Dispersive Liquid-liquid Microextraction Research Articles

Development of a dispersive liquid-liquid microextraction technique for ultra-sensitive detection of gold in environmental samples using atomic absorption spectrometry.

The work examines the determination of gold from environmental samples by dispersive liquid-liquid microextraction (DLLME) method. The method was developed for the separation and determination of Au (III) ions after chelating with bis (salicylaldehyde) ethylenediimine (H2SA2en) Schiff-base as derivatizing reagent. Flame atomic absorption spectrometry (FAAS) and inductively coupled plasma-optical emission spectrometry (ICP-OES) techniques were used for quantitation of Au (III). These techniques are sensitive and rapid for the determination of gold concentrations in ore, water and sediment samples. The influence of factors such as pH, reagent concentration, solvents (extracting) (disperser) and solvent volumes on extraction efficiency of Au (III) ions were studied and optimized by univariate and multivariate techniques. The linearity of the method was in the range of 2 to 12 µg/L with R2 = 0.997. The limit of detection was 1 µg/L, and the limit of quantification was 3 µg/L. The preconcentration factor and enrichment factor values were 44 and 47. The repeatability (the intra-day) and reproducibility (the inter-day) precisions (n = 3) were found to be 0.417-3.56%. The proposed method was successfully applied for the determination of gold in sediment samples of the Indus River, Kori Barrage, goldsmith water, acidic solution of goldsmith and ornament samples collected from Goldsmith Labs and shops. The results found from FAAS were compared with those obtained from ICP-OES technique, and a good correlation with comparable selectivity and sensitivity was specified.

A recent overview of the application of emerging extraction medium-based sample preparation for the determination of aflatoxins and their precursors in food samples.

Food safety problem caused by aflatoxins (AFs) has become a major concern worldwide. However, due to the complexity of food matrices and the low concentration of analytes, the accurate and sensitive determination of AFs and their precursors in the biosynthetic pathway is extremely challenging, so the development of efficient sample preparation techniques has been urgently required. This paper reviews the recent advances in sample preparation based on some emerging extraction media for the determination of AFs and their precursors in different food samples, including ionic liquids (ILs) and IL-based composites, metal-organic frameworks (MOFs) and covalent organic frameworks (COFs). These extraction media can be combined with different sample preparation techniques, such as dispersive liquid-liquid microextraction, solid-phase extraction, and magnetic/dispersive solid-phase extraction, mainly depending on their physicochemical properties. They exhibit efficient extraction and enrichment performance towards AFs and their precursors, which is attributed to their multiple-interaction mechanism and/or porous structure. This review also presents the current challenges and future prospects of these emerging extraction media for sample preparation of AFs and their precursors from food.

A reversed-phase dispersive liquid-liquid micelle-mediated microextraction method coupled to batch injection analysis for electrochemical determination of carbendazim in edible oil samples

A reversed-phase dispersive liquid-liquid micelle-mediated microextraction method coupled to batch injection analysis for electrochemical determination of carbendazim in edible oil samples

Rapid and Simple Dispersive Liquid-Liquid Microextraction (DLLME) Sample Preparation for Propofol Analysis in Hair, Blood, and Urine by Gas Chromatography-Mass Spectrometry.

Propofol is a widely used anesthetic. Although considered safe, propofol-related deaths occur, as it is sometimes abused recreationally or used to commit suicide. A simple, rapid, and reliable method for its analysis in various biological samples is needed. Sample clean-up is a critical step in the analysis, both in terms of time and cost, indeed. Dispersive liquid-liquid microextraction (DLLME) is a simple and fast extraction based on ternary solvent mixtures that uses small volumes of solvent and sample. A DLLME extraction followed by gas chromatography-mass spectrometry (GC-MS) analysis was developed and validated for the analysis of propofol in blood, urine, and hair. The same extraction mixture of 2.5:1 methanol/chloroform was used for the different biological samples. Validation for linearity, LOD, LOQ, precision, accuracy, and recovery gave satisfactory results for the three types of biological samples included in the study, with limits of quantification of 1 μg/mL for urine, 0.2 μg/mL for blood, and 0.1 ng/mg for hair. The DLLME procedure for purification involves a small amount of solvent, thus reducing the cost and the environmental impact. In addition, a high enrichment factor is obtained, and the time for analysis is short. The method was applied to authentic post-mortem samples for the determination of propofol in blood, urine, and hair. Also, segmental hair analysis was performed to assess chronic propofol abuse. The developed method proved to be rapid, simple, and cost-effective for blood, urine, and hair extract clean-up for the determination of propofol by GC/MS.

Thin film microextraction of PAHs from wastewater samples using an oxine modified iron mesh followed by dispersive liquid-liquid microextraction prior to gas chromatography analysis.

In the present research, an attempt has been made to develop a new thin film microextraction method for the extraction of several polycyclic aromatic hydrocarbons from aqueous samples collected from different industrial units prior to their analysis by gas chromatography combined with a flame ionization detector. In this approach, a thin iron mesh was modified by the formation of iron(II) oxinate on its surface and used for the extraction of analytes without an additional sorbent. For this purpose, first, the mesh was immersed in a sulfuric acid solution and then transferred into an 8-hydroxy quinoline (oxine) solution dissolved in ammonia solution. By doing so, iron(II) oxinate was formed on the surface of the mesh and enhanced its adsorption efficiency towards the analytes. It is worth noting that the unique structure of the prepared mesh provided a large contact area and high affinity for adsorption of the analytes. After desorption of the analytes from the sorbent surface with an elution solvent, the analytes were more concentrated by performing dispersive liquid-liquid microextraction. Under optimum conditions, the method demonstrated limits of detection and quantification within the ranges of 0.27-54 and 0.89-1.7 ng mL-1, respectively. The relative standard deviation values for intra- and inter-day precisions ranged from 5.2-8.1% and 8.2-11.6%, respectively. Furthermore, the enrichment factors for the target analytes varied between 200 and 255, while the extraction recoveries fell within the range of 40-51%. These findings illustrate the sensitivity, precision, and effectiveness of the method for quantifying the desired analytes.

Experimental-design-based optimization of dispersive liquid-liquid microextraction coupled with gas chromatography–negative-ion chemical ionization–mass spectrometry for the determination of pyrethroids in agricultural products and drinks

Pyrethroids are synthetic chemicals that account for 16% of the international insecticide market and have been shown to be of varying toxicity to different species. There are various methods available for detecting pyrethroids in agricultural products, but these products must be pre-treated to remove interference from the food matrix, such as through dispersion liquid-liquid microextraction (DLLME). This study employed two experimental design methods to optimize the continuous and discontinuous experimental parameters of DLLME and investigated whether DLLME combined with GC-NICI-MS is effective for detecting pyrethroids in agricultural products. The Taguchi design with an L9(34) orthogonal array and response surface methodology were employed to optimize the discontinuous and continuous parameters of the DLLME process, respectively. To validate the performance of GC-NICI-MS after optimized DLLME, pyrethroids in mixed standard solutions at levels ranging from 0.02 to 50.00 µg/L were measured, and the resultant calibration curves were fitted. Adequate linearity was found for the six investigated pyrethroids (r = 0.9908–0.9960). The limits of detection and quantification ranged from 0.005 to 0.035 µg/L and 0.02 to 0.1 µg/L, respectively. The proposed approach simplifies the optimization of parameters compared to reported methods and achieves considerably lower limits of detection. The concept of mixed application based on the dual experimental design method can be applied to other regulated compounds to enhance the safety of agricultural products. The feasibility of the method was confirmed by successfully detecting pyrethroids in 13 types of teas, fruit, and vegetables.

Development of a new method using dispersive liquid-liquid microextraction with hydrophobic natural deep eutectic solvent for the analysis of multiclass emerging contaminants in surface water by liquid chromatography-mass spectrometry.

A new analytical method was developed for the determination of 14 multiclass emerging organic contaminants in surface waters using LC-MS, and Dispersive Liquid-Liquid Microextraction (DLLME) for extraction. Different Natural Deep Eutectic Solvents (NADESs) composed of terpenes and organic acids were tested as extraction solvents and characterized by Fourier Transform Infrared Spectroscopy (FTIR), Hydrogen Nuclear Magnetic Resonance Spectroscopy (1H-NMR), Differential Scanning Calorimetry (DSC), Thermogravimetric Analysis (TGA), density, and viscosity, eliminating the need to use traditional chlorinated solvents. NADES produced with butyric acid and thymol showed the best results and was selected for application for the first time in the extraction of emerging organic contaminants of different classes in water samples. Vortex was used as the dispersion mode, eliminating the use of the dispersion solvent. Chromatographic conditions and sample preparation were optimized using multivariate experimental designs. The optimized chromatographic conditions included the column oven temperature, mobile phase modifiers, and stationary phase type. The optimized conditions for sample preparation included the extraction temperature and pH, salting out effect, and extraction solvent volume. The analytical performance was evaluated through repeatability and intermediate precision tests, with RSD values below 20%, and recoveries between 70 and 120%. The coefficient of determination was greater than 0.98 for all analytes. LOQs varied between 1.5 and 35 μg L-1. DLLME is a simple technique, it does not require expensive and specific equipment. Furthermore, replacing traditional chlorinated solvents with NADES makes the procedure more environmentally friendly. The method presented here can be applied to a wide range of analytes for the analysis of fresh, brackish, and salt waters. Up to the present moment, this is the first study using NADES based thymol and butyric acid for the determination of multiclass emerging contaminants in surface waters samples.

Dispersive Liquid–Liquid Chelate Microextraction of Rare Earth Elements: Optimization and Greenness Evaluation

An ultrasound-assisted dispersive liquid–liquid microextraction (DLLME) method was developed to concentrate and quantify rare earth elements (REEs) (Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu) in acidic aqueous solutions. Tetrachloroethylene (PCE) was used as the diluent, di–(2–ethyl hexyl) phosphoric acid (D2EHPA) as the extracting agent, and acetone as the dispersant solvent. The method was optimized at pH = 2.3, T = 25 °C, and VS = 400 µL of a PCE ÷ D2EHPA mixture (10 ÷ 1) using the response surface methodology (RSM) with a Box–Behnken design. Under optimal conditions, the method proved efficient for the DLLME of most REEs (Y, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu), where the achieved recoveries were in the range of 61–109%, while relative standard deviations were in the range 11–28%. The proposed method was applied to recover REEs from real coal ash leachate samples. A greenness evaluation using the Green Analytical Procedure Index (GAPI), Analytical GREEnness (AGREE), and Analytical Eco-Scale (AES) methodologies revealed acceptable metric scores of 74, 0.61, and 26.6–79.8, respectively.

A comparative study of SPE- and DLLME-based methods for the determination of opioids and benzodiazepines in urine samples using LC-MS/MS

The determination of drugs of abuse has been gaining increasing attention among the scientific community as drug consumption is considered a major global public health issue. Opioids and benzodiazepines are among the most widely consumed drugs worldwide. Analytical methods for their determination, particularly in urine matrices, primarily rely on chromatographic techniques. However, due to the complexity of the matrix and the low concentration levels at which these drugs are usually present (in the ng/L or µg/L range), efficient sample pre-treatment strategies are essential. This step is of significant importance in the development of environmentally friendly analytical methods. For this reason, in recent years, pre-treatment techniques have been developed based on green analytical chemical principles to address this need.In this context, we present a comparative study of solid phase extraction (SPE) and dispersive liquid–liquid microextraction (DLLME) for the determination of a group of benzodiazepines and opioids in urine samples using liquid chromatography coupled with tandem mass spectrometry (LC-MS/MS). The method, based on SPE, was developed using ExtraBond SCX as the sorbent and 7 mL of 5 % of NH4OH in methanol as the elution solvent, yielding recoveries ranging from 9 to 107 %. The DLLME method used 200 µL of chloroform and 500 µL of ethyl acetate as extractant and dispersant solvents, respectively, achieving recoveries between 14 and 86 %. The DLLME strategy proved to be greener than the SPE method in line with the principles of green analytical chemistry (GAC), as it required lower volumes of solvents, a shorter extraction time, and less energy consumption than the SPE method. Both methods were validated using urine matrices and subsequently applied to 11 urine specimens from women participating in detoxification programmes, confirming the suitability of these methods in toxicological and forensic analyses. The results showed that methadone and diazepam were the most frequently determined compounds, and a trend of polyconsumption was observed in most of the samples.

A miniaturized method for HPLC-MS/MS identification of wine markers in figured pottery

The study of Organic Residue Analysis (ORA) in archaeological pottery aims to detect traces of organic materials, such as food and beverages, that were once contained in the vessels. Chemical analysis of organic residues can confirm hypotheses made by archaeologists regarding some important aspects of ancient daily life, from ancient diet to rituals. If non-invasive analytical techniques, such as spectroscopies, could provide issues with overinterpretation of the data, chromatographic techniques combined with various detectors may be more suitable for separating and identifying the different components within a complex matrix, like archaeological pottery. This research aims to develop a new rapid, reproducible and efficient method for the identification of organic acids as wine markers in archaeological figured vessels through HPLC-MS/MS. The procedure included a derivatization step and an extraction step, both designed based on green analytical chemistry principles. It employed ultrasound-assisted liquid extraction and dispersive liquid-liquid microextraction (dLLME). dLLME allowed to remove compounds that induce signal suppression, thereby minimizing the matrix effect. Except for tartaric acid, which had a recovery around 20%, the other analytes had recoveries that ranged from 40% to 60%, while LODs were comprised between 0.01 and 0.05 ng mL−1. This method was applied to examine the potential presence of wine in figural pottery, validating the method on historical samples in the frame of the wide-scope project Imag-ORA.

Development of a new dispersive liquid-liquid microextraction method to ensure the conformity of cachaça for ethyl carbamate by GCxGC/FID

Development of a new dispersive liquid-liquid microextraction method to ensure the conformity of cachaça for ethyl carbamate by GCxGC/FID

Green solvents in dispersive liquid-liquid microextraction for the determination of carbonyl compounds in coffee extracts

Green solvents in dispersive liquid-liquid microextraction for the determination of carbonyl compounds in coffee extracts

Development, optimization and comparison of solid-liquid and liquid-liquid microextraction for the determination of four flavonols in Schinus molle L. using high-performance liquid chromatography coupled with second-order data modeling.

Flavonoids are particularly interesting because they have a broad spectrum of biological effects, including antioxidant and free radical scavenging activities. In this work, solid-liquid microextraction and dispersive liquid-liquid microextraction enhanced by ultrasound were developed and compared with the conventional method (Soxhlet extraction) to optimize the extraction of four flavonoids: rutin, quercitrin, quercetin, and myricetin in samples of Schinus molle (Aguaribay). During the development of the analytical method, different chemometric tools were used to optimize the microextraction procedure. In addition, an analytical method based on high-performance liquid chromatography with diode array detector (HPLC-DAD) and secondorder calibration using multivariate curve resolution-alternating least square (MCR-ALS) is presented to quantify the flavonoids with limits of quantification between 0.011 and 0.082µgmL-1. Finally, solid-liquid microextraction using 4.00mL water/ethanol (54.3:45.7%), 14s vortex, and 45min was selected as the most suitable method due to its high recovery rate and environmental friendliness (with a greenness score of 0.78). After the optimization step, the concentrations found in the plant samples were 1825.3, 632.6, 110.2, and 18.9µgg-1 for rutin, quercitrin, quercetin, and myricetin, respectively. The present work is the first achievement of simultaneously determining these four analytes with exceptional sensitivity, demonstrating lower LOQs compared to previous reports.

Emulsive Liquid-Liquid Microextraction for the Determination of Phthalic Acid Esters in Environmental Water Samples.

A convenient, rapid, and environmentally friendly method, emulsive liquid-liquid microextraction combined with high-performance liquid chromatography, was established to determine phthalic acid esters in tap, river, lake, and sea water. After the method's optimization, we obtained the appropriate volume of the extractant and pure water, the number of strokes, the separation methods, the mass volume fraction of the demulsifier, the demulsifier volume, the sample volume, the salt amount, and the pH conditions. This method requires only 200 μL of heptanoic acid (fatty acid) as the extractant and 75 mg of sodium acetate as demulsifiers for fast microextraction and separation, respectively, avoiding the use of further equipment. Emulsive liquid-liquid microextraction offers substantial advantages over dispersive liquid-liquid microextraction by eliminating the need for toxic dispersants, thereby preventing any influences of dispersants on the partition coefficients. The linear range of detection ranged from 0.5 to 50 μg L-1, with a limit of detection of 0.2 μg L-1 and a limit of quantitation of 0.5 μg L-1. The recoveries ranged from 80.2% to 106.3%, and the relative standard deviations ranged between 0.5% and 6.7%. Five greenness metrics confirmed that this method is environmentally friendly and aligns with the principles of green analytical chemistry. The proposed method achieved a greenness score of 8.42, surpassing that of other methods as evaluated using the SPMS. The novel method may well be a valuable technique for determining phthalic acid esters in water samples.

Recent advances in green solvents-based liquid-phase microextraction techniques for chromatographic analysis of active components in traditional Chinese medicine.

Traditional Chinese medicine (TCM) is a treasure of China and a crucial part of traditional medicine in the world, particularly in many oriental countries. TCM is the core and basis of traditional medicine in clinical practice for numerous diseases, and performs important function in nutraceuticals and dietary supplements. However, it is extremely difficult to extract each active ingredient from TCM to elucidate the mechanism of TCM clinical efficacy due to numerous compounds in TCM, especially trace compounds. Consequently, liquid-phase microextraction (LPME) techniques, one of the main extraction methods of active ingredients in TCM, have attracted a considerable attention from researchers. In recent years, many novel green solvents based-LPME methods have been reported, such as single-drop microextraction (SDME), hollow-fiber liquid-phase microextraction (HF-LPME), dispersive liquid-liquid microextraction (DLLME), and electro-membrane extraction (EME). Therefore, in this review, we present an up-to-date and comprehensive summary of various LPME techniques, novel green solvents, and their applications in the analysis of active ingredients within the complex TCM samples. We provide a detailed overview of the fundamental principles, modes, and the critical process parameters of the LPME techniques. In addition, we compare different types of green solvents (i.e., deep eutectic solvents, ionic liquids, magnetic ionic liquids, supramolecular solvents, switchable solvents, among others), and the advantages and disadvantages of these solvents are critically evaluated, highlighting their suitability for various applications. Finally, we elucidate the merits and demerits of different LPME methods, discuss their practical applications, and explore their future research directions. This review aims to provide a valuable resource for researchers and practitioners in the field of TCM, promoting research development and application of the advanced and environmentally friendly sample pretreatment techniques.

Application of core-shell magnetic metal-organic framework in developing dispersive micro solid phase extraction combined with dispersive liquid-liquid microextraction for the extraction and enrichment of some pesticides in orange blossom, Aloysia Citrodora, and fennel herbal infusions.

This paper introduces an innovative technique for extracting pesticides from herbal infusions using a core-shell magnetic adsorbent (i.e., Cu-BTC@Fe3O4) where achieving a notable enrichment factor for the target pesticides by coupling with a dispersive liquid-liquid microextraction method. To validate the successful synthesis of the adsorbent, a range of analytical techniques were utilized including vibrating sample magnetometer, scanning electron microscopy, transmission electron microscopy, Fourier transform infrared spectroscopy, X-ray diffraction, energy dispersive X-ray, and Brunauer-Emmett-Teller analyses. A vortex agitation and an external magnetic field were used during the extraction process to aid the analytes' desorption and adsorbent separation, respectively. Also, a mixture of iso-propanol and deionized water was used to desorb the analytes from the adsorbent surface. The resulting supernatant containing the desorbed pesticides was mixed with 1,2-dibromoethane as the extraction solvent and then injected into an aqueous medium. After centrifugation, 1 μL of the sedimented phase was introduced into the gas chromatograph system equipped with a flame ionization detector. The reliability of the proposed methodology was confirmed by obtaining low relative standard deviations (1.0-8.5 %), acceptable extraction recoveries (39-93 %), substantial enrichment factors (195-475), calibration curve linearity (r2=0.993-0.998), and significantly low limits of quantification (0.34-3.0 μg L-1) and detection (1.1-9.9 μg L-1). Absence of matrix effects with relative recovery values of 80-120 % for real samples, minimal use of the adsorbent and extraction solvent, a reduction in extraction time due to the elimination of two centrifugation steps (facilitated by an external magnetic field), and the use of environmentally friendly solvents collectively highlight the advantages and significant values of this approach.

Ultrasound-Assisted Extraction Combined with Dispersive Liquid-Liquid Microextraction Using Low-Density Solvent—a Novel Approach to Determine Fenvalerate in Strawberry Samples

Ultrasound-Assisted Extraction Combined with Dispersive Liquid-Liquid Microextraction Using Low-Density Solvent—a Novel Approach to Determine Fenvalerate in Strawberry Samples

Application of deep eutectic solvent based dispersive liquid–liquid microextraction method followed by HPLC-DAD for quantification of selected neonicotinoid pesticides in vegetable oils

The use of deep eutectic solvents (DES) as alternative green solvents in various analytical chemistry fields has garnered attention of researchers globally. Therefore, this study presents environmentally friendly DES for extraction of selected neonicotinoids (acetamiprid, imidacloprid, thiacloprid and thiamethoxam) prior to their determination using high-performance liquid chromatography- diode array detector (HPLC-DAD). The DES mixture that resulted in the highest extraction recoveries of neonicotinoids (NEOs) was choline chloride with ethylene glycol (CCl:EG) and nuclear magnetic resonance and Fourier transform infrared confirmed the successful synthesized CCl:EG. Thereafter, the CCl:EG was applied in dispersive liquid–liquid microextraction (DLLME) for the preconcentration and extraction of acetamiprid, imidacloprid, thiacloprid and thiamethoxam. The optimum factors affecting extraction efficiency of the DES-DLLME procedure were 0.8 mL (DES volume), 4.5 min (extraction time), 0.5 mL (eluent volume), 7 pH and 75 s (eluent time). The optimized DES-DLLME achieved limit of detection (LOD) and quantification (LOD) range of 0.4–4.95 ng.µL−1 and 1.43–9.70 ng.µL−1 respectively. Additionally, the extraction method achieved good accuracy (79.0–119.6 %), preconcentration factors (39.3–118), interday (0.61–1.62 %) and intraday (0.1–0.98 %) precisions. The greenness assessment of the proposed DES-DLLME method using AGREE, NEMI and AES tools revealed that the method was green. Finally, the developed DES-DLLME method was applied to real vegetable oils and the concentrations were below detection limits.

Three sample preparation methods for clinical determination of CDK4/6 inhibitors with endocrine therapy in breast cancer patient plasma using LC-MS: Cross-validation (red), ecological (green) and economical (blue) assessment

Cyclin D-dependent kinase 4/6 inhibitors palbociclib, ribociclib and abemaciclib, in combination with aromatase inhibitors anastrozole and letrozole or oestrogen receptor degrader fulvestrant, are being assessed as candidates for therapeutic drug monitoring. An ideal bioanalytical method for their determination in patient plasma samples is therefore of high interest, as there is no routine reference method yet available in the clinical practice. In this work, three sample preparation approaches – dispersive liquid-liquid microextraction (DLLME), solid-phase extraction (SPE), and newly developed phospholipid removal (PLR) for LC-MS determination of these six drugs are comprehensively assessed. The methods are validated in the clinically relevant linear ranges with remarkable precision (RSD ≤6.9 %) and accuracy (bias −13.6 – 11.8 %). To compare the procedures in a real-world setting, they are applied on 38 samples from breast cancer patients. The differences between paired results are below 20 % for more than 92 % of the repeats and the RSD is ≤13.1 % between the corresponding results. Statistical comparison of the results reveals excellent overall agreement between the methods (Lin’s concordance correlation coefficient ≥0.9969, maximal Bland-Altman bias 6.3 %). DLLME proved to be the most ecologically acceptable method due to the high degree of miniaturisation (AGREEprep score 0.44), PLR enabled very high sample throughput and cost-effectiveness (BAGI 72.5), while SPE showed the best analytical performance (redness score 100). All three methods are suitable for their designated purpose, and the choice of the ideal method can be made based on the scope of application, available funds and equipment and desired ecological footprint.

Assessment of Lipid Peroxidation Products in Adult Formulas: GC-MS Determination of Carbonyl and Volatile Compounds Under Different Storage Conditions.

The occurrence of carbonyl compounds and volatile organic compounds (VOCs) in adult formulas is a critical issue in product safety and quality. This research manuscript reports the determination of targeted and untargeted carbonyl compounds and VOCs in adult formulas stored at different temperatures (room temperature, 4 °C, and 60 °C) over one month. Gas chromatography-mass spectrometry was utilized for the sample analysis. Ultrasound-assisted dispersive liquid-liquid microextraction at 60 °C for 20 min facilitated the extraction of six carbonyl compounds, while headspace solid-phase microextraction (HS-SPME) was employed for the determination of untargeted VOCs using a DVB/CAR/PDMS fiber, involving 15 min of equilibration and 45 min of extraction at 40 °C with magnetic stirring. Analytical features of the methods were assessed according to Food and Drug Administration guidelines, and good limits of detection and quantitation, linearity, accuracy, and precision were achieved. Notably, the highest levels of carbonyl compounds were found in high-protein formulas, with quantifiable levels of malondialdehyde, acrolein, and formaldehyde detected and quantified in 80% of samples. Additionally, significant levels of VOCs such as hexanal and 2-heptanone were found in samples stored at elevated temperatures. These findings suggest the importance of protein content and storage conditions in the levels of carbonyl compounds and VOCs found in adult formulas, with implications for consumer safety and quality control.