藏北可可西里地区中新世湖相油页岩的生物分子标识及碳同位素异常

对采自藏北可可西时地区中新世湖相油页岩样品进行了有机岩石学和分子地球化学实验分析，目的是通过生物分子生态学方法重建古湖泊系统的演化。两个层次油页岩抽提沥青的GC－MS和GC－IRMS分析表明，剖面下部的油页岩和泥质岩富含β胡萝卜烷和伽马蜡烷，沉积环境是一个水体分层的咸水古湖泊系统。色谱－质谱分析中检出的短链正构烷烃来自于水生生物，而以奇数碳C29为主峰且奇偶优势明显的长链（C23－C31）正烷烃是C3型陆生高等植物输入的。植烷和姥鲛烷被解释为来自生活在透光带上部的藻类和蓝细菌，β胡萝卜烷可能与栖居于透光带下部的喜盐性古细菌及光合细菌有关，藿烷和莫烷代表生活在氧跃面或缺氧底层水中的甲烷菌和化学自养细菌群落。作者发现上部层位油页岩比下部油页岩明显富集^13C，干酪根δ^13C高达－17．76‰，正烷烃单体碳同位素δ^13C平均值为－21．97‰，主峰nC23的δ^13C值可达－15．01‰。经对比证实，这种罕见的^13C 异常是C4型植被或绿藻Botryococcus突然繁盛引起的，这预示着中新世末青藏高原隆升可能达到临界高度，古湖泊生态系统随着气候变化发生了转型和更新。     

抚顺盆地始新统计军屯组油页岩地球化学特征及其地质意义

本文在野外实测剖面基础上,对抚顺盆地始新统计军屯组油页岩开展较为详细的地球化学特征研究,根据微量元素富集程度、元素比值变化及生物标志化合物特征等,探讨了油页岩的有机母质来源、沉积环境及其对油页岩成矿的控制.油页岩中微量元素主要有Li、Ti、Co、Cr、Cu、Ni、Pb、V、Mn、Sr、Ba、Zn、Ga、Rb和cd.有机碳含量较高,平均为12.90%,氯仿沥青"A"组成中饱和烃馏分占优势,有机质以腐泥型为主.样品中检测出丰富的正构烷烃、类异戊二烯烷烃、甾类化合物和萜类化合物.在GC谱图上,正构烷烃呈"前低后高"双峰式分布,主峰碳数分别为nC17,或nC27、nC19或nC_27,nC_31/nC_17为1.12～17.38,重烃组分占优势,CPI值为1.55～1.77,OEP值为1.61～1.81,Pr/Ph为1.53～2.08.甾类化合物以规则甾烷为主,其次为重排甾烷,孕甾烷丰度极低,规则甾烷C_27-C_28-C_29ααα20R构成近对称的"V"字型,∑(C_27+C_28)/∑C_29比值为1.11～1.19,∑C_27/∑C_29比值为0.63～0.77.萜类化合物以C_30藿烷占优势的五环三萜烷为主,含少量三环萜烷,检出少量奥利烷,几乎未见四环萜烷和伽马蜡烷.元素丰度及饱和烃色谱/质谱特征表明抚顺油页岩有机母质来源具水生生物和高等植物双重生源特征;Sr/Ba、V/V+Ni等元素比值,结合生物标志化合物特征及野外地质观察,揭示油页岩形成于淡水缺氧半深湖-深湖环境.湖泊自身生产力为油页岩的形成提供了主要的有机母质来源,稳定缺氧环境有利于有机质的堆积和保存.     

松辽盆地北部上白垩统油页岩地球化学特征及沉积环境初探

松辽盆地北部上白垩统油页岩属中一差油页岩;有机质类型以Ⅰ型为主,Ⅱ.型为辅,处于低成熟一成熟阶段.生物标记化合物都含有丰富的正构烷烃、类异戊二烯型烷烃、萜类化合物和甾类化合物.正构烷烃呈前高后低的单峰型分布,nC₂₃、nC₂₇为主峰碳,重烃组份占绝对优势,OEP值为1.02～6.63,具有明显的奇碳数优势.Pr/Ph比值为0.13～1.37,多数小于0.6,具植烷优势,伽马蜡烷含量较高,油页岩沉积环境为咸化还原环境且盐度较高.萜烷丰度顺序为五环三萜烷>三环萜烷,三环萜烷中C₂₀、C₂₁和C₂₃,丰度相对较高,且C₂₀、C₂₁和C₂₃多呈倒“V”形分布,C₂₃相对富集.甾类化合物主要成份为规则甾烷C₂₇、C₂₈和C₂₉,ααα20RC₂₇、C₂₈和C₂₉甾烷多数呈几乎对称的“V”形分布,C₂₉ >C₂₈ >C₂₇.甾萜烷分布特征反映其原始有机母质构成中既有丰富的菌藻类等低等水生生物,又有一定比例的陆生高等植物混合输入.     

藏北高原双湖地区中侏罗统海相油页岩生物标志化合物分布特征及其意义

重点报道了藏北双湖地区中侏罗统海相油页岩的生物标志化合物特征，首次在该层位油页岩中检出丰富的正烷烃、类异戊二烯烷烃、萜类化合物及甾类化合物。正烷烃图谱呈单峰形，nC15、nC16或nC17为主峰碳，轻烃组份占有绝对优势，OEP值0.93～1.01，无明显的奇偶碳数优势分布；Pr/Ph值为0.77～1.59，在剖面序列中呈波动分布，显示弱植烷优势或姥鲛烷优势；藿烷以C30占优势，萜烷相对丰度五环三萜烷>三环萜烷>四环萜烷；规则甾烷∑（C27+C28）>∑C29，∑C27/∑C29值为0.79～ 1.20，在剖面序列中下部C27甾烷略占优势，上部C29甾烷略占优势，重排甾烷C27/规则甾烷C27值为0.51 ～3.63，在剖面序列中具有显著的波动性，同时检出了少量孕甾烷和4-甲基甾烷。有机质母质构成中，既有丰富的藻类等低等水生生物，可能还有一定比例陆生高等植物输入混合的特点。油页岩处于成熟阶段，整个油页岩剖面序列具有一致的热演化程度。剖面中部油页岩具有极高的原始生产力，氧化-还原条件也是控制油页岩TOC和沥青“A”含量在剖面垂向变化的重要因素。     

银额盆地下白垩统巴音戈壁组油页岩有机地球化学特征及成矿条件

通过对银额盆地下白垩统巴音戈壁组油页岩总有机碳、全硫、岩石热解和生物标志化合物等分析,讨论了巴音戈壁组油页岩有机地球化学特征及成矿条件.研究表明:巴音戈壁组油页岩的有机质丰度较高,干酪根类型为Ⅰ型和Ⅱ1型.正构烷烃呈单峰分布,主碳峰数为nC27或nC31.甾类化合物中重排甾烷含量较低,以规则甾烷为主,C27-C28-C...     

桦甸盆地桦甸组与美国犹他盆地绿河组油页岩生物标志化合物特征对比

在野外地质考察、岩心观察和大量测试数据分析的基础上,对我国东北地区桦甸盆地始新统桦甸组和美国犹他盆地始新统绿河组油页岩中类异戊二烯烷烃、甾类和萜类等生物标志化合物特征进行了详细的对比研究,并探讨其对两地油页岩在有机质来源及古沉积环境上的差异指示意义。结果表明:在GC谱图上,桦甸油页岩Pr/Ph为1.47～2.03,具姥鲛烷优势;而绿河油页岩Pr/Ph为0.34～0.44,具植烷优势。GC-MS分析表明:桦甸油页岩规则甾烷C27-C28-C29呈反"L"型分布,∑(C27+C28)/∑C29为0.63～2.52;绿河油页岩规则甾烷C27-C28-C29呈钝角不对称"V"型分布,∑(C27+C28)/∑C29为0.96～1.20。桦甸油页岩萜类化合物中萜烯>ββ构型霍烷>αβ构型霍烷,以C29萜烯占优势;绿河油页岩中五环三萜烷>三环萜烷>四环萜烷,并检出丰富的γ-蜡烷和β-胡萝卜烷。两地油页岩生物标志化合物特征参数的对比分析揭示:桦甸油页岩为水生生物和高等植物双重生源,但细菌及藻类等水生生物的贡献较大,主要形成于弱还原淡水沉积环境;绿河油页岩有机质来源主要为细菌和藻类等水生生物,主要形成于强还原咸水沉积环境。     

藏北羌塘盆地晚侏罗世海相油页岩生物标志物特征、沉积环境分析及意义

胜利河油页岩位于青藏高原腹地的羌塘盆地,具单层厚度薄、区域延伸长的特点,为羌塘盆地新发现的又一处海相油页岩.采用GC-MS(IRMS)分析方法对该油页岩进行了研究,结果表明,胜利河油页岩(11层以及13层)含有丰富的正烷烃、类异戊二烯烃、萜类化合物和甾类化合物.正构烷烃呈前高后低的单峰型分布,nC15、nC16为主峰碳,轻烃组分占有绝对优势,OEP值0.96～0.97,接近平衡值1.00,Pr/Ph为0.57～0.75,显示弱的植烷优势;萜烷丰度顺序为五环三萜烷》三环萜烷》四环萜烷;规则甾烷呈不对称的"V"字型分布,表现为C27》C29》C28的分布特征.这些特征与剖面中其他岩性的生物标志物特征存在一定的差异,9层泥晶灰岩C21-/C21 值为0.86,轻烃优势并不明显;14层泥灰岩C21-/C21 值为0.41,具有明显的重碳优势;9层泥晶灰岩以及12层泥灰岩规则甾烷呈C29》C27》C28的特征也与油页岩层存在显著的差异.这些差异不仅反映了油页岩层与其他岩性间生物母源输入的差异,也反映了他们之间沉积环境的不同.胜利河地区油页岩的形成是综合因素控制的结果,古地理变化、海平面升降、生物群差异以及气候的变化均对该区油页岩的形成有一定的影响.     

羌塘盆地二叠系展金组烃源岩生物标记化合物特征及意义

本文对羌塘盆地二叠系展金组烃源岩的岩心样品进行了烃源岩基本特征及生物标志化合物特征研究,重点探讨了烃源岩生烃母质来源、沉积环境特征及成熟度特征。研究显示,展金组烃源岩富含正构烷烃、类异戊二烯烷烃、萜类化合物和甾类化合物。其中,正构烷烃多为前高后低的单峰型,具有低碳数优势,n C_(15)、n C_(16)或n C_(17)为主峰碳;规则甾烷中C_(27)-C_(28)-C_(29)呈"V"字型分布,C_(27)占优势;萜烷具有三环萜烷五环三萜烷四环萜烷的相对丰度,三环萜烷/五环三萜烷值在1.1~1.96之间;生烃母质主要来源于海相低等水生生物。Pr/Ph分布范围在0.53~1.16,平均值为0.85,植烷优势较明显;五环三萜烷的Ts/(Tm+Ts)值表明烃源岩形成于还原环境。而伽马蜡烷的含量以及伽马蜡烷/αβ-C30藿烷比值,证明烃源岩沉积时水体盐度为正常盐度。甾烷的C29ααα20S/(20S+20R)和C29αββ/(αββ+ααα)、萜烷的C31αβ~(22)S/(22S+22R)、Ts/(Tm+Ts)值等反映烃源岩成熟度的参数显示,烃源岩处于成熟阶段。     

羌塘盆地昂达尔错地区油苗生物标志化合物特征及其指示意义

本文以油苗抽提物的饱和烃色谱-质谱分析为基础,剖析了羌塘盆地昂达尔错地区油苗的生物标志化合物特征,探讨了其沉积环境和成熟度指示意义。昂达尔错油苗含有丰富的正构烷烃、类异戊二烯烃、萜类化合物和甾类化合物。正构烷烃轻烃组分含量较高,无明显的奇偶优势。Pr/Ph比小于1,显示一定的植烷优势。萜类化合物中五环三萜烷相对含量最高,四环萜烷含量最少,并有一定的伽马蜡烷和升藿烷分布。规则甾烷相对含量为C27C29C28,呈不对称"V"字形分布,异构化成熟度参数值较高,且4-甲基甾烷化合物普遍存在。昂达尔错油苗母源岩沉积于具有较高盐度的还原环境,以藻类、菌类等海相有机质输入为主,油苗有机质处于成熟阶段。     

藏北羌塘盆地羌资1井中侏罗统沥青脉生物标志化合物分布特征及其意义

藏北羌塘盆地羌资1井中侏罗统沥青脉生物标志化合物含有丰富的正烷烃、类异戊二烯烷烃、萜类化合物和甾类化合物。正烷烃图谱形态以单峰形态占优势,主碳峰以nC16、nC17为主,次为nC18、nC20、nC15轻烃组分占有绝对优势,OEP值介于0,69-1．22之间,平均值为0．96,偶碳数优势不明显;Pr／Ph值介于0．35～0．78之间,平均值为0．59,具有明显的植烷优势。萜烷相对丰度表现为五环三萜烷〉三环萜烷〉四环萜烷,γ-蜡烷普遍存在,但相对含量棱低;甾烷主要为规则甾烷,少量孕甾烷,规则甾烷∑（C27＋C28）〉∑C29,∑C27／∑C29介于0．61～2．18之间,平均值为1．06,显示弱的C27甾烷优势或弱的C29甾烷优势。有机质母质构成中,除有丰富的藻类等低等水生生物外,可能还有陆生高等植物输入混合。成熟度参数和镜质体反射率均显示沥青脉中的有机质处于成熟一过成熟阶段。沥青脉形成环境为还原环境。另外,除饱和烃和芳烃含量上有明显差别外,中侏罗统夏里组砂泥岩中的沥青脉与布曲组碳酸盐岩中的沥青脉的生物标志化合物无明显区别。     

Biological marker compounds as indicators of the depositions! history of the Maoming oil shale

The Eocene Maoming oil shale from Guangdong Province occurs as a laterally uniform stratigraphic section, typically 20–25 m thick, from which the aliphatic hydrocarbon constituents of six representative samples were investigated using GC and C-GC-MS. The sediments evaluated included the basal lignite, a vitrinite lens from the overlying claystone, and four intervals from the massive oil shale bed. As expected, the lignite and vitrinite differ markedly from the oil shales. The lignite is dominated by bacterial hopanoids and components of higher plant origin, including C₂₉ steroids and triterpenoids such as oleanenes. Visually, the oil shale samples show corroded and degraded phytoclasts, spores, wispy particles of fluorescent organic material attributable to dinoflagellates and, especially in the uppermost sample, colonial algal bodies. The distributions of biological markers in the oil shales show many features in common, notably a dominance of dinoflagellate-derived 4-methylsteroids, and a significant proportion of higher-plant derived n-alkanes with marked odd-over-even carbon number predominance. Overall, they exhibit several features that resemble characteristics of the Messel shale. The hydrocarbons of the lowest shale horizon suggest that there may have been a gradual transition between deposition of the original peat and the subsequent oil shales. The aliphatic hydrocarbons of the uppermost shale are dominated by a number of C₃₁ and C₃₃ botryococcane homologues and other unusual branched alkanes possibly derived from green algae. All of the samples are immature. Overall, molecular and microscopic examination of the stratigraphic succession of the Maoming oil shale suggests a shallow, lacustrine environment within which peats were deposited. This lake subsequently deepened to support abundant algal populations, especially dinoflagellates, culminating in a dominance of botryococcoid algae.     

Chemo- and Biostratigraphy of the Jurassic Oil Shales from the Qiangtang Basin, Northern Tibet, China: A Case Study of the Toarcian Oceanic Anoxic Event

The marine oil shales of the Qiangtang Basin, northern Tibet, exposed in the Biluo Co, Tuonamu, Shenglihe and Changsheshan areas are believed to be important petroleum source rocks. This work comprehensively analyzed the carbon isotopes, trace elements, and calcareous nannofosills, ammonites and bivalves of the Biluo Co section in the Qiangtang Basin. The organic carbon isotopes show a positive excursion close to 2.17‰(relative to PDB), which, albeit significantly smaller, may also be associated with other Early Toarcian Oceanic Anoxic Events(T-OAE) in the European epicontinental seas and the Tethyan continental margins. Coinciding with the Early Toarcian transgression, the oxygen deficiency in bottom water had led to dysoxic-anoxic conditions and deposition of black shales lacking benthic fauna. Under such condition, the redox-sensitive trace metals such as Mo, V, Ni, Cr, and U were enriched, in conjunction with high planktonic productivity of Watznaueriaceae calcareous nannofossils. Comparison of the results with the records of chemo-and biostratigraphy, as well as the palaeogeography during the Early Jurassic suggests that the anoxia linked to the Early Toarcian oceanic anoxic event was mainly caused by the high surface water temperature, sea-level rise and an increase of surface water productivity.     

陕北油页岩地质特征、成矿规律及开发条件

陕北油页岩主要分布于鄂尔多斯盆地的三叠系延长组和侏罗系安定组、延安组地层中,其中三叠系延长组的长7、长9、长1是油页岩发育的主要层段。地层总体为一产状平缓的向北西西微倾的单斜构造,地表绝大部分被第四系现代风积沙覆盖。油页岩矿石多呈灰黑色片状,主要成分为硬质粘土类矿物,含少量石英、长石细屑及沥青质点。油页岩分布受基底差异运动形成的构造坳陷盆地控制。成矿受岩相古地理环境控制,深湖一半深湖相沉积环境形成的油页岩分布广泛,品质好,浅湖和三角洲相沉积环境形成的油页岩分布范围小、厚度小、含油率低。鄂尔多斯盆地不仅油页岩资源丰富,而且开发条件优越,具有广阔的开发利用前景,对解决我国油气等常规能源供需矛盾突出的问题非常有利。     

致密储层孔隙结构表征技术有效性评价与应用

非常规致密储层类型多,孔隙结构复杂,非均质性强,研究难度大。针对已有致密储层孔隙结构评价技术,重点探讨了CT扫描、气体吸附与压汞分析等技术的有效应用范围,厘定了不同技术应用时需注意的关键问题,指出兼顾分辨率与代表性、提高表征维度、实现动态与静态同步表征是致密储层孔隙结构评价技术优选的关键。通过系统解剖常规砂岩、致密砂岩、致密混积岩、沉凝灰岩、介壳灰岩及泥页岩6种储层,明确不同级别孔隙系统的差异性,针对性地提出了不同储层对应的关键表征技术系列。非常规致密储层孔隙结构研究应加强多尺度数据融合,加强与可动流体评价结合,加强与储层改造研究结合,通过多领域、多学科、多视角联合攻关,实现储层有效性评价,为寻找预测规模有效“甜点区”提供技术支撑。     

Pore Characteristics and Factors Controlling Lacustrine Shales from the Upper Cretaceous Qingshankou Formation of the Songliao Basin,Northeast China: A Study Combining SEM,Low-temperature Gas Adsorption and MICP Experiments

To investigate pore characteristics and the factors controlling lacustrine shales,geochemical,mineralogical and petrophysical experiments were performed on 23 shale samples from the Qingshankou Formation of the Songliao Basin,China.A comparison of mercury injection capillary pressure (MICP) and low-temperature N2 adsorption pore-size distribution showed that MICP has a higher pore-size distribution (PSD) line in its overlapping pore diameter range,which may be elevated by the higher pressure of MICP.Therefore,in the overlapping range,low-temperature N2 adsorption data were preferred in pore characterization.Negative correlations were observed between pore volumes and TOC content,indicating organic matter pores are not well-developed in the studied samples.This may be related to their low grade of maturity and type I kerogens.There existed negative relationships between pore volumes and S1,which illustrated that liquid hydrocarbons occupied some pore space.Micropore volume had a better correlation with S1 than mesopore and macropore volumes,which suggests that liquid hydrocarbons preferentially occur in micropores.No obvious relationships between pore volumes and quartz or feldspar were observed,while pore volumes increased with the increasing clay mineral content.These relationships indicate that intraparticle pores in clay minerals represent the principal pore type.     

藏北高原双湖地区中侏罗统海相油页岩生物标志化合物分布特征及其意义

重点报道了藏北双湖地区中侏罗统海相油页岩的生物标志化合物特征,首次在该层位油页岩中检出丰富的正烷烃、类异戊二烯烷烃、萜类化合物及甾类化合物。正烷烃图谱呈单峰形,nC₁₅、nC₁₆或nC₁₇为主峰碳,轻烃组份占有绝对优势,OEP值 0.93～ 1.0 1,无明显的奇偶碳数优势分布;Pr/Ph值为 0.77～ 1.5 9,在剖面序列中呈波动分布,显示弱植烷优势或姥鲛烷优势;藿烷以C₃₀ 占优势,萜烷相对丰度五环三萜烷 >三环萜烷 >四环萜烷;规则甾烷∑ (C₂₇+C₂₈) >∑C₂₉,∑C₂₇/∑C₂₉值为 0.79～ 1.2 0,在剖面序列中下部C₂₇甾烷略占优势,上部C₂₉甾烷略占优势,重排甾烷C₂₇/规则甾烷C₂₇值为 0.5 1～ 3.6 3,在剖面序列中具有显著的波动性,同时检出了少量孕甾烷和 4-甲基甾烷。有机质母质构成中,既有丰富的藻类等低等水生生物,可能还有一定比例陆生高等植物输入混合的特点。油页岩处于成熟阶段,整个油页岩剖面序列具有一致的热演化程度。剖面中部油页岩具有极高的原始生产力,氧化-还原条件也是控制油页岩TOC和沥青“A”含量在剖面垂向变化的重要因素.     

吉林省中、新生代黑色页岩（油页岩）中某些金属元素富集特征

吉林省中、新生代黑色页岩（油页岩）中Ａｇ、Ｕ、Ｃｏ、Ｎｉ等元素含量偏高；黑色页岩（油页岩）中古生物组合丰富，有机碳含量很高（＞２％）．研究了吉林省中、新生代黑色页岩（油页岩）中稀、贵金属元素富集特征，初步探讨了其富集机理，为吉林省中、新生代含金属的黑色页岩（油页岩）的综合利用提供参考。     

Botryococcus—A planktonic green alga, the source of petroleum through the ages: Transmission electron microscopical studies of oil shales and petroleum source rocks

The hydrocarbon secreting alga Botryococcus has been identified in organic remains of sediments ranging from Precambrian to Recent, and is believed to have been a major source material for petroleum generation throughout the geological time. In some petroleum source rocks of Lower Palaeozoic and Precambrian age, identification of the alga is only possible by electron microscopy. Transmission electron microscopy (TEM) has been used in the present study to identify microstructures of the algal remains in a range of oil shales and petroleum source rocks. It has been established that Botryococcus is the predominant alga in the Kukersite oil shale of Estonia. Similarly, the alga has been shown to be a major contributor to petroleum source rocks in Cambrian and Precambrian sedimentary basins in Australia. TEM has been applied to observations of Botryococcus in torbanites and to products from simulated maturation experiments on torbanite. A comparison with algal remains from Cambrian and Precambrian sediments ranging from undermature to overmature, enabled the distinction of organic matter in various stages of oil generation. Maturation/thermal effects on alginite have been established by reflectance and fluorescence, and compared with experimental results.     

Enrichment and Origin of Some Trace Elements in Black Shales from the Early Cambrian in Eastern Guizhou Province

The analysis is based on the elemental geochemistry, ¹³C, ¹⁸O isotope and lithology combination of the black shale, a set assemblage mud and carbon of lithology , in East Guizhou. The coordinated change in spider diagrams of race elements suggests those elements have the same source. The ¹³C, ¹⁸O isotopes, mode of REE partition and characteristic enrichment of elements assemblage in carbonaceous shale show that the deep thermal fluid is added, and the shelf sea basin edge with distribution of hydrothermal activity is propitious to precipitation of ore elements. Evidence from the ³⁴S isotope and redox-sensitive elements show that the hydrostatic hypoxia environment is also conducive to precipitation of elements. The lithologic features (phosphorus, coal-bearing layers) and high content of organic carbon indicate that the deposits are influenced by the upwelling ocean current.     

Investigation of the fate of nitrogen in Palaeozoic shales of the Central European Basin

Nitrogen geochemistry of Upper Carboniferous shales from the Central European Basin (CEB) was investigated by elemental analysis, stable isotope mass spectrometry and non-isothermal pyrolysis. Total N-contents of Namurian shales from four deep wells (4400–7000 m) in NE Germany ranged between 520 and 2680 ppm. Up to 90% of this nitrogen occurs as ammonium in minerals with δ¹⁵N values between + 1‰ and + 3.5‰. Low nitrogen contents (down to 460 ppm) and high δ¹⁵N values (up to + 5.6‰) in one well in the basin centre suggest a large-scale release of nitrogen associated with isotopic fractionation. Pyrolytic liberation of N₂ from pelagic Namurian A shales of NW and NE Germany occurred at significantly lower temperatures than from paralic Namurian B shales and terrestrial Westphalian samples. On-line isotope analysis of N₂ liberated between 400 and 1200 °C indicates the presence of precursor pools with different thermal stability and nitrogen isotopic composition.