Raquel B. R. Mesquita

A review on sequential injection methods for water analysis

The development of fast, automatic and less expensive methods of analysis has always been the main aim of flow methodologies. The search for new procedures that still maintain the reliability and accuracy of the reference procedures is an ever growing challenge. New requirements are continually added to analytical methodologies, such as lower consumption of samples and reagents, miniaturisation and portability of the equipment, computer interfaces for full decision systems and so on. Therefore, the development of flow methodologies meeting the extra requirements of water analysis is a challenging work. Sequential injection analysis (SIA) presents a set of characteristics that make it highly suitable for water analysis. With sequential injection analysis, most routine determinations in waters can be performed more quickly with much lower reagent consumption when compared to reference procedures. Additionally, SIA can be a valuable tool for analyte speciation and multiparametric analysis. This paper critically reviews the overall work in this area.

Turbidimetric determination of chloride in different types of water using a single sequential injection analysis system

A sequential injection analysis system for the turbidimetric determination of chloride in different types of water is proposed. The determination is based on the reaction of chloride with silver ions and the subsequent measurement of the turbidity caused by silver chloride precipitation. In this method, the use of toxic reagents, such as mercury thiocyanate, commonly employed in most spectrophotometric techniques for chloride determination, is avoided. The main feature of the developed system is the use of a single configuration to carry out the determination over a wide concentration range (2-400 mg L(-1)) by changing only the aspirated sample volume. This characteristic allows the determination of chloride in ground, surface and wastewaters using the same manifold. In addition, a considerable saving of precipitating reagent is achieved due to non-continuous consumption. The results obtained with the developed system were statistically indistinguishable from those of the potentiometric titration reference method. Relative standard deviations for ten consecutive injections were lower than 3.7%, with a sampling frequency of between 55 and 57 determinations per hour.

Development of a flow method for the determination of phosphate in estuarine and freshwaters - Comparison of flow cells in spectrophotometric sequential injection analysis

A sequential injection system with dual analytical line was developed and applied in the comparison of two different detection systems viz; a conventional spectrophotometer with a commercial flow cell, and a multi-reflective flow cell coupled with a photometric detector under the same experimental conditions. The study was based on the spectrophotometric determination of phosphate using the molybdenum-blue chemistry. The two alternative flow cells were compared in terms of their response to variation of sample salinity, susceptibility to interferences and to refractive index changes. The developed method was applied to the determination of phosphate in natural waters (estuarine, river, well and ground waters). The achieved detection limit (0.007 μM PO(4)(3-)) is consistent with the requirement of the target water samples, and a wide quantification range (0.024-9.5 μM) was achieved using both detection systems.

Gas diffusion sequential injection system for the spectrophotometric determination of free chlorine with o-dianisidine

A gas diffusion sequential injection system for spectrophotometric determination of free chlorine is described. The detection is based in the colorimetric reaction between free chlorine and a low toxicity reagent o-dianisidine. A gas diffusion unit is used to isolate free chlorine from the sample in order to avoid possible interferences. This feature results from the conversion of free chlorine to molecular chlorine (gaseous) with sample acidification. With minor changes in the operating conditions, two different dynamic ranges were obtained enhancing the application both to water samples and bleaches. The results obtained with the developed system were compared to the reference method, iodometric titration and proved not to be statistically different. A detection limit of 0.6mg ClO(-)/L was achieved. Repeatability was evaluated from 10 consecutive determinations being the results better than 2%. The two dynamic ranges presented different determination rates: 15h(-1) for 0.6-4.8mg ClO(-)/L (water samples) and 30h(-1) for 0.047-0.188g ClO(-)/L (bleaches).

Removal of fluoxetine and its effects in the performance of an aerobic granular sludge sequential batch reactor

Fluoxetine (FLX) is a chiral fluorinated pharmaceutical mainly indicated for treatment of depression and is one of the most distributed drugs. There is a clear evidence of environmental contamination with this drug. Aerobic granular sludge sequencing batch reactors constitute a promising technology for wastewater treatment; however the removal of carbon and nutrients can be affected by micropollutants. In this study, the fate and effect of FLX on reactor performance and on microbial population were investigated. FLX adsorption/desorption to the aerobic granules was observed. FLX shock loads (≤4μM) did not show a significant effect on the COD removal. Ammonium removal efficiency decreased in the beginning of first shock load, but after 20 days, ammonia oxidizing bacteria became adapted. The nitrite concentration in the effluent was practically null indicating that nitrite oxidizing bacteria was not inhibited, whereas, nitrate was accumulated in the effluent, indicating that denitrification was affected. Phosphate removal was affected at the beginning showing a gradual adaptation, and the effluent concentration was <0.04mM after 70 days. A shift in microbial community occurred probably due to FLX exposure, which induced adaptation/restructuration of the microbial population. This contributed to the robustness of the reactor, which was able to adapt to the FLX load.

Use of tetramethylbenzidine for the spectrophotometric sequential injection determination of free chlorine in waters.

A sequential injection (SI) method was developed for the spectrophotometric determination of chlorine based on the reaction between tetramethylbenzidine (TMB) and free chlorine. The advantages resulting from the use of TMB are considerable: TMB is highly selective for chlorine, it enables a fairly low quantification limit and represents a less toxic alternative to reagents such as tolidine. The use of this reaction in SI adds other advantages as it enhances the degree of automation, minimisation of reagent consumption (6.8mug TMB/assay) and low effluent production (2.5mL/determination). The developed method allowed a quantification limit of 90mug/L with a working range of 0.09-1.30mgOCl(-)/L and a determination rate of 60det./h. Based on these features, the system was applied to tap-water and surface water samples with no previous treatment required. The results obtained with the developed system were compared to the reference method, diethyl-p-phenylelediamine (DPD) colorimetric method, and proved not to be statistically different.

Iron speciation by microsequential injection solid phase spectrometry using 3-hydroxy-1(H)-2-methyl-4-pyridinone as chromogenic reagent

The speciation of iron using the newly synthesized 3-hydroxy-1(H)-2-methyl-4-pyridinone by solid phase spectrophotometry in a microsequential injection lab-on-valve (µSI-LOV-SPS) methodology is described. Iron was retained in a reusable column, Nitrilotriacetic Acid Superflow (NTA) resin, and the ligand was used as both chromogenic and eluting reagent. This approach, analyte retention and matrix removal, enabled the assessment of iron (III) and total iron content in fresh waters and high salinity coastal waters with direct sample introduction, in the range of 20.0-100 µg/L. with a LOD of 9 µg/L. The overall effluent production was 2 mL, corresponding to the consumption of 0.48 µg of 2-metil-3-hydroxy-4-pyridinone, 0.34 mg of NaHCO3, 16 mg of HNO3, 4.4 µg H2O2 and 400µL of sample. Four reference samples were analyzed and a relative deviation<10% was obtained; furthermore, several bathing waters (♯13) were analyzed using the developed method and the results were comparable to those obtained by atomic absorption spectrophotometry (relative deviations<6%).

Exploiting the use of 3,4-HPO ligands as nontoxic reagents for the determination of iron in natural waters with a sequential injection approach

In this paper, the use of 3-hydroxy-4-pyridinone (3,4-HPO) chelators as nontoxic chromogenic reagents for iron determination is proposed. The potential application of these compounds was studied in a sequential injection system. The 3,4-HPO ligands used in this work were specially designed to complex iron(III) at physiologic pH for clinical applications. The developed sequential injection method enabled to study the reaction conditions, such as buffering and interferences. Then, to further improve the low consumption levels, a microsequential injection method was developed and effectively applied to iron determination in bathing waters using 3,4-HPO ligands. The formed iron complex has a maximum absorbance at 460 nm. The advantage of using minimal consumption values associated with sequential injection, together with the lack of toxicity of 3,4-HPO ligands, enabled to present a greener chemistry approach for iron determination in environmental samples within the range 0.10-2.00 mg Fe/L with a LOD of 7 μg/L. The overall effluent production was 350 μL corresponding to the consumption of 0.48 mg of 3,4-HPO ligand, 0.11 mg of NaHCO3, 0.16 mg of HNO3 and 50 μL of sample. Three reference samples were assessed for accuracy studies and a relative deviation <5% was obtained. The results obtained for the assessment of iron in inland bathing waters were statistically comparable to those obtained by the reference procedure.

Development of a sequential injection system for the determination of nitrite and nitrate in waters with different salinity: Application to estuaries in NW Portugal

In this work, a sequential injection methodology for monitoring nitrite and nitrate in estuarine waters without any previous treatment is described. The developed system was applied to the measurement of nitrite and nitrate in estuarine waters of three rivers in the NW Portugal, allowing an automatic, fast (ca 60 h-1) and precise method (relative standard deviation lower than 2%). The procedure was based on the reaction between nitrite, sulfanilamide and N-(1-naphthyl)-ethylenediamine dihydrochloride (N1NED), whereas the determination of nitrate resulted from its reduction to nitrite, using an in-line cadmium column, followed by the same reaction. The samples were collected in three locations for each river (Douro, Cávado and Ave) covering the lower, middle and upper section of the estuaries. Despite the presence of a salinity gradient, this parameter showed no interference in the accuracy of the determinations. The results obtained for the described method for nitrite were statistically comparable to those obtained by the reference procedure. For the determination of nitrate, recovery tests confirmed that the sequential injection methodology provided good quality results.

Development of a sequential injection gas diffusion system for the determination of ammonium in transitional and coastal waters

This work describes the development of a sequential injection system for the ammonium determination in transitional and coastal waters with a wide salinity range. Estuarine waters are rather complex matrices as their characteristics change considerably along the salinity gradient, as well as the ammonium levels. The developed system effectively solves these issues by converting ammonium into ammonia and using a gas diffusion unit (GDU) for matrix removal. The ammonium determination in a wide quantification range (0.1–5.0 mg L−1) was obtained with small changes in the protocol sequence and was applied, not only to estuarine samples, but also well water samples (low salinity) and coastal waters (higher salinity). Spectrophotometry was the chosen detection system to measure the absorbance change in the bromothymol blue acid base indicator caused by the diffusion of ammonia through the GDU. Additionally, the developed system used a green chemistry approach, as there was no indicator reagent consumption per determination, still maintaining a good precision (relative standard deviation lower than 2%) and a low detection limit, 27 μg L−1 (1.5 μM).