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Mineralogical constraints on carbon deportment in phosphate ores: Implications for decarbonizing ore processing 磷矿中碳析出的矿物学限制:对脱碳矿石加工的影响
IF 3.4 3区 地球科学 Q1 GEOCHEMISTRY & GEOPHYSICS Pub Date : 2026-01-01 Epub Date: 2025-12-30 DOI: 10.1016/j.apgeochem.2025.106672
Abdelaziz Zine , Abdellatif Elghali , Radouan El Bamiki , Nouhaila Attalir , Mustapha Mouflih , Jérémie Aubineau , Fleurice Parat , Manuel Munoz , Oussama Khadiri Yazami , Jean-Louis Bodinier
The release of CO2 from carbon-bearing minerals during phosphate ore processing contributes to industrial emissions but remains poorly quantified. This study examines the Bouchane phosphate deposit, part of the Gantour Basin in Morocco, which consists of Upper Cretaceous–Paleogene sedimentary phosphates. The objective is to constrain the proportions and deportment of carbon within its mineral phases and assess their contribution to CO2 release during beneficiation and acidulation. For this purpose, 20 representative samples from a stratigraphic section of the deposit were analyzed for petrographic composition, bulk mineralogy by X-ray diffraction, bulk geochemistry by inductively coupled plasma optical emission spectroscopy (ICP-OES), and total carbon by induction furnace, complemented by in-situ microanalyses using an electron probe micro-analyzer (EPMA) and quantitative automated mineralogy with a TESCAN Integrated Mineral Analyzer (TIMA). Moreover, the modal composition of the studied samples was determined using various approaches such as quantitative X-ray diffraction (QXRD), quantitative automated mineralogy (QAM), element-to-mineral conversion (EMC), and total inversion (TI). The studied samples were predominantly composed of phosphatic coated grains, peloids, coprolites, and skeletal particles. The chemistry of these sediments varied along the stratigraphic section, marked by a dominance of inorganic carbon compared to organic carbon, with a mean content of 11.38 ± 4.58 wt% and 0.68 ± 0.03 wt%, respectively. The developed calculated mineralogy techniques (EMC, TI) proved successful in accurate quantification of the modal composition of the phosphate sediments. Automated mineralogy by TIMA provided a quantification of the percentage of problematic locked carbonates within phosphatic grains, with values below 3 %. These grains were predicted to hold 11 % of the CO2 in carbonate fluorapatite (CFA), and 0.3 % and 0.1 % in calcite and dolomite, respectively. The remaining carbonate phases are removed during washing and flotation. This study shows that adopting holistic approaches in phosphate mining is efficient for developing rapid, low-cost techniques for mineralogical characterization (EMC, TI) and indicates that phosphate rock processing results in limited in situ CO2 release from carbonate minerals.
在磷矿加工过程中,含碳矿物释放的二氧化碳造成了工业排放,但仍难以量化。本研究考察了摩洛哥Gantour盆地的Bouchane磷矿床,该矿床由上白垩统-古近系沉积磷酸盐组成。目的是限制其矿物阶段内碳的比例和形态,并评估其在选矿和酸化过程中对二氧化碳释放的贡献。为此,对该矿床地层剖面的20个代表性样品进行了岩相组成、x射线衍射、电感耦合等离子体发射光谱(ICP-OES)和感应炉总碳分析,并采用电子探针微量分析仪(EPMA)和TESCAN集成矿物分析仪(TIMA)进行了原位微量分析。此外,采用定量x射线衍射(QXRD)、定量自动化矿物学(QAM)、元素-矿物转换(EMC)和全反演(TI)等多种方法确定了所研究样品的模态组成。所研究的样品主要由磷包覆颗粒、类球体、粪化石和骨骼颗粒组成。这些沉积物的化学成分在地层剖面上存在差异,无机碳含量高于有机碳,平均含量分别为11.38±4.58 wt%和0.68±0.03 wt%。开发的计算矿物学技术(EMC, TI)在准确定量磷酸盐沉积物的模态组成方面取得了成功。TIMA自动矿物学提供了磷酸盐颗粒中有问题的锁定碳酸盐百分比的量化,其值低于3%。据预测,这些颗粒在碳酸盐氟磷灰石(CFA)中分别含有11%的二氧化碳,在方解石和白云石中分别含有0.3%和0.1%的二氧化碳。在洗涤和浮选过程中除去剩余的碳酸盐相。该研究表明,在磷矿开采中采用整体方法对于开发快速、低成本的矿物学表征技术(EMC, TI)是有效的,并表明磷矿处理导致碳酸盐矿物的原位CO2释放有限。
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引用次数: 0
A review of Al substitution on the structures and properties of iron (oxyhydr)oxides and their environmental implications Al取代对铁(氧)氧化物结构和性质的影响及其对环境的影响
IF 3.4 3区 地球科学 Q1 GEOCHEMISTRY & GEOPHYSICS Pub Date : 2026-01-01 Epub Date: 2025-12-13 DOI: 10.1016/j.apgeochem.2025.106653
Junkun Yan , Jingjing Hu , Lingyi Li , Wei Cheng
Aluminum (Al) substitution for Fe(III) in iron (oxyhydr)oxides is a widespread phenomenon that significantly modifies the minerals' physicochemical structural properties and reactivity, thereby influencing the environmental behavior of contaminants. Despite the importance of Al-substituted iron (oxyhydr)oxides in geochemical processes, a comprehensive analysis of their structural properties and reactivity has been lacking. This review critically examines the effects of Al substitution on iron (oxyhydr)oxide crystal structure, morphology, surface charge, hydroxyl group characteristics, and recrystallization dynamics. We then elucidate how these structural alterations modulate the adsorption capacity for key environmental contaminants (heavy metals, metalloids, organic compounds, inorganic anions) and influence redox and catalytic processes crucial for contaminant transformation. This work provides essential insights for predicting contaminant behavior in diverse geological settings and inform the design of tailored remediation technologies. Future research directions are proposed to advance understanding of Al-substituted iron (oxyhydr)oxides in critical environmental processes.
在铁(氧合)氧化物中,铝(Al)取代铁(III)是一种普遍存在的现象,它显著改变了矿物的物理化学结构性质和反应性,从而影响了污染物的环境行为。尽管铝取代铁(氧合)氧化物在地球化学过程中的重要性,但对其结构性质和反应性的综合分析一直缺乏。本文综述了Al取代对铁(氧)氧化物晶体结构、形貌、表面电荷、羟基特征和再结晶动力学的影响。然后,我们阐明了这些结构变化如何调节对关键环境污染物(重金属、类金属、有机化合物、无机阴离子)的吸附能力,并影响对污染物转化至关重要的氧化还原和催化过程。这项工作为预测不同地质环境下污染物的行为提供了重要的见解,并为定制修复技术的设计提供了信息。提出了未来的研究方向,以促进对铝取代铁(氧)氧化物在关键环境过程中的认识。
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引用次数: 0
Modelling transport of natural tracers through a Mesozoic aquitard sequence in northern Switzerland 模拟天然示踪剂在瑞士北部中生代含水层序中的运移
IF 3.4 3区 地球科学 Q1 GEOCHEMISTRY & GEOPHYSICS Pub Date : 2026-01-01 Epub Date: 2025-12-13 DOI: 10.1016/j.apgeochem.2025.106654
Jin Ma , Thomas Gimmi , Paul Wersin , Daniel Traber , Michael Schnellmann
Analysing and modelling profiles of natural tracers in rock porewater contribute substantially to the understanding of palaeo-transport processes in clay rocks. Following a recent deep-drilling campaign in northern Switzerland, a large dataset from eight boreholes has become available. It reveals detailed rock and porewater characterisation and provides insights into the investigated 600-700 m-thick Mesozoic succession, which includes a large central aquitard sequence with more than 100 m thick Opalinus Clay. The aquitard sequence is sandwiched between the Malm aquifer (towards the east) or the Hauptrogenstein aquifer (HRS, towards the west) at the top and the Keuper or Muschelkalk aquifers at the base. This study aimed to model and reproduce the high-resolution profiles of four different natural tracers (δ18O, δ2H, Cl, and Br) from these boreholes using a one-dimensional transport model. The model incorporated diffusion properties dependent on temperature, clay-mineral content, and formation-specific anion-accessible porosities. Good agreements were found between the modelled and measured profiles considering diffusive transport and consistent evolution times (i.e., times when groundwater composition changed) for all four tracers. These times were estimated individually for each borehole, suggesting values between 0.1 and 0.7 Ma for the Keuper aquifer, longer times (mostly several Ma, range of 0.6–3 Ma) for the Malm aquifer, and shortest times (mostly less than 150 ka, range of 0.02–0.3 Ma) for the Muschelkalk aquifer. These estimates are broadly consistent with the current knowledge on the palaeo-hydrogeology of the studied region. Extensive sensitivity analyses were performed to assess the impact of various modelling assumptions and simplifications on the fitting quality and estimated evolution times. Variations with regard to assumed initial conditions (within plausible ranges) and palaeo temperatures had only minor effects, while variations of diffusion coefficients or positions of conductive zones can affect local profile shapes and thus evolution times. Finally, no evidence of potential cross-formation flow between the overlying and underlying aquifers (Malm and Keuper) could be identified from simulations including advective transport.
岩石孔隙水天然示踪剂剖面的分析和建模,对认识粘土岩的古运移过程具有重要意义。最近在瑞士北部进行了一次深度钻探活动后,从8个钻孔中获得了一个大型数据集。它揭示了详细的岩石和孔隙水特征,并提供了对所研究的600-700米厚的中生代演替的见解,其中包括一个大型的中央aquitard层序,其中有超过100米厚的蛋白石粘土。该含水层序夹在顶部的马尔姆含水层(向东)或Hauptrogenstein含水层(HRS,向西)和底部的Keuper或Muschelkalk含水层之间。本研究旨在利用一维输运模型,模拟和再现这些井中四种不同天然示踪剂(δ18O、δ2H、Cl−和Br−)的高分辨率剖面。该模型结合了依赖于温度、粘土矿物含量和特定地层阴离子可及孔隙度的扩散特性。考虑到所有四种示踪剂的扩散输运和一致的演化时间(即地下水成分变化的时间),模型和实测剖面之间存在良好的一致性。这些时间分别对每个井眼进行了估计,表明Keuper含水层的时间在0.1至0.7 Ma之间,Malm含水层的时间更长(主要是几Ma,范围为0.6-3 Ma), Muschelkalk含水层的时间最短(主要小于150 ka,范围为0.02-0.3 Ma)。这些估计大体上与研究区域古水文地质的现有知识相一致。进行了广泛的敏感性分析,以评估各种建模假设和简化对拟合质量和估计进化时间的影响。假设的初始条件(在合理范围内)和古温度的变化只有很小的影响,而扩散系数或导电带位置的变化可以影响局部剖面的形状,从而影响演化时间。最后,从包括平流运输在内的模拟中,没有证据表明上覆和下伏含水层(马尔姆和科珀)之间存在潜在的地层交叉流动。
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引用次数: 0
Stability of barite in thermochemical sulfate reduction: implications for primeval organic component preservation and metal sulfide mineralization 热化学硫酸盐还原中重晶石的稳定性:对原始有机成分保存和金属硫化物矿化的意义
IF 3.4 3区 地球科学 Q1 GEOCHEMISTRY & GEOPHYSICS Pub Date : 2026-01-01 Epub Date: 2025-12-22 DOI: 10.1016/j.apgeochem.2025.106666
Yuan Wei , Qian Wan , Wenxuan Hu , Xiaolin Wang
Thermochemical sulfate reduction (TSR) is a common organic-inorganic interaction where sulfates react with hydrocarbons at elevated temperatures, producing reduced sulfur and oxidized carbon. The stability of barite in TSR is a critical scientific question because barite-hosted inclusions are reported to record primeval organic matters and barite can be involved in the formation of Sedimentary Exhalative and Mississippi-Valley type deposits. Here we performed systematic hydrothermal experiments and thermodynamic simulations to identify the key factors controlling TSR between barite and hydrocarbons. Results show that in anhydrous and neutral aqueous environments, barite and hydrocarbons can coexist stably at temperatures below 150 °C. Such condition is comparable with that reported for the formation of ∼3.5 Ga barite in Pilbara Craton, Western Australia, indicating that barite-hosted inclusions can record original information for Archean life evolution. At higher temperature and low pH conditions, barite can react with hydrocarbon to generate H2S and CO2. Fluid acidity (i.e., H+ concentration) and temperature are the most prominent factors controlling the involvement of barite in TSR. Therefore, consumption of preexisting H2S (either TSR or other origin) by precipitation of metal sulfides (e.g., sphalerite and galena) can generate excess H+, which favors the involvement of barite in TSR. Obviously, barite can serve as a sulfur source for the formation of metal sulfide deposits. In conclusion, our findings offer new insights into researches of early Earth environments and the mineralization mechanisms of metal deposits.
热化学硫酸盐还原(TSR)是一种常见的有机-无机相互作用,硫酸盐在高温下与碳氢化合物反应,产生还原硫和氧化碳。重晶石在TSR中的稳定性是一个重要的科学问题,因为有报道称重晶石包裹体记录了原始有机质,重晶石可能参与了沉积喷发型和密西西比河谷型矿床的形成。通过系统的热液实验和热力学模拟,确定了控制重晶石与烃类之间TSR的关键因素。结果表明,在无水和中性水环境中,重晶石和碳氢化合物可以在低于150℃的温度下稳定共存。这一条件与西澳大利亚皮尔巴拉克拉通(Pilbara Craton)约3.5 Ga重晶石的形成条件相当,表明重晶石包裹体可以记录太古宙生命演化的原始信息。在较高的温度和较低的pH条件下,重晶石可以与碳氢化合物反应生成H2S和CO2。流体酸度(即H+浓度)和温度是控制重晶石参与TSR的最重要因素。因此,通过金属硫化物(如闪锌矿和方铅矿)的沉淀消耗预先存在的H2S (TSR或其他来源)可以产生多余的H+,这有利于重晶石参与TSR。显然,重晶石可以作为金属硫化物矿床形成的硫源。总之,我们的发现为研究早期地球环境和金属矿床成矿机制提供了新的思路。
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引用次数: 0
Resolving false positive Eu anomaly in seep carbonates with high Ba/Sm ratio using DGA resin separation 采用DGA树脂分离技术解决高Ba/Sm比碳酸盐岩渗渗Eu假阳性异常
IF 3.4 3区 地球科学 Q1 GEOCHEMISTRY & GEOPHYSICS Pub Date : 2026-01-01 Epub Date: 2025-12-29 DOI: 10.1016/j.apgeochem.2025.106670
Xudong Wang , Lanlan Zhang , Tongtong Bai , Jean-Alix Barrat , Zhaoyang Wang , Zice Jia , Dong Feng
The contents and distribution patterns of rare earth elements (REEs) are powerful tools for reconstructing fluid sources and redox conditions in marine sedimentary environments. However, their accurate determination in carbonate rocks is often complicated by low REE abundances and high barium (Ba) contents, which cause severe isobaric interference with europium (Eu) during conventional ICP-MS analysis due to the formation of BaO+ or BaOH+ polyatomic ions. In this study, we applied a validated DGA resin separation technique to analyze REEs from 30 Ba-rich authigenic carbonate samples from nine seep sites in the Gulf of Mexico. Before and after DGA separation, REE analyses were conducted on both bulk carbonate rock and carbonate fraction of carbonate rock (hereafter carbonate fraction). Ba contents ranged from 201 ppm to 91200 ppm in the bulk carbonate rock, and from 28 ppm to 1700 ppm in the carbonate fraction. Prior to separation, Eu/Eu∗ values ranged from 1.40 to 80.49 in bulk rock and from 1.44 to 17.65 in the carbonate fraction, with strong correlation to Ba/Sm ratios, indicating Ba-induced analytical artifacts. After DGA resin separation, Eu/Eu∗ values decreased to 1.10–1.16 in bulk rock and 1.11–1.22 in the carbonate fraction, confirming the elimination of false Eu anomaly. These results demonstrate that Ba-related interference can lead to substantial misinterpretation of REE data in Ba-rich samples. We advocate for routine chemical separation of REEs from matrix elements prior to ICP-MS analysis to ensure accurate paleoenvironmental reconstructions in seep and other Ba-enriched sedimentary settings.
稀土元素的含量和分布模式是重建海相沉积环境流体来源和氧化还原条件的有力工具。然而,由于低REE丰度和高钡(Ba)含量,在常规的ICP-MS分析过程中,由于BaO+或BaOH+多原子离子的形成,会对铕(Eu)产生严重的等压干扰,使它们在碳酸盐岩中的准确测定变得复杂。在这项研究中,我们应用了一种经过验证的DGA树脂分离技术,分析了墨西哥湾9个渗漏点的30个富ba自生碳酸盐样品中的稀土元素。在DGA分选前后,分别对整体碳酸盐岩和碳酸盐岩中的碳酸段(以下简称碳酸段)进行稀土元素分析。整体碳酸盐岩中Ba含量为201 ppm ~ 91200 ppm,碳酸盐岩馏分中Ba含量为28 ppm ~ 1700 ppm。分离前,大块岩石的Eu/Eu *值在1.40 ~ 80.49之间,碳酸盐部分的Eu/Eu *值在1.44 ~ 17.65之间,与Ba/Sm比值有很强的相关性,表明存在Ba诱发的分析伪影。经DGA树脂分离后,块状岩石中Eu/Eu *值降至1.10 ~ 1.16,碳酸盐部分中Eu/Eu *值降至1.11 ~ 1.22,证实假Eu异常消除。这些结果表明,ba相关的干扰可能导致富ba样品中REE数据的大量误读。我们主张在ICP-MS分析之前,从基质元素中常规分离稀土元素,以确保在渗漏和其他富含ba的沉积环境中精确重建古环境。
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引用次数: 0
Impact of salinity on nitrogen cycling and microbial community functional potential in groundwater of the Yellow river delta 盐度对黄河三角洲地下水氮循环及微生物群落功能势的影响
IF 3.4 3区 地球科学 Q1 GEOCHEMISTRY & GEOPHYSICS Pub Date : 2026-01-01 Epub Date: 2025-12-29 DOI: 10.1016/j.apgeochem.2025.106669
Huan Wang , Chuanshun Zhi , Yufei Jiao , Dan Xu , Wenfeng Gao , Yawei Kou , Xiancang Wu , Jing Bai , Hui Mu , Houliang Lu , Xiaonong Hu
Microorganisms in shallow groundwater of river deltas play a key role in nitrogen cycling, yet little is known about this process in high-salinity regions. This study examines how salinity affects nitrogen cycling and microbial function in the Yellow River Delta's high-salinity groundwater. Through combined hydrochemical, microbial, and genetic analyses, the study reveals that groundwater is high saline, mainly of the Na–Cl type, with ammonium as the dominant nitrogen form under reducing conditions. Microbial communities vary with salinity and redox conditions, and nitrogen cycling is mainly driven by DNRA and denitrification. Functional genes related to nitrogen metabolism strongly correlate with ammonium levels, emphasizing ammonium's regulatory role. Different hydrochemical factors shape nitrogen cycling at varying salinities: pH, I, and Mg2+ at low salinity; K+ and sulfide at medium salinity; and TDS, Cl, SO42−, and Na+ at high salinity. Overall, reductive pathways dominate, with denitrification (35.88 %) and DNRA (31.03 %) as the main processes. Under varying salinity conditions, nitrogen cycling pathways shift significantly: low-salinity favors nitrogen fixation, nitrification and DNRA, promoting both nitrogen input and loss; medium-salinity supports active nitrogen turnover through enhanced nitrification, denitrification, and ANRA; while high salinity leads to DNRA dominance, ammonium accumulation, and reduced nitrogen removal due to suppressed nitrification and denitrification. High-salinity selects for DNRA-performing, salt-tolerant microbes, enriching DNRA genes (narGHI, nirBD), while denitrification genes (nosZ, nirK) are more abundant at lower salinities.
河流三角洲浅层地下水微生物在氮循环中起关键作用,但对高盐度地区的这一过程知之甚少。本研究探讨了盐度对黄河三角洲高盐度地下水氮循环和微生物功能的影响。通过水化学、微生物学和遗传学的综合分析,研究表明,在还原条件下,地下水为高盐型,以Na-Cl型为主,氮以铵态为主。微生物群落随盐度和氧化还原条件的变化而变化,氮循环主要由DNRA和反硝化驱动。氮代谢相关的功能基因与铵水平密切相关,强调铵的调节作用。不同的水化学因素影响不同盐度下的氮循环:pH、I−和Mg2+在低盐度下;中等盐度下的K+和硫化物;TDS、Cl−、SO42−和Na+在高盐度下的分布。总体而言,还原途径占主导地位,反硝化(35.88%)和DNRA(31.03%)是主要过程。在不同盐度条件下,氮循环途径发生显著变化:低盐度有利于固氮、硝化和DNRA,促进了氮的输入和损失;中盐度通过增强硝化、反硝化和ANRA支持活性氮周转;而高盐度则导致DNRA优势,铵态氮积累,并由于抑制硝化和反硝化作用而降低氮的去除。高盐度选择了DNRA执行,耐盐的微生物,丰富DNRA基因(narGHI, nirBD),而反硝化基因(nosZ, nirK)在低盐度下更丰富。
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引用次数: 0
New insights on the Pb isotopic compositions of drinking water lead pipes in the United States 美国饮用水铅管铅同位素组成的新认识
IF 3.4 3区 地球科学 Q1 GEOCHEMISTRY & GEOPHYSICS Pub Date : 2026-01-01 Epub Date: 2025-11-26 DOI: 10.1016/j.apgeochem.2025.106639
George D. Kamenov , Sean Scott
Compilation of high-precision Pb isotope data for Pb pipes can be used to identify human exposure to Pb from lead service lines (LSLs) in the USA. Furthermore, as the Pb used in LSLs was most likely obtained from the same ore deposits as lead used in other objects and materials, the Pb pipe data should provide information about the overall isotopic composition of the U.S. industrial Pb. This work presents new MC-ICP-MS Pb isotope data for 50 Pb pipes, all harvested from the state of Wisconsin. The new data show virtually identical isotopic compositions as the previously published MC-ICP-MS data for USA Pb pipes, indicating that most likely no specific geographical variations can be expected in LSLs Pb isotopes in the USA. Furthermore, the Pb pipe isotope data encompass almost the whole isotope range observed in major domestic and international Pb ore deposits. Therefore, the Pb pipe data should be representative of the Pb isotope range of industrial Pb in the USA. The compiled data reveal the existence of two major Pb isotope clusters. Cluster I is composed of lead obtained from various Pb deposits, including imported lead. Cluster II is composed exclusively of domestic lead obtained from the Mississippi Valley Type ore deposits, and potentially is unique to USA industrial Pb isotope signal. Comparison of the Pb pipe data to USA MC-ICP-MS human blood Pb reveals that most individuals, not exposed to Pb from LSLs, do not fall within the two isotope clusters. Therefore, the identified clusters, in addition to the overall Pb isotope linear trend, can potentially be used in large-scale epidemiological studies to decipher if human Pb exposure in a given region is from LSLs or other sources.
美国铅管道的高精度铅同位素数据汇编可用于确定铅服务管线(LSLs)中人体对铅的暴露。此外,由于LSLs中使用的铅很可能来自与其他物体和材料中使用的铅相同的矿床,铅管数据应该提供有关美国工业铅整体同位素组成的信息。这项工作提出了新的MC-ICP-MS铅同位素数据的50个铅管,全部来自威斯康星州。新数据显示,美国铅管道的同位素组成与之前公布的MC-ICP-MS数据几乎相同,这表明美国LSLs的铅同位素很可能没有特定的地理变化。此外,铅管同位素数据几乎涵盖了国内外主要铅矿床观测到的全部同位素范围。因此,铅管数据应能代表美国工业铅的铅同位素范围。整理的数据显示存在两个主要的Pb同位素团簇。簇I由从各种铅矿床获得的铅组成,包括进口铅。簇II完全由从密西西比河谷型矿床中获得的国内铅组成,可能是美国工业铅同位素信号所独有的。将铅管数据与美国MC-ICP-MS人血铅进行比较,发现大多数未暴露于LSLs的个体不属于这两种同位素簇。因此,除了总体的铅同位素线性趋势外,所确定的聚类可以潜在地用于大规模流行病学研究,以破译特定地区的人类铅暴露是来自LSLs还是其他来源。
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引用次数: 0
Provenance of oilfield brines and vertical connectivity of Middle to Upper Jurassic sequence in eastern Saudi Arabia 沙特阿拉伯东部中、上侏罗统油田卤水物源与垂向连通性
IF 3.4 3区 地球科学 Q1 GEOCHEMISTRY & GEOPHYSICS Pub Date : 2026-01-01 Epub Date: 2025-12-30 DOI: 10.1016/j.apgeochem.2025.106673
Peter Birkle , Ahmed J. Zayer
Knowledge of reservoir connectivity is crucial for optimizing oil recovery, accurately estimating reserves, planning well placement, and improving economics of an oil field. This study combines hydrochemical (major, minor, trace elements) and multi-isotopic techniques (δ2H, δ11B, δ13C, 14C, δ18OH2O, δ18OSO4, δ37Cl, δ81Br, δ34SSO4, 87Sr/86Sr) on oilfield brines to define reservoirs dynamics by tracing fluid provenance and migration. As case study, preserved bottom-hole water samples were recovered along a 1930’ vertical column of seven groundwater horizons from a Middle to Upper Jurassic carbonate-anhydrite sequence in an exploratory well in the eastern region of Saudi Arabia. Geochemical fluid homogeneities reveal hydraulic connectivity between the Lower Tithonian and Upper Kimmeridgian sequence, suggesting the presence of a single reservoir. Isotopic heterogeneities reveal sealing conditions between underlying Lower Kimmeridgian, Oxfordian (Hanifa), and Bathonian (Upper Dhruma) groundwater systems. Interlayered anhydrite strata resulted in possessing ambivalent hydrodynamic functionalities, either as conduits or seals. Studied formation waters are composed of Na–Cl to Na–Ca–Cl water type with a descending salinity from 210,500 mg/L (Tithonian) to 147,800 mg/L (Bathonian). Measured 14C concentrations from 2.01 pmC to 18.77 pmC point to recharge of the Jurassic sequence by infiltrating surface water during Late Pleistocene and Early Holocene, causing the mixing and partial replacement between 37 % and 55 % of fossil oilfield brine. A positive vertical trend of δ18OSO4 - δ34SSO4 ratios, δ13CPDB values between +8.4 ‰ and +16.2 ‰, and depleted δ11B ratios reveal thermocatalytic sulfate reduction, methane production, and desorption of clay material, respectively, as major secondary water-rock interaction processes. As practical benefit, formation water analyses provide a low-cost and low-risk complementary tool to expensive and failure-prone production logging tools for evaluating reservoir conditions. The geochemical detection of hydraulic connectivity or compartmentalization between stratigraphic units represents a complimentary tool to trace the analogue migration of hydrocarbons within single or multiple pay zones.
了解储层连通性对于优化采收率、准确估计储量、规划井位和提高油田经济效益至关重要。本研究结合水化学(主、次、微量元素)和多同位素技术(δ2H、δ11B、δ13C、14C、δ18OH2O、δ18OSO4、δ37Cl、δ81Br、δ34SSO4、87Sr/86Sr)对油田卤水的研究,通过追踪流体的物源和运移来定义储层动力学。作为案例研究,在沙特阿拉伯东部地区的一口勘探井中,沿着1930年代的7个地下水层的垂直柱,从中上侏罗统碳酸盐岩-硬石膏层序中提取了保存完好的井底水样。地球化学流体均质性揭示了下梯统与上基默里纪层序之间的水力连通性,表明存在单一储层。同位素非均质性揭示了下基默里吉纪、牛津纪(哈尼法)和巴统(上德鲁马)地下水系统之间的封闭条件。层间硬石膏层具有双重的水动力功能,既可以作为管道,也可以作为密封。研究的地层水由Na-Cl - Na-Ca-Cl水型组成,盐度从210,500 mg/L(泰桑期)降至147,800 mg/L(巴桑期)。在晚更新世至全新世早期,测量了2.01 ~ 18.77 pmC的14C浓度,表明侏罗纪层序通过地表水渗透补给,导致37% ~ 55%的化石油田卤水混合或部分置换。δ18OSO4 - δ34SSO4比值呈正垂直趋势,δ13CPDB值在+8.4‰~ +16.2‰之间,δ11B比值下降,表明热催化硫酸盐还原、甲烷生成和粘土物质解吸分别是主要的次生水岩相互作用过程。作为实际效益,地层水分析为昂贵且容易失效的生产测井工具提供了一种低成本、低风险的补充工具,用于评估储层状况。地层单元之间的水力连通性或分区性的地球化学检测是追踪单个或多个产层内碳氢化合物模拟运移的一种辅助工具。
{"title":"Provenance of oilfield brines and vertical connectivity of Middle to Upper Jurassic sequence in eastern Saudi Arabia","authors":"Peter Birkle ,&nbsp;Ahmed J. Zayer","doi":"10.1016/j.apgeochem.2025.106673","DOIUrl":"10.1016/j.apgeochem.2025.106673","url":null,"abstract":"<div><div>Knowledge of reservoir connectivity is crucial for optimizing oil recovery, accurately estimating reserves, planning well placement, and improving economics of an oil field. This study combines hydrochemical (major, minor, trace elements) and multi-isotopic techniques (δ<sup>2</sup>H, δ<sup>11</sup>B, δ<sup>13</sup>C, <sup>14</sup>C, δ<sup>18</sup>O<sub>H2O</sub>, δ<sup>18</sup>O<sub>SO4</sub>, δ<sup>37</sup>Cl, δ<sup>81</sup>Br, δ<sup>34</sup>S<sub>SO4</sub>, <sup>87</sup>Sr/<sup>86</sup>Sr) on oilfield brines to define reservoirs dynamics by tracing fluid provenance and migration. As case study, preserved bottom-hole water samples were recovered along a 1930’ vertical column of seven groundwater horizons from a Middle to Upper Jurassic carbonate-anhydrite sequence in an exploratory well in the eastern region of Saudi Arabia. Geochemical fluid homogeneities reveal hydraulic connectivity between the Lower Tithonian and Upper Kimmeridgian sequence, suggesting the presence of a single reservoir. Isotopic heterogeneities reveal sealing conditions between underlying Lower Kimmeridgian, Oxfordian (Hanifa), and Bathonian (Upper Dhruma) groundwater systems. Interlayered anhydrite strata resulted in possessing ambivalent hydrodynamic functionalities, either as conduits or seals. Studied formation waters are composed of Na–Cl to Na–Ca–Cl water type with a descending salinity from 210,500 mg/L (Tithonian) to 147,800 mg/L (Bathonian). Measured <sup>14</sup>C concentrations from 2.01 pmC to 18.77 pmC point to recharge of the Jurassic sequence by infiltrating surface water during Late Pleistocene and Early Holocene, causing the mixing and partial replacement between 37 % and 55 % of fossil oilfield brine. A positive vertical trend of δ<sup>18</sup>O<sub>SO4</sub> - δ<sup>34</sup>S<sub>SO4</sub> ratios, δ<sup>13</sup>C<sub>PDB</sub> values between +8.4 ‰ and +16.2 ‰, and depleted δ<sup>11</sup>B ratios reveal thermocatalytic sulfate reduction, methane production, and desorption of clay material, respectively, as major secondary water-rock interaction processes. As practical benefit, formation water analyses provide a low-cost and low-risk complementary tool to expensive and failure-prone production logging tools for evaluating reservoir conditions. The geochemical detection of hydraulic connectivity or compartmentalization between stratigraphic units represents a complimentary tool to trace the analogue migration of hydrocarbons within single or multiple pay zones.</div></div>","PeriodicalId":8064,"journal":{"name":"Applied Geochemistry","volume":"197 ","pages":"Article 106673"},"PeriodicalIF":3.4,"publicationDate":"2026-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145922381","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"地球科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Kinetic model reveals microbial-mediated hydrogen consumption and abiotic mineral reactions jointly control hydrogen depletion during geological storage 动力学模型表明,微生物介导的氢消耗和非生物矿物反应共同控制了地质储存过程中的氢耗竭
IF 3.4 3区 地球科学 Q1 GEOCHEMISTRY & GEOPHYSICS Pub Date : 2026-01-01 Epub Date: 2025-12-06 DOI: 10.1016/j.apgeochem.2025.106649
Dongfang Ke , Weiqiang Feng , Peng Liao , Rong Li , Ruina Xu , Yu-Min Chou , Peixue Jiang
Underground hydrogen storage (UHS) in porous reservoirs faces biogeochemical challenges such as microbial hydrogen consumption and the generation of secondary gases, which can significantly compromise storage efficiency. To address critical knowledge gaps concerning the interactions between hydrogen, minerals, and microbes under kinetic parameter uncertainty, this study develops a novel co-simulation framework coupling MATLAB with Phreeqc. This integrated model combines kinetic formulations for mineral dissolution and precipitation (e.g., calcite and gypsum), microbial metabolism (e.g., sulfate reduction and methanogenesis), and thermodynamic gas-liquid equilibrium to simulate the complex gas-water-rock interactions during UHS. Simulation results reveal that hydrogen loss (<0.22 %) and purity degradation (<0.0002 %) are negligible under typical anaerobic reservoir conditions, constrained by an intrinsic microbial kinetic threshold. Substantial hydrogen consumption occurs only when the maximum specific reaction rate (Vmax) exceeds 10−4.5 s−1; below this value, hydrogen depletion remains minimal irrespective of variations in mineral reactivity, mineral content, or initial biomass concentration. Abiotic mineral dissolution plays a pivotal role in sustaining microbial activity by supplying essential dissolved inorganic carbon (as a carbon source) and electron acceptors (e.g., SO42−, HCO3). Furthermore, biomass accumulation exhibits self-limiting behavior due to pore-space constraints, indicating limited effectiveness of post-cycle biomass removal strategies. However, under high-kinetic regimes, severe bioclogging and significant hydrogen loss can occur, highlighting the necessity of proactive microbial metabolic suppression to ensure the long-term viability of UHS operations.
多孔储层地下储氢(UHS)面临生物地球化学挑战,如微生物耗氢和二次气的产生,这可能会严重影响储氢效率。为了解决动力学参数不确定性下氢、矿物和微生物之间相互作用的关键知识空白,本研究开发了一个新的联合模拟框架,将MATLAB与Phreeqc耦合在一起。该集成模型结合了矿物溶解和沉淀(如方解石和石膏)、微生物代谢(如硫酸盐还原和甲烷生成)和热力学气液平衡的动力学公式,以模拟UHS过程中复杂的气-水-岩相互作用。模拟结果表明,在典型的厌氧水库条件下,受固有微生物动力学阈值的限制,氢损失(< 0.22%)和纯度降解(<0.0002 %)可以忽略不计。只有当最大比反应速率(Vmax)超过10−4.5 s−1时,才会出现大量的氢消耗;低于这个值,无论矿物反应性、矿物含量或初始生物量浓度的变化如何,氢消耗仍然是最小的。非生物矿物溶解通过提供必需的溶解无机碳(作为碳源)和电子受体(如SO42−,HCO3−),在维持微生物活动中起着关键作用。此外,由于孔隙空间的限制,生物质积累表现出自限制行为,表明循环后生物质去除策略的有效性有限。然而,在高动力学条件下,可能会发生严重的生物堵塞和显著的氢损失,这突出了主动抑制微生物代谢以确保UHS操作的长期可行性的必要性。
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引用次数: 0
Unraveling stress-mediated fluid-fault interactions in 2021–2022 seismic sequence: Insights from unsupervised machine learning and multiparametric hydrochemical anomalies in Xianshuihe fault zone 2021-2022年地震序列中应力-断层相互作用的揭示:来自鲜水河断裂带无监督机器学习和多参数水化学异常的见解
IF 3.4 3区 地球科学 Q1 GEOCHEMISTRY & GEOPHYSICS Pub Date : 2026-01-01 Epub Date: 2025-11-19 DOI: 10.1016/j.apgeochem.2025.106635
Yucong Yan , Zheming Shi , Xiaocheng Zhou , Guangcai Wang , Zuochen Zhang , Yunfei Bai , Zhaojun Zeng , Bingyu Yao , Yuwen Wang , Miao He , Jiao Tian , Ruibin Li , Han Yan
Earthquake-related hydrochemical changes in thermal springs have been widely observed, yet the temporal dynamics and controlling mechanisms of pre- and post-seismic hydrochemical changes remains poorly constrained. By employing unsupervised machine learning (SOM-KM), this study investigates earthquake-induced changes of major elements, trace elements, and hydrogen-oxygen isotopes by high-frequency monitoring data in two thermal springs (XXX and LTG) along the Xianshuihe fault zone during the 2021–2022 Ms ≥ 6.0 earthquake sequence. The result shows that: the XXX spring (Moxi segment) exhibited consistent co-seismic dilution of major ions (Na+, K+, Cl, HCO3) and trace elements, attributed to shallow fracture opening under low normal stress (200–400 MPa), thereby facilitating meteoric water recharge (81–89 % mixing ratio). Conversely, the LTG spring (Kangding segment) showed enrichment of deep-sourced constituents of pre-seismic major elements (Na+, K+, Cl, HCO3) surges during the 2021 Luxian Ms6.0 earthquake, and post-seismic trace element fluctuation in 2022 Ms ≥ 6.0 earthquake sequence, driven by high stress (400–600 MPa) enhancing deep fracture dilation, fluid ascent, and water-rock interaction (obvious δ18O drift). Cross-analysis of hydrogeochemical signatures with geological and geophysical evidence demonstrates that earthquake-induced hyrochemical anomalies are governed by (1) regional tectonics stress; (2) fault-segment heterogeneity; (3) fluid pathway reorganization and water-rock interaction dynamics. This work advances the understanding of fault-zone fluid response mechanisms to seismicity and offers novel insights into crustal fluid-tectonic interactions during earthquake cycles.
地震相关的温泉水化学变化已被广泛观察到,但对地震前后水化学变化的时间动力学和控制机制却知之甚少。采用无监督机器学习(SOM-KM)方法,利用仙水河断裂带XXX和LTG两个温泉在2021-2022年Ms≥6.0级地震序列期间的高频监测数据,研究了主元素、微量元素和氢氧同位素的地震诱发变化。结果表明:XXX泉(磨溪段)主要离子(Na+、K+、Cl−、HCO3−)和微量元素的同震稀释一致,这是由于在低正应力(200 ~ 400 MPa)条件下浅裂缝张开,有利于大气水补给(混合比81 ~ 89%)。相反,LTG泉(康定段)在高应力(400 ~ 600 MPa)的驱动下,在2021年陆县Ms6.0级地震期间表现出震前主元素(Na+、K+、Cl−、HCO3−)深源成分的富集,在2022年Ms≥6.0级地震序列中表现出震后微量元素的波动,增强了深部裂缝扩张、流体上升和水岩相互作用(明显的δ18O漂移)。水文地球化学特征与地质和地球物理证据的交叉分析表明,地震引起的水化学异常受(1)区域构造应力的控制;(2)断层段异质性;(3)流体通道重组与水岩相互作用动力学。这项工作促进了对断裂带流体对地震活动性的响应机制的理解,并为地震周期中地壳流体-构造相互作用提供了新的见解。
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引用次数: 0
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Applied Geochemistry
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