Çevresel matrikslerde bulunan hardal gazı bozunma ürününün eutectic çözücüler ile ekstraksiyonu, kromatografik ve spektrofotometrik analizleri
Extraction of mustard gas degradation products from environmental matrices using eutectic solvents, chromatographic and spectrophotometric analysis
- Tez No: 983728
- Danışmanlar: PROF. DR. AYŞEGÜL GÖLCÜ, DOÇ. DR. MUAMMER KAPLAN
- Tez Türü: Yüksek Lisans
- Konular: Kimya, Chemistry
- Anahtar Kelimeler: Sıvı faz mikroekstraksiyonu, Liquid phase microextraction
- Yıl: 2025
- Dil: Türkçe
- Üniversite: İstanbul Teknik Üniversitesi
- Enstitü: Lisansüstü Eğitim Enstitüsü
- Ana Bilim Dalı: Kimya Ana Bilim Dalı
- Bilim Dalı: Belirtilmemiş.
- Sayfa Sayısı: Belirtilmemiş.
Özet
Kimyasal savaş ajanları (CWA) canlılara zarar vermek, yaralamak, güçsüzleştirmek veya öldürmek amacıyla kullanılan, aşırı derecede toksik sentetik kimyasallardır. Partiküllere adsorbe edilerek veya gaz, sıvı ya da aerosol şeklinde dağılabilirler. Hardal gazı (HD) veya bis(2-kloroetil) sülfür kimyasal savaş ajanları arasında en önemli ajanlardan biridir. HD oldukça toksik bir alkile edici bir maddedir. Hardal gazı çeşitli yollarla çevrede varlığını sürdürebilir ve ortamın hardal gazı ile kirletilmesi durumunda, bu ajanın bozulup bozulmayacağı, oluşan ürünün kimliğinin, toksisitesinin ve miktarının bilinmesi dekontaminasyonu açısından oldukça önemlidir. Kimyasal ajanlar ile kirletilmiş olduğundan şüphelenilen alanlarda hardal gazının varlığını doğrulayabilmek adına hardal gazı ve bozunma ürünlerinin tespiti için hızlı ve güvenilir analitik yöntemler gerekmektedir. Bu çalışmada, hardal gazının bozunma ürünü olan 1,4-ditianın çok-düşük konsantrasyonlarda tayini amacıyla yeşil kimya prensiplerine dayalı bir sıvı faz ekstraksiyon yöntemi geliştirilmiştir. Ekstraksiyon çözücüsü olarak çevresel sürdürülebilirlik, biyouyumluluk ve düşük toksisite avantajları nedeniyle geleneksel organik çözücüler yerine derin ötektik çözücüler (DES) tercih edilmiştir. DES'ler, belirli molar oranlarda karıştırılan bir kuaterner amonyum tuzu ve bir hidrojen bağ donöründen (HBD) oluşmakta olup, düşük maliyetli ve kolay hazırlanabilen çözücülerdir. Bu yaklaşımla daha az toksik ve daha az çözücü tüketen bir ekstraksiyon süreci elde edilmiştir. Geliştirilen yöntemde; DES oranı/hacmi, karıştırma süresi ve THF miktarı gibi tüm deneysel parametreler optimize edilmiş ve analizler gaz kromatografisi (GC) ile gerçekleştirilmiştir. GC sisteminde sıcaklık programı, split oranı ve taşıyıcı gaz akış hızı da metot performansını en üst düzeye çıkaracak şekilde optimize edilmiştir. Yöntemin analitik performans parametreleri incelendiğinde, gözlenebilme limiti (LOD) 44.3 μg/L, tayin limiti (LOQ) ise 147.8 μg/L olarak belirlenmiştir. Ayrıca kalibrasyon eğrisinin geniş bir aralıkta yüksek doğrusallık (R² = 0.9998) sergilediği ve yöntemin gün içi ve günler arası tekrarlanabilirliğinin sırasıyla %6.4 ve %4.3 RSD ile oldukça iyi olduğu tespit edilmiştir. Yöntemin doğruluğunu ve uygulanabilirliğini değerlendirmek amacıyla Kimyasal Silahların Yasaklanması Örgütü (OPCW) tarafından yürütülen yeterlilik testlerinde (PT) kullanılan kompleks matrisleri temsil eden musluk suyu (PEG+DCM) ve toprak (+dizel) örnekleri hazırlanmış ve bu matrislerde geri kazanım çalışmaları gerçekleştirilmiştir. Kalibrasyon eğrisinin doğrusal aralığında 1,4-ditian standardı eklenerek yapılan çalışmalarda, musluk suyu matrisinde %95-108, toprak matrisinde ise %83-105 geri kazanım değerleri elde edilmiştir. Sonuç olarak, bu çalışma ile basit, etkili ve yeşil kimya ilkelerine uygun bir ekstraksiyon yöntemi geliştirilmiş; yüksek geri kazanım yüzdeleri ve düşük tayin limitleriyle karmaşık matrislere uygulanabilirliği başarılı şekilde gösterilmiştir. Ayrıca literatürde 1,4-ditianın analizine yönelik sınırlı sayıda çalışma bulunmakta olup, derin ötektik çözücülerle (DES) geliştirilmiş ilk ekstraksiyon yöntemlerinden biri olması açısından da özgün bir katkı sağlamaktadır.
Özet (Çeviri)
Chemical warfare agents (CWAs) are highly toxic synthetic chemicals used to harm, injure, incapacitate, or kill living organisms. They can be dispersed by being adsorbed on the surface of particles or in the form of gas, liquid, or aerosol. The Organisation for the Prohibition of Chemical Weapons (OPCW), established in the 1990s, aims to eliminate the global use of Chemical Warfare Agents (CWAs). Together with the Chemical Weapons Convention (CWC), the development, production, and use of CWAs have been prohibited. There are laboratories that have obtained the competence to perform the analysis of chemicals listed under the CWC. These laboratories are referred to as OPCW designated laboratories. In order to become an OPCW designated laboratory, it is necessary to participate in the proficiency tests (PTs) organized annually by the OPCW and achieve successful results. Sulfur mustard (HD), or bis(2-chloroethyl) sulfide, is one of the most significant chemical warfare agents. HD is a highly toxic alkylating compound. Sulfur mustard can persist in the environment through various pathways, and in the event of environmental contamination, understanding whether the agent degrades, as well as identifying the degradation products, their toxicity, and their concentrations, is crucial for effective decontamination. In areas suspected of being contaminated with chemical agents, rapid and reliable analytical methods are required to detect sulfur mustard and its degradation products in order to confirm its presence. HD is initially hydrolyzed in environmental samples to form thiodiglycol (TDG). TDG can subsequently undergo oxidation to produce thiodiglycol sulfoxide (TDGO) and thiodiglycol sulfone (TDGOO). In addition, HD with thermal interaction can lead to the formation of cyclic degradation products such as 1,4-dithiane and 1,4-dioxane. While the detection of intact HD in the environment is rare, its metabolites and degradation products are encountered much more frequently. Conclusion, the detection of these chemicals in analyzed samples can serve as reliable evidence of the presence of HD in the environment. 1,4-Dithiane is an organosulfur compound that is not classified as carcinogenic and has a garlic- or onion-like odor. It appears as a thermal degradation product of HD under both normal and high temperatures. Although it is an important compound for demonstrating the presence of HD, there are relatively few studies in the literature focusing on its analysis. Within the scope of this thesis, gas chromatography was used to analyze 1,4-dithiane. Gas chromatography (GC) is a technique employed for the qualitative and quantitative analysis of compounds that are volatile or can be made volatile. The injection system, carrier gas system, column, and detector can be considered as its fundamental components. In a GC system, compounds injected into the column reach the dedector at different times depending on their interactions with the stationary phase. However, not every sample can be analyzed directly by GC due to matrix characteristics or physical forms. Therefore, sample preparation procedures are required. Sample preparation enables the separation of target analytes from the matrix and the preconcentration of those present at trace levels, effectively eliminating matrix interferences. Liquid–liquid extraction (LLE) is a widely used sample preparation technique. It is based on transferring the analyte from an aqueous matrix into an immiscible organic solvent. In LLE, the organic solvent must be immiscible with the matrix and able to dissolve the analytes. However, due to the use of large amounts of high-purity organic solvents, it is not well aligned with green chemistry principles. Consequently, deep eutectic solvents (DESs) have emerged as environmentally friendly alternatives to conventional organic solvents. DESs are known as relatively less toxic, eco-friendly solvents. They are easy, fast, and low-cost to prepare, and they are also biocompatible. In this study, a green chemistry-assisted liquid-phase extraction technique was developed for the trace-level analysis of 1,4-dithiane, a cyclic degradation product of sulfur mustard. Deep eutectic solvents (DESs) were selected as the extraction solvent instead of commonly used organic solvents due to their environmentally friendly properties such as sustainability and biocompatibility. This approach enabled the use of less toxic and smaller volumes of solvent. Additionally, DESs, which are more cost- effective and easier to prepare, are synthesized by mixing a quaternary ammonium salt with a hydrogen bond donor (HBD) in a specific molar ratio. All experimental parameters such as the DES ratio/volume, mixing time, and the amount of THF were optimized for the analysis of 1,4-dithiane at low detection limits using the developed method, and the analysis was performed by gas chromatography. Additionally, GC system parameters including the temperature program, split ratio, and carrier gas flow rate were optimized for the analysis. During the optimization experiments, various conditions were evaluated for each parameter to determine their influence on the analyte signal, while the remaining parameters were maintained constant. All parameters were assessed in triplicate using a 10 mg/L 1,4-dithiane standard solution. After selecting the DES type and molar ratio, the formation of a hydrogen bond between choline chloride and phenol is required for DES formation. To examine the presence of this interaction, the characterization of the DES was carried out using FTIR. The IR spectra of pure choline chloride, pure phenol, and the DES formed from their combination were analyzed. In addition, to investigate the presence and solubility of 1,4-dithiane within the DES phase obtained after extraction, the IR spectra of the DES phase, pure 1,4-dithiane, and the DES itself were examined. As part of the method validation process, the limit of detection (LOD), limit of quantification (LOQ), linear dynamic range (LDR), relative standard deviation (%RSD), and repeatability parameters were determined under optimized conditions. Each analysis was performed seven times for the evaluation of all parameters. The analytical performance of the method was evaluated, and the limit of detection and limit of quantification were found to be 44.3 μg/L and 147.8 μg/L, respectively. When 1,4-dithiane was analyzed using the developed method, the calibration curve exhibited good linearity with a correlation coefficient of 0.9998, and the repeatability, in terms of % relative standard deviation, was found to be 6.4% (intra-day) and 4.3% (inter-day). In order to validate the accuracy and applicability of the method, recovery studies were executed using tap water (PEG+DCM) and soil (+diesel) samples, which were prepared to simulate complex matrices used in proficiency tests (PTs) conducted by the OPCW. Matrix matching strategy was used to reduce the matrix effect in complex samples and ensure accurate quantification. Recovery studies were carried out in the samples by spiking 1,4-dithiane at concentrations within the linear calibration range. Recovery percentages were obtained in the range of 95-108% for the tap water and 83-105% for the soil samples. The proposed simple, effective, and green chemistry-supported method achieved high recovery percentages, and its applicability to complex matrices used in OPCW proficiency tests was demonstrated. Furthermore, although there is a lack of significant studies on the analysis of 1,4-dithiane in the literature, no extraction method has been developed using DES for this purpose.
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