Secondary Organic Aerosols: Chemical Aging, Hygroscopicity, and Cloud Droplet Activation

Atmospheric aerosols have an important impact on the radiation balance, and thus, on the climate of the Earth. Aerosol particles scatter and absorb incoming solar and terrestrial radiation. Apart from this direct effect, aerosol particles act as cloud condensation nuclei (CCN), thereby greatly influencing the microphysics of clouds. Secondary organic aerosols (SOA) are an important fraction of the total aerosol mass. In many environments these organic compounds are mainly products of the oxidation of biogenic volatile organic compounds (VOC). In this study the hygroscopic growth and CCN activation of biogenic SOA were investigated which was formed by the oxidation of VOC with O$_{3}$ and photochemically formed OH radicals under low NO$_{x}$ conditions. For this purpose, a complex mixture of VOC emitted by boreal tree species as gas-phase precursors was used in the Jülich Plant Atmosphere Chamber (JPAC). In long-term studies in the atmosphere simulation chamber SAPHIR $\alpha$α-pinene or a defined mixture of $\alpha$-pinene, $\beta$-pinene, limonene, ocimene,$\Delta$-3-carene served as precursors. Initial precursor concentrations between 40 and 1000 ppbC were investigated. The observed SOA particles were slightly hygroscopic with an average hygroscopicity parameter $\kappa$(CCN) = 0.10 ± 0.02 and $\kappa$(90%RH) = 0.05 ± 0.01. Closure between hygroscopic growth and CCN activation data could be achieved allowing either surface tension reduction, limited solubility, or non-ideality of the solution in the droplet. The SOA solutions in equilibrium with RH <95% are possible highly non-ideal. Therefore the organic-water interaction were investigated by applying the UNIFAC model. Calculations for surrogate compounds exhibited the same strong concentration (i.e. RH) dependence of κ at sub-saturation. The growth curves could be fitted and CCN activation predicted by assuming a binary mixture of water and one hypothetical organic compound. The occurrence of functional groups in this compound was adjusted to reproduce the observed growth curves. However, further information on surface tension and the ratio of the molecular mass and density of the solute is needed to predict activation behavior from hygroscopic growth measurements. A dependence of κ on the ratio of primarily produced OH to initial VOC level was observed. The higher $\kappa$ values for low precursor concentrations could be attributed to a higher OH/VOC level. The detailed chemical composition of the gas-phase precursors had only little effect on $\kappa$. In long term experiments there was no significant effect of the observed chemical aging of the particles on $\kappa$. The observed low variability of $\kappa$ for biogenic SOA particles simplifies their treatment in global models as an average value of $\kappa$ = 0.1 can be used

Joint versus separate inpatient rehabilitation treatment for patients with alcohol use disorder or drug use disorder : an observational study

Background: In many national treatment systems, patients with alcohol use disorders (AUD) and those with drug use disorders (DUD) are treated separately, while other systems provide joint treatment for both kinds of substance use disorders (SUDs). Regarding long-term rehabilitation treatment of DUD and AUD patients, there is however a lack of empirical studies on the comparison between a separate versus joint treatment modality. Methods: Data were gathered from 2 rehabilitation units located in small towns from the same German region. One unit provided treatment to a mixed group of AUD and DUD patients, while the other unit treated the 2 groups separately. Staffing, funding, and treatment programs were otherwise similar between facilities. Data were gathered from standardized routine documentation and standardized interviews. In order to understand correlates of premature treatment termination, a logistic regression analysis was performed, with treatment modality and type of SUD as main predictors, and a range of patient characteristics as covariates. Results: Patients (N=319) were diagnosed with AUD (48%), DUD (34%), or AUD plus DUD (18%). Patients in joint treatment showed a higher prevalence of lapses during treatment than those in separate treatment (26% versus 12%; p=0.009), but there was no significant difference in the prevalence of premature terminations (38% versus 44%, p=0.26). Treatment modality and interaction between modality and type of SUD was not significantly associated with premature termination. Joint treatment completers showed higher satisfaction with treatment than separate treatment completers ( p<0.001). Conclusion: We found no evidence here for a difference between treatment modalities in terms of premature termination rate. Satisfaction level was higher in those who completed joint treatment compared to separate treatment.Peer reviewe

Biochemical characterization of a multi-drug resistant HIV-1 subtype AG reverse transcriptase: antagonism of AZT discrimination and excision pathways and sensitivity to RNase H inhibitors

We analyzed a multi-drug resistant (MR) HIV-1 re- verse transcriptase (RT), subcloned from a patient- derived subtype CRF02 AG, harboring 45 amino acid exchanges, amongst them four thymidine analog mutations (TAMs) relevant for high-level AZT (azi- dothymidine) resistance by AZTMP excision (M41L, D67N, T215Y, K219E) as well as four substitutions of the AZTTP discrimination pathway (A62V, V75I, F116Y and Q151M). In addition, K65R, known to an- tagonize AZTMP excision in HIV-1 subtype B was present. Although MR-RT harbored the most signif- icant amino acid exchanges T215Y and Q151M of each pathway, it exclusively used AZTTP discrimi- nation, indicating that the two mechanisms are mu- tually exclusive and that the Q151M pathway is ob- viously preferred since it confers resistance to most nucleoside inhibitors. A derivative was created, ad- ditionally harboring the TAM K70R and the rever- sions M151Q as well as R65K since K65R antago- nizes excision. MR-R65K-K70R-M151Q was compe- tent of AZTMP excision, whereas other combinations thereof with only one or two exchanges still pro- moted discrimination. To tackle the multi-drug resis- tance problem, we tested if the MR-RTs could still be inhibited by RNase H inhibitors. All MR-RTs exhibited similar sensitivity toward RNase H inhibitors be- longing to different inhibitor classes, indicating the importance of developing RNase H inhibitors further as anti-HIV drugs

Secondary Organic Aerosol Formation from Healthy and Aphid-Stressed Scots Pine Emissions.

One barrier to predicting biogenic secondary organic aerosol (SOA) formation in a changing climate can be attributed to the complex nature of plant volatile emissions. Plant volatile emissions are dynamic over space and time, and change in response to environmental stressors. This study investigated SOA production from emissions of healthy and aphid-stressed Scots pine saplings via dark ozonolysis and photooxidation chemistry. Laboratory experiments using a batch reaction chamber were used to investigate SOA production from different plant volatile mixtures. The volatile mixture from healthy plants included monoterpenes, aromatics, and a small amount of sesquiterpenes. The biggest change in the volatile mixture for aphid-stressed plants was a large increase (from 1.4 to 7.9 ppb) in sesquiterpenes-particularly acyclic sesquiterpenes, such as the farnesene isomers. Acyclic sesquiterpenes had different effects on SOA production depending on the chemical mechanism. Farnesenes suppressed SOA formation from ozonolysis with a 9.7-14.6% SOA mass yield from healthy plant emissions and a 6.9-10.4% SOA mass yield from aphid-stressed plant emissions. Ozonolysis of volatile mixtures containing more farnesenes promoted fragmentation reactions, which produced higher volatility oxidation products. In contrast, plant volatile mixtures containing more farnesenes did not appreciably change SOA production from photooxidation. SOA mass yields ranged from 10.8 to 23.2% from healthy plant emissions and 17.8-26.8% for aphid-stressed plant emissions. This study highlights the potential importance of acyclic terpene chemistry in a future climate regime with an increased presence of plant stress volatiles

Measuring quality of life in opioid dependent people : a systematic review of assessment instruments

Purpose Opioid dependence is a chronic relapsing disorder. Despite increasing research on quality of life (QOL) in people with opioid dependence, little attention has been paid to the instruments used. This systematic review examines the suitability of QOL instruments for use in opioid-dependent populations and the instruments’ quality. Methods A systematic search was performed in the databases Medline, PsycInfo, The Cochrane Library, and CINAHL. Articles were eligible if they assessed QOL of opioid-dependent populations using a validated QOL instrument. Item content relevance to opioid-dependent people was evaluated by means of content analysis, and instrument properties were assessed using minimum standards for patient-reported outcome measures. Results Eighty-nine articles were retrieved, yielding sixteen QOL instruments, of which ten were assessed in this review. Of the ten instruments, six were disease specific, but none for opioid dependence. Two instruments had good item content relevance. The conceptual and measurement model were described in seven instruments. Four instruments were developed with input from the respective target population. Eight instruments had low respondent and administrator burden. Psychometric properties were either not assessed in opioid-dependent populations or were inconclusive or moderate. Conclusions No instrument scored perfectly on both the content and properties. The limited suitability of instruments for opioid-dependent people hinders accurate and sensitive measurement of QOL in this population. Future research is in need of an opioid dependence-specific QOL instrument to measure the true impact of the disease on people’s lives and to evaluate treatment-related services

Comparing secondary organic aerosol (SOA) volatility distributions derived from isothermal SOA particle evaporation data and FIGAERO-CIMS measurements

The volatility distribution of the organic compounds present in secondary organic aerosol (SOA) at different conditions is a key quantity that has to be captured in order to describe SOA dynamics accurately. The development of the Filter Inlet for Gases and AEROsols (FIGAERO) and its coupling to a chemical ionization mass spectrometer (CIMS; collectively FIGAERO-CIMS) has enabled near-simultaneous sampling of the gas and particle phases of SOA through thermal desorption of the particles. The thermal desorption data have been recently shown to be interpretable as a volatility distribution with the use of the positive matrix factorization (PMF) method. Similarly, volatility distributions can be inferred from isothermal particle evaporation experiments when the particle size change measurements are analyzed with process-modeling techniques. In this study, we compare the volatility distributions that are retrieved from FIGAERO-CIMS and particle size change measurements during isothermal particle evaporation with process-modeling techniques. We compare the volatility distributions at two different relative humidities (RHs) and two oxidation conditions. In high-RH conditions, where particles are in a liquid state, we show that the volatility distributions derived via the two ways are similar within a reasonable assumption of uncertainty in the effective saturation mass concentrations that are derived from FIGAERO-CIMS data. In dry conditions, we demonstrate that the volatility distributions are comparable in one oxidation condition, and in the other oxidation condition, the volatility distribution derived from the PMF analysis shows considerably more high-volatility matter than the volatility distribution inferred from particle size change measurements. We also show that the Vogel-Tammann-Fulcher equation together with a recent glass transition temperature parametrization for organic compounds and PMF-derived volatility distribution estimates are consistent with the observed isothermal evaporation under dry conditions within the reported uncertainties. We conclude that the FIGAERO-CIMS measurements analyzed with the PMF method are a promising method for inferring the volatility distribution of organic compounds, but care has to be taken when the PMF factors are analyzed. Future process-modeling studies about SOA dynamics and properties could benefit from simultaneous FIGAERO-CIMS measurements.Peer reviewe

“We were building the plane as we were flying it, and we somehow made it to the other end”: syringe service program staff experiences and well-being during the COVID-19 pandemic

BackgroundSyringe service programs (SSPs) provide essential harm reduction and prevention services for people who inject drugs in the USA, where SSP coverage is expanding. During the COVID-19 pandemic, US SSPs underwent unprecedented shifts in operational procedures (e.g., closures of physical sites, staff redeployment into pandemic response efforts). Given the critical role of US SSP workers in the pandemic, we sought to explore the occupational experiences and well-being of SSP staff to inform future emergency response efforts.MethodsFrom July-October 2020, we conducted semi-structured interviews with staff members of four SSPs in diverse regions of Massachusetts. Trained interviewers administered qualitative interviews virtually. Interviews were coded in NVivo v12 and thematic analysis identified common occupational experiences and related impacts on staff well-being in the context of the COVID-19 pandemic.ResultsAmong 18 participants, 12 (67%) had client-facing roles such as harm reduction specialists and six (33%) worked in program management or leadership. We found that staff were frequently anxious about SARS-CoV-2 transmission, which contributed to staff turnover. SSPs rapidly adapted and expanded their services to meet increasing client needs during the pandemic (e.g., food distribution, COVID-19 testing), leading to staff overexertion. Simultaneously, public health measures such as physical distancing led to staff concerns about reduced social connections with clients and coworkers. Through these challenges, SSPs worked to protect staff well-being by implementing flexible and tangible COVID-19-related policies (e.g., paid sick leave), mental health resources, and frequent communication regarding pandemic-related operational changes.ConclusionSSPs in the USA adapted to the COVID-19 pandemic out of necessity, resulting in operational changes that threatened staff well-being. Despite the protective factors revealed in some narratives, our findings suggest that during prolonged, complex public health emergencies, SSPs may benefit from enhanced occupational supports to prevent burnout and promote wellness for this essential public health workforce

Volatility of Secondary Organic Aerosol from β-Caryophyllene Ozonolysis over a Wide Tropospheric Temperature Range

We investigated secondary organic aerosol (SOA) from β-caryophyllene oxidation generated over a wide tropospheric temperature range (213–313 K) from ozonolysis. Positive matrix factorization (PMF) was used to deconvolute the desorption data (thermograms) of SOA products detected by a chemical ionization mass spectrometer (FIGAERO-CIMS). A nonmonotonic dependence of particle volatility (saturation concentration at 298 K, C298K*) on formation temperature (213–313 K) was observed, primarily due to temperature-dependent formation pathways of β-caryophyllene oxidation products. The PMF analysis grouped detected ions into 11 compound groups (factors) with characteristic volatility. These compound groups act as indicators for the underlying SOA formation mechanisms. Their different temperature responses revealed that the relevant chemical pathways (e.g., autoxidation, oligomer formation, and isomer formation) had distinct optimal temperatures between 213 and 313 K, significantly beyond the effect of temperature-dependent partitioning. Furthermore, PMF-resolved volatility groups were compared with volatility basis set (VBS) distributions based on different vapor pressure estimation methods. The variation of the volatilities predicted by different methods is affected by highly oxygenated molecules, isomers, and thermal decomposition of oligomers with long carbon chains. This work distinguishes multiple isomers and identifies compound groups of varying volatilities, providing new insights into the temperature-dependent formation mechanisms of β-caryophyllene-derived SOA particles

Experimental study of the role of physicochemical surface processing on the IN ability of mineral dust particles

During the measurement campaign FROST 2 (FReezing Of duST 2), the Leipzig Aerosol Cloud Interaction Simulator (LACIS) was used to investigate the influence of various surface modifications on the ice nucleating ability of Arizona Test Dust (ATD) particles in the immersion freezing mode. The dust particles were exposed to sulfuric acid vapor, to water vapor with and without the addition of ammonia gas, and heat using a thermodenuder operating at 250 °C. Size selected, quasi monodisperse particles with a mobility diameter of 300 nm were fed into LACIS and droplets grew on these particles such that each droplet contained a single particle. Temperature dependent frozen fractions of these droplets were determined in a temperature range between −40 °C ≤T≤−28 °C. The pure ATD particles nucleated ice over a broad temperature range with their freezing behavior being separated into two freezing branches characterized through different slopes in the frozen fraction vs. temperature curves. Coating the ATD particles with sulfuric acid resulted in the particles' IN potential significantly decreasing in the first freezing branch (T>−35 °C) and a slight increase in the second branch (T≤−35 °C). The addition of water vapor after the sulfuric acid coating caused the disappearance of the first freezing branch and a strong reduction of the IN ability in the second freezing branch. The presence of ammonia gas during water vapor exposure had a negligible effect on the particles' IN ability compared to the effect of water vapor. Heating in the thermodenuder led to a decreased IN ability of the sulfuric acid coated particles for both branches but the additional heat did not or only slightly change the IN ability of the pure ATD and the water vapor exposed sulfuric acid coated particles. In other words, the combination of both sulfuric acid and water vapor being present is a main cause for the ice active surface features of the ATD particles being destroyed. A possible explanation could be the chemical transformation of ice active metal silicates to metal sulfates. The strongly enhanced reaction between sulfuric acid and dust in the presence of water vapor and the resulting significant reductions in IN potential are of importance for atmospheric ice cloud formation. Our findings suggest that the IN concentration can decrease by up to one order of magnitude for the conditions investigated