Wintertime ammonium nitrate aerosol pollution is a severe air quality issue affecting both developed and rapidly urbanizing regions from Europe to East Asia. In the United States, it is acute in ...western basins subject to inversions that confine pollutants near the surface. Measurements and modeling of a wintertime pollution episode in Salt Lake Valley, Utah, demonstrate that ammonium nitrate is closely related to photochemical ozone through a common parameter, total odd oxygen, Ox,total. We show that the traditional nitrogen oxide and volatile organic compound (NOx‐VOC) framework for evaluating ozone mitigation strategies also applies to ammonium nitrate. Despite being nitrate‐limited, ammonium nitrate aerosol pollution in Salt Lake Valley is responsive to VOCs control and, counterintuitively, not initially responsive to NOx control. We demonstrate simultaneous nitrate limitation and NOx saturation and suggest this phenomenon may be general. This finding may identify an unrecognized control strategy to address a global public health issue in regions with severe winter aerosol pollution.
Plain Language Summary
Particulate matter (PM) is dangerous to human health and impacts visibility and climate. In the United States, Europe, and Asia, PM is severe in urban areas in the winter when ammonium nitrate, NH4NO3, comprises an appreciable fraction of the total PM mass. A key control strategy is to reduce emissions of the limiting reagent. Using measurements from a recent field campaign in the Salt Lake Valley, Utah, which experiences high PM levels in winter, we demonstrate that emission control strategies can be evaluated using the same framework commonly used to control ozone, another common pollutant that occurs at high levels in urban areas in the summer. We show that initial control of the NOx precursor is ineffective at reducing NH4NO3 aerosol in the Salt Lake Valley, while initial control of volatile organic compounds, which are not a direct precursor for either nitrate or ammonium, is effective due to their influence on oxidation cycles. This finding differs from many mitigation strategies in the western United States and may also be relevant to other regions in Europe and Asia which experience high wintertime PM.
Key Points
Wintertime ammonium nitrate aerosol pollution is closely tied to photochemical ozone production through a common parameter, Ox,total
Box modeling reveals ammonium nitrate formation in the Salt Lake Valley is nitrate‐limited but NOx‐saturated
Mitigation strategies that focus on NOx control in some wintertime‐polluted layers may initially increase ammonium nitrate
Signatures of sulfur mass‐independent fractionation (S‐MIF) are observed for sulfur minerals in Archean rocks, and for modern stratospheric sulfate aerosols (SSA) deposited in polar ice. Ultraviolet ...light photolysis of SO2 is thought to be the most likely source for these S‐MIF signatures, although several hypotheses have been proposed for the underlying mechanism(s) of S‐MIF production. Laboratory SO2 photolysis experiments are carried out with a flow‐through photochemical reactor with a broadband (Xe arc lamp) light source at 0.1 to 5 mbar SO2 in 0.25 to 1 bar N2 bath gas, in order to test the effect of SO2 pressure on the production of S‐MIF. Elemental sulfur products yield high δ34S values up to 140 ‰, with δ33S/δ34S of 0.59 ± 0.04 and Δ36S/Δ33S ratios of −4.6 ± 1.3 with respect to initial SO2. The magnitude of the isotope effect strongly depends on SO2 partial pressure, with larger fractionations at higher SO2 pressures, but saturates at an SO2 column density of 1018 molecules cm−2. The observed pressure dependence and δ33S/δ34S and Δ36S/Δ33S ratios are consistent with model calculations based on synthesized SO2 isotopologue cross sections, suggesting a significant contribution of isotopologue self‐shielding to S‐MIF for high SO2 pressure (>0.1 mbar) experiments. Results of dual‐cell experiments further support this conclusion. The measured isotopic patterns, in particular the Δ36S/Δ33S relationships, closely match those measured for modern SSA from explosive volcanic eruptions. These isotope systematics could be used to trace the chemistry of SSA after large Plinian volcanic eruptions.
Key Points
SO2 isotope self‐shielding signatures in stratospheric sulfate aerosols
Laboratory SO2 photolysis to test the origin of mass‐independent isotope effect
Sulfur isotope signatures linked to high SO2 loading in the past
Air pollution monitoring using mobile ground-based measurement platforms can provide high-quality spatiotemporal air pollution information. As mobile air quality monitoring campaigns extend to entire ...fleets of vehicles and integrate smaller-scale air quality sensors, it is important to address the need to assess these measurements in a scalable manner. We explore the collocation-based evaluation of air quality measurements in a mobile platform using fixed regulatory sites as a reference. We compare two approaches: a standard collocation assessment technique, in which the mobile platform is parked near the fixed regulatory site for a period of time, and an expanded approach, which uses measurements while the mobile platform is in motion in the general vicinity of the fixed regulatory site. Based on the availability of fixed-reference-site data, we focus on three pollutants (ozone, nitrogen dioxide, and nitric oxide) with distinct atmospheric lifetimes and behaviors. We compare measurements from a mobile laboratory with regulatory site measurements in Denver, CO, USA, and in the San Francisco Bay Area, CA, USA. Our 1-month Denver dataset includes both parked collocation periods near the fixed regulatory sites and general driving patterns around the sites, allowing a direct comparison of the parked and mobile collocation techniques on the same dataset. We show that the mobile collocation approach produces similar performance statistics, including coefficients of determination and mean bias errors, to the standard parked collocation technique. This is particularly true when the comparisons are restricted to specific road types, with residential streets showing the closest agreement and highways showing the largest differences. We extend our analysis to a larger (yearlong) dataset in California, where we explore the relationships between the mobile measurements and the fixed reference sites on a larger scale. We show that using a 40 h running median converges to within ±4 ppbv of the fixed reference site for nitrogen dioxide and ozone and up to about 8 ppbv for nitric oxide. We propose that this agreement can be leveraged to assess instrument performance over time during large-scale mobile monitoring campaigns. We demonstrate an example of how such relationships can be employed during large-scale monitoring campaigns using small sensors to identify potential measurement biases.
We examined the extent to which three
Fraxinus
cultivars and a wild population that vary in their resistance to Emerald Ash Borer (EAB) could be differentiated on the basis of a suite of constitutive ...chemical defense traits in phloem extracts. The EAB-resistant Manchurian ash (
F. mandshurica
, cv. Mancana) was characterized by having a rapid rate of wound browning, a high soluble protein concentration, low trypsin inhibitor activities, and intermediate levels of peroxidase activity and total soluble phenolic concentration. The EAB-susceptible white ash (
F. americana
, cv. Autumn Purple) was characterized by a slow wound browning rate and low levels of peroxidase activity and total soluble phenolic concentrations. An EAB-susceptible green ash cultivar (
F. pennsylvanica
, cv. Patmore) and a wild accession were similar to each other on the basis of several chemical defense traits, and were characterized by high activities of peroxidase and trypsin inhibitor, a high total soluble phenolic concentration, and an intermediate rate of wound browning. Lignin concentration and polyphenol oxidase activities did not differentiate resistant and susceptible species. Of 33 phenolic compounds separated by HPLC and meeting a minimum criterion for analysis, nine were unique to Manchurian ash, five were shared among all species, and four were found in North American ashes and not in the Manchurian ash. Principal components analysis revealed clear separations between Manchurian, white, and green ashes on the basis of all phenolics, as well as clear separations on the basis of quantities of phenolics that all species shared. Variation in some of these constitutive chemical defense traits may contribute to variation in resistance to EAB in these species.
Ultraviolet photolysis of sulfur dioxide (SO2) is hypothesized to be the source of the sulfur isotope mass-independent fractionation (S-MIF) observed in Archean sulfate and sulfide minerals and ...modern stratospheric sulfate aerosols. A series of photochemical experiments were performed to examine the excitation band dependence of S-MIF during the photochemistry of SO2 under broadband light sources (a xenon arc lamp and a deuterium arc lamp). Optical filters (200±35nm bandpass and 250nm longpass filters) were used to separately access two different excitation bands of SO2 in the 190–220nm and the 250–330nm absorption regions, respectively.
UV irradiation of SO2 in the 190–220nm and 250–330nm regions both produced elemental sulfur (S0) and sulfur trioxide (SO3) as end products but yielded very different sulfur isotope signatures. The elemental sulfur products from direct photolysis in the 190–220nm region were characterized by high δ34S values (154.7–212.0‰), modest Δ33S anomalies of 21±3‰, and relatively constant 33λ (=ln(δ33S+1)/ln(δ34S+1)) values of 0.64±0.3, all with respect to the initial SO2. Photoexcitation in the 250–330nm region produced elemental sulfur with δ34S values of 7.7–29.1‰ and Δ33S values of 15.0±1.6‰. In both excitation regions, the SO3 products were mass dependently fractionated relative to the SO2 reservoir. The two different absorption regions produced contrasting Δ36S/Δ33S signatures in the elemental sulfur products, with Δ36S/Δ33S=−1.9±0.3 and 0.64±0.3 for the 190–220nm and 250–330nm bands, respectively.
Our results provide several critical constraints on the origin of the S-MIF signatures observed in modern stratospheric aerosols and in the Archean geological record. A lack of S-MIF in the sulfate product and positive Δ36S/Δ33S ratios for the elemental sulfur from SO2 photo-oxidation demonstrate that photoexcitation in the 250–330nm region is not a likely source for the S-MIF observed in modern stratospheric aerosols. Large δ34S fractionation, 33λ values, and Δ36S/Δ33S ratios observed for the 190–220nm band are qualitatively consistent with predictions from synthetic isotopologue-specific cross sections. These isotope patterns, however, are not compatible with the Archean rock record. We explore the possibility that S-MIF from both the 190 to 220nm and the 250 to 330nm absorption bands could have contributed to the Archean S-MIF signatures.
Abstract
Wintertime ammonium nitrate aerosol pollution is a severe air quality issue affecting both developed and rapidly urbanizing regions from Europe to East Asia. In the United States, it is ...acute in western basins subject to inversions that confine pollutants near the surface. Measurements and modeling of a wintertime pollution episode in Salt Lake Valley, Utah, demonstrate that ammonium nitrate is closely related to photochemical ozone through a common parameter, total odd oxygen, O
x,total
. We show that the traditional nitrogen oxide and volatile organic compound (NOx‐VOC) framework for evaluating ozone mitigation strategies also applies to ammonium nitrate. Despite being nitrate‐limited, ammonium nitrate aerosol pollution in Salt Lake Valley is responsive to VOCs control and, counterintuitively, not initially responsive to NO
x
control. We demonstrate simultaneous nitrate limitation and NO
x
saturation and suggest this phenomenon may be general. This finding may identify an unrecognized control strategy to address a global public health issue in regions with severe winter aerosol pollution.
Plain Language Summary
Particulate matter (PM) is dangerous to human health and impacts visibility and climate. In the United States, Europe, and Asia, PM is severe in urban areas in the winter when ammonium nitrate, NH
4
NO
3
, comprises an appreciable fraction of the total PM mass. A key control strategy is to reduce emissions of the limiting reagent. Using measurements from a recent field campaign in the Salt Lake Valley, Utah, which experiences high PM levels in winter, we demonstrate that emission control strategies can be evaluated using the same framework commonly used to control ozone, another common pollutant that occurs at high levels in urban areas in the summer. We show that initial control of the NO
x
precursor is ineffective at reducing NH
4
NO
3
aerosol in the Salt Lake Valley, while initial control of volatile organic compounds, which are not a direct precursor for either nitrate or ammonium, is effective due to their influence on oxidation cycles. This finding differs from many mitigation strategies in the western United States and may also be relevant to other regions in Europe and Asia which experience high wintertime PM.
Key Points
Wintertime ammonium nitrate aerosol pollution is closely tied to photochemical ozone production through a common parameter, O
x,total
Box modeling reveals ammonium nitrate formation in the Salt Lake Valley is nitrate‐limited but NO
x
‐saturated
Mitigation strategies that focus on NO
x
control in some wintertime‐polluted layers may initially increase ammonium nitrate
Signatures of mass-independent isotope fractionation (MIF) are found in the oxygen (¹⁶O, ¹⁷O, ¹⁸O) and sulfur (³²S, ³³S, ³⁴S, ³⁶S) isotope systems and serve as important tracers of past and present ...atmospheric processes. These unique isotope signatures signify the breakdown of the traditional theory of isotope fractionation, but the physical chemistry of these isotope effects remains poorly understood. We report the production of large sulfur isotope MIF, with Δ ³³S up to 78‰ and Δ ³⁶S up to 110‰, from the broadband excitation of SO ₂ in the 250–350-nm absorption region. Acetylene is used to selectively trap the triplet-state SO ₂ (Formula ³B ₁), which results from intersystem crossing from the excited singlet (Formula ¹A ₂/Formula ¹B ₁) states. The observed MIF signature differs considerably from that predicted by isotopologue-specific absorption cross-sections of SO ₂ and is insensitive to the wavelength region of excitation (above or below 300 nm), suggesting that the MIF originates not from the initial excitation of SO ₂ to the singlet states but from an isotope selective spin–orbit interaction between the singlet (Formula ¹A ₂/Formula ¹B ₁) and triplet (Formula ³B ₁) manifolds. Calculations based on high-level potential energy surfaces of the multiple excited states show a considerable lifetime anomaly for ³³SO ₂ and ³⁶SO ₂ for the low vibrational levels of the Formula ¹A ₂ state. These results demonstrate that the isotope selectivity of accidental near-resonance interactions between states is of critical importance in understanding the origin of MIF in photochemical systems.
Recent global QCD analysis of jet production and other polarized scattering data have found the presence of negative solutions for the gluon helicity distribution in the proton, $\Delta g$, along ...with the traditional $\Delta g > 0$ solutions. We consider polarized semi-inclusive deep-inelastic scattering for hadrons produced with large transverse momentum as a means of constraining the dependence of $\Delta g$ on the parton momentum fraction, $x$. Focusing on the double longitudinal spin asymmetry, we identify the kinematics relevant for future experiments at Jefferson Lab and the Electron-Ion Collider which are particularly sensitive to the polarized gluon channel and could discriminate between the different $\Delta g$ behaviors.
We perform a new global analysis of spin-dependent parton distribution functions with the inclusion of Ioffe time pseudo-distributions computed in lattice QCD (LQCD), which are directly sensitive to ...the gluon helicity distribution, $\Delta g$. These lattice data have an analogous relationship to parton distributions as do experimental cross sections, and can be readily included in global analyses. We focus in particular on the constraining capability of current LQCD data on the sign of $\Delta g$ at intermediate parton momentum fractions $x$, which was recently brought into question by analysis of data in the absence of parton positivity constraints. We find that present LQCD data cannot discriminate between positive and negative $\Delta g$ solutions, although significant changes in the solutions for both the gluon and quark sectors are observed.
Hypertrophic cardiomyopathy is the leading cause of sudden cardiac death (SCD) in children and young adults. Our objective was to develop and validate a SCD risk prediction model in pediatric ...hypertrophic cardiomyopathy to guide SCD prevention strategies.
In an international multicenter observational cohort study, phenotype-positive patients with isolated hypertrophic cardiomyopathy <18 years of age at diagnosis were eligible. The primary outcome variable was the time from diagnosis to a composite of SCD events at 5-year follow-up: SCD, resuscitated sudden cardiac arrest, and aborted SCD, that is, appropriate shock following primary prevention implantable cardioverter defibrillators. Competing risk models with cause-specific hazard regression were used to identify and quantify clinical and genetic factors associated with SCD. The cause-specific regression model was implemented using boosting, and tuned with 10 repeated 4-fold cross-validations. The final model was fitted using all data with the tuned hyperparameter value that maximizes the c-statistic, and its performance was characterized by using the c-statistic for competing risk models. The final model was validated in an independent external cohort (SHaRe Sarcomeric Human Cardiomyopathy Registry, n=285).
Overall, 572 patients met eligibility criteria with 2855 patient-years of follow-up. The 5-year cumulative proportion of SCD events was 9.1% (14 SCD, 25 resuscitated sudden cardiac arrests, and 14 aborted SCD). Risk predictors included age at diagnosis, documented nonsustained ventricular tachycardia, unexplained syncope, septal diameter
-score, left ventricular posterior wall diameter
score, left atrial diameter
score, peak left ventricular outflow tract gradient, and presence of a pathogenic variant. Unlike in adults, left ventricular outflow tract gradient had an inverse association, and family history of SCD had no association with SCD. Clinical and clinical/genetic models were developed to predict 5-year freedom from SCD. Both models adequately discriminated between patients with and without SCD events with a c-statistic of 0.75 and 0.76, respectively, and demonstrated good agreement between predicted and observed events in the primary and validation cohorts (validation c-statistic 0.71 and 0.72, respectively).
Our study provides a validated SCD risk prediction model with >70% prediction accuracy and incorporates risk factors that are unique to pediatric hypertrophic cardiomyopathy. An individualized risk prediction model has the potential to improve the application of clinical practice guidelines and shared decision making for implantable cardioverter defibrillator insertion. Registration: URL: https://www.clinicaltrials.gov; Unique identifier: NCT0403679.
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