A survey of bisphenol A and other bisphenol analogues in foodstuffs from nine cities in China

Bisphenol A (BPA) is a high-production-volume chemical that is widely used in polycarbonate plastics and epoxy food-can coatings. Following several studies that have reported adverse effects of BPA over the past decade, other bisphenol analogues, such as bisphenol F (BPF), bisphenol S (BPS), bisphenol AF (BPAF), and bisphenol B (BPB), have been gradually developed as substitutes for BPA in several applications. Nevertheless, few studies have reported on the occurrence of compounds other than BPA in foodstuffs. In this study, 289 food samples (13 categories: cereals and cereal products, meat and meat products, fish and seafood, eggs, milk and milk products, bean products, fruits, vegetables, cookies/snacks, beverages, cooking oils, condiments, and others), collected from nine cities in China, were analysed for eight bisphenol analogues using high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS). BPA and BPF were found widely in foodstuffs at concentrations ranging from below the limit of quantitation (LOQ) to 299 ng g^–1 (mean = 4.94 ng g^–1) and from below the LOQ to 623 ng g^–1 (mean = 2.50 ng g^–1), fresh weight, respectively. The highest total concentrations of bisphenols (∑BPs: sum of eight bisphenols) were found in the category of vegetables that included canned products (mean = 27.0 ng g^–1), followed by fish and seafood (16.5 ng g^–1) and beverages (15.6 ng g^–1). ∑BP concentrations (mean = 2–3 ng g^–1) in milk and milk products, cooking oils, and eggs were low. Food samples sold in metallic cans contained higher mean ∑BP concentrations (56.9 ng g^–1) in comparison with those packaged in glass (0.43 ng g^–1), paper (11.9 ng g^–1), or plastic (6.40 ng g^–1). The daily dietary intakes of bisphenols were estimated, based on the mean concentrations measured and daily consumption rates of foods, to be 646 and 664 ng kg^–1 bw day^–1 for men and women, respectively.     

Are Chileans exposed to dietary furan?

Chilean consumer preferences include foods that may contain considerable amounts of furan, a potential human carcinogen. However, there is no information regarding dietary exposure to furan in Chile. Thus, the objective of this work was to determine the Chilean exposure to dietary furan. To accomplish this objective, the furan concentration of 14 types of commercial foods processed at high temperature were analysed based on a modified headspace-GC/MS (HS-GC/MS) method in which the limits of detection for different food matrices ranged from 0.01 to 0.6 ng g^?1. In addition, a risk assessment was made with exposure estimates based on dietary data from national studies on different age groups (9-month-old babies, school children, adults and elderly people). Of the food items surveyed “American”-type coffee (espresso coffee plus hot water) obtained from automatic coffee machine (936 ng g^?1) and low moisture starchy products like crisps and “soda”-type crackers showed the highest furan concentrations (259 and 91 ng g^?1, respectively). Furthermore, furan was also found in samples of breakfast cereals (approximately 20 ng g^?1), jarred fruit baby foods (8.5 ng g^?1) and orange juice (7.0 ng g^?1). School children (aged 9–13 years) represented the highest intake of furan (about 500 ng kg^?1_bw day^?1), with margins of exposure of 2479 and 2411, respectively, which points to a possible public health risk.     

Analysis and risk assessment of ethyl carbamate in various fermented foods

Ethyl carbamate (EC) was analyzed in fermented foods, comprising various matrices; subsequently, a risk assessment for EC was carried out. In total, 128 fermented foods were purchased from department stores and traditional markets in Korea. The samples comprised 55 lactic acid–fermented vegetable (kimchi), 53 fermented soybean paste (doenjang, gochujang, cheonggukjang, and ssamjang), 20 fermented fish products (jeotgal), 18 yoghurt, 37 bread, 12 cheese, and 23 vinegar samples. The level of EC in fermented soybean pastes ranged from not detectable to 240.2 ng g^?1. EC was not detected in kimchi, jeotgals, yoghurt, and cheese. Bread and vinegar contained EC up to 3.70 and 16.79 ng g^?1, respectively. The estimated daily intake and chronic daily intake of EC were 1.98 ng kg body weight (bw)^?1 day^?1, 1.50 ng kg bw^?1 day^?1, respectively. Excess cancer risk and margin of exposure of EC were 7.5 × 10^?8 and 151,515, respectively.     

Occurrence of 13 volatile organic compounds in foods from the Canadian total diet study

Volatile organic compounds (VOCs) are ubiquitous in the environment due to evaporation and incomplete combustion of fuels, use of consumer and personal care products, etc. and they can accumulate in foods. Some VOCs in foods can also be formed during food processing and preparation and migrate from food packaging. In this pilot study, a GC-MS method based on headspace solid-phase microextraction (SPME) was validated and used to analyse selected individual foods which can be consumed directly and 153 different total diet composite food samples for 13 VOCs. Vinyl chloride was not detected in any of the 153 composite food samples, while the other 12 VOCs were detected at various frequencies, with m-xylene being the most frequently detected (in 151 of the 153 samples), followed by toluene (145), 1,3,5-trimethylbenzene (140), ethylbenzene (139), styrene (133), 1,2,4-trimethylbenzene (122), benzene (96), p-dichlorobenzene (95), n-butylbenzene (55), chloroform (45), naphthalene (45) and trichloroethylene (31). Concentrations of the 12 VOCs in most of the food composite samples were low, with the 90th percentiles from 1.6 ng g^–1 for n-butylbenzene to 20 ng g^–1 for toluene. However, some VOCs were detected at higher levels with maxima, for example, of 948 ng g^–1 for m-xylene and 320 ng g^–1 for ethylbenzene in chewing gum, 207 ng g^–1 for styrene and 157 ng g^–1 for toluene in herbs and spices. VOCs were detected at higher levels in most of the individual food items than their corresponding composite samples, for example, the average chloroform concentration in the individual canned soft drinks was 20 ng g^–1 compared with 3.0 ng g^–1 in their composite, and the average toluene concentration in the individual canned citrus juice was 96 ng g^–1 compared with 0.68 ng g^–1 in their composite. Thus, for determination of VOCs in foods which can be consumed directly, their individual food items should be analysed whenever possible for accurate exposure assessment.     

Determination of free and total bisphenol A in human milk samples from Canadian women using a sensitive and selective GC-MS method

A sensitive and selective GC-MS method was developed and used to analyse human milk samples for both free and total bisphenol A (BPA). Total BPA was detected in 72 of the 278 human milk samples (25.9%) at concentrations from < 0.036 to 2.5 ng g^–1 with a geometric mean (GM) of 0.13 ng g^–1 and median of 0.11 ng g^–1, while free BPA was detected in fewer samples, 46 of the 278 samples (16.5%) at concentrations ranging from < 0.036 to 2.3 ng g^–1 with a GM of 0.11 ng g^–1 and median of 0.10 ng g^–1. Ratios of [free BPA]/[total BPA] for the positive samples ranged from 7.9% to 100% with a GM of 57.2% and median of 70.3%. Concentrations of free and total BPA in most samples were low with 0.39 and 0.65 ng g^–1 at the 95th percentile for free and total BPA, respectively, and they are also lower than those reported in other countries. Based on the low frequency of detection of free BPA in human milk samples, in general, dietary exposure to BPA for Canadian breast-fed infants is expected to be somewhat lower compared with exposure among formula-fed infants.     

Determination of Histamine and Tyramine in Canned Fish Samples by Headspace Solid-Phase Microextraction Based on a Nanostructured Polypyrrole Fiber Followed by Ion Mobility Spectrometry

This paper describes the development of a simple, rapid, and selective method based on headspace solid-phase microextraction (HS-SPME) combined with ion mobility spectrometry (IMS) for the simultaneous determination of histamine (HIS) and tyramine (TYR) in the canned fish samples. The spectra interferences were eliminated by using a new alternate reagent gas and resulted in an increased sensitivity and selectivity of IMS technique. A dodecylbenzenesulfonate-doped polypyrrole coating was used as a fiber for HS-SPME method. The calibration curves were linear in the range of 30–300 ng g^?1 (R ² > 0.994). Limits of detection for HIS and TYR were 3 and 4 ng g^?1, respectively. The proposed method was successfully applied to determine HIS and TYR in different canned fish samples without derivatization steps. Method validation was conducted by comparing our results with those obtained through gas chromatography-mass spectrometry method.     

Measurement of ampicillin residue levels in chicken eggs during and after medicated feed administration by LC-MS/MS

A simple and sensitive LC-MS/MS method was developed and validated for the determination of ampicillin (ABPC) in chicken eggs. Residues were extracted by reverse-phase solid-phase extraction. Chromatographic separation was performed using a reverse-phase column with an elution gradient. The limits of detection and quantification were 0.01 and 0.1 ng g^?1, respectively. For the 0.1–50 ng g^?1 concentration range, mean recovery and accuracy values were 93.9–98.5% and 100.2–118.0%, respectively. ABPC residue concentrations in eggs before, during and after 7 days of medicated feeding of maximum dosage (40 mg kg^?1 body weight day^?1) of ABPC were determined with the LC-MS/MS method. The maximum concentration of ABPC in eggs was 3.6 ± 1.7 ng g^?1 (mean ± SD) on the last day of the administration period. Residue concentrations of ABPC in eggs during and after ABPC administration were not over the Japanese maximum residue limit of 0.01 mg kg^?1.     

Determination of bisphenol A in canned fatty foods by coacervative microextraction,liquid chromatography and fluorimetry

Decanoic acid reverse micelle-based coacervates were used to provide simple, rapid and almost solventless extraction of bisphenol A (BPA) from canned fatty foods. The procedure involved the extraction of 200–400 mg of homogenised food sample with an aqueous solution containing 20% THF and 200 mg of decanoic acid, conditions under which the coacervate (around 550 µl) formed in situ and instantaneously. The overall sample treatment took about 30 min and several samples could be simultaneously treated using conventional laboratory equipment. No clean-up or solvent evaporation were required before determination of BPA by liquid chromatography and fluorescence detection. Recoveries in samples were between 90 and 99%, with relative standard deviations in the range 2–7%. The limit of quantification ranged 29–15 ng g^?1 for 200–400 mg of sample, being far below the current specific migration limit (SML) set by the European Commission (600 ng g^?1). The method was successfully applied to the determination of BPA in the solid content of canned fish (from 20 to 129 ng g^?1) and meat (from undetected to 37 ng g^?1).     

Furan in commercial baby foods from the Spanish market: estimation of daily intake and risk assessment

ABSTRACT

The occurrence of furan in commercial baby food samples from the Spanish market was evaluated using an automated headspace solid-phase microextraction method coupled to gas chromatography-mass spectrometry (HS-SPME-GC-MS). A total of 76 baby food samples including infant formula, baby cereals, fruit in cans and/or jars, vegetables, meat, and fish, were surveyed for furan content. The lowest concentration of this compound was found in infant formula (<0.02–0.33 ng ml^?1), and cereal-based food (0.15–2.1 ng g^?1) while baby food containing fish showed the highest concentrations (19–84 ng g^?1). Following recommendation of the European Food Safety Authority (EFSA), the effect on furan content was evaluated of consumer home preparation of foods, heating and handling. Furan concentrations were reduced by up to 35% when samples were heated in a dish using microwave oven and by up to 53% when a hot water bath was used. Finally, we estimated the furan intake from baby food consumption (0.002–1.18 µg kg^?1 body weight day^?1) and we calculated the margin of exposure (MOE) from samples as purchased and also after home preparation of the food. For infant formula and cereal baby foods, the MOEs (26,278–412,776) indicated no infant health concern or priority, while for meat and fish-based baby foods the values pointed to a potential public health risk, even considering the furan losses during preparation at home.     

Determination of oxytetracycline residue in shrimp using a portable time-resolved analyzer and HPLC�CMS/MS validation

Oxytetracycline residue in shrimp muscle was determined using a portable time-resolved analyzer. After extraction in EDTA-metaphosphoric acid and filtration, the analyte was cleaned up using hydrophilic-lipophilic balance cartridges. Europium-sensitized luminescence (ESL) was measured at ??_ex = 385 nm and ??_em = 620 nm. Recoveries were 80.3 and 79.7% at 100 ng g^?1 and 2 ??g g^?1, respectively. The signal intensity was linear (r ² ?? 0.996) in each decade in the 5?C5,000 ng g^?1 range. Averaged relative standard deviation was ~2% and limit of detection was 8.3 ng g^?1. This instrument-method combination enabled sensitive in-situ quantification of OTC residue in shrimp. The ESL results were validated by HPLC?CMS/MS.     

Fusarium species identification and fumonisin production in maize kernels from Shandong Province,China, from 2012 to 2014

A total of 225 maize kernel samples were collected from Shandong Province in China from 2012 to 2014 and analysed for contamination with Fusarium spp. and fumonisins (FBs) using molecular methods and high-performance liquid chromatography with fluorescence detection. The results showed that the average incidences of Fusarium spp. in 2012, 2013 and 2014 were 23.3%, 37.1% and 36.5%, respectively, Fusarium verticillioides being the predominant species. In 2012, the average contamination level of FBs was 3071 ng g^?1, which was higher than that in 2014 (2913 ng g^?1) and 2013 (2072 ng g^?1). Of all samples, 13% and 19% had FB contamination levels higher than 2000 and 4000 ng g^?1, which are the maximum limits as set by the Food and Drug Administration of the United States and the European Commission, respectively. Therefore, efforts should be taken to minimise the potential risk of FBs to the health of humans and animals.     

Aspergillus and aflatoxin in groundnut (Arachis hypogaea L.) and groundnut cake in Eastern Ethiopia

This study was conducted to assess major Aspergillus species and aflatoxins associated with groundnut seeds and cake in Eastern Ethiopia and evaluate growers’ management practices. A total of 160 groundnut seed samples from farmers’ stores and 50 groundnut cake samples from cafe and restaurants were collected. Fungal isolation was done from groundnut seed samples. Aspergillus flavus was the dominant species followed by Aspergillus parasiticus. Aflatoxin analyses of groundnut seed samples were performed using ultra performance liquid chromatography; 22.5% and 41.3% of samples were positive, with total aflatoxin concentrations of 786 and 3135 ng g^?1 from 2013/2014 and 2014/2015 samples, respectively. The level of specific aflatoxin concentration varied between 0.1 and 2526 ng g^?1 for B₂ and B₁, respectively. Among contaminated samples of groundnut cake, 68% exhibited aflatoxin concentration below 20 ng g^?1, while as high as 158 ng g^?1 aflatoxin B₁ was recorded. The study confirms high contamination of groundnut products in East Ethiopia.     

LC-TOF/MS determination of phthalates in edible salts from food markets in Korea

Residual quantities of 12 phthalates have been monitored in edible salts (raw salts, refined salts, refined salts with additives and baked salts) available in Korean food markets. Liquid–liquid extraction followed by liquid chromatography time-of-flight mass spectrometry (LC-TOF/MS) was used to analyse the samples. The method was validated and showed linear correlation (R ² > 0.996) in the range 0.5–100 ng g^?1 for all target analytes. Recoveries were 85.9–108.4%, except for diethyl phthalate (DEP). Relative standard deviations (RSDs) were 2.7–6.0% and the limits of detection (LODs) were 1.2–2.8 ng g^?1. Although the contamination of phthalates in salt would be trivial in comparison to those of other main foods and below the reference dose of the Chronic Oral Exposure recommended by US-EPA, the availability of reference data could be valuable for food chemists and salt manufacturers.     

Influence of food condiments on the formation of carcinogenic heterocyclic amines in cooked chicken and determination by LC-MS/MS

Heterocyclic amines (HCAs) are known to be suspected human carcinogens produced by high-temperature cooking of protein-rich foods such as meat and fish. In the present study, the influence of numerous food condiments on the formation of HCAs in cooked chicken was investigated. Chicken samples were subjected to pan-frying under controlled temperature. The levels of HCAs DMIP, MeIQx, 4,8-DiMeIQx, PhIP, harman and norharman were found to be between 0.93 and 27.52 ng g^?1, whereas IQ, MeIQ, AαC, MeAαC, Trp-P-1 and Trp-P-2 were found either below the limit of quantification or not detected in the control sample. Nevertheless, for samples cooked using food condiments, the amounts of HCAs (DMIP, MeIQx, 4,8-DiMeIQx and PhIP) were between 0.14 and 19.57 ng g^?1; harman and norharman were detected at higher concentrations up to 17.77 ng g^?1 while IQ and MeIQ were at levels below the limit of quantification; and AαC, MeAαC, Trp-P-1 and Trp-P-2 were not detected in any of the samples. The outcomes revealed that the formation of HCAs (except harman and norharman) diminished after the addition of food condiments. Edible oil contributed to the highest levels of HCA formation, followed by garlic, paprika, pepper and tomato.     

Monitoring of 29 weight loss compounds in foods and dietary supplements by LC-MS/MS

Because of the rapid growth in dietary supplement availability and public concern for weight control, the investigation of foods and various dietary supplements illegally adulterated with weight loss compounds has become increasingly important. A total of 29 weight loss compounds, including sennoside, sibutramine, ephedrine and their analogues, found to be adulterated in foods and dietary supplements were simultaneously examined by LC-MS/MS. The 188 samples were collected between 2009 and 2012 in South Korea, and method validation was performed to determine the adulterants to the weight loss compounds. LODs, LOQs and linearity ranged from 0.03 to 7.5 ng ml^?1, from 0.08 to 30.00 ng ml^?1, and from 0.990 to 0.999, respectively. The results showed that nine weight loss compounds, namely bisacodyl, desmethylsibutramine, didesmethylsibutramine, ephedrine, fluoxetine, pseudoephedrine, sennoside A, sennoside B and sibutramine, were detected in 62 of all collected samples and were found in order of frequency as follows: sibutramine, 25.7%; sennoside A, 22.9%; sennoside B, 20.0%; fluoxetine, 8.6%; desmethylsibutramine, 7.1%; bisacodyl, ephedrine, and pseudoephedrine, 4.3%; and didesmethylsibutramine, 2.9%. Sibutramine, which was the most frequently found adulterant, ranged in levels from 0.03 to 132.40 mg g^?1 (2010), from 0.88 to 76.2 mg g^?1 (2011), and from 0.07 to 0.24 mg g^?1 (2012). Although the concentrations of most compounds ranged widely, some compounds such as bisacodyl and fluoxetine were found at high concentrations in several samples.     

Determination of Phthalates into Vegetable Oils by Isotopic Dilution Gas Chromatography Mass Spectrometry

The presented method for the determination of a number of phthalic acid esters into oily media is based on their extraction by acetonitrile with precipitation under freezing and subsequent solid-phase extraction using alumina. This technique was checked as the best procedure to separate lipophilic phthalates from fatty media achieving elimination of contamination by excess use of solvents. Extracted phthalates are determined in acetonitrile solutions with gas chromatography in conjunction to isotopic dilution mass spectrometry using D4 isotopic labeled derivatives. Full validation of the method was carried out and background effect was examined. Method calibration for extraction from oil resulted in limit of detection (LOD) of 7–10 ng g^?1 and limit of quantification (LOQ) of 20–50 ng g^?1 for DMP, DEP, DiBP, DBP, DEHP, and BBP and in LOD 500 ng g^?1 and LOQ of 1,500 ng g^?1 for DiNP and DiDP. Real samples of virgin olive oil from olive press establishments from three different areas were analyzed and the phthalates content was below detection limit for all phthalic esters under consideration for nonindustrial areas and in measurable concentrations for industrial areas specifically with regard to DiBP.     

Occurrence of polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs) and polychlorinated biphenyls (PCBs) in eggs from free-range hens in Campania (southern Italy) and risk evaluation

ABSTRACT

Hens’ eggs collected in home-producing farms located in different areas of the Campania region of southern Italy were analysed for six NDL-polychlorobiphenyls (PCB indicators), 17 polychlorodibenzo-p-dioxins (PCDDs) and polychlorodibenzofurans (PCDFs), and 12 congeners of dioxin-like PCBs (DL-PCBs). In the investigated area, waste from civil, industrial and hospital activities was illegally dumped and in many cases burned, so the area is called the ‘Land of fire’. This illicit practice has been considered the main source of pollution in this territory and the cause of the persistent organic pollutants’ (POPs) contamination in the neighbouring lands intended for agricultural use and livestock. The results, which were obtained from the analysis of 56 samples of eggs, showed levels of contamination by dioxins and PCBs that have often exceeded the action levels set by European Union Recommendation 711/2013 and sometimes even exceeded the maximum levels set by Commission Regulation (EU) 1259/2011. The median PCDD/Fs was 0.41 pg TEQ g^?1 fat (range = 0.01–6.18 pg TEQ g^?1 fat) and the median concentration of DL-PCBs was 0.70 pg TEQ g^?1 fat (range = 0.01–14.60 pg TEQ g^?1 fat), whereas NDL-PCBs median was 7.35 ng g^?1 fat (range = 0.48–67.55 ng g^?1 fat). Nevertheless, the estimated weekly intake (EWI) calculated for consumers of eggs home produced in Campania is lower than the tolerable weekly intake (TWI) established by the European Union Scientific Committee on Food (SCF).     

Levels and distribution of PBDEs and PFASs in pork from different European countries

ABSTRACT

Meat and meat products are included in a great number of human diets. However, the great consumption of meat needs to be controlled for the presence of traces of contaminants. The European Commission has not stated maximum limits for some environmental pollutants such as the perfluoroalkyl substances (PFASs) and polybrominated diphenyl ether (PBDE); the European Food Safety Authority (EFSA) Scientific Panel has recommended that more occurrence data for PFASs in food should be collected to improve the accuracy of future exposure calculations. Therefore, the distribution of PFASs and PBDEs trace contaminants from eight EU Member States were investigated through liquid chromatography coupled to high-resolution mass spectrometry (LC-HRMS) and Gas Chromatography-Mass Spectrometry (GC-MS/MS). No PFASs were detected, except perfluorooctanoic acid, in only one Austrian sample at the concentration of 0.531 ng g^?1. PBDEs were detected in 3 out of 77 samples: one from Germany showed the presence of all congeners analysed in the concentration range 0.53–0.77 ng g^?1, the others, from Netherland and Italy, respectively contained PBDE 153 (0.53 ng g^?1) and PBDE 100 (0.62 ng g^?1). The results show that the analysed samples do not pose a risk for human beings in regard to PFASs and PBDEs. Further studies are needed to keep monitoring their presence in foodstuff, as it has been suggested by European Commission.     

Optimization of Headspace Single-Drop Microextraction Coupled with Gas Chromatography–Mass Spectrometry for Determining Volatile Oxidation Compounds in Mayonnaise by Response Surface Methodology

In this assay, headspace single-drop microextraction (HS-SDME) coupled with gas chromatography–mass spectrometry (GC–MS) as a simple, low-cost and rapid method has been developed and validated for determining volatile oxidation compounds including hexanal and heptanal in mayonnaise. The main microextraction variables affecting the HS-SDME procedure such as extraction temperature and time, stirring rate, and amount of NaCl were optimized by response surface methodology employing a central composite design. Obtained results demonstrated that higher yield of extracted analytes could be achieved under the following optimal conditions: extraction temperature of 45 °C, extraction time of 16 min, stirring rate at 700 rpm, and addition of 2 g NaCl. The optimized HS-SDME/GC–MS method was validated for oxidized mayonnaise samples (50 °C/48 h) by calculating analytical parameters (linearity, precision, accuracy, and sensitivity). Good linearity (R ²?>?0.99) was observed by plotting calibration curves of extracted hexanal and heptanal over the concentration range of 0.025–10 μg g^?1, and the repeatability of the method, expressed as relative standard deviation, were found to be 4.04 % for hexanal and 3.68 % for heptanal (n?=?7). After the microextraction process of spiked mayonnaise sample, high levels of relative recovery were obtained for hexanal (107.33 %) and heptanal (91.43 %). The detection limits were 0.008 ng g^?1 and 0.021 ng g^?1 for hexanal and heptanal, respectively, while quantification limits of hexanal and heptanal were calculated to be 0.027 ng g^?1 and 0.071 ng g^?1, respectively. The possibility of the HS-SDME followed GC–MS to determine and quantify volatile oxidation compounds such as hexanal and heptanal was confirmed by analyzing commercial fresh mayonnaise stored at 4 and 25 °C during 3 months.     

Monitoring by LC-MS/MS of 48 compounds of sildenafil,tadalafil, vardenafil and their analogues in illicit health food products in the Korean market advertised as enhancing male sexual performance

More than 46 phosphodiesterase type 5 (PDE5) inhibitor analogues have been found to be present as illegal adulterants in various forms of health food products (powder, tablet, capsule, etc.), thereby placing the health of consumers at risk through product intake. In this study, 164 samples advertised to be effective at enhancing male sexual performance were collected over a 4-year period (2009–2012) from the Korean on-line or off-line market and screened. An LC-MS/MS method was employed to screen for the presence of 48 compounds including sildenafil, tadalafil, vardenafil and their analogues. Method validation established LOQs (0.30–10.00 ng ml^?1 or ng g^?1) and recoveries (spiked in liquid sample, 84–112%; spiked in solid sample, 83–110%). Most of the illicit products screened were adulterated with 14 of the PDE5 derivatives under examination, including considerable amounts of sildenafil and tadalafil; of the 48 compounds, tadalafil was the most frequent adulterant (42.6%), followed by sildenafil (27.9%). Specifically, tadalafil concentration ranges (mg g^?1) in the samples collected over the 4-year period were determined as follows: 2.91–52.20 (2009), 4.50–108.10 (2010), 0.37–101.40 (2011), and 0.08–138.69 mg g^?1 (2012). The concentration ranges (mg g^?1) of sildenafil were also at high levels: 4.90–117.96 (2009), 1.30–369.93 (2010), 0.03–241.77 (2011), and 18.34–297.91 mg g^?1 (2012). The results of screening for PDE5 inhibitor pharmaceuticals as adulterants in illicit health food products are of great significance with respect to the protection of public health and consumer safety.