Shipboard determination of arsenite and total dissolved inorganic arsenic in estuarine and coastal waters with an automated on-site-applicable atomic fluorescence spectrometer

The speciation of trace level arsenic (As) in estuarine and coastal waters is crucial for both biogeochemical and toxicological studies of this toxic metalloid. However, the accurate and on-site determination of As in complex seawater matrices is challenging because of the low concentration of As, the easy conversion of arsenite (As(III)) to arsenate (As(V)), and the considerable effect of salinity on the determination of As via conventional methods. In this study, a custom-made shipboard atomic fluorescence spectrometer (AFS) is reported for the on-site speciation of inorganic As in estuarine and coastal waters. After comprehensive optimization of the instru-mental and chemical parameters, the method demonstrated high sensitivity (limits of detection: 0.02 mu g L-1), good linearity (R2 > 0.999 for all calibration curves up to 8 mu g L-1), high precision (relative standard deviations (RSDs) of less than 2% at 1 mu g L-1 over a year-long evaluation), and excellent performance for sample analysis for different matrices with varying salinities (recoveries: 96.3%-105.3%). The portable and field-applicable AFS was successfully applied to the on-site and shipboard simultaneous determination of As(III) and total dissolved inorganic arsenic (TDIAs) in the coastal waters of Shandong, Jiangsu, Zhejiang, Fujian, and Guangdong province of China, demonstrating its robustness and applicability in harsh conditions.