Chlorine Chemistry Research Articles

A Large Source of Atomic Chlorine From ClNO2 Photolysis at a U.K. Landfill Site

AbstractNitryl chloride (ClNO2) acts as a source of highly reactive chlorine atoms as well as an important NOx reservoir. Measurements of ClNO2 at an operational U.K. landfill site are reported here for the first time. A peak concentration of 4 ppb of ClNO2 was found with a peak mean nighttime maximum of 0.9 ppb. Using models based upon the photolysis of observed ClNO2 and atmospheric chlorine chemistry, chlorine atom concentrations reaching in excess of 1.20 × 105 molecules/cm3 in the early morning following sunrise are calculated. These concentrations are approximately 10 times higher than previously reported in the United Kingdom, suggesting a significant impact on the oxidizing capacity around such sites. Given the ubiquity of landfill sites regionally and globally, and the large abundances of Cl atoms from the photolysis of ClNO2, chlorine chemistry has a significant impact on ozone formation and volatile organic compounds oxidation as shown by WRF‐Chem modeling.

Springtime Nitrogen Oxide-Influenced Chlorine Chemistry in the Coastal Arctic.

Atomic chlorine (Cl) is a strong atmospheric oxidant that shortens the lifetimes of pollutants and methane in the springtime Arctic, where the molecular halogens Cl2 and BrCl are known Cl precursors. Here, we quantify the contributions of reactive chlorine trace gases and present the first observations, to our knowledge, of ClNO2 (another Cl precursor), N2O5, and HO2NO2 in the Arctic. During March - May 2016 near Utqiaġvik, Alaska, up to 21 ppt of ClNO2, 154 ppt of Cl2, 27 ppt of ClO, 71 ppt of N2O5, 21 ppt of BrCl, and 153 ppt of HO2NO2 were measured using chemical ionization mass spectrometry. The main Cl precursor was calculated to be Cl2 (up to 73%) in March, while BrCl was a greater contributor (63%) in May, when total Cl production was lower. Elevated levels of ClNO2, N2O5, Cl2, and HO2NO2 coincided with pollution influence from the nearby town of Utqiaġvik and the North Slope of Alaska (Prudhoe Bay) Oilfields. We propose a coupled mechanism linking NOx with Arctic chlorine chemistry. Enhanced Cl2 was likely the result of the multiphase reaction of Cl-(aq) with ClONO2, formed from the reaction of ClO and NO2. In addition to this NOx-enhanced chlorine chemistry, Cl2 and BrCl were observed under clean Arctic conditions from snowpack photochemical production. These connections between NOx and chlorine chemistry, and the role of snowpack recycling, are important given increasing shipping and fossil fuel extraction predicted to accompany Arctic sea ice loss.

An Investigation of the Role of Rapid Chlorine Hydrolysis on the Performance of Electrochemically-Mediated Desalination

A recent United Nations report estimates that more than two billion people presently lack access to clean drinking water and more than four billion people lack access to proper sanitation. Furthermore, steadily rising populations, a changing climate, and growth in the agriculture, energy, and manufacturing sectors jeopardize future water security in many parts of the world. Accordingly, energy-efficient separations of salts and trace contaminates from water represent one of the most significant (and difficult) challenges facing humankind. To address this problem, we have previously reported the development of a promising approach to the separation of salts from seawater which we refer to as electrochemically-mediated desalination (EMD). EMD is an electrokinetic technique which utilizes the electric field gradient formed local to an anode during chloride oxidation to separate charged species from pure water. Despite experimental and computational study of EMD, a deep understanding of phenomena fundamental to the technique has yet to be attained. To this end, we performed time-resolved high resolution electric field gradient measurements and direct conductivity measurements during electrochemical chloride oxidation within a simple system composed of microelectrodes embedded in a straight microchannel. We were surprised by the findings of these measurements. Specifically, a large electric field gradient was measured upstream of the anode during chloride oxidation, however, a local increase in solution conductivity was measured at the same axial position along the channel length during chloride oxidation. To address these seemingly contradictory findings, the experimental system was simulated by finite element modeling. Simulation results showed that electrochemically generated chlorine undergoes rapid hydrolysis and produces substantial quantities of HOCl, H+, and Cl- near the anode. This finding corroborates the experimentally observed increase in solution conductivity near the anode during chloride oxidation. Consequently, we hypothesize that the observed electric field gradient is not indicative of local solution conductivity, but rather is related to a surface interaction between a product of chloride oxidation and the Pt microband electrode used to probe the electric field gradient. Ongoing research seeks to confirm this claim. Ultimately, we conclude that complex aqueous chlorine chemistry significantly limits the utility of chlorine generation for the formation of a local electric field gradient and seawater desalination.

Utilizing surface modification in plasma‐enhanced cyclic etching of tantalum nitride to surpass lithographic limits

AbstractPitch subdivision of tantalum nitride (TaN) lines is demonstrated across a 200 mm wafer using a cyclic quasi‐atomic layer etch process in an inductively coupled plasma reactor. Chlorine (Cl2) and hydrogen (H 2) chemistries are introduced sequentially to an argon plasma in discrete steps to etch the TaN film. The starting lithographic pattern with critical dimension (CD) of approximately 82 nm and pitch of 200 nm thus yields lines of approximately 40 nm CD and 100 nm pitch with minimal line edge roughness increase. We identify a synergistic effect between H 2‐exposed TaN and Cl 2 plasma as contributing to this result, as well as a potential link to surface oxidation. Optical emission spectroscopy analysis of the plasma discharge is used to characterize reactive species densities and explain the observed changes in profile.

Chemical ionization quadrupole mass spectrometer with an electrical discharge ion source for atmospheric trace gas measurement

Abstract. We present a chemical ionization quadrupole mass spectrometer (CI-QMS) with a radio-frequency (RF) discharge ion source through N2∕CH3I as a source of primary ions. In addition to the expected detection of PAN, peracetic acid (PAA) and ClNO2 through well-established ion–molecule reactions with I− and its water cluster, the instrument is also sensitive to SO2, HCl and acetic acid (CH3C(O)OH) through additional ion chemistry unique to our ion source. We present ionization schemes for detection of SO2, HCl and acetic acid along with illustrative datasets from three different field campaigns underlining the potential of the CI-QMS with an RF discharge ion source as an alternative to 210Po. The additional sensitivity to SO2 and HCl makes the CI-QMS suitable for investigating the role of sulfur and chlorine chemistry in the polluted marine and coastal boundary layer.

Direct Electrolytic Splitting of Seawater: Opportunities and Challenges

Hot, coastal, hyper-arid regions with intense solar irradiation and strong on- and off-shore wind patterns are ideal locations for the production of renewable electricity using wind turbines or photovoltaics. Given ample access to seawater and scarce freshwater resources, such regions make the direct and selective electrolytic splitting of seawater into molecular hydrogen and oxygen a potentially attractive technology. The key catalytic challenge consists of the competition between anodic chlorine chemistry and the oxygen evolution reaction (OER). This Perspective addresses some aspects related to direct seawater electrolyzers equipped with selective OER and hydrogen evolution reaction (HER) electrocatalysts. Starting from a historical background to the most recent achievements, it will provide insights into the current state and future perspectives of the topic. This Perspective also addresses prospects of the combination of direct seawater electrolysis with hydrogen fuel cell technology (reversible seaw...

Atomic layer germanium etching for 3D Fin-FET using chlorine neutral beam

In case of using pure chlorine chemistry, Ge etching reactivity is three times higher than Si etching reactivity because of the larger lattice spacing in Ge. As a result, during the chlorine plasma etching of a Ge Fin structure, there are serious problems such as a large side-etching and large surface roughness on the Ge sidewall. Conversely, the authors found that several-ten nanometer-width Ge Fin structures with defect-free, vertical, and smooth sidewalls were successively delineated by chlorine neutral beam etching. Based on these results, the problems caused by chlorine plasma etching are considered to be due to the enhancement of chemical reactivity caused by defect on the sidewall with the irradiation of ultraviolet/vacuum ultra violet (UV/VUV) photons. Namely, it is clarified that the neutral beam etching could achieve real atomic layer etching by controlling the defect without any UV/VUV photons on the sidewall surface for future nanoscale Ge Fin structures.

Snowpack measurements suggest role for multi-year sea ice regions in Arctic atmospheric bromine and chlorine chemistry

As sources of reactive halogens, snowpacks in sea ice regions control the oxidative capacity of the Arctic atmosphere. However, measurements of snowpack halide concentrations remain sparse, particularly in the high Arctic, limiting our understanding of and ability to parameterize snowpack participation in tropospheric halogen chemistry. To address this gap, we measured concentrations of chloride, bromide, and sodium in snow samples collected during polar spring above remote multi-year sea ice (MYI) and first-year sea ice (FYI) north of Greenland and Alaska, as well as in the central Arctic, and compared these measurements to a larger dataset collected in the Alaskan coastal Arctic by Krnavek et al. (2012). Regardless of sea ice region, these surface snow samples generally featured lower salinities, compared to coastal snow. Surface snow in FYI regions was typically enriched in bromide and chloride compared to seawater, indicating snowpack deposition of bromine and chlorine-containing trace gases and an ability of the snowpack to participate further in bromine and chlorine activation processes. In contrast, surface snow in MYI regions was more often depleted in bromide, indicating it served as a source of bromine-containing trace gases to the atmosphere prior to sampling. Measurements at various snow depths indicate that the deposition of sea salt aerosols and halogen-containing trace gases to the snowpack surface played a larger role in determining surface snow halide concentrations compared to upward brine migration from sea ice. Calculated enrichment factors for bromide and chloride, relative to sodium, in the MYI snow samples suggests that MYI regions, in addition to FYI regions, have the potential to play an active role in Arctic boundary layer bromine and chlorine chemistry. The ability of MYI regions to participate in springtime atmospheric halogen chemistry should be considered in regional modeling of halogen activation and interpretation of satellite-based tropospheric bromine monoxide column measurements.

Heterogeneous Chlorination of Squalene and Oleic Acid.

Washing with chlorine bleach leads to high mixing ratios of gas-phase HOCl. Using two methods that are sensitive to surface film composition-attenuated total reflection fourier transform infrared (ATR-FTIR) spectroscopy and direct analysis in real time mass spectrometry (DART-MS)-we present the first study of the chlorination chemistry that occurs when gaseous HOCl reacts with thin films of squalene and oleic acid. At mixing ratios of 600 ppbv, HOCl forms chlorohydrins by adding across carbon-carbon double bonds without breaking the carbon backbone. The initial uptake of one HOCl molecule occurs on the time scale of a few minutes at these mixing ratios. For oleic acid, ester formation proceeds immediately thereafter, leading to dimeric and trimeric chlorinated products. For squalene, subsequent HOCl uptake occurs until all six of its carbon-carbon double bonds become chlorinated within 1-2 h. These results indicate that chlorination of skin oil, which contains substantial carbon unsaturation, is likely to occur rapidly under common cleaning conditions, potentially leading to the irritation associated with chlorinated bleach. This chemistry will likely also proceed with cooking oils, in the human respiratory system which has unsaturated surfactants as important components of lung fluid, and with organic components of the sea surface microlayer.

Formation and emission of hydrogen chloride in indoor air

To improve our understanding of chlorine chemistry indoors, reactive chlorine species such as hydrogen chloride (HCl) must be analyzed using fast time-response measurement techniques. Although well studied outdoors, sources of HCl indoors are unknown. In this study, mixing ratios of gaseous HCl were measured at 0.5Hz in the indoor environment using a cavity ring-down spectroscopy (CRDS) instrument. The CRDS measurement rate provides a major advance in observational capability compared to other established techniques. Measurements of HCl were performed during three types of household activities: (a) floor exposure to bleach, (b) chlorinated and nonchlorinated detergent use in household dishwashers, and (c) cooking events. Surface application of bleach resulted in a reproducible increase of 0.1 ppbv in the affected room. Emissions of HCl from automated dishwashers were observed only when chlorinated detergents were used, with additional HCl emitted during the drying cycle. Increased mixing ratios of HCl were also observed during meal preparation on an electric element stovetop. These observations of HCl derived from household activities indicate either direct emission or secondary production of HCl via chlorine atoms is possible. Calculations of photolysis rate constants of chlorine atom precursors provide evidence that photolysis may contribute to indoor HCl levels.

Determining the Efficacy, Safety and Suitability of Disinfectants to Prevent Emerging Infectious Disease Transmission

The scale of the 2014–2017 West African Ebola Virus Disease outbreak overwhelmed the international response capacity. This has led to inconsistencies in international guidance documents, particularly around chlorine disinfection of surfaces and hands to prevent transmission. To provide evidence for the disinfection recommendations, three research strands were conducted: (1) impacts of chlorine chemistry; (2) efficacy of surface cleaning recommendations; and (3) safety and efficacy of handwashing recommendations. Strand 1 research found that the compound chemistry of the chlorine source has an impact on the chlorine solution shelf-life (<1 day–30 days), with testing of chlorine solutions recommended to ensure accuracy. Strand 2 research found that surface cleaning with 0.5% chlorine solutions with a 15-min exposure time is efficacious in reducing transmission risk. Strand 3 research found that community handwashing with chlorine solutions is as safe and efficacious as handwashing with soap and water or sanitizer, which offers a benefit of reducing pathogens in the rinsing water. Using calcium hypochlorite as the chlorine source compound provided a particularly good performance in chemistry and handwashing studies. The research was successful at providing information to align with the inconsistent international guidelines. Further research is needed to proactively establish the efficacy, safety and suitability of disinfection for the seven viral pathogens that are considered likely to cause severe outbreaks with few/no medical countermeasures.

Particulate organohalogens in edible brown seaweeds

Brown algae, rich in antioxidants and other bioactive compounds, are important dietary seaweeds in many cultures. Like other marine macroalgae, brown seaweeds are known to accumulate the halogens iodine and bromine. Comparatively little is known about the chemistry of chlorine in seaweeds. We used synchrotron-based X-ray absorption spectroscopy to measure total non-volatile organochlorine and -bromine in five edible brown seaweeds: Laminaria digitata, Fucus vesiculosus, Pelvetia canaliculata, Saccharina latissima, and Undaria pinnatifida. Organochlorine concentrations range from 120 to 630 mg·kg−1 dry weight and organobromine from 150 to 360 mg·kg−1, comprising mainly aromatic organohalogens in both cases. Aliphatic organochlorine exceeds aliphatic organobromine but is positively correlated with it among the seaweeds. Higher organochlorine levels appear in samples with more lipid moieties, suggesting lipid chlorination as a possible formation pathway. Particulate organohalogens are not correlated with antioxidant activity or polyphenolic content in seaweed extracts. Such compounds likely contribute to organohalogen body burden in humans and other organisms.

On the discrepancy of HCl processing in the core of the wintertime polar vortices

Abstract. More than 3 decades after the discovery of the ozone hole, the processes involved in its formation are believed to be understood in great detail. Current state-of-the-art models can reproduce the observed chemical composition in the springtime polar stratosphere, especially regarding the quantification of halogen-catalysed ozone loss. However, we report here on a discrepancy between simulations and observations during the less-well-studied period of the onset of chlorine activation. During this period, which in the Antarctic is between May and July, model simulations significantly overestimate HCl, one of the key chemical species, inside the polar vortex during polar night. This HCl discrepancy is also observed in the Arctic. The discrepancy exists in different models to varying extents; here, we discuss three independent ones, the Chemical Lagrangian Model of the Stratosphere (CLaMS) as well as the Eulerian models SD-WACCM (the specified dynamics version of the Whole Atmosphere Community Climate Model) and TOMCAT/SLIMCAT. The HCl discrepancy points to some unknown process in the formulation of stratospheric chemistry that is currently not represented in the models. We characterise the HCl discrepancy in space and time for the Lagrangian chemistry–transport model CLaMS, in which HCl in the polar vortex core stays about constant from June to August in the Antarctic, while the observations indicate a continuous HCl decrease over this period. The somewhat smaller discrepancies in the Eulerian models SD-WACCM and TOMCAT/SLIMCAT are also presented. Numerical diffusion in the transport scheme of the Eulerian models is identified to be a likely cause for the inter-model differences. Although the missing process has not yet been identified, we investigate different hypotheses on the basis of the characteristics of the discrepancy. An underestimated HCl uptake into the polar stratospheric cloud (PSC) particles that consist mainly of H2O and HNO3 cannot explain it due to the temperature correlation of the discrepancy. Also, a direct photolysis of particulate HNO3 does not resolve the discrepancy since it would also cause changes in chlorine chemistry in late winter which are not observed. The ionisation caused by galactic cosmic rays provides an additional NOx and HOx source that can explain only about 20 % of the discrepancy. However, the model simulations show that a hypothetical decomposition of particulate HNO3 by some other process not dependent on the solar elevation, e.g. involving galactic cosmic rays, may be a possible mechanism to resolve the HCl discrepancy. Since the discrepancy reported here occurs during the beginning of the chlorine activation period, where the ozone loss rates are small, there is only a minor impact of about 2 % on the overall ozone column loss over the course of Antarctic winter and spring.

Halogen Chemistry of Hydrothermal Micas: a Possible Geochemical Tool in Vectoring to Ore for Porphyry Copper-Gold Deposit

Porphyry copper-gold deposit commonly exhibits an extensive alteration zone of hydrothermal micas particularly biotite and sericite. This study is aimed to analyze and utilize the chemistry of halogen fluorine and chlorine of biotite and sericite to be a possible tool in vectoring to ore for copper porphyry deposits. To achieve the objectives, several selected altered rock samples were taken crossing the Batu Hijau copper-gold mine from inner to outer of the deposit, and hydrothermal micas contained by the rocks were analyzed petrographically and chemically. Mineral chemistry was detected by electron microprobe analyzer, whilst biotite is petrographically classified as either magmatic or hydrothermal types. Sericite replacing plagioclase occurred as fine-grained mineral and predominantly associated with argillic-related alteration types. Biotites in the Batu Hijau deposit are classified as phlogopite with a relatively low mole fraction magnesium (XMg) (~0.75) compared to the “typical” copper porphyry deposit (~0.82). The relationship between the XMg and halogen contents are generally consistent with “Fe-F and Mg-Cl avoidance rules”. F content in biotite and sericite decrease systematically from inner part of the deposit which is represented by early biotite (potassic) zone where the main copper-gold hosted, to the outer part of the deposit. However, chlorine in both biotite and sericite from each of the alteration zones shows a relative similar concentration, which suggests that it is not suitable to be used in identification of the alteration zones associated with strong copper-gold mineralization. H2O content of the biotite and sericite also exhibits a systematic increase outward which may also provide a possible geochemical vector to ore for the copper porphyry deposits. This is well correlated with fluorine content of biotite in rocks and bulk concentration of copper from the corresponding rocks.

The relevance of reactions of the methyl peroxy radical (CH3O2) and methylhypochlorite (CH3OCl) for Antarctic chlorine activation and ozone loss

The maintenance of large concentrations of active chlorine in Antarctic spring allows strong chemical ozone destruction to occur. In the lower stratosphere (approximately 16–18 km, 85–55 hPa, 390–430 K) in the core of the polar vortex, high levels of active chlorine are maintained, although rapid gas-phase production of HCl occurs. The maintenance is achieved through HCl null cycles in which the HCl production is balanced by immediate reactivation. The chemistry of the methyl peroxy radical (CH3O2) is essential for these HCl null cycles and thus for Antarctic chlorine and ozone loss chemistry in the lower stratosphere in the core of the polar vortex. The key reaction here is the reaction ; this reaction should not be neglected in simulations of polar ozone loss. Here we investigate the full chemistry of CH3O2 in box-model simulations representative for the conditions in the core of the polar vortex in the lower stratosphere. These simulations include the reaction CH3O2 + Cl, the product methylhypochlorite (CH3OCl) of the reaction CH3O2 + ClO, and the subsequent chemical decomposition of CH3OCl. We find that when the formation of CH3OCl is taken into account, it is important that also the main loss channels for CH3OCl, namely photolysis and reaction with Cl are considered. Provided that this is the case, there is only a moderate impact of the formation of CH3OCl in the reaction CH3O2 + ClO on polar chlorine chemistry in our simulations. Simulated peak mixing ratios of CH3OCl ( ppb) occur at the time of the lowest ozone mixing ratios. Further, our model simulations indicate that the reaction CH3O2 + Cl does not have a strong impact on polar chlorine chemistry. During the period of the lowest ozone concentrations in late September, enhanced values of CH3O2 are simulated and, as a consequence, also enhanced values of formaldehyde (about 100 ppt) and methanol (about 5 ppt).

First Acid Ionization Constant of the Drinking Water Relevant Chemical Cyanuric Acid from 5 to 35 °C.

Cyanuric acid is present in drinking water when chemicals commonly referred to as dichlor (anhydrous sodium dichloroisocyanurate or sodium dichloroisocyanurate dihydrate) or trichlor (trichloroisocyanuric acid) are used as alternative free chlorine sources. Cyanuric acid and its ionization products combine with hypochlorous acid, forming various chlorinated cyanurates through a series of equilibrium reactions. Methods to measure the free chlorine (hypochlorous acid plus hypochlorite ion) concentration in systems adding cyanuric acid exhibit measurement bias. To overcome this limitation, one option is use of the established water chemistry of the free chlorine and cyanuric acid system to estimate free chlorine concentrations. Unfortunately, the equilibrium water chemistry has only been determined for 25 °C, limiting the usefulness of the water chemistry estimate in actual drinking water systems where temperatures may vary over a wide range (e.g., 5 to 35 °C). As a first step in extending the water chemistry model to relevant drinking water temperatures, the first acid ionization constant (K6) for cyanuric acid (H3Cy) and its first ionization product (H2Cy-) was determined using spectrophotometric techniques from 5 to 35 °C where or and ΔH° = 33.4 ± 1.7 kJ mol-1. As an example of temperature's impact (pH 7), the H2Cy- fraction of total cyanurate (sum of H3Cy and H2Cy-) effectively doubles from 5 to 35 °C. With K6's temperature dependence established, studies can be conducted to update the existing water chemistry model with temperature dependence, allowing free chlorine concentration simulation in drinking water systems with cyanuric acid present.

Gas-grain Fluorine and Chlorine Chemistry in the Interstellar Medium

Abstract We have studied the formation of fluorine- and chlorine-bearing species for a variety of dense interstellar conditions using a gas-grain network. Our homogeneous models have been constructed for low-temperature dense clouds, as well as warm-up regions. In addition to the observed species HF, , HCl, , and , we have included a number of additional halogen-containing molecules, and explored their gas-phase and grain-surface chemistry. These molecules include neutral species such as Cl2, ClO, CCl, and HCCl, as well as the carbon–halogen species CH2Cl and CH3Cl, and ionic species such as , , CH3ClH+, , , and . Predictions are made for the abundances of these species as functions of time, and comparisons are made with the observed abundances obtained for halogen species in dense regions, which include HF, HCl, CH3Cl, and CF+. The peak fractional abundance of the newly detected gas-phase CH3Cl is predicted to be in our warm-up simulations, depending upon density and the age of the pre-warm-up phase after which warm-up begins. These values can be compared with the observed abundance of methyl chloride in the hot corino IRAS 16293-2422 if the abundance of methanol is known.

Secondary organic aerosol from chlorine-initiated oxidation of isoprene

Abstract. Recent studies have found concentrations of reactive chlorine species to be higher than expected, suggesting that atmospheric chlorine chemistry is more extensive than previously thought. Chlorine radicals can interact with hydroperoxy (HOx) radicals and nitrogen oxides (NOx) to alter the oxidative capacity of the atmosphere. They are known to rapidly oxidize a wide range of volatile organic compounds (VOCs) found in the atmosphere, yet little is known about secondary organic aerosol (SOA) formation from chlorine-initiated photooxidation and its atmospheric implications. Environmental chamber experiments were carried out under low-NOx conditions with isoprene and chlorine as primary VOC and oxidant sources. Upon complete isoprene consumption, observed SOA yields ranged from 7 to 36 %, decreasing with extended photooxidation and SOA aging. Formation of particulate organochloride was observed. A high-resolution time-of-flight chemical ionization mass spectrometer was used to determine the molecular composition of gas-phase species using iodide–water and hydronium–water cluster ionization. Multi-generational chemistry was observed, including ions consistent with hydroperoxides, chloroalkyl hydroperoxides, isoprene-derived epoxydiol (IEPOX), and hypochlorous acid (HOCl), evident of secondary OH production and resulting chemistry from Cl-initiated reactions. This is the first reported study of SOA formation from chlorine-initiated oxidation of isoprene. Results suggest that tropospheric chlorine chemistry could contribute significantly to organic aerosol loading.

Germany gets boost in chlorine chemistry

AkzoNobel and Vinnolit are both expanding capacity in Germany for chlorine-based chemicals. AkzoNobel recently replaced mercury-cell chlorine production at its site in Frankfurt with more modern membrane technology. The project yielded additional chlorine capacity, which the company will use to expand output of chloromethanes. Vinnolit, the German affiliate of U.S.-based Westlake Chemical, is also installing a membrane chlorine unit, at its Gendorf, Germany, site. The company will use the additional output to expand vinyl chloride capacity. It expects to wrap up the projects by 2021.

Ground and Airborne U.K. Measurements of Nitryl Chloride: An Investigation of the Role of Cl Atom Oxidation at Weybourne Atmospheric Observatory

AbstractNitryl chloride (ClNO2) measurements from the Weybourne Atmospheric Observatory (WAO) are reported from March to April 2013 using a quadruple chemical ionization mass spectrometer with the I− ionization scheme. WAO is a rural coastal site with generally low NOx concentrations, a type of location poorly studied for ClNO2 production. Concentrations of ClNO2 exceeded that of the limit of detection (0.8 ppt) on each night of the campaign, as did concentrations of N2O5, which was also measured simultaneously with the Cambridge Broadband Cavity Enhanced Absorption Spectrometer. A peak concentration of 65 ppt of ClNO2 is reported here. Vertical profiles of ClNO2 from early‐ to middle‐morning flights in close proximity to WAO are also reported, showing elevated concentrations at low altitude. The photolysis of observed ClNO2 and a box model utilizing the Master Chemical Mechanism modified to include chlorine chemistry was used to calculate Cl atom concentrations. This model utilized numerous VOCs from the second Tropospheric Organic Chemistry project in 2004, at the same location and time of year. From this the relative importance of the oxidation of three groups of measured VOCs (alkanes, alkenes, and alkynes) by OH radicals, Cl atoms, and O3 is compared. Cl atom oxidation was deemed generally insignificant at this time and location for total oxidation due to the much lower concentration of ClNO2 observed, even following the night of greatest ClNO2 production.