Porous polymer monolithic columns to investigate the interaction of humic substances with herbicides and emerging pollutants by affinity chromatography.

Background: Understanding the interaction mechanisms and the relevant binding constants between humic acids and emerging or regulated pollutants is of utmost importance in predicting their geochemical mobility, bioavailability, and degradation. Fluorescence spectroscopy, UV-vis spectroscopy, equilibrium dialysis, and solid-phase extraction combined with liquid chromatography-mass spectrometry have been employed to elucidate interactions of humic acids with organic micropollutants, especially pharmaceutical drugs. These methods demand large sample volumes, long equilibration times, and laborious extraction steps which may imply analytical errors.

Empirical adsorption kinetics: comparing linear and nonlinear regression analysis emphasizing the need for high throughput analysis.

This paper evaluates linear and nonlinear regression analysis to describe the empirical adsorption kinetics using pseudo-first-order (PFO) and pseudo-second-order (PSO) models. These models have been used to characterize the performance of adsorbents for environmental remediation and environmental modeling. Data were simulated using the PFO and PSO models with 1, 2, and 5% noise levels and fitted by nonlinear and linearized PFO and PSO equations.

Nonlinear regression for treating adsorption isotherm data to characterize new sorbents: Advantages over linearization demonstrated with simulated and experimental data.

This paper demonstrates that determining adsorption capacity and affinity through data fitting of adsorption isotherms by nonlinear regression (NLR) is more accurate than linearized Langmuir equations. Linearization errors and the subjective choice of data points used to apply the linear regression analysis may deviate the fitted adsorption parameters (constants and adsorption capacities) from the expected values. The deviation magnitude increases for heterogeneous sorbents such as environmental particles and molecularly imprinted polymers, which adsorb by more than one sorption mechanism or adsorption sites of diverse chemical natures.

Ethylene vinyl acetate copolymer is an efficient and alternative passive sampler of hydrophobic organic contaminants. A comparison with silicone rubber.

There is a growing demand for assessing the concentrations of Hydrophobic Organic Contaminants (HOCs) in aquatic environments, including Persistent Organic Pollutants (POPs). The hydrophobicity of POPs challenges their quantification in waters due to the sub-trace concentrations, especially when using conventional spot sampling. The results from the conventional samples are only a "snapshot" of the concentrations (if detected) at the specific sampling moment.

Polymer monoliths for the concentration of viruses from environmental waters: A review.

Even at low concentrations in environmental waters, some viruses are highly infective, making them a threat to human health. They are the leading cause of waterborne enteric diseases. In agriculture, plant viruses in irrigation and runoff water threat the crops.

Construction of polymer monolithic columns in polypropylene ink-pen tubes for separation of proteins by cation-exchange chromatography.

We describe the synthesis of polymer monoliths inside polypropylene tubes from ink pens. These tubes are cheap, chemically stable, and resistant to pressure. UV-initiated grafting with 5 wt% benzophenone in methanol for 20 min activated the internal surface, thus enabling the covalent binding of ethylene glycol dimethacrylate, also via photografting.

Fast construction of polymer monolithic columns inside fluorinated ethylene propylene (FEP) tubes for separation of proteins by reversed-phase liquid chromatography.

This paper describes the preparation of polymer monolithic columns in the confines of fluorinated ethylene propylene (FEP) tubes. These tubes are cheap, chemically stable, and widely used in flow analysis laboratories. UV-initiated grafting with 5 wt% benzophenone in methanol for 1 h activated the internal surface walls, thus enabling the further covalent binding of ethylene glycol dimethacrylate (EDMA) from a 15 wt% solution in methanol, also via photografting.

Fe(III)-polyhydroxy cations supported onto K10 montmorillonite for removal of phosphate from waters.

Since phosphate is strongly related to eutrophication of environmental waters, several research groups quest for materials that can efficiently remove phosphate from wastewaters before it contaminates lakes and reservoirs. In the present work, a commercial clay mineral (K10 montmorillonite) modified with Fe polyhydroxy cations was investigated as an adsorbent for phosphate. The incorporation of the polycations did not alter the main conformational characteristics of the montmorillonite, as verified by specific surface area measurements, X-ray diffractometry, FTIR, electron microscopy, and zeta potential titrations.

Enhanced Separation Capability of Sequential Injection Chromatography for Fluorimetric Determination of Intracellular Dissolved Free Amino Acids in Marine Microalgae.

This chapter describes improvements in a sequential injection method to automate the fluorimetric determination of amino acids by pre-column derivatization with o-phthaldialdehyde in presence of 2-mercaptoethanol. Separation is achieved by reversed-phase liquid chromatography in a 50 × 4.6 mm C silica-based monolithic column.

Adsorption of glyphosate on Brazilian subtropical soils rich in iron and aluminum oxides.

We investigated the adsorption of glyphosate onto five subtropical soils of Paraná and São Paulo states, Brazil, a region of intense agricultural activities, aiming at the determination of kinetic and isotherm adsorption parameters which enable the evaluation of the potential leaching of the herbicide. The adsorption was fast, being described by the pseudo-second order and intraparticle diffusion models, thus suggesting that mixed mechanisms are involved. The Oxisol containing the highest concentrations of metal oxides (209.

Poly glycidyl methacrylate-co-ethylene dimethacrylate porous monolith as a versatile platform for the development of separations and solid-phase extractions in sequential injection analyzers.

We demonstrated that the porous structure and the reactivity of the epoxy group in the poly glycidyl methacrylate-co-ethylene dimethacrylate monolith can be a platform for the development of separation and extraction methods based on sequential injection analysis. The epoxy group was functionalized to produce monoliths affording complexing and ion exchange properties. Derivatization with iminodiacetate and sodium sulfite produced weak and strong cation exchangers, respectively.

Complexing porous polymer monoliths for online solid-phase extraction of metals in sequential injection analysis with electrochemical detection.

A monolithic column affording complexing groups was synthesized for automated solid-phase extraction of potentially toxic metal ions in a low-pressure sequential injection analyzer. Poly(glycidyl methacrylate-co-ethylene dimethacrylate) monoliths were synthesized by free-radical polymerization in the coffins of fused silica-lined stainless-steel tubes (2.10 mm i.

An electrochemical sequential injection method to investigate the adsorption of selenite on Fe(III) polyhydroxy cations intercalated vermiculite.

A sequential injection - square wave anodic stripping voltammetry (SI-SWASV) method for determination of Se(IV) at a gold working electrode was developed to investigate the adsorption of Se(IV) onto vermiculite intercalated with Fe(III) polyhydroxy cations. The limits of detection and quantification were 0.060 and 0.

Porous monoliths for on-line sample preparation: A review.

This review aims at presenting the state of the art concerning monolithic materials for on-line sample preparation emphasizing solid-phase extraction, matrix exchange, and analyte conversion. Emphasis was given to organic and silica-based, as well as hybrid monoliths reported in the literature mostly after 2010. The first part of this review presents materials and strategies for enrichment of inorganic species in environmental and biological samples using mostly ICP-MS detectors.

Semi-micro reversed-phase liquid chromatography for the separation of alkyl benzenes and proteins exploiting methacrylate- and polystyrene-based monolithic columns.

Monolithic columns were synthesized inside 1.02 mm internal diameter fused-silica lined stainless-steel tubing. Styrene and butyl, hexyl, lauryl, and glycidyl methacrylates were the functional monomers.

Separation of proteins by cation-exchange sequential injection chromatography using a polymeric monolithic column.

Since sequential injection chromatography (SIC) emerged in 2003, it has been used for separation of small molecules in diverse samples, but separations of high molar mass compounds such as proteins have not yet been described. In the present work a poly(glycidyl methacrylate-co-ethylene dimethacrylate) (GMA-co-EDMA) monolithic column was prepared by free radical polymerization inside a 2.1-mm-i.

Porous polymer monolithic columns with gold nanoparticles as an intermediate ligand for the separation of proteins in reverse phase-ion exchange mixed mode.

A new approach has been developed for the preparation of mixed-mode stationary phases to separate proteins. The pore surface of monolithic poly(glycidyl methacrylate-co-ethylene dimethacrylate) capillary columns was functionalized with thiols and coated with gold nanoparticles. The final mixed mode surface chemistry was formed by attaching, in a single step, alkanethiols, mercaptoalkanoic acids, and their mixtures on the free surface of attached gold nanoparticles.

Evaluation of sequential injection chromatography for reversed phase separation of triazine herbicides exploiting monolithic and core-shell columns.

This paper describes the development of reversed phase sequential injection chromatography (SIC) methods for separation of simazine (SIM) and atrazine (AT), as well as their metabolites deethylatrazine (DEA), deisopropylatrazine (DIA) and hydroxyatrazine (HAT) exploiting silica based monolithic (50 × 4.6 mm) and core-shell (30 × 4.6 mm, 2.

Influence of humic acid on adsorption of Hg(II) by vermiculite.

Geochemical mobility of Hg(II) species is strongly affected by the interactions of these compounds with naturally occurring adsorbents such as humic acids, clay minerals, oxides, etc. Interactions among these sorbents affect their affinity for Hg(II) and a full understanding of these processes is still lacking. The present work describes the influence of a humic acid (HA) sample on the adsorption of Hg(II) by vermiculite (VT).

Online sequential-injection chromatography with stepwise gradient elution: a tool for studying the simultaneous adsorption of herbicides on soil and soil components.

The adsorption of triazine herbicides simazine (SIM), atrazine (ATR), and propazine (PRO) as well as the metabolites deisopropylatrazine (DIA), deethylatrazine (DEA), and 2-hydroxyatrazine (HAT) on soil, humic acid, and soil modified with humic acidic was studied by sequential-injection chromatography with UV detection at 223 nm. An online monitoring system was assembled, which was composed of a tangential filter and a peristaltic pump for the circulation of the soil (25 g L(-1)) or humic acid (2.5 g L(-1)) suspensions.

Monolithic columns in plant proteomics and metabolomics.

Since "omics" techniques emerged, plant studies, from biochemistry to ecology, have become more comprehensive. Plant proteomics and metabolomics enable the construction of databases that, with the help of genomics and informatics, show the data obtained as a system. Thus, all the constituents of the system can be seen with their interactions in both space and time.

Complexation of Hg(II) by humic acid studied by square wave stripping voltammetry at screen-printed gold electrodes.

This paper reports the development of a sequential injection (SI) method to study the complexation of Hg(II) by humic acid (HA) using square wave anodic stripping voltammetry at a screen-printed gold electrode (SPGE). The SI system injected samples (in 0.020 mol L(-1) NaNO(3) and pH 6.

Improvements in the separation capabilities of sequential injection chromatography: determination of intracellular dissolved free amino acid profiles in three taxonomic groups of microalgae.

Introduction: Dissolved free amino acids (DFAA) in intracellular extracts of marine microalgae can be determined by sequential injection chromatography (SIC). This technique uses portable, low-cost instrumentation but its applications have been limited to short monolithic columns because of components not resistant to high pressures.

Objective: To develop a SIC method for determination of DFAA by exploring an instrument modified to handle pressures of 1000 psi.

Study of photorespiration in marine microalgae through the determination of glycolic acid using hydrophilic interaction liquid chromatography.

Determination of organic acids in intracellular extracts and in the cultivation media of marine microalgae aid investigations about metabolic routes related to assimilation of atmospheric carbon by these organisms, which are known by their role in the carbon dioxide sink. The separation of these acids was investigated by hydrophilic interaction liquid chromatography (HILIC) using isocratic elution with a mobile phase composed of 70:30 v/v acetonitrile/20 mmol/L ammonium acetate buffer (pH 6.8) and detection at 220 nm.