[Metabolomic interference induced by short-chain chlorinated paraffins in human normal hepatic cells].

Short-chain chlorinated paraffins (SCCPs) are an emerging class of persistent organic pollutants (POPs) that are widely detected in environmental matrices and human samples. Because of their environmental persistence, long-range transport potential, bioaccumulation potential, and biotoxicity, SCCPs pose a significant threat to human health. In this study, metabolomics technology was applied to reveal the metabolomic interference in human normal hepatic (L02) cells after exposure to low (1 µg/L), moderate (10 µg/L), and high (100 µg/L) doses of SCCPs. Principal component analysis (PCA) and metabolic effect level index (MELI) values showed that all three SCCP doses caused notable metabolic perturbations in L02 cells. A total of 72 metabolites that were annotated by MS/MS and matched with the experimental spectra in the Human Metabolome Database (HMDB) or validated by commercially available standards were selected as differential metabolites (DMs) across all groups. The low-dose exposure group shared 33 and 36 DMs with the moderate- and high-dose exposure groups, respectively. The moderate-dose exposure group shared 46 DMs with the high-dose exposure group. In addition, 33 DMs were shared among the three exposure groups. Among the 72 DMs, 9, 9, and 45 metabolites participated in the amino acid, nucleotide, and lipid metabolism pathways, respectively. The results of pathway enrichment analysis showed that the most relevant metabolic pathways affected by SCCPs were the lipid metabolism, fatty acid ß-oxidation, and nucleotide metabolism pathways, and that compared with low-dose exposure, moderate- and high-dose SCCP exposures caused more notable perturbations of these metabolic pathways in L02 cells. Exposure to SCCPs perturbed glycerophospholipid and sphingolipid metabolism. Significant alterations in the levels of phosphatidylcholines, phosphatidylethanolamines, and sphingomyelins indicated SCCP-induced biomembrane damage. SCCPs inhibited fatty acid ß-oxidation by decreasing the levels of short- and medium-chain acylcarnitines in L02 cells, indicating that the energy supplied by fatty acid oxidation was reduced in these cells. Furthermore, compared with low- and moderate-dose SCCPs, high-dose SCCPs produced a significantly stronger inhibition of fatty acid ß-oxidation. In addition, SCCPs perturbed nucleotide metabolism. The higher hypoxanthine levels observed in L02 cells after SCCP exposures indicate that SCCPs may induce several adverse effects, including hypoxia, reactive oxygen species production, and mutagenesis in L02 cells.

Dietary exposure and risk assessment of chlorinated paraffins in roots and rhizomes of traditional Chinese medicine herbs.

Traditional Chinese medicine (TCM) provides therapeutic and health care effects through dietary intake. Owing to the susceptibility of plants to contaminations, a risk assessment system is urgently needed to ensure the safe use of TCMs. In this study, the contamination levels and risks associated with the dietary intake of short-chain chlorinated paraffins (SCCPs) and medium-chain chlorinated paraffins (MCCPs) were investigated in six kinds of frequently-used TCM herbs. The concentrations varied from 144.4 to 1527.8 ng·g-1 dw for SCCPs and non-detect to 1214.1 ng·g-1 dw for MCCPs, with mean values of 551.5 and 259.8 ng·g-1 dw, respectively. A geographic distribution analysis indicated that the concentrations of CPs in TCMs were mainly associated with their levels of contamination in the ambient environment. Carbon atom-chlorine congener profiles of CPs were dominated by C10Cl7-8 and C14Cl7-8 congeners, accounting for 20.1% and 32.4% of the total SCCP and MCCP concentrations, respectively. Principal component analysis indicated that the TCM species might be the main factor influencing the accumulation of SCCPs congeners. Finally, a risk assessment reveals that the estimated daily intake and margin of exposure were far below levels that might pose a health risk, indicating an acceptable dietary intake of SCCPs and MCCPs in the studied TCMs. This is the first report of CPs in the TCM herbs and the obtained results are expected to aid in future evaluation of the quality of TCMs and ensuring diet and drug safety.

Are fish oil-based dietary supplements a significant source of exposure to chlorinated paraffins?

Chlorinated paraffins (CPs) are an emerging group of environmental pollutants associated with adverse effects on human health (such as endocrine disruption and possible carcinogenicity). CPs are classified into several groups: short- (SCCPs), medium- (MCCPs) and long-chain chlorinated paraffins (LCCPs). In this study, CPs were determined in fish oil-based omega-3 dietary supplements (DS) representing widely consumed products that might be contaminated with various lipophilic contaminants including CPs. The CPs were isolated from DS (n = 85) by solid phase extraction. The SCCPs and MCCPs were determined by gas chromatography coupled with high-resolution mass spectrometry operated in a negative chemical ionisation mode. The LCCPs (up to C21) were screened using supercritical fluid chromatography coupled with high-resolution mass spectrometry with electrospray ionisation operated in negative mode. The CP concentrations varied from <0.01 to 56.48 µg/g fat for SCCPs (median 0.12 µg/g fat; limit of quantification, LOQ, for SCCPs was exceeded in 51 out of 85 samples) and from <0.03-89.08 µg/g fat for MCCPs (median 0.26 µg/g fat; LOQ for MCCPs was exceeded in 66 out of 85 samples), respectively. The LCCPs were not quantified in this study, nevertheless their limit of detection (0.5 µg/g fat) was exceeded in 7 out of 85 samples. Due to high levels of CPs, DS might pose as a significant source of CPs exposure to some population groups.

Short- and medium-chain chlorinated paraffins in green tea from 11 Chinese provinces and their migration from packaging.

Chlorinated paraffins (CPs) have been found to occur ubiquitously in foodstuff of both animal and plant origin. However, limited information is available on the content of CPs in green tea, one of the most commonly consumed beverages worldwide. Herein, 107 commercial green tea samples originating from 11 provinces of China, were collected to study the occurrence of short- and medium-chain chlorinated paraffins (SCCPs and MCCPs, respectively). The concentration of SCCPs in all green tea samples ranged from 4.99 to 717 ng/g (mean: 55.7 ng/g), while MCCPs ranged from 2.55 to 543 ng/g (mean: 33.5 ng/g). CP profiles in green tea samples from different provinces exhibited no regional differences. To identify the potential sources of CPs in green tea, 19 tea packaging samples were collected and analyzed, showing that SCCPs and MCCPs existed at much higher concentrations in the tea packaging material than in the teas. Migration tests indicated that CPs could migrate from packaging into teas during storage, with the migration velocity and efficiency of SCCPs being higher than MCCPs.

Short- and medium-chain chlorinated paraffins in commercial complementary baby food produced in different European countries: Occurrence, congener group profiles, portion-based dietary intake, and risk assessment.

This study was performed to evaluate the presence of chlorinated paraffins (CPs) in complementary baby food from different European countries, to assess portion-based dietary intake of CPs, and to characterize possible risks to children arising from CPs uptake. In total, 86 baby food samples from 22 countries were grouped into eight food-type categories considering the WHO classification. In six out of eight sample categories, predominance of medium-chain CPs (MCCPs) concentrations over short-chain CPs (SCCPs) was observed and, contrary to expectations, samples that contained ingredients of animal origin (e.g., meat or fish) did not display elevated CPs levels. The median ∑CPs concentrations for selected sample categories ranged from 0.8 ng g-1 for desert to 2.8 ng g-1 found in dry cereal and porridge subgroups, while the highest CPs concentration of 387 ng g-1 was observed in dry porridge. Among the selected groups of baby foods, portion-based intake of ∑CPs varied from 1.0 to 43.6 ng kg-1 body weight (b.w.) while exposure estimations indicated that portion-based dietary exposure through consumption of complementary baby food was the highest for infants aged 3-12 months due to the lower body weight. The risk characterization according to the European Food Safety Authority (EFSA) approach showed that the margin of exposure (MOE) figures higher than the critical value for ∑CPs, indicating that the dietary exposures through consumption of complementary baby food are unlikely to be of significant health concern for children. However, it should be pointed out that the performed risk assessment covered only SCCPs and MCCPs, while the occurrence of other groups from CPs and CPs related compounds (e.g., very short-chain CPs, chlorinated alkenes, or long-chain CPs (LCCPs)) was not addressed.

Application of the GC-HRMS based method for monitoring of short- and medium-chain chlorinated paraffins in vegetable oils and fish.

The aim of this study was to develop methods for the determination of short- and medium-chain chlorinated paraffins (SCCPs; MCCPs) in vegetable oils and fish employing gas chromatography coupled with high-resolution mass spectrometry because of a lack of information on the presence of chlorinated paraffins in food consumed in Europe. For isolation of CPs from fish, an ethyl acetate extraction followed by a clean-up of the extract by gel permeation chromatography was performed. The same purification step was used for the isolation of CPs from the vegetable oils. The concentration range for SCCPs was <10-389 ng/g lipid weight (lw, mean 36 ng/g lw for the oils and 28 ng/g lw for the fish) and that for MCCPs was <20-543 ng/g lw (mean 55 ng/g lw for the oils and 59 ng/g lw for the fish). There was found a high variability in concentrations of CPs influenced by area of origin.

Metabolomic mechanisms of short chain chlorinated paraffins toxicity in rats.

Short chain chlorinated paraffins (SCCPs) have received increased interest worldwide since they were added to the list of controlled POPs in Annex A of the Stockholm Convention in 2017. Although many toxicological studies have already shown that SCCPs are hepatotoxic, nephrotoxic, and thyrotoxic to rodents, there have been few studies to date that have characterized changes in the metabolic pathways targeted by SCCPs. In this study, a UPLC-Q-TOF-MS based plasma metabolomics approach was used to investigate the toxicity of SCCPs in rats. Liver and kidney injury occurred rapidly after high-dose SCCP exposure, and the most relevant pathways affected were energy metabolism, amino acid metabolism, glycerophospholipid metabolism, nucleotide metabolism, and vitamin B metabolism. Exposure to SCCPs inhibited the tricarboxylic acid cycle and accelerated degradation. Fluctuating levels of phospholipids and nucleotides may have contributed to the neurotoxicity of SCCPs. In addition, the down regulation of folic acid induced by SCCPs may have led to malformations during the early development of laboratory animals. These results suggested that high exposure levels of SCCPs may have serious health risks and more research is needed to assess the health status of relevant occupational groups.

Effect of short-chain chlorinated paraffins on metabolic profiling of male SD rats.

The toxic effect of high-dose of short-chain chlorinated paraffins (SCCPs) has been extensively studied, however the possible health risks induced by SCCPs at low-dose remain largely unknown. In this study, a comprehensive toxicology analysis of SCCPs was conducted with the exposure levels from the environmental dose to the Lowest Observed Adverse Effect Level (LOAEL) of 100 mg/kg/day. General toxicology analysis revealed inconspicuous toxicity of the environmental dose of SCCPs, high dose SCCP exposure inhibited the growth rate and increased the liver weight of rat. Metabolomics analysis indicated that SCCP-induced toxicity was triggered at environmentally relevant doses. First, inhibition of energy metabolism was observed with the decrease in blood glucose and the dysfunction of TCA cycle, which may have contributed to lower body weight gain in rats exposed to a high dose of SCCPs. Second, the increase of free fatty acids indicated the acceleration of lipid metabolism to compensate for the energy deficiency caused by hypoglycemia. Lipid oxidative metabolism inevitably leads to oxidative stress and stimulates the up-regulation of antioxidant metabolites such as GSH and GSSH. The up-regulation of polyunsaturated fatty acids (PUFAs) and phospholipids composed of arachidonic acid indicates the occurrence of inflammation. Dysfunction of lipid metabolism can be an indicator of SCCP-induced liver injury.

Screening for chlorinated paraffins in vegetable oils and oil-based dietary supplements by planar solid phase extraction.

Extraction of chlorinated paraffins (CPs) in samples with high fat content is generally performed by a sulfuric acid treatment and liquid-liquid partitioning in n-hexane, followed by clean-up by column chromatography. Analysis and quantitation are commonly carried out via gas chromatography coupled with electron capture negative ionization mass spectrometry (GC/ECNI-MS) when low- and high-resolution MS (LRMS and HRMS) are used. In this work, we present a completely different and innovative approach for the determination of CPs by applying the planar solid phase extraction (pSPE) concept for a rapid and selective screening. pSPE offers the concentration of the analytes in a single target zone followed by the densitometric determination of the total CP content. After sulfuric acid treatment and liquid-liquid partition into n-hexane, pSPE was performed on silica gel plates employing a twofold development with cyclohexane/toluene (94:6, v/v) and methylene chloride/n-hexane (9:1, v/v) as mobile phases. CPs were quantified via the visual (VIS) absorption of the target zone after derivatization with o-tolidine, and amounts were calculated as the sum by means of a reference CP. Limits of detection and quantitation for the reference CP were 0.2 and 0.7 mg/kg oil, respectively, and recoveries from different vegetable oils were near 100%. The analysis of total CPs in dietary supplement samples by pSPE-VIS compared to GC/ECNI-HRMS proved the method as a reliable and suitable screening tool providing an appropriate alternative to existing time-consuming and complex methods.

High amounts of chlorinated paraffins in oil-based vitamin E dietary supplements on the German market.

Chlorinated paraffins (CPs) are a group of man-made pollutants of growing environmental concern. Short-chain chlorinated paraffins (SCCPs) were recently classified as persistent organic pollutants (POPs), while medium-chain chlorinated paraffins (MCCPs) are still unregulated. Foodstuff is a major pathway for the human CP intake, and the regular diet has been analyzed in several studies recently. However, dietary supplements (DS) had not been analyzed on CPs. Our goal was to investigate the occurrence of CPs in DS and to evaluate the possible threat for the consumers. DS (n = 25) made from plant or fish oils were selected on the German market with main emphasis on vitamin E products. The lipid components were removed by sulphuric acid treatment and silica gel column chromatography. CP quantification was performed via gas chromatography coupled to electron capture negative ion mass spectrometry. Six vitamin E preparations containing palm oil showed alarmingly high CP concentrations of >35 µg/g fat. Six other DS contained much lower CP amounts (<4 µg/g fat). If consumed as recommended, the mean daily intake of CPs (5.5 µg SCCPs + 38 µg MCCPs) via palm oil based DS surpassed that of the regular diet by a factor of 4 for SCCPs and 13 for MCCPs, exceeding the PCB intake via food by up to two orders of magnitude. Samples reached up to 26% of the TDI of MCCPs for an average European adult. Consequently, the P95 intake of those samples would amount to ~43 mg CPs per year. The CP contamination probably originated from raw material, as CPs were also found in palm oils and vitamin E concentrates made from palm oil. Our findings suggest that DS can contain high amounts of contaminants that compromise the purpose of the product and should be considered for regular CP monitoring.

The role of edible oils in low molecular weight organogels rheology and structure.

In this paper, the role of solvent characteristics on the rheological and physicochemical properties of organogels was investigated using different techniques. Vegetable oils, such as rice, sunflower and castor oil were used as solvents, for producing organogels with monoglycerides of fatty acids or a mixture of fatty alcohols (policosanol) as gelators. Moreover, two non-edible oils (silicon and paraffin oil) were also used for analysing the properties of solvents completely different in nature with respect to the edible ones, for a better interpretation of the given results. Organogels were investigated from a rheological point of view and through a microscopic analysis, given by polarised light (POM) and atomic force (AFM) microscopy, and X-rays to study the crystallinity of the system. The IR technique was used to analyse the intermolecular interactions, resulting in interesting information about the effect of oil polarity on the driving forces promoting structuration. This investigation showed that when solvents of a similar chemical nature are used, their physical properties, mainly oil polarity, are strictly related to the properties of the organogel, such as the onset of crystallisation temperature, the stiffness of the final material and its crystallinity. Anyway, these physical parameters seem insufficient to describe properly the role of solvents when oils of a different chemical nature are compared.

Short-chain chlorinated paraffins in cooking oil and related products from China.

Short-chain chlorinated paraffins (SCCPs) are emerging persistent organic pollutants. It has been found that dietary intakes of SCCPs in China have recently increased and are now higher than in Japan and Korea. The contribution of cooking oil to dietary exposure to SCCPs in China was evaluated by analyzing SCCPs in cooking oil, raw seeds used to produce cooking oil, and fried confectionery products collected in China in 2010 and 2012. Detectable amounts of SCCP homologs were found in 48 out of the 49 cooking oil samples analyzed, and the SCCP concentrations varied widely, from <9 to 7500 ng g(-1). Estimated dietary intakes of total SCCPs in cooking oil ranged from <0.78 to 38 µg d(-1). The estimated dietary intake of SCCPs was relatively high (mean 14.8 µg d(-1)) for residents of Beijing. Fried confectionery was found to contain SCCP concentrations of 11-1000 ng g(-1). Cooking oil might therefore be one of the sources of SCCPs to Chinese diets. SCCPs were also detected in raw seeds used to produce cooking oil, but the concentrations varied widely. The SCCP homolog patterns in the raw seed and cooking oil samples were different, implying that the seeds used to produce the oil (and therefore the soil on which the seeds were produced) were unlikely to be the sources of SCCPs in cooking oil. Further investigations are needed to determine the routes through which cooking oil becomes contaminated with SCCPs during the production and processing of the oil.

Coated kapok fiber for removal of spilled oil.

Based on raw kapok fiber, two kinds of oil absorbers with high sorption capacity were prepared by a facile solution-immersion process. The coated polymer with low surface energy and rough fiber surface play important role in the retention of oil. The as-prepared fiber can quickly absorb gasoline, diesel, soybean oil, and paraffin oil up to above 74.5%, 66.8%, 64.4% and 47.8% of oil sorption capacity of raw fiber, respectively. The absorbed oils can be easily recovered by a simple vacuum filtration and the recovered coated-fiber still can be used for several cycles without obvious loss in oil sorption capacity. The thermodynamic study indicates that the adsorption process is spontaneous and exothermic, with complex physisorption and chemisorption. The results suggest that the coated fiber can be used as a low-cost alternative for the removal of oil spilled on water surface.

Active paraffin-based paper packaging for extending the shelf life of cherry tomatoes.

A new active paraffin coating for paper and board was evaluated for antimicrobial protection and decay retardation for cherry tomatoes. Different active agents were evaluated against Alternaria alternata fungus both in vitro and in vivo using artificially inoculated cherry tomatoes. Bark cinnamon and oregano essential oil showed the best performance (versus clove and leaf cinnamon essential oils) when incorporated to active paper or board used for packaging at nominal concentrations of 3 and 6% (w/w), respectively. Almost total inhibition of the fungus was obtained when 6% of bark cinnamon essential oil was applied to the packaging material. A number of physicochemical parameters such as pH, weight loss, water activity, and color were monitored, and no significant differences between active, blank, and control samples were found for weight loss and color difference. The maximum transfer of trans-cinnamaldehyde and carvacrol to the food was detected after 1 or 2 days of storage. Sensorial analysis was performed, and panelists were not able to detect changes in cinnamon-based packaged tomatoes but they could in the oregano-based tomatoes.

A novel way to enhance the oil recovery ratio by Streptococcus sp. BT-003.

Degrading hydrocarbon by Streptococcus sp. BT-003 as a kind of microbe for oil recovery was analyzed in this paper. The Streptococcus sp. BT-003 showed that it could use crude oil as the sole source of carbon and produce organic acid, bio-gas and polysaccharide which were propitious to emulsify and reduce the viscosity of crude oil. After cultivating 8-14 h, the viscosity of crude oil reduced from 8000-15000 mPa . s to 50-250 mPa . s. The content of organic acid increased 8-15 times, and carbon dioxide and polysaccharide reached 55 ml/l and 8 g/l respectively. Paraffin and resin reduced by 60-95%, and light components increased obviously. Fluid rheology was better than before, the interfacial tension between the crude oil and water were reduced effectively.

Activated aluminum oxide selectively retaining long chain n-alkanes: Part II. Integration into an on-line high performance liquid chromatography-liquid chromatography-gas chromatography-flame ionization detection method to remove plant paraffins for the determination of mineral paraffins in foods and environmental samples.

Aluminum oxide activated by heating to 300-400 degrees C retains n-alkanes with more than about 20 carbon atoms, whereas iso-alkanes largely pass non-retained (with characteristics described in more detail in Part I). This property is useful for the analysis of mineral oil contamination of foods and other matrices: it enables the removal of plant n-alkanes, typically ranging from C(23) to C(33), when they disturb the analysis of mineral paraffins (usually almost exclusively consisting of iso-alkanes). An on-line HPLC-LC-GC-FID method is proposed in which a first silica gel HPLC column isolates the paraffins from the bulk of edible oils or extracts and is backflushed with dichloromethane. In a second separation step, a 10 cm x 2 mm i.d. column packed with activated aluminum oxide separates the long chain n-alkanes from the fraction of the iso-alkanes which is transferred to GC-FID by the on-column interface and the retention gap technique. The retained n-alkanes are removed by flushing with iso-octane.

[Studies on the chemical constituents from Inula cappa (II)].

OBJECTIVE: To study the chemical constituents of the root of Inula cappa. METHOD: The compounds were isolated and purified by recrystallization and chromatography with silica gel column and Sephadex LH-20 column. Their structures were identified by physico-chemical properties and spectral analysis. RESULTS: Seven compounds were isolated as scopolin (I), octacosanoic acid (II), tritriacontane (III), (2S,3S,4R,8E)-2-[(2'R)-2'-hydroxydocosanosylamino]-octadecane-1,3,4-triol(IV),(2S,3S,4R,8E)-2-[(2'R)-2'-hydroxytricosanosylamino]-octadecane-1,3,4-triol(V), (2S,3S,4R,8E)-2-[(2'R)-2'-hydroxytetracosanosylamino]-octadecane-1,3,4-triol(VI), (2S,3S,4R,8E)-2-[(2'R)-2'-hydroxypentacosanosylamino]-octadecane-1,3,4-triol(VIII), (2S,3S,4R,8E)-2-[(2'R)-2'-hydroxyhexacosanosylamino]-octadecane-1,3,4-triol(VIII). CONCLUSION: All compounds were isolated from Inula cappa for the first time.

Pesticide and plasticizer residues in bergamot essential oils from Calabria (Italy).

Organophosphorus and organochlorine pesticides, phosphorated plasticizers, chloroparaffins and phthalate esters contamination in bergamot essential oils produced in Calabria in the crop years 1999-2000 was studied by HRGC in connection with detectors FPD, ECD, MS. Residues of dicofol and tetradifon were found in oils from both crop years. The mean dicofol concentration was 0.26 mg/l in samples from 1999 and 0.20 mg/l in those from 2000; the mean tetradifon content was 0.06 mg/l for both the crop years. Among plasticizers, residues of diisobutyl phthalate, di-n-butyl phthalate, and bis(2-ethylhexyl) phthalate were found in samples from crop years 1999 and 2000, the mean content were 1.22 and 1.23 mg/l, 1.51 and 1.65 mg/l, 1.38 and 1.42 mg/l respectively.

Relative hopane content confirming the mineral origin of hydrocarbons contaminating foods and human milk.

Hopanes, triterpenoid hydrocarbons formed under geological conditions, were analysed to confirm the mineral origin of the unresolved complex mixtures of hydrocarbons observed in the gas chromatography with flame ionization detection chromatograms of human milk and certain foodstuffs. The 'relative hopane content' (RHC) is introduced, i.e. it is the area ratio of the sum of the hopanes and the paraffins in the same segment of the chromatogram. The RHC in various mineral oil products (motor oils, hydraulic oils, lubricating oils, Vaseline) was 3.4%, with a relative standard deviation of 19%. The RHC determined in samples of vegetable oils, mussels and clams as well as of human milk containing an unresolved complex mixture of hydrocarbons was in the same range, confirming that these samples were contaminated by mineral oil material.

[Analysis of saturated paraffins in petroleum by fast gas chromatography].

A fast capillary gas chromatographic method for the analysis of saturated paraffin in crude oil and rock extracts is described. By using a 20 m narrow bore capillary column, the analytical time has been shortened to 15 min, 5 times faster in comparison with 80 to 90 min by conventional capillary columns, which resulted in higher throughput, higher efficiency and better separation. The fast method is fully in compliance with the Petroleum Industrial Standard--SY/T5120-1997 and paves the way for the fast analysis of paraffin isomers, such as steroidal paraffin and terpane by gas chromatography/mass spectrometry (GC/MS) and that of aromatics by gas chromatography.