Determination of Thiram and Aminocarb Pesticides in Natural Water Samples Using Flow Injection with Tris(2,2′-bipyridyl)-ruthenium(II)-diperiodatoargentate(III) Chemiluminescence Detection

Abstract

A simple and sensitive flow-injection (FI) method is reported for the determination of thiram and aminocarb pesticides in natural water samples based on the strong enhancing effects of these pesticides on the tris(2,2′-bipyridyl)ruthenium(II)-diperiodatoargentate(III) (Ru(bipy)3 2+ -DPA) chemiluminescence (CL) system. Under the optimum experimental conditions, the CL intensity was linear over the range of 1.0 -1000 and 1.0 -10000 ng mL -1 (R 2 = 0.9998 (n = 7) and 0.9994 (n = 11)) for thiram and aminocarb, respectively, with relative standard deviations (RSDs; n = 3) in the range 1.0 -2.6%. The limits of detection (S/N = 3) were 0.1 ng mL -1 for both pesticides with injection throughputs of 150 h -1 . The key chemical and physical variables (reagent concentrations, flow rates, sample volume, PMT voltage) were optimized and potential interferences investigated. The method was successfully applied to natural water samples and the results obtained were not significantly different (95% confidence interval) from results obtained by the previously reported FI-CL and HPLC methods. Thiram could be determined in the presence of aminocarb using Triton X-100. The possible CL reaction mechanism is also discussed briefly.

Determination of thiram residues in fresh water using flow injection diperiodatonickelate(IV)–quinine chemiluminescence detection

“…Table 2 presents the analytical performance of the proposed approach and its comparison with traditional techniques such as HPLC–UV, HPLC–MS, LC–MS, GC–MS, voltammetry, FI–EC, SERS, FI–FTIR, GTA, AES, FL, and spectrophotometry/colorimetry used for the determination of THI fungicide in diverse samples. The sensitivity of the proposed method is higher than that in most of these techniques and comparable or slightly less sensitive than RP‐HPLC–UV, [ 8 ] CL ,52 and FI–CL [ 53 ] when analyzing THI in water samples, but these methods [ 8,10 ] have narrow linear range comparatively. The proposed approach has several characteristics such as good sensitivity, low cost, minimal sample preparation, required low sample volume, and high injection frequency.…”

“…A limited number of batch and FI methods based on different CL systems have been described to determine THI in environmental, pharmaceutical, food, and biological samples. [ 51–56 ] Girotti et al .51 described the CL‐enzyme‐linked immunosorbent assay (CL‐ELISA) for measuring THI in honeybee extracts using polyclonal antibodies, horseradish peroxidase as labeling enzyme, and luminol. The average recovery values of 72% and 60% are reported using solid‐phase extraction (SPE) and liquid–liquid extraction techniques when spiking 0.075 μg ml −1 THI to the honeybee extract, respectively.…”

“…The average recovery values of 72% and 60% are reported using solid‐phase extraction (SPE) and liquid–liquid extraction techniques when spiking 0.075 μg ml −1 THI to the honeybee extract, respectively. Li et al .52 devised a CL‐based nano‐sensor composed of bis(2,4,6‐trichlorophenyl)oxalate, H 2 O 2 , and gold nanoparticles to detect THI fungicide residues based on its inhibiting effect on light emission intensity with an LOD of 0.35 nM, a recovery rate of 93%–110%, and a detection time of 40 s. Asghar et al .53 reported a simple FI method based on the enhancive effect of THI and aminocarb pesticides on the Ru (bipy) 3 2+ ‐DPA CL reaction in natural water with an RSD of 1.0%–2.6%, a sampling frequency of 150 h −1 , and a recovery rate of 95 ± 4%–106 ± 2% ( n = 3) for THI. Asghar et al .54 described another FI approach based on the oxidation of THI fungicide with KBrO 3 under acidic conditions subsequently utilizing quinine as the sensitizer with an RSD of 0.94%–1.76% ( n = 4), an injection throughput of 200 h −1 , and a recovery of 91%–110% THI in water.…”

A review of recent developments based on chemiluminescence detection systems for pesticides analysis

“…Pérez‐Ruiz et al . [ 67,73 ] proposed an FI–CL determination of carbamates using a [ 59 ] Ru(bipy) 3 2+ system. This was based on the on‐line conversion of carbamates to MA that was reacted (as a reducing agent) with Ru(bipy) 3 3+ generated through the on‐line photo‐oxidation of Ru(bipy) 3 2+ with peroxydisulfate, producing [Ru(bipy) 3 2+ ]*.…”

“…Asghar et al . [ 59 ] also reported a tris(2,2′‐bipy)ruthenium (II)–diperiodatoargentate (III) (Ru(bipy) 3 2+ –DPA) CL system with an FI analytical method to analyze thiram and aminocarb pesticides in natural water samples. It was based on the enhancing effect of these pesticides on the CL signal generated using a developed system.…”