Underwater determination of calcium and strontium ions in oilfield produced water by laser-induced breakdown spectroscopy (LIBS).

Laser-induced breakdown spectroscopy (LIBS) was applied to the determination of scaling ions in oilfield-produced water employing underwater measurements. Initially, the stability of plasma was verified using four different optical setups and expansion of the laser beam, and a combination of an achromatic lens with a meniscus lens were necessary to stabilize the plasma. Preliminary experiments demonstrated that only the determinations of Ca(II) and Sr(II) ions were feasible while the signal for the Mg(II) ion was absent and the sensitivity for Ba(II) was very low. The laser pulse repetition rate was evaluated and rates of 10 and 20 Hz provided a more stable breakdown in water compared to repetition rates of 2 to 7 Hz, besides imparting higher intense signals. The increase in salinity showed a small matrix effect, decreasing the sensitivities of the calibration curves by 8-13% when standard solutions with a salinity of 30‰ were used instead of water. Under optimized conditions with a laser pulse energy of 31 mJ, gate delay of 300 ns, gate width of 5.0 µs, repetition rate of 10 Hz, and accumulation of 500 laser shots, a linear range from 25 to 150 mg L-1 was obtained, with limits of detection of 0.58 and 0.85 mg L-1 for Ca(II) and Sr(II), respectively. The underwater determination of scaling ions in produced water by LIBS provided results that do not significantly differ from those obtained by inductively coupled plasma atomic emission spectroscopy (ICP OES) at a confidence level of 95%, with relative errors of up to 5.2%. These results demonstrate the potential of underwater LIBS measurements as an analytical tool for the determination of alkaline-earth metal ions in produced water, which can help the oil industry to overcome the problems related to scale formation.

A fluorescent magnetic core-shell nanosensor for detection of copper ions in natural waters.

A nanosensor based on magnetic core-shell nanoparticles functionalized with rhodamine derivative, N-(3-carboxy)acryloyl rhodamine B hydrazide (RhBCARB), using (3-aminopropyl)triethoxysilane (APTES) as a linker, has been synthesized for detection of Cu(II) ions in water. The magnetic nanoparticle and the modified rhodamine were fully characterized, showing a strong orange emission sensitive to Cu(II) ions. The sensor shows a linear response from 10 to 90 µg L-1, detection limit of 3 µg L-1 and no interference of Ni(II), Co(II), Cd(II), Zn(II), Pb(II), Hg(II) and Fe(II) ions. The nanosensor performance is similar to those described in the literature, being a viable option for the determination of Cu(II) ions in natural waters. In addition, the magnetic sensor can be easily removed from the reaction medium with the aid of a magnet and its signal recovered in acidic solution, allowing its reuse in subsequent analysis.

Analysis of sugars and sweeteners via terahertz time-domain spectroscopy.

A THz-TDS spectrometer (terahertz time-domain spectroscopy) with ASOPS technology (asynchronous optical sampling) was employed in this study, aiming to explore the potential of the technique and to develop analytical applications for the identification of some saccharides. Analytical curves with linear responses were obtained in the saccharide concentration range from 1.7 to 11.7 (w/w). The characteristic peaks used for each sugar for univariate calibrations were fructose (1.704 THz), sucrose (1.827 THz), glucose (1.435 THz), lactose (1.373 THz), saccharin (2.664 THz), and sucralose (2.219 THz). Limits of detection around 1.0% (m/m) were obtained. Gaussian peak fitting was also employed as a tool to aid in the identification of saccharide components in mixtures and it was observed that the region between 0.5 and 2.0 THz is more adequate for such analysis since scattering is less evident. It was observed that in a mixture of sucrose, glucose and lactose (5% or 10% (m/m) each) in the range of 1.31 to 1.51 THz some sub-peaks of pure lactose and glucose can be identified.

Detection of Low Lithium Concentrations Using Laser-Induced Breakdown Spectroscopy (LIBS) in High-Pressure and High-Flow Conditions.

This paper describes the effects of laser pulse rate and solution flow rate on the determination of lithium at high pressure for water and 2.5% sodium chloride solutions using laser-induced breakdown spectroscopy (LIBS). Preliminary studies were performed with 0-40 mg L-1 Li solutions, at ambient pressure and at 210 bar, and in static and flowing (6 mL · min-1) regimes, for a combination of four different measurement conditions. The sensitivity of calibration curves depended on the pressure and the flow rate, as well as the laser pulse rate. The sensitivity of the calibration curve increased about 10% and 18% when the pressure was changed from 1 to 210 bar for static and flowing conditions, respectively. However, an effect of flow rate at high pressure for both 2 and 10 Hz laser pulse rates was observed. At ambient pressure, the effect of flow rate was negligible, as the sensitivity of the calibration curve decreased around 2%, while at high pressure the sensitivity increased around 4% when measurements were performed in a flow regime. Therefore, it seems there is a synergistic effect between pressure and flow rate, as the sensitivity increases significantly when both changes are considered. When the pulse rate is changed from 2 to 10 Hz, the sensitivity increases 26-31%, depending on the pressure and flow conditions. For lithium detection limit studies, performed with a laser pulse energy of 2.5 mJ, repetition rate of 10 Hz, gate delay of 500 ns, gate width of 1000 ns, and 1000 accumulations, a value around 40 µg L-1 was achieved for Li solutions in pure water for all four measurement conditions, while a detection limit of about 92 µg L-1 was determined for Li in 2.5% sodium chloride solutions, when high pressure and flowing conditions were employed. The results obtained in the present work demonstrate that LIBS is a powerful tool for the determination of Li in deep ocean conditions such as those found around hydrothermal vent systems.

Development of a reusable fluorescent nanosensor based on rhodamine B immobilized in Stöber silica for copper ion detection.

This work has the goal of developing and evaluating a reusable fluorescent nanosensor for detection of Cu(ii) ion in aqueous solution, based on the immobilization of rhodamine B in silica nanoparticles prepared according to a modified Stöber method. In order to do this, a standard ammonium hydroxide ethanolic solution was mixed to ethanol under constant stirring, followed by the addition of tetraethoxysilane (TEOS). To immobilize the fluorescent reagent in the silica nanoparticles, rhodamine B ethanolic solution was added to the reacting mixture at different times (2; 3; 4 and 5 h) after starting the synthesis (which always lasts 7 h). The nanosensor obtained with the addition of rhodamine B after 5 h of synthesis showed the best sensitivity, measured as the fluorescence quenching, which was proportional to Cu(ii) ion. The nanosensor was selective to Cu(ii) ions and showed a linear range from 2.0 to 12.0 µmol L-1, detection limit of 0.40 µmol L-1, quantification limit of 1.3 µmol L-1, response time of 50 s, being possible to be reused 3 times. The nanosensor was applied to the determination of Cu(ii) in sugar cane spirit and the results obtained did not show significant differences from those obtained by atomic absorption spectrometry at a confidence level of 95%.

A Simple Device for Lens-to-Sample Distance Adjustment in Laser-Induced Breakdown Spectroscopy (LIBS).

A simple device based on two commercial laser pointers is described to assist in the analysis of samples that present uneven surfaces and/or irregular shapes using laser-induced breakdown spectroscopy (LIBS). The device allows for easy positioning of the sample surface at a reproducible distance from the focusing lens that conveys the laser pulse to generate the micro-plasma in a LIBS system, with reproducibility better than ±0.2 mm. In this way, fluctuations in the fluence (J cm-2) are minimized and the LIBS analytical signals can be obtained with a better precision even when samples with irregular surfaces are probed.

iHEART: a miniaturized near-infrared in-line gas sensor using heart-shaped substrate-integrated hollow waveguides.

A novel heart-shaped substrate-integrated hollow waveguide (hiHWG) was integrated with a near-infrared micro-spectrometer (µNIR) for sensing natural gases, resulting in an ultra-compact near-infrared gas sensing system - iHEART. The iHEART system was evaluated using two different µNIR spectrometers, and the performance was compared with a laboratory NIR spectrometer for gas analysis based on an acousto-optic tunable filter (AOTF). The spectral data were pre-processed using the 1(st) derivative Savitzky-Golay algorithm, and then used for establishing multivariate regression models based on partial least squares (PLS). The root mean square errors of prediction (RMSEPs) obtained for major components of natural gas with both iHEART systems were similar to those associated with the AOTF spectrophotometer combined with a conventional long-path measurement cell. It was demonstrated that the iHEART system has significant potential for the development of compact in-line gas sensing systems, thus facilitating monitoring of (petro)chemically relevant processes and products. However, the flexibility and modularity of the system also allows tailoring iHEART to a wide range of other relevant analytical measurement scenarios requiring short response times and minute gas sample volumes.

Sensing hydrocarbons with interband cascade lasers and substrate-integrated hollow waveguides.

Tunable diode laser absorption spectroscopy (TDLAS) is an excellent analytical technique for gas sensing applications. In situ sensing of relevant hydrocarbon gases is of substantial interest for a variety of in-field scenarios including environmental monitoring and process analysis, ideally providing accurate, molecule specific, and rapid information with minimal sampling requirements. Substrate-integrated hollow waveguides (iHWGs) have demonstrated superior properties for gas sensing applications owing to minimal sample volumes required while simultaneously serving as efficient photon conduits. Interband cascade lasers (ICLs) are recently emerging as mid-infrared light sources operating at room temperature, with low power consumption, and providing excellent potential for integration. Thereby, portable and handheld mid-infrared sensing devices are facilitated. Methane (CH4) is among the most frequently occurring, and thus, highly relevant hydrocarbons requiring in situ emission monitoring by taking advantage of its distinct molecular absorption around 3 µm. Here, an efficient combination of iHWGs with ICLs is presented providing a methane sensor calibrated in the range of 100 to 2000 ppmv with a limit of detection at 38 ppmv at the current stage of development. Furthermore, a measurement precision of 0.62 ppbv during only 1 s of averaging time has been demonstrated, thereby rendering this sensor concept useful for in-line and on-site emission monitoring and process control applications.

Photostable, Oxygen-Sensitive Optical Probe Based on a Homonuclear Terbium(III) Complex Covalently Bound to Functionalized Polydimethylsiloxane.

A new oxygen-sensitive optical probe based on the [Tb(3,5-dcba)3 ]⋅1/2 H2 O (3,5-dcba=3,5-dichlorobenzoate) complex, which is chemically attached to a phosphine-oxide-functionalized polydimethylsiloxane is presented. The hybrid material shows green emission and transparency in the visible range. The optically sensitive probe is photostable under excitation at 350 nm and shows the highest oxygen sensitivity, I0 /I100 equal to 8.9 at 1 atm, among probes based on homonuclear lanthanide compounds. Furthermore its reversibility is demonstrated after several cycles ranging from 100 % N2 to 100 % O2 with response time of 8.5 s (N2 →O2 ) and recovery time of 49.5 s (O2 →N2 ).

Analysis of immersed silica optical microfiber knot resonator and its application as a moisture sensor.

An embedded silica optical microfiber knot resonator humidity sensor is presented. As silica has a poor response to environmental humidity changes, a surrounding layer of Nafion is used as a transducer. Spectral characterization and also a procedure to determine the coupling and total loss coefficients are presented. Sensitivity as high as (0.29±0.01) nm/% relative humidity has been noticed. Possible issues that emerge from the use of Nafion such as bulk swelling, refractive index hysteresis, as well as a saturation process, are discussed.

Fluorescent ion-imprinted polymers for selective Cu(II) optosensing.

This paper describes the synthesis and characterization of a fluorescent ion-imprinted polymer (IIP) for selective determination of copper ions in aqueous samples. The IIP has been prepared using a novel functional monomer, 4-[(E)-2-(4'-methyl-2,2'-bipyridin-4-yl)vinyl]phenyl methacrylate (abbreviated as BSOMe) that has been spectroscopically characterized in methanolic solution, in the absence and in the presence of several metal ions, including Cd(II), Cu(II), Hg(II), Ni(II), Pb(II), and Zn(II). The stability constant (2.04 × 10(8) mol(-2) l(2)) and stoichiometry (L(2)M) of the BSOMe complex with Cu(II) were extracted thereof. Cu(II)-IIPs were prepared by radical polymerization using stoichiometric amounts of the fluorescent monomer and the template metal ion. The resulting cross-linked network did not show any leaching of the immobilized ligand allowing determination of Cu(II) in aqueous samples by fluorescence quenching measurements. Several parameters affecting optosensor performance have been optimized, including sample pH, ionic strength, or polymer regeneration for online analysis of water samples. The synthesized Cu(II)-IIP exhibits a detection limit of 0.04 µmol l(-1) for the determination of Cu(II) in water samples with a reproducibility of 3%, exhibiting an excellent selectivity towards the template ion over other metal ions with the same charge and close ionic radius. The IIP-based optosensor has been repeatedly used and regenerated for more than 50 cycles without a significant decrease in the luminescent properties and binding affinity of the sensing phase.

Simultaneous determination of copper, mercury and zinc in water with a tailored fluorescent bipyridine ligand entrapped in silica sol-gel.

A novel fluorescent ligand, (4-[(E)-2-(4'-methyl-2,2'-bipyridin-4-yl)vinyl]phenol) (abbreviated BSOH), has been designed and prepared for simultaneous determination of heavy metals in water. Its photophysical and photochemical properties in the absence and in the presence of Cd(II), Cu(II), Hg(II), Ni(II) and Zn(II) were determined, and the respective complexation constants (7.4 × 10(3)-2.8 × 10(8) l mol(-1)) and stoichiometries were extracted thereof. The Stern-Volmer emission intensity and lifetime plots indicate an efficient static quenching of the indicator dye with the heavy metals. The BSOH fluorescent reagent has been successfully immobilised in a silica sol-gel matrix for automation of the analytical method, and the sensing phase demonstrated a reversible response to Cu(II), Hg(II) and Zn(II) but not to Cd(II) and Ni(II). Characterisation of the sensor showed that its response to those heavy metals is linear in the 2.5 to 50 µmol l(-1) range, with a response time (t (90)) on the order of 100 min, providing detection limits of 9.0 × 10(-7), 4.7 × 10(-7) and 2.9 × 10(-7) mol l (-1) for Zn(II), Cu(II) and Hg(II), respectively. Due to the stability of the immobilised ligand, which presented no leaching from the sol-gel matrix, the simultaneous determination of the three cations in water was feasible by employing multivariate calibration techniques coupled to fluorescence quenching measurements. The sensor was validated with recovery tests by addition of Cu(II) and Hg(II) ions to spring waters, providing results with standard errors lower than 4.1 µmol l (-1).

A microfluidic device with integrated fluorimetric detection for flow injection analysis.

This work describes the development of flow analysis microsystems with integrated fluorimetric detection cells. Channels (width of 300-540 microm and depth of 200-590 microm) were manufactured by deep-UV lithography in urethane-acrylate (UA) resin. Plastic optical fibers (diameter of 250 microm) were coupled to a 2.0-mm-long detection channel in order to guide the excitation radiation from an LED (470 nm) and collect the emitted radiation at a right angle towards a photomultiplier. A single-line miniaturized system, with a total internal volume of 10.4 microL, was evaluated by means of standard fluorescein solutions (0.53-2.66 micromol L(-1), pH 8.5). The analytical signals presented a linear relationship in the concentration range studied, with a relative standard deviation of 1.9% (n = 5), providing a detection limit of 0.37 micromol L(-1) and an analytical frequency of 60 samples/h, using a flow rate of 60 microL min(-1). Optical microscopy images and videos acquired in real time for the hydrodynamic injection of 130 and 320 nL of sample solutions indicated the good performance of the proposed sampling strategy. Another microsystem with a total internal volume of 38 microL was developed, incorporating a confluence point for two solutions. This device was applied to the determination of the total concentration of Ca(2+) and Mg(2+) in commercial mineral waters using the calcein method. Microscopy images and videos demonstrated the mixing efficiency of the solutions in the microchannels. A linear relationship was observed for the analytical signal in the Ca(2+) concentration range from 25 to 125 micromol L(-1), with relative standard deviations of 3.5%. The analysis of mineral waters with the proposed system provided results that did not differ significantly from those obtained by the EDTA titration method at a confidence level of 95%. These results demonstrate the viability of developing micro flow injection systems with an integrated fluorimetric detection cell.

Simultaneous determination of methanol and ethanol in gasoline using NIR spectroscopy: effect of gasoline composition.

Near infrared (NIR) spectroscopy was employed for simultaneous determination of methanol and ethanol contents in gasoline. Spectra were collected in the range from 714 to 2500 nm and were used to construct quantitative models based on partial least squares (PLS) regression. Samples were prepared in the laboratory and the PLS regression models were developed using the spectral range from 1105 to 1682 nm, showing a root mean square error of prediction (RMSEP) of 0.28% (v/v) for ethanol for both PLS-1 and PLS-2 models and of 0.31 and 0.32% (v/v) for methanol for the PLS-1 and PLS-2 models, respectively. A RMSEP of 0.83% (v/v) was obtained for commercial samples. The effect of the gasoline composition was investigated, it being verified that some solvents, such as toluene and o-xylene, interfere in ethanol content prediction, while isooctane, o-xylene, m-xylene and p-xylene interfere in the methanol content prediction. Other spectral ranges were investigated and the range 1449-1611 nm showed the best results.

Construction and evaluation of a flow injection micro-analyser based on urethane-acrylate resin.

A flow injection micro-analyser with an integrated injection device and photometric detection is described. Channels measuring 205-295 microm depth by 265-290 microm maximum width were manufactured by deep UV lithography on two layers of urethane-acrylate oligomers-based photoresist. Hypodermic syringe needles (450 microm diameter) were connected to the channels for introduction of solutions into the system. Plastic optical fibres were connected to the ends of a 5.0 mm long channel, in order to conduct the light from and to a homemade photometer. The device has a total volume of 7.0 microL and three different sample volumes (0.09, 0.22 and 0.30 microL) can be inserted into the system by choosing the appropriate loop of the hydrodynamic injection approach. The micro-analyser, designed as a single line manifold, was evaluated by determining chloride in waters (mercuric thiocyanate method), and chromium (VI) in wastewater and total chromium in metallic alloys (diphenylcarbazide method). For chloride determination two micro-pumps were employed to impel the solutions, while for chromium determination this task was performed by a conventional peristaltic pump. The results obtained in all determinations did not differ significantly from the reference methods at a confidence level of 95%. In the chloride determination, a flow rate of 50 microL min(-1) was used, providing a sample frequency of 45 injection h(-1), generating ca. 0.7 mg of Hg(II) after an 8-h working day (ca. 20 mL of solution). This result suggests the potential of the micro-analyser towards the reduction of waste, following the philosophy of Green Chemistry.

A simple method for water discrimination based on an light emitting diode (LED) photometer.

This work describes the use of a multi-LED photometer for discrimination of mineral water samples, employing chromogenic reagents and chemometric techniques. Forty-five water samples (including 7 different brands of mineral water and samples of deionised, distilled and tap waters) were analysed in a monosegmented flow system, using three different chromogenic reagents (murexide, PAR and eriochrome black T) in a pH 10.0 NH3/NH4(+) buffer in separate injections. Measurements were performed at 470, 500, 525, 562, 590, 612, 636 and 654 nm. Analyses were carried out using PCA, employing data sets including absorbance values obtained with one, two or all three reagents, which comprise 8, 16 or 24 variables, respectively. The best result was obtained with the data set from murexide and eriochrome black T, providing a clear distinction between 9 groups (distilled and deionised waters were classified in the same group). Based on the loading values, it was possible to select four wavelengths (470, 500, 590 and 654 nm) that provided a similar discrimination. With the use of these four LED, an HCA was performed, providing discrimination between 8 groups at a similarity level of 0.88. A model based on SIMCA allowed correctly classifying 94% of the samples. The discrimination between different groups is due to the metal ion contents in the water samples, mainly calcium and magnesium. Therefore, the use of common complexing reagents, such as murexide and erichrome black T, a multi-LED photometer and chemometric techniques provide an easy and simple method for water discrimination.

Optical sensor for sulfur dioxide determination in wines.

A method for the determination of free and total sulfur dioxide in wines, based on the use of an optical sensor that employs a dichlorobis(diphenylphosphino)methane dipalladium I complex [Pd(2)(dppm)(2)Cl(2)] immobilized in a PVC membrane plasticized with o-nitrophenyloctylether (o-NPOE) is described. A sensing membrane [4.2% Pd(2)(dppm)(2)Cl(2), 20.8% PVC, and 75% o-NPOE] was adapted to the tip of a bifurcated optical fiber bundle to perform reflectance measurements at 550 nm. The detection system consisted of two cells (40 mL), which hold the sample solution (plus reagents) and the optical sensor, respectively. For the determination of free SO(2), a wine sample was mixed with H(2)SO(4) solution in the sample cell, into which N(2) was bubbled, providing mixing of the solutions and conducting the SO(2) formed toward the detection cell. For determination of total SO(2), a KOH solution was mixed with the wine in the sample cell. Afterward, an H(2)SO(4) solution was added to the cell, and then N(2) was bubbled to conclude the measurement. Linear responses up to 50 and 150 mg L(-1) were obtained for free and total SO(2), with detection limits of 0.37 and 0.70 mg L(-1), respectively. The repeatability of the method was evaluated by carrying out 10 measurements using a single wine sample, providing relative standard deviation values of 2.2 and 2.5% for free and total SO(2), respectively. The sensing membrane prepared from 10 muL of the cocktail solution lasted for 80 measurements, whereas those prepared from 200 muL can be used for 250 measurements. The method was applied to free and total SO(2) determination in wines, and the results did not show significant difference from those obtained with the Ripper reference method at a confidence level of 95%.

Assessment of infrared spectroscopy and multivariate techniques for monitoring the service condition of diesel-engine lubricating oils.

This paper presents two methodologies for monitoring the service condition of diesel-engine lubricating oils on the basis of infrared spectra. In the first approach, oils samples are discriminated into three groups, each one associated to a given wear stage. An algorithm is proposed to select spectral variables with good discriminant power and small collinearity for the purpose of discriminant analysis classification. As a result, a classification accuracy of 93% was obtained both in the middle (MIR) and near-infrared (NIR) ranges. The second approach employs multivariate calibration methods to predict the viscosity of the lubricant. In this case, the use of absorbance measurements in the NIR spectral range was not successful, because of experimental difficulties associated to the presence of particulate matter. Such a problem was circumvented by the use of attenuated total reflectance (ATR) measurements in the MIR spectral range, in which an RMSEP of 3.8cSt and a relative average error of 3.2% were attained.

Silicone sensing phase for detection of aromatic hydrocarbons in water employing near-infrared spectroscopy.

The use of silicone for detection of aromatic hydrocarbons in water using near-infrared spectroscopy is proposed. A sensing phase of poly(dimethylsiloxane) (PDMS) was prepared, and a rod of this material was adapted to a transflectance probe for measurements from 850 to 1800 nm. Deionized water samples contaminated separately with known amounts of benzene, toluene, ethylbenzene, and m-xylene were used for evaluation of the PDMS sensing phase, and measurements were made in a closed reactor with constant stirring. Equilibrium states were obtained after 90, 180, 360, and 405 min for benzene, toluene, ethylbenzene, and m-xylene, respectively. The PDMS sensing phase showed a reversible response, presenting linear response ranges up to 360, 290, 100, and 80 mg L(-1), with detection limits of 8.0, 7.0, 2.6, and 3.0 mg L(-1) for benzene, toluene, ethylbenzene, and m-xylene, respectively. Reference spectra obtained with different rods showed a relative standard deviation of 0.5%, indicating repeatability in the sensing phase preparation. A relative standard deviation of 6.7% was obtained for measurements performed with six different rods, using a 52 mg L(-1) toluene aqueous solution. The sensing phase was evaluated for identification of sources of contamination of water in simulated studies, employing Brazilian gasoline type A (without ethanol), gasoline type C (with 25% of anhydrous ethanol), and diesel fuel. Principal component analysis was able to classify the water in distinct groups, contaminated by gasoline A, gasoline C, or diesel fuel.