MONITORING OF WASTE WATERS QUALITY USING AMULTISENSOR SYSTEM

C. Jiménez-Jorquera; J. Orozco

; M. Gutiérrez

Instituto de Microelectrónica de Barcelona (IMB-CNM), CSIC. Campus UAB, 08193-Bellaterra, Spain.E-mail: cecilia.jimenez@imb-cnm.csic.es

Present adress: Observatoire Oceanologique, Laboratoire Arago, Avenue du Fontaulé, BP 44,66651 Banyuls Sur Mer, France. E-mail: jahir.orozco@obs-banyuls.fr.

ABSTRACT

Access to potable water and the assessment of its quality, normally through physicochemicaland biological monitoring, are neuralgic issues worldwide. An important aspect in themonitoring of water quality is the identification of pollution events to determine theappropriate treatment and to preserve public health and ecosystems. This work investigatesthe use of a multisensor system for monitoring the quality of wastewaters. The proposedsystem is comprised of an array of electrochemical sensors fabricated with microelectronictechnology which offers advantages like reproducible fabrication, miniaturized size, massiveproduction and high benefit/cost ratio. Here we present the application of these sensors tomeasure some parameters-pH, conductivity, ORP and electrochemical oxygen demand(EOD)- of waste waters from a winemaking process.

RESUMEN

El acceso al agua potable y la evaluación de su calidad, realizada normalmente a través decontroles biológicos y físico-químicos, son temas de gran transcendencia para todo el mundo.Un aspecto importante en el control de la calidad del agua es la identificación de casos decontaminación para poder así determinar el tratamiento adecuado y preservar la salud públicay los ecosistemas. Este trabajo indaga sobre el uso de un sistema multisensor para monitorizarla calidad de aguas residuales. El sistema propuesto se compone de un conjunto de sensoreselectroquímicos fabricados con tecnología microelectrónica que ofrece ventajas, tales como lafabricación reproducible, el tamaño miniaturizado, la producción masiva y una elevadarelación beneficio / coste. Aquí presentamos la aplicación de estos sensores para mediralgunos parámetros como el pH, la conductividad, el potencial redox y la demandaelectroquímica de oxígeno (DEO) en aguas residuales provenientes de un proceso deelaboración de vino.

RESUM

L’accés a l’aigua potable i la avaluació de la seva qualitat, realitzada normalment mitjançantcontrols biològics i fisicoquímics, són aspectes de gran transcendència per a tot el món. Unaspecte important en el control de la qualitat de l’aigua és la identificació de casos decontaminació per a poder determinar el tractament adequat en cada cas y preservar la salutpública i els ecosistemes. Aquest treball investiga sobre l’ús d’un sistema multisensor per al1

monitoratge de la qualitat d’aigües residuals. El sistema proposat està format per un conjuntde sensors electroquímics fabricats amb tecnologia microelectrònica, la qual ofereix una sèried’avantatges, com la fabricació reproduïble, la mida miniaturitzada, la producció massiva yuna elevada relació benefici / cost. Aquí presentem l’aplicació d’aquests sensors per amesurar alguns paràmetres com el pH, la conductivitat, el potencial redox i la demandaelectroquímica d’oxigen (DEO) en aigües residuals provinents d’un procés d’elaboració de vi.

INTRODUCTION

Water is fundamental for all the Earth’s life forms and a key issue in social and economicaldevelopment. Nowadays, due to the increase of demand of potable water and pollution,natural water sources have became insufficient to supply all the necessities. Access to potablewater and the assessment of its quality, normally through physicochemical and biologicalmonitoring, are neuralgic issues worldwide. The directives concerning to water quality forhuman consumption and wastewater quality are very strict. To accomplish internationalnormative, analytical systems are being placed with more extent in water treatment plants orindustrial waste water collectors to evaluate and control water quality parameters. Currently,there are a few probes in the market for in-field analysis -mainly for pH, ORP, conductivityand temperature- based on conventional electrodes (Naim et al., 1994; Spagnl et al., 2001) butthe majority of pollutants are measured in the laboratory with standard analytical techniquesThe use of solid-state sensor arrays and microsensors for in-field monitoring of environmentalparameters is gaining interest due to their advantages over conventional sensors. Specifically,microelectrodes fabricated with semiconductor technology are small, robust, able tointegration, have low output impedance and rapid response. They are potentially useful forenvironmental applications since they can be mounted in small and compact probes designedfor in-field measurements (Artigas et al., 2001; Orozco et al., 2006; Orozco et al., 2007) orintegrated in flow systems for on-line monitoring (Jiménez et al., 1996; Artigas et al., 2003).These systems permits automatic sampling and calibration, sample treatment and sensorconditioning, they can be installed near the sampling place (i.e. rivers, lakes, industrialwastes) and can also accomplish some of the requirements for in-field monitoring like lowpower consumption, high autonomy and robustness. In that way it is possible to obtaininformation in real time and minimize variations in the sample composition due totransportation or storage.The measurement of Chemical Oxygen Demand (COD) is usually performed in an effluent asindicator of its degree of contamination by organic matter. The COD of a sample is defined asthe amount of oxidizing agent, expressed as the equivalent amount of oxygen, which isnecessary for the chemical oxidation of the sample. Usually, it is determined by means of strong oxidizing agents such as dichromate and permanganate (Greenberg, 1999). However,these procedures are not automatic, are time-consuming and require acid digestion, which ishighly pollutant and dangerous. The electrochemical oxygen demand (EOD) is an alternativeparameter defined as the oxygen amount equivalent to the charge consumed duringelectrochemical oxidation of the sample. As such, the EOD value usually differs from theCOD data. However, measurement of the EOD can be a suitable method when a simple andfast estimation of the contamination grade by organic matter is required.Having in mind the lack of robust and feasible sensors for in-field analysis, we havedeveloped microsensors for the detection of electrochemical oxygen demand (EOD),2

conductivity and pH, together with a temperature probe. These sensors have been applied foranalyse waste water samples from a winemaking process line.

EXPERIMENTALDevices

ISFETs with a pH-sensitive Si

gate were fabricated in the IMB with a modified aluminiumgate NMOS technology (Jiménez et al., 2005). Pt and Au microelectrodes were fabricatedusing standard microelectronic technology. The silicon wafer was oxidized (1000 nm of SiO

)and titanium or chrome (20 nm) and platinum or gold (100 nm) layers were deposited andpatterned by lift-off to form the electrodes and contact pads. For the conductivity and ORPsensor, the design was based on a 4-electrode geometry, consisting of two external electrodesof 2000 µm x 700 µm and two internal electrodes of 2000 µm x 240 µm spaced 240 µm. This4-electrodes configuration was used for the conductivity sensor. For ORP measurements thepotential of only one of these 4 electrodes was measured against an Ag/AgCl (3.0 M KCl)double junction reference electrode (Orion 92-02-00). The amperometric electrode for theEOD sensor fabrication was based on a Pt electrode of 2x2 mm

.Once fabricated the chips (ISFETs and microelectrodes) they were glued and wire-bonded toa standard printed circuit board (PCB) strips. Finally, they were encapsulated with aphotocurable polymer.EOD sensors were fabricated by depositing on top of the amperometric electrodes acomposite. Composites were prepared with polystyrene, graphite as conductive material and amixture of AgO-CuO as catalysts. The preparation and deposition of the composite isexplained in ref. (Orozco et al., 2008).

Samples

Samples were obtained from the Torres S.A. wine cellar. In that cellar they have awastewatertreatment plant(WWTP). The analytical data for pH, conductivity and COD obtained withstandard methods of six samples collected from the influent and six collected from theeffluent of the plant are presented in Table 1.Samples were measured directly with pH, ORP and conductivity sensors. To measure EODsamples were diluted 1:1 in 0.1 M NaOH before analysis in order to get the suitable pHconditions (pH 12.8

0.5).

RESULTS AND DISCUSSION

The samples were analysed with the microsensors after their calibration to assure their goodperformance (Orozco, J. et al 2007). The signal obtained was interpolated in the calibrationcurve and analytical data was compared with that obtained from the laboratory of the winecellar.Measurement of pH and conductivity presented errors up to 10 %. For pH the average errorwas 10.6% for influent samples and 1.4 % for effluent samples. As shown in Figure 1a pHvalues measured with the ISFET were in general higher than with the glass electrode, and forthe influent samples the difference was greater, maybe due to the presence of suspensionmatter in the samples. For conductivity values average errors were 2.5% for the influent and4.8 % for the effluent samples. Here the dispersion of values is greater for the effluent3