MEASUREMENT UNCERTAINTY IN THE ANALYSIS OF SELECTED POLYCYCLIC AROMATIC HYDROCARBONS IN ENVIRONMENTAL WATER BY MAGNETIC MOLECULARLY IMPRINTED POLYMER-BASED MICRO-SOLID PHASE EXTRACTION- LIQUID CHROMATOGRAPHY

Malaysian Journal of Analytical Sciences, Vol 28 No 4 (2024): 859 - 871

measurement uncertainty IN THE ANALYSIS OF selected polycyclic aromatic hydrocarbons in environmental water BY Magnetic molecularly imprinted polymer-based micro-solid phase EXTRACTION- LIQUID CHROMATOGRAPHY

(Ketidakpastian Pengukuran dalam Analisis Hidrokarbon Aromatik Polisiklik Terpilih di dalam Air Persekitaran dengan Pengekstrakan Fasa Pepejal-Mikro berasaskan Polimer Bercetakan Molekul Bermagnet-Kromatografi Cecair)

Nor Syuhadaa Che Abdullah¹, Marinah Mohd Ariffin¹, Wan Mohd Afiq Wan Mohd Khalik^1,2, Farhanini Yusoff¹, Sazlinda Kamaruzaman³, and Saw Hong Loh^1*

¹Faculty of Science and Marine Environment, Universiti Malaysia Terengganu, Kuala Nerus, Terengganu, Malaysia

²Water Analysis Research Centre, Faculty of Science and Technology, Universiti Kebangsaan Malaysia, 43600 Bangi, Selangor, Malaysia

³Department of Chemistry, Faculty of Science, Universiti Putra Malaysia, 43400 UPM Serdang, Selangor, Malaysia

^*Corresponding author: lohsh@umt.edu.my

Received: 10 May 2024; Accepted: 7 July 2024; Published: 27 August 2024

Abstract

Sample preparation is important to produce a clean extract to enhance detection sensitivity and minimize instrument maintenance. A micro-solid phase extraction (µ-SPE) technique using magnetic molecularly imprinted polymers (magnetic-MIPs) as the adsorbents combined with micro-high performance liquid chromatography and ultraviolet detection (µ-HPLC-UV) has been developed for the determination of selected polycyclic aromatic hydrocarbons (PAHs), namely benzo[a]pyrene, phenanthrene, fluoranthene and pyrene in environmental water samples. The magnetic-MIPs were characterized using scanning electron microscopy, Brunauer–Emmett–Teller, thermogravimetric analysis and vibrating sample magnetometer to finalize the physical properties of the magnetic-MIPs. The µ-SPE was then optimized using one variable at a time approach to enhance the extraction efficiency. Under the optimal extraction conditions, the feasibility of using magnetic-MIPs as the adsorbents for the extraction of the selected PAHs was proven with a wide linearity range (5-250 µg L^-1), good repeatability (relative standard deviation <10%), ultra-trace detection limits (0.01-0.02 µg L^-1) and good relative recovery (80.2-119.3%) for the application in the environmental water. The doubt of using the µ-SPE was investigated by calculating the measurement uncertainty. The estimated combined standard uncertainties for the determination of the selected PAHs were in the range of 0.0678-0.0890. It was concluded that the uncertainty of the µ-SPE-µ-HPLC-UV is mainly attributed to its accuracy. Nevertheless, the results showed that the measurement uncertainty of the proposed magnetic-MIPs-based µ-SPE-µ-HPLC-UV was at an acceptable level. The method is beneficial to the routine analysis, especially in providing simple and sensitive determination of the selected PAHs in environmental water. The µ-SPE technique consumes minimal amounts of solvent and traces of adsorbents, which then greatly minimizes the waste and analysis costs in routine analysis.

Keywords: chromatography, measurement uncertainty, molecularly imprinted polymer, PAHs, water

Abstrak

Penyediaan sampel adalah penting untuk menghasilkan ekstrak bersih untuk meningkatkan sensitiviti pengesanan dan meminimumkan penyelenggaraan instrumen. Teknik pengekstrakan fasa pepejal-mikro (µ-SPE) menggunakan polimer bercetakan molekul bermagnet (MIPs bermagnet) sebagai penjerap yang digabungkan dengan kromatografi cecair berprestasi tinggi-mikro dan pengesanan ultraungu (µ-HPLC-UV) telah dibangunkan untuk penentuan hidrokarbon aromatik polisiklik (PAHs) terpilih, iaitu benzo[a]pirena, fenanthrena, fluoranthena dan pirena di dalam sampel air persekitaran. MIPs bermagnet telah dicirikan menggunakan mikroskop elektron pengimbasan, Brunauer-Emmett-Teller, analisis termogravimetrik dan magnetometer sampel bergetar untuk memuktamadkan sifat fizikal MIPs bermagnet. µ-SPE kemudiannya dioptimumkan menggunakan pendekatan satu pembolehubah pada satu masa untuk meningkatkan kerberkesanan pengekstrakan. Di bawah keadaan pengekstrakan yang optimum, kebolehlaksanaan menggunakan MIPs bermagnet sebagai penjerap untuk pengekstrakan PAHs terpilih telah dibuktikan dengan julat kelinearan yang luas (5-250 µg L^-1), kebolehulangan yang baik (sisihan piawai relatif <10%), had pengesanan ultra-surihan (0.01-0.02 µg L^-1) dan pemulihan relatif yang baik (80.2-119.3%), terutamanya untuk aplikasi di dalam air persekitaran. Keraguan menggunakan µ-SPE ini telah disiasat dengan mengira ketidakpastian pengukuran. Anggaran gabungan ketidakpastian piawai bagi penentuan PAHs terpilih adalah dalam julat 0.0678-0.0890. Disimpulkan bahawa ketidakpastian µ-SPE-µ-HPLC-UV disebabkan terutamanya oleh ketepatannya. Namun begitu, keputusan ini menunjukkan bahawa ketidakpastian pengukuran µ-SPE-µ-HPLC-UV berasaskan MIP bermagnet yang dicadangkan berada pada tahap yang boleh diterima. Kaedah ini bermanfaat kepada analisis rutin terutamanya dalam menyediakan penentuan mudah dan sensitif PAHs terpilih di dalam air persekitaran. Teknik µ-SPE hanya menggunakan sedikit pelarut dan penjerap yang dapat meminimumkan sisa dan kos analisis dalam analisis rutin.

Kata kunci: kromatografi, ketidakpastian pengukuran, polimer bercetakan molekul, PAHs, air

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