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

Dissolved carbon and CDOM in lake ice and underlying waters along a salinity gradient in shallow lakes of Northeast China

The variations of DOC and DIC concentrations in lake ice and underlying waters were examined in 40 shallow lakes across the Songnen Plain, Northeast China. The lakes, frozen annually during winter, included freshwater and brackish systems (EC > 1000 μS cm−1; range: 171–12607 μS cm−1 in underlying water). Results showed that lake ice contained lower DOC (7.2 mg L−1) and DIC (6.7 mg L−1) concentration compared to the underlying waters (58.2 and 142.4 mg L−1, respectively). Large differences in DOC and DIC concentrations of underlying waters were also observed between freshwater (mean ± SD: 22.3 ± 11.5 mg L−1, 50.7 ± 20.6 mg L−1) and brackish lakes (83.3 ± 138.0 mg L−1, 247.0 ± 410.5 mg L−1). A mass balance model was developed to describe the relative distribution of solutes and chemical attributes between ice and the underlying waters. Results showed that water depth and ice thickness were the key factors regulating the spatial distribution of solutes in the frozen lakes. Chromophoric dissolved organic matter (CDOM) absorption coefficient at 320 nm, aCDOM(320) and specific UV absorbance (SUVA254) were used to characterize CDOM composition and quality. Compared to the underlying waters, CDOM present in ice largely included low aromaticity organic substances, an outcome perhaps facilitated by ice formation and photo-degradation. In ice and underlying freshwaters, CDOM predominantly included organic C fractions of high aromaticity, while low aromaticity organic substances were observed for brackish lakes. Results of this study suggest that, if water salinity increases due to climate change and anthropogenic activities, significant changes can occur in the dissolved carbon and fate of CDOM in these shallow lakes

Optical properties and bioavailability of dissolved organic matter along a flow-path continuum from soil pore waters to the Kolyma River mainstem, East Siberia

The Kolyma River in northeast Siberia is among the six largest Arctic rivers and drains a region underlain by vast deposits of Holocene-aged peat and Pleistocene-aged loess known as yedoma, most of which is currently stored in ice-rich permafrost throughout the region. These peat and yedoma deposits are important sources of dissolved organic matter (DOM) to inland waters that in turn play a significant role in the transport and ultimate remineralization of organic carbon to CO2 and CH4 along the terrestrial flow-path continuum. The turnover and fate of terrigenous DOM during offshore transport largely depends upon the composition and amount of carbon released to inland and coastal waters. Here, we measured the ultraviolet-visible optical properties of chromophoric DOM (CDOM) from a geographically extensive collection of waters spanning soil pore waters, streams, rivers, and the Kolyma River mainstem throughout a  ∼  250 km transect of the northern Kolyma River basin. During the period of study, CDOM absorption coefficients were found to be robust proxies for the concentration of DOM, whereas additional CDOM parameters such as spectral slopes (S) were found to be useful indicators of DOM quality along the flow path. In particular, the spectral slope ratio (SR) of CDOM demonstrated statistically significant differences between all four water types and tracked changes in the concentration of bioavailable DOC, suggesting that this parameter may be suitable for clearly discriminating shifts in organic matter characteristics among water types along the full flow-path continuum across this landscape. However, despite our observations of downstream shifts in DOM composition, we found a relatively constant proportion of DOC that was bioavailable ( ∼  3–6 % of total DOC) regardless of relative water residence time along the flow path. This may be a consequence of two potential scenarios allowing for continual processing of organic material within the system, namely (a) aquatic microorganisms are acclimating to a downstream shift in DOM composition and/or (b) photodegradation is continually generating labile DOM for continued microbial processing of DOM along the flow-path continuum. Without such processes, we would otherwise expect to see a declining fraction of bioavailable DOC downstream with increasing residence time of water in the system. With ongoing and future permafrost degradation, peat and yedoma deposits throughout the northeast Siberian region will become more hydrologically active, providing greater amounts of DOM to fluvial networks and ultimately to the Arctic Ocean. The ability to rapidly and comprehensively monitor shifts in the quantity and quality of DOM across the landscape is therefore critical for understanding potential future feedbacks within the Arctic carbon cycle

Technical Note: Comparison of storage strategies of sea surface microlayer samples

The sea surface microlayer (SML) is an important biogeochemical system whose physico-chemical analysis often necessitates some degree of sample storage. However, many SML components degrade with time so the development of optimal storage protocols is paramount. We here briefly review some commonly used treatment and storage protocols. Using freshwater and saline SML samples from a river estuary, we investigated temporal changes in surfactant activity (SA) and the absorbance and fluorescence of chromophoric dissolved organic matter (CDOM) over four weeks, following selected sample treatment and storage protocols. Some variability in the effectiveness of individual protocols most likely reflects sample provenance. None of the various protocols examined performed any better than dark storage at 4 °C without pre-treatment. We therefore recommend storing samples refrigerated in the dark

Sources and transformations of dissolved lignin phenols and chromophoric dissolved organic matter in Otsuchi Bay, Japan

Dissolved lignin phenols and optical properties of dissolved organic matter (DOM) were measured to investigate the sources and transformations of terrigenous DOM (tDOM) in Otsuchi Bay, Japan. Three rivers discharge into the bay, and relatively high values of syringyl:vanillyl phenols (0.73 ± 0.07) and cinnamyl:vanillyl phenols (0.33 ± 0.10) indicated large contributions of non-woody angiosperm tissues to lignin and tDOM. The physical mixing of river and seawater played an important role in controlling the concentrations and distributions of lignin phenols and chromophoric DOM (CDOM) optical properties in the bay. Lignin phenol concentrations and the CDOM absorption coefficient at 350 nm, a(350), were strongly correlated in river and bay waters. Measurements of lignin phenols and CDOM in bay waters indicated a variety of photochemical and biological transformations of tDOM, including oxidation reactions, photobleaching and a decrease in molecular weight. Photodegradation and biodegradation of lignin and CDOM were investigated in decomposition experiments with river water and native microbial assemblages exposed to natural sunlight or kept in the dark. There was a rapid and substantial removal of lignin phenols and CDOM during the first few days in the light treatment, indicating transformations of tDOM and CDOM can occur soon after discharge of buoyant river water into the bay. The removal of lignin phenols was slightly greater in the dark (34%) than in the light (30%) during the remaining 59 days of the incubation. Comparison of the light and dark treatments indicated biodegradation was responsible for 67% of total lignin phenols removal during the 62-day incubation exposed to natural sunlight, indicating biodegradation is a dominant removal process in Otsuchi Bay.Ministry of Education, Culture, Sports, Science, and Technology; 1504137 - National Science Foundatio

Using Moored Arrays and Hyperspectral Aerial Imagery to Develop Nutrient Criteria for New Hampshire\u27s Estuaries

Increasing nitrogen concentrations and declining eelgrass beds in Great Bay, NH are clear indicators of impending problems for the state’s estuaries. A workgroup established in 2005 by the NH Department of Environmental Services and the NH Estuaries Project (NHEP) adopted eelgrass survival as the water quality target for nutrient criteria development for NH’s estuaries. In 2007, the NHEP received a grant from the U.S. Environmental Protection Agency to collect water quality information including that from moored sensors and hyper-spectral imagery data of the Great Bay Estuary. Data from the Great Bay Coastal Buoy, part of the regional Integrated Ocean Observing System (IOOS), were used to derive a multivariate model of water clarity with phytoplankton, Colored Dissolved Organic Matter (CDOM), and non-algal particles. Non-algal particles include both inorganic and organic matter. Most of the temporal variability in the diffuse attenuation coefficient of Photosynthetically Available Radiation (PAR) was associated with non-algal particles. However, on a mean daily basis non-algal particles and CDOM contributed a similar fraction (~30 %) to the attenuation of light. The contribution of phytoplankton was about a third of the other two optically important constituents. CDOM concentrations varied with salinity and magnitude of riverine inputs demonstrating its terrestrial origin. Non-algal particle concentration also varied with river flow but also wind driven resuspension. Twelve of the NHEP estuarine assessment zones were observed with the hyperspectral aerial imagery on August 29 and October 17. A concurrent in situ effort included buoy measurements, continuous along-track sampling, discrete water grab samples, and vertical profiles of light attenuation. PAR effective attenuation coefficients retrieved from deep water regions in the imagery agreed well with in-situ observations. Water clarity was lower and optically important constituent concentrations were higher in the tributaries. Eelgrass survival depth, estimated as the depth at which 22% of surface light was available, ranged from less than half a meter to over two meters. The best water clarity was found in the Great Bay (GB), Little Bay (LB), and Lower Piscataqua River (LPR) assessment zones. Absence of eelgrass from these zones would indicate controlling factors other than water clarity

Oxygen photolysis in the Mauritanian upwelling: Implications for net community production

We carried out 16 photochemical experiments of filtered surface water in a custom-built solar simulator and concomitant measurements of in vitro gross primary production (GPP) and respiration (R) in the Mauritanian upwelling during a Lagrangian study following three sulfur hexafluoride–labeled patches of upwelled water (P1 to P3). Oxygen photolysis rates were correlated with the absorbance of chromophoric dissolved organic matter (CDOM) at 300 nm, suggesting first-order kinetics with respect to CDOM. An exponential fit was used to calculate the apparent quantum yield (AQY) for oxygen photolysis, giving an average AQY of 0.00053 mmol O2 (mole photons m22 s21)21 at 280 nm and slope of 0.0012 nm21. Modeled photochemical oxygen demand (POD) at the surface (3–16 mmol m23 d21) occasionally exceeded R and was dominated by ultraviolet radiation (71– 79%). Euphotic-layer integrated GPP decreased with time during both P-1 and P-3, whereas R remained relatively constant and POD increased during P-1 and decreased during P-3. On Day 4 of P-3, GPP and POD maxima coincided with high CDOM absorbance, suggesting ‘‘new’’ CDOM production. Omitting POD may lead to an underestimation of net community production (NCP), both through in vitro and geochemical methods (here by 2–22%). We propose that oxygen-based NCP estimates should be revised upward. For the Mauritanian upwelling, the POD-corrected NCP was strongly correlated with standard NCP with a slope of 1.0066 6 0.0244 and intercept of 46.51 6 13.15 mmol m22 d21

Effects of integration time on in-water radiometric profiles

This work investigates the effects of integration time on in-water downward irradiance E-d, upward irradiance E-u and upwelling radiance L-u profile data acquired with free-fall hyperspectral systems. Analyzed quantities are the subsurface value and the diffuse attenuation coefficient derived by applying linear and non-linear regression schemes. Case studies include oligotrophic waters (Case-1), as well as waters dominated by colored dissolved organic matter (CDOM) and non-algal particles (NAP). Assuming a 24-bit digitization, measurements resulting from the accumulation of photons over integration times varying between 8 and 2048ms are evaluated at depths corresponding to: 1) the beginning of each integration interval (FST); 2) the end of each integration interval (LST); 3) the averages of FST and LST values (AVG); and finally 4) the values weighted accounting for the diffuse attenuation coefficient of water (WGT). Statistical figures show that the effects of integration time can bias results well above 5% as a function of the depth definition. Results indicate the validity of the WGT depth definition and the fair applicability of the AVG one. Instead, both the FST and LST depths should not be adopted since they may introduce pronounced biases in E-u and L-u regression products for highly absorbing waters. Finally, the study reconfirms the relevance of combining multiple radiometric casts into a single profile to increase precision of regression products. (C) 2018 Optical Society of America under the terms of the OSA Open Access Publishing Agreement

Estimating specific inherent optical properties of tropical coastal waters using bio-optical model inversion and in situ measurements: case of the Berau estuary, East Kalimantan, Indonesia

Specific inherent optical properties (SIOP) of the Berau coastal waters were derived from in situ measurements and inversion of an ocean color model. Field measurements of water-leaving reflectance, total suspended matter (TSM), and chlorophyll a (Chl a) concentrations were carried out during the 2007 dry season. The highest values for SIOP were found in the turbid waters, decreasing in value when moving toward offshore waters. The specific backscattering coefficient of TSM varied by an order of magnitude and ranged from 0.003 m2 g-1, for clear open ocean waters, to 0.020 m2 g-1, for turbid waters. On the other hand, the specific absorption coefficient of Chl a was relatively constant over the whole study area and ranged from 0.022 m2 mg-1, for the turbid shallow estuary waters, to 0.027 m2 mg-1, for deeper shelf edge ocean waters. The spectral slope of colored dissolved organic matter light absorption was also derived with values ranging from 0.015 to 0.011 nm-1. These original derived values of SIOP in the Berau estuary form a corner stone for future estimation of TSM and Chl a concentration from remote sensing data in tropical equatorial water