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.     

Late-glacial and Holocene vegetation and climatic history of the Cass Basin, central South Island, New Zealand

Lithology, pollen, macrofossils, and stable carbon isotopes from an intermontane basin bog site in southern New Zealand provide a detailed late-glacial and early Holocene vegetation and climate record. Glacial retreat occurred before 17,000 cal yr B.P., and tundra-like grassland–shrubland occupied the basin shortly after. Between 16,500 and 14,600 cal yr B.P., a minor regional expansion of forest patches occurred in response to warming, but the basin remained in shrubland. Forest retreated between 14,600 and 13,600 cal yr B.P., at about the time of the Antarctic Cold Reversal. At 13,600 cal yr B.P., a steady progression from shrubland to tall podocarp forest began as the climate ameliorated. Tall, temperate podocarp trees replaced stress-tolerant shrubs and trees between 12,800 and 11,300 cal yr B.P., indicating sustained warming during the Younger Dryas Chronozone (YDC). Stable isotopes suggest increasing atmospheric humidity from 11,800 to 9300 cal yr B.P. Mild (annual temperatures at least 1°C higher than present), and moist conditions prevailed from 11,000 to 10,350 cal yr B.P. Cooler, more variable conditions followed, and podocarp forest was completely replaced by montane Nothofagus forest at around 7500 cal yr B.P. with the onset of the modern climate regime. The Cass Basin late-glacial climate record closely matches the Antarctic ice core records and is in approximate antiphase with the North Atlantic.     

Response of xenotime to prograde metamorphism

Xenotime is a widespread accessory mineral in lower greenschist to upper amphibolite facies metasedimentary rocks from the Palaeoproterozoic Mount Barren Group, southwestern Australia. Xenotime is closely associated with detrital zircon, commonly forming syntaxial outgrowths, in samples of sandstone, micaceous quartzite, slate, phyllite, garnet-bearing semi-pelites, and in kyanite-, garnet-, and staurolite-bearing mica schists. In situ geochronology of xenotime from lower greenschist sandstones has previously yielded multiple U–Pb ages with peaks at ~2.0, ~1.7, and ~1.65 Ga, interpreted to represent the age of detritus, early diagenesis, and a later thermal event, respectively. New U–Pb dating of xenotime in slate yields a major population at ~1.7 Ga with a minor population at ~1.2 Ga, reflecting diagenetic and metamorphic growth, respectively, whereas xenotime in phyllite forms a minor age population at ~1.7 Ga and a main peak at ~1.2 Ga. Mid-greenschist facies semi-pelitic schists (quartz-muscovite-garnet) contain xenotime that formed before 1.8 Ga and at 1.2 Ga, representing detrital and peak metamorphic ages, respectively. Xenotime in samples of amphibolite facies schist (650°C and ~8 kbars) yields U–Pb ages of ~1.2 Ga, coinciding with the time of peak metamorphism. A single analysis of a xenotime core from an amphibolite facies schist gave an age of ~1.8 Ga, consistent with the presence of detrital xenotime. Our results suggest that detrital xenotime may be preserved under greenschist facies conditions, but is largely replaced during upper amphibolite facies conditions. Detrital xenotime is replaced through dissolution–reprecipitation reactions forming compositionally distinct rims during greenschist and amphibolite facies metamorphism at 1.2 Ga. Diagenetic xenotime is present in lower greenschist facies samples, but was not observed in metasedimentary rocks that had experienced temperatures above mid-greenschist facies metamorphism (450°C). The apparent disappearance of detrital and diagenetic xenotime and appearance of metamorphic xenotime during prograde metamorphism indicates that some of the yttrium, heavy rare earth elements, and phosphorus needed for metamorphic xenotime growth are probably derived from the replacement of detrital and diagenetic xenotime.     

GGR Critical Review of Analytical Developments in 2003

The articles that comprise this critical review serve to draw attention to research papers published in specific fields of interest during 2003, provide critical comment on the relevance and importance of individual publications in these fields, and offer an overview of the comparative importance of advances in particular areas. In this way, these articles aim to assist experts in the field by keeping them informed of relevant recent publications, as well as providing an important resource for students or early career researchers who are embarking on studies in an area new to them. This year, five papers provide summaries of developments in bulk sample determinations employing (1) ICP-AES and ICP-MS (trace elements), (2) XRF and atomic absorption spectrometry and INAA, (3) isotope ratio measurements (TIMS, MC-ICP-MS, ICP-MS, ToF), as well as in situ measurements conducted using (4) secondary ion mass spectrometry and (5) laser ablation ICP-MS (trace element and isotope ratio determinations).     

Trace element distribution in the soils above deeply weathered pegmatites, Virginia, U.S.A.: implications for exploration

Chemical partitioning data are of fundamental interest to exploration geochemists. This paper is one of the few studies which has investigated the relative proportions of the rare elements in various soil extracts. The dispersion of trace elements from weathering pegmatites in Powhatan Country, Virginia, was found to be restricted to the immediate vicinity of the pegmatites. A sequential extraction procedure was used to measure the distribution of Be, La, Nb, Sn, U, Li, and Ni,among the following fractions of the B soil horizons: exchangeable, Fe and Mn oxyhydroxide, residual, and aqua regia digestion. The elements Sn, Be, Li, and U were found to be associated with soils over the complex Herbb No. 2 pegmatite, whereas La and Ni were generally associated with the background soils.A geochemical exploration model was developed using stepwise discriminant function analysis to determine the combination of elements and soil extracts that best differentiates between complex pegmatitic, simple pegmatitic, and background soils. Log-transformed aqua regia extract concentrations of Sn, La, U, and Li were the most effective variables when used to separate complex pegmatitic from simple pegmatitic soils.     

崎岖地形动植物栖息地生态环境遥感制图与应用

传统制图方法周期长、成本较高,影响了大面积精细动植物栖息地生态环境制图的生产。鉴此,本文采用IKONOS(VHR)图像对香港郊野公园崎岖地形的动植物栖息地生态环境制图进行了研究。由于香港植被的多样性,而且观察的动植物相互作用出现于结构的层面,所以对动植物栖息地的分类应以结构为基础而非以植物为基础。本文利用图像处理技术,运用决策树之多层次地物导向分割分类(MOOSC)方法绘制九种动植物栖息地类型图。MOOSC方法和其他现有的几种分类方法相比,其分类精度高、成本低。     

Intraseasonal oscillation of the rainfall variability over Rwanda and evaluation of its subseasonal forecasting skill

非洲中东部地区的经济主要依靠自给农业支撑,该地区农业经济对降水的变化尤为敏感.本文以卢旺达为例,观测分析指出卢旺达的次季节降雨主要集中在10-25天;根据次季节尺度降水变率的单点相关方法,发现卢旺达的次季节降水变率和周围区域变化一致;进一步合成结果显示该地区次季节降水变率与异常西风有关,这可追溯到赤道地区西传的赤道Rossby波.最后,本文评估了当前动力模式ECMWF对 卢旺达地区(即非洲中东部)次季节降水变率的预报能力,发现EC模式在对该区域降水和相关风场指数的预报技巧都在18天左右,且预报技巧表现出一定的年际差异,这可能与热带太平洋的背景海温信号有关.该工作增进了当 前对非洲中东部地区的次季节降水变率和预测水平的认知,并且对该地区国家粮食安全和防灾减灾具有启示性意义.