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Nitrous oxide variability along an estuary influenced by agricultural land use (Guadalquivir estuary, SW Spain) 受农业用地影响的河口(西班牙西南部瓜达尔基维尔河口)的氧化亚氮变化情况
IF 3 3区 地球科学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-11-01 DOI: 10.1016/j.marchem.2024.104467
J. Sánchez-Rodríguez , A. Sierra , S. Moreno , J. Forja , T. Ortega
The Guadalquivir Estuary is the largest estuary in the southwest basin of the Iberian Peninsula, which is subject to strong anthropogenic influence such as the damming or the multitude of crop fields on its margins. Nitrous Oxide (N2O) variability is analysed considering the influence of temperature, salinity, water-atmosphere fluxes, benthic fluxes, reactivity and lateral inputs. N2O increases along the salinity gradient, with values ranging from 5.9 to 103.3 nmol L−1. Thus, values of N2O concentration are very close to equilibrium with the atmosphere at the mouth, while in the inner zone the fluxes to the atmosphere are higher, showing the greatest variability of N2O in the estuary (74.26 ± 7.41 μmol m−2 d−1). Sediments act as a source of N2O to the water column, with benthic fluxes presenting a wide range from 2 to 20 μmol m−2 d−1. Denitrification processes in the sediments may be important in the inner part of the estuary, where negative benthic fluxes of nitrate have been observed. Production rates of N2O in the water column are estimated from incubation experiments, resulting in higher production with temperature, and lower with salinity. Lateral inputs are calculated by balance of the different processes characterized and seems to be an important factor influencing N2O variability in the inner zone of the estuary.
瓜达尔基维尔河口是伊比利亚半岛西南盆地最大的河口,受到人类活动的强烈影响,如在其边缘筑坝或种植大量农作物。考虑到温度、盐度、水-大气通量、底栖生物通量、反应性和横向输入的影响,对一氧化二氮(N2O)的变化进行了分析。一氧化二氮随盐度梯度增加,浓度值从 5.9 到 103.3 nmol L-1 不等。因此,河口的一氧化二氮浓度值非常接近与大气的平衡值,而内区向大气的通量较高,显示出河口一氧化二氮的变化最大(74.26 ± 7.41 μmol m-2 d-1)。沉积物是水体中一氧化二氮的来源,底栖通量的范围很广,从 2 μmol m-2 d-1 到 20 μmol m-2 d-1。沉积物中的反硝化过程在河口内侧可能很重要,在河口内侧已观察到硝酸盐的负底栖通量。水体中一氧化二氮的产生率是通过培养实验估算得出的,温度越高,产生率越高,盐度越低,产生率越低。侧向输入量是通过平衡不同过程的特征计算出来的,似乎是影响河口内区一氧化二氮变化的一个重要因素。
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引用次数: 0
Seasonal variation of CO2 air-sea flux and effects of warming in the Kuroshio Current of the East China Sea 东海黑潮二氧化碳海气通量的季节变化及变暖的影响
IF 3 3区 地球科学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-11-01 DOI: 10.1016/j.marchem.2024.104469
Shou-En Tsao , Po-Yen Shen , Chun-Mao Tseng
The partial pressure of CO2 (pCO2) and associated CO2 air-sea flux exhibit highly heterogeneous temporal and spatial patterns in ocean margins. In this study, we analyzed a three-year time-series of data sampled during 2011–2014 along the Kuroshio Current within the East China Sea (ECS) to investigate the seasonal pattern of carbonate chemistry and CO2 air-sea fluxes. Annually, the Kuroshio within the ECS operates as a net CO2 sink at approximately 1.3 mol C m−2 yr−1, less than estimates over the ECS shelf (∼1.8 mol C m−2 yr−1). The thermal control of pCO2 makes the Kuroshio a strong CO2 sink in winter, with a transition to net-neutral, or a weak CO2 source in summer. On an interannual basis, however, the seasonal CO2 air-sea fluxes in the Kuroshio may undergo shifts if warming conditions continue.
大洋边缘的二氧化碳分压(pCO2)和相关的二氧化碳海气通量呈现出高度异质性的时空模式。在本研究中,我们分析了 2011-2014 年中国东海(ECS)黑潮沿岸三年的时间序列数据,研究了碳酸盐化学和二氧化碳海气通量的季节模式。每年,东海海域内黑潮的二氧化碳净吸收汇约为 1.3 mol C m-2 yr-1,低于东海大陆架的估计值(1.8 mol C m-2 yr-1)。对 pCO2 的热控制使黑潮在冬季成为一个强大的二氧化碳汇,在夏季过渡到净中性或弱二氧化碳源。不过,如果气候继续变暖,黑潮的季节性二氧化碳海气通量可能会发生变化。
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引用次数: 0
Reactivity and fluxes of antimony in a macrotidal estuarine salinity gradient: Insights from single and triple quadrupole ICP-MS performances 大潮汐河口盐度梯度中锑的反应性和通量:从单四极杆和三重四极杆 ICP-MS 性能中获得的启示
IF 3 3区 地球科学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-11-01 DOI: 10.1016/j.marchem.2024.104465
Teba Gil-Díaz , Frédérique Pougnet , Lionel Dutruch , Jörg Schäfer , Alexandra Coynel
Trace element analyses in brackish waters are challenging for many elements at ppb/ppt levels and analytical methods. In this work, we compare two methods using inductively coupled plasma mass spectrometry (ICP-MS) for quantifying antimony (Sb). Results of a previous study along the salinity gradient in a macrotidal estuary (i.e., the Gironde Estuary, France) using isotopic dilution via single quadrupole ICP-MS are compared to reanalyzed aliquots of the same samples. Direct analyses of estuarine water samples via standard additions (N = 52) were performed with a QQQ-ICP-MS (new generation, iCAP TQ Thermo®) to determine dissolved (< 0.2 μm filtered and UV-irradiated replicates) Sb concentrations during two contrasting hydrological conditions (low vs high freshwater discharges). Despite following good analytical practices on both studies, the use of the new analytical device provides more robust results and highlighted a characteristic 121Sb isotopic interference in estuarine samples at S > 20, efficiently eliminated by the QQQ-ICP-MS performance. This means that Sb reactivity shows an additive, non-conservative behavior in the Gironde Estuary, with a more defined bell-shaped profile in low discharge compared to high discharge conditions. This approach allows to quantify for the first time in the literature Sb dissolved net fluxes from the Gironde Estuary to the Atlantic coast and provides an updated value for the seawater endmember. This study opens future applications of QQQ-ICP-MS for quantifying on a more routine basis dissolved trace elements in brackish waters, providing guidelines and good practices for field studies regarding Sb determination in estuarine systems.
咸水中许多元素的ppb/ppt含量和分析方法对痕量元素分析都具有挑战性。在这项工作中,我们比较了使用电感耦合等离子体质谱法(ICP-MS)量化锑(Sb)的两种方法。通过单四极 ICP-MS 进行同位素稀释,将之前在一个大潮汐河口(即法国吉伦特河口)沿盐度梯度进行的研究结果与重新分析的相同样本等分进行了比较。使用 QQQ-ICP-MS(新一代,iCAP TQ Thermo®)对通过标准添加物直接分析的河口水样(N = 52)进行了分析,以确定在两种截然不同的水文条件下(淡水排放量少与淡水排放量多)的溶解锑浓度(< 0.2 μm 过滤和紫外线照射重复样品)。尽管这两项研究都遵循了良好的分析方法,但使用新的分析设备得出的结果更加可靠,并突出显示了河口样本在 S > 20 时的 121Sb 同位素干扰特征,QQQ-ICP-MS 的性能有效地消除了这一干扰。这意味着,在吉伦特河口,锑的反应性显示出一种添加性的非保守行为,与高排水量条件相比,低排水量条件下的钟形曲线更为清晰。这种方法首次在文献中量化了从吉伦特河口到大西洋沿岸的锑溶解净通量,并提供了海水末端分子的最新值。这项研究开启了 QQQ-ICP-MS 在咸水溶解痕量元素常规量化方面的未来应用,为河口系统锑测定方面的实地研究提供了指南和良好实践。
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引用次数: 0
Tracing marine and terrestrial biochemical signatures of particulate organic matter in an Arctic fjord (Kongsfjorden) 追踪北极峡湾(孔斯峡湾)颗粒有机物的海洋和陆地生物化学特征
IF 3 3区 地球科学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-11-01 DOI: 10.1016/j.marchem.2024.104468
Archana Singh , Anand Jain , Richa Singh , Keisham S. Singh , Biswajit Roy , Manish Tiwari , Divya David T. , Ashok Jagtap
Arctic fjords are hotspot for organic matter (OM) transformation and storage, however, the composition and sources of the particulate organic matter (POM) are still not completely understood. Further, due to the ongoing enhancement in the glacier melting, runoff, and precipitation, the coastal Arctic is expecting considerable increase in POM inputs. Therefore, we investigated the biochemical composition of the POM through the application of stable isotopes, C:N ratio, and biomolecules, across different regions and depths in Kongsfjorden (Svalbard) during the late-summer. We observed that Kongsfjorden-POM was characterized by low δ13C (−29.0 to −26.7 ‰) with similar values at different locations (inner to outer) of the fjord at each depth. However, C:N ratio showed increasing trend (5.7 to 10.9) from outer to inner fjord indicating marine to terrestrial transition. Monosaccharide distribution (such as fucose, galactose, arabinose, xylose, ribose, and rhamnose) and their diagnostic ratios supported the marine versus terrestrial gradient in the POM characteristics in the surface water across the fjord. Only the outermost station showed consistent biochemical distribution indicative of phytoplanktonic sources in the POM, while the rest of the fjord showed mixed signatures of marine and terrestrial sources. Higher abundance of mannuronic acid (26.6–50.8 mol%) at the middle and bottom depths highlighted possible macroalgal contribution to the POM. The stratified surface water had a relatively higher (0.5–2 ‰) δ13C and carbohydrates (40–65 μg/L) than the middle and bottom depths, with a strong positive correlation between δ13C and particulate carbohydrates, indicating a stratification-induced distribution of POM. The study showed the importance of non-phytoplanktonic OM sources, such as terrestrial, freshwater and macroalgae POM in the fjord water column, and the fate of labile (carbohydrates) fraction that predominates in stratified surface waters. Therefore, the future warm and wet Arctic will most likely lead to changes in the fate of the organic matter in the fjord water.
北极峡湾是有机物(OM)转化和储存的热点地区,但人们对颗粒有机物(POM)的组成和来源还不完全了解。此外,由于冰川融化、径流和降水量的不断增加,北极沿岸的 POM 输入量预计将大幅增加。因此,我们在康斯峡湾(斯瓦尔巴群岛)的夏末,通过应用稳定同位素、碳氮比和生物大分子,研究了不同区域和不同深度的 POM 的生物化学组成。我们观察到,康斯峡湾-POM 的特点是 δ13C 值低(-29.0 至 -26.7‰),峡湾不同位置(从内到外)每个深度的δ13C 值相似。然而,从峡湾外侧到内侧,C:N 比值呈上升趋势(5.7 至 10.9),表明海洋向陆地过渡。单糖分布(如岩藻糖、半乳糖、阿拉伯糖、木糖、核糖和鼠李糖)及其诊断比值支持了整个峡湾表层水 POM 特征的海洋-陆地梯度。只有最外围的观测站显示出一致的生化分布,表明 POM 中存在浮游植物来源,而峡湾的其它地方则显示出海洋和陆地来源的混合特征。中层和底层水域的甘露醇酸含量较高(26.6-50.8 mol%),这说明大型藻类可能对 POM 有贡献。分层表层水的δ13C和碳水化合物(40-65 μg/L)含量(0.5-2 ‰)相对高于中层和底层水,δ13C与颗粒碳水化合物之间存在很强的正相关性,表明POM的分布是由分层引起的。该研究表明了峡湾水体中陆地、淡水和大型藻类 POM 等非浮游生物 OM 来源的重要性,以及在分层表层水体中占主导地位的可溶性(碳水化合物)部分的归宿。因此,未来温暖湿润的北极很可能会导致峡湾水体中有机物的去向发生变化。
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引用次数: 0
Dynamic manganese cycling in the northern Gulf of Mexico 墨西哥湾北部的动态锰循环
IF 3 3区 地球科学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-11-01 DOI: 10.1016/j.marchem.2024.104466
Jessalyn E. Davis , Rebecca S. Robinson , Emily R. Estes , Veronique E. Oldham , Evan A. Solomon , Roger P. Kelly , Katherine E. Bell , Joseph A. Resing , Randelle M. Bundy
Transport processes along the river-ocean continuum influence delivery of nutrients, carbon and trace metals from terrestrial systems to the marine environment, impacting coastal primary productivity and water quality. Although trace metal transformations have been studied extensively in the Mississippi River Delta region of the Northern Gulf of Mexico, investigations of manganese (Mn) and the presence of ligand-stabilized, dissolved manganese (Mn(III)-L) and its role in the transformation of trace elements and organic matter during riverine transport and estuarine mixing have not been considered. This study examined the chemical speciation of dissolved and particulate Mn in the water column and sediment porewaters in the Mississippi River and Northern Gulf of Mexico in March of 2021 to explore transformations in Mn speciation along the river-ocean continuum and the impact of different processes on the distribution of Mn. Total dissolved Mn concentrations were highest in the Mississippi River and decreased offshore, while Mn(III)-L contributed most to the dissolved Mn pool in near-shore waters. Porewater profiles indicated that ligand stabilization prevented dissolved Mn(III) reduction below the depth of oxygen penetration and in the presence of equimolar dissolved iron(II). Dissolved Mn(III)-L was enriched in bottom waters at all Northern Gulf of Mexico stations, and diffusive flux modelling of porewater dissolved Mn suggested that reducing sediments were a source of dissolved Mn to the overlying water column in the form of both reduced Mn(II) and Mn(III)-L. A simple box model of the Mn cycle in the Northern Gulf of Mexico indicates that Mn(III)-L is required to balance the Mn budget in this region and is an integral, and previously unconsidered, piece of the Mn cycle in the Northern Gulf of Mexico. The presence of Mn(III)-L in this system likely has an outsized impact on trace element scavenging rates, oxidative capacity, and the carbon cycle that have not been previously appreciated.
{"title":"Dynamic manganese cycling in the northern Gulf of Mexico","authors":"Jessalyn E. Davis ,&nbsp;Rebecca S. Robinson ,&nbsp;Emily R. Estes ,&nbsp;Veronique E. Oldham ,&nbsp;Evan A. Solomon ,&nbsp;Roger P. Kelly ,&nbsp;Katherine E. Bell ,&nbsp;Joseph A. Resing ,&nbsp;Randelle M. Bundy","doi":"10.1016/j.marchem.2024.104466","DOIUrl":"10.1016/j.marchem.2024.104466","url":null,"abstract":"<div><div>Transport processes along the river-ocean continuum influence delivery of nutrients, carbon and trace metals from terrestrial systems to the marine environment, impacting coastal primary productivity and water quality. Although trace metal transformations have been studied extensively in the Mississippi River Delta region of the Northern Gulf of Mexico, investigations of manganese (Mn) and the presence of ligand-stabilized, dissolved manganese (Mn(III)-L) and its role in the transformation of trace elements and organic matter during riverine transport and estuarine mixing have not been considered. This study examined the chemical speciation of dissolved and particulate Mn in the water column and sediment porewaters in the Mississippi River and Northern Gulf of Mexico in March of 2021 to explore transformations in Mn speciation along the river-ocean continuum and the impact of different processes on the distribution of Mn. Total dissolved Mn concentrations were highest in the Mississippi River and decreased offshore, while Mn(III)-L contributed most to the dissolved Mn pool in near-shore waters. Porewater profiles indicated that ligand stabilization prevented dissolved Mn(III) reduction below the depth of oxygen penetration and in the presence of equimolar dissolved iron(II). Dissolved Mn(III)-L was enriched in bottom waters at all Northern Gulf of Mexico stations, and diffusive flux modelling of porewater dissolved Mn suggested that reducing sediments were a source of dissolved Mn to the overlying water column in the form of both reduced Mn(II) and Mn(III)-L. A simple box model of the Mn cycle in the Northern Gulf of Mexico indicates that Mn(III)-L is required to balance the Mn budget in this region and is an integral, and previously unconsidered, piece of the Mn cycle in the Northern Gulf of Mexico. The presence of Mn(III)-L in this system likely has an outsized impact on trace element scavenging rates, oxidative capacity, and the carbon cycle that have not been previously appreciated.</div></div>","PeriodicalId":18219,"journal":{"name":"Marine Chemistry","volume":"267 ","pages":"Article 104466"},"PeriodicalIF":3.0,"publicationDate":"2024-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142703071","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
Boron to salinity ratios in the Fram Strait entering the Central Arctic: The role of sea ice formation and future predictions 进入北极中部的弗拉姆海峡的硼盐比值:海冰形成的作用和未来预测
IF 3 3区 地球科学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-10-22 DOI: 10.1016/j.marchem.2024.104463
Samantha Rush , Penny Vlahos , Chang-Ho Lee , Kitack Lee , Lauren J. Barrett
The Arctic Ocean's sea ice loss dynamically impacts carbon uptake potential, as assessed through measured carbonate parameters, such as total alkalinity. In the open ocean, boron (B) is the third largest contributor to alkalinity via borate and is usually accounted for through the conservative boron to salinity ratio (B/S), and not directly measured. Here, we present findings on non-conservative boron dynamics, that results in significant B/S deviations, observed in ice melt zone waters, snow, slush, brine, and annual sea ice (n = 169) in the Fram Strait entering the Central Arctic. These samples were collected during the onset of the melt season on the 2023 ARTofMELT expedition, covering a wide practical salinity range (2–59). Barring snow, the average B/S ratio across the study was 0.1321 ± 0.0032 mg kg−1−1, similar to the mean B/S ratio measured amongst several polar water masses near Iceland, as well as the accepted B/S for other ocean regions. Results indicate minor deviations from accepted B/S ratios (indicating conservative behavior) across the sample practical salinity range and reflect an uncertainty in the borate contribution to total alkalinity of less than 2.9 μmol kg−1 at in-situ temperatures. B fractionation appears to occur during sea ice formation, causing greater B in the sea ice reservoir whereas brine, slush, lead, and under-ice water reservoirs are depleted in B. As such, under-ice and lead, brine, and slush samples all had measured B/S ratios (0.1305 ± 0.0011, 0.1305 ± 0.0018, and 0.1304 ± 0.0017 mg kg−1−1, respectively) lower than the established ratio whereas the average sea ice B/S ratio (0.1331 ± 0.0035 mg kg−1−1) was closest to accepted values (0.1336 ± 0.0005 mg kg−1−1). Arctic open ocean samples also had a lower B/S ratio (0.1304 ± 0.0014 mg kg−1−1). Our findings, together with a previous Arctic B ice study, suggest that B (probably in the form of B(OH)4) is incorporated into authigenic CaCO3 minerals, replacing CO32− within the mineral lattice during sea ice formation. This process consequentially lowers the B/S ratio in the open Arctic Ocean, compared to the established global ocean ratio. Nevertheless, the incorporation of B into the sea ice reservoir does not fully account for the deficit of B in the Arctic Ocean samples, suggesting further accounting of B Arctic pathways is necessary. In future climate scenarios involving increased sea ice melt, the transition from multiyear to annual sea ice, permafrost thaw, and increased riverine discharge, the behavior of B in the Arctic Ocean is expected to become more dynamic.
北冰洋海冰的消失对碳吸收潜力产生了动态影响,这可以通过测量碳酸盐参数(如总碱度)来评估。在开阔的海洋中,硼(B)是通过硼酸盐造成碱度的第三大因素,通常通过保守的硼盐比值(B/S)来计算,而不是直接测量。在此,我们介绍了在进入北极中部的弗拉姆海峡的冰融化区水域、雪、泥泞、盐水和年度海冰(n = 169)中观察到的非保守硼动态研究结果,这种非保守硼动态会导致显著的 B/S 偏差。这些样本是在 2023 年 ARTofMELT 探险队的融化季节开始时采集的,覆盖了很宽的实际盐度范围(2-59)。除积雪外,整个研究的平均 B/S 比值为 0.1321 ± 0.0032 mg kg-1 ‰-1,与冰岛附近几个极地水团中测得的平均 B/S 比值以及其他海洋区域公认的 B/S 比值相似。结果表明,在整个样本实际盐度范围内,B/S 比值与公认的 B/S 比值有轻微偏差(表明行为保守),并反映出在原位温度下,硼酸盐对总碱度的贡献的不确定性小于 2.9 μmol kg-1。硼分馏似乎发生在海冰形成过程中,导致海冰储层中的硼含量增加,而盐水、泥浆、铅和冰下水储层中的硼含量减少。分别为 0.1305 ± 0.0011、0.1305 ± 0.0018 和 0.1304 ± 0.0017 毫克/千克-1 ‰-1)低于既定比率,而平均海冰 B/S 比率(0.1331 ± 0.0035 毫克/千克-1 ‰-1)最接近公认值(0.1336 ± 0.0005 毫克/千克-1 ‰-1)。北极公海样本的 B/S 比值也较低(0.1304 ± 0.0014 mg kg-1 ‰-1)。我们的研究结果以及之前的北极 B 冰研究表明,在海冰形成过程中,B(可能以 B(OH)4- 的形式)被掺入到自生 CaCO3 矿物中,取代了矿物晶格中的 CO32-。与已确定的全球海洋比率相比,这一过程降低了北冰洋开放海域的 B/S 比率。尽管如此,海冰储层中硼的吸收并不能完全解释北冰洋样本中硼的缺失,这表明有必要进一步解释硼的北冰洋路径。在未来的气候情景中,海冰融化增加、海冰从多年期向全年期过渡、永久冻土融化以及河流排水量增加,预计北冰洋中硼的行为将变得更加动态。
{"title":"Boron to salinity ratios in the Fram Strait entering the Central Arctic: The role of sea ice formation and future predictions","authors":"Samantha Rush ,&nbsp;Penny Vlahos ,&nbsp;Chang-Ho Lee ,&nbsp;Kitack Lee ,&nbsp;Lauren J. Barrett","doi":"10.1016/j.marchem.2024.104463","DOIUrl":"10.1016/j.marchem.2024.104463","url":null,"abstract":"<div><div>The Arctic Ocean's sea ice loss dynamically impacts carbon uptake potential, as assessed through measured carbonate parameters, such as total alkalinity. In the open ocean, boron (B) is the third largest contributor to alkalinity via borate and is usually accounted for through the conservative boron to salinity ratio (B/S), and not directly measured. Here, we present findings on non-conservative boron dynamics, that results in significant B/S deviations, observed in ice melt zone waters, snow, slush, brine, and annual sea ice (<em>n</em> = 169) in the Fram Strait entering the Central Arctic. These samples were collected during the onset of the melt season on the 2023 ARTofMELT expedition, covering a wide practical salinity range (2–59). Barring snow, the average B/S ratio across the study was 0.1321 ± 0.0032 mg kg<sup>−1</sup> ‰<sup>−1</sup>, similar to the mean B/S ratio measured amongst several polar water masses near Iceland, as well as the accepted B/S for other ocean regions. Results indicate minor deviations from accepted B/S ratios (indicating conservative behavior) across the sample practical salinity range and reflect an uncertainty in the borate contribution to total alkalinity of less than 2.9 μmol kg<sup>−1</sup> at in-situ temperatures. B fractionation appears to occur during sea ice formation, causing greater B in the sea ice reservoir whereas brine, slush, lead, and under-ice water reservoirs are depleted in B. As such, under-ice and lead, brine, and slush samples all had measured B/S ratios (0.1305 ± 0.0011, 0.1305 ± 0.0018, and 0.1304 ± 0.0017 mg kg<sup>−1</sup> ‰<sup>−1</sup>, respectively) lower than the established ratio whereas the average sea ice B/S ratio (0.1331 ± 0.0035 mg kg<sup>−1</sup> ‰<sup>−1</sup>) was closest to accepted values (0.1336 ± 0.0005 mg kg<sup>−1</sup> ‰<sup>−1</sup>). Arctic open ocean samples also had a lower B/S ratio (0.1304 ± 0.0014 mg kg<sup>−1</sup> ‰<sup>−1</sup>). Our findings, together with a previous Arctic B ice study, suggest that B (probably in the form of B(OH)<sub>4</sub><sup>−</sup>) is incorporated into authigenic CaCO<sub>3</sub> minerals, replacing CO<sub>3</sub><sup>2−</sup> within the mineral lattice during sea ice formation. This process consequentially lowers the B/S ratio in the open Arctic Ocean, compared to the established global ocean ratio. Nevertheless, the incorporation of B into the sea ice reservoir does not fully account for the deficit of B in the Arctic Ocean samples, suggesting further accounting of B Arctic pathways is necessary. In future climate scenarios involving increased sea ice melt, the transition from multiyear to annual sea ice, permafrost thaw, and increased riverine discharge, the behavior of B in the Arctic Ocean is expected to become more dynamic.</div></div>","PeriodicalId":18219,"journal":{"name":"Marine Chemistry","volume":"267 ","pages":"Article 104463"},"PeriodicalIF":3.0,"publicationDate":"2024-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142528416","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"地球科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Biogeochemical sulfur transformations in the cohesive and permeable tidal flat sediments of Jade Bay (North Sea) 翡翠湾(北海)粘性和渗透性潮滩沉积物中硫的生物地球化学转化
IF 3 3区 地球科学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-10-22 DOI: 10.1016/j.marchem.2024.104464
Alexey Kamyshny Jr , Debora Sela , Rotem Klein , Alexandra V. Turchyn , Gilad Antler , Holger Freund
Intertidal flats are highly productive coastal marine ecosystems which are affected by fast changes in environmental conditions and host dynamic biogeochemical cycles in their sediments. Bioturbation by burrowing organisms and roots of plants strongly affects speciation and cycling of redox-sensitive elements in intertidal sediments. In this work, we have studied the impact of sediment type and vegetation on the cycling of redox-sensitive elements including sulfur, iron, and manganese in sandy and muddy tidal flats sediments in the Jade Bay (North Sea) and adjacent area. The redox speciation of these elements was analyzed in the pore-waters and the total sediment. The isotopic compositions of sulfur species were measured in non-vegetated sediments and in sediments which are inhabited by various plants. In the cohesive sediments, which are not affected by vegetation, a decrease in sulfate concentration, coupled with the presence of relatively high concentrations of hydrogen sulfide in the pore-waters and the presence of sulfide minerals as well the isotopic compositions of sulfur species are consistent with fast rates of sulfate reduction in the sediments. In the cohesive sediments affected by roots of Salicornia stricta and sediments desiccation, a cryptic sulfur cycle, which is characterized by microbial sulfate reduction coupled to fast reoxidation of hydrogen sulfide by Fe(III) (hydr)oxides and, possibly, by oxygen is present. Below the roots penetration depth, speciation of redox-sensitive elements is similar to those in the baren sediments. In the cohesive sediments affected by the roots of Spartina anglica and Triglochin maritima, which have longer roots, a cryptic sulfur cycle was detected in the upper 30 cm of sediments. At the sites that are characterized by permeable surface sediments and alternating permeable and cohesive layers in the deeper sediments, the composition of the sediment has a similar or even more significant impact on the speciation of the redox-sensitive elements than penetration of relatively weak roots of Spartina anglica. These sediments are characterized by the formation of hydrogen sulfide and sulfide oxidation intermediates in the cohesive layers and their diffusion to (and oxidation at) the boundaries between cohesive and permeable sediments. We conclude that in the cohesive sediments, the penetration of roots and desiccation leads to the formation of overall oxidized conditions, while in the sediments with alternating layers, permeability may provide a more significant control for speciation of redox-sensitive elements.
潮间带滩涂是高产的沿海海洋生态系统,受到环境条件快速变化的影响,其沉积物中的生物地球化学循环充满活力。穴居生物和植物根系的生物扰动强烈影响着潮间带沉积物中氧化还原敏感元素的种类和循环。在这项工作中,我们研究了沉积物类型和植被对翡翠湾(北海)及邻近地区沙质和泥质潮滩沉积物中硫、铁和锰等氧化还原敏感元素循环的影响。分析了孔隙水和总沉积物中这些元素的氧化还原分型。在无植被沉积物和有各种植物栖息的沉积物中测量了硫的同位素组成。在未受植被影响的粘性沉积物中,硫酸盐浓度下降,孔隙水中硫化氢浓度相对较高,硫化物矿物的存在以及硫的同位素组成都表明沉积物中硫酸盐的还原速度很快。在受盐生植物根系和沉积物干燥影响的粘性沉积物中,存在一个隐秘的硫循环,其特点是微生物的硫酸盐还原与硫化氢被铁(III)(氢)氧化物(可能还有氧气)快速再氧化相结合。在根系渗透深度以下,对氧化还原敏感的元素种类与巴伦沉积物中的相似。在受根系较长的 Spartina anglica 和 Triglochin maritima 根系影响的粘性沉积物中,在上层 30 厘米的沉积物中检测到隐性硫循环。在表层沉积物具有渗透性、深层沉积物中的渗透层和粘合层交替出现的地点,沉积物的成分对氧化还原敏感元素的种类影响类似于或甚至大于根系相对较弱的红豆杉根系的渗透。这些沉积物的特点是:硫化氢和硫化物氧化中间产物在粘性层中形成,并扩散到粘性沉积物和渗透性沉积物之间的边界(并在边界处氧化)。我们的结论是,在粘性沉积物中,根系的渗透和干燥会导致整体氧化条件的形成,而在具有交替层的沉积物中,渗透性可能对氧化还原敏感元素的标本化提供更重要的控制。
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引用次数: 0
Corrigendum to “Characterizing the stable oxygen isotopic composition of the Southeast Indian Ocean” [Marine Chemistry 262 (2024) 104397] 东南印度洋稳定氧同位素组成的特征"[《海洋化学》262 (2024) 104397]更正
IF 3 3区 地球科学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-10-14 DOI: 10.1016/j.marchem.2024.104460
Ryan H. Glaubke , Amy J. Wagner , Elisabeth L. Sikes
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引用次数: 0
Spatial and temporal dynamics of groundwater biogeochemistry in the deep subsurface of a high-energy beach 高能海滩深层地下水生物地球化学的时空动态变化
IF 3 3区 地球科学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-10-11 DOI: 10.1016/j.marchem.2024.104461
Anja Reckhardt , Rena Meyer , Stephan L. Seibert , Janek Greskowiak , Magali Roberts , Simone Brick , Grace Abarike , Kojo Amoako , Hannelore Waska , Kai Schwalfenberg , Iris Schmiedinger , Oliver Wurl , Michael Ernst Böttcher , Gudrun Massmann , Katharina Pahnke
Intertidal sandy beach systems are considered complex biogeochemical reactors. At beach sites that are subject to high tidal and wave energy, seawater circulation can reach tens of meters deep into the subsurface and changing environmental conditions are assumed to lead to dynamic groundwater flow paths, saltwater-freshwater mixing zones, and a spatio-temporally variable groundwater biogeochemistry. Previous studies mainly focused on the upper meters of subterranean estuaries (STE), while the deep subsurface remained a black box. This study presents spatial (cross-shore) and temporal (∼ six-weekly, over 1.5 years) dynamics of the groundwater biogeochemistry that were observed down to 24 m below the ground surface (mbgs) of a sandy high-energy beach on Spiekeroog Island (Germany).
In addition to redox conditions along a cross-shore transect ranging from oxic to Fe oxide reducing/slightly sulfidic, we found a previously unknown, distinct vertical redox zonation as well. Temporal variations of the biogeochemistry within low salinity groundwater at the most landward station close to the dune base were mainly driven by storm flood related seawater infiltration. Around the high water line, the extent of the upper saline plume (USP) varied over time. Furthermore, temporal dynamics of the O2 saturation at 6 mbgs indicated a seasonally shifting depth of the oxycline at this location. In the lower intertidal zone, groundwater solute concentrations displayed a temporally variable zone of deep freshwater discharge.
Regarding the impact of the deep STE on the groundwater biogeochemistry of the discharge zone, our data revealed that nutrient, Mn, and Fe release along the deep flow paths through the USP towards the discharge zone was limited, likely due decreasing availability of labile organic matter and subsequent slowing down of metabolic processes with depth. High concentrations of metabolites in the upper ∼ 2 mbgs of the discharge zone were, therefore, rather attributed to the incorporation of labile organic matter during continuous and storm flood related sediment relocation and/or the contribution of older waters, e.g., the subtidal saltwater wedge.
潮间带沙滩系统被认为是复杂的生物地球化学反应器。在潮汐能和波浪能较强的海滩地点,海水循环可深入地下数十米,环境条件的变化被认为会导致动态地下水流路径、咸淡水混合区和时空多变的地下水生物地球化学。以往的研究主要集中在地下河口(STE)的上层,而深层地下水仍是一个黑箱。本研究介绍了在德国斯皮克罗格岛(Spiekeroog Island)高能量沙质海滩地表下 24 米处观察到的地下水生物地球化学的空间(跨海岸)和时间(每六周一次,历时 1.5 年)动态变化。在靠近沙丘基部的最靠近陆地的站点,低盐度地下水中生物地球化学的时间变化主要是由暴雨洪水相关的海水渗透造成的。在高水位线附近,上盐羽流(USP)的范围随时间而变化。此外,6 mbgs 处的氧气饱和度的时间动态变化表明,该处的富氧层深度随季节变化。关于深层 STE 对排泄区地下水生物地球化学的影响,我们的数据显示,营养物质、锰和铁沿着穿过 USP 的深层水流路径向排泄区的释放是有限的,这可能是由于可溶解有机物的可用性降低以及随之而来的新陈代谢过程随深度的减慢。因此,排泄区上部 ∼ 2 mbgs 的代谢物浓度较高,可能是由于在与沉积物迁移相关的持续和暴雨洪水过程中吸附了可溶性有机物,以及/或老水(例如潮下咸水楔)的作用。
{"title":"Spatial and temporal dynamics of groundwater biogeochemistry in the deep subsurface of a high-energy beach","authors":"Anja Reckhardt ,&nbsp;Rena Meyer ,&nbsp;Stephan L. Seibert ,&nbsp;Janek Greskowiak ,&nbsp;Magali Roberts ,&nbsp;Simone Brick ,&nbsp;Grace Abarike ,&nbsp;Kojo Amoako ,&nbsp;Hannelore Waska ,&nbsp;Kai Schwalfenberg ,&nbsp;Iris Schmiedinger ,&nbsp;Oliver Wurl ,&nbsp;Michael Ernst Böttcher ,&nbsp;Gudrun Massmann ,&nbsp;Katharina Pahnke","doi":"10.1016/j.marchem.2024.104461","DOIUrl":"10.1016/j.marchem.2024.104461","url":null,"abstract":"<div><div>Intertidal sandy beach systems are considered complex biogeochemical reactors. At beach sites that are subject to high tidal and wave energy, seawater circulation can reach tens of meters deep into the subsurface and changing environmental conditions are assumed to lead to dynamic groundwater flow paths, saltwater-freshwater mixing zones, and a spatio-temporally variable groundwater biogeochemistry. Previous studies mainly focused on the upper meters of subterranean estuaries (STE), while the deep subsurface remained a black box. This study presents spatial (cross-shore) and temporal (∼ six-weekly, over 1.5 years) dynamics of the groundwater biogeochemistry that were observed down to 24 m below the ground surface (mbgs) of a sandy high-energy beach on Spiekeroog Island (Germany).</div><div>In addition to redox conditions along a cross-shore transect ranging from oxic to Fe oxide reducing/slightly sulfidic, we found a previously unknown, distinct vertical redox zonation as well. Temporal variations of the biogeochemistry within low salinity groundwater at the most landward station close to the dune base were mainly driven by storm flood related seawater infiltration. Around the high water line, the extent of the upper saline plume (USP) varied over time. Furthermore, temporal dynamics of the O<sub>2</sub> saturation at 6 mbgs indicated a seasonally shifting depth of the oxycline at this location. In the lower intertidal zone, groundwater solute concentrations displayed a temporally variable zone of deep freshwater discharge.</div><div>Regarding the impact of the deep STE on the groundwater biogeochemistry of the discharge zone, our data revealed that nutrient, Mn, and Fe release along the deep flow paths through the USP towards the discharge zone was limited, likely due decreasing availability of labile organic matter and subsequent slowing down of metabolic processes with depth. High concentrations of metabolites in the upper ∼ 2 mbgs of the discharge zone were, therefore, rather attributed to the incorporation of labile organic matter during continuous and storm flood related sediment relocation and/or the contribution of older waters, e.g., the subtidal saltwater wedge.</div></div>","PeriodicalId":18219,"journal":{"name":"Marine Chemistry","volume":"267 ","pages":"Article 104461"},"PeriodicalIF":3.0,"publicationDate":"2024-10-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142446926","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"地球科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Carbonate system and acidification of the Adriatic Sea 亚得里亚海的碳酸盐系统与酸化
IF 3 3区 地球科学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-10-11 DOI: 10.1016/j.marchem.2024.104462
Carolina Cantoni , Cinzia De Vittor , Jadran Faganeli , Michele Giani , Nives Kovač , Alenka Malej , Nives Ogrinc , Samo Tamše , Valentina Turk
Although the marginal seas represent only 7 % of the total area of the ocean, CO2 fluxes are important for the carbon budget, exposing them to the intense process of anthropogenic ocean acidification. The Adriatic Sea is currently a CO2 sink (−0.5 to −1 mol C m−2 y−1) with an annual flux comparable to the net sink rates in the NW Mediterranean. Based on a comparison of two winter cruises carried out in the 25-years interval between 1983 and 2008, an acidification rate of 0.003 pHT units y−1 was estimated in the northern Adriatic which is similar to the Mediterranean open waters (with recent estimations of −0.0028 ± 0.0003 pHT units y−1) and the surface coastal waters (−0.003 ± 0.001 and − 0.0044 ± 0.00006 pHT units y−1). The computed Revelle factor for the Adriatic Sea (approximately 10) indicates that the buffer capacity is rather high and that the waters do not appear to be particularly exposed to acidification. Total alkalinity (TA) in the Adriatic (2.6–2.7 mmol kg−1) is in the upper range of TA measured in the Mediterranean Sea. This is primarily due to the riverine inputs which transport carbonates dissolved from the Alpine dolomites and karstic watersheds. The Adriatic Sea is the second sub-basin (319 Gmol y−1), following the Aegean Sea (which receives the TA contribution from the Black Sea), that contribute to the riverine TA discharges into the Mediterranean Sea. About 60 % of the TA inflow into the Adriatic Sea is attributed to discharge from the Po River with a TA of ∼3 mmol kg−1 and TA decreases with increasing salinity. The north Adriatic dense water spreading and cascading is an efficient mechanism for exporting TA and DIC at depth, from the northern Adriatic towards the bottom of the South Adriatic Pit and possibly to the eastern Mediterranean. Saturation states indicate that the waters of the Adriatic are supersaturated throughout the year with respect to aragonite (ΩAr). However, the saturation state is considerably lower in the bottom water layers, due to the prevalence of the bottom layer and benthic remineralisation in the stratification period. Effects on calcifying organisms and phytoplankton are expected in the future.
虽然边缘海只占海洋总面积的 7%,但二氧化碳通量对碳预算非常重要,使其受到人为海洋酸化过程的严重影响。亚得里亚海目前是一个二氧化碳汇(-0.5 至 -1 摩尔 C m-2 y-1),其年通量与地中海西北部的净汇率相当。根据对 1983 年至 2008 年 25 年间两次冬季巡航的比较,估计亚得里亚海北部的酸化率为 0.003 pHT 单位年-1,与地中海开阔水域(最近的估计值为-0.0028 ± 0.0003 pHT 单位年-1)和沿岸表层水域(-0.003 ± 0.001 和 - 0.0044 ± 0.00006 pHT 单位年-1)相似。计算得出的亚得里亚海雷维尔因子(约 10)表明,亚得里亚海的缓冲能力相当高,水体似乎并不特别容易酸化。亚得里亚海的总碱度(TA)(2.6-2.7 mmol kg-1)处于地中海测得的总碱度的上限范围。这主要是由于从阿尔卑斯白云岩和喀斯特流域溶解的碳酸盐被河流输入所致。亚得里亚海是继爱琴海(接收来自黑海的 TA 量)之后,第二个向地中海排放河流 TA 量的子流域(319 Gmol y-1)。流入亚得里亚海的 TA 大约有 60% 来自波河,其 TA 为 3 mmol kg-1 左右,TA 随盐度增加而减少。北亚得里亚海稠密水域的扩散和层叠是将 TA 和 DIC 从亚得里亚海北部向南亚得里亚海海坑底部并可能向地中海东部深度输出的有效机制。饱和状态表明,亚得里亚海水域的文石(ΩAr)全年都处于过饱和状态。不过,底层水的饱和状态要低得多,这是由于底层水和底栖生物在分层期的再矿化现象普遍存在。预计未来会对钙化生物和浮游植物产生影响。
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Marine Chemistry
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