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Compositions and hydrocarbon generation potentials of Scrippsiella trochoidea under increasing temperature 温度升高下特氏斯克里普氏菌的组成及生烃潜力
IF 3.4 3区 地球科学 Q1 GEOCHEMISTRY & GEOPHYSICS Pub Date : 2026-02-01 Epub Date: 2026-01-16 DOI: 10.1016/j.apgeochem.2026.106679
Wei Cao , Xianglan Kong , Jingdong Mao , Jianfang Hu , Yong Ran
Rising global temperature is exerting a notable effect on the photosynthetic process of marine algae, which in turn may affect the structure and distribution of marine primary producers on a global scale. Sea surface temperature exerts a multifaceted influence on the growth, composition and structure of dinoflagellate, as well as on inorganic carbon fixation. This paper investigates the effect of temperature change on the growth of one dinoflagellate specie Scrippsiella trochoidea, and examines the variations in the organic carbon structure of its cell wall. This study is pioneering in its exploration of the impact of temperature on the structural organisation of organic matter in the dinoflagellate, with a particular focus on methylene carbon. The results indicate that Scrippsiella trochoidea exhibits a propensity to synthesise elevated levels of aliphatic compounds and proteins, particularly long-chain aliphatic biopolymers, at elevated incubation temperature. Moverover, a highly positive correlation is identified between the incubation temperature and the methylene carbon structure in the alkyl carbon structure. Such compositional and structural changes can have a significant impact on the potential yield of oil and gas through the process of algal pyrolysis.
全球气温上升对海洋藻类的光合作用过程产生了显著影响,进而可能影响全球范围内海洋初级生产者的结构和分布。海面温度对鞭毛藻的生长、组成和结构以及无机碳的固定具有多方面的影响。本文研究了温度变化对一种鞭毛藻生长的影响,并考察了其细胞壁有机碳结构的变化。这项研究在探索温度对鞭毛藻中有机物结构组织的影响方面具有开创性,特别关注亚甲基碳。结果表明,在较高的孵育温度下,特氏斯克里普菌表现出合成高水平脂肪族化合物和蛋白质的倾向,特别是长链脂肪族生物聚合物。此外,在烷基碳结构中,培养温度与亚甲基碳结构之间存在高度正相关。这种成分和结构的变化会对藻类热解过程中油气的潜在产量产生重大影响。
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引用次数: 0
Dissolved lithium content and aqueous geochemistry of the Haynesville Shale of East Texas and Northwest Louisiana 德克萨斯州东部和路易斯安那州西北部海恩斯维尔页岩的溶解锂含量和水地球化学
IF 3.4 3区 地球科学 Q1 GEOCHEMISTRY & GEOPHYSICS Pub Date : 2026-02-01 Epub Date: 2026-01-17 DOI: 10.1016/j.apgeochem.2026.106707
Jean-Philippe Nicot, Lucy T. Ko, Roxana Darvari, Brent A. Elliott
We describe dissolved lithium content of water produced from the Haynesville Shale, a low-permeability, gas-producing formation of Jurassic age overlying the lithium-rich and stratigraphically close Smackover Formation. The 57 water samples and 5 rock samples were analyzed for major and minor elements and for stable water isotopes, and Li and Sr isotopes (selected samples). The samples show an average of 71.7 mg/L Li (16–125 mg/L range) for an average TDS of 126.7 g/L (55–206 g/L range). They also show that the Haynesville and Smackover dissolved lithium have distinct diagenetic pathways with a large gap in δ7Li values (3.27 ‰, n = 7 and 10.20 ‰, n = 4, respectively). However, δ7Li of Haynesville produced water and rock (−4.03 ‰, n = 5) are consistent with fractionation of lithium partitioned into clay minerals relative to the resident water. The Haynesville Shale strontium isotope 87Sr/86Sr ratio (0.70830, n = 5) is higher than that of the time-period sea (0.7070), and consistent with a clastic 87Sr increase in a closed system, but lower than that of the published Arkansas carbonate-rich Upper Smackover values (0.70895, n = 72), which denotes a stronger clastic influence there. Water isotopes confirm that the samples represent formation water and have been little impacted by hydraulic fracturing or water condensation during sampling. However, low water production combined with marginal Li concentrations does not make the Haynesville Shale a primary target for lithium production.
研究人员描述了Haynesville页岩水中溶解锂的含量。Haynesville页岩是一个低渗透的侏罗纪产气地层,位于富含锂且地层紧密的Smackover地层之上。对57份水样和5份岩样(选定样品)进行了主、微量元素、稳定水同位素和Li、Sr同位素分析。样品显示平均锂含量为71.7 mg/L (16-125 mg/L范围),平均TDS为126.7 g/L (55-206 g/L范围)。Haynesville和Smackover溶解锂具有不同的成岩路径,δ7Li值差异较大(分别为3.27‰,n = 7和10.20‰,n = 4)。而Haynesville采出水和岩石的δ7Li值(- 4.03‰,n = 5)与锂分馏成粘土矿物相一致。Haynesville页岩锶同位素87Sr/86Sr比值(0.70830,n = 5)高于同期海的87Sr/86Sr比值(0.70830,n = 5),符合封闭体系中碎屑87Sr的增加,但低于已公布的阿肯色州富碳酸盐Upper Smackover值(0.70895,n = 72),表明该区碎屑影响较强。水同位素证实,样品代表地层水,在取样过程中几乎没有受到水力压裂或冷凝水的影响。然而,低产水量加上边际锂浓度并不能使Haynesville页岩成为锂生产的主要目标。
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引用次数: 0
Behaviour of Mo(VI), Eu(III) and U(VI) in calcium-silicate-hydrate phases: Immobilisation and dynamic remobilisation under repository-relevant conditions Mo(VI), Eu(III)和U(VI)在钙硅酸盐水合物相中的行为:在储存库相关条件下的固定化和动态再活化
IF 3.4 3区 地球科学 Q1 GEOCHEMISTRY & GEOPHYSICS Pub Date : 2026-02-01 Epub Date: 2026-01-05 DOI: 10.1016/j.apgeochem.2026.106684
Aaron Haben, Nico Bachmann, Jan Jakob Langer, Ralf Kautenburger
Calcium-silicate-hydrate (C–S–H) phases play an essential role as a geotechnical barrier in high-level nuclear waste (HLW) repositories. To guarantee the long-term safety of a HLW disposal site, it is important to know how and to which degree radionuclides are retained by C–S–H phases. To this date, only little to no data on the remobilisation dynamics of the repository-relevant elements Mo(VI), Eu(III) and U(VI) under realistic conditions are available. In this study, C–S–H phases incorporating these elements were synthesised, the element immobilisation was quantified via ICP-QQQ and their structure was investigated via X-ray diffractometry. All C–S–H phases had a calcium-silicon ratio (C/S) of 1.066 ± 0.003 and no relevant structural influences of the studied elements could be observed. In all cases, quantitative immobilisation was observed for Eu(III) and U(VI), whereas Mo(VI) was retained/incorporated to only about 50 %. Afterwards, their leaching behaviour with ultrapure water was studied in batch and mini-column experiments (MCE). Mo(VI) was remobilised quickly, while Eu(III) and U(VI) were retained nearly quantitatively. Due to the more realistic and therefore more representative conditions, further experiments to investigate the effects of three repository-relevant parameters were conducted only using MCE. A higher ionic strength significantly enhanced U(VI) remobilisation, while Eu(III) and Mo(VI) remained nearly unaffected. The displacement agents Fe(III) and Tb(III) only affected Mo(VI)'s remobilisation by retarding it. The addition of a complexing agent (2-phosphonobutane-1,2,4-tricarboxylic acid; PBTC) led to a delayed remobilisation of Mo(VI), while Eu(III) and U(VI) were remobilised to some degree after sufficient PBTC eluation. Overall, this work delivers important information on key processes relevant to nuclear waste disposal.
硅酸钙水合物(C-S-H)相在高放核废料(HLW)储存库中起着重要的岩土屏障作用。为了保证高放射性废物处置场地的长期安全,了解放射性核素如何以及在多大程度上被C-S-H相保留是很重要的。到目前为止,关于在现实条件下与储存库有关的元素Mo(VI)、Eu(III)和U(VI)的再动员动态,只有很少甚至没有数据。本研究合成了含有这些元素的C-S-H相,通过ICP-QQQ定量了元素的固定作用,并通过x射线衍射研究了它们的结构。所有C - S - h相的钙硅比(C/S)均为1.066±0.003,未观察到所研究元素对结构的影响。在所有情况下,Eu(III)和U(VI)都被定量固定,而Mo(VI)仅保留/结合到约50%。在此基础上,采用间歇式和微型柱式实验研究了它们在超纯水中的浸出行为。Mo(VI)被迅速调动,而Eu(III)和U(VI)几乎被定量保留。由于条件更真实,因此更具有代表性,因此仅使用MCE进行了进一步的实验,以研究三个与库相关的参数的影响。较高的离子强度显著增强了U(VI)的再活化,而Eu(III)和Mo(VI)几乎不受影响。置换剂Fe(III)和Tb(III)仅通过延缓Mo(VI)的再活化来影响Mo(VI)的再活化。配合剂(2-膦丁烷-1,2,4-三羧酸;PBTC)的加入导致Mo(VI)的再活化延迟,而Eu(III)和U(VI)在充分的PBTC洗脱后在一定程度上被再活化。总的来说,这项工作提供了与核废料处理有关的关键过程的重要信息。
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引用次数: 0
Influences of microplastic-dissolved organic matter-arsenic interactions on arsenic fate in geogenic contaminated groundwater: Mechanistic insights from kinetic-thermodynamic investigations and modeling 微塑性-溶解有机质-砷相互作用对地质污染地下水中砷命运的影响:来自动力学-热力学研究和建模的机制见解
IF 3.4 3区 地球科学 Q1 GEOCHEMISTRY & GEOPHYSICS Pub Date : 2026-02-01 Epub Date: 2026-01-16 DOI: 10.1016/j.apgeochem.2026.106704
Yaping Zhang , Kunfu Pi , Xianjun Xie , Ziyi Xiao , Jianbo Shi , Qianyong Liang , Yuxia Li
Arsenic (As) mobility and fate in geogenic contaminated groundwater can be impacted by co-occurring microplastics and dissolved organic matter (DOM). However, molecular mechanisms and kinetic constraints underlying microplastics-DOM-As interactions remain to be deciphered. By employing polystyrene microplastics (PSMPs) as a representative type of microplastics found in Datong high-As groundwater (As >10 μg/L), this research investigated thermodynamically and kinetically adsorption of As(III) and As(V) by microplastics as well as the critical effects of DOM. At groundwater pH of 6.8, adsorption of both As species occurred via oxygen-containing functional groups on PSMPs surfaces, but As(V) adsorption was quicker and greater than As(III) due to macrocolloids-like nature of PSMPs. Humic acids (HA) and fulvic acids (FA) compete for adsorption sites, alter surface properties, and facilitate aggregation of PSMPs, thereby reducing available surface sites for As binding. Interactions among PSMPs, HA/FA, and As species lead to formation of complexes including PSMPs-FA/HA-As and FA/HA-As. Furthermore, HA and FA can change the diffusion coefficients and boundary layer thickness of As within PSMPs pores to alter adsorption kinetics. Our results provide novel mechanistic insights into joint roles of PSMPs and DOM in As mobilization/immobilization dynamics within geogenic contaminated groundwater. Moreover, this research consolidates theoretical foundation for understanding influences of emerging contaminants on environmental geochemical behaviors of geogenic As in pumped aquifers.
微塑料和溶解性有机物(DOM)的共存影响了砷在地源污染地下水中的迁移和归宿。然而,微塑料- dom - as相互作用的分子机制和动力学约束仍有待破译。以大同市高砷地下水(as >10 μg/L)中具有代表性的聚苯乙烯微塑料(PSMPs)为研究对象,研究了微塑料对as (III)和as (V)的热力学和动力学吸附以及DOM的临界效应。在地下水pH为6.8时,两种As均通过含氧官能团吸附在PSMPs表面,但由于PSMPs的大胶体性质,As(V)的吸附速度更快且大于As(III)。腐植酸(HA)和黄腐酸(FA)竞争吸附位点,改变表面性质,促进PSMPs聚集,从而减少可用的表面As结合位点。PSMPs、HA/FA和As之间的相互作用导致PSMPs-FA/HA-As和FA/HA-As复合物的形成。此外,HA和FA可以改变PSMPs孔隙中As的扩散系数和边界层厚度,从而改变吸附动力学。我们的研究结果为PSMPs和DOM在地质污染地下水中As的动员/固定动力学中的联合作用提供了新的机制见解。此外,本研究为认识新兴污染物对抽水蓄水层地质砷环境地球化学行为的影响奠定了理论基础。
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引用次数: 0
Groundwater hydrogeochemical evolution and driving forces in a typical arid closed intermountain basin on Tibetan Plateau: a quantitative framework 青藏高原典型干旱封闭山间盆地地下水水文地球化学演化与驱动力:一个定量框架
IF 3.4 3区 地球科学 Q1 GEOCHEMISTRY & GEOPHYSICS Pub Date : 2026-02-01 Epub Date: 2026-01-21 DOI: 10.1016/j.apgeochem.2026.106711
Yong Xiao , Liwei Wang , Jie Wang , Xu Guo , Zhihong Zhang , Jiahua Wei , Zhen Zhao , Shaokang Yang , Huijuan Chen , Nuan Yang , Guangbin Zhu
Groundwater is of paramount significance for sustaining the socio-economic development and ecological health of arid endorheic intermountain basins. However, its availability is severely limited by hydrochemical composition, which remains inadequately quantified. This study takes the Chaka Basin on the Tibetan Plateau as an example to elucidate the spatial patterns, driving forces, and their quantitative contributions of groundwater geochemistry in such arid endorheic basins. Results indicate that groundwater is generally alkaline with substantial spatial variability in salinity. Near the mountain pass, groundwater remains fresh (TDS <1 g/L), retaining favorable hydrochemical characteristics inherited from mountain-sourced recharge. Salinity increases progressively along the groundwater flow path, with a notable contrast between phreatic and confined aquifers in the middle-lower reaches. Phreatic groundwater shows high TDS (>10 g/L near the terminal lake), while confined groundwater remains relatively fresh under the same settings, largely due to evaporation. Hydrogeochemical compositions are predominantly contributed by water–rock interactions, including evaporite dissolution (40.18 %), silicate weathering (16.31 %), and fluoride mineral dissolution/ion exchange (13.08 %). Human activities, such as agricultural practices (16.31 %) and domestic sewage discharge (13.41 %), also exert considerable contributions. A conceptual model was developed to elucidate the spatial patterns and quantitative formation mechanisms of groundwater chemistry. These findings provide a systematic framework for understanding the hydrogeochemical evolution and availability of groundwater quality in arid endorheic basins worldwide.
地下水对维持干旱内河山间盆地的社会经济发展和生态健康具有至关重要的意义。然而,它的可用性受到水化学成分的严重限制,其数量仍然不充分。本文以青藏高原恰卡盆地为例,探讨了干旱内陆河流域地下水地球化学的空间格局、驱动力及其定量贡献。结果表明,地下水总体呈碱性,盐度具有较大的空间变异性。在山口附近,地下水保持新鲜(TDS <1 g/L),保留了从山源补给中继承的有利的水化学特征。盐度沿地下水流道逐渐增加,在中下游潜水含水层和承压含水层之间有明显的对比。潜水地下水的TDS较高(终端湖附近为10 g/L),而承压地下水在相同设置下仍保持相对新鲜,这主要是由于蒸发作用。水文地球化学成分主要由水岩相互作用组成,包括蒸发岩溶解(40.18%)、硅酸盐风化(16.31%)和氟化物矿物溶解/离子交换(13.08%)。人类活动,如农业实践(16.31%)和生活污水排放(13.41%),也发挥了相当大的作用。为了阐明地下水化学的空间格局和定量形成机制,建立了一个概念模型。这些发现为理解全球干旱内陆盆地水文地球化学演化和地下水质量有效性提供了系统框架。
{"title":"Groundwater hydrogeochemical evolution and driving forces in a typical arid closed intermountain basin on Tibetan Plateau: a quantitative framework","authors":"Yong Xiao ,&nbsp;Liwei Wang ,&nbsp;Jie Wang ,&nbsp;Xu Guo ,&nbsp;Zhihong Zhang ,&nbsp;Jiahua Wei ,&nbsp;Zhen Zhao ,&nbsp;Shaokang Yang ,&nbsp;Huijuan Chen ,&nbsp;Nuan Yang ,&nbsp;Guangbin Zhu","doi":"10.1016/j.apgeochem.2026.106711","DOIUrl":"10.1016/j.apgeochem.2026.106711","url":null,"abstract":"<div><div>Groundwater is of paramount significance for sustaining the socio-economic development and ecological health of arid endorheic intermountain basins. However, its availability is severely limited by hydrochemical composition, which remains inadequately quantified. This study takes the Chaka Basin on the Tibetan Plateau as an example to elucidate the spatial patterns, driving forces, and their quantitative contributions of groundwater geochemistry in such arid endorheic basins. Results indicate that groundwater is generally alkaline with substantial spatial variability in salinity. Near the mountain pass, groundwater remains fresh (TDS &lt;1 g/L), retaining favorable hydrochemical characteristics inherited from mountain-sourced recharge. Salinity increases progressively along the groundwater flow path, with a notable contrast between phreatic and confined aquifers in the middle-lower reaches. Phreatic groundwater shows high TDS (&gt;10 g/L near the terminal lake), while confined groundwater remains relatively fresh under the same settings, largely due to evaporation. Hydrogeochemical compositions are predominantly contributed by water–rock interactions, including evaporite dissolution (40.18 %), silicate weathering (16.31 %), and fluoride mineral dissolution/ion exchange (13.08 %). Human activities, such as agricultural practices (16.31 %) and domestic sewage discharge (13.41 %), also exert considerable contributions. A conceptual model was developed to elucidate the spatial patterns and quantitative formation mechanisms of groundwater chemistry. These findings provide a systematic framework for understanding the hydrogeochemical evolution and availability of groundwater quality in arid endorheic basins worldwide.</div></div>","PeriodicalId":8064,"journal":{"name":"Applied Geochemistry","volume":"198 ","pages":"Article 106711"},"PeriodicalIF":3.4,"publicationDate":"2026-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146024121","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
The impact of a NaNO3 plume in a deep geological repository on the diffusion of dissolved gases in clay 深层地质库中NaNO3羽流对粘土中溶解气体扩散的影响
IF 3.4 3区 地球科学 Q1 GEOCHEMISTRY & GEOPHYSICS Pub Date : 2026-02-01 Epub Date: 2026-01-06 DOI: 10.1016/j.apgeochem.2026.106681
Elke Jacops , Chloé Roonacker , Hannes Claes , Lander Frederickx , Anneleen Vanleeuw , Quoc Tri Phung , Jerry Peprah Owusu , Sergey V. Churakov , Jon Harrington , Andrew Wiseall , Christophe Bruggeman
In the framework of the geological disposal of high and intermediate-level long-lived radioactive waste, the Boom Clay is considered as a potential host formation in Belgium. Boom Clay has suitable characteristics that limit the mass transport of dissolved species. Since gas generation in geological repositories is unavoidable, its dissipation needs to be evaluated. This study focuses on the gas diffusion properties in the case of a geochemical perturbation of the near field of Boom Clay, caused by NaNO3 leaching from Eurobitumen bituminised waste. The diffusion of 4 gases (He, CH4, Xe, and C2H6) was measured in intact and chemically (with NaNO3) disturbed samples and the change in diffusion coefficients after perturbation was assessed. Intact and disturbed samples were petrographically and petrophysically characterised. Results of this study show that most of the clay properties are not altered by the chemical perturbation. The parameter which changed significantly is the specific surface area, which decreased 40–60 % in the chemically disturbed samples. Water transport (hydraulic conductivity) is not influenced by the perturbation. For diffusivity of dissolved gases and HTO, the differences are not significant as they are within the uncertainty boundaries. Molecular dynamics simulations in montmorillonite revealed that the clay interlayer might potentially shrink or even collapse due to the chemical and osmotic potential differences induced by geochemical perturbation (NaNO3). The reduced volume of the interlayer porosity did not impact the diffusion of dissolved gases. The key message of this study is that a perturbation of clay with 1 M NaNO3 will not significantly alter the transport properties of dissolved gases in the near field. This information is of relevance for the development of a geological disposal concept of bituminised waste in Boom Clay.
在高水平和中水平长寿命放射性废物的地质处置框架中,Boom粘土被认为是比利时潜在的宿主地层。Boom Clay具有适当的特性,限制了溶解物种的质量迁移。由于地质储气库的生气是不可避免的,因此需要对其耗散进行评估。本研究的重点是在由Eurobitumen沥青化废物中NaNO3浸出引起的Boom粘土近场地球化学扰动情况下的气体扩散特性。测量了4种气体(He, CH4, Xe和C2H6)在完整样品和化学(NaNO3)扰动样品中的扩散,并评估了扰动后扩散系数的变化。对完整样品和扰动样品进行了岩石学和岩石物理表征。研究结果表明,化学扰动对粘土的大部分性质没有影响。变化较大的参数是比表面积,化学扰动后的样品比表面积下降了40 - 60%。水的输送(水力导电性)不受扰动的影响。对于溶解气体的扩散系数和HTO,由于它们在不确定度范围内,差异不显著。蒙脱土分子动力学模拟表明,由于地球化学扰动(NaNO3)引起的化学和渗透电位差,蒙脱土间层可能会收缩甚至坍塌。层间孔隙度的减小对溶解气体的扩散没有影响。本研究的关键信息是,1 M NaNO3对粘土的扰动不会显著改变近场溶解气体的输运性质。这一信息对于在Boom Clay中发展沥青化废物的地质处置概念是相关的。
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引用次数: 0
HyPiT: A thermodynamic database for modeling geochemical systems up to high temperatures, pressures and salinities HyPiT:一个热力学数据库,用于模拟高温、高压和盐度的地球化学系统
IF 3.4 3区 地球科学 Q1 GEOCHEMISTRY & GEOPHYSICS Pub Date : 2026-02-01 Epub Date: 2026-02-04 DOI: 10.1016/j.apgeochem.2026.106727
Arnault Lassin , Christophe Chiaberge , Sylvain Guignot , Johann Tuduri , Laurent André
Modeling water-rock interactions in underground environments requires the use of thermodynamic databases that account for the complexity of groundwater chemical compositions under relevant pressure and temperature conditions. A key issue concerning saline groundwaters is their high ionic strength, which are often not reliably calculated and calls for the use of specific thermodynamic approaches. Among such approaches, the Pitzer model appears to be one of the most promising. However, its applicability to underground fluids is limited by the fact that the values of its numerous parameters are only known for a subset of chemical systems and, more particularly, are often missing for trace elements and at temperatures other than 25 °C. This paper describes a new way to develop a relevant thermodynamic database to account for the trace elements in these types of deep environments. It combines two in-house databases: Thermoddem, which relies on the B-dot Extended Debye-Hückel activity model, and PhreeSCALE, which uses the Pitzer formalism. The resulting Hybrid Pitzer-Thermoddem (HyPiT) thermodynamic database (TDB) integrates a simplified Pitzer model to account for major and trace elements. Based on a series of recent works (Simoes et al., 2016, 2017a, 2017b), the Pitzer binary interaction parameters, β(0) and β(1) and their first derivative with respect to temperature (dβ(0)/dT and dβ(1)/dT) are determined for simulating the first order interactions between trace elements and major species. The HyPiT database is successfully applied to different geochemical systems relevant to underground environments. They include (i) the solubility of gypsum in NaCl and sea-type brines of varying ionic strength at temperatures between 0 and 25 °C, (ii) the solubility of barite in NaCl brines at 25, 60 and 80 °C, (iii) the solubility of calcite in 0.1 and 4 M NaCl brines for temperatures and pressures up 250 °C and 1450 bars, respectively, (iv) the solubility of amorphous silica up to 150 °C in various single electrolyte solutions, namely HCl, NaCl, MgCl2, HNO3, NaNO3, Na2SO4, and MgSO4. Particular attention is also given to the modeling of iron-bearing systems such as the speciation of FeIII in LiCl solutions up to 20 mol/kg.
模拟地下环境中的水岩相互作用需要使用热力学数据库,这些数据库考虑了相关压力和温度条件下地下水化学成分的复杂性。关于含盐地下水的一个关键问题是它们的高离子强度,这通常不能可靠地计算,需要使用特定的热力学方法。在这些方法中,皮策模型似乎是最有希望的方法之一。然而,它对地下流体的适用性受到以下事实的限制:它的许多参数的值仅对化学系统的一个子集已知,更具体地说,在25°C以外的温度下,经常缺少微量元素。本文介绍了一种建立相关热力学数据库的新方法,以解释这些类型的深部环境中的微量元素。它结合了两个内部数据库:依赖于b点扩展debye - h ckel活动模型的Thermoddem和使用Pitzer形式化的PhreeSCALE。由此产生的混合Pitzer- thermoddem (HyPiT)热力学数据库(TDB)集成了一个简化的Pitzer模型,以考虑主要和痕量元素。基于最近的一系列研究(Simoes et al., 2016, 2017a, 2017b),确定了用于模拟微量元素与主要物种之间一级相互作用的Pitzer二元相互作用参数β(0)和β(1)及其对温度的一阶导数(dβ(0)/dT和dβ(1)/dT)。HyPiT数据库成功应用于与地下环境相关的不同地球化学系统。包括(i)石膏的溶解度氯化钠和不同离子强度的海式卤水在温度0 - 25°C, (ii)的溶解度重晶石氯化钠卤水在25日,60 - 80°C, (iii)方解石的溶解性0.1和4 M氯化钠卤水为温度和压力250°C和1450条,分别(iv)非晶硅150°C的溶解度在各种单一电解质的解决方案,即盐酸、氯化钠,MgCl2,硝酸,NaNO3 Na2SO4, MgSO4。还特别关注了含铁系统的建模,例如在高达20 mol/kg的LiCl溶液中FeIII的形态。
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引用次数: 0
Age-dependent cementitious leachate effects on metal and radionuclide sorption to sediments from a subsurface waste-disposal site 年龄依赖性胶凝渗滤液对地下废物处理场沉积物中金属和放射性核素吸附的影响
IF 3.4 3区 地球科学 Q1 GEOCHEMISTRY & GEOPHYSICS Pub Date : 2026-02-01 Epub Date: 2026-01-14 DOI: 10.1016/j.apgeochem.2026.106701
Peng Lin , Karah Greene , Wei Xing , Steven Simner , Christina Logan , Richard Henry , Daniel I. Kaplan
<div><div>Risk assessment to evaluate long-term disposal for heavy metal and radioactive constituents at the subsurface engineered disposal facilities rely on distribution coefficients (<em>K</em><sub><em>d</em></sub> <em>=</em> <em>C</em><sub><em>solid</em></sub><em>/C</em><sub><em>liquid</em></sub>). Low-level solid and liquid radioactive waste is disposed in the subsurface environment using various cementitious engineered barriers. This study measured <em>K</em><sub><em>d</em></sub> values to quantify the sorption–including adsorption, absorption, and/or precipitation for multiple metals/radionuclides in subsurface sediments impacted by cementitious leachates representing different cement aging stages, experimentally introduced as Cs(I), Sr(II), Ni(II), Eu(III), Th(IV), U(VI), Cr(VI), and Tc(VII), serving as chemical analogs of different chemical groups. Simulated groundwater (Stage IV) was used as a baseline besides three leachate simulants: freshly made concrete leachate (Stage I), portlandite (Stage II), and calcite (Stage III) to calculate the cementitious leachate impact factor (<em>f</em><sub>CementLeach</sub>), defined as <em>K</em><sub><em>d</em></sub>-CementLeach/<em>K</em><sub><em>d</em></sub>-groundwater. Results showed significant changes in sorption between groundwater and leachate simulants. Monovalent cation analog Cs exhibited <em>K</em><sub><em>d</em></sub> values of 28–2390 L/kg (sandy) and 84–4230 L/kg (clayey), with <em>f</em><sub>CementLeach</sub> up to 62 in sandy sediments impacted by young grout leachate. Divalent cations (Ni and Sr) and trivalent/tetravalent cations (Eu, Th) also showed strong enhancements in high-pH cementitious leachate environments; for example, Eu <em>K</em><sub><em>d</em></sub> increased from 25 L/kg in Stage IV groundwater to >67000 L/kg in leachates. Tetravalent cation analog Th showed very strong sorption (>10000 L/kg) in young and aged leachates, consistent with prior trivalent cation trends (Eu). Enhanced retention of multivalent cations (e.g., Ni<sup>2+</sup>, Eu<sup>3+</sup>, Th<sup>4+</sup>, and UO<sub>2</sub><sup>2+</sup>) in cementitious leachate-impacted sediments reflects not only surface sorption processes but also precipitation under elevated pH conditions, particularly in young grout leachate environments. Such precipitation-driven mechanisms were not evident for Cs<sup>+</sup>. Across cement aging stages, enhanced (Stage III) and/or reduced sorption (Stage II) can be observed for anionic species CrO<sub>4</sub><sup>2−</sup>, while <sup>99</sup>TcO<sub>4</sub><sup>−</sup>, a key risk driver, displayed minimal sorption and negligible response to cementitious leachates. These results represent the first extensive dataset quantifying cementitious leachate effects on sorption to sediments for different types of cation and anion metal contaminants. It also underscores how the evolution of cementitious barriers reshapes groundwater chemistry, directly influencing the predicted mobil
评估地下工程处置设施中重金属和放射性成分长期处置的风险评估依赖于分布系数(Kd = Csolid/ cliquids)。低水平固体和液体放射性废物在地下环境中使用各种胶凝工程屏障进行处理。本研究测量了Kd值,以量化受水泥渗滤液影响的地下沉积物中多种金属/放射性核素的吸附,包括吸附、吸收和/或沉淀,这些金属/放射性核素代表了不同的水泥老化阶段,实验中引入了Cs(I)、Sr(II)、Ni(II)、Eu(III)、Th(IV)、U(VI)、Cr(VI)和Tc(VII),作为不同化学基的化学类似物。除了三种渗滤液模拟物:现浇混凝土渗滤液(阶段I)、波特兰土(阶段II)和方解石(阶段III)外,还使用模拟地下水(阶段IV)作为基线,计算胶凝渗滤液影响因子(fCementLeach),定义为Kd-CementLeach/Kd-groundwater。结果表明,地下水和渗滤液模拟物的吸附变化显著。一价阳离子类似物Cs的Kd值分别为28-2390 L/kg(砂质)和84-4230 L/kg(粘土),在受幼浆渗滤液影响的砂质沉积物中,fCementLeach高达62。二价阳离子(Ni和Sr)和三价/四价阳离子(Eu、Th)在高ph胶凝渗滤液环境中也表现出较强的增强;例如,Eu Kd从IV期地下水的25 L/kg增加到渗滤液的67000 L/kg。四价阳离子类似物Th在年轻和老年渗滤液中表现出很强的吸附(>10000 L/kg),与先前的三价阳离子趋势(Eu)一致。多价阳离子(如Ni2+、Eu3+、Th4+和UO22+)在胶凝渗滤液影响下的保留增强,不仅反映了表面吸附过程,也反映了pH升高条件下的沉淀,特别是在年轻的灌浆渗滤液环境中。这种降水驱动机制在Cs+中并不明显。在水泥老化阶段,阴离子物种CrO42−的吸附增强(III阶段)和/或减少(II阶段),而99TcO4−是一个关键的风险驱动因素,对胶凝渗出液的吸附最小,反应可以忽略不计。这些结果代表了第一个广泛的数据集,量化胶结渗滤液对沉积物中不同类型的阳离子和阴离子金属污染物的吸附作用。它还强调了胶凝屏障的演变如何重塑地下水化学,直接影响风险评估中重金属和放射性核素的预测流动性。
{"title":"Age-dependent cementitious leachate effects on metal and radionuclide sorption to sediments from a subsurface waste-disposal site","authors":"Peng Lin ,&nbsp;Karah Greene ,&nbsp;Wei Xing ,&nbsp;Steven Simner ,&nbsp;Christina Logan ,&nbsp;Richard Henry ,&nbsp;Daniel I. Kaplan","doi":"10.1016/j.apgeochem.2026.106701","DOIUrl":"10.1016/j.apgeochem.2026.106701","url":null,"abstract":"&lt;div&gt;&lt;div&gt;Risk assessment to evaluate long-term disposal for heavy metal and radioactive constituents at the subsurface engineered disposal facilities rely on distribution coefficients (&lt;em&gt;K&lt;/em&gt;&lt;sub&gt;&lt;em&gt;d&lt;/em&gt;&lt;/sub&gt; &lt;em&gt;=&lt;/em&gt; &lt;em&gt;C&lt;/em&gt;&lt;sub&gt;&lt;em&gt;solid&lt;/em&gt;&lt;/sub&gt;&lt;em&gt;/C&lt;/em&gt;&lt;sub&gt;&lt;em&gt;liquid&lt;/em&gt;&lt;/sub&gt;). Low-level solid and liquid radioactive waste is disposed in the subsurface environment using various cementitious engineered barriers. This study measured &lt;em&gt;K&lt;/em&gt;&lt;sub&gt;&lt;em&gt;d&lt;/em&gt;&lt;/sub&gt; values to quantify the sorption–including adsorption, absorption, and/or precipitation for multiple metals/radionuclides in subsurface sediments impacted by cementitious leachates representing different cement aging stages, experimentally introduced as Cs(I), Sr(II), Ni(II), Eu(III), Th(IV), U(VI), Cr(VI), and Tc(VII), serving as chemical analogs of different chemical groups. Simulated groundwater (Stage IV) was used as a baseline besides three leachate simulants: freshly made concrete leachate (Stage I), portlandite (Stage II), and calcite (Stage III) to calculate the cementitious leachate impact factor (&lt;em&gt;f&lt;/em&gt;&lt;sub&gt;CementLeach&lt;/sub&gt;), defined as &lt;em&gt;K&lt;/em&gt;&lt;sub&gt;&lt;em&gt;d&lt;/em&gt;&lt;/sub&gt;-CementLeach/&lt;em&gt;K&lt;/em&gt;&lt;sub&gt;&lt;em&gt;d&lt;/em&gt;&lt;/sub&gt;-groundwater. Results showed significant changes in sorption between groundwater and leachate simulants. Monovalent cation analog Cs exhibited &lt;em&gt;K&lt;/em&gt;&lt;sub&gt;&lt;em&gt;d&lt;/em&gt;&lt;/sub&gt; values of 28–2390 L/kg (sandy) and 84–4230 L/kg (clayey), with &lt;em&gt;f&lt;/em&gt;&lt;sub&gt;CementLeach&lt;/sub&gt; up to 62 in sandy sediments impacted by young grout leachate. Divalent cations (Ni and Sr) and trivalent/tetravalent cations (Eu, Th) also showed strong enhancements in high-pH cementitious leachate environments; for example, Eu &lt;em&gt;K&lt;/em&gt;&lt;sub&gt;&lt;em&gt;d&lt;/em&gt;&lt;/sub&gt; increased from 25 L/kg in Stage IV groundwater to &gt;67000 L/kg in leachates. Tetravalent cation analog Th showed very strong sorption (&gt;10000 L/kg) in young and aged leachates, consistent with prior trivalent cation trends (Eu). Enhanced retention of multivalent cations (e.g., Ni&lt;sup&gt;2+&lt;/sup&gt;, Eu&lt;sup&gt;3+&lt;/sup&gt;, Th&lt;sup&gt;4+&lt;/sup&gt;, and UO&lt;sub&gt;2&lt;/sub&gt;&lt;sup&gt;2+&lt;/sup&gt;) in cementitious leachate-impacted sediments reflects not only surface sorption processes but also precipitation under elevated pH conditions, particularly in young grout leachate environments. Such precipitation-driven mechanisms were not evident for Cs&lt;sup&gt;+&lt;/sup&gt;. Across cement aging stages, enhanced (Stage III) and/or reduced sorption (Stage II) can be observed for anionic species CrO&lt;sub&gt;4&lt;/sub&gt;&lt;sup&gt;2−&lt;/sup&gt;, while &lt;sup&gt;99&lt;/sup&gt;TcO&lt;sub&gt;4&lt;/sub&gt;&lt;sup&gt;−&lt;/sup&gt;, a key risk driver, displayed minimal sorption and negligible response to cementitious leachates. These results represent the first extensive dataset quantifying cementitious leachate effects on sorption to sediments for different types of cation and anion metal contaminants. It also underscores how the evolution of cementitious barriers reshapes groundwater chemistry, directly influencing the predicted mobil","PeriodicalId":8064,"journal":{"name":"Applied Geochemistry","volume":"198 ","pages":"Article 106701"},"PeriodicalIF":3.4,"publicationDate":"2026-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145974370","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
Predicting the kinetics of Cu release and transport in contaminated soils in the field 田间污染土壤Cu释放和运移动力学预测
IF 3.4 3区 地球科学 Q1 GEOCHEMISTRY & GEOPHYSICS Pub Date : 2026-02-01 Epub Date: 2026-01-12 DOI: 10.1016/j.apgeochem.2026.106698
Liang Dong , Rong Li , Wenxia Wang , Zhifang Xiao , Zezhen Ren , Qianting Ye , Zhenqing Shi
Accurately predicting heavy metal release from contaminated soils remains challenging because of heterogeneous sorption sites, dynamic organic-matter turnover, and transient hydrological forcing. Here we develop a unified multi-process kinetics model that couples multi-site adsorption–desorption, vertically resolved dissolved organic carbon (DOC) dynamics, and water flow–solute transport to simulate copper (Cu) release in two contaminated field sites during rainfall events. We further accelerate the numerical solver with a machine-learning surrogate model, achieving more than 100-fold speed-up. Rainfall–evaporation experiments at two Cu-contaminated soils with contrasting textures and contamination levels showed that less than 5 % of total Cu was labile, and that soil organic matter dominated Cu binding. The model reproduced depth-resolved dissolved Cu profiles with symmetric mean absolute percentage errors of 26–30 %, by capturing rainfall-driven dilution, adsorption–desorption kinetics, and DOC-mediated mobilization. Our results show that short-term Cu mobility is controlled primarily by its labile fraction rather than total concentration, and that coupling carbon cycling with hydrodynamics is essential for field-scale predictions. This transferable modeling framework enables mechanistic and site-specific forecasts of heavy-metal fate under diverse and changing environmental conditions.
准确预测重金属从污染土壤释放仍然具有挑战性,因为不均匀的吸附位置,动态有机质周转和瞬态水文强迫。在此,我们建立了一个统一的多过程动力学模型,该模型耦合了多位点吸附-解吸,垂直溶解有机碳(DOC)动力学和水流-溶质运移,以模拟降雨事件中两个污染场地的铜(Cu)释放。我们使用机器学习代理模型进一步加速数值求解器,实现了超过100倍的加速。在两种不同质地和污染程度的Cu污染土壤上进行的降雨蒸发试验表明,Cu的挥发性低于5%,土壤有机质对Cu的结合起主导作用。该模型通过捕获降雨驱动的稀释、吸附-解吸动力学和doc介导的动员,再现了深度分辨的溶解铜剖面,对称平均绝对百分比误差为26 - 30%。我们的研究结果表明,短期铜迁移率主要由其不稳定部分而不是总浓度控制,并且将碳循环与流体动力学相结合对于现场规模的预测至关重要。这种可转移的建模框架能够在不同和不断变化的环境条件下对重金属的命运进行机械和特定地点的预测。
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引用次数: 0
Application of sediment quality guidelines and geochemical indices to evaluate the impact of trace metals on sediments from a fish farming area in the Rosário reservoir, Brazil 应用沉积物质量准则和地球化学指数评价微量金属对巴西Rosário水库养鱼区沉积物的影响
IF 3.4 3区 地球科学 Q1 GEOCHEMISTRY & GEOPHYSICS Pub Date : 2026-02-01 Epub Date: 2026-02-02 DOI: 10.1016/j.apgeochem.2026.106726
Hênio do Nascimento Melo Júnior , Francisco José de Paula Filho , Jorge Marcel Coelho Menezes , Henrique Douglas Melo Coutinho , Raimundo Nonato Pereira Teixeira , Hênio Vitor Sobral Melo
The expansion of global aquaculture includes, among other techniques, net-pen fish farming in semiarid regions, where studies remain scarce. This study assessed the sediment geochemistry of the Rosário Reservoir in Brazil, aiming to assess the influence of net-pen aquaculture on sediment quality. Sampling was conducted in control (CTRL), cultivation (CTV), and post-cultivation (PCTV) areas, with 10 replicates each. Tests included particle size distribution, organic matter content, trace metals (Fe, Mn, Zn, Cu, Cr, Cd, Pb, and Ni), sediment quality guidelines, multivariate statistics (Pearson's correlation, similarity analysis, and principal component analysis), and geochemical indices (Contamination Factor, Pollution Load Index, Nemerow Pollution Index, and Combined Pollution Index). Sediments were determined to be clayey–silty loam, with an organic matter content of 18.76 ± 4.27%. The highest metal concentrations occurred in the CTV (Fe, Mn, Zn, and Cr) and PCTV (Cd, Cu, Pb, and Ni) areas, with Ni exceeding sediment quality thresholds. The multivariate testing shows that aquaculture is a source of metals and organic matter. Geochemical indices revealed mostly low to moderate pollution, with localized polluted conditions. Overall, fish farming had a limited impact on trace metal accumulation. The methodological framework proved effective for environmental monitoring and management, supporting both qualitative and quantitative assessments of aquaculture-related impacts.
全球水产养殖的扩大,除其他技术外,还包括在半干旱地区进行网笼养鱼,而这些地区的研究仍然很少。本研究对巴西Rosário水库的沉积物地球化学进行了评价,旨在评价网圈养殖对沉积物质量的影响。在对照区(CTRL)、培养区(CTV)和培养后区(PCTV)取样,每区10个重复。试验包括粒径分布、有机质含量、微量金属(Fe、Mn、Zn、Cu、Cr、Cd、Pb和Ni)、沉积物质量指南、多变量统计(Pearson相关、相似分析和主成分分析)和地球化学指标(污染因子、污染负荷指数、Nemerow污染指数和综合污染指数)。沉积物为粘粉质壤土,有机质含量为18.76±4.27%。最高的金属浓度出现在CTV (Fe, Mn, Zn和Cr)和PCTV (Cd, Cu, Pb和Ni)区域,其中Ni超过了沉积物质量阈值。多变量检验表明,水产养殖是金属和有机物的来源。地球化学指标以低至中度污染为主,存在局部污染条件。总体而言,养鱼对微量金属积累的影响有限。方法框架证明对环境监测和管理是有效的,支持对与水产养殖有关的影响进行定性和定量评估。
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引用次数: 0
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Applied Geochemistry
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