A modified micro-solid phase extraction device for in-port elution and injection into portable liquid chromatography: A proof-of-concept study.

A micro-solid phase extraction (micro-SPE) device packed with a C18 sorbent (10 mg) has been developed for the enrichment and purification of organic water pollutants prior to their analysis using a portable liquid chromatograph with a dual UV detector. To this end, the sorbent was immobilized at the inlet of a 4 mm syringe filter (0.20 µm), which was modified to reduce its internal volume. The filter was coupled to the needle of the chromatograph. After loading the sample and cleaning the sorbent for analyte purification, the device was installed into the injection port of the chromatograph, and the target compounds were desorbed and transferred directly to the chromatographic column with a small volume of organic solvent. Under optimized conditions, sample volumes as large as 50 mL could be processed with the micro-SPE device, while the analytes were desorbed with only 60 µL of methanol. As a result, efficient preconcentration could be reached, as demonstrated for different water contaminants, namely aclonifen, bifenox, tritosulfuron, triflusulfuron-methyl and caffeine. The proposed micro-SPE device was applied to the analysis of different types of water (river, well, sea, ditch and wastewater). The recoveries of the target compounds in samples ranged from 76 % to 109 %, which allowed their detection at low to sub µg/L levels. All operations were carried out manually, and thus, no additional laboratory instruments such as centrifuges, stirrers or evaporators were required. This proof-of-concept study shows that the proposed micro-SPE approach can be considered a reliable and effective option for the on-site analysis of pollutants in environmental water samples by portable liquid chromatography.

Study of the degradation of diphenyl-ether herbicides aclonifen and bifenox in different environmental waters.

The degradation of the diphenyl-ether herbicides aclonifen (ACL) and bifenox (BF) in water samples has been studied under different laboratory conditions, using in-tube solid-phase microextraction (IT-SPME) coupled to capillary liquid chromatography (capLC). The working conditions were selected in order to detect also bifenox acid (BFA), a compound formed as a result of the hydroxylation of BF. Samples (4 mL) were processed without any previous treatment, which allowed the detection of the herbicides at low ppt levels. The effects of temperature, light and pH on the degradation of ACL and BF have been tested using standard solutions prepared in nanopure water. The effect of the sample matrix has been evaluated by analysing different environmental waters spiked with the herbicides, namely ditch water, river water and seawater. The kinetics of the degradation have been studied and the half-life times (t1/2) have been calculated. The results obtained have demonstrated that the sample matrix is the most important parameter affecting the degradation of the tested herbicides. The degradation of both ACL and BF was much faster in ditch and river water samples, where t1/2 values of only a few days were observed. However, both compounds showed a better stability in seawater samples, where they can persist for several months. In all matrices ACL was found to be more stable than BF. In samples where BF had been substantially degraded, BFA was also detected, although the stability of this compound was also limited. Other degradation products have been detected along the study.

Determination of caffeine in dietary supplements by miniaturized portable liquid chromatography.

In this study three miniaturized liquid chromatography (LC) instruments have been evaluated and compared for the analysis of caffeine in dietary supplements, namely a benchtop capillary LC (capLC) system, a benchtop nano LC (nanoLC)system and a portable LC system. Commercial products derived from different sources of caffeine have been analyzed. Under optimized conditions, the methods based on benchtop systems were superior in terms of sensitivity. The limits of detection (LODs) found with the capLC and nanoLC systems were 0.01 and 0.003 µg mL-1, respectively, whereas the LOD obtained with the portable LC instrument was of 1 µg mL-1. The portable LC-based method was superior in terms of simplicity and throughput (total analysis time < 15 min). On the basis of the results obtained, a new method for the rapid measurement of caffeine in dietary supplements by portable miniaturized LC is presented. This method provided good linearity within the 1-20 µg mL-1 interval, and it allowed the quantification of caffeine even in products derived from decaffeinated green coffee extracts. The contents of caffeine found with the proposed portable LC method in the real samples analyzed ranged from 1.38 to 7 mg per gram of product, which were values statistically equivalent to those found with the benchtop capLC and nanoLC methods, being the precision, expressed as relative standard deviation (RDS), of 2 -14% (n = 3). The proposed portable LC based method can be used as a simple and rapid alternative to estimate the quality, effectiveness and safety of dietary supplements, regarding their caffeine content.

Scopolamine analysis in beverages: Bicolorimetric device vs portable nano liquid chromatography.

Scopolamine (SCP) is often involved in sexual assaults and robberies, particularly in recreational environments. Therefore, analytical tools are required for the analysis of this compound amenable for the field. In this work, a sensor for SCP is described based on the entrapment of KMnO4 into polydimethylsiloxane (PDMS). The possibility of using KMnO4 in combination with the reagent 1,2-naphtoquinone-4-sulfonate (NQS) giving a double sensor acting as a bicolorimetric device is also demonstrated. In contact with the sample, the PDMS composite delivers MnO4-, which reacts rapidly with SCP under basic conditions causing a change of the color of the solution that can be related to the concentration of drug using both, absorbances and color coordinates, while the NQS part of the sensor remains unchanged. After an exposure time to the sensors of 10 min, satisfactory linearity was obtained for concentrations of SCP up to 865 µg/mL, being the limit of detection (LOD) 108 µg/mL. A method using a portable nano liquid chromatograph with detection at 255 nm has been also developed; in this case the LOD was 100 µg/mL and the working linear interval was 250-2000 µg/mL. The precision, expressed as relative standard deviation (RDS), was ≤8% for both methods. Different beverages (cola, cola-whisky, tonic water-vodka, red wine and green tea) were assayed. The potential of the two proposed approaches for on-site tests is discussed.

Exploring hand-portable nano-liquid chromatography for in place water analysis: Determination of trimethylxanthines as a use case.

Analytical performance and optimization of figures of merit of a portable nano liquid chromatograph (NanoLC) with UV detection at 255 nm have been established for in place analysis. Methylxanthines: caffeine, theophylline and theobromine were selected as target analytes. A fast lab method based on IT-SPME coupled on line with capillary liquid chromatograph (CapLC) with diode array detection (DAD) was employed for comparative studies. IT-SPME and solid phase extraction were coupled off-line to NanoLC for improving instrumental parameters, mainly detection capacity and selectivity. IT-SPME or SPE/portable NanoLC based methods were superior in terms of chromatographic resolution and organic solvent consumption per sample, around 200 µL vs 10 mL for IT-SPME-CapLC-DAD. Limits of detection (LODs) obtained with the SPE/portable NanoLC were 2-10 ng/mL, which can be suitable for testing the presence of the analytes in several environmental waters in the field. As predictable, the lab method provided better LODs, between 0.1 and 0.5 ng/mL. Good linearity was achieved for both methods and precision was similar for them (≤7%). Both systems were tested for the analysis of real water samples with suitable results.

Minimizing the impact of sample preparation on analytical results: In-tube solid-phase microextraction coupled on-line to nano-liquid chromatography for the monitoring of tribenuron methyl in environmental waters.

The degradation kinetics and residual levels of the sulfonylurea herbicide tribenuron-methyl (TBM) in different environmental waters were studied using in tube-solid phase microextraction (IT-SPME) coupled on-line to nano-liquid chromatography (nanoLC) and UV diode array detection (DAD). This approach combines the high extraction efficiency of IT-SPME using polymeric coatings reinforced with metal oxide nanoparticles and the high sensitivity attainable by nanoLC, making possible the determination of TBM at low ppb levels (limit of detection, 0.25 ppb) without altering the sample matrix. The present study demonstrated that the preservation of the sample properties is essential to ensure accurate results at these concentration levels due to the high tendency of TBM to hydrolyze, particularly under the acidic conditions involved in most protocols used for sample treatment. The approach used in the present study was applied to evaluate the degradation of this herbicide under different conditions (UV radiation, pH), as well as to study the evolution of its concentration in different environmental waters, namely sea, river, ditch and transition waters. When the samples were exposed to identical conditions, significant differences in the degradation rate of TBM were found depending on the water matrix. The results obtained indicate that this herbicide can persist from several days to weeks depending on the type of water.

Bimodal copper oxide nanoparticles doped phase for the extraction of highly polar compounds by in-tube solid-phase microextraction coupled on-line to nano-liquid chromatography.

Polymers obtained from tetraethyl orthosilicate (TEOS) and triethoxymethylsilane (MTEOS) have been functionalized with different metal and metal oxide nanoparticles (NPs), and used as coatings of extractive capillaries for the extraction of polar compounds by in-tube solid-phase microextraction (IT-SPME) coupled on-line to nano-liquid chromatography (nano-LC). The extraction capabilities of the new phases have been studied using several triazinic herbicides with log of octanol/water partition coefficients (Kow) ranging from -0.7 to 3.21 under reversed phase chromatographic conditions. Best extraction efficiencies for the most polar compounds (log Kow ≤ 2.3) were typically obtained with the CuO NPs doped phase. The TEOS-MTEOS polymer can be modified with two types of NPs in order to obtain extractive phases capable of interacting with compounds of a wide range of polarities; alternatively, two capillaries each with a different type of NPs can be combined in series with the same goal. Under the later approach the limits of detection (LODs) found for the tested herbicides were 0.02-1.5 µg/L, and the precision expressed as relative standard deviation (RSD) varied from 2 to 10% (n = 3). The recoveries found in sea water samples ranged from 80 to 107%. In addition, the developed CuO NPs doped phase can be used in hydrophilic interaction chromatography (HILIC), which is the separation mode recommended for highly polar compounds. This has been illustrated using the amino acids tyrosine (log Kow = -2.26) and tryptophan (log Kow = -1.06) as model compounds, being their respective LOD 0.1 and 0.3 µg/mL. Examples of application of the developed bimodal extractive phase to different environmental and waste waters are given in order to show its utility and versatility.

Quantitative Analysis of Terpenic Compounds in Microsamples of Resins by Capillary Liquid Chromatography.

A method has been developed for the separation and quantification of terpenic compounds typically used as markers in the chemical characterization of resins based on capillary liquid chromatography coupled to UV detection. The sample treatment, separation and detection conditions have been optimized in order to analyze compounds of different polarities and volatilities in a single chromatographic run. The monoterpene limonene and the triterpenes lupeol, lupenone, ß-amyrin, and α-amyrin have been selected as model compounds. The proposed method provides linear responses and precision (expressed as relative standard deviations) of 0.6% to 17%, within the 0.5-10.0 µg mL-1 concentration interval; the limits of detection (LODs) and quantification (LOQs) were 0.1-0.25 µg mL-1 and 0.4-0.8 µg mL-1, respectively. The method has been applied to the quantification of the target compounds in microsamples. The reliability of the proposed conditions has been tested by analyzing three resins, white copal, copal in tears, and ocote tree resin. Percentages of the triterpenes in the range 0.010% to 0.16% were measured using sample amounts of 10-15 mg, whereas the most abundant compound limonene (≥0.93%) could be determined using 1 mg portions of the resins. The proposed method can be considered complementary to existing protocols aimed at establishing the chemical fingerprint of these kinds of samples.

Establishing the occurrence and profile of polycyclic aromatic hydrocarbons in marine sediments: The eastern Mediterranean coast of Spain as a case study.

Sampling, cost-effective analysis, diagnosis of sources of pollution and assessment of potential toxicological effects were included in the case study. Marine sediments collected from 24 points along the eastern Mediterranean coast of Spain (Comunitat Valenciana region) in 2010, 2011, 2012 and 2015 have been analysed for polycyclic aromatic hydrocarbons. Fluoranthene, pyrene, chrysene, benzo[b]fluoranthene and benzo[a]pyrene were the most found. An analysis of the relative abundance of selected PAHs revealed that petrogenic and mixed petrogenic/pyrogenic sources are predominant in the area. The total concentrations of the target compounds ranged from 14.7 to 615.3 ng/g dry weight. The effects range-low (ERL) guideline values were used to assess potential toxicological effects. Rarely adverse biological effects can be expected in the tested area. The level of pollution by PAHs in the area can be considered low, although occasionally high values can be found, particularly in areas with high population or ship traffic.

Modifying the reactivity of copper (II) by its encapsulation into polydimethylsiloxane: A selective sensor for ephedrine-like compounds.

This paper demonstrates that the reactivity of copper (II) can be modified through its entrappment in a polymeric matrix of polydimethylsiloxane (PDMS), which makes possible the reaction into the support instead of in solution. Amino-containing compounds such as amino acids, proteins and sugars, which react with Cu (II) in solution, do not react inside the polymer. As a prove of concept, a highly specific Cu (II) PDMS-based sensor for ephedrines has been developed in this work. When the sensors are put into contact with solutions of these drugs under basic conditions, a change in their color from pale green to purple is observed. This change enables the visual identification of ephedrine (Eph) in a few min, as well as its quantification using both reflectance diffuse measurements of the sensors and color intensities of their digitalized images. The sensors show suitable analytical performance for Eph-like compounds, and provide limits of detection (LODs) of 0.3-1.0 mg, and relative standard deviations (RDSs) < 10%. The method has been applied to both the qualitative and quantitative analysis of different types of liquid and solid samples (intravenous injection solution of Eph, dietary supplements and illicit drug-street samples) without the need of any special sample treatment.

A new tool for direct non-invasive evaluation of chlorophyll a content from diffuse reflectance measurements.

Chlorophyll is a key biochemical component that is responsible for photosynthesis and is an indicator of plant health. The effect of stressors can be determined by measuring the amount of chlorophyll a, which is the most abundant chlorophyll, in vegetation in general. Nowadays, invasive methods and vegetation indices are used for establishing chlorophyll amount or an approximation to this value, respectively. This paper demonstrates that H-point curve isolation method (HPCIM) is useful for isolating the signal of chlorophyll a from non-invasive diffuse reflectance measurements of leaves. Spinach plants have been chosen as an example. For applying the HPCIM only the registers of both, a standard and the sample are needed. The results obtained by HPCIM and the invasive method were statistically similar for spinach leaves: 144±6mg/m2 (n=5) and 155±40mg/m2 (n=5), respectively. However, more precise values were achieved with the HPCIM, which also involved minimal experimental effort. The HPCIM method was applied to spinach plants stressed by the action of several pesticides and water scarcity, showing a decrease of chlorophyll a content with time, which is related with a loss of health. The results obtained were compared with those achieved by two different reflectance vegetation indices (Macc01 and NDVI). Although NDVI and HPCIM gave similar footprints for the plants tested, vegetation indices fail in the estimation of real content of the chlorophyll a. The HPCIM could contribute to improve the knowledge of the chlorophyll a content of vegetation like health indicator, by applying it to a much employed non-invasive technique such as diffuse reflectance, which can be used in place or in remote sensing mode.

A solid colorimetric sensor for the analysis of amphetamine-like street samples.

A solid sensor obtained by embedding 1,2-naphthoquinone-4-sulfonate (NQS) into polydimethylsiloxane/tetraethylortosilicate/silicon dioxide nanoparticles composite has been developed to identify and determine amphetamine (AMP), methamphetamine (MAMP), 3,4-methylenedioxymetamphetamine (MDMA) and 3,4-methylenedioxyamphetamine (MDA). The analytes are derivatized inside the composite for 10 min to create a colored product which can be then quantified by measuring the diffuse reflectance or the color intensity after processing the digitalized image. Satisfactory limits of detection (0.002-0.005 g mL-1) and relative standard deviations (<10%) have been achieved. The proposed kit has been successfully validated and applied to the analysis of amphetamine-like drugs street samples. The kit allows the in-situ screening of the mentioned illicit drugs owing to its simplicity, rapidity and portability, with excellent sensor stability and at a very low-cost.

Determination of amphetamines in hair by integrating sample disruption, clean-up and solid phase derivatization.

The utility of matrix solid phase dispersion (MSPD) for the direct analysis of amphetamines in hair samples has been evaluated, using liquid chromatography (LC) with fluorescence detection and precolumn derivatization. The proposed approach is based on the employment of MSPD for matrix disruption and clean-up, followed by the derivatization of the analytes onto the dispersant-sample blend. The fluorogenic reagent 9-fluorenylmethyl chloroformate (FMOC) has been used for derivatization. Different conditions for MSPD, analyte purification and solid phase derivatization have been tested, using amphetamine (AMP), methamphetamine (MET), ephedrine (EPE) and 3,4-methylenedioxymethamphetamine (MDMA) as model compounds. The results have been compared with those achieved by using ultrasound-assisted alkaline digestion and by MSPD combined with conventional solution derivatization. On the basis of the results obtained, a methodology is proposed for the analysis of amphetamines in hair which integrates sample disruption, clean-up and derivatization using a C18 phase. Improved sensitivity is achieved with respect to that obtained by the alkaline digestion or by the MSPD followed by solution derivatization methods. The method can be used for the quantification of the tested amphetamines within the 2.0-20.0ng/mg concentration interval, with limits of detection (LODs) of 0.25-0.75ng/mg. The methodology is very simple and rapid (the preparation of the sample takes less than 15min).

Selective and sentivive method based on capillary liquid chromatography with in-tube solid phase microextraction for determination of monochloramine in water.

Due to the difficulties of working with chloramines, a critical examination of monochloramine standard preparation has been performed in order to select the best synthesis conditions. The analyte has been determined by in-tube solid phase extraction coupled to capillary liquid chromatography with UV detection (IT-SPME Capillary LC DAD). Potential factors affecting the response of monochloramine such as the pH of mobile phase and the volume of sample processed by IT-SPME Capillary LC DAD have been investigated and optimized. According to the results of the study, 0.1 mL or 4.0 mL of sample at neutral pH were loaded in the chromatographic system. A sensitive and selective method has been developed for the determination of monochloramine in water. Validation of the method has been performed. The linear range was 0.09-5mg/L with linear regression coefficients (R(2)) greater than 0.995. Method reproducibility expressed as relative standard deviation (RSD, %), was lower than 15%. The limits of detection (LODs) were 0.029 and 0.01 mg/L by processing 0.100mL or 4 mL of the samples, respectively, being below the maximum residues levels allowed for this compound. The sensitivity achieved by the developed method was better than that obtained by the reference method. The developed method was applied to water samples (tap and swimming pool water).

Development of a polydimethylsiloxane-thymol/nitroprusside composite based sensor involving thymol derivatization for ammonium monitoring in water samples.

This report describes a polydimethylsiloxane (PDMS)-thymol/nitroprusside delivery composite sensor for direct monitoring of ammonium in environmental water samples. The sensor is based on a PDMS support that contains the Berthelot's reaction reagents. To prepare the PDMS-thymol/nitroprusside composite discs, thymol and nitroprusside have been encapsulated in the PDMS matrix, forming a reagent release support which significantly simplifies the analytical measurements, since it avoids the need to prepare derivatizing reagents and sample handling is reduced to the sampling step. When, the PDMS-thymol/nitroprusside composite was introduced in water samples spontaneous release of the chromophore and catalyst was produced, and the derivatization reaction took place to form the indothymol blue. Thus, qualitative analysis of NH4(+) could be carried out by visual inspection, but also, it can be quantified by measuring the absorbance at 690 nm. These portable devices provided good sensitivity (LOD<0.4 mg L(-1)) and reproducibility (RSD <10%) for the rapid detection of ammonium. The PDMS-NH4(+) sensor has been successfully applied to determine ammonium in water samples and in the aqueous extracts of particulate matter PM10 samples. Moreover, the reliability of the method for qualitative analysis has been demonstrated. Finally, the advantages of the PDMS-NH4(+) sensor have been examined by comparing some analytical and complementary characteristics with the properties of well-established ammonium determination methods.

On-line in-tube solid phase microextraction-capillary liquid chromatography method for monitoring degradation products of di-(2-ethylhexyl) phthalate in waters.

The main di-(2-ethylhexyl) phthalate (DEHP) degradation products, (2-ethylhexyl) phthalate (MEHP), diethyl phthalate (DEP) and dibutyl phthalate (DBP), have been tested. The proposed cost-effective method combines on-line, in-tube solid-phase micro extraction (IT-SPME) in in-valve configuration and capillary liquid chromatography with UV diode array detection (Cap-LC-DAD). Acidification of the samples at pH 3 improved markedly the estimation of MEHP. Aliquots of 4mL of acidified water samples were directly processed. After sample loading, the analytes were desorbed with the mobile-phase and transferred to the monolithic capillary column. Satisfactory linearity and precision, absence of matrix effect and suitable limits of detection (LODs): 0.005, 0.1, 0.1 and 1.5µg/L for MEHP, DEP, DEHP and DBP, respectively have been achieved. The main advantages are speed and the reduction of background signal by minimizing sample preparation. Real water samples have been analyzed.

Rapid analysis of effluents generated by the dairy industry for fat determination by preconcentration in nylon membranes and attenuated total reflectance infrared spectroscopy measurement.

This paper describes a new approach for the determination of fat in the effluents generated by the dairy industry which is based on the retention of fat in nylon membranes and measurement of the absorbances on the membrane surface by ATR-IR spectroscopy. Different options have been evaluated for retaining fat in the membranes using milk samples of different origin and fat content. Based on the results obtained, a method is proposed for the determination of fat in effluents which involves the filtration of 1 mL of the samples through 0.45 µm nylon membranes of 13 mm diameter. The fat content is then determined by measuring the absorbance of band at 1745 cm(-1). The proposed method can be used for the direct estimation of fat at concentrations in the 2-12 mg/L interval with adequate reproducibility. The intraday precision, expressed as coefficients of variation CVs, were ≤ 11%, whereas the interday CVs were ≤ 20%. The method shows a good tolerance towards conditions typically found in the effluents generated by the dairy industry. The most relevant features of the proposed method are simplicity and speed as the samples can be characterized in a few minutes. Sample preparation does not involve either additional instrumentation (such as pumps or vacuum equipment) or organic solvents or other chemicals. Therefore, the proposed method can be considered a rapid, simple and cost-effective alternative to gravimetric methods for controlling fat content in these effluents during production or cleaning processes.

A cost-effective method for estimating di(2-ethylhexyl)phthalate in coastal sediments.

This study describes the development of a new method for the analysis of di(2-ethylhexyl)phthalate (DEHP) using 0.1-0.3 g of sediment sample, based on matrix solid phase dispersion (MSPD) using C18 as dispersant phase (0.4 g) and acetonitrile-water as eluting solvent (3.4 mL 1:3.25, v/v). No evaporation step is required. 3 mL of extracts were processed on-line by in-tube solid phase microextraction (IT-SPME) coupled to capillary liquid chromatography (CapLC) and diode array detector (DAD). A short analytical column Zorbax SB C18 (35×0.5 mm, 5 µm) provided suitable results. FTIR-ATR was employed for characterizing sediment samples and MSPD procedure. The total analysis time was less than 20 min (MSPD takes about 10 min). The utility of the described approach has been tested by analyzing several real samples. No matrix effect was found. Achieved precision was less than 10% for DEHP estimation. Detection limits in samples were 270 and 90 µg/kg for 0.1 and 0.3 g of taken sediment, respectively.

Study of the influence of temperature and precipitations on the levels of BTEX in natural waters.

Assessment of seasonal changes in surface water quality is an important aspect for evaluating temporal variation of water due to natural or anthropogenic inputs of point and non-point sources. The objective of this paper was to investigate the influence of seasonal temperature fluctuations and precipitations on the levels of BTEX in natural waters. Principal component analysis (PCA) was used to evaluate the seasonal correlations of BTEX levels in water and to extract the parameters that are most important in assessing seasonal variations of water quality. This study was carried out as a part of VOCs monitoring program in natural water samples from Mediterranean coast. To carry out this project, a multiresidue analytical method was used. The method was based on headspace solid-phase microextraction (HS-SPME) followed by gas chromatography coupled to flame ionization detector (FID). The limits of detection LODs found for the tested analyte tested were in the 0.001-1 µg/L range. These values were adequate for the analysis of these compounds in water samples according to the regulated values. Water samples from different points of the Mediterranean coast were analyzed during a period of three years, and were taken four times per year. Most of the compounds were below the limit established by the legislation. The results obtained by a chemometric study indicated that temperature and precipitations can be related on the BTEX levels found in water. A regression model between temperature or precipitations and BTEX concentration was obtained, thus these models can be used as predictive model for detection any non-normal concentration level.

More about sampling and estimation of mercaptans in air samples.

Several strategies have been developed for sampling and determination of volatile thiols. The selectivity and sensitivity of the proposed methodologies are achieved by using a specific derivatizing reagent. The different procedures assayed are based on air sampling followed by derivatization of the analytes with OPA and isoleucine in alkaline solution. The derivatization products are separated and determined by liquid chromatography and fluorescence detection. To start, the derivatization conditions and stability of the derivates have been studied in order to establish the storage conditions. In general, the strategies studied consisted on trapping and detivatization the thiol compound on different support; a solution (Impinger) or sorbent (C18 cartridges or glass fiber filter). The analytical properties of the different strategies have been obtained and compared. Procedures are recommended upon specific situations.