Aerosol Filter Samples Research Articles

New measurements reveal a large contribution of nitrogenous molecules to ambient organic aerosol

AbstractNitrogen is a significant element that constitutes ambient organic aerosol. Individual N-containing organic molecules are known to have both natural and anthropogenic sources and implicated in a wide-ranging health and environmental effects. Yet, unlike carbon (C), the total quantity of aerosol organic nitrogen (ON) remains largely unquantified, hindering a quantitative understanding of their major sources and impacts. Here, aerosol ON is quantitatively surveyed in hundreds of aerosol filter samples collected from sites of varying urban influence in China using our recently developed method that permits simple, and yet sensitive, simultaneous detection of inorganic and organic nitrogen. Annual average ON concentration was in the range of 0.4–1.4 μg N m−3, representing 17–31% of aerosol total nitrogen. Monte Carlo simulations constrained by paired ON and OC measurements suggest N-containing organic molecules contributed typically 37–50%, with a 95% confidence interval of [12%, 94%], to ambient organic aerosols. Source apportionment analysis reveals that biomass burning and secondary formation are dominant ON sources, accounting for 21–24% and ~ 30% of ON, respectively. Primary biological aerosol is also a significant source of ON (7–18%), with its contribution more prominent in non-urban atmospheres. The results provide the quantitative data for the extent of presence of organic nitrogenous aerosol and the origin of their major sources. Such data, we anticipate, would bring forth a breakthrough in our ability to describe and model organic aerosols and to assess their environmental impacts, such as atmospheric nitrogen nutrient inputs to ecosystems.

Quantifying metallic components in aerosol filter samples using micro-synchrotron radiation X-ray fluorescence: With quartz filter as an example

Metals in atmospheric fine particulate matter (PM2.5) are presumed to have toxic effects. For environmental epidemiological studies, measuring the metallic components of PM2.5 collected by personal samplers and quartz fiber filters (QFF) has two key advantages: reducing exposure misclassification and enabling analyses of multiple (organic and inorganic) components on a single filter. We developed a sensitive, low-sample-consumption method to quantify the metallic components of PM2.5 collected on QFFs using micro-synchrotron radiation X-ray fluorescence (μ-SRXRF). Teflon filter is used here as a reference to test the substrate applicability of QFF. This method requires only a 5-mm-diameter portion of a QFF and can simultaneously quantify 15 metals with atomic numbers Z = 19–34 (i.e., K–Se, excluding Sc). The analysis time for each sample was 120–360 s, and the method detection limits were 0.04–36.6 ng/m3. We validated this method by performing cross-comparisons with two external methods: offline inductively coupled plasma mass spectrometry (ICP-MS) and online X-ray fluorescence (XRF). The slopes of the linear fits between the μ-SRXRF and offline ICP-MS methods varied from 0.40 to 1, with R2 values ranging from 0.62 to 0.98. The slopes of the linear fits between the μ-SRXRF and online XRF methods were between 0.29 and 0.89, with R2 values ranging from 0.39 to 0.80. We applied the proposed method to analyze 391 personal PM2.5 samples collected in an epidemiological study conducted in urban Beijing. By comparing the results with the ambient concentrations from a fixed monitoring site, we found that the concentrations of some metallic components in personal PM2.5 samples were significantly different from those in the corresponding fixed-site samples, with up to an order of magnitude difference. Because personal sampling can reduce the potential for exposure misclassifications, the high-resolution temporal analysis of metallic components in personal samples using the μ-SRXRF method could be a useful approach for exploring the health risks and identifying the sources of metallic components of PM2.5.

Field observations of C2 and C3 organosulfates and insights into their formation mechanisms at a suburban site in Hong Kong

Organosulfates (OSs) are formed from volatile organic compounds (VOCs) and their oxidation products in the presence of sulfate particles. While OSs represent an important component in secondary organic aerosol, the knowledge of their formation driving force, mechanisms, and environmental impact remain inadequately understood. In this study, we report ambient observations of C2–3 oxygenated VOCs derived OSs (C2–3 OSs) at a suburban location of Hong Kong during autumn 2016. The C2–3 OSs, including glycolaldehyde sulfate (GS), hydroxyacetone sulfate (HAS), glycolic acid sulfate (GAS), and lactic acid sulfate (LAS), were quantified/semi-quantified using offline liquid chromatography-mass spectrometry analysis of aerosol filter samples. The average sum concentration of C2–3 OSs was 36 ng/m3. Correlation analysis revealed that sulfate, surface area, and liquid water content were important factors influencing C2–3 OS formation. Online measurement with an iodide High-Resolution Time-of-Flight Chemical-Ionization Mass Spectrometer (HR-ToF-CIMS) coupled with the Filter Inlet for Gases and AEROsols (FIGAERO) was also conducted to monitor C2–3 OSs, and their potential oxygenated VOC precursors in both gas- and particle-phase, and aerosol acidity tracer simultaneously. Our measurements support that glycolaldehyde/glyoxal, hydroxyacetone, glycolic acid/glyoxal, and lactic acid/methylglyoxal are likely precursors for GS, HAS, GAS, and LAS, respectively. Additionally, we found strong correlation between C2–3 OSs and H3S2O8−, a marker for aerosol acidity, providing field observational evidence for acid-catalyzed formation of small OSs. Based on both online and offline measurements, acid-catalyzed formation mechanisms in particle/aqueous phase are proposed. Specifically, the unique structure of adjacent carbonyl and hydroxyl groups in the C2–3 oxygenated VOC precursors can facilitate the formation of (1) a five-member ring intermediate via intramolecular hydrogen bond to react with sulfur trioxide through heterogenous reaction or (2) cyclic sulfate intermediate via particle-phase reaction with sulfuric acid to generate C2–3 OSs. These proposed mechanisms provide an alternative pathway for the liquid-phase production of C2–3 OSs.

Large differences of highly oxygenated organic molecules (HOMs) and low-volatile species in secondary organic aerosols (SOAs) formed from ozonolysis of β-pinene and limonene

Abstract. Secondary organic aerosols (SOAs) play a key role in climate change and public health. However, the oxidation state and volatility of SOAs are still not well understood. Here, we investigated the highly oxygenated organic molecules (HOMs) in SOAs formed from ozonolysis of β-pinene and limonene. Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) was used to characterize HOMs in aerosol filter samples, and a scanning mobility particle sizer (SMPS) was used to measure the concentration and size distribution of SOA particles. The relative abundance of HOMs (i.e., ratio of summed mass spectrometry peak intensity of HOMs to totally identified organic compounds) in limonene SOA was 14 %–20 %, higher than in β-pinene SOA (3 %–13 %), exhibiting different trends with increasing ozone concentrations. β-pinene oxidation-derived HOMs exhibit higher yield at high ozone concentration, accompanied by substantial formation of ultra-low-volatile organic compounds (ULVOCs). Limonene oxidation-derived HOMs exhibit higher yield at moderate ozone concentrations, with semi-, low-, and extremely low-volatile organic compounds (SVOCs, LOVCs, and ELVOCs) play a major role. Combined experimental evidence and theoretical analysis indicate that oxygen-increasing-based peroxy radical chemistry is a plausible mechanism for the formation of oxygenated organic compounds with 10 carbon atoms. Our findings show that HOMs and low-volatile species in β-pinene and limonene SOA are largely different. The ozone concentration-driven SOA formation and evolution mechanism for monoterpenes is suggested to be considered in future climate or exposure risk models, which may enable more accurate air quality prediction and management.

Characteristics and Oxidative Potential of Ambient PM2.5 in the Yangtze River Delta Region: Pollution Level and Source Apportionment

Fine particulate matter (PM2.5) is a major contributor to the degree of air pollution, and it is associated with a range of adverse health impacts. Moreover, the oxidative potential (OP, as a tracer of oxidative stress) of PM2.5 has been thought to be a possible determinant of its health impact. In this study, the OP of 136 fine aerosol filter samples collected in Changzhou in two seasons (spring and summer) were determined using a dithiothreitol (DTT) assay. Source apportionments of the PM2.5 and DTT activity were further performed. Our results showed that the daily average ± standard deviation of the DTTv (volume-normalized DTT activity) in the PM2.5 was 1.16 ± 0.58 nmol/min/m3 and 0.85 ± 0.16 nmol/min/m3 in the spring and summer, respectively, and the DTTm (mass-normalized DTT activity) was 13.56 ± 5.45 pmol/min/μg and 19.97 ± 6.54 pmol/min/μg in the spring and summer, respectively. The DTTv was higher in the spring compared to the summer while the opposite was true for the DTTm. Most of the detected components (including the organic component, element component, NH4+, Mn, Cu, Zn, etc.) exhibited a moderately positive correlation with the DTTv, but the opposite was found with the DTTm. An aerodyne high-resolution aerosol mass spectrometer (HP-AMS) was deployed to probe the chemical properties of the water-soluble organic matter (WSOA). Positive matrix factorization (PMF) coupled with multiple linear regression was used to obtain the relative source contributions to the DTT activity for the WSOA in the PM2.5. The results showed that the sensitivity sequences of the DTTv to the WSOA sources were oxygenated organic aerosol (OOA) > biomass burning OA (BBOA) > hydrocarbon-like OA (HOA) in the spring and HOA > nitrogen-enriched OA (NOA) > OOA in the summer. The PMF suggested the highest contribution from traffic emissions to the DTTv of the PM2.5 in both seasons. Our findings point to the importance of both organic components from secondary formation and transition metals to adverse health effects in this region. This study can provide an important reference for adopting appropriate public health policies regarding the detrimental outcomes of exposure to PM2.5.

Development of graphitization method for low carbon aerosol filter samples with Automated Graphitization System AGE-3

The wide applications of the radiocarbon (14C) approach in environmental, archeological, and geological research often necessitates the analysis of microgram-sized samples. The ability to measure low carbon samples is particularly relevant for aerosol particle filters, especially for samples from pristine environments. For this purpose, we investigated the sample dilution method for graphitization of low-carbon samples (20–200 μg C) with an Automated Graphitization System (AGE-3), and applied a mass balance equation for the calculation of 14C values. Materials with known 14C values (standards NIST-OXII and IAEA-C7) were diluted with 14C-free phthalic anhydride (PhA) until sufficient mass (500 μg C) for graphitization with the AGE-3 system was acquired. Reliable 14C values were obtained for samples with carbon amount in the range of 40–200 μg. Next, we adapted the dilution method for estimation of aerosol sample 14C values. Using it, we attained a precision of 0.71 ± 0.83 pMC for 14C measurements of aerosol samples containing 40–200 μg C. A shift of radiocarbon values to 5.07 pMC (average 3.08 ± 1.7 pMC) was observed for samples with low carbon content (<20 μg C). We determined that a precision of 2–3 pMC is acceptable for aerosol particle source apportionment studies. Using the sample dilution method, graphitization with AGE-3 of aerosol samples with carbon content >40 μg becomes a viable and efficient way of sample preparation for 14C analysis.

Particle characterization and quantification of organic and inorganic compounds from Chinese and Iranian aerosol filter samples using scanning laser desorption/ionization mass spectrometry

Besides their influence on climate and cloud formation, many organic and inorganic substances in aerosol particles pose a risk to human health. Namely, polycyclic aromatic hydrocarbons (PAH) and heavy metals are suspected to be carcinogenic or acutely toxic. The detection and quantification of such compounds is difficult if only small amounts of particulate matter (PM) are available. In addition, filter samples are often complex and time-consuming to prepare for chromatographic measurements and elemental analysis. Here, we present a method based on high-resolution atmospheric pressure laser desorption ionization mass spectrometry imaging (AP-LDI-MSI) and statistical analysis which allows the analysis and characterization of very small sample quantities (< 30 µg) without any sample preparation. The power and simplicity of the method is demonstrated by two filter samples from heavily polluted mega cities. The samples were collected in Tehran (Iran) and Hangzhou (China) in February 2018. In the course of the measurement, more than 3200 sum formulae were assigned, which allowed a statistical evaluation of colocalized substances within the particles on the filter samples. This resulted in a classification of the different particle types on the filters. Finally, both megacities could be distinguished based on characteristic compounds. In the samples from Tehran, the number of sulphur-containing organic compounds was up to 6 times as high as the samples from Hangzhou, possibly due to the increasing efforts of the Chinese government to reduce sulphur emissions in recent years. Additionally, quantification of 13 PAH species was carried out via standard addition. Especially, the samples from Tehran showed elevated concentrations of PAHs, which in the case of higher-molecular-weight species (> m/z 228) were mostly more than twice as high as in Hangzhou. Both cities showed high levels of heavy metals and potentially harmful organic compounds, although their share of total particulate matter was significantly higher in the samples from Tehran. The pre-treatment of the samples was reduced to a minimum with this method, and only small amounts of particles were required to obtain a comprehensive picture for a specific filter sample. The described method provides faster and better control of air pollution in heavily polluted megacities.Graphical abstract

Measurement report: The chemical composition of and temporal variability in aerosol particles at Tuktoyaktuk, Canada, during the Year of Polar Prediction Second Special Observing Period

Abstract. The chemical composition, sources, and concentrations of aerosol particles vary on a seasonal basis in the Arctic. While existing research has focused on understanding the occurrence of aerosol particles during the Arctic winter and spring, less is known of their occurrence during the Arctic summer. In this study, atmospheric aerosol particle chemical composition and concentration were determined during July–September 2018 at Tuktoyaktuk, NT, Canada (69.4∘ N, 133.0∘ W), to coincide with the Year of Polar Prediction's Second Special Observing Period in the Arctic. The chemical composition of fine (PM2.5) and coarse (PM10–2.5) aerosol filter samples suggests the ocean, mineral and/or road dust, and combustion were sources of the sampled aerosol particles. Mass concentrations of PM2 and PM10, estimated from optical particle counter measurements, remained within a similar range during the study. However, elevated mass concentrations coincided with a festival in the community of Tuktoyaktuk, suggesting local human activity was an important source of aerosol particles. Mass concentrations of PM2, which promote negative health effects in humans, were significantly lower at Tuktoyaktuk than the national air quality standard recommended by the government of Canada. These measurements provide an important baseline to compare with future measurements associated with the assessment of aerosol chemistry and air quality in the Arctic.

An automated method for thermal-optical separation of aerosol organic/elemental carbon for 13C analysis at the sub-μgC level: A comprehensive assessment

We describe and thoroughly evaluate a method for 13C analysis in different fractions of carbonaceous aerosols, especially elemental carbon (EC). This method combines a Sunset thermal-optical analyzer and an isotope ratio mass spectrometer (IRMS) via a custom-built automated separation, purification, and injection system. Organic carbon (OC), EC, and other specific fractions from aerosol filter samples can be separated and analyzed automatically for 13C based on thermal-optical protocols (EUSAAR_2 in this study) at sub-μgC levels. The main challenges in isolating EC for 13C analysis are the possible artifacts during OC/EC separation, including the premature loss of EC and the formation of pyrolyzed OC (pOC) that is difficult to separate from EC. Since those artifacts can be accompanied with isotope fractionation, their influence on the stable isotopic composition of EC was comprehensively investigated with various test compounds. The results show that the thermal-optical method is relatively successful in OC/EC separation for 13C analysis. The method was further tested on real aerosols samples. For biomass-burning source samples, (partial) inclusion of pOC into EC has negligible influence on the 13C signature of EC. However, for ambient samples, the influence of pOC on the 13C signature of EC can be significant, if it is not well separated from EC, which is true for many current methods for measuring 13C on EC. A case study in Xi'an, China, where pOC is enriched in 13C compared to EC, shows that this can lead to an overestimate of coal and an underestimate of traffic emissions in isotope-based source apportionment.

Investigation of structural changes of atmospheric aerosol samples during two thermal–optical measurement procedures (EUSAAR2, NIOSH870)

Abstract. Thermal–optical measurement techniques are widely used for the monitoring of carbonaceous aerosols. Although results of different thermal–optical measurement techniques are comparable for total carbon, they can vary widely for values of elemental carbon especially in the presence of brown carbon. Charring of organic material during the inert heating phase of thermal–optical measurements has been found to be a major confounder, but no literature about investigations of structural changes during this process in atmospheric aerosols is available. In a recent study we investigated these structural changes for combustion aerosol standard (CAST) soot. Now we apply this approach to selected atmospheric aerosol filter samples and a subset of eight washed filter samples with low loadings of water-soluble organic carbon (WSOC). To investigate structural changes, Raman spectra were obtained for samples heated to the corresponding temperature levels and gas atmospheres of the EUSAAR2 and NIOSH870 protocols. The temperature levels where changes in the Raman spectra occurred (i.e., changes in structure) varied for different samples. For the washed samples with low WSOC loadings and absence of other water-soluble aerosol components such as inorganic salts, changes in structural ordering and darkening of the samples were not observed. We were able to show for the first time that the darkening of a sample (measured in terms of transmission laser signal) is not necessarily caused by an increase of structural ordering in the sample. Possible transformations at lower temperatures could include a formation of non-graphitic light-absorbing intermediate organic carbon, a release of C−H groups or a decrease of carbonyl groups.

North Atlantic marine organic aerosol characterized by novel offline thermal desorption mass spectrometry: polysaccharides, recalcitrant material, and secondary organics

Abstract. The composition of organic compounds in marine aerosols and the relative contributions of primary and secondary organic compounds remain uncertain. We report results from a novel approach to characterize and quantify organic components of the marine aerosol. Size-segregated discrete aerosol filter samples were collected at sea in the North Atlantic from both ambient aerosol and artificially generated primary sea spray over four cruises timed to capture the seasonal phytoplankton bloom dynamics. Samples were analyzed by Fourier transform infrared spectroscopy (FTIR), extracted into water, and analyzed by offline thermal desorption chemical ionization mass spectrometry (TDCIMS) and ion chromatography (IC). A positive matrix factorization (PMF) analysis identified several characteristic aerosol components in the TDCIMS mass spectra. Among these is a polysaccharide factor representing about 10 %–30 % of the submicron organic aerosol mass. Aerosol polysaccharide : sodium mass ratios were consistently higher in ambient air than in the artificially generated sea spray, and we hypothesize that this results from more rapid wet deposition of sodium-rich aerosol. An unquantified recalcitrant factor of highly thermally stable organics showed significant correlation with FTIR-measured alcohol groups, consistently the main organic functional group associated with sea spray aerosol. We hypothesize that this factor represents recalcitrant dissolved organic matter (DOM) in seawater and that by extension alcohol functional groups identified in marine aerosol may more typically represent recalcitrant DOM rather than biogenic saccharide-like material, contrary to inferences made in previous studies. The recalcitrant factor showed little seasonal variability in its contribution to primary marine aerosol. The relative contribution of polysaccharides was highest in late spring and summer in the smallest particle size fraction characterized (&lt;180 nm).

Water Adsorption vs Phase Transition of Aerosols Monitored by a Quartz Crystal Microbalance.

A quartz crystal microbalance (QCM) with a high sensitivity of 0.1 ng was applied to monitor the oscillation frequency variation (Δf) of standard single species, two-component systems with typical ambient aerosol compositions, and ambient aerosol filter samples as a function of relative humidity (RH) and determine their deliquescence RH (DRH) and phase transition. Δf is associated with the adsorption or desorption process of water molecules for solid samples and physical properties of the sample film during solid-to-aqueous phase transition (deliquescence). During the pre-deliquescence stage, the water adsorption process led to the increased mass with decreasing Δf, especially for the hydrates such as MgCl2 and Ca(NO3)2, which have more than 20% and 40% increased mass, respectively. The water adsorption process might cause a mass deviation of ambient particulate matter measurement using similar instrument principles. During the deliquescence stage, the observed rapid increasing Δf with RH was caused by a significant change in the physical properties (such as density and viscosity) of the sample film. The determined DRH for a given single-component system is consistent with the results estimated from the thermodynamic models. For a complex system, the QCM can determine the DRH1st well as the eutonic point and track the possible variation of the physical properties of inorganic or with organic acid mixture systems. During the post-deliquescence stage, the gradual increasing trend of Δf with RH for Ca(NO3)2 and an external mixture of NaCl-Ca(NO3)2 was mainly contributed by a stronger RH dependent of physical properties for Ca(NO3)2(aq). Overall, this study provides the possible physical properties variation of common aerosol composition as a function of RH, which was consistent with the results calculated from the thermodynamic models. The stronger water adsorption for MgCl2 and Ca(NO3)2 with solid-like viscosity at RH < DRH might lead to different chemical reactivities in the atmospheric chemistry in addition to the radiative forcing of aerosols caused by the hysteresis.

Smoke shade as a historic proxy for elemental carbon

The blackness of aerosol filter samples, meant as a proxy for particulate mass concentration, is the earliest parameter for which monitoring data exist. The smoke shade method (developed in the late 1910s) was the standardised approach to collect samples. The blackness was visually appraised by a comparison with a set of reference sheets covered with an increasing number of layers (shades) of a suspension of carbon black (ink). Samples were assigned a shade number (SN) according to the number of shades of ink on the reference sheet with a corresponding blackness. Automated hourly sampling started in 1921. After World War II, the blackness was measured with a reflectometer and light absorption was translated to the parameter British Smoke (BrS). One unit of SN was equivalent to a specific loading of BrS of 8 μg cm−2. BrS in turn is a proxy for elemental carbon (EC) as we showed in an earlier publication, where we found that a value of BrS of 8 μg cm−2 corresponded to an EC load of 1.4 μg cm−2. SNs can thereby be translated to historic EC loadings/concentrations. In an evaluation of SN-data, we noticed that average pre-war values were mostly at the lower detection limit (one SN) and overestimated because reference sheets faded over time. Data for smog periods with their elevated SNs, however, are quite reliable and can be used for exposure estimates. After World War II, daily sampling resulted in higher filter loadings and reliable average values. Wintertime concentrations corresponding to up to 100 μg m−3 EC were reached. On the other hand, the increased loadings due to the long sampling times resulted in a decrease of the upper limit of detection to an extent that it was exceeded at most of the measuring stations during the “Great Smog” of London in 1952. In this study, we analysed SN data from this episode in depth. At one measuring site, precautions were taken to minimise the loading by using a large filter, but even then the maximum SN was at the upper limit of detection. From a one-to-one relation of BrS and gravimetric mass, established during later smog periods, we deduced that the maximum 2-day mass concentration of EC must have been around 1000 μg m−3. This value is twenty times the new EU-limit for workplace EC exposure (EU 2019) and the 24-h ambient PM10 mass concentration.

On the equivalency of Black Smoke / British Smoke and historic Elemental Carbon

Elemental Carbon (EC) is a good indicator for aerosol air quality and a main component in global warming; therefore data on its historic concentration would be highly valuable for an assessment of historic levels. There were already major sources of EC in Europe in the early 20th century, but the component has only been measured since the late 1980s when analysis procedures were developed and even until recently data are scarce. However, historic EC-concentrations may be deducible from the parameter British Smoke (BrS), respectively the equivalent parameter Black Smoke (BS; in continental Europe), monitored on a daily basis since the late 1940s. Values of the parameter were based on the light-absorptivity of aerosol filter samples and these should be a measure for EC, because it is/was the dominant light-absorbing species in the countries in which the method was used. We show here that BrS was a linear proxy for EC in the standardisation studies performed in the early 1960s, based on the approach of “proportional” sampling. In this procedure filter samples were collected in parallel sampling lines with increasing filter loadings of the same aerosol. The light-absorption as a function of mass loading, of a variety of aerosol types, followed a generic curve. This graph was normalised in the “BrS-curve” by setting BrS equal to the average mass loading of the urban aerosol in the tests. Because of the proportional sampling the mass-loading of the component EC followed, by necessity, the BrS-curve as a function of light-absorption. The proportionality factor between BrS and EC is not known because the latter parameter was not analysed then. When EC became measured, the major source of urban EC was diesel exhaust. We show that filter samples with urban aerosols containing EC deriving from diesel combustion and from domestic coal use give similar light-absorption signals when probed with the BrS/BS-method. This implies that the equivalency factor between EC and BS, as assessed in recent years, must also have applied in the past. In the intercomparison studies that we found in literature the correlation factor (R2) between EC and BS was on average 0.85, but the absolute EC values were quite different because of the different analysis methods used for EC. We converted the EC-data to values comparable to the new EU-standard “EUSAAR2-TOT”. We then arrive at an equivalency factor of 0.15 (±25%) respectively 0.18 (±25%) to translate historic BS or BrS data to concentrations of EC.

Measurement uncertainty arising from sampling of environmental samples

In 2017, a new revision of the ISO/IEC 17025 standard was issued. One of the important changes is that the uncertainty arising from sampling has to be evaluated. Based on this new requirement, we evaluated the contribution of the sampling procedure to the total uncertainty budget of the high-resolution gamma-ray spectrometry of environmental soil, tap water and aerosol filter samples. We performed statistical analyses of measurements of sets of samples taken from the same target in the same general time period. The determination of sampling uncertainty was based on the evaluation of the standard deviation of the set of measurement results and the combined uncertainty budget of sample preparation and analysis. When the spatial and temporal heterogeneities are low, the sampling uncertainty is estimated to be around 5% (k = 1) for soil samples and 30–40% (k = 1) for air samples. For single tap water samples collected consecutively, sampling uncertainty does not have a significant contribution to the complete uncertainty budget.

Quantifying organic matter and functional groups in particulate matter filter samples from the southeastern United States – Part 1: Methods

Abstract. Comprehensive techniques to describe the organic composition of atmospheric aerosol are needed to elucidate pollution sources, gain insights into atmospheric chemistry, and evaluate changes in air quality. Fourier transform infrared absorption (FT-IR) spectrometry can be used to characterize atmospheric organic matter (OM) and its composition via functional groups of aerosol filter samples in air monitoring networks and research campaigns. We have built FT-IR spectrometry functional group calibration models that improve upon previous work, as demonstrated by the comparison of current model results with those of previous models and other OM analysis methods. Laboratory standards that simulated the breadth of the absorbing functional groups in atmospheric OM were made: particles of relevant chemicals were first generated, collected, and analyzed. Challenges of collecting atmospherically relevant particles and spectra were addressed by including interferences of particle water and other inorganic aerosol constituents and exploring the spectral effects of intermolecular interactions. Calibration models of functional groups were then constructed using partial least-squares (PLS) regression and the collected laboratory standard data. These models were used to quantify concentrations of five organic functional groups and OM in 8 years of ambient aerosol samples from the southeastern aerosol research and characterization (SEARCH) network. The results agreed with values estimated using other methods, including thermal optical reflectance (TOR) organic carbon (OC; R2=0.74) and OM calculated as a difference between total aerosol mass and inorganic species concentrations (R2=0.82). Comparisons with previous calibration models of the same type demonstrate that this new, more complete suite of chemicals has improved our ability to estimate oxygenated functional group and overall OM concentrations. Calculated characteristic and elemental ratios including OM∕OC, O∕C, and H∕C agree with those from previous work in the southeastern US, substantiating the aerosol composition described by FT-IR calibration. The median OM∕OC ratio over all sites and years was 2.1±0.2. Further results discussing temporal and spatial trends of functional group composition within the SEARCH network will be published in a forthcoming article.

Hypobromite oxidation combined with hydroxylamine hydrochloride reduction method for analyzing ammonium nitrogen isotope in atmospheric samples.

Ammonium salts, including ammonium nitrate, ammonium sulfate and ammonium hydrogen sulfate, are the main components of secondary inorganic aerosols and play an important role in the formation of haze events. The sources and transformation processes of atmospheric ammonium have received more and more attention. In this study, we modified the previous stable isotope analysis technique by improving the injection volume and adding a pH adjustment step, which gave a rapid and accurate measurement of ammonium nitrogen isotope ratio in atmospheric aerosol samples. Firstly, we added alkaline hypobromite to the extracted solution of the atmospheric aerosol filter samples (0.25 μg·mL-1 ammonium nitrogen in 4 mL) to oxidize ammonium (NH4+) to nitrite (NO2-). Then, after adjusting the pH, nitrite (NO2-) was reduced to nitrous oxide (N2O) by hydroxylamine hydrochloride under pH <0.3. Finally, nitrous oxide (N2O) was analyzed by Precon-GasBench-IRMS system to measure ammonium nitrogen isotope ratio. Our approach required low amount of NH4+ and avoided the use of highly toxic and explosive reagents. Meanwhile, the precision of our method could reach as high as 0.2‰ (n=10). This method could increase the NH4+ reduction efficiency to 100% at a condition of pH <0.3 and satisfy the demands of precision and accuracy for determination of ammonium nitrogen isotope in atmospheric aerosol samples. This method would help us better understand the sources, evolutions, chemical and deposition processes of atmospheric ammonium.

Electrochemical dithiothreitol assay for large-scale particulate matter studies

Particulate matter (PM) air pollution is associated with human morbidity and mortality. Measuring PM oxidative potential has been shown to provide a predictive measurement between PM exposure and adverse health impacts. The dithiothreitol (DTT) assay is commonly used to measure the oxidative potential of PM2.5 (PM less than 2.5 μm aerodynamic diameter). In the common, kinetic form of this assay, the decay of DTT is quantified over time (indirectly) using 5,5'-dithiobis(2-nitrobenzoic acid) (DTNB, Ellman's reagent) via UV/vis absorbance spectroscopy. The loss of DTT can also be quantified directly using electrochemical detection. The objectives of this work were (1) to evaluate the electrochemical assay, using commercially available equipment, relative to the UV/vis absorbance assay, and (2) to apply the electrochemical method to a large (>100) number of PM2.5 aerosol filter samples. Also presented here is the comparison an end-point assay to the kinetic assay, in an attempt to reduce the time, labor, and materials neccssary to quantify PM oxidative potential. The end-point, electrochemical assay gave comparable results to the UV/vis absorbance assay for PM filter sample analysis. Finally, high filter mass loadings (higher than about 0.5 μg PM per mm2 filter) lead to sub-optimal DTT assay performance, which suggests future studies should limit particle mass loadings on filters.

The importance of blowing snow to halogen-containing aerosol in coastal Antarctica: influence of source region versus wind speed

Abstract. A fundamental understanding of the processes that control Antarctic aerosols is necessary in determining the aerosol impacts on climate-relevant processes from Antarctic ice cores to clouds. The first in situ observational online composition measurements by an aerosol mass spectrometer (AMS) of Antarctic aerosols were only recently performed during the Two-Season Ozone Depletion and Interaction with Aerosols Campaign (2ODIAC). 2ODIAC was deployed to sea ice on the Ross Sea near McMurdo Station over two field seasons: austral spring–summer 2014 and winter–spring 2015. The results presented here focus on the overall trends in aerosol composition primarily as functions of air masses and local meteorological conditions. The results suggest that the impact of long-range air mass back trajectories on either the absolute or relative concentrations of the aerosol constituents measured by (and inferred from) an AMS at a coastal location is small relative to the impact of local meteorology. However, when the data are parsed by wind speed, two observations become clear. First, a critical wind speed is required to loft snow from the surface, which, in turn, increases particle counts in all measured size bins. Second, elevated wind speeds showed increased aerosol chloride and sodium. Further inspection of the AMS data shows that the increased chloride concentrations have more of a “fast-vaporizing” nature than chloride measured at low wind speed. Also presented are the Cl:Na ratios of snow samples and aerosol filter samples, as measured by ion chromatography, as well as non-chloride aerosol constituents measured by the AMS. Additionally, submicron aerosol iodine and bromine concentrations as functions of wind speed are also presented. The results presented here suggest that aerosol composition in coastal Antarctica is a strong function of wind speed and that the mechanisms determining aerosol composition are likely linked to blowing snow.

Quantification of oxygenated polycyclic aromatic hydrocarbons in ambient aerosol samples using in-injection port thermal desorption-gas chromatography/mass spectrometry: Method exploration and validation

In-injection port thermal desorption (TD) was evaluated for determination of particulate phase oxygenated-polycyclic aromatic hydrocarbons (O-PAHs) collected on filters coupled with a gas chromatography/mass spectrometry (GC/MS). The analytical parameters were optimized with standard testing and ambient samples. Ten of the most abundant O-PAHs in ambient air were included in the demonstration. A desorption temperature of 275 °C for 9 min was sufficient to transfer entire target compounds to the analytical system. Good linearity (R2 >0.99) on the calibrations for each analyte was achieved. The limit of detection (LOD) ranged from 21 to 269 pg per loading. Method precisions, determined by replicate analyses of calibration standards and ambient samples, was less than 10% for target compounds. Comparisons were conducted on batches of 28 ambient aerosol filter samples using our TD and the traditional SE methods. Reasonably good agreement (R2 = 0.98) by the two methods was demonstrated for most of O-PAHs. The in-injection port TD can improve laboratory efficiency and reduce solvent-based costs for the measurement of O-PAHs.