Martyn Ward - Academia.edu (original) (raw)

Papers by Martyn Ward

Atmospheric nitrogen oxides (NO + NO 2 = NO x) have been measured at the Cape Verde Atmospheric O... more Atmospheric nitrogen oxides (NO + NO 2 = NO x) have been measured at the Cape Verde Atmospheric Observatory (CVAO) in the tropical Atlantic (16 • 51 N, 24 • 52 W) since October 2006. These measurements represent a unique time series of NO x in the background remote troposphere. Nitrogen dioxide (NO 2) is measured via photolytic conversion to nitric oxide (NO) by ultraviolet light-emitting diode arrays followed by chemiluminescence detection. Since the measurements began, a blue light converter (BLC) has been used for NO 2 photolysis, with a maximum spectral output of 395 nm from 2006 to 2015 and of 385 nm from 2015 onwards. The original BLC used was constructed with a Teflon-like material and appeared to cause an overestimation of NO 2 when illuminated. To avoid such interferences, a new additional photolytic converter (PLC) with a quartz photolysis cell (maximum spectral output also 385 nm) was implemented in March 2017. Once corrections are made for the NO 2 artefact from the original BLC, the two NO 2 converters are shown to give comparable NO 2 mixing ratios (BLC = 0.99 × PLC + 0.7 ppt, linear least-squares regression), giving confidence in the quantitative measurement of NO x at very low levels. Data analysis methods for the NO x measurements made at CVAO have been developed and applied to the entire time series to produce an internally consistent and high-quality long-term data set. NO has a clear diurnal pattern with a maximum mixing ratio of 2-10 ppt during the day depending on the season and ∼ 0 ppt during the night. NO 2 shows a fairly flat diurnal signal, although a small increase in daytime NO x is evident in some months. Monthly average mixing ratios of NO 2 vary between 5 and 30 ppt depending on the season. Clear seasonal trends in NO and NO 2 levels can be observed with a maximum in autumn and winter and a minimum in spring and summer.

AGUFM, Dec 1, 2009

The tropics emit a huge amount of volatile organic compounds (VOCs) into the Earth's atmosph... more The tropics emit a huge amount of volatile organic compounds (VOCs) into the Earth's atmosphere. The processes by which these gases are oxidised to form secondary organic aerosol (SOA) are currently not well understood or quantified. Intensive field measurements were carried out as part of the Oxidant and Particle Photochemical Processes (OP3) and the Aerosol Coupling in the Earth System (ACES) projects around pristine rainforest in Malaysian Borneo. This is the first campaign of its type in a South East Asian rainforest. We present detailed organic aerosol composition measurements made using an Aerodyne High Resolution Time of Flight Aerosol Mass Spectrometer (HR-ToF-AMS) at Bukit Atur, a Global Atmosphere Watch site located in the Danum Valley Conservation Area. This is a state-of-the-art field deployable instrument that can provide real time composition, mass loading and aerodynamic particle sizing information. In addition, the mass spectral resolution is sufficient to perform an analysis of the elemental composition of the organic species present. Off line analysis of filter samples was performed using comprehensive two-dimensional gas chromatography coupled to time of flight mass spectrometry (GCxGC/ToFMS). This technique provide a more detailed chemical characterisation of the SOA, allowing direct links back to gas phase precursors. The ground site data are compared with Aerodyne Compact Time of Flight Aerosol Mass Spectrometer (C-ToF-AMS) measurements made on the UK Facility for Airborne Atmospheric Measurements (FAAM) BAe-146 research aircraft. Airborne measurements were made above pristine rainforest surrounding the Danum Valley site, as well as nearby oil palm agricultural sites and palm oil rendering plants. Proton Transfer Reaction Mass Spectrometry (PTRMS) measurements of VOCs were made at the ground site and from the FAAM aircraft. Novel organic aerosol was measured by both AMSs, and identified by GCxGC/ToFMS analysis. The aerosol component was compared to gas phase precursor measurements. We will discuss the likely sources of this aerosol component.

eLife, Jan 27, 2016

Proteins persist longer in the fossil record than DNA, but the longevity, survival mechanisms and... more Proteins persist longer in the fossil record than DNA, but the longevity, survival mechanisms and substrates remain contested. Here, we demonstrate the role of mineral binding in preserving the protein sequence in ostrich (Struthionidae) eggshell, including from the palaeontological sites of Laetoli (3.8 Ma) and Olduvai Gorge (1.3 Ma) in Tanzania. By tracking protein diagenesis back in time we find consistent patterns of preservation, demonstrating authenticity of the surviving sequences. Molecular dynamics simulations of struthiocalcin-1 and -2, the dominant proteins within the eggshell, reveal that distinct domains bind to the mineral surface. It is the domain with the strongest calculated binding energy to the calcite surface that is selectively preserved. Thermal age calculations demonstrate that the Laetoli and Olduvai peptides are 50 times older than any previously authenticated sequence (equivalent to ~16 Ma at a constant 10°C).

Atmospheric Chemistry and Physics, 2011

Isoprene is the most abundant non-methane biogenic volatile organic compound (BVOC), but the proc... more Isoprene is the most abundant non-methane biogenic volatile organic compound (BVOC), but the processes governing secondary organic aerosol (SOA) formation from isoprene oxidation are only beginning to become understood and selective quantification of the atmospheric particulate burden remains difficult. Organic aerosol above a tropical rainforest located in Danum Valley, Borneo, Malaysia, a high isoprene emission region, was studied during Summer 2008 using Aerosol Mass Spectrometry and offline detailed characterisation using comprehensive two dimensional gas chromatography. Observations indicate that a substantial fraction (up to 15% by mass) of atmospheric sub-micron organic aerosol was observed as methylfuran (MF) after thermal desorption. This observation was associated with the simultaneous measurements of established gas-phase isoprene oxidation products methylvinylketone (MVK) and methacrolein (MACR). Observations of MF were also made during experimental chamber oxidation of isoprene. Positive matrix factorisation of the AMS organic mass spectral time series produced a robust factor which accounts for an average of 23% (0.18 µg m −3), reaching as much as 53% (0.50 µg m −3

Environmental Science: Processes & Impacts, 2017

Atmospheric Chemistry and Physics, Jul 10, 2019

Ambient particulate matter (PM) can contain a mix of different toxic species derived from a wide ... more Ambient particulate matter (PM) can contain a mix of different toxic species derived from a wide variety of sources. This study quantifies the diurnal variation and nocturnal abundance of 16 polycyclic aromatic hydrocarbons (PAHs), 10 oxygenated PAHs (OPAHs) and 9 nitrated PAHs (NPAHs) in ambient PM in central Beijing during winter. Target compounds were identified and quantified using gas chromatography-time-of-flight mass spectrometry (GC-Q-ToF-MS). The total concentration of PAHs varied between 18 and 297 ng m −3 over 3 h daytime filter samples and from 23 to 165 ng m −3 in 15 h night-time samples. The total concentrations of PAHs over 24 h varied between 37 and 180 ng m −3 (mean: 97 ± 43 ng m −3). The total daytime concentrations during high particulate loading conditions for PAHs, OPAHs and NPAHs were 224, 54 and 2.3 ng m −3 , respectively. The most abundant PAHs were fluoranthene (33 ng m −3), chrysene (27 ng m −3), pyrene (27 ng m −3), benzo[a]pyrene (27 ng m −3), benzo[b]fluoranthene (25 ng m −3), benzo[a]anthracene (20 ng m −3) and phenanthrene (18 ng m −3). The most abundant OPAHs were 9,10-anthraquinone (18 ng m −3), 1,8-naphthalic anhydride (14 ng m −3) and 9-fluorenone (12 ng m −3), and the three most abundant NPAHs were 9-nitroanthracene (0.84 ng m −3), 3-nitrofluoranthene (0.78 ng m −3) and 3-nitrodibenzofuran (0.45 ng m −3). PAHs and OPAHs showed a strong positive correlation with the gas-phase abundance of NO, CO, SO 2 and HONO, indicating that PAHs and OPAHs can be associated with both local and regional emissions. Diagnostic ratios suggested emissions from traffic road and coal combustion were the predominant sources of PAHs in Beijing and also revealed the main source of NPAHs to be secondary photochemical formation rather than primary emissions. PM 2.5 and NPAHs showed a strong correlation with gas-phase HONO. 9-Nitroanthracene appeared to undergo a photodegradation during the daytime and showed a strong positive correlation with ambient HONO (R = 0.90, P < 0.001). The lifetime excess lung cancer risk for those species that have available toxicological data (16 PAHs, 1 OPAH and 6 NPAHs) was calculated to be in the range 10 −5 to 10 −3 (risk per million people ranges from 26 to 2053 cases per year).

Atmospheric Chemistry and Physics, Nov 21, 2013

Emissions of biogenic volatile organic compounds are though to contribute significantly to second... more Emissions of biogenic volatile organic compounds are though to contribute significantly to secondary organic aerosol formation in the tropics, but understanding these transformation processes has proved difficult, due to the complexity of the chemistry involved and very low concentrations. Aerosols from above a Southeast Asian tropical rainforest in Borneo were characterised using liquid chromatography-ion trap mass spectrometry, high-resolution aerosol mass spectrometry and Fourier transform ion cyclotron resonance mass spectrometry (FTICRMS) techniques. Oxygenated compounds were identified in ambient organic aerosol that could be directly traced back to isoprene, monoterpenes and sesquiterpene emissions, by combining field data on chemical structures with mass spectral data generated from synthetically produced products created in a simulation chamber. Eighteen oxygenated species of biogenic origin were identified in the rainforest aerosol from the precursors isoprene, α-pinene, limonene, α-terpinene and βcaryophyllene. The observations provide the unambiguous field detection of monoterpene and sesquiterpene oxidation products in SOA above a pristine tropical rainforest. The presence of 2-methyl tetrol organosulfates and an associated sulfated dimer provides direct evidence that isoprene in the presence of sulfate aerosol can make a contribution to biogenic organic aerosol above tropical forests. High-resolution mass spectrometry indicates that sulfur can also be incorporated into oxidation products arising from monoterpene precursors in tropical aerosol.

Environmental Science & Technology, May 18, 2021

The life-critical matrices of air and water are among the most complex chemical mixtures that are... more The life-critical matrices of air and water are among the most complex chemical mixtures that are ever encountered. Ultrahigh-resolution mass spectrometers, such as the Orbitrap, provide unprecedented analytical capabilities to probe the molecular composition of such matrices, but the extraction of non-targeted chemical information is impractical to perform via manual data processing. Automated non-targeted tools rapidly extract the chemical information of all detected compounds within a sample dataset. However, these methods have not been exploited in the environmental sciences. Here, we provide an automated and (for the first time) rigorously tested methodology for the nontargeted compositional analysis of environmental matrices using coupled liquid chromatography−mass spectrometric data. First, the robustness and reproducibility was tested using authentic standards, evaluating performance as a function of concentration, ionization potential, and sample complexity. The method was then used for the compositional analysis of particulate matter and surface waters collected from worldwide locations. The method detected >9600 compounds in the individual environmental samples, arising from critical pollutant sources, including carcinogenic industrial chemicals, pesticides, and pharmaceuticals among others. This methodology offers considerable advances in the environmental sciences, providing a more complete assessment of sample compositions while significantly increasing throughput.

Analytica Chimica Acta

sample reproducibility is typically <2% at >8 nM and ~4% at <8 nM. Since there is no environmenta... more sample reproducibility is typically <2% at >8 nM and ~4% at <8 nM. Since there is no environmental certified reference material for iodine species, the measurements made on seawater samples using this IC method were compared to those obtained using established analytical techniques; iodide voltammetry and iodate spectrophotometry. We calculated recoveries of 102 ± 16% (n = 107) for iodide and 116 ± 9% (n = 103) for iodate, the latter difference may be due to an underestimation of iodate by the spectrophotometric method. We further compared a chemical oxidation and reduction of the sample to an ultraviolet digestion to establish the total dissolved iodine content, the average recovery following chemical amendments was 98 ± 4% (n = 92). The new method represents a simple, efficient, green, precise and sensitive method for measuring dissolved speciated iodine in complex matrices.

Environmental Science: Processes & Impacts, 2021

VOCs are used ubiquitously in consumer products. This population study investigates a wide-range ... more VOCs are used ubiquitously in consumer products. This population study investigates a wide-range of VOC concentrations indoors and links high butane concentrations with universal and frequent aerosol use.

Atmospheric Measurement Techniques, 2021

Biomass burning emits significant quantities of intermediate-volatility and semi-volatile organic... more Biomass burning emits significant quantities of intermediate-volatility and semi-volatile organic compounds (I/SVOCs) in a complex mixture, probably containing many thousands of chemical species. These components are significantly more toxic and have poorly understood chemistry compared to volatile organic compounds routinely quantified in ambient air; however, analysis of I/SVOCs presents a difficult analytical challenge. The gases and particles emitted during the test combustion of a range of domestic solid fuels collected from across Delhi were sampled and analysed. Organic aerosol was collected onto Teflon (PTFE) filters, and residual low-volatility gases were adsorbed to the surface of solid-phase extraction (SPE) discs. A new method relying on accelerated solvent extraction (ASE) coupled to comprehensive two-dimensional gas chromatography with time-of-flight mass spectrometry (GC × GC-ToF-MS) was developed. This highly sensitive and powerful analytical technique enabled over 3000 peaks from I/SVOC species with unique mass spectra to be detected. A total of 15 %-100 % of gas-phase emissions and 7 %-100 % of particle-phase emissions were characterised. The method was analysed for suitability to make quantitative measurements of I/SVOCs using SPE discs. Analysis of SPE discs indicated phenolic and furanic compounds were important for gas-phase I/SVOC emissions and levoglucosan to the aerosol phase. Gas-and particle-phase emission factors for 21 polycyclic aromatic hydrocarbons (PAHs) were derived, including 16 compounds listed by the US EPA as priority pollutants. Gas-phase emissions were dominated by smaller PAHs. The new emission factors were measured (mg kg −1) for PAHs from combustion of cow dung cake (615), municipal solid waste (1022), crop residue (747), sawdust (1236), fuelwood (247), charcoal (151) and liquefied petroleum gas (56). The results of this study indicate that cow dung cake and municipal solid waste burning are likely to be significant PAH sources, and further study is required to quantify their impact alongside emissions from fuelwood burning.

Environmental Science & Technology, 2021