长江故道底栖动物群落特征及资源衰退原因分析

选取青藏高原南北断面气候环境条件差异明显的大枪勇错、空姆错、纳木错、克鲁克湖和小柴达木湖的表层沉积物进行了陆源正构烷烃（C25-C31）的提取分析．通过将这些生物标志物δD值与源区生长季节大气降水国值进行比较,发现两者有很好的相关性．说明陆源沉积正构烷烃记录了生长季节降水同位素信号正构烷烃n-C25、n-C27与大气降水间氢同位素分馏在-45‰至-70‰之间,而n-C29、n—C31与大气降水间氧同位素分馏在-70‰至-95‰之间,沿青藏高原南北断面分馏恒定,分馏平均值分别是-57‰和-82‰通过对比欧洲断面的-130‰分馏值,可以看出青藏高原南北断面陆源沉积正构烷烃与大气降水间表观同位素分馏小很多。     

秦安中新世风尘堆积正构烷烃的分布特征及古环境意义

甘肃秦安的新近纪风成红土堆积是东亚大陆古环境演化的重要载体之一,但相对第四纪黄土而言,对其记录的古环境信息仍缺乏生物标志化合物方面的研究.本文对秦安QA-I剖面早-中中新世代表性黄土和古土壤层样品开展了初步的正构烷烃分析,并与前人发表的不同时期的风成沉积和水成沉积代表性样品进行对比.结果显示:(1)QA-I剖面中的正构烷烃碳数分布范围为C_(14)~C_(35),其中来源于微生物的低碳数部分(C_(14)~C_(20))的含量明显高于来自高等植物叶蜡的高碳数部分(C_(26)~C_(35)),主峰碳处于C_(16)~C_(18),中碳数部分(C21~C_(25))的相对含量最低,这些特征与第四纪黄土及晚中新世-上新世三趾马红土中一些强发育的古土壤层类似,但与弱风化的黄土和三趾马红土及水成沉积明显不同;(2)QA-I剖面样品的高碳数部分虽具有一定的奇偶优势,但碳优势指数(CPI)明显较各类风化较弱的样品低.上述结果显示,秦安中新世风尘红土堆积经历了较强烈的风化成壤和微生物作用,导致其中的长链正构烷烃较显著的氧化和降解,并以微生物贡献的短链正构烷烃为主.微生物对全岩有机质(TOC)的贡献以及对TOC碳同位素的影响需在古环境重建中予以充分考虑.     

轮南油田代表性原油正构烷烃单体氢同位素组成、分布与母源信息

采用先进的色谱-高温热转变-同位素比值质谱(GC-TC-IRMS)分析技术, 首次对塔里木盆地轮南油田部分原油正构烷烃进行了单体氢同位素组成分析. 所测定的不同储层的原油样品, 正构烷烃单体氢同位素组成相近, 反映了原油母源沉积环境的相似性, 均来源于海相沉积环境. 与理论推算值(−150‰)和报道的Williston盆地奥陶系生源的原油正构烷烃氢同位素数据(nC₁₃~nC₂₇, −160‰~−90‰)相比, 轮南油田原油正构烷烃单体氢同位素组成较重(nC₁₂~nC₂₇, −120‰~−60‰). 从母质形成的生物化学过程和烃类生成的热成熟作用过程分析, 相对咸水沉积环境下形成的母质及相对较高的成熟度可能是造成上述轮南油田原油正构烷烃氢同位素组成与分布偏重的主要原因.     

青藏高原地区湖泊正构烷烃有机单体氢同位素组成及其水文与环境应用

湖泊沉积物中正构烷烃氢同位素组成(δD)广泛应用于古环境变化研究,但其正构烷烃通常包含多种植物来源,使其作为环境和气候指标进行解释时面临许多挑战.我们系统调查了青藏高原地区15个湖泊中51个沉水植物(包括39个眼子菜、1个狐尾藻和11个川蔓藻),13个藻类(包括5个轮藻、3个刚毛藻和5个水绵)以及20个湖边陆生植物(包括10个灌木和10个草本植物)正构烷烃的δD值.结果表明:藻类和沉水植物C29正构烷烃δD值与湖水δD值显著正相关(藻类:R~2=0.85,p0.01,n=9;沉水植物:R~2=0.90,p0.01,n=25),表明这些藻类和沉水植物正构烷烃的δD值反映了湖水δD值的变化.不同种属的藻类和沉水植物,以及不同水文条件下生长的同一种属植物,其氢同位素分馏值(ε_(a/w))并不稳定,表明生物合成和环境条件(如盐度)可能会影响藻类和沉水植物的δD值.希里沟湖(封闭湖)中川蔓藻的δD值显著偏正于其湖边草本植物的δD值(one-way ANOVA,p0.01),但可鲁克湖(开放湖)中的轮藻植物与其湖边草本植物的δD值接近(one-way ANOVA,p=0.8260.05),表明干旱半干旱地区湖泊中藻类和沉水植物仅在封闭湖记录了湖水相对于大气降水富集δD值的信号.对每一个藻类和沉水植物样品,不同碳数正构烷烃δD值无明显差别,表明结合Paq和平均链长(ACL)等指标,不同碳数正构烷烃δD值的差值能帮助我们判断沉积物中正构烷烃的植物来源,及分析古湖泊盆地的沉积类型(开放沉积或封闭沉积).     

水生植物烷基脂类含量和分布特征及其单体氢同位素组成

水生植物是湖泊沉积物中内源有机质的主要来源,但目前研究者对水生植物正构烷烃和脂肪酸分布特征的研究有限,极大地限制了湖泊沉积物同位素地球化学在环境变化研究中的应用.文章总结了全球湖泊已报道水生植物脂类结果,结合在中国主要湖泊新获得的脂类数据,系统讨论了湖泊水生植物脂类分布特征.我们发现水生植物基本以中等链长脂类(C_(23)～C_(25)正构烷烃和C_(22)～C_(24)脂肪酸)为主峰碳,与陆生植物存在差别(以长链脂类为主峰碳),但一些水生植物样品的长链正构烷烃(如C_(27)和C_(29))和长链脂肪酸(如C_(26)和C_(28))也具有较高丰度.沉水植物具有较高含量的长链正构烷烃(平均47μg g~(-1))和长链脂肪酸(平均170μg g~(-1)),与陆生植物脂类含量接近,表明当湖泊中沉水植物大量生长时,其可能对沉积物的长链脂类存在较大贡献.但藻类长链正构烷烃和长链脂肪酸的含量较低(平均含量分别为2和9μg g~(-1)),表明其对沉积物长链脂类的影响可能较小.通过对水生植物和陆生植物脂类分子指标进行比较,我们发现ACL_(14-32)和ATR_(14-18)值能有效将藻类和其他植物来源的脂肪酸区分开,Paq′值能很好地将沉水植物和陆生植物来源的正构烷烃区分开.每个水生植物样品不同奇碳数正构烷烃(C_(21)～C_(31))和不同偶碳数脂肪酸(C_(20)～C_(30))分子间δD值无明显差别,表明湖泊沉积物脂类分子间δD值的差异可能具有区分其输入来源,以及反映湖泊水文条件的潜力.     

中国南方更新世网纹红土对全球气候变化的响应: 分子化石记录

利用GC/MS对江西修水更新世网纹红土的分子化石进行了系统分析, 检测出微量的分子化石包括正构烷烃、一元正脂肪酸、一元正脂肪醇、α-正构脂肪酮等. 易遭受后期改造的含氧分子化石(酸、醇)参数在红土剖面中波动的规律性不明显; 相反, 相对较为稳定的正构烷烃具有很有意义的规律性变化, 其中, 代表木本植物与草本植物相对变化的正构烷烃比值C₂₇ /C₃₁以及反映低等菌藻生物与高等植物相对变化的正构烷烃比值C_15~21/C_22~33与深海氧同位素气候曲线的第4~20阶段具有很好的可对比性. 正构烷烃分子化石记录证实了在中国南方广泛分布的被认为是湿热气候条件下形成的更新世网纹红土, 受制于全球气候变化的驱动, 是我国又一大全球变化研究的重要载体.     

珠江流域20世纪环境变化的叶蜡正构烷烃δ~(13)C沉积记录

分析了珠江口外两个短沉积柱状样的叶蜡正构烷烃单体稳定碳同位素组成(δ~(13)C),讨论了它在揭示年代际尺度上流域环境变化的能力.长链正构烷烃主峰为C_(29)或C_(31),且表现出明显的奇数碳优势,说明这些烷烃主要来自维管束植物的叶蜡.所有的沉积样品中,C_(29)和C_(31)正构烷烃的δ~(13)C值在-28.8‰-31.2‰变化,这与珠江流域以C_3植物为主的陆地生态系统相吻合.两个沉积柱的δ~(13)C时间变化序列是相似的.从20世纪初期到70年代末这段时间都呈现出一个持续减小的趋势.但在随后的大约15年时间里,δ~(13)C值趋势反转,开始不断增大.在校正了大气CO_2浓度上升和δ~(13)Catm下降所带来的影响后,δ~(13)C_(29)记录基本上仍保留了上述变化规律,但在80年代δ~(13)C值的上升趋势表现得更加明显.通过与实测资料比较,我们认为,1980年之前δ~(13)C校正值的轻微减小趋势应该和珠江流域降水量的增加有关,之后的δ~(13)C值上升则很可能是受干旱气候条件以及人为森林砍伐的影响.因此,我们的结果表明,埋藏于珠江口外沉积物中的叶蜡正构烷烃可以很好地反映该流域在过去一个世纪里的气候变化和人类活动情况.     

华北草地生态群落下表土中长链正构烷烃单体氢同位素组成

为了查明单一生态系统下表土中高等植物来源长链正构烷烃单体氢同位素（δ^13Cn-alkanes）的变化特征,从华北张家口市万全县大麻坪玄武岩风化壳随机采集了12个表层土壤样品,用来分析其长链正构烷烃分子组成特征及其单体碳（δ^13Cn-alkanes）、氢同位素,同时分析了其总有机质碳同位素（TOC,δ^13Cn）变化.结果表明δ^13Cn和来源于陆生高等植物的4个代表性的占优势地位的长链正构烷烃（n-C27,n-C29,n-C31,n-C33）的13Cn-alkanes在这12个样品中都非常稳定,仅有很小的变化幅度,这两类碳同位素数据均表明其上覆植被的光合作用类型构成非常均一,可以视为由纯C3草本植物构成.相应的这4个主要长链正构烷烃的Dn-alkanes变化幅度比较大,整体而言,相对丰度越高的同族体分子,其Dn-alkanes更为偏负,且其变化幅度更小.然而,这4个主要长链正构烷烃加权平均Dn-alkanes值约30‰的变化幅度小于先前研究当中报道的同一地点不同现代陆生C3草本植物之间长链正构烷烃Dn-alkanes值的变化幅度,甚至小于同一植物种长链正构烷烃Dn-alkanes值的季节变化幅度.由于表土和沉积物中长链正构烷烃来源上的相似性,即它们都来源于多种植物的混合,因此,我们的结果对于沉积物,尤其是其有机质为原地植物来源的陆相沉积物的长链正构烷烃单体氢同位素组成的古气候、古环境、古水文信息的精确解译,具有一定的参考价值.     

青藏高原雪冰中正构烷烃的组成特征及其环境意义

研究了青藏高原的祁连山七一冰川、东昆仑山玉珠峰冰川、唐古拉山小冬克玛底冰川以及念青唐古拉山羊八井地区古仁河口冰川雪冰样品中自然来源和人类活动排放产生正构烷烃的含量变化及其分子组合特征。结果表明,正构烷烃的含量从青藏高原东北部到南部依次减小,与高原南部的达索普冰川、阿尔泰山的Belukha冰川和Sofiyskiy冰川没有数量级上的差别,但是都高于格陵兰冰芯记录,表明亚洲大陆冰川雪冰中人为来源和自然来源的正构烷烃具有比格陵兰冰芯较高的负载量。正构烷烃的分布特征表明,它们主要来自高等植物蜡和化石燃料燃烧的产物,低等生物贡献很小。生物来源的正构烷烃在总正构烷烃中的百份含量低于人类活动排放产生,表明快速的工业化发展已经影响到青藏高原冰川中有机污染物的组成变化。从青藏高原中南部到东北部,∑nC21^-／∑nC22^＋和（nC15＋nC17＋nC19）／（nC27＋nC29＋nC31）的比值依次降低,正构烷烃的碳优势指数（Carbon Preference Index,CPI）值逐渐升高（玉珠峰受人为影响严重除外）,说明从高原中南到东北部,高等植物和陆生植物的贡献增大,海洋中的菌藻类低等生物和水生生物贡献减小。     

长江口悬浮颗粒物中有机质来源及厌氧氨氧化活动的季节性变化

人类活动导致的富营养化与赤潮爆发致使近年来长江口缺氧区日益扩大,厌氧氨氧化过程已经被指出在缺氧区的氮循环中发挥着重要作用.梯烷脂作为一种生物标志物已被用来指示不同生态系统中厌氧氨氧化活动,但悬浮颗粒物中厌氧氨氧化菌和梯烷脂的来源尚不明确.本文通过对春、夏季节长江口悬浮颗粒物中多参数生物标志物进行分析,来研究梯烷脂的来源及其对厌氧氨氧化活动和缺氧区的指示.陆源生物标志物(长链正构烷烃和直链醇)、海源生物标志物(菜子甾醇和甲藻甾醇)和相对陆源有机质指标TMBR(terrestrial and marine biomarker ratio)、BIT(branched and isoprenoid tetraether)的时空分布结果表明,海源有机质在春季(55%)和夏季(86%)都占主要地位.梯烷脂与海源和陆源生物标志物的相关性表明,梯烷脂主要在水体中原位产生,长江口悬浮颗粒物中梯烷脂的浓度主要反映了水体中厌氧氨氧化活动的强度,但梯烷脂的浓度也会受到厌氧氨氧化菌种群结构的影响.本文研究结果表明,厌氧氨氧化活动在长江口海域广泛存在,夏季较高的梯烷脂含量(特别是在上升流区)对应着较低的溶解氧的含量,表明其指示缺氧区的可能性.     

Compound-specific stable carbon isotopic composition of petroleum hydrocarbons as a tool for tracing the source of oil spills

With the increasing demand for and consumption of crude oils, oil spill accidents happen frequently during the transportation of crude oils and oil products, and the environmental hazard they pose has become increasingly serious in China. The exact identification of the source of spilled oil can act as forensic evidence in the investigation and handling of oil spill accidents. In this study, a weathering simulation experiment demonstrates that the mass loss of crude oils caused by short-term weathering mainly occurs within the first 24h after a spill, and is dominated by the depletion of low-molecular weight hydrocarbons (相似文献   

Source,depositional environment and maturity levels of some crude oils in southwest Niger Delta,Nigeria

A suite of crude oil samples,that had not been previously characterized geochemically,was collected from two oil fields in the southwest Niger Delta Nigeria.The saturate biomarkers were used to evaluate geochemical characteristics such as depositional environments,sources of organic matter and extent of biodegradation using gas chromatography-flame ionization detector and gas chromatography-mass spectrometry.Distribution of n-alkanes(Pr/Ph,and isoprenoide/n-alkanes ratios),the abundance of hopanes,oleanane skeleton and C27-C29 steranes in the oils indicate that they were formed from mixed sources(marine and terrestrial kerogen) deposited in an oxic paleoenvironment with no particular maturity trend.These parameters also permit the source grouping of the oils into two families.     

The effects of oil exploration and production in the Fladen Ground: composition and concentration of hydrocarbons in sediment samples collected during 2001 and their comparison with sediment samples collected in 1989

Due to the potentially accumulative nature of the Fladen Ground, an area of intense oil activity in the North Sea, a survey was carried out in 1989 to map the distribution of contamination in relation to these oil activities. All the sediments collected were screened by ultraviolet fluorescence (UVF) for polycyclic aromatic hydrocarbons (PAHs) and selected samples were analysed for n-alkanes (by GC-FID), PAHs and biomarkers (by GC-MSD). This survey was repeated in 2001, with all the 1989 sites being resampled. All of these sediments were analysed for UVF oil equivalents, PAHs, n-alkanes and biomarkers. The concentrations of these parameters decreased between 1989 and 2001, with average decreases ranging from 43% to 88%. In addition, no significant difference was found, for all the parameters, between near field (<5 km from an oil installation) and far field (>5 km from an oil installation) sites in 2001 indicating that the Fladen Ground is approaching a 'steady state' or background concentration for contamination.     

Multidimensional analytical models for isotope ratios in groundwater pollutant plumes of organic contaminants undergoing different biodegradation kinetics

This work presents analytical models which are able to predict contours of concentrations and isotope ratios of organic pollutants in homogeneous aquifers. Four analytical solutions of the advective–dispersive transport equation for reactive transport from the literature differing in assumptions regarding biodegradation kinetics were used. Stable isotope ratios are computed after modelling the individual reactive transport of isotopic species in the aquifer, which respond differently to fractionation by biodegradation or sorption. The main finding of this study is that the isotope ratios in the plumes are very sensitive to the assumptions underlying the biodegradation kinetics in the models. When biodegradation occurs throughout the core of the plume as first-order reaction, the transversal gradients in isotope ratios are smooth. When biodegradation occurs in a bi-molecular reaction with an electron acceptor (modelled by double-Monod kinetics), steep transversal isotope gradients are predicted. When the reaction rates approach instantaneous reaction along the plume fringes, isotope shifts in the core of the plume disappear. A model incorporating plume and fringe degradation produces the most plausible predictions of isotope ratios in this study. It is shown furthermore that isotope fractionation by sorption causes an even different pattern of isotope ratios, with positive shifts restricted to near the forerunning front of an expanding plume. The models developed in this work can serve for the validation of numerical models and may be incorporated in natural attenuation support systems such as e.g. BIOSCREEN.     

Distribution of lipids in modern soils from various regions with continuous climate (moisture-heat) change in China and their climate significance

Total 26 modern soil samples were collected from various regions under different climate conditions from tropical to arid temperate in China and systematically analyzed for their organic matters by GC/MS in order to evaluate climatic impacts on soil organic components. Abundant lipids molecules were recognized, including n-alkanes, n-alkenones, and long-chain branched alkanes. We find the predominance of main peaks of long-chain n-alkanes (nC29,nC31,nC33) and short-chain ones(nC16,nC17,nC18) records information of soil generation in warm-humid and cold-dry regions. The proportion of n-alkanes(nC16 nC17 nC18)to(nC29 nC31 nC33)varies in good agreement with moisture-heat conditions and thus probably can serve as a new index for climate change. The ratios of C21-/nC22 ,nC17/nC31 and (nC15 nC17 nC19)/(nC27 nC29 nC31)of n-alkanes, indicating respectively input ratios of lower bacterial alga, aquatic organisms, and higher plants and terraneous organisms, co-vary well in different climate regions from forest to grassland and desert, suggesting that they have also reflected the difference of climates between monsoon region and inland one. The C21-/C22 ratio of n-alkan-2-one records largely the discrepancy of temperature from north to south of China bordered by the Qinling Mountains, but less humidity. The C21-/C22 ratio of n-alkan-3-ones changes well with climatic factors, such as temperature and humidity. The biogenic source of series A-D long-chain branched alkanes may be derived from some kinds of special epiphyte that most likely live in weak oxic-anoxic and moisture-heat environments, suggesting their distribution record as well some information on climatic change. All these researches demonstrate that the distributions of lipids molecules in modern soils in China record well signals of climates from quite different climatic regions, and can serve as important climatic proxies to reveal climatic change over China.     

Distribution of lipids in modem soils from various regions with continuous climate (moisture-heat) change in China and their climate significance

Total 26 modern soil samples were collected from various regions under different climate conditions from tropical to arid temperate in China and systematically analyzed for their organic matters by GC/MS in order to evaluate climatic impacts on soil organic components. Abundant lipids molecules were recognized, including n-alkanes, n-alkenones, and long-chain branched alkanes. We find the predominance of main peaks of long-chain n-alkanes (nC29,nC31,nC33) and short-chain ones(nC16,nC17,nC18) records information of soil generation in warm-humid and cold-dry regions. The proportion of n-alkanes(nC16+nC17+nC18)to(nC29+nC31+nC33)varies in good agreement with moisture-heat conditions and thus probably can serve as a new index for climate change. The ratios of C21-/nC22+,nC17/nC31 and (nC15+nC17+nC19)/(nC27+nC29+nC31)of n-alkanes, indicating respectively input ratios of lower bacterial alga, aquatic organisms, and higher plants and terraneous organisms, co-vary well in different climate regions from forest to grassland and desert, suggesting that they have also reflected the difference of climates between monsoon region and inland one. The C21-/C22+ ratio of n-alkan-2-one records largely the discrepancy of temperature from north to south of China bordered by the Qinling Mountains, but less humidity. The C21-/C22+ ratio of n-alkan-3-ones changes well with climatic factors, such as temperature and humidity. The biogenic source of series A-D long-chain branched alkanes may be derived from some kinds of special epiphyte that most likely live in weak oxic-anoxic and moisture-heat environments, suggesting their distribution record as well some information on climatic change. All these researches demonstrate that the distributions of lipids molecules in modern soils in China record well signals of climates from quite different climatic regions, and can serve as important climatic proxies to reveal climatic change over China.     

Distribution of lipids in modern soils from various regions with continuous climate (moisture-heat) change in China and their climate significance

Total 26 modern soil samples were collected from various regions under different climate conditions from tropical to arid temperate in China and systematically analyzed for their organic matters by GC/MS in order to evaluate climatic impacts on soil organic components. Abundant lipids molecules were recognized, including n-alkanes, n-alkenones, and long-chain branched alkanes. We find the pre- dominance of main peaks of long-chain n-alkanes (nC29, nC31, nC33) and short-chain ones (nC16, nC17, nC18) records information of soil generation in warm-humid and cold-dry regions. The proportion of n-alkanes (nC16 nC17 nC18) to (nC29 nC31 nC33) varies in good agreement with moisture-heat conditions and thus probably can serve as a new index for climate change. The ratios of C21-/nC22 , nC17/nC31 and (nC15 nC17 nC19) / ( nC27 nC29 nC31) of n-alkanes, indicating respectively input ratios of lower bacterial alga, aquatic organisms, and higher plants and terraneous organisms, co-vary well in different climate regions from forest to grassland and desert, suggesting that they have also reflected the difference of climates between monsoon region and inland one. The C21-/C22 ratio of n-alkan-2-one records largely the discrepancy of temperature from north to south of China bordered by the Qinling Mountains, but less humidity. The C21-/C22 ratio of n-alkan-3-ones changes well with climatic factors, such as tem- perature and humidity. The biogenic source of series A-D long-chain branched alkanes may be derived from some kinds of special epiphyte that most likely live in weak oxic-anoxic and moisture-heat envi- ronments, suggesting their distribution record as well some information on climatic change. All these researches demonstrate that the distributions of lipids molecules in modern soils in China record well signals of climates from quite different climatic regions, and can serve as important climatic proxies to reveal climatic change over China.     

巢湖沉积物柱样中正构烷烃初探

对巢湖湖心沉积物柱样样品的正构烷烃和有机碳进行了分析,利用正构烷烃碳数分布类型、L／H、OEP指标和有机碳数据,对该区近110年来正构烷烃的来源进行初步探讨。研究结果表明：21-25cm和16-20cm处正构烷烃以高等植物和低等生物输入并重;11．15cm即1952-1967年处具有外源性石油污染;从10cm开始,正构烷烃以细菌、藻类为代表的低等生物输人为主;尤其是1-5cm样品正构烷烃和TOC含量明显高值,表明该时期湖泊富营养化加剧。     

Molecular fossil and paleovegetation records of paleosol S4 and adjacent loess layers in the Luochuan loess section, NW China

Using gas chromatography-mass spectrometry (GC-MS) technique, a series of biomarkers were identi- fied, including n-alkanes, n-alkane-2-ones, isoprenoid etc. from the loess-paleosol samples collected from the S4 and adjacent L5, L4 of the Luochuan loess section, Northwestern China. Based on these data, especially n-alkanes and high-resolution magnetic susceptibility and grain size data, the pa- leoenvironment and paleovegetation history during S4 was reconstructed. The CPI (Carbon Predomi- nance Index) and correlation between n-alkanes and magnetic susceptibility and grain size data dem- onstrated that the molecular fossils in paleosol and loess layers can reflect the vegetation condition during the loess-paleosol formation, if the allochthonous organic inputs could be excluded reasonably. The ACL (average chain length) index is correlated well with paleomagnetic susceptibility and grain size variations, displaying their good synchrony with warm and humid climate. However, it relatively lagged behind the paleomagnetic susceptibility and the grain size variations when the climate began to deteriorate. During the formation period of paleosol, the n-alkanes was dominated by C31 homologue, indicating that the primary organic input originated from herbs. Our study also demonstrated that the herbs were more flourish than wood plants in Loess Plateau, especially in the Luochuan area during the warm and humid phase, and there was no typical forest vegetation developed in the studied period.     

Biased estimates of the isotope ratios of steady‐state evaporation from the assumption of equilibrium between vapour and precipitation

Stable water isotope ratios are measured as a tracer of environmental processes in materials such as leaves, soils, and lakes. Water in these archives may experience evaporation, which increases the abundance of heavy isotopologues proportionally to the gradients in humidity and isotope ratio between the evaporating water and the surrounding atmosphere. The isotope ratio of the atmosphere has been difficult to measure until recently, and measurements remain scarce. As a result, several assumptions have been adopted to estimate isotope ratios of atmospheric water vapour. Perhaps the most commonly employed assumption in terrestrial environments is that water vapour is in isotopic equilibrium with precipitation. We evaluate this assumption using an eight‐member ensemble of general circulation model (GCM) simulations that include explicit calculation of isotope ratios in precipitation and vapour. We find that across the model ensemble, water vapour is typically less depleted in heavy isotopologues than expected if it were in equilibrium with annual precipitation. Atmospheric vapour likely possesses higher‐than‐expected isotope ratios because precipitation isotope ratios are determined by atmospheric conditions that favour condensation, which do not reflect atmospheric mixing and advection processes outside of precipitation events. The effect of this deviation on theoretical estimates of isotope ratios of evaporating waters scales with relative humidity. As a result, the equilibrium assumption gives relatively accurate estimates of the isotope ratios of evaporating waters in low latitudes but performs increasingly poorly at increasing latitudes. Future studies of evaporative water pools should include measurements of atmospheric isotope ratios or constrain potential bias with isotope‐enabled GCM simulations.