Accurate,
determinations of macronutrients (phosphate (PO
), nitrate (NO
), and silicic acid (H
SiO
)) in seawater in real time are essential to obtain information on their distribution, flux, and ...role in marine biogeochemical cycles. The development of robust sensors for long-term
analysis of macronutrients in seawater is a great challenge. Here, we present improvements of a commercial automated sensor for nutrients (including PO
, H
SiO
, and NO
plus NO
), suitable for a variety of aquatic environments. The sensor uses the phosphomolybdate blue method for PO
, the silicomolybdate blue method for H
SiO
and the Griess reagent method for NO
, modified with vanadium chloride as reducing agent for the determination of NO
. Here, we report the optimization of analytical conditions, including reaction time for PO
analysis, complexation time for H
SiO
analysis, and analyte to reagent ratio for NO
analysis. The instrument showed wide linear ranges, from 0.2 to 100 μM PO
, between 0.2 and 100 μM H
SiO
, from 0.5 to 100 μM NO
, and between 0.4 and 100 μM NO
, with detection limits of 0.18 μM, 0.15 μM, 0.45 μM, and 0.35 μM for PO
, H
SiO
, NO
, and NO
, respectively. The analyzer showed good precision with a relative standard deviation of 8.9% for PO
, 4.8% for H
SiO
, and 7.4% for NO
plus NO
during routine analysis of certified reference materials (KANSO, Japan). The analyzer performed well in the field during a 46-day deployment on a pontoon in the Kiel Fjord (located in the southwestern Baltic Sea), with a water supply from a depth of 1 m. The system successfully collected 443, 440, and 409
data points for PO
, Σ(NO
+ NO
), and H
SiO
, respectively. Time series data agreed well with data obtained from the analysis of discretely collected samples using standard reference laboratory procedures and showed clear correlations with key hydrographic parameters throughout the deployment period.
Autonomous
monitoring of orthophosphate (PO
), an important nutrient for primary production in natural waters, is urgently needed. Here, we report on the development and validation of an
autonomous ...electrochemical analyzer for PO
in seawater. The approach is based on the use of flow injection analysis in conjunction with a dual electrochemical cell (i.e., a bi-potentiostat detector (FIA-DECD) that uses two working electrodes sharing the same reference and counter electrode. The two working electrodes are used (molybdate/carbon paste electrode (CPE) and CPE) to correct for matrix effects. Optimization of squarewave voltammetry parameters (including step potential, amplitude, and frequency) was undertaken to enhance analytical sensitivity. Possible interferences from non-ionic surfactants and humic acid were investigated. The limit of quantification in artificial seawater (30 g/L NaCl, pH 0.8) was 0.014 µM for a linear concentration range of 0.02-3 µM. The system used a Python script for operation and data processing. The analyzer was tested for ship-board PO
determination during a four-day research cruise in the North Sea. The analyzer successfully measured 34 samples and achieved a good correlation (Pearson' R = 0.91) with discretely collected water samples analyzed using a laboratory-based colorimetric reference analyzer.
•A novel stoichiometric approach called the Cseep method was developed and used to.•Predict natural DIC variations around the Goldeneye site in the north-western North Sea.•Establish a process-based ...baseline DIC concentration (Cb) with minimal variability.•Determine CO2 seepage detection threshold (DT) to reliably differentiate subsea released−CO2 signal from natural variability.•Quantify DIC concentration of subsea released−CO2 dissolved in the sampled seawater.
Carbon Capture and Storage (CCS) is a potential significant mitigation strategy to combat climate change and ocean acidification. The technology is well understood but its current implementation must be scaled up nearly by a hundredfold to become an effective tool that helps meet mitigation targets. Regulations require monitoring and verification at storage sites, and reliable monitoring strategies for detection and quantification of seepage of the stored carbon need to be developed. The Cseep method was developed for reliable determination of CO2 seepage signal in seawater by estimating and filtering out natural variations in dissolved inorganic carbon (C). In this work, we analysed data from the first-ever subsea CO2 release experiment performed in the north-western North Sea by the EU STEMM−CCS project. We successfully demonstrated the ability of the Cseep method to (i) predict natural C variations around the Goldeneye site over seasonal to interannual time scales; (ii) establish a process-based baseline C concentration with minimal variability; (iii) determine CO2 seepage detection threshold (DT) to reliably differentiate released−CO2 signal from natural variability and quantify released−CO2 dissolved in the sampled seawater. DT values were around 20 % of the natural C variations indicating high sensitivity of the method. Moreover, with the availability of DT value, the identification of released−CO2 required no pre-knowledge of seepage occurrence, but we used additional available information to assess the confidence of the results. Overall, the Cseep method features high sensitivity, automation suitability, and represents a powerful future monitoring tool both for large and confined marine areas.
•Approaches for CO2 leakage detection, attribution and quantification monitoring exist.•Many approaches cover multiple monitoring tasks simultaneously.•Sonars and chemical sensors on ships or AUVs ...can cover large areas.•Newer, more specific technologies can detect, verify and quantify smaller, localised leaks.
Environmental monitoring of offshore Carbon Capture and Storage (CCS) complexes requires robust methodologies and cost-effective tools to detect, attribute and quantify CO2 leakage in the unlikely event it occurs from a sub-seafloor reservoir. Various approaches can be utilised for environmental CCS monitoring, but their capabilities are often undemonstrated and more detailed monitoring strategies need to be developed. We tested and compared different approaches in an offshore setting using a CO2 release experiment conducted at 120 m water depth in the Central North Sea. Tests were carried out over a range of CO2 injection rates (6 - 143 kg d−1) comparable to emission rates observed from abandoned wells. Here, we discuss the benefits and challenges of the tested approaches and compare their relative cost, temporal and spatial resolution, technology readiness level and sensitivity to leakage. The individual approaches demonstrate a high level of sensitivity and certainty and cover a wide range of operational requirements. Additionally, we refer to a set of generic requirements for site-specific baseline surveys that will aid in the interpretation of the results. Critically, we show that the capability of most techniques to detect and quantify leakage exceeds the currently existing legal requirements.
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
⋅cm
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.
Concentrations of heme b were determined in a mesocosm experiment situated in Gullmar Fjord off Sweden. The mesocosm experiment lasted for ca. one hundred days and was characterised by the growth of ...a primary nutrient replete and a secondary nutrient deplete phytoplankton bloom. Heme b varied between 40 ± 10 pmol L-1 in the prebloom period up to a maximum of 700 ± 400 pmol L-1 just prior to the time of the primary chlorophyll a maximum. Thereafter, heme b concentrations decreased again to an average of 120 ± 60 pmol L-1. When normalised to total particulate carbon, heme b was most abundant during the initiation of the nutrient replete spring bloom, when ratios reached 52 ± 24 μmol mol-1; ten times higher than values observed both pre and post the primary bloom. Concentrations of heme b correlated with those of chlorophyll a. Nevertheless, differences were observed in the relative concentrations of the two parameters, with heme b concentrations increasing relative to chlorophyll a during the growth of the primary bloom, decreasing over the period of the secondary bloom and increasing again through the latter period of the experiment. Heme b abundance was therefore influenced by nutrient concentrations and also likely by changing community composition. In half of the mesocosms, pCO2 was elevated and maintained at ca.1000 μatm, however we observed no significant differences between heme b in plus or ambient pCO2 mesocosms, either in absolute terms, or relative to total particulate carbon and chlorophyll a. The results obtained in this study contribute to our understanding of the distribution of this significant component of the biogenic iron pool, and provide an iron replete coastal water end member that aids the interpretation of the distributions of heme b in more iron deplete open ocean waters.
High quality pH measurements are required in estuarine and coastal waters to assess the impacts of anthropogenic atmospheric CO
2
emissions on the marine carbonate system, including the resulting ...decrease in pH. In addition, pH measurements are needed to determine impacts on carbonate chemistry of phytoplankton blooms and their breakdown, following enhanced anthropogenic nutrient inputs. The spectrophotometric pH technique provides high quality pH data in seawater, and is advantageous for long-term deployments as it is not prone to drift and does not require
in situ
calibration. In this study, a field application of a fully automated submersible spectrophotometric analyzer for high-resolution
in situ
pH measurements in dynamic estuarine and coastal waters is presented. A Lab-on-Chip (LOC) pH sensor was deployed from a pontoon in the inner Kiel Fjord, southwestern Baltic Sea, for a total period of 6 weeks. We present a time-series of
in situ
pH
T
(total pH scale) and ancillary data, with sensor validation using discretely collected samples for pH
T
and laboratory analysis. The difference between the sensor and laboratory analyses of discrete samples was within ±0.015 pH
T
unit, with a mean difference of 0.001 (n=65), demonstrating that the LOC sensor can provide stable and accurate pH
T
measurements over several weeks.
Ocean acidification may affect zooplankton directly by decreasing in pH, as well as indirectly via trophic pathways, where changes in carbon availability or pH effects on primary producers may ...cascade up the food web thereby altering ecosystem functioning and community composition. Here, we present results from a mesocosm experiment carried out during 113 days in the Gullmar Fjord, Skagerrak coast of Sweden, studying plankton responses to predicted end-of-century pCO2 levels. We did not observe any pCO2 effect on the diversity of the mesozooplankton community, but a positive pCO2 effect on the total mesozooplankton abundance. Furthermore, we observed species-specific sensitivities to pCO2 in the two major groups in this experiment, copepods and hydromedusae. Also stage-specific pCO2 sensitivities were detected in copepods, with copepodites being the most responsive stage. Focusing on the most abundant species, Pseudocalanus acuspes, we observed that copepodites were significantly more abundant in the high-pCO2 treatment during most of the experiment, probably fuelled by phytoplankton community responses to high-pCO2 conditions. Physiological and reproductive output was analysed on P. acuspes females through two additional laboratory experiments, showing no pCO2 effect on females' condition nor on egg hatching. Overall, our results suggest that the Gullmar Fjord mesozooplankton community structure is not expected to change much under realistic end-of-century OA scenarios as used here. However, the positive pCO2 effect detected on mesozooplankton abundance could potentially affect biomass transfer to higher trophic levels in the future.
COVID-19 has resulted in widespread changes, including within the realm of sports. Professional soccer has adapted by allowing more substitutions, leading to tactical adjustments and potential ...physical benefits. Accordingly, this study analyzed the impact of the new rule in Italian top-level soccer, focusing on substitution patterns and performance differences between the pre-COVID (2017–2018, 2018–2019 seasons) and post COVID (2020–2021, 2021–2022 seasons) eras. As such, publicly available data from 1520 matches (760 matches per era) were recorded. The sample included matches played from 40 Italian top division teams in both the pre- and post-COVID eras. Analyses confirmed substitutions follow a consistent temporal pattern throughout the match in both eras, highlighting a slight difference in second-half management, and showed the new rule is still not used to its full potential, thus raising concerns about teams’ financial strength, as not all managers possess “deep benches” (i.e., a large number of top-level players available to play). Further analyses revealed a statistically significant increment (p = 0.002) in the quantity of collectively produced sprints in the post-COVID era compared to the pre-COVID one. The results from this study emphasize the need to carefully address sprint preparation and repeated sprint abilities, also considering factors such as the number of substitutes and their skill level.
Orthologs separate after lineages split from each other and paralogs after gene duplications. Thus, orthologs are expected to remain more functionally coherent across lineages, while paralogs have ...been proposed as a source of new functions. Because protein functional divergence follows from non-synonymous substitutions, we performed an analysis based on the ratio of non-synonymous to synonymous substitutions (dN/dS), as proxy for functional divergence. We used five working definitions of orthology, including reciprocal best hits (RBH), among other definitions based on network analyses and clustering. The results showed that orthologs, by all definitions tested, had values of dN/dS noticeably lower than those of paralogs, suggesting that orthologs generally tend to be more functionally stable than paralogs. The differences in dN/dS ratios remained suggesting the functional stability of orthologs after eliminating gene comparisons with potential problems, such as genes with high codon usage biases, low coverage of either of the aligned sequences, or sequences with very high similarities. Separation by percent identity of the encoded proteins showed that the differences between the dN/dS ratios of orthologs and paralogs were more evident at high sequence identity, less so as identity dropped. The last results suggest that the differences between dN/dS ratios were partially related to differences in protein identity. However, they also suggested that paralogs undergo functional divergence relatively early after duplication. Our analyses indicate that choosing orthologs as probably functionally coherent remains the right approach in comparative genomics.
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