Description: Highlights • Biogeochemical processes create CO2 sources/sinks by altering seawater AT and CT • Source/sink strength depends on local seawater ‘isocapnic quotient’ (Q) • Q depends on seawater temperature and the state of the marine carbonate system • Spatiotemporal variability in Q drives heterogeneous CO2 source/sink magnitude • Future warming and CO2 emissions will modify Q and the size of CO2 sources/sinks Abstract The ocean holds a large reservoir of carbon dioxide (CO2), and mitigates climate change through uptake of anthropogenic CO2. Fluxes of CO2 between the atmosphere and surface ocean are regulated by a number of physical and biogeochemical processes, resulting in a spatiotemporally heterogeneous CO2 distribution. Determining the influence of each individual process is useful for interpreting marine carbonate system observations, and is also necessary to investigate how changes in these drivers could affect air-sea CO2 exchange. Biogeochemical processes exert an influence primarily through modifying seawater dissolved inorganic carbon (CT) and total alkalinity (AT), thus changing the seawater partial pressure of CO2 (psw). Here, we propose a novel conceptual framework through which the size of the CO2 source or sink generated by any biogeochemical process, denoted Φ, can be evaluated. This is based on the ‘isocapnic quotient’ (Q), which defines the trajectory through (AT,CT) phase space for which there is no change in psw. We discuss the limitations and uncertainties inherent in this technique, which are negligible for most practical purposes, and its links with existing, related approaches. We investigate the effect on Φ of spatiotemporal heterogeneity in Q in the present day surface ocean for several key biogeochemical processes. This leads the magnitude of the CO2 source or sink generated by processes that modify AT to vary spatiotemporally. Finally, we consider how the strength of each process as a CO2 source or sink may change in a warmer, higher-CO2 future ocean.

Description: Highlights • Pb concentrations and isotope ratios presented for GEOTRACES section GA06. • Northern and southern hemisphere water masses have distinct Pb isotope ratios. • Pb isotope ratios consistent with ventilation timescales of northern water masses. • Mixing complicates interpretation of Pb distributions in southern water masses. Abstract Anthropogenic emissions have dominated marine Pb sources during the past century. Here we present Pb concentrations and isotope compositions for ocean depth profiles collected in the eastern Tropical Atlantic Ocean (GEOTRACES section GA06), to trace the transfer of anthropogenic Pb into the ocean interior. Variations in Pb concentration and isotope composition were associated with changes in hydrography. Water masses ventilated in the southern hemisphere generally featured lower 206Pb/207Pb and 208Pb/207Pb ratios than those ventilated in the northern hemisphere, in accordance with Pb isotope data of historic anthropogenic Pb emissions. The distributions of Pb concentrations and isotope compositions in northern sourced waters were consistent with differences in their ventilation timescales. For example, a Pb concentration maximum at intermediate depth (600–900 m, 35 pmol kg−1) in waters sourced from the Irminger/Labrador Seas, is associated with Pb isotope compositions (206Pb/207Pb = 1.1818–1.1824, 208Pb/207Pb = 2.4472–2.4483) indicative of northern hemispheric emissions during the 1950s and 1960s close to peak leaded petrol usage, and a transit time of ∼50–60 years. In contrast, North Atlantic Deep Water (2000–4000 m water depth) featured lower Pb concentrations and isotope compositions (206Pb/207Pb = 1.1762–1.184, 208Pb/207Pb = 2.4482–2.4545) indicative of northern hemispheric emissions during the 1910s and 1930s and a transit time of ∼80–100 years. This supports the notion that transient anthropogenic Pb inputs are predominantly transferred into the ocean interior by water mass transport. However, the interpretation of Pb concentration and isotope composition distributions in terms of ventilation timescales and pathways is complicated by (1) the chemical reactivity of Pb in the ocean, and (2) mixing of waters ventilated during different time periods. The complex effects of water mass mixing on Pb distributions is particularly apparent in seawater in the Tropical Atlantic Ocean which is ventilated from the southern hemisphere. In particular, South Atlantic Central Water and Antarctic Intermediate Water were dominated by anthropogenic Pb emitted during the last 50–100 years, despite estimates of much older average ventilation ages in this region.

Description: The GEOTRACES Intermediate Data Product 2017 (IDP2017) is the second publicly available data product of the international GEOTRACES programme, and contains data measured and quality controlled before the end of 2016. The IDP2017 includes data from the Atlantic, Pacific, Arctic, Southern and Indian oceans, with about twice the data volume of the previous IDP2014. For the first time, the IDP2017 contains data for a large suite of biogeochemical parameters as well as aerosol and rain data characterising atmospheric trace element and isotope (TEI) sources. The TEI data in the IDP2017 are quality controlled by careful assessment of intercalibration results and multi-laboratory data comparisons at crossover stations. The IDP2017 consists of two parts: (1) a compilation of digital data for more than 450 TEIs as well as standard hydrographic parameters, and (2) the eGEOTRACES Electronic Atlas providing an on-line atlas that includes more than 590 section plots and 130 animated 3D scenes. The digital data are provided in several formats, including ASCII, Excel spreadsheet, netCDF, and Ocean Data View collection. Users can download the full data packages or make their own custom selections with a new on-line data extraction service. In addition to the actual data values, the IDP2017 also contains data quality flags and 1-σ data error values where available. Quality flags and error values are useful for data filtering and for statistical analysis. Metadata about data originators, analytical methods and original publications related to the data are linked in an easily accessible way. The eGEOTRACES Electronic Atlas is the visual representation of the IDP2017 as section plots and rotating 3D scenes. The basin-wide 3D scenes combine data from many cruises and provide quick overviews of large-scale tracer distributions. These 3D scenes provide geographical and bathymetric context that is crucial for the interpretation and assessment of tracer plumes near ocean margins or along ridges. The IDP2017 is the result of a truly international effort involving 326 researchers from 22 countries. This publication provides the critical reference for unpublished data, as well as for studies that make use of a large cross-section of data from the IDP2017.

Description: Oxygen minimum zones (OMZs) cover extensive areas of eastern boundary ocean regions and play an important role in the cycling of the essential micronutrient iron (Fe). The isotopic composition of dissolved Fe (dFe) in shelf and slope waters on the Senegalese margin was determined to investigate the processes leading to enhanced dFe concentrations (up to 2 nM) in this tropical North Atlantic OMZ. On the shelf, the delta Fe-56 value of dFe (relative to the reference material IRMM-014) was as low as -0.33 parts per thousand, which can be attributed to input of dFe from both reductive and nonreductive dissolution of sediments. Benthic inputs of dFe are subsequently upwelled to surface waters and recycled in the water column by biological uptake and remineralisation processes. Remineralised dFe is characterised by relatively high delta Fe-56 values (up to + 0.41 parts per thousand), and the contribution of remineralised Fe to the total dFe pool increases with distance from the shelf. Remineralisation plays an important role in the redistribution of dFe that is mainly supplied by benthic and atmospheric inputs, although dust inputs, estimated from dissolved aluminium concentrations, were low at the time of our study (2-9 nmol dFe m(-2) d(-1)). As OMZs are expected to expand as climate warms, our data provide important insights into Fe sources and Fe cycling in the tropical North Atlantic Ocean.

Description: Constraints on the variability of chromium (Cr) isotopic compositions in the modern ocean are required to validate the use of Cr isotopic signatures in ancient authigenic marine sediments for reconstructing past levels of atmospheric and ocean oxygenation. This study presents dissolved Cr concentrations (Cr-T, where Cr-T = Cr(VI) + Cr(III)) and Cr isotope data (delta Cr-53) for shelf, slope and open ocean waters within the oxygen minimum zone (OMZ) of the eastern sub-tropical Atlantic Ocean. Although dissolved oxygen concentrations were as low as 44-90 mu mol kg(-1) in the core of the OMZ, there was no evidence for removal of Cr(VI). Nonetheless, there was significant variability in seawater delta Cr-53, with values ranging from 1.08 to 1.72 parts per thousand. Shelf Cr-T concentrations were slightly lower (2.21 +/- 0.07 nmol kg(-1)) than in open ocean waters at the same water depth (between 0 and 160 m, 2.48 +/- 0.07 nmol kg(-1)). The shelf waters also had higher delta Cr-53 values (1.41 +/- 0.14 parts per thousand compared to 1.18 +/- 0.05 parts per thousand for open ocean waters shallower than 160 m). This is consistent with partial reduction of Cr(VI) to Cr(III), with subsequent removal of isotopically light Cr(III) onto biogenic particles. We also provide evidence for input of relatively isotopically heavy Cr from sediments on the shelf. Intermediate and deep water masses (AAIW and NADW) show a rather limited range of delta Cr-53 values (1.19 +/- 0.09 parts per thousand) and inputs of Cr from remineralisation of organic material or re-oxidation of Cr (III) appear to be minimal. Authigenic marine precipitates deposited in deep water in the open ocean therefore have the potential to faithfully record seawater delta Cr-53, whereas archives of seawater delta Cr-53 derived from shelf sediments must be interpreted with caution.

Description: The aggregation behaviour of polymer-coated silver nanoparticles (AgNPs) was characterized in NaCl solutions, and in two seawaters of different salinities and dissolved organic matter (DOM) contents. Representative organic coatings i.e. tannic acid (TA), alginic acid (ALG), two gum Arabic samples (GAL and GAH), branched polyethylenimine (BPEI), and non-ionic surfactants (reference material NM-300K) were selected to cover a wide range of zeta-potentials. The stability in NaCl solutions, as determined from the rate of variation in hydrodynamic size within a timeframe of one hour, followed the order BPEI ≫ NM-300K ≈ GAL ≫ ALG ≈ TA ≫ GAH. In the seawater samples the order was NM-300K ≈ GAL ≫ ALG 〉 GAH 〉 TA ≈ BPEI, and only TA, GAL and NM-300K batches behaved as expected from the NaCl experiments. Remarkably, the BPEI sample showed the largest aggregation rate in the seawater sample with the highest DOM concentration (277 μM C). The GAH sample displayed a non-monotonic variation in aggregation rate with NaCl concentration, apparently due to concomitant precipitation of AgCl. The results indicate that non-electrostatic stabilization mechanisms and DOM-coating interactions are important for the prediction of stability and persistence of polymer-coated AgNPs in seawater.

Description: Copper (Cu) is both an essential micronutrient and toxic to photosynthesizing microorganisms at low concentrations. Its dissolved vertical distribution in the oceans is unusual, being neither a nutrient-type nor scavenged-type element. This distribution is attributed to biological uptake in the surface ocean with remineralisation at depth, combined with strong organic complexation by dissolved ligands, scavenging onto particles, and benthic sedimentary input. We present coupled dissolved and particulate phase Cu isotope data along the UK-GEOTRACES South Atlantic section, alongside higher resolution dissolved and particulate phase Cu concentration measurements. Our dissolved phase isotope data contribute to an emerging picture of homogeneous deep ocean δ65Cu, at about +0.65‰ (relative to NIST SRM 976). We identify two pools of Cu in the particulate phase: a refractory, lithogenic pool, at about 0‰, and a labile pool accessed via a weak acidic leach, at about +0.4‰. These two pools are comparable to those previously observed in sediments. We observe deviations towards lighter δ65Cu values in the dissolved phase associated with local enrichments in particulate Cu concentrations along the continental slopes, and in the surface ocean. Copper isotopes are thus a sensitive indicator of localised particle-associated benthic or estuarine Cu inputs. The measurement of Cu isotopes in seawater is analytically challenging, and we call for an intercalibration exercise to better evaluate the potential impacts of UV-irradiation, storage time, and different analytical procedures.

Description: The stoichiometric dissociation constants of carbonic acid ( and ) were determined by measurement of all four measurable parameters of the carbonate system (total alkalinity, total dissolved inorganic carbon, pH on the total proton scale, and CO2 fugacity) in natural seawater and seawater-derived brines, with a major ion composition equivalent to that Reference Seawater, to practical salinity (SP) 100 and from 25 °C to the freezing point of these solutions and –6 °C temperature minimum. These values, reported in the total proton scale, provide the first such determinations at below-zero temperatures and for SP 〉 50. The temperature (T, in Kelvin) and SP dependence of the current and (as negative common logarithms) within the salinity and temperature ranges of this study (33 ≤ SP ≤ 100, –6 °C ≤ t ≤ 25 °C) is described by the following best-fit equations: = –176.48 + 6.14528 – 0.127714 SP + 7.396×10–5 + (9914.37 – 622.886 + 29.714 SP) T–1 + (26.05129 – 0.666812 ) lnT (σ = 0.011, n = 62), and = –323.52692 + 27.557655 + 0.154922 SP – 2.48396×10–4 + (14763.287 – 1014.819 – 14.35223 SP) T–1 + (50.385807 – 4.4630415 ) lnT (σ = 0.020, n = 62). These functions are suitable for application to investigations of the carbonate system of internal sea ice brines with a conservative major ion composition relative to that of Reference Seawater and within the temperature and salinity ranges of this study.

Description: The oceans are a major sink for anthropogenic atmospheric carbon dioxide, and the uptake causes changes to the marine carbonate system and has wide ranging effects on flora and fauna. It is crucial to develop analytical systems that allow us to follow the increase in oceanic pCO(2) and corresponding reduction in pH. Miniaturised sensor systems using immobilised fluorescence indicator spots are attractive for this purpose because of their simple design and low power requirements. The technology is increasingly used for oceanic dissolved oxygen measurements. We present a detailed method on the use of immobilised fluorescence indicator spots to determine pH in ocean waters across the pH range 7.6-8.2. We characterised temperature (-0.046 pH/degrees C from 5 to 25 degrees C) and salinity dependences (-0.01 pH/psu over 5-35), and performed a preliminary investigation into the influence of chlorophyll on the pH measurement. The apparent pK(a) of the sensor spots was 6.93 at 20 degrees C. A drift of 0.00014 R (ca. 0.0004 pH, at 25 degrees C, salinity 35) was observed over a 3 day period in a laboratory based drift experiment. We achieved a precision of 0.0074 pH units, and observed a drift of 0.06 pH units during a test deployment of 5 week duration in the Southern Ocean as an under way surface ocean sensor, which was corrected for using certified reference materials. The temperature and salinity dependences were accounted for with the algorithm, R = (0.00034 - 0.17.pH + 0.15.S-2 + 0.0067.T - 0.0084.S) . 1.075. This study provides a first step towards a pH optode system suitable for autonomous deployment. The use of a short duration low power illumination (LED current 0.2 mA, 5 mu s illumination time) improved the lifetime and precision of the spot. Further improvements to the pH indicator spot operations include regular application of certified reference materials for drift correction and cross-calibration against a spectrophotometric pH system. Desirable future developments should involve novel fluorescence spots with improved response time and apparent pK(a) values closer to the pH of surface ocean waters.

Description: Polar oceans are particularly vulnerable to ocean acidification due to their low temperatures and reduced buffering capacity, and are expected to experience extensive low pH conditions and reduced carbonate mineral saturations states (Ω) in the near future. However, the impact of anthropogenic CO2 on pH and Ω will vary regionally between and across the Arctic and Southern Oceans. Here we investigate the carbonate chemistry in the Atlantic sector of two polar oceans, the Nordic Seas and Barents Sea in the Arctic Ocean, and the Scotia and Weddell Seas in the Southern Ocean, to determine the physical and biogeochemical processes that control surface pH and Ω. High-resolution observations showed large gradients in surface pH (0.10 to 0.30) and aragonite saturation state (Ωar) (0.2 to 1.0) over small spatial scales, and these were particularly strong in sea-ice covered areas (up to 0.45 in pH and 2.0 in Ωar). In the Arctic, sea-ice melt facilitated bloom initiation in light-limited and iron replete (dFe〉0.2 nM) regions, such as the Fram Strait, resulting in high pH (8.45) and Ωar (3.0) along the sea-ice edge. In contrast, accumulation of dissolved inorganic carbon derived from organic carbon mineralisation under the ice resulted in low pH (8.05) and Ωar (1.1) in areas where thick ice persisted. In the Southern Ocean, sea-ice retreat resulted in bloom formation only where terrestrial inputs supplied sufficient iron (dFe〉0.2 nM), such as in the vicinity of the South Sandwich Islands where enhanced pH (8.3) and Ωar (2.3) were primarily due to biological production. In contrast, in the adjacent Weddell Sea, weak biological uptake of CO2 due to low iron concentrations (dFe〈0.2 nM) resulted in low pH (8.1) and Ωar (1.6). The large spatial variability in both polar oceans highlights the need for spatially resolved surface data of carbonate chemistry variables but also nutrients (including iron) in order to accurately elucidate the large gradients experienced by marine organisms and to understand their response to increased CO2 in the future.