Atmospheric particulate nitrate sampling errors due to reactions with particulate and gaseous strong acids

doi:10.1016/0004-6981(81)90110-4

Atmospheric Environment (1967)

Volume 15, Issue 6, 1981, Pages 1087-1089

https://doi.org/10.1016/0004-6981(81)90110-4 Get rights and content

Abstract

The significance of particulate nitrate loss from inert filters due to reactions with particulate and gaseous strong acids was assessed. Laboratory as well as atmospheric results from California's South Coast Air Basin support such loss by reaction of ammonium nitrate with paniculate H₂SO₄. Nitrate loss by reaction with gaseous HCl, not previously reported, was found to be significant in laboratory trials.

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Cited by (70)

High time-resolved measurements of water-soluble sulfate, nitrate and ammonium in PM <inf>2.5</inf> and their precursor gases over the Eastern Mediterranean
2019, Science of the Total Environment
Citation Excerpt :
Even though, aerosol nitrate concentration was influenced by wet scavenging in winter, it exhibited lower concentrations in summer. This might be attributed to (i) evaporation of nitrate due to either elevated temperatures (reaching up to 40 °C during the day), (ii) reaction between H2SO4 and NH4NO3 (Appel et al., 1980; Appel and Tokiwa, 1981) or (iii) emission from vehicles and stagnant air masses in winter (Di Gilio et al., 2015). High concentrations of SO2 were observed in winter compared to summer.
High time-resolved measurements of aerosol SO₄²⁻, NO₃⁻, NH₄⁺ and their precursor gases HNO₃, SO₂, NH₃ between 27 and 02 January/February and 19–01 August/September 2015 were carried out by applying AIM-IC at a rural site located on the coast of the Eastern Mediterranean, Erdemli, Turkey. The comparison between online and offline techniques revealed better correlation coefficients for SO₄²⁻ and NH₄⁺ (r > 0.90) than that of NO₃⁻ (0.63). Mean concentrations of water-soluble species were found in decreasing order SO₄²⁻ (2814 ng m⁻³) > NH₄⁺ (1371 ng m⁻³) > NO₃⁻ (495 ng m⁻³). NH₃ (3390 ng m⁻³) concentration was more than enough to neutralize SO₂ (879 ng m⁻³) and HNO₃ (346 ng m⁻³). The gas-to-particle conversion ratios (>0.3) implied that SO₄²⁻, NO₃⁻ and NH₄⁺ were mainly influenced by non-local sources. SO₄²⁻, NO₃⁻, NH₄⁺, HNO₃, SO₂ exhibited remarkable decrease (leastways 40%) in the atmosphere over the Eastern Mediterranean throughout fifteen years. In winter, day time NH₃ concentrations illustrated significant relationship with temperature (positive) and humidity (negative), implying evaporation of dew or emission from plant stoma. Whereas, diurnal cycle of SO₄²⁻ and SO₂ was considerably influenced by populated City of Mersin in winter. During summer, HNO₃ and SO₂ (r = 0.74) demonstrated similar diurnal cycle, suggesting a common source for these precursor gases whilst NH₃ was considerably affected by biomass burning emissions. Variability of all species was governed by local or nearly mesoscale transport in winter possibly due to frequent rain events. In summer, air flow from Eastern Mediterranean denoted aged air masses (GPC > 0.65) containing rather uniform concentrations of SO₄²⁻ (~65 nmol m⁻³) and NH₄⁺ (~140 nmol m⁻³). The highest NH₃ along with the greatest % K_BB contribution to PM_2.5 mass was observed under the influence of Northerly airflow, exhibiting significance of biomass burning emissions as a source of NH₃ in summer.
Uncertainties in the measurements of water-soluble organic nitrogen in the aerosol
2016, Atmospheric Environment
Citation Excerpt :
In these studies, aerosol samples are usually collected by filter sampling using a quartz fiber filter that had been often pre-heated to remove the organic blank. In the measurements of the particulate inorganic nitrogen compounds, such as NO3− and NH4+, by the filter sampling, volatilization loss of particulate species collected on the filter (negative artifact) and adsorption of gaseous species on the filter materials or particulate substances already collected on the filter (positive artifact) have been pointed out in many previous studies (Stelson et al., 1979; Appel et al., 1980, 1984; Appel and Tokiwa, 1981; Andersen and Hovmand, 1994). To avoid these artifacts, the collection of gas samples by a denuder before the aerosol collection has been recommended in previous studies, which can separately quantify these inorganic nitrogen compounds in the particulate and gas phases with less uncertainty (Shaw et al., 1982; Harrison and Kitto, 1990; Andersen and Hovmand, 1994; Matsumoto and Okita, 1998).
In order to evaluate the positive and negative artifacts in the measurements of the water-soluble organic nitrogen (WSON) in the aerosols by filter sampling, comparative experiments between the filter sampling and denuder-filter sampling were conducted during both the warm and cold seasons. The results suggest that the traditional filter sampling underestimates the concentrations of the particulate WSON due to its volatilization loss, but this effect on the ratio of the WSON to the water-soluble total nitrogen (WSTN) was small probably because inorganic nitrogen species were also lost during the filter sampling. Approximately 32.5% of the WSON in the PM_2.5 was estimated to be lost during the filter sampling. The denuder–filter sampling also demonstrated the existence of the WSON in the gas phase with approximately quarter concentrations of the WSON in the PM_2.5. On the other hand, the filter sampling would overestimate the gaseous WSON concentration due to the loss of the WSON from the aerosol collection filter.
Simultaneous online monitoring of inorganic compounds in aerosols and gases in an industrialized area
2013, Atmospheric Environment
Citation Excerpt :
Filter measurements may have become routine but because of their low accuracy it is not simple to quantify ambient aerosols (Appel, 1993; Chang et al., 2001). Furthermore, the atmospheric evaporation of semi-volatile aerosol species and the possible loss of some compounds due to surface reactions due to long time-scale sampling periods have been reported (Appel and Tokiwa, 1981; Appel et al., 1981; Chang et al., 2001; Perrino et al., 1988). It has been estimated that 50% of particulate nitrate (on average) is lost due to volatilization during sampling by Teflon filters (Chang et al., 2001).
The automatic MARGA (monitor for aerosols and gases in ambient air) sampling system was used to measure the inorganic ions Cl^–, NO₃^–, SO₄^2–, Na⁺, NH₄⁺, K⁺, Mg²⁺ and Ca²⁺ in the PM_2.5 aerosol phase and the corresponding inorganic gases HCl, HNO₂, SO₂, HNO₃ and NH₃ present in the gas phase. Samples were collected and analyzed hourly for 3 months between April and June, 2011, from a sampling site in Singapore close to a heavy industrial area containing extensive petrochemical refineries. The data (hourly and daily average) were analyzed, compared and discussed based on the ratios of HNO₂/HNO₃ and NH₃/NH₄⁺, the levels of nitrate and sulfate, the total nitrogen, the distribution of particulate matter and gaseous compounds, and the acidity of the aerosols. SO₂ was the most abundant gas that appeared in an order of magnitude higher concentration than the other trace gases, and correspondingly SO₄^2– was found to be at least 3–10 times higher than other anionic aerosol species. The concentration of major ions in aerosol samples and the related gaseous compounds followed the order of: SO₄^2– > NH₄⁺ > NO₃^– > K⁺ > Na⁺ > Cl^– > Ca²⁺ > Mg²⁺ and SO₂ > NH₃ > HNO₂ > HNO₃, respectively. The maximum values for many of the target analytes occurred during the hazy period in May when there was significant contamination from regional fires. The elevated levels of HNO₂ compared to HNO₃ and high levels of HNO₃ were rationalized based on artifacts in the denuder sampling methodology.
Semi-continuous measurement of PM<inf>2.5</inf> ionic composition at several rural locations in the United States
2008, Atmospheric Environment
Citation Excerpt :
Filter measurements are often integrated over long time periods (e.g., 12–24 h or more), thereby limiting our knowledge of finer timescale variability in particle concentrations and our ability to relate observed particle composition to particular emissions, transport patterns or meteorological situations (Orsini et al., 2003; Sullivan et al., 2004; Weber et al., 2001; Wittig et al., 2004). Long sampling periods that include large variations in environmental conditions also can contribute to aerosol sampling artifacts, including losses of semi-volatile components from the filter medium (Appel, 1993; Appel and Tokiwa, 1981; Chow et al., 2005; Hering and Cass, 1999; Hering et al., 1988; Koutrakis et al., 1992; Pang et al., 2001; Yu et al., 2006). In order to provide better insight into aerosol sources, atmospheric transport, and chemical reactions, a number of approaches have been developed recently to allow aerosol chemical composition measurements on much faster timescales (Buhr et al., 1995; Karlsson et al., 1997; Khlystov et al., 1995; Oms et al., 1996; Orsini et al., 2003; Simon and Dasgupta, 1993; Simon and Dasgupta, 1995; Slanina et al., 2001; Stolzenburg and Hering, 2000; Trebs et al., 2004; Weber et al., 2001; Zellweger et al., 1999).
To improve understanding of the nature and variability of the ionic fraction of atmospheric fine aerosol particles in non-urban environments, one to two month measurement campaigns were conducted at several rural locations in the United States. Study sites included Yosemite National Park (NP) (July–September 2002), Bondville, Illinois (February 2003), San Gorgonio Wilderness Area, California (April and July 2003), Grand Canyon National Park, Arizona (May 2003), Brigantine National Wildlife Refuge (NWR), New Jersey (November 2003), and Great Smoky Mountains National Park, Tennessee (July/August 2004). PM_2.5 ion composition was measured at 15 min intervals using a Particle-Into-Liquid-Sampler (PILS) coupled to two ion chromatographs. Comparisons of PILS measurements with parallel traditional 24 h denuder/filter-pack measurements reveal generally good agreement between the two techniques for major species, although PILS measurements of PM_2.5 NH₄⁺ are biased low by approximately 4–20%. High time resolution PILS aerosol concentration measurements provide better estimates of the range of aerosol concentrations at the rural locations than the 24 h integrated filter data. Ratios of peak 15 min to 24 h nitrate concentrations, for example, ranged from 1.7 at Brigantine NWR to 7.0 at Great Smoky Mountains NP. A strong influence of diurnal upslope/downslope transport patterns was observed on aerosol concentrations at several locations, including Yosemite NP, San Gorgonio Wilderness Area, and Great Smoky Mountains NP, with peak concentrations typically occurring during afternoon upslope transport. High time resolution aerosol composition measurements also provide new insight into relationships between individual aerosol species and the influence of environmental conditions on aerosol composition. Observations at several locations revealed important information about mechanisms of particle nitrate formation. At Yosemite and Grand Canyon National Parks, for example, evidence was observed for reaction of nitric acid or its precursors with sea salt or soil dust. Observations from several sites also revealed the importance of aerosol acidity (Great Smoky Mountains NP, Bondville) and temperature/humidity (San Gorgonio) on fine particle ammonium nitrate formation.
A side-by-side comparison of filter-based PM<inf>2.5</inf> measurements at a suburban site: A closure study
2007, Atmospheric Environment
Assessing the effects of air quality on public health and the environment requires reliable measurement of PM_2.5 mass and its chemical components. This study seeks to evaluate PM_2.5 measurements that are part of a newly established national network by comparing them with more versatile sampling systems. Experiments were carried out during 2002 at a suburban site in Maryland, United States, where two samplers from the US Environmental Protection Agency (US EPA) Speciation Trends Network: Met One Speciation Air Sampling System—STN_S and Thermo Scientific Reference Ambient Air Sampler—STN_R, two Desert Research Institute Sequential Filter Samplers—DRI_F, and a continuous TEOM monitor (Thermo Scientific Tapered Element Oscillating Microbalance, 1400a) sampled air in parallel. These monitors differ not only in sampling configuration but also in protocol-specific laboratory analysis procedures. Measurements of PM_2.5 mass and major contributing species (i.e., sulfate, ammonium, organic carbon, and total carbon) were well correlated among the different methods with r-values >0.8. Despite the good correlations, daily concentrations of PM_2.5 mass and major contributing species were significantly different at the 95% confidence level from 5% to 100% of the time. Larger values of PM_2.5 mass and individual species were generally reported from STN_R and STN_S. These differences can only be partially accounted for by known random errors. Variations in flow design, face velocity, and sampling artifacts possibly influenced the measurement of PM_2.5 speciation and mass closure. Statistical tests indicate that the current uncertainty estimates used in the STN and DRI network may underestimate the actual uncertainty.
Loss of fine particle ammonium from denuded nylon filters
2006, Atmospheric Environment
Ammonium is an important constituent of fine particulate mass in the atmosphere, but can be difficult to quantify due to possible sampling artifacts. Losses of semivolatile species such as NH₄NO₃ can be particularly problematic. In order to evaluate ammonium losses from aerosol particles collected on filters, a series of field experiments was conducted using denuded nylon and Teflon filters at Bondville, IL (February 2003), San Gorgonio, CA (April 2003 and July 2004), Grand Canyon NP, AZ (May, 2003), Brigantine, NJ (November 2003), and Great Smoky Mountains National Park (NP), TN (July–August 2004). Samples were collected over 24 h periods. Losses from denuded nylon filters ranged from 10% (monthly average) in Bondville, IL to 28% in San Gorgonio, CA in summer. Losses on individual sample days ranged from 1% to 65%. Losses tended to increase with increasing diurnal temperature and relative humidity changes and with the fraction of ambient total N(−III) (particulate NH₄⁺+gaseous NH₃) present as gaseous NH₃. The amount of ammonium lost at most sites could be explained by the amount of NH₄NO₃ present in the sampled aerosol. Ammonium losses at Great Smoky Mountains NP, however, significantly exceeded the amount of NH₄NO₃ collected. Ammoniated organic salts are suggested as additional important contributors to observed ammonium loss at this location.

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^☆: The statements and conclusions in this report are those of the authors and not necessarily those of the California Air Resources Board. The mention of commercial products, their: sources, or use in connection with material reported herein is not to be construed as either an actual or implied endorsement of such product.

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Short communicationAtmospheric particulate nitrate sampling errors due to reactions with particulate and gaseous strong acids☆

Abstract

Atmospheric Environment

Atmospheric Environment

Analytica chim. Acta

Atmospheric Environment

Atmospheric Environment

Determination of sulfuric acid, total particle-phase acidity and nitric acid in ambient air

Final Report to the California Air Resources Board for Contract No. A6-209-30. NTIS Report PB 80-145980

Sampling of nitrates in ambient air

Atmospheric Environment

Short communication
Atmospheric particulate nitrate sampling errors due to reactions with particulate and gaseous strong acids☆