Open ocean carbon monoxide photo-production

Sunlight-initiated photolysis of chromophoric dissolved organic matter (CDOM) is the dominant source of carbon monoxide (CO) in the open-ocean. A modelling study was conducted to constrain this source. Spectral solar irradiance was obtained from two models (GCSOLAR and SMARTS2). Water-column CDOM and total light absorption were modelled using spectra collected along a Meridional transect of the Atlantic ocean using a 200-cm pathlength liquid waveguide UV-visible spectrophotometer. Apparent quantum yields for the production of CO (AQYCO) from CDOM were obtained from a parameterisation describing the relationship between CDOM light absorption coefficient and AQYCO and the CDOM spectra collected. The sensitivity of predicted rates to variations in model parameters (solar irradiance, cloud cover, surface-water reflectance, CDOM and whole water light absorbance, and AQYCO was assessed. The model\u27s best estimate of open-ocean CO photoproduction was 47 +/- 7 Tg CO-C yr-1, with lower and upper limits of 38 and 84 Tg CO-C yr-1, as indicated by sensitivity analysis considering variations in AQYs, CDOM absorbance, and spectral irradiance. These results represent significant constraint of open-ocean CO photoproduction at the lower limit of previous estimates. Based on these results, and their extrapolation to total photochemical organic carbon mineralisation, we recommend a downsizing of the role of photochemistry in the open-ocean carbon cycle. (c) 2006 Elsevier Ltd. All rights reserved

A Climate Change Atlas for the Ocean

Author Posting. © Oceanography Society, 2011. This article is posted here by permission of Oceanography Society for personal use, not for redistribution. The definitive version was published in Oceanography 24, no. 2 (2011): 13–16, doi:10.5670/oceanog.2011.42.At both regional and national levels, there is an urgent need to develop a clear picture of how climate change will alter multiple environmental properties in the ocean. Specifically, what will such cumulative alterations mean for local biological productivity, ecosystem services, climate feedbacks, and related effects ranging from biodiversity to economics? Currently, a wide range of confounding issues, such as the plethora and complexity of information in the public domain, hinders accommodating climate change into future planning and development of ocean resource management strategies. This impediment is especially true at the regional level, for example, within national Exclusive Economic Zones (EEZs), where critical management decisions are made but for which substantial uncertainty clouds climate change projections and ecosystem impact assessments. Evaluating the susceptibility of a nation's marine resources to climate change requires knowledge of the geographic and seasonal variations in environmental properties over an EEZ and the range, spatial patterns, and uncertainty of projected climate change in those properties (Boyd et al., 2007). Furthermore, information is needed on the climate sensitivity of the biological species or strains that comprise particular marine resources (Boyd et al., 2007; Nye et al., 2009) and/or contribute to food-web interactions, and also on potential implications for human resource exploitation patterns and intensity

Implementation of marine CO2 removal for climate mitigation: The challenges of additionality, predictability, and governability

Achieving net zero CO2 emissions requires gigatonne-scale atmospheric CO2 removal (CDR) to balance residual emissions that are extremely difficult to eliminate. Marine CDR (mCDR) methods are seen increasingly as potentially important additions to a global portfolio of climate policy actions. The most widely considered mCDR methods are coastal blue carbon and seaweed farming that primarily depend on biological manipulations; ocean iron fertilisation, ocean alkalinity enhancement, and direct ocean capture that depend on chemical manipulations; and artificial upwelling that depends on physical manipulation of the ocean system. It is currently highly uncertain which, if any, of these approaches might be implemented at sufficient scale to make a meaningful contribution to net zero. Here, we derive a framework based on additionality, predictability, and governability to assess implementation challenges for these mCDR methods. We argue that additionality, the net increase of CO2 sequestration due to mCDR relative to the baseline state, will be harder to determine for those mCDR methods with relatively large inherent complexity, and therefore higher potential for unpredictable impacts, both climatic and non-climatic. Predictability is inherently lower for mCDR methods that depend on biology than for methods relying on chemical or physical manipulations. Furthermore, predictability is lower for methods that require manipulation of multiple components of the ocean system. The predictability of an mCDR method also affects its governability, as highly complex mCDR methods with uncertain outcomes and greater likelihood of unintended consequences will require more monitoring and regulation, both for risk management and verified carbon accounting. We argue that systematic assessment of additionality, predictability, and governability of mCDR approaches increases their chances of leading to a net climatic benefit and informs political decision-making around their potential implementation

Methanethiol, Dimethyl Sulfide and Acetone Over Biologically Productive Waters in the Southwest Pacific Ocean

Atmospheric methanethiol (MeSHa), dimethyl sulfide (DMSa) and acetone (acetonea) were measured over biologically productive frontal waters in the remote southwest Pacific Ocean in summertime 2012 during the Surface Ocean Aerosol Production (SOAP) voyage. MeSHa mixing ratios varied from below the detection limit (\u3c 10 ppt) up to 65 ppt and were 3 %–36 % of parallel DMSa mixing ratios. MeSHa and DMSa were correlated over the voyage (R2=0.3, slope = 0.07) with a stronger correlation over a coccolithophore-dominated phytoplankton bloom (R2=0.5, slope 0.13). The diurnal cycle for MeSHa shows similar behaviour to DMSa with mixing ratios varying by a factor of ∼ 2 according to time of day with the minimum levels of both MeSHa and DMSa occurring at around 16:00 LT (local time, all times in this paper are in local time). A positive flux of MeSH out of the ocean was calculated for three different nights and ranged from 3.5 to 5.8 µmol m−2 d−1, corresponding to 14 %–24 % of the DMS flux (MeSH ∕ (MeSH + DMS)). Spearman rank correlations with ocean biogeochemical parameters showed a moderate-to-strong positive, highly significant relationship between both MeSHa and DMSa with seawater DMS (DMSsw) and a moderate correlation with total dimethylsulfoniopropionate (total DMSP). A positive correlation of acetonea with water temperature and negative correlation with nutrient concentrations are consistent with reports of acetone production in warmer subtropical waters. Positive correlations of acetonea with cryptophyte and eukaryotic phytoplankton numbers, and high-molecular-weight sugars and chromophoric dissolved organic matter (CDOM), suggest an organic source. This work points to a significant ocean source of MeSH, highlighting the need for further studies into the distribution and fate of MeSH, and it suggests links between atmospheric acetone levels and biogeochemistry over the mid-latitude ocean. In addition, an intercalibration of DMSa at ambient levels using three independently calibrated instruments showed ∼ 15 %–25 % higher mixing ratios from an atmospheric pressure ionisation chemical ionisation mass spectrometer (mesoCIMS) compared to a gas chromatograph with a sulfur chemiluminescence detector (GC-SCD) and proton transfer reaction mass spectrometer (PTR-MS). Some differences were attributed to the DMSa gradient above the sea surface and differing approaches of integrated versus discrete measurements. Remaining discrepancies were likely due to different calibration scales, suggesting that further investigation of the stability and/or absolute calibration of DMS standards used at sea is warranted

Quantified effect of seawater biogeochemistry on the temperature dependence of sea spray aerosol fluxes

Future change in sea surface temperature may influence climate via various air-sea feedbacks and pathways. In this study, we investigate the influence of surface seawater biogeochemical composition on the temperature dependence of sea spray number emission fluxes. Dependence of sea spray fluxes was investigated in different water masses (i.e. subantarctic, subtropical and frontal bloom) with contrasting biogeochemical properties across a temperature range from ambient (13&ndash;18 &deg;C) to 2 &deg;C, using seawater circulating in a plunging jet sea spray generator. We observed sea spray total concentration to increase significantly at temperatures below 8 &deg;C, with an average 4-fold increase at 2 &deg;C relative to initial concentration at ambient temperatures. This temperature dependence was more pronounced for smaller size sea spray particles (i.e. nucleation and Aitken modes). Moreover, temperature dependence varied with water mass type and so biogeochemical properties. While the sea spray flux at moderate temperatures (8&ndash;11 &deg;C) was highest in frontal bloom waters, the effect of low temperature on the sea spray flux was highest with subtropical seawaters. The temperature dependence of sea spray flux was also inversely proportional to the seawater cell abundance of the cyanobacterium Synechococcus, which facilitated parameterization of temperature dependence of sea spray emission fluxes as a function of Synechococcus for future implementation in modelling exercises.</p

Marine Carbonyl Sulfide (OCS) and Carbon Disulfide (CS\u3csub\u3e2\u3c/sub\u3e): A Compilation of Measurements in Seawater and the Marine Boundary Layer

Carbonyl sulfide (OCS) and carbon disulfide (CS2) are volatile sulfur gases that are naturally formed in seawater and exchanged with the atmosphere. OCS is the most abundant sulfur gas in the atmosphere, and CS2 is its most important precursor. They have attracted increased interest due to their direct (OCS) or indirect (CS2 via oxidation to OCS) contribution to the stratospheric sulfate aerosol layer. Furthermore, OCS serves as a proxy to constrain terrestrial CO2uptake by vegetation. Oceanic emissions of both gases contribute a major part to their atmospheric concentration. Here we present a database of previously published and unpublished (mainly shipborne) measurements in seawater and the marine boundary layer for both gases, available at https://doi.org/10.1594/PANGAEA.905430 (Lennartz et al., 2019). The database contains original measurements as well as data digitalized from figures in publications from 42 measurement campaigns, i.e., cruises or time series stations, ranging from 1982 to 2019. OCS data cover all ocean basins except for the Arctic Ocean, as well as all months of the year, while the CS2 dataset shows large gaps in spatial and temporal coverage. Concentrations are consistent across different sampling and analysis techniques for OCS. The database is intended to support the identification of global spatial and temporal patterns and to facilitate the evaluation of model simulations

The impacts of ocean acidification on marine trace gases and the implications for atmospheric chemistry and climate

Surface ocean biogeochemistry and photochemistry regulate ocean–atmosphere fluxes of trace gases critical for Earth’s atmospheric chemistry and climate. The oceanic processes governing these fluxes are often sensitive to the changes in ocean pH (or pCO2) accompanying ocean acidification (OA), with potential for future climate feedbacks. Here, we review current understanding (from observational, experimental and model studies) on the impact of OA on marine sources of key climate-active trace gases, including dimethyl sulfide (DMS), nitrous oxide (N2O), ammonia and halocarbons. We focus on DMS, for which available information is considerably greater than for other trace gases. We highlight OA-sensitive regions such as polar oceans and upwelling systems, and discuss the combined effect of multiple climate stressors (ocean warming and deoxygenation) on trace gas fluxes. To unravel the biological mechanisms responsible for trace gas production, and to detect adaptation, we propose combining process rate measurements of trace gases with longer term experiments using both model organisms in the laboratory and natural planktonic communities in the field. Future ocean observations of trace gases should be routinely accompanied by measurements of two components of the carbonate system to improve our understanding of how in situ carbonate chemistry influences trace gas production. Together, this will lead to improvements in current process model capabilities and more reliable predictions of future global marine trace gas fluxes

Insights Into the Biogeochemical Cycling of Iron, Nitrate, and Phosphate Across a 5,300 km South Pacific Zonal Section (153°E-150°W)

Iron, phosphate, and nitrate are essential nutrients for phytoplankton growth, and hence, their supply into the surface ocean controls oceanic primary production. Here we present a GEOTRACES zonal section (GP13; 30–33°S, 153°E–150°W) extending eastward from Australia to the oligotrophic South Pacific Ocean gyre outlining the concentrations of these key nutrients. Surface dissolved iron concentrations are elevated at >0.4 nmol L−1 near continental Australia (west of 165°E) and decreased eastward to ≤0.2 nmol L−1 (170°W–150°W). The supply of dissolved iron into the upper ocean (<100 m) from the atmosphere and vertical diffusivity averaged 11 ± 10 nmol m−2 d−1. In the remote South Pacific Ocean (170°W–150°W), atmospherically sourced iron is a significant contributor to the surface dissolved iron pool with average supply contribution of 23 ± 17% (range 3% to 55%). Surface water nitrate concentrations averaged 5 ± 4 nmol L−1 between 170°W and 150°W, while surface water phosphate concentrations averaged 58 ± 30 nmol L−1. The supply of nitrogen into the upper ocean is primarily from deeper waters (24–1647 μmol m−2 d−1) with atmospheric deposition and nitrogen fixation contributing <1% to the overall flux along the eastern part of the transect. The deep water N:P ratio averaged 14.5 ± 0.5 but declined to <1 above the deep chlorophyll maximum (DCM) indicating a high N:P assimilation ratio by phytoplankton leading to almost quantitative removal of nitrate. The supply stoichiometry for iron and nitrogen relative to phosphate at and above the DCM declines eastward leading to two biogeographical provinces: one with diazotroph production and the other without diazotroph production.This research was supported by the New Zealand Foundation for Research, Science and Technology Coasts and Oceans Outcome-Based Investment (COIX0501), and the Australian Research Council Discovery Projects (DP1092892 and DP110100108) and Future Fellowships (FT130100037) programs, University of Tasmania, internal grants to A. R. B. (refs B0018994, B0019024, and L0018934), and University of Technology Sydney Chancellor Fellowship to CSH