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Summertime Arctic aerosol size distributions are strongly controlled by natural regional emissions. Within this context, we use a chemical transport model with sizeresolved aerosol microphysics (GEOS-Chem-TOMAS) to interpret measurements of aerosol size distributions from the Canadian Arctic Archipelago during the summer of 2016, as part of the "NETwork on Climate and Aerosols: Addressing key uncertainties in Remote Canadian Environments" (NETCARE) project. Our simulations suggest that condensation of secondary organic aerosol (SOA) from precursor vapors emitted in the Arctic and near Arctic marine (ice-free seawater) regions plays a key role in particle growth events that shape the aerosol size distributions observed at Alert (82.5° N, 62.3° W), Eureka (80.1° N, 86.4° W), and along a NETCARE ship track within the Archipelago. We refer to this SOA as Arctic marine SOA (AMSOA) to reflect the Arctic marine-based and likely biogenic sources for the precursors of the condensing organic vapors. AMSOA from a simulated flux (500 μgm-2 day-1, north of 50° N) of precursor vapors (with an assumed yield of unity) reduces the summertime particle size distribution model-observation mean fractional error 2- to 4-fold, relative to a simulation without this AMSOA. Particle growth due to the condensable organic vapor flux contributes strongly (30 %-50 %) to the simulated summertime-mean number of particles with diameters larger than 20 nm in the study region. This growth couples with ternary particle nucleation (sulfuric acid, ammonia, and water vapor) and biogenic sulfate condensation to account for more than 90% of this simulated particle number, which represents a strong biogenic influence. The simulated fit to summertime size-distribution observations is further improved at Eureka and for the ship track by scaling up the nucleation rate by a factor of 100 to account for other particle precursors such as gas-phase iodine and/or amines and/or fragmenting primary particles that could be missing from our simulations. Additionally, the fits to the observed size distributions and total aerosol number concentrations for particles larger than 4 nm improve with the assumption that the AMSOA contains semivolatile species: the model-observation mean fractional error is reduced 2- to 3-fold for the Alert and ship track size distributions. AMSOA accounts for about half of the simulated particle surface area and volume distributions in the summertime Canadian Arctic Archipelago, with climaterelevant simulated summertime pan-Arctic-mean top-of-theatmosphere aerosol direct (-0:04Wm-2) and cloud-albedo indirect (-0:4Wm-2) radiative effects, which due to uncertainties are viewed as an order of magnitude estimate. Future work should focus on further understanding summertime Arctic sources of AMSOA.

The performance of the Weather Research and Forecasting regional model with chemistry (WRF-Chem) in simulating the spatial and temporal variations in aerosol mass, composition, and size over California is quantified using the extensive meteorological, trace gas, and aerosol measurements collected during the California Nexus of Air Quality and Climate Experiment (CalNex) and the Carbonaceous Aerosol and Radiative Effects Study (CARES) conducted during May and June of 2010. The overall objective of the field campaigns was to obtain data needed to better understand processes that affect both climate and air quality, including emission assessments, transport and chemical aging of aerosols, aerosol radiative effects. Simulations were performed that examined the sensitivity of aerosol concentrations to anthropogenic emissions and to long-range transport of aerosols into the domain obtained from a global model. The configuration of WRF-Chem used in this study is shown to reproduce the overall synoptic conditions, thermally driven circulations, and boundary layer structure observed in region that controls the transport and mixing of trace gases and aerosols. Reducing the default emissions inventory by 50% led to an overall improvement in many simulated trace gases and black carbon aerosol at most sites and along most aircraft flight paths; however, simulated organic aerosol was closer to observed when there were no adjustments to the primary organic aerosol emissions. We found that sulfate was better simulated over northern California whereas nitrate was better simulated over southern California. While the overall spatial and temporal variability of aerosols and their precursors were simulated reasonably well, we show cases where the local transport of some aerosol plumes were either too slow or too fast, which adversely affects the statistics quantifying the differences between observed and simulated quantities. Comparisons with lidar and in situ measurements indicate that long-range transport of aerosols from the global model was likely too high in the free troposphere even though their concentrations were relatively low. This bias led to an over-prediction in aerosol optical depth by as much as a factor of 2 that offset the underpredictions of boundary-layer extinction resulting primarily from local emissions. Lowering the boundary conditions of aerosol concentrations by 50% greatly reduced the bias in simulated aerosol optical depth for all regions of California. This study shows that quantifying regional-scale variations in aerosol radiative forcing and determining the relative role of emissions from local and distant sources is challenging during 'clean' conditions and that a wide array of measurements are needed to ensure model predictions are correct for the right reasons. In this regard, the combined CalNex and CARES data sets are an ideal test bed that can be used to evaluate aerosol models in great detail and develop improved treatments for aerosol processes.

Organic aerosols (OA) in Pasadena are characterized using multiple measurements from the California Research at the Nexus of Air Quality and Climate Change (CalNex) campaign. Five OA components are identified using positive matrix factorization including hydrocarbon-like OA (HOA) and two types of oxygenated OA (OOA). The Pasadena OA elemental composition when plotted as H:C versus O:C follows a line less steep than that observed for Riverside, CA. The OOA components from both locations follow a common line, however, indicating similar secondary organic aerosol (SOA) oxidation chemistry at the two sites such as fragmentation reactions leading to acid formation. In addition to the similar evolution of elemental composition, the dependence of SOA concentration on photochemical age displays quantitatively the same trends across several North American urban sites. First, the OA/ΔCO values for Pasadena increase with photochemical age exhibiting a slope identical to or slightly higher than those for Mexico City and the northeastern United States. Second, the ratios of OOA to odd-oxygen (a photochemical oxidation marker) for Pasadena, Mexico City, and Riverside are similar, suggesting a proportional relationship between SOA and odd-oxygen formation rates. Weekly cycles of the OA components are examined as well. HOA exhibits lower concentrations on Sundays versus weekdays, and the decrease in HOA matches that predicted for primary vehicle emissions using fuel sales data, traffic counts, and vehicle emission ratios. OOA does not display a weekly cycle - after accounting for differences in photochemical aging - which suggests the dominance of gasoline emissions in SOA formation under the assumption that most urban SOA precursors are from motor vehicles. © 2013. Her Majesty the Queen in Right of Canada. American Geophysical Union.

Recent laboratory and field studies have indicated that glyoxal is a potentially large contributor to secondary organic aerosol mass. We present in situ glyoxal measurements acquired with a recently developed, high sensitivity spectroscopic instrument during the CalNex 2010 field campaign in Pasadena, California. We use three methods to quantify the production and loss of glyoxal in Los Angeles and its contribution to organic aerosol. First, we calculate the difference between steady state sources and sinks of glyoxal at the Pasadena site, assuming that the remainder is available for aerosol uptake. Second, we use the Master Chemical Mechanism to construct a two-dimensional model for gas-phase glyoxal chemistry in Los Angeles, assuming that the difference between the modeled and measured glyoxal concentration is available for aerosol uptake. Third, we examine the nighttime loss of glyoxal in the absence of its photochemical sources and sinks. Using these methods we constrain the glyoxal loss to aerosol to be 0-5 × 10-5 s-1 during clear days and (1 ± 0.3) × 10-5 s-1 at night. Between 07:00-15:00 local time, the diurnally averaged secondary organic aerosol mass increases from 3.2 μg m-3 to a maximum of 8.8 μg m -3. The constraints on the glyoxal budget from this analysis indicate that it contributes 0-0.2 μg m-3 or 0-4% of the secondary organic aerosol mass. Copyright 2011 by the American Geophysical Union.

Traffic emissions are an important source of air pollution worldwide, but in the Middle East, this problem is exacerbated by weak or no enforcement of emission regulations. Comprehensive measurements of fine PM emission factors (EFs) from road transport in the region have not yet been conducted, but such data are necessary for quantitative assessments of the health impact of transport emissions in the region. To address this need, PM 2.5 samples collected inside the Salim Slam tunnel in Beirut, Lebanon were analyzed for carbonaceous matter (organic carbon (OC) and elemental carbon (EC)), water-soluble ions, elements, and selected organic compounds. The OC/EC ratio was 1.8 for the total fleet and 2.6 for light-duty vehicles (LDV), in agreement with the dominant proportion of gasoline LDV in the Lebanese fleet. A Cu/Sb ratio of 4.2 ± 0.1 was observed, offering a valuable metric for detecting brake wear emissions in subsequent studies conducted in the region. The EFs of carbonaceous matter, elements and ions generally varied by a factor 0.1 and 10 in comparison to literature values, while those for alkanes and polycyclic aromatic hydrocarbons were similar to the upper values previously reported. The average number size distribution was characterized by a single mode around 35 nm. The particles number EF (for diameters between 10 and 480 nm) was within the range of 10 14 -10 15 particles per kg of fuel. The chemical mass balance model showed an average contribution to EF of 62% from non-exhaust sources. This study highlights the need for more enforceable stringent vehicular regulations because of the local practices (i.e., removal of catalyst) and some EF values are very high compared to other studies/countries., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

The chemical composition of PM 2.5 at two sites in Lebanon, a country in the East Mediterranean - Middle East region, is investigated in the spring and summer seasons. The average PM 2.5 concentrations were of (29 ± 16) µg/m 3 for Beirut urban site and (32 ± 14) µg/m 3 for Beirut suburban site. This study showed that the geographic location of the East Mediterranean region, such as its proximity to the Mediterranean Sea and the dust storm intrusion are a significant contributor to the high PM levels from natural sources, which cannot be mitigated, rendering the PM 2.5 WHO annual Air Quality guideline unattainable due to high natural background, which also applies to the entire Middle East region. Turkey and Eastern Europe are the dominant origin of air masses throughout our sampling days, suggesting the long-range transport as an important potential contributor to the high observed concentrations of V, Ni, and sulfate in this region most probably in other East Mediterranean countries than Lebanon too. Main local sources determined through the chemical speciation including organics are road transport, resuspension of dust and diesel private generators. A health risk assessment of airborne metals was performed and the carcinogenic risk for all the metals exceeded by 42 (adults) and 14 (children) times the acceptable risk level (10 -6 ) at both sites. Vanadium was the predominant carcinogenic metal, emphasizing the need to replace energy production with cleaner energy on a regional level and highlighting the severe impact of air pollution on the health of inhabitants in this region's main cities., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022. Published by Elsevier B.V.)

Source contributions to PM 2.5 concentrations were evaluated in Greater Beirut (Lebanon), a typical East Mediterranean-Middle East (EMME) city, using Positive Matrix Factorization with two approaches. The first approach included only inorganic species (PMF-trad) and the other approach added organic markers (PMF-org). PMF-org identified 4 additional sources, and large discrepancies in contributions were observed for some major sources found in both approaches, highlighting the importance of including organic markers. The traffic factor was underestimated in PMF-trad by 2 to 7 folds. Moreover, results showed that this city is prone to high desert dust concentrations originating from uncontrollable dust storm events, like all cities in the Middle East. A PM 2.5 mitigation plan taking into account the potency of the identified sources was developed. Sources like diesel generators or traffic presented smaller contributions in term of mass compared to desert dust, however the health impact of the latter is relatively small and actions should target sources with the highest potency. Local emission inventories in the EMME region are scarce and studies typically rely on global emission inventories for local air quality management plans, but these inventories significantly underestimate Beirut's road transport emissions by more than an order of magnitude., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Inc. All rights reserved.)

Analyzing the orientation of polymeric crystalline lamella at the surface of thin films can be challenging. Even though atomic force microscopy (AFM) is often sufficient for this analysis, there are cases when imaging is not sufficient to confidently determine lamellar orientation. Here, we used sum frequency generation (SFG) spectroscopy to analyze the lamellar orientation at the surface of semi-crystalline isotactic polystyrene (iPS) thin films. The SFG orientation analysis indicated that the iPS chains are oriented perpendicular to the substrate (flat-on lamellar orientation), which was confirmed by AFM. By analyzing the evolution of the SFG spectral features with the progress of crystallization, we demonstrated that the ratios of the SFG intensities of the phenyl ring resonances are a good indication of the surface crystallinity. Furthermore, we explored the challenges associated with SFG measurements of heterogeneous surfaces, which is commonly present in many semi-crystalline polymeric films. To the best of our knowledge, this is the first time that the surface lamellar orientation of semi-crystalline polymeric thin films was determined by SFG. Also, this work pioneers in reporting the surface conformation of semi-crystalline and amorphous iPS thin films by SFG and in linking the SFG intensity ratios to the progress of the crystallization and the surface crystallinity. This study demonstrates the potential applicability of SFG spectroscopy in the conformational analysis of polymeric crystalline structures at interfaces and opens the way to the investigation of more complex polymeric structures and crystalline arrangements, especially for the case of buried interfaces, where AFM imaging is not an option., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier B.V. All rights reserved.)

The dependence between the conformation of polystyrene (PS) and its molecular weight (Mw) in the vicinity of a metal interface was investigated by sum frequency generation (SFG) spectroscopy. Tilt angles θ ≥ 50 ° (the angle between the C 2 axis of the pendant phenyl ring and the surface normal) were observed for all samples because of the interaction between the aromatic rings and the metal surface. Furthermore, it was found that θ decreases with increasing Mw for PS samples ranging from 20 × 10 3 g/mol to 400 × 10 3 g/mol. The intensity of the backbone SFG signal was higher for high Mw PS, compared to low Mw PS, indicating a greater number of backbone interactions with the silver substrate surface for the high Mw sample. These structural differences are driven by different entropic and enthalpic contributions to the free energy of adsorption for different polymer molecular weights. Differences in the polymer free volume and in the relative amount of chain ends with higher mobility may also influence the chain conformation. These results suggest that important interfacial properties of polymeric thin films, such as adhesion and wettability, could be tailored by modifying the polymer Mw to achieve the desired interfacial conformation.

Despite the central role of reactive organic carbon (ROC) in the formation of secondary species that impact global air quality and climate, our assessment of ROC abundance and impacts is challenged by the diversity of species that contribute to it. We revisit measurements of ROC species made during two field campaigns in the United States: the 2013 SOAS campaign in forested Centreville, AL, and the 2010 CalNex campaign in urban Pasadena, CA. We find that average measured ROC concentrations are about twice as high in Pasadena (73.8 μgCsm -3 ) than in Centreville (36.5 μgCsm -3 ). However, the OH reactivity (OHR) measured at these sites is similar (20.1 and 19.3 s -1 ). The shortfall in OHR when summing up measured contributions is 31%, at Pasadena and 14% at Centreville, suggesting that there may be a larger reservoir of unmeasured ROC at the former site. Estimated O 3 production and SOA potential (defined as concentration × yield) are both higher during CalNex than SOAS. This analysis suggests that the ROC in urban California is less reactive, but due to higher concentrations of oxides of nitrogen and hydroxyl radicals, is more efficient in terms of O 3 and SOA production, than in the forested southeastern U.S.

A gap in emission inventories of urban volatile organic compound (VOC) sources, which contribute to regional ozone and aerosol burdens, has increased as transportation emissions in the United States and Europe have declined rapidly. A detailed mass balance demonstrates that the use of volatile chemical products (VCPs)-including pesticides, coatings, printing inks, adhesives, cleaning agents, and personal care products-now constitutes half of fossil fuel VOC emissions in industrialized cities. The high fraction of VCP emissions is consistent with observed urban outdoor and indoor air measurements. We show that human exposure to carbonaceous aerosols of fossil origin is transitioning away from transportation-related sources and toward VCPs. Existing U.S. regulations on VCPs emphasize mitigating ozone and air toxics, but they currently exempt many chemicals that lead to secondary organic aerosols., (Copyright © 2018 The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. No claim to original U.S. Government Works.)

We present results from a high-resolution chemical ionization time-of-flight mass spectrometer (HRToF-CIMS), operated with two different thermal desorption inlets, designed to characterize the gas and aerosol composition. Data from two field campaigns at forested sites are shown. Particle volatility distributions are estimated using three different methods: thermograms, elemental formulas, and measured partitioning. Thermogram-based results are consistent with those from an aerosol mass spectrometer (AMS) with a thermal denuder, implying that thermal desorption is reproducible across very different experimental setups. Estimated volatilities from the detected elemental formulas are much higher than from thermograms since many of the detected species are thermal decomposition products rather than actual SOA molecules. We show that up to 65% of citric acid decomposes substantially in the FIGAERO-CIMS, with ∼20% of its mass detected as gas-phase CO 2 , CO, and H 2 O. Once thermal decomposition effects on the detected formulas are taken into account, formula-derived volatilities can be reconciled with the thermogram method. The volatility distribution estimated from partitioning measurements is very narrow, likely due to signal-to-noise limits in the measurements. Our findings indicate that many commonly used thermal desorption methods might lead to inaccurate results when estimating volatilities from observed ion formulas found in SOA. The volatility distributions from the thermogram method are likely the closest to the real distributions.

Carbonaceous particulate matter (PM), comprising black carbon (BC), primary organic aerosol (POA) and secondary organic aerosol (SOA, from atmospheric aging of precursors), is a highly toxic vehicle exhaust component. Therefore, understanding vehicle pollution requires knowledge of both primary emissions, and how these emissions age in the atmosphere. We provide a systematic examination of carbonaceous PM emissions and parameterisation of SOA formation from modern diesel and gasoline cars at different temperatures (22, -7 °C) during controlled laboratory experiments. Carbonaceous PM emission and SOA formation is markedly higher from gasoline than diesel particle filter (DPF) and catalyst-equipped diesel cars, more so at -7 °C, contrasting with nitrogen oxides (NO X ). Higher SOA formation from gasoline cars and primary emission reductions for diesels implies gasoline cars will increasingly dominate vehicular total carbonaceous PM, though older non-DPF-equipped diesels will continue to dominate the primary fraction for some time. Supported by state-of-the-art source apportionment of ambient fossil fuel derived PM, our results show that whether gasoline or diesel cars are more polluting depends on the pollutant in question, i.e. that diesel cars are not necessarily worse polluters than gasoline cars.

Airborne particulate matter less than 2.5 μm in diameter (PM 2.5 ) negatively impacts air quality in cities throughout the world where it has been linked to increased cardiac and respiratory morbidity and mortality. For this reason PM 2.5 standards have been established by many countries and the World Health Organization. However, these guidelines are regularly exceeded in North America, Europe and East Asia. While PM 2.5 is often reported as a single atmospheric species, it is actually a mixture of organic and inorganic compounds. The organic fraction, termed organic aerosol (OA), contributes approximately 20-70% of the PM 2.5 mass globally, and OA itself is a complex mixture of thousands of compounds. Characterizing the chemical properties of OA represents a major analytical challenge that has motivated the development of a range of new instruments. The focus of this perspective is the use of field-deployable mass spectrometers and in particular the Aerodyne Aerosol Mass Spectrometer (AMS) for chemically characterizing submicron particles. Field measurements of the composition of PM 2.5 are directly relevant to evaluating its health impact because reductions in life expectancy due to PM 2.5 vary according to composition. In addition, AMS measurements are especially useful for characterizing OA. The sources of OA are not well understood as evidenced by the performance of many air quality models, including those run by government agencies, which lack accurate and well constrained parameterizations for simulating secondary OA concentrations in urban regions. Given that OA is an important component of the total PM 2.5 mass, this uncertainty makes accurate evaluation of the impact of PM 2.5 on public health difficult, especially when evaluating future mitigation strategies. The development of the AMS has been a critical step towards addressing this public health challenge in that it provides quantitative data regarding particulate matter and OA concentration and composition that can be used to constrain uncertainties in air quality models.

Secondary organic aerosol (SOA) is formed from the atmospheric oxidation of gas-phase organic compounds leading to the formation of particle mass. Gasoline- and diesel-powered motor vehicles, both on/off-road, are important sources of SOA precursors. They emit complex mixtures of gas-phase organic compounds that vary in volatility and molecular structure-factors that influence their contributions to urban SOA. However, the relative importance of each vehicle type with respect to SOA formation remains unclear due to conflicting evidence from recent laboratory, field, and modeling studies. Both are likely important, with evolving contributions that vary with location and over short time scales. This review summarizes evidence, research needs, and discrepancies between top-down and bottom-up approaches used to estimate SOA from motor vehicles, focusing on inconsistencies between molecular-level understanding and regional observations. The effect of emission controls (e.g., exhaust aftertreatment technologies, fuel formulation) on SOA precursor emissions needs comprehensive evaluation, especially with international perspective given heterogeneity in regulations and technology penetration. Novel studies are needed to identify and quantify "missing" emissions that appear to contribute substantially to SOA production, especially in gasoline vehicles with the most advanced aftertreatment. Initial evidence suggests catalyzed diesel particulate filters greatly reduce emissions of SOA precursors along with primary aerosol.

Mounting evidence from field and laboratory observations coupled with atmospheric model analyses shows that primary combustion emissions of organic compounds dynamically partition between the vapor and particulate phases, especially as near-source emissions dilute and cool to ambient conditions. The most recent version of the Community Multiscale Air Quality model version 5.2 (CMAQv5.2) accounts for the semivolatile partitioning and gas-phase aging of these primary organic aerosol (POA) compounds consistent with experimentally derived parameterizations. We also include a new surrogate species, potential secondary organic aerosol from combustion emissions (pcSOA), which provides a representation of the secondary organic aerosol (SOA) from anthropogenic combustion sources that could be missing from current chemical transport model predictions. The reasons for this missing mass likely include the following: (1) unspeciated semivolatile and intermediate volatility organic compound (SVOC and IVOC, respectively) emissions missing from current inventories, (2) multigenerational aging of organic vapor products from known SOA precursors (e.g., toluene, alkanes), (3) underestimation of SOA yields due to vapor wall losses in smog chamber experiments, and (4) reversible organic compounds-water interactions and/or aqueous-phase processing of known organic vapor emissions. CMAQ predicts the spatially averaged contribution of pcSOA to OA surface concentrations in the continental United States to be 38.6 and 23.6 % in the 2011 winter and summer, respectively. Whereas many past modeling studies focused on a particular measurement campaign, season, location, or model configuration, we endeavor to evaluate the model and important uncertain parameters with a comprehensive set of United States-based model runs using multiple horizontal scales (4 and 12 km), gas-phase chemical mechanisms, and seasons and years. The model with representation of semivolatile POA improves predictions of hourly OA observations over the traditional nonvolatile model at sites during field campaigns in southern California (CalNex, May-June 2010), northern California (CARES, June 2010), the southeast US (SOAS, June 2013; SEARCH, January and July, 2011). Model improvements manifest better correlations (e.g., the correlation coefficient at Pasadena at night increases from 0.38 to 0.62) and reductions in underprediction during the photochemically active afternoon period (e.g., bias at Pasadena from -5.62 to -2.42 μg m -3 ). Daily averaged predictions of observations at routine-monitoring networks from simulations over the continental US (CONUS) in 2011 show modest improvement during winter, with mean biases reducing from 1.14 to 0.73μg m -3 , but less change in the summer when the decreases from POA evaporation were similar to the magnitude of added SOA mass. Because the model-performance improvement realized by including the relatively simple pcSOA approach is similar to that of more-complicated parameterizations of OA formation and aging, we recommend caution when applying these more-complicated approaches as they currently rely on numerous uncertain parameters. The pcSOA parameters optimized for performance at the southern and northern California sites lead to higher OA formation than is observed in the CONUS evaluation. This may be due to any of the following: variations in real pcSOA in different regions or time periods, too-high concentrations of other OA sources in the model that are important over the larger domain, or other model issues such as loss processes. This discrepancy is likely regionally and temporally dependent and driven by interferences from factors like varying emissions and chemical regimes., Competing Interests: Competing interests. The authors declare that they have no conflict of interest.

Acceptance and Commitment Therapy (ACT) provides a theoretical rationale for "acceptance" of thoughts and feelings, and proscribes suppression, a more intuitive and commonly used coping strategy. Suppression is theorized to have negative consequences not applicable to acceptance, including depletion in self-control and ironic postsuppression rebound effects. However, it remains largely unknown whether these strategies differentially affect frequency of drug-related thoughts, craving intensity, drug use behavior, or other relevant outcomes. Adult smokers (N = 162) were randomly assigned to receive a brief laboratory-based coping intervention (acceptance or suppression) or were not given coping instructions (control group) and then were exposed to smoking cues. Results indicated that the suppression group was successful at suppressing thoughts of smoking, as they reported fewer thoughts of smoking than the other two groups. Also, both coping strategies were associated with benefits with respect to craving and affect. However, there were no group differences in depletion, and rebound effects did not occur when coping was discontinued. Following the laboratory session, all participants attempted to quit or at least reduce their smoking for 3 days; the acceptance and suppression groups resumed use of their strategy. At 3-day follow-up, the acceptance and suppression groups reported greater self-efficacy for avoiding smoking when experiencing craving compared to the control group. However, there were no group differences in the number of cigarettes smoked during the 3 days. This study provides support for the value of acceptance-based coping, but it also suggests that more research is needed to differentiate its benefits compared to suppression., (2013 APA, all rights reserved)

In this perspectives article, we reflect upon the existence of chirality in atmospheric aerosol particles. We then show that organic particles collected at a field site in the central Amazon Basin under pristine background conditions during the wet and dry seasons consist of chiral secondary organic material. We show how the chiral response from the aerosol particles can be imaged directly without the need for sample dissolution, solvent extraction, or sample preconcentration. By comparing the chiral-response images with optical images, we show that chiral responses always originate from particles on the filter, but not all aerosol particles produce chiral signals. The intensity of the chiral signal produced by the size resolved particles strongly indicates the presence of chiral secondary organic material in the particle. Finally, we discuss the implications of our findings on chiral atmospheric aerosol particles in terms of climate-related properties and source apportionment.

Utilizing vibrational sum frequency generation (SFG), we characterized the structure of adsorbed cetyltrimethylammonium chloride (CTAC) at the silica/aqueous interface in the presence of 10 to 500 mM NaCl and as a function of surfactant surface coverage. For low ionic strengths (10 mM NaCl), results indicate that adsorbed aggregates do not change conformation with increasing surface coverage. Instead, the surfactant adsorbs as micelle-like structures at concentrations considerably lower than surface saturation and the CMC. At high ionic strengths (300-500 mM NaCl), the structure of the adlayer is considerably different: The SFG results indicate that for 30 microM bulk CTAC the surfactant packs with fewer gauche defects in the hydrocarbon backbone, which is attributed to reduced Coulomb repulsion between the positively charged surfactant headgroups, and the results also indicate that CTAC adsorbs as monomers at low surface coverage but then rearranges into aggregates at higher surface coverage.

Electrostatics and counterions play important roles in many supramolecular processes, including surfactant adsorption and aggregation at interfaces. Here, we assess their influence on how the common surfactant cetyltrimethylammonium (CTA) interacts with fused silica/aqueous interfaces by determining thermodynamic, kinetic, and electrostatic parameters for CTA adsorption across a range of NaCl concentrations (10-500 mM NaCl) using second harmonic generation (SHG). Using vibrational sum frequency generation (SFG), we demonstrate that vibrationally resonant contributions and nonresonant background contributions to the SFG signal intensity that depend on the interfacial potential can be quantified simultaneously during the adsorption process, which provides insight into the nonequilibrium dynamics of CTA adsorption. By analyzing the adsorption free energies as a function of interfacial potential at these four salt concentrations, the charge density per adsorbate is determined, indicating that CTA coadsorbs with counterions at a ratio of approximately 4 to 3 (i.e., 4 CTA(+) ions for every 3 Cl(-) ion). The chemical (i.e., non-Coulombic) portion of the free energy is found to dominate the overall free energy of adsorption, indicating that CTA adsorption at these ionic strengths is primarily driven by the favorable hydrophobic interactions between interdigitated surfactant hydrocarbon chains in the adsorbed aggregate. By applying Gouy-Chapman-Stern theory to our data, an average charge density of 2.8(3) x 10(13) charges/cm(2), which corresponds to 0.7 to 1.7 molecules/nm(2), was obtained for the four NaCl concentrations.

Myeloid zinc finger 1 (MZF1) is a transcription factor that plays an important role in blood cell development. Previous reports indicate MZF1 is an essential factor whose abnormal expression results in cancer. However, the molecular mechanisms by which MZF1 functions in development and contributes to cancer progression remain unknown. MZF1 is a member of the SCAN domain family of zinc finger proteins (SCAN-ZFP) that form dimers via their highly conserved SCAN motif. To better understand the molecular mechanism of MZF1 function, we sought to characterize the cellular localization pattern of MZF1 in the context of SCAN dimerization. Here we provide evidence that MZF1 is a constituent of promyelocytic leukemia nuclear bodies (PML-NBs) and that the SCAN domain is necessary for association with these intranuclear structures. In addition, the SCAN-ZFP member ZNF24 was identified as a novel heterodimeric partner of MZF1 that also associates with PML-NBs in a unique ring-type pattern. Finally, we provide support that MZF1 protein may be modified by SUMOylation, which provides further support for localization of MZF1 protein complexes to PML-NBs. Altogether, these data suggest that MZF1 is recruited to PML-NBs and that the SCAN domain may play an integral role in regulating the localization of heterodimeric protein complexes to these intranuclear structures.

Here, we report the solution structure of ZNF593, a protein identified in a functional study as a negative modulator of the DNA-binding activity of the Oct-2 transcription factor. ZNF593 contains a classic C(2)H(2) zinc finger domain flanked by about 40 disordered residues on each terminus. Although the protein contains a high degree of intrinsic disorder, the structure of the zinc finger domain was resolved by NMR spectroscopy without a need for N- or C-terminal truncations. The tertiary structure of the zinc finger domain is composed of a beta-hairpin that positions the cysteine side chains for zinc coordination, followed by an atypical kinked alpha-helix containing the two histidine side chain ligands. The structural topology of ZNF593 is similar to a fragment of the double-stranded RNA-binding protein Zfa and the C-terminal zinc finger of MBP-1, a human enhancer binding protein. The structure presented here will provide a guide for future functional studies of how ZNF593 negatively modulates the DNA-binding activity of Oct-2, a POU domain-containing transcription factor. Our work illustrates the unique capacity of NMR spectroscopy for structural analysis of folded domains in a predominantly disordered protein.

Inorganic anions and cations are ubiquitous in environmental chemistry. Here, we use second harmonic generation to track the interaction of the environmentally important metal cations barium, strontium, and cadmium and the nitrate anion with fused quartz/water interfaces at pH 7. Using a dynamic flow system, we assess the extent of reversibility in the binding process and report the absolute number density of adsorbed cations, their charge densities, and their free energies of adsorption. We also present resonantly enhanced second harmonic generation experiments that show that nitrate is surface active and report the free energies and binding constants for the adsorption process. The second harmonic generation spectrum of surface-bound nitrate shows a new adsorption band that cuts further into the solar spectrum than nitrate in the aqueous or solid state. The results that we obtain for all four inorganic ions and the implications for tropospheric and aquatic chemistry as well as geochemistry are discussed in the context of fundamental science as well as pollutant transport models.

We report resonantly enhanced surface second harmonic generation (SHG) measurements to track the interaction of the EPA priority toxic metal pollutant chromium(VI) with fused quartz/water interfaces containing tailor-made amino acids that serve as model systems for environmental and biological interfaces. chi3 measurements of amido acid functionalized fused quartz/water interfaces are consistent with two acid-base equilibria, suggesting the formation of a laterally hydrogen-bonded environment similar to what is observed for aliphatic carboxylic acids. Chromate adsorption isotherms recorded at pH 7 are suggestive of an intramolecular chelation mechanism that becomes important when four or more hydrogen-bonding moieties are displayed toward the incoming chromate. The strong binding affinities of the amido acid functionalized fused quartz/water interfaces toward chromate are consistent with nearly 50% slower transport rates with respect to free-flowing groundwater, indicating that, in the absence of redox processes, peptide materials in heterogeneous geochemical environments can significantly increase chromate residence times. The strong evidence for synergistic effects dominating the interactions of chromate with surface-bound amido acids indicates that chemical complexity can be systematically addressed using tailor-made organic surfaces and interfaces.

We have applied an efficient solid-phase protein refolding method to the milligram scale production of natively folded recombinant chemokine proteins. Chemokines are intensely studied proteins because of their roles in immune system regulation, response to inflammation, fetal development, and numerous disease states including, but not limited to, HIV-1/AIDS, cancer metastasis, Crohn's disease, asthma and arthritis. Many investigators use recombinant chemokines for research purposes, however these proteins partition almost exclusively to the inclusion body fraction when produced in Escherichia coli. A major hurdle is to correctly refold the chemokine and oxidize the two highly conserved disulfide bonds found in nearly all chemokines. Conventional methods for oxidation and refolding by dialysis or extreme dilution are effective but slow and yield large volumes of dilute chemokine. Here we use an on-column approach for rapid refolding and oxidation of four chemokines, CXCL12/SDF-1alpha (stromal cell-derived factor-1alpha), CCL5/RANTES, XCL1/lymphotactin, and CX3CL1/fractalkine. NMR spectra of SDF-1alpha, RANTES, lymphotactin, and fractalkine indicate these chemokines adopt native structures. On-column refolded SDF-1alpha is fully active in an intracellular calcium flux assay. Our success with multiple SDF-1alpha mutants and members of all four chemokine subfamilies suggests that on-column refolding is a robust method for preparative-scale production of recombinant chemokine proteins.

The SCAN domain mediates interactions between members of a subfamily of zinc-finger transcription factors and is found in more than 60 C2H2 zinc finger genes in the human genome, including the tumor suppressor gene myeloid zinc finger 1 (MZF1). Glutathione-S-transferase pull-down assays showed that the MZF1 SCAN domain self-associates, and a Kd value of 600 nM was measured by intrinsic tryptophan fluorescence polarization. The MZF1 structure determined by NMR spectroscopy revealed a domain-swapped dimer. Each monomer consists of five alpha helices in two subdomains connected by the alpha2-alpha3 loop. Residues from helix 3 of each monomer compose the core of the dimer interface, while the alpha1-alpha2 loop and helix 2 pack against helices 3 and 5 from the opposing monomer. Comprehensive sequence analysis is coupled with the first high-resolution structure of a SCAN dimer to provide an initial view of the recognition elements that govern dimerization for this large family of transcription factors.

Most deaf or hard of hearing students do not read proficiently (Karchmer, Milone, & Wolk, 1979; Allen, 1986), yet Winzer (1985) found no agreement as to the best way to teach reading to them. We reviewed the literature in related fields in an attempt to assist teachers and parents in identifying practices that are supported by research and linked to literacy attainment. We were especially impressed by the work of Adams (1990) with regard to the practices that promote proficient reading in hearing students, as well as by that of Hoggan and Strong (1994), who studied the techniques of those working with students with language disabilities. The result of our review was a rationale and description of ten practices that we suggest are essential to include when reading to students if they are to become proficient readers themselves. Our work is particularly applicable when adults are using the methods of read aloud, adult/student shared reading, and adult guided reading. These essential practices can be modeled by teachers for parents and others working with students as they develop reading skills.

The "inclusion" movement has resulted in a shift of placement for children who are deaf or hard of hearing. Over 50% of students who are deaf or hard of hearing are now attending academic classes with hearing students in public school settings (Schildroth & Hotto, 1993). As the enrollment of deaf and hard of hearing students in public schools continues to increase, so does the need for qualified educational interpreters. The present study was designed to investigate nationwide the in-service training that general-education teachers receive with regard to the roles and responsibilities of educational interpreters. One hundred elementary and secondary general education teachers were surveyed, yielding a 59% return rate. Less than 33% of those teachers who returned surveys had attended in-services on the topic of educational interpreters. Neither the academic level (i.e., elementary and secondary) of the teachers who participated or the number of students who were deaf or hard of hearing and in attendance at a school influenced the number of in-services provided on the topic of interpreting.