Atmospheric chemistry of HFE-7000 (CF(3)CF (2)CF (2)OCH (3)) and 2,2,3,3,4,4,4-heptafluoro-1-butanol (CF (3)CF (2)CF (2)CH (2)OH): kinetic rate coefficients and temperature dependence of reactions with chlorine atoms

Background, aim, and scope  The adverse environmental impacts of chlorinated hydrocarbons on the Earth’s ozone layer have focused attention on the effort to replace these compounds by nonchlorinated substitutes with environmental acceptability. Hydrofluoroethers (HFEs) and fluorinated alcohols are currently being introduced in many applications for this purpose. Nevertheless, the presence of a great number of C–F bonds drives to atmospheric long-lived compounds with infrared absorption features. Thus, it is necessary to improve our knowledge about lifetimes and global warming potentials (GWP) for these compounds in order to get a complete evaluation of their environmental impact. Tropospheric degradation is expected to be initiated mainly by OH reactions in the gas phase. Nevertheless, Cl atoms reaction may also be important since rate constants are generally larger than those of OH. In the present work, we report the results obtained in the study of the reactions of Cl radicals with HFE-7000 (CF₃CF₂CF₂OCH₃) (1) and its isomer CF₃CF₂CF₂CH₂OH (2). Materials and methods  Kinetic rate coefficients with Cl atoms have been measured using the discharge flow tube–mass spectrometric technique at 1 Torr of total pressure. The reactions of these chlorofluorocarbons (CFCs) substitutes have been studied under pseudo-first-order kinetic conditions in excess of the fluorinated compounds over Cl atoms. The temperature ranges were 266–333 and 298–353 K for reactions of HFE-7000 and CF₃CF₂CF₂CH₂OH, respectively. Results  The measured room temperature rate constants were k(Cl+CF₃CF₂CF₂OCH₃) = (1.24 ± 0.28) × 10⁻¹³ cm³ molecule⁻¹ s⁻¹and k(Cl+CF₃CF₂CF₂CH₂OH) = (8.35 ± 1.63) × 10⁻¹³ cm³ molecule⁻¹ s⁻¹ (errors are 2σ + 10% to cover systematic errors). The Arrhenius expression for reaction 1 was k ₁(266–333 K) = (6.1 ± 3.8) × 10⁻¹³exp[−(445 ± 186)/T] cm³ molecule⁻¹ s⁻¹ and k ₂(298–353 K) = (1.9 ± 0.7) × 10⁻¹²exp[−(244 ± 125)/T] cm³ molecule⁻¹ s⁻¹ (errors are 2σ). The reactions are reported to proceed through the abstraction of an H atom to form HCl and the corresponding halo-alkyl radical. At 298 K and 1 Torr, yields on HCl of 0.95 ± 0.38 and 0.97 ± 0.16 (errors are 2σ) were obtained for CF₃CF₂CF₂OCH₃ and CF₃CF₂CF₂CH₂OH, respectively. Discussion  The obtained kinetic rate constants are related to the previous data in the literature, showing a good agreement taking into account the error limits. Comparing the obtained results at room temperature, k ₁ and k ₂, HFE-7000 is significantly less reactive than its isomer C₃F₇CH₂OH. A similar behavior has been reported for the reactions of other fluorinated alcohols and their isomeric fluorinated ethers with Cl atoms. Literature data, together with the results reported in this work, show that, for both fluorinated ethers and alcohols, the kinetic rate constant may be considered as not dependent on the number of –CF₂– in the perfluorinated chain. This result may be useful since it is possible to obtain the required physicochemical properties for a given application by changing the number of –CF₂– without changes in the atmospheric reactivity. Furthermore, lifetimes estimations for these CFCs substitutes are calculated and discussed. The average estimated Cl lifetimes are 256 and 38 years for HFE-7000 and C₃H₇CH₂OH, respectively. Conclusions  The studied CFCs’ substitutes are relatively short-lived and OH reaction constitutes their main reactive sink. The average contribution of Cl reactions to global lifetime is about 2% in both cases. Nevertheless, under local conditions as in the marine boundary layer, τ _Cl values as low as 2.5 and 0.4 years for HFE-7000 and C₃H₇CH₂OH, respectively, are expected, showing that the contribution of Cl to the atmospheric degradation of these CFCs substitutes under such conditions may constitute a relevant sink. In the case of CF₃CF₂CF₂OCH₃, significant activation energy has been measured, thus the use of kinetic rate coefficient only at room temperature would result in underestimations of lifetimes and GWPs. Recommendations and perspectives  The results obtained in this work may be helpful within the database used in the modeling studies of coastal areas. The knowledge of the atmospheric behavior and the structure–reactivity relationship discussed in this work may also contribute to the development of new environmentally acceptable chemicals. New volatile materials susceptible of emission to the troposphere should be subject to the study of their reactions with OH and Cl in the range of temperature of the troposphere. The knowledge of the temperature dependence of the kinetic rate constants, as it is now reported for the case of reactions 1 and 2, will allow more accurate lifetimes and related magnitudes like GWPs. Nevertheless, a better knowledge of the vertical Cl tropospheric distribution is still required.     

Carbon source/sink function of a subtropical, eutrophic lake determined from an overall mass balance and a gas exchange and carbon burial balance

Although studies on carbon burial in lake sediments have shown that lakes are disproportionately important carbon sinks, many studies on gaseous carbon exchange across the water-air interface have demonstrated that lakes are supersaturated with CO(2) and CH(4) causing a net release of CO(2) and CH(4) to the atmosphere. In order to more accurately estimate the net carbon source/sink function of lake ecosystems, a more comprehensive carbon budget is needed, especially for gaseous carbon exchange across the water-air interface. Using two methods, overall mass balance and gas exchange and carbon burial balance, we assessed the carbon source/sink function of Lake Donghu, a subtropical, eutrophic lake, from April 2003 to March 2004. With the overall mass balance calculations, total carbon input was 14 905 t, total carbon output was 4950 t, and net carbon budget was +9955 t, suggesting that Lake Donghu was a great carbon sink. For the gas exchange and carbon burial balance, gaseous carbon (CO(2) and CH(4)) emission across the water-air interface totaled 752 t while carbon burial in the lake sediment was 9477 t. The ratio of carbon emission into the atmosphere to carbon burial into the sediment was only 0.08. This low ratio indicates that Lake Donghu is a great carbon sink. Results showed good agreement between the two methods with both showing Lake Donghu to be a great carbon sink. This results from the high primary production of Lake Donghu, substantive allochthonous carbon inputs and intensive anthropogenic activity. Gaseous carbon emission accounted for about 15% of the total carbon output, indicating that the total output would be underestimated without including gaseous carbon exchange.     

Post-mating odor in females of the solitary bee, Andrena nigroaenea (Apoidea, Andrenidae), inhibits male mating behavior

We investigated odor changes and their behavioral significance in the solitary, ground-nesting bee Andrena nigroaenea. We used gas chromatography with electroantennographic detection and performed behavioral tests with males in the field using natural odor samples and synthetic compounds. We found that only cuticle extracts of young females elicited copulation attempts in the males. We demonstrated that among the 17 compounds which triggered electroantennographic responses, all-trans-farnesyl hexanoate and all-trans-farnesol were significantly more abundant in unattractive cuticle extracts of A. nigroaenea females. Dufour’s gland extracts of these females also contained greater amounts of both compounds. In bioassays using synthetic farnesyl hexanoate and farnesol we found that these compounds inhibit copulation behavior in the males. Farnesyl hexanoate is probably synthesized in Dufour’s gland and used by females for lining brood cells. We interpret the semiochemical function of farnesyl hexanoate and its precursor farnesol to have evolved secondarily. As an outcome of sexual selection, it facilitates the discrimination by males of receptive females from nesting and thus already mated individuals. The dual function of these compounds represents an elegant parsimony in the chemical communication system of this insect. Received: 19 January 2000 / Revised: 29 May 2000 / Accepted: 24 June 2000     

Environmental regulatory failure and metal contamination at the Giap Lai pyrite mine, Northern Vietnam

The causes for the failure in enforcement of environmental regulations at the Giap Lai pyrite mine in northern Vietnam are considered and the environmental impacts that are associated with this mine are evaluated. It is shown that sulphide-rich tailings and waste rock in the mining area represent significant sources of acid rock drainage (ARD). The ARD is causing elevated metal levels in downstream water bodies, which in turn, represent a threat to both human health and to aquatic ecosystems. Metal concentrations in impacted surface waters have increased after mine closure, suggesting that impacts are becoming progressively more serious. No post-closure, remediation measures have been applied at the mine, in spite of the existence of environmental legislation and both central and regional institutions charged with environmental supervision and control. The research presented here provides further emphasis for the recommendation that, while government institutions may need to be strengthened, and environmental regulations need to be in place, true on the ground improvement in environmental quality in Vietnam and in many other developing countries require an increased focus on promoting public awareness of industrial environmental issues.     

Effect of synthesis parameters on single gas permeation through T-type zeolite membranes

In this research, nanoporous zeolite T membranes were synthesized at three levels of synthesis temperature: 100, 120 and 140 °C and synthesis time: 15, 30 and 50 h and characterized by gas permeation. Effects of synthesis parameters on CO₂ and CH₄ permeances and CO₂/CH₄ ideal separation factors were studied. All experiments were conducted at 1 bar feed pressure and 30 °C module temperature. Normally, it is anticipated that increasing synthesis temperature and synthesis time increase gas permeances and consequently decrease ideal separation factor. This prediction was not observed in the case of synthesis temperature increase from 100 to 120 °C as well as synthesis time increase from 15 to 30 h, due to the dual effect of increasing synthesis temperature and synthesis time on gas permeances and ideal separation factor. More zeolites are deposited and larger crystals are formed at higher synthesis temperatures and times. Forming the larger crystals accelerates the rate of zeolite layer integration, which is responsible for gas separation, in one hand and reduces the density of deposited zeolite layer on the support, due to the formation of more voids, on the other hand. In terms of maximizing the CO₂/CH₄ ideal separation factor, medium synthesis temperature and synthesis time (120 °C and 30 h) can be selected, however, maximum gas permeances are obtained at low levels of synthesis temperature and time (100 °C and 15 h). According to the ranges of gas permeances (10⁻¹¹ to 10⁻⁶ mol/m² s Pa) and CO₂/CH₄ ideal separation factors (1.4–70.3), it is concluded that the zeolite T membranes synthesized at optimum conditions can be employed for membrane separation of CO₂/CH₄ mixtures.     

布什政府温室气体减排政策评析

美国作为世界政治经济大国和世界第一大温室气体排放国家，其温室气体减排政策备受关注。布什政府上台后不久宣布拒绝接受《京都议定书》，并于2002年2月提出“全球气候变化计划”。布什政府实际上在以各种借口推托美国应该承担的温室气体减排国际责任，这将对以UNFCCC为基础的全球气候合作产生消极影响，并对全球气候政策提出挑战。     

烟气气体常数的确定及与监测质量的关系

阐述了烟气气体常数的确定及与烟尘监测的关系。以各种煤的烟气组分和《锅炉烟尘测试方法》为依据，提出干、湿烟气气体常数代表值各为２７２．６和２７９、７Ｊ／ｋｇ．ｋ，并就代表值的适用性进行了讨论。指出将干烟气组分看作近于气所导致的误差，并对有关公式提出了修改意见。     

降水对农田排水沟渠中氮磷流失的影响

以浙江嘉兴双桥农场为研究对象,分析降水对农田沟渠中氮、磷流失的影响,揭示氮、磷在降水径流中流失的一般规律. 在单晚稻生长期间,同步监测了施肥后的2次降水量和沟渠径流量,并对2次降水径流的全过程进行污染物含量的测定,对农田排水沟渠径流量与污染物含量随2次降水变化过程进行监测.结果表明:污染物含量变化呈现出大致相同的趋势,且污染物含量峰值比流量峰值提前2～3 h;在降水初期,污染物含量随径流量的增大而升高;随着流量的继续增大,含量呈下降趋势. 施肥后4 d内降水的农田沟渠中氮、磷随径流的流失量比4 d后大. 影响氮、磷流失的因素主要有降水量、降水时间间隔、径流量、施肥的种类和数量、土壤前期含水量以及沟渠中的沉积物等. 氮流失的主要形态为氨氮和硝氮;磷流失的主要形态为磷酸盐. 通过回归分析发现,径流量与氮、磷排放负荷间符合多项式关系.      

碳酸盐岩抑制煤中有害元素释放和迁移能力的研究

为了揭示碳酸盐岩地质背景下碳酸盐岩对煤中有害元素的抑制作用,以煤和碳酸盐岩为实验材料设计了3个不同组合的淋溶柱,采用淋溶实验方法,探讨了碳酸盐岩对煤中Fe、Mn、Cu、As等元素释放和迁移的抑制能力.结果表明:碳酸盐岩能有效中和煤中黄铁矿等硫化矿物氧化产生的酸,淋溶液pH值显著升高;碳酸盐岩对煤中硫的释放和迁移能力的抑制作用不明显,对煤中Fe、Cu和As元素的释放和迁移的抑制能力较强,但对煤中Mn、Pb和Cd元素的释放和迁移的抑制能力相对较弱.碳酸盐岩能有效抑制酸性矿山废水的形成和演化,可作为碳酸盐岩地区酸性矿山废水防治的理想材料.     

增江流域河流颗粒有机碳的来源、含量变化及输出通量

对华南增江径流进行了 1个水文年度的 1 5次等时段采样 ,分析了河流悬移质中主要生源元素 (C、N、H)的含量 ,并估算了不同物源的贡献 .结果表明 ,增江悬移质中的有机碳以水生藻类的贡献为主 ,土壤侵蚀来源的有机碳在悬移质粗粒组中的份额平均为 37 2 4 % ,在细粒组中仅占 1 1 1 1 % 增江流域颗粒有机碳的输出通量为 0 83× 1 0 6g·km-2 ·a-1 ,其中来自土壤的颗粒有机碳通量为 0 2 2× 1 0 6g·km-2 ·a-1 .