In this paper, measurements of air pollutants made at a ground site near Fort McKay in the Athabasca oil sands region as part of a multi-platform campaign in the summer of 2013 are presented. The observations included measurements of selected volatile organic compounds (VOCs) by a gas chromatograph-ion trap mass spectrometer (GC-ITMS). This instrument observed a large, analytically unresolved hydrocarbon peak (with a retention index between 1100 and 1700) associated with intermediate-volatility organic compounds (IVOCs). However, the activities or processes that contribute to the release of these IVOCs in the oil sands region remain unclear. Principal component analysis (PCA) with varimax rotation was applied to elucidate major source types impacting the sampling site in the summer of 2013. The analysis included 28 variables, including concentrations of total odd nitrogen (NOy), carbon dioxide (CO2), methane (CH4), ammonia (NH3), carbon monoxide (CO), sulfur dioxide (SO2), total reduced-sulfur compounds (TRSs), speciated monoterpenes (including alpha- and beta-pinene and limonene), particle volume calculated from measured size distributions of particles less than 10 and 1 mu m in diameter (PM10-1 and PM1), particle-surface-bound polycyclic aromatic hydrocarbons (pPAHs), and aerosol mass spectrometer composition measurements, including refractory black carbon (rBC) and organic aerosol components. The PCA was complemented by bivariate polar plots showing the joint wind speed and direction dependence of air pollutant concentrations to illustrate the spatial distribution of sources in the area. Using the 95% cumulative percentage of variance criterion, 10 components were identified and categorized by source type. These included emissions by wet tailing ponds, vegetation, open pit mining operations, upgrader facilities, and surface dust. Three components correlated with IVOCs, with the largest associated with surface mining and likely caused by the unearthing and processing of raw bitumen.
Determination of the limiting nutrient of phytoplankton is critical to the lake eutrophication management. The average value of total nitrogen/total phosphorus (TN/TP) ratio is widely used to determine the limiting nutrient; while it suffers from the risk of the incorrect description of data and neglecting dynamics of the nutrient limitation. A probabilistic method was thereby proposed in this study to explore dynamics of nutrient limitation, including (a) indicator definition as the probability of TN/TP ratio failing in Redfield ratio line (PFR), indicating the possibility of TN limitation, to improve a probabilistic measure for the nutrient limitation; (b) Bayesian ANOVA analysis for posterior distributions of different treatments; and (c) dynamics determination as PFRs to show dynamics of nutrient limitation. Lake Xingyun in Southwestern China was taken as a case to explore the interannual and seasonal dynamics of the nutrient limitation. According to modeling results, we deducted that (a) for the interannual dynamics, the limiting nutrient shifted from TP to TN; and (b) for the seasonal dynamics, TN and TP were co-limiting. Deductions were further confirmed by the observed data. With the proposed probabilistic method, the co-limitation of TN and TP was identified for the seasonal dynamics; while using the average ratio solely denied the possibility of co-limitation. The current study also revealed that, due to neglecting the interannual and seasonal dynamics of nutrient limitation, the average ratio might mislead the eutrophication management strategy by recommending reducing TN and TP concentration together. The proposed probabilistic method demonstrated that TN was the limiting nutrient during the growing season of the phytoplankton in recent years and actions should focus on the TN concentration reduction. (C) 2017 Elsevier B.V. All rights reserved.
Methacrolein (MACR) is an abundant multifunctional carbonyl compound with highreactivity in the atmosphere. In this study, we investigated the hydroxyl radical initiatedoxidation of MACR at various NO/MACR ratios (0 to 4.04) and relative humidities (< 3% to80%) using a flow tube. Meanwhile, a box model based on the Master Chemical Mechanismwas performed to test our current understanding of the mechanism. In contrast to thereasonable predictions for hydroxyacetone production, the modeled yields of formaldehyde(HCHO) were twice higher than the experimental results. The discrepancy was ascribed tothe existence of unconsidered non-HCHO forming channels in the chemistry of CH3C(=CH2)OO., which account for approx. 50%. In addition, the production of hydroxyacetoneand HCHO were affected by water vapor as well as the initial NO/MACR ratio. The yields ofHCHO were higher under humid conditions than that under dry condition. The yields ofhydroxyacetone were higher under humid conditions at low-NOx level, while lower athigh-NOx level. The reasonable explanation for the lower hydroxyacetone yield underhumid conditions at high-NOx level is that water vapor promotes the production ofmethacrolein nitrate in the reaction of HOCH2C(CH3)(OO.)CHO with NO due to the peroxyradical-water complex formation, which was evidenced by calculational results. And theminimum equilibrium constant of this water complex formation was estimated to be1.89 × 10−18 cm3/molecule. These results provide new insights into the MACR oxidationmechanismand the effects of water vapor.
The magmatic-hydrothermal evolution of porphyry-style mineralization in the shallow crust that is linked to magmatic processes at depth has been extensively studied using bulk-sample isotopic analysis combined with relative timing constraints. However, a lack of evaluation of the fluid evolution process against an absolute time frame limits further understanding of the ore-forming process. Here, we quantify the fluid evolution process within an absolute time frame for the first time by integrating new in situ oxygen isotope data from the Qulong porphyry Cu-Mo deposit (Tibet) with existing fluid inclusion data and high-precision Re-Os dates of co-precipitated hydrothermal quartz and molybdenite, respectively. We demonstrate that vein quartz records primary oxygen isotopic compositions and reached oxygen isotope equilibrium with ore-forming fluids, and therefore is an archive of the isotopic composition and source of the ore-forming fluids. The delta O-18(quartz) and delta O-18(fluid) values, in absolute time, show periodic fluctuations that indicate the presence of three intermittent pulses of magmatic fluid flux, which have been balanced by meteoric water. As such, the flux of magmatic fluid during ore formation was pulsed, rather than being continuous. The overall highest delta O-18(fluid) in the first pulse of mineralization, with a gradual decrease to the second and third pulses, is suggestive of a progressive reduction in the magmatic component of the hydrothermal fluids and, by inference, the mineralizing potential of the hydrothermal fluids. This view is supported by a decrease in sulfide-bearing fluid inclusions and metal grade through time. Our findings favor multiple fluid-release events from a single cooling magmatic reservoir, although multiple fluid-melt recharge events remain a competitive alternative. An additional implication is that the magmatic reservoir may have a lifespan of hundreds of thousands of years, with fluid release events occurring over tens of thousands of years.
Aircraft-based measurements of methane (CH4) and other air pollutants in the Athabasca Oil Sands Region (AOSR) were made during a summer intensive field campaign between 13 August and 7 September 2013 in support of the Joint Canada-Alberta Implementation Plan for Oil Sands Monitoring. Chemical signatures were used to identify CH4 sources from tailings ponds (BTEX VOCs), open pit surface mines (NOy and r BC) and elevated plumes from bitumen upgrading facilities (SO2 and NOy). Emission rates of CH4 were determined for the five primary surface mining facilities in the region using two mass-balance methods. Emission rates from source categories within each facility were estimated when plumes from the sources were spatially separable. Tailings ponds accounted for 45% of total CH4 emissions measured from the major surface mining facilities in the region, while emissions from operations in the open pit mines accounted for +/- 50 %. The average open pit surface mining emission rates ranged from 1.2 to 2.8 t of CH4 h(-1) for different facilities in the AOSR. Amongst the 19 tailings ponds, Mildred Lake Settling Basin, the oldest pond in the region, was found to be responsible for the majority of tailings ponds emissions of CH4 (> 70 %). The sum of measured emission rates of CH4 from the five major facilities, 19.2 +/- 1.1 tCH(4) h(-1), was similar to a single mass-balance determination of CH4 from all major sources in the AOSR determined from a single flight downwind of the facilities, 23.7 +/- 3.7 tCH(4) h(-1). The measured hourly CH4 emission rate from all facilities in the AOSR is 48 +/- 8% higher than that extracted for 2013 from the Canadian Greenhouse Gas Reporting Program, a legislated facility-reported emissions inventory, converted to hourly units. The measured emissions correspond to an emissions rate of 0.17 +/- 0.01 TgCH(4) yr(-1) if the emissions are assumed as temporally constant, which is an uncertain assumption. The emission rates reported here are relevant for the summer season. In the future, effort should be devoted to measurements in different seasons to further our understanding of the seasonal parameters impacting fugitive emissions of CH4 and to allow for better estimates of annual emissions and year-to-year variability.
We study the effects of infrared radiation on a two-dimensional Bardeen–Cooper–Schrieffer superconductor coupled with a normal metal substrate through a tunneling barrier. The phase transition is analyzed by inspecting the stability of the system against perturbations of pairing potentials. We find an oscillating gap phase with a frequency not directly related to the radiation frequency, but instead resulting from the asymmetry of electron density of states of the system as well as the tunneling amplitude. When such a superconductor is in contact with another superconductor, gives rise to an unusual alternating Josephson current .
The North China Plain has been identified as a significant hotspot of ammonia (NH3) due to extensive agricultural activities. Satellite observations suggest a significant increase of about 30% in tropospheric gas-phase NH3 concentrations in this area during 2008-2016. However, the estimated NH3 emissions decreased slightly by 7% because of changes in Chinese agricultural practices, i.e., the transition in fertilizer types from ammonium carbonate fertilizer to urea, and in the livestock rearing system from free-range to intensive farming. We note that the emissions of sulfur dioxide (SO2) have rapidly declined by about 60% over the recent few years. By integrating measurements from ground and satellite, a long-term anthropogenic NH3 emission inventory, and chemical transport model simulations, we find that this large SO2 emission reduction is responsible for the NH3 increase over the North China Plain. The simulations for the period 2008-2016 demonstrate that the annual average sulfate concentrations decreased by about 50 %, which significantly weakens the formation of ammonium sulfate and in- creases the average proportions of gas-phase NH3 within the total NH3 column concentrations from 26% (2008) to 37% (2016). By fixing SO2 emissions of 2008 in those multi-year simulations, the increasing trend of the tropospheric NH3 concentrations is not observed. Both the decreases in sulfate and increases in NH3 concentrations show highest values in summer, possibly because the formation of sulfate aerosols is more sensitive to SO2 emission reductions in summer than in other seasons. Besides, the changes in NOx emissions and meteorological conditions both decreased the NH3 column concentrations by about 3% in the study period. Our simulations suggest that the moderate reduction in NOx emissions (16 %) favors the formation of particulate nitrate by elevating ozone concentrations in the lower troposphere.