We report a 1,2,3-triazol fluoroionophore for detecting Na(+) that shows in vitro enhancement in the Na(+)-induced fluorescence intensity and decay time. The Na(+)-selective molecule 1 was incorporated into a hydrogel as a part of a fiber optical sensor. This sensor allows the direct determination of Na(+) in the range of 1-10 mM by measuring reversible fluorescence decay time changes.
Herein, we present a small and versatile optode system with integrated battery and logger for monitoring of O2, pH, and pCO2 in seawater. Three sensing materials designed for seawater measurements are optimized with respect to dynamic measurement range and long‐term stability. The spectral properties of the sensing materials were tailored to be compatible with a commercially available laboratory oxygen logger that was fitted into a pressure housing. Interchangeable sensor caps with appropriate “sensing chemistry” are conveniently attached to the end of the optical fiber. This approach allows using the same instrument for multiple analytes, which offers great flexibility and minimizes hardware costs. Applications of the new optode system were demonstrated by recording depth profiles for the three parameters during a research cruise in the Baltic Sea and by measuring surface water transects of pH. The optode was furthermore used to monitor the concentration of dissolved oxygen in a seagrass meadow in the Limfjord, Denmark, and sensor packages consisting of pO2, pH, and pCO2 were deployed in the harbors of Kiel, Germany, and Southampton, England, for 6 d. The measurements revealed that the system can resolve typical patterns in seawater chemistry related to spatial heterogeneities as well as temporal changes caused by biological and tidal activity.
The trace metal iron (Fe) is an essential micronutrient for phytoplankton growth and limits, or co-limits primary production across much of the world's surface ocean. Iron is a redox sensitive element, with Fe(II) and Fe(III) co-existing in natural waters. Whilst Fe(II) is the most soluble form, it is also transient with rapid oxidation rates in oxic seawater. Measurements of Fe(II) are therefore preferably undertaken in situ. For this purpose an autonomous wet chemical analyzer based on lab-on-chip technology was developed for the in situ determination of the concentration of dissolved (<0.45 µm) Fe species (Fe(II) and labile Fe) suitable for deployments in a wide range of aquatic environments. The spectrophotometric approach utilizes a buffered ferrozine solution and a ferrozine/ascorbic acid mixture for Fe(II) and labile Fe(III) analyses, respectively. Diffusive mixing, color development and spectrophotometric detection take place in three separate flow cells with different lengths such that the analyzer can measure a broad concentration range from low nM to several µM of Fe, depending on the desired application. A detection limit of 1.9 nM Fe was found. The microfluidic analyzer was tested in situ for nine days in shallow waters in the Kiel Fjord (Germany) along with other sensors as a part of the SenseOCEAN EU-project. The analyzer's performance under natural conditions was assessed with discrete samples collected and processed according to GEOTRACES protocol [acidified to pH < 2 and analyzed via inductively coupled plasma mass spectrometry (ICP-MS)]. The mechanical performance of the analyzer over the nine day period was good (consistent high precision of Fe(II) and Fe(III) standards with a standard deviation of 2.7% (n = 214) and 1.9% (n = 217), respectively, and successful completion of every programmed data point). However, total dissolved Fe was consistently low compared to ICP-MS data. Recoveries between 16 and 75% were observed, indicating that the analyzer does not measure a significant fraction of natural dissolved Fe species in coastal seawater. It is suggested that an acidification step would be necessary in order to ensure that the analyzer derived total dissolved Fe concentration is reproducible and consistent with discrete values.
A spectrophotometric approach for quantification of dissolved manganese (DMn) with 1-(2-pyridylazo)-2-naphthol (PAN) has been adapted for in situ application in coastal and estuarine waters. The analyser uses a submersible microfluidic lab-on-chip device, with low power (~ 1.5 W) and reagent consumption (63 µL per sample). Laboratory characterization showed an absorption coefficient of 40,838 ± 1127 L⋅mol−1⋅cm−1 and a detection limit of 27 nM, determined for a 34.6 mm long optical detection cell. Laboratory tests showed that long-term stability of the PAN reagent was achieved by addition of 4% v/v of a non-ionic surfactant (Triton-X100). To suppress iron (Fe) interferences with the PAN reagent, the Fe(III) masking agents deferoxamine mesylate (DFO-B) or disodium 4,5-dihydroxy-1,3-benzenedisulfonate (Tiron) were added and their Fe masking efficiencies were investigated. The analyser was tested during a deployment over several weeks in Kiel Fjord (Germany), with successful acquisition of 215 in situ data points. The time series was in good agreement with DMn concentrations determined from discretely collected samples analysed via inductively coupled plasma mass spectrometry (ICP-MS), exhibiting a mean accuracy of 87% over the full deployment duration (with an accuracy of > 99% for certain periods) and clear correlations to key hydrographic parameters.
<p>Understanding river-sea-systems requires a thorough understanding of processes that span different Earth system compartments. To overcome issues related to the interaction of different scientific disciplines and compartments, such as different measurement and calibration standards, quality control approaches and data formats for specific environmental parameters, joint measurement campaigns have been initiated within the Helmholtz Association&#8217;s MOSES (Modular Observation Solutions for Earth Systems) project. Following multiple senor comparison and intercalibration campaigns in 2019, MOSES&#8217; Hydrological Extremes event chain working group initiated joint field campaigns in summer 2020 covering the Elbe river from the Czech-German border to the tidal Elbe and further on into the estuary and the German Bight.</p><p>The fundamental objective was to establish scientifically sound and resilient multi-ship applicable sampling procedures and to create reference data for the main environmental parameters for future investigation of extreme events such as flooding and drought and their overall impact on the catchment region and the adjacent estuarine area of a large European fresh water / marine system. The campaign involved four research vessels, four research centers and spanned nearly two months. Measurements included standard hydrological and oceanographic parameters, as well as quantities relevant to the nutrient and carbonate system. Furthermore, selected water quality indicators and atmospheric measurements were performed. In the fresh water section of the Elbe river measurements were taken while drifting with the water mass. In the tidal section of the river sampling was done against the ebb current while in the North Sea a grid covering a large part of the German exclusive economic zone (EEZ) was sampled.</p><p>We detected a longitudinal increase of phytoplankton biomass along the 585 km freshwater part of the river towards the tidal system. In contrast, concentrations of dissolved nitrate and phosphate decreased to low values due the uptake by planktonic algae. The concentration of dissolved CO<sub>2</sub> decreased caused by increasing photosynthesis while the concentration of methane increased along the river stretch, particularly in the most downstream part when sedimentation of phytoplankton increased the organic load of sediments. The tidal part of the transect showed a strong influence of Hamburg harbor on almost all quantities, while downstream towards the estuary, the effects of the tidal cycle dominated variabilities. In the marine area, elevated chlorophyll concentrations were mainly found near the west coast of Schleswig-Holstein, probably mostly influenced by the Eider river outflow or the adjacent tidal flats. While most of the measured parameters showed an expected behavior relative to their individual compartments, the transfer of quantities between the compartments revealed rather complex and sometimes difficult to understand behaviors and patterns, especially when considering a functional quantitative analysis. The first results of this trans-compartment campaign showed that a quantitative understanding of the fate and dynamics of water constituents across compartments from the spring to the sea needs enhanced scientific collaboration and awareness to finally come to a better integrated understanding of physical, biogeochemical and biological processes from the local to the global scale.</p>
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