scholarly journals Iodide-CIMS and <i>m/z</i> 62: The detection of HNO<sub>3</sub> as NO<sub>3</sub><sup>−</sup> in the presence of PAN, peracetic acid and O<sub>3</sub>

2021 ◽  
Author(s):  
Raphael Dörich ◽  
Philipp Eger ◽  
Jos Lelieveld ◽  
John N. Crowley
Keyword(s):  
Peracetic Acid ◽  
Laboratory Experiments ◽  
Field Experiments ◽  
Direct Reaction ◽  
Iodic Acid ◽  
Night Time ◽  
Airborne Measurements ◽  
Mixing Ratios ◽  
Cluster Ion ◽  
Humidity Dependence

Abstract. Chemical Ionisation Mass Spectrometry (CIMS) using I− (the iodide anion) as primary chemi-ion has previously been used to measure NO3 and N2O5 both in laboratory and field experiments. We show that reports of the large daytime mixing ratios of NO3 and N2O5 (usually only present in detectable amounts at night-time) are likely to be heavily biased by the ubiquitous presence of HNO3 in the troposphere and lower stratosphere. We demonstrate in a series of laboratory experiments that the CIMS detection of HNO3 at m/z 62 using I− ions is efficient in the presence of PAN or peracetic acid (PAA) and especially O3. We have characterised the dependence of the sensitivity to HNO3 detection on the presence of acetate anions (CH3CO2−, m/z 59, from either PAN or PAA). The loss of CH3CO2− via conversion to NO3− in the presence of HNO3 may represent a significant bias in I-CIMS measurements of PAN and CH3C(O)OOH. The largest sensitivity to HNO3 at m/z 62 is achieved in the presence of ambient levels of O3 whereby the thermodynamically disfavoured, direct reaction of I− with HNO3 to form NO3− is bypassed by the formation of IOX− which react with HNO3 to form e.g. iodic acid and NO3−. The ozone and humidity dependence of the detection of HNO3 at m/z 62 was characterised in laboratory experiments and applied to daytime, airborne measurements in which very good agreement with measurements of the I−(HNO3) cluster-ion (specific for HNO3 detection) was obtained.

scholarly journals Iodide CIMS and <i>m</i>∕<i>z</i> 62: the detection of HNO<sub>3</sub> as NO<sub>3</sub><sup>−</sup> in the presence of PAN, peroxyacetic acid and ozone

2021 ◽  
Vol 14 (8) ◽  
pp. 5319-5332
Author(s):  
Raphael Dörich ◽  
Philipp Eger ◽  
Jos Lelieveld ◽  
John N. Crowley
Keyword(s):  
Laboratory Experiments ◽  
Field Experiments ◽  
Direct Reaction ◽  
Peroxyacetic Acid ◽  
Iodic Acid ◽  
Airborne Measurements ◽  
Mixing Ratios ◽  
Cluster Ion ◽  
Humidity Dependence ◽  
The Impact

Abstract. Chemical ionisation mass spectrometry (CIMS) using I− (the iodide anion), hereafter I-CIMS, as a primary reactant ion has previously been used to measure NO3 and N2O5 both in laboratory and field experiments. We show that reports of large daytime mixing ratios of NO3 and N2O5 (both usually present in detectable amounts only at night) are likely to be heavily biased by the ubiquitous presence of HNO3 in the troposphere and lower stratosphere. We demonstrate in a series of laboratory experiments that the CIMS detection of HNO3 at m/z 62 using I− ions is efficient in the presence of peroxy acetyl nitric anhydride (PAN) or peroxyacetic acid (PAA) and especially O3. We have characterised the dependence of the sensitivity to HNO3 detection on the presence of acetate anions (CH3CO2-, m/z 59, from either PAN or PAA). The loss of CH3CO2- via conversion to NO3- in the presence of HNO3 may represent a significant bias in I-CIMS measurements of PAN and PAA in which continuous calibration (e.g. via addition of isotopically labelled PAN) is not carried out. The greatest sensitivity to HNO3 at m/z 62 is achieved in the presence of ambient levels of O3 whereby the thermodynamically disfavoured, direct reaction of I− with HNO3 to form NO3- is bypassed by the formation of IOx-, which reacts with HNO3 to form, for example, iodic acid and NO3-. The ozone and humidity dependence of the detection of HNO3 at m/z 62 was characterised in laboratory experiments and applied to daytime, airborne measurements in which good agreement with measurements of the I−(HNO3) cluster ion (specific for HNO3 detection) was obtained. At high ozone mixing ratios, we show that the concentration of I− ions in our ion–molecule reactor (IMR) is significantly depleted. This is not reflected by changes in the measured I− signal at m/z 127 as the IOx- formed does not survive passage through the instrument but is likely detected after fragmentation to I−. This may result in a bias in measurements of trace gases using I-CIMS in stratospheric air masses unless a calibration gas is continuously added or the impact of O3 on sensitivity is characterised.

Concentration of Impurities during Melting of Snow Made from Secondary Sewage Effluent

1986 ◽  
Vol 18 (2) ◽  
pp. 151-156 ◽  
Author(s):  
R. Zapf-Gilje ◽  
S. O. Russell ◽  
D. S. Mavinic
Keyword(s):  
Potassium Chloride ◽  
Chloride Solution ◽  
Laboratory Experiments ◽  
Field Experiments ◽  
Low Cost ◽  
Sewage Effluent ◽  
Potassium Chloride Solution ◽  
Laboratory Results ◽  
Solution Field ◽  
Concentration Of Impurities

When snow is made from sewage effluent, the impurities become concentrated in the early melt leaving the later runoff relatively pure. This could provide a low cost method of separating nutrients from secondary sewage effluent. Laboratory experiments showed that the degree of concentration was largely independent of the number of melt freeze cycles or initial concentration of impurity in the snow. The first 20% of melt removed with it 65% of the phosphorus and 90% of the nitrogen from snow made from sewage effluent; and over 90% of potassium chloride from snow made from potassium chloride solution. Field experiments with a salt solution confirmed the laboratory results.

scholarly journals One-Year Characterization and Reactivity of Isoprene and Its Impact on Surface Ozone Formation at A Suburban Site in Guangzhou, China

Atmosphere ◽  
2019 ◽  
Vol 10 (4) ◽  
pp. 201 ◽  
Author(s):  
Yu Zou ◽  
Xue Jiao Deng ◽  
Tao Deng ◽  
Chang Qin Yin ◽  
Fei Li
Keyword(s):  
Surface Ozone ◽  
Atmospheric Composition ◽  
Anthropogenic Factors ◽  
Mixing Ratio ◽  
Night Time ◽  
Subtropical Zone ◽  
Guangzhou City ◽  
Mixing Ratios ◽  
One Year ◽  
Suburban Site

Isoprene has a potentially large effect on ozone (O3) formation in the subtropical, highly polluted city of Guangzhou. Online measurements of isoprene in Guangzhou city are scarce; thus, isoprene levels were monitored for one year at the Guangzhou Panyu Atmospheric Composition Station (GPACS), a suburban site in Guangzhou, using an online gas chromatography-flame ionization detector (GC–FID) system to investigate the characterization and reactivity of isoprene and its effect on the O3 peak profile in different seasons. The results showed that the daily average mixing ratios of isoprene at GPACS were 0.40, 2.20, 1.40, and 0.13 mixing ratio by volume (ppbv) in spring, summer, autumn, and winter, respectively. These values were considerably higher than the mixing ratios of isoprene in the numerous other subtropical and temperate cities around the world. Furthermore, isoprene ranked first with regard to O3 formation potential (OFP) and propylene-equivalent mixing ratio among 56 measured non–methane hydrocarbons (NMHCs). The ratios of isoprene to cis-2-butene, an exhaust tracer, were determined to estimate the fractions of biogenic and anthropogenic emissions. The results revealed a much greater contribution from biogenic than anthropogenic factors during the daytime in all four seasons. In addition, night-time isoprene emissions were mostly associated with vehicles in winter, and the residual isoprene that remained after photochemical loss during the daytime also persisted into the night. The high levels of isoprene in summer and autumn may cause the strong and broad peaks of the O3 profile because of its association with the most favorable meteorological conditions (e.g., high temperature and intense solar radiation) and the highest OH mixing ratio, which could affect human health by exposing people to a high O3 mixing ratio for prolonged periods. The lower mixing ratios of isoprene resulted in a weak and sharp peak in the O3 profile in both spring and winter. The high level of isoprene in the subtropical zone could accentuate its large impact on atmospheric oxidant capacity and air quality in Guangzhou city.

scholarly journals Source attributions of pollution to the Western Arctic during the NASA ARCTAS field campaign

2013 ◽  
Vol 13 (9) ◽  
pp. 4707-4721 ◽  
Author(s):  
H. Bian ◽  
P. R. Colarco ◽  
M. Chin ◽  
G. Chen ◽  
J. M. Rodriguez ◽  
...  
Keyword(s):  
Biomass Burning ◽  
Field Experiments ◽  
Transport Model ◽  
Background Level ◽  
Anthropogenic Emissions ◽  
Airborne Measurements ◽  
Ch4 Production ◽  
Regional Sources ◽  
Western Arctic ◽  
Co Concentrations

Abstract. We use the NASA GEOS-5 transport model with tagged tracers to investigate the contributions of different regional sources of CO and black carbon (BC) to their concentrations in the Western Arctic (i.e., 50–90° N and 190–320° E) in spring and summer 2008. The model is evaluated by comparing the results with airborne measurements of CO and BC from the NASA Arctic Research of the Composition of the Troposphere from Aircraft and Satellites (ARCTAS) field campaigns to demonstrate the strengths and limitations of our simulations. We also examine the reliability of tagged CO tracers in characterizing air mass origins using the measured fossil fuel tracer of dichloromethane and the biomass burning tracer of acetonitrile. Our tagged CO simulations suggest that most of the enhanced CO concentrations (above background level from CH4 production) observed during April originate from Asian anthropogenic emissions. Boreal biomass burning emissions and Asian anthropogenic emissions are of similar importance in July domain wise, although the biomass burning CO fraction is much larger in the area of the ARCTAS field experiments. The fraction of CO from Asian anthropogenic emissions is larger in spring than in summer. European sources make up no more than 10% of CO levels in the campaign domain during either period. Comparisons of CO concentrations along the flight tracks with regional averages from GEOS-5 show that the along-track measurements are representative of the concentrations within the large domain of the Western Arctic in April but not in July.

scholarly journals Interactions Between Chill-Hours and Degree-Days Affect Carpogenic Germination in Monilinia vaccinii-corymbosi

2001 ◽  
Vol 91 (1) ◽  
pp. 77-83 ◽  
Author(s):  
H. Scherm ◽  
A. T. Savelle ◽  
P. L. Pusey
Keyword(s):  
Laboratory Experiments ◽  
Field Experiments ◽  
Degree Days ◽  
Carpogenic Germination ◽  
Conditioning Period ◽  
Low Degree ◽  
Heating Degree Days ◽  
Relationship Of ◽  
High Degree ◽  
The Relationship

The relationship of cumulative chill-hours (hours with a mean temperature <7.2°C) and heating degree-days (base 7.2°C) to carpogenic germination of pseudosclerotia of Monilinia vaccinii-corymbosi, which causes mummy berry disease of blueberry, was investigated. In two laboratory experiments, pseudosclerotia collected from rabbiteye blueberry in Georgia were conditioned at 5 to 6°C for 26 to 1,378 h prior to placement in conditions favorable for germination and apothecium development. The number of chill-hours accumulated during the conditioning period affected the subsequent proportion of pseudosclerotia that germinated and produced apothecia, with the greatest incidence of carpogenic germination occurring after intermediate levels of chilling (≈700 chill-hours). The minimum chilling requirement for germination and apothecium production was considerably lower than that reported previously for pseudo-sclerotia from highbush blueberry in northern production regions. The rate of carpogenic germination was strongly affected by interactions between the accumulation of chill-hours and degree-days during the conditioning and germination periods; pseudosclerotia exposed to prolonged chilling periods, once transferred to suitable conditions, germinated and produced apothecia more rapidly (after fewer degree-days had accumulated) than those exposed to shorter chilling periods. Thus, pseudosclerotia of M. vaccinii-corymbosi are adapted to germinate carpogenically following cold winters (high chill-hours, low degree-days) as well as warm winters (low chill-hours, high degree-days). Results were validated in a combined field-laboratory experiment in which pseudosclerotia that had received various levels of natural chilling were allowed to germinate in controlled conditions in the laboratory, and in two field experiments in which pseudosclerotia were exposed to natural chilling and germination conditions. A simple model describing the timing of apothecium emergence in relation to cumulative chill-hours and degree-days was developed based on the experiments. The model should be useful for better timing of field scouting programs for apothecia to aid in management of primary infection by M. vaccinii-corymbosi.

scholarly journals An aircraft gas chromatograph–mass spectrometer System for Organic Fast Identification Analysis (SOFIA): design, performance and a case study of Asian monsoon pollution outflow

2017 ◽  
Vol 10 (12) ◽  
pp. 5089-5105 ◽  
Author(s):  
Efstratios Bourtsoukidis ◽  
Frank Helleis ◽  
Laura Tomsche ◽  
Horst Fischer ◽  
Rolf Hofmann ◽  
...  
Keyword(s):  
Time Resolution ◽  
Asian Monsoon ◽  
Electrical Safety ◽  
Back Trajectory ◽  
Airborne Measurements ◽  
Mixing Ratios ◽  
Fast Identification ◽  
Chemistry Research ◽  
Identification Analysis

Abstract. Volatile organic compounds (VOCs) are important for global air quality and oxidation processes in the troposphere. In addition to ground-based measurements, the chemical evolution of such species during transport can be studied by performing in situ airborne measurements. Generally, aircraft instrumentation needs to be sensitive, robust and sample at higher frequency than ground-based systems while their construction must comply with rigorous mechanical and electrical safety standards. Here, we present a new System for Organic Fast Identification Analysis (SOFIA), which is a custom-built fast gas chromatography–mass spectrometry (GC-MS) system with a time resolution of 2–3 min and the ability to quantify atmospheric mixing ratios of halocarbons (e.g. chloromethanes), hydrocarbons (e.g isoprene), oxygenated VOCs (acetone, propanal, butanone) and aromatics (e.g. benzene, toluene) from sub-ppt to ppb levels. The relatively high time resolution is the result of a novel cryogenic pre-concentration unit which rapidly cools (∼ 6 °C s−1) the sample enrichment traps to −140 °C, and a new chromatographic oven designed for rapid cooling rates (∼ 30 °C s−1) and subsequent thermal stabilization. SOFIA was installed in the High Altitude and Long Range Research Aircraft (HALO) for the Oxidation Mechanism Observations (OMO) campaign in August 2015, aimed at investigating the Asian monsoon pollution outflow in the tropical upper troposphere. In addition to a comprehensive instrument characterization we present an example monsoon plume crossing flight as a case study to demonstrate the instrument capability. Hydrocarbon, halocarbon and oxygenated VOC data from SOFIA are compared with mixing ratios of carbon monoxide (CO) and methane (CH4), used to define the pollution plume. By using excess (ExMR) and normalized excess mixing ratios (NEMRs) the pollution could be attributed to two air masses of distinctly different origin, identified by back-trajectory analysis. This work endorses the use of SOFIA for aircraft operation and demonstrates the value of relatively high-frequency, multicomponent measurements in atmospheric chemistry research.

scholarly journals Night-time chemistry above London: measurements of NO<sub>3</sub> and N<sub>2</sub>O<sub>5</sub> from the BT Tower during REPARTEE-II

2010 ◽  
Vol 10 (6) ◽  
pp. 14347-14386
Author(s):  
A. K. Benton ◽  
J. M. Langridge ◽  
S. M. Ball ◽  
W. J. Bloss ◽  
M. Dall'Osto ◽  
...  
Keyword(s):  
Nitrogen Oxides ◽  
Absorption Spectroscopy ◽  
Nitrogen Compounds ◽  
Equilibrium Partitioning ◽  
Night Time ◽  
Positive Correlation ◽  
Mixing Ratios ◽  
Enhanced Absorption ◽  
Cavity Enhanced Absorption Spectroscopy ◽  
The Mean

Abstract. Broadband cavity enhanced absorption spectroscopy (BBCEAS) has been used to measure the sum of concentrations of NO3 and N2O5 from the BT (telecommunications) Tower 160 m above street level in central London during the REPARTEE II campaign in October and November 2007. Substantial variability was observed in these night-time nitrogen compounds: peak NO3+N2O5 mixing ratios reached 800 pptv, whereas the mean night-time NO3+N2O5 was approximately 30 pptv. Additionally, [NO3+N2O5] showed negative correlations with [NO] and [NO2] and a positive correlation with [O3]. Co-measurements of temperature and NO2 from the BT Tower were used to calculate the equilibrium partitioning between NO3 and N2O5 which was always found to strongly favour N2O5 (NO3/N2O5=0.01 to 0.04). Two methods are used to calculate the lifetimes for NO3 and N2O5, the results being compared and discussed in terms of the implications for the night-time oxidation of nitrogen oxides and the night-time sinks for NOy.

scholarly journals Technical Note: Determination of formaldehyde mixing ratios in polluted air with PTR-MS: laboratory experiments and field measurements

2007 ◽  
Vol 7 (5) ◽  
pp. 12845-12876
Author(s):  
S. Inomata ◽  
H. Tanimoto ◽  
S. Kameyama ◽  
U. Tsunogai ◽  
H. Irie ◽  
...  
Keyword(s):  
Proton Transfer ◽  
Field Measurements ◽  
Proton Transfer Reaction ◽  
Technical Note ◽  
Detection Sensitivity ◽  
Optical Absorption Spectroscopy ◽  
High Time Resolution ◽  
Mixing Ratios ◽  
Proton Transfer Reactions ◽  
Humidity Dependence

Abstract. Formaldehyde (HCHO), the most abundant carbonyl compound in the atmosphere, is generated as an intermediate product in the oxidation of nonmethane hydrocarbons. Proton transfer reaction mass spectrometry (PTR-MS) has the capability to detect HCHO from ion signals at m/z 31 with high time-resolution. However, the detection sensitivity is low compared to other detectable species, and is considerably affected by humidity, due to back reactions between protonated HCHO and water vapor prior to analysis. We performed a laboratory calibration of HCHO by PTR-MS and examined the detection sensitivity and humidity dependence at various field strengths. Subsequently, we deployed the PTR-MS instrument in a field campaign at Mount Tai in China in June 2006 to measure HCHO in various meteorological and photochemical conditions; we also conducted intercomparison measurements by Multi-Axis Differential Optical Absorption Spectroscopy (MAX-DOAS). Correction of interference in the m/z 31 signals by fragments from proton transfer reactions with methyl hydroperoxide, methanol, and ethanol greatly improves agreement between the two methods, giving the correlation [HCHO]MAX-DOAS = (0.99±0.16) [HCHO]PTR-MS + (0.02±0.38), where error limits represent 95% confidence levels.

scholarly journals The chemistry influencing ODEs in the Polar Boundary Layer in spring: a model study

2008 ◽  
Vol 8 (2) ◽  
pp. 7391-7453 ◽  
Author(s):  
M. Piot ◽  
R. von Glasow
Keyword(s):  
Boundary Layer ◽  
Ozone Depletion ◽  
Chemical Species ◽  
Field Measurements ◽  
The Arctic ◽  
Direct Reaction ◽  
Mixing Ratios ◽  
Model Study ◽  
Sensitivity Studies ◽  
Chemical Conditions

Abstract. Near-total depletions of ozone have been observed in the Arctic spring since the mid 1980s. The autocatalytic cycles involving reactive halogens are now recognized to be of main importance for Ozone Depletion Events (ODEs) in the Polar Boundary Layer (PBL). We present sensitivity studies using the model MISTRA in the box-model mode on the influence of chemical species on these ozone depletion processes. In order to test the sensitivity of the chemistry under polar conditions, we compared base runs undergoing fluxes of either Br2, BrCl, or Cl2 to induce ozone depletions, with similar runs including a modification of the chemical conditions. The role of HCHO, H2O2, DMS, Cl2, C2H4, C2H6, HONO, NO2, and RONO2 was investigated. Cases with elevated mixing ratios of HCHO, H2O2, DMS, Cl2, and HONO induced a shift in bromine speciation from Br/BrO to HOBr/HBr, while high mixing ratios of C2H6 induced a shift from HOBr/HBr to Br/BrO. Cases with elevated mixing ratios of HONO, NO2, and RONO2 induced a shift to BrNO2/BrONO2. The shifts from Br/BrO to HOBr/HBr accelerated the aerosol debromination, but also increased the total amount of deposited bromine at the surface (mainly via increased deposition of HOBr). These shifts to HOBr/HBr also hindered the BrO self-reaction. In these cases, the ozone depletion was slowed down, where increases in H2O2 and HONO had the greatest effect. The tests with increased mixing ratios of C2H4 highlighted the decrease in HOx which reduced the production of HOBr from bromine radicals. In addition, the direct reaction of C2H4 with bromine atoms led to less available reactive bromine. The aerosol debromination was therefore strongly reduced. Ozone levels were highly affected by the chemistry of C2H4. Cl2-induced ozone depletions were found unrealistic compared to field measurements due to the rapid production of CH3O2, HOx, and ROOH which rapidly convert reactive chlorine to HCl in a "chlorine counter-cycle". This counter-cycle efficiently reduces the concentration of reactive halogens in the boundary layer. Depending on the relative bromine and chlorine mixing ratios, the production of CH3O2, HOx, and ROOH from the counter-cycle can significantly affect the bromine chemistry. Therefore, the presence of both bromine and chlorine in the air may unexpectedly lead to a slow down in ozone destruction. For all NOy species studied (HONO, NO2, RONO2) the chemistry is characterized by an increased bromine deposition on snow reducing the amount of reactive bromine in the air. Ozone is less depleted under conditions of high mixing ratios of NOx. The production of HNO3 led to the acid displacement of HCl, and the release of chlorine out of salt aerosols (Cl2 or BrCl) increased.

scholarly journals Planning MAR Schemes Using Physical Models: Comparison of Laboratory and Field Experiments

2019 ◽  
Vol 9 (18) ◽  
pp. 3652
Author(s):  
Jana Sallwey ◽  
Felix Barquero ◽  
Thomas Fichtner ◽  
Catalin Stefan
Keyword(s):  
Vadose Zone ◽  
Laboratory Experiments ◽  
Field Experiments ◽  
Managed Aquifer Recharge ◽  
Physical Models ◽  
Aquifer Recharge ◽  
Operational Parameters ◽  
Flow Processes ◽  
Models Comparison ◽  
Other Regarding

Infiltration experiments in the context of managed aquifer recharge (MAR) are often conducted to assess the processes influencing the operation of full-scale MAR schemes. For this, physical models such as laboratory experiments and, less often, field experiments are used to determine process specifics or operational parameters. Due to several assumptions, scale-related limitations, and differing boundary conditions, the upscaling of results from the physical models is not straightforward. Investigations often lead to over- or underestimations of flow processes that constrain the translation of results to field-like conditions. To understand the restrictions and potential of different physical models for MAR assessment, surface infiltration experiments in different scales and dimensions, which maintained the same operational parameters, were conducted. The results from the different setups were compared against each other regarding the reproduction water flow in the vadose zone and the influence of parameters such as soil type and climate. Results show that mostly qualitative statements can be made, whereas quantitative analysis through laboratory experiments is limited.

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