Direct barite determination using SEM/EDS-ACC system: implication for constraining barium carriers and barite preservation in marine sediments

Barite (BaSO₄) in marine sediments is considered as a proxy of surface ocean productivity and is widely used for paleo-productivity reconstructions. However, direct barite determination is not achieved by currently used methods, which rely on the measurement of total barium by inductively coupled plasma–mass spectrometry (ICP-MS) and instrumental neutron activation analysis (INAA) and correction from the allogenic Ba contribution. We report here on a technique that directly counts individual barite crystals using a scanning electron microscope (SEM) coupled to an energy dispersive spectrometer (EDS) equipped with an automated particle counting and classification (ACC) system. We show that barite–Ba concentrations can be deduced from the abundance, shape and size distributions of barite crystals with current precision and sensitivity as high as ±5 wt.% (2σ confidence limit) and 10 ppm, respectively. This technique, coupled with ICP-MS and INAA techniques for total Ba measurements, was applied to sediment samples from the tropical North Atlantic and the Central North Pacific oceans. Results show that: (1) barite and detrital aluminosilicates are the two main carriers of Ba in the investigated sediments; (2) calculated Ba/Al ratios range from 0.005 to 0.008 with an average value around 0.0066, in close agreement with previously reported values; (3) barite might not be the major source for released barium out of sediments and we suggest instead adsorbed barium as a potential source.