofuel combustion (e.g. agricultural residue burning and domestic burning for heating). Highest tropospheric HCHO VCDs were observed in agricultural residue burning periods with favourable meteorological conditions for photochemical formation, which in previous studies have shown an implication for high ambient ozone also over the IGP. Highest AOD is observed in the monsoon season, indicating possible hygroscopic growth of the aerosol particles. Most of the NO2 is located close to the surface, whereas significant HCHO is present at higher altitudes up to 600 m during summer indicating active photochemistry at high altitudes. The vertical distribution of aerosol, NO2, and HCHO follows the change in boundary layer height (BLH), from the ERA5 dataset of European Centre for Medium-Range Weather Forecasts, between summer and winter. However, deep convection during the monsoon transports the pollutants at high altitudes similar to summer despite a shallow ERA5 BLH. Strong gradients in the vertical profiles of HCHO are observed during the months when primary anthropogenic sources dominate the formaldehyde production. High-resolution MODIS AOD measurements correlate well but were systematically higher than MAX-DOAS AODs. The ground-based MAX-DOAS measurements were used to evaluate three NO2 data products and two HCHO data products of the Ozone Monitoring Instrument (OMI) for the first time over India and the IGP. NO2 VCDs from OMI correlate reasonably with MAX-DOAS VCDs but are lower by ∼30 %–50 % due to the difference in vertical sensitivities and the rather large OMI footprint. OMI HCHO VCDs exceed the MAX-DOAS VCDs by up to 30 %. We show that there is significant scope for improvement in the a priori vertical profiles of trace gases, which are used in OMI retrievals. The difference in vertical representativeness was found to be crucial for the observed biases in NO2 and HCHO surface VMR intercomparisons. Using the ratio of NO2 and HCHO VCDs measured from MAX-DOAS, we have found that the peak daytime ozone production regime is sensitive to both NOx and VOCs in winter but strongly sensitive to NOx in other seasons.

In complex atmospheric emission environments such as urban agglomerates, multiple sources control the ambient chemical composition driving air quality and regional climate. In contrast to pristine sites, where reliance on single or a few chemical tracers is often adequate for resolving pollution plumes and source influences, the comprehensive chemical fingerprinting of sources using non-methane hydrocarbons (NMHCs) and the identification of suitable tracer molecules and emission ratios becomes necessary. Here, we characterise and present chemical fingerprints of some major urban and agricultural emission sources active in South Asia, such as paddy stubble burning, garbage burning, idling vehicular exhaust and evaporative fuel emissions. A total of 121 whole air samples were actively collected from the different emission sources in passivated air sampling steel canisters and then analysed for 49 NMHCs (22 alkanes, 16 aromatics, 10 alkenes and one alkyne) using thermal desorption gas chromatography flame ionisation detection. Several new insights were obtained. Propane was found to be present in paddy stubble fire emissions (8 %), and therefore, for an environment impacted by crop residue fires, the use of propane as a fugitive liquefied petroleum gas (LPG) emission tracer must be done with caution. Propene was found to be ∼ 1.6 times greater (by weight) than ethene in smouldering paddy fires. Compositional differences were observed between evaporative emissions of domestic LPG and commercial LPG, which are used in South Asia. While the domestic LPG vapours had more propane (40 ± 6 %) than n-butane (19 ± 2 %), the converse was true for commercial LPG vapours (7 ± 6 % and 37 ± 4 %, respectively). Isoprene was identified as a new tracer for distinguishing paddy stubble and garbage burning in the absence of isoprene emissions at night from biogenic sources. Analyses of source-specific inter-NMHC molar ratios revealed that toluene/benzene ratios can be used to distinguish among paddy stubble fire emissions in the flaming (0.38 ± 0.11) and smouldering stages (1.40 ± 0.10), garbage burning flaming (0.26 ± 0.07) and smouldering emissions (0.59 ± 0.16), and traffic emissions (3.54 ± 0.21), whereas i-pentane ∕ n-pentane can be used to distinguish biomass burning emissions (0.06–1.46) from the petrol-dominated traffic and fossil fuel emissions (2.83–4.13). i-butane ∕ n-butane ratios were similar (0.20–0.30) for many sources and could be used as a tracer for photochemical ageing. In agreement with previous studies, i-pentane, propane and acetylene were identified as suitable chemical tracers for petrol vehicular and evaporative emissions, LPG evaporative and vehicular emissions and flaming-stage biomass fires, respectively. The secondary pollutant formation potential and human health impact of the sources was also assessed in terms of their hydroxyl radical (OH) reactivity (s−1), ozone formation potential (OFP; gO3/gNMHC) and fractional benzene, toluene, ethylbenzene and xylenes (BTEX) content. Petrol vehicular emissions, paddy stubble fires and garbage fires were found to have a higher pollution potential (at ≥95 % confidence interval) relative to the other sources studied in this work. Thus, many results of this study provide a new foundational framework for quantitative source apportionment studies in complex emission environments.

In September 2016, 36 spectrometers from 24 institutes measured a number of key atmospheric pollutants for a period of 17 d during the Second Cabauw Intercomparison campaign for Nitrogen Dioxide measuring Instruments (CINDI-2) that took place at Cabauw, the Netherlands (51.97∘ N, 4.93∘ E). We report on the outcome of the formal semi-blind intercomparison exercise, which was held under the umbrella of the Network for the Detection of Atmospheric Composition Change (NDACC) and the European Space Agency (ESA). The three major goals of CINDI-2 were (1) to characterise and better understand the differences between a large number of multi-axis differential optical absorption spectroscopy (MAX-DOAS) and zenith-sky DOAS instruments and analysis methods, (2) to define a robust methodology for performance assessment of all participating instruments, and (3) to contribute to a harmonisation of the measurement settings and retrieval methods. This, in turn, creates the capability to produce consistent high-quality ground-based data sets, which are an essential requirement to generate reliable long-term measurement time series suitable for trend analysis and satellite data validation. The data products investigated during the semi-blind intercomparison are slant columns of nitrogen dioxide (NO2), the oxygen collision complex (O4) and ozone (O3) measured in the UV and visible wavelength region, formaldehyde (HCHO) in the UV spectral region, and NO2 in an additional (smaller) wavelength range in the visible region. The campaign design and implementation processes are discussed in detail including the measurement protocol, calibration procedures and slant column retrieval settings. Strong emphasis was put on the careful alignment and synchronisation of the measurement systems, resulting in a unique set of measurements made under highly comparable air mass conditions. The CINDI-2 data sets were investigated using a regression analysis of the slant columns measured by each instrument and for each of the target data products. The slope and intercept of the regression analysis respectively quantify the mean systematic bias and offset of the individual data sets against the selected reference (which is obtained from the median of either all data sets or a subset), and the rms error provides an estimate of the measurement noise or dispersion. These three criteria are examined and for each of the parameters and each of the data products, performance thresholds are set and applied to all the measurements. The approach presented here has been developed based on heritage from previous intercomparison exercises. It introduces a quantitative assessment of the consistency between all the participating instruments for the MAX-DOAS and zenith-sky DOAS techniques.

Biogenic volatile organic compounds exert a strong influence on regional air quality and climate through their roles in the chemical formation of ozone and fine-mode aerosol. Dimethyl sulfide (DMS), in particular, can also impact cloud formation and the radiative budget as it produces sulfate aerosols upon atmospheric oxidation. Recent studies have reported DMS emissions from terrestrial sources; however, their magnitudes have been too low to account for the observed ecosystem-scale DMS emission fluxes. Big-leaf mahogany (Swietenia macrophylla King) is an agroforestry and natural forest tree known for its high-quality timber and listed under the Convention on International Trade in Endangered Species (CITES). It is widely grown in the American and Asian environments (>2.4 million km2 collectively). Here, we investigated emissions of monoterpenes, isoprene and DMS as well as seasonal carbon assimilation from four big-leaf mahogany trees in their natural outdoor environment using a dynamic branch cuvette system, high-sensitivity proton transfer reaction mass spectrometer and cavity ring-down spectrometer. The emissions were characterized in terms of environmental response functions such as temperature, radiation and physiological growth phases including leaf area over the course of four seasons (summer, monsoon, post-monsoon, winter) in 2018–2019. We discovered remarkably high emissions of DMS (average in post-monsoon: ∼19 ng g−1 leaf dry weight h−1) relative to previous known tree DMS emissions, high monoterpenes (average in monsoon: ∼15 µg g−1 leaf dry weight h−1, which is comparable to oak trees) and low emissions of isoprene. Distinct linear relationships existed in the emissions of all three BVOCs with higher emissions during the reproductive phase (monsoon and post-monsoon seasons) and lower emissions in the vegetative phase (summer and winter seasons) for the same amount of cumulative assimilated carbon. Temperature and PAR dependency of the BVOC emissions enabled formulation of a new parameterization for use in global BVOC emission models. Using the measured seasonal emission fluxes, we provide the first estimates for the global emissions from mahogany trees which amount to circa 210–320 Gg yr−1 for monoterpenes, 370–550 Mg yr−1 for DMS and 1700–2600 Mg yr−1 for isoprene. Finally, through the results obtained in this study, we have been able to discover and identify mahogany as one of the missing natural sources of ambient DMS over the Amazon rainforest as well. These new emission findings, indication of seasonal patterns and estimates will be useful for initiating new studies to further improve the global BVOC terrestrial budget.

In this study we undertook quantitative source apportionment for 32 volatile organic compounds (VOCs) measured at a suburban site in the densely populated northwest Indo-Gangetic Plain using the US EPA PMF 5.0 model. Six sources were resolved by the PMF model. In descending order of their contribution to the total VOC burden these are “biofuel use and waste disposal” (23.2 %), “wheat-residue burning”(22.4 %), “cars” (16.2 %), “mixed daytime sources”(15.7 %) “industrial emissions and solvent use”(11.8 %), and “two-wheelers” (8.6 %). Wheat-residue burning is the largest contributor to the total ozone formation potential (32.4 %). For the emerging contaminant isocyanic acid, photochemical formation from precursors (37 %) and wheat-residue burning (25 %) were the largest contributors to human exposure. Wheat-residue burning was also the single largest source of the photochemical precursors of isocyanic acid, namely, formamide, acetamide and propanamide, indicating that this source must be most urgently targeted to reduce human concentration exposure to isocyanic acid in the month of May. Our results highlight that for accurate air quality forecasting and modeling it is essential that emissions are attributed only to the months in which the activity actually occurs. This is important for emissions from crop residue burning, which occur in May and from mid-October to the end of November. The SOA formation potential is dominated by cars (36.9 %) and two-wheelers (21.1 %), which also jointly account for 47% of the human class I carcinogen benzene in the PMF model. This stands in stark contrast to various emission inventories which estimate only a minor contribution of the transport sector to the benzene exposure (∼10 %) and consider residential biofuel use, agricultural residue burning and industry to be more important benzene sources. Overall it appears that none of the emission inventories represent the regional emissions in an ideal manner. Our PMF solution suggests that transport sector emissions may be underestimated by GAINSv5.0 and EDGARv4.3.2 and overestimated by REASv2.1, while the combined effect of residential biofuel use and waste disposal emissions as well as the VOC burden associated with solvent use and industrial sources may be overestimated by all emission inventories. The agricultural waste burning emissions of some of the detected compound groups (ketones, aldehydes and acids) appear to be missing in the EDGARv4.3.2 inventory.

Prior studies on martensitic steel microstructures have either delineated the prior austenite grain boundaries via chemical etching or reconstructed the prior austenite grains from crystallographic orientations measured with electron backscattered diffraction (EBSD). To appropriately validate the reconstruction algorithms, the EBSD data need to be collected on martensitic microstructures, where the prior austenite grain boundaries are delineated with techniques such as chemical etching that can serve as ground truth for comparison with the reconstructed prior austenite grains. In this article, the method of correlative microscopy is employed to collect scanning electron microscope (SEM) image and automated EBSD scan data from the same region of an appropriately etched steel specimen. The SEM images and automated EBSD scan data are presented for five different fields of view in the specimen. These datasets are analyzed and discussed in the accompanying article titled “Correlative microscopy for quantification of prior austenite grain size in AF9628 steel” [1]. Keywords: Martensitic steel, Chemical etching, Scanning electron microscopy, Electron backscatter diffraction (EBSD), Prior austenite grain boundary (PAGB)

Eleven of the world's 20 most polluted cities are located in India and poor air quality is already a major public health issue. However, anthropogenic emissions are predicted to increase substantially in the short-term (2030) and medium-term (2050) futures in India, especially if no further policy efforts are made. In this study, the EMEP/MSC-W chemical transport model has been used to predict changes in surface ozone (O3) and fine particulate matter (PM2.5) for India in a world of changing emissions and climate. The reference scenario (for present-day) is evaluated against surface-based measurements, mainly at urban stations. The evaluation has also been extended to other data sets which are publicly available on the web but without quality assurance. The evaluation shows high temporal correlation for O3 (r = 0.9) and high spatial correlation for PM2.5 (r = 0.5 and r = 0.8 depending on the data set) between the model results and observations. While the overall bias in PM2.5 is small (lower than 6 %), the model overestimates O3 by 35 %. The underestimation in NOx titration is probably the main reason for the O3 overestimation in the model. However, the level of agreement can be considered satisfactory in this case of a regional model being evaluated against mainly urban measurements, and given the inevitable uncertainties in much of the input data.For the 2050s, the model predicts that climate change will have distinct effects in India in terms of O3 pollution, with a region in the north characterized by a statistically significant increase by up to 4 % (2 ppb) and one in the south by a decrease up to −3 % (−1.4 ppb). This variation in O3 is assumed to be partly related to changes in O3 deposition velocity caused by changes in soil moisture and, over a few areas, partly also by changes in biogenic non-methane volatile organic compounds.Our calculations suggest that PM2.5 will increase by up to 6.5 % over the Indo-Gangetic Plain by the 2050s. The increase over India is driven by increases in dust, particulate organic matter (OM) and secondary inorganic aerosols (SIAs), which are mainly affected by the change in precipitation, biogenic emissions and wind speed.The large increase in anthropogenic emissions has a larger impact than climate change, causing O3 and PM2.5 levels to increase by 13 and 67 % on average in the 2050s over the main part of India, respectively. By the 2030s, secondary inorganic aerosol is predicted to become the second largest contributor to PM2.5 in India, and the largest in the 2050s, exceeding OM and dust.

A positive matrix factorization model (US EPA PMF version 5.0) was applied for the source apportionment of the dataset of 37 non-methane volatile organic compounds (NMVOCs) measured from 19 December 2012 to 30 January 2013 during the SusKat-ABC international air pollution measurement campaign using a proton-transfer-reaction time-of-flight mass spectrometer in the Kathmandu Valley. In all, eight source categories were identified with the PMF model using the new constrained model operation mode. Unresolved industrial emissions and traffic source factors were the major contributors to the total measured NMVOC mass loading (17.9 and 16.8 %, respectively) followed by mixed industrial emissions (14.0 %), while the remainder of the source was split approximately evenly between residential biofuel use and waste disposal (10.9 %), solvent evaporation (10.8 %), biomass co-fired brick kilns (10.4 %), biogenic emissions (10.0 %) and mixed daytime factor (9.2 %). Conditional probability function (CPF) analyses were performed to identify the physical locations associated with different sources. Source contributions to individual NMVOCs showed that biomass co-fired brick kilns significantly contribute to the elevated concentrations of several health relevant NMVOCs such as benzene. Despite the highly polluted conditions, biogenic emissions had the largest contribution (24.2 %) to the total daytime ozone production potential, even in winter, followed by solvent evaporation (20.2 %), traffic (15.0 %) and unresolved industrial emissions (14.3 %). Secondary organic aerosol (SOA) production had approximately equal contributions from biomass co-fired brick kilns (28.9 %) and traffic (28.2 %). Comparison of PMF results based on the in situ data versus REAS v2.1 and EDGAR v4.2 emission inventories showed that both the inventories underestimate the contribution of traffic and do not take the contribution of brick kilns into account. In addition, the REAS inventory overestimates the contribution of residential biofuel use and underestimates the contribution of solvent use and industrial sources in the Kathmandu Valley. The quantitative source apportionment of major NMVOC sources in the Kathmandu Valley based on this study will aid in improving hitherto largely un-validated bottom-up NMVOC emission inventories, enabling more focused mitigation measures and improved parameterizations in chemical transport models.

We analysed the extensive dataset from the HUMPPA-COPEC 2010 and the HOPE 2012 field campaigns in the boreal forest and rural environments of Finland and Germany, respectively, and estimated the abundance of stabilised Criegee intermediates (SCIs) in the lower troposphere. Based on laboratory tests, we propose that the background OH signal observed in our IPI-LIF-FAGE instrument during the aforementioned campaigns is caused at least partially by SCIs. This hypothesis is based on observed correlations with temperature and with concentrations of unsaturated volatile organic compounds and ozone. Just like SCIs, the background OH concentration can be removed through the addition of sulfur dioxide. SCIs also add to the previously underestimated production rate of sulfuric acid. An average estimate of the SCI concentration of ∼ 5.0 × 104 molecules cm−3 (with an order of magnitude uncertainty) is calculated for the two environments. This implies a very low ambient concentration of SCIs, though, over the boreal forest, significant for the conversion of SO2 into H2SO4. The large uncertainties in these calculations, owing to the many unknowns in the chemistry of Criegee intermediates, emphasise the need to better understand these processes and their potential effect on the self-cleaning capacity of the atmosphere.

Uttarakhand being a mountainous state having maximum area under forest cover, about 65% and provides large amount of freshwater river for Ganga basin where habitation and agriculture are dominant. The rising demand of drinking water due to population growth also leads to the water scarcity in the terms of availability of quality drinking water. Contamination mentioned by Central Pollution Control Board (CPCB), 2009 and low per capita availability of quality drinking water reported by Department of Science and Technology (Government of India), 2010-2015, are the key issues of the state. To understand the availability of safe drinking water it is necessary to understand the overall hydrology of the basin in a spatial domain. The utilization of advance tools and techniques such as spatial models, geo statistical tools, high resolution remote sensing data and numerical hydrological model in the present study will enhance and ensure the water quality issue of Himalayan state of Uttarakhand which is expected to serve the society living along the river basin as well as in mountainous systems. The study will ensure the availability of sufficient quality drinking water to the communities in the selected watershed of each districts, considering the environmental aspects and human health while assessing 26 water quality parameters like color, odour,taste, turbidity, pH, total hardness, iron, chloride, chlorine, fluoride, total dissolved solids, calcium, magnesium, copper ,manganese, sulphate, nitrate, phenolic compound, arsenic, cadmium, lead, zinc, chromium, alkalinity and coliform bacteria etc. and also provide feasible solution of sustainable availability of water. Geospatial water quality and quantity model help to find out the spatio-temporal analysis of contamination and particles movement in the watersheds. Modern geo statistical simulation algorithms can produce multiple subsurface realizations that are in agreement with the conceptual geological models. The quality modeling and monitoring will help in providing portable surface and ground waters to the citizens.

The Kathmandu Valley in Nepal suffers from severe wintertime air pollution. Volatile organic compounds (VOCs) are key constituents of air pollution, though their specific role in the valley is poorly understood due to insufficient data. During the SusKat-ABC (Sustainable Atmosphere for the Kathmandu Valley–Atmospheric Brown Clouds) field campaign conducted in Nepal in the winter of 2012–2013, a comprehensive study was carried out to characterise the chemical composition of ambient Kathmandu air, including the determination of speciated VOCs, by deploying a proton transfer reaction time-of-flight mass spectrometer (PTR-TOF-MS) – the first such deployment in South Asia. In the study, 71 ion peaks (for which measured ambient concentrations exceeded the 2σ detection limit) were detected in the PTR-TOF-MS mass scan data, highlighting the chemical complexity of ambient air in the valley. Of the 71 species, 37 were found to have campaign average concentrations greater than 200 ppt and were identified based on their spectral characteristics, ambient diel profiles and correlation with specific emission tracers as a result of the high mass resolution (m ∕ Δm > 4200) and temporal resolution (1 min) of the PTR-TOF-MS. The concentration ranking in the average VOC mixing ratios during our wintertime deployment was acetaldehyde (8.8 ppb) > methanol (7.4 ppb) > acetone + propanal (4.2 ppb) > benzene (2.7 ppb) > toluene (1.5 ppb) > isoprene (1.1 ppb) > acetonitrile (1.1 ppb) > C8-aromatics ( ∼ 1 ppb) > furan ( ∼ 0.5 ppb) > C9-aromatics (0.4 ppb). Distinct diel profiles were observed for the nominal isobaric compounds isoprene (m ∕ z = 69.070) and furan (m ∕ z = 69.033). Comparison with wintertime measurements from several locations elsewhere in the world showed mixing ratios of acetaldehyde ( ∼ 9 ppb), acetonitrile ( ∼ 1 ppb) and isoprene ( ∼ 1 ppb) to be among the highest reported to date. Two "new" ambient compounds, namely formamide (m ∕ z = 46.029) and acetamide (m ∕ z = 60.051), which can photochemically produce isocyanic acid in the atmosphere, are reported in this study along with nitromethane (a tracer for diesel exhaust), which has only recently been detected in ambient studies. Two distinct periods were selected during the campaign for detailed analysis: the first was associated with high wintertime emissions of biogenic isoprene and the second with elevated levels of ambient acetonitrile, benzene and isocyanic acid from biomass burning activities. Emissions from biomass burning and biomass co-fired brick kilns were found to be the dominant sources for compounds such as propyne, propene, benzene and propanenitrile, which correlated strongly with acetonitrile (r2 > 0.7), a chemical tracer for biomass burning. The calculated total VOC OH reactivity was dominated by acetaldehyde (24.0 %), isoprene (20.2 %) and propene (18.7 %), while oxygenated VOCs and isoprene collectively contributed to more than 68 % of the total ozone production potential. Based on known secondary organic aerosol (SOA) yields and measured ambient concentrations in the Kathmandu Valley, the relative SOA production potential of VOCs were benzene > naphthalene > toluene > xylenes > monoterpenes > trimethylbenzenes > styrene > isoprene. The first ambient measurements from any site in South Asia of compounds with significant health effects such as isocyanic acid, formamide, acetamide, naphthalene and nitromethane have been reported in this study. Our results suggest that mitigation of intense wintertime biomass burning activities, in particular point sources such biomass co-fired brick kilns, would be important to reduce the emission and formation of toxic VOCs (such as benzene and isocyanic acid) in the Kathmandu Valley.

The investigation of hydroxyl radical (OH) chemistry during intensive field campaigns has led to the development of several techniques dedicated to ambient measurements of total OH reactivity, which is the inverse of the OH lifetime. Three techniques are currently used during field campaigns, including the total OH loss rate method, the pump–probe method, and the comparative reactivity method. However, no formal intercomparison of these techniques has been published so far, and there is a need to ensure that measurements of total OH reactivity are consistent among the different techniques. An intercomparison of two OH reactivity instruments, one based on the comparative reactivity method (CRM) and the other based on the pump–probe method, was performed in October 2012 in a NOx-rich environment, which is known to be challenging for the CRM technique. This study presents an extensive description of the two instruments, the CRM instrument from Mines Douai (MD-CRM) and the pump–probe instrument from the University of Lille (UL-FAGE), and highlights instrumental issues associated with the two techniques. It was found that the CRM instrument used in this study underestimates ambient OH reactivity by approximately 20 % due to the photolysis of volatile organic compounds (VOCs) inside the sampling reactor; this value is dependent on the position of the lamp within the reactor. However, this issue can easily be fixed, and the photolysis of VOCs was successfully reduced to a negligible level after this intercomparison campaign. The UL-FAGE instrument may also underestimate ambient OH reactivity due to the difficulty to accurately measure the instrumental zero. It was found that the measurements are likely biased by approximately 2 s-1, due to impurities in humid zero air. Two weeks of ambient sampling indicate that the measurements performed by the two OH reactivity instruments are in agreement, within the measurement uncertainties for each instrument, for NOx mixing ratios up to 100 ppbv. The CRM technique has hitherto mainly been used in low-NOx environments, i.e. environments with ambient NOx mixing ratios lower than a few ppbv, due to a measurement artifact generated by ambient NO inside the sampling reactor. However, this study shows that this technique can also be used under NOx-rich conditions if a NOx-dependent correction is carefully applied on the OH reactivity measurements. A full suite of 52 VOCs, NOx, and other inorganic species were monitored during this intercomparison. An investigation of the OH reactivity budget for this urban site suggests that this suite of trace gases can account for the measured total OH reactivity.

The hydroxyl radical (OH) plays a key role in the atmosphere, as it initiates most of the oxidation processes of volatile organic compounds (VOCs), and can ultimately lead to the formation of ozone and secondary organic aerosols (SOAs). There are still uncertainties associated with the OH budget assessed using current models of atmospheric chemistry and direct measurements of OH sources and sinks have proved to be valuable tools to improve our understanding of the OH chemistry. The total first order loss rate of OH, or total OH reactivity, can be directly measured using three different methods, such as the following: total OH loss rate measurement, laser-induced pump and probe technique and comparative reactivity method. Observations of total OH reactivity are usually coupled to individual measurements of reactive compounds in the gas phase, which are used to calculate the OH reactivity. Studies using the three methods have highlighted that a significant fraction of OH reactivity is often not explained by individually measured reactive compounds and could be associated to unmeasured or unknown chemical species. Therefore accurate and reproducible measurements of OH reactivity are required. The comparative reactivity method (CRM) has demonstrated to be an advantageous technique with an extensive range of applications, and for this reason it has been adopted by several research groups since its development. However, this method also requires careful corrections to derive ambient OH reactivity. Herein we present an intercomparison exercise of two CRM instruments, CRM-LSCE (Laboratoire des Sciences du Climat et de l'Environnement) and CRM-MD (Mines Douai), conducted during July 2013 at the Mediterranean site of Ersa, Cape Corsica, France. The intercomparison exercise included tests to assess the corrections needed by the two instruments to process the raw data sets as well as OH reactivity observations. The observation was divided in three parts: 2 days of plant emissions (8–9 July), 2 days of ambient measurements (10–11 July) and 2 days (12–13 July) of plant emissions. We discuss in detail the experimental approach adopted and how the data sets were processed for both instruments. Corrections required for the two instruments lead to higher values of reactivity in ambient air; overall 20 % increase for CRM-MD and 49 % for CRM-LSCE compared to the raw data. We show that ambient OH reactivity measured by the two instruments agrees very well (correlation described by a linear least squares fit with a slope of 1 and R2 of 0.75). This study highlights that ambient measurements of OH reactivity with differently configured CRM instruments yield consistent results in a low NOx (NO + NO2), terpene rich environment, despite differential corrections relevant to each instrument. Conducting more intercomparison exercises, involving more CRM instruments operated under different ambient and instrumental settings will help in assessing the variability induced due to instrument-specific corrections further.

In this study we use a high-quality data set of in situ ozone measurements at a suburban site called Mohali in the state of Punjab to estimate ozone-related crop yield losses for wheat, rice, cotton and maize for Punjab and the neighbouring state Haryana for the years 2011–2013. We intercompare crop yield loss estimates according to different exposure metrics, such as AOT40 (accumulated ozone exposure over a threshold of 40) and M7 (mean 7-hour ozone mixing ratio from 09:00 to 15:59), for the two major crop growing seasons of kharif (June–October) and rabi (November–April) and establish a new crop-yield–exposure relationship for southern Asian wheat, maize and rice cultivars. These are a factor of 2 more sensitive to ozone-induced crop yield losses compared to their European and American counterparts. Relative yield losses based on the AOT40 metrics ranged from 27 to 41 % for wheat, 21 to 26 % for rice, 3 to 5 % for maize and 47 to 58 % for cotton. Crop production losses for wheat amounted to 20.8 ± 10.4 million t in the fiscal year of 2012–2013 and 10.3 ± 4.7 million t in the fiscal year of 2013–2014 for Punjab and Haryana taken together. Crop production losses for rice totalled 5.4 ± 1.2 million t in the fiscal year of 2012–2013 and 3.2 ± 0.8 million t in the year 2013–2014 for Punjab and Haryana taken together. The Indian National Food Security Ordinance entitles ~ 820 million of India's poor to purchase about 60 kg of rice or wheat per person annually at subsidized rates. The scheme requires 27.6 Mt of wheat and 33.6 Mt of rice per year. The mitigation of ozone-related crop production losses in Punjab and Haryana alone could provide > 50 % of the wheat and ~ 10 % of the rice required for the scheme. The total economic cost losses in Punjab and Haryana amounted to USD 6.5 ± 2.2 billion in the fiscal year of 2012–2013 and USD 3.7 ± 1.2 billion in the fiscal year of 2013–2014. This economic loss estimate represents a very conservative lower limit based on the minimum support price of the crop, which is lower than the actual production costs. The upper limit for ozone-related crop yield losses in all of India currently amounts to 3.5–20 % of India's GDP. The mitigation of high surface ozone would require relatively little investment in comparison to the economic losses incurred presently. Therefore, ozone mitigation can yield massive benefits in terms of ensuring food security and boosting the economy. The co-benefits of ozone mitigation also include a decrease in the ozone-related mortality and morbidity and a reduction of the ozone-induced warming in the lower troposphere.

Measurements of OH and HO2 radicals were conducted in a pine-dominated forest in southern Finland during the HUMPPA-COPEC-2010 (Hyytiälä United Measurements of Photochemistry and Particles in Air – Comprehensive Organic Precursor Emission and Concentration study) field campaign in summer 2010. Simultaneous side-by-side measurements of hydroxyl radicals were conducted with two instruments using chemical ionization mass spectrometry (CIMS) and laser-induced fluorescence (LIF), indicating small systematic disagreement, OHLIF / OHCIMS = (1.31 ± 0.14). Subsequently, the LIF instrument was moved to the top of a 20 m tower, just above the canopy, to investigate the radical chemistry at the ecosystem–atmosphere interface. Comprehensive measurements including observations of many volatile organic compounds (VOCs) and the total OH reactivity were conducted and analysed using steady-state calculations as well as an observationally constrained box model. Production rates of OH calculated from measured OH precursors are consistent with those derived from the steady-state assumption and measured total OH loss under conditions of moderate OH reactivity. The primary photolytic sources of OH contribute up to one-third to the total OH production. OH recycling, which occurs mainly by HO2 reacting with NO and O3, dominates the total hydroxyl radical production in this boreal forest. Box model simulations agree with measurements for hydroxyl radicals (OHmod. / OHobs. = 1.00 ± 0.16), while HO2 mixing ratios are significantly under-predicted (HO2mod. / HO2obs. = 0.3 ± 0.2), and simulated OH reactivity does not match the observed OH reactivity. The simultaneous under-prediction of HO2 and OH reactivity in periods in which OH concentrations were simulated realistically suggests that the missing OH reactivity is an unaccounted-for source of HO2. Detailed analysis of the HOx production, loss, and recycling pathways suggests that in periods of high total OH reactivity there are additional recycling processes forming OH directly, not via reaction of HO2 with NO or O3, or unaccounted-for primary HOx sources. Under conditions of moderate observed OH reactivity and high actinic flux, an additional RO2 source of approximately 1 × 106 molec cm−3 s−1 would be required to close the radical budget. Nevertheless, a major fraction of the OH recycling occurs via the reaction of HO2 with NO and O3 in this terpene-dominated environment.

One seventh of the world's population lives in the Indo-Gangetic Plain (IGP) and the fertile region sustains agricultural food crop production for much of South Asia, yet it remains one of the most under-studied regions of the world in terms of atmospheric composition and chemistry. In particular, the emissions and chemistry of volatile organic compounds (VOCs) that form surface ozone and secondary organic aerosol through photochemical reactions involving nitrogen oxides are not well understood. In this study, ambient levels of VOCs such as methanol, acetone, acetaldehyde, acetonitrile and isoprene were measured for the first time in the IGP. A new atmospheric chemistry facility that combines India's first high-sensitivity proton transfer reaction mass spectrometer, an ambient air quality station and a meteorological station, was used to quantify in situ levels of several VOCs and air pollutants in May 2012 at a suburban site in Mohali (northwest IGP). Westerly winds arriving at high wind speeds (5–20 m s−1) in the pre-monsoon season at the site were conducive for chemical characterization of regional emission signatures. Average levels of VOCs and air pollutants in May~2012 ranged from 1.2 to 2.7 nmol mol−1 for aromatic VOCs, 5.9 to 37.5 nmol mol−1 for the oxygenated VOCs, 1.4 nmol mol−1 for acetonitrile, 1.9 nmol mol−1 for isoprene, 567 nmol mol−1 for carbon monoxide, 57.8 nmol mol−1 for ozone, 11.5 nmol mol−1 for nitrogen oxides, 7.3 nmol mol−1 for sulfur dioxide, 104 μg m−3 for PM2.5 and 276 μg m−3 for PM10. By analyzing the one-minute in situ data with meteorological parameters and applying chemical tracers (e.g., acetonitrile for biomass burning) and inter-VOC correlations, we were able to constrain major emission source activities on both temporal and diel scales. Wheat residue burning caused massive increases (> 3 times the baseline values) for all the measured VOCs and primary pollutants. Other forms of biomass burning at night were also a significant source of oxygenated VOCs and isoprene (r2 with acetonitrile &geq;0.5 for nighttime data), which is remarkable in terms of atmospheric chemistry implications. Surface ozone exceeded the 8 h national ambient air quality limit of 100 μg O3 m−3 (~50 ppbv) on a daily basis, except for 17 May 2012, when a severe dust storm event (PM2.5 > 800 μg m−3; PM10 > 2700 μg m−3) characterized by long-range transport from the west impacted the site. The novel data set and results point to the occurrence of high primary emissions of reactive VOCs. They also highlight the urgent need for establishing more comprehensive observational facilities in the IGP to constrain the spatial and seasonal variability of atmospheric chemical constituents. Such efforts will enable a mechanistic-level understanding of the in situ chemical processes controlling the formation of surface ozone, a necessary step for effective ozone mitigation and improvement of the regional air quality.

The DOMINO (Diel Oxidant Mechanisms in relation to Nitrogen Oxides) campaign was carried out from 21 November to 8 December 2008 at the El Arenosillo station (SW of Spain) in a coastal-rural environment. The main weather conditions are analysed using local meteorological variables, meteorological soundings and synoptic maps, as well as back trajectories of the air masses using the HYSPLIT (Hybrid Single-Particle Lagrangian Integrated Trajectory Model) model and a high spatial resolution of meteorological fields. Measurements of the main meteorological parameters were collected both from the surface and from a tall tower. A detailed land use analysis was performed on a 80 km scale showing the main types of vegetation and land use. Also the main anthropogenic atmospheric emission sources – both industrial-urban from Huelva and from the urban Seville area – are shown. A study to identify air mass origins and their variation with height was carried out. In this intensive campaign, air masses coming from different areas with different emission sources were observed: from the NW, with a highly industrial-urban character; continental flows from northerly directions; from the NE, with a pathway starting over the Seville metropolitan area and then continuing over the Doñana National Park; and maritime air masses coming from the Atlantic Ocean. To study the chemistry in the four atmospheric scenarios identified, gas -phase measurements of primary and secondary species such as ozone, NO, NO2 and SO2, biogenic and anthropogenic VOCs (volatile organic compounds) like benzene and isoprene, as well as total particle concentration and chemical composition of the aerosols are compared and discussed. The highest levels for total particle concentration, NO, NO2, SO2, benzene, PM10, PM2.5 and chemical elements such as As or Cu were found under flows associated with industrial-urban emissions from the Huelva–Portugal sector which are transported to the site before significant removal by chemical or deposition mechanism can occur. The air masses from the north were affected mainly by crustal elements and biogenic sources, the latter being exemplified by the biogenic species such as isoprene, particularly in the first part of the campaign. The urban air from the Seville area, before arriving at El Arenosillo, traversed the Doñana National Park and therefore was affected by industrial-urban and biogenic emissions. This aged air parcel can transport low levels of NOx, total particle concentration and SO2 as well as ozone and isoprene. Marine air masses from the Atlantic Ocean influence El Arenosillo frequently. Under these conditions, the lowest levels of almost all the species – with the exception of ozone levels associated to long-range transport – were measured.

Peroxy radicals were measured by a PeRCA (Peroxy Radical Chemical Amplifier) instrument in the boundary layer during the DOMINO (Diel Oxidant Mechanisms In relation to Nitrogen Oxides) campaign at a coastal, forested site influenced by urban-industrial emissions in southern Spain in late autumn. Total peroxy radicals (RO2* = HO2 + ΣRO2) generally showed a daylight maximum between 10 and 50 pptv at 13:00 UTC, with an average of 18 pptv over the 15 days of measurements. Emissions from the industrial area of Huelva often impacted the measurement site at night during the campaign. The processing of significant levels of anthropogenic organics leads to an intense nocturnal radical chemistry accompanied by formation of organic peroxy radicals at comparable levels to those of summer photochemical conditions with peak events up to 60–80 pptv. The RO2 production initiated by reactions of NO3 with organic trace gases was estimated to be significant, but not sufficient to account for the concentrations of RO2* observed in air masses carrying high pollutant loading. The nocturnal production of peroxy radicals in those periods seems therefore to be dominated by ozonolysis of volatile organic compounds, in particular alkenes of industrial petrochemical origin. RO2* diurnal variations were consistent with HO2 measurements available at the site. HO2/RO2* ratios generally varied between 0.3 and 0.6, though on some occasions this ratio was likely to have been affected by instrumental artifacts (overestimated HO2) associated with high RO2 loads.

The primary and most important oxidant in the atmosphere is the hydroxyl radical (OH). Currently OH sinks, particularly gas phase reactions, are poorly constrained. One way to characterize the overall sink of OH is to measure directly the ambient loss rate of OH, the total OH reactivity. To date, direct measurements of total OH reactivity have been either performed using a Laser-Induced Fluorescence (LIF) system ("pump-and-probe" or "flow reactor") or the Comparative Reactivity Method (CRM) with a Proton-Transfer-Reaction Mass Spectrometer (PTR-MS). Both techniques require large, complex and expensive detection systems. This study presents a feasibility assessment for CRM total OH reactivity measurements using a new detector, a Gas Chromatographic Photoionization Detector (GC-PID). Such a system is smaller, more portable, less power consuming and less expensive than other total OH reactivity measurement techniques. Total OH reactivity is measured by the CRM using a competitive reaction between a reagent (here pyrrole) with OH alone and in the presence of atmospheric reactive molecules. The new CRM method for total OH reactivity has been tested with parallel measurements of the GC-PID and the previously validated PTR-MS as detector for the reagent pyrrole during laboratory experiments, plant chamber and boreal field studies. Excellent agreement of both detectors was found when the GC-PID was operated under optimum conditions. Time resolution (60–70 s), sensitivity (LOD 3–6 s−1) and overall uncertainty (25% in optimum conditions) for total OH reactivity were similar to PTR-MS based total OH reactivity measurements. One drawback of the GC-PID system was the steady loss of sensitivity and accuracy during intensive measurements lasting several weeks, and a possible toluene interference. Generally, the GC-PID system has been shown to produce closely comparable results to the PTR-MS and thus in suitable environments (e.g. forests) it presents a viably economical alternative for groups interested in total OH reactivity observations.

Hydroxyl radicals play a central role in the troposphere as they control the lifetime of many trace gases. Measurement of OH reactivity (OH loss rate) is important to better constrain the OH budget and also to evaluate the completeness of measured VOC budget. Total atmospheric OH reactivity was measured for the first time in an European Megacity: Paris and its surrounding areas with 12 million inhabitants, during the MEGAPOLI winter campaign 2010. The method deployed was the Comparative Reactivity Method (CRM). The measured dataset contains both measured and calculated OH reactivity from CO, NOx and VOCs measured via PTR-MS, GC-FID and GC-MS instruments. The reactivities observed in Paris covered a range from 10 s−1 to 130 s−1, indicating a large loading of chemical reactants. The present study showed that, when clean marine air masses influenced Paris, the purely local OH reactivity (20 s−1) is well explained by the measured species. Nevertheless, when there is a continental import of air masses, high levels of OH reactivity were obtained (120–130 s−1) and the missing OH reactivity measured in this case jumped to 75%. Using covariations of the missing OH reactivity to secondary inorganic species in fine aerosols, we suggest that the missing OH reactants were most likely highly oxidized compounds issued from photochemically processed air masses of anthropogenic origin.

Ambient total OH reactivity was measured at the Finnish boreal forest station SMEAR II in Hyytiälä (Latitude 61°51' N; Longitude 24°17' E) in July and August 2010 using the Comparative Reactivity Method (CRM). The CRM – total OH reactivity method – is a direct, in-situ determination of the total loss rate of hydroxyl radicals (OH) caused by all reactive species in air. During the intensive field campaign HUMPPA-COPEC 2010 (Hyytiälä United Measurements of Photochemistry and Particles in Air – Comprehensive Organic Precursor Emission and Concentration study) the total OH reactivity was monitored both inside (18 m) and directly above the forest canopy (24 m) for the first time. The comparison between these two total OH reactivity measurements, absolute values and the temporal variation have been analyzed here. Stable boundary layer conditions during night and turbulent mixing in the daytime induced low and high short-term variability, respectively. The impact on total OH reactivity from biogenic emissions and associated photochemical products was measured under "normal" and "stressed" (i.e. prolonged high temperature) conditions. The advection of biomass burning emissions to the site caused a marked change in the total OH reactivity vertical profile. By comparing the OH reactivity contribution from individually measured compounds and the directly measured total OH reactivity, the size of any unaccounted for or "missing" sink can be deduced for various atmospheric influences. For "normal" boreal conditions a missing OH reactivity of 58%, whereas for "stressed" boreal conditions a missing OH reactivity of 89% was determined. Various sources of not quantified OH reactive species are proposed as possible explanation for the high missing OH reactivity.

In this study air masses are characterized in terms of their total OH reactivity which is a robust measure of the "reactive air pollutant loading". The measurements were performed during the DOMINO campaign (Diel Oxidant Mechanisms In relation to Nitrogen Oxides) held from 21/11/2008 to 08/12/2008 at the Atmospheric Sounding Station – El Arenosillo (37.1° N–6.7° W, 40 m a.s.l.). The site was frequently impacted by marine air masses (arriving at the site from the southerly sector) and air masses from the cities of Huelva (located NW of the site), Seville and Madrid (located NNE of the site). OH reactivity values showed strong wind sector dependence. North eastern "continental" air masses were characterized by the highest OH reactivities (average: 31.4 ± 4.5 s−1; range of average diel values: 21.3–40.5 s−1), followed by north western "industrial" air masses (average: 13.8 ± 4.4 s−1; range of average diel values: 7–23.4 s−1) and marine air masses (average: 6.3 ± 6.6 s−1; range of average diel values: below detection limit −21.7 s−1), respectively. The average OH reactivity for the entire campaign period was ~18 s−1 and no pronounced variation was discernible in the diel profiles with the exception of relatively high values from 09:00 to 11:00 UTC on occasions when air masses arrived from the north western and southern wind sectors. The measured OH reactivity was used to constrain both diel instantaneous ozone production potential rates and regimes. Gross ozone production rates at the site were generally limited by the availability of NOx with peak values of around 20 ppbV O3 h−1. Using the OH reactivity based approach, derived ozone production rates indicate that if NOx would no longer be the limiting factor in air masses arriving from the continental north eastern sector, peak ozone production rates could double. We suggest that the new combined approach of in-situ fast measurements of OH reactivity, nitrogen oxides and peroxy radicals for constraining instantaneous ozone production rates, could significantly improve analyses of upwind point sources and their impact on regional ozone levels.

We study the interactions between atmospheric boundary layer (ABL) dynamics and atmospheric chemistry using a mixed-layer model coupled to chemical reaction schemes. Guided by both atmospheric and chemical measurements obtained during the DOMINO (Diel Oxidant Mechanisms in relation to Nitrogen Oxides) campaign (2008), numerical experiments are performed to study the role of ABL dynamics and the accuracy of chemical schemes with different complexity: the Model for Ozone and Related chemical Tracers, version 4 (MOZART-4) and a reduced mechanism of this chemical system. Both schemes produce satisfactory results, indicating that the reduced scheme is capable of reproducing the O3-NOx-VOC-HOx diurnal cycle during conditions characterized by a low NOx regime and small O3 tendencies (less than 1 ppb per hour). By focusing on the budget equations of chemical species in the mixed-layer model, we show that for species like O3, NO and NO2, the influence of entrainment and boundary layer growth is of the same order as chemical production/loss. This indicates that an accurate representation of ABL processes is crucial in understanding the diel cycle of chemical species. By comparing the time scales of chemical reactive species with the mixing time scale of turbulence, we propose a classification based on the Damköhler number to further determine the importance of dynamics on chemistry during field campaigns. Our findings advocate an integrated approach, simultaneously solving the ABL dynamics and chemical reactions, in order to obtain a better understanding of chemical pathways and processes and the interpretation of the results obtained during measurement campaigns.

This paper describes the background, instrumentation, goals, and the regional influences on the HUMPPA-COPEC intensive field measurement campaign, conducted at the Boreal forest research station SMEAR II (Station for Measuring Ecosystem-Atmosphere Relation) in Hyytiälä, Finland from 12 July–12 August 2010. The prevailing meteorological conditions during the campaign are examined and contrasted with those of the past six years. Back trajectory analyses show that meteorological conditions at the site in 2010 were characterized by a higher proportion of southerly flow than in the other years studied. As a result the summer of 2010 was anomalously warm and high in ozone making the campaign relevant for the analysis of possible future climates. A comprehensive land use analysis, provided on both 5 and 50 km scales, shows that the main vegetation types surrounding the site on both the regional and local scales are: coniferous forest (Scots pine and/or Norway spruce); mixed forest (Birch and conifers); and woodland scrub (e.g. Willows, Aspen); indicating that the campaign results can be taken as representative of the Boreal forest ecosystem. In addition to the influence of biogenic emissions, the measurement site was occasionally impacted by sources other than vegetation. Specific tracers have been used here to identify the time periods when such sources have impacted the site namely: biomass burning (acetonitrile and CO), urban anthropogenic pollution (pentane and SO2) and the nearby Korkeakoski sawmill (enantiomeric ratio of chiral monoterpenes). None of these sources dominated the study period, allowing the Boreal forest summertime emissions to be assessed and contrasted with various other source signatures.

We have modelled the total atmospheric OH-reactivity in a boreal forest and investigated the individual contributions from gas phase inorganic species, isoprene, monoterpenes, and methane along with other important VOCs. Daily and seasonal variation in OH-reactivity for the year 2008 was examined as well as the vertical OH-reactivity profile. We have used SOSA; a one dimensional vertical chemistry-transport model (Boy et al., 2011a) together with measurements from Hyytiälä, SMEAR II station, Southern Finland, conducted in August 2008. Model simulations only account for ~30–50% of the total measured OH sink, and in our opinion, the reason for missing OH-reactivity is due to unmeasured unknown BVOCs, and limitations in our knowledge of atmospheric chemistry including uncertainties in rate constants. Furthermore, we found that the OH-reactivity correlates with both organic and inorganic compounds and increases during summer. The summertime canopy level OH-reactivity peaks during night and the vertical OH-reactivity decreases with height.

We construct a global atmospheric budget for acetaldehyde using a 3-D model of atmospheric chemistry (GEOS-Chem), and use an ensemble of observations to evaluate present understanding of its sources and sinks. Hydrocarbon oxidation provides the largest acetaldehyde source in the model (128 Tg a−1, a factor of 4 greater than the previous estimate), with alkanes, alkenes, and ethanol the main precursors. There is also a minor source from isoprene oxidation. We use an updated chemical mechanism for GEOS-Chem, and photochemical acetaldehyde yields are consistent with the Master Chemical Mechanism. We present a new approach to quantifying the acetaldehyde air-sea flux based on the global distribution of light absorption due to colored dissolved organic matter (CDOM) derived from satellite ocean color observations. The resulting net ocean emission is 57 Tg a−1, the second largest global source of acetaldehyde. A key uncertainty is the acetaldehyde turnover time in the ocean mixed layer, with quantitative model evaluation over the ocean complicated by known measurement artifacts in clean air. Simulated concentrations in surface air over the ocean generally agree well with aircraft measurements, though the model tends to overestimate the vertical gradient. PAN:NOx ratios are well-simulated in the marine boundary layer, providing some support for the modeled ocean source. We introduce the Model of Emissions of Gases and Aerosols from Nature (MEGANv2.1) for acetaldehyde and ethanol and use it to quantify their net flux from living terrestrial plants. Including emissions from decaying plants the total direct acetaldehyde source from the land biosphere is 23 Tg a−1. Other terrestrial acetaldehyde sources include biomass burning (3 Tg a−1) and anthropogenic emissions (2 Tg a−1). Simulated concentrations in the continental boundary layer are generally unbiased and capture the spatial gradients seen in observations over North America, Europe, and tropical South America. However, the model underestimates acetaldehyde levels in urban outflow, suggesting a missing source in polluted air. Ubiquitous high measured concentrations in the free troposphere are not captured by the model, and based on present understanding are not consistent with concurrent measurements of PAN and NOx: we find no compelling evidence for a widespread missing acetaldehyde source in the free troposphere. We estimate the current US source of ethanol and acetaldehyde (primary + secondary) at 1.3 Tg a−1 and 7.8 Tg a−1, approximately 60{%} and 480% of the corresponding increases expected for a national transition from gasoline to ethanol fuel.

In this study we present measurements of selected trace gases and aerosols made in a boreal forest during the BACCI-QUEST IV intensive field campaign in Hyytiälä, Finland in April 2005. Springtime diel and vertical variations of VOCs are discussed in connection with the variations in other trace gases and with the prevailing meteorological conditions. A daytime and a nighttime event have been analysed in detail. The nighttime particle event occurred synchronously with huge increases in monoterpenes, while the second event type involved nucleation and was anti-correlated with sulphuric acid. Here we discuss the possible origins of these two distinct forms of aerosol production at the Hyytiälä site using the measurement data, air mass back trajectories and the optical stereoisomery of monoterpenes. Optical stereoisomery is used in source identification to distinguish between unnatural and natural monoterpene emissions.

Tropical forests are a strong source of biogenic volatile organic compounds (BVOCs) to the atmosphere which can potentially impact the atmospheric oxidation capacity. Here we present airborne and ground-based BVOC measurements representative for the long dry season covering a large area of the northern Amazonian rainforest (6–3° N, 50–59° W). The measurements were conducted during the October 2005 GABRIEL (Guyanas Atmosphere-Biosphere exchange and Radicals Intensive Experiment with the Learjet) campaign. The vertical (35 m to 10 km) and diurnal (09:00–16:00) profiles of isoprene, its oxidation products methacrolein and methyl vinyl ketone and methanol and acetone, measured by PTR-MS (Proton Transfer Reaction Mass Spectrometry), have been used to empirically estimate their emission fluxes from the forest canopy on a regional scale. The mixed layer isoprene emission flux, inferred from the airborne measurements above 300 m, is 5.7 mg isoprene m−2 h−1 after compensating for chemistry and ~6.9 mg isoprene m−2 h−1 taking detrainment into account. This surface flux is in general agreement with previous tropical forest studies. Inferred methanol and acetone emission fluxes are 0.5 mg methanol m−2 h−1 and 0.35 mg acetone m−2 h−1, respectively. The BVOC measurements were compared with fluxes and mixing ratios simulated with a single-column chemistry and climate model (SCM). The inferred isoprene flux is substantially smaller than that simulated with an implementation of a commonly applied BVOC emission algorithm in the SCM.

We present an evaluation of sources, sinks and turbulent transport of nitrogen oxides, ozone and volatile organic compounds (VOC) in the boundary layer over French Guyana and Suriname during the October 2005 GABRIEL campaign by simulating observations with a single-column chemistry and climate model (SCM) along a zonal transect. Simulated concentrations of O3 and NO as well as NO2 photolysis rates over the forest agree well with observations when a small soil-biogenic NO emission flux was applied. This suggests that the photochemical conditions observed during GABRIEL reflect a pristine tropical low-NOx regime. The SCM uses a compensation point approach to simulate nocturnal deposition and daytime emissions of acetone and methanol and produces daytime boundary layer mixing ratios in reasonable agreement with observations. The area average isoprene emission flux, inferred from the observed isoprene mixing ratios and boundary layer height, is about half the flux simulated with commonly applied emission algorithms. The SCM nevertheless simulates too high isoprene mixing ratios, whereas hydroxyl concentrations are strongly underestimated compared to observations, which can at least partly explain the discrepancy. Furthermore, the model substantially overestimates the isoprene oxidation products methlyl vinyl ketone (MVK) and methacrolein (MACR) partly due to a simulated nocturnal increase due to isoprene oxidation. This increase is most prominent in the residual layer whereas in the nocturnal inversion layer we simulate a decrease in MVK and MACR mixing ratios, assuming efficient removal of MVK and MACR. Entrainment of residual layer air masses, which are enhanced in MVK and MACR and other isoprene oxidation products, into the growing boundary layer poses an additional sink for OH which is thus not available for isoprene oxidation. Based on these findings, we suggest pursuing measurements of the tropical residual layer chemistry with a focus on the nocturnal depletion of isoprene and its oxidation products.

Hydroxyl (OH) radicals play a vital role in maintaining the oxidizing capacity of the atmosphere. To understand variations in OH radicals both source and sink terms must be understood. Currently the overall sink term, or the total atmospheric reactivity to OH, is poorly constrained. Here, we present a new on-line method to directly measure the total OH reactivity (i.e.~total loss rate of OH radicals) in a sampled air mass. In this method, a reactive molecule (X), not normally present in air, is passed through a glass reactor and its concentration is monitored with a suitable detector. OH radicals are then introduced in the glass reactor at a constant rate to react with X, first in the presence of zero air and then in the presence of ambient air containing VOCs and other OH reactive species. Comparing the amount of X exiting the reactor with and without the ambient air allows the air reactivity to be determined. In our existing set up, X is pyrrole and the detector used is a proton transfer reaction mass spectrometer. The present dynamic range for ambient air reactivity is about 6 to 300 s−1, with an overall maximum uncertainty of 25% above 8 s−1 and up to 50% between 6–8 s−1. The system has been tested and calibrated with different single and mixed hydrocarbon standards showing excellent linearity and accountability with the reactivity of the standards. Potential interferences such as high NO in ambient air, varying relative humidity and photolysis of pyrrole within the setup have also been investigated. While interferences due changing humidity and photolysis of pyrrole are easily overcome by ensuring that humidity in the set up does not change drastically and the photolytic loss of pyrrole is measured and taken into account, respectively, NO>10 ppb in ambient air remains a significant interference for the current configuration of the instrument. Field tests in the tropical rainforest of Suriname (~53 s) and the urban atmosphere of Mainz (~10 s-1) Germany, show the promise of the new method and indicate that a significant fraction of OH reactive species in the tropical forests is likely missed by current measurements. Suggestions for improvements to the technique and future applications are discussed.

The ocean's influence on volatile organic compounds (VOCs) in the atmosphere is poorly understood. This work characterises the oceanic emission and/or uptake of methanol, acetone, acetaldehyde, isoprene and dimethyl sulphide (DMS) as a function of photosynthetically active radiation (PAR) and a suite of biological parameters. The measurements were taken following a phytoplankton bloom, in May/June 2005 with a proton transfer reaction mass spectrometer (PTR-MS), from mesocosm enclosures anchored in the Raunefjord, Southern Norway. The net flux of methanol was always into the ocean, and was stronger at night. Isoprene and acetaldehyde were emitted from the ocean, correlating with light (ravcorr, isoprene=0.49; ravcorr, acetaldehyde=0.70) and phytoplankton abundance. DMS was also emitted to the air but did not correlate significantly with light (ravcorr, dms=0.01). Under conditions of high biological activity and a PAR of ~450 μmol photons m−2 s−1, acetone was emitted from the ocean, otherwise it was uptaken. The inter-VOC correlations were highest between the day time emission fluxes of acetone and acetaldehyde (rav=0.96), acetaldehyde and isoprene (rav=0.88) and acetone and isoprene (rav=0.85). The mean fluxes for methanol, acetone, acetaldehyde, isoprene and DMS were −0.26 ng m−2 s−1, 0.21 ng m−2 s−1, 0.23 ng m−2 s−1, 0.12 ng m−2 s−1 and 0.3 ng m−2 s−1, respectively. This work shows that compound specific PAR and biological dependency should be used for estimating the influence of the global ocean on atmospheric VOC budgets.

Purpose: Very few studies conducted in India have analyzed insurance policies and clinical trial agreement (CTA) submitted to ethics committee (EC). This study was conducted to review and find out deficiencies in it. Materials and Methods: This was a retrospective observational study. All the protocols for regulatory clinical trials and academic research sponsored by the Indian Council of Medical Research or other funding agency were included. Insurance documents and CTA submitted with the study protocols were analyzed. Results: A total of seventy CTA and insurance policies were analyzed. CTA mentioned that parties involved in 60 (86%) forms, scope of the agreement in 15 (21%) forms, responsibilities of the party in 68 (97%) forms, and payment details in 58 (83%) forms. Nearly 88.5% of the insurance policies mentioned whether the policy covers the participants for injury due to all clauses and 91% of the policies mentioned the validity period of insurance. Conclusion: It was found that both the documents contained almost all the required elements. This was probably because this institutional EC insisted on and thoroughly reviewed the documents to ensure that adequate compensation of research-related injuries has been provided for and this fact is informed to the trial subject. As very few studies are available in the literature, we could not compare majority of the findings of this study with others.