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Comparative analysis of HPLC methods for measuring phytoplankton pigments in the Western Mediterranean Sea: A contribution to the satellite Cal/Val activities 测定西地中海浮游植物色素的HPLC方法的比较分析:对卫星Cal/Val活动的贡献
IF 3 3区 地球科学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2025-04-09 DOI: 10.1016/j.marchem.2025.104516
Elisabetta Canuti , F. Artuso , A. Di Cicco
High-performance liquid chromatography (HPLC) is the gold standard for calibrating and validating satellite-derived Chlorophyll a (TChl a) concentration. Other phytoplankton pigments quantified by HPLC can provide taxonomic and functional insights into the composition and abundance of phytoplankton communities. This study assesses the uncertainties associated with HPLC measurements by comparing results from two analytical laboratories, one from the Joint Research Centre (JRC) and the other from the Italian National Agency for New Technologies, Energy, and Sustainable Economic Development (ENEA). These laboratories employed different analytical methods to examine natural water samples from the oligotrophic waters of the Western Mediterranean Sea, collected during the Sentinel 2017 campaign. Chlorophyll a concentrations in these samples ranged from 0.048 to 0.653 mg m−3 in the JRC dataset. The present study evaluated phytoplankton community composition using multiple techniques, including chemotaxonomic methods based on the analysis of biomarker pigments and CHEMTAX method (Mackey et al., 1996), alongside unsupervised machine learning approaches such as Hierarchical Clustering Analysis (HCA), Principal Components Analysis (PCA), and Network-Community Analysis (NCA). Significant differences in pigment quantification were observed between the two laboratories, particularly for chlorophylls c (85.5 % difference) and peridinin (56.6 % difference). However, differences in total TChl a quantification were within 6.1 %, indicating that both laboratories are capable of supporting satellite data validation and algorithm development (Hooker et al., 2000). The results highlighted both limitations and advantages of this comparative approach, related to different methods for estimating uncertainties, providing insights into the consistency and reliability of HPLC measurements in a challenging low concentration matrix.
高效液相色谱法(HPLC)是校准和验证卫星衍生叶绿素a (TChl a)浓度的金标准。其他浮游植物色素的定量可以为浮游植物群落的组成和丰度提供分类和功能方面的见解。本研究通过比较两个分析实验室(一个来自联合研究中心(JRC),另一个来自意大利国家新技术、能源和可持续经济发展机构(ENEA))的结果来评估与HPLC测量相关的不确定度。这些实验室采用了不同的分析方法来检查西地中海寡营养水域的天然水样,这些水样是在2017年哨兵行动期间收集的。在JRC数据集中,这些样品中的叶绿素a浓度范围为0.048至0.653 mg m - 3。本研究使用多种技术评估浮游植物群落组成,包括基于生物标记色素分析的化学分类方法和CHEMTAX方法(Mackey et al., 1996),以及无监督机器学习方法,如层次聚类分析(HCA)、主成分分析(PCA)和网络群落分析(NCA)。两个实验室在色素定量方面存在显著差异,特别是叶绿素c(差异85.5%)和橄榄素(差异56.6%)。然而,总TChl a量化的差异在6.1%以内,这表明两个实验室都有能力支持卫星数据验证和算法开发(Hooker et al., 2000)。结果强调了这种比较方法的局限性和优点,涉及到不同的方法来估计不确定度,为HPLC测量在具有挑战性的低浓度矩阵中的一致性和可靠性提供了见解。
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引用次数: 0
Variation in chemical composition of dissolved organic matter during the winter to spring transition in the northern Barents Sea 巴伦支海北部冬季至春季过渡期间溶解有机质化学成分的变化
IF 3 3区 地球科学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2025-04-08 DOI: 10.1016/j.marchem.2025.104517
Maria G. Digernes , Jeffrey A. Hawkes , Oliver Müller , Stephen G. Kohler , Murat V. Ardelan
Molecular characterization of dissolved organic matter (DOM) from the Arctic Ocean is scarce, especially during the winter, which is a crucial period for water mass mixing and carbon cycling. The northern Barents Sea extending into the Arctic Ocean is experiencing global warming at a rate 5–7 times faster than the global average, leading to drastic chemical, physical and ecosystem changes. We sampled a transect along this region during early winter (December), late winter (March) and spring (May) and analyzed seawater samples using high-resolution mass spectrometry. Our results show significant changes in DOM composition driven by biological seasonality and water circulation such as lateral and vertical water transport, whereas water masses did not exhibit significant correlations with DOM composition. Our mass spectrometry-based results indicate that ionizable DOM compounds in early winter contained a greater proportion of unsaturated compounds relative to late winter and spring, as shown by weighted average hydrogen to carbon atomic ratios (H/Cwa) (−0.029, Mann-Whitney U test, p < 0.001). Higher DOM lability in late winter was associated with higher nitrogen containing formulas which could be a result of DOM products from viral processes. Deep waters in the Arctic Basin and on the Barents Sea shelf break show greater lability in spring suggesting an influence of water circulation from the biologically active shelf regions. In early winter, higher weighted average aromaticity index (AImod), double-bond equivalents (DBE) and relative intensities of CHO formulas over heteroatom (N, S)-containing formulas were observed, thus supporting the presence of DOM with higher recalcitrance. Early winter also exhibited a significantly higher number of terrigenous peaks (t-Peaks) (p < 0.001), suggesting seasonal removal of these riverine markers. This DOC may be transported to deeper ocean layers during winter water mixing. Our findings bridge the gap in winter DOM molecular characterization, which allows for future assessments of potential changes in the Arctic DOM reactivity.
北冰洋溶解有机物(DOM)的分子特征研究很少,特别是在冬季,这是水团混合和碳循环的关键时期。延伸到北冰洋的北巴伦支海正以比全球平均速度快5-7倍的速度经历着全球变暖,导致了剧烈的化学、物理和生态系统变化。我们在冬初(12月)、冬末(3月)和春季(5月)对该地区的样带进行采样,并使用高分辨率质谱分析海水样本。结果表明,生物季节性和水循环(横向和垂直水运)对DOM组成的影响显著,而水团对DOM组成的影响不显著。通过加权平均氢碳原子比(H/Cwa) (- 0.029, Mann-Whitney U检验,p <;0.001)。冬末DOM的高不稳定性与高含氮配方有关,这可能是病毒过程产生的DOM产物的结果。北极盆地和巴伦支海大陆架断裂的深水在春季表现出更大的不稳定性,这表明来自生物活跃的大陆架区域的水循环的影响。初冬时,CHO分子式的加权平均芳香性指数(AImod)、双键当量(DBE)和相对强度均高于含杂原子(N, S)的分子式,支持DOM的存在,且具有较高的顽固性。初冬陆源峰(t-Peaks)的数量也显著增加(p <;0.001),表明这些河流标记物是季节性去除的。在冬季海水混合时,DOC可能被输送到更深的海洋层。我们的发现弥补了冬季DOM分子表征方面的空白,为未来评估北极DOM反应性的潜在变化提供了可能。
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引用次数: 0
Benthic biogeochemical processes and fluxes in the hypoxic and acidified northern Gulf of Mexico (nGoM), part I: Carbonate dissolution from in situ microprofiles 缺氧和酸化的墨西哥湾北部底栖生物地球化学过程和通量,第一部分:原位微剖面的碳酸盐溶解
IF 3 3区 地球科学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2025-04-01 DOI: 10.1016/j.marchem.2025.104515
Eva Ferreira , Bruno Lansard , Gaël Monvoisin , Evan Magette , Anthony Boever , Hanna Bridgham , Bruno Bombled , Jordon Scott Beckler , Martial Taillefert , Christophe Rabouille
The northern Gulf of Mexico (nGoM) experiences seasonal coastal hypoxia due to nutrient enrichment from the Mississippi-Atchafalaya River basin, leading to one of the world's largest hypoxic zones. In these shallow zones, benthic processes play an essential role in driving/maintaining deoxygenation and acidification of bottom waters. In this regard, this paper investigates carbonate dissolution processes in surface sediment of the nGoM during hypoxic conditions in summer 2022, as the main acidification feedback mechanism, with a specific focus on the effects of bottom water acidification. A strong linear relationship is observed between oxygen and pH, with a pH difference of 0.37 between the most oxygenated and the nearly anoxic station, reaching a value of 7.63. Using high-resolution techniques, this study combines pH and O₂ microprofiling (200 μm) with benthic measurements of carbonate system parameters (pH, DIC, TA, Ca2+) to assess carbonate dissolution at millimeter-scale resolution. The pH microprofiles reveal a significant decrease in the first 3 cm, with pore water pH reaching values of 6.90 at the most hypoxic station. Despite undersaturation with respect to aragonite and occasionally calcite, Ca2+ profiles indicate no significant carbonate dissolution, suggesting stability of calcium carbonate in these sediments during the summer. This lack of dissolution, likely influenced by the absence of aragonite, and possible inhibitory effects of dissolved organic carbon and orthophosphate, points to a limited buffering capacity in these sediments. These insights are essential for refining models predicting coastal acidification and hypoxia responses to environmental stressors in the nGoM and similar eutrophic systems.
由于密西西比-阿恰法拉亚河流域的营养物质富集,墨西哥湾北部经历了季节性的沿海缺氧,导致了世界上最大的缺氧区之一。在这些浅水区,底栖生物过程在驱动/维持底水脱氧和酸化方面起着至关重要的作用。因此,本文研究了2022年夏季低氧条件下nGoM表层沉积物中的碳酸盐溶解过程,作为主要的酸化反馈机制,重点研究了底水酸化的影响。氧与pH之间存在很强的线性关系,最富氧站与几乎缺氧站的pH值相差0.37,达到7.63。利用高分辨率技术,本研究将pH和O₂微谱(200 μm)与碳酸盐系统参数(pH, DIC, TA, Ca2+)的底栖测量相结合,以毫米级分辨率评估碳酸盐溶解。pH微剖面在前3 cm显著降低,最缺氧站孔隙水pH值达到6.90。尽管文石和方解石处于欠饱和状态,但Ca2+剖面显示没有明显的碳酸盐溶解,这表明这些沉积物中的碳酸钙在夏季具有稳定性。这种溶解的缺乏,可能受到文石缺乏的影响,以及溶解的有机碳和正磷酸盐可能的抑制作用,表明这些沉积物的缓冲能力有限。这些见解对于改进预测nGoM和类似富营养化系统中环境压力源的沿海酸化和缺氧反应的模型至关重要。
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引用次数: 0
Samarium (Sm3+) and copper (Cu2+) complexation property with dissolved organic matter 钐(Sm3+)和铜(Cu2+)与溶解有机物的络合性能
IF 3 3区 地球科学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2025-03-20 DOI: 10.1016/j.marchem.2025.104514
Nabila Abbad , Roland Redon , Benjamin Oursel , Christophe Lepoupon , Gaël Durrieu , Houssam Hajjoul , Stéphane Mounier
This study investigates the speciation of Samarium (III) in the presence of natural organic matter, standard humic and fulvic acids from the Suwannee River. Fluorescence quenching and Time-Resolved Laser Fluorescence Spectroscopy (TRLFS) were employed to analyze various samples, using logarithmic additions of Sm3+ and Cu2+. The 1 L:1 M and 1 L:1 M:H models were applied to account for pH effects, yielding pH-independent complexant parameters KSm and KCu as well as CLSmandCLCuthat revealed specific binding sites. A notably higher affinity was observed for humic acids with Sm3+ compared to Cu2+. The logarithms of the complexation constant for the Sm3+ were 5.4, 5.2 and 4.7 for SRNOM, SRHA and SRFA, respectively. Fluorescence quenching analyses identified two distinct fluorescent components related to dissolved organic matter, showing different affinities for Sm3+ and Cu2+ that varied with pH. Humic acids exhibited the highest complexation capacity for Sm3+, attributed to their structural properties, with complexation capacities of 4.77 10−4, 0.82 and 4.46 10−3 mol of Sm per g of SRNOM, SRHA and SRFA, respectively. Temporal deconvolution of fluorescence responses revealed a tri-exponential decay with three lifetimes (τ1, τ2 and τ3) remaining relatively constant during Sm3+ or Cu2+ titrations, confirming that the fluorescence quenching is primarily a static mechanism. Speciation modeling demonstrated a shift from humic-associated complexes in freshwater to carbonate complexes in seawater as salinity increases. These findings highlight the importance of accurately characterizing DOM complexation properties to understand the environmental behavior of trace metals, particularly in response to salinity and carbon concentration gradients in estuarine systems.
本研究调查了来自苏瓦尼河的钐 (III) 在天然有机物、标准腐殖酸和富勒酸存在下的分型情况。采用荧光淬灭和时间分辨激光荧光光谱法(TRLFS)分析各种样品,使用 Sm3+ 和 Cu2+ 的对数添加量。应用 1 L:1 M 和 1 L:1 M:H 模型来考虑 pH 值的影响,得出了与 pH 值无关的络合剂参数 KSm 和 KCu 以及 CLSm 和 CLCuth,它们揭示了特定的结合位点。与 Cu2+ 相比,腐植酸与 Sm3+ 的亲和力明显更高。SRNOM、SRHA 和 SRFA 与 Sm3+ 的络合常数对数分别为 5.4、5.2 和 4.7。荧光淬灭分析确定了与溶解有机物有关的两种不同的荧光成分,它们对 Sm3+ 和 Cu2+ 的亲和力随 pH 值的变化而不同。腐植酸对 Sm3+ 的络合能力最高,这与它们的结构特性有关,每克 SRNOM、SRHA 和 SRFA 对 Sm 的络合能力分别为 4.77 10-4、0.82 和 4.46 10-3 摩尔。荧光响应的时间解卷积显示了一种三指数衰减,在 Sm3+ 或 Cu2+ 滴定过程中,三个寿命(τ1、τ2 和 τ3)保持相对恒定,这证实荧光淬灭主要是一种静态机制。物种模型显示,随着盐度的增加,淡水中的腐殖质相关复合物会转变为海水中的碳酸盐复合物。这些发现凸显了准确描述 DOM 复合物特性对了解痕量金属环境行为的重要性,尤其是对河口系统中盐度和碳浓度梯度的响应。
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引用次数: 0
Influence of seasonal changes in organic matter pool on copper bioavailability in a stratified estuary 层状河口有机质库季节变化对铜生物有效性的影响
IF 3 3区 地球科学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2025-03-19 DOI: 10.1016/j.marchem.2025.104513
Saša Marcinek, Ana-Marija Cindrić, Dario Omanović
This work presents a detailed analysis of seasonal changes in copper (Cu) organic speciation and its bioavailability in the Krka River estuary, a highly stratified microtidal system characterized by low riverine input of dissolved organic matter (DOM) and trace metals but experiencing heightened anthropogenic Cu pressures during summer as a result of increased touristic activities. Total dissolved Cu concentrations ranged from 3.4 nmol L−1 in winter up to 25.8 nmol L−1 in summer, with substantial summer increase limited to water layer above the halocline. Two distinct ligand classes were identified in all samples, with conditional stability constants of logK1 = 13.2 ± 0.5 and logK2 = 11.2 ± 0.4. Dissolved organic carbon (DOC) and concentrations of both ligand classes were higher in summer than in winter, with strong indications of their in situ production driven by enhanced primary production and/or intensified microbial activity. In winter, despite the low DOC levels (avg 63.3 μmol L−1), DOM above the halocline showed pronounced terrestrial signature with higher density of Cu-binding sites compared to DOM in summer with nearly twice as high DOC levels (avg 113.5 μmol L−1). The results suggest that terrestrial humic substances (HS) dominated the ligand pool in these waters during winter (estimated 80 % of total ligand pool), possibly contributing to both ligand classes. While HS remained an important fraction of the ligand pool in the summer (estimated 30 % of total ligand pool), the terrestrial signature of DOM in this season was minimal, pointing to their production within the estuary. The summer increase in ligand concentrations above the halocline was accompanied by a reduction in their binding strengths (by approximately 0.5 log units) compared to winter, along with a decrease in DOM molecular weight, possibly influenced by solar irradiation. Seasonal anthropogenic Cu input was successfully buffered by the ambient ligand pool, keeping the concentration of free Cu-ions, its most bioavailable specie, well below documented toxicity levels for Cu (maximum of 2.54 pmol L−1). The seasonal DOM variations resulted in a ∼ two-fold increase in the Cu-binding capacity in summer (33 nmol L−1) compared to winter (17 nmol L−1). Despite the increased buffering capacity in summer, Cu levels are approaching this safety limit, which may increase its bioavailability to a concerning level, a risk much lower in winter when Cu inputs are minimal. These results underscore the critical role of DOM in mitigating seasonal anthropogenic Cu inputs, while also highlighting the need for further investigation into the long-term resilience of estuarine systems under shifting environmental and anthropogenic pressures.
本文详细分析了克尔卡河河口铜(Cu)有机形态及其生物可利用性的季节变化。克尔卡河河口是一个高度分层的微潮系统,其特征是河流输入的溶解有机物(DOM)和微量金属较少,但由于旅游活动的增加,夏季人为Cu压力增加。总溶解Cu浓度冬季为3.4 nmol L−1,夏季为25.8 nmol L−1,夏季的大幅增加仅限于盐跃层以上水层。在所有样品中鉴定出两种不同的配体类别,条件稳定性常数logK ' 1 = 13.2±0.5和logK ' 2 = 11.2±0.4。两类配体的溶解有机碳(DOC)和浓度在夏季都高于冬季,这表明它们的原位生产是由初级生产增强和/或微生物活动增强驱动的。在冬季,虽然DOC水平较低(平均63.3 μmol L−1),但盐跃层以上DOM表现出明显的陆地特征,cu结合位点密度较夏季DOM高(平均113.5 μmol L−1)近2倍。结果表明,陆源腐殖质(HS)在冬季的配体库中占主导地位(估计占总配体库的80%),可能对这两类配体都有贡献。虽然HS在夏季仍然是配体库的重要组成部分(估计占总配体库的30%),但该季节DOM的陆地特征最小,表明它们在河口内产生。与冬季相比,夏季盐跃层上方配体浓度的增加伴随着其结合强度的降低(约0.5 log单位),以及DOM分子量的降低,这可能受到太阳照射的影响。环境配体池成功地缓冲了季节性人为Cu输入,使其最具生物可利用性的游离Cu离子浓度远低于文献记载的Cu毒性水平(最大值为2.54 pmol L−1)。DOM的季节性变化导致夏季铜结合能力(33 nmol L−1)比冬季(17 nmol L−1)增加了2倍。尽管夏季的缓冲能力有所增加,但Cu含量正在接近这一安全极限,这可能使其生物利用度增加到一个有关的水平,而在Cu输入最少的冬季,这一风险要低得多。这些结果强调了DOM在减轻季节性人为Cu输入方面的关键作用,同时也强调了进一步研究河口系统在不断变化的环境和人为压力下的长期恢复能力的必要性。
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引用次数: 0
Diatom-driven processes lead to the assimilation of elements from silicate minerals into their frustules 硅藻驱动的过程导致硅酸盐矿物中的元素被同化到它们的结晶体中
IF 3 3区 地球科学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2025-03-19 DOI: 10.1016/j.marchem.2025.104512
Tasuku Akagi, Sophia Welti, Rei Tajiri, Kazuhiko Shimada
To examine whether diatoms dissolve silicate minerals and incorporate foreign metals into their frustules, culture experiments were performed using Achnanthes kuwaitensis Hendey, Eucampia sp. and Coscinodiscus wailesii. These comprised two comparative experiments: (i) an analysis of diatom activities (population, transparent exopolymer particles (TEP) secretion and the Al/Si of frustules) in the presence/absence of feldspar particles, and (ii) an examination of mineral surfaces in the presence/absence of diatoms. Although the presence/absence of silicate minerals did not incur marked differences in diatom population, TEP secretion increased in the presence of silicate particles. Further, it was observed that the girdles of Coscinodiscus frustules showed double Si peaks and the outer layers of the girdles had significantly higher Al/Si ratios than the inner layers when feldspar particles were present. In the diatom cultures, feldspar particles largely disappeared in extended cultivation, and those still present showed rounded or fractured edges, features that were not seen in the absence of diatoms. The presence of diatoms appeared to have more influence on silicate minerals than the presence of silicate minerals on diatom activities. The C/Si ratios of the rounded feldspar grain edges in the Coscinodiscus cultures were significantly higher than those of stepwise edges, that we interpret to indicate that diatoms secrete TEP to dissolve silicate minerals. Two observations substantiated this hypothesis: pH decreases around diatoms, and incorporation of the mineral particles in TEP coatings.
Nevertheless, the physiological advantage for diatoms to dissolve silicate minerals remains unclear. Given the difference in TEP secretion between two different feldspar minerals, we believe that diatoms actively dissolve silicates in order to incorporate silica. We thus propose a mechanism by which diatoms dissolve silicate minerals. This may explain the inclusion of foreign elements at levels, whose relative concentrations are similar to those in terrigenous matter, in diatom frustules.
为了研究硅藻是否能溶解硅酸盐矿物并将外来金属融入到它们的结壳中,我们用阿克南提(Achnanthes kuwaitensis Hendey)、尤卡皮(Eucampia)和瓦利塞(Coscinodiscus wailesii)进行了培养实验。这些实验包括两个比较实验:(i)在长石颗粒存在/不存在的情况下分析硅藻活性(种群,透明外聚合物颗粒(TEP)分泌和晶体的Al/Si),以及(ii)在硅藻存在/不存在的情况下检查矿物表面。尽管矽酸盐矿物的存在和不存在对硅藻种群没有显著影响,但硅酸盐颗粒存在时,TEP的分泌增加。此外,在长石颗粒存在的情况下,尾盘晶体的环带呈现双Si峰,且环带外层的Al/Si比值明显高于内层。在硅藻培养中,长石颗粒在扩展培养中大部分消失,那些仍然存在的长石颗粒呈现圆形或断裂的边缘,这些特征在没有硅藻的情况下是看不到的。硅藻的存在对硅酸盐矿物的影响似乎大于硅酸盐矿物对硅藻活动的影响。硅藻培养物中圆形长石颗粒边缘的C/Si比值显著高于阶梯边缘,表明硅藻分泌TEP来溶解硅酸盐矿物。两个观察结果证实了这一假设:硅藻周围的pH值降低,以及TEP涂层中矿物颗粒的掺入。然而,硅藻溶解硅酸盐矿物的生理优势尚不清楚。鉴于两种不同长石矿物之间TEP分泌的差异,我们认为硅藻主动溶解硅酸盐以纳入二氧化硅。因此,我们提出了一种硅藻溶解硅酸盐矿物的机制。这也许可以解释硅藻中外来元素的含量,其相对浓度与陆源物质相似。
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引用次数: 0
Regression-based characterization of the marine carbonate system across shelf and nearshore waters of Queen Charlotte Sound 夏洛特女王湾陆架及近岸海域海相碳酸盐体系的回归表征
IF 3 3区 地球科学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2025-03-14 DOI: 10.1016/j.marchem.2025.104511
A.A. Hare , W. Evans , H.V. Dosser , J.M. Jackson , S.R. Alin , C. Hannah , T. Ross , J.M. Klymak
Marine carbonate system measurements are essential for understanding ocean acidification and CaCO3 saturation states, and their response to oceanographic and anthropogenic processes. Acquiring such measurements in remote coastal areas is limited by challenges in the development and deployment of autonomous sensors for these parameters, and by the complexity and costs of directly measuring them. We address this challenge by extending an established method of estimating carbonate system parameters through proxy variables to the remote waters of Queen Charlotte Sound, British Columbia. Paired regressions are developed from bottle samples and common hydrographic measurements for both offshore and coastal waters that intersect in this region but retain distinct relationships between total alkalinity and salinity. Application of these regression models to regional autonomous glider data demonstrates that established features of this shelf system can be characterized from a carbonate system perspective along a contiguous transect from land to the shelf break, despite greater regression uncertainties in coastal water. These results also provide new insight into the dynamics of aragonite saturation on the shelf in relation to regional winds. This approach extends a tool to gain knowledge of the marine carbonate system to a coastal region of the northeast Pacific Ocean where hydrographic data used as proxies are more commonly available.
海洋碳酸盐系统测量对于了解海洋酸化和CaCO3饱和状态及其对海洋和人为过程的响应至关重要。在偏远沿海地区获取此类测量数据受到开发和部署这些参数的自主传感器的挑战,以及直接测量这些参数的复杂性和成本的限制。为了应对这一挑战,我们将一种通过代理变量估计碳酸盐岩系统参数的既定方法扩展到不列颠哥伦比亚省夏洛特女王湾的偏远水域。配对回归是根据瓶子样品和在该地区相交的近海和沿海水域的常见水文测量结果开发的,但总碱度和盐度之间保留了明显的关系。将这些回归模型应用于区域自主滑翔机数据表明,尽管沿海水域的回归不确定性较大,但从碳酸盐岩体系的角度来看,从陆地到陆架断裂的连续样带可以表征该陆架体系的既定特征。这些结果也为大陆架文石饱和度与区域风的关系提供了新的见解。这种方法将一种获取海相碳酸盐体系知识的工具扩展到东北太平洋沿海地区,在那里,水文数据更常用作代用。
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引用次数: 0
Copper speciation in a tropical mangrove forest of Southeast Asia 东南亚热带红树林中的铜物种分化
IF 3 3区 地球科学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2025-03-11 DOI: 10.1016/j.marchem.2025.104510
Ying Ping Lee , Kuo Hong Wong , Hajime Obata , Mohd Zaki Kamsah , Mohd Hisyam Rasidi
Mangrove forests are vital ecosystems that protect coastlines, sequester carbon, and support diverse food webs. Elucidation of the behaviors of nutrients, trace elements, and organic matters in these regions is crucial to understand the impact of human activities and the potential effects of climate change. In this study, we revealed the distributions and bioavailability of a trace metal, copper (Cu), and conducted the first study of Cu speciation in a mangrove region in Southeast Asia. Dissolved Cu (dCu) concentrations ranged from 0.3 to 2.3 nmol L−1 in the study region, which are relatively low compared to most other coastal regions globally. Two classes of Cu-binding organic ligands with average conditional stability constants, log K, of 15.5 and 13.2, respectively, were detected in mangrove waters. Complexing capacities of the ligands generally decrease in low salinity waters with low dCu concentrations. Concentrations of the stronger-binding class of organic ligand (L1) were higher than those of dCu, reducing the bioavailable Cu2+ concentration to less than femtomolar levels, potentially inducing Cu-limitation to microorganism growth. To further understand the biogeochemical processes of trace metals in mangrove regions, future studies should prioritize obtaining baseline data using standardized sampling and analytical techniques to ensure consistent and reliable results.
红树林是保护海岸线、固碳和支持多样化食物网的重要生态系统。阐明这些地区的营养物质、微量元素和有机物的行为对了解人类活动的影响和气候变化的潜在影响至关重要。在这项研究中,我们揭示了微量金属铜(Cu)的分布和生物利用率,并首次对东南亚红树林地区的铜标本进行了研究。研究区域的溶解铜(dCu)浓度介于 0.3 至 2.3 nmol L-1 之间,与全球大多数其他沿海地区相比相对较低。在红树林水域检测到两类铜结合有机配体,其平均条件稳定常数 log K 分别为 15.5 和 13.2。配体的络合能力在 dCu 浓度较低的低盐度水域中普遍下降。结合力较强的一类有机配体(L1)的浓度高于 dCu 的浓度,使生物可利用的 Cu2+ 浓度降低到飞摩尔水平以下,从而可能导致 Cu 限制微生物的生长。为进一步了解红树林地区痕量金属的生物地球化学过程,今后的研究应优先使用标准化的采样和分析技术获取基线数据,以确保结果的一致性和可靠性。
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引用次数: 0
Surface macro- and micro-nutrients within the Copper River plume region respond to along-shore winds 铜河羽流区域的表层宏量和微量营养物质对沿岸风有响应
IF 3 3区 地球科学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2025-02-21 DOI: 10.1016/j.marchem.2025.104508
E.L.S. Ortega, I. Reister, S.L. Danielson, A.M. Aguilar-Islas
The Copper River is a major source of freshwater to the Northern Gulf of Alaska (NGA) shelf with a seasonal cycle that reaches peak discharge in summer. This glacially-fed river also provides a large input of dissolved chemicals to the NGA, and because of its large particle load, it impacts the distribution of particle-reactive elements. Summertime sampling of shelf water properties was carried out within the Copper River plume region during two years: first during a period of upwelling-favorable winds and higher river discharge (4–7 July 2019) and later during lower river discharge and more typical downwelling conditions (11–13 July 2020). Although these wind conditions were observed in separate years, both can occur over the course of a single summer. We found that the export of most nutrients to surface shelf waters was enhanced under upwelling-favorable winds accompanied by higher river discharge compared to downwelling conditions and lower discharge. For example, greater cross-shelf plume transport in 2019 resulted in higher mid-shelf surface inventories for nitrate + nitrite (N + N), silicic acid (H4SiO4), phosphate (PO43−), dissolved Fe (dFe), and dissolved Cu (dCu) compared to 2020. Entrainment of relatively macronutrient-rich subsurface waters under upwelling conditions may also have contributed to the enhancement of these mid-shelf nutrient inventories. The observed high N:P ratios in plume waters were likely driven by the scavenging of P within particle-laden plume waters. Similarly, we observed lower than expected [dFe] (1.58 to 6.12 nM) in particle-laden plume waters, likely a result of enhanced scavenging combined with low concentrations of dissolved Fe-binding ligands. Although dNi and dZn have a river source, we observed lower concentrations in surface shelf waters under upwelling conditions, suggesting enhanced dilution by relatively micronutrient-poor subsurface waters. Results highlight the influence of sub-seasonal variations in atmospheric forcing on nutrient distributions and suggest that this forcing also impacts the location and timing of primary production hotspots during summer, adding to the ecological mosaic of the NGA across a range of temporal and spatial scales.
铜河是阿拉斯加北部海湾(NGA)大陆架的主要淡水来源,其季节性循环在夏季达到峰值。这条冰川补给的河流也为NGA提供了大量的溶解化学物质输入,并且由于其大颗粒负荷,它影响了颗粒活性元素的分布。夏季对铜河羽流区域的陆架水性质进行了为期两年的采样:首先是在上升流有利的风向和较高的河流流量期间(2019年7月4日至7日),然后是在较低的河流流量和更典型的下行条件下(2020年7月11日至13日)。虽然这些风况是在不同的年份观察到的,但它们都可能在一个夏天发生。研究发现,在上升流有利的条件下,大多数营养物质向陆架表层水的输出都比下升流有利的条件下和低流量的条件下增强。例如,与2020年相比,2019年更大的跨大陆架羽流运输导致硝酸盐+亚硝酸盐(N + N)、硅酸(H4SiO4)、磷酸盐(PO43−)、溶解铁(dFe)和溶解铜(dCu)的中大陆架表面库存增加。在上升流条件下,相对丰富的大量营养物质的地下水的夹带也可能有助于这些中陆架营养物质库存的增加。烟柱水体的高氮磷比可能是由烟柱水体对磷的清除作用引起的。同样,我们观察到,在颗粒富集的羽流水中,[dFe](1.58至6.12 nM)低于预期,这可能是由于清除能力增强以及低浓度溶解的铁结合配体的结果。虽然dNi和dZn有河流来源,但我们观察到在上升流条件下,陆架表层水体中dNi和dZn的浓度较低,这表明相对微量营养素贫乏的地下水增强了它们的稀释作用。研究结果强调了大气强迫的亚季节变化对养分分布的影响,并表明这种强迫还影响夏季初级生产热点的位置和时间,从而增加了NGA在不同时空尺度上的生态马赛克。
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引用次数: 0
Dissolved iron release by sediment and dust particles in Antarctic seawater greater than glacial flour and sea-ice particles 南极海水中沉积物和尘埃颗粒释放的溶解铁大于冰川粉和海冰颗粒
IF 3 3区 地球科学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2025-02-21 DOI: 10.1016/j.marchem.2025.104509
Matthew Corkill , Klaus Martin Meiners , Pat Wongpan , Pier van der Merwe , Layla Creac'h , Sandrin Feig , Talitha Nelson , Abigail Jessica Rose Smith , Ashley T. Townsend , Samantha Twiname , Delphine Lannuzel
Primary productivity by phytoplankton in the Southern Ocean can be limited by low iron concentrations. Iron limitation in the surface ocean around Antarctica may be alleviated by particle dissolution of dust from exposed rock, glacial flour, resuspended marine sediment, and sea ice. Ligands, which are ubiquitous in seawater, chelate some metals and keep them in solution. Ligands are thereby thought to increase metal solubility, including iron. Leaching studies of Antarctic particles from various sources are rare but important due to observed and predicted changes occurring around Antarctica, e.g., changes in sea ice and ice-free areas on the continent. Here, we quantified the solubility of iron in different particle types using vertical flow-through leaching experiments that simulated sinking through the water column and ran for 78 min of flow at 4 °C under trace metal-clean conditions. Both unaltered and ultraviolet-irradiated seawater leaching solution treatments were used to test the effect of organic ligands on iron dissolution, which was found to be non-significant. Sediment and dust released the most dissolved iron to seawater, followed by glacial flour, and then sea-ice particles (9.00 ± 9.92 × 10−2 and 3.18 ± 3.79 × 10−2, 1.97 ± 1.79 × 10−4, 1.37 ± 0.90 × 10−9 g DFe/100 g material, respectively). We discuss these laboratory results in relation to particle availability and how this may affect the supply of dissolved iron to Antarctic surface waters.
南大洋浮游植物的初级生产力可能受到低铁浓度的限制。由于暴露的岩石、冰川粉、再悬浮的海洋沉积物和海冰中粉尘的颗粒溶解,南极洲周围海洋表面的铁限制可能会得到缓解。配体在海水中无处不在,它能螯合一些金属并使其保持在溶液中。因此,配体被认为可以增加金属的溶解度,包括铁。对来自各种来源的南极颗粒进行浸出研究是罕见的,但由于南极周围发生的观测和预测变化,例如南极大陆海冰和无冰区的变化,研究很重要。在这里,我们通过垂直流动浸出实验来量化铁在不同颗粒类型中的溶解度,模拟通过水柱下沉,在4°C的微量金属清洁条件下运行78分钟的流动。在未改变和紫外线照射的海水浸出液处理下,测试了有机配体对铁溶解的影响,发现有机配体对铁溶解的影响不显著。沉积物和粉尘向海水释放的溶解铁最多,其次是冰川粉,其次是海冰颗粒(分别为9.00±9.92 × 10−2和3.18±3.79 × 10−2,1.97±1.79 × 10−4,1.37±0.90 × 10−9 g DFe/100 g材料)。我们将讨论这些实验室结果与颗粒有效性的关系,以及这可能如何影响南极地表水中溶解铁的供应。
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引用次数: 0
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Marine Chemistry
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