Electromembrane extraction of aristolochic acids: New insights in separation of bioactive ingredients of traditional Chinese medicines.

Aristolochic acid (AA) I and AA II, which have been classified as carcinogenic to human and have been proven to be nephrotoxic, are bioactive ingredients of many traditional Chinese medicines (TCMs). Thus, development of an efficient approach for separation and determination of AA I and AA II in biological samples and herbal plants is of significance. Herein, electromembrane extraction (EME) was for the first time used to separate AA I and AA II. It is noted that also for the first time 1-decanol was discovered and used as an efficient SLM solvent for EME of acidic compounds. The proposed EME system was used to extract AA I and AA II from urine samples (recovery≥68%). The approach of EME combined with LC-MS (EME-LC/MS) was evaluated using urine samples. The linear range for AA I and AA II was 10-1000 ng mL-1 (R2≥0.9970), and the limits of detection (LOD, S/N = 3) for AA I and AA II were 2.7 and 2.9 ng mL-1, respectively. Finally, this EME-LC/MS approach was employed to discover AA I and AA II in the herbal plants. In addition, using standard addition method, AA I in Aristolochicaceae-Liao Asarum (ALA) and Radix Aristolochice (RA) were 0.23 and 2044.13 µg g-1, and AA II in ALA and RA were 0 and 338.48 µg g-1, respectively. The repeatability of EME-LC/MS at all cases for both urine samples and herbal plants was below 15% (RSD-value). We believe that EME would be a useful tool to isolate bioactive ingredients of TCMs from complex samples for different purposes.

Selective tools for the solid-phase extraction of Ochratoxin A from various complex samples: immunosorbents, oligosorbents, and molecularly imprinted polymers.

The evolution of instrumentation in terms of separation and detection has allowed a real improvement of the sensitivity and the analysis time. However, the analysis of ultra-traces of toxins such as ochratoxin A (OTA) from complex samples (foodstuffs, biological fluids…) still requires a step of purification and of preconcentration before chromatographic determination. In this context, extraction sorbents leading to a molecular recognition mechanism appear as powerful tools for the selective extraction of OTA and of its structural analogs in order to obtain more reliable and sensitive quantitative analyses of these compounds in complex media. Indeed, immunosorbents and oligosorbents that are based on the use of immobilized antibodies and of aptamers, respectively, and that are specific to OTA allow its selective clean-up from complex samples with high enrichment factors. Similar molecular recognition mechanisms can also be obtained by developing molecularly imprinted polymers, the synthesis of which leads to the formation of cavities that are specific to OTA, thus mimicking the recognition site of the biomolecules. Therefore, the principle, the advantages, the limits of these different types of extraction tools, and their complementary behaviors will be presented. The introduction of these selective tools in miniaturized devices will also be discussed.

Radón y sus efectos en la salud en trabajadores de minas de uranio / Radon and its effects on the health of uranium mine workers

INTRODUCCIÓN: El radón es un gas presente en subsuelo, especialmente en minas de uranio, que produce consecuencias sobre la salud, entre las que destaca el cáncer de pulmón. En EEUU es la segunda causa de mortalidad por esta enfermedad. Pese a la fuerte relación causal no existe normativa específica europea de regulación en mineros. OBJETIVOS: Identificar el efecto del radón y sus derivados sobre la salud de los trabajadores de minas de uranio; describir la asociación entre exposición a radón y a otros minerales sobre la salud y asociación entre radón y consumo de tabaco. METODOLOGÍA: Realizamos una revisión bibliográfica de literatura publicada entre 2007 y 2014, en bases de datos biomédicas, utilizando los criterios de inclusión y exclusión previamente establecidos. RESULTADOS: Se revisan 32 artículos, encontrando un aumento significativo de cáncer pulmonar (SMR-2.03, IC95% 1.96-2.10), incluso a dosis bajas (300-WLM) así como otros cánceres (laringe, gástrico, hepático y leucemia) y enfermedades cerebrovasculares, controlando posibles factores de confusión (tabaco, silicosis, cuarzo y arsénico) no encontrando relación significativa ni sinergias. CONCLUSIÓN: Existe asociación entre la exposición al radón y cáncer pulmonar en minas de uranio, con un periodo medio de latencia de 20 años, determinado por la dosis de radón y el tiempo de exposición. No se ha demostrado riesgo de desarrollar otros tipos de tumores, y los estudios que lo sugieren son poco consistentes

INTRODUCTION: Radon is a gas that can be found underground, particularly in uranium mines, and which has consequences on health, namely lung cancer. It is the second cause of mortality for this disease in the United States. In spite of the strong causal relationship between both elements, there are no specific European regulations concerning miners. OBJECTIVES: To identify the effect of radon and its derivatives on the health of uranium mine workers; to describe the association between exposure to radon and other minerals and health as well as the association between radon and tobacco consumption. METHODS: We perform a bibliographic review of the literature that has been published from 2007 to 2014 in different biomedical databases, using previously established inclusion and exclusion criteria. RESULTS: 32 articles were reviewed and a significant increase of lung cancer was observed (SMR: 2.03, 95% CI: 1.96-2.10) even for low doses (WLM: 300) as well as other types of cancer (laryngeal, gastric and hepatic cancer and leukemia) and cerebrovascular diseases, after adjusting for other confounding factors (tobacco consumption, silicosis, exposure to quartz and arsenic) in which no significant associations or synergies were found. CONCLUSION: There is an association between exposure to radon and lung cancer in uranium mines, with an average latency period of 20 years, determined by the dose of radon and the time of exposure. We did not find risk of developing other types of tumors, and the studies that suggest this hypothesis are inconsistent

Liquid chromatography-tandem mass spectrometry (LC-MS/MS) method for the direct detection of 2-monochloropropanediol (2-MCPD) esters in edible oils.

A new analytical method has been developed and validated for the detection and quantification of 2-monochloropropanediol (2-MCPD) esters in edible oils. The target compounds are potentially carcinogenic contaminants formed during the processing of edible oils. As the 2-MCPD esters that occur most frequently in refined edible oils were not commercially available, standards were synthesized with identity and purity (95+%) confirmed by liquid chromatography-tandem mass spectrometry (LC-MS/MS) and (1)H NMR. Target analytes are separated from edible oil matrices using a two-step solid-phase extraction (SPE) procedure. The extracts are then analyzed using LC-MS/MS with electrospray ionization (ESI). The method has been validated for 11 2-MCPD diesters and 3 2-MCPD monoesters in soybean oil, olive oil, and palm oil using an external calibration curve. The ranges of average recoveries and relative standard deviations (RSD) across the three oil matrices at three spiking concentrations are 79-106% (3-13% RSD) for the 2-MCPD diesters and 72-108% (4-17% RSD) for the 2-MCPD monoesters, with limits of quantitation at or below 30 ng/g for the diesters and 90 ng/g for the monoesters.

Batch and continuous removal of arsenic using hyacinth roots.

Arsenic is considered a primary pollutant in drinking water because of its high toxicity. The unique property of water hyacinth roots (Eichhornia crassipes) to remove heavy metals is of great signiicance for the development of a cost-effective phytoremediation technology. An experimental test program was conducted at the United States Environmental Protection (USEPA) Test and Evaluation (T&E) Facility in Cincinnati, Ohio, to investigate the potential of water hyacinth roots to remove arsenic from spiked drinking water samples. Water hyacinth roots were washed, dried, and powdered to provide dried hyacinth roots (DHR) for batch and continuous column experiments, Various quantities of DHR were added to water spiked with 300 micrograms per liter (microg/L) arsenic. A concentration of 20 g/L DHR was found adequate for greater than 90% arsenic removal in the batch tests. Based on the batch test results, continuous column experiments were performed using a 2-L column. In a continuous system, 15 L of water containing 300 microg/L arsenic were treated to below 20 microg/L using 50 g DHR, and 44 L of water containing 600 microg/L arsenic were treated to below 20 microg/L using 100 g DHR, giving a specific accumulation rate of approximately 260 microg As/g DHR.

Determination of the cyanobacterial toxin cylindrospermopsin in algal food supplements.

For the analysis of blue-green algal food supplements for cylindrospermopsin (CYN), a C18 solid-phase extraction column and a polygraphitized carbon solid-phase extraction column in series was an effective procedure for the clean-up of extracts. Determination of CYN was by liquid chromatography with ultraviolet light detection. At extract spiking levels of CYN equivalent to 25-500 µg g(-1), blue-green algal supplement recoveries were in the range 70-90%. CYN was not detected in ten samples of food supplements and one chocolate product, all containing blue-green algae. The limit of detection for the method was 16 µg g(-1), and the limit of quantification was 52 µg g(-1).

Irritant and co-carcinogenic diterpene esters from the latex of Euphorbia cauducifolia L.

Ten (1-10) irritant and mild co-carcinogenic diterpene esters were isolated from the latex of Euphorbia cauducifolia L. using bioassay-guided countercurrent distribution and other chromatographic techniques. The isolated compounds were characterized on the basis of spectroscopic results and mass measurements. As an outcome, the ingenane-type esters were established with the following structures: 3-O-angeloyl-17-O-palmatoylingenol (1), 3-O-palmatoyl-5-O-angeloylingenol (2), 5-O-angeloyl-17-O-palmatoylingenol (3), 3-O-angeloyl-5-O-palmatoylingenol (4), 17-O-(2Z,4E,6Z)-2,4,6-tetradecatrienoyl-20-O-palmatoylingenol (5), 5-O-angeloyl-17-O-benzoylingenol (6), 5-O-angeloyl-17,20-diacetoxyingenol (7), 3-O-angeloyl-17-O-benzoyl-20-acetoxyingenol (8), 3-acetoxy-5-O-angeloyl-17-O-benzoylingenol (9), and 5-O-angeloyl-3,17,20-triacetoxyingenol (10). Their biological screening revealed that they are moderate irritants, and low to moderate tumor promoters compared to TPA, but hardly showed any solitary carcinogenic activity. The isolated esters represent new compounds and were not reported before from any source.

The use of stir bar sorptive extraction--a potential alternative method for the determination of furan, evaluated using two example food matrices.

A comparison is made between static headspace analysis and stir bar sorptive extraction (SBSE) for the quantitative determination of furan. The SBSE technique was optimised and evaluated using two example food matrices (coffee and jarred baby food). The use of the SBSE technique in most cases, gave comparable results to the static headspace method, using the method of standard additions with d4-labelled furan as an internal standard. Using the SBSE method, limits of detection down to 2 ng g(-1) were achieved, with only a 1 h extraction. The method was performed at ambient temperatures, thus eliminating the possibility of formation of furan during extraction.

Reduction of beta-asarone in acori rhizoma by decoction.

Beta-asarone, the major constituent of the essential oil from the traditional Chinese herbal drug "Acori rhizoma" is regarded as carcinogenic in rodents and potentially genotoxic. Thus, the limit for the ingestion of this constituent from herbal medicinal products has been set at 0.115 mg beta-asarone/person/day. The present study demonstrates that a decoction procedure, traditionally used for Chinese herbal preparations and intended as the standard procedure in Ph. Eur., was able to significantly reduce the amount of beta-asarone. HPLC analysis indicated that the content of beta-asarone in dried herbal drug ranged from 15.22 to 25.34 mg/g. During a 1-hour decoction, the amount of beta-asarone decreased more than 85 % and the aqueous extract contained the equivalent of only 0.46-2.19 mg beta-asarone per gram of herbal drug. If this aqueous extract was heated for a further 2 hours, the final content of beta-asarone was reduced to the equivalent of no more than 0.005 mg per gram of herbal drug. This low level of beta-asarone should be acceptable for therapeutic use. It was noted that decoction of Acori rhizoma in the presence of other herbal substances impaired, to some extent, the reduction in beta-asarone.

La acrilamida, contaminante químico de procesado: revisión / Acrylamide formation in foods: a review Acrylamide

La acrilamida, 'probable carcinógeno para los humanos',mutágeno de categoría 2 y tóxico para la reproducción de categoría 3según la UE, se comporta como neurotóxico tras exposiciones agudas. A pesar de que se recomienda disminuir los niveles de exposición, el tabaquismo, la exposición ocupacional y la exposición dietética son fuentes de acrilamida para el hombre. De entre todos los alimentos, son los ricos en carbohidratos y los elaborados a altas temperaturas, los que mayores niveles de este tóxico presentan. En la presente revisión se explica la formación de acrilamida en los alimentos, se describen sus efectos tóxicos, se citan los métodos analíticos usados en su determinación, se recopilan datos sobre los niveles detectados en distintos alimentos y se enumeran los datos más recientes sobre la ingesta en distintas poblaciones (AU)

Acrylamide formation in foods: A review Acrylamide,'probable carcinogenic for humans', mutagenic type 2 and toxic for reproduction type 3 for the European Union, produces neurotoxicity after acute expositions. Although recommendations are given to minimize the exposition levels to this compound, smoking and occupational and dietary exposures are important acrylamide sources. Among foods, those rich in carbohydrates and those cooked at high temperatures present the highest acrylamide concentrations. The present revision points out the acrylamide formation in foods, its toxic effects and the analytical methods used in its determination. Moreover, data are given about acrylamide levels in foods and dietary intakes in different populations (AU)

Development of a tubular high-density plasma reactor for water treatment.

Experiments have yielded a number of important insights into the energy distribution, sparging and oxidation of methyl tert-butyl ether (MTBE), benzene, ethylbenzene, toluene, m- and p-xylene, and o-xylene (BTEX) in a dense medium plasma reactor (DMPR). It has been found that the DMPR transferred a relatively small amount of electrical energy, approximately 4% in the form of sensible heat, to the surrounding bulk liquid. Rate constants associated with plasma initiated oxidation, interphase mass transfer and photolysis were determined using a combination of non-linear least squares analysis and Matlab optimization for each species. The rate constants developed for the DMPR, in conjunction with a species mass balance on a prototype tubular high-density plasma reactor, have been applied to determine the removal rates of MTBE and the BTEXs when operating in batch and continuous flow configurations. The dependence of contaminant concentration on parameters such as treatment time, the number of pin electrodes, electrode gap, and volumetric flow rate has been determined. It was found that, under various design specifications and operating conditions, the tubular high-density plasma reactor may be an effective tool for the removal of volatile organic compounds from aqueous solutions.

Odor and volatile organic compound removal from wastewater treatment plant headworks ventilation air using a biofilter.

Laboratory-scale experiments and field studies were performed to evaluate the feasibility of biofilters for sequential removal of hydrogen sulfide and volatile organic compounds (VOCs) from wastewater treatment plant waste air. The biofilter was designed for spatially separated removal of pollutants to mitigate the effects of acid production resulting from hydrogen sulfide oxidation. The inlet section of the upflow units was designated for hydrogen sulfide removal and the second section was designated for VOC removal. Complete removal of hydrogen sulfide (H2S) and methyl tert-butyl ether (MTBE) was accomplished at loading rates of 8.3 g H2S/(m3 x h) (15-second empty bed retention time [EBRT]) and 33 g MTBE/(m3 x h) (60-second EBRT), respectively. In field studies performed at the Hyperion Treatment Plant in Los Angeles, California, excellent removal of hydrogen sulfide, moderate removal of nonchlorinated VOCs such as toluene and benzene, and poor removal of chlorinated VOCs were observed in treating the headworks waste air. During spiking experiments on the headworks waste air, the percentage removals were similar to the unspiked removals when nonchlorinated VOCs were spiked; however, feeding high concentrations of chlorinated VOCs reduced the removal percentages for all VOCs. Thus, biofilters offer a distinct advantage over chemical scrubbers currently used at publicly owned treatment works in that they not only remove odor and hydrogen sulfide efficiently at low cost, but also reduce overall toxicity by partially removing VOCs and avoiding the use of hazardous chemicals.

Detection of aristolochic acid in Chinese phytomedicines and dietary supplements used as slimming regimens.

Over the last 10 years, numerous cases of intoxications, leading for the most part to end-stage renal failure, have been reported after consumption of slimming regimens made of Chinese herbal preparations. These intoxications were associated with species of the Aristolochia genus, such as Aristolochia fangchi (Aristolochiaceae), known to contain very nephrotoxic and carcinogenic metabolites named aristolochic acids. Several commercial dietary supplements, teas and phytomedicines used as slimming regimens were analysed for their aristolochic acid I content. A preliminary detection of this toxic compound was made by thin-layer chromatography. The presence of aristolochic acid I in these preparations was confirmed by a HPLC/UV-DAD/MS analysis. A quantitative determination of aristolochic acid I was also achieved in the incriminated preparations using both UV and MS detection. Out of 42 analysed preparations, four were found to contain aristolochic acid I and two were suspected to contain aristolochic acid derivatives. Immediate removal of these products from the Swiss market was called for.

Evaluation of carcinogenic/co-carcinogenic activity of chikusaku-eki, a bamboo charcoal by-product used as a folk remedy, in BALB/c 3T3 cells.

Chikusaku-eki is an acidic dark brown liquid obtained as a by-product from bamboo charcoal burners. The solution diluted with water is gaining widespread popularity in Japan as a folk medicine for skin diseases such as scabies, eczema, and atopic dermatitis. In this study, the carcinogenic and tumor-promoting potential of chikusaku-eki was determined using the BALB/c 3T3 A31-1-1 cell transformation system. Carcinogenic activity was tested by treating A31-1-1 cells for 24 h with 0.06% solution, a dose resulting in 35% clonogenic cell survival. In both 2-O-tetradecanoylphorbol-13-acetate (TPA)-treated and non-treated groups, chikusaku-eki did not initiate carsinogenesis. Following initiation with 3-methylcholanthrene (3-MCA), A31-1-1 cells were chronically treated with a non-toxic concentration range of chikusaku-eki (< or = 0.01%), but chikusaku-eki did not act as a tumor promoter. Thus, chikusaku-eki was not carcinogenic/co-carcinogenic in the in vitro cell transformation assay examined in this study after being diluted more than 10(4)-fold with water.

Potential carcinogenic and inhibitory activity of compounds isolated from Lilium candidum L.

This paper deals with determination of potential carcinogenic and inhibitory activity of 10 compounds isolated from the ethanolic extract of Lilium candidum L. perfonned by DC polarography. The series of investigated compounds consisted of two spirostanol saponins, two pyroline derivatives, jatropham and its glucoside, flavonol kaempferol, 2-fenylethyl-alpha-L-arabinopyranosyl-(1-->6)-beta-D-glucopyranoside, 2-phenylethylpalmitate and methylsuccinic acid. Carcinogenic, resp. mutagenic activity data for these compounds, with the exception of kaempferol, are not available in scientific literature. All tested compounds were reduced in N,N-dimethylformamide in one or two well defined steps. They also fonned a reversible complex with alpha-lipoic acid, a compound serving as an indicator of carcinogenic activity. The marginal diffuse current values of these complexes served as a criterion of a very low potential carcinogenicity. The inhibitory activity of isolates were studied in the presence of 12-O-tetradecanoylphorbol-13-acetate, a specific tumor promoter for an epidermal carcinogenesis, and in the presence of a polyaromatic substance 7,12-dimetylbenz(a)anthracene known as a carcinogen. The spirostanol saponins possessed the highest inhibitory activity (> 70%) and jatropham (66%). The inhibitory activity of jatropham glucoside was significantly lower (49%). Practically zero inhibitory activity was measured for the 2-phenylethylpalmitate and methylsuccinic acid.

Medicinal plants in China containing pyrrolizidine alkaloids.

Medicinal plants and remedies are widely used for various ailments throughout the world. Many of these plants contain pyrrolizidine alkaloids (PAs) which are hepatotoxic, pneumotoxic, genotoxic, neurotoxic, and cytotoxic. As a result of their use in Traditional Chinese Medicine (TCM), medicinal plants are becoming increasingly important not only in China but also in many other countries. This paper will therefore give, a critical overview of PA-containing plants belonging mainly to the families Boraginaceae, Leguminosae (Tribus Crotalarieae), and Asteraceae (Tribus Senecioneae and Eupatorieae). The PAs contained in the 38 plants described here differ widely in their structure and toxicity. Their metabolism and the resulting toxicity will be discussed, the dehydroalkaloids (DHAlk) produced in the liver playing a key role in cases of intoxications.

Characterization of two structural forms of otonecine-type pyrrolizidine alkaloids from Ligularia hodgsonii by NMR spectroscopy.

Clivorine (1) and ligularine (2), two hepatotoxic otonecine-type pyrrolizidine alkaloids isolated from Ligularia hodgsonii, an antitussive traditional Chinese medicine, were investigated in CDCl(3) and D(2)O by various NMR techniques to delineate why this type of alkaloid displays uncharacteristic solubility properties by dissolving in both nonpolar organic and aqueous solutions. The results demonstrated that both alkaloids exist in a non-ionized form in CDCl(3), but in an ionized form in D(2)O, suggesting that this unique dual solubility may play a role in the intoxication resultant from consumption of water extracts of herbs, including herbal teas, containing otonecine-type pyrrolizidine alkaloids.

Iridals from Iris tectorum and Belamcanda chinensis.

Three iridals, iridotectorals A and B, and iridobelamal. A, were isolated from rhizomes of Iris tectorum and Belamcanda chinensis, respectively, along with five known iridals. Their structures were elucidated on the basis of spectral evidence. The human promyelocytic leukemia (HL-60) cell-adhesion activity of the eight iridals is also discussed.

Identification of carcinogens in cooking oil fumes.

According to earlier studies, fumes from cooking oils were found to be genotoxic in several short-term tests such as the Ames test, sister chromatid exchange, and SOS chromotest. Fume samples from six different commercial cooking oils (safflower, olive, coconut, mustard, vegetable, and corn) frequently used in Taiwan were collected. Polycyclic aromatic hydrocarbons (PAHs) were extracted from the air samples and identified by high-performance liquid chromatography and confirmed by gas chromatography/mass spectrometry. Extracts of fumes from safflower oil, vegetable oil, and corn oil contained benzo[a]pyrene (BaP), dibenz[a,h]anthracene (DBahA), benzo[b]fluoranthene (BbFA), and benzo[a]anthracene (BaA). Concentrations of BaP, DbahA, BbFA, and BaA were 2.1, 2.8, 1.8, and 2.5 microg/m3 in fumes from safflower oil; 2.7, 3.2, 2.6, and 2.1 microg/m3 in vegetable oil; and 2.6, 2.4, 2.0, and 1.9 microg/m3 in corn oil, respectively. The authors constructed models to study the efficacy of table-edged fume extractors used commonly by Taiwanese restaurants. Concentrations of BaP were significantly decreased when the fume extractor was working (P<0.05) and the average reduction in percentage was 75%. The other identified PAHs were undetected. These results indicated that exposure to cooking oil fumes could possibly increase exposure to PAHs, which may be linked to an increased risk of lung cancer. The potential carcinogenic exposure could be reduced by placing table-edged fume extractors near cooking pots.