Photo-initiated ion formation from octaethyl-porphyrin and its zinc chelate as a model for electron transfer in reaction centers

Ion formation from the reaction of triplet (T) and ground state (P) octaethyl-porphyrin (OEP) and zinc octaethyl porphyrin (ZnOEP) and the corresponding cross-reactions have been measured in dry acetonitrile. A uniquely sensitive and fast conductance apparatus and a pulsed dye laser allowed the measurements to be made at the necessarily very low concentrations of T. The hemogeneous reaction of T (ZnOEP) and P (ZnOEP) occurs with rat constant k(1) = 2.0 x 10(8) M(-1)s(-1) and an ion yield of 67%. The similar homogeneous reaction of OEP has k(2) = 1.3 x 10(8)M(-1)s(-1) but an ion yield of only 3%. The cross-reaction of T (OEP) with P (ZnOEP) has k(3) = 1.5 x 10(8) M(-1)s(-1) and an ion yield of 27%, while the inverse cross-reaction of T (ZnOEP) with P (OEP) has k(4) = 3 x 10(8) M(-1)s(-1) and an ion yield of 20%. Thus, the rate constants are only slightly affected but the yields are sensitive to the porphyrin. The possible formation of the heterogeneous ions ZnOEP+ + OEP-, thermodynamically favored by 0.3 V over the homogeneous ions, has little influence on the observed yields. The data are explained by electron transfer and Coulomb field-electon spin-controlled escape of the initial ion-pair

Evaluation of a commercially available rapid urinary porphobilinogen test

Background: Demonstration of substantially increased urinary excretion of porphobilinogen is the cornerstone of diagnosing acute porphyria crisis. Because porphobilinogen testing is not implemented on clinical chemistry analysers, respective analyses are available in rather few clinical laboratories. The aim of this study was to critically describe and to evaluate a semi-quantitative rapid test for urinary porphobilinogen determination which is commercially available and recommended by the American Porphyria Foundation. Methods: Urinary samples from patients with acute intermittent porphyria and control samples were analysed and the semi-quantitative results were compared with the results obtained by a manual quantitative spectrophotometric method. Results: In all 32 samples studied, acceptable agreement between the results of the rapid test and the quantitative test was observed. Handling of the test was found to be convenient. Conclusions: The assay was found to be reliable and has the potential to increase the availability of porphobilinogen testing in the field

Source-receptor relationships between East Asian sulfur dioxide emissions and Northern Hemisphere sulfate concentrations

International audienceWe analyze the effect of varying East Asian (EA) sulfur emissions on sulfate concentrations in the Northern Hemisphere, using a global coupled oxidant-aerosol model (MOZART-2). We conduct a base and five sensitivity simulations, in which sulfur emissions from each continent are tagged, to establish the source-receptor (S-R) relationship between EA sulfur emissions and sulfate concentrations over source and downwind regions. We find that from west to east across the North Pacific, EA sulfate contributes approximately 80%?20% of sulfate at the surface, but at least 50% at 500 hPa. In addition, EA SO2 emissions account for approximately 30%?50% and 10%?20% of North American background sulfate over the western and eastern US, respectively. The contribution of EA sulfate to the western US at the surface is highest in MAM and JJA, but is lowest in DJF. Reducing EA SO2 emissions will significantly decrease the spatial extent of the EA sulfate influence over the North Pacific both at the surface and at 500 mb in all seasons, but the extent of influence is insensitive to emission increases, particularly in DJF and JJA. We find that EA sulfate concentrations over most downwind regions respond nearly linearly to changes in EA SO2 emissions, but sulfate concentrations over the EA source region increase more slowly than SO2 emissions, particularly at the surface and in winter, due to limited availability of oxidants (mostly H2O2). We find that similar estimates of the S-R relationship for trans-Pacific transport of EA sulfate would be obtained using either sensitivity or tagging techniques. Our findings suggest that future changes in EA sulfur emissions may cause little change in the sulfate induced health impact over downwind continents but SO2 emission reductions may significantly reduce the sulfate related climate cooling over the North Pacific and the United States

Origin and radiative forcing of black carbon transported to the Himalayas and Tibetan Plateau

The remote and high elevation regions of central Asia are influenced by black carbon (BC) emissions from a variety of locations. BC deposition contributes to melting of glaciers and questions exist, of both scientific and policy interest, as to the origin of the BC reaching the glaciers. We use the adjoint of the GEOS-Chem model to identify the location from which BC arriving at a variety of locations in the Himalayas and Tibetan Plateau originates. We then calculate its direct and snow-albedo radiative forcing. We analyze the seasonal variation in the origin of BC using an adjoint sensitivity analysis, which provides a detailed map of the location of emissions that directly contribute to black carbon concentrations at receptor locations. We find that emissions from northern India and central China contribute the majority of BC to the Himalayas, although the precise location varies with season. The Tibetan Plateau receives most BC from western and central China, as well as from India, Nepal, the Middle East, Pakistan and other countries. The magnitude of contribution from each region varies with season and receptor location. We find that sources as varied as African biomass burning and Middle Eastern fossil fuel combustion can significantly contribute to the BC reaching the Himalayas and Tibetan Plateau. We compute radiative forcing in the snow-covered regions and find the forcing due to the BC induced snow-albedo effect to vary from 5–15 W m<sup>−2</sup> within the region, an order of magnitude larger than radiative forcing due to the direct effect, and with significant seasonal variation in the northern Tibetan Plateau. Radiative forcing from reduced snow albedo likely accelerates glacier melting. Our analysis may help inform mitigation efforts to slow the rate of glacial melt by identifying regions that make the largest contributions to BC deposition in the Himalayas and Tibetan Plateau

The impact of China's vehicle emissions on regional air quality in 2000 and 2020: a scenario analysis

The number of vehicles in China has been increasing rapidly. We evaluate the impact of current and possible future vehicle emissions from China on Asian air quality. We modify the Regional Emission Inventory in Asia (REAS) for China's road transport sector in 2000 using updated Chinese data for the number of vehicles, annual mileage, and emission factors. We develop two scenarios for 2020: a scenario where emission factors remain the same as they were in 2000 (No-Policy, NoPol), and a scenario where Euro 3 vehicle emission standards are applied to all vehicles (except motorcycles and rural vehicles). The Euro 3 scenario is an approximation of what may be the case in 2020 as, starting in 2008, all new vehicles in China (except motorcycles) were required to meet the Euro 3 emission standards. Using the Weather Research and Forecasting model coupled with Chemistry (WRF/Chem), we examine the regional air quality response to China's vehicle emissions in 2000 and in 2020 for the NoPol and Euro 3 scenarios. We evaluate the 2000 model results with observations in Japan, China, Korea, and Russia. Under NoPol in 2020, emissions of carbon monoxide (CO), nitrogen oxides (NO<sub>x</sub>), non-methane volatile organic compounds (NMVOCs), black carbon (BC), and organic carbon (OC) from China's vehicles more than double compared to the 2000 baseline. If all vehicles meet the Euro 3 regulations in 2020, however, these emissions are reduced by more than 50% relative to NoPol. The implementation of stringent vehicle emission standards leads to a large, simultaneous reduction of the surface ozone (O<sub>3</sub>) mixing ratios and particulate matter (PM<sub>2.5</sub>) concentrations. In the Euro 3 scenario, surface O<sub>3</sub> is reduced by more than 10 ppbv and surface PM<sub>2.5</sub> is reduced by more than 10 μg m<sup>−3</sup> relative to NoPol in Northeast China in all seasons. In spring, surface O<sub>3</sub> mixing ratios and PM<sub>2.5</sub> concentrations in neighboring countries are also reduced by more than 3 ppbv and 1 μg m<sup>−3</sup>, respectively. We find that effective regulation of China's road transport sector will be of significant benefit for air quality both within China and across East Asia as well

Analysis of transpacific transport of black carbon during HIPPO-3: implications for black carbon aging

Long-range transport of black carbon (BC) is a growing concern as a result of the efficiency of BC in warming the climate and its adverse impact on human health. We study transpacific transport of BC during HIPPO-3 using a combination of inverse modeling and sensitivity analysis. We use the GEOS-Chem chemical transport model and its adjoint to constrain Asian BC emissions and estimate the source of BC over the North Pacific. We find that different sources of BC dominate the transport to the North Pacific during the southbound (29 March 2010) and northbound (13 April 2010) measurements in HIPPO-3. While biomass burning in Southeast Asia (SE) contributes about 60% of BC in March, more than 90% of BC comes from fossil fuel and biofuel combustion in East Asia (EA) during the April mission. GEOS-Chem simulations generally resolve the spatial and temporal variation of BC concentrations over the North Pacific, but are unable to reproduce the low and high tails of the observed BC distribution. We find that the optimized BC emissions derived from inverse modeling fail to improve model simulations significantly. This failure indicates that uncertainties in BC removal as well as transport, rather than in emissions, account for the major biases in GEOS-Chem simulations of BC over the North Pacific. The aging process, transforming BC from hydrophobic into hydrophilic form, is one of the key factors controlling wet scavenging and remote concentrations of BC. Sensitivity tests on BC aging (ignoring uncertainties of other factors controlling BC long range transport) suggest that in order to fit HIPPO-3 observations, the aging timescale of anthropogenic BC from EA may be several hours (faster than assumed in most global models), while the aging process of biomass burning BC from SE may occur much slower, with a timescale of a few days. To evaluate the effects of BC aging and wet deposition on transpacific transport of BC, we develop an idealized model of BC transport. We find that the mid-latitude air masses sampled during HIPPO-3 may have experienced a series of precipitation events, particularly near the EA and SE source region. Transpacific transport of BC is sensitive to BC aging when the aging rate is fast; this sensitivity peaks when the aging timescale is in the range of 1–1.5 d. Our findings indicate that BC aging close to the source must be simulated accurately at a process level in order to simulate better the global abundance and climate forcing of BC

Environmental Consequences of Potential Strategies for China to Prepare for Natural Gas Import Disruptions

Worldwide efforts to switch away from coal have increased the reliance on natural gas imports for countries with inadequate domestic production. In preparing for potential gas import disruptions, there have been limited attempts to quantify the environmental and human health impacts of different options and incorporate them into decision-making. Here, we analyze the air pollution, human health, carbon emissions, and water consumption impacts under a set of planning strategies to prepare for potentially fully disrupted natural gas imports in China. We find that, with China’s current natural gas storage capacity, compensating for natural gas import disruptions using domestic fossil fuels (with the current average combustion technology) could lead up to 23,300 (95% CI: 22,100–24,500) excess premature deaths from air pollution, along with increased carbon emissions and aggravated water stress. Improving energy efficiency, more progressive electrification and decarbonization, cleaner fossil combustion, and expanding natural gas storage capacity can significantly reduce the number of excess premature deaths and may offer opportunities to reduce negative carbon and water impacts simultaneously. Our results highlight the importance for China to increase the domestic storage capacity in the short term, and more importantly, to promote a clean energy transition to avoid potentially substantial environmental consequences under intensifying geopolitical uncertainties in China. Therefore, mitigating potential negative environmental impacts related to insecure natural gas supply provides additional incentives for China to facilitate a clean and efficient energy system transition