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In this work, an expeditious method based on the multi-commutated flow-analysis concept with potentiometric detection is proposed to perform determinations of the emergent contaminant perchlorate in vegetable matrices down to nanomolar concentration. To accomplish the task, a tubular shaped potentiometric sensor selective to perchlorate ion was constructed with a PVC membrane containing 12mmol/kg of the polyamine bisnaphthalimidopropyl-4,4'-diaminodiphenylmethane and 2-nitrophenyl phenyl ether 68% (w/w) as plasticizer casted on a conductive epoxy resin. Under optimal flow conditions, the sensor responded linearly in the concentration range of 6.3×10 -7 -1.0×10 -3 mol/L perchlorate. In order to extend the determinations to lower concentrations (4.6(±1.3)×10 -10 mol/L perchlorate), a column packed with 70mg of sodium 2,5,8,11,14-pentaoxa-1-silacyclotetradecane-polymer was coupled to the flow-system thus enabling prior pre-concentration of the perchlorate. The proposed procedure provides a simpler alternative for the determination of perchlorate in foods, nowadays only allowed by sophisticated and expensive equipment and laborious methods., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

The authors have developed a sensitive spectrophotometric method for determination of sulfonamide derivatives such as sulfanilamide (SAA), sulfadiazine (SDZ), sulfacetamide (SCT) sulfamethoxazole (SMX), sulfamerazine (SMR), sulfadimethoxine (SDX), sulfamethiazole (SMT) and Sulfathiazole (STZ). This method is based on the Bratton-Marshall reaction, which involves the diazotization of sulfonamides with sodium nitrite under acidic conditions, followed by coupling with N-(1-naphtyl) ethylenediamine dihydrochloride (NED) to form a pink colored compound. Therefore, the Bratton-Marshall method was modified by optimizing the reaction conditions, which allows us to determine a low concentration range of sulfonamides compared to the reported methods. The limits of detection and quantification obtained were 0.019-0.05 and 0.06-0.16μgmL -1 , respectively. In comparison with other reported methods using different coupling agents, the proposed method was found to be the most simple and sensitive for sulfonamides determination. In this paper, the modified method was successfully employed for the determination of sulfonamides in drinking water, seawater and pharmaceutical and veterinary formulations. The purpose of this work is to optimize and develop a simple method for extraction and concentration of sulfonamides present as residues in seawater and their quantification with the recommended spectrophotometric method. Solid phase extraction (SPE) of sulfonamides from seawater samples was evaluated using Oasis HLB cartridges (3mL, 540mg). The recovery efficiency was investigated in the sulfonamides concentration range comprised between 0.19 and 126ngmL -1 . The ease of use of this extraction method makes it very useful for routine laboratory work., (Copyright © 2017 Elsevier B.V. All rights reserved.)

Radium (Ra) at environmental relevant levels in natural waters was determined by ICP-MS after an off-line pre-concentration procedure. The latter consisted of Ra selective elution from potential interfering elements (i.e. other alkaline earth cations: Ba 2+ , Sr 2+ , Ca 2+ , Mg 2+ ) on a series of two different ion exchange resins (AG50W-X8 and Sr-resin). The overall analytical method was optimized according to the instrumental performance, the volume of water sample loaded on resins, and the sample salinity. Longer acquisition time (up to 150 s) was required to ensure stable measurement of Ra by ICP-MS at ultra trace level (1.0pgL -1 ). For a synthetic groundwater spiked with Ra at 10.0pgL -1 , the analytical procedure demonstrated efficient separation of the analyte from its potential interfering elements and a complete recovery, independent of the sample volume tested from 10 up to 100mL. For synthetic seawater spiked at a level of 10.0pgL -1 of Ra, the total load of salts on the two resins should not exceed 0.35g in order to ensure a complete separation and recovery of Ra. The method was validated on natural waters (i.e. groundwater, freshwater and seawater samples) spiked with Ra at different levels (0.0, 0.5, 1.0 and 5.0pgL -1 ). Absolute Ra detection limits were determined at 0.020pgL -1 (0.73mBqL -1 ) and 0.12pgL -1 (4.4mBqL -1 ) respectively for 60.0mL of freshwater sample and for 10.0mL of seawater., (Copyright © 2017 Elsevier B.V. All rights reserved.)

Producing molecular imprinting-based materials has received increasing attention due to recognition selectivity, stability, cast effectiveness, and ease of production in various forms for a wide range of applications. The molecular imprinting technique has a variety of applications in the areas of the food industry, environmental monitoring, and medicine for diverse purposes like sample pretreatment, sensing, and separation/purification. A versatile usage, stability and recognition capabilities also make them perfect candidates for use in forensic sciences. Forensic science is a demanding area and there is a growing interest in molecularly imprinted polymers (MIPs) in this field. In this review, recent molecular imprinting applications in the related areas of forensic sciences are discussed while considering the literature of last two decades. Not only direct forensic applications but also studies of possible forensic value were taken into account like illicit drugs, banned sport drugs, effective toxins and chemical warfare agents in a review of over 100 articles. The literature was classified according to targets, material shapes, production strategies, detection method, and instrumentation. We aimed to summarize the current applications of MIPs in forensic science and put forth a projection of their potential uses as promising alternatives for benchmark competitors.

A novel continuous flow microfluidic platform specifically designed for environmental monitoring of O/W emulsions during an aftermath of oil spills is reported herein. Ionized polycyclic aromatic hydrocarbons which are toxic are readily released from crude oil to the surrounding water phase through the smaller oil droplets with enhanced surface area. Hence, a multi-module microfluidic device is fabricated to form ion enrichment zones in the water phase of O/W emulsions for the ease of detection and to separate micron-sized oil droplets from the O/W emulsions. Fluorescein ions in the water phase are used to simulate the presence of these toxic ions in the O/W emulsion. A DC-biased AC electric field is employed in both modules. In the first module, a nanoporous Nafion membrane is used for activating the concentration polarization effect on the fluorescein ions, resulting in the formation of stable ion enrichment zones in the water phase of the emulsion. A 35.6% amplification of the fluorescent signal is achieved in the ion enrichment zone; corresponding to 100% enrichment of the fluorescent dye concentration. In this module, the main inlet is split into two channels by using a Y-junction so that there are two outlets for the oil droplets. The second module located downstream of the first module consists of two oil droplet entrapment zones at two outlets. By switching on the appropriate electrodes, either one of the two oil droplet entrapment zones can be activated and the droplets can be blocked in the corresponding outlet., (© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

This study demonstrated a technique using forward osmosis (FO) to pre-concentrate the organic matter in raw wastewater, thereby transforming low strength wastewater into an anaerobically digestible solution. The chemical oxygen demand (COD) of raw wastewater was concentrated up to approximately eightfold at a water recovery of 90%. Thus, even low strength wastewater could be pre-concentrated by FO to the range suitable for biogas production via anaerobic treatment. Excessive salinity accumulation in pre-concentrated wastewater was successfully mitigated by adopting ionic organic draw solutes, namely, sodium acetate, and EDTA-2Na. These two draw solutes are also expected to benefit the digestibility of the pre-concentrated wastewater compared to the commonly used draw solute sodium chloride. Significant membrane fouling was observed when operating at 90% water recovery using raw wastewater. Nevertheless, membrane fouling was reversible and was effectively controlled by optimising the hydrodynamic conditions of the cross-flow FO system., (Crown Copyright © 2016. Published by Elsevier B.V. All rights reserved.)

In order to preserve iron-rich samples for arsenic speciation analysis, mineral acids or EDTA are typically added to prevent oxidation and precipitation of iron. However, when sulfide is present, and thioarsenates ([HAs(V)S(-II)nO4-n](2-), n = 1-4) can form, these methods are unsuitable due to arsenic sulfide precipitation or artifact speciation changes. Here, a new method based on separating the anionic arsenic species from cationic iron in the presence of sulfide via solid phase extraction (SPE) has been investigated. Synthetic solutions containing arsenite, arsenate, monothioarsenate, and trithioarsenate were passed through the anion-exchange resin AG2-X8, after which the resin was washed, eluted, and speciation of each step analyzed by IC-ICP-MS. Retention on the resin of 96.8 ± 0.2%, 98.8 ± 0.2%, and 99.6 ± 0.3% was found for arsenate, monothioarsenate, and trithioarsenate, respectively. Cationic iron (90 μM Fe(II)) was not retained (0.4 ± 0.2%). Uncharged arsenite passed through the resin in the absence of sulfide, while 47.3% of arsenite were retained at tenfold sulfide excess via thiol groups binding to the organic resin structure. Elution with 3 × 15 mL of 0.5 M salicylate, including a soak time, resulted in quantitative recovery of all retained species. Stability of the retained species on the resin was tested with iron-rich, natural waters from a Czech mineral spring. Arsenate, monothioarsenate, dithioarsenate, and trithioarsenate were successfully separated from iron and recovered after 6 d. Thus, SPE presents a viable answer to the problem of preserving arsenic in the presence of both iron and sulfide., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

1-(2-pyridylazo)-2-naphthol (PAN) is a heterocyclic azo compound that forms inner, mostly reddish colored, water-insoluble chelates with many transition metal ions with metal ion-ligand ratios of 1:1 or 1:2. PAN is rather unselective but it does not form complexes with the alkali and alkaline earth metals, Ge(IV), As, Se and Te. Numerous reported techniques of pre-concentration have been considered for analyzing the role of PAN on the physiochemical outcome of the procedures. PAN been used as a chelating precipitant, flocculant, auxiliary complexing agent, as a ligand for anchoring on other supports with the purpose of introducing chelating property as well as selectivity. The role of PAN in the different techniques of pre-concentration, namely co-precipitation, membrane filtration, micro-extraction, cloud point extraction and solid phase extraction, has been investigated. PAN influences the optimum experimental parameters, namely pH, temperature, time, amount, tolerance limit, etc.

In this work, a novel Fe(III) ion imprinted polymer as a sorbent for extraction of iron ions from different samples was synthesized. Precipitation of thermal copolymerization was used for preparation of polymeric sorbent. In this technique, methacrylic acid, ethylene glycoldimethacrylate, 2,2'-azobisisobutyronitrile and (DHBPT)2 {(DHBPT)2=3,6-bis (3,5-dimethyl-1-H-pyrzol-1-yl)-1,2-dihydro-1,2,4,5-tetrazine)} were used as monomer, cross-linker, initiator and ligand, respectively, in the presence of Fe(III) ions and ethanol as a porogenic solvent. Moreover, control polymer (NIP) particles were similarly prepared without the Fe(III) ions. XRD, FT-IR, SEM and nitrogen adsorption-desorption techniques have been used to characterization of these prepared polymeric samples. Iron ion imprinted polymer particles, abbreviated as Fe(III)-IIP, were leached with 50 mL of HCl (50% (v/v)). Absorption capacity for ion imprinted polymer was calculated about 40.41 mg·g(-1). Per-concentration of iron ion was investigated as a function of pH, weight of IIP, adsorption and desorption times, and volumes of sample. FAAS technique was used to determination of Fe(III) ion in the foods and waters samples., (Copyright © 2015 Elsevier B.V. All rights reserved.)

Anthropogenic (137)Cs activity concentration, in surface sea water along the western and eastern coast of India has been estimated using the in-situ pre-concentration approach. Activity levels of (137)Cs ranges from 0.09-1.30Bqm(-3) with an overall mean of 0.69±0.29Bqm(-3). Latitudinal variation and higher depletion in activity concentration of (137)Cs at few locations were observed. Temporal change of (137)Cs in sea water along Indian coast unveils a lower effective half-life of 13.8±0.7y in comparison to Asia Pacific regional sea water. The results prevailed that the spatial distribution confers no fresh input of (137)Cs in Indian coastal region., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

The article presents a new method of modification of hydrophobic sorbents. To improve sorption pre-concentration of polar organic compounds in the air analysis, these sorbents are coated with cobalt chloride. This modification increases retention volume of lower alcohols by 5-10 fold as compared to that of unmodified sorbents and solves the problem of gas-chromatographic determination at 1-2 ppb (micrograms/m(3)) by using the most common flame ionization detector. It should be noted that the modification of hydrophobic sorbents by cobalt chloride has little influence on their porosimetry parameters (specific surface area, proportions of meso- and micropores) and modified sorbents are capable of retaining hydrophobic nonpolar and weakly polar analytes as well as original unmodified sorbents. Thus, a fairly simple procedure leads to a large positive effect., (Copyright © 2015 Elsevier B.V. All rights reserved.)

Portable and compact instruments for separating and detecting organic compounds are needed in the field for environmental studies. This is especially the case for pollution studies as in-field detection of organic compounds helps identify sources of pollution. Here we describe the development of a compact GC and simple pre-concentrator coupled to a MS detector. This simple system can easily be incorporated into portable instrumentation. Combining the pre-concentrator and compact column has the advantage of decoupling separation from manual injection and enhances separation of environmentally relevant polar organic compounds, such as levoglucosan. A detection limit of 2.2 ng was obtained for levoglucosan. This simple design has the potential to expand the use of gas chromatography as a routine in-field separation technique., (Copyright © 2015 Elsevier B.V. All rights reserved.)

Harvesting is one of the key challenges to determine the feasibility of producing biodiesel from algae. This paper presents experimental results for a cost-effective system to harvest Chaetoceros calcitrans, using natural sedimentation, flocculation, and inducing pH. No efficient sedimentation of microalgal cells was observed only by gravity. By alkalinity-induced flocculation, at a pH value of 9.51, 86% recovery of the cells was achieved with a sedimentation rate of 125 cm/h and a concentration factor (CF) of 4 (volume/volume (v/v)) in 10 min. The maximum photochemical quantum yield of photosystem II (Fv/Fm) of concentrated cells was almost the same as fresh culture (0.621). Commercial flocculants, aluminium sulphate and poly-aluminium chloride (PAC), were also successful in harvesting the studied algal cells. Optimum concentration of aluminium sulphate (AS) could be concluded as 10 ppm with 87.6% recovery and 7.10 CF (v/v) in 30 min for cost-efficient harvesting, whereas for PAC it was 20 ppm with 74% recovery and 6.6 CF (v/v). Fv/Fm yields of concentrated cells with AS and PAC showed a 1% reduction compared to fresh culture. Mg+2 was the triggering ion for alkalinity-induced flocculation in the conditions studied. The rheology behaviour of the concentrated cells was Newtonian with values between 2.2×10(-3) and 2.3×10(-3) Pa s at 30°C.

Ring-opening reaction with synchronous hydrolysis was used to prepare 4-butylaniline-modified attapulgite (abbreviated as BA-ATP) for pre-concentration of bisphenol A (BPA) in trace quantity. The preparation was achieved under mild condition, and the material was characterized by Fourier transform infrared spectroscopy (FT-IR), elemental analysis, nuclear magnetic resonance (NMR) and scanning electron microscopy. BA-ATP was used in solid phase extraction (SPE), and SPE was performed in a neutral condition without regard to ionic strength. The results indicate that BA-ATP has high affinity to BPA with a maximum adsorption amount of 44mg g(-1), and the adsorption can be described by Langmuir isotherm model. The content of bisphenol A in water samples was analyzed by HPLC method with the pre-concentration using BA-ATP. The limit of detection (LOD) can be as low as 3.9ng mL(-1), and the average recoveries are in a range of 93-97% with relative standard deviation (RSD) of less than 2%., (Copyright © 2015 Elsevier B.V. All rights reserved.)

An improved sample preparation procedure for trace-levels of lanthanides in uranium-bearing samples was developed. The method involves a simple co-precipitation using Fe(III) carrier in ammonium carbonate medium to remove the uranium matrix. The procedure is an effective initial pre-concentration step for the subsequent extraction chromatographic separations. The applicability of the method was demonstrated by the measurement of REE pattern and 143 Nd/ 144 Nd isotope ratio in uranium ore concentrate samples.

Novel strategies are proposed to circumvent the main drawbacks of flow-based cloud point extraction (CPE). The surfactant-rich phase (SRP) was directly retained into the optical path of the spectrophotometric cell, thus avoiding its dilution previously to the measurement and yielding higher sensitivity. Solenoid micro-pumps were exploited to improve mixing by the pulsed flow and also to modulate the flow-rate for retention and removal of the SRP, thus avoiding the elution step, often carried out with organic solvents. The heat released and the increase of the salt concentration provided by an on-line neutralization reaction were exploited to induce the cloud point without an external heating device. These innovations were demonstrated by the spectrophotometric determination of iron, yielding a linear response from 10 to 200 μg L(-1) with a coefficient of variation of 2.3% (n=7). Detection limit and sampling rate were estimated at 5 μg L(-1) (95% confidence level) and 26 samples per hour, respectively. The enrichment factor was 8.9 and the procedure consumed only 6 μg of TAN and 390 μg of Triton X-114 per determination. At the 95% confidence level, the results obtained for freshwater samples agreed with the reference procedure and those obtained for digests of bovine muscle, rice flour, brown bread and tort lobster agreed with the certified reference values. The proposed procedure thus shows advantages in relation to previously proposed approaches for flow-based CPE, being a fast and environmental friendly alternative for on-line separation and pre-concentration., (Copyright © 2014 Elsevier B.V. All rights reserved.)

We juxtapose methods of synthesis of non-polar surface-layered sorbents on the platform of a carrier, which combines macro-porous coarse-dispersed polytetrafluoroethylene with micro-dispersed activated carbon. Further, we present data about the sorption properties of the said materials alongside perspectives of their analytical applications. Our study established that with respect to efficacy of dynamic sorption from gaseous phases these sorbents outperform bulk-porous analogues in their normal, granular form., (© 2013 Elsevier B.V. All rights reserved.)

In this article, we demonstrate a novel approach to enhancing the sensitivity of enzyme-linked immunosorbent assays (ELISA) through pre-concentration of the enzyme reaction product (resorufin/4-methylumbelliferone) in free solution. The reported pre-concentration was accomplished by transporting the resorufin/4-methylumbelliferone molecules produced in the ELISA process towards a high ionic-strength buffer stream in a microfluidic channel while applying a voltage drop across this merging region. A sharp change in the electric field around the junction of the two liquid streams was observed to abruptly slow down the negatively charged resorufin/4-methylumbelliferone species leading to the reported pre-concentration effect based on the field amplified stacking (FAS) technique. It has been shown that the resulting enhancement in the detectability of the enzyme reaction product significantly improves the signal-to-noise ratio in the system thereby reducing the smallest detectable analyte concentration in the ELISA method. Applying the above-described approach, we were able to detect mouse anti-BSA and human TNF-α at concentrations nearly 60-fold smaller than that possible on commercial microwell plates. For the human TNF-α sample, this improvement in assay sensitivity corresponded to a limit of detection (LOD) of 0.102pg mL(-1) using the FAS based microfluidic ELISA method as compared to 7.03pg mL(-1) obtained with the traditional microwell plate based approach. Moreover, because our ELISAs were performed in micrometer sized channels, they required sample volumes about two orders of magnitude smaller than that consumed in the latter case (1μL versus 100μL)., (Copyright © 2013 Elsevier B.V. All rights reserved.)

This paper describes a novel sorbent based on 4-(2-pyridylazo) resorcinol functionalised magnetic nanoparticles and its application for the extraction and pre-concentration of trace amounts of Cu(II) and Pb(II) ions. The nanosorbent was characterised by Fourier transform infrared spectroscopy, X-ray powder diffraction, thermal analysis, elemental analysis and scanning electron microscopy. The effects of various parameters such as pH, sorption time, sorbent dosage, elution time, volume and concentration of eluent were investigated. Following the sorption and elution of analytes, Cu(II) and Pb(II) ions were quantified by flame atomic absorption spectrometry. The limits of detection were 0.07 and 0.7 μg l(-1) for Cu(II) and Pb(II), respectively. The relative standard deviations of the method were less than 7%. The sorption capacity of this new sorbent were 92 and 78 mg g(-1) for Cu(II) and Pb(II), respectively. Finally this nanosorbent was applied to the rapid extraction of trace quantities of Cu(II) and Pb(II) ions in different real samples and satisfactory results were obtained.

A method using dispersive liquid-liquid micro-extraction (DLLME) and detection by inductively coupled plasma optical emission spectroscopy (ICP-OES) was developed for the determination of trace elements in seafood samples. The procedure allowed the simultaneous determination of Cd(II), Pb(II), Ni(II) Cu(II) and Co(II) after pre-concentration using sodium diethyldithiocarbamate (DDTC) as a chelating agent. Under optimised conditions, the method had a limit of detection (LOD) of 0.03, 0.11, 0.12, 0.18 and 0.12 µg l(-1) for Cd(II), Pb(II), Ni(II) Cu(II) and Co(II), respectively. The following enrichment factors were obtained: 16 (Cd), 34 (Pb), 20 (Ni) 34 (Cu) and 12 (Co). The procedure was applied for the determination of these elements in seafood (shrimp, mussel, bass and mullet) samples. The method is simple, efficient and easy to perform for the simultaneous determination of elements in seafood samples by ICP-OES.

Chelex-100, Dowex 50W-x8 and Dowex MAC-3 exchange resins were investigated for separation and pre-concentration of trace amounts of Cd, Cr, Cu, Fe, Mn, Pb, Ti and Zn in alcohols with respect to retention and desorption characteristics. Dowex 50W-x8 was found to be the best sorbent with percentages recoveries >95%. In addition, Chelex-100 appeared to be suitable for the pre-concentration of Cu, Fe and Zn, whereas Dowex MAC-3 was selective for Cu and Fe. Therefore, Dowex 50W-x8 was used for further investigations. The relative standard deviations <4% (n=20), limits of detection and quantification were 0.1-1.2 μg L(-1) and 0.3-1.5 μg L(-1), respectively. The SPE method was validated against a certified reference material and the results were in agreement with certified values. The accuracy of the optimized method was verified by the recovery test in the spiked alcohol samples. The accuracy and spike recovery test for different metal ions were in the range 98-102% and 95-105%, respectively. The optimized method was applied to the separation and pre-concentration of metal ions in different commercial alcohol samples., (Copyright © 2013 Elsevier B.V. All rights reserved.)