Winnie U. Chu, Matthew R. Mazloff, Ariane Verdy, Sarah G. Purkey, Bruce D. Cornuelle
Global climate change has impacted ocean biogeochemistry and physical dynamics, causing increases in acidity and temperature, among other phenomena. These changes can lead to deleterious effects on marine ecosystems and communities that rely on these ecosystems for their livelihoods. To better quantify these changes, an array of floats fitted with biogeochemical sensors (BGC-Argo) is being deployed throughout the ocean. This paper presents an algorithm for deriving a deployment strategy that maximizes the information captured by each float. The process involves using a model solution as a proxy for the true ocean state and carrying out an iterative process to identify optimal float deployment locations for constraining the model variance. As an example, we use the algorithm to optimize the array for observing ocean surface dissolved carbon dioxide concentrations (pCO2) in a region of strong air–sea gas exchange currently being targeted for BGC-Argo float deployment. We conclude that 54% of the pCO2 variability in the analysis region could be sampled by an array of 50 Argo floats deployed in specified locations. This implies a relatively coarse average spacing, though we find the optimal spacing is nonuniform, with a denser sampling being required in the eastern equatorial Pacific. We also show that this method could be applied to determine the optimal float deployment along ship tracks, matching the logistics of real float deployment. We envision this software package to be a helpful resource in ocean observational design anywhere in the global oceans.
{"title":"Optimizing observational arrays for biogeochemistry in the tropical Pacific by estimating correlation lengths","authors":"Winnie U. Chu, Matthew R. Mazloff, Ariane Verdy, Sarah G. Purkey, Bruce D. Cornuelle","doi":"10.1002/lom3.10641","DOIUrl":"10.1002/lom3.10641","url":null,"abstract":"<p>Global climate change has impacted ocean biogeochemistry and physical dynamics, causing increases in acidity and temperature, among other phenomena. These changes can lead to deleterious effects on marine ecosystems and communities that rely on these ecosystems for their livelihoods. To better quantify these changes, an array of floats fitted with biogeochemical sensors (BGC-Argo) is being deployed throughout the ocean. This paper presents an algorithm for deriving a deployment strategy that maximizes the information captured by each float. The process involves using a model solution as a proxy for the true ocean state and carrying out an iterative process to identify optimal float deployment locations for constraining the model variance. As an example, we use the algorithm to optimize the array for observing ocean surface dissolved carbon dioxide concentrations (pCO<sub>2</sub>) in a region of strong air–sea gas exchange currently being targeted for BGC-Argo float deployment. We conclude that 54% of the pCO<sub>2</sub> variability in the analysis region could be sampled by an array of 50 Argo floats deployed in specified locations. This implies a relatively coarse average spacing, though we find the optimal spacing is nonuniform, with a denser sampling being required in the eastern equatorial Pacific. We also show that this method could be applied to determine the optimal float deployment along ship tracks, matching the logistics of real float deployment. We envision this software package to be a helpful resource in ocean observational design anywhere in the global oceans.</p>","PeriodicalId":18145,"journal":{"name":"Limnology and Oceanography: Methods","volume":"22 11","pages":"840-852"},"PeriodicalIF":2.1,"publicationDate":"2024-08-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/lom3.10641","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142181786","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}
Zhentao Sun, Xinyu Li, Zhangxian Ouyang, Charles Featherstone, Eliot A. Atekwana, Najid Hussain, Wei-Jun Cai
Dissolved inorganic carbon (DIC) and its stable carbon isotope (δ13C-DIC) are valuable parameters for studying the aquatic carbon cycle and quantifying ocean anthropogenic carbon accumulation rates. However, the potential of this coupled pair is underexploited as only 15% or less of cruise samples have been analyzed for δ13C-DIC because the traditional isotope analysis is labor-intensive and restricted to onshore laboratories. Here, we improved the analytical precision and reported the protocol of an automated, efficient, and high-precision method for ship-based DIC and δ13C-DIC analysis based on cavity ring-down spectroscopy (CRDS). We also introduced a set of stable in-house standards to ensure accurate and consistent DIC and δ13C-DIC measurements, especially on prolonged cruises. With this method, we analyzed over 1600 discrete seawater samples over a 40-d cruise along the North American eastern ocean margin in summer 2022, representing the first effort to collect a large dataset of δ13C-DIC onboard of any oceanographic expedition. We evaluated the method's uncertainty, which was 1.2 μmol kg−1 for the DIC concentration and 0.03‰ for the δ13C-DIC value (1σ). An interlaboratory comparison of onboard DIC concentration analysis revealed an average offset of 2.0 ± 3.8 μmol kg−1 between CRDS and the coulometry-based results. The cross-validation of δ13C-DIC in the deep-ocean data exhibited a mean difference of only −0.03‰ ± 0.07‰, emphasizing the consistency with historical data. Potential applications in aquatic biogeochemistry are discussed.
{"title":"Simultaneous onboard analysis of seawater dissolved inorganic carbon (DIC) concentration and stable isotope ratio (δ13C-DIC)","authors":"Zhentao Sun, Xinyu Li, Zhangxian Ouyang, Charles Featherstone, Eliot A. Atekwana, Najid Hussain, Wei-Jun Cai","doi":"10.1002/lom3.10642","DOIUrl":"10.1002/lom3.10642","url":null,"abstract":"<p>Dissolved inorganic carbon (DIC) and its stable carbon isotope (<i>δ</i><sup>13</sup>C-DIC) are valuable parameters for studying the aquatic carbon cycle and quantifying ocean anthropogenic carbon accumulation rates. However, the potential of this coupled pair is underexploited as only 15% or less of cruise samples have been analyzed for <i>δ</i><sup>13</sup>C-DIC because the traditional isotope analysis is labor-intensive and restricted to onshore laboratories. Here, we improved the analytical precision and reported the protocol of an automated, efficient, and high-precision method for ship-based DIC and <i>δ</i><sup>13</sup>C-DIC analysis based on cavity ring-down spectroscopy (CRDS). We also introduced a set of stable in-house standards to ensure accurate and consistent DIC and <i>δ</i><sup>13</sup>C-DIC measurements, especially on prolonged cruises. With this method, we analyzed over 1600 discrete seawater samples over a 40-d cruise along the North American eastern ocean margin in summer 2022, representing the first effort to collect a large dataset of <i>δ</i><sup>13</sup>C-DIC onboard of any oceanographic expedition. We evaluated the method's uncertainty, which was 1.2 <i>μ</i>mol kg<sup>−1</sup> for the DIC concentration and 0.03‰ for the <i>δ</i><sup>13</sup>C-DIC value (1<i>σ</i>). An interlaboratory comparison of onboard DIC concentration analysis revealed an average offset of 2.0 ± 3.8 <i>μ</i>mol kg<sup>−1</sup> between CRDS and the coulometry-based results. The cross-validation of <i>δ</i><sup>13</sup>C-DIC in the deep-ocean data exhibited a mean difference of only −0.03‰ ± 0.07‰, emphasizing the consistency with historical data. Potential applications in aquatic biogeochemistry are discussed.</p>","PeriodicalId":18145,"journal":{"name":"Limnology and Oceanography: Methods","volume":"22 11","pages":"862-875"},"PeriodicalIF":2.1,"publicationDate":"2024-08-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142181787","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}
Nitrification rate measurements provide critical information on the performance of an environmental process central to the N cycle and are best studied using isotope labeling techniques. However, combining the high sensitivity of isotope labeling techniques with selected inhibition of nitrifiers as a whole or of specific nitrifier guilds has not been established in limnology. This can be achieved with different concentrations of the commonly used nitrification inhibitor allylthiourea (ATU). In the 15N-ammonium oxidation technique, the converted isotope label is typically captured in an excess pool of 14N-nitrite. Here, we assessed how different storage conditions affect the stability of the nitrite pool in freshwater samples treated with ATU. When stored frozen, the nitrite pool was rapidly destabilized to 25–31% after 7 d of storage and even to less than 5% after storage exceeding 90 d for samples treated with ATU, thus making them unusable for rate determinations in these cost and labor-intensive experiments. In comparison, this was not the case in marine samples or freshwater samples not treated with ATU, where the nitrite pool remained stable. Building on these results, we tested two options to stabilize nitrite during the storage of freshwater samples. The nitrite pool was stable if samples were stored at 4°C instead of freezing. We recommend this option for short-term storage. For long-term storage, samples should be supplemented with 0.5 mmol L−1 NaCl to increase salinity before freezing. As in marine samples, this stabilized the nitrite pool. Our results provide important guidance for the storage of non-saline samples used for nitrification rate measurements in freshwater environments.
{"title":"Stabilization of nitrite in the presence of the nitrification inhibitor allylthiourea (ATU) in freshwater nitrification rate measurements","authors":"Jade Bosviel, Katharina Kitzinger, Michael Pester","doi":"10.1002/lom3.10643","DOIUrl":"10.1002/lom3.10643","url":null,"abstract":"<p>Nitrification rate measurements provide critical information on the performance of an environmental process central to the N cycle and are best studied using isotope labeling techniques. However, combining the high sensitivity of isotope labeling techniques with selected inhibition of nitrifiers as a whole or of specific nitrifier guilds has not been established in limnology. This can be achieved with different concentrations of the commonly used nitrification inhibitor allylthiourea (ATU). In the <sup>15</sup>N-ammonium oxidation technique, the converted isotope label is typically captured in an excess pool of <sup>14</sup>N-nitrite. Here, we assessed how different storage conditions affect the stability of the nitrite pool in freshwater samples treated with ATU. When stored frozen, the nitrite pool was rapidly destabilized to 25–31% after 7 d of storage and even to less than 5% after storage exceeding 90 d for samples treated with ATU, thus making them unusable for rate determinations in these cost and labor-intensive experiments. In comparison, this was not the case in marine samples or freshwater samples not treated with ATU, where the nitrite pool remained stable. Building on these results, we tested two options to stabilize nitrite during the storage of freshwater samples. The nitrite pool was stable if samples were stored at 4°C instead of freezing. We recommend this option for short-term storage. For long-term storage, samples should be supplemented with 0.5 mmol L<sup>−1</sup> NaCl to increase salinity before freezing. As in marine samples, this stabilized the nitrite pool. Our results provide important guidance for the storage of non-saline samples used for nitrification rate measurements in freshwater environments.</p>","PeriodicalId":18145,"journal":{"name":"Limnology and Oceanography: Methods","volume":"22 10","pages":"752-758"},"PeriodicalIF":2.1,"publicationDate":"2024-08-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/lom3.10643","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142181788","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}
Bahar Mozfar, Anders Thorsen, Alejandro Mateos-Rivera, Geir Dahle, Rasmus Skern-Mauritzen, Henning Wehde, Bjørn A. Krafft
Accurate taxonomic classification and developmental stage determination of fish eggs are crucial for ecological monitoring, conservation efforts, and stock assessments. Traditional methods for fish and fisheries rely on visual examination of morphological traits, but they face challenges due to species overlap especially for early stages. Molecular tools, such as DNA barcoding, offer higher resolution in taxonomic identification but may not provide developmental stage information. This study explores the effectiveness of different formaldehyde fixation concentrations and storage procedures on fish eggs collected from Lofoten, Norway, for both visual and molecular analysis. Visual analysis successfully identified developmental stage for all fixation solutions. Molecular barcoding using the 16S rRNA gene identified up to 100% of eggs at the species level, with decreasing success rates over time when stored in formaldehyde fixation. The highest DNA barcoding success rates were accomplished using 4% formaldehyde fixation for 12- or 24-h following transfer to ethanol. Using 0.5% and 1% formaldehyde fixation up to 8 weeks also resulted in high DNA success rates, but results deteriorated with increasing storage time. This study provides valuable insights for integrating visual and molecular methods for fish egg analysis, with practical implications for sample preservation during marine surveys.
{"title":"Integrating visual and molecular approaches for fish eggs analysis: A study on formaldehyde fixation and storage procedures","authors":"Bahar Mozfar, Anders Thorsen, Alejandro Mateos-Rivera, Geir Dahle, Rasmus Skern-Mauritzen, Henning Wehde, Bjørn A. Krafft","doi":"10.1002/lom3.10640","DOIUrl":"10.1002/lom3.10640","url":null,"abstract":"<p>Accurate taxonomic classification and developmental stage determination of fish eggs are crucial for ecological monitoring, conservation efforts, and stock assessments. Traditional methods for fish and fisheries rely on visual examination of morphological traits, but they face challenges due to species overlap especially for early stages. Molecular tools, such as DNA barcoding, offer higher resolution in taxonomic identification but may not provide developmental stage information. This study explores the effectiveness of different formaldehyde fixation concentrations and storage procedures on fish eggs collected from Lofoten, Norway, for both visual and molecular analysis. Visual analysis successfully identified developmental stage for all fixation solutions. Molecular barcoding using the 16S rRNA gene identified up to 100% of eggs at the species level, with decreasing success rates over time when stored in formaldehyde fixation. The highest DNA barcoding success rates were accomplished using 4% formaldehyde fixation for 12- or 24-h following transfer to ethanol. Using 0.5% and 1% formaldehyde fixation up to 8 weeks also resulted in high DNA success rates, but results deteriorated with increasing storage time. This study provides valuable insights for integrating visual and molecular methods for fish egg analysis, with practical implications for sample preservation during marine surveys.</p>","PeriodicalId":18145,"journal":{"name":"Limnology and Oceanography: Methods","volume":"22 11","pages":"853-861"},"PeriodicalIF":2.1,"publicationDate":"2024-08-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/lom3.10640","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141885101","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}
Anna-Marie Klamt, Theis Kragh, Ronnie N. Glud, Cecilie M. Wagner, Kasper Reitzel
Diffusive equilibrium in thin films (DET) probes are passive samplers that are designed to reflect in situ porewater concentrations. In this study, we show that the gel and the plastic housing of DET probes store a substantial amount of oxygen (O2) that affects the chemical composition of porewater. To ensure complete deoxygenation, DET probes need to be treated for 7 d with continuous nitrogen flow. Such fully deoxygenated probes can be handled in the air (exposure time: < 90 s) and deployed to sediments through oxic water (exposure time: < 2 s) without significant ad(b)sorption of O2. Furthermore, we deployed a set of untreated (i.e., in equilibrium with atmospheric O2) and a set of fully deoxygenated DET probes to lake sediments. The O2 present in untreated DET probes altered iron (Fe) and phosphate (P) porewater profiles significantly. This is caused by the oxidation, immobilization, and accumulation of redox-sensitive Fe (oxyhydr)oxides in the probe over time. Since P has a high binding affinity to Fe (oxyhydr)oxides, it is not in equilibrium with the porewater and is overestimated as well. Our results highlight the importance of thorough deoxygenation of DET probes before deployment in sediments, especially when addressing redox-sensitive porewater species.
薄膜中的扩散平衡(DET)探头是一种被动采样器,旨在反映原位孔隙水浓度。在这项研究中,我们发现 DET 探针的凝胶体和塑料外壳会储存大量氧气 (O2),从而影响孔隙水的化学成分。为确保完全脱氧,DET 探针需要在氮气持续流动的情况下处理 7 天。这种完全脱氧的探针可以在空气中处理(暴露时间:90 秒),并通过含氧水(暴露时间:2 秒)部署到沉积物中,而不会产生大量的氧气吸附。此外,我们还在湖泊沉积物中布放了一组未经处理(即与大气中的 O2 处于平衡状态)的 DET 探针和一组完全脱氧的 DET 探针。未经处理的 DET 探针中存在的氧气显著改变了铁(Fe)和磷酸盐(P)的孔隙水剖面。这是由于对氧化还原敏感的铁(氧氢)氧化物在探针中随着时间的推移发生氧化、固定和积累而造成的。由于 P 与铁氧水氧化物有很高的结合亲和力,它与孔隙水不平衡,因此也被高估了。我们的研究结果突显了在沉积物中部署 DET 探针前彻底脱氧的重要性,尤其是在处理对氧化还原反应敏感的孔隙水物种时。
{"title":"Presence of oxygen in diffusive equilibrium in thin films (DET) probes: Effect on phosphate and iron porewater profiles and advice for correct deoxygenation and handling procedures","authors":"Anna-Marie Klamt, Theis Kragh, Ronnie N. Glud, Cecilie M. Wagner, Kasper Reitzel","doi":"10.1002/lom3.10639","DOIUrl":"10.1002/lom3.10639","url":null,"abstract":"<p>Diffusive equilibrium in thin films (DET) probes are passive samplers that are designed to reflect in situ porewater concentrations. In this study, we show that the gel and the plastic housing of DET probes store a substantial amount of oxygen (O<sub>2</sub>) that affects the chemical composition of porewater. To ensure complete deoxygenation, DET probes need to be treated for 7 d with continuous nitrogen flow. Such fully deoxygenated probes can be handled in the air (exposure time: < 90 s) and deployed to sediments through oxic water (exposure time: < 2 s) without significant ad(b)sorption of O<sub>2</sub>. Furthermore, we deployed a set of untreated (i.e., in equilibrium with atmospheric O<sub>2</sub>) and a set of fully deoxygenated DET probes to lake sediments. The O<sub>2</sub> present in untreated DET probes altered iron (Fe) and phosphate (P) porewater profiles significantly. This is caused by the oxidation, immobilization, and accumulation of redox-sensitive Fe (oxyhydr)oxides in the probe over time. Since P has a high binding affinity to Fe (oxyhydr)oxides, it is not in equilibrium with the porewater and is overestimated as well. Our results highlight the importance of thorough deoxygenation of DET probes before deployment in sediments, especially when addressing redox-sensitive porewater species.</p>","PeriodicalId":18145,"journal":{"name":"Limnology and Oceanography: Methods","volume":"22 10","pages":"759-770"},"PeriodicalIF":2.1,"publicationDate":"2024-07-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/lom3.10639","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141783544","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}
Claudia Frey, Weiyi Tang, Bess B. Ward, Moritz F. Lehmann
<p>The nitrogen (N) and oxygen (O) stable isotope analysis of dissolved nitrous oxide (N<sub>2</sub>O) can provide important constraints on the sources and cycling of N<sub>2</sub>O in aquatic environments. The isotopic composition of aqueous N<sub>2</sub>O, both in field (natural abundance) or experimental (<sup>15</sup>N-labeling) samples, however, may be altered by abiotic reactions involving nitrite (<span></span><math>