Waterpipe smoke: A considerable source of human exposure against furanic compounds

Smoking of waterpipes became increasingly popular in the Western hemisphere in recent years. Yet, up to now only little is known about the health hazards and on the composition of waterpipe smoke. To obtain more information on the ingredients present in waterpipe smoke we utilized two different approaches. Based on headspace-solid-phase microextraction–gas chromatography–mass spectrometry (HS-SPME–GC–MS) instrumentation we identified new compounds present in the waterpipe smoke. Additional reversed-phase-high performance liquid chromatography–diode array detection (RP-HPLC–DAD) then led us to perform reliable quantification of the newly detected chemical species. Upon identification of a range of different furanic compounds such as 5-(hydroxymethyl)-2-furaldehyde (HMF), 2-furaldehyde, and others, we developed an easy-to-perform and fast RP-HPLC–DAD method to quantify these compounds in the complex matrix of waterpipe smoke. The detection limits range from 0.04 μg for HMF to 7.1 μg for 3-furan methanol per smoking session. Linearity, intra- and inter-day precision and recovery were determined and proved excellent. We analyzed 5 waterpipe tobacco brands and found up to 62.3 ± 11 mg of HMF generated during one waterpipe smoking session. The applied smoking protocol comprised 171 puffs of 530 mL each and 2.6 s duration every 20 s. Our results reveal that waterpipe smoking constitutes a major source of HMF exposure. Furthermore, we found a distinct filter effect of the bowl water for all furanic compounds investigated except HMF.     

A sensitive flow analysis system for the fluorimetric determination of low levels of formaldehyde in alcoholic beverages

A sensitive FIA method was developed for the selective determination of formaldehyde in alcoholic beverages. This method is based on the reaction of Fluoral-P (4-amine-3-pentene-2-one) with formaldehyde, leading to the formation of 3,5-diacetyl-1,4-dihydrolutidine (DDL), which fluoresces at λ_ex = 410 nm and λ_em = 510 nm. The analytical parameters were optimized by the response surface method using the Box-Behnken design. The proposed flow injection system allowed for the determination of up to 3.33 × 10⁻⁵ mol L⁻¹ of formaldehyde with R.S.D. < 2.5% and a detection limit of 3.1 ng mL⁻¹. The method was successfully applied to determine formaldehyde in alcoholic beverages, without requiring any sample pretreatment, and the results agreed with the reference at a 95% confidence level by paired t-test. In the optimized condition, the FIA system proved able to analyze up to 60 samples/h.     

Non-invasive detection of cocaine dissolved in beverages using displaced Raman spectroscopy

We demonstrate the potential of Raman spectroscopy to detect cocaine concealed inside transparent glass bottles containing alcoholic beverages. A clear Raman signature of cocaine with good signal-to-noise was obtained from a ∼300 g solution of adulterated cocaine (purity 75%) in a 0.7 L authentic brown bottle of rum with 1 s acquisition time. The detection limit was estimated to be of the order of 9 g of pure cocaine per 0.7 L (∼0.04 moles L⁻¹) with 1 s acquisition time. The technique holds great promise for the fast, non-invasive, detection of concealed illicit compounds inside beverages using portable Raman instruments, thus permitting drug trafficking to be combated more effectively.     

Optimization of headspace solid-phase microextraction for analysis of ethyl carbamate in alcoholic beverages using a face-centered cube central composite design

The headspace solid-phase microextraction (HS-SPME) of ethyl carbamate from alcoholic beverages was optimized for the first time using a face-centered cube central composite design (CCD). The factors expected to influence the extraction process are discussed. Firstly, some of factors are fixed based on the opinion of expert and previous experiments, which reduce the number of factors and then avoid very complex response models and large variability. Secondly, for three remaining inexplicit factors, sample temperature, pH and %NaCl, a face-centered cube central composite design was performed and a response surface equation was derived. The statistical parameters of the derived model were r = 0.974 and F = 20.183. The optimum conditions were obtained using a grid method. Next, the method was analytically evaluated using the optimum conditions. The detection limit, relative standard deviation, linear range and recovery were 3 μg L⁻¹, 4.3-8.6%, 10-160 μg L⁻¹, and 92.8-97.5%, respectively. Finally, the method was applied to a variety of alcoholic beverages.     

Analysis of potential and free furfural compounds in milk-based formulae by high-performance liquid chromatography. Evolution during storage

A simple and reproducible HPLC-diode array detection method for the qualitative and quantitative analysis of potential and free furfural compounds (5-hydroxymethyl-2-furaldehyde, HMF; 2-furaldehyde, F; 2-furyl methyl ketone, FMC; and 5-methyl-2-furaldehyde, MF) in milk-based formulae was developed and validated. The method showed good linearity with determination coefficients over 0.999. The limits of detection and quantification were acceptable for all furfurals. The relative standard deviations (RSDs) for repeatability and reproducibility were <4.28. Recoveries in all furfurals were between 94.5 and 98.7%. In addition, we report the evolution over shelf life of furfural compound levels in an experimental powder formula for pregnant women stored at 25 and 37 degrees C from production until 15 months.     

Determination of ochratoxin A and T-2 toxin in alcoholic beverages by hollow fiber liquid phase microextraction and ultra high-pressure liquid chromatography coupled to tandem mass spectrometry

A new method for the determination of ochratoxin A and T-2 toxin in alcoholic beverages (wine and beer) by hollow fiber liquid microextraction was optimized. The extraction step was followed by ultra high-pressure liquid chromatography coupled to tandem mass spectrometry (UHPLC-MS/MS). The extraction procedure was based on the extraction of mycotoxins from the sample to the organic solvent (1-octanol) immobilized in the fiber, and afterwards, they were desorbed in a mixture of acetonitrile/water (80:20, v/v) at pH 7 prior to chromatographic determination. Different variables affecting the extraction process such as organic solvent, salt content, extraction time and desorption solution were studied. The developed method was validated in wine and beer, using white wine and alcoholic beer as representative matrices for both types of samples. Relative recoveries higher than 70% were obtained for the selected mycotoxins. Good linearity (R² > 0.993) was obtained and quantification limits (0.02-0.09 μg L⁻¹) below European regulatory levels were achieved. Repeatability, expressed as relative standard deviation, was always lower than 12%, whereas interday precision was lower than 21%. The proposed method was applied to the analysis of several types of wines and beers and ochratoxin A was detected in a rosé wine at 1.1 μg L⁻¹.     

An RP-HPLC determination of 5-hydroxymethylfurfural in honey The case of strawberry tree honey

The use of the RP-HPLC official method of the International Honey Commission (IHC) for the determination of 5-hydroxymethylfurfural (HMF) in strawberry tree honey (Arbutus unedo, a typical Sardinian honey) has brought to light a specific and heavy chromatographic interference that prevents accurate quantification. The interference has been identified as homogentisic acid (HA), i.e. the marker of the botanical origin of the honey. For this reason, an alternative RP-HPLC method is proposed. The bias-free method allows a complete separation of HMF from HA to the baseline level and is faster and more precise than the RP-HPLC official method: the detection and quantification limits are 1.9 and 4.0 mg kg⁻¹, respectively, whereas the repeatability is ca. 2% in the HMF concentration range of 5-140 mg kg⁻¹.     

NMR investigation of acrolein stability in hydroalcoholic solution as a foundation for the valid HS-SPME/GC–MS quantification of the unsaturated aldehyde in beverages

Acrolein (propenal) is found in many foods and beverages and may pose a health hazard due to its cytotoxicity. Considerable knowledge gaps regarding human exposure to acrolein exist, and there is a lack of reliable analytical methods. Hydroalcoholic dilutions prepared for calibration purposes from pure acrolein show considerable degradation of the compound and nuclear magnetic resonance (NMR) spectroscopy showed that 1,3,3-propanetriol and 3-hydroxypropionaldehyde are formed. The degradation can be prevented by addition of hydroquinone as stabilizer to the calibration solutions, which then show linear concentration-response behaviour required for quantitative analysis. The stabilized calibration solutions were used for quantitative headspace solid-phase microextraction/gas chromatography–mass spectrometry (HS-SPME/GC–MS) determination of acrolein in alcoholic beverages with a detection limit of 14 μg L⁻¹. Of 117 tested alcoholic beverages, 64 were tested positive with the highest incidence in grape marc spirits and whiskey (100%, mean 252 μg L⁻¹), followed by fruit spirits (86%, mean 591 μg/L⁻¹), tequila (86%, mean 404 μg L⁻¹), Asian spirits (43%, mean 54 μg L⁻¹) and wine (9%, mean 0.7 μg L⁻¹). Acrolein could not be detected in beer, vodka, absinthe and bottled water. Six of the fruit and grape marc spirits had acrolein levels above the World Health Organization (WHO) provisional tolerable concentration of 1.5 mg L⁻¹.     

Mapping of protein:protein contact surfaces by hydrogen/deuterium exchange,followed by on-line high-performance liquid chromatography-electrospray ionization Fourier-transform ion-cyclotron-resonance mass analysis

Furfural contents in adapted and follow-up infant formulas were measured by RP-HPLC. The evolution of furfural compound contents during storage (a year at 20 and 37 degrees C) was studied. 2-Furylmethylketone and 5-methyl-2-furaldehyde were not detectable in analysed samples. The differences in the furfural compounds at point zero between both infant formulas has to be ascribed to the differences in protein and iron contents. An increase in free 5-hydroxymethyl-2-furfuraldehyde (HMF), 2-furaldehyde (F) and HMF+F contents was observed in all samples, although the differences were not statistically significant. The storage temperature affected the total HMF content and the storage time affected the total HMF and F contents.     

Automated determination of diazepam in spiked alcoholic beverages associated with drug-facilitated crimes

In this work, a multipumping flow system (MPFS) coupled to a photodegradation unit was developed, for the first time, for the determination of diazepam (a benzodiazepine) in spiked alcoholic beverages by fluorimetry. The main features of MPFS such as, high portability, versatility and straightforward automation and control combined with the efficiency and simplicity of photodegradation and the selectivity and sensitivity of fluorimetric detection makes the developed analytical methodology an attractive tool and a valuable contribution for the prevention of drug-facilitated crimes (DFC). Drug-facilitated crimes involve the unauthorized administration of strong central nervous system depressant drugs, which have the capability of preventing victims from resist to the action of the perpetrator or fighting off. Most often, the drugs identified as being used in DFC are surreptitiously placed in drinks served to potential victims in entertainment places, like night clubs.Five commercial alcoholic beverages (Eristoff^®, Smirnoff^®, Bacardi^®, Dry Gin^® and Brazilian Cachaça 51^®) spiked with diazepam were analyzed by the proposed methodology, and the results revealed good agreement with those obtained through a HPLC comparison procedure. Relative deviations comprised between −1.97 and 2.05% were achieved, and additionally, the application of a paired t-test, revealed the absence of any statistical difference for a confidence level of 95% (n = 5). The detection limit was approximately 2.02 mg L⁻¹.     

Fluorimetric determination of histamine in wine and cider by using an anion-exchange column-FIA system and factorial design study

A study has been performed of the conditions for the reaction of histamine with o-phthaldehyde in a flow injection analysis system employing three channels, using an anion-exchange column to eliminate sample matrix interferences. Factorial design was used to determine which operational parameters should be included in the optimization and their optimal values were found. The method developed shows good selectivity for histamine determination in alcoholic beverages. A linear response of up to 2.0 mg l⁻¹ was observed and the detection and quantification limits were 30 and 101 μg l⁻¹, respectively. The repeatability, measured by the R.S.D. for 10 replicate injections, was 0.84 and 0.52% for histamine solutions of 0.20 and 2.0 mg l⁻¹, respectively. The recoveries obtained in wine and cider samples were close to 100% and a sample frequency of 24 samples per hour was achieved.     

Facile synthesis of N-acetyl-L-cysteine capped ZnS quantum dots as an eco-friendly fluorescence sensor for Hg2+

This paper described an investigation of a novel eco-friendly fluorescence sensor for Hg²⁺ ions based on N-acetyl-l-cysteine (NAC)-capped ZnS quantum dots (QDs) in aqueous solution. By using safe and low-cost materials, ZnS QDs modified by NAC were easily synthesized in aqueous medium via a one-step method. The quantitative detection of Hg²⁺ ions was developed based on fluorescence quenching of ZnS QDs with high sensitivity and selectivity. Under optimal conditions, its response was linearly proportional to the concentration of Hg²⁺ ions in a range from 0 to 2.4 × 10⁻⁶ mol L⁻¹ with a detection limit of 5.0 × 10⁻⁹ mol L⁻¹. Most of common physiologically relevant cations and anions did not interfere with the detection of Hg²⁺. The proposed method was applied to the trace determination of Hg²⁺ ions in water samples. The possible quenching mechanism was also examined by fluorescence and UV-vis absorption spectra.     

High-performance liquid chromatographic determination of furfural and hydroxymethylfurfural in apple juices and concentrates

Summary A rapid and sensitive method for determining 2-furaldehyde (FUR) and 5-hydroxymethyl-2-furaldehyde (HMF) in apple juices and juice concentrates has been developed. The method for FUR and HMF involves the solid-liquid extraction of the juice by using a C-18 cartridge prior to reversed-phase separation with detection at 280 nm. The mobile phase was acetonitrile-water (8/92, v/v) at a flow rate of 1.0 ml/min. Recoveries from apple juices and juice concentrates spiked at different levels ranged from 94.1 to 104.0 (FUR) and 94.5 to 100.5 (HMF). The quantification limit for both, FUR and HMF, was 5 ppb.     

Visual and surface plasmon resonance sensor for zirconium based on zirconium-induced aggregation of adenosine triphosphate-stabilized gold nanoparticles

Owing to its high affinity with phosphate, Zr(IV) can induce the aggregation of adenosine 5′-triphosphate (ATP)-stabilized AuNPs, leading to the change of surface plasmon resonance (SPR) absorption spectra and color of ATP-stabilized AuNP solutions. Based on these phenomena, visual and SPR sensors for Zr(IV) have been developed for the first time. The A_660 nm/A_518 nm values of ATP-stabilized AuNPs in SPR absorption spectra increase linearly with the concentrations of Zr(IV) from 0.5 μM to 100 μM (r = 0.9971) with a detection limit of 95 nM. A visual Zr(IV) detection is achieved with a detection limit of 30 μM. The sensor shows excellent selectivity against other metal ions, such as Cu²⁺, Fe³⁺, Cd²⁺, and Pb²⁺. The recoveries for the detection of 5 μM, 10 μM, 25 μM and 75 μM Zr(IV) in lake water samples are 96.0%, 97.0%, 95.6% and 102.4%, respectively. The recoveries of the proposed SPR method are comparable with those of ICP-OES method.     

A simple strategy for determining ethanol in all types of alcoholic beverages based on its on-line liquid-liquid extraction with chloroform, using a flow injection system and Fourier transform infrared spectrometric detection in the mid-IR

In this work, a simple strategy for the determination of ethanol in all types of alcoholic beverages using Fourier transform infrared spectrometric detection has been developed. The methodological proposal includes the quantitative on-line liquid-liquid extraction of ethanol with chloroform, through a sandwich type cell equipped with a PTFE membrane, using a two-channel manifold; and direct measurement of the analyte in the organic phase, by means of Fourier transform infrared spectrometry. The quantification was carried out measuring the ethanol absorbance at 877 cm⁻¹_, corrected by means of a baseline established between 844 and 929 cm⁻¹. The procedure, which does not require any sample pretreatment (except for the simple degassing of beer and gassy wine samples, and a simple dilution of spirits with water), was applied to determine ethanol in different alcoholic beverages such as beers, wines and spirits. The results obtained highly agree with those obtained by a derivative FTIR spectrometric procedure, and by head space-gas chromatography with FID detection. The proposed method is simple, fast, precise and accurate. Moreover, it can be easily adapted to any infrared spectrometer equipped with a standard transmission IR cell, and provides attractive analytical features, which are comparable to, or better than those offered by other published methods. In consequence, it represents a valid alternative for the determination of ethanol in alcoholic beverages, and could be suitable for the routine control analysis.     

Flow injection chemiluminescence determination of the total phenolics levels in plant-derived beverages using soluble manganese(IV)

This study established a flow injection (FI) methodology for the determination of the total phenolic content in plant-derived beverages based on soluble manganese(IV) chemiluminescence (CL) detection. It was found that mixing polyphenols with acidic soluble manganese(IV) in the presence of formaldehyde evoked chemiluminescence. Based on this finding, a new FI-CL method was developed for the estimation of the total content of phenolic compounds (expressed as milligrams of gallic acid equivalent per litre of drink) in a variety of wine, tea and fruit juice samples. The proposed method is sensitive with a detection limit of 0.02 ng mL⁻¹ (gallic acid), offers a wide linear dynamic range (0.5-400 ng mL⁻¹) and high sample throughput (247 samples h⁻¹). The relative standard deviation for 15 measurements was 3.8% for 2 ng mL⁻¹ and 0.45% for 10 ng mL⁻¹ of gallic acid. Analysis of 36 different samples showed that the results obtained by the proposed FI-CL method correlate highly with those obtained by spectrophotometric methods commonly used for the evaluation of the total phenolic/antioxidant level. However, the FI-CL method was found to be far simpler, more rapid and selective, with almost no interference from non-phenolic components of the samples examined.     

Highly sensitive and reproducible cyclodextrin-modified gold electrodes for probing trace lead in blood

A highly sensitive and reproducible lead sensor based on a cyclodextrin-modified gold electrode was created. A self-assembled monolayer (SAM) of thiolated β-cyclodextrin (6-(2-mercapto-ethylamino)-6-deoxy-β-cyclodextrin (MEA-β-CD)) was prepared and modified on a gold electrode (MCGE) for specific Pb²⁺-sensing. Thus the mercury-free sensors for Pb²⁺ assay based on MCGE were established. A linear calibration response for Pb²⁺ was found in the range of 1.7 × 10⁻⁸ M to 9.3 × 10⁻⁷ M. The detection limit was 7.1 × 10⁻⁹ M (with S/N > 3), which was 10 times lower than other reported methods of detection Pb²⁺ with CD. The measurement results via this method for real blood samples were well agree with those obtained by ICP-AES, and thus presented a novel strategy in design of specific lead sensors with high sensitivity and stability for analysis of trace Pb²⁺ in real blood samples.     

Electrochemical determination of maltol in beverages with glassy carbon electrode and its silica sol-gel modified electrode

The electrochemical behavior of maltol on a glassy carbon (GC) electrode was investigated. The results were applied to differential pulse voltammetric determination of maltol in beverages pretreated by ultrafiltration. Under the optimum experimental conditions, the linear range is 1×10⁻⁵ to 6×10⁻⁴ mol l⁻¹ maltol and the relative standard deviation for 0.4 mmol l⁻¹ maltol is 0.6% (n=9). The detection limit was 5 μmol l⁻¹. Furthermore, silica sol-gel film on GC electrode could be used as suitable selective membrane, which integrated selective membrane on the electrode and substituted for the pretreatment of ultrafiltration. Under the above conditions, maltol was determined by semi-differential linear sweep voltammetry at a silica sol-gel modified GC electrode in the concentration range of 5×10⁻⁶ to 5×10⁻⁴ mol l⁻¹. The detection limit was 2 μmol l⁻¹ and the relative standard deviation for 0.1 mmol l⁻¹ maltol was 0.7% (n=7). The proposed method is of sensitivity, simplicity, rapidness and no contamination. It had been applied to the direct determination of maltol in beverages such as grape wines, drinks and beers without any pretreatment. The results obtained with the present method were satisfactory with those obtained by spectrophotometry. It could be used as a simple and practical method for the determination of the flavor enhancer maltol in beverages.     

Simultaneous determination of two active ingredients in Flos daturae by capillary electrophoresis with electrochemiluminescence detection

The coupling of Ru(bpy)₃²⁺ based electrochemiluminescence (ECL) detection with capillary electrophoresis (CE) was developed for the simultaneous determination of the two major active ingredients (atropine and scopolamine) in Flos daturae. Parameters related to the separation and detection were discussed and optimized. It was proved that 20 mM phosphate buffer at pH 8.48 could achieve the most favorable resolution, and the high sensitivity of detection was obtained by maintaining the detection potential at 1.2 V. Under the optimized conditions: ECL detection at 1.2 V, 20 mM phosphate buffer at pH 8.48, 5 mM Ru(bpy)₃²⁺ and 50 mM phosphate buffer at pH 7.48 in the detection reservoir, detection limits of 5 × 10⁻⁸ mol/l for atropine and 1 × 10⁻⁶ mol/l for scopolamine were obtained. Relative standard derivations of the ECL intensity and the migration time were 5.16 and 0.71% for atropine and 5.07 and 1.22% for scopolamine, respectively. Developed method was successfully applied to determine the amounts of both alkaloids in Flos daturae. A baseline separation for atropine and scopolamine was achieved within 11 min.     

Simultaneous extraction and preconcentration of uranium and thorium in aqueous samples by new modified mesoporous silica prior to inductively coupled plasma optical emission spectrometry determination

A new synthesized modified mesoporous silica (MCM-41) using 5-nitro-2-furaldehyde (fural) was applied as an effective sorbent for the solid phase extraction of uranium(VI) and thorium(IV) ions from aqueous solution for the measurement by inductively coupled plasma optical emission spectrometry (ICP OES). The influences of some analytical parameters on the quantitative recoveries of the analyte ions were investigated in batch method. Under optimal conditions, the analyte ions were sorbed by the sorbent at pH 5.5 and then eluted with 1.0 mL of 1.0 mol L⁻¹ HNO₃. The preconcentration factor was 100 for a 100 mL sample volume. The limits of detection (LOD) obtained for uranium(VI) and thorium(IV) were 0.3 μg L⁻¹. The maximum sorption capacity of the modified MCM-41 was found to be 47 and 49 mg g⁻¹ for uranium(VI) and thorium(IV), respectively. The sorbent exhibited good stability, reusability, high adsorption capacity and fast rate of equilibrium for sorption/desorption of uranium and thorium ions. The applicability of the synthesized sorbent was examined using CRM and real water samples.