Development of a microplate-format direct optode sensor for ultra-high-throughput environmental and wastewater monitoring of Pb2

Abstract

Although many Pb²⁺-selective optodes have been developed so far, methods using optical sensor membranes have not become widespread in environmental analytical practice. In order to create a bulk optode sensor, which can overcome all of the main drawbacks in the application of conventional optode membranes, - i.e., pH-dependence, long response time and the leakage of the ionic components - unusually thick PVC membrane was developed, embedded in microtiter plates and operated on a novel concept. This is the first reported work, which applies a plate-format optode as well as a direct optode-type sensing membrane for determination of Pb²⁺. We reported here also the first example for the application of an ionic component-free bulk optode membrane to avoid the membrane leakage, improve the regenerability and extend the lifetime of the membrane. The reported sensor has a LOD above 4.0 × 10^-7 M (∼83 μg L^-1), thus it is unsuitable for the effective monitoring of drinking waters, but considered to be a promising method for monitoring contamination episodes. On the other hand, the widest pH-independent working range of 4.3 < pH < 7.0 among bulk optodes reported in the literature was realized and an unprecedentedly fast response time of <10 s was achieved. The effectiveness of the applied method was investigated by measuring Pb²⁺-spiked multicomponent aqueous solutions as simulated environmental or wastewater samples containing near equimolar amounts of Ag⁺, Ca²⁺, Co²⁺, Cu²⁺, K⁺, Mg²⁺, Na⁺ and Zn²⁺ as acetate salts. In the presence of these potential competing ions with a concentration not greater than the typical ionic strength of surface freshwaters (∼10^-3 M) the reported sensor proved to be appropriate for the selective detection of Pb²⁺ without any preparation of the samples (e.g., preconcentration, buffering, addition of excipients, etc.) with a required sample volume of only 100 μL. An outstanding analytical performance could be achieved within an average time of less, than 5 s/sample. The reported fluorescent probe is considered to be a promising method for replacing atomic absorption spectroscopy- (AAS), anodic stripping voltammetry- (ASV) or inductively coupled plasma- (ICP) based techniques as well as conventional ion-selective bulk membranes in high-throughput preliminary environmental monitoring of Pb²⁺, as it provides a cheap and unprecedentedly fast qualitative analysis of contaminated surface and wastewaters.

Keywords: Acridono-crown ether; Lead ions; Microplate-format direct optode; Multicomponent water samples; Ultra-high-throughput monitoring.