A high‐performance, safer and semi‐automated approach for the δ 18 O analysis of diatom silica and new methods for removing exchangeable oxygen

The determination of the oxygen isotope composition of diatom silica in sediment cores is important for paleoclimate reconstruction, especially in non-carbonate sediments, where no other bioindicators such as ostracods and foraminifera are available. Since most currently available analytical techniques are time-consuming and labour-intensive, we have developed a new, safer, faster and semi-automated online approach for measuring oxygen isotopes in biogenic silica. Improvements include software that controls the measurement procedures and a video camera that remotely records the reaction of the samples under BrF(5) with a CO(2) laser. Maximum safety is guaranteed as the laser-fluorination unit is arranged under a fume hood in a separate room from the operator. A new routine has been developed for removing the exchangeable hydrous components within biogenic silica using ramp degassing. The sample plate is heated up to 1100 degrees C and cooled down to 400 degrees C in approximately 7 h under a flow of He gas (the inert Gas Flow Dehydration method--iGFD) before isotope analysis. Two quartz and two biogenic silica samples (approximately 1.5 mg) of known isotope composition were tested. The isotopic compositions were reproducible within an acceptable error; quartz samples gave a mean standard deviation of <0.15 per thousand (1sigma) and for biogenic silica <0.25 per thousand (1sigma) for samples down to approximately 0.3 mg. The semi-automated fluorination line is the fastest method available at present and enables a throughput of 74 samples/week.