An Algorithm for the Determination of All Significant Pathways in Chemical Reaction Systems     

Ralph Lehmann 《Journal of Atmospheric Chemistry》2004,47(1):45-78

When the output of a complex chemical model is analysed, a typical topic isthe determination of pathways, i.e., reaction sequences, that produce ordestroy a chemical species of interest.A representative example is the investigation of catalytic ozone destruction cycles in the stratosphere.An algorithm for the automatic determination of pathways in any given reactionsystem is presented. Under the assumption that reaction rates are known, it finds all significant pathways, i.e., all pathways with a rate above a prescribed threshold.The algorithm forms pathways step by step, starting from single reactions.The chemical species in the system are consecutively considered as `branching points'.For every branching-point species, each pathway producing it is connected witheach pathway consuming it.Rates proportional to `branching probabilities' are calculated.Pathways with a rate that is smaller than a prescribed threshold arediscarded.If a newly formed pathway contains sub-pathways, e.g., null cycles, it is split into these simpler pathways.In order to demonstrate the performance of the algorithm, it has been applied to the determination of catalytic ozone destruction cycles and methaneoxidation pathways in the stratosphere.  相似文献   

Development characteristics of interlayer oxidation zone type of sandstone uranium deposits in the southwestern Turfan-Hami basin   总被引：3，自引：0，他引：3  

YANG Dianzhong  XIA Bin & WU Guogan Guangzhou Institute of Geochemistry  Chinese Academy of Sciences  Guangzhou  China 《中国科学D辑(英文版)》2004,47(5)

The known uranium ore and anomaly occur-rences are distributed mainly in the southwestern part of the Turfan-Hami basin. The focus of current explo-ration is placed on the leachable interlayered oxidation zone type of sandstone uranium deposits. Uranium deposits in the sedimentary basin can be classified into three types in accordance with their host rock types, i.e. the sandstone-type uranium deposits, the coal rock-type uranium deposits and the mud-stone-type uranium deposits. The sandstone…  相似文献   

Stability of arsenopyrite and As(III) in low-temperature acidic solutions   总被引：1，自引：0，他引：1  

YU Yunmei  ZHU Yongxuan & GAO Zhenmin Key Laboratory of Ore Deposit Geochemistry  Chinese Academy of Sciences  Guiyang  China 《中国科学D辑(英文版)》2004,47(5)

Arsenopyrite is one of the most important pri-mary arsenic mineral. In the Eh-pH diagram of the As-O2-S-H2O system, if the total arsenic concentration (TAs) is taken to be 0.75 mg/L, the total sulfur con-centration, 32 mg/L, the temperature, 25℃and the pressure, one atmosphere pressure for the discrimina-tion of arsenic species, it may be found that under hy-pergene conditions, arsenopyrite is a moderately stable mineral. Only in the strongly alkaline and reducing environment can arsenopy…  相似文献   

二连盆地可地浸砂岩型铀成矿的再认识   总被引：2，自引：3，他引：2  

刘武生  王正邦  谢佑新 《铀矿地质》2004,20(2):65-70

笔者从铀成矿条件入手 ,分析了二连盆地在基底演化期、含矿建造形成期以及后生改造成矿期各阶段对可地浸砂岩型铀矿的控制作用 ,认为二连盆地在含矿建造形成期是由众多分割性强的 ,构造演化和沉积变迁自成体系 ,并具有多物源、近物源特点的小凹陷所组成。同时 ,综合其他控制砂岩型铀矿的因素 ,确定了二连盆地是以发育潜水 层间氧化带砂岩型铀矿为其主要成矿类型 ,且矿床规模以中、小型为主 ,具有成群成带产出的特点。  相似文献   

Sulfur Isotopic Study of the Toyoha Deposit, Hokkaido, Japan Comparison between the Earlier-Stage and the Later-Stage Veins     

Morihisa HAMADA  Akira IMAI 《Resource Geology》2000,50(2):113-122

Abstract: The sulfur isotopic ratios (δ³⁴S) of ore minerals from the Toyoha deposit, Hokkaido, one of the largest Pb–Zn–Ag polymetallic vein-type deposits in Japan, were studied. More than 90% of the δ³⁴S values of the studied sulfide minerals collected from the Toyoha deposit range from +5 to +9%, with an average of approximately +7% irrespective of the mineral species, veins, elevations, depth, mineralization stages and mineral assemblages. Relatively uniform δ³⁴S values obtained in this study suggest that the reduced aqueous sulfur species predominated over the oxidized sulfur in the ore solution throughout the mineralization stages. Thus, the source of sulfur for the ore sulfides is postulated to be magmatic.
The temperature obtained from the fluid inclusion study and the temperature of the sulfur isotopic geothermometer are not consistent. This suggests that each mineral precipitated under disequilibrated conditions with respect to the sulfur isotope.
The change in redox conditions presumably encountered between the mineralization stages did not account for the isotopic fluctuations since the isotopic exchanges between the oxidized and reduced aqueous sulfurs are much slower than the rate of oxidation of the ore solution.  相似文献   

A Study of DMS Oxidation in the Tropics: Comparison of Christmas Island Field Observations of DMS, SO2, and DMSO with Model Simulations   总被引：2，自引：0，他引：2  

G. Chen  D. D. Davis  P. Kasibhatla  A. R. Bandy  D. C. Thornton  B. J. Huebert  A. D. Clarke  B. W. Blomquist 《Journal of Atmospheric Chemistry》2000,37(2):137-160

This study reports comparisonsbetween model simulations, based on current sulfurmechanisms, with the DMS, SO₂ and DMSOobservational data reported by Bandy et al.(1996) in their 1994 Christmas Island field study. For both DMS and SO₂, the model results werefound to be in excellent agreement with theobservations when the observations were filtered so asto establish a common meteorological environment. Thisfiltered DMS and SO₂ data encompassedapproximately half of the total sampled days. Basedon these composite profiles, it was shown thatoxidation of DMS via OH was the dominant pathway withno more than 5 to 15% proceeding through Cl atoms andless than 3% through NO₃. This analysis wasbased on an estimated DMS sea-to-air flux of 3.4 ×10⁹ molecs cm^-2 s^-1. The dominant sourceof BL SO₂ was oxidation of DMS, the overallconversion efficiency being evaluated at 0.65 ± 0.15. The major loss of SO₂ was deposition to theocean's surface and scavenging by aerosol. Theresulting combined first order k value was estimated at 1.6 × 10^-5 s^-1. In contrast to the DMSand SO₂ simulations, the model under-predictedthe observed DMSO levels by nearly a factor of 50. Although DMSO instrument measurement problems can notbe totally ruled out, the possibility of DMSO sourcesother than gas phase oxidation of DMS must beseriously considered and should be explored in futurestudies.  相似文献   

The Influence of Oxalate on Fe-Catalyzed S(IV) Oxidation by Oxygen in Aqueous Solution     

A. Wolf  F. Deutsch  P. Hoffmann  H. M. Ortner 《Journal of Atmospheric Chemistry》2000,37(2):125-135

This study demonstrates that oxalate has a strong inhibiting effect onFe-catalyzed S(IV) oxidation by oxygen in aqueous solution. While thepseudo-first order rate constant of S(IV) oxidation was determined to be1.6 × 10³ M^-1 s^-1 in experimentswithout oxalate, the oxidation of S(IV) was totally inhibited at a molarconcentration ratio of iron:oxalate = 1:5 at an oxalate concentration of 4M. Under these conditions, the Fe(II)/Fe(III) ratio remained nearlyconstant during the observed reaction time. The determined rate constants wereindependent of the initial oxidation state of iron. However, with increasingconcentrations of oxalate, a longer induction period is observed forexperiments with iron initially in the Fe(II) oxidation state.  相似文献   

环境样品中痕量元素的化学形态分析Ⅰ．分析技术在化学形态分析中的应用   总被引：21，自引：7，他引：21  

何红蓼 李冰杨红霞  倪哲明 《岩矿测试》2005,24(1):51-58

文章介绍了形态分析的基本概念,常用的联用分析技术,如气相色谱原子吸收光谱、气相色谱原子荧光光谱、气相色谱微波诱导等离子体原子发射光谱、气相色谱电感耦合等离子体质谱、高效液相色谱电感耦合等离子体质谱等在环境样品(水、土壤、沉积物)中痕量元素化学形态(价态、金属有机化合物等)分析中的应用,土壤和沉积物中污染元素的顺序提取步骤,以形态分析发展动态。引用文献72篇。  相似文献   

论晋北石炭二叠系紫色高岭石粘土的成因   总被引：3，自引：0，他引：3  

刘长龄  王双彬 《岩石学报》1987,3(2)

晋北地区石炭二叠系煤层中与四号及九号煤伴生的含有机质的软质耐火粘土,即高岭石粘上,俗称紫矸或紫木节。对紫矸的成因过去有两种看法:(1)原生沉积的;(2)后期风化残积“由煤变来的”。笔者认为除这两个因素同时存在外,还与成岩后生作用中有机酸的淋滤和高岭石的重结晶、有序化等有关,尤其是后期风化表生作用使有机质氧化淋滤去SiO_2形成一水软铝石、褪色、溶蚀多孔、质地疏松,形成今日所见紫色高岭石粘土。  相似文献   

Methoxy formation in the reaction of CH3O2 radicals with NO     

R. Zellner  B. Fritz  K. Lorenz 《Journal of Atmospheric Chemistry》1986,4(2):241-251

Formation of methoxy (CH₃O) radicals in the reaction (1) CH₃O₂+NOCH₃O+NO₂ at 298 K has been observed directly using time resolved LIF. The branching ratio % MathType!MTEF!2!1!+-% feaafeart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn% hiov2DGi1BTfMBaeXatLxBI9gBaerbd9wDYLwzYbItLDharqqtubsr% 4rNCHbGeaGqiVu0Je9sqqrpepC0xbbL8F4rqqrFfpeea0xe9Lq-Jc9% vqaqpepm0xbba9pwe9Q8fs0-yqaqpepae9pg0FirpepeKkFr0xfr-x% fr-xb9adbaqaaeGaciGaaiaabeqaamaabaabaaGcbaGaeqOXdyMaae% 4qaiaabIeadaWgaaWcbaGaae4maaqabaGccaqGpbGaaeiiaiaabIca% ieqacaWF9aGaa8hiaiaa-nbicaWFGaGaeuiLdqKaai4waiaaboeaca% qGibWaaSbaaSqaaiaabodaaeqaaOGaae4taiaac2facaWFVaGaeuiL% dqKaai4waiaaboeacaqGibWaaSbaaSqaaiaabodaaeqaaOGaae4tam% aaBaaaleaacaqGYaaabeaakiaac2facaqGPaaaaa!4E31!\[\phi {\rm{CH}}_{\rm{3}} {\rm{O (}} = -- \Delta [{\rm{CH}}_{\rm{3}} {\rm{O}}]/\Delta [{\rm{CH}}_{\rm{3}} {\rm{O}}_{\rm{2}} ]{\rm{)}}\] has been determined by quantitative cw-UV-laser absorption at 257 nm of CH₃O₂ and CH₃ONO, the product of the consecutive methoxy trapping reaction (2) % MathType!MTEF!2!1!+-% feaafeart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn% hiov2DGi1BTfMBaeXatLxBI9gBaerbd9wDYLwzYbItLDharqqtubsr% 4rNCHbGeaGqiVu0Je9sqqrpepC0xbbL8F4rqqrFfpeea0xe9Lq-Jc9% vqaqpepm0xbba9pwe9Q8fs0-yqaqpepae9pg0FirpepeKkFr0xfr-x% fr-xb9adbaqaaeGaciGaaiaabeqaamaabaabaaGcbaGaae4qaiaabI% eadaWgaaWcbaGaae4maaqabaGccaqGpbacbeGaa83kaiaa-bcaieaa% caGFobGaa43taiaa+bcacaGFOaGaa83kaiaa+1eacaGFPaGaa4hiai% abgkziUkaabccacaqGdbGaaeisamaaBaaaleaacaqGZaaabeaakiaa% b+eacaqGGaGaaeOtaiaab+eacaqGGaGaa4hkaiaa-TcacaGFnbGaa4% xkaiaa+5cacaGFGaGaa4hiaiabeA8aMnaaBaaajqwaacqaaiaaboea% caqGibWaaSbaaKazcaiabaGaae4maaqabaqcKfaGaiaab+eaaSqaba% aaaa!55AC!\[{\rm{CH}}_{\rm{3}} {\rm{O}} + NO ( + M) \to {\rm{ CH}}_{\rm{3}} {\rm{O NO }}( + M). \phi _{{\rm{CH}}_{\rm{3}} {\rm{O}}} \] is found to be (1.0±0.2). The rate constant k ₁ is (7±2) 10^-12 cm³/molecule · s in good agreement with previous results.  相似文献