Isotopomer analysis of production and consumption mechanisms of N2O and CH4 in an advanced wastewater treatment system

Wastewater treatment processes are believed to be anthropogenic sources of nitrous oxide (N(2)O) and methane (CH(4)). However, few studies have examined the mechanisms and controlling factors in production of these greenhouse gases in complex bacterial systems. To elucidate production and consumption mechanisms of N(2)O and CH(4) in microbial consortia during wastewater treatment and to characterize human waste sources, we measured their concentrations and isotopomer ratios (elemental isotope ratios and site-specific N isotope ratios in asymmetric molecules of NNO) in water and gas samples collected by an advanced treatment system in Tokyo. Although the estimated emissions of N(2)O and CH(4) from the system were found to be lower than those from the typical treatment systems reported before, water in biological reaction tanks was supersaturated with both gases. The concentration of N(2)O, produced mainly by nitrifier-denitrification as indicated by isotopomer ratios, was highest in the oxic tank (ca. 4000% saturation). The dissolved CH(4) concentration was highest in in-flow water (ca. 3000% saturation). It decreased gradually during treatment. Its carbon isotope ratio indicated that the decrease resulted from bacterial CH(4) oxidation and that microbial CH(4) production can occur in anaerobic and settling tanks.     

Methane, carbon dioxide, and nitrous oxide emissions from septic tank systems

Emissions of CH4, CO2, and N2O from conventional septic tank systems are known to occur, but there is a dearth of information as to the extent. Mass emission rates of CH4, CO2, and N2O, as measured with a modified flux chamber approach in eight septic tank systems, were determined to be 11, 33.3, and 0.005 g capita(-1) day(-1), respectively, in this research. Existing greenhouse gas (GHG) emission models based on BOD (biochemical oxygen demand) loading have estimated methane emissions to be as high as 27.1 g CH4 capita(-1) day(-1), more than twice the value measured in our study, and concluded that septic tanks are potentially significant sources of GHGs due to the large number of systems currently in use. Based on the measured CH4 emission value, a revised CH4 conversion factor of 0.22 (compared to 0.5) for use in the emissions models is suggested. Emission rates of CH4, CO2, and N2O were also determined from measurements of gas concentrations and flow rates in the septic vent system and were found to be 10.7, 335, and 0.2 g capita(-1)day(-1), respectively. The excellent agreement in the CH4 emission rates between the flux chamber and the vent values indicates the dominant CH4 source is the septic tank.     

Measurement of N2, N2O, NO, and CO2 emissions from soil with the gas-flow-soil-core technique

Here we describe a newly designed system with three stand-alone working incubation vessels for simultaneous measurements of N(2), N(2)O, NO, and CO(2) emissions from soil. Due to the use of a new micro thermal conductivity detector and the redesign of vessels and gas sampling a so-far unmatched sensitivity (0.23 μg N(2)-N h(-1) kg(-1) ds or 8.1 μg N(2)-N m(-2) h(-1)) for detecting N(2) gas emissions and repeatability of experiments could be achieved. We further tested different incubation methods to improve the quantification of N(2) emission via denitrification following the initialization of soil anaerobiosis. The best results with regard to the establishment of a full N balance (i.e., the changes in mineral N content being offset by simultaneous emission of N gases) were obtained when the anaerobic soil incubation at 25 °C was preceded by soil gas exchange under aerobic conditions at a lower incubation temperature. The ratios of N and C gas emission changed very dynamically following the initialization of anaerobiosis. For soil NO(3)(-) contents of 50 mg N kg(-1) dry soil (ds) and dissolved organic carbon (DOC) concentrations of approximately 300 mg C kg(-1) ds, the cumulative emissions of N(2), N(2)O, and NO were 24.3 ± 0.1, 12.6 ± 0.4, and 10.1 ± 0.3 mg N kg(-1) ds, respectively. Thus, N gas emissions accounted (on average) for 46.2% (N(2)), 24.0% (N(2)O), and 19.2% (NO) of the observed changes in soil NO(3)(-). The maximum N(2) emission reached 1200 μg N h(-1) kg(-1) ds, whereas the peak emissions of N(2)O and NO were lower by a factor of 2-3. The overall N(2):N(2)O and NO:N(2)O molar ratios were 1.6-10.0 and 1.6-2.3, respectively. The measurement system provides a reliable tool for studying denitrification in soil because it offers insights into the dynamics and magnitude of gaseous N emissions due to denitrification under various incubation conditions.     

Thermodynamic stability, spectroscopic identification, and gas storage capacity of CO2-CH4-N2 mixture gas hydrates: implications for landfill gas hydrates

Landfill gas (LFG), which is primarily composed of CH(4), CO(2), and N(2), is produced from the anaerobic digestion of organic materials. To investigate the feasibility of the storage and transportation of LFG via the formation of hydrate, we observed the phase equilibrium behavior of CO(2)-CH(4)-N(2) mixture hydrates. When the specific molar ratio of CO(2)/CH(4) was 40/55, the equilibrium dissociation pressures were gradually shifted to higher pressures and lower temperatures as the mole fraction of N(2) increased. X-ray diffraction revealed that the CO(2)-CH(4)-N(2) mixture hydrate prepared from the CO(2)/CH(4)/N(2) (40/55/5) gas mixture formed a structure I clathrate hydrate. A combination of Raman and solid-state (13)C NMR measurements provided detailed information regarding the cage occupancy of gas molecules trapped in the hydrate frameworks. The gas storage capacity of LFG hydrates was estimated from the experimental results for the hydrate formations under two-phase equilibrium conditions. We also confirmed that trace amounts of nonmethane organic compounds do not affect the cage occupancy of gas molecules or the thermodynamic stability of LFG hydrates.     

On the sources of methane to the los angeles atmosphere

We use historical and new atmospheric trace gas observations to refine the estimated source of methane (CH(4)) emitted into California's South Coast Air Basin (the larger Los Angeles metropolitan region). Referenced to the California Air Resources Board (CARB) CO emissions inventory, total CH(4) emissions are 0.44 ± 0.15 Tg each year. To investigate the possible contribution of fossil fuel emissions, we use ambient air observations of methane (CH(4)), ethane (C(2)H(6)), and carbon monoxide (CO), together with measured C(2)H(6) to CH(4) enhancement ratios in the Los Angeles natural gas supply. The observed atmospheric C(2)H(6) to CH(4) ratio during the ARCTAS (2008) and CalNex (2010) aircraft campaigns is similar to the ratio of these gases in the natural gas supplied to the basin during both these campaigns. Thus, at the upper limit (assuming that the only major source of atmospheric C(2)H(6) is fugitive emissions from the natural gas infrastructure) these data are consistent with the attribution of most (0.39 ± 0.15 Tg yr(-1)) of the excess CH(4) in the basin to uncombusted losses from the natural gas system (approximately 2.5-6% of natural gas delivered to basin customers). However, there are other sources of C(2)H(6) in the region. In particular, emissions of C(2)H(6) (and CH(4)) from natural gas seeps as well as those associated with petroleum production, both of which are poorly known, will reduce the inferred contribution of the natural gas infrastructure to the total CH(4) emissions, potentially significantly. This study highlights both the value and challenges associated with the use of ethane as a tracer for fugitive emissions from the natural gas production and distribution system.     

Real-time measurements of SO2, H2CO, and CH4 emissions from in-use curbside passenger buses in New York City using a chase vehicle

The Aerodyne Mobile Laboratory "chased" in-use curbside passenger buses operated by various operators in New York City. With the cooperation of New York State's Metropolitan Transit Authority, the relationships between the emissions of the several gas-phase species and particulate loadings were investigated across several bus technologies, bus types, and fuels (diesel, ultralow sulfur diesel, and compressed natural gas, CNG). The CNG buses followed did not employ an oxidation catalyst. The buses characterized were not prescreened in any fashion and were measured while deployed on their normal in-service routes. This paper focuses on the fuel-based mass emissions of SO2, H2CO, and CH4, measured using tunable infrared laser differential absorption spectroscopy. Sulfur dioxide emissions from buses known to be burning ultralow sulfur diesel (<30 ppm(m) S) were 16 times lower than those from buses burning normal commercial diesel fuel, nominally less than 300 ppm(m) sulfur. Emissions of formaldehyde and methane from in-use CNG buses were approximately 15 times greater than those from diesel powered buses.     

Temperature effects on the removal of potential HFC replacements, CF3CH2CH2OH and CF3(CH2)2CH2OH, initiated by OH radicals

The gas-phase kinetic coefficients of OH radicals with two primary fluorinated alcohols, CF(3)CH(2)CH(2)OH (k(1)) and CF(3)(CH(2))(2)CH(2)OH (k(2)), potential replacements of hydrofluorocarbons (HFCs), are reported here as a function of temperature (T = 263-358 K) for the first time. k(1) and k(2) (together referred as k(i)) were measured under pseudo-first-order conditions with respect to the initial OH concentration using the pulsed laser photolysis/laser induced fluorescence technique. The observed temperature dependence of k(i) (in cm(3) molecule(-1) s(-1)) is described by the following Arrhenius expressions: k(1)(T) = (2.82 ± 1.28) × 10(-12) exp{-(302 ± 139)/T} cm(3) molecule(-1) s(-1) and k(2)(T) = (1.20 ± 0.73) × 10(-11) exp{-(425 ± 188)/T} cm(3) molecule(-1) s(-1).The uncertainties in the Arrhenius parameters are at a 95% confidence level (± 2σ). Uncertainties in k(i)(T) include both statistical and systematic errors. Activation energies were (2.5 ± 1.2) kJ/mol and (3.6 ± 1.6) kJ/mol for the OH-reaction with CF(3)CH(2)CH(2)OH and CF(3)(CH(2))(2)CH(2)OH, respectively. The global lifetime (τ) at 275 K for CF(3)CH(2)CH(2)OH and CF(3)(CH(2))(2)CH(2)OH due to the OH-reaction was estimated to be ca. 2 weeks and 5 days, respectively. The reported Arrhenius parameters can be used in 3D models that take into account the geographical region and season of emissions for estimating a matrix of instantaneous lifetimes. As a consequence of the substitution of the -CH(3) group by a -CH(2)OH group in HFCs, such as CF(3)CH(2)CH(3) and CF(3)(CH(2))(2)CH(3), the tropospheric lifetime with respect to the OH reaction is significantly shorter and, since their radiative forcing is similar, global warming potentials of CF(3)CH(2)CH(2)OH and CF(3)(CH(2))(2)CH(2)OH are negligible. Therefore, CF(3)CH(2)CH(2)OH and CF(3)(CH(2))(2)CH(2)OH seem to be suitable alternatives to HFCs.     

Potential restrictions for CO2 sequestration sites due to shale and tight gas production

Carbon capture and geological sequestration is the only available technology that both allows continued use of fossil fuels in the power sector and reduces significantly the associated CO(2) emissions. Geological sequestration requires a deep permeable geological formation into which captured CO(2)can be injected, and an overlying impermeable formation, called a caprock, that keeps the buoyant CO(2) within the injection formation. Shale formations typically have very low permeability and are considered to be good caprock formations. Production of natural gas from shale and other tight formations involves fracturing the shale with the explicit objective to greatly increase the permeability of the shale. As such, shale gas production is in direct conflict with the use of shale formations as a caprock barrier to CO(2) migration. We have examined the locations in the United States where deep saline aquifers, suitable for CO(2) sequestration, exist, as well as the locations of gas production from shale and other tight formations. While estimated sequestration capacity for CO(2) sequestration in deep saline aquifers is large, up to 80% of that capacity has areal overlap with potential shale-gas production regions and, therefore, could be adversely affected by shale and tight gas production. Analysis of stationary sources of CO(2) shows a similar effect: about two-thirds of the total emissions from these sources are located within 20 miles of a deep saline aquifer, but shale and tight gas production could affect up to 85% of these sources. These analyses indicate that colocation of deep saline aquifers with shale and tight gas production could significantly affect the sequestration capacity for CCS operations. This suggests that a more comprehensive management strategy for subsurface resource utilization should be developed.     

Technology limits for reducing EU transport sector CO2 emissions

Using a new data set describing the techno-economic characteristics of current and projected future transport technologies and a synthesis of existing transport demand models, lifecycle CO(2) emissions from 27 EU countries (EU27) were estimated in the absence and presence of new policy interventions to 2050. Future CO(2) emissions are strongly dependent on geographical scope and economic growth assumptions, and to a lesser extent on uncertainties in technology characteristics, but in the absence of new policy intervention they continue to rise from present-day values in all three scenarios examined. Consequently, EU27 emissions goals, which may require a 60% decrease in transport sector greenhouse gas emissions from year-1990 values by 2050, will be difficult to meet. This is even the case under widespread adoption of the most promising technologies for all modes, due primarily to limitations in biofuel production capacity and a lack of technologies that would drastically reduce CO(2) emissions from heavy trucks and intercontinental aviation.     

Long-Term Energy and Climate Implications of Carbon Capture and Storage Deployment Strategies in the US Coal-Fired Electricity Fleet

To understand the long-term energy and climate implications of different implementation strategies for carbon capture and storage (CCS) in the US coal-fired electricity fleet, we integrate three analytical elements: scenario projection of energy supply systems, temporally explicit life cycle modeling, and time-dependent calculation of radiative forcing. Assuming continued large-scale use of coal for electricity generation, we find that aggressive implementation of CCS could reduce cumulative greenhouse gas emissions (CO(2), CH(4), and N(2)O) from the US coal-fired power fleet through 2100 by 37-58%. Cumulative radiative forcing through 2100 would be reduced by only 24-46%, due to the front-loaded time profile of the emissions and the long atmospheric residence time of CO(2). The efficiency of energy conversion and carbon capture technologies strongly affects the amount of primary energy used but has little effect on greenhouse gas emissions or radiative forcing. Delaying implementation of CCS deployment significantly increases long-term radiative forcing. This study highlights the time-dynamic nature of potential climate benefits and energy costs of different CCS deployment pathways and identifies opportunities and constraints of successful CCS implementation.     

Biodiesel production in a semiarid environment: a life cycle assessment approach

While the use of biodiesel appears to be a promising alternative to petroleum fuel, the replacement of fossil fuel by biofuel may not bring about the intended climate cooling because of the increased soil N2O emissions due to N-fertilizer applications. Using a life cycle assessment approach, we assessed the influence of soil nitrous oxide (N2O) emissions on the life cycle global warming potential of the production and combustion of biodiesel from canola oil produced in a semiarid climate. Utilizing locally measured soil N2O emissions, rather than the Intergovernmental Panel on Climate Change (IPCC) default values, decreased greenhouse gas (GHG) emissions from the production and combustion of 1 GJ biodiesel from 63 to 37 carbon dioxide equivalents (CO2-e)/GJ. GHG were 1.1 to 2.1 times lower than those from petroleum or petroleum-based diesel depending on which soil N2O emission factors were included in the analysis. The advantages of utilizing biodiesel rapidly declined when blended with petroleum diesel. Mitigation strategies that decrease emissions from the production and application of N fertilizers may further decrease the life cycle GHG emissions in the production and combustion of biodiesel.     

Conversion of CHF3 to CH2=CF2 via reaction with CH4 and CaBr2

Reaction of CHF3 and CH4 over CaBr2 was investigated at 400-900 degrees C as a potential route for transforming the highly potent greenhouse gas, CHF3, into the valuable product CH2=CF2. The homogeneous reaction of CHF3 with CH4 was also studied to assist in understanding the chemistries involved. Compared to the gas phase reaction, the addition of CaBr2 as a reactant increases the conversion of CHF3 and CH4 significantly at low temperatures while to a lesser extent at higher temperatures. In the absence of CaBr2, besides the target product, CH2=CF2, a large amount of C2F4 forms. On addition of CaBr2, the rate of formation of C2F4 drops dramatically to near zero, while the rate of formation of CH2=CF2 increases considerably at temperatures below 880 degrees C. Experimental and theoretical studies suggest that CHF3 strongly interacts with CaBr2, resulting in the fluorination of CaBr2 to CaF2, the release of active Br species results in the selective formation of CBrF3. The subsequent reactions involving Br, methane, and CBrF3 play a major role in the observed enhanced yield of CH2=CF2.     

Calculator tool for determining greenhouse gas emissions for biosolids processing and end use

A greenhouse gas (GHG) calculator tool (Biosolids Emissions Assessment Model, BEAM) was developed for the Canadian Council of Ministers of the Environment to allow municipalities to estimate GHG emissions from biosolids management. The tool was developed using data from peer reviewed literature and municipalities. GHG emissions from biosolids processing through final end use/disposal were modeled. Emissions from nine existing programs in Canada were estimated using the model. The program that involved dewatering followed by combustion resulted in the highest GHG emissions (Mg CO(2)e 100 Mg(-1) biosolids (dry wt.). The programs that had digestion followed by land application resulted in the lowest emissions (-26 and -23 Mg CO(2)e 100 Mg(-1) biosolids (dry wt.). Transportation had relatively minor effects on overall emissions. The greatest areas of uncertainty in the model include N(2)O emissions from land application and biosolids processing. The model suggests that targeted use of biosolids and optimizing processes to avoid CH(4) and N(2)O emissions can result in significant GHG savings.     

Growth and metabolic activity of Shewanella putrefaciens maintained under different CO2 and O2 concentrations

Growth, trimethylamine (TMA), off-odour and biogenic amine production by a strain of Shewanella putrefaciens isolated from spoiled hake (Merlucius merluccius L.) and cultured in a model system, were tested under four different gas compositions (60% CO2/40% O2, 60% CO2/15% O2/25% N2, 40% CO2/60% O2, 40% CO2/40% O2/20% N2) and under air. After 3 weeks of incubation, the control (air) batch showed the highest microbial counts (> 9 log cfu/ml) and TMA concentrations (45 mg N-TMA/100 ml), and strong putrid off-odours were detected from day 15. High amounts of putrescine and cadaverine were produced in this batch, but histamine increased only slightly. Batches under controlled atmospheres showed reduced growth, TMA, off-odour and biogenic amine production. The 40% CO2/60% O2 mixture had the strongest inhibitory effect on bacterial growth, while the 60% CO2/15% O2/25% N2 mixture was less effective. Putrescine and histamine production was lowest in S. putrefaciens under the 40% CO2/60% O2 mixture. However, the level of histamine in S. putrefaciens was higher under 40% CO2/40% O2/20% N2 than when the bacteria was incubated in air. Under the gas mixtures, there was a similar decrease in the production of cadaverine and agmatine by S. putrefaciens, irrespective of the gas concentrations. The production of 2-phenylethylamine appeared to be inhibited under any atmospheric condition.     

Influence of the concentration of CO2 and SO2 on the absorption of CO2 by a lithium orthosilicate-based absorbent

A novel, high temperature solid absorbent based on lithium orthosilicate (Li(4)SiO(4)) has shown promise for postcombustion CO(2) capture. Previous studies utilizing a clean, synthetic flue gas have shown that the absorbent has a high CO(2) capacity, >25 wt %, along with high absorption rates, lower heat of absorption and lower regeneration temperature than other solids such as calcium oxide. The current effort was aimed at evaluating the Li(4)SiO(4) based absorbent in the presence of contaminants found in typical flue gas, specifically SO(2), by cyclic exposure to gas mixtures containing CO(2), H(2)O (up to 25 vol. %), and SO(2) (up to 0.95 vol. %). In the absence of SO(2), a stable CO(2) capacity of ～ 25 wt % over 25 cycles at 550 °C was achieved. The presence of SO(2), even at concentrations as low as 0.002 vol. %, resulted in an irreversible reaction with the absorbent and a decrease in CO(2) capacity. Analysis of SO(2)-exposed samples revealed that the absorbent reacted chemically and irreversibly with SO(2) at 550 °C forming Li(2)SO(4). Thus, industrial application would require desulfurization of flue gas prior to contacting the absorbent. Reactivity with SO(2) is not unique to the lithium orthosilicate material, so similar steps would be required for other absorbents that chemically react with SO(2).     

Methane emissions from vehicles

Methane (CH4) is an important greenhouse gas emitted by vehicles. We report results of a laboratory study of methane emissions using a standard driving cycle for 30 different cars and trucks (1995-1999 model years) from four different manufacturers. We recommend the use of an average emission factor for the U.S. on-road vehicle fleet of (g of CH/g of CO2) = (15 +/- 4) x 10(-5) and estimate that the global vehicle fleet emits 0.45 +/- 0.12 Tg of CH4 yr(-1) (0.34 +/- 0.09 Tg of C yr(-1)), which represents < 0.2% of anthropogenic CH4 emissions. This estimate includes the effects of vehicle aging, cold start, and hot running emissions. The contribution of CH4 emissions from vehicles to radiative forcing of climate change is 0.3-0.4% of that of CO2 emissions from vehicles. The environmental impact of CH4 emissions from vehicles is negligible and is likely to remain so for the foreseeable future.     

Atmospheric chemistry of N-methyl perfluorobutane sulfonamidoethanol, C4F9SO2N(CH3)CH2CH2OH: kinetics and mechanism of reaction with OH

Relative rate methods were used to measure the gas-phase reaction of N-methyl perfluorobutane sulfonamidoethanol (NMeFBSE) with OH radicals, giving k(OH + NMeFBSE) = (5.8 +/- 0.8) x 10(-12) cm3 molecule(-1) s(-1) in 750 Torr of air diluent at 296 K. The atmospheric lifetime of NMeFBSE is determined by reaction with OH radicals and is approximately 2 days. Degradation products were identified by in situ FTIR spectroscopy and offline GC-MS and LC-MS/MS analysis. The primary carbonyl product C4F9SO2N(CH3)CH2CHO, N-methyl perfluorobutane sulfonamide (C4F9SO2NH(CH3)), perfluorobutanoic acid (C3F7C(O)OH), perfluoropropanoic acid (C2F5C(O)OH), trifluoroacetic acid (CF3C(O)OH), carbonyl fluoride (COF2), and perfluorobutane sulfonic acid (C4F9SO3H) were identified as products. A mechanism involving the addition of OH to the sulfone double bond was proposed to explain the production of perfluorobutane sulfonic acid and perfluorinated carboxylic acids in yields of 1 and 10%, respectively. The gas-phase N-dealkylation product, N-methyl perfluorobutane sulfonamide (NMeFBSA), has an atmospheric lifetime (>20 days) which is much longer than that of the parent compound, NMeFBSE. Accordingly,the production of NMeFBSA exposes a mechanism by which NMeFBSE may contribute to the burden of perfluorinated contamination in remote locations despite its relatively short atmospheric lifetime. Using the atmospheric fate of NMeFBSE as a guide, it appears that anthropogenic production of N-methyl perfluorooctane sulfonamidoethanol (NMeFOSE) contributes to the ubiquity of perfluoroalkyl sulfonate and carboxylate compounds in the environment.     

Nitrous oxide fluxes in three experimental boreal forest reservoirs

Global atmospheric concentrations of nitrous oxide (N2O), a powerful greenhouse gas, continue to increase. While many sources and sinks have been identified, there is little known about how existing and newly constructed reservoirs, such as those created for hydroelectric production, impact current atmospheric N2O concentrations. We hypothesized that N2O fluxes to the atmosphere would increase because enhanced nutrient availability and increased soil respiration following the flooding of soils during reservoir creation would favor denitrification. Furthermore, we hypothesized that emissions would be linked to the amount of organic carbon contained in the flooded landscape. These hypotheses were tested by creating three experimental reservoirs over boreal upland subcatchments that ranged in the amount of organic carbon stored in soils and vegetation. Diffusive surface N2O fluxes within each reservoir were estimated using surface water concentrations of N2O and the thin boundary layer method. Surface fluxes ranged from -1.0 to -3.5 microg N2O m(-2) d(-1), and water column N2O concentrations indicated that contrary to expectations, the reservoirs were acting as slight sinks for atmospheric N2O. This net consumption of N2O was likely related to an excess of labile carbon and low concentrations of oxygen (O2) and nitrate (NO3-) in the flooded soils. Therefore, it is postulated that reservoir creation by flooding boreal soils will likely have little or no net effect of adding additional N2O to the current greenhouse gas (GHG) atmospheric burden, at least over the short term.     

Life-cycle nitrogen trifluoride emissions from photovoltaics

Amorphous- and nanocrystalline-silicon thin-film photovoltaic modules are made in high-throughput manufacturing lines that necessitate quickly cleaning the reactor. Using NF?, a potent greenhouse gas, as the cleaning agent triggered concerns as recent reports reveal that the atmospheric concentrations of this gas have increased significantly. We quantified the life-cycle emissions of NF? in photovoltaic (PV) manufacturing, on the basis of actual measurements at the facilities of a major producer of NF? and of a manufacturer of PV end-use equipment. From these, we defined the best practices and technologies that are the most likely to keep worldwide atmospheric concentrations of NF? at very low radiative forcing levels. For the average U.S. insolation and electricity-grid conditions, the greenhouse gas (GHG) emissions from manufacturing and using NF? in current PV a-Si and tandem a-Si/nc-Si facilities add 2 and 7 g CO?(eq)/kWh, which can be displaced within the first 1-4 months of the PV system life.     

Characterizing geochemical reactions in unsaturated mine waste-rock piles using gaseous O2, CO2, 12CO2, and 13CO2

In situ determinations of geochemical reaction rates in mine waste-rock piles remain a challenge. Depth-profiles of field O2 and CO2 pore-gas concentrations, delta13C(CO2) values, and moisture contents were used to characterize and quantify geochemical reaction rates in two waste-rock piles at the Key Lake Uranium Mine in northern Saskatchewan, Canada. Traditionally, the presence of O2 concentrations less than atmospheric in waste-rock piles has been attributed to mineral oxidation. This study showed that the interpretation of O2 and CO2 concentration profiles alone could not be used to identify the depths of dominant geochemical reactions in the piles and could lead to erroneous estimates of reaction rates. Modeling of the delta13C(CO2) depth profiles clearly showed that the gas concentration profiles present in the piles were the result of the oxidation of organic matter present below the piles, a mechanism not previously reported in the literature. Based on these findings, the rates of reactions in the organic zone were determined. The oxidation of organic matter at the base of waste-rock piles should be considered in future mine-waste pore-gas studies, in addition to sulfide oxidation and carbonate buffering.