Development of an autonomous on-site dissolved inorganic carbon analyzer using conductometric detection.

BACKGROUND: The increase in anthropogenic CO2 concentrations in the Earth's atmosphere since the industrial revolution has resulted in an increased uptake of CO2 by the oceans, leading to ocean acidification. Dissolved Inorganic Carbon (DIC) is one of the key variables to characterize the seawater carbonate system. High quality DIC observations at a high spatial-temporal resolution is required to improve our understanding of the marine carbonate system. To meet the requirements, autonomous DIC analyzers are needed which offer a high sampling frequency, are cost-effective and have a low reagent and power consumption. RESULTS: We present the development and validation of a novel analyzer for autonomous measurements of DIC in seawater using conductometric detection. The analyzer employs a gas diffusion sequential injection approach in a "Tube In A Tube" configuration that facilitates diffusion of gaseous CO2 from an acidified sample through a gas permeable membrane into a stream of an alkaline solution. The change in conductivity in the alkaline medium is proportional to the DIC concentration of the sample and is measured using a detection cell constructed of 4 hollow brass electrodes. Physical and chemical optimizations of the analyzer yielded a sampling frequency of 4 samples h-1 using sub mL reagent volumes for each measurement. Temperature and salinity effects on DIC measurements were mathematically corrected to increase accuracy. Analytical precision of ±4.9 µmol kg-1 and ±9.7 µmol kg-1 were achieved from measurements of a DIC reference material in the laboratory and during a field deployment in the southwest Baltic Sea, respectively. SIGNIFICANCE: This study describes a simple, cost-effective, autonomous, on-site benchtop DIC analyzer capable of measuring DIC in seawater at a high temporal resolution as a step towards an underwater DIC sensor. The analyzer is able to measure a wide range of DIC concentrations in both fresh and marine waters. The achieved accuracy and precision offer an excellent opportunity to employ the analyzer for ocean acidification studies and CO2 leakage detection in the context of Carbon Capture and Storage operations.

A detectable change in the air-sea CO2 flux estimate from sailboat measurements.

The sailboat Seaexplorer collected underway sea surface partial pressure of CO2 (pCO2) data for 129 days (2018-2021), including an Antarctic circumnavigation. By comparing ensembles of data-driven air-sea CO2 fluxes computed with and without sailboat data and applying a detection algorithm, we show that these sailboat observations significantly increase the regional carbon uptake in the North Atlantic and decrease it in the Southern Ocean. While compensating changes in both basins limit the global effect, the Southern Ocean-particularly frontal regions (40°S-60°S) during summertime-exhibited the largest air-sea CO2 flux changes, averaging 20% of the regional mean. Assessing the sensitivity of the air-sea CO2 flux to measurement uncertainty, the results stay robust within the expected random measurement uncertainty (± 5 µatm) but remain undetectable with a measurement offset of 5 µatm. We thus conclude that sailboats fill essential measurement gaps in remote ocean regions.

Seawater physics and chemistry along the Med-SHIP transects in the Mediterranean Sea in 2016.

The Mediterranean Sea has been sampled irregularly by research vessels in the past, mostly by national expeditions in regional waters. To monitor the hydrographic, biogeochemical and circulation changes in the Mediterranean Sea, a systematic repeat oceanographic survey programme called Med-SHIP was recommended by the Mediterranean Science Commission (CIESM) in 2011, as part of the Global Ocean Ship-based Hydrographic Investigations Program (GO-SHIP). Med-SHIP consists of zonal and meridional surveys with different frequencies, where comprehensive physical and biogeochemical properties are measured with the highest international standards. The first zonal survey was done in 2011 and repeated in 2018. In addition, a network of meridional (and other key) hydrographic sections were designed: the first cycle of these sections was completed in 2016, with three cruises funded by the EU project EUROFLEETS2. This paper presents the physical and chemical data of the meridional and key transects in the Western and Eastern Mediterranean Sea collected during those cruises.

Sailing through the southern seas of air-sea CO2 flux uncertainty.

The Southern Ocean is among the largest contemporary sinks of atmospheric carbon dioxide on our planet; however, remoteness, harsh weather and other circumstances have led to an undersampling of the ocean basin, compared with its northern hemispheric counterparts. While novel data interpolation methods can in part compensate for such data sparsity, recent studies raised awareness that we have hit a wall of unavoidable uncertainties in air-sea [Formula: see text] flux reconstructions. Here, we present results from autonomous observing campaigns using a novel platform to observe remote ocean regions: sailboats. Sailboats are at present a free of charge environmentally friendly platform that recurrently pass remote ocean regions during round-the-globe racing events. During the past 5 years, we collected [Formula: see text] measurements of the sea surface partial pressure of [Formula: see text] (p[Formula: see text]) around the globe including the Southern Ocean throughout an Antarctic circumnavigation during the Vendée Globe racing event. Our analysis demonstrates that the sailboat tracks pass regions where large uncertainty in the air-sea [Formula: see text] flux reconstruction prevails, with regional oversaturation or undersaturation of the sea surface p[Formula: see text]. Sailboat races provide an independent cross-calibration platform for autonomous measurement devices, such as Argo floats, ultimately strengthening the entire Southern Ocean observing system. This article is part of a discussion meeting issue 'Heat and carbon uptake in the Southern Ocean: the state of the art and future priorities'.

A near-synoptic survey of ocean microplastic concentration along an around-the-world sailing race.

Litter and plastic pollution in the marine environment is of major concern when considering the health of ocean ecosystems, and have become an important focus of ocean research during recent years. There is still significant uncertainty surrounding the distribution and impact of marine plastic litter on ocean ecosystems, and in particular on the nano- and microplastic fractions that are difficult to observe and may be harmful to marine organisms. Current estimates of ocean plastic concentrations only account for a small fraction of the approximated 8 million tons of plastic litter entering the oceans on an annual basis. Here, we present the distribution of 100-500 µm microplastic particles within the ocean mixed layer, covering a significant fraction of the ocean, in a near-synoptic survey. During The Ocean Race 2017/2018 edition (formerly known as Volvo Ocean Race), two yachts served as ships of opportunity that regularly took samples of microplastics on a regular schedule during their circumnavigation. This effort resulted in information on microplastic distribution along the race track in the ocean's upper, well-mixed, layer. We found concentrations ranging from 0-349 particles per cubic meter, but with large spatial variability. There was a tendency toward higher concentrations off south-western Europe and in the southwest Pacific, and indications of long-range transport of microplastic with major ocean currents.

Vertical distribution of perfluoroalkyl substances in water columns around the Japan sea and the Mediterranean Sea.

Perfluoroalkyl substances (PFASs) have become an important class of global environmental contaminants, yet their vertical profile in the marine water column is still less understood, especially for the semi-closed seas. In this study, the contamination level and spatial distribution of 8 PFASs were investigated in both surface and vertical water samples from two semi-closed seas, the Japan Sea and the Mediterranean Sea. Similar levels and compositions of PFASs were found between these two seas. The vertical profile of PFASs in the Mediterranean Sea was variable while that was relatively steady in the Japan Sea, probably due to their different pollution sources. The accumulation rate of PFASs from the East China Sea to the Japan Sea was calculated, for which perfluorooctanesulfonic acid and perfluorooctanoic acid were found to have high accumulation potency in both surface and deep water; most of the investigated PFASs were accumulated in the deep water due to the long residence time while they were more likely to escape to the Pacific Ocean in the surface water. This work aimed (i) to study the distribution of PFASs in both surface and vertical water samples in two semi-closed seas, namely the Japan Sea and for the first time the Mediterranean Sea, (ii) to assess the temporal trend in the Japan Sea, and (iii) to firstly investigate the potential transport of PFASs from the East China Sea and Taiwan Strait in order to estimate the inventory of PFASs in whole water mass in the Japan Sea.

The oceanic sink for anthropogenic CO2 from 1994 to 2007.

We quantify the oceanic sink for anthropogenic carbon dioxide (CO2) over the period 1994 to 2007 by using observations from the global repeat hydrography program and contrasting them to observations from the 1990s. Using a linear regression-based method, we find a global increase in the anthropogenic CO2 inventory of 34 ± 4 petagrams of carbon (Pg C) between 1994 and 2007. This is equivalent to an average uptake rate of 2.6 ± 0.3 Pg C year-1 and represents 31 ± 4% of the global anthropogenic CO2 emissions over this period. Although this global ocean sink estimate is consistent with the expectation of the ocean uptake having increased in proportion to the rise in atmospheric CO2, substantial regional differences in storage rate are found, likely owing to climate variability-driven changes in ocean circulation.

39Ar dating with small samples provides new key constraints on ocean ventilation.

Ocean ventilation is the integrated effect of various processes that exchange surface properties with the ocean interior and is essential for oxygen supply, storage of anthropogenic carbon and the heat budget of the ocean, for instance. Current observational methods utilise transient tracers, e.g. tritium, SF6, CFCs and 14C. However, their dating ranges are not ideal to resolve the centennial-dynamics of the deep ocean, a gap filled by the noble gas isotope 39Ar with a half-life of 269 years. Its broad application has been hindered by its very low abundance, requiring 1000 L of water for dating. Here we show successful 39Ar dating with 5 L of water based on the atom-optical technique Atom Trap Trace Analysis. Our data reveal previously not quantifiable ventilation patterns in the Tropical Atlantic, where we find that advection is more important for the ventilation of the intermediate depth range than previously assumed. Now, the demonstrated analytical capabilities allow for a global collection of 39Ar data, which will have significant impact on our ability to quantify ocean ventilation.

Iron Biogeochemistry in the High Latitude North Atlantic Ocean.

Iron (Fe) is an essential micronutrient for marine microbial organisms, and low supply controls productivity in large parts of the world's ocean. The high latitude North Atlantic is seasonally Fe limited, but Fe distributions and source strengths are poorly constrained. Surface ocean dissolved Fe (DFe) concentrations were low in the study region (<0.1 nM) in summer 2010, with significant perturbations during spring 2010 in the Iceland Basin as a result of an eruption of the Eyjafjallajökull volcano (up to 2.5 nM DFe near Iceland) with biogeochemical consequences. Deep water concentrations in the vicinity of the Reykjanes Ridge system were influenced by pronounced sediment resuspension, with indications for additional inputs by hydrothermal vents, with subsequent lateral transport of Fe and manganese plumes of up to 250-300 km. Particulate Fe formed the dominant pool, as evidenced by 4-17 fold higher total dissolvable Fe compared with DFe concentrations, and a dynamic exchange between the fractions appeared to buffer deep water DFe. Here we show that Fe supply associated with deep winter mixing (up to 103 nmol m-2 d-1) was at least ca. 4-10 times higher than atmospheric deposition, diffusive fluxes at the base of the summer mixed layer, and horizontal surface ocean fluxes.

Estimation of anthropogenic CO2 inventories in the ocean.

A significant impetus for recent ocean biogeochemical research has been to better understand the ocean's role as a sink for anthropogenic CO2. In the 1990s the global carbon survey of the World Ocean Circulation Experiment (WOCE) and the Joint Global Ocean Flux Study (JGOFS) inspired the development of several approaches for estimating anthropogenic carbon inventories in the ocean interior. Most approaches agree that the total global ocean inventory of Cant was around 120 Pg C in the mid-1990s. Today, the ocean carbon uptake rate estimates suggest that the ocean is not keeping pace with the CO2 emissions growth rate. Repeat occupations of the WOCE/JGOFS survey lines consistently show increases in carbon inventories over the last decade, but have not yet been synthesized enough to verify a slowdown in the carbon storage rate. There are many uncertainties in the future ocean carbon storage. Continued observations are necessary to monitor changes and understand mechanisms controlling ocean carbon uptake and storage in the future.

Medusa: a sample preconcentration and GC/MS detector system for in situ measurements of atmospheric trace halocarbons, hydrocarbons, and sulfur compounds.

Significant changes have occurred in the anthropogenic emissions of many compounds related to the Kyoto and Montreal Protocols within the past 20 years and many of their atmospheric abundances have responded dramatically. Additionally, there are a number of related natural compounds with underdetermined source or sink budgets. A new instrument, Medusa, was developed to make the high frequency in situ measurements required for the determination of the atmospheric lifetimes and emissions of these compounds. This automated system measures a wide range of halocarbons, hydrocarbons, and sulfur compounds involved in ozone depletion and/or climate forcing, from the very volatile perfluorocarbons (PFCs, e.g., CF(4) and CH(3)CF(3)) and hydrofluorocarbons (HFCs, e.g., CH(3)CF(3)) to the higher-boiling point solvents (such as CH(3)Cl(3) and CCl(2)=CCl(2)) and CHBr(3). A network of Medusa systems worldwide provides 12 in situ ambient air measurements per day of more than 38 compounds of part per trillion mole fractions and precisions up to 0.1% RSD at the five remote field stations operated by the Advanced Global Atmospheric Gases Experiment (AGAGE). This custom system couples gas chromatography/mass spectrometry (GC/MSD) with a novel scheme for cryogen-free low-temperature preconcentration (-165 degrees C) of analytes from 2 L samples in a two-trap process using HayeSep D adsorbent.

An estimate of anthropogenic CO2 inventory from decadal changes in oceanic carbon content.

Increased knowledge of the present global carbon cycle is important for our ability to understand and to predict the future carbon cycle and global climate. Approximately half of the anthropogenic carbon released to the atmosphere from fossil fuel burning is stored in the ocean, although distribution and regional fluxes of the ocean sink are debated. Estimates of anthropogenic carbon (C(ant)) in the oceans remain prone to error arising from (i) a need to estimate preindustrial reference concentrations of carbon for different oceanic regions, and (ii) differing behavior of transient ocean tracers used to infer C(ant). We introduce an empirical approach to estimate C(ant) that circumvents both problems by using measurement of the decadal change of ocean carbon concentrations and the exponential nature of the atmospheric C(ant) increase. In contrast to prior approaches, the results are independent of tracer data but are shown to be qualitatively and quantitatively consistent with tracer-derived estimates. The approach reveals more C(ant) in the deep ocean than prior studies; with possible implications for future carbon uptake and deep ocean carbonate dissolution. Our results suggest that this approachs applied on the unprecedented global data archive provides a means of estimating the C(ant) for large parts of the world's ocean.