In situ evaluation of DGT techniques for measurement of trace metals in estuarine waters: a comparison of four binding layers with open and restricted diffusive layers

Abstract

Four different DGT binding layers were used to make selective measurements of trace metals in coastal waters within The Broadwater (Gold Coast, Queensland). Chelex and PAMPAA (polyacrylamide-polyacrylic acid) binding layers were used to measure cations (Cd, Co, Cu, Mn, Ni, Pb, Zn), and Metsorb was used to measure anions (Al, As, Mo, Sb, V, W). A mixed binding layer (MBL) containing both Chelex and Metsorb was used to measure each of the trace metals and determine diffusive boundary layer (DBL) thicknesses. DGT measurements that were not corrected for the DBL thickness (0.049–0.087) were underestimated by 70% on average. Good agreement was observed between DGT-MBL and DGT-Chelex for measurement of Cd, Co, Cu, Ni, Pb and Zn, and between DGT-MBL and DGT-Metsorb for As, Sb and V. DGT-MBL measured significantly higher concentrations for Mn (compared with DGT-Chelex) and Al (compared with DGT-Metsorb). DGT-Chelex measured only 6–8% of Al species measured by either DGT-MBL or DGT-Metsorb. DGT-PAMPAA measurements of Cu, Pb and Al were lower than those of either DGT-MBL or DGT-Chelex varying from 74–81% for Cu to 54–70% for Pb and 51–55% for anionic Al(OH)₄⁻, suggesting that this binding layer may make more selective measurements. All measured trace metal concentrations were well below ANZECC water quality guidelines, except for Cu which was 2 to 10 times higher than trigger values. Each of the DGT techniques was deployed using both open and restricted diffusive layers (ODL and RDL). Most trace metal measurements were not significantly different with ODL and RDL for all binding layers. However, concentrations of Cu (C_RDL/C_ODL = 0.68–0.75) and Al (C_RDL/C_ODL = 0.73–0.79) were significantly different with DGT-MBL, DGT-Chelex and DGT-Metsorb.