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At least 19 records

Method for determining stable isotope ratios of dissolved organic carbon in interstitial and other natural marine waters

A procedure is described for the analysis of the stable carbon isotopic composition of dissolved organic carbon (DOC) in natural waters from marine and higher-salinity environments. Rapid (less than 5 min) and complete oxidation of DOC is achieved using a modification of previous photochemical oxidation techniques. The CO2 evolved from DOC oxidation can be collected in less than 10 min for isotopic analysis. The procedure is at present suitable for oxidation and collection of 1-5 micromoles of carbon and has an associated blank of 0.1-0.2 micromole of carbon. Complete photochemical oxidation of DOC standards was demonstrated by quantitative recovery of CO2 as measured manometrically. Isotopic analyses of standards by photochemical and high-temperature sealed-tube combustion methods agreed to within 0.3%. Photochemical oxidation of DOC in a representative sediment pore-water sample was also quantitative, as shown by the excellent agreement between the photochemical and sealed-tube methods. The delta 13C values obtained for pore-water DOC using the two methods of oxidation were identical, suggesting that the modified photochemical method is adequate for the isotopically non-fractionated oxidation of pore-water DOC. The procedure was evaluated through an analysis of DOC in pond and pore waters from a hypersaline microbial mat environment. Concentrations of DOC in the water column over the mat displayed a diel pattern, but the isotopic composition of this DOC remained relatively constant (average delta 13C = -12.4%). Pore-water DOC exhibited a distinct concentration maximum in the mat surface layer, and delta 13C of pore-water DOC was nearly 8% lighter at 1.5-2.0-cm depth than in the mat surface layer (0-0.5-cm depth). These results demonstrate the effectiveness of the method in elucidating differences in DOC concentration and delta 13C over biogeochemically relevant spatial and temporal scales. Carbon isotopic analysis of DOC in natural waters, especially pore waters, should be a useful probe of biogeochemical processes in recent environments.

NASA Discipline Exobiology↗

Remote Sensing of Dissolved Organic Carbon (DOC) Stocks, Fluxes and Transformations Along the Land-Ocean Aquatic Continuum: Advances, Challenges, and Opportunities

From stream headwaters to the deep ocean, dissolved organic carbon (DOC) is ubiquitous across the world’s aquatic systems, where it fulfills important biogeochemical and ecological functions. Importantly, DOC is a dynamic component of the carbon cycle and represents a global reservoir (mass of carbon) equivalent in size to the atmospheric CO 2 pool. The mobilization, transport, and transformations of DOC along the land-ocean aquatic continuum biogeochemically connect terrestrial landscapes, freshwater and marine ecosystems, and the atmosphere. As a result, DOC budgets are vulnerable to climate- and human-driven changes. Having the ability to quantify DOC stocks, fluxes, and transformations consistently and accurately in aquatic systems is therefore critical to our understanding of DOC’s functions in the environment and of their susceptibility to change. In recent years, optical techniques and synoptic earth observations have opened new doors to achieve this objective on a global scale. In this review, we explore how in situ measurements, earth observations, and the models they inform have facilitated the large-scale quantification of DOC stocks, fluxes, and transformations along the land-ocean aquatic continuum and how they have helped shape our current understanding of the global DOC cycle. The review also explores the limitations and challenges we still face today, and discusses how upcoming and future sensors are expected to provide new insights into our understanding of the global DOC cycle.

Dissolved organic carbon↗

On the Use of Ocean Color Remote Sensing to Measure the Transport of Dissolved Organic Carbon by the Mississippi River Plume

We investigated the use of ocean color remote sensing to measure transport of dissolved organic carbon (DOC) by the Mississippi River to the Gulf of Mexico. From 2000 to 2005 we recorded surface measurements of DOC, colored dissolved organic matter (CDOM), salinity, and water-leaving radiances during five cruises to the Mississippi River Plume. These measurements were used to develop empirical relationships to derive CDOM, DOC, and salinity from monthly composites of SeaWiFS imagery collected from 1998 through 2005. We used river flow data and a two-end-member mixing model to derive DOC concentrations in the river end-member, river flow, and DOC transport using remote sensing data. We compared our remote sensing estimates of river flow and DOC transport with data collected by the United States Geological Survey (USGS) from 1998 through 2005. Our remote sensing estimates of river flow and DOC transport correlated well (r2 ~ 0.70) with the USGS data. Our remote sensing estimates and USGS field data showed low variability in DOC concentrations in the river end-member (7-11%), and high seasonal variability in river flow (~50%). Therefore, changes in river flow control the variability in DOC transport, indicating that the remote sensing estimate of river flow is the most critical element of our DOC transport measurement. We concluded that it is possible to use this method to estimate DOC transport by other large rivers if there are data on the relationship between CDOM, DOC, and salinity in the river plume.

DelCastillo, Carlos E.↗

A Synthesis of Light Absorption Properties of the Arctic Ocean: Application to Semi-analytical Estimates of Dissolved Organic Carbon Concentrations from Space

The light absorption coefficients of particulate and dissolved materials are the main factors determining the light propagation of the visible part of the spectrum and are, thus, important for developing ocean color algorithms. While these absorption properties have recently been documented by a few studies for the Arctic Ocean [e.g., Matsuoka et al., 2007, 2011; Ben Mustapha et al., 2012], the datasets used in the literature were sparse and individually insufficient to draw a general view of the basin-wide spatial and temporal variations in absorption. To achieve such a task, we built a large absorption database at the pan-Arctic scale by pooling the majority of published datasets and merging new datasets. Our results showed that the total non-water absorption coefficients measured in the Eastern Arctic Ocean (EAO; Siberian side) are significantly higher 74 than in the Western Arctic Ocean (WAO; North American side). This higher absorption is explained 75 by higher concentration of colored dissolved organic matter (CDOM) in watersheds on the Siberian 76 side, which contains a large amount of dissolved organic carbon (DOC) compared to waters off 77 North America. In contrast, the relationship between the phytoplankton absorption (a()) and chlorophyll a (chl a) concentration in the EAO was not significantly different from that in the WAO. Because our semi-analytical CDOM absorption algorithm is based on chl a-specific a() values [Matsuoka et al., 2013], this result indirectly suggests that CDOM absorption can be appropriately erived not only for the WAO but also for the EAO using ocean color data. Derived CDOM absorption values were reasonable compared to in situ measurements. By combining this algorithm with empirical DOC versus CDOM relationships, a semi-analytical algorithm for estimating DOC concentrations for coastal waters at the Pan-Arctic scale is presented and applied to satellite ocean color data.

Pan-Arctic↗

Estuarine Dissolved Organic Carbon Flux from Space: With Application to Chesapeake and Delaware Bays

This study uses a neural network model trained with in situ data, combined with satellite data and hydrodynamic model products, to compute the daily estuarine export of dissolved organic carbon (DOC) at the mouths of Chesapeake Bay (CB) and Delaware Bay (DB) from 2007 to 2011. Both bays show large flux variability with highest fluxes in spring and lowest in fall as well as interannual flux variability (0.18 and 0.27 Tg C/year in 2008 and 2010 for CB; 0.04 and 0.09 Tg C/year in 2008 and 2011 for DB). Based on previous estimates of total organic carbon (TOCexp) exported by all Mid-Atlantic Bight estuaries (1.2 Tg C/year), the DOC export (CB + DB) of 0.3 Tg C/year estimated here corresponds to 25% of the TOCexp. Spatial and temporal covariations of velocity and DOC concentration provide contributions to the flux, with larger spatial influence. Differences in the discharge of fresh water into the bays (74 billion m(exp3)/year for CB and 21 billion m9exp3)/year for DB) and their geomorphologies are major drivers of the differences in DOC fluxes for these two systems. Terrestrial DOC inputs are similar to the export of DOC at the bay mouths at annual and longer time scales but diverge significantly at shorter time scales (days to months). Future efforts will expand to the Mid-Atlantic Bight and Gulf of Maine, and its major rivers and estuaries, in combination with coupled terrestrial-estuarine-ocean biogeochemical models that include effects of climate change, such as warming and CO2 increase.

Signorini, Sergio↗

Estuarine Dissolved Organic Carbon Flux From Space: With Application to Chesapeake and Delaware Bays

This study uses a neural network model trained with in situ data, combined with satellite data and hydrodynamic model products, to compute the daily estuarine export of dissolved organic carbon (DOC) at the mouths of Chesapeake Bay (CB) and Delaware Bay (DB) from 2007 to 2011. Both bays show large flux variability with highest fluxes in spring and lowest in fall as well as interannual flux variability (0.18 and 0.27 Tg C/year in 2008 and 2010 for CB; 0.04 and 0.09 Tg C/year in 2008 and 2011 for DB). Based on previous estimates of total organic carbon (TOCexp) exported by all Mid-Atlantic Bight estuaries (1.2 Tg C/year), the DOC export (CB + DB) of 0.3 Tg C/year estimated here corresponds to 25% of the TOCexp. Spatial and temporal covariations of velocity and DOC concentration provide contributions to the flux, with larger spatial influence. Differences in the discharge of fresh water into the bays (74 billion cu. m/year for CB and 21 billion cu. m/year for DB) and their geomorphologies are major drivers of the differences in DOC fluxes for these two systems. Terrestrial DOC inputs are similar to the export of DOC at the bay mouths at annual and longer time scales but diverge significantly at shorter time scales (days to months). Future efforts will expand to the Mid-Atlantic Bight and Gulf of Maine, and its major rivers and estuaries, in combination with coupled terrestrial-estuarine-ocean biogeochemical models that include effects of climate change, such as warming and CO2 increase.

Estuarine DOC export↗

Remote Sensing of CDOM, CDOM Spectral Slope, and Dissolved Organic Carbon in the Global Ocean

A Global Ocean Carbon Algorithm Database (GOCAD) has been developed from over 500 oceanographic field campaigns conducted worldwide over the past 30 years including in situ reflectances and coincident satellite imagery, multi- and hyperspectral Chromophoric Dissolved Organic Matter (CDOM) absorption coefficients from 245–715 nm, CDOM spectral slopes in eight visible and ultraviolet wavebands, dissolved and particulate organic carbon (DOC and POC, respectively), and inherent optical, physical, and biogeochemical properties. From field optical and radiometric data and satellite measurements, several semi-analytical, empirical, and machine learning algorithms for retrieving global DOC, CDOM, and CDOM slope were developed, optimized for global retrieval, and validated. Global climatologies of satellite-retrieved CDOM absorption coefficient and spectral slope based on the most robust of these algorithms lag seasonal patterns of phytoplankton biomass belying Case 1 assumptions, and track terrestrial runoff on ocean basin scales. Variability in satellite retrievals of CDOM absorption and spectral slope anomalies are tightly coupled to changes in atmospheric and oceanographic conditions associated with El Niño Southern Oscillation (ENSO), strongly covary with the multivariate ENSO index in a large region of the tropical Pacific, and provide insights into the potential evolution and feedbacks related to sea surface dissolved carbon in a warming climate. Further validation of the DOC algorithm developed here is warranted to better characterize its limitations, particularly in mid-ocean gyres and the southern oceans.

Dissolved organic carbon↗

BOREAS TGB-5 Dissolved Organic Carbon Data from NSA Beaver Ponds

The BOReal Ecosystem-Atmosphere Study Trace Gas Biogeochemistry (BOREAS TGB-5) team collected several data sets related to carbon and trace gas fluxes and concentrations in the Northern Study Area (NSA). This data set contains concentrations of dissolved organic and inorganic carbon species from water samples collected at various NSA sites. In particular, this set covers the NSA Tower Beaver Pond Site and the NSA Gillam Road Beaver Pond Site, including data from all visits to open water sampling locations during the BOREAS field campaigns from April to September 1994. The data are provided in tabular ASCII files.

Bourbonniere, Rick↗

Interpretation of the coastal zone color scanner signature of the Orinoco River plume

The Caribbean Sea is an area that traditionally has been considered oligotrophic, even though the Orinoco River contributes large quantities of fresh water, nutrients, and other dissolved material to this region during the wet boreal (fall) season. Little is known about the impact of this seasonal river plume, which extends from Venezuela to Puetro Rico shortly after maximum discharge. Here, we present results from a study of the bio-optical characteristics of the Orinoco River plume during the rainy season. The objective was to determine whether the coastal zone color scanner (CZCS) and the follow-on sea-viewing wide-field-of-view sensor (SeaWiFS) satellite instrument can be used to assess the concentrations of substances in large river plumes. Recent in situ shipboard measurements were compared to values from representative historical CZCS images using established bio-optical models. Our goal was to deconvolve the signatures of colored dissolved organic carbon and phytoplankton pigments within satellite images of the Orinoco River plume. We conclude that the models may be used for case 2 waters and that as much as 50 percent of the remotely sensored chlorophyll biomass within the plume is an artifact due to the presence of dissolved organic carbon. Dissolved organic carbon originates from a number of sources, including decay of dead organisms, humic materials from the soil, and gelbstoff.

Hochman, Herschel T.↗

Algorithm Development and Validation for Satellite-Derived Distributions of DOC and CDOM in the US Middle Atlantic Bight

In coastal ocean waters, distributions of dissolved organic carbon (DOC) and chromophoric dissolved organic matter (CDOM) vary seasonally and interannually due to multiple source inputs and removal processes. We conducted several oceanographic cruises within the continental margin of the U.S. Middle Atlantic Bight (MAB) to collect field measurements in order to develop algorithms to retrieve CDOM and DOC from NASA's MODIS-Aqua and SeaWiFS satellite sensors. In order to develop empirical algorithms for CDOM and DOC, we correlated the CDOM absorption coefficient (a(sub cdom)) with in situ radiometry (remote sensing reflectance, Rrs, band ratios) and then correlated DOC to Rrs band ratios through the CDOM to DOC relationships. Our validation analyses demonstrate successful retrieval of DOC and CDOM from coastal ocean waters using the MODIS-Aqua and SeaWiFS satellite sensors with mean absolute percent differences from field measurements of < 9 %for DOC, 20% for a(sub cdom)(355)1,6 % for a(sub cdom)(443), and 12% for the CDOM spectral slope. To our knowledge, the algorithms presented here represent the first validated algorithms for satellite retrieval of a(sub cdom) DOC, and CDOM spectral slope in the coastal ocean. The satellite-derived DOC and a(sub cdom) products demonstrate the seasonal net ecosystem production of DOC and photooxidation of CDOM from spring to fall. With accurate satellite retrievals of CDOM and DOC, we will be able to apply satellite observations to investigate interannual and decadal-scale variability in surface CDOM and DOC within continental margins and monitor impacts of climate change and anthropogenic activities on coastal ecosystems.

Mannino, Antonio↗