Peroxyacetyl Nitrate (PAN) Measurements During the POPCORN Campaign

During the POPCORN campaign between 3 and 24 August 1994 we measured peroxyacetyl nitrate (PAN) in a rural area of Mecklenburg-Vorpommern (North-Eastern Germany) above a corn field. A total of about 5000 PAN measurements were carried out within the three weeks of the campaign. Measured PAN mixing ratios ranged from below the detection limit of 10 ppt up to an afternoon maximum of 1 ppb. The mean value of all data was 140 ppt. The daily mean PAN mixing ratios were typically in the range of 50 to 250 ppt, but during a clean air episode PAN mixing ratios of well below 40 ppt were observed. The characteristic relative diurnal variation of the PAN mixing ratios with a late night/early morning minimum and an afternoon maximum persisted during these episodes. The daily averages of the PAN mixing ratios showed clear episodic variations which coincided with the duration of typical synoptic episodes of two to six days duration. Based on the measurements of the various parameters determining the PAN formation and destruction rates, the local budget for PAN was calculated. During daytime the calculated net photochemical formation rate of PAN was nearly always significantly higher than the observed change of the PAN concentration. This demonstrates that substantial amounts of PAN (often in the range of several hundred ppt/h) were exported from the corn field. The resulting removal of NOx to some extent effects the budget of nitrogen oxides (NOx), but the export of odd oxygen radicals in the form of PAN during daytime often amounted up to 30–50% of the OH-radical formation by ozone photolysis. Thus the importance of PAN as reservoir and transport medium for odd oxygen radicals can be very substantial and may have a significant impact on the budget and distribution of odd oxygen radicals.     

POPCORN: A Field Study of Photochemistry in North-Eastern Germany

The intensive field study POPCORN (Photo-Oxidant Formation by Plant Emitted Compounds and OH Radicals in North-Eastern Germany) was carried out in a rural area of North-Eastern Germany during August 1994. An overview of the objectives, measurements and major results of this campaign is presented. Measurements of a set of relevant atmospheric trace compounds, including the hydroxyl radical, along with meteorological data were performed to increase the understanding of OH radical chemistry and photo-oxidant formation. Additionally, plant emissions and the exchange of trace gases between a maize field and the atmosphere were investigated. Budgets of selected trace gases were calculated to assess the relative importance of local sources, chemistry or transport. Intercomparisons between measurement techniques were a central issue of POPCORN and included measurements of OH, hydrocarbons, formaldehyde, photolysis frequencies and vertical fluxes. OH radical concentrations were measured simultaneously by LIF (Laser Induced Fluorescence) and DOAS (Differential Optical Absorption Spectroscopy). Both methods showed good agreement. Maximum OH concentrations were around 107 cm–3 and the diurnal cycles closely followed the rate of primary production via ozone photolysis. Generally, the trace gas composition during POPCORN was characterized by relatively low concentrations of most compounds, e.g. CO: 85–200 ppb, ethane: 0.6–2 ppb, and moderate NOx levels: 0.5–5 ppb (at noontime). Concentrations of individual biogenic volatile organic compounds (VOC) were mostly well below 100 ppt. However, formaldehyde and acetaldehyde which partly originate from biological sources were observed at mixing ratios of some ppb.     

Measurements of Volatile Organic Compounds (VOC) During POPCORN 1994: Applying a New On-Line GC–MS-Technique

Atmospheric concentrations of ca. 250 C6–C15 hydrocarb on and C4–C12 oxygenated volatile organic compounds (VOC) including alkanes, benzene and alkyl benzenes, monoterpenes and aldehydes were measured in August 1994 during the POPCORN campaign (POPCORN = Photo-Oxidant formation by Plant emitted Compounds and OH Radicals in North-Eastern Germany). About 80 substances together contributed 90% of the atmospheric carbon in this range of molecular weight. During this field campaign VOC-emissions from several crop and tree species and the ambient concentrations of CO, C2–C7 non-methane hydrocarbons (NMHC), C1 and C2 aldehydes, nitrogen oxides, ozone and hydroxyl-radicals (OH) were also measured. These data were used to interpret the VOC measurements presented here. The on-line GC–MS used for the VOC measurements combines adsorptive sampling with thermal desorption and GC–MS analysis in an automated system. Internal standards were used to quantify the measurements. Ozone was destroyed prior to the sample preconcentration through the gas phase reaction with NO. Aromatic compounds like benzene, toluene and xylenes were the most abundant compound class among the measured substances, -pinene and 3-carene, most probably originating from pineforests ca. 1 km away from the measuring site, were the most abundant monoterpenes. The highest mixing ratios of most compounds were measured in nights with strong inversion situations. The toluene mixing ratios then reached 630 pptv; -pinene mixing ratios went up to 430 pptv. The median of all toluene and -pinene measurements during the campaign was 125 pptv or 22 pptv, respectively. These values are on the lower end of ambient measurements reported for continental sites. In most samples also n-pentanal, n-hexananl, n-nonanal and n-undecanal were present. Median mixing ratios were 9, 16, 14 and 8 pptv, respectively. Emission studies indicate that these highly reactive compounds are most probably emitted from maize. It is shown by a simple first order approach that the potential for ozone formation during the POPCORN campaign was roughly equal for anthropogenic and biogenic VOC. From measured concentrations of ozone, OH-radicals, methane, CO, C2–C15 nonmethane hydrocarbons (NMHC) and C5–C11 aldehydes a photochemical production of ozone in the order of 3.5 ppb/h can be estimated. Apart from formaldehyde and acetaldehyde, which are at least partly products of VOC oxidation, the substance group with the largest contribution to the VOC turnover are the monoterpenes. They contribute ca. 30%. However, the mechanism of terpene oxidation is very complex and presently only partly understood. Thus the actual contribution of monoterpenes to ozone formation is very uncertain. Other measured compound classes such as light alkenes, alkanes, aromatics, and C5–C11 aldehydes contribute each between 10% and 15% to ozone formation. The measuring site was not influenced directly from strong biogenic or anthropogenic sources, and the results obtained during the POPCORN campaign can be regarded as a typical picture of a remote rural central European environment.     

In-situ Measurements of Tropospheric Hydroxyl Radicals by Folded Long-Path Laser Absorption During the Field Campaign POPCORN

Absolutely calibrated in-situ measurements of tropospheric hydroxyl radicals, formaldehyde, sulfur dioxide, and naphthalene (C10H8) were performed by long-path laser absorption spectroscopy during the field campaign POPCORN. The absorption light path was folded into an open optical multiple reflection cell with a mirror separation of 38.5 m. Using a light path length of 1848 m and an integration time of 200 s, the average 1-detection limits of OH, HCHO, SO2 and C10H8 during POPCORN were 8.7 · 105 cm–3, 8.3 · 109 cm–3, 2.4 · 109 cm–3, 1.5 · 108 cm–3, respectively. In total, 392 identifications of OH in air spectra were made in a rural environment between August 5 and August 23, 1994. We present and discuss OH absorption spectra and diurnal OH concentration profiles of three days which are representative for measurements under different pollution conditions during POPCORN. The observed maximum and median OH radical concentrations are 1.3 · 107 OH/cm3 and 4.0 · 106 OH/cm3, respectively. The measured diurnal variation of the OH concentration shows a good correlation with the primary formation reaction of OH radicals which is the photolysis of ambient ozone. Deviations from this correlation in the morning and evening hours, when the OH concentration is higher than expected from the ozone photolysis, demonstrate the importance of other photochemical HOx production pathways during POPCORN.     

Measurements of Carbon Monoxide and Nonmethane Hydrocarbons During POPCORN

During the field campaign POPCORN (Photo oxidant formation by plant emitted compounds and OH radicals in North-eastern Germany) in Pennewitt (Mecklenburg-Vorpommern, Germany) in August 1994, carbon monoxide and nonmethane hydrocarbons were measured over a large maize field by in-situ gas chromatography. Throughout the campaign CO and NMHC showed, even for a remote rural area, unexpectedly low mixing ratios. Except a few episodes, CO mixing ratios were around 120 ppb. Ethane was the only hydrocarbon showing mixing ratios exceeding 1 ppb. The mixing ratios of all other NMHC ranged between several hundred ppt and the lower limit of detection which was between 20 and 5 ppt depending on the compound. During three frontal passages CO and NMHC mixing ratios increased significantly, while between August 13 and 16, 1994, polar air masses were encountered with CO and NMHC mixing ratios dropping to values which are typical for North Atlantic background air. During this period average CO mixing ratios were 85 ppb and ethane as the most abundant hydrocarbon decreased to 650 ppt. The large-scale meteorological situation is reflected in an unusual frequency distribution of CO. The distribution shows three maxima which can be assigned to the periods of the frontal passages, to the observation of polar air masses and the rest of the campaign. Two-day backward trajectories were calculated in order to obtain information about the origin of the air masses transported to the site. The observed NMHC and CO data can be attributed to the origin of the air masses and the air mass trajectories. NMHC and CO mixing ratios were well correlated indicating that these compounds originated from similar mostly anthropogenic sources. An exception was isoprene which showed no correlation with CO. With values below 100 ppt the mixing ratio of isoprene, which is emitted by terrestrial vegetation, was also unexpectedly low during the first half of the campaign although the maximum temperatures were around 35°C.     

The distribution of acetaldehyde in the lower troposphere during TROPOZ II

A series of 72 measurements of the acetaldehyde (CH₃CHO) mixing ratio were made in the lower troposphere during TROPOZ II. These measurements are the first ever made of the background level of this trace gas in the free troposphere. The data show a vertical decrease of the CH₃CHO mixing ratio with increasing altitude and indicate higher CH₃CHO concentrations in the Northern Hemisphere — in general agreement with a model-derived average CH₃CHO distribution. Deviations of the observed CH₃CHO mixing ratios from the modelled mean distribution are correlated with similar deviations in the corresponding HCHO mixing ratios.     

Characteristics, loss and gain of atmospheric carbonyl compounds in winters of 2008–2010 in Pearl River Delta region, China

Formaldehyde (HCHO), acetaldehyde (CH₃CHO) and acetone (CH₃COCH₃) were measured at Wanqingsha (WQS) in south China during November-December 2008–2010. Carbonyl compound pollution characteristics under the influence of the financial crisis (FC) were studied. Atmospheric carbonyl compound concentrations in the 2008 and 2009 sampling periods were affected by the 2008 FC. The industrial downturn plus the high closing down number of the small enterprises with limited emission treatment during the FC played an important role in the reduction of the industry-related CH₃CHO and CH₃COCH₃. In 2010, the recovery of industrial activities occurred, but affected by traffic restriction enforcement in Guangzhou over the Asian Games period, HCHO concentration (daytime 7.59?±?2.59 μg m^?3) was lower than expectation. Carbonyl compounds in WQS site were highly influenced by regional pollution transport from different upwind urban cities and industrial districts in the north-northwest to northeast wind sector in winter. Also, the interaction of the winter monsoon with the warm ocean along the coastline as well as day and night boundary layer mixing height variation affected carbonyl compound concentrations in WQS. The daytime mean dry deposition losses of HCHO and CH₃CHO were first time model-estimated for 2009 and 2010. For loss of HCHO in the early afternoon, photolysis was the dominant sink, followed by dry deposition and removal by OH radical (?OH), while for CH₃CHO, dry deposition was dominant. For the gain of HCHO and CH₃CHO, the production rates during early afternoon in 2009 and 2010 were estimated by an indirect approach.     

Field Measurements of Atmospheric Photolysis Frequencies for O3, NO2, HCHO, CH3CHO, H2O2, and HONO by UV Spectroradiometry

A calibrated spectroradiometer was used for the measurement of spectra of the absolute actinic flux F during the POPCORN field campaign in Pennewitt (53.8° N, 11.7° E, sea level) in August 1994. The obtained set of actinic flux spectra was used to determine the photolysis frequencies J(O1D), J(NO2), J(HCHO), J(H2O2), J(HONO), and J(CH3CHO), using molecular photodissociation data from literature. The accuracy of the actinic flux measurement was about ±5%. The accuracy of the photolysis frequency determination is limited by the uncertainties of the molecular absorption cross section and quantum yield data. A good agreement within the experimental uncertainties was found in comparison with measurements of J(O1D) and J(NO2) by filterradiometer which were calibrated absolutely against chemical actinometer. A comparison of this work's photolysis frequency measurements at 40° solar zenith angle with respective measured and modeled data from the literature also shows good agreement for most of the processes considered in this work. However, in the case of J(NO2) data reported in the literature as a function of solar zenith angle differences up to a factor of 1.6 with respect to this work's J(NO2) data are observed. Since this is far beyond the estimated experimental uncertainties, other atmospheric variables, such as aerosols, seem to affect J(NO2) to an extent that is underestimated by now and make indirect comparisons of J(NO2) measurements difficult.     

Measurements of formaldehyde in the troposphere by tunable diode laser absorption spectroscopy

Measurements of formaldehyde, HCHO, using tunable diode laser abssrption spectroscopy (TDLAS) are reported for four sites in North America. The TDLAS apparatus and its application to these measurements is described. Detection limits of ca. 0.25 ppbv were obtained with a three-minute time resolution. Two distinct types of diurnal behaviour were observed: in the absence of local pollution sources the HCHO diurnal variation was weak and HCHO is not lost during the night. We conclude that the lifetime of HCHO with respect to dry deposition was greater than 50 h at the least-polluted site. At sites downwind of pollution sources, the HCHO peaks near noon and declines in the afternoon. At the least-polluted location, the most probable value for HCHO was 0.25–0.5 ppbv, while hourly averaged values up to 12 ppbv were observed at the other locations.     

Surface ozone measurements in the Venezuelan tropical savannah

A one-year set of surface ozone measurements in a four-station network located in the Venezuelan savannah is reported. The diurnal ozone variation is typical of continental stations with a maximum in the afternoon, when vertical turbulent mixing is strongest. The annual O₃ average concentration, based on the monthly averages of daily maxima, was 17±2 ppb, which is in good agreement with values reported for similar latitudes. The boundary-layer ozone levels did not fall below 8 ppb, in contrast with previous sporadic measurements made in tropical latitudes. No evidence was found that mesoscale O₃ downdrafts in the ITCZ in the South American continent are an important source of surface ozone. Finally, it is suggested that the relatively high ozone levels observed at the end of the dry season are probably of photochemical origin.     

DOAS observations of formaldehyde and its impact on the HO<Subscript>x</Subscript> balance in the tropical Atlantic marine boundary layer

Measurements of formaldehyde (HCHO) were made at the Cape Verde Atmospheric Observatory between November 2006 and June 2007 using the Long-Path Differential Optical Absorption Spectroscopy (LP-DOAS) technique. Observations show that typical HCHO mixing ratios ranged between 350 and 550 pptv (with typical 2-σ uncertainties of ~110 pptv), with several events of high HCHO, the maximum being 1,885?±?149 pptv. The observations indicate a lack of strong seasonal or diurnal variations, within the uncertainty of the measurements. A box model is employed to test whether the observations can be explained using known hydrocarbon photochemistry; the model replicates well the typical diurnal profile and monthly mean values. The model results indicate that on average 20% of HO₂ production and 10% of OH destruction can be attributed to the mean HCHO levels, suggesting that even at these low average mixing ratios HCHO plays an important role in determining the HO_x (HO₂+OH) balance of the remote marine boundary layer.     

重庆远郊与市区SO_2的对比测量分析

1987年9月在重庆远郊四面山与市区观音桥同时进行了SO_2的对比测量.资料分析表明:(1)晴天时四面山SO_2日变化呈三峰三谷分布,峰值都为13—14ppb,分别在05:00,11:00及18:00时,而夜间的SO_2几乎都接近0ppb;市区观音桥的SO_2日变化呈双峰双谷分布,主峰在08:00时左右出现,浓度值达425ppb.(2)降雨条件下,四面山SO_2全部被清洗,接近0 ppb,市区的SO_2也受到明显冲洗.(3)四面山SO_2日平均浓度为2ppb,而市区观音桥日平均浓度为120ppb,市区的S     

MEASUREMENTS OF REACTIVE NITROGEN SPECIES IN THE EASTERN CHINA DURING THE EXPERIMENT PEM-WEST A

Measurements of NO_x(NO+NO_2),HNO_3,particulate nitrate,and total odd nitrogen NO_y were made at Linatmosphere regional background station during the NASA GTE/PEM-WEST A in the fall of 1991.NO_x and Nwere measured using chemiluminescence detectors.HNO_3 and aerosol nitrate(NO_3~-)were collected by a filter systNO_x concentration exhibits a significant diurnal variation:maximum occurring in the evening and postsunrise wpeak occurring following sunrise.Unlike NO_x,NO_y does not show distinct diurnal variations.From the ratiosday/night NO_x concentration and the diurnal cycles of two kinds of weather conditions,it is clear thatphotochemical production of NO_x varies with solar radiation.NO_x is the major component of total odd nitroNO_y and NO_2 is the major portion of NO_x as well.The regional background concentrations of NO_x,NO_y,aerosoltrate(NO_3~-)and HNO_3 range from 4.77 to 7.02 ppb,9.24 to 10.95 ppb,0.33 to 2.38 ppb and 0.31 to 0.97 ppb in a dayaverage,respectively.In the eastern China,the biomass burning is an important local emission source of nitrospecies.The ratios of NO/NO_2,NO_x/NO_y,HNO_3/NO_y,NO_3~-/NO_y and HNO_3/NO_x are also discussed inpaper.     

The tropospheric distribution of formaldehyde during TROPOZ II

A series of 149 measurements of the HCHO mixing ratio were made between 0 and 10 km altitude and 70° N to 60° S latitude during TROPOZ II. The data show a vertical decrease of the HCHO mixing ratio with altitude at all latitudes and a broad latitudinal maximum in the HCHO mixing ratio between 30° N and 30° S at all altitudes. The measured mixing ratios of HCHO are considerably higher than those expected from CH₄ oxidation alone, but agree broadly with the average latitude by altitude distribution of HCHO derived by a 2D model including emissions of C₁–C₇ hydrocarbons. A number of the regional scale deviations of the measured HCHO distribution from the average modelled one can be explained in terms of the local wind field.     

Mixing Ratios and Photostationary State of NO and NO2 Observed During the POPCORN Field Campaign at a Rural Site in Germany

Ambient mixing ratios of NO, NO2, and O3 were determined together with the photolysis frequency of NO2, JNO2, at a rural, agricultural site in Germany. The data were collected during the POPCORN-campaign from August 1 to August 24, 1994, in a maize field 6 m above ground. The medians of the NO, NO2, and O3 mixing ratios between 10:00 and 14:00 UT were 0.25, 1.09, and 45 ppbv, respectively. The corresponding median of JNO2 was 6.0 · 10–3 s–1. NOx = NO + NO2 showed a strong diurnal variation with maximum mixing ratios at night, suggestive of a strong local surface source of NO, probably by microbial activity in the soil. The estimated average emission rate was 40 ng(N) m–2 s–1 of NOx, the major part of it probably in the form of NO. The available measurements allowed the estimation of the local NOx budget. At night the budget is almost closed and the measured NOx mixing ratios can be explained by the local source, local dry deposition of NO2, formation of NO3 and N2O5, and vertical exchange of air across the nocturnal inversion. During day-time, the local surface source of NO is not sufficient to explain the measured mixing ratios, and horizontal advection of NOx to the site must be included. The NO2/NO ratio during the morning und late afternoon is lower than predicted from the photostationary state owing to the local NO surface source, but is regulary higher during the hours around noon. For noon, August 10, 1994, the NO2/NO ratio was used to derive the momentary lower limit for the concentration of the peroxy-radicals of 2.2 · 109 cm–3 (86 pptv).     

Diurnal cycles of formic and acetic acids in the northern part of the Guayana shield,Venezuela

Formic and acetic acids were measured in a scrub-grass savanna and in a nearby semideciduous forest. Gaseous HCOOH and CH₃COOH were collected using the mist-scrubber technique, and were determined using ion chromatography. A strong diurnal cycle was observed at both sites, with higher mixing ratios during daytime. Concentrations in the savanna were always higher than in the forest. Most of the time HCOOH/CH₃COOH ratios greater than one were recorded at the savanna site, and ratios less than one at the forest site. Boundary-layer mixing ratios in the savanna region, derived from measurements during midday, are 1.3±0.4 ppbv and 0.7±0.3 ppbv for HCOOH and CH₃COOH. Dry depositions velocities between 0.5 and 1 cm s^-1 were estimated for the savanna region. Atmospheric residence times of <3 days and >5 days were estimated for the rainy and dry season, respectively.     

A study of ozone in the Colorado mountains

The seasonal and diurnal variations of ozone mixing ratios have been observed at Niwot Ridge. Colorado. The ozone mixing ratios have been correlated with the NO _x (NO+NO₂) mixing ratios measured concurrently at the site. The seasonal and diurnal variations in O₃ can be reasonably well understood by considering photochemistry and transport. In the winter there is no apparent systematic diurnal variation in the O₃ mixing ratio because there is little diurnal change of transport and a slow photochemistry. In the summer, the O₃ levels at the site are suppressed at night due to the presence of a nocturnal inversion layer that isolated ozone near the surface, where it is destroyed. Ozone is observed to increase in the summer during the day. The increases in ozone correlate with increasing NO _x levels, as well as with the levels of other compounds of anthropogenic origin. We interpret this correlation as in-situ or in-transit photochemical production of ozone from these precursors that are transported to our site. The levels of ozone recorded approach 100 ppbv at NO _x mixing ratios of approximately 3 ppbv. Calculations made using a simple clean tropospheric chemical model are consistent with the NO _x -related trend observed for the daytime ozone mixing ratio. However, the chemistry, which does not include nonmethane hydrocarbon photochemistry, underestimates the observed O₃ production.     

Seasonal and Diurnal Variation of Surface Ozone and a Preliminary Analysis of Exceedance of its Critical Levels at a Semi-arid Site in India

The mixing ratios of surface O₃ were measured at St. John's College, Agra, an urban and traffic influenced area for the period of 2000–2002. The monthly averaged O₃ mixing ratios ranged between 8 to 40 ppb with an annual average of 21 ppb. Strong diurnal and seasonal variations in O₃ mixing ratios were observed throughout the year except for monsoon season. The mixing ratios of O₃ follow the surface temperature cycle and solar radiation (r = 0.72 and r = 0.65 with temperature and solar radiation, respectively). Concentrations were higher with winds associated with NE and NW direction indicating the impact of pollution sources on surface O₃ concentration. Exceedance of ozone critical level was calculated using the AOT 40 index and found to be 840 ppb.h and 2430 ppb.h for summer and winter seasons, respectively. The present O₃ exposures are lower than the critical level of O₃ and suggest that the present level of O₃ does not have any impact on reduction in crop yields.     

Highly Time Resolved Measurements of OH during POPCORN Using Laser-Induced Fluorescence Spectroscopy

Tropospheric hydroxyl radical (OH) concentrations were measured by laser-induced fluorescence (LIF) during the POPCORN field campaign in August 1994 at a rural site in the North East of Germany. Ambient air spectra were recorded by tuning the laser wavelength over a spectral region covering the Q11(3), Q21(3), and P11(1) rotational transitions of the (0-0) band in the A-X system of OH around 308 nm. The observed spectra clearly identify the OH radical in the atmosphere. Besides the OH absorption lines there was no sign of any other narrow-band spectral structure nearby demonstrating the high specificity of the method. For OH measurements with a typical time resolution of 60–100 seconds per data point the laser wavelength was tuned repetitively over small spectral intervals covering the peak position of the P11(1) OH-line and background positions. A total of 2300 measurements were recorded including diurnal cycles of OH with more than 300 data points. The OH as well as the LIF background signal data will be presented. In a first analysis the background signal will be characterized and the correlation between OH and the ozone photolysis frequency will be derived.     

Aircraft Measurements of Dimethyl Sulfide (DMS) Using a Whole Air Sampling Technique

We present a technique for the measurement of dimethyl sulfide (DMS) from airborne and ground-based platforms, using whole air sampling followed by gas chromatography with mass spectrometer and flame ionization detection. DMS measurements that were obtained during the 1999 NASA Pacific Exploratory Mission-Tropics B showed excellent agreement with independent in-flight DMS measurements, over a wide range of concentrations. The intercomparison supports two key results from this study, first that DMS can be accurately quantified based on ethane and propane per-carbon-response-factors (PCRFs), and second that DMS is stable in water-doped electropolished stainless steel canisters for at least several weeks. In addition, our sampling frequency and duration are flexible and allow detail in the vertical structure of DMS to be well captured. Sampling times as fast as 8 s were achieved and these data are suitable for DMS flux calculations using the mixed-layer gradient technique. Correlations between DMS and other marine tracers can also be readily investigated by this whole air sampling technique, because DMS is analyzed together with more than 50 simultaneously sampled hydrocarbons, halocarbons, and alkyl nitrates. The detection limit of the DMS measurements is 1 part per trillion by volume (pptv), and we conservatively estimate the accuracy to be ±20% or 3 pptv, whichever is larger. The measurement precision (1 ) is 2–4% at high mixing ratios (> 25 pptv), and 1 pptv or 15%, whichever is larger, at low mixing ratios (<10 pptv).