Kinetics of the Gas-Phase Reactions of OH Radicals, NO3 Radicals and O3 with Three C7-Carbonyls Formed From The Atmospheric Reactions of Myrcene, Ocimene and Terpinolene

Rate constants for the gas-phase reactions of OH radicals, NO₃ radicals and O₃ with the C₇-carbonyl compounds 4-methylenehex-5-enal [CH₂=CHC(=CH₂)CH₂CH₂CHO], (3Z)- and (3E)-4-methylhexa-3,5-dienal [CH₂=CHC(CH₃)=CHCH₂CHO] and 4-methylcyclohex-3-en-1-one, which are products of the atmospheric degradations of myrcene, Z- and E-ocimene and terpinolene, respectively, have been measured at 296 ± 2 K and atmospheric pressure of air using relative rate methods. The rate constants obtained (in cm³ molecule^–1 s^–1 units) were: for 4-methylenehex-5-enal, (1.55 ± 0.15) × 10^–10, (4.75 ± 0.35) × 10^–13 and (1.46 ± 0.12) × 10^–17 for the OH radical, NO₃ radical and O₃ reactions, respectively; for (3Z)-4-methylhexa-3,5-dienal: (1.61 ± 0.35) × 10^–10, (2.17 ± 0.30) × 10^–12, and (4.13 ± 0.81) × 10^–17 for the OH radical, NO₃ radical and O₃ reactions, respectively; for (3E)-4-methylhexa-3,5-dienal: (2.52 ± 0.65) × 10^–10, (1.75 ± 0.27) × 10^–12, and (5.36 ± 0.28) × 10^–17 for the OH radical, NO₃ radical and O₃ reactions, respectively; and for 4-methylcyclohex-3-en-1-one: (1.10 ± 0.19) × 10^–10, (1.81 ± 0.35) × 10^–12, and (6.98 ± 0.40) × 10^–17 for the OH radical, NO₃ radical and O₃ reactions, respectively. These carbonyl compounds are all reactive in the troposphere, with daytime reaction with the OH radical and nighttime reaction with the NO₃ radical being predicted to dominate as loss processes and with estimated lifetimes of about an hour or less.     

Mass transport triggered by heavy rainfall: the role of endorheic basins and epikarst in a regional karst aquifer

This study aims at recognizing the mechanisms of mass transport between the karst surface and the saturated zone in a morphostructural relief of the Mesozoic karst carbonate platform of Murgia (Puglia, Southern Italy). The large dimension of the karst aquifer, the regional scale of the flow system, the boundary condition constituted by the sea, and the lack of freshwater springs constrain to the use of wells as monitoring points and limit the study area to the recharge area comprising 986 endorheic basins. The concentrations of non‐reactive tracers (nitrates) in the waters of autogenic recharge (from endorheic basins) have been modeled through the evaluation of effective infiltration, land use, and nitrogen surplus, with reference to a time window, which includes a low precipitation period followed by significant rainfall events. The comparison between the modeled nitrate concentrations and the nitrate concentrations measured in ground waters, coupled with the analysis of groundwater chemograms and records of hydraulic heads (all referred to the same time window), allows inferring the mechanism of mass transport between the karst surface and the groundwater table. The mass transport conceptual model requires the presence of the epikarst. The infiltration of significant rainfall in the endorheic basins after a low precipitation period displaces waters stored in the epikarst toward the saturated zone. Ground waters in the post‐event period show higher concentrations of nitrates, lower concentrations of total organic carbon, and higher Mg/Ca ratios than both those of the pre‐event period and the autumn‐winter recharge period. The post‐event recharge from epikarst storage determines a transient hazard of groundwater pollution with a time lag from the occurrence of the heavy rainfall.     

Gas phase reactions of alkyl nitrates with hydroxyl radicals under tropospheric conditions in comparison with photolysis

Rate constants for the reaction of OH radicals with some branched alkyl nitrates have been measured applying a competitive technique. Methyl nitrite photolysis in synthetic air was used as OH radical source at 295±2 K and 1000 mbar total pressure. Using a rate constant of 2.53×10^-12 cm³ s^-1 for the reaction of OH radicals with n-butane as reference, the following rate constants were obtained (units: 10^-12 cm³ s^-1): isopropyl nitrate, 0.59±0.22; isobutyl nitrate, 1.63±0.20; 3-methyl-2-butyl nitrate, 1.95±0.15; 2-methyl-1-butyl nitrate, 2.50±0.15; 3-methyl-1-butyl nitrate, 2.55±0.35. These values have been combined with the literature data to recalculate the substituent factors F(X) for the different nitrate groups which can be used to predict OH rate constants for organic nitrates for which experimental data are not available.Preliminary measurements of the photolysis frequency of isopropyl nitrate have shown that for this nitrate as a model substance, OH reactions and direct photolysis are of equal importance under tropospheric conditions.     

Bacterial contribution to sedimentary organic matter; a comparative study of lipid moieties in bacteria and Recent sediments

A systematic study of the lipid composition of thirteen bacterial species and three Recent sediments (methanogenic sediment, cyanobacterial mat and evaporative gypsum crust) was undertaken in an attempt to recognize bacterial organic matter in sediments. A sequential method, which distinguishes between three different modes of occurrence of lipid moieties (free, OH⁻- and H⁺-labile), was applied. The acid-labile fractions are discussed.The three main groups of bacteria, archaebacteria, gram-positive eubacteria and gram-negative eubacteria, are easily distinguished. Methanogenic and extremely halophilic archaebacteria are characterized by the presence of diphytanyl glyceryl ether and the absence of fatty acids. The gram-positive eubacteria contain primarily iso- and anteiso-branched fatty acids whereas the gram-negative bacteria and sediments are dominated by β- and α-hydroxy fatty acids. A wide variety of H⁺-labile hydroxy fatty acids was observed which included several, as yet unknown, structures.β-Hydroxy fatty acids in this H⁺-labile mode of occurrence are exclusively present in bacteria. Their distribution patterns in sediments are considered “fingerprints” of past and present bacterial populations. The specific differences in β -hydroxy fatty acid compositions observed in the different bacteria and the three sediments investigated, suggest that amide-linked β-hydroxy fatty acid patterns are useful as markers of bacterial populations and therefore of environmental conditions.     

Studies on the behaviour of nutrients in the Mandovi Estuary during premonsoon

Behaviour of silicate, nitrate and phosphate in the Mandovi Estuary was studied during the premonsoon season. The study shows that silicate is removed from the water column while nitrate showed an internal source. This nitrate source has been identified as the wash water from an iron ore screening plant which discharges the muddy waste directly into the river. Applying mixing relations, the distribution of this nitrate both up- and downstream of the outfall has been studied. Phosphate showed very low concentrations in the low salinity region; however, its concentration increased slightly towards the higher salinity region.     

Tidal effect on dynamics of pore water nitrate in intertidal sediment of a eutrophic Estuary

To evaluate the effect of the tidal cycle on the pore water nitrate dynamics in intertidal sediment, concentrations of inorganic nitrogen in water and sediment were monitored during tidal cycles in the mud flat of Tama Estuary, Japan. During submergence, nitrate concentration was highest in the overlying water and decreased monotonically with increasing depth in the sediment, suggesting that the primary source of nitrate in the sediment was nitrate transported from the overlying water. Pore water nitrate decreased remarkably during the initial 3–4 hours after the onset of exposure. Thereafter, it was constant or slightly increased until tidal flooding.In situ accumulation of nitrate at the end of exposure, however, did not exceed the nitrate concentrations in the overlying water. The inhibition of nitrate reduction and the stimulation of nitrification would explain the change of nitrate concentration, both consistent with the input of oxygen into the sediment following a 10 mm drop of the water table. In Tama Estuary sediments, the effect of the tidal cycle on the removal of combined nitrogen is rather negative, because high nitrate concentrations in the overlying water canceled the positive effect of nitrate accumulation by nitrification during exposure, while tidal oxygen intrusion have an inhibitory effection sedimentary denitrification.     

酒泉东盆地地下水“三氮”分布特征及健康风险分析

为探讨河西走廊地下水“三氮”的污染现状和个人健康风险。本文以酒泉东盆地为例,通过数据统计、空间分布趋势、污染源和影响因素分析的手段,从“三氮”分布、迁移和影响因素及其健康风险评价进行研究。结果表明：在其独特的地形地貌、氧化还原环境、包气带和含水层岩性、潜水的埋深、酸碱环境和地下径流条件等自然因素以及生态环境的破坏和城市化的发展等人为因素影响下,研究区地下水“三氮”总体含量较低,污染相对较轻,仅有一处NO₃^--N含量超过标准限值;区域分布上,“三氮”含量具有明显的北高南低的规律,NO₃^--N和NO₂^--N含量东、西两侧高,中间低,NH₄⁺-N含量由西北向东南逐渐减少。“三氮”个人年健康风险的整体分布趋势基本一致,由西部人口密集区域向东部人口非密集区域逐渐递减。     

居留南极对考察队员血浆色氨酸及尿中5－羟吲哚乙酸水平的影响

为探讨南极考察队员行为／性格变化的物质基础，观察了驻长城站考察队员血浆色氨酸（Ｔｒｐ）与尿中５－羟吲哚乙酸（５－ＨＩＡＡ）变化。第８次队及第１１次队两批队员变化规律相同，即血浆Ｔｒｐ降低，尿中排出５－ＨＩＡＡ增加，血浆Ｔｒｐ变化较尿排出５－ＨＩＡＡ变化出现早，恢复慢。本文讨论了血浆Ｔｒｐ、尿中５－ＨＩＡＡ变化与行为／性格变化间可能的关系     

Near UV absorption spectra and photolysis products of difunctional organic nitrates: Possible importance as NO x reservoirs

Difunctional organic nitrates are important products of the atmospheric reaction of NO₃ radicals with unsaturated hydrocarbons about which relatively little is known. In a continuation of the investigation of the atmospheric chemistry of such compounds, the UV absorption spectra of the following organic dinitrates and keto nitrates have been quantitively measured in the gas phase at 298±2 K and atmospheric pressure: 1,2-propandiol dinitrate, CH₃CH(ONO₂)CH₂(ONO₂); 1,2-butandiol dinitrate, CH₃CH₂CH(ONO₂)CH₂(ONO₂); 2,3-butandiol dinitrate, CH₃CH(ONO₂)CH(ONO₂)CH₃;cis 1,4-dinitrooxy-2-butene, CH₂(ONO₂)CH=CHCH₂(ONO₂); 3,4-dinitrooxy-1-butene, CH₂(ONO₂CH(ONO₂)CH=CH₂; -nitrooxy acetone, CH₃COCH₂(ONO₂); 1-nitrooxy-2-butanone, CH₃CH₂COCH₂(ONO₂); 3-nitrooxy-2-butanone, CH₃CH(ONO₂)COCH₃.Although the UV spectra of the nitrates are all very similar in shape those of the keto nitrates are red-shifted compared to the dinitrates and in the spectral range of atmospheric interest (>290 nm) their absorption cross-sections are approximately a factor of 5 higher. The cross-sections of the dinitrates are a factor of 2 higher than those reported in the literature for the corresponding alkyl mononitrates.The UV absorption cross-sections of the difunctional nitrates were used in combination with solar actinic flux data to estimate photolysis frequencies and consequently atmospheric lifetimes for these compounds. The results indicate that for the saturated difunctional nitrates studied in this work photolysis will generally be somewhat some important than reaction with OH radicals as an atmospheric removal process. However, for unsaturated nitrates loss due to reaction with OH will dominate over photolysis as an atmospheric sink.Preliminary FT-IR analyses of the photolysis products of -nitrooxy acetone, 3-nitrooxy-2-butanone and 2,3-butandiol dinitrate using both mercury and fluorescent lamps indicate that NO₂ is released in the primary step. The further reactions of the radicals thus produced result in the formation of CO, aldehydes and PAN. The possible significance of the results for difunctional organic nitrate as reservoirs for reactive odd nitrogen NO _y in the atmosphere, especially during the night, is briefly discussed.     

铬酸根离子在羟基铁离子-蒙脱石体系中的吸附行为研究

采矿、电镀、制革等行业废物排放及含Cr矿物风化可造成一些地区土壤和地下水的Cr污染 .Cr主要以三价和六价形式存在 ,其中Cr(Ⅵ )有强的迁移能力 ,对动植物均有很强的毒害性 .研究了在氧化、酸性条件下 ,土壤及土壤溶液中的蒙脱石和羟基铁离子共存时对铬酸根离子 (主要以HCrO2 - 4和CrO2 - 4等Cr(Ⅵ )形式存在 )的吸附行为 .进行了蒙脱石、羟基铁离子、Cr(Ⅵ )离子添加顺序不同的 3个系列的实验 ,重点研究了Cr的初始质量浓度、溶液 pH值、环境温度、吸附时间、溶液离子强度对 3个系列Cr吸附行为的影响 ,并与羟基铁离子体系进行了对比 .结果表明 ,蒙脱石 -羟基铁离子体系的Cr吸附能力明显强于蒙脱石而低于羟基铁离子 ,其Cr吸附率随Cr初始质量浓度、温度的升高和吸附时间的延长而降低 ,随离子强度的升高而升高 ,而pH值对不同系列的Cr吸附率有不尽相同的影响 .