A potential proxy for seasonal hypoxia: LA-ICP-MS Mn/Ca ratios in benthic foraminifera from the Yangtze River Estuary

Abstract

We have examined the possible use of Mn/Ca ratios in benthic foraminifera as a proxy for hypoxia, which has increasingly become a serious environmental issue in many coastal zones. We collected samples from the Yangtze River Estuary, one of the largest and most intense seasonally hypoxic zones in the world. In order to obtain high quality Mn/Ca data, unaffected by contamination, we examined two different cleaning protocols and instrument-based analysis methods. Our results showed that a relatively simple physical cleaning approach coupled to laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) provided excellent results on single specimens. Our observations were comparable to ICP analyses of solutions made up from dozens or even hundreds of specimens and involving complicated sample pretreatments. Using the LA methodology, we analyzed Mn/Ca ratios from living Florilus decorus (F. decorus) specimens from stations in the Yangtze River Estuary with varying bottom water dissolved oxygen (DO) concentrations. Our results showed that Mn/Ca ratios in penultimate chambers of living benthic foraminifera are sensitive to bottom water DO concentrations. We also observed significant variations of both Mn/Ca and Mg/Ca ratios from different chambers within foraminiferal shell specimens. These fluctuations were likely a response to changing ambient water DO and temperature during the specimen’s growth history. Combined use of foraminiferal Mn/Ca ratios together with other proxies could provide a powerful tool for historical reconstruction of low oxygen conditions in seasonal hypoxia areas.