Hydroxy Nitrate Research Articles

Detailed investigation of zinc coating behaviours in various deep eutectic solvents

Determining the optimum conditions of a metal coating is significant for its possible applications in many fields. The present work described the electrodynamic process of zinc coating from six different deep eutectic solvents (DESs), especially type-III DES systems prepared with a quaternary ammonium salt and hydrogen bond type. Non-reversible processes without oxidation were found in DES systems prepared with choline chloride and zinc nitrate salts, and also, propylene glycol and zinc nitrate salts, termed as type-II and type-IV, respectively. The most attracted type-III DES prepared by a mixture of 1 molar choline chloride and 2 molar ethylene glycols, commercially known as Ethaline (E200), were examined for its electronucleation and possible reactions for zinc electrodeposition. For the first time, the Pt working electrode was investigated under high-resolution optical microscopy to visualize the in-situ morphology change during oxidation and reduction in E200. Furthermore, the morphological change during the anodic dissolution of zinc was also investigated in situ under a high-resolution microscope. It was found that insoluble species forming during anodic dissolution blocks the surface. Bulk electrolysis was performed in these solvents to investigate the formed zinc nucleates' morphological differences. XRD analysis was performed to differentiate the crystal planes of each deposition obtained from six DESs. It was found that the type-II and type-IV DESs consisting of zinc nitrates revealed zinc hydroxy nitrate dominated zinc deposition, which can be helpful in various applications.

Capability of Copper Hydroxy Nitrate (Cu2(OH)3NO3) as an Additive to Develop Antibacterial Polymer Contact Surfaces: Potential for Food Packaging Applications

The globalization of the market, as well as the increasing world population, which require a higher demand for food products, pose a great challenge to ensure food safety and prevent food loss and waste. In this sense, active materials with antibacterial properties are an important alternative in the prolongation of shelf life and ensuring food safety. In this work, the ability of copper(II) hydroxy nitrate (CuHS) to obtain antibacterial films based on low density polyethylene (LDPE) and polylactic acid (PLA), was evaluated. The thermal properties of the composites, evaluated using thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC), showed that the concentrations of added CuHS do not particularly change these characteristics with respect to the neat polymer matrix films. The mechanical properties, determined using dynamic mechanical analysis (DMTA), indicate a small increase in the brittleness of the material in PLA-based composites. The antibacterial properties against Listeria monocytogenes and Salmonella enterica were evaluated using a surface contact test, and a bacterial reduction of at least 8 to 9 logarithmic units for the composites with 0.3% CuHS, both in LDPE and PLA and against both bacteria, were achieved. The reusability of the composite films after their first use demonstrated a higher stability against Listeria monocytogenes. The migration and cytotoxicity of the composites loaded with 0.3% CuHS was evaluated, demonstrating the safety of these materials, which reinforces their potential use in food packaging applications.

Effects of acetate and nitrate ions on radical and intercalation reactions initiated by CuZn hydroxy double salts

The role of hydroxy double salts (HDS) in the effective removal of organic contaminants from water is still controversial among researchers. In this work HDS materials, copper-zinc hydroxy acetate (CuZn-HA), and copper-zinc hydroxy nitrate (CuZn-HN) were produced and treated with aqueous methyl orange (MO), acid red 44 (AR44), or congo red (CR) under ambient conditions. Evidence from dye removal testing, materials analyses, and spin trapping measurements suggested possible three removal processes, dye sorption, intercalation reactions, and ·OH radicals assisted oxidation for suitable matching between dye and HDS material. Such three processes are responsible for the complete color (from the aqueous 500 ppm MO and AR44) and TOC removal achieved by using the CuZn-HN. The structural stability of the dye and HDS chemical composition play a key role on the oxidative reactivity and the intercalation ability of the dye in HDS structure.

An investigation of petrochemical emissions during KORUS-AQ: Ozone production, reactive nitrogen evolution, and aerosol production

Emissions and secondary photochemical products from the Daesan petrochemical complex (DPCC), on the west coast of South Korea, were measured from the NASA DC-8 research aircraft during the Korea-United States Air Quality campaign in 2016. The chemical evolution of petrochemical emissions was examined utilizing near-source and downwind plume transects. Small alkenes, such as ethene (C2H4), propene (C3H6), and 1,3-butadiene (C4H6), dominated the hydroxyl (OH) radical reactivity near the source region. The oxidation of these alkenes in the petrochemical plumes led to efficient conversion of nitrogen oxides (NOx) to nitric acid (HNO3), peroxycarboxylic nitric anhydrides (PANs), and alkyl nitrates (ANs), where the sum of the speciated reactive nitrogen contributes more than 80% of NOy within a few hours. Large enhancements of short-lived NOx oxidation products, such as hydroxy nitrates (HNs) and peroxyacrylic nitric anhydride, were observed, in conjunction with high ozone levels of up to 250 ppb, which are attributed to oxidation of alkenes such as 1,3-butadiene. Instantaneous ozone production rates, P(O3), near and downwind of the DPCC ranged from 9 to 24 ppb h−1, which were higher than those over Seoul. Ozone production efficiencies ranged from 6 to 10 downwind of the DPCC and were lower than 10 over Seoul. The contributions of alkenes to the instantaneous secondary organic aerosol (SOA) production rate, P(SOA), were estimated to be comparable to those of more common SOA precursors such as aromatics at intermediate distances from the DPCC. A model case study constrained to an extensive set of observations provided a diagnostic of petrochemical plume chemistry. The simulated plume chemistry reproduced the observed evolution of ozone and short-lived reactive nitrogen compounds, such as PANs and HNs as well as the rate and efficiency of ozone production. The simulated peroxy nitrates (PNs) budget included large contributions (approximately 30%) from unmeasured PNs including peroxyhydroxyacetic nitric anhydride and peroxybenzoic nitric anhydride. The large, predicted levels of these PAN compounds suggest their potential importance in chemical evolution of petrochemical plumes. One unique feature of the DPCC plumes is the substantial contribution of 1,3-butadiene to ozone and potentially SOA production. This work suggests that reductions in small alkene, especially 1,3-butadiene, emissions from the DPCC should be a priority for reducing downwind ozone.

Evaluation of isoprene nitrate chemistry in detailed chemical mechanisms

Abstract. Isoprene nitrates are important chemical species in the atmosphere which contribute to the chemical cycles that form ozone and secondary organic aerosol (SOA) with implications for climate and air quality. Accurate chemical mechanisms are important for the prediction of the atmospheric chemistry of species such as isoprene nitrates in chemical models. In recent years, studies into the chemistry of isoprene nitrates have resulted in the development of a range of mechanisms available for use in the simulation of atmospheric isoprene oxidation. This work uses a 0-D chemical box model to assess the ability of three chemically detailed mechanisms to predict the observed diurnal profiles of four groups of isoprene-derived nitrates in the summertime in the Chinese megacity of Beijing. An analysis of modelled C5H9NO5 isomers, including isoprene hydroperoxy nitrate (IPN) species, highlights the significant contribution of non-IPN species to the C5H9NO5 measurement, including the potentially large contribution of nitrooxy hydroxyepoxide (INHE). The changing isomer distribution of isoprene hydroxy nitrates (IHNs) derived from OH-initiated and NO3-initiated chemistry is discussed, as is the importance of up-to-date alkoxy radical chemistry for the accurate prediction of isoprene carbonyl nitrate (ICN) formation. All mechanisms under-predicted C4H7NO5 as predominately formed from the major isoprene oxidation products, methyl vinyl ketone (MVK) and methacrolein (MACR). This work explores the current capability of existing chemical mechanisms to accurately represent isoprene nitrate chemistry in urban areas significantly impacted by anthropogenic and biogenic chemical interactions. It suggests considerations to be taken when investigating isoprene nitrates in ambient scenarios, investigates the potential impact of varying isomer distributions on iodide chemical ionisation mass spectrometry (I−-CIMS) calibrations, and makes some proposals for the future development of isoprene mechanisms.

Photocatalytic Behavior of Supported Copper Double Salt: The Role of Graphene Oxide

The design of a photocatalyst that may work efficiently with sunlight is a fundamental concern to fight against environmental pollution and electrochemical hydrogen storage devices. In this work, it has been found that the green microwave-assisted decoration of graphene by copper double salt (DS) enhances visible sunlight photocatalysis efficiency. Nanohybrids of graphene oxide decorated with Cu(I) and Cu(II) oxides and copper hydroxy nitrate double salt were selected as photocatalysts for the degradation of rhodamine B in aqueous solution to study the effect of the graphene oxide support. The photodegradation process followed a pseudo–first-order kinetics for the bare catalysts, but the supported catalysts were best fitted to the Langmuir-Hinshelwood model. Supported systems were more efficient in terms of turnover and apparent rate constants. Diffuse reflectance spectroscopy with the use of Kubelka-Munk function allowed to measure bandgap energies. It was found that the absorption edge was reduced about 30% for the supported systems.

Condensed Phase Kinetic Studies of Hydroxynitrates Derived from the Photooxidation of Carene, Limonene, trans-Carveol, and Perillic Alcohol

Organic hydroxynitrates (HNs) are key products of hydrocarbon oxidation in the atmosphere. Understanding the fate and processing of these molecules is critical due to their function in the sequestration of NOx species from the atmosphere and in the formation of secondary organic aerosol. However, the direct study of individual HNs’ reactivity has been largely hindered by the lack of authentic standards which has further limited the ability to deconvolute the role of structural features. Herein, we report the kinetic stabilities of six biogenic volatile organic compound-derived HN in acidified single-phase organic/water matrices. Lifetimes for tertiary HNs ranged from 15 min to 6.4 h, whereas secondary HN varied from 56 days to 2.1 years. Product analysis highlights the role that additional non-hydrolysis reactions have in the condensed phase conversion of HNs. This work provides the first evidence for the structural dependence of HN stability in bulk mixed media.

Rapid hydrolysis of tertiary isoprene nitrate efficiently removes NOx from the atmosphere

The formation of a suite of isoprene-derived hydroxy nitrate (IHN) isomers during the OH-initiated oxidation of isoprene affects both the concentration and distribution of nitrogen oxide free radicals (NOx). Experiments performed in an atmospheric simulation chamber suggest that the lifetime of the most abundant isomer, 1,2-IHN, is shortened significantly by a water-mediated process (leading to nitric acid formation), while the lifetime of a similar isomer, 4,3-IHN, is not. Consistent with these chamber studies, NMR kinetic experiments constrain the 1,2-IHN hydrolysis lifetime to less than 10 s in deuterium oxide (D2O) at 298 K, whereas the 4,3-IHN isomer has been observed to hydrolyze much less efficiently. These laboratory findings are used to interpret observations of the IHN isomer distribution in ambient air. The IHN isomer ratio (1,2-IHN to 4,3-IHN) in a high NOx environment decreases rapidly in the afternoon, which is not explained using known gas-phase chemistry. When simulated with an observationally constrained model, we find that an additional loss process for the 1,2-IHN isomer with a time constant of about 6 h best explains our atmospheric measurements. Using estimates for 1,2-IHN Henry's law constant and atmospheric liquid water volume, we show that condensed-phase hydrolysis of 1,2-IHN can account for this loss process. Simulations from a global chemistry transport model show that the hydrolysis of 1,2-IHN accounts for a substantial fraction of NOx lost (and HNO3 produced), resulting in large impacts on oxidant formation, especially over forested regions.

New Insights into the Radical Chemistry and Product Distribution in the OH-Initiated Oxidation of Benzene.

Emissions of aromatic compounds cause air pollution and detrimental health effects. Here, we explore the reaction kinetics and products of key radicals in benzene photo-oxidation. After initial OH addition and reaction with O2, the effective production rates of phenol and bicyclic peroxy radical (BCP-peroxy) are experimentally constrained at 295 K to be 420 ± 80 and 370 ± 70 s-1, respectively. These rates lead to approximately 53% yield for phenol and 47% yield for BCP-peroxy under atmospheric conditions. The reaction of BCP-peroxy with NO produces bicyclic hydroxy nitrate with a branching ratio <0.2%, indicating efficient NOx recycling. Similarly, the reaction of BCP-peroxy with HO2 largely recycles HOx, producing the corresponding bicyclic alkoxy radical (BCP-oxy). Because of the presence of C-C double bonds and multiple functional groups, the chemistry of BCP-oxy and other alkoxy radicals in the system is diverse. Experimental results suggest the aldehydic H-shift and ring-closure to produce an epoxide functionality could be competitive with classic decomposition of alkoxy radicals. These reactions are potential sources of highly oxygenated molecules. Finally, despite the large number of compounds observed in our study, we are unable to account for ∼20% of the carbon flow.

Facile and rapid decoration of graphene oxide with copper double salt, oxides and metallic copper as catalysts in oxidation and coupling reactions

We present a new facile and rapid microwave-assisted method to synthesize four different copper nanocompounds on the surface of graphene oxide (GO). By starting from a mixture of copper nitrate and GO, copper hydroxy nitrate double salt (DS) (Cu2(OH)3(NO3)), copper (II) and copper (I) oxides and metallic copper (Cu0) were synthesized and supported simultaneously. The catalytic performance of the four copper/GO nanohybrids as well as some unsupported particles in some common organic reactions has been checked. The studied materials present a high versatility in C–C, C–N, and C–S couplings as well as in catalytic selective oxidation reactions. The performance of DS/GO as an heterogeneous catalyst is presented for the first time and shows the highest activity among all the copper/GO nanohybrid studied systems. The results open up the possibility of a more thorough study of the catalytic performance of the supported copper double salt in other different catalytic and consecutive processes of organic synthesis.

Isomeric Identification of Particle-Phase Organic Nitrates through Gas Chromatography and Time-of-Flight Mass Spectrometry Coupled with an Electron Capture Negative Ionization Source.

Organic nitrates (ONs) are an important component of secondary organic aerosols that play significant roles in atmospheric chemical processes such as ozone formation and as a reservoir of nitrogen oxides (NOx). However, hindered by the availability of analytical techniques, characteristics of ON molecules remain unclear in regions influenced by anthropogenic volatile organic compounds (VOCs) and pollution. In this study, we achieved isomeric identification of particle-phase ONs in such regions. Using gas chromatography and time-of-flight mass spectrometry with an electron capture negative ionization source, we established a systematic procedure for screening unknown ONs in fine particulate matter (PM) collected in Beijing based primarily on the characteristic fragment ions of NO2- and [M-NO2]-/[M-NO2-H2]-. We found 78 ON candidates, 12 of which were confirmed using synthesized standards. Seventy-three of these detected ONs might originate from anthropogenic VOC precursors especially alkenes. Significantly, we observed two isomers generated from straight-chain 1-alkenes, namely, 2-hydroxy-1-nitrate and 1-hydroxy-2-nitrate. The signal ratios of the two isomers suggested that these hydroxy nitrates are mainly produced photochemically rather than through nighttime reactions. This study provides a promising method for identifying ONs in atmospheric PM and elucidating their formation pathways.

Impact of foliar fertilization with nanosized zinc hydroxy nitrate on maize yield and quality

The objective of this study was to investigate the impact of foliar zinc application in the form of zinc hydroxy nitrate suspensions on maize grain yield and quality and on zinc distribution in the plant organs. The preparation of the zinc hydroxide nitrate (Zn5(OH)8(NO3)2·2H2O) was performed by pouring a NaOH solution into Zn(NO3)2·6H2O under vigorous stirring. All samples were characterized in detail by X-ray diffraction, scanning electron microscopy, thermal analysis, and inductively coupled plasma (ICP) mass spectrometry to determine their content, morphology and physicochemical properties. The field experiment was conducted at the Research Farm, Agricultural University, Bulgaria, via a randomized block design with eight variants in 3 replications. A significant (p &lt; 0.05) effect on Zn accumulation in the maize stems and leaves by foliar zinc application during the first growth stage was found. The accumulation of zinc was followed by its remobilization from the stems to other plant organs during the second growth stage. It was concluded that the synthesized zinc hydroxy nitrate has potential as a long-term foliar fertilizer. Ensuring the optimal concentration of Zn at different times during the vegetative period lead to a substantial increase in the grain yield along with an improvement in the quality of the corn grain for all variants compared to those of the control.

Characterization of trace aerosol compositions produced during the OH radical-initiated photooxidation of β-pinene

The detailed molecular composition of laboratory-generated secondary organic aerosols (SOA) during the high-NO photooxidation of β-pinene (βP) was investigated using a novel thermal desorption dichloromethane-assisted low-pressure photoionization mass spectrometry (TD-CH2Cl2-assisted LPPI-MS) technique. We found that protonated norpinone gave the highest signal intensity, which supported that assumption that this compound was the key oxidation species responsible for promoting βP-SOA formation. In addition to the previously identified monomers (i.e., 2,2-dimethylcyclobutyl-1,3-dicarboxaldehyde (m/z 140), pinene aldehyde (m/z 150), myrtenol (m/z 152), (2,2-dimethyl-3-acetyl)-cyclobutylformate (m/z 156), pinene acid (m/z 166), and isomers of pinalic-3-acid (m/z 170)), two additional nitrogen-containing species (i.e., C10 hydroxy nitrate and C10 carbonyl nitrate) were also observed at m/z values of 214 and 216 in the mass spectrum of βP-SOA. Furthermore, the losses of 18 (H2O), 46 (NO2), and 64 (H2O + NO2) were attributed to the typical fragmentation pathways of the two nitrogen-containing species. Overall, these results not only contribute to an improved understanding of βP-SOA formation, but they also indicate that TD-CH2Cl2-assisted LPPI-MS can be used as a novel detection means to study SOA formation.

In Situ In-House Powder X-ray Diffraction Study of Zero-Valent Copper Formation in Supercritical Methanol

Nano-/microcrystalline copper is widely used in catalysts, and it has potential for being used as conductive additive to ink for inkjet printed electronics. Copper is attractive, because it has excellent electrical conductivity and low cost compared to noble metals. The nucleation and phase transitions from the precursor to the final micrometer sized Cu in supercritical methanol have been studied for the first time using in-house in situ powder X-ray diffraction (PXRD). Temperatures have a significant impact on the reduction process of Cu2+; at a low synthesis temperature (250 °C), it was observed how the Cu2+ precursor initially formed copper hydroxy nitrate (Cu2(OH)3NO3) and transformed to copper(II)oxide (CuO), i.e., no reduction took place. At 300 °C, multiple phase transformation could be observed from initial copper hydroxy nitrate to zerovalent copper; the in situ investigations reveal the following phase transitions; CuII2(OH)3NO3 → CuIIO → CuI2O → Cu0. Increasing the synthesis temperature causes ...

Unimolecular Reactions of Peroxy Radicals Formed in the Oxidation of α-Pinene and β-Pinene by Hydroxyl Radicals.

Atmospheric oxidation of monoterpenes (emitted primarily by evergreen trees) is known to contribute to the formation and growth of aerosol particles. While recent research has tied the formation of organic aerosol to unimolecular chemistry of the organic peroxy radicals (RO2) formed in the oxidation of monoterpenes, the fundamental physical chemistry of these RO2 remains obscure. Here we use isomer-specific measurements and ab initio calculations to determine the unimolecular reaction rates and products of RO2 derived from the hydroxyl radical (OH) oxidation of α-pinene and β-pinene. Among all of the structural isomers of the first-generation RO2 from both monoterpenes, we find that the first-generation RO2 produced following opening of the four-membered ring undergo fast unimolecular reactions (4 ± 2 and 16 ± 5 s-1 for α-pinene and β-pinene, respectively) at 296 K, in agreement with high-level ab initio calculations. The presence of the hydroxy group and carbon-carbon double bond in the ring-opened RO2 enhances the rates of these unimolecular reactions, including endo-cyclization and H-shift via transition states involving six- and seven-membered rings. These reaction rate coefficients are sufficiently large that unimolecular chemistry is the dominant fate of these monoterpene-derived RO2 in the atmosphere. In addition, the overall yields of first-generation α-pinene and β-pinene hydroxy nitrates, C10H17NO4, at 296 K and 745 Torr are measured to be 3.3 ± 1.5% and 6.4 ± 2.1%, respectively, for conditions where all RO2 are expected to react with NO ([NO] > 1000 ppbv). These yields are lower than anticipated.

Transition metal based CuxNiyCoz-x-yO4 spinel composite solar selective absorber coatings for concentrated solar thermal applications

Solar selective absorber coatings, combining of nanostructured, ternary transition metal spinel structure and composite oxides were prepared by a series of transition metal (Co, Ni and Cu) based nitrate salts. A single-layered structure of crystalline phase spinel-type oxide AB2O4 in the framework of simple wet chemical route and dip coating method was prepared in the crystalline structure of CuxNiyCoz-x-yO4. The X-ray diffraction profile of the oxide film was found to coincide with that of crystalline [Cu2+0.31Co3+0.16Co2+0.53]A[Cu2+0.17Ni3+0.16Co3+1.67]BO4 in the ICDD database. Precursor salts were heated at a particular temperature to form hydroxy nitrate solution followed by suitable solvent with different binders to form adherent sol for dip coating technique. By optimizing sol concentration, withdrawal speed and annealing temperature, uniform absorber layer with solar absorptance of 0.91 and emittance of 0.14 were achieved in a single layer coating with a composite oxide formation. The optical, structural and morphological properties of the optimized coatings of single layer CuxNiyCoz-x-yO4 spinel and composite oxide have been characterized by UV–Vis–NIR spectrophotometer, emissometer, X-ray diffraction, field emission - scanning electron microscopy, transmission electron microscopy and X-ray photoelectron spectroscopy.

Gas Phase Conversion of UN and UC in Nitrating Atmosphere

The gas-phase conversion of UN and UC into water-soluble compounds in the atmosphere NOx–H2O (vapor)–air and HNO3 (vapor)–air in the interval 298–423 K was investigated. It is shown that in the gasphase conversion process UN is converted into water-soluble compounds (nitrates, hydroxy nitrates). It is found that the gas-phase conversion of UN in the atmosphere NOx–H2O (vapor)–air is less efficient than in the atmosphere HNO3 (vapor)–air. In the process of gas-phase conversion of UC in a nitrating atmosphere the main products of conversion are uranyl nitrate hydrates. In addition, carbon-containing products are formed and their removal requires ozonation of the solutions formed as a result of contact between water and the products of UC conversion.

Synthesis of CdO Ultradisperse Powders Using Atmospheric Pressure Glow Discharge in Contact With Solution and the Investigation of Intermediate Products

A new plasma-solution method of the CdO ultradisperse powders synthesis was described. The atmospheric pressure direct current discharge was excited in the ambient air by applying a high direct voltage to two pointed titanium electrodes placed above liquid anode and liquid cathode in the H-shaped cell. The discharge current was 40 mA and the total input power was about 40 W. The action of the DC glow discharge on the cadmium nitrate water solution in the absence of additional reagents and without electrodes-solution contact was shown to result in the production of the solids in the liquid phase. The kinetics of particles formation was studied using turbidimetry and nephelometry methods. Powders’ chemical composition and morphology was obtained using X-ray diffraction spectroscopy (XRD), electron-dispersive X-ray spectroscopy (EDX), thermogravimetric analysis (TGA), differential-scanning calorimetry (DSC) and scanning electron microscopy (SEM). It was found that as-synthesized powders are not the pure cadmium hydroxide but the mixture of the cadmium nitrate, hydroxy nitrate and hydroxide. Some assumptions regarding the mechanisms and pathway of the chemical processes both under the plasma action on the solution and during the calcination of as-synthesized powders were discussed.

Nitrate radical oxidation of &amp;lt;i&amp;gt;γ&amp;lt;/i&amp;gt;-terpinene: hydroxy nitrate, total organic nitrate, and secondary organic aerosol yields

Abstract. Polyolefinic monoterpenes represent a potentially important but understudied source of organic nitrates (ONs) and secondary organic aerosol (SOA) following oxidation due to their high reactivity and propensity for multi-stage chemistry. Recent modeling work suggests that the oxidation of polyolefinic γ-terpinene can be the dominant source of nighttime ON in a mixed forest environment. However, the ON yields, aerosol partitioning behavior, and SOA yields from γ-terpinene oxidation by the nitrate radical (NO3), an important nighttime oxidant, have not been determined experimentally. In this work, we present a comprehensive experimental investigation of the total (gas + particle) ON, hydroxy nitrate, and SOA yields following γ-terpinene oxidation by NO3. Under dry conditions, the hydroxy nitrate yield = 4(+1/−3) %, total ON yield = 14(+3/−2) %, and SOA yield ≤ 10 % under atmospherically relevant particle mass loadings, similar to those for α-pinene + NO3. Using a chemical box model, we show that the measured concentrations of NO2 and γ-terpinene hydroxy nitrates can be reliably simulated from α-pinene + NO3 chemistry. This suggests that NO3 addition to either of the two internal double bonds of γ-terpinene primarily decomposes forming a relatively volatile keto-aldehyde, reconciling the small SOA yield observed here and for other internal olefinic terpenes. Based on aerosol partitioning analysis and identification of speciated particle-phase ON applying high-resolution liquid chromatography–mass spectrometry, we estimate that a significant fraction of the particle-phase ON has the hydroxy nitrate moiety. This work greatly contributes to our understanding of ON and SOA formation from polyolefin monoterpene oxidation, which could be important in the northern continental US and the Midwest, where polyolefinic monoterpene emissions are greatest.

Measurement of isoprene nitrates by GCMS

Abstract. According to atmospheric chemistry models, isoprene nitrates play an important role in determining the ozone production efficiency of isoprene; however this is very poorly constrained through observations as isoprene nitrates have not been widely measured. Measurements have been severely restricted largely due to a limited ability to measure individual isoprene nitrate isomers. An instrument based on gas chromatography/mass spectrometry (GCMS) and the associated calibration methods are described for the speciated measurements of individual isoprene nitrate isomers. Five of the primary isoprene nitrates which formed in the presence of NOx by reaction of isoprene with the hydroxyl radical (OH) in the Master Chemical Mechanism are identified using known isomers on two column phases and are fully separated on the Rtx-200 column. Three primary isoprene nitrates from the reaction of isoprene with the nitrate radical (NO3) are identified after synthesis from the already identified analogous hydroxy nitrate. A Tenax adsorbent-based trapping system allows the analysis of the majority of the known hydroxy and carbonyl primary isoprene nitrates, although not the (1,2)-IN isomer, under field-like levels of humidity and showed no impact from typical ambient concentrations of NOx and ozone.