中国湖相碳酸盐岩时空分布与碳氧同位素特征*

湖相碳酸盐岩产状多样,多以夹层形式分布在碎屑岩剖面中,也见以结核或钙质微体化石等薄层赋存于泥岩、页岩等碎屑岩中,具有层数多、单层薄、呈韵律性变化等特点。受构造背景、物源输入和古环境等因素控制,中国湖相碳酸盐沉积最早出现于二叠纪,主要发育时段为古近纪,具有沉积时间跨度大、分布面积广的特征。湖相碳酸盐岩按成因可分为原生沉积型、成岩改造型和热液喷流型3类。中国湖相碳酸盐岩的碳氧同位素特征可揭示原生和成岩过程中水介质环境的差异性: (1)δ¹³C和 δ¹⁸O 密切相关,且δ¹³C多正偏,指示封闭型咸水、半咸水湖泊环境;(2)δ¹³C和 δ¹⁸O 无相关性,且δ¹³C多负偏,指示开放型湖泊环境;(3)δ¹³C严重正偏,指示成岩作用时发酵带的环境受到古细菌参与的甲烷生成作用的影响。     

天津平原区浅层地下水水化学特征及碳酸盐风化碳汇研究

大气 CO₂浓度在控制全球气候变化方面具有至关重要的作用,研究碳循环、CO₂收支平衡和精确评估是制定区域CO₂减排策略和寻找新的碳汇途径最重要的组成部分。碳酸盐风化碳汇是全球碳循环研究的一个重要方向。为此,本研究以天津平原区浅层地下水为研究对象,通过对地下水调查及水样的采集与分析,运用水化学分析方法分析了地下水水化学特征,并估算了地下水总储存量、DIC储量和碳酸盐风化碳汇量。研究结果表明:浅层地下水化学场自北部山前平原向南部冲积平原和滨海平原,呈现出自北而南和由北西向南东的水平水化学分带规律,地下水由低浓度的淡水、微咸水变为高浓度咸水,沿此方向水化学类型由HCO₃-Ca·Na·Mg→Cl·SO₄-Na→Cl·HCO₃-Na→Cl-Na型转变;淡水区、微咸水区和咸水区面积分别为733、3 034和6 564 km²。地下水水化学组分中Ca²⁺、Mg²⁺和 {\mathrm{HCO}}_3^{-}主要来源于碳酸盐的溶解作用。研究区浅层地下水总储存量为2 241 640万m³,总DIC储量为8.13×10⁶ t,总碳汇量为4.11×10⁶ t。研究区浅层地下水淡水区、微咸水区和咸水区地下水储存量分别为157 799万、6 245 936万和1 459 247万 m³,DIC浓度分别为19200、19200和19342 mg/L,DIC储量分别为0.67×10⁶、1.65×10⁶和0.58×10⁶ t,碳汇量分别为0.22×10⁶、0.90×10⁶和2.98×10⁶ t。沿地下水流向,DIC、储量和碳汇量的空间分布均呈现出由低到高的趋势。     

土地利用变化对高寒草甸土壤有机质更新的影响

对青藏高原海北站区的自然土壤和扰动土壤进行高分辨率采样,测定土壤根系、有机碳及其¹⁴C含量;用¹⁴C示踪技术探讨土地利用变化对高寒草甸土壤有机质更新的影响.研究表明,土地利用变化对高寒草甸土壤碳循环影响显著.耕作活动导致扰动土壤有机碳储量比自然土壤增加29.35%;扰动土壤剖面10~50 cm深土壤有机质的¹⁴C含量相对富集;自然土壤大多数有机碳储存在土壤表层,更新时间<50 a,同一深度扰动土壤有机碳储量显著少,更新时间长(171~294 a);自然土壤10 cm以下有机碳主要为更新时间>1 000 a的稳定碳所控制,扰动土壤的相应值出现在40 cm以下;自然土壤有机质更新产生的CO₂通量为114 gC·m^-2·a^-1,扰动土壤为48.7 gC·m^-2·a^-1.     

高砷地下水中溶解性有机碳和无机碳稳定同位素特征

随着稳定同位素分析技术的逐步完善,碳稳定同位素被广泛应用于地球化学领域。高砷地下水砷的生物地球化学循环是目前环境化学研究热点之一。分析概括了碳稳定同位素应用于地下水领域的研究现状,介绍了地下水中有机碳和无机碳稳定同位素的前处理方法以及测试技术。在此基础上,选取了内蒙古河套平原具有代表性的高砷地下水进行氧化还原敏感组分、碳稳定同位素的测定与分析。结果表明,As分布极不均匀,其含量为1.24~387 μg/L。地下水溶解性有机碳(DOC)含量相对较高,与溶解性无机碳(DIC)浓度基本呈正相关。δ¹³C_DIC相对δ¹³C_DOC较富集¹³C;δ¹³C_DIC-δ¹³C_DOC与δ¹³C_DIC之间具有显著的正相关关系;表明δ¹³C_DIC值越贫化,δ¹³C_DIC-δ¹³C_DOC越小,地下水中来源于有机物氧化分解的无机碳越多,进一步说明有机碳的氧化分解在无机碳稳定同位素贫化过程中起主要作用。此外,δ¹³C_DIC-δ¹³C_DOC与As浓度呈一定的负相关关系;表明有机物的微生物降解对砷的富集具有明显的促进作用。微生物可利用的碳源增加,促进异养微生物的代谢,并消耗氧气,最终形成有利于地下水As富集的还原环境。     

豫西下二叠统太原组遗迹化石与古氧相的响应特征*

基于对豫西禹州和焦作地区下二叠统太原组中的遗迹化石组成与产状特征的研究,以及对不同颜色Zoophycos潜穴充填物中碳氧同位素和微量元素含量的测试分析,取得成果如下: (1)灰白色充填物中δ¹³C值较低,主要介于-2‰~-4‰之间;灰色充填物中δ¹³C值大多在-0.8‰~-2‰之间。二者的V/(V+Ni)值均小于0.46,Ce/La值均小于1.5。反映其为富氧相,即氧化环境。(2)红褐色充填物中δ¹³C值一般在-0.2‰~-0.9‰之间,V/(V+Ni)值大于0.46,反映其为贫氧相,即弱还原环境。(3)黑色充填物中δ¹³C值最高,多数在0.2‰~1.6‰之间,Ce/La值大于1.8,反映其为厌氧相,即还原环境。综合分析上述特征,提出了3种古氧相(富氧相、贫氧相和厌氧相)的遗迹化石响应关系及其形成的沉积背景模式。这一研究成果可为精细分析豫西下二叠统太原组碳酸盐岩的沉积环境演变规律提供直观的生物遗迹识别标志。     

重庆东部地区寒武系龙王庙组碳、氧同位素特征及其意义

在野外露头和镜下薄片观察分析的基础上,对重庆东部地区下寒武统龙王庙组83个碳酸盐岩样品的碳、氧同位素进行测试,并分析了其所保留的海水原始信息的有效性。结果表明,扣除无效数据后,重庆地区龙王庙组δ¹³C值分布在-4.300‰~2.694‰之间,平均值为-0.031‰;δ¹⁸O值分布在-9.880‰~-0.100‰之间,平均值为-7.396‰;纵向上,碳同位素值整体呈现先降低后升高的趋势,底部、中上部及顶部为正值且变化幅度小;中下部整体为负值且波动幅度大,正、负漂移事件频发。古环境恢复结果显示,龙王庙期重庆东部地区整体处于海相沉积环境,海水盐度在龙王庙组早期较低,晚期较高;海水温度主要介于20~30,℃之间,属温暖或炎热的亚热带气候;龙王庙期共经历3期海退—海侵作用,海平面上升、海洋生产力增加、有机碳快速埋藏使得海洋中¹³C含量升高,反之则使其降低。龙王庙组沉积中期与末期,δ¹³C值负偏,水体较浅,盐度较高,是白云岩发育的最有利阶段。     

南伊沟水体水化学及氢氧同位素特征分析

南伊沟是林芝地区重要水源涵养区,研究南伊沟水体水化学和氢氧同位素特征,揭示“三水转化”规律,对提高林芝地区水体水文地球化学研究程度,支撑当地林水关系研究,服务高原地区水生态保护具有重要意义。运用水化学和氢氧同位素分析方法,分析了地区水化学特征、水岩作用情况和水循环特征。结果表明: 南伊沟水体为极低矿化度淡水,地表水水化学类型为HCO₃-Ca·Mg型和SO₄·HCO₃-Ca·Mg型,地下水水化学类型为HCO₃-Ca·Na型; 地表水和地下水的水化学离子成分主要受岩石风化控制,离子来源主要受碳酸盐岩溶解和硅酸盐岩风化影响,地表水中Na⁺、K⁺、Cl^-主要来源于盐岩溶解,同时还受降雨影响,地表水和地下水中Ca²⁺、Mg²⁺主要来源于碳酸盐岩矿物溶解; 地下水和地表水水岩作用较弱,对比上游雅鲁藏布江和拉萨河地表水,大部分δ¹⁸O、δD值具有明显的高度效应和大陆效应; 南伊沟枯水年内强烈的不平衡蒸发作用是导致地区大气降雨线斜率和截距偏小的主要原因之一。     

四川广元上寺剖面二叠系栖霞组沉积碳库与有机碳埋藏

通过比对四川广元上寺剖面二叠系栖霞组碳同位素变化,探讨了该区烃源岩发育的古生态环境。 由于二叠纪高CO₂ 浓度背景使得古海洋海水中相对富集¹³C ,因此二叠纪海相沉积的四川广元上寺剖面栖霞组碳 酸盐岩碳同位素均为正值。广元上寺剖面栖霞组底部向上碳酸盐岩碳同位素逐渐正偏,显示从栖霞组底部沉积 时期开始海平面逐渐上升,向相对缺氧沉积环境过渡。栖霞组中部古海洋生产力增高,使得总有机碳同位素正 偏。受总有机碳同位素波动的影响,碳同位素分馏值( ∈_TOC)在整个栖霞组波动频繁。根据平衡状态下碳循环 有机碳埋藏分数模型,计算了整个栖霞组有机碳埋藏分数,结果显示有机碳埋藏分数 (f_org)在整个栖霞组都较 高,符合二叠纪的碳埋藏在整个显生宙处于最高阶段的地质背景。栖霞组中部高 TOC含量层位对应 f_org逐渐增 高,反映f_org 与有机碳沉积的保存环境密切相关,说明利用古海洋生产力和 f_org 的变化,可在一定程度上指示原始 碳埋藏量的变化。     

贵州开阳以东震旦系陡山沱组磷矿富磷机制与“三位一体”预测找矿重大突破*

贵州开阳以东磷矿整装勘查区位处扬子陆块东南边缘,是中国富磷矿最集中分布区。通过对开阳磷矿沉积学、岩石学、地层学和古地理学综合研究认为,开阳地区磷矿成矿受黔中古陆长期剥蚀夷平形成的无障壁海岸的海滩环境控制,高品位磷块岩矿石岩相组合特征、矿物学特征和沉积规律指示了开阳磷矿动态“三阶段成矿作用”过程(即原始生物—化学成磷作用、波浪簸选(机械)成矿作用和暴露淋滤成矿作用),波浪簸选成矿作用是形成厚度大、品位高富磷矿床的主导因素。按照“三位一体”成矿地质理论,确定了以沿黔中古陆北缘开阔海滩相层状展布的磷矿体展布特征,建立了区域成矿模式和地质找矿预测模型,并圈定临滨带为富磷矿重点预测靶区,开展找矿预测。通过产—学—研联合攻关,实现了磷矿理论创新,突破了该区原有磷矿找矿理论瓶颈,成矿范围从250^km²增至1000^km²,预测资源量从0.9442×10⁸t增至13×10⁸t。通过部分区块的工程验证,获得估算磷矿资源量(推断量+预测量)5.4892×10⁸t,尤其新增富磷矿3.57×10⁸t,取得中国富磷矿找矿重大突破。     

重庆南川三汇场寒武系碳酸盐岩中不同期次大气淡水作用的证据

多期构造叠加及多种成岩环境下的早古生代碳酸盐岩储集层形成机理十分复杂。重庆南川三汇场剖面寒武系碳酸盐岩出露完整,是研究沉积与成岩史的理想解剖点之一。研究表明,三汇场剖面寒武系白云岩分别经历了早期海水胶结、大气淡水淋滤、准同生白云岩化、中浅层埋藏、中期构造大气水作用、中晚期埋藏及热液作用和构造晚期表生大气水成岩作用,不同期次的大气淡水作用特征不同。在早成岩期,沿向上变浅的高频层序界面附近发育了鲕模孔、窗格溶孔等组构性溶孔,胶结物和充填物的δ¹⁸O、δ¹³C值均比同期海水负偏,⁸⁷Sr/⁸⁶Sr值与同期海水相近,不发光(CL),含有较小的液相包裹体;加里东晚期—海西期,发育了非组构扩溶孔洞缝,伴有氧化沥青,不发光充填物的δ¹⁸O、δ¹³C负偏、⁸⁷Sr/⁸⁶Sr值正偏,发育含烃的低温不混溶包裹体,并叠加后期的深埋藏及热液成岩作用;燕山期和喜马拉雅期, 发育孤立的非组构溶蚀孔洞、缝洞,多被巨晶方解石或黏土充填,方解石中δ¹⁸O、δ¹³C强烈负偏($\delta^{13}C_{PDB}$=-4.6‰~-23.4‰,$\delta^{18}C_{PDB}$=-8.6‰~-17.8‰)、含有低温不混溶包裹体(<28.5℃),是有机质或生物甲烷(细)菌参于下的表生大气水成岩作用产物。     

Carbon Isotopic Constrains on the Sources and Controls of the Terrestrial Carbon Transported in the Four Large Rivers in China

The Changjiang， Huanghe， Zhujiang and Heilongjiang are the four largest rivers in China and they transport large amount of fresh water and terrigenous materials， including both inorganic and organic carbon into the ocean. The sources of the terrestrial carbon transported in the four rivers， however， have not been well constrained and compared. In this study， we used carbon isotopes （¹³C and ¹⁴C） combined with concentration measurements to investigate and compare the sources and fluxes of Dissolved Inorganic Carbon （DIC）， Particulate Inorganic Carbon （PIC）， Dissolved Organic Carbon （DOC） and Particulate Organic Carbon （POC） in the four rivers. The contributions of the potential sources to both DIC and DOC were quantitatively calculated using a dual isotope and three end member model. The results showed that the concentrations and isotope characteristics of the carbon pools in the river depended largely on the geological setting， surrounding environment and the anthropogenic influence of the drainage basins. Compared with other large rivers in the world， the concentrations of DIC in the Changjiang， Huanghe and Zhujiang were higher， but the DIC fluxes in the Huanghe and Zhujiang were lower. The DOC concentrations in the Heilongjiang River were higher and lower in the other three rivers compared with the average value of the world largest 25 rivers. The Changjiang， Huanghe and Zhujiang all transport millennia aged carbon. The old riverine DIC reflects the influence of chemical weathering of carbonate rocks and the old DOC reflects influence mainly from pre-aged soil OC. These ancient terrestrial carbon discharged by the rivers could have significant effects on the carbon cycle and ecosystems in the China's marginal seas.     

碳同位素技术在碳质气溶胶源解析中应用的研究进展

概述了国内外14C和13C技术在大气碳质气溶胶源解析中应用的研究进展,指出14C在碳质气溶胶源解析研究中具有不可替代的独特优势,联合采用14C和13C技术有利于解决多种排放源的区分问题;随着碳质气溶胶组分分离技术的进步,对有机碳(0C)和黑碳(BC)等组分中14C的研究获得重要进展;除需深入研究13C的分馏机制外,建立各种排放源在不同区域的δ13C值域“特征谱”的重要性也日益突出;结合14C和13C以外的其他示踪剂、模型和分析方法将提供更多关于气溶胶来源的信息,并减小来源贡献率估算的不确定性.     

A study of the chemistry of pore fluids and authigenic carbonates in methane seep environments: Kodiak Trench, Hydrate Ridge, Monterey Bay, and Eel River Basin

Analyses of the chemical and isotopic composition of carbonates rocks recovered from methane seepage areas of the Kodiak Trench, Hydrate Ridge, Monterey Bay Clam Flats, and the Eel River Basin, coupled with the studies of the chemistry of the pore fluids, have shown that these carbonates have grown within the sediment column. Geochemical profiles of pore fluids show that, in deep water seeps (Kodiak Trench—4450 m; Monterey Bay—1000 m; Hydrate Ridge—650 m), δ¹³C (DIC) values are low (isotopically light), whereas in the Eel River area ( 350–500 m), δ¹³C (DIC) values are much higher (isotopically heavier). In all cases, the δ¹³C values indicate that processes of methane oxidation, associated with sulfate reduction, are dominant in the shallow sediments. Data on the isotopic composition of authigenic carbonates found at sites in Kodiak Trench, Eel River Basin South, and Eel River Basin North indicate a variable composition and origin in different geochemical environments. Some of the authigenic carbonates from the study sites show a trend in their δ¹³C values similar to those of the pore fluids obtained in their vicinity, suggesting formation at relatively shallow depths, but others indicate formation at greater sediment depths. The latter usually consist of high magnesium calcite or dolomite, which, from their high values of δ¹³C (up to 23‰;) and δ¹⁸O (up to 7.5‰), suggest formation in the deeper horizons of the sediments, in the zone of methanogenesis. These observations are in agreement with observations by other workers at Hydrate Ridge, in Monterey Bay, and in the Eel River Basin.     

The Paleoceanography during the Time with High δ13C of Phanerozoic marine carbonates

Carbon isotopic composition of marine carbonates is a record for various important geological events in the process of earth development and evolution. The carbonates of Carboniferous, Permian and Triassic, as the transition from Paleozoic to Mesozoic-Cenozoic have very high ¹³C value. Taking this as the main point, and combined with the oxygen, strontium isotopic composition in carbonates, distribution of carbonate basin area through geologic time, the correlation of carbon isotopic composition of marine carbonates to sea level change, organic carbon burial flux, exchange of CO₂ content in atmosphere and ocean, and long cycle evolution of the earth ecosystems were approached. The results are shown as follows: ①The interval of ¹³C >3‰ during Phanerozoic was concentrated in Carboniferous, Permian and the beginning of Triassic, but the beginning of Triassic was characterized by higher frequency and larger fluctuations in ¹³C value during a short time, whereas the Carboniferous-Permian presented a continuously stable high ¹³C value, indicating a larger amount of organic carbon accumulation in this time interval. Relatively high ¹⁸O values during this time was also observed, showing a long time of glaciations and cold climate, which suggest a connection among rapid organic carbon burial, cold climate, as well as pCO₂ and pO₂ states of atmosphere. ②The over consumption of atmosphere CO₂ by green plants during the time with high ¹³C of seawater forced CO₂ being transferred from ocean to atmosphere for the balance, but the decrease in the seawater amount and water column pressure caused by the global cooling could weaken dissolution capacity of CO₂ in seawater and carbon storage of marine carbonates, and also reduce the carbonate sedimentary rate and decrease the carbonate basin area globally from Devonian to Carboniferous and Permian. During the middle-late Permian carbonate was widely replaced by siliceous sediments even though in shallow carbonate platform, which resulted in the decrease of marine invertebrates, suggesting the Permian chert event should be global. ③The Phanerozoic ⁸⁷Sr/⁸⁶Sr trend of seawater showed a sharp fall in Permian and drop to a minimum at the end of the Permian, indicting input of strontium from the submarine hydrothermal systems (mantle flux). Such process should accompany with a supplement of CO₂ from deep earth to atmosphere and ocean system, but the process associated with widespread volcanism and rises of earth’s surface temperature pricked up the mass extinction during the time of end Permian. ④Cold climate and increase of continental icecap volume, the amalgamation of northern Africa and Laurentia continentals were the main reasons responsible for the sea level drop, but the water consumption result from the significantly increased accumulation of organic carbon should also be one of the reasons for the sea level drop on the order of tens of meters. ⑤The mass extinction at the end Permian was an inevitable event in the process of earth system adjustment. It was difficult for marine invertebrates to survive because of the continuously rapid burial of organic carbon, and of the decrease of sea water amount and its dissolution ability to CO₂. At last, at the end of Paleozoic, the supplement of CO₂ to atmosphere and ocean by widely magma activities resulted in a high temperature of earth surface and intensified mass extinction.     

四川盆地东部地区寒武系洗象池群碳酸盐岩碳、氧同位素特征及其意义*

四川盆地东部地区寒武系洗象池群碳酸盐岩的碳、氧同位素组成受后期成岩作用影响较小,基本保留了原始海洋的同位素组成,笔者根据采集的111个碳、氧同位素数据,研究、讨论了盆地东部地区中上寒武统碳酸盐岩碳、氧同位素组成、演化及地质意义。研究表明,δ¹³C值变化介于-3.36‰~2.65‰之间,均值为-1.027‰,绝大多数的样品都分布在-2‰~2‰的区间,δ¹⁸O值分布于-11.1‰~-6.01‰之间,均值为-7.991‰,在-10‰~-6‰的范围内波动。通过对碳、氧同位素数据分析研究,认为四川盆地东部地区洗象池群主要发育在盐度较高、温暖—炎热的近岸海相沉积环境;洗象池群沉积早期和中期经历了短暂而快速的海侵后进入缓慢的海退,在晚期缓慢海侵后的快速海退,碳同位素组成反映的海平面变化趋势与沉积相演化一致。洗象池群沉积中期显著的碳同位素正向漂移,标志着较高的生产力和有机碳埋藏率,具有重要的石油地质学意义。     

青藏高原北部植物叶片碳同位素组成的空间特征

测定了青藏高原北部13个地点101份草本植物叶片碳同位素组成(δ¹³C值), 结果发现, 植物叶片δ¹³C值的分布范围在-29.2‰～-23.8‰之间, 平均值约为-26.89‰, 明显低于全球高海拔植物叶片δ¹³C值(-2.6‰) ; 而植物叶片δ¹³C值随海拔和经、纬度的变化趋势与其它同类报道相似:随着海拔的升高和经、纬度的降低, 植物叶片δ¹³C值呈现升高趋势. 叶片δ¹³C值也随土壤含水量和土壤温度的变化而变化:土壤含水量越高, 土壤温度越低, 植物叶片δ¹³C值越小, 但它们之间的相关关系不具统计学意义. 初步分析表明, 大气压力 (CO₂分压)和温度的协同变化导致了叶片δ¹³C值随着海拔变化的分布格局, 而温度和相对湿度的变化是引起叶片δ¹³C值的经、纬度效应的主要因子.