Amperometric and spectrophotometric determination of carbaryl in natural waters and commercial formulations

The work presented describes the development and evaluation of two flow-injection analysis (FIA) systems for the automated determination of carbaryl in spiked natural waters and commercial formulations. Samples are injected directly into the system where they are subjected to alkaline hydrolysis thus forming 1-naphthol. This product is readily oxidised at a glassy carbon electrode. The electrochemical behaviour of 1-naphthol allows the development of an FIA system with an amperometric detector in which 1-naphthol determination, and thus measurement of carbaryl concentration, can be performed. Linear response over the range 1.0×10–7 to 1.0×10–5 mol L–1, with a sampling rate of 80 samples h–1, was recorded. The detection limit was 1.0×10–8 mol L–1. Another FIA manifold was constructed but this used a colorimetric detector. The methodology was based on the coupling of 1-naphthol with phenylhydrazine hydrochloride to produce a red complex which has maximum absorbance at 495 nm. The response was linear from 1.0×10–5 to 1.5×10–3 mol L–1 with a detection limit of 1.0×10–6 mol L–1. Sample-throughput was about 60 samples h–1. Validation of the results provided by the two FIA methodologies was performed by comparing them with results from a standard HPLC–UV technique. The relative deviation was <5%. Recovery trials were also carried out and the values obtained ranged from 97.0 to 102.0% for both methods. The repeatability (RSD, %) of 12 consecutive injections of one sample was 0.8% and 1.6% for the amperometric and colorimetric systems, respectively.

A Multiple Criteria Utility-based Approa h for the Unit Commitment with Wind Power and Pumped Storage Hydro

The integration of wind power in eletricity generation brings new challenges to unit commitment due to the random nature of wind speed. For this particular optimisation problem, wind uncertainty has been handled in practice by means of conservative stochastic scenario-based optimisation models, or through additional operating reserve settings. However, generation companies may have different attitudes towards operating costs, load curtailment, or waste of wind energy, when considering the risk caused by wind power variability. Therefore, alternative and possibly more adequate approaches should be explored. This work is divided in two main parts. Firstly we survey the main formulations presented in the literature for the integration of wind power in the unit commitment problem (UCP) and present an alternative model for the wind-thermal unit commitment. We make use of the utility theory concepts to develop a multi-criteria stochastic model. The objectives considered are the minimisation of costs, load curtailment and waste of wind energy. Those are represented by individual utility functions and aggregated in a single additive utility function. This last function is adequately linearised leading to a mixed-integer linear program (MILP) model that can be tackled by general-purpose solvers in order to find the most preferred solution. In the second part we discuss the integration of pumped-storage hydro (PSH) units in the UCP with large wind penetration. Those units can provide extra flexibility by using wind energy to pump and store water in the form of potential energy that can be generated after during peak load periods. PSH units are added to the first model, yielding a MILP model with wind-hydro-thermal coordination. Results showed that the proposed methodology is able to reflect the risk profiles of decision makers for both models. By including PSH units, the results are significantly improved.