夏季长江河口潮间带反硝化作用和N2O的排放与吸收

采用培养箱乙炔抑制和现场静态箱法,于夏季(7月)在长江河口潮滩潮间带进行了采样,研究表明,长江河口潮滩水体自身N2O产生速率很低,在潮汐淹没期沉积物是上覆水体N2O的来源,其来自沉积物中反硝化、硝化等氮素循环的多个反应过程,沉积物中N2O自然产生速率在0.10～8.50μmol/(m2·h)之间,反硝化速率在21.91～35.87μmol/(m2·h)之间。退潮出露期中潮滩是大气N2O的排放源犤交换速率在-11.03～13.17μmol/(m2·h)之间犦,5～10cm地温是影响N2O排放速率的显著性因素;低潮滩-大气界面N2O排放、吸收速率在-5.75～0.49μmol/(m2·h)之间。总体上看,中潮滩是大气N2O的排放源;而低潮滩对大气N2O有明显的吸收作用。潮滩植被(海三棱草和底栖藻类)的光合作用明显抑制了N2O的排放并可能导致吸收,而其呼吸作用则增加了N2O的排放,潮间带-大气界面N2O的排放和吸收与CO2的排放、吸收有显著的正相关关系。     

三峡水库香溪河支流水域温室气体排放通量观测

开展对香溪河支流水体的温室气体排放观测,有助于增加对三峡水库支流温室气体排放情况的了解以及水华对温室气体排放的影响.研究采用静态箱-气相色谱法,于2009年10月至2010年10月先后11次开展对香溪河支流水体3种温室气体(二氧化碳、甲烷、氧化亚氮)排放强度的观测,结果表明:观测期间香溪河支流的二氧化碳平均排放通量约为76.52 mg/(m2·h),排放强度与水体中叶绿素a浓度呈显著负相关,支流水华期间,二氧化碳排放通量小于0,表现为对大气中二氧化碳的吸收;支流甲烷平均排放通量约为0.244 9 mg/(m2·h);氧化亚氮平均排放水平约为0.011 7 mg/(m2·h).通过将甲烷平均排放水平与三峡水库其它区域开展的研究结果进行对比表明:三峡水库的甲烷排放水平很低,明显不同于已有基于国外水库平均排放水平对三峡水库全区甲烷排放的估算结果.     

长白山火山区温泉温室气体排放通量研究

温泉是深部岩浆活动在地表的直接表现,并且向大气圈排放大量的温室气体.然而,国内尚无火山区温泉排放的温室气体通量研究报道.我国长白山火山区水热活动强烈,主要有湖滨温泉带、聚龙温泉群、锦江温泉以及火山口外围的十八道沟温泉.本文利用数字皂膜流量计测量温泉气体排放通量,并结合前人对长白山火山区温泉气体成分的研究成果,估算了研究区温泉所排放的温室气体通量.结果表明,长白山火山区温泉排放的CO2通量为6.9×104t·a-1,CH4排放通量为428.44t·a-1,与意大利Pantelleria Island火山区温泉排放的温室气体通量规模相当.本文的测试结果表明:数字皂膜流量计在火山区温室气体排放通量估算研究中的应用是可行的.     

太湖梅梁湾温室气体(CO2,CH4和N2O)浓度的昼夜变化及其控制因素

营养盐载荷增加、富营养化以及全球增温等对湖泊温室气体的影响目前认识还很有限,原因之一在于对湖泊温室气体产生的动力过程了解不够深入,缺少高时间分辨率的现场观测数据.为了解决这一问题,在富营养的太湖梅梁湾水体,每一小时收集一个样品,直接分析N2O和CH4饱和度、CO2分压(pCO2)以及其他地球化学参数.在7月份的观测中,N2O和CH4显示出显著的昼夜变化规律.相关性分析表明,有机质降解是调节湖泊N2O和CH4变化的重要因素之一.虽然人为活动是控制湖泊温室气体大规模变化的主要因素,但沉积物一水界面的生物地球化学过程对温室气体浓度在短时间尺度上的变化有着重要的影响.研究结果揭示了湖泊温室气体除了受人为活动影响外,湖泊自身的生物地球化学过程也是重要的调控因素之一.     

川中丘陵水旱轮作土壤—小麦系统CO2排放及其影响因素

利用静态箱／气相色谱法对川中丘陵区水旱轮作区的小麦进行全生长季CO2排放观测。结果表明：①土壤-小麦系统的CO2排放通量存在着明显的日变化。凌晨 4：00～6：00排放量最低，随着温度的升高，CO2的排放量逐渐增大，在午后 1：00～3：00达到峰值。分析表明，气温和地表温度与土壤-小麦系统CO2排放通量之间存在显著的相关关系。②土壤-小麦系统CO2排放都有明显的季节变化。分析表明，小麦生物量和气温与土壤-小麦系统CO2排放季节变化之间存在显著的相关关系。③在小麦各个生育期中，CO2平均排放通量常规处理＞无氮处理＞空白＞裸地。水旱轮作区小麦常规处理、无氮处理、空白点和裸地的CO2排放通量的平均值分别为574．51、362．23、 239．91、129．47 m g／（ m 2· h）。     

过去1 000 a大气中主要温室气体冰芯记录研究概述

对南北两极和中低纬度山地冰芯中开展的温室气体的相关研究进行了回顾.结果显示:在1000aBP到工业革命阶段,大气中CO2,CH4和N2O等温室气体的浓度及气体稳定同位素受各种自然来源影响显著,平均含量较低,浓度波动也较小;工业革命之后,随着人类工农业等活动对环境的影响的加剧,大气中3种温室气体的含量呈现出剧烈的上升趋势.2007年IPCC第四次评估报告显示,目前CO2、CH4和N2O气体浓度的全球大气平均含量分别达到379mL·m-3、1774μL·m-3和319μL·m-3.对影响工业革命前南极、格陵兰及青藏高原冰芯中温室气体的含量的因素总结发现,由于受不同的温度、杂质含量等条件的影响,温室气体含量区域差异较大.1800A.D.以前,格陵兰冰芯中CO2的含量较南极冰芯高出9mL·m-3,青藏高原达索普冰芯CH4平均含量较南极和格陵兰冰盖高出15%～20%,格陵兰冰芯中的N2O含量也明显高于南极冰芯.工业革命以后,冰芯中3种气体浓度表现出强烈的上升趋势,并均达到1000A.D.以来的最高值.     

黄海秋季典型站位沉降颗粒物的垂直通量

2002年9月,在海州湾外侧(E1站)、黄海冷水团(E2站)和黄、东海毗邻水域(E3站)分别放置沉积物捕获器采集沉降颗粒物,研究其垂直通量.结果显示,E1、E2和E3站底层颗粒物沉降通量分别为215.44 g/(m2·d)、165.51 g/(m2·d)、873.91 g/(m2·d),POC沉降通量分别为3.15 g/(m2·d)、2.22 g/(m2·d)、10.49 g/(m2·d).生源颗粒物是E1站位次表层POC的主要来源.E3站水体底层的大量悬浮颗粒物主要来自沉积物的再悬浮,再悬浮强烈程度及影响深度均高于E1站.通过模型计算出E2站底层颗粒物再悬浮比率平均(±SD)为95.65(±2.14)%,底表沉积物再悬浮通量占总再悬浮通量的百分比(X值)为89.53%,显示秋季底部平流对黄海冷水团区再悬浮通量影响不大,但这种影响在夏季相对较强.E2站POC净沉降通量为192 mg/(m2·d),生源颗粒物是此站位POC通量的主要贡献者.由于温跃层的长期存在,营养盐贫乏,生物生长受到抑制,导致黄海冷水团区秋季POC通量小于夏季.     

非火山地热区玛旁雍热田土壤CO_2脱气研究

地热活动是地球脱气的重要形式之一,其过程常伴随大量温室气体排放。选取非火山地热区西藏玛旁雍热田作为研究对象,基于菲克扩散定律对地热田区土壤CO_2脱气量进行评估。结果表明:该区一般土壤CO_2脱气通量为0.167~0.771 kg/(m2·a),含喷气孔区域土壤CO_2脱气通量为2.054~7.877 kg/(m2·a),含喷气孔地区的土壤CO_2脱气通量是一般土壤脱气量的18.9倍;与全球火山区土壤脱气量(0.001~2.25 Mt/(m2·a))相比,其值显著偏低;但比青藏高原高寒草原生态系统土壤的CO_2排放量(187.46 g/(m2·a))大。结合区域地质背景推测地热系统中的CO_2含量主要来源于岩浆脱气和热液同长石等围岩矿物的蚀变反应。区内土壤CO_2的低脱气通量受透水性较差的碎屑岩沉积盖层约束。     

青藏高原腹地不同退化程度高寒沼泽草甸生长季节CO2排放通量及其主要环境控制因子研究

采用静态箱～便携式红外色谱法对青藏高原风火山地区3种不同退化程度高寒沼泽草甸CO2排放通量进行了研究. 结果表明: 在整个生长期内3种不同退化程度沼泽草甸均表现为正排放, 排放高峰集中在7-8月份, 平均排放通量分别高达111.48 mg·m-2·d-1(未退化)、 77.28 mg·m-2·d-1(中度退化)和38.12 mg·m-2·d-1(严重退化). 不同退化程度沼泽草甸之间CO2排放通量存在明显差异, 表现为未退化>中度退化>严重退化. 气温、 5 cm土壤温度和湿度与3种不同退化程度高寒沼泽草甸CO2排放通量之间均呈显著正相关关系, 是控制CO2排放的主要环境因子.     

温室气体浓度变化及其源与汇研究进展

对工业革命以来大气中主要温室气体浓度变化和增长趋势作了简介。概述了冰芯研究的最新成果:420 ka BP以来CO2浓度变化情况及其揭示的气候变化机制;全新世期间CH4浓度的波动;气候事件中N2O浓度的快速波动及工业化前的水平。总结了全球温室气体源与汇的研究现状,重点介绍了全球碳循环研究中的未知汇问题,列举了根据不同资料和模型估计的陆地碳汇位置和幅度以及影响因素对陆地碳汇的贡献等认识上的差异。简单介绍了国内有关温室气体源与汇研究,如稻田CH4排放、岩溶系统碳循环和黄土中温室气体组分特征等方面的研究成果和认识。     

Internally-Consistent Thermodynamic Data for Minerals in the System Na2O-K2O-CaO-MgO-FeO-Fe2O3-Al2O3-SiO2-TiO2-H2O-CO2

Internally consistent standard state thermodynamic data arepresented for 67 minerals in the system Na₂O-K₂O-CaO-MgO-FeO-Fe₂O₃-Al₂O₃-SiO₂-TiO₂-H₂O-CO₂.The method of mathematical programming was used to achieve consistencyof derived properties with phase equilibrium, calorimetric,and volumetric data, utilizing equations that account for thethermodynamic consequences of first and second order phase transitions,and temperature-dependent disorder. Tabulated properties arein good agreement with thermophysical data, as well as beingconsistent with the bulk of phase equilibrium data obtainedin solubility studies, weight change experiments, and reversalsinvolving both single and mixed volatile species. The reliabilityof the thermodynamic data set is documented by extensive comparisons(Figs. 4–45) between computed equilibria and phase equilibriumdata. The high degree of consistency obtained with these diverseexperimental data gives confidence that the refined thermodynamicproperties should allow accurate prediction of phase relationshipsamong stoichiometric minerals in complex chemical systems, andprovide a reasonable basis from which activity models for mineralsmay be derived.     

Siderit-Magnesit-Mischkristallbildung im system Mg2+-Fe2+-CO 3 2− -Cl 2 2− -H2O

The formation of the solid solution series MgCO₃-FeCO₃ in the system Mg²⁺-Fe²⁺-CO ₃ ^2? -Cl ₂ ^2? -H₂O has been investigstad between 200° C and 500° C. The experimental results show that the composition of any of these carbonates strongly depends on the temperature: At high temperatures mixed crystals rich in MgCO₃ are formed and low temperatures lead to the formation of FeCO₃-rich carbonates. Thus, at 200° C a Fe-poor (Mg-rich) solution is in equilibrium with a Fe-rich carbonate. At temperatures higher than 350° C a Fe-rich (Mg-poor) solution coexists with a Fe-poor (Mg-rich) solid phase; see Fig. 1. At 350° C a solution with a mole fraction^mFe²⁺/(^mFe²⁺+^mMg²⁺) of 0.20 leads to the formation of magnesite very poor in Fe, whereas at 250° C the same solution is in equilibrium with sideroplesit, containing 80 Mol-% FeCO₃, see Figs. 2 and 3. The importance of the experimental results for the formation of deposits of magnesite and siderite is discussed.     

Electrochemical Evidence for Pentasulfide Complexes with Mn2+, Fe2+, Co2+, Ni2+, Cu2+ and Zn2+

A series of stable pentasulfide complexes of the common base metals, Mn, Fe, Co, Ni, Cu and Zn exist in aqueous solutions at ambient temperatures. Pure sodium pentasulfide was prepared and reacted with the divalent cations of Mn, Fe, Co, Ni, Cu and Zn in aqueous solution at ambient temperature. The S52- complexes were found to exist as determined by voltammetric methods.Pentasulfide complexes with compositions assigned as [M(1-S5)] and [M2(- S5)]2+ occur for Mn, Fe, Co and Ni where only one terminal S atom in the S52- binds to one metal (1 = mono-dentate ligand or M-S-S-S-S-S, = ligand bridging two metal centers or M-S-S-S-S-S-M). Conditional stability constants are similar for all four metals with log 1 between 5.3 and 5.7 and log 2 between 11.0 and 11.6. The constants for these pentasulfide complexes are similar to the tetrasulfide complexes and are approximately 0.4–0.8 log units higher than for comparable bisulfide complexes [M(SH)]+ as expected based on the higher nucleophilicity of S52- compared to HS-. Voltammetric results indicate that these are labile complexes.As with the bisulfide and tetrasulfide complexes, Zn(II) and Cu(II) are chemically distinct from the other metals. Zn(II) reacts with pentasulfide to form a stable monomeric pentasulfide chelate, [Zn(1-S5)] with log = 8.7. Cu(II) reacts with pentasulfide to form a complex with the probable stoichiometry [Cu(S5)]2 with log estimated to be 20.2. As with the other four metals, these complexes are comparable with the tetrasulfide complexes. Discrete voltammetric peaks are observed for these complexes and indicate they are electrochemically inert to dissociation. Reactions of Zn(II) and Cu(II) also lead to significant breakup of the polysulfide.The relative strength of the complexes is Cu > Zn > Mn, Fe, Co, Ni. Cu displaces Zn from [Zn(1- S5)] and both Cu and Zn displace Mn, Fe, Co and Ni from their pentasulfide complexes.     

Single crystal raman studies of pyrite-type RuS2, RuSe2, OsS2, OsSe2, PtP2, and PtAs2

Single crystal Raman spectra of pyrite-type RuS₂, RuSe₂, OsS₂, OsSe₂, PtP₂, and PtAs₂ are presented and discussed with reference to the energies of the X-X stretching modes _x-x (A _g, F _g) and the X₂ librations (E, 2F_g). The main results obtained are (i) strong Raman resonance effects, (ii) different sequences for _x-x (A _g) and (E _g), i.e., R_{x_2 } $$ " align="middle" border="0"> for PtP₂ and PtAs₂ and R_{x_2 } $$ " align="middle" border="0"> for OsS₂, owing to the interplay of intraionic and interionic lattice forces, (iii) greater strengths for the intraionic P-P and As-As bonds compared to the S-S and Se-Se bonds, respectively, and (iv) a strong influe_gnce of the metal ions on the strength of the X-X bonds.This is contribution LXI of a series of papers on lattice vibration spectra     

Gehlenite stability in the system CaO-Al2O3-SiO2-H2O-CO2

P, T, \(X_{{\text{CO}}_{\text{2}} }\) relations of gehlenite, anorthite, grossularite, wollastonite, corundum and calcite have been determined experimentally at P _f =1 and 4 kb. Using synthetic starting minerals the following reactions have been demonstrated reversibly

1. 2 anorthite+3 calcite=gehlenite+grossularite+3 CO₂.
2. anorthite+corundum+3 calcite=2 gehlenite+3 CO₂.
3. 3anorthite+3 calcite=2 grossularite+corundum+3CO₂.
4. grossularite+2 corundum+3 calcite=3 gehlenite+3 CO₂.
5. anorthite+2 calcite=gehlenite+wollastonite+2CO₂.
6. anorthite+wollastonite+calcite=grossularite+CO₂.
7. grossularite+calcite=gehlenite+2 wollastonite+CO₂.

In the T, \(X_{{\text{CO}}_{\text{2}} }\) diagram at P _f =1 kb two isobaric invariant points have been located at 770±10°C, \(X_{{\text{CO}}_{\text{2}} }\) =0.27 and at 840±10°C, \(X_{{\text{CO}}_{\text{2}} }\) =0.55. Formation of gehlenite from low temperature assemblages according to (4) and (2) takes place at 1 kb and 715–855° C, \(X_{{\text{CO}}_{\text{2}} }\) =0.1–1.0. In agreement with experimental results the formation of gehlenite in natural metamorphic rocks is restricted to shallow, high temperature contact aureoles.     

Heat capacity of minerals in the system Na2O-K2O-CaO-MgO-FeO-Fe2O3-Al2O3-SiO2-TiO2-H2O-CO2: representation,estimation, and high temperature extrapolation

A revised equation is proposed to represent and extrapolate the heat capacity of minerals as a function of temperature: C _P=k₀+k₁ T ^–0.5+k₂ T ^–2+k₃ T ^–3 (where k₁, k₂0).This equation reproduces calorimetric data within the estimated precision of the measurements, and results in residuals for most minerals that are randomly distributed as a function of temperature. Regression residuals are generally slightly greater than those calculated with the five parameter equation proposed by Haas and Fisher (1976), but are significantly lower than those calculated with the three parameter equation of Maier and Kelley (1932).The revised equation ensures that heat capacity approaches the high temperature limit predicted by lattice vibrational theory (C _P=3R+²VT/). For 16 minerals for which and have been measured, the average C _Pat 3,000 K calculated with the theoretically derived equation ranges from 26.8±0.8 to 29.3±1.9 J/(afu·K) (afu = atoms per formula unit), depending on the assumed temperature dependence of . For 91 minerals for which calorimetric data above 400 K are available, the average C _Pat 3,000 K calculated with our equation is 28.3±2.0 J/(afu·K). This agreement suggests that heat capacity extrapolations should be reliable to considerably higher temperatures than those at which calorimetric data are available, so that thermodynamic calculations can be applied with confidence to a variety of high temperature petrologic problems.Available calorimetric data above 250 K are fit with the revised equation, and derived coefficients are presented for 99 minerals of geologic interest. The heat capacity of other minerals can be estimated (generally within 2%) by summation of tabulated oxide component C _Pcoefficients which were obtained by least squares regression of this data base.     

Studies in the system KAlSiO4-BaAl2Si2O8-SiO2-H2O

Various members of the KAlSi₃O₈-BaAl₂Si₂O₈ feldspar series are hydrothermally synthesized. Cellparameters of these are calculated from diffractometer patterns and found to be similar to those of Gay and Roy. A variation diagram is constructed correlating Cn-content and values of Δ_FeKα(2θ₍₁₁₁₎CaF₂—2θ₍₀₀₄₎Fs_ss), which gives $${\text{Mol}}\% {\text{ Cn = 229}}{\text{.83}}\Delta {\text{2}}\theta ---{\text{190}}{\text{.81}}$$ by a least square regression fitting. Phase equilibria relation in the solidus-liquidus-region for the KAlSi₃O₈-BaAl₂Si₂O₈-H₂O system at 1000 kg/cm² are investigated. It is found to be a case of simple solid solution in a binary system, with reservations at the potassium-rich side of the system. Goranson (1938) gives a temperature of about 1000°C at 1000 kg/cm² \(P_{{\text{H}}_{\text{2}} {\text{O}}} \) for the incongruent melting of sanidine, but the authors prefer a value around 930°C at the same \(P_{{\text{H}}_{\text{2}} {\text{O}}} \) . Reaction products of starting materials on the join KAlSi₂O₆-BaAl₂Si₂O₈ and KAlSiO₄-BaAl₂Si₂O₈ gave no experimental hint for replacement of K⁺ by Ba⁺⁺.