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Spatial and temporal carbonate chemistry variability on coral reefs is influenced by a combination of seawater hydrodynamics, geomorphology, and biogeochemical processes, though their relative influence varies by site. It is often assumed that the water column above most reefs is well-mixed with small to no gradients outside of the benthic boundary layer. However, few studies to date have explored the processes and properties controlling these multi-dimensional gradients. Here, we investigated the lateral, vertical, and temporal variability of seawater carbonate chemistry on a Bermudan rim reef using a combination of spatial seawater chemistry surveys and autonomous in situ sensors. Instruments were deployed at Hog Reef measuring current flow, seawater temperature, salinity, pH T , p CO 2 , dissolved oxygen (DO), and total alkalinity (TA) on the benthos, and temperature, salinity, DO, and p CO 2 at the surface. Water samples from spatial surveys were collected from surface and bottom depths at 13 stations covering ∼3 km 2 across 4 days. High frequency temporal variability in carbonate chemistry was driven by a combination of diel light and mixed semi-diurnal tidal cycles on the reef. Daytime gradients in DO between the surface and the benthos suggested significant water column production contributing to distinct diel trends in pH T , p CO 2 , and DO, but not TA. We hypothesize these differences reflect the differential effect of biogeochemical processes important in both the water column and benthos (organic carbon production/respiration) vs. processes mainly occurring on the benthos (calcium carbonate production/dissolution). Locally at Hog Reef, the relative magnitude of the diel variability of organic carbon production/respiration was 1.4–4.6 times larger than that of calcium carbonate production/dissolution, though estimates of net organic carbon production and calcification based on inshore-offshore chemical gradients revealed net heterotrophy (−118 ± 51 mmol m –2 day –1 ) and net calcification (150 ± 37 mmol CaCO 3 m –2 day –1 ). These results reflect the important roles of time and space in assessing reef biogeochemical processes. The spatial variability in carbonate chemistry parameters was larger laterally than vertically and was generally observed in conjunction with depth gradients, but varied between sampling events, depending on time of day and modifications due to current flow. 

Abstract Total alkalinity (A_T) is an important parameter in the study of aquatic biogeochemical cycles, chemical speciation modeling, and many other important fundamental and anthropogenic (e.g., industrial) processes. We know little about its short‐term variability, however, because studies are based on traditional bottle sampling typically with coarse temporal resolution. In this work, an autonomous A_Tsensor, named the Submersible Autonomous Moored Instrument for Alkalinity (SAMI‐alk), was tested for freshwater applications. A comprehensive evaluation was conducted in the laboratory using freshwater standards. The results demonstrated excellent precision and accuracy (± 0.1%–0.4%) over the A_Trange from 800 to 3000 μmol L⁻¹. The system had no drift over an 8 d test and also demonstrated limited sensitivity to variations in temperature and ionic strength. Three SAMI‐alks were deployed for 23 d in the Clark Fork River, Montana, with a suite of other sensors. Compared to discrete samples, in situ accuracy for the three instruments were within 10–20 μmol L⁻¹(0.3–0.6%), indicating good performance considering the challenges of in situ measurements in a high sediment, high biofouling riverine environment with large and rapid changes in temperature. These data reveal the complex A_Tdynamics that are typically missed by coarse sampling. We observed A_Tdiel cycles as large as 60–80 μmol L⁻¹, as well as a rapid change caused by a runoff event. Significant errors in inorganic carbon system modeling result if these short‐term variations are not considered. This study demonstrates both the feasibility of the technology and importance of high‐resolution A_Tmeasurements. 

This dataset consists of the Surface Ocean CO2 Atlas Version 2022 (SOCATv2022) data product files. The ocean absorbs one quarter of the global CO2 emissions from human activity. The community-led Surface Ocean CO2 Atlas (www.socat.info) is key for the quantification of ocean CO2 uptake and its variation, now and in the future. SOCAT version 2022 has quality-controlled in situ surface ocean fCO2 (fugacity of CO2) measurements on ships, moorings, autonomous and drifting surface platforms for the global oceans and coastal seas from 1957 to 2021. The main synthesis and gridded products contain 33.7 million fCO2 values with an estimated accuracy of better than 5 μatm. A further 6.4 million fCO2 sensor data with an estimated accuracy of 5 to 10 μatm are separately available. During quality control, marine scientists assign a flag to each data set, as well as WOCE flags of 2 (good), 3 (questionable) or 4 (bad) to individual fCO2 values. Data sets are assigned flags of A and B for an estimated accuracy of better than 2 μatm, flags of C and D for an accuracy of better than 5 μatm and a flag of E for an accuracy of better than 10 μatm. Bakker et al. (2016) describe the quality control criteria used in SOCAT versions 3 to 2022. Quality control comments for individual data sets can be accessed via the SOCAT Data Set Viewer (www.socat.info). All data sets, where data quality has been deemed acceptable, have been made public. The main SOCAT synthesis files and the gridded products contain all data sets with an estimated accuracy of better than 5 µatm (data set flags of A to D) and fCO2 values with a WOCE flag of 2. Access to data sets with an estimated accuracy of 5 to 10 (flag of E) and fCO2 values with flags of 3 and 4 is via additional data products and the Data Set Viewer (Table 8 in Bakker et al., 2016). SOCAT publishes a global gridded product with a 1° longitude by 1° latitude resolution. A second product with a higher resolution of 0.25° longitude by 0.25° latitude is available for the coastal seas. The gridded products contain all data sets with an estimated accuracy of better than 5 µatm (data set flags of A to D) and fCO2 values with a WOCE flag of 2. Gridded products are available monthly, per year and per decade. Two powerful, interactive, online viewers, the Data Set Viewer and the Gridded Data Viewer (www.socat.info), enable investigation of the SOCAT synthesis and gridded data products. SOCAT data products can be downloaded. Matlab code is available for reading these files. Ocean Data View also provides access to the SOCAT data products (www.socat.info). SOCAT data products are discoverable, accessible and citable. The SOCAT Data Use Statement (www.socat.info) asks users to generously acknowledge the contribution of SOCAT scientists by invitation to co-authorship, especially for data providers in regional studies, and/or reference to relevant scientific articles. The SOCAT website (www.socat.info) provides a single access point for online viewers, downloadable data sets, the Data Use Statement, a list of contributors and an overview of scientific publications on and using SOCAT. Automation of data upload and initial data checks allows annual releases of SOCAT from version 4 onwards. SOCAT is used for quantification of ocean CO2 uptake and ocean acidification and for evaluation of climate models and sensor data. SOCAT products inform the annual Global Carbon Budget since 2013. The annual SOCAT releases by the SOCAT scientific community are a Voluntary Commitment for United Nations Sustainable Development Goal 14.3 (Reduce Ocean Acidification) (#OceanAction20464). More broadly the SOCAT releases contribute to UN SDG 13 (Climate Action) and SDG 14 (Life Below Water), and to the UN Decade of Ocean Science for Sustainable Development. Hundreds of peer-reviewed scientific publications and high-impact reports cite SOCAT. The SOCAT community-led synthesis product is a key step in the value chain based on in situ inorganic carbon measurements of the oceans, which provides policy makers with critical information on ocean CO2 uptake in climate negotiations. The need for accurate knowledge of global ocean CO2 uptake and its (future) variation makes sustained funding of in situ surface ocean CO2 observations imperative.