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Mercury (Hg) is a global pollutant whose atmospheric deposition is a major input to the terrestrial and oceanic ecosystems. Gas‐particle partitioning (GPP) of gaseous oxidized mercury (GOM) redistributes speciated Hg between gas and particulate phase and can subsequently alter Hg deposition flux. Most 3‐dimensional chemical transport models either neglected the Hg GPP process or parameterized it with measurement data limited in time and space. In this study, CMAQ‐newHg‐Br (Ye et al., 2018, https://doi.org/10.1002/2017ms001161) was updated to CMAQ‐newHg‐Br v2 by implementing a new GPP scheme and the most up‐to‐date Hg redox chemistry and was run for the northeastern United States over January‐November 2010. CMAQ‐newHg‐Br v2 reproduced the measured spatiotemporal distributions of gaseous elemental mercury (GEM) and particulate bound mercury (PBM) concentrations and Hg wet deposition flux within reasonable ranges and simulated dry deposition flux in agreement with previous studies. The GPP scheme improved the simulation of PBM via increasing winter‐, spring‐ and fall‐time PBM concentrations by threefold. It also improved simulated Hg wet deposition flux with an increase of 2.1 ± 0.7 μgm2 in the 11‐month accumulated amount, offsetting half of the decreasing effect of the updated chemistry (−4.2 ± 1.8 μgm2). Further, the GPP scheme captured the observed Kp‐T relationship as reported in previous studies without using measurement data and showed advantages at night and in rural/remote areas where existing empirical parameterizations failed. Our study demonstrated CMAQ‐newHg‐Br v2 a promising assessment tool to quantify impacts of climate change and emission reduction policy on Hg cycling. Plain Language Summary: Mercury is a toxic global pollutant and can enter the food chain through atmospheric deposition to ecosystems. Atmospheric mercury was defined operationally in the forms of gaseous elemental mercury (GEM), gaseous oxidized mercury (GOM) and particulate bound mercury (PBM). GEM is relatively inert, but GOM and PBM are highly soluble and readily removed from the air via deposition. GEM gets oxidized to GOM and GOM can be transformed to PBM through gas particle partitioning (GPP). CMAQ‐newHg‐Br v2 was updated from its predecessor via implementing the most up‐to‐date Hg redox chemistry and a new GPP scheme. The model improved the simulation of GEM, PBM, and Hg wet deposition. Most notably the model reproduced the observed partitioning coefficient and temperature relationship (Kp‐T) and improved nighttime and less polluted PBM simulations. CMAQ‐newHg‐Br v2 can be used to assess how climate change and emission reduction policy impact environmental Hg cycling. Key Points: CMAQ‐newHg‐Br was updated to version 2 with a new gas‐particle partitioning (GPP) scheme and the most up‐to‐date Hg redox chemistryCMAQ‐newHg‐Br v2 better simulated gaseous elemental mercury (GEM), particulate bound mercury (PBM) and Hg wet depositionThe new GPP scheme captured the observed Kp‐T relation not using measurement data and improved nighttime and less polluted simulations [ABSTRACT FROM AUTHOR]

Although FNO has long been considered a computationally challenging molecule, no thorough study of this species has been performed with methods of electron correlation beyond second-order Mo\ller–Plesset perturbation theory (MP2) and the singles and doubles configuration interaction (CISD) method. We have investigated the equilibrium structure, vibrational spectra, and relative energetics of FNO using high-levels of ab initio theory. Methods include third and fourth-order Mo\ller–Plesset perturbation (MP3 and MP4), singles and doubles coupled-cluster (CCSD) theory, and the CCSD(T) method, which incorporates a perturbational estimate of the effects of connected triple excitations. The quadratic configuration interaction method including single, double, and triple excitations [QCISD(T)] method is also used. Computations using these methods are performed with medium and large basis sets. Geometries calculated at the Hartree–Fock level are grossly in error, while going to the CISD, MP3, MP4, and CCSD methods produces increasingly better results. The CCSD(T) and QCISD(T) methods yield quite accurate structures; surprisingly, the MP2 results are almost as good. The quality of the calculated relative energetics closely follows that of the structure predictions, except that the MP2 level of theory now performs slightly worse than MP3, MP4, and CCSD methods. [ABSTRACT FROM AUTHOR]

Simultaneous measurements of absolute concentrations of H2O and OH radicals in an atmospheric AC discharge using continuous wave cavity ringdown spectroscopy (cw-CRDS) are reported. Formation of OH radicals and plasma temperatures are characterized by optical emission spectroscopy. The concentration of OH radical at the edge of the discharge plume at 380 K is measured by the cw-CRDS technique to be 1.1 ×1015 molecule cm-3. Ringdown measurements of the H2O (120-000) band and the OH first overtone around 1515 nm enable us to determine an OH generation yield, $\Phi =\frac{N_{\rm OH} }{N_{\rm H_2 O}}$, to be 4.8 ×10-3, where NOH and $$ N_{H_2 O} $$ are the number densities of OH and H2O, respectively. The minimum detectable absorption coefficient of the cw-CRDS system is 8.9 ×10-9 cm-1, which corresponds to a 1σ detection limit of OH number density of 1.2 ×1013 molecule cm-3 in the discharge. This experimental approach is demonstrated for the first time ever in an AC discharge, and can be applied in general to a variety of atmospheric plasmas to help study OH formation mechanisms and OH-related plasma applications. [ABSTRACT FROM AUTHOR]

College students are struggling to maintain well-being, with mental health challenges becoming exceedingly disruptive. Health and wellness coaching can be utilized in the college setting in addition to counseling to connect college students with resources, provide support through accountability and unconditional positive regard, and promote personal growth. Trauma-informed care is an effective approach for supporting those who may be or are experiencing trauma and is shown to be relevant in the college setting. This paper describes a rationale for integrating trauma-informed care and health and wellness coaching to enhance overall college student well-being, foster academic achievement, and create a safe, inclusive environment for growth.

Background: Although prior national reports have identified trends in the underutilization of transcatheter aortic valve replacement (TAVR) in Afro-American and Latino populations, racial and ethnic healthcare disparities in TAVR use in the State of Connecticut have not been previously reported., Methods: We conducted a retrospective analysis of 1461 patients undergoing TAVR at our institute between from 2012 to 2020. Baseline demographics, procedural characteristics, clinical outcomes, median incomes and insurance coverage were compared between 1417 Caucasian and 44 minority patients, including 23 patients designated as Afro-American and 10 designated as Latino. Demographics of TAVR utilization at our institution were further compared to 6 additional Connecticut TAVR centers using Connecticut Hospital Association (CHA) ChimeData detailing hospital discharges for DRG 266 and 267., Results: In comparison to Caucasian patients, minority cohorts were younger (75.7 ± 9.0 vs 81.5 ± 5.1 years, p < 0.001) and had more co-morbidities including diabetes (64% vs 34%, p < 001), coronary artery disease (95% vs 78%, p = 0.039), end stage renal disease requiring dialysis (9% vs 3%, p = 0.009) and atrial fibrillation (77% vs 62%, p = 0.041). The two groups did not differ with respect to other risk factors or co-morbidities, baseline echocardiographic or CTA findings, STS risk score, or procedural technique. Minority patients had a longer length of hospital stay (9.5 ± 9.0 vs 6.4 ± 6.9 days, p = 0.003), but did not differ with respect to procedural complications. Socioeconomic differences between the two groups included lower median incomes and higher rates of Medicaid or no insurance coverage for minority versus Caucasian patients. CHA ChimeData revealed a similar underutilization of TAVR in minority subgroups in the remaining 6 Connecticut TAVR centers., Conclusions: Despite statewide demographics describing 10.7% and 15.7% of the total population as Afro-American and Latino, respectively, only 3.0% of the total TAVR procedures performed at a large Connecticut health care facility were performed in minority subgroups. Despite having a higher burden of co-morbidities, minority patients had similar outcomes compared to Caucasian patients. Similar racial and ethnic disparities in TAVR utilization were confirmed statewide using CHA ChimeData., (Copyright © 2021 Elsevier Inc. All rights reserved.)

Importance: Patients with breast cancer remain at risk of relapse after adjuvant therapy. Celecoxib has shown antitumor effects in preclinical models of human breast cancer, but clinical evidence is lacking., Objective: To evaluate the role of celecoxib as an addition to conventional therapy for women with ERBB2 (formerly HER2)-negative primary breast cancer., Design, Setting, and Participants: The Randomized European Celecoxib Trial (REACT) was a phase 3, randomized, double-blind study conducted in 160 centers across the UK and Germany testing 2 years of adjuvant celecoxib vs placebo among 2639 patients recruited between January 19, 2007, and November 1, 2012, with follow-up 10 years after treatment completion. Eligible patients had completely resected breast cancer with local and systemic therapy according to local practice. Patients with ERBB2-positive or node-negative and T1, grade 1 tumors were not eligible. Randomization was in a 2:1 ratio between celecoxib or placebo. Statistical analysis was performed from May 5, 2019, to March 5, 2020., Interventions: Patients received celecoxib, 400 mg, or placebo once daily for 2 years., Main Outcomes and Measures: The primary end point was disease-free survival (DFS), analyzed in the intention-to-treat population using Cox proportional hazards regression and log-rank analysis. Follow-up is complete., Results: A total of 2639 patients (median age, 55.2 years [range, 26.8-86.0 years]) were recruited; 1763 received celecoxib, and 876 received placebo. Most patients' tumors (1930 [73%]) were estrogen receptor positive or progesterone receptor positive and ERBB2 negative. A total of 1265 patients (48%) had node-positive disease, and 1111 (42%) had grade 3 tumors. At a median follow-up of 74.3 months (interquartile range, 61.4-93.6 years), DFS events had been reported for 487 patients (19%): 18% for those who received celecoxib (n = 323; 5-year DFS rate = 84%) vs 19% for those who received placebo (n = 164; 5-year DFS rate = 83%); the unadjusted hazard ratio was 0.97 (95% CI, 0.80-1.17; log-rank P = .75). Rates of toxic effects were low across both treatment groups, with no evidence of a difference., Conclusions and Relevance: In this randomized clinical trial, patients showed no evidence of a DFS benefit for 2 years' treatment with celecoxib compared with placebo as adjuvant treatment of ERBB2-negative breast cancer. Longer-term treatment or use of a higher dose of celecoxib may lead to a DFS benefit, but further studies would be required to test this possibility., Trial Registration: ClinicalTrials.gov Identifier: NCT02429427 and isrctn.org Identifier: ISRCTN48254013.

This is a single-center cross-sectional study of consecutive patients who presented to an urban emergency department (ED) with firearm injuries between July 1, 2014 and June 30, 2016. The objective of this study was to describe the characteristics of patients in this cohort and identify those at risk of firearm re-injury to inform future interventions. Patients in this cohort with both initial and recidivistic firearm injures were found to be predominately young, African American men., Objective: To describe the characteristics of patients who present to the emergency department (ED) with firearm injuries and identify those at risk of firearm re-injury., Methods: This is a single-center cross-sectional study of consecutive patients who presented to the ED with firearm injuries between July 1, 2014 and June 30, 2016. We collected data on patient demographics, history of previous traumatic injury including firearm injury, and whether the firearm injury was self-inflicted. We also evaluated characteristics of patients in this cohort who returned to the ED with firearm re-injury within a one year follow-up period., Results: This study included 1226 unique patients. Our data demonstrate that patients presenting to the ED for firearm injury were predominately young, African American males. Fourteen percent had a history of a previous firearm injury and 20% had a history of other non-firearm assault. Patients who had been shot previously were more likely to be African American, male, uninsured, unemployed, and have a history of other non-accidental trauma. Eight percent of firearm injuries were self-inflicted. All 35 patients who sustained a new firearm injury within 1 year of the index injury were African American males with a median age of 23., Conclusions: Among patients treated in the ED for firearm injuries, young, African American males are disproportionately at risk of firearm injury and re-injury. ED visits for traumatic injury represent an opportunity to provide social work, case work, and counseling-based interventions to help disrupt the cycle of violence in high-risk individuals.

Objective: To comprehensively evaluate and compare utilization, outcomes, and especially costs of transfemoral (TF), transapical (TA), and transaortic (TAO) transcatheter aortic valve replacement (TAVR)., Methods: All Medicare fee-for-service patients undergoing TF (n = 4065), TA (n = 691), or TAO (n = 274) TAVR between January 1, 2011, and November 30, 2012, were identified using Health Care Procedure Classification Codes present on Medicare claims. Hospital charges from Medicare claims were converted to costs using hospital-specific Medicare cost-to-charge ratios., Results: TA and TAO patients were similar in age, race, and common comorbidities. Compared with TF patients, TA and TAO patients were more likely to be female and to have peripheral vascular disease, chronic lung disease, and renal failure. Thirty-day mortality rates were higher among TA and TAO patients than among TF patients (TA, 9.6%; TAO, 8.0%; TF, 5.0%; P < .001). Adjusted mortality beyond 1 year did not differ by access. TA patients were more likely to require cardiopulmonary bypass (CPB). Increased adjusted mortality was associated with CPB (hazard ratio, 2.13; P < .01) and increased 30-day cost ($62,000 [interquartile range (IQR)], $45,100-$86,400 versus $48,800 [IQR, $38,100-$62,900]; P < .01). Cost at 30 days was lowest for TF ($48,600) compared with TA ($49,800; P < .01) and TAO ($53,200; P = .03)., Conclusions: For patients ineligible to receive TF TAVR, TAO and TA approaches offer similar clinical outcomes at similar cost with acceptable operative and 1-year survival, except for higher rates of CPB use in TA patients. CPB was associated with worse survival and increased costs., (Copyright © 2017. Published by Elsevier Inc.)

Background: There is growing interest in aortic valve-sparing and valve repair operations, but the ideal operation and timing of intervention in these generally younger patients undergoing operations for aortic insufficiency (AI) and dilated ascending aorta remains controversial., Methods: Root replacements at a single institution from 2002 to 2014 were reviewed. Inclusion criteria were age younger than 70 and presence of moderate or greater aortic insufficiency (AI), with or without aortic aneurysm. Of 1,425 root replacements, 220 patients were considered in the final analysis., Results: Moderate AI was present in 87 patients and severe AI in 133 patients. The 30-day mortality was 0% in moderate AI patients and 2% (n = 3) in severe AI patients (p = 0.3). Freedom from reoperation was 95% at 10 years. Severe preoperative AI was associated with worse long-term survival compared with moderate AI (hazard ratio, 2.6; p = 0.04). Patients undergoing root replacement with moderate AI had similar survival compared with the age- and gender-matched United States population (log-rank p = 0.93), whereas patients with severe AI had significantly worse survival (log-rank p = 0.02). Other multivariable predictors of decreased long-term survival were age (hazard ratio, 1.1; p = 0.01) and preoperative renal failure (hazard ratio, 6.9; p < 0.01)., Conclusions: Elective root replacement operations in patients younger than 70 are associated with low rates of mortality and reoperation, which should be considered the benchmark operation for aortic valve-sparing or repair operations in similar patients. Worse survival was associated with severe AI and older age, suggesting earlier intervention may be an appropriate therapeutic strategy in selected patients., (Copyright © 2016 The Society of Thoracic Surgeons. Published by Elsevier Inc. All rights reserved.)

Objective: To assess the long-term impact of implementation intention formation in reducing consultations for emergency contraception and pregnancy testing among teenage women., Design: Teenage women visiting a family planning clinic were randomly assigned to implementation intention versus control conditions., Main Outcome Measures: Objective measures of consultation outcomes were obtained from clinic records at 2-year follow-up (N = 227)., Results: Rates of consultation for emergency contraception and pregnancy testing in the implementation intentions condition were 19% and 33% lower, respectively, compared to the rates observed in the control condition. Pregnancy rates were 43% lower. Intervention participants who consulted for emergency contraception and pregnancy testing at baseline were more than twice as likely to change to consulting for contraceptive supplies over the follow-up period compared to equivalent control participants (19% vs. 9%)., Conclusion: The impact of implementation intention formation on reducing pregnancy risk among teenagers is durable over 2 years. Implementation intentions were successful in changing behavior among precisely those participants who were at greatest risk of becoming pregnant., ((c) 2011 APA, all rights reserved.)

Objective: This study examined the impact of implementation intention formation in reducing consultations for emergency contraception and pregnancy testing in young women., Design: Teenage girls (N = 261) visiting a family planning clinic were randomly assigned to implementation intention versus control conditions and completed questionnaires at recruitment., Main Outcome Measures: Objective measures of consultation outcomes were obtained from clinic records at baseline and 9-month follow-up (n = 200)., Results: Forming implementation intentions significantly reduced consultations for emergency contraception and pregnancy testing at follow-up compared with the control group (38% vs. 55%). There were also differences between the groups in consultation outcomes over time. For instance, whereas 31% of implementation intention participants changed from consulting for emergency contraception and pregnancy testing at baseline to consulting for contraceptive supplies only at follow-up, only 16% of control participants did so., Conclusion: These results suggest that implementation intention formation is a simple yet effective means of promoting pregnancy prevention among teenagers., (PsycINFO Database Record (c) 2009 APA, all rights reserved.)

The atmospheric degradation pathways of the atmospherically important terpenes alpha-pinene and beta-pinene are studied using density functional theory. We employ the correlation functional of Lee, Yang, and Parr and the three-parameter HF exchange functional of Becke (B3LYP) together with the 6-31G(d) basis set. The C-C bond scission reactions of the beta-hydroxyalkoxy radicals that are formed after OH addition to alpha-pinene and beta-pinene are investigated. Both of the alkoxy radicals formed from the alpha-pinene-OH adduct possess a single favored C-C scission pathway with an extremely low barrier (approximately 3 kcal/mol) leading to the formation of pinonaldehyde. Neither of these pathways produces formaldehyde, and preliminary computational results offer some support for suggestions that 1,5 or 1,6 H-shift (isomerization) reactions of alkoxy radicals contribute to formaldehyde production. In the case of the alkoxy radical formed following OH addition to the methylene group of beta-pinene, there exists two C-C scission reactions with nearly identical barrier heights (approximately 7.5 kcal/mol); one leads to known products (nopinone and formaldehyde) but the ultimate products of the competing reaction are unknown. The single C-C scission pathway of the other alkoxy radical from beta-pinene possesses a very low (approximately 4 kcal/mol) barrier. The kinetically favored C-C scission reactions of all four alkoxy radicals appear to be far faster than expected rates of reaction with O2. The rearrangement of the alpha-pinene-OH adduct, a key step in the proposed mechanism of formation of acetone from alpha-pinene, is determined to possess a barrier of 11.6 kcal/mol. This value is consistent with another computational result and is broadly consistent with the modest acetone yields observed in product yield studies.