Removal of polycyclic aromatic hydrocarbons by low density polyethylene from liquid model and roasted meat

Low density polyethylene (LDPE) was used to remove polycyclic aromatic hydrocarbons (PAHs) from liquid media and roasted meat by sorption. Three liquid models and five carcinogenic PAHs were employed to monitor the sorption process, and amounts of chemicals were determined by GC-FID. More than 50% of the total adsorption occurred within 24 h for the selected PAHs in the three model systems. The water–oil system yielded the highest PAHs removal by LDPE; and the system containing phospholipid resisted the diffusion and resulted in the least adsorption among three models. Certain residual PAHs in the LDPE were significantly decreased to a range of 70.8–84.0% after 3 h of UV radiation, and benzo(a)pyrene was the most sensitive to UV among these PAHs. Removal of PAHs in roasted meat packaged under vacuum was achieved, and potent contamination by the PAHs in the LDPE may be avoided by subsequent UV irradiation.     

葵花籽油中多环芳烃及色泽的吸附脱除研究

利用混合吸附剂对葵花籽油中16种多环芳烃(PAH16)及色泽进行吸附脱除。通过单因素试验考察了活性白土、活性炭、混合吸附剂用量、吸附温度、吸附时间对葵花籽油中PAH16及色泽脱除效果的影响,并采用正交试验对吸附脱除条件进行了优化。结果显示,在混合吸附剂用量为活性白土3%+活性炭1%、吸附温度110℃、吸附时间35 min的最优条件下,葵花籽油中BaP(苯并[a]芘)、PAH4(欧盟限定的4种多环芳烃)、HPAHs(6种重质多环芳烃)、LPAHs(10种轻质多环芳烃)、PAH16的脱除率分别为99.88%、95.49%、97.63%、83.63%、85.71%,残留量分别为0.02、2.09、0.83、42.18、43.01μg/kg,BaP和PAH4残留量达到并明显优于出口欧盟的要求,同时油脂脱色率为79.43%,达到了一级油的色泽指标。     

Removal of polycyclic aromatic hydrocarbons from water by migration into polyethylene

Water was spiked with three polycyclic aromatic hydrocarbons (PAHs) and filled into a steel diffusion chamber. Low-density polyethylene sheet combined of five polyethylene foils was used as a partition in the chamber. Depth of PAHs migration into the sheet was followed for 143 h, using high performance liquid chromatography with selective fluorimetric detection after extraction of PAHs from the foils peeled off. On the basis of the results obtained, the process of PAHs migration into PE was characterised as a one-dimensional diffusion into polyethylene bulk. The diffusion coefficients were calculated for individual compounds using the second Fick law. It was concluded that PAHs are primarily adsorbed on the polyethylene surface with subsequent migration into bulk polymer. Transportation of PAHs through the bulk can be described satisfactorily by Fickian laws of diffusion and is consistent with the theory of the depth adsorption of PAHs in polyethylene.     

纳米氧化锌/低密度聚乙烯膜中锌向食品的迁移研究

目的研究纳米氧化锌/低密度聚乙烯膜(low density polyethylene film,LDPE)中锌(Zn)向食品的迁移行为,探究其迁移规律。方法选取2种食品模拟物(3%乙酸及超纯水)及真实食品(食用白醋及瓶装水),在3种不同实验温度下(70、40及20℃),研究锌向食品模拟物的迁移规律。采用扫描电子显微镜(scanning electron microscope,SEM)和原子力显微镜(atomic force microscope,AFM)表征纳米ZnO/LDPE膜的表面形貌。结果锌向酸性模拟物中的迁移率远远大于水性模拟物中的迁移率,其中锌向酸性模拟物中的最大迁移率分别为22.7%,20.3%及18.6%(ZL-1,ZL-2及ZL-2#),向水性模拟物中的最大迁移率分别为9.9%,5.7%及4.9%(ZL-1,ZL-2及ZL-2#);锌向酸性食品的迁移量(1.59~5.03 mg/g)同样高于向水性食品的迁移量(2.98~24.60μg/g);随着纳米ZnO的初始含量变大迁移率变小;而偶联剂的加入对锌的迁移有一定的抑制作用。随着纳米ZnO浓度的增加,在薄膜中观察到纳米ZnO的不规则形貌。结论纳米ZnO/LDPE膜不适合在高温下包装食物,且其在酸性食品中的安全隐患高于水性食品。     

Removal of polycyclic aromatic hydrocarbons from contaminated soil by aqueous DNA solution

An aqueous DNA solution was applied for the extraction of polycyclic aromatic hydrocarbons (PAHs) from a spiked soil. Solubilities of 0.56, 11.78, and 11.24 mg L(-1) for anthracene, phenanthrene, and pyrene, respectively, were achieved after 1 day equilibration in 1% DNA. Using a spiked soil that contained 72 mg kg(-1) anthracene, 102 mg kg(-1) phenanthrene, and 99 mg kg(-1) pyrene, extractions of close to 88, 78, and 94%, respectively, were attained with 5% DNA at a 1:50 soil/extractant ratio. Maximum PAH dissolution occurred after 4-6 h. Comparative tests showed the main advantage of DNA over methyl-beta- and gamma-cyclodextrins and Tween 80 for pyrene removal. An ionic strength of 0.1 M NaCl was found necessary for maximum PAH dissolution and extraction. The performance of hexane regenerated DNA also remained stable after three stages of recycling. These results show the huge potential of DNA as an aqueous washing agent for PAH-contaminated soil.     

Assessment of contamination source and quality control approach for polycyclic aromatic hydrocarbons in wood-pressed rapeseed oil

Contamination sources of polycyclic aromatic hydrocarbons (PAHs) in the raw material, oil production and storage processes of wood-pressed rapeseed oil were investigated in this study. The results showed that benzo[a]pyrene (BaP) and PAH4 (sum of BaP, benzo[a]fluoranthene, benzo[b]fluoranthene and chrysene) were unevenly distributed in the kernel (0.56–0.98 and 2.84–8.64 μg/kg, respectively) and hull (1.53–3.17 and 13.49–22.31 μg/kg, respectively) of the rapeseed raw materials. The contents of BaP and PAH4 continuously increased during the process of wood-pressed rapeseed oil, ranging from 2.21 to 10.93 and 9.36 to 40.03 μg/kg, thus demonstrating that a wide range of pollution sources of PAHs existed for the test wood-pressed rapeseed oils. The initial temperature and time of roasting should be controlled at <210°C and <60 min, due to the generation of PAHs in rapeseed by over-roasting. In addition, contact tools and substance such as lubricating oil (from the mill), heat-transfer oil (from roasting machine), rubber gaskets and straws should be properly screened. The BaP and PAH4 of rapeseed placed in the roasting area increased from 0.5 to 2.24 and from 2.08 to 9.03 μg/kg, respectively. Therefore, roasting fume control and treatment systems are necessary and the roasting section should be strictly isolated from the other stages. Storage can slightly lower the PAHs amounts in the rapeseed oil, which made the contents of BaP and PAH4 decrease from 27.00 to 24.70 and from 138.63 to 117.58 μg/kg, respectively. Quality control measures of PAHs in wood-pressed rapeseed oil were proposed and implemented, and the final oil products’ BaP and PAH4 were kept below 2 and 10 μg/kg, respectively, which meets the European Commission Regulation No. 835/2011.     

脱色工艺对菜籽油中多环芳烃脱除效果的影响

研究了脱色工艺对菜籽油中多环芳烃(PAHs)的脱除作用。通过单因素实验分别考察了吸附剂种类及添加量、脱色温度和脱色时间对菜籽油中PAHs的脱除效果,并采用正交实验对吸附脱除菜籽油中PAHs的工艺条件进行优化。结果表明:在1#活性炭和活性白土复合吸附剂的添加量(占油质量)为0. 25%+1%、脱色时间30 min、脱色温度110℃时,BaP和PAH4的残留量分别为0. 23、1. 17μg/kg,均达到欧盟No 835/2011的限量值要求,且PAH4脱除率达到94. 7%。     

SiO x layer as functional barrier in polyethylene terephthalate (PET) bottles against potential contaminants from post-consumer recycled PET

The barrier effect of a silicon oxide (SiO _x ) coating on the inner surface of PET bottles, in terms of the ability to reduce the migration of post-consumer compounds from the PET bottle wall into food simulants (3% acetic acid and 10% ethanol), was investigated. The barrier effect was examined by artificially introducing model substances (surrogates) into the PET bottle wall to represent a worst-case scenario. Test bottles with three different spiking levels up to ～1000 mg kg^?1 per surrogate were blown and coated on the inner surface. The SiO _x -coated bottles and the non-coated reference bottles were filled with food simulants. From the specific migration of the surrogates with different bottles wall concentrations, the maximum surrogate concentrations in the bottle wall corresponding to migration of 10 µg l^?1 were determined. It was shown that the SiO _x coating layer is an efficient barrier to post-consumer compounds. The maximum bottle wall concentrations of the surrogates corresponding to migration of 10 µg l^?1 were in the range of 200 mg kg^?1 for toluene and ～900 mg kg^?1 for benzophenone. Consequently, the SiO _x coating allows use of conventionally recycled post-consumer PET flakes (without a super-clean recycling process) for packaging aqueous and low alcoholic foodstuffs (under cold-fill conditions) and protects food from migration of unwanted contaminants from post-consumer PET.     

Sources of contamination by polycyclic aromatic hydrocarbons in Spanish virgin olive oils

The presence of polycyclic aromatic hydrocarbons (PAHs) in virgin olive oils results from contamination on olive skins and the oil itself during processing. Determination of nine PAHs was carried out by isolation of the hydrocarbon fraction and subsequent clean-up by solid phase extraction, followed by RP-HPLC analysis using a programmable fluorescence detector. Contamination of olive skins depends directly on environmental pollution levels and inversely on fruit size. In the oil mill, PAHs levels were increased by contamination from combustion fumes during the extraction process. Other procedures, such as washing or talc addition during extraction, did not affect PAHs levels. High concentrations of PAHs were only found as a consequence of accidental exposure to contamination, such as direct contact of olives with diesel exhaust and oil extraction in a polluted environment.     

Sources of contamination by polycyclic aromatic hydrocarbons in Spanish virgin olive oils

The presence of polycyclic aromatic hydrocarbons (PAHs) in virgin olive oils results from contamination on olive skins and the oil itself during processing. Determination of nine PAHs was carried out by isolation of the hydrocarbon fraction and subsequent clean-up by solid phase extraction, followed by RP-HPLC analysis using a programmable fluorescence detector. Contamination of olive skins depends directly on environmental pollution levels and inversely on fruit size. In the oil mill, PAHs levels were increased by contamination from combustion fumes during the extraction process. Other procedures, such as washing or talc addition during extraction, did not affect PAHs levels. High concentrations of PAHs were only found as a consequence of accidental exposure to contamination, such as direct contact of olives with diesel exhaust and oil extraction in a polluted environment.     

Migration kinetics of mineral oil hydrocarbons from recycled paperboard to dry food: monitoring of two real cases

Mineral oil hydrocarbons present in printing inks and recycled paper migrate from paper-based food packaging to foods primarily through the gas phase. Migration from two commercial products packed in recycled paperboard, i.e. muesli and egg pasta, was monitored up to the end of their shelf life (1 year) to study the influence of time, storage conditions, food packaging structure and temperature. Mineral oil saturated and aromatic hydrocarbons (MOSH and MOAH, respectively), and diisopropyl naphthalenes (DIPN) were monitored using online HPLC-GC/FID. Storage conditions were: free standing, shelved, and packed in transport boxes of corrugated board, to represent domestic, supermarket and warehouse storage, respectively. Migration to food whose packs were kept in transport boxes was the highest, especially after prolonged storage, followed by shelved and free-standing packs. Tested temperatures were representative of refrigeration, room temperature, storage in summer months and accelerated migration testing. Migration was strongly influenced by temperature: for egg pasta directly packed in paperboard, around 30 mg kg^?1 of MOSH migrated in 8 months at 20°C, but in only 1week at 40°C. Muesli was contained into an internal polyethylene bag, which firstly adsorbed hydrocarbons and later released them partly towards the food. Differently, the external polypropylene bag, containing pasta and recycled paper tray, strongly limited the migration towards the atmosphere and gave rise to the highest level of food contamination. Tests at increased temperatures not only accelerated migration, but also widened the migration of hydrocarbons to higher molecular masses, highlighting thus a difficult interpretation of data from accelerated simulation.     

Pyrolytic formation of polycyclic aromatic hydrocarbons from sesquiterpenes

The products of the pyrolysis of four sesquiterpenes, β-caryophyllene, α-cedrene, longifolene and valencene, have been examined. Pyrolysis was carried out at 300, 400 and 500°C, the products determined by GC-MS and then examined for similarities and differences using multivariate data analysis. Analysis showed that longifolene was most resistant and caryophyllene least resistant to pyrolysis with cedrene and valencene occupying intermediate positions. While the compounds were largely unchanged at 300°C, polycyclic aromatic hydrocarbons (PAHs) were major components of the pyrolysates at 400 and 500°C. No less than nine of the 16 EPA priority pollutants were present in the pyrolysates at the higher temperatures.     

Saturated and aromatic mineral oil hydrocarbons from paperboard food packaging: estimation of long-term migration from contents in the paperboard and data on boxes from the market

In the absence of a functional barrier, mineral oil hydrocarbons from printing inks and recycled fibres tend to migrate from paper-based food-packaging materials through the gas phase into dry food. Concentrations easily far exceed the limit derived from the acceptable daily intake (ADI) of the Joint FAO/WHO Expert Committee on Food Additives (JECFA). Since the estimation of long-term migration into the food by testing at 40°C for 10 days is difficult, it seems preferable (and easier) to use the mineral oil content in the paperboard. Evaporation experiments showed that hydrocarbons eluted up to about n-C₂₄ are sufficiently volatile for relevant migration into dry food: in worst-case situations, about 80% migrate into the packed food. The extraction of the paperboard was optimised to give good recovery of the relevant hydrocarbons, but to discriminate against those of high molecular mass which tend to disturb gas chromatographic analysis in on-line coupled normal phase HPLC-GC-FID. Even though some of the relevant hydrocarbons had already evaporated, the average concentration of?<?C₂₄ mineral oil saturated hydrocarbons (MOSH) in the paperboard boxes of 102 products from the Swiss and Italian market was 626?mg?kg^?1. Nearly 15% of investigated boxes still contained more than 1000?mg?kg^?1?<?C₂₄ MOSH up to over 3000?mg?kg^?1 (maximum?=?3500?mg?kg^?1). This amount of MOSH in the board have the potential of contaminating the packed food at a level exceeding the limit, derived from the JECFA ADI, hundreds of times.     

食品接触材料中多环芳烃在食品模拟物中的迁移规律研究

采用气相色谱-质谱联用法,对食品接触材料中多环芳烃在水、乙酸(体积分数为3%)、乙醇(体积分数为10%)和异辛烷等4种食品模拟物中的迁移规律进行了研究,研究迁移量与实验的温度、时间和模拟物属性等参数的关系。结果表明:模拟物的属性对迁移行为有显著影响,迁移量随温度的升高和时间的增加而变大。     

浊点萃取法预浓缩食用油中多环芳烃的研究

随着食品安全意识的提高,食用油中多环芳烃的检测与分离越来越引起人们的重视,而传统液液萃取法较为繁琐,重复率也较低,因此高效的分离,富集方法研究受到关注.近年来,一种新型的基于表面活性剂相分离现象的分离方法--浊点萃取(Cloud Point Extraction,CPE),逐渐成为研究热点.与液液萃取相比,CPE具有操作简单、过程短、萃取率高等优点;此外,由于CPE过程中不使用有机溶剂,在降低成本的同时,它又是一种环境友好的萃取分离方法.通过实验各操作参数对萃取性能的影响.获得最佳操作条件,指出采用CPE方法对食用油中多环芳烃进行预浓缩的可能性.     

Temperature-dependent diffusion coefficient of oil from different sunflower seeds during extraction with hexane

Oil extraction from confectionery, oilseed and wild sunflower seeds with n-hexane was investigated by laboratory tests carried out in a stirred batch extractor at several temperatures (40, 50 and 60 °C). The rates of extraction were determined from ground sunflower seeds (particle sizes between 0.420 and 1.000 mm). The oil yield in the extract increased with higher contact time and extraction temperature in all the cases. Equilibrium constants at 50 °C for different solvent-ground seed ratios are reported. A mathematical model of oil extraction from seeds of sunflowers, based on a modified diffusive process in spherical geometry of particles, was proposed. The analysis of significance of the coefficient of fitting regression models showed significant differences between temperatures for each genotype and between genotypes at each temperature. The resulting diffusion coefficient ranged from 1.34 × 10⁻¹² to 1.87 × 10⁻¹² m²/s for confectionery, 2.06 × 10⁻¹² to 5.03 × 10⁻¹² m²/s for oilseed, and 9.06 × 10⁻¹³ to 1.18 × 10⁻¹² m²/s for wild sunflower. The temperature dependence of the diffusion coefficient was represented by an Arrhenius-type equation for each sunflower seed studied. Activation energy values of 13.74, 33.95 and 11.32 kJ/mol were obtained for confectionery, oilseed and wild sunflower, respectively.     

Radiolysis products and sensory properties of electron-beam-irradiated high-barrier food-packaging films containing a buried layer of recycled low-density polyethylene

The aim was to study the effect of electron-beam irradiation on the production of radiolysis products and sensory changes in experimental high-barrier packaging films composed of polyamide (PA), ethylene-vinyl alcohol (EVOH) and low-density polyethylene (LDPE). Films contained a middle buried layer of recycled LDPE, while films containing 100% virgin LDPE as the middle buried layer were taken as controls. Irradiation doses ranged between zero and 60 kGy. Generally, a large number of radiolysis products were produced during electron-beam irradiation, even at the lower absorbed doses of 5 and 10 kGy (approved doses for food ‘cold pasteurization’). The quantity of radiolysis products increased with irradiation dose. There were no significant differences in radiolysis products identified between samples containing a recycled layer of LDPE and those containing virgin LDPE (all absorbed doses), indicating the ‘functional barrier’ properties of external virgin polymer layers. Sensory properties (mainly taste) of potable water were affected after contact with irradiated as low as 5 kGy packaging films. This effect increased with increasing irradiation dose.     

Study of barrier properties and chemical resistance of recycled PET coated with amorphous carbon through a plasma enhanced chemical vapour deposition (PECVD) process

Many studies have been carried out in order to make bottle-to-bottle recycling feasible. The problem is that residual contaminants in recycled plastic intended for food packaging could be a risk to public health. One option is to use a layer of virgin material, named functional barrier, which prevents the contaminants migration process. This paper shows the feasibility of using polyethylene terephthalate (PET) recycled for food packaging employing a functional barrier made from hydrogen amorphous carbon film deposited by Plasma Enhanced Chemical Vapour Deposition (PECVD) process. PET samples were deliberately contaminated with a series of surrogates using a FDA protocol. After that, PET samples were coated with approximately 600 and 1200 Angstrons thickness of amorphous carbon film. Then, the migration tests using as food simulants: water, 10% ethanol, 3% acetic acid, and isooctane were applied to the sample in order to check the chemical resistance of the new coated material. After the tests, the liquid extracts were analysed using a solid-phase microextraction device (SPME) coupled to GC-MS.     

不同植物油制取工艺对毛油中多环芳烃含量的影响

以花生仁、芝麻、油菜籽为原料,采用不同工艺分别制取毛油,并对毛油中多环芳烃(PAHs)含量进行检测分析,探究制油工艺对毛油中PAHs含量的影响。结果表明:6个浸出毛油样品中Ba P、PAH4、PAH16平均含量分别是6个压榨毛油样品的1.53、1.45、1.08倍,说明PAHs在浸出溶剂正己烷中有很好的溶解度,因此油籽无论脱皮与否所制取浸出毛油中PAHs含量均高于压榨毛油;6个脱皮油籽所制取毛油中Ba P、PAH4、PAH16平均含量分别是未脱皮油籽毛油的1.51、1.61、1.53倍,即无论是压榨法还是浸出法,脱皮油籽所制取毛油中PAHs含量均高于未脱皮油籽毛油。这可能是因为种皮主要成分为粗纤维,而PAHs的亲脂性使其更容易富集在种仁中。