The measurement of elements in PM10 was performed with 1 h time resolution at a rural freeway site during summer 2015 in Switzerland using the Xact1 625 Ambient Metals Monitor. On average the Xact ...elements (without accounting for oxygen and other associated elements) make up about 20 % of the total PM10 mass (14.6 µg m−3). We conducted source apportionment by positive matrix factorisation (PMF) of the
elemental mass measurable by the Xact (i.e. major elements heavier than
Al), defined here as PM10el. Eight different sources were identified in PM10el (elemental PM10) mass driven by the sum of 14 elements (notable elements in brackets): Fireworks-I (K, S, Ba and Cl), Fireworks-II (K), sea salt (Cl), secondary sulfate (S), background dust (Si, Ti), road dust (Ca), non-exhaust traffic-related elements (Fe) and industrial elements (Zn and Pb). The major components were secondary sulfate and non-exhaust traffic-related elements followed by background dust and road dust factors, explaining 21 %, 20 %, 18 % and 16 % of the analysed PM10 elemental mass, respectively, with the factor mass not corrected for oxygen content. Further, there were minor contributions (on the order of a few percent) of sea salt and industrial sources. The regionally influenced secondary sulfate factor showed negligible resuspension, and concentrations were similar throughout the day. The significant loads of the non-exhaust traffic-related and road dust factors with strong diurnal variations highlight the continuing importance of vehicle-related air pollutants at this site. Enhanced control of PMF implemented via the SourceFinder software (SoFi Pro version 6.2, PSI, Switzerland) allowed for a successful apportionment of transient sources such as the two firework factors and sea salt, which remained mixed when analysed by unconstrained PMF.
The Xact 625 Ambient Metals Monitor was tested during a 3-week field campaign at the rural, traffic-influenced site Härkingen in Switzerland during the summer of 2015. The field campaign encompassed ...the Swiss National Day fireworks event, providing increased concentrations and unique chemical signatures compared to non-fireworks (or background) periods. The objective was to evaluate the data quality by intercomparison with other independent measurements and test its applicability for aerosol source quantification. The Xact was configured to measure 24 elements in PM10 with 1 h time resolution. Data quality was evaluated for 10 24 h averages of Xact data by intercomparison with 24 h PM10 filter data analysed with ICP-OES for major elements, ICP-MS for trace elements, and gold amalgamation atomic absorption spectrometry for Hg. Ten elements (S, K, Ca, Ti, Mn, Fe, Cu, Zn, Ba, Pb) showed excellent correlation between the compared methods, with r2 values ≥ 0.95. However, the slopes of the regressions between Xact 625 and ICP data varied from 0.97 to 1.8 (average 1.28) and thus indicated generally higher Xact elemental concentrations than ICP for these elements. Possible reasons for these differences are discussed, but further investigations are needed. For the remaining elements no conclusions could be drawn about their quantification for various reasons, mainly detection limit issues. An indirect intercomparison of hourly values was performed for the fireworks peak, which brought good agreement of total masses when the Xact data were corrected with the regressions from the 24 h value intercomparison. The results demonstrate that multi-metal characterization at high-time-resolution capability of Xact is a valuable and practical tool for ambient monitoring.
Measuring the chemical composition of airborne particulate matter (PM) can provide valuable information on the concentration of regulated toxic metals, support modelling approaches for source ...detection and assist in the identification and validation of abatement techniques. Undertaking these at a high time resolution (1 h or less) enables receptor modelling techniques to be more robustly linked to emission processes. This study describes a comprehensive laboratory and field evaluation of a high time resolution x-ray fluorescence (XRF) instrument (CES XACT 625) for a range of elements (As, Ba, Ca, Cd, Ce, Cl, Cr, Cu, Fe, K, Mn, Mo, Ni, Pb, Pt, S, Sb, Se, Si, Sr, Ti, V and Zn) against alternative techniques: high time resolution mass measurements, high time resolution ion chromatography, aerosol mass spectrometry, and established filter-based, laboratory analysis using inductively coupled plasma mass spectrometry (ICP-MS). Laboratory evaluation was carried out using a novel mass-based calibration technique to independently assess the accuracy of the XRF against laboratory generated aerosols, which resulted in slopes that were not significantly different from unity. This demonstrated that generated particles can serve as an alternative calibration method for this instrument.The XACT was evaluated in three contrasting field deployments; a heavily trafficked roadside site (PM10 and PM2.5), an industrial location downwind of a nickel refinery (PM10) and an urban background location influenced by nearby industries and motorways (PM10). The XRF technique agreed well with the ICP-MS measurements of daily filter samples in all cases with a median R2 of 0.93 and a median slope of 1.07 for the elements As, Ba, Ca, Cr, Cu, Fe, K, Mn, Ni, Pb, Se, Sr, Ti, V and Zn. Differences in the results were attributed to a combination of inlet location and sampling temperature, variable blank levels in filter paper and recovery rates from acid digestion. The XRF technique also agreed well with the other high time resolution measurements but showed a clear positive difference (slopes between 1.41 and 4.6), probably due to differences in the size selection methodology, volatility and water solubility of the PM in aerosol mass spectrometry (SO4) and ion chromatography (Ca, Cl, K and SO4), respectively.A novel filter analysis technique using the XACT showed promising initial results: filters analysed off-line with the XACT compared well to in situ XACT measurements with a median R2 of 0.96 and median slope of 1.07. The resulting range of slopes was comparable to slopes produced in the ICP-MS comparison. This technique provides an opportunity to use the XACT when it is not deployed in the field; thus expanding the potential use of this instrument in future studies.
Relative strengths of amide NH···O- and carboxyl OH···O- hydrogen bonds were investigated via conformational analysis of succinamate and monohydrogen succinate anions with the aid of vicinal ...proton−proton NMR couplings and B3LYP DFT quantum mechanical calculations for a variety of solvents. New experimental results for succinamate are compared with those obtained from previous studies of monohydrogen succinate. While some computational results for monohydrogen succinate were published previously, the results contained herein are the product of a more powerful methodology than that used earlier. The experimental results clearly show that intramolecular hydrogen-bond formation is more favored in aprotic solvents than in protic solvents for both molecules. Furthermore, the preference of the succinate monoanion for the gauche conformation is much stronger in aprotic solvents than that of succinamate, indicating that the OH···O- hydrogen bond is substantially stronger than its NH···O- counterpart, despite the ∼5 kcal cost for formation of the E configuration of the carboxyl group needed to make an intramolecular hydrogen bond. The actual energy differences between formation of internal hydrogen bonds for monohydrogen succinate and succinamate anion were estimated by comparison of the relative values of K 1 of the respective acids in water and DMSO by a procedure first developed by Westheimer. Recent theoretical work with succinamate highlights the necessity of considering substituent orientational degrees of freedom to understand the conformational equilibria of the central CH2−CH2 torsions in disubstituted ethanes. Similar methodology is applied here to succinic acid monoanion, by mapping potential-energy surfaces with respect to the CH2−CH2 torsional, carboxyl-substituent rotational, and carboxyl−proton E/Z isomeric degrees of freedom. Boltzmann populations were compared with gauche populations estimated from the experimentally determined coupling constants. The quantum mechanical results for succinamate show a much weaker tendency toward hydrogen bonding than for the succinic acid monoanion. However, the theoretical methods employed appear to substantially overestimate contributions from intramolecularly hydrogen-bonded structures for the succinic acid monoanion when compared with experimental results. Natural bond orbital analysis, applied to the quantum mechanical wave functions of fully optimized gauche and trans structures, showed a strong correlation between the population of amide σ*N - H and carboxyl σ*O - H antibonding orbitals and apparent hydrogen-bonding behavior.
Three new methods applicable to the determination of hazardous metal concentrations in stationary source emissions were developed and evaluated for use in U.S. Environmental Protection Agency (EPA) ...compliance applications. Two of the three independent methods, a continuous emissions monitor-based method (Xact) and an X-ray-based filter method (XFM), are used to measure metal emissions. The third method involves a quantitative aerosol generator (QAG), which produces a reference aerosol used to evaluate the measurement methods. A modification of EPA Method 301 was used to validate the three methods for As, Cd, Cr, Pb, and Hg, representing three hazardous waste combustor Maximum Achievable Control Technology (MACT) metal categories (low volatile, semivolatile, and volatile). The modified procedure tested the methods using more stringent criteria than EPA Method 301; these criteria included accuracy, precision, and linearity. The aerosol generation method was evaluated in the laboratory by comparing actual with theoretical aerosol concentrations. The measurement methods were evaluated at a hazardous waste combustor (HWC) by comparing measured with reference aerosol concentrations. The QAG, Xact, and XFM met the modified Method 301 validation criteria. All three of the methods demonstrated precisions and accuracies on the order of 5%. In addition, correlation coefficients for each method were on the order of 0.99, confirming the methods' linear response and high precision over a wide range of concentrations. The measurement methods should be applicable to emissions from a wide range of sources, and the reference aerosol generator should be applicable to additional analytes. EPA recently approved an alternative monitoring petition for an HWC at Eli Lilly's Tippecanoe site in Lafayette, IN, in which the Xact is used for demonstrating compliance with the HWC MACT metal emissions (low volatile, semivolatile, and volatile). The QAG reference aerosol generator was approved as a method for providing a quantitative reference aerosol, which is required for certification and continuing quality assurance of the Xact.
Vicinal proton−proton NMR couplings have been employed to estimate the differences in conformational equilibria for 1,4-butanedioic-2,3-13C2 acid in the progression of its diprotic to monoprotic to ...di-ionized forms as a function of solvent in water and in a series of alcohols ranging from methanol to tert-butyl alcohol. Except for water, the percentage of gauche increases from diacid to monoanion and then decreases from monoanion to dianion. The substantial gauche preference for the monoanion species in the less-polar alcohols is clearly the result of intramolecular hydrogen bonding.
Vicinal proton−proton NMR couplings and ab initio quantum mechanics have been used to investigate solvent effects on conformational equilibria of butanedinitrile. The trans and gauche conformations ...are about equally favored at room temperature in solvents of low dielectric constant while the equilibrium is essentially the statistical proportions of one-third trans and two-thirds gauche in water with a high dielectric constant. The coupling assignments were confirmed with the aid of stereospecific deuterium-labeled (R,R or S,S)-1,2-dideuteriobutanedinitrile. The calculations support the observed trends. Similar results were observed for 1,2-dibromo- and dichloroethanes.
Vicinal proton−proton NMR couplings have been used to compare the influences of water and tetrahydrofuran (THF) as solvents on the conformational equilibria of 1,4-butanedioic (succinic) acid and its ...mono- and dianionic salts. An earlier NMR investigation (Lit, E. S.; Mallon, F. K.; Tsai, H. Y.; Roberts, J. D. J. Am Chem. Soc. 1993, 115, 9563−9567) showed that, in water, the conformational preferences for the gauche conformations for butanedioic acid and its monoanion and dianion were, respectively, ∼84%, 66%, and 43%, essentially independent of the nature of the cation or concentration. We now report the corresponding gauche percentages calculated in the same way for 0.05 M solutions in THF to be 66%, 90−100%, and 46−64%. Substantial evidence was adduced for the rotational angle between the substituents in the monoanion being ∼70°. The positions of conformational equilibria of the salts in THF, particularly of the dianion, were found to be rather insensitive to concentration and temperature, but more sensitive to the amount of water present. Ab initio quantum-mechanical calculations for 1,4-butanedioate dianion indicate that, as expected for the gas phase, the trans conformation of the dianion should be heavily favored over the gauche, but, in both THF and water, the gauche conformation is calculated to predominate with rotational angles substantially less than 60°. This conclusion is, in fact, generally consistent with the experimental vicinal proton couplings, which are wholly inconsistent with the trans conformation.
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