Determination of quantum yields for the photolysis of Fe(III)-hydroxo complexes in aqueous solution using a novel kinetic method

The determination of quantum yields for the photolysis of Fe(III)-hydroxo complexes is important for the quantitative investigation of hydroxyl radical (*OH) production, not only in a natural water body, but also in the photo-Fenton process. A novel kinetic method, using a *OH probe compound, was established for the determination of the quantum yields in this study. The method was based on measuring the pseudo-first-order rate constant of the photodecomposition of dimethylsulfoxide (DMSO) in which DMSO and its primary products scavenged the *OH at an identical rate. The preliminary experiments for the photodecomposition kinetics supported the suitability of DMSOs as a probe compound for determining quantum yields. The individual quantum yields for the photolysis of the monomeric Fe(III) complexes, in the wavelength range 240-380 nm, were determined by the photodecomposition kinetics of the hydroxyl radical (*OH) probe compound (DMSO). The determined values of the individual quantum yields were 0.046+/-0.00052 for Fe3+ (H2O)6 (hexaaquo ion) and 0.69+/-0.025 for Fe(OH)2+ (H2O)5 (hydroxypentaaquo ion) at 254 nm, and showed decreasing values with increasing wavelength, in the ranges of 240-380 nm. The quantum yields between 240 and 280 nm were newly reported in this study, and the values obtained between 280 and 380 nm were in good agreement with the literature values.     

The use of PLS algorithms and quantum chemical parameters derived from PM3 hamiltonian in QSPR studies on direct photolysis quantum yields of substituted aromatic halides

The Partial Least-Squares (PLS) method was used to further study Quantitative Structure-Property Relationship (QSPR) for photohydrolysis quantum yields of selected aromatic halides. The cluster of substituted bromobenzenes and iodobenzenes was further grouped into two clusters, substituted bromobenzenes and substituted iodobenzenes, for which QSPRs were obtained, respectively. The QSPRs obtained by PLS are more significant than those obtained in previous studies. The studies showed that only when the compounds belonging to different groups are studies separately, inherent relationships between molecular properties and their structure characteristics can be revealed. It can be generally concluded that the photohydrolysis quantum yields of the substituted aromatic halides are dependent on the overall characters of the molecules, the characters of the carbon–halogen bonds to be broken in the photolysis, and the character of the halogen atoms to be replaced in the photolysis. Electronegativity has great relevance to the photohydrolysis processes of the compounds. Substituted aromatic halides with large average molecular polarizability and molecular weight values tend to have low photolysis quantum yields.     

The photolysis of organic substances under atmospheric conditions with a cylindrical photoreactor using ethyl nitrite and nitrogen dioxide

The first-order rate constants of 8 organic substances were measured using the ethyl nitrite and nitrogen dioxide photolyses and their relative rates with respect to n-hexane rate constant were calculated. These were compared with literature data. Relatively small photolysis rates of alkane and aromatics were shown for our photosystems and the alkenes were rapidly photolyzed. For mixed photooxidation reactions of various organics, it would be reasonable for organics of the group classified by their molecular structures to be discussed on their reactivities with OH radicals.     

A combined plasma photolysis (CPP) method for removal of CS2 from gas streams at atmospheric pressure

A combined plasma photolysis (CPP) reactor that utilizes a dielectric barrier discharge (DBD) plasma and 207 nm UV radiation from discharge-driven KrBr^* excimers was designed and constructed. Gas streams containing CS₂ were treated with stand-alone DBD and CPP at atmospheric pressure. In comparison to DBD, CPP greatly enhanced the removal efficiency at the same applied voltage, waste gas concentration and gas residence time. Thus the applied voltage could be reduced to a certain extent in the plasma processing of industrial wastes. Influences of the KrBr^* radiation, inlet CS₂ concentration and gas residence time on CS₂ removal by CPP were also studied. In addition, the likely reaction mechanisms for the removal of CS₂ by CPP are suggested based on the byproducts analysis. The enhanced removal efficiency and reaction mechanisms implied that the CPP process would probably be suitable for the removal of a large number of gaseous pollutants.     

Biogeochemical transformation of greenhouse gas emissions from terrestrial to atmospheric environment and potential feedback to climate forcing

Environmental Science and Pollution Research - Carbon dioxide (CO2) is mainly universal greenhouse gas associated with climate change. However, beyond CO2, some other greenhouse gases (GHGs) like...     

Investigation of the ultraviolet photolysis method for the determination of organic nitrogen in aerosol samples

The research objective was to adapt the ultraviolet (UV)-photolysis method to determine dissolved organic nitrogen (DON) in aqueous extracts of aerosol samples. DON was assumed to be the difference in total concentration of inorganic nitrogen forms before and after sample irradiation. Using a 2(2) factorial design the authors found that the optimal conversion of urea, amino acids (alanine, aspartic acid, glycine, and serine), and methylamine for a reactor temperature of 44 degrees C occurred at pH 2.0 with a 24-hr irradiance period at concentrations <33 microM of organic nitrogen. Different decomposition mechanisms were evident: the photolysis of amino acids and methylamine released mainly ammonium (NH4+), but urea released a near equimolar ratio of NH4+ and nitrate (NO3-). The method was applied to measure DON in the extracts of aerosol samples from Tampa, FL, over a 32-day sampling period. Average dissolved inorganic (DIN) and DON concentrations in the particulate matter fraction PM10 were 78.1 +/- 29.2 nmol-Nm(-3) and 8.3 +/- 4.9 nmol-Nm(-3), respectively. The ratio between DON and total dissolved nitrogen ([TDN] = DIN + DON) was 10.1 +/- 5.7%, and the majority of the DON (79.1 +/- 18.2%) was found in the fine particulate matter (PM2.5) fraction. The average concentrations of DIN and DON in the PM2.5 fraction were 54.4 +/- 25.6 nmol-Nm(-3) and 6.5 +/- 4.4 nmol-Nm(-3), respectively.     

Determination of wavelength-averaged,near UV quantum yields for environmental chemicals

The present study describes a procedure for determination of an average quantum yield for the wavelength range of 310 to 410 nm. Solutions of the pollutant in sealed Pyrex tubes are irradiated in a Rayonet photoreactor fitted with fluorescent lamps emitting maximally at 355 nm. The integrated spectral overlap and the photolysis half-life for both the chemical actinometer and the pollutant are determined and from these data the quantum yield is calculated. The method has been evaluated by measuring quantum yields for organophosphorus, chlorinated hydrocarbon, and dinitroaniline pesticides and $\text{p}$-nitroanisole/pyridine mixtures. Corrected quantum yields are obtained on simultaneous irradiation of the trifluralin actinometer.     

Trends in atmospheric reactive nitrogen for the Eastern United States

Reactive nitrogen can travel far from emission sources and impact sensitive ecosystems. From 2002 to 2006, policy actions have led to decreases in NO(x) emissions from power plants and motor vehicles. In this study, atmospheric chemical transport modeling demonstrates that these emissions reductions have led to a downward trend in ambient measurements of transported reactive nitrogen, especially atmospheric concentrations and wet deposition of nitrate. The trend in reduced nitrogen, namely ammonium, is ambiguous. As reduced nitrogen becomes a larger fraction of the reactive nitrogen budget, wide-spread NH(3) measurements and improved NH(3) emissions assessments are a critical need.     

中国温室气体减排适宜方案的选择

气候变化是当今世界关注的全球性问题。在总结国际上各主要利益集团的减排方案和对策的基础上,根据国际和国内专家的理解并结合中国国情,首先选出适合中国的经济政策和技术政策;在此基础上,运用层次分析法分析这些对策,确定其可行性和优先顺序,提出适合中国的减排对策方案建议。     

The regulatory role of endogenous iron on greenhouse gas emissions under intensive nitrogen fertilization in subtropical soils of China

Environmental Science and Pollution Research - Anaerobic batch experiments were conducted to study the regulatory role of endogenous iron in greenhouse gas emissions under intensive nitrogen...     

填埋场沼气发电的温室气体减排效益分析

填埋场沼气是垃圾卫生填埋场产生的可利用资源.以深圳下坪垃圾填埋场为例,定量分析垃圾填埋气体发电的温室气体减排效益.结果表明,填埋场沼气发电具有很好的经济效益和环境效益,可作为与发达国家进行CDM(清洁发展机制)项目合作的优先技术领域.     

Assembling plant diversity mitigates greenhouse gas emissions and achieves high nitrogen removal when treating the low-C/N wastewater by constructed wetlands

Environmental Science and Pollution Research - The low carbon-to-nitrogen (C/N) ratio in wastewater will inhibit pollutant removal, and more seriously, it will cause an increment of nitrous oxide...     

油气处理场站温室气体甲烷排放特征与量化

油气生产过程是甲烷重点排放源,对气候变化产生显著影响。采用便携式火焰离子检测器 (FID) 和Hi-Flow大流量仪等设备,对我国某油田3座油气处理场站甲烷泄漏排放特征进行了研究,明确了组件泄漏率,量化了重点源项甲烷排放速率,构建了设备设施甲烷排放因子,开展了甲烷排放量核算并提出了管控建议。结果表明,该油田油气处理场站设备组件与管线的甲烷泄漏率为0.7%~1.2%,压力表、阀门和储罐等在泄漏源项中占比较高。不同类型泄漏组件甲烷排放速率具有显著差异,处理场站的甲烷排放速率为111.66~274.63 L·min⁻¹。单个储罐和场站的甲烷排放因子分别为989.9 L·h⁻¹和0.19 L·m⁻³。3座场站年度甲烷排放量为303 783.40 m³,储罐是首要排放源,对总排放量贡献占比为94.1%。组件泄漏导致的甲烷排放主要源于高强度排放源,15%的泄漏点贡献了排放量的88.4%。该研究结果可为油田油气处理场站泄漏防控和温室气体排放控制提供参考。     

Compositions and greenhouse gas emission factors of flared and vented gas in the Western Canadian Sedimentary Basin

A significant obstacle in evaluating mitigation strategies for flaring and venting in the upstream oil and gas industry is the lack of publicly available data on the chemical composition of the gas. This information is required to determine the economic value of the gas, infrastructure and processing requirements, and potential emissions or emissions credits, all of which have significant impact on the economics of such strategies. This paper describes a method for estimating the composition of solution gas being flared and vented at individual facilities, and presents results derived for Alberta, Canada, which sits at the heart of the Western Canadian Sedimentary Basin. Using large amounts of raw data obtained through the Alberta Energy Resources Conservation Board, a relational database was created and specialized queries were developed to link production stream data, raw gas samples, and geography to create production-linked gas composition profiles for approximately half of the currently active facilities. These were used to create composition maps for the entire region, to which the remaining facilities with unknown compositions were geographically linked. The derived data were used to compute a range of solution gas composition profiles and greenhouse gas emission factors, providing new insight into flaring and venting in the region and enabling informed analysis of future management and mitigation strategies.

Implications: Accurate and transparent determination of environmental impacts of flaring and venting of gas associated with oil production, and potential benefits of mitigation, is severely hampered by the lack of publicly available gas composition data. In jurisdictions within the Western Canadian Sedimentary Basin, frameworks exist for regulating and trading carbon offset credits but current potential for mitigation is limited by a lack of standardized methods for calculating CO₂ equivalent emissions. The composition and emission factor data derived in this paper will be useful to industry, regulators, policy researchers, and entrepreneurs seeking statistically significant and openly available data necessary to manage and mitigate upstream flaring and venting activity and estimate greenhouse gas impacts.     

Direct VUV photolysis of chlorinated methanes and their mixtures in a nitrogen stream

The gas-phase decomposition of CCl(4), CHCl(3) and CH(2)Cl(2) and their binary mixtures was studied in a flow-type reactor in a nitrogen gas stream, using a low-pressure mercury vapour lamp covered with a high-purity silica quartz sleeve. The 184.9 nm vacuum-ultraviolet (VUV) light emitted is able to rupture the C-Cl bond in these target substances. For H-containing compounds, the decomposition takes place not only by direct photolysis, but also by H abstraction by .Cl formed during the direct photolysis of the target substances. The relative contributions of direct photolysis and .Cl-sensitized reactions to the decomposition were estimated at different initial concentrations. The addition of CCl(4) to CHCl(3) or CH(2)Cl(2) increased their decomposition rates via increase of the .Cl concentration, whereas the addition of CH(2)Cl(2) to CHCl(3) decreased its degradation rate, suggesting that CH(2)Cl(2) acts as a .Cl radical scavenger. The variation of the product distribution confirms the effect of the composition of the irradiated gas mixtures on the relative contributions of .Cl-sensitized reactions and direct photolysis.     

Regional and sectoral assessment of greenhouse gas emissions in India

In this paper the authors have estimated for 1990 and 1995 the inventory of greenhouse gases CO₂, CH₄ and N₂O for India at a national and sub-regional district level. The district level estimates are important for improving the national inventories as well as for developing sound mitigation strategies at manageable smaller scales. Our estimates indicate that the total CO₂, CH₄ and N₂O emissions from India were 592.5, 17, 0.2 and 778, 18, 0.3 Tg in 1990 and 1995, respectively. The compounded annual growth rate (CAGR) of these gases over this period were 6.3, 1.2 and 3.3%, respectively. The districts have been ranked according to their order of emissions and the relatively large emitters are termed as hotspots. A direct correlation between coal consumption and districts with high CO₂ emission was observed. CO₂ emission from the largest 10% emitters increased by 8.1% in 1995 with respect to 1990 and emissions from rest of the districts decreased over the same period, thereby indicating a skewed primary energy consumption pattern for the country. Livestock followed by rice cultivation were the dominant CH₄ emitting sources. The waste sector though a large CH₄ emitter in the developed countries, only contributed about 10% the total CH₄ emission from all sources as most of the waste generated in India is allowed to decompose aerobically. N₂O emissions from the use of nitrogen fertilizer were maximum in both the years (more than 60% of the total N₂O). High emission intensities, in terms of CO₂ equivalent, are in districts of Gangetic plains, delta areas, and the southern part of the country. These overlap with districts with large coal mines, mega power plants, intensive paddy cultivation and high fertilizer use. The study indicates that the 25 highest emitting districts account for more than 37% of all India CO₂ equivalent GHG emissions. Electric power generation has emerged as the dominant source of GHG emissions, followed by emissions from steel and cement plants. It is therefore suggested, to target for GHG mitigation, the 40 largest coal-based thermal plants, five largest steel plants and 15 largest cement plants in India as the first step.     

Bottom-up re-estimations of greenhouse gas and atmospheric pollutants derived from straw burning of three cereal crops production in China based on a national questionnaire

Environmental Science and Pollution Research - Crop straw open burning is considered as an important source of greenhouse gas and atmospheric pollutants emissions, which affects global climate...