Evaluation of 1-Nitropyrene as a Surrogate Measure for Diesel Exhaust.

We investigated the viability of particle bound 1-nitropyrene (1-NP) air concentration measurements as a surrogate of diesel exhaust (DE) exposure, as compared with industry-standard elemental carbon (EC) and total carbon (TC) measurements. Personal exposures are reported for 18 employees at a large underground metal mine during four different monitoring campaigns. Full-shift personal air exposure sampling was conducted using a Mine Safety and Health Administration (MSHA) compliant diesel particulate matter (DPM) impactor cassette downstream of a GS-1 cyclone pre-selector. Each DPM filter element was analyzed for EC and organic carbon (OC) using NIOSH Method 5040. After EC and OC analysis, the remaining portion of each DPM filter was analyzed for 1-NP using liquid chromatography tandem mass spectrometry (LC/MS/MS). We observed high correlations between the quantiles of 1-NP and EC exposures across 10 different work shift task groups (r = 0.87 to 0.96), and a linear relationship with a slope between 6.0 to 6.9 pg 1-NP per µg EC. However, correlation between 1-NP and EC was weak (r =0.34) for the 91 individual sample pairs due to low EC concentrations and possible heterogeneity of DE composition. While both 1-NP and EC differentiated between high and low exposure groups categorized by job location, measurements of 1-NP, but not EC further differentiated between specific job activities. Repeated measurements on individual subjects verified the relationship between 1-NP and EC and demonstrated substantial within-subject variability in exposure. The detection limit of TC air concentration ranged between 18 and 28 µg m-3 and was limited by OC contamination of the quartz filters in the MSHA compliant DPM samplers.

Use of mobile and passive badge air monitoring data for NOX and ozone air pollution spatial exposure prediction models.

Air pollution exposure prediction models can make use of many types of air monitoring data. Fixed location passive samples typically measure concentrations averaged over several days to weeks. Mobile monitoring data can generate near continuous concentration measurements. It is not known whether mobile monitoring data are suitable for generating well-performing exposure prediction models or how they compare with other types of monitoring data in generating exposure models. Measurements from fixed site passive samplers and mobile monitoring platform were made over a 2-week period in Baltimore in the summer and winter months in 2012. Performance of exposure prediction models for long-term nitrogen oxides (NOX) and ozone (O3) concentrations were compared using a state-of-the-art approach for model development based on land use regression (LUR) and geostatistical smoothing. Model performance was evaluated using leave-one-out cross-validation (LOOCV). Models performed well using the mobile peak traffic monitoring data for both NOX and O3, with LOOCV R2s of 0.70 and 0.71, respectively, in the summer, and 0.90 and 0.58, respectively, in the winter. Models using 2-week passive samples for NOX had LOOCV R2s of 0.60 and 0.65 in the summer and winter months, respectively. The passive badge sampling data were not adequate for developing models for O3. Mobile air monitoring data can be used to successfully build well-performing LUR exposure prediction models for NOX and O3 and are a better source of data for these models than 2-week passive badge data.

Ambient Air Quality Measurements from a Continuously Moving Mobile Platform: Estimation of Area-Wide, Fuel-Based, Mobile Source Emission Factors Using Absolute Principal Component Scores.

We have applied the absolute principal component scores (APCS) receptor model to on-road, background-adjusted measurements of NOx, CO, CO2, black carbon (BC), and particle number (PN) obtained from a continuously moving platform deployed over nine afternoon sampling periods in Seattle, WA. Two Varimax-rotated principal component features described 75% of the overall variance of the observations. A heavy-duty vehicle feature was correlated with black carbon and particle number, whereas a light-duty feature was correlated with CO and CO2. NOx had moderate correlation with both features. The bootstrapped APCS model predictions were used to estimate area-wide, average fuel-based emission factors and their respective 95% confidence limits. The average emission factors for NOx, CO, BC and PN (14.8, 18.9, 0.40 g/kg, and 4.3×1015 particles/kg for heavy duty vehicles, and 3.2, 22.4, 0.016 g/kg, and 0.19×1015 particles/kg for light-duty vehicles, respectively) are consistent with previous estimates based on remote sensing, vehicle chase studies, and recent dynamometer tests. Information on the spatial distribution of the concentrations contributed by these two vehicle categories relative to background during the sampling period was also obtained.

Ultrafine particle size as a tracer for aircraft turbine emissions.

Ultrafine particle number (UFPN) and size distributions, black carbon, and nitrogen dioxide concentrations were measured downwind of two of the busiest airports in the world, Los Angeles International Airport (LAX) and Hartsfield-Jackson International Airport (ATL - Atlanta, GA) using a mobile monitoring platform. Transects were located between 5 km and 10 km from the ATL and LAX airports. In addition, measurements were taken at 43 additional urban neighborhood locations in each city and on freeways. We found a 3-5 fold increase in UFPN concentrations in transects under the landing approach path to both airports relative to surrounding urban areas with similar ground traffic characteristics. The latter UFPN concentrations measured were distinct in size distributional properties from both freeways and across urban neighborhoods, clearly indicating different sources. Elevated concentrations of Black Carbon (BC) and NO2 were also observed on airport transects, and the corresponding pattern of elevated BC was consistent with the observed excess UFPN concentrations relative to other urban locations.

Correlations between short-term mobile monitoring and long-term passive sampler measurements of traffic-related air pollution.

Mobile monitoring has provided a means for broad spatial measurements of air pollutants that are otherwise impractical to measure with multiple fixed site sampling strategies. However, the larger the mobile monitoring route the less temporally dense measurements become, which may limit the usefulness of short-term mobile monitoring for applications that require long-term averages. To investigate the stationarity of short-term mobile monitoring measurements, we calculated long term medians derived from a mobile monitoring campaign that also employed 2-week integrated passive sampler detectors (PSD) for NOx, Ozone, and nine volatile organic compounds at 43 intersections distributed across the entire city of Baltimore, MD. This is one of the largest mobile monitoring campaigns in terms of spatial extent undertaken at this time. The mobile platform made repeat measurements every third day at each intersection for 6-10 minutes at a resolution of 10 s. In two-week periods in both summer and winter seasons, each site was visited 3-4 times, and a temporal adjustment was applied to each dataset. We present the correlations between eight species measured using mobile monitoring and the 2-week PSD data and observe correlations between mobile NOx measurements and PSD NOx measurements in both summer and winter (Pearson's r = 0.84 and 0.48, respectively). The summer season exhibited the strongest correlations between multiple pollutants, whereas the winter had comparatively few statistically significant correlations. In the summer CO was correlated with PSD pentanes (r = 0.81), and PSD NOx was correlated with mobile measurements of black carbon (r = 0.83), two ultrafine particle count measures (r =0.8), and intermodal (1-3 µm) particle counts (r = 0.73). Principal Component Analysis of the combined PSD and mobile monitoring data revealed multipollutant features consistent with light duty vehicle traffic, diesel exhaust and crankcase blow by. These features were more consistent with published source profiles traffic-related air pollutants than features based on the PSD data alone. Short-term mobile monitoring shows promise for capturing long-term spatial patterns of traffic-related air pollution, and is complementary to PSD sampling strategies.

Urinary polycyclic aromatic hydrocarbon metabolites as biomarkers to woodsmoke exposure - results from a controlled exposure study.

Woodsmoke contains harmful components - such as fine particulate matter (PM2.5) and polycyclic aromatic hydrocarbons (PAHs) - and impacts more than half of the global population. We investigated urinary hydroxylated PAH metabolites (OH-PAHs) as woodsmoke exposure biomarkers in nine non-smoking volunteers experimentally exposed to a wood fire. Individual urine samples were collected from 24-h before to 48-h after the exposure and personal PM2.5 samples were collected during the 2-h woodsmoke exposure. Concentrations of nine OH-PAHs increased by 1.8-7.2 times within 2.3-19.3 h, and returned to baseline approximately 24 h after the exposure. 2-Naphthol (2-NAP) had the largest post-exposure increase and exhibited a clear excretion pattern in all participants. The level of urinary OH-PAHs, except 1-hydroxypyrene (1-PYR), correlated with those of PM2.5, levoglucosan and PAHs in personal PM2.5 samples. This finding suggests that several urinary OH-PAHs, especially 2-NAP, are potential exposure biomarkers to woodsmoke; by contrast, 1-PYR may not be a suitable biomarker. Compared with levoglucosan and methoxyphenols - two other urinary woodsmoke biomarkers that were measured in the same study and reported previously - OH-PAHs might be better biomarkers based on sensitivity, robustness and stability, particularly under suboptimal sampling and storage conditions, like in epidemiological studies carried out in less developed areas.

Multi-pollutant mobile platform measurements of air pollutants adjacent to a major roadway.

A mobile monitoring platform developed at the University of Washington Center for Clean Air Research (CCAR) measured 10 pollutant metrics (10 s measurements at an average speed of 22 km/hr) in two neighborhoods bordering a major interstate in Albuquerque, NM, USA from April 18-24 2012. 5 days of data sharing a common downwind orientation with respect to the roadway were analyzed. The aggregate results show a three-fold increase in black carbon (BC) concentrations within 10 meters of the edge of roadway, in addition to elevated nanoparticle concentration and particulate matter with aerodynamic diameter < 1 µm (PN1) concentrations. A 30% reduction in ozone concentration near the roadway was observed, anti-correlated with an increase in the oxides of nitrogen (NOx). In this study, the pollutants measured have been expanded to include polycyclic aromatic hydrocarbons (PAH), particle size distribution (0.25-32 µm), and ultra-violet absorbing particulate matter (UVPM). The raster sampling scheme combined with spatial and temporal measurement alignment provide a measure of variability in the near roadway concentrations, and allow us to use a principal component analysis to identify multi-pollutant features and analyze their roadway influences.

Dielectric dependence of single-molecule photoluminescence intermittency: nile red in poly(vinylidene fluoride).

The dependence of single-molecule photoluminescence intermittency (PI) or "blinking" on the local dielectric constant (ε) is examined for nile red (NR) in thin films of poly(vinylidene fluoride) (PVDF). In previous studies, variation of the local dielectric constant was accomplished by studying luminophores in chemically and structurally different hosts. In contrast, the NR/PVDF guest-host pair allows for the investigation of PI as a function of ε while keeping the chemical composition of both the luminophore and host unchanged. The solvatochromic properties of NR are used to measure the local ε, while fluctuations in NR emission intensity over time provide a measure of the PI. PVDF is an ideal host for this study because it provides submicron-sized dielectric domains that vary from nonpolar (ε ≈ 2) to very polar (ε ≈ 70). The results presented here demonstrate that the local dielectric environment can have a pronounced effect on PI. We find that the NR emissive events increase 5-fold with an increase in ε from 2.2 to 74. A complex dependence on ε is also observed for NR nonemissive event durations, initially increasing as ε increases from 2.2 to 3.4 but decreasing in duration with further increase in ε. The variation in emissive event durations with ε is reproduced using a photoinduced electron-transfer model involving electron transfer from NR to PVDF. In addition, an increase in NR photostability with an increase in ε is observed, suggesting that the dielectric environment plays an important role in defining the photostability of NR in PVDF.

Measuring the spatial distribution of dielectric constants in polymers through quasi-single molecule microscopy.

The variation in dielectric constant is measured for thin films of poly(methyl methacrylate) (PMMA) and poly(vinylidene fluoride) (PVDF) using confocal fluorescence microscopy. Spatial variation in the local dielectric constant of the polymer films on the ~250 nm length scale is measured using the solvochromatic emission from incorporated nile red (NR) at "quasi-single molecule" (10(-7) M) and true single molecule (SM) concentrations (10(-9) M). Correlation of the NR fluorescence wavelength maximum with dielectric constant is used to transform images of NR's emission maxima to spatial variation in local dielectric constant. We demonstrate that the distributions of dielectric environments measured in the quasi- and true SM approaches are equivalent; however, the enhanced signal rates present in the quasi-SM approach result in this technique being more efficient. In addition, the quasi-SM technique reports directly on the continuous spatial variation in dielectric constant, information that is difficult to obtain in true SM studies. With regards to the polymers of interest, the results presented here demonstrate that a limited distribution of dielectric environments is present in PMMA; however, a broad distribution of environments exists in PVDF consistent with this polymer existing as a distribution of structural phases.

Proton transfer and photoluminescence intermittency of single emitters in dyed crystals.

The role of proton transfer in the photoluminescence intermittency (PI) of single molecules of violamine R (VR) overgrown in potassium acid phthalate (KAP) crystals is evaluated in comparisons of protonated (KAP) and deuterated (DKAP) mixed crystals between 23 and 60 °C. The PI is analyzed by the construction of cumulative distribution functions that are statistically compared. We find that the on- and off-interval duration distributions change with isotopic substitution consistent with proton transfer contributing to the PI of VR. The on- and off-interval duration distributions have distinct temperature dependencies consistent with different mechanisms for dark state production and decay. Additional evidence for proton-transfer is provided by distributions of single molecule emission-energy maxima that reflect emission from protonated and deprotonated VR. A mechanism for the PI of KAP is presented, where the dark state is assigned to formation of the colorless, leuco form of VR, formed by proton transfer from VR to the KAP lattice, and decay of the dark state involves ring-opening promoted by proton transfer from KAP to VR. The distributed kinetics for dark-state production and decay are modeled using a log-normal distribution for the PI data in preference to a power-law previously assumed. A discussion of the log-normal distribution with regards to PI and proton transfer is presented.

Photoluminescence intermittency from single quantum dots to organic molecules: emerging themes.

Recent experimental and theoretical studies of photoluminescence intermittency (PI) or "blinking" exhibited by single core/shell quantum dots and single organic luminophores are reviewed. For quantum dots, a discussion of early models describing the origin of PI in these materials and recent challenges to these models are presented. For organic luminophores the role of electron transfer, proton transfer and other photophysical processes in PI are discussed. Finally, new experimental and data analysis methods are outlined that promise to be instrumental in future discoveries regarding the origin(s) of PI exhibited by single emitters.

Two mechanisms for fluorescence intermittency of single violamine R molecules.

The environment and temperature-dependent photoluminescence (PL) intermittency or "blinking" demonstrated by single violamine R (VR) molecules is investigated in two environments: poly(vinyl alcohol) (PVOH) and single crystals of potassium acid phthalate (KAP). In addition, temperatures ranging from 23 °C to 85 °C are studied, spanning the glass-transition temperature of PVOH (T(g) = 72 °C). The PL intermittency exhibited by VR is analyzed using probability histograms of emissive and non-emissive periods. In both PVOH and KAP, these histograms are best fit by a power law, consistent with the kinetics for dark state production and decay being dispersed as observed in previous studies. However, these systems have different temperature dependences, signifying two different blinking mechanisms for VR. In PVOH, the on- and off-event probability histograms do not vary with temperature, consistent with electron transfer via tunneling between VR and the polymer. In KAP the same histograms are temperature dependent, and show that blinking slows down at higher temperatures. This result is inconsistent with an electron-transfer process being responsible for blinking. Instead, a non-adiabatic proton-transfer between VR and KAP is presented as a model consistent with this temperature dependence. In summary, the results presented here demonstrate that for a given luminophore, the photochemical processes responsible for PL intermittency can change with environment.

Unraveling the dispersed kinetics of dichlorofluorescein in potassium hydrogen phthalate crystals.

The connection between photoluminescence (PL) intermittency and excited-state kinetics is explored for 2',7'-dichlorofluorescein (DCF) isolated in crystals of potassium acid phthalate (KAP) using time-tagged, time-resolved, time-correlated single-photon counting (T3R-TCSPC). In this technique, PL intermittency or "blinking" is measured in conjunction with the time of photon arrival relative to photoexcitation, allowing for the correlation of emissive intensities and excited-state decay kinetics of single molecules. The blinking trace is parsed into emissive and nonemissive segments using change-point-detection analysis, and the duration of these segments are used to quantify PL intermittency. The results presented here demonstrate that two populations of DCF exist in KAP, with one population demonstrating single-exponential excited state decay over the course of the blinking trace, and the other demonstrating stretched-exponential decay. Molecules demonstrating single-exponential decay also demonstrate modest intensity variation in the blinking trace. Correlation of the emission intensity and excited-state lifetimes demonstrates that for these molecules spectral diffusion is largely responsible for the evolution in emission intensity. In contrast, molecules demonstrating nonexponential excited-state decay vary in emission intensity. Correlation of the emissive intensities with the excited-state lifetimes demonstrates that these molecules undergo changes in both radiative and nonradiative decay rate constants as well as spectral diffusion. These observations suggest that DCF exists in two environments in KAP differentiated by the propensity for proton-transfer with the surrounding KAP matrix. The results presented here provide further insight into the origin of PL intermittency demonstrated by DCF in KAP and related systems.

Proton-transfer mechanism for dispersed decay kinetics of single molecules isolated in potassium hydrogen phthalate.

The excited-state decay kinetics of single 2',7'-dichlorofluorescein (DCF) molecules oriented and overgrown within crystals of potassium acid phthalate (KAP) are reported. Time-correlated single-photon counting measurements (TCSPC) of 56 DCF molecules in KAP reveal that single-exponential decay is exhibited by roughly half of the molecules. The remainder demonstrates complex excited-state decay kinetics that are well fit by a stretched exponential function consistent with dispersed kinetics. Histograms of single-molecule luminescence energies revealed environmental fluctuations and distinct chemical species. The TCSPC results are compared to Monte Carlo simulations employing a first-passage model for excited-state decay. Agreement between experiment and theory, on both bulk and single-molecule levels, suggests that a subset of the DCF molecules in KAP experience fluctuations in the surrounding environment that modify the energy barrier to proton transfer leading to dispersed kinetics.

Frequency-switching inversion-recovery for severely hyperfine-shifted NMR: evidence of asymmetric electron relaxation in high-spin Co(II).

A new method for reliably measuring longitudinal relaxation rates for severely hyperfine-shifted NMR signals in aqueous solutions is presented. The method is illustrated for a well-defined cobalt tetracysteinate, with relevance to cobalt-substituted metalloproteins. The relaxation measurements are indicative of asymmetric electronic relaxation of the high-spin Co(II) ion.