An ICP-MS procedure to determine Cd, Co, Cu, Ni, Pb and Zn in oceanic waters using in-line flow-injection with solid-phase extraction for preconcentration.

An automated procedure including both in-line preconcentration and multi-element determination by an inductively coupled plasma mass spectrometer (ICP-MS) has been developed for the determination of Cd, Co, Cu, Ni, Pb and Zn in open-ocean samples. The method relies on flow injection of the sample through a minicolumn of chelating (iminodiacetate) sorbent to preconcentrate the trace metals, while simultaneously eliminating the major cations and anions of seawater. The effectiveness of this step is tested and reliability in results are secured with a rigorous process of quality assurance comprising 36 calibration and reference samples in a run for analysis of 24 oceanic seawaters in a 6-h program. The in-line configuration and procedures presented minimise analyst operations and exposure to contamination. Seawater samples are used for calibration providing a true matrix match. The continuous automated pH measurement registers that chelation occurs within a selected narrow pH range and monitors the consistency of the entire analytical sequence. The eluent (0.8M HNO3) is sufficiently strong to elute the six metals in 39 s at a flow rate of 2.0 mL/min, while being compatible for prolonged use with the mass spectrometer. Throughput is one sample of 7 mL every 6 min. Detection limits were Co 3.2 pM, Ni 23 pM, Cu 46 pM, Zn 71 pM, Cd 2.7 pM and Pb 1.5 pM with coefficients of variation ranging from 3.4% to 8.6% (n=14) and linearity of calibration established beyond the observed concentration range of each trace metal in ocean waters. Recoveries were Co 96.7%, Ni 102%, Cu 102%, Zn 98.1%, Cd 92.2% and Pb 97.6%. The method has been used to analyse ~800 samples from three voyages in the Southern Ocean and Tasman Sea. It has the potential to be extended to other trace elements in ocean waters.

Flow-injection analysis with fluorescence detection for the determination of trace levels of ammonium in seawater.

A method using flow-injection, gas-diffusion, derivatisation and then fluorescent detection has been established for ammonium ion determination in seawater. The fluorescent derivative formed by reacting ortho-phthaldialdehyde (OPA) and sulfite with ammonia gives high sensitivity while removing potential interferences. This is required to measure the low concentrations of ammonium often seen in the open ocean. The experimental conditions (flow-rate, reagent concentrations, membrane configurations, etc.) were manipulated to improve performance. For a sample throughput of 30 samples h(-1), the limit of detection was 7 nM, the coefficient of variation was 5.7% at 800 nM, and the calibration curve was linear to at least 4 micromol L(-1). Interferences were minimised by a gaseous diffusion step. Volatile small molecular-weight amines as interferents were discriminated against by this method. They neither passed through the membrane as efficiently as ammonia, nor reacted as readily with OPA when sulfite was the reductant. Contamination by ammonia from laboratory and shipboard sources complicates application of the method to natural waters, especially measurement of low concentrations (<100 nM) in open-ocean waters. Steps to overcome contamination are described in detail. Some results are presented for ammonium determination in Southern Ocean and Huon Estuary (Tasmania) waters.