Winkler's method overestimates dissolved oxygen in seawater: Iodate interference and its oceanographic implications     

George T.F. Wong  Kuo-Yuan Li 《Marine Chemistry》2009,115(1-2):86-91

Dissolved oxygen in seawater has been determined by using the Winkler's reaction scheme for decades. An interference in this reaction scheme that has been heretofore overlooked is the presence of naturally occurring iodate in seawater. Each mole of iodate can result in an apparent presence of 1.5 mol of dissolved oxygen. At the concentrations of iodate in the surface and deep open ocean, it can lead to an overestimation of 0.52 ± 0.15 and 0.63 ± 0.05 μmol kg^− 1 of oxygen in these waters respectively. In coastal and inshore waters, the effect is less predictable as the concentration of iodate is more variable. The solubility of oxygen in seawater was likely overestimated in data sources that were based on the Winkler's reaction scheme for the determination of oxygen. The solubility equation of García and Gordon [Garcia H.E., Gordon, L.I., 1992. Oxygen solubility in seawater: Better fitting equations. Limnol. Oceanogr. 37, 1307–1312] derived from the results of Benson and Krause [Benson, F.B., Krause, D. Jr., 1984. The concentration and isotopic fractionation of oxygen dissolved in freshwater and seawater in equilibrium with the atmosphere. Limnol. Oceanogr. 29, 620–632] is free from this source of error and is recommended for general use. By neglecting the presence of iodate, the average global super-saturation of oxygen in the surface oceans and the corresponding efflux of oxygen to the atmosphere both have been overestimated by about 8%. Regionally, in areas where the degree of super-saturation or under-saturation of oxygen in the surface water is small, such as in the tropical oceans, the net air–sea exchange flux can be grossly under- or overestimated. Even the estimated direction of the exchange can be reversed. Furthermore, the presence of iodate can lead to an overestimation of the saturation anomaly of oxygen in the upper ocean attributed to biological production by 0.23 ± 0.07%. AOU may have been underestimated by 0.52 ± 0.15 and 0.63 ± 0.05 μmol kg^− 1 in the surface mixed layer and deep water, while preformed phosphate and preformed nitrate may have been overestimated by 0.004 ± 0.001 and 0.06 ± 0.02 μmol kg^− 1 in the surface mixed layer, and 0.005 ± 0.0004 and 0.073 ± 0.006 μmol kg^− 1 in the deep water. These are small but not negligible corrections, especially in areas where the values of these parameters are small. At the increasing level of sophistication in the interpretation of oxygen data, this source of error should now be taken into account. Nevertheless, in order to avoid confusion, an internationally accepted standard needs to be adopted before these corrections can be applied.  相似文献   

地幔转换带中的水及其地球动力学意义   总被引：3，自引：0，他引：3       下载免费PDF全文

杨翠平  金振民  吴耀 《地学前缘》2010,17(3):114

综述了近20年国际上地幔转换带中水的研究进展。前人研究表明,地球深部的水主要以OH-(hy-droxyl)形式存储在名义上无水矿物(NAMs)中。高温高压实验研究表明,地幔转换带中的主要矿物均具有较高的储水能力,且在转换带的温压条件下,其储水能力随着温度的升高而降低,其中瓦兹利石(β-Ol)和林伍德石(γ-Ol)的储水能力为2%～3%,超硅石榴子石(Mj)的储水能力为0.1%左右,据此估算地幔转换带的储水能力约为1.2%～1.91%,是地表水总量的3.9～6.2倍;而转换带除外的上地幔和下地幔主要矿物的含水量或储水能力均小于0.1%,因此与上、下地幔相比,地幔转换带可能是地幔的主要储水库。尽管地幔转换带具有较强的储水能力,但对地幔转换带的实际含水量还存在干、湿两方面的地质和地球物理证据和争议。地幔转换带中的水会对转换带中一系列的过程产生重要影响,当水含量增加时,橄榄石(Ol)向β-Ol、γ-Ol分解以及超硅石榴石的分解反应分别向低压、高压和低压方向迁移,从而由橄榄石向β-Ol和γ-Ol分解两个相变反应界定的转换带宽度也会增加;水还会使地幔深部的部分熔融温度降低,熔体的密度降低;同时,水的加入可以很好地解释地幔岩"pyrolite"模型在410km不连续面处产生的与地震波测量不相符突变,也可以解决全地幔对流模式所不能解释的地幔成分分层问题。因此,深入研究和探讨转换带中的水对地球深部动力学过程的影响,包括中国东部地区受太平洋板块深俯冲作用的影响,均具有重要的约束和研究意义。  相似文献   

Phase Equilibrium and Phase Diagram of the Ternary System(MgCl_2 + MgB_2O_4 + H_2O) at 288 and 298 K     

GUO Yafei  SUN Shiru  GAO Diaolin  YU Xiaoping  WANG Shiqiang  DENG Tianlong 《《地质学报》英文版》2014,88(Z1):326-327

正1 Introduction The brines with high concentrations of magnesium and boron resources are widely distributed in the Qaidam Basin of the Qinghai-Tibet plateau,China(ZhengTang,1988).Although some works on the ternary system  相似文献   

The Metastable Phase Equilibria of the MeX-MgCl_2-H_2O Systems     

ZENG Ying  YU Xudong  MU Pengtao  FENG Shan 《《地质学报》英文版》2014,88(Z1):398-398

正1 Introduction The Pingluoba brine,which characterized as high concentration with sodium,potassium,boron,lithium,and rubidium,possess great development value.The main composition of the brine can be summarized to the  相似文献   

稀有金属矿物溶解度对花岗伟晶岩成矿作用的制约     

唐勇  覃山县  赵景宇  吕正航  刘喜强  王宏  陈剑争  张辉 《地学前缘》2022,29(1):81-92

花岗伟晶岩型矿床是稀有金属矿床重要的类型之一。在花岗伟晶岩中,稀有金属元素Li、Be、Nb和Ta主要以独立矿物的形式存在,前人对稀有金属独立矿物在硅酸盐熔体中的溶解度及其影响因素展开了系统研究。本文综合分析了已有的实验数据,其结果表明,影响稀有金属独立矿物溶解度最为重要的2个参数是温度(T)和铝饱和指数(ASI)。因此本文建立了稀有金属独立矿物,尤其是铌锰矿和钽锰矿溶解度,与温度(T)和铝饱和指数(ASI)之间的定量关系: lg [w(Li)/10^-6]=-0.37×[1 000/(T/K)]+4.56,R²=0.44 lg [w(BeO)/10^-6]=-4.21×[1 000/(T/K)]+6.86,R²=0.91 lg [K_sp(Nb)/(mg²·kg^-2)]=-(2.86±0.14)×ASI_(Mn+Li)-(4.95±0.31)×[1 000/(T/K)]+(4.20+0.28),R²=0.86 lg [K_sp(Ta)/(mg²·kg^-2)]=-(2.46±0.11)×ASI_(Mn+Li)-(4.86±0.30)×[1 000/(T/K)]+(4.00+0.30),R²=0.80 式中,温度T为热力学温度,ASI_(Mn+Li)(ASI=Al₂O₃/(CaO+Na₂O+K₂O+Li₂O+MnO),摩尔分数比)和T的适用范围分别为0.6~1.2和1 073~1 373 K的范围内。上述公式为估算硅酸盐熔体中稀有金属含量提供了便利,为量化花岗伟晶岩成矿模型提供了基础。 稀有金属独立矿物溶解度随温度降低和铝饱和指数的增加而急剧降低,因此,在岩浆演化过程中,由岩浆侵位、分离结晶以及流体作用等因素引起的岩浆温度降低和铝饱和指数的增加,是导致稀有金属独立矿物结晶的主要机制。  相似文献   

钨在矿物/熔体和溶液/熔体中的分配行为及其对成矿作用的影响   总被引：1，自引：0，他引：1  

喻晓  赵博  张德会  黄诚  王新彦  和成忠 《矿物岩石地球化学通报》2015,(3)

总结了钨(W)在地球不同圈层、不同相以及不同集合体之间的分配行为,并据此来探讨与花岗岩有关的热液型钨矿床的某些成因机制,并将W矿化所需的较高的浓集系数归因于这一系列不均匀分配行为的累积。同时强调了W在溶液/熔体体系,尤其是富F体系中的分配行为是理解其成矿机理的关键。热液中W主要以钨酸(根)和碱性钨酸盐离子存在,后因流经理化条件(温度、盐度、p H值)骤变而沉淀成矿。  相似文献   

Solubility of Anhydrite, CaSO4, in NaCl-H2O Solutions at High Pressures and Temperatures: Applications to Fluid-Rock Interaction   总被引：1，自引：0，他引：1  

NEWTON  ROBERT C.; MANNING  CRAIG E. 《Journal of Petrology》2005,46(4):701-716

Anhydrite solubility in H₂O–NaCl solutions was measuredat 6–14 kbar, 600–800°C and NaCl mole fractions(X_NaCl) of 0–0·3 in piston–cylinder apparatus.Solubilities were determined by weight changes of natural anhydritein perforated Pt envelopes confined with fluid in larger Ptcapsules. In initially pure H₂O at 10 kbar and 800°C, CaSO₄concentration is low (0·03 molal), though much largerthan at the same temperature and 1 kbar. Hematite-buffered experimentsshowed slightly lower solubilities than unbuffered runs. CaSO₄solubility increases enormously with NaCl activity: at 800°Cand 10 kbar and X_NaCl of 0·3, CaSO₄ molality is 200 timeshigher than with pure H₂O. Whereas CaSO₄ solubility in pureH₂O decreases with rising T at low T and P, the high-P resultsshow that anhydrite solubility increases with T at constantP at all X_NaCl investigated. The effects of salinity and temperatureare so great at 10 kbar that critical mixing between sulfate-richhydrosaline melts and aqueous salt solutions is probable at900°C at X_NaCl 0·3. Recent experimental evidencethat volatile-laden magmas crystallizing in the deep crust mayevolve concentrated salt solutions could, in light of the presentwork, have important implications regarding such diverse processesas Mount Pinatubo-type S-rich volcanism, high-f O₂ regionalmetamorphism, and emplacement of porphyry Cu–Mo ore bodies,where anhydrite–hematite alteration and fluid inclusionsreveal the action of very oxidized saline solutions rich insulfur. KEY WORDS: anhydrite; sulfur; solubility; metamorphic brines; granulites  相似文献   

Ionic association in H₂O–CO₂ fluids at mid-crustal conditions     

J. V. WALTHER 《Journal of Metamorphic Geology》1992,10(6):789-797

The equilibrium constant, K _a, of the association reaction to form ion pairs from charged solute species in supercritical solutions can be calculated from a model based on published equations. Log K _a at constant pressure is a linear function of the inverse in the dielectric constant of the fluid times temperature. The dielectric properties of H₂O and CO₂ at supercritical pressures and temperatures can also be evaluated using the Kirkwood equation. Using Looyenga mixing rules, the dielectric constant of H₂O–CO₂ mixtures can be obtained and the change in log K _a with addition of CO₂ in aqueous solutions evaluated. These changes in log K _a with addition of CO₂ are consistent with measured changes of log K _a with addition of Ar in supercritical H₂O–Ar solutions.
Log K _a of KCl and NaCl increase to an increasing extent as the mole fraction of CO₂ increases in H₂O–CO₂ solutions. For instance, at 2 kbar and constant temperature between 400 and 600° C, log K _a of KCl increases by about two orders of magnitude whilst that of NaCl increases by over four orders of magnitude as the CO₂ mole fraction increases from 0.0 to 0.35. Such changes in log K _a will have dramatic effects on the solubility of minerals in CO₂-rich environments.  相似文献   

Prediction of heavy metal solubility in agricultural topsoils around two smelters by the physico-chemical parameters of the soils   总被引：1，自引：0，他引：1  

Matthieu?Fran?oisEmail author  Henri-Charles?Dubourguier  Dongyan?Li  Francis?Douay 《Aquatic Sciences - Research Across Boundaries》2004,66(1):78-85

  相似文献   

大气气溶胶中的铁及其溶解度研究综述          下载免费PDF全文

齐宇轩  周杨 《山东气象》2021,41(2):1-13

生物活性铁(Fe) 进入生物地球化学循环中能够调节碳循环,影响海洋初级生产力,间接影响全球气候变化。决定 Fe生物可利用度的关键因子是可溶Fe含量,其中大气气溶胶的长距离传输是上层海洋获取生物可利用Fe的重要来源。近年来,对气溶胶中的Fe及溶解度的研究取得了重要进展,包括对不同区域Fe质量浓度和溶解度的观测以及对Fe溶解度影响因素的讨论。基于以上研究成果,汇总了近二十年全球部分陆地和海洋站点观测所得的不同粒径气溶胶颗粒物中的Fe质量浓度及其溶解度数据;重点介绍了气溶胶沉降入海洋前影响Fe溶解度的主要因素,包括Fe的来源、大气物理过程以及大气化学和传输混合过程等,并就各影响因素间的关联及相对重要性展开讨论;对未来气溶胶 Fe的研究方向和方法提出建议。  相似文献