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In this study fine particulate matter (PM2.5) levels throughout the Copenhagen metro system are measured for the first time and found to be â¼10 times the roadside levels in Copenhagen. In this Part 2 article, low-cost sensor (LCS) nodes designed for personal-exposure monitoring are tested against a conventional mid-range device (TSI DustTrak), and gravimetric methods. The nodes were found to be effective for personal exposure measurements inside the metro system, with R2 values of > 0.8 at 1-min and > 0.9 at 5-min time-resolution, with an average slope of 1.01 in both cases, in comparison to the reference, which is impressive for this dynamic environment. Micro-environment (ME) classification techniques are also developed and tested, involving the use of auxiliary sensors, measuring light, carbon dioxide, humidity, temperature and motion. The output from these sensors is used to distinguish between specific MEs, namely, being aboard trains travelling above- or under- ground, with 83 % accuracy, and determining whether sensors were aboard a train or stationary at a platform with 92 % accuracy. This information was used to show a 143 % increase in mean PM2.5 concentration for underground sections relative to overground, and 22 % increase for train vs. platform measurements. The ME classification method can also be used to improve calibration models, assist in accurate exposure assessment based on detailed time-activity patterns, and facilitate field studies that do not require personnel to record time-activity diaries.
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Poluição do ArRESUMO
We report the observation of recoil inversion of the CO (v=0, J_{CO}=66) state in the UV dissociation of lab-frame oriented carbonyl sulfide (OCS). This state is ejected in the opposite direction with respect to all other (>30) states and in absence of any OCS rotation, thus resulting in spatial filtering of this particular high-J rovibrational state. This inversion is caused by resonances occurring in shallow local minima of the molecular potential, which bring the sulfur closer to the oxygen than the carbon atom, and is a striking example where such subtleties severely modify the photofragment trajectories. The resonant behavior is observed only in the photofragment trajectories and not in their population, showing that stereodynamic measurements from oriented molecules offer an indispensable probe for exploring energy landscapes.
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Halogens in the troposphere are increasingly recognized as playing an important role for atmospheric chemistry, and possibly climate. Bromine and iodine react catalytically to destroy ozone (O3), oxidize mercury, and modify oxidative capacity that is relevant for the lifetime of greenhouse gases. Most of the tropospheric O3 and methane (CH4) loss occurs at tropical latitudes. Here we report simultaneous measurements of vertical profiles of bromine oxide (BrO) and iodine oxide (IO) in the tropical and subtropical free troposphere (10 °N to 40 °S), and show that these halogens are responsible for 34% of the column-integrated loss of tropospheric O3. The observed BrO concentrations increase strongly with altitude (â¼ 3.4 pptv at 13.5 km), and are 2-4 times higher than predicted in the tropical free troposphere. BrO resembles model predictions more closely in stratospheric air. The largest model low bias is observed in the lower tropical transition layer (TTL) over the tropical eastern Pacific Ocean, and may reflect a missing inorganic bromine source supplying an additional 2.5-6.4 pptv total inorganic bromine (Bry), or model overestimated Bry wet scavenging. Our results highlight the importance of heterogeneous chemistry on ice clouds, and imply an additional Bry source from the debromination of sea salt residue in the lower TTL. The observed levels of bromine oxidize mercury up to 3.5 times faster than models predict, possibly increasing mercury deposition to the ocean. The halogen-catalyzed loss of tropospheric O3 needs to be considered when estimating past and future ozone radiative effects.
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We present a first principles study of the carbon dioxide (CO2) photodissociation process in the 150- to 210-nm wavelength range, with emphasis on photolysis below the carbon monoxide + singlet channel threshold at ~167 nm. The calculations reproduce experimental absorption cross-sections at a resolution of ~0.5 nm without scaling the intensity. The observed structure in the 150- to 210-nm range is caused by excitation of bending motion supported by the deep wells at bent geometries in the and potential energy surfaces. Predissociation below the singlet channel threshold occurs via spin-orbit coupling to nearby repulsive triplet states. Carbon monoxide vibrational and rotational state distributions in the singlet channel as well as the triplet channel for excitation at 157 nm satisfactorily reproduce experimental data. The cross-sections of individual CO2 isotopologues ((12)C(16)O2, (12)C(17)O(16)O, (12)C(18)O(16)O, (13)C(16)O2, and (13)C(18)O(16)O) are calculated, demonstrating that strong isotopic fractionation will occur as a function of wavelength. The calculations provide accurate, detailed insight into CO2 photoabsorption and dissociation dynamics, and greatly extend knowledge of the temperature dependence of the cross-section to cover the range from 0 to 400 K that is useful for calculations of propagation of stellar light in planetary atmospheres. The model is also relevant for the interpretation of laboratory experiments on mass-independent isotopic fractionation. Finally, the model shows that the mass-independent fractionation observed in a series of Hg lamp experiments is not a result of hyperfine interactions making predissociation of (17)O containing CO2 more efficient.
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Atmosfera/análise , Dióxido de Carbono/química , Modelos Químicos , Fotólise , Raios Ultravioleta , Monóxido de Carbono/química , Isótopos/química , Marte , Rotação , Temperatura , VibraçãoRESUMO
We revisit a dangling theoretical question of whether the surface reconstruction of the Si(100) surface would energetically favor the symmetric or buckled dimers on the intrinsic potential energy surfaces at 0 K. This seemingly simple question is still unanswered definitively since all existing density functional based calculations predict the dimers to be buckled, while most wavefunction based correlated treatments prefer the symmetric configurations. Here, we use the doubly hybrid density functional (DHDF) geometry optimizations, in particular, XYGJ-OS, complete active space self-consistent field theory, multi-reference perturbation theory, multi-reference configuration interaction (MRCI), MRCI with the Davidson correction (MRCI + Q), multi-reference average quadratic CC (MRAQCC), and multi-reference average coupled pair functional (MRACPF) methods to address this question. The symmetric dimers are still shown to be lower in energy than the buckled dimers when using the CASPT2 method on the DHDF optimized geometries, consistent with the previous results using B3LYP geometries [Y. Jung, Y. Shao, M. S. Gordon, D. J. Doren, and M. Head-Gordon, J. Chem. Phys. 119, 10917 (2003)]. Interestingly, however, the MRCI + Q, MRAQCC, and MRACPF results (which give a more refined description of electron correlation effects) suggest that the buckled dimer is marginally more stable than its symmetric counterpart. The present study underlines the significance of having an accurate description of the electron-electron correlation as well as proper multi-reference wave functions when exploring the extremely delicate potential energy surfaces of the reconstructed Si(100) surface.
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Silício/química , Dimerização , Estrutura Molecular , Propriedades de SuperfícieRESUMO
Natural climate variation, such as that caused by volcanoes, is the basis for identifying anthropogenic climate change. However, knowledge of the history of volcanic activity is inadequate, particularly concerning the explosivity of specific events. Some material is deposited in ice cores, but the concentration of glacial sulfate does not distinguish between tropospheric and stratospheric eruptions. Stable sulfur isotope abundances contain additional information, and recent studies show a correlation between volcanic plumes that reach the stratosphere and mass-independent anomalies in sulfur isotopes in glacial sulfate. We describe a mechanism, photoexcitation of SO2, that links the two, yielding a useful metric of the explosivity of historic volcanic events. A plume model of S(IV) to S(VI) conversion was constructed including photochemistry, entrainment of background air, and sulfate deposition. Isotopologue-specific photoexcitation rates were calculated based on the UV absorption cross-sections of (32)SO2, (33)SO2, (34)SO2, and (36)SO2 from 250 to 320 nm. The model shows that UV photoexcitation is enhanced with altitude, whereas mass-dependent oxidation, such as SO2 + OH, is suppressed by in situ plume chemistry, allowing the production and preservation of a mass-independent sulfur isotope anomaly in the sulfate product. The model accounts for the amplitude, phases, and time development of Δ(33)S/δ(34)S and Δ(36)S/Δ(33)S found in glacial samples. We are able to identify the process controlling mass-independent sulfur isotope anomalies in the modern atmosphere. This mechanism is the basis of identifying the magnitude of historic volcanic events.
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Atmosfera/análise , Mudança Climática , Luz , Modelos Químicos , Dióxido de Enxofre/química , Erupções Vulcânicas/efeitos adversos , Fotoquímica , Dióxido de Enxofre/efeitos da radiação , Isótopos de EnxofreRESUMO
We investigate the contributions of the lowest two (1)A" states in the UV photodissociation of N(2)O employing three-dimensional potential energy surfaces and transition dipole moment functions. Because the transition dipole moments are much smaller than for the 2 (1)A' state, we conclude that excitation of the (1)A" states has a marginal effect. The dense vibrational spectrum of the quasi-bound 2(1)A" state possibly explains some of the tiny, noise-like structures of the measured absorption spectrum.
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Óxido Nitroso/química , Teoria Quântica , Processos Fotoquímicos , Raios UltravioletaRESUMO
The sulfur kinetic isotope effect (KIE) in the reaction of carbonyl sulfide (OCS) with O((3)P) was studied in relative rate experiments at 298 ± 2 K and 955 ± 10 mbar. The reaction was carried out in a photochemical reactor using long path FTIR detection, and data were analyzed using a nonlinear least-squares spectral fitting procedure with line parameters from the HITRAN database. The ratio of the rate of the reaction of OC(34)S relative to OC(32)S was found to be 0.9783 ± 0.0062 ((34)ε = (-21.7 ± 6.2)). The KIE was also calculated using quantum chemistry and classical transition state theory; at 300 K, the isotopic fractionation was found to be (34)ε = -14.8. The OCS sink reaction with O((3)P) cannot explain the large fractionation in (34)S, over +73, indicated by remote sensing data. In addition, (34)ε in OCS photolysis and OH oxidation are not larger than 10, indicating that, on the basis of isotopic analysis, OCS is an acceptable source of background stratospheric sulfate aerosol.