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).

Water as a green solvent for sustainable sample preparation: single drop microextraction of N-nitrosamines from losartan tablets.

Water, renowned for its sustainability and minimal toxicity, is an ideal candidate for environmentally friendly solvent-based microextraction. However, its potential as an extractant solvent in miniaturized sample preparation remains largely unexplored. This paper pioneers using water as the extraction solvent in headspace single-drop microextraction (HS-SDME) for N-nitrosamines from losartan tablets. Autonomous HS-SDME is executed by an Arduino-controlled, lab-made Cartesian robot, using water for the online preconcentration of enriched extracts through direct injection into a column-switching system. Critical experimental parameters influencing HS-SDME performance are systematically explored through univariate and multivariate experiments. While most previously reported methods for determining N-nitrosamines in pharmaceutical formulations rely on highly selective mass spectrometry detection techniques to handle the strong matrix effects typical of pharmaceutical samples, the water-based HS-SDME method efficiently eliminates the interfering effects of a large amount of the pharmaceutical active ingredient and tablet excipients, allowing straightforward analysis using high-performance liquid chromatography with ultraviolet detection (HPLC-UV-Vis). Under optimized conditions, the developed method exhibits linear responses from 100 to 2400 ng g-1, demonstrating appropriate detectability, precision, and accuracy for the proposed application. Additionally, the environmental sustainability of the method is assessed using the AGREEprep methodology, positioning it as an outstanding green alternative for determining hazardous contaminants in pharmaceutical products.

Development of a dispersive solid phase microextraction method based on the application of MgAl, NiAl, and CoAl-layered double hydroxides for the efficient removal of α- and ß-naphthol isomers from water samples by capillary electrophoresis.

The present work describes a quick, simple, and efficient method based on the use of layered double hydroxides (LDH) coupled to dispersive solid phase micro-extraction (DSPME) to remove α-naphthol (α-NAP) and ß-naphthol (ß-NAP) isomers from water samples. Three different LDHs (MgAl-LDH, NiAl-LDH, and CoAl-LDH) were used to study how the interlayer anion and molar ratio affected the removal performance. The critical factors in the DSPME procedure (pH, LDH amount, contact time) were optimized by the univariate method under the optimal conditions: pH, 4-8; LDH amount, 5 mg; and contact time, 2.5 min. The method can be successfully applied in real sample waters, removing NAP isomers even in ultra-trace concentrations. The large volume sample stacking (LVSS-CE) technique provides limits of detections (LODs) of 5.52 µg/L and 6.36 µg/L for α-naphthol and ß-naphthol, respectively. The methodology's precision was evaluated on intra- and inter-day repeatability, with %RSD less than 10% in all cases. The MgAl/Cl--LDH selectivity was tested in the presence of phenol and bisphenol A, with a removal rate of >92.80%. The elution tests suggest that the LDH MgAl/Cl--LDH could be suitable for pre-concentration of α-naphthol and ß-naphthol in future works.

Analysis of chlordecone and its transformation products in environmental waters by a new SPME-GC-MS method and comparison with LLE-GC-MS/MS and LLE-LC-MS/MS: A case study in the French West Indies.

Among the numerous organochlorines (OCs) applied in the French West Indies (FWI), chlordecone (hydrated form C10Cl10O2H2; CLD) still causes major environmental pollution nowadays. A recent report revealed the unexpected presence in FWI environment of transformation products (TPs) of CLD not routinely monitored due to a lack of commercial standards. Here, we present a method for surface waters and groundwaters to analyze CLD, its main TPs (hydroCLDs, chlordecol (CLDOH), 10-monohydroCLDOH and polychloroindenes) and other OCs. We developed an SPME-GC-SIM/MS method with a PDMS-DVB fiber. Since CLDOH-d commonly used as internal standard (IS) proved unsuitable, we synthesized several IS candidates, and finally identified 10-monohydro-5-methyl-chlordecol as a satisfactory IS for CLDOH and 10-monohydroCLDOH avoiding the use of 13C-labelled analogue. LODs for CLD and its TPs varied from 0.3 to 10 ng/L, equal to or below LODs of the two laboratories, BRGM (the French geological survey) and LDA26 (one of the French Departmental Analytical Laboratories), requested in FWI pollution monitoring that used liquid-liquid extractions and advanced facilities (LLE-GC-MS/MS and LLE-LC-MS/MS methods, respectively). Then, we extended the multi-residue method to 30 OCs (CLD and its TPs, mirex, ß-HCH, lindane, dieldrin, aldrin, HCB, hexachlorobutadiene, TCE, PCE) and applied it to 30 surface and ground waters from FWI. While CLD, 8- and 10-monohydroCLD, CLDOH, 10-monohydroCLDOH, dieldrin, and ß-HCH were detected and quantified, pentachloroindene, another CLD TP, was sporadically found in trace levels. A comparison with BRGM and LDA26 confirmed the interest of the SPME method. Results suggested an underestimation of CLDOH and an overestimation of high CLD concentrations with one of the currently used routine protocol. In light of these findings, previous temporal monitoring of environmental waters in FWI were re-examined and revealed some atypical values, which may indeed be due to analytical bias. These discrepancies call for intensified efforts to reliably quantify CLD and its TPs.

A novel honeycomb-like 3D-printed device for rotating-disk sorptive extraction of organochlorine and organophosphorus pesticides from environmental water samples.

In this study, 3D-printing based on fused-deposition modeling (FDM) was employed as simple and cost-effective strategy to fabricate a novel format of rotating-disk sorptive devices. As proof-of-concept, twenty organochlorine and organophosphorus pesticides were determined in water samples through rotating-disk sorptive extraction (RDSE) using honeycomb-like 3D-printed disks followed by gas chromatography coupled to mass spectrometry (GC-MS). The devices that exhibited the best performance were comprised of polyamide + 15 % carbon fiber (PA + 15 % C) with the morphology being evaluated through X-ray microtomography. The optimized extraction conditions consisted of 120 min of extraction using 20 mL of sample at stirring speed of 1100 rpm. Additionally, liquid desorption using 800 µL of acetonitrile for 25 min at stirring speed of 1100 rpm provided the best response. Importantly, the methodology also exhibited high throughput since an extraction/desorption platform that permitted up to fifteen simultaneous extractions was employed. The method was validated, providing coefficients of determination higher than 0.9706 for all analytes; limits of detection (LODs) and limits of quantification (LOQs) ranged from 0.15 to 3.03 µg L-1 and from 0.5 to 10.0 µg L-1, respectively. Intraday precision ranged from 4.01 to 18.73 %, and interday precision varied from 4.83 to 20.00 %. Accuracy was examined through relative recoveries and ranged from 73.29 to 121.51 %. This method was successfully applied to analyze nine groundwater samples from monitoring wells of gas stations in São Paulo. Moreover, the greenness was assessed through AGREEprep metrics, and an overall score of 0.69 was obtained indicating that the method proposed can be considered sustainable.

Deep eutectic solvents as a green alternative for trace element analysis in food and beverage samples: Recent advances and challenges.

Metals and metalloids have different effects on human health even at trace levels. Some of them are essential for living organisms while others can be toxic. Therefore, the determination of trace elements in food and beverage is highly important to understand their impact in human health. A new generation of solvents named deep eutectic solvents (DES) has emerged as a green alternative for trace element analysis, owing to their low toxicity, biodegradability, and high extraction capacity. In recent years, the application of DES in extraction techniques for trace element analysis in food and beverage samples has increased significantly. This review summarizes recent advances and challenges on the application of DES to develop microextraction techniques useful for the analysis of samples with complex matrices. The importance of the use of biodegradable substances instead of classic organic solvents, which are toxic, volatile, and flammable in methods for elemental analysis with a positive environmental impact is also highlighted. Finally, conclusions and future challenges arising from the use of DES in microextraction techniques are discussed.

Solid-phase microextraction coupled to comprehensive multidimensional gas chromatography for food analysis.

Solid-phase microextraction and comprehensive multidimensional gas chromatography represent two milestone innovations that occurred in the field of separation science in the 1990s. They have a common root in their introduction and have found a perfect coupling in their evolution and applications. This review will focus on food analysis, where the paradigm has changed significantly over time, moving from a targeted analysis, focusing on a limited number of analytes at the time, to a more holistic approach for assessing quality in a larger sense. Indeed, not only some major markers or contaminants are considered, but a large variety of compounds and their possible interaction, giving rise to the field of foodomics. In order to obtain such detailed information and to answer more sophisticated questions related to food quality and authenticity, the use of SPME-GC × GC-MS has become essential for the comprehensive analysis of volatile and semi-volatile analytes. This article provides a critical review of the various applications of SPME-GC × GC in food analysis, emphasizing the crucial role this coupling plays in this field. Additionally, this review dwells on the importance of appropriate data treatment to fully harness the results obtained to draw accurate and meaningful conclusions.

Green analytical toxicology method for determination of synthetic cathinones in oral fluid samples by microextraction by packed sorbent and liquid chromatography-tandem mass spectrometry.

PURPOSE: We developed and validated a method for quantitative analysis of ten synthetic cathinones in oral fluid (OF) samples, using microextraction by packed sorbent (MEPS) for sample preparation followed by liquid chromatography‒tandem mass spectrometry (LC‒MS/MS). METHOD: OF samples were collected with a Quantisal™ device and 200 µL was extracted using a C18 MEPS cartridge installed on a semi-automated pipette and then analyzed using LC‒M/SMS. RESULTS: Linearity was achieved between 0.1 and 25 ng/mL, with a limit of detection (LOD) of 0.05 ng/mL and a limit of quantification (LOQ) of 0.1 ng/mL. Imprecision (% relative standard deviation) and bias (%) were better than 11.6% and 7.5%, respectively. The method had good specificity and selectivity against 9 different blank OF samples (from different donors) and 68 pharmaceutical and drugs of abuse with concentrations varying between 400 and 10,000 ng/mL. No evidence of carryover was observed. The analytes were stable after three freeze/thaw cycles and when kept in the autosampler (10 °C) for up to 24 h. The method was successfully applied to quantify 41 authentic positive samples. Methylone (mean 0.6 ng/mL, median 0.2 ng/mL), N-ethylpentylone (mean 16.7 ng/mL, median 0.35 ng/mL), eutylone (mean 39.1 ng/mL, median 3.6 ng/mL), mephedrone (mean 0.5 ng/mL, median 0.5 ng/mL), and 4-chloroethcathinone (8.1 ng/mL) were quantified in these samples. CONCLUSION: MEPS was an efficient technique for Green Analytical Toxicology purposes, which required only 650 µL organic solvent and 200 µL sodium hydroxide, and the BIN cartridge had a lifespan of 100 sample extractions.

Identification of volatile organic compounds in purple and white soybean flowers by HS-SPME/GC-MS.

This study aimed to establish a method for the extraction, enrichment, and identification of volatile organic compounds (VOCs) released by the flowers of purple (BRS 399) and white (DONMARIO 6563) soybean varieties. We tested the Static Headspace (HS) and Solid Phase Microextraction (SPME) methods using various fibre types: PDMS (Polydimethylsiloxane), PDMS/DVB (Divinylbenzene), and PDMS/DVB/CAR (Carboxen). We employed gas chromatography-mass spectrometry (GC-MS) to identify the VOCs. The SPME method with PDMS/DVB and PDMS/DVB/CAR fibres yielded the highest number of extracted compounds for both soybean cultivars. Notably, 67 compounds were detected in Glycine max. L for the first time. Using the developed method, we were able to detect 52 and 57 VOCs in the purple and white soybean varieties, respectively, including ketones, alcohols, aldehydes and benzenoids. In conclusion, the method we developed effectively identified VOCs in soybean flowers, thus enriching our understanding of the interactions between soybean flowers and their pollinators.

A green method for the determination of illicit drugs in wastewater and surface waters-based on a semi-automated liquid-liquid microextraction device.

Liquid-phase microextraction (LPME) is a simple, low-cost, and eco-friendly technique that enables the detection of trace concentrations of organic contaminants in water samples. In this work, a novel customized microextraction device was developed for the LPME extraction and preconcentration of nine illicit drugs in surface water and influent and effluent wastewater samples, followed by analysis by GC-MS without derivatization. The customized device was semi-automated by coupling it with a peristaltic pump to perform the collection of the upper layer of the organic phase. The extraction parameters affecting the LPME efficiency were optimized. The optimized conditions were: 100 µL of a toluene/DCM/EtAc mixture as extractor solvent; 30min of extraction time under vortex agitation (500rpm) and a solution pH of 11.6. The limits of detection and quantification ranged from 10.5ng L-1 (ethylone) to 22.0ng L-1 (methylone), and from 34.9ng L-1 to 73.3ng L-1 for these same compounds, respectively. The enrichment factors ranged from 39.7 (MDMA) to 117 (cocaethylene) and the relative recoveries ranged from 80.4% (N-ethylpentylone) to 120% (cocaine and cocaine-d3). The method was applied to real surface water, effluent, and influent wastewater samples collected in Salvador City, Bahia, Brazil. Cocaine was the main drug detected and quantified in wastewater samples, and its concentration ranged from 312ng L-1 to 1,847ng L-1. Finally, the AGREE metrics were applied to verify the greenness of the proposed method, and an overall score of 0.56 was achieved, which was considered environmentally friendly.

An open-source smart fraction collector for isocratic preparative liquid chromatography.

Preparative liquid chromatography is a technique for separating complex samples or isolating pure compounds from complex extracts. It involves eluting samples through a packed column and selectively collecting or isolating the separated bands in a sequence of fractions. Depending on the column length and the sample complexity, a large number of fractions may be obtained, making fraction collection a laborious and time-consuming process. Manual fraction collection is also tedious, error-prone, less reproducible, and susceptible to contamination. Several commercial and lab-made solutions are available for automated fraction collection, but most systems do not synchronize with the instrument detector and collect fractions at fixed volumes or time intervals. We have assembled a low-cost Arduino-based smart fraction collector that can record the signal from the UV-vis detector of the chromatography instrument and enable the automated selective collection of the targeted bands. The system consists of a robot equipped with position sensors and a 3-way solenoid valve that switches the column effluent between the waste or collection positions. By proper programming, an Arduino board records the detector response and actuates the solenoid valve, the position sensors, and the stepper motors to collect the target chromatographic bands.

Automated microextraction by packed sorbent of endocrine disruptors in wastewater using a high-throughput robotic platform followed by liquid chromatography-tandem mass spectrometry.

An automated microextraction by packed sorbent followed by liquid chromatography-tandem mass spectrometry (MEPS-LC-MS/MS) method was developed for the determination of four endocrine disruptors-parabens, benzophenones, and synthetic phenolic antioxidants-in wastewater samples. The method utilizes a lab-made repackable MEPS device and a multi-syringe robotic platform that provides flexibility to test small quantities (2 mg) of multiple extraction phases and enables high-throughput capabilities for efficient method development. The overall performance of the MEPS procedure, including the investigation of influencing variables and the optimization of operational parameters for the robotic platform, was comprehensively studied through univariate and multivariate experiments. Under optimized conditions, the target analytes were effectively extracted from a small sample volume of 1.5 mL, with competitive detectability and analytical confidence. The limits of detection ranged from 0.15 to 0.30 ng L-1, and the intra-day and inter-day relative standard deviations were between 3 and 21%. The method's applicability was successfully demonstrated by determining methylparaben, propylparaben, butylated hydroxyanisole, and oxybenzone in wastewater samples collected from the São Carlos (SP, Brazil) river. Overall, the developed method proved to be a fast, sensitive, reliable, and environmentally friendly analytical tool for water quality monitoring.

Microextraction by packed sorbent of N-nitrosamines from Losartan tablets using a high-throughput robot platform followed by liquid chromatography-tandem mass spectrometry.

The development of a fast, cost-effective, and efficient microextraction by packed sorbent setup was achieved by combining affordable laboratory-repackable devices of microextraction with a high-throughput cartesian robot. This setup was evaluated for the development of an analytical method to determine N-nitrosamines in losartan tablets. N-nitrosamines pose a significant concern in the pharmaceutical market due to their carcinogenic risk, necessitating their control and quantification in pharmaceutical products. The parameters influencing the performance of this sample preparation for N-nitrosamines were investigated through both univariate and multivariate experiments. Microextractions were performed using just 5.0 mg of carboxylic acid-modified polystyrene divinylbenzene copolymer as the extraction phase. Under the optimized conditions, the automated setup enabled the simultaneous treatment of six samples in less than 20 min, providing reliable analytical confidence for the proposed application. The analytical performance of the automated high-throughput microextraction by the packed sorbent method was evaluated using a matrix-matching calibration. Quantification was performed using ultra-high-performance liquid chromatography-tandem mass spectrometry with chemical ionization at atmospheric pressure. The method exhibited limits of detection as low as 50 ng/g, good linearity, and satisfactory intra-day (1.38-18.76) and inter-day (2.66-20.08) precision. Additionally, the method showed accuracy ranging from 80% to 136% for these impurities in pharmaceutical formulations.

Pesticide residues in herbs and their transfer for infusions.

In this work, a cost-effective gas chromatography-mass spectrometry method was validated for the analysis of twenty-five pesticide residues in herbs and infusions using a quick, easy, cheap, effective, rugged, and safe procedure or a dispersive liquid-liquid microextraction method, respectively. Figures of merit of the method showed good accordance with current guidelines. From the 58 herb samples studied (pertaining to 20 different species), 80% presented at least one detectable pesticide, with 62% of them above the maximum residual level. Results showed that pesticide residues from naturally contaminated herbs were not transferred at a significant rate to the herbal infusions. When a control assay was conducted by spiking a blank herb sample with a large amount of each pesticide (7 mg/L) 15 analytes were detected below the limit of quantification in the infusion.

Modern automated microextraction procedures for bioanalytical, environmental, and food analyses.

Sample preparation frequently is considered the most critical stage of the analytical workflow. It affects the analytical throughput and costs; moreover, it is the primary source of error and possible sample contamination. To increase efficiency, productivity, and reliability, while minimizing costs and environmental impacts, miniaturization and automation of sample preparation are necessary. Nowadays, several types of liquid-phase and solid-phase microextractions are available, as well as different automatization strategies. Thus, this review summarizes recent developments in automated microextractions coupled with liquid chromatography, from 2016 to 2022. Therefore, outstanding technologies and their main outcomes, as well as miniaturization and automation of sample preparation, are critically analyzed. Focus is given to main microextraction automation strategies, such as flow techniques, robotic systems, and column-switching approaches, reviewing their applications to the determination of small organic molecules in biological, environmental, and food/beverage samples.

Environmentally friendly and novel solid-liquid phase microextraction of maneb fungicide in fruits and vegetables.

The dithiocarbamates class has been widely used in agriculture practices because of lower toxicity and instability than organophosphates and carbamates. Among them, the maneb has been used to produce several fruits and vegetables, but its high ingestion can adversely affect human health. This work developed the Solid-Liquid Phase Microextraction (SLPME) for extraction of the maneb in foods sample with posterior determination by Flow injection analysis-Flame Absorption Atomic Spectroscopy (FIA-FAAS). Curve analytical had a linear range from 0.9 to 20.0 µmol L-1 maneb (A = 5.94 × 10-4 C (µmol L-1) + 6.93 × 10-4), good repeatability (4.07%) and reproducibility (3.39%), limits of quantification (5.98 µmol L-1) and detection (0.197 µmol L-1), which was above of the established by regulatory agencies. The extraction of the maneb was performed using 685 µL of the solution of the 1.00 × 10-3 mol L-1 of EDTA, and it has excellent recovery values from 80.85 to 106.51%. Therefore, the developed SLPME demonstrated an alternative environmentally friendly for quickly extracting maneb from food samples (apple, papaya, and tomato).

Determination of gas-polydimethylsiloxane distribution constants of major Cannabis terpenes and terpenoids by capillary gas-liquid chromatography.

Terpenes and terpenoids are the principal responsible for the aroma of Cannabis, playing an important role in the interaction with the environment. Analytical determination of these compounds can be done by headspace coupled to solid phase micro-extraction (HS-SPME) and then injected in a gas chromatograph. In the present study, we determined distribution constants between gas and polydimetylsiloxane (PDMS), a conventional SPME liquid phase, at three temperatures between 303.15 and 343.15 K for major Cannabis terpenes and terpenoids employing a method based in gas chromatography using four capillary columns for monoterpenes and five columns for sesquiterpenes. In addition, van't Hoff regressions (logKfg vs T-1) were obtained in order to estimate logKfg at 298.15 K aiming to compare with bibliographic values (experimental or estimated ones). An excellent agreement was found between them. The method, based on chromatographic theory is robust and relatively simple. It is expected that the herein obtained data could be useful for selecting SPME fiber type and dimensions, estimating extraction efficiencies, as well as to develop prediction models and validate them.

Multivariate optimization of dispersive liquid-liquid microextraction using ionic liquid for the analysis of ultraviolet filters in natural waters.

In this work, a vortex-assisted dispersive liquid-liquid microextraction method, using an ionic liquid as the extracting solvent was developed, for the simultaneous analysis of three UV filters in different water samples. The extracting and dispersive solvents were selected in a univariate way. Then, the parameters such as the volume of the extracting and dispersive solvents, pH and ionic strength were evaluated using a full experimental design 24, followed by Doehlert matrix. The optimized method consisted of 50 µL of extracting solvent (1-octyl-3-methylimidazolium hexafluorophosphate), 700 µL of dispersive solvent (acetonitrile) and pH of 4.5. When combined with high-performance liquid chromatography, the method limit of detection ranged from 0.3 to 0.6 µg L-1, enrichment factors between 81 and 101%, and the relative standard deviation between 5.8 and 10.0%. The developed method demonstrated effectiveness in concentrating UV filters in both river and seawater samples, being a simple and efficient option for this type of analysis.

Aromatic hydrocarbons extracted by headspace and microextraction methods in water-soluble fractions from crude oil, fuels and lubricants.

Two extraction protocols were developed for the determination of mono- and poly-aromatic hydrocarbons in water-soluble fractions from gasoline, diesel, crude, mineral insulating, and lubricant oils. Development of the procedures was based on clean miniaturized strategies, such as headspace extraction and vortex-assisted dispersive liquid micro-extraction, together with quantification by gas chromatography-mass spectrometry. The mono-aromatic hydrocarbons were extracted using the headspace extraction method. The linear range obtained was 10-500 µg L-1, with r2 > 0.99. Based on the parameters of the analytical curves, detection and quantification limits of 2.56-3.20 and 7.76-9.71 µg L-1 were estimated. In addition, the method showed adequate recoveries of 69.4-83.5%, with a satisfactory precision of 4.7-17.1% (n = 5). Micro-extraction was applied for the poly-aromatics and the most favorable variables were sample volume (5.00 mL) in sodium chloride medium (1%, w/v), trichloromethane as extractor solvent (75 µL), acetone as disperser (925 µL) and vortexing for 1 min. Under these conditions, analytical curves of 0.15-4.00 µg L-1 were obtained and limits of determination and quantification were 0.03-0.15 and 0.09-0.46 µg L-1, respectively. Recovery values of 87.6-124.5% and a maximum relative standard deviation of 18.9% (n = 5) verify satisfactory accuracy and precision. This led to the achievement of enrichment factors for poly-aromatic hydrocarbons of 41-89 times. Finally, the methods were employed in samples of water-soluble fractions for the determination of analytes. The values followed the order: gasoline > diesel > crude > lubricant > mineral insulating oil. These results indicate an increase in lighter fractions, followed by poly-aromatics in more refined products.

Effect of Huanglongbing on the Volatile Organic Compound Profile of Fruit Juice and Peel Oil in 'Ray Ruby' Grapefruit.

Along with orange and mandarin, grapefruit production in Florida has declined sharply due to Huanglongbing (HLB), or citrus greening disease, caused by Candidatus Liberibacter asiaticus (CLas). HLB affects the volatile profiles of juice and peel oil in oranges, but there is limited information on grapefruit. In this research, 'Ray Ruby' grapefruit were harvested in 2020 and 2021 from healthy (HLB-) and HLB-affected (HLB+) trees. Peel oil was extracted by hydrodistillation, and the volatiles were analyzed by direct injection of the oil samples into gas chromatography-mass spectrometry (GC-MS). Volatiles in the juice were analyzed by headspace (HS)-solid-phase microextraction (SPME) coupled with GC-MS. HLB significantly altered the volatile profiles of peel oil and juice in 'Ray Ruby' grapefruit. Juice samples of HLB+ fruits had lower decanal, nonanal, and octanal, important citrus juice flavor compounds. HLB+ samples also showed reduced content of nonterpene compounds, other aliphatic and terpene aldehydes, and terpene ketones. Ethanol, acetaldehyde, ethyl acetate, and ethyl butanoate were increased in HLB+ juice samples, indicating an HLB-induced stress response. The most abundant compounds D-limonene and ß-caryophyllene, as well as other sesquiterpenes, were increased in HLB+ juice and peel oil samples. On the other hand, the oxidative/dehydrogenated terpenes were increased by HLB in peel oil but decreased in the juice sample. Nootkatone, the key grapefruit volatile was consistently reduced by HLB in both peel oil and juice samples. The impact of HLB on nootkatone deteriorated the quality of both juice and peel oil in grapefruits.