PROPOSAL ABSTRACT:  

 
Name of Principal
Investigator: Adolfo Marican Riquelme

Proposal Title: Synthesis and evaluation of sorbent phases based on hydrogels

for the microextraction and quantitative determination of
organophosphorus pesticides and carbamates from aqueous
solutions.

The use of pesticides in agriculture helps increase crop yields to meet the demands of the growing human
population. However, continuous application can cause chronic abnormalities in humans and destroy the
environment and biodiversity. There are numerous pesticides in use in our country, among the most used
are carbamates and organophosphorus. Within these group are Carbofuran, Methomyl, Dimethoate, and
Methamidophos. Due to the high toxicity of them in terms of their effects on human health, by acute or
chronic exposure, the sampling in people who show some symptom of poisoning is crucial for an opportune
diagnosis. In this sense, urine is a good selection as a sample for analysis because it can be obtained in large
volumes, being a non-invasive sampling, so that the repetition of sampling is not problematic.

The preparation of the sample starts from the improvement of the selectivity and sensitivity of the analyses,
improving the analytical criteria and/or protecting the instruments from possible damages. Thus, the
preparation of the sample is of the utmost importance to obtain the analytes of interest in a suitable injection
solution capable of providing reliable and precise results. There are a number of ways to extract and
preconcentrate analytes from aqueous samples for later determination by HPLC or GC. Considering the
limitations of the different extraction methodologies, their ease of use and implementation, the use of organic
solvents, extraction time, high levels of preconcentration, economic cost, reusability, etc., two techniques
stand out for the treatment of liquid samples: stir-bar sorptive extraction (SBSE) and a derivation of this,
rotating-disk sorptive extraction (RDSE). SBSE is based on sorption extraction. In SBSE, the sorbent (PDMS,
generally) is coated on a magnetic stirring bar and liquid samples are simply stirred with this bar. After
extraction, the stir bar is removed and dried with a soft tissue. The analytes are desorbed through thermal
desorption followed by GC analysis and liquid desorption followed by HPLC analysis. SBSE has the following
drawbacks: (a) increasing the rotational velocity of the sorptive bar may cause physical damage in PDMS
phase due to its direct contact with the bottom of the sample vial during the extraction; (b) stir bars offer a
low extraction PDMS area-to-volume ratio affecting the analyte mass transfer to the phase, and (c) the high
cost of acquisition of the stir bars because they cannot be made easily in the laboratory. RDSE is a technique
that consists in extracting low-polarity analytes onto a rotating Teflon disk coated with PDMS film in one of
its surfaces. This configuration allows immobilizing a larger exposed surface area of PDMS than the stir bar
used in SBSE. In addition, the disc can be rotated at high speeds without damaging the phase, facilitating
mass transfer to the PDMS surface. Basically, in RDSE, the contact surface between the sorbent phase is
much larger than in the case of SBSE.

In both sorption extraction techniques, the use of sorbent phases is basically limited by the polarity of the
analytes that are to be extracted, and by the contact surface of the phase exposed to the aqueous phase.
The pesticides to be analyzed in the proposed project have different polarities. In this sense, the use of a
single sorbent phase such as PDMS offers many limitations to the determination of all these compounds. On
the other hand, the contact surface between the sorbent phase and the aqueous phase containing the
analytes can be increased, by changing the shape of the phase, for example, using spheres (“beads”) or
sheets of some polymer that has affinity with the analytes of interest. The polymeric compound to be used
must be able to work in a wide range of pH, be insoluble in water, be resistant to mechanical agitation, and
with the possibility of being reused. The aim of this project is to evaluate the efficiency of new
insoluble materials based on hydrogels as a potential sorption phase to extract and
preconcentrate methamidophos, dimethoate, carbofuran and methomyl from aqueous matrices
and their subsequent desorption for its determination by chromatography. To achieve this goal,
materials based on natural and synthetic polymers will be used. More specifically, a set of compounds
synthesized using polyelectrolyte complex formed by chitosan and calcium alginate, and hydrogels based on
poly(vinyl alcohol) (PVA) crosslinked with malic acid (MA) in different proportions of PVA:MA will be tested.
The results of this research project will provide a fast, efficient and cheap solution for the sample
treatment determining the toxic pesticides in aqueous solutions. The advantages lie in the proposed
materials which have several characteristics like high insolubility, easy to handle, prepare, and separate from
the test solution.
Concurso de Proyectos FONDECYT de Iniciación en Investigación 2018