Influence of the Sea Surface Microlayer on Oceanic Iodine Emissions.

The influence of organic compounds on iodine (I2) emissions from the O3 + I- reaction at the sea surface was investigated in laboratory and modeling studies using artificial solutions, natural subsurface seawater (SSW), and, for the first time, samples of the surface microlayer (SML). Gas-phase I2 was measured directly above the surface of liquid samples using broadband cavity enhanced absorption spectroscopy. I2 emissions were consistently lower for artificial seawater (AS) than buffered potassium iodide (KI) solutions. Natural seawater samples showed the strongest reduction of I2 emissions compared to artificial solutions with equivalent [I-], and the reduction was more pronounced over SML than SSW. Emissions of volatile organic iodine (VOI) were highest from SML samples but remained a negligible fraction (<1%) of the total iodine flux. Therefore, reduced iodine emissions from natural seawater cannot be explained by chemical losses of I2 or hypoiodous acid (HOI), leading to VOI. An interfacial model explains this reduction by increased solubility of the I2 product in the organic-rich interfacial layer of seawater. Our results highlight the importance of using environmentally representative concentrations in studies of the O3 + I- reaction and demonstrate the influence the SML exerts on emissions of iodine and potentially other volatile species.

Enhanced wintertime oxidation of VOCs via sustained radical sources in the urban atmosphere.

Daytime atmospheric oxidation chemistry is conventionally considered to be driven primarily by the OH radical, formed via photolytic sources. In this paper we examine how, during winter when photolytic processes are slow, chlorine chemistry can have a significant impact on oxidative processes in the urban boundary layer. Photolysis of nitryl chloride (ClNO2) provides a significant source of chlorine atoms, which enhances the oxidation of volatile organic compounds (VOCs) and the production of atmospheric pollutants. We present a set of observations of ClNO2 and HONO made at urban locations in central England in December 2014 and February 2016. While direct emissions and in-situ chemical formation of HONO continue throughout the day, ClNO2 is only formed at night and is usually completely photolyzed by midday. Our data show that, during winter, ClNO2 often persists through the daylight hours at mixing ratios above 10-20 ppt (on average). In addition, relatively high mixing ratios of daytime HONO (>65 ppt) provide a strong source of OH radicals throughout the day. The combined effects of ClNO2 and HONO result in sustained sources of Cl and OH radicals from sunrise to sunset, which form additional ozone, PAN, oxygenated VOCs, and secondary organic aerosol. We show that radical sources such as ClNO2 and HONO can lead to a surprisingly photoactive urban atmosphere during winter and should therefore be included in atmospheric chemical models.

Marine iodine emissions in a changing world.

Iodine is a critical trace element involved in many diverse and important processes in the Earth system. The importance of iodine for human health has been known for over a century, with low iodine in the diet being linked to goitre, cretinism and neonatal death. Research over the last few decades has shown that iodine has significant impacts on tropospheric photochemistry, ultimately impacting climate by reducing the radiative forcing of ozone (O3) and air quality by reducing extreme O3 concentrations in polluted regions. Iodine is naturally present in the ocean, predominantly as aqueous iodide and iodate. The rapid reaction of sea-surface iodide with O3 is believed to be the largest single source of gaseous iodine to the atmosphere. Due to increased anthropogenic O3, this release of iodine is believed to have increased dramatically over the twentieth century, by as much as a factor of 3. Uncertainties in the marine iodine distribution and global cycle are, however, major constraints in the effective prediction of how the emissions of iodine and its biogeochemical cycle may change in the future or have changed in the past. Here, we present a synthesis of recent results by our team and others which bring a fresh perspective to understanding the global iodine biogeochemical cycle. In particular, we suggest that future climate-induced oceanographic changes could result in a significant change in aqueous iodide concentrations in the surface ocean, with implications for atmospheric air quality and climate.

Aboveground Carbon Storage and Its Links to Stand Structure, Tree Diversity and Floristic Composition in South-Eastern Tanzania.

African savannas and dry forests represent a large, but poorly quantified store of biomass carbon and biodiversity. Improving this information is hindered by a lack of recent forest inventories, which are necessary for calibrating earth observation data and for evaluating the relationship between carbon stocks and tree diversity in the context of forest conservation (for example, REDD+). Here, we present new inventory data from south-eastern Tanzania, comprising more than 15,000 trees at 25 locations located across a gradient of aboveground woody carbon (AGC) stocks. We find that larger trees disproportionately contribute to AGC, with the largest 3.7% of individuals containing half the carbon. Tree species diversity and carbon stocks were positively related, implying a potential functional relationship between the two, and a 'win-win' scenario for conservation; however, lower biomass areas also contain diverse species assemblages meaning that carbon-oriented conservation may miss important areas of biodiversity. Despite these variations, we find that total tree abundance and biomass is skewed towards a few locally dominant species, with eight and nine species (5.7% of the total) accounting for over half the total measured trees and carbon, respectively. This finding implies that carbon production in these areas is channelled through a small number of relatively abundant species. Our results provide key insights into the structure and functioning of these heterogeneous ecosystems and indicate the need for novel strategies for future measurement and monitoring of carbon stocks and biodiversity, including the use for larger plots to capture spatial variations in large tree density and AGC stocks, and to allow the calibration of earth observation data.

Online and offline mass spectrometric study of the impact of oxidation and ageing on glyoxal chemistry and uptake onto ammonium sulfate aerosols.

Recent laboratory and modelling studies have shown that reactive uptake of low molecular weight alpha-dicarbonyls such as glyoxal (GLY) by aerosols is a potentially significant source of secondary organic aerosol (SOA). However, previous studies disagree in the magnitude of the uptake of GLY, the mechanism involved and the physicochemical factors affecting particle formation. In this study, the chemistry of GLY with ammonium sulfate (AS) in both bulk laboratory solutions and in aerosol particles is investigated. For the first time, Aerosol Time of Flight Mass Spectrometry (ATOFMS), a single particle technique, is used together with offline (ESI-MS and LC-MS2) mass spectrometric techniques to investigate the change in composition of bulk solutions of GLY and AS resulting from aqueous photooxidation by OH and from ageing of the solutions in the dark. The mass spectral ions obtained in these laboratory studies were used as tracers of GLY uptake and chemistry in AS seed particles in a series of experiments carried out under dark and natural irradiated conditions at the outdoor European Photo-reactor (EUPHORE). Glyoxal oligomers formed were not detected by the ATOFMS, perhaps due to inefficient absorption at the laser wavelength. However, the presence of organic nitrogen compounds, formed by reaction of GLY with ammonia was confirmed, resulting in an increase in the absorption efficiency of the aerosol, and this increased the number of particles successfully ionised by the ATOFMS. A number of light absorbing organic nitrogen species, including 1H-imidazole, 1H-imidazole-2-carboxaldehyde, 2,2'-bis-imidazole and a glyoxal substituted 2,2'-bisimidazole, previously identified in aqueous laboratory solutions, were also identified in chamber aerosol and formed on atmospherically relevant timescales. An additional compound, predicted to be 1,2,5-oxadiazole, had an enhanced formation rate when the chamber was open and is predicted to be formed via a light activated pathway involving radical oxidation of ammonia to hydroxylamine, followed by subsequent reaction with glyoxal to form an intermediate glyoxime.

A broadband absorption spectrometer using light emitting diodes for ultrasensitive, in situ trace gas detection.

A broadband absorption spectrometer has been developed for highly sensitive and target-selective in situ trace gas measurements. The instrument employs two distinct modes of operation: (i) broadband cavity enhanced absorption spectroscopy (BBCEAS) is used to quantify the concentration of gases in sample mixtures from their characteristic absorption features, and (ii) periodic measurements of the cavity mirrors' reflectivity are made using step-scan phase shift cavity ringdown spectroscopy (PSCRDS). The latter PSCRDS method provides a stand-alone alternative to the more usual method of determining mirror reflectivities by measuring BBCEAS absorption spectra for calibration samples of known composition. Moreover, the instrument's two modes of operation use light from the same light emitting diode transmitted through the cavity in the same optical alignment, hence minimizing the potential for systematic errors between mirror reflectivity determinations and concentration measurements. The ability of the instrument to quantify absorber concentrations is tested in instrument intercomparison exercises for NO(2) (versus a laser broadband cavity ringdown spectrometer) and for H(2)O (versus a commercial hygrometer). A method is also proposed for calculating effective absorption cross sections for fitting the differential structure in BBCEAS spectra due to strong, narrow absorption lines that are under-resolved and hence exhibit non-Beer-Lambert law behavior at the resolution of the BBCEAS measurements. This approach is tested on BBCEAS spectra of water vapor's 4v+delta absorption bands around 650 nm. The most immediate analytical application of the present instrument is in quantifying the concentration of reactive trace gases in the ambient atmosphere. The instrument's detection limits for NO(3) as a function of integration time are considered in detail using an Allan variance analysis. Experiments under laboratory conditions produce a 1sigma detection limit of 0.25 pptv for a 10 s acquisition time, which improves with further signal averaging to 0.09 pptv in 400 s. Finally, an example of the instrument's performance under field work conditions is presented, in this case of measurements of the sum of NO(3)+N(2)O(5) concentrations in the marine boundary layer acquired during the Reactive Halogens in the Marine Boundary Layer field campaign.

A compact broadband cavity enhanced absorption spectrometer for detection of atmospheric NO(2) using light emitting diodes.

A compact and low power detector has been developed for the in situ measurement of atmospheric NO(2) using broadband cavity enhanced absorption spectroscopy. Absorption by the O(2)-O(2) collisional pair was used to determine the cavity mirror reflectivity, thus enabling the retrieval of absolute absorber concentrations by differential spectral fitting techniques. Quantitative amounts of ambient NO(2) (between 3 and 32 parts per billion) were retrieved from spectra recorded in the presence of ambient aerosol with statistical uncertainties approaching 100 ppt for a 60 s averaging period. The instrument's response was compared to that of a commercial chemiluminescence detector and was found to agree to within 6%.