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6CCVD Research

Comparison of Chromatographic and Electrochemical Methods for Detecting and Quantifying Sunscreen Agents and Their Degradation Products in Water Matrices

At a Glance

Section titled “At a Glance”
MetadataDetails
Publication Date2025-05-14
JournalApplied Sciences
AuthorsLaysa Renata Duarte Brito Sabino, Mayra Kerolly Sales Monteiro, Letícia Gracyelle Alexandre Costa, Elisama Vieira dos Santos, Carlos A. Martínez‐Huitle
InstitutionsUniversidade Federal do Rio Grande do Norte, National Agency of Petroleum, Natural Gas and Biofuels
Citations1
AnalysisFull AI Review Included

Executive Summary

Section titled “Executive Summary”
  • Method Validation: A reliable electroanalytical method utilizing a Glassy Carbon Sensor (GCS) and Differential Pulse Voltammetry (DPV) was successfully validated for the detection and quantification of Octocrylene (OC), a major UV filter, in complex water matrices.
  • Superior Sensitivity: The GCS/DPV method demonstrated higher sensitivity compared to High-Performance Liquid Chromatography (HPLC), achieving a Limit of Detection (LOD) of 0.11 ± 0.01 mg L-1, which is approximately three times lower than the HPLC LOD (0.35 ± 0.02 mg L-1).
  • Matrix Compatibility: The electroanalytical approach, using an organic/inorganic solvent-electrolyte system, effectively eliminated the need for complex sample extraction procedures typically required by chromatography, simplifying analysis of real water samples.
  • Reliability and Accuracy: Statistical comparison confirmed that OC concentration results obtained by GCS/DPV were statistically equivalent to those obtained by HPLC (95% confidence level) across various sunscreen formulations and swimming pool water samples.
  • Treatment Monitoring: The GCS was effectively used to monitor the degradation kinetics of OC during Electrochemical Advanced Oxidation (EAO) treatment using a Boron-Doped Diamond (BDD) anode.
  • Degradation Efficiency: OC removal was highly efficient, with degradation rates increasing significantly when the applied current density was raised from 5 mA cm-2 to 10 mA cm-2, driven by hydroxyl radicals and active chlorine species.

Technical Specifications

Section titled “Technical Specifications”
ParameterValueUnitContext
GCS LOD (DPV)0.11 ± 0.01mg L-1Limit of Detection (Electroanalysis)
GCS LOQ (DPV)0.86 ± 0.04mg L-1Limit of Quantification (Electroanalysis)
HPLC LOD0.35 ± 0.02mg L-1Limit of Detection (Chromatography)
HPLC LOQ2.86 ± 0.12mg L-1Limit of Quantification (Chromatography)
GCS Linear Range (DPV)0.09-1.08mg L-1OC concentration in BR buffer
HPLC Linear Range1.00-5.00mg L-1OC concentration in BR buffer
GCS Working Area3.14 ± 0.10mm2Exposed geometric area
BDD Anode Active Area69.4 ± 0.5cm2Electrochemical flow cell
Electrode Gap (BDD/SS)1.7 ± 0.5cmDistance between BDD anode and SS cathode
Applied Current Density (Low)5mA cm-2OC degradation monitoring
Applied Current Density (High)10mA cm-2OC degradation monitoring
Electrolyte (Electroanalysis)0.04MBritton-Robinson (BR) buffer, pH 6.0
HPLC Eluent Composition80/20Acetonitrile/WaterIsocratic mode
Swimming Pool Matrix0.002MResidual Chloride (Cl-) concentration
OC Maximum Concentration10%Allowed in sunscreen formulations (EU/US)

Key Methodologies

Section titled “Key Methodologies”

  1. Octocrylene (OC) Quantification via Electroanalysis (GCS/DPV):

    • Electrode Setup: Three-electrode cell using a Glassy Carbon Sensor (GCS) as the working electrode, Ag/AgCl (3M KCl) as the reference, and Platinum as the counter electrode.
    • Surface Preparation: GCS surface was polished with polishing paper before and after every measurement to ensure reproducibility and sensitivity.
    • Electrolyte: 10 mL of 0.04 M Britton-Robinson (BR) buffer (pH 6) was used.
    • Technique Parameters (DPV): Cathodic scan performed from -0.8 V (initial) to -1.5 V (final); Step Potential: +0.005 V; Modulation Amplitude: +0.1 V; Equilibrium Time: 10 s.
    • Sample Analysis: Standard addition method employed for quantifying OC in sunscreen formulations and water matrices to effectively minimize matrix interference.

  2. OC Quantification via Chromatography (HPLC):

    • System: Ultimate 3000 HPLC equipped with a C18 column.
    • Operation: Isocratic mode.
    • Mobile Phase: 80/20 acetonitrile/water mixture.

  3. Electrochemical Advanced Oxidation (EAO) Treatment:

    • Reactor Setup: Electrochemical flow cell connected to a 2 L storage solution tank.
    • Anode Material: Boron-Doped Diamond (BDD) circular plate (69.4 cm2 active area).
    • Cathode Material: Stainless Steel (SS).
    • Operating Conditions: Galvanostatic control applied at current densities of 5 mA cm-2 and 10 mA cm-2 for 180 minutes.
    • Water Circulation: Peristaltic pump maintained a flow rate of approximately 19 L h-1 for continuous circulation of the contaminated water (swimming pool water or 0.002 M NaCl solution).
    • Degradation Mechanism: OC removal is achieved through the synergistic effect of electrogenerated hydroxyl radicals (·OH) at the BDD surface and active chlorine species (Cl2, HOCl, ClO-) produced from the chloride matrix.

Commercial Applications

Section titled “Commercial Applications”

  • Environmental and Water Quality Monitoring:

    • Deployment of GCS-based sensors for real-time, cost-effective monitoring of emerging contaminants (like UV filters and pharmaceuticals) in municipal swimming pools, recreational waters, and industrial effluents.
    • Provides a rapid, field-deployable alternative to expensive, time-consuming laboratory techniques (HPLC).

  • Advanced Wastewater Treatment (BDD Technology):

    • Design and optimization of Electrochemical Advanced Oxidation Processes (EAOPs) using Boron-Doped Diamond (BDD) anodes for the mineralization of recalcitrant organic pollutants.
    • Applicable in industrial water reclamation and tertiary treatment facilities where high oxidative power is required to eliminate persistent compounds (e.g., in carwash wastewater or pharmaceutical effluents).

  • Electrochemical Sensor Manufacturing:

    • Development of robust, reproducible carbonaceous sensors (GCS) for high-sensitivity detection protocols.
    • Integration into quality control systems for the cosmetic and chemical industries to rapidly verify UV filter concentrations in product formulations.

  • Chlorination and Disinfection Systems:

    • Relevance to in-line electro-chlorination systems (e.g., those provided by Ecas4 Australia Pty Ltd.) that use NaCl as a precursor, highlighting the importance of controlling current density to maximize contaminant degradation while preventing the formation of toxic byproducts (chlorate, perchlorate).
View Original Abstract

Comparing electroanalysis and chromatography, this study highlights that electroanalysis, specifically using a glassy carbon sensor (GCS), is the most appropriate choice for quantifying recalcitrant organic compounds. Octocrylene (OC), an organic compound commonly found in sunscreens, is of particular concern in swimming pool water monitoring, as its presence above legal limits poses health risks. OC quantification was performed using both high performance liquid chromatography (HPLC) and electroanalysis in sunscreen formulations and water matrices. The limits of detection (LODs) and quantification (LOQ) for OC were approximately 0.11 ± 0.01 mg L−1 and 0.86 ± 0.04 mg L−1 by electroanalysis, and 0.35 ± 0.02 mg L−1 and 2.86 ± 0.12 mg L−1 by HPLC. Electroanalysis successfully quantified OC in real sunscreen samples, and the results were comparable to those obtained by HPLC. The matrices tested—swimming pool water and distilled water (containing 0.002 M Cl−) contaminated with 0.4 ± 0.2 g L−1 of sunscreen (based on a maximum concentration in sunscreen and cosmetic formulations of 10%)—showed OC concentrations below 10% in the formulation, with no significant differences observed between the two techniques. GCS was further utilized to monitor OC degradation via anodic oxidation at current densities of 5 and 10 mA cm−2, using a boron-doped diamond (BDD) anode. The combined approach demonstrated high efficacy in both detecting and eliminating OC from various water matrices, making it a reliable and efficient alternative for environmental and water quality monitoring.

Tech Support

Section titled “Tech Support”

Original Source

Section titled “Original Source”

References

Section titled “References”
  1. 2014 - Contact and photocontact allergy to octocrylene: A review [Crossref]
  2. 2017 - Degradation of octocrylene using combined ozonation and electrolysis process: Optimization by response surface methodology [Crossref]
  3. 2021 - Benzophenone accumulates over time from the degradation of Octocrylene in commercial sunscreen products [Crossref]
  4. 2020 - Pharmaceuticals as emerging contaminants in the aquatic environment of Latin America: A review [Crossref]
  5. 2011 - Safety Evaluation of sunscreen formulations containing titanium dioxide and zinc oxide nanoparticles in UV-B sunburned skin: An in vitro and in vivo study [Crossref]
  6. 2011 - Electrochemical behavior and voltammetric determination of paracetamol on nafion/TiO2-graphene modified glassy carbon electrode [Crossref]

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