Surface silicate distribution in the Chukchi-shelf region during the Arctic summer cruises using programmable flow injection technique

Abstract

The surface Arctic Ocean is subject to rapidly changing freshwater inputs, from increasing ice melt and riverine inputs. Close monitoring of inflow waters from the Pacific and Atlantic is also needed for understanding the balance of geochemical cycles and making future predictions in the Arctic.  However, our knowledge of ocean biogeochemical data is very limited, necessitating an expansion of spatial and temporal coverage. However, the acquisition of ocean samples is hindered by the intricate sampling and analytical procedures employed both at sea and on land. In our recent work [Hatta et al, 2021; 2023], a miniaturized, automated, microfluidic analyzer for nutrient analysis was developed using the programmable flow injection (pFI) technique.  This innovative system achieves accurate measurements with minimal reagent use, computer-controlled manipulations, and auto-calibration techniques, thus it is a promising oceanographic tool for increasing sample acquisition and determination, as well as minimizing human error.  For the pFI technique, the traditional silicate (Si) molybdenum blue method was modified by combining oxalate and ascorbic acid into a single reagent. This new method obtained a limit of detection of 514 nM Si, r.s.d. 2.1%, sampling frequency rate of 40 samples per hour, reagent consumption of 700 microliters per sample, and use of deionized (DI) water as a carrier solution. Phosphate (P) does not interfere significantly in this technique if the Si:P ratio is 4:1 or larger. Additionally, since there is no salinity influence, samples collected from the open ocean, coastal areas, or rivers can all be determined accurately using a DI water-based standard calibration covering a single small range by diluting samples to fall within this limited range. In this contribution, this new shipboard method using programmable Flow Injection will be presented along with high-resolution Si data from the Chukchi shelf.  These data were obtained every 10-20 minutes by directly connecting the pFI platform to the underway water sampling system during the RV Mirai summer cruises. This new analytical platform will allow us to significantly expand our database and thus help to constrain and quantify geochemical processes and budgets in the Arctic Ocean.