Dissolved rare earth elements in river waters draining karst terrains in Guizhou Province,China

Winter seasonal concentrations of dissolved rare earth elements (REE) of two major river systems (the Wujiang River system and the Yuanjiang River system) in karst-dominated regions in winter were measured by using a method involving solvent extraction and back-extraction and subsequent ICP-MS measurements. The dissolved REE concentrations in the rivers and their tributaries are lower than those in most of the large rivers in the world. High pH and high cation (i.e., Na⁺ + Ca²⁺) concentrations of the rivers are the most important factors controlling the concentrations of dissolved REE in the river water. The dissolved load (<0.22 μm) REE distribution patterns of high-pH river waters are very different from those of low-pH river waters. The shale (PAAS)-normalized REE patterns for the dissolved loads are characterized by light REE-enrichment and heavy REE-enrichment. Water in the upper reaches of the Wujiang River generally shows light REE-enriched patterns, while that in the middle and lower reaches generally shows heavy REE-enriched patterns. The Yuanjiang River is heavy REE enriched with respect to the light REE in the same samples. Water of the Wuyanghe River draining dolomite-dominated terrains has the highest heavy REE-enrichment. Most river water samples show the shale-normalized REE patterns with negative Ce and Eu anomalies, especially water from Wuyanghe River. Y/Ho ratios show that the water/particle interaction might have played an important role in fractionation between HREE and LREE.     

天然气中甲烷和CO_2的二元同位素特征

不同成因的天然气由于形成温度不同,往往会有不同的稳定同位素特征。但是,由于经常不能同时获得天然气以及它的生成母体的同位素成分,很难用单独的C或H同位素成分来确定它的形成温度。在形成天然气时,不同的温度会形成不同的二元同位素的浓度,温度越低,二元同位素的比例越大,因此只需要知道天然气本身的二元同位素的浓度,就可以确定形成温度,从而避免了需要知道天然气生成母体的同位素成分这一难题。本文利用高级量子化学计算,预测了不同温度下天然气中甲烷和CO2气体的二元同位素(Clumped isotope)的特征,提供用于天然气成因分析的新方法。     

Factors controlling carbon isotope ratios of dissolved inorganic carbon in two major tributaries of the Han River,Korea

Understanding the carbon cycle of the Han River system in Korea is of prime interest in managing and preserving this valuable water resource for more than 20 million residents in the area. As a part of a comprehensive carbon cycling study for the Han River system, this report focuses on the carbon isotope compositions of dissolved inorganic carbon (DIC) in its two major tributaries, the North and the South Han Rivers. The major difference in carbonate chemistry of the tributaries originates primarily from the lithology of the catchment areas. The South Han River, draining a carbonate‐dominant terrain, has much higher alkalinities and DIC concentrations, whereas the lower concentrations in the North Han River indicate little influence of carbonate weathering. Likewise, δ¹³C_DIC values in the South Han River indicate that the DIC input from the carbonate rocks is important in controlling carbon isotope ratios of DIC. For the North Han River, the oxidation of organic material influences the amount of riverine DIC and δ¹³C_DIC values to a greater extent. Overall, remarkable seasonal and spatial variations of river chemistry and carbon isotope compositions of DIC reflect the variability in geo‐hydrologic characteristics, in the water regime, and in metabolic activities in the river water and/or the drainage areas. Copyright © 2006 John Wiley & Sons, Ltd.     

阿尔泰山南缘中泥盆世苦橄岩中单斜辉石的成分特征及其地质意义

岛弧苦橄岩非常稀少,但在阿尔泰山南缘却分布有世界上罕见的中泥盆世厚大苦橄岩层。本文对该地区苦橄岩及其共生的玄武岩中单斜辉石的矿物化学成分进行了电子探针分析,结果表明,苦橄岩中的单斜辉石全部为透辉石,玄武岩中的单斜辉石种属有普通辉石和透辉石两类,但玄武岩中的单斜辉石成分呈连续演化关系。根据单斜辉石-熔体平衡原理计算了苦橄岩中单斜辉石斑晶形成的温度和压力,其变化范围主要集中在1350～1387℃和16.6～21.3kPa,相应的深度为55～70km,大致代表了苦橄岩岩浆房的深度。与此不同的是,玄武岩中单斜辉石斑晶结晶的深度较苦橄岩浅,为37～41km,暗示玄武岩浆是在相对低压条件下分离结晶后形成的演化岩浆。基于单斜辉石的成分和演化,确定了该地区火山岩属亚碱性系列,其构造背景为岛弧环境。     

Alkaline gabbroids of the Chirii outcrop (North Minusa depression): mineralogy and melt evolution

We studied the chemical composition of rock-forming minerals in gabbroids from the Chirii outcrop and the evolutionary features of parental basic melt during the crystallization of these rocks. Results were compared with data for basanites from pipes of the North Minusa depression. The mineralogical composition and thermobarogeochemical data of the gabbroids were examined in detail, and chemical analyses of rock-forming minerals (clinopyroxene, plagioclase, amphibole, biotite, titanomagnetite, and apatite) were carried out. Based on the homogenization temperatures of primary melt inclusions, we established the minimum temperatures and sequence of mineral crystallization in the gabbroids: clinopyroxene (>1160 °C), plagioclase, magnetite → amphibole (>950 °C) → biotite. The rock crystallization proceeded at shallow depths. Thermometric data are confirmed by results of modeling of equilibrium gabbroid crystallization. The crystallization of parental basic melt was accompanied by the accumulation of SiO₂, Al₂O₃, alkalies, and Cl and depletion in femic components. The melt evolved to granodiorite and alkali-syenite compositions. Compared with basanites from pipes, the parental melt had a longer evolution. The geochemical features of the gabbroids indicate that they, like basanites, crystallized from intraplate alkali-basaltoid magmas. But in petrochemistry and mineralogy the Chirii gabbroids differ considerably from the pipe basanites.     

On the fast movements of the thermosphere: an interpretation

We examine the oscillations of the meridional neutral wind in the F region as seen by the EISCAT radar. We propose an interpretation in term of eddies (tourbillons) of typical size of a few tens to a few hundreds of kilometers. The observed rotation velocity is a few hundreds of meters per second. We suggest that the tourbillons are a common feature of thermospheric movements. We propose an optical experiment to check the validity of this assumption.     

Sensitivity Analysis of Photochemical Indicators for O<Subscript>3</Subscript> Chemistry Using Automatic Differentiation

Photochemical indicators for determination of O₃–NO_x–ROG sensitivity and their sensitivity to model parameters are studied for a variety of polluted conditions using a comprehensive mixed-phase chemistry box model and the novel automatic differentiation ADIFOR tool. The main chemical reaction pathways in all phases, interfacial mass transfer processes, and ambient physical parameters that affect the indicators are identified and analyzed. Condensed mixed-phase chemical mechanisms are derived from the sensitivity analysis.Our results show that cloud chemistry has a significant impact on the indicators and their sensitivities, particularly on those involving H₂O₂, HNO₃, HCHO, and NO_z. Caution should be taken when applying the established threshold values of indicators in regions with large cloud coverage. Among the commonly used indicators, NO_y and O₃/NO_y are relatively insensitive to most model parameters, whereas indicators involving H₂O₂, HNO₃, HCHO, and NO_z are highly sensitive to changes in initial species concentrations, reaction rate constants, equilibrium constants, temperature, relative humidity, cloud droplet size, and cloud water content.     

Multi-Phase Chemistry of C<Subscript>2</Subscript> and C<Subscript>3</Subscript> Organic Compounds in the Marine Atmosphere

A box model is used to explore the detailed chemistry of C₂ and C₃ organic compounds in the marine troposphere by tracing the individual reaction paths resulting from the oxidation of ethane, ethene, acetylene, propane, propene and acetic acid. The mechanisms include chemical reactions in the gas phase and in the aqueous phase of clouds and aerosol particles at cloud level under conditions resembling those in the northern hemisphere. Organic hydroperoxides are found to be important intermediate products, with subsequent reactions leading partly to the formation of mixed hydroxy or carbonyl hydroperoxides that are readily absorbed into cloud water, where they contribute significantly to the formation of multifunctional organic compounds and organic acids. Organic hydroperoxides add little to the oxidation of sulfur dioxide dissolved in the aqueous phase, which is dominated by H₂O₂. Next to acetaldehyde and acetone, glycol aldehyde, glyoxal, methyl glyoxal and hydroxy propanone are prominent oxidation products in the gas and the aqueous phase. Acetaldehyde is not efficiently converted to acetic acid in clouds; the major local sources of acetic acid are gas-phase reactions. Other acids produced include hydroperoxy acetic, glycolic, glyoxylic, oxalic, pyruvic, and lactic acid. The mechanism of Schuchmann et al. (1985), which derives glycolic and glyoxylic acid from the oxidation of acetate, is found unimportant in the marine atmosphere. The principal precursors of glyoxylic acid are glyoxal and glycolic acid. The former derives mainly from acetylene and ethene, the latter from glycolaldehyde, also an oxidation product of ethene. The oxidation of glyoxylic acid leads to oxalic acid, which accumulates and is predicted to reach steady state concentrations in the range 30–90 ng m⁻³. This is greater, yet of the same magnitude, than the concentrations observed over the remote Pacific Ocean.     

The developmental history of Adirondack (N.Y.) lakes

We utilized paleoecological techniques to reconstruct long-term changes in lake-water chemistry, lake trophic state, and watershed vegetation and soils for three lakes located on an elevational gradient (661–1150 m) in the High Peaks region of the Adirondack Mountains of New York State (U.S.A.). Diatoms were used to reconstruct pH and trophic state. Sedimentary chrysophytes, chlorophylls and carotenoids supplied corroborating evidence. Pollen, plant macrofossils, and metals provided information on watershed vegetation, soils, and biogeochemical processes. All three lakes were slightly alkaline pH 7–8 and more productive in the late-glacial. They acidified and became less productive at the end of the late-glacial and in the early Holocene. pH stabilized 8000–9000 yr B.P. at the two higher sites and by 6000 yr B.P. at the lowest. An elevational gradient in pH existed throughout the Holocene. The highest site had a mean Holocene pH close to or below 5; the lowest site fluctuated around a mean of 6. The higher pH and trophic state of the late-glacial was controlled by leaching of base cations from fresh unweathered till, a process accelerated by the development of histosols in the watersheds as spruce-dominated woodlands replaced tundra. An apparent pulse of lake productivity at the late-glacial-Holocene boundary is correlated with a transient, but significant, expansion of alder (Alnus crispa) populations. The alder phase had a significant impact on watershed (and hence lake) biogeochemistry. The limnological changes of the Holocene and the differences between lakes were a function of an elevational gradient in temperature, hydrology (higher precipitation and lower evapotranspiration at higher elevation), soil thickness (thinner tills at higher elevation), soil type (histosols at higher elevation), vegetation (northern hardwoods at lower elevation, spruce-fir at higher), and different Holocene vegetational sequences in the three watersheds.This is the thirteenth of a series of papers to be published by this journal that was presented in the paleolimnology sessions organized by R. B. Davis and H. Löffler for the XIIth Congress of the International Union for Quaternary Research (INQUA), which took place in Ottawa, Canada in August 1987. Dr. Davis is serving as guest editor of this series.     

Influence of sea salt on stream water chemistry in an upland afforested catchment

The chemistry of bulk precipitation and stream water was monitored in an acidic afforested catchment at Llyn Brianne in upland Wales between 1985 and 1990. Throughfall, stemflow and soil water chemistry were also monitored between 1988 and 1989. Marine-derived solutes dominated the ionic composition of precipitation and stream water, which had mean Cl concentrations of 113 μequiv. 1^?1 and 245 μequiv. 1^?1, respectively. The higher concentrations in stream water reflect occult and dry deposition on the forest canopy and the effect of interception and transpiration losses. Chloride variations in stream water (112-454μequiv. 1^?1) were damped compared with bulk precipitation (28-762μequiv. 1^?1) due to the mixing of event (‘new’) water with pre-event (‘old’) water in the catchment soils. A storm episode monitored in the catchment in April 1989 was associated with high sea salt inputs and Cl concentrations in throughfall (1466μequiv. 1^?1) and storm runoff were exceptionally high (392μequiv. 1^?1). The Cl signal in stream water during the episode was consistent with an event (‘new’) water contribution to the storm response. However, a short-term hydrochemical budget estimated that although Cl outputs from the catchment during the event (1.17 kg ha^?1) were equivalent to 8% of inputs in throughfall and stemflow, the storm runoff was equivalent to 32% of effective precipitation. This indicates that pre-event (‘old’) water was the dominant source (> 75%) of storm runoff. Although sea salt inputs during the event had a marked impact on stream water chemistry, the anomalously high levels of acidity sometimes associated with sea salt events were not observed in this particular study.