This paper describes the automation of a fully electrochemical system for preconcentration, cleanup, separation and detection, comprising the hyphenation of a thin layer electrochemical flow cell with CE coupled with contactless conductivity detection (CE-C⁴D). Traces of heavy metal ions were extracted from the pulsed-flowing sample and accumulated on a glassy carbon working electrode by electroreduction for some minutes. Anodic stripping of the accumulated metals was synchronized with hydrodynamic injection into the capillary. The effect of the angle of the slant polished tip of the CE capillary and its orientation against the working electrode in the electrochemical preconcentration (EPC) flow cell and of the accumulation time were studied, aiming at maximum CE-C⁴D signal enhancement. After 6 min of EPC, enhancement factors close to 50 times were obtained for thallium, lead, cadmium and copper ions, and about 16 for zinc ions. Limits of detection below 25 nmol/L were estimated for all target analytes but zinc. A second separation dimension was added to the CE separation capabilities by staircase scanning of the potentiostatic deposition and/or stripping potentials of metal ions, as implemented with the EPC-CE-C⁴D flow system. A matrix exchange between the deposition and stripping steps, highly valuable for sample cleanup, can be straightforwardly programmed with the multi-pumping flow management system. The automated simultaneous determination of the traces of five accumulable heavy metals together with four non-accumulated alkaline and alkaline earth metals in a single run was demonstrated, to highlight the potentiality of the system.
Present study evaluated the relationship between estrogenic hormones concentrations (17ethinylestradiol and 17β-estradiol) in surface waters in the Metropolitan Region of São Paulo (Brazil) and environmental variables. Four sampling stations were monitored ranging from a protected area to streams discharging human effluent in and around Billings Reservoir. Four sampling campaigns were carried out in each seasonal period: DRY and WET. Samples for hormone analysis (in ng L -1 ) were concentrated (1000X) using solid phase extraction C 18 cartridges and analysed by liquid chromatography coupled to quadrupole mass spectrometry detection, with 100 ng L -1 limit of quantification. Water temperature, pH, electrical conductivity (EC) and total dissolved solids were determined in situ; total phosphorus and Sinapis alba bioassays were performed subsequently. Reservoir active capacity (AC) and precipitation were also obtained. Estrogenic hormones concentrations were always below limit of quantification at pristine site; at the other sampling stations, 17β-estradiol concentrations varied from below limit of quantification to 1,720 ng L -1 and 17ethinylestradiol from below limit of quantification to 1,200 ng L -1 , with the highest concentrations found in the streams discharging into the reservoir. These streams showed higher Pearson's correlation between 17-ethinylestradiol, total phosphorus, and electrical conductivity when compared with reservoir stations. Germination index and EC presented negative correlation (Pearson's r = -0.61), denoting a phytotoxicity increase with EC increment. AC influenced the dilution of pollutants and showed negative correlations with total phosphorus (Pearson's r = -0.56). These results highlight the relevance of including streams in water monitoring programs, since they are important pollutants loads into watersheds.
The analytical determination of atmospheric pollutants still presents challenges due to the low-level concentrations (frequently in the μg m(-3) range) and their variations with sampling site and time. In this work, a capillary membrane diffusion scrubber (CMDS) was scaled down to match with capillary electrophoresis (CE), a quick separation technique that requires nothing more than some nanoliters of sample and, when combined with capacitively coupled contactless conductometric detection (C(4)D), is particularly favorable for ionic species that do not absorb in the UV-vis region, like the target analytes formaldehyde, formic acid, acetic acid and ammonium. The CMDS was coaxially assembled inside a PTFE tube and fed with acceptor phase (deionized water for species with a high Henry's constant such as formaldehyde and carboxylic acids, or acidic solution for ammonia sampling with equilibrium displacement to the non-volatile ammonium ion) at a low flow rate (8.3 nL s(-1)), while the sample was aspirated through the annular gap of the concentric tubes at 2.5 mL s(-1). A second unit, in all similar to the CMDS, was operated as a capillary membrane diffusion emitter (CMDE), generating a gas flow with know concentrations of ammonia for the evaluation of the CMDS. The fluids of the system were driven with inexpensive aquarium air pumps, and the collected samples were stored in vials cooled by a Peltier element. Complete protocols were developed for the analysis, in air, of NH(3), CH(3)COOH, HCOOH and, with a derivatization setup, CH(2)O, by associating the CMDS collection with the determination by CE-C(4)D. The ammonia concentrations obtained by electrophoresis were checked against the reference spectrophotometric method based on Berthelot's reaction. Sensitivity enhancements of this reference method were achieved by using a modified Berthelot reaction, solenoid micro-pumps for liquid propulsion and a long optical path cell based on a liquid core waveguide (LCW). All techniques and methods of this work are in line with the green analytical chemistry trends.
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