Posts Tagged 'methods'

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A geographic weighted regression approach for improved total alkalinity estimates in the Northern Gulf of Mexico

Published 10 January 2022 Science Closed
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Highlights

  • Algorithms were developed to estimate total alkalinity in northern Gulf of Mexico.
  • Use of chlorophyll a addressed the biological and chemical complexities.
  • Geographically weighted regression produced the best estimates.

Abstract

Total alkalinity (TA) is one of the important parameters to show the intensity of seawater buffer against ocean acidification. TA dynamics in the northern Gulf of Mexico (N-GoM) is significantly affected by the Mississippi River. An empirical TA algorithm is offered here which accounts for the local effects of coastal processes. In situ data collected during numerous research cruises in the N-GoM were compiled and used to develop TA algorithms using sea surface temperature (SST) and sea surface salinity (SSS) as explanatory variables. After improving the coefficients and functional form of this algorithm, chlorophyll a (Chl-a) was included as an additional explanatory variable, which worked as a proxy for addressing the pronounced effects of biological forcing on coastal waters. Finally, a geographically weighted regression algorithm was developed in the form TA = exp[Xo + X1(SSS-35)2+X2(SSSxSST)1/2+X3chl-a] to address spatial non-stationarity, which produced improved estimates of TA in the N-GoM.

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Micro-CT image gallery visually presenting the effects of ocean warming and acidification on marine gastropod shells

Published 5 January 2022 Science Closed
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Background

Digitisation of specimens (e.g. zoological, botanical) can provide access to advanced morphological and anatomical information and promote new research opportunities. The micro-CT technology may support the development of “virtual museums” or “virtual laboratories” where digital 3D imaging data are shared widely and freely. There is currently a lack of universal standards concerning the publication and curation of micro-CT datasets.

New information

The aim of the current project was to create a virtual gallery with micro-CT scans of individuals of the marine gastropod Hexaplex trunculus, which were maintained under a combination of increased temperature and low pH conditions, thus simulating future climate change scenarios. The 3D volume-rendering models created were used to visualise the structure properties of the gastropods shells. Finally, the 3D analysis performed on the micro-CT scans was used to investigate potential changes in the shell properties of the gastropods. The derived micro-CT 3D images were annotated with detailed metadata and can be interactively displayed and manipulated using online tools through the micro-CT virtual laboratory, which was developed under the LifeWatchGreece Research Infrastructure for the dissemination of virtual image galleries collection supporting the principles of FAIR data.

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Biogeochemical feedbacks to ocean acidification in a cohesive photosynthetic sediment

Published 10 December 2021 Science Closed
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Ecosystem feedbacks in response to ocean acidification can amplify or diminish diel pH oscillations in productive coastal waters. Benthic microalgae generate such oscillations in sediment porewater and here we ask how CO2 enrichment (acidification) of the overlying seawater alters these in the absence and presence of biogenic calcite. We placed a 1-mm layer of ground oyster shells, mimicking the arrival of dead calcifying biota (+Calcite), or sand (Control) onto intact silt sediment cores, and then gradually increased the pCO2 in the seawater above half of +Calcite and Control cores from 472 to 1216 μatm (pH 8.0 to 7.6, CO2:HCO3− from 4.8 to 9.6 × 10−4). Porewater [O2] and [H+] microprofiles measured 16 d later showed that this enrichment had decreased the O2 penetration depth (O2-pd) in +Calcite and Control, indicating a metabolic response. In CO2-enriched seawater: (1) sediment biogeochemical processes respectively added and removed more H+ to and from the sediment porewater in darkness and light, than in ambient seawater increasing the amplitude of the diel porewater [H+] oscillations, and (2) in darkness, calcite dissolution in +Calcite sediment decreased the porewater [H+] below that in overlying seawater, reversing the sediment–seawater H+ flux and decreasing the amplitude of diel [H+] oscillations. This dissolution did not, however, counter the negative effect of CO2 enrichment on O2-pd. We now hypothesise that feedback to CO2 enrichment—an increase in the microbial reoxidation of reduced solutes with O2—decreased the sediment O2-pd and contributed to the enhanced porewater acidification.

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Ocean alkalinity enhancement – avoiding runaway CaCO3 precipitation during quick and hydrated lime dissolution

Published 10 December 2021 Science Closed
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Ocean Alkalinity Enhancement (OAE) has been proposed as a method to remove carbon dioxide (CO2) from the atmosphere and to counteract ocean acidification. It involves the dissolution of alkaline minerals such as quick lime, CaO, and hydrated lime, Ca(OH)2. However, a critical knowledge gap exists regarding their dissolution in natural seawater. Particularly, how much can be dissolved before secondary precipitation of calcium carbonate (CaCO3) occurs is yet to be established. Secondary precipitation should be avoided as it reduces the atmospheric CO2 uptake potential of OAE. Here we show that both CaO and Ca(OH)2 powders (> 63 µm of diameter) dissolved in seawater within a few hours. However, CaCO3 precipitation, in the form of aragonite, occurred at a saturation (ΩAr) threshold of about 5. This limit is much lower than what would be expected for typical pseudo-homogeneous precipitation in the presence of colloids and organic materials. Secondary precipitation at unexpectedly low ΩAr was the result of so-called heterogeneous precipitation onto mineral phases, most likely onto CaO and Ca(OH)2 prior to full dissolution. Most importantly, this led to runaway CaCO3 precipitation by which significantly more alkalinity (TA) was removed than initially added, until ΩAr reached levels below 2. Such runaway precipitation would reduce the CO2 uptake efficiency from about 0.8 moles of CO2 per mole of TA down to only 0.1 mole of CO2 per mole of TA. Runaway precipitation appears to be avoidable by dilution below the critical ΩAr threshold of 5, ideally within hours of the addition to minimise initial CaCO3 precipitation. Finally, model considerations suggest that for the same ΩAr threshold, the amount of TA that can be added to seawater would be more than three times higher at 5 °C than at 30 °C, and that equilibration to atmospheric CO2 levels during mineral dissolution would further increase it by a factor of ~6 and ~3 respectively.

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Surface pCO2 variability in two contrasting basins of North Indian Ocean using satellite data

Published 6 December 2021 Science Closed
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Highlights

  • The spatiotemporal variability of surface pCO2 in the BoB is dominated by the influx of riverine freshwater.
  • SST and chlorophyll are the decisive factors governing the variability of pCO2 in the AS.
  • Tropical cyclone induced surface cooling and biogeochemical processes, affecting the pCO2 distribution in the BoB.

Abstract

The spatial and temporal variability of the partial pressure of carbon dioxide (pCO2) over the northern tropical Indian Ocean was estimated based on satellite-derived sea surface temperature (SST), sea surface salinity (SSS), and chlorophyll concentration (Chl-a). The distribution of sea surface pCO2 is controlled by various physical processes, such as mixing, entrainment, upwelling, and advection, and by associated biological processes, such as phytoplankton blooms. The results showed lower surface water pCO2 over the Bay of Bengal (BoB) (< 300 μatm) as compared to the Arabian Sea (AS), which could be attributed to low salinity during the northeast monsoon season (December–January) in the BoB. High pCO2 values (> 500 μatm) were found near the Somali coast during the southwest monsoon season (June–August) caused by intense coastal upwelling. The pCO2 over BoB (400–450 μatm) was more than that of the AS in the fall inter-monsoon season (September–November) as a response to the relatively warmer SST over the BoB. The highest spatiotemporal variability of surface pCO2 was observed in the western AS near to the coast and over the northern BoB as a response to the higher variability in biological productivity and salinity, respectively, over these regions. The effect of tropical cyclones on pCO2 variability over the BoB was also assessed in this study. The sea surface pCO2 values were found to be much smaller along the cyclone track after the passage of cyclones because of the strong SST drop and the sudden phytoplankton blooms caused by the entrainment and vertical mixing of subsurface cold and nutrient-rich water with surface water. The cyclone-induced surface cooling and the associated decrease in surface water pCO2 were found to be higher after the passage of the Madi cyclone compared to the Hudhud cyclone.

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Buffered accelerated weathering of limestone for storing CO2: chemical background

Published 1 December 2021 Science Closed
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Highlights

  • A method to store permanently CO2 in seawater in form of bicarbonates is discussed.
  • The method is an evolution of the Accelerated Weathering of Limestone (AWL).
  • Ca(OH)2 is added to buffer the unreacted CO2 before the discharge in seawater.
  • BAWL overcomes the main limitations of AWL and buffers ocean acidification.
  • A preliminary storage cost is 100 € per tonne of CO2 coming from an external source.

Abstract

We present an evolution of the Accelerated Weathering of Limestone (AWL) method to store CO2 in seawater in the form of bicarbonates. Buffered Accelerated Weathering of Limestone (BAWL) is designed to produce a buffered ionic solution, at seawater pH, which derives from the reaction between a CO2 stream and a powder of micron-sized calcium carbonate particles in a long tubular reactor. Addition of calcium hydroxide to buffer the unreacted CO2 before the discharge in seawater is also provided. BAWL aims to overcome the main limitations of AWL, such as the high amount of water needed, the large size of the reactor, the risk of CO2 degassing back into the atmosphere, if the ionic solution is released into shallow waters, as well as the induced seawater acidification. This paper presents the chemical background of the technology and evaluates its feasibility by considering the chemical equilibria in the different phases of the process. The CO2 emitted for limestone calcination leads to a 24% CO2 penalty; a preliminary cost analysis assesses a storage cost of 100 € per tonne of CO2 from an external source. It finally discusses the main features to be considered for the design at the industrial scale.

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Data-based estimates of interannual sea–air CO2 flux variations 1957–2020 and their relation to environmental drivers

Published 23 November 2021 Science Closed
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This study considers year-to-year and decadal variations as well as secular trends of the sea–air CO2 flux over the 1957–2020 period, as constrained by the pCO2 measurements from the SOCAT data base. In a first step, we relate interannual anomalies in ocean-internal carbon sources and sinks to local interannual anomalies in sea surface temperature (SST), the temporal changes of SST (dSST/dt), and squared wind speed (u2), employing a multi-linear regression. In the tropical Pacific, we find interannual variability to be dominated by dSST/dt, as arising from variations in the upwelling of colder and more carbon-rich waters into the mixed layer. In the eastern upwelling zones as well as in circumpolar bands in the high latitudes of both hemispheres, we find sensitivity to wind speed, compatible with the entrainment of carbon-rich water during wind-driven deepening of the mixed layer and wind-driven upwelling. In the Southern Ocean, the secular increase in wind speed leads to a secular increase in the carbon source into the mixed layer, with an estimated reduction of the sink trend in the range 17 to 42 %. In a second step, we combined the result of the multi-linear regression and an explicitly interannual pCO2-based additive correction into a “hybrid” estimate of the sea–air CO2 flux over the period 1957–2020. As a pCO2 mapping method, it combines (a) the ability of a regression to bridge data gaps and extrapolate into the early decades almost void of pCO2 data based on process-related observables and (b) the ability of an autoregressive interpolation to follow signals even if not represented in the chosen set of explanatory variables. The “hybrid” estimate can be applied as ocean flux prior for atmospheric CO2 inversions covering the whole period of atmospheric CO2 data since 1957.

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Experimentally decomposing phytoplankton community change into ecological and evolutionary contributions

Published 19 November 2021 Science Closed
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  1. Shifts in microbial communities and their functioning in response to environmental change result from contemporary interspecific and intraspecific diversity changes. Interspecific changes are driven by ecological shifts in species composition, while intraspecific changes are here assumed to be dominated by evolutionary shifts in genotype frequency. Quantifying the relative contributions of interspecific and intraspecific diversity shifts to community change thus addresses the essential, yet understudied question as to how important ecological and evolutionary contributions are to total community changes. This debate is to date practically constrained by (a) a lack of studies integrating across organizational levels and (b) a mismatch between data requirements of existing partitioning metrics and the feasibility to collect such data, especially in microscopic organisms like phytoplankton.
  2. We experimentally assessed the relative ecological and evolutionary contributions to total phytoplankton community changes using a new design and validated its functionality by comparisons to established partitioning metrics. We used a community of coexisting Emiliania huxleyi and Chaetoceros affinis with initially nine genotypes each. First, we exposed the community to elevated CO2 concentration for 80 days (~50 generations) to induce interspecific and intraspecific diversity changes and a total abundance change. Second, we independently manipulated the induced interspecific and intraspecific diversity changes in an assay to quantify the corresponding ecological and evolutionary contributions to the total change. Third, we applied existing partitioning metrics to our experimental data and compared the outcomes.
  3. Total phytoplankton abundance declined to one-fifth in the high CO2 exposed community compared to ambient conditions. Consistently across all applied partitioning metrics, the abundance decline could predominantly be explained by ecological shifts and to a low extent by evolutionary changes.
  4. We discuss potential consequences of the observed community changes on ecosystem functioning. Furthermore, we explain that the low evolutionary contributions likely resulted of intraspecific diversity changes that occurred irrespectively of CO2. We discuss how the assay could be upscaled to more realistic settings, including more species and drivers. Overall, the presented calculations of eco-evolutionary contributions to phytoplankton community changes constitute another important step towards understanding future phytoplankton shifts, and eco-evolutionary dynamics in general.
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The promotion of stress tolerant Symbiodiniaceae dominance in juveniles of two coral species due to simulated future conditions of ocean warming and acidification

Published 12 November 2021 Science Closed
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The symbiotic relationship between coral and its endosymbiotic algae, Symbiodiniaceae, greatly influences the hosts’ potential to withstand environmental stress. To date, the effects of climate change on this relationship has primarily focused on adult corals. Uncovering the effects of environmental stress on the establishment and development of this symbiosis in early life stages is critical for predicting how corals may respond to climate change. To determine the impacts of future climate projections on the establishment of symbionts in juvenile corals, ITS2 amplicon sequencing of single coral juveniles was applied to Goniastrea retiformis and Acropora millepora before and after exposure to three climate conditions of varying temperature and pCO2 levels (current and RCP8.5 in 2050 and 2100). Compared to ambient conditions, juvenile corals experienced shuffling in the relative abundance of Cladocopium (C1m, reduction) to Durusdinium (D1 and D1a, increase) over time. We calculated a novel risk metric incorporating functional redundancy and likelihood of impact on host physiology to identify the loss of D1a as a ‘low risk’ to the coral compared to the loss of “higher risk” taxa like D1 and C1m. Although the increase in stress tolerant Durusdinium under future warming was encouraging for A. millepora, by 2100, G. retiformis communities displayed signs of symbiosis de-regulation, suggesting this acclimatory mechanism may have species-specific thresholds. These results emphasize the need for understanding of long-term effects of climate change induced stress on coral juveniles and their potential for increased acclimation to heat tolerance through changes in symbiosis.

Originality Statement Here we assessed changes in the uptake and establishment of Symbiodiniaceae in the early lifehistory stages of two coral species under future climate scenarios. Our study represents the first such assessment of future climate change projections (increased temperature and pCO2) influencing Symbiodiniaceae acquisition and specifically shows a community structure dominated by the stress tolerant genus Durusdinium. We also develop a novel risk metric that includes taxonomic function and redundancy to estimate the impact of symbiont taxa changes on coral physiology. Through the risk metric, we relate the stress-induced changes in symbiont community structure to the likelihood of functional loss to better understand the extent to which these changes may lead to a decrease in coral health.

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Development of ocean acidification endpoint characterization model for life cycle assessment

Published 10 November 2021 Science Closed
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Ocean acidification, also referred to as the evil twin of global warming, occurs due to the CO2 absorption of the oceans from the atmosphere. Both the pH and carbonate saturations are altered with this absorption process. The optimal operating conditions of the biological systems in the marine environment are therefore no longer maintained. The marine species are reacting in various ways to this change, eventually leading to a loss in biodiversity. With the current trend in emissions, the pH levels of the oceans are expected to decrease from 8.1 to 7.8 by the end of the century. In combination with the other stressors, it is projected that OA will have a wide range of impacts on marine life and its services to humanity. The representation of these implications is limited in environmental assessment tools such as Life Cycle Assessment.

This research explores the relationship between the changing acidity of the oceans and marine biodiversity loss. This relation is quantified through utilizing the ecotoxicology impact assessment approach for LCA. Following this approach, an endpoint characterization model is developed for ocean acidification. The approach consists of the development and integration of fate, exposure, effect and damage models. The fate model, expressing the relation between the GHG emissions (CO2, CO, CH4) and change in acidity of the ocean is based on the work of Bach et al. (2016). The effect model has been developed by constructing species sensitivity distributions utilizing species response data from 5 taxonomic groups (mollusca, echinodermata, fish, cnidaria, crustacea) to obtain the potentially affected fraction of species with changing pH. Furthermore, 3 different categorizations (climate zones, calcification, exposure duration) were made to assess their effects on species responses. The results revealed that there is no significant difference in responses based on different exposure durations or climate zones. Calcifying species on the other hand is found to have a higher sensitivity to ocean acidification as the change in carbonate chemistry directly influences the shell and skeleton formation of these organisms. Lastly, these models were integrated into an endpoint characterization model for ocean acidification. From the 3 GHG emissions included within the scope of this research, CO2 has the highest (CFCO2 = 4.883 × 104 (𝑃𝐷𝐹)𝑚3/𝑘𝑔𝐺𝐻𝐺) and CH4 has the lowest (CFCH4 = 4.072 × 104 𝑃𝐷𝐹)𝑚3/𝑘𝑔𝐺𝐻𝐺) impact on marine biodiversity loss due to OA. These ecosystem damage indicators can be utilized in the impact assessment phase of the Life Cycle Assessment to translate the inventory results into impact on marine biodiversity.

Through the quantification of the impacts of ocean acidification, the effects of this major stressor on marine life can be better understood and targeted strategies can be developed. However, more research is required to increase the robustness of these models through expanding the species scope and incorporating temporal and geographical aspects into the models. Furthermore, the cascading effects of the changing ocean pH are still unknown and its consequences on ecosystems and socio-economic structures are unprecedented. To establish science-based targets and strategies to conserve the species richness in marine life, the extent of our understanding of the damage caused by anthropogenic actions needs to be further explored and estimated for the future.

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A low-cost, accessible, and high-performing Arduino-based seawater pH control system for biological applications

Published 10 November 2021 Science Closed
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Highlights

  • Seawater pH control system for marine biological experiments.
  • Low-cost aquarium pH control alternative to more expensive options.
  • Accessible to researchers with little instrument development or coding experience.
  • Adaptable system to fit a variety of marine species and experimental designs.

Abstract

In the last two decades, the need for seawater pH control methodologies paralleled the rise in attention to the biological impacts of ocean acidification. Many effective and high-performing systems have been created, but they are often expensive, complex, and difficult to establish. We developed a system that is similarly high performing, but at a low cost and with a simple and accessible design. This system is controlled by an Arduino Nano, an open-source electronics platform, which regulates the flow of CO2 gas through electric solenoid valves. The Arduino and other inexpensive materials total ∼$150 (plus CO2 gas and regulator), and a new treatment can be added for less than $35. Easy-to-learn code and simple wire-to-connect hardware make the design extremely accessible, requiring little time and expertise to establish. The system functions with a variety of pH probes and can be adapted to fit a variety of experimental designs and organisms. Using this set up, we were able to constrain seawater pH within a range of 0.07 pH units. Our system thus maintains the performance and adaptability of existing systems but expands their accessibility by reducing cost and complexity.

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Reagentless acid–base titration for alkalinity detection in seawater

Published 9 November 2021 Science Closed
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Herein, we report on a reagentless electroanalytical methodology for automatized acid–base titrations of water samples that are confined into very thin spatial domains. The concept is based on the recent discovery from our group (Wiorek, A. Anal. Chem. 2019, 91, 14951−14959), in which polyaniline (PANI) films were found to be an excellent material to release a massive charge of protons in a short time, achieving hence the efficient (and controlled) acidification of a sample. We now demonstrate and validate the analytical usefulness of this approach with samples collected from the Baltic Sea: the titration protocol indeed acts as an alkalinity sensor via the calculation of the proton charge needed to reach pH 4.0 in the sample, as per the formal definition of the alkalinity parameter. In essence, the alkalinity sensor is based on the linear relationship found between the released charge from the PANI film and the bicarbonate concentration in the sample (i.e., the way to express alkalinity measurements). The observed alkalinity in the samples presented a good agreement with the values obtained by manual (classical) acid–base titrations (discrepancies <10%). Some crucial advantages of the new methodology are that titrations are completed in less than 1 min (end point), the PANI film can be reused at least 74 times over a 2 week period (<5% of decrease in the released charge), and the utility of the PANI film to even more decrease the final pH of the sample (pH ∼2) toward applications different from alkalinity detection. Furthermore, the acidification can be accomplished in a discrete or continuous mode depending on the application demands. The new methodology is expected to impact the future digitalization of in situ acid–base titrations to obtain high-resolution data on alkalinity in water resources.

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An updated version of the global interior ocean biogeochemical data product, GLODAPv2.2021

Published 3 November 2021 Science Closed
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The Global Ocean Data Analysis Project (GLODAP) is a synthesis effort providing regular compilations of surface-to-bottom ocean biogeochemical bottle data, with an emphasis on seawater inorganic carbon chemistry and related variables determined through chemical analysis of seawater samples. GLODAPv2.2021 is an update of the previous version, GLODAPv2.2020. The major changes are: data from 43 new cruises were added, data coverage extended until 2020, removal of all data with missing temperatures, and the inclusion of a digital object identifier (doi) for each cruise in the product files. In addition, a number of minor corrections to GLODAPv2.2020 data were performed. GLODAPv2.2021 includes measurements from more than 1.3 million water samples from the global oceans collected on 989 cruises. The data for the 12 GLODAP core variables (salinity, oxygen, nitrate, silicate, phosphate, dissolved inorganic carbon, total alkalinity, pH, CFC-11, CFC-12, CFC-113, and CCl4) have undergone extensive quality control with a focus on systematic evaluation of bias. The data are available in two formats: (i) as submitted by the data originator but updated to WOCE exchange format and (ii) as a merged data product with adjustments applied to minimize bias. For this annual update, adjustments for the 43 new cruises were derived by comparing those data with the data from the 946 quality-controlled cruises in the GLODAPv2.2020 data product using crossover analysis. Comparisons to estimates of nutrients and ocean CO2 chemistry based on empirical algorithms provided additional context for adjustment decisions in this version. The adjustments are intended to remove potential biases from errors related to measurement, calibration, and data handling practices without removing known or likely time trends or variations in the variables evaluated. The compiled and adjusted data product is believed to be consistent to better than 0.005 in salinity, 1 % in oxygen, 2 % in nitrate, 2 % in silicate, 2 % in phosphate, 4 µmol kg-1 in dissolved inorganic carbon, 4 µmol kg-1 in total alkalinity, 0.01–0.02 in pH (depending on region), and 5 % in the halogenated transient tracers. The other variables included in the compilation, such as isotopic tracers and discrete CO2 fugacity (fCO2), were not subjected to bias comparison or adjustments.

The original data, their documentation and doi codes are available at the Ocean Carbon Data System of NOAA NCEI (https://www.ncei.noaa.gov/access/ocean-carbon-data-system/oceans/GLODAPv2_2021/, last access: 07 July 2021). This site also provides access to the merged data product, which is provided as a single global file and as four regional ones – the Arctic, Atlantic, Indian, and Pacific oceans – under https://doi.org/10.25921/ttgq-n825 (Lauvset et al., 2021). These bias-adjusted product files also include significant ancillary and approximated data, and can be accessed via www.glodap.info (last access: 29 June 2021). These were obtained by interpolation of, or calculation from, measured data. This living data update documents the GLODAPv2.2021 methods and provides a broad overview of the secondary quality control procedures and results.

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Rapid enhancement of multiple ecosystem services following the restoration of a coastal foundation species

Published 26 October 2021 Science Closed
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The global decline of marine foundation species (kelp forests, mangroves, salt marshes, and seagrasses) has contributed to the degradation of the coastal zone and threatens the loss of critical ecosystem services and functions. Restoration of marine foundation species has had variable success, especially for seagrasses, where a majority of restoration efforts have failed. While most seagrass restorations track structural attributes over time, rarely do restorations assess the suite of ecological functions that may be affected by restoration. Here we report on the results of two small-scale experimental seagrass restoration efforts in a central California estuary where we transplanted 117 0.25-m2 plots (2,340 shoots) of the seagrass species Zostera marina. We quantified restoration success relative to persistent reference beds, and in comparison to unrestored, unvegetated areas. Within three years, our restored plots expanded ˜8,500%, from a total initial area of 29 to 2,513 m2. The restored beds rapidly began to resemble the reference beds in (1) seagrass structural attributes (canopy height, shoot density, biomass), (2) ecological functions (macrofaunal species richness and abundance, epifaunal species richness, nursery function), and (3) biogeochemical functions (modulation of water quality). We also developed a multifunctionality index to assess cumulative functional performance, which revealed restored plots are intermediate between reference and unvegetated habitats, illustrating how rapidly multiple functions recovered over a short time period. Our comprehensive study is one of few published studies to quantify how seagrass restoration can enhance both biological and biogeochemical functions. Our study serves as a model for quantifying ecosystem services associated with the restoration of a foundation species and demonstrates the potential for rapid functional recovery that can be achieved through targeted restoration of fast-growing foundation species under suitable conditions.

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A monthly surface pCO2 product for the California Current Large Marine Ecosystem

Published 26 October 2021 Science Closed
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To calculate the direction and rate of carbon dioxide gas (CO2) exchange between the ocean and atmosphere, it is critical to know the partial pressure of CO2 in surface seawater (pCO2(sw)). Over the last decade, a variety of data products of global monthly pCO2(sw) have been produced, primarily for the open ocean on 1° latitude by 1° longitude grids. More recently, monthly products of pCO2(sw) that are more finely spatially resolved in the coastal ocean have been made available. A remaining challenge in the development of pCO2(sw) products is the robust characterization of seasonal variability, especially in nearshore coastal environments. Here we present a monthly data product of pCO2(sw) at 0.25° latitude by 0.25° longitude resolution in the Northeast Pacific Ocean, centered around the California Current System (CCS). The data product (RFR-CCS; Sharp et al., 2021; https://doi.org/10.5281/zenodo.5523389) was created using the most recent (2021) version of the Surface Ocean CO2 Atlas (Bakker et al., 2016) from which pCO2(sw) observations were extracted and fit against a variety of satellite- and model-derived surface variables using a random forest regression (RFR) model. We validate RFR-CCS in multiple ways, including direct comparisons with observations from moored autonomous surface platforms, and find that the data product effectively captures seasonal pCO2(sw) cycles at nearshore mooring sites. This result is notable because alternative global products for the coastal ocean do not capture local variability effectively in this region. We briefly review the physical and biological processes — acting across a variety of spatial and temporal scales — that are responsible for the latitudinal and nearshore-to-offshore pCO2(sw) gradients seen in RFR-CCS reconstructions of pCO2(sw).

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New and updated global empirical seawater property estimation routines

Published 22 October 2021 Science Closed
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We introduce three new Empirical Seawater Property Estimation Routines (ESPERs) capable of predicting seawater phosphate, nitrate, silicate, oxygen, total titration seawater alkalinity, total hydrogen scale pH (pHT), and total dissolved inorganic carbon (DIC) from up to 16 combinations of seawater property measurements. The routines generate estimates from neural networks (ESPER_NN), locally interpolated regressions (ESPER_LIR), or both (ESPER_Mixed). They require a salinity value and coordinate information, and benefit from additional seawater measurements if available. These routines are intended for seawater property measurement quality control and quality assessment, generating estimates for calculations that require approximate values, original science, and producing biogeochemical property context from a data set. Relative to earlier LIR routines, the updates expand their functionality, including new estimated properties and combinations of predictors, a larger training data product including new cruises from the 2020 Global Data Analysis Project data product release, and the implementation of a first-principles approach for quantifying the impacts of anthropogenic carbon on DIC and pHT. We show that the new routines perform at least as well as existing routines, and, in some cases, outperform existing approaches, even when limited to the same training data. Given that additional training data has been incorporated into these updated routines, these updates should be considered an improvement over earlier versions. The routines are intended for all ocean depths for the interval from 1980 to ~2030 c.e., and we caution against using the routines to directly quantify surface ocean seasonality or make more distant predictions of DIC or pHT.

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SeaFlux: harmonization of air–sea CO2 fluxes from surface pCO2 data products using a standardized approach

Published 22 October 2021 Science Closed
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Air–sea flux of carbon dioxide (CO2) is a critical component of the global carbon cycle and the climate system with the ocean removing about a quarter of the CO2 emitted into the atmosphere by human activities over the last decade. A common approach to estimate this net flux of CO2 across the air–sea interface is the use of surface ocean CO2 observations and the computation of the flux through a bulk parameterization approach. Yet, the details for how this is done in order to arrive at a global ocean CO2 uptake estimate vary greatly, enhancing the spread of estimates. Here we introduce the ensemble data product, SeaFlux (Gregor and Fay, 2021, https://doi.org/10.5281/zenodo.5482547​​​​​​​, https://github.com/luke-gregor/pySeaFlux, last access: 9 September 2021​​​​​​​); this resource enables users to harmonize an ensemble of products that interpolate surface ocean CO2 observations to near-global coverage with a common methodology to fill in missing areas in the products. Further, the dataset provides the inputs to calculate fluxes in a consistent manner. Utilizing six global observation-based mapping products (CMEMS-FFNN, CSIR-ML6, JENA-MLS, JMA-MLR, MPI-SOMFFN, NIES-FNN), the SeaFlux ensemble approach adjusts for methodological inconsistencies in flux calculations. We address differences in spatial coverage of the surface ocean CO2 between the mapping products, which ultimately yields an increase in CO2 uptake of up to 17 % for some products. Fluxes are calculated using three wind products (CCMPv2, ERA5, and JRA55). Application of a scaled gas exchange coefficient has a greater impact on the resulting flux than solely the choice of wind product. With these adjustments, we present an ensemble of global surface ocean pCO2 and air–sea carbon flux estimates. This work aims to support the community effort to perform model–data intercomparisons which will help to identify missing fluxes as we strive to close the global carbon budget.

Continue reading ‘SeaFlux: harmonization of air–sea CO2 fluxes from surface pCO2 data products using a standardized approach’

A novel lab-on-chip spectrophotometric pH sensor for autonomous in situ seawater measurements to 6000 m depth on stationary and moving observing platforms

Published 19 October 2021 Science Closed
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We report a new, autonomous Lab-on-Chip (LOC) microfluidic pH sensor with a 6000 m depth capability, ten times the depth capability of the state of the art autonomous spectrophotometric sensor. The pH is determined spectrophotometrically using purified meta-Cresol Purple indicator dye offering high precision (<0.001 pH unit measurement reproducibility), high frequency (every 8 min) measurements on the total proton scale from the surface to the deep ocean (to 600 bar). The sensor requires low power (3 W during continuous operation or ∼1300 J per measurement) and low reagent volume (∼3 μL per measurement) and generates small waste volume (∼2 mL per measurement) which can be retained during deployments. The performance of the LOC pH sensor was demonstrated on fixed and moving platforms over varying environmental salinity, temperature, and pressure conditions. Measurement accuracy was +0.003 ± 0.022 pH units (n = 47) by comparison with validation seawater sample measurements in coastal waters. The combined standard uncertainty of the sensor in situ pHT measurements was estimated to be ≤0.009 pH units at pH 8.5, ≤ 0.010 pH units at pH 8.0, and ≤0.014 pH units at pH 7.5. Integrated on autonomous platforms, this novel sensor opens new frontiers for pH observations, especially within the largest and most understudied ecosystem on the planet, the deep ocean.

Continue reading ‘A novel lab-on-chip spectrophotometric pH sensor for autonomous in situ seawater measurements to 6000 m depth on stationary and moving observing platforms’

Long-term stability and storage of meta-cresol purple solutions for seawater pH measurements

Published 19 October 2021 Science Closed
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Changes in seawater pH resulting from anthropogenic influence, termed ocean acidification, have significant implications. Monitoring and evaluating ocean acidification requires highly precise measurements comparable among many laboratories over decades. Short-term repeatability can be achieved with spectrophotometric methods, but comparability among studies is much less certain. The indicator used plays an important role in measurement quality. Meta-cresol purple (mCp), which is used for most seawater pH measurements, is known to break down under exposure to ultraviolet light, which can impact the long-term stability of the indicator, and thus the quality of the measurements. Here, certified reference material and 2-hydroxymethyl-1,3-propanediol (TRIS) buffers were used to assess the long-term stability of mCp solutions. Purified indicator solutions were found to be stable (within 0.0025) at room temperature in a dark container for at least 5.3 years. Uncertainties in unpurified indicators made the stability assessment inconclusive. Such long-term stability minimizes one potential source of uncertainty when comparing measurements and can reduce costs and waste by not prematurely disposing of indicator solutions that remain useable. Changes in the pH of the indicator solution indicate the indicator perturbation correction should be regularly determined. The A434imp correction method for determining impurities could be used as a quality assurance measure by making measurements over the life of the indicator solution to monitor for changes in the solution. However, the choice of molar absorptivities required for the calculation impacts the magnitude of the correction and thus warrants further study to improve best practices for making corrections to impure indicators.

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Tracking coastal acidification from erosion of gastropod shells: spatial sensitivity and organism size effect

Published 7 October 2021 Science Closed
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The rapidly changing marine environmental chemistry associated with growing industrialisation, urban population expansion, and the unabated rise in atmospheric CO2 necessitates monitoring. Traditional approaches using metres, dataloggers, and buoys to monitor marine acidification have limited application in coastal oceans and intertidal zones subjected to direct wave action. The present study trialled a system to biomonitor coastal acidification (carbonate ion and pH) based on the dissolution of living gastropod shells. We extended on an approach that ranked shell erosion (SER) in Nerita chamaeleon (Nc) in environments where such erosion was found to correlate with exposure to acidified water. We assessed the spatial scale at which the Nc-SER marker could detect change in acidification along rocky shores, and whether snail body size affected this marker. We found that proportional and unique Nc-SERs not only varied between acidified and non-acidified reference shores at a coarse spatial scale (10 km), but also in predictable ways at fine scales (metres), vertically and horizontally within a shore. Differences between acidified and reference shores in the relationship for snail size and Nc-SER were accentuated by less weathered shells at reference localities, highlighting the value of including small, juvenile snails in monitoring protocols. Gastropod shells are shown to be useful for assessing point sources of acidification and the spatial area of affected coastal zones. This cost-effective and easy-to-use approach (potentially even by citizen-scientists) offers an early warning system of acidification of rocky shore ecosystems, where the deployment of instruments is precluded.

Continue reading ‘Tracking coastal acidification from erosion of gastropod shells: spatial sensitivity and organism size effect’

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