ATR-FTIR sensor development for continuous on-line monitoring of chlorinated aliphatic hydrocarbons in a fixed-bed bioreactor

Abstract

This article describes the continuous on‐line monitoring of a dechlorination process by a novel attenuated total reflection‐Fourier transform infrared (ATR‐FTIR) sensor. This optical sensor was developed to measure noninvasively part‐per‐million (ppm) concentrations of trichloroethylene (TCE), tetrachloroethylene (PCE), and carbon tetrachloride (CT) in the aqueous effluent of a fixed‐bed dechlorinating bioreactor, without any prior sample preparation. The sensor was based on an ATR internal reflection element (IRE) coated with an extracting hydrophobic polymer, which prevented water molecules from interacting with the infrared (IR) radiation. The selective diffusion of chlorinated compound molecules from aqueous solution into the polymer made possible their detection by the IR beam. With the exclusion of water the detection limits were lowered, and measurements in the low ppm level became possible. The best extracting polymer was polyisobutylene (PIB) in the form of a 5.8‐μm thick film, which afforded a detection limit of 2, 3, and 2.5 mg/L (ppm) for TCE, PCE, and CT, respectively. Values of the enrichment factors between the polymer coating and the water matrix of these chloro‐organics were determined experimentally and were compared individually with predictions obtained from the slopes of absorbance/concentration curves for the three analytes. Before coupling the ATR‐FTIR sensor to the dechlorinating bioreactor, preliminary spectra of the chlorinated compounds were acquired on a laboratory scale configuration in stop‐flow and flow‐through closed‐loop modes. In this way, it was possible to study the behavior and direct response of the optical sensor to any arbitrary concentration change of the analytes. Subsequently, the bioreactor was monitored with the infrared sensor coupled permanently to it. The sensor tracked the progression of the analytes' spectra over time without perturbing the dechlorinating process. To calibrate the ATR‐FTIR sensor, a total of 13 standard mixtures of TCE, PCE and CT at concentrations ranging from 0 to 60 ppm were selected according to a closed symmetrical experimental design derived from a 32 full‐factorial design. The above range of concentrations chosen for calibration reflected typical values during normal bioreactor operation. Several partial least squares (PLS) calibration models were generated to resolve overlapping absorption bands. The standard error of prediction (SEP) ranged between 0.6 and 1 ppm, with a relative standard error of prediction (RSEP) between 3 and 6% for the three analytes. The accuracy of this ATR‐FTIR sensor was checked against gas chromatography (GC) measurements of the chlorocompounds in the bioreactor effluents. The results demonstrate the efficiency of this new sensor for routine continuous on‐line monitoring of the dechlorinating bioreactor. This strategy is promising for bioprocess control and optimization. © 2000 John Wiley & Sons, Inc. Biotechnol Bioeng 68: 473–487, 2000.

Direct quantification of aromatic hydrocarbons in geochemical fluids with a mid-infrared attenuated total reflection sensor

“…http://dx.doi.org/10.1016/j.orggeochem.2012.11.011 and quantification in geochemical fluids (Mizaikoff, 2003;Pejcic et al, 2009b;Gonzalvez et al, 2011). Due to its inherent selectivity the ATR-FTIR has been successfully used to detect a wide variety of organic compounds such as phenols (Yang and Cheng, 2001), caffeine (Alcudia-Leon et al, 2008), organophosphonates (Bryant et al, 2007), adamantane , alkyl halides (Acha et al, 2000;Yang and Ramesh, 2005), aromatic hydrocarbons (Karlowatz et al, 2004;Pejcic et al, 2009a;Young et al, 2011), and for the detection of oil-in-water as well as water-in-oil (Luzinova et al, 2012a,b). The sensor consists of an IR light source, a MIR transparent waveguide to propagate the signal, and an optical transducer/detector.…”

Modelling of Fickian diffusion to enhance polymer-modified sensor performance

“…The potential of an optical sensor based upon mid-IR spectroscopy, utilising internal reflection elements (IRE) coated with polymer enrichment membranes, for the analysis of environmentally significant species has been extensively reported [1][2][3][4][5][6][7][8][9]. To-date the specific mathematical treatment of analyte diffusion within enrichment membranes, utilising polymer-modified IREs, has been reported in a limited manner [10][11][12][13][14][15].…”

Sensores ópticos com detecção no infravermelho próximo e médio

“…Acha e colaboradores 52 recobriram um cristal de ATR de seleneto de zinco com poliisobutileno e polietileno de baixa densidade no desenvolvimento de um sensor para monitoramento contínuo de tricloroetileno, tetracloroetileno e tetracloreto de carbono em um biorreator de leito fixo empregado em um processo de descloração. A etapa de extração/concentração dos hidrocarbonetos clorados no filme polimérico eliminou a interferência da água, possibilitando a obtenção de limites de detecção de 2,0; 3,0 e 2,5 mg L -1 para os três hidrocarbonetos clorados, respectivamente.…”