Inter-comparison of salt effect correction for δ 18 O and δ 2 H measurements in seawater by CRDS and IRMS using the gas-H 2 O equilibration method

The isotope composition of seawater is an efficient method for detecting mixing between water masses. To measure long term or large scale hydrological processes at the ocean surface, it is necessary to be able to precisely compare datasets produced by different laboratories. The oxygen and hydrogen isotope (δ18O and δ2H) composition of marine waters can be measured using isotope ratio mass spectrometry (IRMS) and near-infrared laser absorption spectroscopy (LS) techniques. The IRMS and equilibration method is thought to provide results on the activity scale, while LS provides results on the concentration scale. However, the effect of dissolved seawater salts on the measurement is not sufficiently assessed and seems sometimes contradictory in the literature. For this purpose, we made artificial seawater and a pure NaCl solution from a freshwater of known isotope composition. The solutions were measured by four different laboratories allowing us to compare the two techniques. We show that minor corrections are necessary to correct seawater measurements for the salt effect and report them on the concentration scale. Interestingly, seawater measurements using LS (type Picarro) coupled to a liner are not on the concentration scale and require a correction of ~ 0.09‰ for δ18O, while the correction is relatively less significant for δ2H (~ 0.13‰). Moreover, we found for IRMS measurements that the salt effect can differ between different laboratories but seems reproducible for a given laboratory. A natural sea water sample was then analyzed by the different laboratories participating in the study. We found that applying the corrections increases the reproducibility of the isotope measurement significantly, with inter-laboratory standard deviation decreasing from 0.06 to 0.02‰ and 0.55 to 0.23‰ for δ18O and δ2H, respectively. Thus, comparing sea water datasets produced in different laboratories requires that each laboratory carries out its own calibration with artificial seawater and presents measurements on the concentration scale

Nitrate supply routes and impact of internal cycling in the North Atlantic Ocean inferred from nitrate isotopic composition

In this study we report full‐depth water column profiles for nitrogen and oxygen isotopic composition (δ15N and δ18O) of nitrate (NO3‐) during the GEOTRACES GA01 cruise (2014). This transect intersects the double gyre system of the subtropical and subpolar regions of the North Atlantic separated by a strong transition zone, the North Atlantic Current. The distribution of NO3‐ δ15N and δ18O shows that assimilation by phytoplankton is the main process controlling the NO3‐ isotopic composition in the upper 150 m, with values increasing in a NO3‐ δ18O versus δ15N space along a line with a slope of one towards the surface. In the subpolar gyre, a single relationship between the degree of NO3‐ consumption and residual NO3‐ δ15N supports the view that NO3‐ is supplied via Ekman upwelling and deep winter convection, and progressively consumed during the Ekman transport of surface water southward. The co‐occurrence of partial NO3‐ assimilation and nitrification in the deep mixed layer of the subpolar gyre elevates subsurface NO3‐ δ18O in comparison to deep oceanic values. This signal propagates through isopycnal exchanges to greater depths at lower latitudes. With recirculation in the subtropical gyre, cycles of quantitative consumption‐nitrification progressively decrease subsurface NO3‐ δ18O toward the δ18O of regenerated NO3‐. The low NO3‐ δ15N observed south of the Subarctic Front is mostly explained by N2 fixation, although a contribution from the Mediterranean outflow is required to explain the lower NO3‐ δ15N signal observed between 600 and 1500 m depth close to the Iberian margin

Antarctic sea ice trophic status

This study focuses on analyses and validation of 1 month forecasts (OMFs) of weak Indian monsoons based on 10 member ensemble hindcasts (retrospective forecasts) of the NCEP Climate Forecast System (CFS) model for the period 1981–2008. The weak monsoon episodes chosen for the analysis correspond to summer monsoon months which were characterized by significant deficits in the All-India monthly rainfall of − 20% of the climatological normal. Examination of the CFS-OMFs shows poor skill of the model in capturing the observed rainfall and circulation anomalies during weak monsoons. The present analysis suggests that deficiencies in realistically capturing the ocean-atmosphere coupling in the tropical Indian Ocean (IO) introduces biases in simulating sea surface temperature and rainfall anomalies in the equatorial region, which in turn affects the monsoon precipitation forecasts over the sub-continent. In particular, the mean thermocline in the near-equatorial IO is found to be practically flat in the CFS model, so that the near-equatorial anomalies in the model are not strong enough to weaken the summer monsoon circulation and reduce the monsoon precipitation over India. By examining a 100 year free run of the CFS model, it is seen that moderate monsoon-droughts simulated by the model have weak teleconnections with the equatorial IO dynamics. On the other hand, intense monsoon-droughts in the CFS-model are found be remarkably linked with the equatorial IO anomalies. It is suggested that improving the slope of the equatorial IO thermocline and allowing for more realistic IO-monsoon coupling in the CFS-model would be an important step for improving the skill of extended-range monsoon forecasts

Methods for biogeochemical studies of sea ice: The state of the art, caveats, and recommendations

AbstractOver the past two decades, with recognition that the ocean’s sea-ice cover is neither insensitive to climate change nor a barrier to light and matter, research in sea-ice biogeochemistry has accelerated significantly, bringing together a multi-disciplinary community from a variety of fields. This disciplinary diversity has contributed a wide range of methodological techniques and approaches to sea-ice studies, complicating comparisons of the results and the development of conceptual and numerical models to describe the important biogeochemical processes occurring in sea ice. Almost all chemical elements, compounds, and biogeochemical processes relevant to Earth system science are measured in sea ice, with published methods available for determining biomass, pigments, net community production, primary production, bacterial activity, macronutrients, numerous natural and anthropogenic organic compounds, trace elements, reactive and inert gases, sulfur species, the carbon dioxide system parameters, stable isotopes, and water-ice-atmosphere fluxes of gases, liquids, and solids. For most of these measurements, multiple sampling and processing techniques are available, but to date there has been little intercomparison or intercalibration between methods. In addition, researchers collect different types of ancillary data and document their samples differently, further confounding comparisons between studies. These problems are compounded by the heterogeneity of sea ice, in which even adjacent cores can have dramatically different biogeochemical compositions. We recommend that, in future investigations, researchers design their programs based on nested sampling patterns, collect a core suite of ancillary measurements, and employ a standard approach for sample identification and documentation. In addition, intercalibration exercises are most critically needed for measurements of biomass, primary production, nutrients, dissolved and particulate organic matter (including exopolymers), the CO2 system, air-ice gas fluxes, and aerosol production. We also encourage the development of in situ probes robust enough for long-term deployment in sea ice, particularly for biological parameters, the CO2 system, and other gases.This manuscript is a product of SCOR working group 140 on Biogeochemical Exchange Processes at Sea-Ice Interfaces (BEPSII); we thank BEPSII chairs Jacqueline Stefels and Nadja Steiner and SCOR executive director Ed Urban for their practical and moral support of this endeavour. This manuscript was first conceived at an EU COST Action 735 workshop held in Amsterdam in April 2011; in addition to COST 735, we thank the other participants of the “methods” break-out group at that meeting, namely Gerhard Dieckmann, Christoph Garbe, and Claire Hughes. Our editors, Steve Ackley and Jody Deming, and our reviewers, Mats Granskog and two anonymous reviewers, provided invaluable advice that not only identified and helped fill in some gaps, but also suggested additional ways to make what is by nature a rather dry subject (methods) at least a bit more interesting and accessible. We also thank the librarians at the Institute of Ocean Sciences for their unflagging efforts to track down the more obscure references we required. Finally, and most importantly, we thank everyone who has braved the unknown and made the new measurements that have helped build sea-ice biogeochemistry into the robust and exciting field it has become.This is the final published article, originally published in Elementa: Science of the Anthropocene, 3: 000038, doi: 10.12952/journal.elementa.00003

Temporal controls on silicic acid utilisation along the West Antarctic Peninsula

The impact of climatic change along the Antarctica Peninsula has been widely debated in light of atmospheric/oceanic warming and increases in glacial melt over the past half century. Particular concern exists over the impact of these changes on marine ecosystems, not only on primary producers but also on higher trophic levels. Here we present a record detailing the historical controls on the biogeochemical cycling of silicic acid [Si(OH)4] on the west Antarctica Peninsula margin, a region in which the modern phytoplankton environment is constrained by seasonal sea-ice. We demonstrate that Si(OH)4 cycling through the Holocene alternates between being primarily regulated by sea-ice or glacial discharge from the surrounding grounded ice-sheet. With further climate-driven change and melting forecast for the 21st Century, our findings document the potential for biogeochemical cycling and multi-trophic interactions along the peninsula to be increasingly regulated by glacial discharge, altering food-web interactions