Removal of Refractory Dissolved Organic Carbon in the Amundsen Sea, Antarctica.

The removal mechanism of refractory deep-ocean dissolved organic carbon (deep-DOC) is poorly understood. The Amundsen Sea Polynya (ASP) serves as a natural test basin for assessing the fate of deep-DOC when it is supplied with a large amount of fresh-DOC and exposed to strong solar radiation during the polynya opening in austral summer. We measured the radiocarbon content of DOC in the water column on the western Amundsen shelf. The radiocarbon content of DOC in the surface water of the ASP reflected higher primary production than in the region covered by sea ice. The radiocarbon measurements of DOC, taken two years apart in the ASP, were different, suggesting rapid cycling of DOC. The increase in DOC concentration was less than expected from the observed increase in radiocarbon content from those at the greatest depths. Based on a radiocarbon mass balance, we show that deep-DOC is consumed along with fresh-DOC in the ASP. Our observations imply that water circulation through the surface layer, where fresh-DOC is produced, may play an important role in global DOC cycling

Decade time scale variability of ventilation in the North Atlantic: High‐precision measurements of bomb radiocarbon in banded corals

The first high-precision radiocarbon measurements for the upper ocean are presented for banded corals from two sites in the North Atlantic Ocean. The striking dissimilarities between the post-1950 records at Bermuda in the Sargasso Sea and the Florida Straits in the Gulf Stream illustrate the different mixing processes in the upper ocean at each site. Convective overturn associated with 18 ø degree water formation during late winter in the northern Sargasso Sea facilitates storage of considerable quantities of bomb radiocarbon at depth, which accounts for the damping of the A•4C signal at Bermuda during the 1960's. A multibox isopycnal mixing model is used to estimate the ventilation rate of the upper 700 m of the water column in the Sargasso Sea from 1950 to 1983. An inverse model is used; that is, the water mass renewal rate was calculated for the post-bomb period in order to satisfy the bomb radiocarbon time history in the corals. Sea water radiocarbon measurements made during the GEOSECS (1972-1973) and Transient Tracers in the Ocean (1980-1981) surveys are used to constrain the subsurface radiocarbon values calculated by the model. Results show that the rate of water mass renewal in the Sargasso Sea was high during 1963-1964, decreased during the late 1960s, and remained low during most of the 1970s. The •4C-derived record of water mass renewal precedes by about 4 years that derived from isopycnal salinity in the Sargasso Sea [Jenkins, 1982], illustrating that the coral •C record is controlled to a large extent by changes in ocean circulation rather than by atmospheric exchange of C02

Lipid-like material as the source of the uncharacterized organic carbon in the ocean?

The composition and formation mechanisms of the uncharacterized fraction of oceanic particulate organic carbon (POC) are not well understood. We isolated biologically important compound classes and the acid-insoluble fraction, a proxy of the uncharacterized fraction, from sinking POC in the deep Northeast Pacific and measured carbon isotope ratios to constrain the source(s) of the uncharacterized fraction. Stable carbon and radiocarbon isotope signatures of the acid-insoluble fraction were similar to those of the lipid fraction, implying that the acid-insoluble fraction might be composed of selectively accumulated lipid-like macromolecules

The feasibility of isolation and detection of fullerenes and carbon nanotubes using the benzene polycarboxylic acid method.

The incorporation of fullerenes and carbon nanotubes into electronic, optical and consumer products will inevitably lead to the presence of these anthropogenic compounds in the environment. To date, there have been few studies isolating these materials from environmental matrices. Here we report a method commonly used to quantify black carbon (BC) in soils, the benzene polycarboxylic acid (BPCA) method, for measurement of two types of single walled carbon nanotubes (SWCNTs), two types of fullerenes and two forms of soot. The distribution of BC products (BPCAs) from the high pressure and high temperature oxidation illustrates the condensed nature of these compounds because they form predominantly fully substituted mellitic acid (B6CA). The conversion of carbon nanoparticles to BPCAs was highest for fullerenes (average of 23.2+/-4.0% C recovered for both C(60) and C(70)) and lowest for non-functionalized SWCNTs (0.5+/-0.1% C). The recovery of SWCNTs was 10 times higher when processed through a cation-exchange column, indicating the presence of metals in SWCNTs compromises the oxidation chemistry. While mixtures of SWCNTs, soot and sediment revealed small losses of black carbon during sample processing, the method is suitable for quantifying total BC. The BPCA distribution of mixtures did not agree with theoretical mixtures using model polyaromatic hydrocarbons, suggesting the presence of a matrix effect. Future work is required to quantify different types of black carbon within the same sample

Quantification of extraneous carbon during compound specific radiocarbon analysis of black carbon.

Radiocarbon ((14)C) is a radioactive isotope that is useful for determining the age and cycling of carbon-based materials in the Earth system. Compound specific radiocarbon analysis (CSRA) provides powerful insight into the turnover of individual components that make up the carbon cycle. Extraneous or nonspecific background carbon (C(ex)) is added during sample processing and subsequent isolation of CSRA samples. Here, we evaluate the quantity and radiocarbon signature of C(ex) added from two sources: preparative capillary gas chromatography (PCGC, C(PCGC)) and chemical preparation of CSRA of black carbon samples (C(chemistry)). We evaluated the blank directly using process blanks and indirectly by quantifying the difference in the isotopic composition between processed and unprocessed samples for a range of sample sizes. The direct and indirect assessment of C(chemistry+PCGC) agree, both in magnitude and radiocarbon value (1.1 +/- 0.5 microg of C, fraction modern = 0.2). Half of the C(ex) is introduced before PCGC isolation, likely from coeluting compounds in solvents used in the extraction method. The magnitude of propagated uncertainties of CSRA samples are a function of sample size and collection duration. Small samples collected for a brief amount of time have a smaller propagated (14)C uncertainty than larger samples collected for a longer period of time. CSRA users are cautioned to consider the magnitude of uncertainty they require for their system of interest, to frequently evaluate the magnitude of C(ex) added during sampling processing, and to avoid isolating samples < or = 5 microg of carbon

The feasibility of isolation and detection of fullerenes and carbon nanotubes using the benzene polycarboxylic acid method.

The incorporation of fullerenes and carbon nanotubes into electronic, optical and consumer products will inevitably lead to the presence of these anthropogenic compounds in the environment. To date, there have been few studies isolating these materials from environmental matrices. Here we report a method commonly used to quantify black carbon (BC) in soils, the benzene polycarboxylic acid (BPCA) method, for measurement of two types of single walled carbon nanotubes (SWCNTs), two types of fullerenes and two forms of soot. The distribution of BC products (BPCAs) from the high pressure and high temperature oxidation illustrates the condensed nature of these compounds because they form predominantly fully substituted mellitic acid (B6CA). The conversion of carbon nanoparticles to BPCAs was highest for fullerenes (average of 23.2+/-4.0% C recovered for both C(60) and C(70)) and lowest for non-functionalized SWCNTs (0.5+/-0.1% C). The recovery of SWCNTs was 10 times higher when processed through a cation-exchange column, indicating the presence of metals in SWCNTs compromises the oxidation chemistry. While mixtures of SWCNTs, soot and sediment revealed small losses of black carbon during sample processing, the method is suitable for quantifying total BC. The BPCA distribution of mixtures did not agree with theoretical mixtures using model polyaromatic hydrocarbons, suggesting the presence of a matrix effect. Future work is required to quantify different types of black carbon within the same sample

Quantification of extraneous carbon during compound specific radiocarbon analysis of black carbon.

Radiocarbon ((14)C) is a radioactive isotope that is useful for determining the age and cycling of carbon-based materials in the Earth system. Compound specific radiocarbon analysis (CSRA) provides powerful insight into the turnover of individual components that make up the carbon cycle. Extraneous or nonspecific background carbon (C(ex)) is added during sample processing and subsequent isolation of CSRA samples. Here, we evaluate the quantity and radiocarbon signature of C(ex) added from two sources: preparative capillary gas chromatography (PCGC, C(PCGC)) and chemical preparation of CSRA of black carbon samples (C(chemistry)). We evaluated the blank directly using process blanks and indirectly by quantifying the difference in the isotopic composition between processed and unprocessed samples for a range of sample sizes. The direct and indirect assessment of C(chemistry+PCGC) agree, both in magnitude and radiocarbon value (1.1 +/- 0.5 microg of C, fraction modern = 0.2). Half of the C(ex) is introduced before PCGC isolation, likely from coeluting compounds in solvents used in the extraction method. The magnitude of propagated uncertainties of CSRA samples are a function of sample size and collection duration. Small samples collected for a brief amount of time have a smaller propagated (14)C uncertainty than larger samples collected for a longer period of time. CSRA users are cautioned to consider the magnitude of uncertainty they require for their system of interest, to frequently evaluate the magnitude of C(ex) added during sampling processing, and to avoid isolating samples < or = 5 microg of carbon