ALBERT

Description: Due to its accurate and precise character, spectrophotometric pH detection is a common technique applied in measurement methods for carbonate system parameters. However, impurities in the used pH indicator dyes can influence the measurements quality. During our work described here, we focused on impacts of impurities in the pH indicator dye bromocresol green (BCG) on spectrophotometric seawater total alkalinity (AT) measurements. In order to evaluate the extent of such influences, purified BCG served as a reference. First, a high-performance liquid chromatography (HPLC) purification method for BCG was developed as such a method did not exist at the time of this study. An analysis of BCG dye from four different vendors with this method revealed different types and quantities of impurities. After successful purification, AT measurements with purified and unpurified BCG were carried out using the novel autonomous analyzer CONTROS HydroFIA® TA. Long-term measurements in the laboratory revealed a direct influence of impurity types and quantities on the drift behavior of the analyzer. The purer the BCG, the smaller was the AT increase per measurement. The observed drift is generally caused by deposits in the optical pathway mainly generated by the impurities. However, the analyzers drift behavior could not be fully overcome. Furthermore, we could show that a certain impurity type in some indicator dyes changed the drift pattern from linear to nonlinear, which can impair long-term deployments of the system. Consequently, such indicators are impractical for these applications. Laboratory performance characterization experiments revealed no improvement of the measurement quality (precision and bias) by using purified BCG as long as the impurities of the unpurified dye do not exceed a quantity of 2 % (relationship of peak areas in the chromatogram). However, BCG with impurity quantities higher than 6 % provided AT values which failed fundamental quality requirements. In conclusion, to gain optimal AT measurements especially during long-term deployments, an indicator purification is not necessarily required as long as the purchased dye has a purity level of at least 98 % and is free of the named impurity type. Consequently, high-quality AT measurements do not require pure but the purest BCG that is purchasable.

Description: Large amounts of methane (CH4) could be released as a result of the gradual or abrupt thawing of Arctic permafrost due to global warming. Once available, this potent greenhouse gas is emitted into the atmosphere or transported laterally into aquatic ecosystems via hydrologic connectivity at the surface or via groundwaters. While high northern latitudes contribute up to 5 % of total global CH4 emissions, the specific contribution of Arctic rivers and streams is largely unknown. We analyzed high-resolution continuous CH4 concentrations measured between 15 and 17 June 2019 (late freshet) in a ∼120 km transect of the Kolyma River in northeast Siberia. The average partial pressure of CH4 (pCH4) in tributaries (66.8–206.8 µatm) was 2–7 times higher than in the main river channel (28.3 µatm). In the main channel, CH4 was up to 1600 % supersaturated with respect to atmospheric equilibrium. Key sites along the riverbank and at tributary confluences accounted for 10 % of the navigated transect and had the highest pCH4 (41 ± 7 µatm) and CH4 emissions (0.03 ± 0.004 ) compared to other sites in the main channel, contributing between 14 % to 17 % of the total CH4 flux in the transect. These key sites were characterized by warm waters (T〉14.5 ∘C) and low specific conductivities (κ〈88 µS cm−1). The distribution of CH4 in the river could be linked statistically to T and κ of the water and to their proximity to the shore z, and these parameters served as predictors of CH4 concentrations in unsampled river areas. The abundance of CH4-consuming bacteria and CH4-producing archaea in the river was similar to those previously detected in nearby soils and was also strongly correlated to T and κ. These findings imply that the source of riverine CH4 is closely related with sites near land. The average total CH4 flux density in the river section was 0.02 ± 0.006 , equivalent to an annual CH4 flux of 1.24×107 g CH4 yr−1 emitted during a 146 d open water season. Our study highlights the importance of high-resolution continuous CH4 measurements in Arctic rivers for identifying spatial and temporal variations, as well as providing a glimpse of the magnitude of riverine CH4 emissions in the Arctic and their potential relevance to regional CH4 budgets.

Description: The ocean and inland waters are two separate regimes, with concentrations in greenhouse gases differing on orders of magnitude between them. Together, they create the land–ocean aquatic continuum (LOAC), which comprises itself largely of areas with little to no data with regards to understanding the global carbon system. Reasons for this include remote and inaccessible sample locations, often tedious methods that require collection of water samples and subsequent analysis in the lab, and the complex interplay of biological, physical and chemical processes. This has led to large inconsistencies, increasing errors and has inevitably lead to potentially false upscaling. A set-up of multiple pre-existing oceanographic sensors allowing for highly detailed and accurate measurements was successfully deployed in oceanic to remote inland regions over extreme concentration ranges. The set-up consists of four sensors simultaneously measuring pCO2, pCH4 (both flow-through, membrane-based non-dispersive infrared (NDIR) or tunable diode laser absorption spectroscopy (TDLAS) sensors), O2 and a thermosalinograph at high resolution from the same water source. The flexibility of the system allowed for deployment from freshwater to open ocean conditions on varying vessel sizes, where we managed to capture day–night cycles, repeat transects and also delineate small-scale variability. Our work demonstrates the need for increased spatiotemporal monitoring and shows a way of homogenizing methods and data streams in the ocean and limnic realms.

Description: Methane (CH4) is one of the substantial greenhouse gases in our atmosphere and its concentration has increased by ~ 4 % over the last decade. Although sources driving these increases are not well constrained, one potential contribution comes from wetlands, which are usually intertwined with rivers, channels and lakes, creating a considerable need to acquire higher resolution data to facilitate 5 modelling and predictions. Here we took a fully contained sensor set-up to obtain measurements of CO2, CH4, O2 and auxiliary parameters, installed on a houseboat for accessibility, to assess and analyse surface water concentrations within the Danube Delta, Romania. Over 3 seasons, we transected a ~ 400 km route with concentration mapping and additional stations for monitoring diel cycles. Overall, the delta was a source for CH4 throughout all seasons, with concentrations ranging between 0.113–15.6 μmol L−1. The dataset was split into three different subsystems; lakes, rivers and channels, with channels 10 showing the highest variability. We found large to extreme diel cycles in both the lakes and channels, with concentrations varying by an order of magnitude between these two systems. The observed strong diel cycle within the lake suggests daily vertical stratification allowing for macrophytes to create a temporal oxycline due to lack of light and movement between the stems as previously suggested. While throughout the day, there was a consistent overall surface concentration of CH4 at around 0.4 μmol L−1, there was a clear linear trend with an O2:CH4 molar ratio of −50:1 during the phase of nocturnal convection 15 with the two water stratified bodies mixing during the night. Daily spot sampling techniques and neglecting such diel cycles reducing the estimated average methane concentrations by 25 % and increase by 3.3 % for channels and lakes, respectively. On an individual lake basis, spot sampling can potentially incur an uncertainty range of a factor of 4.5. Analyses also included a ‘hot spot’, with a 10-fold stronger methane increase (4–15.6 μmol L−1) overnight compared to the lake, with an almost immediate and extreme decrease in CH4 following sunrise. Calculated diffusive CH4 fluxes for the overall delta yielded an 20 average of 49 ± 61 μmol m−2 h−1 corresponding to an extrapolated annual flux of 0.43 ± 0.53 μmol m−2 yr−1. Our data illustrate the importance of collecting information on diel cycles in different habitats to improve the emission estimates from wetland systems.

Description: Accurate assessment of anthropogenic carbon dioxide (CO2) emissions and their redistribution among the atmosphere, ocean, and terrestrial biosphere in a changing climate is critical to better understand the global carbon cycle, support the development of climate policies, and project future climate change. Here we describe and synthesize datasets and methodology to quantify the five major components of the global carbon budget and their uncertainties. Fossil CO2 emissions (E-FOS) are based on energy statistics and cement production data, while emissions from land-use change (E-LUC), mainly deforestation, are based on land use and land-use change data and bookkeeping models. Atmospheric CO2 concentration is measured directly, and its growth rate (G(ATM)) is computed from the annual changes in concentration. The ocean CO2 sink (S-OCEAN) is estimated with global ocean biogeochemistry models and observation-based data products. The terrestrial CO2 sink (S-LAND) is estimated with dynamic global vegetation models. The resulting carbon budget imbalance (B-IM), the difference between the estimated total emissions and the estimated changes in the atmosphere, ocean, and terrestrial biosphere, is a measure of imperfect data and understanding of the contemporary carbon cycle. All uncertainties are reported as +/- 1 sigma. For the first time, an approach is shown to reconcile the difference in our E-LUC estimate with the one from national greenhouse gas inventories, supporting the assessment of collective countries' climate progress. For the year 2020, E-FOS declined by 5.4 % relative to 2019, with fossil emissions at 9.5 +/- 0.5 GtC yr(-1) (9.3 +/- 0.5 GtC yr(-1) when the cement carbonation sink is included), and E-LUC was 0.9 +/- 0.7 GtC yr(-1), for a total anthropogenic CO2 emission of 10.2 +/- 0.8 GtC yr(-1) (37.4 +/- 2.9 GtCO(2)). Also, for 2020, G(ATM) was 5.0 +/- 0.2 GtC yr-1 (2.4 +/- 0.1 ppm yr(-1)), S-OCEAN was 3.0 +/- 0.4 GtC yr(-1), and S-LAND was 2.9 +/- 1 GtC yr(-1), with a B-IM of -0.8 GtC yr(-1). The global atmospheric CO2 concentration averaged over 2020 reached 412.45 +/- 0.1 ppm. Preliminary data for 2021 suggest a rebound in E-FOS relative to 2020 of +4.8 % (4.2 % to 5.4 %) globally. Overall, the mean and trend in the components of the global carbon budget are consistently estimated over the period 1959-2020, but discrepancies of up to 1 GtC yr(-1) persist for the representation of annual to semi-decadal variability in CO2 fluxes. Comparison of estimates from multiple approaches and observations shows (1) a persistent large uncertainty in the estimate of land-use changes emissions, (2) a low agreement between the different methods on the magnitude of the land CO2 flux in the northern extra-tropics, and (3) a discrepancy between the different methods on the strength of the ocean sink over the last decade. This living data update documents changes in the methods and datasets used in this new global carbon budget and the progress in understanding of the global carbon cycle compared with previous publications of this dataset (Friedlingstein et al., 2020, 2019; Le Quere et al., 2018b, a, 2016, 2015b, a, 2014, 2013). The data presented in this work are available at (Friedlingstein et al., 2021).

Description: Mesoscale eddies are abundant in the eastern tropical North Atlantic and act as oases for phytoplankton growth due to local enrichment of nutrients in otherwise oligotrophic waters. It is not clear whether these eddies can efficiently transfer organic carbon and other flux components to depth and if they are important for the marine carbon budget. Due to their transient and regionally restricted nature, measurements of eddies' contribution to bathypelagic particle flux are difficult to obtain. Rare observations of export flux associated with low-oxygen eddies have suggested efficient export from the surface to the deep ocean, indicating that organic carbon flux attenuation might be low. Here we report on particle flux dynamics north of the Cabo Verde islands at the oligotrophic Cape Verde Ocean Observatory (CVOO; approx. 17∘35′ N, 24∘15′ W). The CVOO site is located in the preferred pathways of highly productive eddies that ultimately originate from the Mauritanian upwelling region. Between 2009 and 2016, we collected biogenic and lithogenic particle fluxes with sediment traps moored at ca. 1 and 3 km water depths at the CVOO site. From concurrent hydrography and oxygen observations, we confirm earlier findings that highly productive eddies are characterized by colder and less saline waters and a low-oxygen signal as well. Overall, we observed quite consistent seasonal flux patterns during the passage of highly productive eddies in the winters of 2010, 2012 and 2016. We found flux increases at 3 km depth during October–November when the eddies approached CVOO and distinct flux peaks during February–March, clearly exceeding low oligotrophic background fluxes during winter 2011 and showing an enhanced particle flux seasonality. During spring, we observed a stepwise flux decrease leading to summer flux minima. The flux pattern of biogenic silicate (BSi) showed a stronger seasonality compared to organic carbon. Additionally, the deep fluxes of total mass showed an unusually higher seasonality compared to the 1 km traps. We assume that BSi and organic carbon/lithogenic material had different sources within the eddies. BSi-rich particles may originate at the eddy boundaries where large diatom aggregates are formed due to strong shear and turbulence, resulting in gravitational settling and, additionally, in an active local downward transport. Organic carbon associated with lithogenic material is assumed to originate from the interior of eddies or from mixed sources, both constituting smaller, dust-ballasted particles. Our findings suggest that the regularly passing highly productive eddies at CVOO repeatedly release characteristic flux signals to the bathypelagic zone during winter–spring seasons that are far above the oligotrophic background fluxes and sequester higher organic carbon than during oligotrophic settings. However, the reasons for a lower carbon flux attenuation below eddies remain elusive.

Description: Estuaries are an important contributor to the global carbon budget, facilitating carbon removal, transfer, and transformation between land and the coastal ocean. Estuaries are susceptible to global climate change and anthropogenic perturbations. We find that a long-term significant mid-estuary increase in dissolved inorganic carbon (DIC) of 6–21 µmol kg−1 yr−1 (1997–2020) in a temperate estuary in Germany (Elbe Estuary) was driven by an increase in upper-estuary particulate organic carbon (POC) content of 8–14 µmol kg−1 yr−1. The temporal POC increase was due to an overall improvement in water quality observed in the form of high rates of primary production and a significant drop in biological oxygen demand. The magnitude of mid-estuary DIC gain was equivalent to the increased POC production in the upper estuary, suggesting that POC is effectively remineralized and retained as DIC in the mid-estuary, with the estuary acting as an efficient natural filter for POC. In the context of this significant long-term DIC increase, a recent extended drought period (2014–2020) significantly lowered the annual mean river discharge (468 ± 234 m3 s−1) compared to the long-term mean (690 ± 441 m3 s−1, 1960–2020), while the late spring internal DIC load in the estuary doubled. The drought induced a longer dry season, starting in May (earlier than normal), increased the residence time in the estuary and allowed for a more complete remineralization period of POC. Annually, 77 %–94 % of the total DIC export was laterally transported to the coastal waters, reaching 89 ± 4.8 Gmol C yr−1, and thus, between 1997 and 2020, only an estimated maximum of 23 % (10 Gmol C yr−1) was released via carbon dioxide (CO2) evasion. Export of DIC to coastal waters decreased significantly during the drought, on average by 24 % (2014–2020: 38 ± 5.4 Gmol C yr−1), compared to the non-drought period. In contrast, there was no change in the water–air CO2 flux during the drought. We have identified that seasonal changes in DIC processing in an estuary require consideration when estimating both the long-term and future changes in water–air CO2 flux and DIC export to coastal waters. Regional and global carbon budgets should therefore take into account carbon cycling estimates in estuaries, as well as their changes over time in relation to impacts of water quality changes and extreme hydrological events.

Description: Since a pH sensor has become available that is principally suitable for use on demanding autonomous measurement platforms, the marine CO2 system can be observed independently and continuously by Biogeochemical Argo floats. This opens the potential to detect variability and long-term changes in interior ocean inorganic carbon storage and quantify the ocean sink for atmospheric CO2. In combination with a second parameter of the marine CO2 system, pH can be a useful tool to derive the surface ocean CO2 partial pressure (pCO2). The large spatiotemporal variability in the marine CO2 system requires sustained observations to decipher trends and study the impacts of short-term events (e.g., eddies, storms, phytoplankton blooms) but also puts a high emphasis on the quality control of float-based pH measurements. In consequence, a consistent and rigorous quality control procedure is being established to correct sensor offsets or drifts as the interpretation of changes depends on accurate data. By applying current standardized routines of the Argo data management to pH measurements from a pH / O2 float pilot array in the subpolar North Atlantic Ocean, we assess the uncertainties and lack of objective criteria associated with the standardized routines, notably the choice of the reference method for the pH correction (CANYON-B, LIR-pH, ESPER-NN, and ESPER-LIR) and the reference depth for this adjustment. For the studied float array, significant differences ranging between ca. 0.003 pH units and ca. 0.04 pH units are observed between the four reference methods which have been proposed to correct float pH data. Through comparison against discrete and underway pH data from other platforms, an assessment of the adjusted float pH data quality is presented. The results point out noticeable discrepancies near the surface of 〉 0.004 pH units. In the context of converting surface ocean pH measurements into pCO2 data for the purpose of deriving air–sea CO2 fluxes, we conclude that an accuracy requirement of 0.01 pH units (equivalent to a pCO2 accuracy of 10 µatm as a minimum requirement for potential future inclusion in the Surface Ocean CO2 Atlas, SOCAT, database) is not systematically achieved in the upper ocean. While the limited dataset and regional focus of our study do not allow for firm conclusions, the evidence presented still calls for the inclusion of an additional independent pH reference in the surface ocean in the quality control routines. We therefore propose a way forward to enhance the float pH quality control procedure. In our analysis, the current philosophy of pH data correction against climatological reference data at one single depth in the deep ocean appears insufficient to assure adequate data quality in the surface ocean. Ideally, an additional reference point should be taken at or near the surface where the resulting pCO2 data are of the highest importance to monitor the air–sea exchange of CO2 and would have the potential to very significantly augment the impact of the current observation network.

Description: The presented pilot for the Synthesis Product for Ocean Time Series (SPOTS) includes data from 12 fixed ship-based time-series programs. The related stations represent unique open-ocean and coastal marine environments within the Atlantic Ocean, Pacific Ocean, Mediterranean Sea, Nordic Seas, and Caribbean Sea. The focus of the pilot has been placed on biogeochemical essential ocean variables: dissolved oxygen, dissolved inorganic nutrients, inorganic carbon (pH, total alkalinity, dissolved inorganic carbon, and partial pressure of CO2), particulate matter, and dissolved organic carbon. The time series used include a variety of temporal res- olutions (monthly, seasonal, or irregular), time ranges (10–36 years), and bottom depths (80–6000 m), with the oldest samples dating back to 1983 and the most recent one corresponding to 2021. Besides having been harmo- nized into the same format (semantics, ancillary data, units), the data were subjected to a qualitative assessment in which the applied methods were evaluated and categorized. The most recently applied methods of the time- series programs usually follow the recommendations outlined by the Bermuda Time Series Workshop report (Lorenzoni and Benway, 2013), which is used as the main reference for “method recommendations by prevalent initiatives in the field”. However, measurements of dissolved oxygen and pH, in particular, still show room for improvement. Additional data quality descriptors include precision and accuracy estimates, indicators for data variability, and offsets compared to a reference and widely recognized data product for the global ocean: the GLobal Ocean Data Analysis Project (GLODAP). Generally, these descriptors indicate a high level of continuity in measurement quality within time-series programs and a good consistency with the GLODAP data product, even though robust comparisons to the latter are limited. The data are available as (i) a merged comma-separated file that is compliant with the World Ocean Circulation Experiment (WOCE) exchange format and (ii) a format dependent on user queries via the Environmental Research Division’s Data Access Program (ERDDAP) server of the Global Ocean Observing System (GOOS). The pilot increases the data utility, findability, accessibility, interoperability, and reusability following the FAIR philosophy, enhancing the readiness of biogeochemical time series. It facilitates a variety of applications that benefit from the collective value of biogeochemical time-series observations and forms the basis for a sustained time-series living data product, SPOTS, complementing relevant products for the global interior ocean carbon data (GLobal Ocean Data Analysis Project), global surface ocean carbon data (Surface Ocean CO2 Atlas; SOCAT), and global interior and surface methane and nitrous oxide data (MarinE MethanE and NiTrous Oxide product). Aside from the actual data compilation, the pilot project produced suggestions for reporting metadata, im- plementing quality control measures, and making estimations about uncertainty. These recommendations aim to encourage the community to adopt more consistent and uniform practices for analysis and reporting and to update these practices regularly. The detailed recommendations, links to the original time-series programs, the original data, their documentation, and related efforts are available on the SPOTS website. This site also pro- vides access to the data product (DOI: https://doi.org/10.26008/1912/bco-dmo.896862.2, Lange et al., 2024) and ancillary data.

Description: Surface current drifters were deployed east of Brava island (Cape Verde archipelago, Atlantic ocean) from the RV Meteor during the cruise M160, which took place between 22. November and 20. December 2019. The drifters were deployed in 3 clusters with 3 drifters per cluster. The utilized drifters are the MD03i from Albatros Marine Technologies, Spain. They have a cylinder shape with a 10 cm diameter and 32 cm length. About 8 cm protrude from the water surface and a drogue of both 50 cm length and diameter is attached to each drifter 50 cm below the sea surface so that difter represent currents in the upper 1 m surface layer. The drifter obtains the GPS position and transmits it via the satellite communication system Iridium to the vessel. The overall ratio of drag area inside to drag area outside the water is 33.2.