Aging of Volatile Organic Compounds in October 2017 Northern California Wildfire Plumes.

In the western United States, the number and severity of large wildfires have been growing for decades. Biomass burning (BB) is a major source of volatile organic compounds (VOCs) to the atmosphere both globally and regionally. Following emission, BB VOCs are oxidized while being transported downwind, producing ozone, secondary organic aerosols, and secondary hazardous VOCs. In this research, we measured VOCs using proton transfer reaction time-of-flight mass spectrometry (PTR-ToF-MS) in an urban area 55-65 km downwind of the October 2017 Northern California wildfires. Nonaromatic oxygenated compounds were the dominant component of BB VOCs measured. In the smoke plumes, the VOCs account for 70-75% of the total observed organic carbon, with the remainder being particulate matter (with a diameter of <2.5 µm, PM2.5). We show that the correlation of VOCs with furan (primary BB VOC) and maleic anhydride (secondary BB VOC) can indicate the origin of the VOCs. This was further confirmed by the diurnal variations of the VOCs and their concentration-weighted trajectories. Oxidation during transport consumed highly reactive compounds including benzenoids, furanoids, and terpenoids and produced more oxygenated VOCs. Furthermore, wildfire VOCs altered the ozone formation regime and raised the O3 levels in the San Francisco Bay Area.

Anthropogenic and Biogenic Contributions to the Organic Composition of Coastal Submicron Sea Spray Aerosol.

The organic composition of coastal sea spray aerosol is important for both atmospheric chemistry and public health but remains poorly characterized. Coastal waters contain an organic material derived from both anthropogenic processes, such as wastewater discharge, and biological processes, including biological blooms. Here, we probe the chemical composition of the organic fraction of sea spray aerosol over the course of the 2019 SeaSCAPE mesocosm experiment, in which a phytoplankton bloom was facilitated in natural coastal water from La Jolla, California. We apply untargeted two-dimensional gas chromatography to characterize submicron nascent sea spray aerosol samples, reporting ∼750 unique organic species traced over a 19 day phytoplankton bloom experiment. Categorization and quantitative compositional analysis reveal three major findings. First, anthropogenic species made up 30% of total submicron nascent sea spray aerosol organic mass under the pre-bloom condition. Second, biological activity drove large changes within the aerosolized carbon pool, decreasing the anthropogenic mass fraction by 89% and increasing the biogenic and biologically transformed fraction by a factor of 5.6. Third, biogenic marine organics are underrepresented in mass spectral databases in comparison to marine organic pollutants, with more than twice as much biogenic aerosol mass attributable to unlisted compounds.

High-Resolution Exposure Assessment for Volatile Organic Compounds in Two California Residences.

Time spent in residences substantially contributes to human exposure to volatile organic compounds (VOCs). Such exposures have been difficult to study deeply, in part because VOC concentrations and indoor occupancy vary rapidly. Using a fast-response online mass spectrometer, we report time-resolved exposures from multi-season sampling of more than 200 VOCs in two California residences. Chemical-specific source apportionment revealed that time-averaged exposures for most VOCs were mainly attributable to continuous indoor emissions from buildings and their static contents. Also contributing to exposures were occupant-related activities, such as cooking, and outdoor-to-indoor transport. Health risk assessments are possible for a subset of observed VOCs. Acrolein, acetaldehyde, and acrylic acid concentrations were above chronic advisory health guidelines, whereas exposures for other assessable species were typically well below the guideline levels. Studied residences were built in the mid-20th century, indicating that VOC emissions even from older buildings and their contents can substantially contribute to occupant exposures.

Atmospheric Benzothiazoles in a Coastal Marine Environment.

Organic emissions from coastal waters play an important but poorly understood role in atmospheric chemistry in coastal regions. A mesocosm experiment focusing on facilitated biological blooms in coastal seawater, SeaSCAPE (Sea Spray Chemistry and Particle Evolution), was performed to study emission of volatile gases, primary sea spray aerosol, and formation of secondary marine aerosol as a function of ocean biological and chemical processes. Here, we report observations of aerosol-phase benzothiazoles in a marine atmospheric context with complementary measurements of dissolved-phase benzothiazoles. Though previously reported dissolved in polluted coastal waters, we report the first direct evidence of the transfer of these molecules from seawater into the atmosphere. We also report the first gas-phase observations of benzothiazole in the environment absent a direct industrial, urban, or rubber-based source. From the identities and temporal dynamics of the dissolved and aerosol species, we conclude that the presence of benzothiazoles in the coastal water (and thereby their emissions into the atmosphere) is primarily attributable to anthropogenic sources. Oxidation experiments to explore the atmospheric fate of gas-phase benzothiazole show that it produces secondary aerosol and gas-phase SO2, making it a potential contributor to secondary marine aerosol formation in coastal regions and a participant in atmospheric sulfur chemistry.

Paracrine costimulation of IFN-γ signaling by integrins modulates CD8 T cell differentiation.

The cytokine IFN-γ is a critical regulator of immune system development and function. Almost all leukocytes express the receptor for IFN-γ, yet each cell type elicits a different response to this cytokine. Cell type-specific effects of IFN-γ make it difficult to predict the outcomes of the systemic IFN-γ blockade and limit its clinical application, despite many years of research. To better understand the cell-cell interactions and cofactors that specify IFN-γ functions, we focused on the function of IFN-γ on CD8 T cell differentiation. We demonstrated that during bacterial infection, IFN-γ is a dominant paracrine trigger that skews CD8 T cell differentiation toward memory. This skewing is preferentially driven by contact-dependent T cell-T cell (T-T) interactions and the localized IFN-γ secretion among activated CD8 T cells in a unique splenic microenvironment, and is less sensitive to concurrent IFN-γ production by other immune cell populations such as natural killer (NK) cells. Modulation of CD8 T cell differentiation by IFN-γ relies on a nonconventional IFN-γ outcome that occurs specifically within 24 hours following infection. This is driven by IFN-γ costimulation by integrins at T-T synapses, and leads to synergistic phosphorylation of the proximal STAT1 molecule and accelerated IL-2 receptor down-regulation. This study provides evidence of the importance of context-dependent cytokine signaling and gives another example of how cell clusters and the microenvironment drive unique biology.

Leadership Approaches to Staff Health and Wellness During COVID-19 Pandemic.

Background: COVID-19 disease as caused by a coronavirus called SARS-CoV-2 has taken the world by storm with upwards of 8 million confirmed infections in more than 190 countries. At the writing of this article, over 2 million Americans are confirmed infected and 117,000 have died. Rapid changes to manage COVID-19 care creates significant physical and emotional stress for healthcare employees, including pharmacy staff. Objective: This article provides pharmacy leaders with advice in leading through COVID-19 to promote staff resiliency. Methods: The specific leadership strategies include: (1) identifying and addressing fundamental needs; (2) communicating updated and reliable information; and (3) providing psychological and mental health support. Conclusion: Using various techniques described will help to preserve workforce resilience in providing patient-centered pharmacy services. After reading this article, pharmacy directors will have strategies and resources to maintain employee resiliency during this difficult time.

Guidelines for Leading a Safe Medication Error Reporting Culture.

Background: A safe medication error reporting culture is one that promotes, fosters, and rewards the reporting of errors and events across the spectrum of harm (none to significant harm). For this culture to develop, leaders must key department cultural norms. These cultural norms include making employees feel psychologically safe to report errors, and to establish a culture of error review and follow-up that complies with best practices. Objective: This article reviews how pharmacy leaders can establish this environment by describing (1) setting an appropriate vision for safety as a priority; (2) establishing and actively supporting the concept of psychological safety; and (3) implementing medication error review that support an effective safety culture. Finally, the article discusses a case where the relationships between psychological safety, safety culture, and reporting culture are described. Methods: This article reviews the literature and authors' experiences in designing a safety culture for a pharmacy department. Concluson: A safe reporting culture requires leaders to be humble, engage their staff in dialogue, objectively measure culture, consistently provide feedback, and empower its people. Employing these leadership traits with best practices can improve overall medication safety and the quality of patient-centered pharmacy services.

Pain Management Stewardship Programs, Part I: A Review of Legislative and Regulatory Changes.

Background: Opioid use is classified as an epidemic by many due to the impact of these medications on society. Federal and state laws for prescribing and dispensing opioids have changed rapidly in a short period of time to hopefully balance proper pain control with their use. Pharmacy directors must be informed of these rapid changes to effectively work as part of any opioid stewardship team. Objective: The objective of this study was to provide foundational leadership guidance to pharmacy directors on current opioid legislation, literature, and best practices to assist in improving opioid use. Methods: A review of the literature from 2003 to the present was conducted along with collating important up to date resources and other publications that provide foundational information to help support a comprehensive management of opioid use. A summary of these data has been collated into an easy to use table and summarized throughout this article. Conclusion: The information provided in this article helps to properly inform pharmacy leaders to the resources available to improve the prescribing, dispensing, and monitoring of opioids and alternatives.

Dissecting the stem cell niche with organoid models: an engineering-based approach.

For many tissues, single resident stem cells grown in vitro under appropriate three-dimensional conditions can produce outgrowths known as organoids. These tissues recapitulate much of the cell composition and architecture of the in vivo organ from which they derive, including the formation of a stem cell niche. This has facilitated the systematic experimental manipulation and single-cell, high-throughput imaging of stem cells within their respective niches. Furthermore, emerging technologies now make it possible to engineer organoids from purified cellular and extracellular components to directly model and test stem cell-niche interactions. In this Review, we discuss how organoids have been used to identify and characterize stem cell-niche interactions and uncover new niche components, focusing on three adult-derived organoid systems. We also describe new approaches to reconstitute organoids from purified cellular components, and discuss how this technology can help to address fundamental questions about the adult stem cell niche.

Comparison of 3 Surveillance Methods to Detect Potential Controlled Substance Diversion in an Academic Medical Center.

Objectives: To compare 3 methods of detecting potential diversion of controlled substances (CS) by health care personnel from inpatient units in a large, academic medical center. Methods: Three different reports were retrospectively analyzed and evaluated to determine which employees are "high-risk" for diversion over a 30-day period using defined criteria. Reports were derived from automated dispensing machines (ADMs), purchased third-party software (TPS), and the electronic health record (EHR). The primary outcome was the percentage of employees in each report who were deemed to be high-risk for CS diversion (positive predictive value [PPV]). Secondary outcomes included the number of false positives and description of high-risk users on each report. Descriptive statistics were used to analyze differences between methods. Results: The PPV was highly variable between reports. The PPVs among the ADM, TPS, and EHR reports were 3.28%, 6.82%, and 23.88%, respectively. False positives were high among all reports (96.72%, 93.18%, and 76.12% for the ADM, TPS, and EHR reports, respectively). Conclusions: A report from the EHR has the highest PPV to detect high-risk employees who may be diverting CS. However, false positives were high for all reports, indicating that significant improvements are needed in the development of accurate and reliable software to detect potential and actual CS diversion.

Current Threats to Maintaining a Secure Pharmaceutical Supply Chain in an Online World.

Background: Maintaining integrity of the pharmaceutical supply chain is critical to providing medications that are free from adulteration (counterfeit, substandard or unapproved medications), making them safe for patient use. Purchasing pharmaceuticals through the Internet can be associated with a risk of receiving adulterated medicines. Objective: The objective of this study was to review the current threats to maintaining a secure pharmaceutical supply chain, specifically focused on Internet-based procurement of medications. Methods: A review of the literature was conducted along with collating important up to date resources and other publications that provide foundational information to understanding the risks and prevention strategies for online purchasing of pharmaceuticals. Conclusion: The information provided in this article helps to properly inform pharmacy leaders to the resources available to protect against the risks of on-line purchasing of pharmaceuticals.

Correction: Quantification of isomerically summed hydrocarbon contributions to crude oil by carbon number, double bond equivalent, and aromaticity using gas chromatography with tunable vacuum ultraviolet ionization.

Correction for 'Quantification of isomerically summed hydrocarbon contributions to crude oil by carbon number, double bond equivalent, and aromaticity using gas chromatography with tunable vacuum ultraviolet ionization' by Jeremy A. Nowak et al., Analyst, 2018, 143, 1396-1405.

Characterizing sources and emissions of volatile organic compounds in a northern California residence using space- and time-resolved measurements.

We investigate source characteristics and emission dynamics of volatile organic compounds (VOCs) in a single-family house in California utilizing time- and space-resolved measurements. About 200 VOC signals, corresponding to more than 200 species, were measured during 8 weeks in summer and five in winter. Spatially resolved measurements, along with tracer data, reveal that VOCs in the living space were mainly emitted directly into that space, with minor contributions from the crawlspace, attic, or outdoors. Time-resolved measurements in the living space exhibited baseline levels far above outdoor levels for most VOCs; many compounds also displayed patterns of intermittent short-term enhancements (spikes) well above the indoor baseline. Compounds were categorized as "high-baseline" or "spike-dominated" based on indoor-to-outdoor concentration ratio and indoor mean-to-median ratio. Short-term spikes were associated with occupants and their activities, especially cooking. High-baseline compounds indicate continuous indoor emissions from building materials and furnishings. Indoor emission rates for high-baseline species, quantified with 2-hour resolution, exhibited strong temperature dependence and were affected by air-change rates. Decomposition of wooden building materials is suggested as a major source for acetic acid, formic acid, and methanol, which together accounted for ~75% of the total continuous indoor emissions of high-baseline species.

Quantification of isomerically summed hydrocarbon contributions to crude oil by carbon number, double bond equivalent, and aromaticity using gas chromatography with tunable vacuum ultraviolet ionization.

The ability to structurally characterize and isomerically quantify crude oil hydrocarbons relevant to refined fuels such as motor oil, diesel, and gasoline represents an extreme challenge for chromatographic and mass spectrometric techniques. This work incorporates two-dimensional gas chromatography coupled to a tunable vacuum ultraviolet soft photoionization source, the Chemical Dynamics Beamline 9.0.2 of the Advanced Light Source at the Lawrence Berkeley National Laboratory, with a time-of-flight mass spectrometer (GC × GC-VUV-TOF) to directly characterize and isomerically sum the contributions of aromatic and aliphatic species to hydrocarbon classes of four crude oils. When the VUV beam is tuned to 10.5 ± 0.2 eV, both aromatic and aliphatic crude oil hydrocarbons are ionized to reveal the complete chemical abundance of C9-C30 hydrocarbons. When the VUV beam is tuned to 9.0 ± 0.2 eV only aromatic hydrocarbons are ionized, allowing separation of the aliphatic and aromatic fractions of the crude oil hydrocarbon chemical classes in an efficient manner while maintaining isomeric quantification. This technique provides an effective tool to determine the isomerically summed aromatic and aliphatic hydrocarbon compositions of crude oil, providing information that goes beyond typical GC × GC separations of the most dominant hydrocarbon isomers.

Comprehensive Analysis of Changes in Crude Oil Chemical Composition during Biosouring and Treatments.

Biosouring in crude oil reservoirs by sulfate-reducing microbial communities (SRCs) results in hydrogen sulfide production, precipitation of metal sulfide complexes, increased industrial costs of petroleum production, and exposure issues for personnel. Potential treatment strategies include nitrate or perchlorate injections into reservoirs. Gas chromatography with vacuum ultraviolet ionization and high-resolution time-of-flight mass spectrometry (GC-VUV-HTOF) and Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) combined with electrospray ionization were applied in this study to identify hydrocarbon degradation patterns and product formations in crude oil samples from biosoured, nitrate-treated, and perchlorate-treated bioreactor column experiments. Crude oil hydrocarbons were selectively transformed based on molecular weight and compound class in the biosouring control environment. Both the nitrate and the perchlorate treatments significantly reduced sulfide production; however, the nitrate treatment enhanced crude oil biotransformation, while the perchlorate treatment inhibited crude oil biotransformation. Nitrogen- and oxygen-containing biodegradation products, particularly with chemical formulas consistent with monocarboxylic and dicarboxylic acids containing 10-60 carbon atoms, were observed in the oil samples from both the souring control and the nitrate-treated columns but were not observed in the oil samples from the perchlorate-treated column. These results demonstrate that hydrocarbon degradation and product formation of crude oil can span hydrocarbon isomers and molecular weights up to C60 and double-bond equivalent classes ranging from straight-chain alkanes to polycyclic aromatic hydrocarbons. Our results also strongly suggest that perchlorate injections may provide a preferred strategy to treat biosouring through inhibition of biotransformation.

Restructuring a Pharmacy Department: Leadership Strategies for Managing Organizational Change.

Background: The Director's Forum series is designed to guide pharmacy leaders in establishing patient-centered services in hospitals and health-systems. This article focuses on leadership strategies for managing organizational change within a pharmacy department. Objective: The goals of this article are to describe the foundations of pharmacy organizational structure changes and strategies to efficiently and effectively manage the associated change. Methods: This article will aim to (1) describe the organizational structure change process, (2) list known rules to follow when redesigning an organizational structure, (3) briefly describe the organizational change at the Ohio State Wexner Medical Center, and (4) describe leadership strategies to overcome potential challenges of organizational changes. Conclusion: The strategies discussed in this article and proposed sample template for organizational change process may be used by a pharmacy department in an effort to restructure their department.

One Chance for Your Best First Impression: Tips for New Pharmacists.

Background: New practitioner pharmacists enter the workplace with an array of knowledge and skills ready to engage in patient care. However, obtaining a first postgraduate position or earning a desired promotion poses a challenge when the candidate pool is filled with many similarly skilled professionals. Objective: Educate new practitioner pharmacists on ways to pitch their new skills and make a memorable first impression among their competition. Methods: This article aims to (1) enhance their career prospects by practicing their soft skills, (2) develop strategies to build credibility and creating a personal brand and (3) describe efforts to showcase their professional identity. Conclusions: Preceptors and mentors can help by providing effective feedback to new pharmacists in efforts to improve performance and enhance soft skills.

Drug Pricing Transparency: The New Retail Revolution.

As spending on medications in the United States increases with each passing year, the need for drug pricing transparency by manufacturers also increases. Drug spending, excluding rebates and discounts, was $309.5 billion in 2015, up 8.5% from 2014. Drug pricing transparency has been a topic of debate across the health care system. This column reviews the issue of drug pricing and emphasizes the need for transparency in this area. We will discuss factors that influence drug pricing, policies and ways to reduce the rising costs of drugs, and the role of pharmacy leaders in managing this problem. A multitude of factors are driving the country to spend more and more on medications; pharmacy leaders can employ various strategies to counteract this escalation of drug prices. After reviewing this article, the pharmacy director will have an increased ability to address drug pricing issues with stakeholders as they develop patient-centered pharmacy services.

A Just Culture Approach to Managing Medication Errors.

Medication errors continue to be a concern of health care providers and the public, in particular how to prevent harm from medication mistakes. Many health care workers are afraid to report errors for fear of retribution including the loss of professional licensure and even imprisonment. Most health care workers are silent, instead of admitting their mistake and discussing it openly with peers. This can result in further patient harm if the system causing the mistake is not identified and fixed; thus self-denial may have a negative impact on patient care outcomes. As a result, pharmacy leaders, in collaboration with others, must put systems in place that serve to prevent medication errors while promoting a "Just Culture" way of managing performance and outcomes. This culture must exist across disciplines and departments. Pharmacy leaders need to understand how to classify behaviors associated with errors, set realistic expectations, instill values for staff, and promote accountability within the workplace. This article reviews the concept of Just Culture and provides ways that pharmacy directors can use this concept to manage the degree of error in patient-centered pharmacy services.

Time Resolved Measurements of Speciated Tailpipe Emissions from Motor Vehicles: Trends with Emission Control Technology, Cold Start Effects, and Speciation.

Experiments were conducted at the California Air Resources Board Haagen-Smit Laboratory to understand changes in vehicle emissions in response to stricter emissions standards over the past 25 years. Measurements included a wide range of volatile organic compounds (VOCs) for a wide range of spark ignition gasoline vehicles meeting varying levels of emissions standards, including all certifications from Tier 0 up to Partial Zero Emission Vehicle. Standard gas chromatography (GC) and high performance liquid chromatography (HLPC) analyses were employed for drive-cycle phase emissions. A proton-transfer-reaction mass spectrometer measured time-resolved emissions for a wide range of VOCs. Cold-start emissions occur almost entirely in the first 30-60 s for newer vehicles. Cold-start emissions have compositions that are not significantly different across all vehicles tested and are markedly different from neat fuel. Hot-stabilized emissions have varying importance depending on species and may require a driving distance of 200 miles to equal the emissions from a single cold start. Average commute distances in the U.S. suggest the majority of in-use vehicles have emissions dominated by cold starts. The distribution of vehicle ages in the U.S. suggests that within several years only a few percent of vehicles will have significant driving emissions compared to cold-start emissions.