Samples (25 mL) for POC concentration and stable isotopic composition were filtered through pre-combusted 0.7 μm nominal pore-size glass fiber filters (Whatman GF/F, Maidstone, UK). The filter was then dried at T = 55 °C, fumed with hydrochloric acid to remove particulate inorganic carbon, subsampled with a 13 mm punch and encapsulated into tin caps for further analysis ([54 (link),55 (link)] and references therein).
POC concentrations of all samples were measured using a CE Elantech NC2100 (Thermo Scientific, Lakewood, NJ, USA) according to the protocol of the United States Environmental Protection Agency [56 ] (with acetanilide (99.9% purity, C8H19NO CASRN 103-84-4) as a standard. Briefly, the encapsulated samples were combusted at 980 °C in the elemental analyzer. The combustion products were passed over a copper tube with chromium oxide/cobaltous acetate oxide as catalysts to aid the conversion of carbon into carbon dioxide. The mixture was released to thermal conductivity detectors to measure the levels of carbon in a sample ([55 (link)] and references therein). The measured values are corrected with those of known standards. POC concentration is given in mmol·L−1.
Bulk carbon isotopic composition (13C POC) was analyzed by continuous flow on an Elemental Analyzer (EA, Flash 2000; Thermo Scientific, Bremen, Germany) coupled to a Delta V+ isotope ratio mass spectrometer (Thermo Scientific, Bremen, Germany). Calibration was performed with certified international standards and in-house standards described in Table 1.
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