Nitrate Radicals Suppress Biogenic New Particle Formation from Monoterpene Oxidation.

Highly oxygenated organic molecules (HOMs) are a major source of new particles that affect the Earth's climate. HOM production from the oxidation of volatile organic compounds (VOCs) occurs during both the day and night and can lead to new particle formation (NPF). However, NPF involving organic vapors has been reported much more often during the daytime than during nighttime. Here, we show that the nitrate radicals (NO3), which arise predominantly at night, inhibit NPF during the oxidation of monoterpenes based on three lines of observational evidence: NPF experiments in the CLOUD (Cosmics Leaving OUtdoor Droplets) chamber at CERN (European Organization for Nuclear Research), radical chemistry experiments using an oxidation flow reactor, and field observations in a wetland that occasionally exhibits nocturnal NPF. Nitrooxy-peroxy radicals formed from NO3 chemistry suppress the production of ultralow-volatility organic compounds (ULVOCs) responsible for biogenic NPF, which are covalently bound peroxy radical (RO2) dimer association products. The ULVOC yield of α-pinene in the presence of NO3 is one-fifth of that resulting from ozone chemistry alone. Even trace amounts of NO3 radicals, at sub-parts per trillion level, suppress the NPF rate by a factor of 4. Ambient observations further confirm that when NO3 chemistry is involved, monoterpene NPF is completely turned off. Our results explain the frequent absence of nocturnal biogenic NPF in monoterpene (α-pinene)-rich environments.

Iodine oxoacids enhance nucleation of sulfuric acid particles in the atmosphere.

The main nucleating vapor in the atmosphere is thought to be sulfuric acid (H2SO4), stabilized by ammonia (NH3). However, in marine and polar regions, NH3 is generally low, and H2SO4 is frequently found together with iodine oxoacids [HIOx, i.e., iodic acid (HIO3) and iodous acid (HIO2)]. In experiments performed with the CERN CLOUD (Cosmics Leaving OUtdoor Droplets) chamber, we investigated the interplay of H2SO4 and HIOx during atmospheric particle nucleation. We found that HIOx greatly enhances H2SO4(-NH3) nucleation through two different interactions. First, HIO3 strongly binds with H2SO4 in charged clusters so they drive particle nucleation synergistically. Second, HIO2 substitutes for NH3, forming strongly bound H2SO4-HIO2 acid-base pairs in molecular clusters. Global observations imply that HIOx is enhancing H2SO4(-NH3) nucleation rates 10- to 10,000-fold in marine and polar regions.

Molecular Understanding of the Enhancement in Organic Aerosol Mass at High Relative Humidity.

The mechanistic pathway by which high relative humidity (RH) affects gas-particle partitioning remains poorly understood, although many studies report increased secondary organic aerosol (SOA) yields at high RH. Here, we use real-time, molecular measurements of both the gas and particle phase to provide a mechanistic understanding of the effect of RH on the partitioning of biogenic oxidized organic molecules (from α-pinene and isoprene) at low temperatures (243 and 263 K) at the CLOUD chamber at CERN. We observe increases in SOA mass of 45 and 85% with increasing RH from 10-20 to 60-80% at 243 and 263 K, respectively, and attribute it to the increased partitioning of semi-volatile compounds. At 263 K, we measure an increase of a factor 2-4 in the concentration of C10H16O2-3, while the particle-phase concentrations of low-volatility species, such as C10H16O6-8, remain almost constant. This results in a substantial shift in the chemical composition and volatility distribution toward less oxygenated and more volatile species at higher RH (e.g., at 263 K, O/C ratio = 0.55 and 0.40, at RH = 10 and 80%, respectively). By modeling particle growth using an aerosol growth model, which accounts for kinetic limitations, we can explain the enhancement in the semi-volatile fraction through the complementary effect of decreased compound activity and increased bulk-phase diffusivity. Our results highlight the importance of particle water content as a diluting agent and a plasticizer for organic aerosol growth.

High Gas-Phase Methanesulfonic Acid Production in the OH-Initiated Oxidation of Dimethyl Sulfide at Low Temperatures.

Dimethyl sulfide (DMS) influences climate via cloud condensation nuclei (CCN) formation resulting from its oxidation products (mainly methanesulfonic acid, MSA, and sulfuric acid, H2SO4). Despite their importance, accurate prediction of MSA and H2SO4 from DMS oxidation remains challenging. With comprehensive experiments carried out in the Cosmics Leaving Outdoor Droplets (CLOUD) chamber at CERN, we show that decreasing the temperature from +25 to -10 °C enhances the gas-phase MSA production by an order of magnitude from OH-initiated DMS oxidation, while H2SO4 production is modestly affected. This leads to a gas-phase H2SO4-to-MSA ratio (H2SO4/MSA) smaller than one at low temperatures, consistent with field observations in polar regions. With an updated DMS oxidation mechanism, we find that methanesulfinic acid, CH3S(O)OH, MSIA, forms large amounts of MSA. Overall, our results reveal that MSA yields are a factor of 2-10 higher than those predicted by the widely used Master Chemical Mechanism (MCMv3.3.1), and the NOx effect is less significant than that of temperature. Our updated mechanism explains the high MSA production rates observed in field observations, especially at low temperatures, thus, substantiating the greater importance of MSA in the natural sulfur cycle and natural CCN formation. Our mechanism will improve the interpretation of present-day and historical gas-phase H2SO4/MSA measurements.

Synergistic HNO3-H2SO4-NH3 upper tropospheric particle formation.

New particle formation in the upper free troposphere is a major global source of cloud condensation nuclei (CCN)1-4. However, the precursor vapours that drive the process are not well understood. With experiments performed under upper tropospheric conditions in the CERN CLOUD chamber, we show that nitric acid, sulfuric acid and ammonia form particles synergistically, at rates that are orders of magnitude faster than those from any two of the three components. The importance of this mechanism depends on the availability of ammonia, which was previously thought to be efficiently scavenged by cloud droplets during convection. However, surprisingly high concentrations of ammonia and ammonium nitrate have recently been observed in the upper troposphere over the Asian monsoon region5,6. Once particles have formed, co-condensation of ammonia and abundant nitric acid alone is sufficient to drive rapid growth to CCN sizes with only trace sulfate. Moreover, our measurements show that these CCN are also highly efficient ice nucleating particles-comparable to desert dust. Our model simulations confirm that ammonia is efficiently convected aloft during the Asian monsoon, driving rapid, multi-acid HNO3-H2SO4-NH3 nucleation in the upper troposphere and producing ice nucleating particles that spread across the mid-latitude Northern Hemisphere.

Impact of Insurance Provider on Postoperative Hospital Length of Stay After Spine Surgery.

OBJECTIVE: Differences in insurer and payer status have been shown to increase patient hospital length of stay (LOS) by delaying the approval of transfer to a rehabilitation facility. The aim of the current study is to determine the impact of the type of insurance provider on postoperative hospital LOS after spine surgery. METHODS: In our single-institution retrospective study, all patients undergoing elective spine surgery between August 2018 and August 2019 as part of an enhanced recovery after surgery (ERAS) protocol were enrolled in a prospectively collected registry. Insurance payer type was analyzed to determine its effect on total patient LOS after surgery. RESULTS: A total of 106 patients were included in the study. Insurance payers studied were Medicare, private insurers (preferred provider organization and health maintenance organization), and the Veterans Affairs payer TriWest. Patients in all groups had comparable demographic characteristics and procedural variables. There was a statistically significant difference in days stayed beyond medical clearance among the 3 insurance provider groups (P < 0.001); TriWest patients stayed an average of 3.2 days beyond clearance, compared with private insurance (1.2 days) and Medicare (0.3 days). Individual subanalysis of the ERAS complex pathway population mirrored these findings. CONCLUSIONS: Hospitalization beyond medical clearance after spine surgery follows a predictable pattern regardless of ERAS pathway complexity, with Medicare having a shorter delay in approving patient progression than private insurance, which has less of a delay than Triwest.

Improving ACGME Compliance for Obstetric Anesthesiology Fellows Using an Automated Email Notification System.

BACKGROUND: The Accreditation Council for Graduate Medical Education establishes minimum case requirements for trainees. In the subspecialty of obstetric anesthesiology, requirements for fellow participation in nonobstetric antenatal procedures pose a particular challenge due to the physical location remote from labor and delivery and frequent last-minute scheduling. OBJECTIVES: In response to this challenge, we implemented an informatics-based notification system, with the aim of increasing fellow participation in nonobstetric antenatal surgeries. METHODS: In December 2014 an automated email notification system to inform obstetric anesthesiology fellows of scheduled nonobstetric surgeries in pregnant patients was initiated. Cases were identified via daily automated query of the preoperative evaluation database looking for structured documentation of current pregnancy. Information on flagged cases including patient medical record number, operating room location, and date and time of procedure were communicated to fellows via automated email daily. Median fellow participation in nonobstetric antenatal procedures per quarter before and after implementation were compared using an exact Wilcoxon-Mann-Whitney test due to low baseline absolute counts. The fraction of antenatal cases representing nonobstetric procedures completed by fellows before and after implementation was compared using a Fisher's exact test. RESULTS: The number of nonobstetric antenatal cases logged by fellows per quarter increased significantly following implementation, from median 0[0,1] to 3[1,6] cases/quarter (p = 0.007). Additionally, nonobstetric antenatal cases completed by fellows as a percentage of total antenatal cases completed increased from 14% in preimplementation years to 52% in postimplementation years (p < 0.001). CONCLUSION: Through an automated email system to identify nonobstetric antenatal procedures in pregnant patients, we were able to increase the number of these cases completed by fellows during 3 years following implementation.

Postpartum Headache-Unmasking the Zebra Among the Horses: A Case Report.

Postdural puncture headache (PDPH) is a complication of dural puncture. An epidural blood patch (EBP) is the standard treatment; however, when EBP fails, alternative treatments and/or diagnoses must be considered. We present a case of orthostatic headache initially diagnosed as PDPH but likely due to spontaneous intracranial hypotension. It is imperative for anesthesiologists, as members of an interdisciplinary peripartum team, to be familiar with the evaluation and treatment of postpartum headache and recognize when further workup and consultation may be indicated.

Does the Technique for Assessing Loss of Resistance Alter the Magnitude of Epidural Needle Tip Overshoot?

INTRODUCTION: Postdural puncture headache due to accidental dural puncture is a consequence of excessive needle tip overshoot distance after entering the epidural space via a loss of resistance (LOR) technique. We are not aware of any quantitative comparison of the magnitude of needle tip overshoot (distance traveled by the needle tip beyond the point where LOR can be discerned) for the various LOR assessment techniques that are taught. Such a comparison may provide insight into contributing factors of accidental dural puncture and associated postdural puncture headache. METHODS: A custom-built simulator was used to evaluate the following 3 LOR assessment techniques: incremental needle advancement, intermittent LOR assessment (II); continuous needle advancement, high-frequency intermittent LOR assessment (CI); and continuous needle advancement, continuous LOR assessment (CC). RESULTS: There were significant mean differences in maximum overshoot past a virtual LOR plane due to technique (F(2,124) = 79.31, P < 0.001) (Fig. 2). Specifically, maximum overshoot was greater with technique II [mean = 3.8 mm, 95% confidence interval (CI) = 3.4-4.3] versus either CC (mean = 1.9 mm, 95% CI = 1.5-1.8, P < 0.001) or CI (mean = 1.4 mm, 95% CI = 0.9-2.3, P < 0.001). Differences in maximum overshoot between CC and CI were not statistically different (P = 0.996). Maximum overshoot was greater at 4 cm (mean = 3.0 mm, 95% CI = 2.6-3.4) compared with 5 cm (mean = 2.3 mm, 95% CI = 2.0-2.5, P = 0.044), 6 cm (mean = 2.0 mm, 95% CI = 1.9-2.2, P = 0.054), 7 cm (mean = 1.9 mm, 95% CI = 1.7-2.1, P = 0.002), and 8 cm (mean = 1.8 mm, 95% CI = 1.6-2.1, P = 0.001). In addition, maximum overshoot at 5 cm was greater than that at 7 cm (P = 0.020) and 8 cm (P = 0.037). The other LOR depths were not statistically significantly different from each other. Depth did not have a significant interaction with technique (P = 0.517). Technique preference had neither a significant relationship to maximum overshoot (P = 0.588) nor a significant interaction with LOR assessment technique (P = 0.689). DISCUSSION: Technique II LOR assessment produced the greatest needle overshoot past the simulated LOR plane after obtaining LOR. This was consistent across all LOR depths. In this bench study, the II technique resulted in the deepest needle tip maximum overshoot. We are in the process of designing a clinical study to collect similar data in patients.

Hydrothermal Liquefaction of Loblolly Pine: Effects of Various Wastes on Produced Biocrude.

In this study, feedstock interaction of cow manure and digested sewage sludge on hydrothermal liquefaction (HTL) of loblolly pine (LP) was evaluated. Noncatalytic HTL experiments were performed at reaction temperatures of 250, 275, and 300 °C at a constant reaction time of 30 min. Cyclohexane and acetone were used for biocrude extraction separately. The study focuses on the characteristics of the produced biocrude, and thus, physicochemical properties of biocrudes were examined by gas chromatography-mass spectrometry, Fourier-transform infrared spectroscopy, density, and viscosity measurements, in addition to comparing mass and energy yields. On a LP basis, the biocrude yield reached as high as 30 and 17% for acetone and cyclohexane extraction, respectively, at the highest reaction temperature. Elemental carbon and energy contents increased with increasing HTL temperature for all cases. Alkalinity of the HTL process liquid (aqueous phase) increases from the HTL of sludge, and thus, it favored the formation of nonpolar compounds in biocrude. On the other hand, acidity of the reaction medium increases with the HTL of manure and pine, and thus, phenolic compounds in biocrude were increasing. Cyclohexane was more effective for sludge/LP biocrude extraction, whereas acetone was effective for manure/LP. Density of cyclohexane extracted sludge/LP biocrudes at 300 °C was less than 1000 kg m-3, whereas acetone-extracted biocrudes had densities greater than 1000 kg m-3. For all the biocrudes, viscosity was reduced considerably for the mixtures when compared to biocrudes from LP alone.

Should Nitrous Oxide Be Used for Laboring Patients?

Nitrous oxide, long used during labor in Europe, is gaining popularity in the United States. It offers many beneficial attributes, with few drawbacks. Cost, safety, and side effect profiles are favorable. Analgesic effectiveness is highly variable, yet maternal satisfaction is often high among the women who choose to use it. Despite being less effective in treating labor pain than neuraxial analgesic modalities, nitrous oxide serves the needs and preferences of a subset of laboring parturients. Nitrous oxide should, therefore, be considered for inclusion in the repertoire of modalities used to alleviate pain and facilitate effective coping during labor.

Nitrous Oxide During Labor: Maternal Satisfaction Does Not Depend Exclusively on Analgesic Effectiveness.

BACKGROUND: Evidence on the analgesic effectiveness of nitrous oxide for labor pain is limited. Even fewer studies have looked at patient satisfaction. Although nitrous oxide appears less effective than neuraxial analgesia, it is unclear whether labor analgesic effectiveness is the most important factor in patient satisfaction. We sought to compare the relationship between analgesic effectiveness and patient satisfaction with analgesia in women who delivered vaginally using nitrous oxide, neuraxial analgesia (epidural or combined spinal-epidural [CSE]), or both (neuraxial after a trial of nitrous oxide). METHODS: A standardized survey was recorded on the first postpartum day for all women who received anesthetic care for labor and delivery. Data were queried for women who delivered vaginally with nitrous oxide and/or neuraxial labor analgesia over a 34-month period in 2011 to 2014. Parturients with complete data for analgesia quality and patient satisfaction were included. Analgesia and satisfaction scores were grouped into 8 to 10 high, 5 to 7 intermediate, and 0 to 4 low. These scores were compared with the use of ordinal logistic regression across 3 groups: nitrous oxide alone, epidural or CSE alone, or nitrous oxide followed by neuraxial (epidural or CSE) analgesia. RESULTS: A total of 6507 women received anesthesia care and delivered vaginally. Complete data were available for 6242 (96%) women; 5261 (81%) chose neuraxial analgesia and 1246 (19%) chose nitrous oxide. Of the latter, 753 (60%) went on to deliver with nitrous oxide alone, and 493 (40%) switched to neuraxial analgesia. Most parturients who received neuraxial analgesia (>90%) reported high analgesic effectiveness. Those who used nitrous oxide alone experienced variable analgesic effectiveness, with only one-half reporting high effectiveness. Among all women who reported poor analgesia effectiveness (0-4; n = 257), those who received nitrous oxide alone were more likely to report high satisfaction (8-10) than women who received epidural analgesia alone (OR 2.5; 95% CI 1.4-4.5; P = .002). Women who reported moderate analgesia (5-7) and received nitrous oxide only were more likely to report high satisfaction compared with the other groups. Among women who reported a high level of analgesic effectiveness, satisfaction with anesthesia was high and not different among groups. CONCLUSIONS: Patients who received nitrous oxide alone were as likely to express satisfaction with anesthesia care as those who received neuraxial analgesia, even though they were less likely to report excellent analgesia. Although pain relief contributes to the satisfaction with labor analgesia care, our results suggest that analgesia is not the only contributor to maternal satisfaction.