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This work describes the development of a microfluidic paper-based analytical device (μPAD) for the determination of copper in fresh and marine waters. A functionalized rhodamine-based chelator was synthesized and used as a chromogenic reagent, forming a highly intense pink complex with the analyte. The aim was to create a paper device that offers optimal performance and provides in-situ, rapid and cost-effective analysis in line with World Health Organization guidelines. The influence on the determination of several physical and chemical parameters was evaluated aiming to achieve the best performance. Under optimised conditions, a linear correlation was established in the range of 0.05-0.50 mg L -1 of copper, with a limit of detection of 10 μg L -1 . The accuracy of the proposed method was assessed by comparing the results obtained with the developed μPAD and the results obtained with Inductively Coupled Plasma measurements (RE < 10 %). Recovery studies were also performed using different types of water samples with no need for any prior sample pre-treatment: tap, well, river and seawater. The average recovery percentage of 101 % (RSD = 4.3 %) was obtained, a clear indication of no multiplicative matrix interferences., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Authors. Published by Elsevier B.V. All rights reserved.)

Iodine is an essential micronutrient for humans due to its fundamental role in the biosynthesis of thyroid hormones. As a key parameter to assess health conditions, iodine intake needs to be monitored to ascertain and prevent iodine deficiency. Iodine is available from various food sources (such as seaweed, fish, and seafood, among others) and dietary supplements (multivitamins or mineral supplements). In this work, a microfluidic paper-based analytical device (μPAD) to quantify iodide in seaweed and dietary supplements is described. The developed μPAD is a small microfluidic device that emerges as quite relevant in terms of its analytical capacity. The quantification of iodide is based on the oxidation of 3,3',5,5'-tetramethylbenzidine (TMB) by hydrogen peroxide in the presence of iodine, which acts as the catalyst to produce the blue form of TMB. Additionally, powder silica was used to intensify and uniformize the colour of the obtained product. Following optimization, the developed μPAD enabled iodide quantification within the range of 10-100 µM, with a detection limit of 3 µM, and was successfully applied to seaweeds and dietary supplements. The device represents a valuable tool for point-of-care analysis, can be used by untrained personnel at home, and is easily disposable, low-cost, and user-friendly.

A multiparametric sequential injection system for the determination of phosphate, nitrite, nitrate, potassium, and iron(III) in a single manifold was developed. The main goal of the proposed method was to develop an efficient tool to assess a number of essential chemical compounds in soils, providing the corresponding information on soil fertility and, additionally, information on possible groundwater contamination. The method was applied for the quantification of the aforementioned parameters in simulated leachates produced in laboratory-scale core columns. The relative standard deviations of ten replicate analyses of a standard were: 6% for phosphate; 2% for nitrite; 2% for nitrate; 5% for potassium; and 6% for iron(III). The limits of detection and quantification were: 2.15 and 7.18 μmol/L for phosphate determination; 0.22 and 0.73 μmol/L for nitrite determination; 3.42 and 8.00 μmol/L for nitrate determination; 39 μmol/L (limit of detection) for potassium determination; and 0.46 and 1.85 μmol/L for iron(III) determination. The sequential injection system was successfully applied for the quantification of multiple soil chemical components (PO 4 3- , NO 2 - , NO 3 - , K + , and Fe 3+ ) in soil leachates. The analysis of a sample, involving all the analytes, has a duration of 28 min., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 The Authors. Published by Elsevier B.V. All rights reserved.)

This work describes the development of a flow injection method to determine hydroxyproline (HYP), one of collagen's most abundant amino acids. Collagen is a protein with several applications and high nutritional value. Evaluating the feasibility of using collagen from fish skin over its mammalian source is essential. The determination of HYP requires the pre-treatment and hydrolysis of the fish skin to break down collagen into its amino acids, and the HYP value quantified relates to the collagen content. The determination was based on the HYP oxidation with permanganate in an alkaline medium and the consequent decrease of colour intensity registered. Under optimal conditions, the developed method enables the determination of the HYP within the dynamic range of 23.8 to 500 mg L -1 , with a limit of detection (LOD) of 2.6 mg L -1 and a limit of quantification (LOQ) of 23.8 mg L -1 . Different samples were processed, and the digests were analysed by the proposed method and with the conventional procedure with good correlation (relative error < 7%). Moreover, the analyte quantification is performed faster, simpler, and more accurately, with less toxic solutions. The reproducibility of the developed method was also evaluated by calculating the relative standard deviation of the calibration curve slope (RSD < 1%).

Non-transferrin-bound iron (NTBI) is a group of circulating toxic iron forms, which occur in iron overload or health conditions with dysregulation of iron metabolism. NTBI is responsible for increased oxidative stress and tissue iron loading. Despite its relevance as a biochemical marker in several diseases, a standardized assay is still lacking. Several methods were developed to quantify NTBI, but results show high inter-method and even inter-laboratory variability. Thus, the development of a consistent NTBI assay is a major goal in the management of iron overload and related clinical conditions. In this work, a micro sequential injection lab-on-valve (μSI-LOV) method in a solid phase spectrophotometry (SPS) mode was developed for the quantification of NTBI, using a bidentate 3,4-hydroxypyridinone (3,4-HPO) ligand anchored to sepharose beads as a chromogenic reagent. To attain SPS, the functionalized beads were packed into a column in the flow cell, and the analyte, NTBI retained as iron (III), formed a colored complex at the beads while eliminating the sample matrix. The dynamic concentration range was 1.62-7.16 μmol L -1 of iron (III), with a limit of detection of 0.49 μmol L -1 and a limit of quantification of 1.62 μmol L -1 . The proposed μSI-LOV-SPS method is a contribution to the development of an automatic method for the quantification of the NTBI in serum samples., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 The Authors. Published by Elsevier B.V. All rights reserved.)

A microfluidic paper-based device (µPAD) has been combined with metal-organic frameworks (MOFs) for total phenolic compounds (TPC) quantification in fruit samples for the first time. The performance of the µPAD, based upon the vertical flow approach, was enhanced in order to determine the TPC content with high accuracy in fruit samples. The method was based on the traditional Folin-Ciocalteu Index using gallic acid or oenotannin as reference phenolic compounds. This novel design and construction of the device are in agreement with the principles of Green Chemistry avoiding wax technology (lower toxicity). The analytical parameters that affect the colorimetric method (using digital imaging of the colored zone) performance were optimized including design, sample volume, and MOF amount. Then, the analytical features of the developed method were investigated such as dynamic range (1.6-30 mg L -1 ), limit of detection (0.5 mg L -1 ), and precision (RSD < 9%). Besides, the in-field analysis is achievable with a color stability up to 6 h after the loading process of the sample and storage stability for at least 15 days without performance losses (under vacuum at - 20 °C). Furthermore, the MOF ZIF-8@paper was characterized to study its composition and the successful combination. The feasibility of the proposed method was demonstrated by determining the TPC in 5 fruit samples using oenotannin as reference solute. The accuracy was validated by comparison of the data with the results obtained with the recommended protocol proposed by the International Organisation of Vine and Wine (OIV)., (© 2023. The Author(s).)

In this work, the design and development of a microfluidic paper-based device (μPAD) for the quantification of total phenolic compounds (TPC) in wines is described. The developed μPAD was based upon the vertical flow concept and the colour reaction used was the known Folin-Ciocalteu reaction using gallic acid as reference phenolic compound. After studying operational parameters, namely type of paper, reagents and sample volume, a dynamic range of 5-50 mg L -1 was obtained with a limit of detection of 1.2 mg L -1 . The described device proved to have good precision (relative standard deviation < 5%) and no significant interferences were observed from known compounds present in wines. Furthermore, the stability of the colour product and of the device itself were assessed; the μPAD was stable for 30 days (in the dark at room temperature) and it could be scanned up to 8 h after sample introduction. The developed μPAD pose as a simple method for TPC quantification and was successfully applied to several wine samples including sparkling and table wines with two different approaches: i) using gallic acid as reference compound with standard addition; and ii) using taniraisin with external calibration. The accuracy of the proposed μPAD method was assessed by comparison with the reference spectrophotometric method according to the International Organisation of Vine and Wine (OIV) recommendations., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier B.V. All rights reserved.)

A flow-based method for the spectrophotometric determination of chromium (VI) in recreational waters with different salinities was developed. Chromium can occur in the environment in different oxidation states with different related physiological properties. With regard to chromium, the speciation is particularly important, as the hexavalent chromium is considered to be carcinogenic. To achieve that purpose, the use of the diphenylcarbazide (DPC) selective colored reaction with the hexavalent chromium was the chosen strategy. The main objective was to develop a direct and simple spectrophotometric method that could cope with the analysis of different types of environmental waters, within different salinity ranges (fresh to marine waters). The potential interference of metal ions, that can usually be present in environmental waters, was assessed and no significant interferences were observed (<10%). For a complete Cr(VI) determination (three replicas) cycle, the corresponding reagents consumption was 75 µg of DPC, 9 mg of ethanol and 54 mg of sulfuric acid. Each cycle takes about 5 min, including the system clean-up. The limit of detection was 6.9 and 12.2 µg L−1 for waters with low and high salt content, respectively. The method was applied for the quantification of chromium (VI) in both fresh and marine water, and the results were in agreement with the reference procedure.

In this work, a flow-based spectrofluorimetric method for iodine determination was developed. The system consisted of a miniaturized chip-based flow manifold for solutions handling and with integrated spectrofluorimetric detection. A multi-syringe module was used as a liquid driver. Iodide was quantified from its catalytic effect on the redox reaction between Ce(IV) and As(III), based on the Sandell-Kolthoff reaction. The method was applied for the determination of iodine in salt, pharmaceuticals, supplement pills, and seaweed samples without off-line pre-treatment. An in-line oxidation process, aided by UV radiation, was implemented to analyse some samples (supplement pills and seaweed samples) to eliminate interferences and release iodine from organo-iodine compounds. This feature, combined with the fluorometric reaction, makes this method simpler, faster, and more sensitive than the classic approach of the Sandell-Kolthoff reaction. The method allowed iodine to be determined within a range of 0.20-4.0 µmol L -1 , with or without the in-line UV digestion, with a limit of detection of 0.028 µmol L -1 and 0.025 µmol L -1 , respectively.

The aim of this work was to develop a sequential injection (SI) method for the determination of the micronutrients iron and manganese, in soil leachates, as a tool to assess potential groundwater contamination. The described sequential injection method was based on the reaction of iron with chelator MRB12, a greener alternative chromogenic reagent, and the reaction of manganese with zincon, within a single manifold. The developed SI method enabled the determination of iron in the range 0.10-1.00 mg L -1 , and manganese in the range 0.25-2.5 mg L -1 with a limit of detection of 0.08 mg L -1 for iron and 0.24 mg L -1 for manganese. The determination of both parameters was made in 6 minutes, in triplicate. The application to monitor laboratory scale soil core columns (LSSCs), as a simulation of the soil leaching process, proved its efficiency to assess potential contamination of ground waters. Iron and manganese contents were effectively analysed in two different scenarios to mimic the leaching process with rainwater and fertilizer.

The aim of this work was the development of an automatic sequential injection analysis method to monitor the ozonation process for water disinfection. The determination was based on the reaction between bromate and o-dianisidine in the presence of bromide in acidic medium. The determination parameters were studied and adjusted to enable bromate quantification in the range 0.35-4.0 mg BrO 3 - /L with a limit of detection of 20 μg BrO 3 - /L. The choice of a sequential injection procedure enabled a minimal consumption of reagents and no need for sample pre-treatment. The developed sequential injection proved to be accurate with < 5% relative deviation when compared to ICP-MS and an average of 101% in recovery percentages studies. It was effectively applied to monitor an ozonation process enabling the follow-up of the process with real-time quantification of the bromate content., (© 2022. The Author(s), under exclusive licence to The Japan Society for Analytical Chemistry.)

Chronic Kidney Disease (CKD) is a growing public-health concern worldwide. Patients exhibit compromised immunity and are more prone to infection than other populations. Therefore, oral colonization by clinically relevant members of the Enterobacteriaceae family, major agents of both nosocomial and dialysis-associated infections with frequent prevalence of antibiotic resistances, may constitute a serious risk. Thus, this study aimed to assess the occurrence of clinically relevant enterobacteria and their antibiotic resistance profiles in the oral cavity of CKD patients undergoing peritoneal dialysis (CKD-PD) and compare it to healthy controls. Saliva samples from all the participants were cultured on MacConkey Agar and evaluated regarding the levels of urea, ammonia, and pH. Bacterial isolates were identified and characterized for antibiotic resistance phenotype and genotype. The results showed that CKD-PD patients exhibited significantly higher salivary pH, urea, and ammonia levels than controls, that was accompanied by higher prevalence and diversity of oral enterobacteria. Out of all the species isolated, only the prevalence of Raoultella ornithinolytica varied significantly between groups, colonizing the oral cavity of approximately 30% of CKD-PD patients while absent from controls. Antibiotic resistance phenotyping revealed mostly putative intrinsic resistance phenotypes (to amoxicillin, ticarcillin, and cephalothin), and resistance to sulfamethoxazole (~43% of isolates) and streptomycin (~17%). However, all isolates were resistant to at least one of the antibiotics tested and multidrug resistance isolates were only found in CKD-PD group (31,6%). Mobile genetic elements and resistance genes were detected in isolates of the species Raoultella ornithinolytica , Klebsiella pneumoniae , Klebsiella oxytoca , Escherichia coli , and Enterobacter asburiae , mostly originated from CKD-PD patients. PD-related infection history revealed that Enterobacteriaceae were responsible for ~8% of peritonitis and ~ 16% of exit-site infections episodes in CKD-PD patients, although no association was found to oral enterobacteria colonization at the time of sampling. The results suggest that the CKD-induced alterations of the oral milieu might promote a dysbiosis of the commensal oral microbiome, namely the proliferation of clinically relevant Enterobacteriaceae potentially harboring acquired antibiotic resistance genes. This study highlights the importance of the oral cavity as a reservoir for pathobionts and antibiotic resistances in CKD patients undergoing peritoneal dialysis., Competing Interests: The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest., (Copyright © 2021 Costa, Merino-Ribas, Ferreira, Campos, Silva, Pereira, Garcia, Azevedo, Mesquita, Rangel, Manaia and Sampaio-Maia.)

Iron is an important micronutrient involved in several mechanisms in the human body and can be an important biomarker. In this work, a simple and disposable microfluidic paper-based analytical device (µPAD) was developed for the quantification of iron in urine samples. The detection was based on the colorimetric reaction between iron(II) and bathophenanthroline and the reduction of iron(III) to iron(II) with hydroxylamine. The developed µPAD enabled iron determination in the range 0.07-1.2 mg/L, with a limit of detection of 20 µg/L and a limit of quantification of 65 µg/L, thus suitable for the expected values in human urine. Additionally, targeting urine samples, the potential interference of the samples color was overcome by incorporating a sample blank assessment for absorbance subtraction. Stability studies revealed that the device was stable for 15 days prior to usage and that the formed colored product was stable for scanning up to 3 h. The accuracy of the developed device was established by analyzing urine samples (#26) with the developed µPAD and with the atomic absorption spectrometry method; the relative deviation between the two sets of results was below 9.5%., (© 2021. Springer-Verlag GmbH Germany, part of Springer Nature.)

In this work, the design of a microfluidic paper-based analytical device (μPAD) for the quantification of nitrate in urine samples was described. Nitrate monitoring is highly relevant due to its association to some diseases and health conditions. The nitrate determination was achieved by combining the selectivity of the nitrate reductase enzymatic reaction with the colorimetric detection of nitrite by the well-known Griess reagent. For the optimization of the nitrate determination μPAD, several variables associated with the design and construction of the device were studied. Furthermore, the interference of the urine matrix was evaluated, and stability studies were performed, under different conditions. The developed μPAD enabled us to obtain a limit of detection of 0.04 mM, a limit of quantification of 0.14 mM and a dynamic concentration range of 0.14-1.0 mM. The designed μPAD proved to be stable for 24 h when stored at room temperature in air or vacuum atmosphere, and 60 days when stored in vacuum at -20 °C. The accuracy of the nitrate μPAD measurements was confirmed by analyzing four certified samples (prepared in synthetic urine) and performing recovery studies using urine samples.

The presence of toxic compounds in wastewater can cause problems for organic matter and nutrient removal. In this study, the long-term effect of a model xenobiotic, 2-fluorophenol (2-FP), on ammonia-oxidizing bacteria (AOB), nitrite oxidizing bacteria (NOB) and phosphate accumulating organisms (PAO) in aerobic granular sludge was investigated. Phosphate (P) and ammonium (N) removal efficiencies were high (>93%) and, after bioaugmentation with 2-FP degrading strain FP1, 2-FP was completely degraded. Neither N nor P removal were affected by 50 mg L -1 of 2-FP in the feed stream. Changes in the aerobic granule bacterial communities were followed. Numerical analysis of the denaturing gradient gel electrophoresis (DGGE) profiles showed low diversity for the ammonia monooxygenase (amoA) gene with an even distribution of species. PAOs, including denitrifying PAO (dPAO), and AOB were present in the 2-FP degrading granules, although dPAO population decreased throughout the 444 days reactor operation. The results demonstrated that the aerobic granules bioaugmented with FP1 strain successfully removed N, P and 2-FP simultaneously.

In this work, two different microfluidic paper-based analytical devices (μPADs) were developed for the quantification of nitrite and nitrate in human saliva samples, in order to aid in the diagnosis of some diseases and health conditions associated with these ions. The development of these nitrite and nitrate μPADs involved several studies to optimize their design and construction, including an interference assessment and stability studies. These μPADs allowed a nitrite determination in a range of 5-250 μM with limits of detection and quantification of 0.05 μM and 0.17 μM, respectively, and a nitrate determination in the range 0.2-1.2 mM with limits of detection and quantification of 0.08 mM and 0.27 mM, respectively. As for the stability, both of the μPADs were stable when stored in vacuum at 4 °C (the nitrite μPAD for at least 60 days and the nitrate μPAD for at least of 14 days) and, after the sample placement, the nitrite and nitrate μPADs could be scanned within the first 4 and 2 h, respectively. The nitrite μPAD measurements were compared with the ones obtained from the standard colorimetric method and there were no statistically significant differences between these two methods. To evaluate the accuracy of nitrate μPAD measurements, 4 certified water samples were used and recovery studies using saliva samples were performed., (Copyright © 2020 Elsevier B.V. All rights reserved.)

A bi-parametric sequential injection method for the determination of copper(II) and zinc(II) when present together in aqueous samples was developed. This was achieved by using a non-specific colorimetric reagent (4-(2-pyridylazo)resorcinol, PAR) together with two ion-exchange polymeric materials to discriminate between the two metal ions. A polymer inclusion membrane (PIM) and a chelating resin (Chelex 100) were the chosen materials to retain zinc(II) and copper(II), respectively. The influence of the flow system parameters, such as composition of the reagent solutions, flow rates and standard/sample volume, on the method sensitivity were studied. The interference of several common metal ions was assessed, and no significant interferences were observed (<10% signal deviation). The limits of detection were 3.1 and 5.6 µg L -1 for copper(II) and zinc(II), respectively; the dynamic working range was from 10 to 40 µg L -1 for both analytes. The newly developed sequential injection analysis (SIA) system was applied to natural waters and soil leachates, and the results were in agreement with those obtained with the reference procedure.

A flow-based method for the spectrophotometric determination of iron in recreational waters, both fresh and marine (variable salinity content), was developed. For that purpose, 3-hydroxy-4-pyrydinone ligand functionalized with an ether function was synthetized and used as chromogenic chelator (1-(3'-methoxypropyl)-2-methyl-3-benzyloxy-4-(1H)pyridinone - MRB13) for iron quantification. This water-soluble reagent was previously reported as a greener alternative to quantify iron, due to its low toxicity and a more environmental friendly synthesis. Furthermore, it also displayed a high affinity and specificity for iron. With the main objective of quantifying iron in a variety of water types (different matrices and iron content), two strategies were developed, one of them including on-line solid-phase extraction (SPE), and the other without resorting to a SPE process. Water matrix clean-up and iron enrichment was achieved using a nitrilotriacetic acid resin column. The potential interference of metal ions usually present in water samples was assessed and no significant interference (<10%) was observed. The limits of detection were 11 and 2.9 μg L -1 without and with SPE, respectively. For one determination (three replicates), the corresponding consumption of MRB13 is 90 μg, sodium hydroxide is 1.4 mg, and boric acid is 5.6 mg. The method was applied to certified water samples and the results were in agreement with certified values. The developed method was also applied to fresh and marine water, and recovery ratios of 103 ± 4 and 101 ± 7 without and with SPE, respectively, were achieved., (Copyright © 2020 Elsevier B.V. All rights reserved.)

This article reports on the development and validation of a disposable microfluidic paper-based analytical device (μPAD) for on-hand, in-situ, and cheap Fe(III) determination in natural waters complying with World Health Organization guidelines. The developed μPAD used 3-hydroxy-4-pyridinone (3,4-HPO) as a colour reagent due to its considerably lower toxicity than traditionally used iron analytical reagents. It was selected among a group of hydrophilic 3,4-HPO chelators containing ether-derived chains in their structure which were prepared using green methods. The relatively high water solubility of these chelators improved the detection limit and applicability as μPAD reagents. Under optimal conditions, the μPAD is characterised by a quantification range between 0.25 and 2.0 mg/L, a detection limit of 55 μg/L and 15 min of analysis time. The signal stability extends up to 4 h and the device is stable for at least one month. The reagent consumption is below 0.2 mg per analysis and the μPAD method was validated by analysis certified reference materials and by comparison with atomic absorption results (RD < 10%). The newly developed μPAD was successfully applied to the determination of iron in river, well and tap waters with no need of any prior sample pre-treatment., Competing Interests: Declaration of competing interests The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier B.V. All rights reserved.)

This work presents a portable microfluidic paper-based analytical device (micro-PAD) card for the quantification of total ammonia nitrogen in human saliva. The amount of total ammonia nitrogen in saliva can be an indicator of the status of the oral microbiome with potential correlation to kidney health problems. The developed micro-PAD card comprises twenty units consisting of three stacked layers of circular discs: the sample layer, paper discs impregnated with sodium hydroxide solution, the PTFE membrane layer, and the detection layer, paper discs impregnated with bromothymol blue. The twenty units were aligned on transparent laminating pouches laminated to form the micro-PAD card (7.5 cm × 10.5 cm). Saliva samples can be directly dispensed onto the micro-PAD card and the detection was achieved by the BTB indicator color change, from yellow to blue, after conversion of ammonium into ammonia and diffusion of the ammonia gas through a hydrophobic layer. The determination of total ammonia nitrogen in saliva using the developed micro-PAD card intended to be very simple method and operated without the need of laboratory equipment. A quantification limit of 11.3 NH 4 + mg L -1 and linear application range from up to 150 NH 4 + mg L -1 were obtained making it suitable for the expected concentrations of total ammonia nitrogen in human saliva. It was successfully applied to saliva samples and its validation obtained by comparison against a potentiometric method. The card is stable for at least 1 month making it ideal as a portable device for point-of-care diagnosis. Graphical Abstract.

Iodine deficiency remains a worldwide problem with two billion individuals having insufficient iodine intake. Universal salt iodisation was declared by UNICEF and WHO as a safe, cost-effective, and sustainable way to tackle iodine deficiency. In Portugal, the few studies available unravel an iodine status below the WHO guidelines for pregnant women and school-aged children. In the present study, the iodine levels of household salt consumed in Portugal was assessed, for the first time. Non-iodised (median 14 ppm) and fortified (median 48 ppm) marine salt samples showed iodine levels lower than the minimum and above the maximum threshold recommended by non-mandatory Portuguese law and WHO recommendations, respectively. This study calls attention to the fact that marine salt per se, in spite of containing a natural high amount of iodine, requires further fortification in order to be used as an effective tool to deal with iodine insufficiency.

In this work, the hexadentate 3,4-hydroxypyridinone ligand was used as reagent for the spectrophotometric quantification of iron(III) in fresh and sea waters, using a micro sequential injection lab-on-valve (µSI-LOV) system in a solid phase spectrometry (SPS) mode. To implement SPS, thus eliminating the sample matrix, a packed column in the flow cell was used; the chosen sorbent was Nitrilotriacetic Acid Superflow resin (NTA). The possibility of performing an analytical curve resorting to just one standard was also demonstrated. The consumption of the hexadentante ligand was about 30 µg per determination and the effluent production lower than 2.5 mL. The dynamic concentration range was 0.45-9.0 µmol L -1 , with a limit of detection of 0.13 µmol L -1 and limit of quantification 0.43 µmol L -1 . The proposed µSI-LOV-SPS methodology was successfully applied to river, ground, estuarine, tap, and sea waters., (Copyright © 2018 Elsevier B.V. All rights reserved.)

The use of saliva for diagnose and surveillance of systemic illnesses, and general health has been arousing great interest worldwide, emerging as a highly desirable goal in healthcare. The collection is non-invasive, stress-free, inexpensive, and simple representing a major asset. Glucose, calcium, and magnesium concentration are three major parameters evaluated in clinical context due to their essential role in a wide range of biochemical reactions, and consequently many health disorders. In this work, a spectrophotometric sequential injection method is described for the fast screening of glucose, calcium, and magnesium in saliva samples. The glucose determination reaction involves the oxidation of the aldehyde functional group present in glucose with simultaneous reduction of 3,5-dinitrosalicylic acid (DNS) to 3-amino, 5-nitrosalicylic acid under alkaline conditions, followed by the development of colour. The determination of both metals is based on their reaction with cresolphtalein complexone (CPC), and the interference of calcium in the magnesium determination minimized by ethylene glycol-bis[β-aminoethyl ether]-N,N,N',N'-tetraacetic acid (EGTA). The developed multi-parametric method enabled dynamic ranges of 50 - 300 mg/dL for glucose, 0.1 - 2 mg/dL for calcium, and 0.1 - 0.5 mg/dL for magnesium. Determination rates of 28, 60, 52 h -1 were achieved for glucose, calcium, and magnesium, respectively. Less than 300 µL of saliva is required for the multi-parametric determination due to saliva viscosity and inherent necessity of dilution prior to analysis. RSDs lower than 5% were obtained, and the results agreed with those obtained by reference methods, while recovery tests confirmed its accuracy., (Copyright © 2018 Elsevier B.V. All rights reserved.)

A sequential injection (SI) system equipped with in-line solid phase extraction column and in-line soil mini-column is proposed for determination of zinc and copper in soil leachates. The spectrophotometric determination (560 nm) is based on the reaction of both analytes with 1-(2-Pyridylazo)-2-naphthol (PAN). Zinc is determined after retaining copper on a cationic resin (Chelex100) whereas copper is determined from the difference of the absorbance measured for both analytes, introduced into the system with the use of a different channel, and zinc absorbance. The influence of several potential interferences was studied. Using the developed method, zinc and copper were determined within the concentration ranges of 0.005-0.300 and 0.011-0.200 mg L -1 , and with a relative standard deviation lower than 6.0% and 5.1%, respectively. The detection limits are 1.4 and 3.0 µg/L for determination of zinc and copper, respectively. The developed SI method was verified by the determination of both analytes in synthetic and certified reference materials of water samples, and applied to the determination of the analytes in rain water and soil leachates from laboratory scale soil core column and in-line soil mini-column., (Copyright © 2018 Elsevier B.V. All rights reserved.)

The determination of iron and copper exploiting a microsequential injection lab-on-valve system with online spectrophotometric detection is described. A new, environmental friendly 3-hydroxy-4-pyridinone chelator, functionalized with a polyethylene glycol chain (MRB12) to improve water solubility, was used for iron determination. For copper determination, 1-(2-pyridylazo)-2-naphthol (PAN) was used. Different parameters affecting the formation of the complexes were studied, namely sample volume, reagent concentration, and buffer composition and concentration. The optimized conditions, 150µL of sample volume and 250mgL -1 of MRB12 for iron determination, and 200µL of sample and 120mgL -1 of PAN for copper determination, enabled an LOD of 15 and 18µgL -1 for iron and copper, respectively. The robustness of the developed procedure was assessed by the calculation of the relative standard deviation (RSD), 5% for iron determination and 2% for copper determination. The accuracy of the method was assessed comparing the results with two certified samples (RD<7.5%) and calculating recovery percentages with five river water samples (average<107%)., (Copyright © 2017 Elsevier B.V. All rights reserved.)

In this work, a potentiometric flow injection method is described for the fast bi-parametric determination of iodide and iodate in urine and salt samples. The developed methodology aimed for iodine speciation with a potentially portable system (running on batteries). The iodate reduction to iodide was effectively attained in line within the same manifold. The iodide determination was accomplished in the dynamic range of 2.50×10 -6 -1.00×10 -3 M and the total iodine dynamic range, resulted from iodide plus iodate, was 3.50×10 -6 -2.00×10 -3 M. The calculated limits of detection were 1.39×10 -6 M and 1.77×10 -6 M for iodide and iodate, respectively. A determination rate of 21h -1 for the bi-parametric iodide and iodate determination was obtained for sample injection. The urine samples (RSD <5.8% for iodide and RSD <7.0% for iodate) results were in agreement with those obtained by the classic Sandell-Kolthoff reaction colorimetric reference procedure (RD <7.0%) and standard samples from Centers for Disease Control and Prevention, Atlanta, USA (CDC) international inter-laboratory EQUIP program. The developed flow method was also successfully applied to the iodide and iodate determination in salt samples (RSD <3.1% for iodate and iodide), with comparable results to conventional procedures. No significant interferences were observed interference percentage <9% for both determinations., (Copyright © 2017 Elsevier B.V. All rights reserved.)

A new paired ion electrospray ionization tandem mass spectrometry method for determination of anionic surfactants in water samples was developed. In this method, dicationic ion-pairing reagents were complexed with monoanionic analytes to facilitate analyte detection in positive mode electrospray ionization - mass spectrometry. Single ion monitoring and selected reaction monitoring on a triple quadrupole instrument were performed and compared. Four dicationic reagents were tested for the determination of perfluorooctanoic acid (PFOA), perfluorooctane sulfonate (PFOS), sodium dodecyl sulfate (SDS), dodecylbenzene sulfonic acid (DBS), and stearic acid (SA), among other common anions. The obtained limits of detection were compared with those from previous literature. Solid phase extraction using a C18 cartridge was performed in order to eliminate matrix interferences. A literature review was compiled for the methods published between 2010 and 2015 for determination of anionic surfactants. The optimized method was more sensitive than previously developed methods with LOD values of 2.35, 35.4, 37.0, 1.68, and 0.675 pg for SDS, SA, DBS, PFOS, and PFOA, respectively. The developed method was effectively applied for the determination of anionic surfactants in different water samples such as bottled drinking water, cooking water, tap water, and wastewater., (Copyright © 2015 Elsevier B.V. All rights reserved.)

The present work describes the development of a µSI-LOV method for the simultaneous screening of cadmium and lead in potentially contaminated water samples. To attain the biparametric determination, dithizone was chosen as the spectrophotometric reagent as it forms a colored complex with both metal ions, at different pH conditions. The cadmium determination was attained in strong alkaline conditions (pH≈12); the lead determination was calculated by the difference with the determination of both metals in mild alkaline conditions (pH≈8). The colored complex was measured at 550 nm and the method presented a LOD of 34 μg L(-1) for cadmium and 56 μg L(-1) for lead, with a sample consumption of 20 µL per assay and a determination rate of 55 h(-1). The results obtained were in agreement with those obtained by FAAS. The developed method was efficiently applied to the screening of cadmium and lead in marine port waters., (Copyright © 2015 Elsevier B.V. All rights reserved.)

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.