Advances and Applications of Hybrid Graphene-Based Materials as Sorbents for Solid Phase Microextraction Techniques.

The advancement of traditional sample preparation techniques has brought about miniaturization systems designed to scale down conventional methods and advocate for environmentally friendly analytical approaches. Although often referred to as green analytical strategies, the effectiveness of these methods is intricately linked to the properties of the sorbent utilized. Moreover, to fully embrace implementing these methods, it is crucial to innovate and develop new sorbent or solid phases that enhance the adaptability of miniaturized techniques across various matrices and analytes. Graphene-based materials exhibit remarkable versatility and modification potential, making them ideal sorbents for miniaturized strategies due to their high surface area and functional groups. Their notable adsorption capability and alignment with green synthesis approaches, such as bio-based graphene materials, enable the use of less sorbent and the creation of biodegradable materials, enhancing their eco-friendly aspects towards green analytical practices. Therefore, this study provides an overview of different types of hybrid graphene-based materials as well as their applications in crucial miniaturized techniques, focusing on offline methodologies such as stir bar sorptive extraction (SBSE), microextraction by packed sorbent (MEPS), pipette-tip solid-phase extraction (PT-SPE), disposable pipette extraction (DPX), dispersive micro-solid-phase extraction (d-µ-SPE), and magnetic solid-phase extraction (MSPE).

Curry-Odorants and Their Metabolites Transfer into Human Milk and Urine.

SCOPE: The excretion of dietary odorants into urine and milk is evaluated and the impact of possible influencing factors determined. Furthermore, the metabolic relevance of conjugates for the excretion into milk is investigated. METHODS AND RESULTS: Lactating mothers (n = 20) are given a standardized curry dish and donated one milk and urine sample each before and 1, 2, 3, 4.5, 6, and 8 h after the intervention. The concentrations of nine target odorants in these samples are determined. A significant transition is observed for linalool into milk, as well as for linalool, cuminaldehyde, cinnamaldehyde, and eugenol into urine. Maximum concentrations are reached within 1 h after the intervention in the case of milk and within 2-3 h in the case of urine. In addition, the impact of glucuronidase treatment on odorant concentrations is evaluated in a sample subset of twelve mothers. Linalool, eugenol, and vanillin concentrations increased 3-77-fold in milk samples after treatment with ß-glucuronidase. CONCLUSION: The transfer profiles of odorants into milk and urine differ qualitatively, quantitatively, and in temporal aspects. More substances are transferred into urine and the transfer needs a longer period compared with milk. Phase II metabolites are transferred into urine and milk.

Covalent organic framework/layered double hydroxide composite-coated poly(ether ether ketone) jacket for stir bar sorptive extraction of Sudan dyes.

A novel coating for stir bar sorptive extraction was developed by growing a covalent organic framework, TpPa-1 (derived from phenylenediamine and 1,3,5-trimethylphloroglucinol), onto the surface of Ni-Al layered double hydroxide. Using a poly(ether ether ketone) tube as the supporting substrate, a TpPa-1/layered double hydroxide-coated stir bar was fabricated and demonstrated excellent extraction performance for Sudan dyes. Notably, its extraction efficiency significantly exceeded that of stir bars modified with only TpPa-1 or Ni-Al layered double hydroxide. Based on this innovative coating, a stir bar sorptive extraction-high performance liquid chromatography method was established. This method exhibited low limits of detection (0.04-0.08 ng/mL) for the analysis of Sudan dyes. It also featured a wide linear range (0.25-100 or 200 ng/mL) and demonstrated good repeatability with relative standard deviations ≤6.22%. The recoveries obtained for spiked lake water and chili powder samples were 93.5%-105.2% and 87.8%-100.6%, respectively, demonstrating the practical potential of the developed method for detecting trace Sudan dyes in real samples.

Determination of breast cancer biomarkers with poly acrylic acid/ MIL-88(Fe)-NH2 hydrogel as a coating for stir bar sorptive extraction.

The Poly acrylic acid/MIL-88(Fe)-NH2 composite material, carefully prepared, is employed as a sorbent for the stir bar. The best formula of the composite was selected by investigation of two parameters including the cross-linker of PAA and MIL-88(Fe)-NH2 content. The prepared stir bar was used for extraction of 2-pentanone, 2-heptanone, ethyl propionate, para-xylene, 1,2,4-trimethylbenzene, o-cresol, m-cresol in urine samples as breast cancer biomarkers with gas chromatography-flame ionization detector. The prepared Poly acrylic acid / MIL-88(Fe)-NH2 as sorbent for the stir bar demonstrate good repeatability of one bar (relative standard deviation (RSD%) < 4.61 %) and satisfactory reproducibility between two bars (RSD% < 6.85 %). The central composite design method was applied for the optimization of extraction parameters. Under the optimum conditions, linear dynamic ranges for compounds were in the acceptable range with correlation coefficients higher than 0.99. Detection limits of them were less than 1.71 µg L-1.

Mycotoxins-Imprinted Polymers: A State-of-the-Art Review.

Mycotoxins are toxic metabolites of molds which can contaminate food and beverages. Because of their acute and chronic toxicity, they can have harmful effects when ingested or inhaled, posing severe risks to human health. Contemporary analytical methods have the sensitivity required for contamination detection and quantification, but the direct application of these methods on real samples is not straightforward because of matrix complexity, and clean-up and preconcentration steps are needed, more and more requiring the application of highly selective solid-phase extraction materials. Molecularly imprinted polymers (MIPs) are artificial receptors mimicking the natural antibodies that are increasingly being used as a solid phase in extraction methods where selectivity towards target analytes is mandatory. In this review, the state-of-the-art about molecularly imprinted polymers as solid-phase extraction materials in mycotoxin contamination analysis will be discussed, with particular attention paid to the use of mimic molecules in the synthesis of mycotoxin-imprinted materials, to the application of these materials to food real samples, and to the development of advanced extraction methods involving molecular imprinting technology.

Effects of gallic acid on the release of aroma compounds in Moutai Baijiu.

Due to the trace concentrations of gallic acid (GA), the interaction mechanism between GA and flavor compounds is limited, and the effects on the aroma compounds of Moutai Baijiu are even more unclear. In this study, the aroma compounds and phenolic compounds in Moutai Baijiu were investigated by stir bar sorptive extraction (SBSE), gas chromatography-olfactometry (GC-O), gas chromatography-mass spectrometry (GC-MS) and liquid chromatography-mass spectrometry (LC-MS). A total of 63 volatiles and 10 phenolic compounds were identified, and 16 esters and 4 alcohols were identified as the important aroma substances (odor activity values ≥1). The effect of GA on the release of aroma compounds was investigated by sensory analysis and partition coefficient. The results showed that GA mainly inhibited the volatilization of alcohols, low concentrations of GA promoted the release of esters, and high concentrations slowed down or even inhibited the release effect affected by the hydrophobicity of aroma compounds. UV spectroscopy and thermodynamic analysis further revealed that the interaction of GA with 1-propanol was attributed mainly to hydrogen bonding and van der Waals forces, and the interaction with other compounds was mainly influenced by hydrophobic effects. These results show that gallic acid can effectively control the release of the aromas of Moutai Baijiu, highlight the important role of GA on the volatiles of baijiu, and provide theoretical support for further healthy improvement of the sensory quality of baijiu.

A two-run heart-cut multidimensional gas chromatography method using flame ionization and mass spectrometry for automated and robust determination of nearly complete wine aroma-volatile profiles.

A quantitative analytical method capable of determining the concentrations of 81 aroma-relevant wine volatiles covering nine orders of magnitude was developed and validated in this study. The method is based on stir bar sorptive extraction (SBSE) of 200 µL of wine diluted with 1.8 mL NaCl brine with pH 3.5. Volatiles thermally desorbed from the stir bars were separated in two runs in a heart-cut multidimensional gas chromatographic system and quantified using either a flame ionization detector (FID) in the first dimension (27 aroma compounds) or a mass spectrometer in the second dimension (54 aroma compounds, transferred to 22 cuts). Typical limits of compound detection lay around 0.02 mg/L by FID or ranged from 0.001 to 0.30 µg/L by mass spectrometry detector, liying below the corresponding odor thresholds in all cases. Linearity, reproducibility, and recovery were considered satisfactory for most compounds, with typical R2 values of 0.989-0.999, relative standard deviation below 10 % for 37 compounds and between 10 and 20 % for 44 compounds, and recovery rates of approximately 100 % (85-109 %) for all but acetaldehyde. An analysis of 20 wine samples completed our validation of the method, showing that a single-sample preparation procedure combined with heart-cut multidimensional two-detector gas chromatography can determine wine volatile concentrations ranging from 350 mg/L of isoamyl alcohol to 3.8 ng/L of 3-isobutyl-2-methoxypyrazine.

Determination of parabens in breast milk using stir bar sorptive extraction coupled with UHPLC-UV.

We developed an analytical method based on ultra-high performance liquid chromatography with UV detection, using a stir bar coated with amino/hydroxyl bifunctional microporous organic network (B-MON), for the analysis of parabens in breast milk samples. B-MON demonstrated superior performance with maximal methylparaben adsorption of 112.15 mg/g. Kinetic fitting revealed that outer diffusion was the key limiting step, and the adsorption was chemisorption. The thermodynamic analysis demonstrated that increased methylparaben adsorption was found at higher temperatures in spontaneous processes. The developed approach showed excellent linearity (R2 ≥ 0.9964) and a low detection limit (0.01 µg/L). Recoveries ranged from 85.8 to 105.5 % and the relative standard deviation was lower than 9.2 %. Based on the daily exposure assessment, these pollutants do not pose unacceptable health hazards to babies. However, the high detection frequencies (41.9%-93.5 %) suggest that breast milk still should be monitored.

Headspace stir-bar sorptive extraction combined with gas chromatography-mass spectrometry for trace analysis of volatile organic compounds in Schisandra chinensis Baillon (omija).

Analyzing volatile organic compounds (VOCs) in food is crucial but challenging. Schisandra chinensis Baillon (omija) is an herbal plant with various functional health activities. Previous VOC analyses focused on S. chinensis fruit but not its leaves. Therefore, VOCs in S. chinensis fruit and leaves were analyzed using headspace stir-bar sorptive extraction (HS-SBSE)-GC-MS, and optimal conditions were established. Various factors, such as the sample preparation method, twister stir-bar type, sample amount, extraction temperature, and extraction time, expected to affect extraction were carefully optimized. Under the optimal conditions, 35 and 40 VOCs were identified in S. chinensis fruit and leaves, respectively. This HS-SBSE method is capable of rapid analysis and a low contamination rate without requiring organic solvents. These findings provide practical guidelines for HS-SBSE applications in various food matrices by providing analytical methods for VOC detection.

Method development of stir bar sportive extraction coupled with thermal desorption-gas chromatography-mass spectrometry for the analysis of phthalates in Peruvian pisco.

In this work, for the first time, a stir bar sorptive extraction (SBSE) coupled with thermal desorption-gas chromatography-mass spectrometry (TD-GC-MS) was developed and validated for the determination of seven phthalates in Peruvian pisco. The phthalate compounds considered were dimethyl phthalate (DMP), diethyl phthalate (DEP), bis(2-ethylhexyl) hexahydrophthalate (BEHP), benzyl butyl phthalate (BBP), di-n-butyl phthalate (DBP), di-isodecyl phthalate (DIDP) and di-isobutyl phthalate (DIBP). The best overall analytical conditions obtained from the optimization were as follow: extraction time of 120 min, size of polydimethylsiloxane (PDMS) twister (20 mm length x 1 mm thickness), NaCl content (20 %) and sample volume (40 mL). The in-house validation of SBSE/TD-GC-MS method was performed taking into account the ISO/IEC 17,025 requirements and EURACHEM/CITAC guideline. Under optimal conditions, very low limits of detection of 1.3-0.21 µg L-1 were obtained. Furthermore, the limits of quantification ranged from 4.2-70 µg L-1, and the correlation coefficients were found to be ≥ 0.991. The method was precise, with relative standard deviations (RSD, %) for inter twister repeatability and the inter day repeatability precisions from 1.1 to 11 and from 6.2 to 15.9, respectively. The pisco samples were analysed with recoveries between 91-124.4%, and DBP, BEHP, and BBP were the most commonly found compounds in the samples. The optimized methodology was also evaluated in terms of green character, and it obtained almost the best AGREE score when it was compared with other previous methods for the analysis of phthalates in alcoholic beverages. Therefore, the SBSE/TD-GC-MS method has proved to be suitable for routine practice because it is simple, less laborious, economical, precise, accurate and green, and it would be applicable for pisco safety regulations.

Unveiling the Aromas and Sensory Evaluation of Hakko Sobacha: A New Functional Non-Dairy Probiotic Fermented Drink.

At the dawn of a food transition encouraging the consumption of healthy and sustainable non-dairy probiotic products, the development of a fermented functional drink based on Sobacha is considered. Sobacha is an infusion of roasted buckwheat seeds widely consumed in Asian countries for its health benefits. As fermentation improves the nutritional and organoleptic status of grains, the mixed fermentation process involved in the development of kombucha beverages (fermented sweet tea) is conducted by inoculating a symbiotic culture of bacteria and yeasts into the transposable matrix (Sobacha instead of tea). Sobacha, a healthy pseudo-cereal matrix with promising aromas, could be fermented to potentially develop an innovative drink, named "Hakko Sobacha". This neologism would reveal the fermented character of the infusion, Hakko meaning fermented in Japanese. Considering the beverage characterization, the kinetics of the volatile organic compound syntheses were determined using stir-bar sorptive extraction followed by gas chromatography coupled to mass spectrometry analysis. Odor-active compounds were theoretically calculated to estimate the flavor composition. Finally, sensory analyses highlighted the appreciation and preferences of the consumer towards the beverages. The fermentative yield differences observed between the two buckwheat concentration modalities tested seemed to be correlated with the sugar and nutrient levels available from the starch (buckwheat) matrix. Having characterized Hakko Sobacha, this study proposed the possibility of developing new beverages by monitoring the fermentative process. This should enable improved control and enhancement of their sensorial properties, which could in turn lead to greater customer acceptability.

Rapid, efficient, and green analytical technique for determination of fluorotelomer alcohol in water by stir bar sorptive extraction.

Fluorotelomer alcohols (FTOHs) are one of the major classes of per- and polyfluoroalkyl substances (PFAS). Due to their potential toxicity, persistence, and ubiquitous presence in the environment, some common PFAS are voluntarily phased out; while FTOHs are used as alternatives to conventional PFAS. FTOHs are precursors of perfluorocarboxylic acids (PFCAs) and therefore they are commonly detected in water matrices, which eventually indicate PFAS contamination in drinking water supplies and thus a potential source of human exposure. Even though studies have been conducted nationwide to evaluate the degree of FTOHs in the water environment, robust monitoring is lacking because of the unavailability of simple and sustainable analytical extraction and detection methods. To fill the gap, we developed and validated a simple, rapid, minimal solvent use, no clean-up, and sensitive method for the determination of FTOHs in water by stir bar sorptive extraction (SBSE) coupled with thermal desorption-gas chromatography-mass spectrometry (TD-GC-MS). Three commonly detected FTOHs (6:2 FTOH, 8:2 FTOH, and 10:2 FTOH) were selected as the model compounds. Factors such as extraction time, stirring speed, solvent composition, salt addition, and pH were investigated to achieve optimal extraction efficiency. This "green chemistry" based extraction provided good sensitivity and precision with low method limits of detection ranging from 2.16 ng/L to 16.7 ng/L and with an extraction recovery ranging 55%-111%. The developed method were tested on tap water, brackish water, and wastewater influent and effluent. 6:2 FTOH and 8:2 FTOH were detected in two wastewater samples at 78.0 and 34.8 ng/L, respectively. This optimized SBSE-TD-GC-MS method will be a valuable alternative to investigate FTOHs in water matrices.

Optimization of thermal desorption conditions of stir bar sorptive extraction facilitated by machine learning.

Stir bar sorptive extraction is an effective technique for trapping odorants, but there are limited studies on the effect of varying thermal desorption conditions on desorption efficiency of odorants. Therefore, we conducted this study to explore the relationship between desorption conditions and desorption efficiency for 18 odorants with diverse physicochemical properties using instrumental analysis and mathematical modeling. We trained four types of machine learning models using a dataset comprising 864 different combinations of four desorption conditions (each three levels) and physicochemical properties. The prediction value of the selected model was validated using a validation dataset of six new odorants. The Random Forest model had the highest performance (R = 0.910). The order of feature importance using this model was as follows: cryo-focusing temperature, molecular weight, log P, boiling point, desorption temperature, desorption time, and helium flow. For testing on new odorants, the correlations between predicted and experimental data for terpene (R = 0.99), alcohol (R = 0.98), ester (R = 0.92), sulfide (R = 0.89), phenol (R = 0.88), and aldehyde (R = 0.61) were determined.

Stir-bar sorptive extraction based on hydroxyl-functionalized zirconium-metal-organic framework for the detection of three quinolones in actual samples.

A novel analytical method based on stir-bar sorptive extraction was proposed for the determination of three trace quinolones in fish and shrimp samples. UiO-66-(OH)2 , a hydroxyl-functionalized zirconium metal-organic framework, has been coated on frosted glass rods by an in situ growth method. The product, UiO-66-(OH)2 modified frosted glass rods, has been characterized and key parameters have been optimized in combination with ultra-high-performance liquid chromatography. The detection limits of enoxacin, norfloxacin, and ciprofloxacin were 0.48-0.8 ng ml-1 , and the detection concentrations were in the range of 10-300 ng ml-1 , showing a good linear relationship. This method was used for the determination of three quinolones in aquatic organisms, and the recoveries in spiked fish and shrimp muscle tissue samples were 74.8%-105.4% and 82.5%-115.8%, respectively. The relative standard deviations were less than 6.9%. The established method combined stir-bar sorptive extraction based on UiO-66-(OH)2 modified frosted glass rods with ultra-high-performance liquid chromatography, has good application prospects for the detection of quinolone residues in fish and shrimp muscle samples.

Characterization of Aroma Active Compound Production during Kombucha Fermentation: Towards the Control of Sensory Profiles.

Since the sensorial profile is the cornerstone for the development of kombucha as a beverage with mass market appeal, advanced analytical tools are needed to gain a better understanding of the kinetics of aromatic compounds during the fermentation process to control the sensory profiles of the drink. The kinetics of volatile organic compounds (VOCs) was determined using stir bar sorptive extraction-gas chromatography-mass spectrometry, and odor-active compounds were considered to estimate consumer perception. A total of 87 VOCs were detected in kombucha during the fermentation stages. The synthesis of mainly phenethyl alcohol and isoamyl alcohol probably by Saccharomyces genus led to ester formation. Moreover, the terpene synthesis occurring at the beginning of fermentation (Δ-3-carene, α-phellandrene, γ-terpinene, m- and p-cymene) could be related to yeast activity as well. Principal component analysis identified classes that allowed the major variability explanation, which are carboxylic acids, alcohols, and terpenes. The aromatic analysis accounted for 17 aroma-active compounds. These changes in the evolution of VOCs led to flavor variations: from citrus-floral-sweet notes (geraniol and linalool domination), and fermentation brought intense citrus-herbal-lavender-bergamot notes (α-farnesene). Finally, sweet-floral-bready-honey notes dominated the kombucha flavor (2-phenylethanol). As this study allowed to estimate kombucha sensory profiles, an insight for the development of new drinks by controlling the fermentation process was suggested. Such a methodology should allow a better control and optimization of their sensory profile, which could in turn lead to greater consumer acceptance.

A high-throughput analysis of volatile compounds with various polarities using headspace stir bar sorptive extraction.

Long sample extraction time is usually necessary in the analysis of volatile flavour compounds to achieve high extraction efficiency. However, the long extraction time reduces sample throughput, which results in waste of labour and energy. Therefore, in this study, an improved headspace-stir bar sorptive extraction was developed to extract volatile compounds with varying polarities in a short time. With the aim of achieving high throughput, extraction conditions were selected and optimised based on the combinations of different extraction temperatures (80-160 °C), extraction times (1-61 min), and sample volumes (50-850 µL) through the response surface methodology with Box-Behnken design. After obtaining the preliminary optimal conditions (160 °C, 25 min, and 850 µL), the effect of cold stir bars with shorter extraction time on the extraction efficiency was evaluated. The cold stir bar improved the overall extraction efficiency with better repeatability, and the extraction time was further shortened to 1 min. Then, the effects of different ethanol concentrations and salt additions (sodium chloride or sodium sulfate) were studied, and 10% ethanol concentration with no salt addition provided the highest extraction efficiency for most compounds. Finally, it was verified that the high-throughput extraction condition was feasible for the volatile compounds spiked in a honeybush infusion.

A Schiff base networks coated stir bar for sorptive extraction of pyrethroid pesticide residues in tobacco.

Schiff base networks (SNWs) were introduced as a new stir bar coating, and a method of SNWs- coated stir bar sorptive extraction (SBSE) coupled to high performance liquid chromatography-ultraviolet detector (HPLC-UV) was developed for determination of pyrethroid pesticide residues in tobacco. The prepared amorphous SNWs polymer from melamine and 3,5-dihydroxybenzaldehyde riches in triazine rings, hydroxyl groups and amino groups, and the SNWs/polydimethylsiloxane (PDMS) stir bar prepared by sol-gel method can extract weakly polar pyrethroid pesticides through hydrophobic, π-π and hydrogen bonding. The SNWs/PDMS stir bar exhibited high extraction efficiency toward pyrethroid pesticides (70-76%) and good mechanical stability with reused time more than 50 times. Under the optimal experimental conditions, the limits of detection were 0.20 - 0.66 µg/L with relative standard deviation varying in the range of 2.3-8.2%, which meets the requirements of trace analysis of pesticide residues in the tobacco industry. The method was applied to the determination of six pyrethroid pesticides in cigarette samples, and the recovery for the spiked samples ranged from 82 to 117%, showing a great applicability for the analysis of pesticide residues in real samples with a complex sample matrix.

Porous aromatic framework/polydimethylsiloxane coated stir bar sorptive extraction coupled with high performance liquid chromatography-diode array detection of trace polychlorinated biphenyls analysis in environmental waters.

A porous aromatic framework (PAF-47) synthesized through Suzuki coupling reaction was introduced to prepare PAF-47/polydimethylsiloxane (PDMS) coated stir bar by sol-gel technique. PAF-47/PDMS coating provided high extraction recovery (77.6-90.6%, the ratio of actual enrichment factor (EF) to theoretical EF) for five polychlorinated biphenyls (PCBs) in a relatively short time (60 min), exhibiting a faster extraction kinetics over commercial PDMS coating (12/24 h). Based on this, a new method based on PAF-47/PDMS coated stir bar sorptive extraction and high-performance liquid chromatography-diode array detection was proposed for trace analysis of target PCBs in environmental water. Under the optimized conditions, the limits of detection for five PCBs were within 44-70 ng/L, with actual EF of 64.0-71.5-fold (maximal EF of 83.3-fold). This method was successfully used to detect trace PCBs in Yangtze River water and East Lake water, with recoveries of 81.0-113% and 86.1-111%, respectively.

Characterization of aroma compounds and effects of amino acids on the release of esters in Laimao baijiu.

BACKGROUND: Laimao baijiu is a typical soy-sauce aroma-type baijiu in China. Amino acids are non-volatile compounds in baijiu and are beneficial to human health. Aroma is one of the important indicators that are used to evaluate the quality of baijiu. The interaction between aroma-active compounds and non-volatile compounds can also affect the release of aroma compounds. In this study, we identified the active-aroma compounds and amino acids in Laimao baijiu by stir bar sorptive extraction (SBSE), gas chromatography-olfactometry (GC-O), gas chromatography-mass spectrometry (GC-MS), and ultra-performance liquid chromatography-mass spectrometry (UPLC-MS). The interaction between amino acids and key esters was investigated by sensory analysis and partition coefficients. RESULTS: A total of 63 aroma compounds and 21 amino acids were identified. Twenty-one esters were identified from them as major aroma-active ester compounds with odor activity values ≥ 1. Finally, sensory analysis revealed that l-alanine had a significant effect on the strength of the aromas of esters, suggesting that low concentrations of amino acids were more likely to promote the release of esters and high concentrations were more likely to inhibit this. The partition coefficient can be a good explanation for this phenomenon. CONCLUSION: l-Alanine can significantly affect the aroma intensity of key ester aroma compounds in Laimao baijiu, and the effects of different concentrations of amino acids are different. This work shows that amino acids, as non-volatile compounds, have a regulatory effect on the release of aroma compounds in alcoholic beverages, which may provide new technical support for the aroma modulation of alcoholic beverages. © 2022 Society of Chemical Industry.

Solvent-assisted stir bar sorptive extraction and gas chromatography-mass spectrometry with simultaneous olfactometry for the characterization of aroma compounds in Japanese Yamahai-brewed sake.

Yamahai-brewed sake, a Japanese alcoholic beverage brewed from rice and produced via natural lactic acid fermentation, has a complex and rich flavor compared with Sokujo-brewed sake, brewed with a general method using pure lactic acid. This study aimed to characterize the aroma compounds in Yamahai-brewed sake using solvent-assisted stir bar sorptive extraction (SA-SBSE) with gas chromatography-olfactometry/mass spectrometry (GC-O/MS) and to confirm the enhanced sensitivity of GC-O/MS with SA-SBSE compared with SBSE alone. SA-SBSE with GC-O/MS increased the number of detected odor-active compounds and improved the FD factor sensitivity of Yamahai-brewed sake. SA-SBSE-GC-MS analysis of three pairs of Yamahai-brewed and Sokujo-brewed sake showed higher polar aroma compound content in Yamahai-brewed sake with a low rice polishing ratio. Quantification of 11 characteristic aroma compounds with a wide range of log Kow values revealed that several compounds, including ethyl mandelate, ethyl 2-hydroxy-4-methylvalerate, and the newly identified γ-6-(Z)-dodecenolactone, were more abundant in Yamahai-brewed sake.