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Chloropropanols such as 3-monochloropropane-1,2-diol (3-MCPD) and 1,3-dichloro-2-propanol (1,3-DCP) have drawn increasing attention due to their release from food contact paper and their potential carcinogenic effects. In this study, the effects were investigated of water extraction conditions on release of chloropropanols from food contact paper, and the extraction efficiencies of chloropropanols by water extract and migration method were compared. Cold water was found to be more severe than hot water for extraction of chloropropanols, with the highest water extraction value obtained at 23°C. Two hours of extraction was sufficient as the chloropropanols can be fully extracted from food contact paper within a short period of time. Increase of temperature in the range of 10°C-60°C had little impact on release of chloropropanols, however, the extraction of chloropropanols decreased when high temperatures (80°C or above) were applied due to volatilisation losses. Hence, attention should be paid when choosing extract conditions representing the worst-case scenario. The water extraction value using EN 645 method gives higher results compared to migration test described in GB 31604.1 and GB 5009.156, suggesting that the water extract method was probably more severe. For migration test, aqueous-based simulants were found to be more conservative than oil-based simulants, suggesting the conventional experiment conditions applicable for compliance test of chloropropanols migration can be simplified and optimised.

Mineral oil hydrocarbons (MOH) in milk powders, particularly in infant formulas, have been and continue to be a major concern to the public worldwide. These contaminants are likely derived from environmental pollution, manufacturing process and packaging materials. In this study, 23 Chinese commercial milk powder products packaged in four types of materials, i.e. metal cans, paper containers, paperboard boxes with internal bags, and aluminium foil-plastic bags, were collected and stored for 1 year. The total and surface MOH in these samples were detected and compared before and after storage to understand the MOH migration during storage, despite no mineral oil saturated hydrocarbons (MOAH) were detected. The contents of mineral oil saturated hydrocarbons (MOSH) and polyolefin oligomeric saturated hydrocarbons (POSH) in metal cans were the least among the four packages and changed little during storage, which suggested that little MOH migration occurred in metal material. Despite all the food contact materials in the other three packagings were the aluminium foil-plastic composite, the similar low migration occurred in the aluminium foil-plastic bags and internally contained composite bag(s) in paperboard boxes. However, both total and surface MOSH and POSH easily migrated from the paper-plastic-aluminium composite of paper containers during storage. These findings are helpful for the selection of packaging materials in manufacturing milk powder products or other foods.

Mineral oil saturated and aromatic hydrocarbons (MOSH/MOAH) are food contaminants, mainly due migration from packaging materials made from recycled fibers, but other routes of entry into food have also been identified. Legal limits for MOSH and MOAH in food and food contact materials currently are not set, but are to be expected in the near future. For the analysis of MOSH and MOAH, the very well developed and highly automated on-line liquid chromatography–gas chromatography with flame ionization detection (LC–GC–FID) is commonly used. However, this approach is time-consuming, and data interpretation is a very challenging task. Therefore, a planar solid phase extraction (pSPE) method was developed for a rapid and efficient MOSH and MOAH screening in paper and cardboard. Based on high-performance thin-layer chromatography (HPTLC), pSPE offers the simultaneous clean-up and analysis of up to 20 samples in parallel, while MOSH and MOAH analytes were focused in two distinct target zones on silica gel HPTLC plates after a twofold development. Plate impregnation with primuline allowed the detection of MOSH by fluorescence, while MOAH were detected by UV light absorption. The pSPE screening approach provided limits of detection of 7.2 and 2.3 ng/zone for MOSH and MOAH, respectively, corresponding to 1.8 and 0.6 mg/kg paper. Coupling of pSPE with GC revealed the common MOSH and MOAH peak humps, while marker substances offered the identification of the mineral oil origin or information about recycled fiber materials. As compared to SPE–GC–FID analyses, the determined quantities of MOSH and MOAH in cardboard samples indicated pSPE as a rapid and suitable screening tool. The co-migration of polyolefin oligomeric saturated hydrocarbons, native n-alkanes, terpenes and possibly essential oils or sterol esters, however, can result in an overestimation of MOSH and MOAH. Hence, samples with pSPE results above a given limit are subsequently analyzed by GC (pSPE–GC) for confirmation and detailed evaluation.

Bisphenol A (BPA) is found in polycarbonate plastic and epoxy resins and is used in a variety of commercial and consumer products. The leaching of BPA can result in human exposure via inhalation, ingestion, and dermal routes. As a result, humans have been exposed in their home and work environment to BPA. Conventional methods for BPA exposure assessment rely on cumbersome laboratory instrumentation with high capital and operational expenditures which limit the number of samples that can be analyzed. We report here the design of a compact portable colorimetric paper-based biosensing device with integrated sampling/analysis units for field-based measurements of BPA in indoor dust. The system employs interchangeable low-cost paper-based enzyme sensors as a test zone for BPA detection interfaced with an air-sampling cassette as a sample collection area. The sensor response was concentration-dependent with a detection limit of 0.28 μg/g. The sensor was validated with the conventional gas chromatography method and used to detect BPA exposure in household dust. BPA concentrations ranged from 0.05 to 3.87 μg/g in 57 household dust samples when both methods were used. The potential of this method for field measurements of dust samples is discussed.

Widening the methodology of chromophore analysis in pulp and paper science, a sensitive gas-chromatographic approach with electron-capture detection is presented and applied to model samples and real-world historic paper material. Trifluoroacetic anhydride was used for derivatization of the chromophore target compounds. The derivative formation was confirmed by NMR and accurate mass analysis. The method successfully detects and quantifies hydroxyquinones which are key chromophores in cellulosic matrices. The analytical figures of merit appeared to be in an acceptable range with an LOD down to approx. 60 ng/g for each key chromophore, which allows for their successful detection in historic sample material.

Bisphenol A (BPA; 4-[2-(4-hydroxyphenyl)propan-2-yl]phenol), a suspected endocrine disruptor with a weak estrogenic activity, is used in a variety of consumer products, including food-contact materials made of paper and cardboard products. Due to restrictions on the use of BPA because of its potential health risks, BPA is gradually being replaced by other bisphenols because no limitations exist for these substances. This study presents a method for the simultaneous analysis of BPA, bisphenol AF (BPAF), bisphenol B (BPB), bisphenol E (BPE), bisphenol F (BPF) and bisphenol S (BPS) in paper and board products using gas chromatography-tandem mass spectrometry (GC-MS/MS). Paper samples were extracted by liquid extraction, as well as by Folch extraction, derivatised with N,O-bis(trimethylsilyl)trifluoroacetamide (BSTFA) and the results compared. The developed method showed good linearity (R

The present work reports on the development of a pressure-affected based headspace (HS) analytical technique for the determination of calcium carbonate content in paper samples. By the acidification, the carbonate in the sample was converted to CO 2 and released into the headspace of a closed vial and then measured by gas chromatography (GC). When the amount of carbonate in the sample is significant, the pressure created by the CO 2 affects the accuracy of the method. However, the pressure also causes a change in the O 2 signal in the HS-GC measurement, which is a change that can be used as an indirect measure of the carbonate in the sample. The results show that the present method has a good precision (the relative standard deviation

This study reports on a rapid method for the determination of methanol in paper-based materials by alkaline extraction, coupled with headspace analysis. Methanol partition equilibria between solid–liquid phases and vapor–liquid phases were conducted in two separate containers, from which an equation for calculating the total methanol content in the original paper sample was derived. It was found that the extraction equilibrium of methanol from solid sample could be achieved within 5 min at room temperature using a high-speed disintegrator, and a subsequent neutralization step is an effective way to prevent methanol from being regenerated at high temperature during headspace equilibration. The results showed that the relative standard deviations for reproducibility tests were in the range of 1.86–6.03%, and the recoveries were in the range of 92.3–107%. The present method is simple and practical; it can be an efficient tool for quantifying the methanol content in paper-based materials and thus play an important role in the investigation of methanol migration behavior in food and beverage packaging.

Conventional migration testing for long-term storage at ambient temperature with Tenax® was applied to a recycled paperboard as well as to the same paperboard with a polyethylene or polypropylene film in between. Test conditions were from the European Union plastic Regulation 10/2011, that is, 10 days at 60°C, but previous standard conditions of 10 days at 40°C were also applied. The results were compared with the migration into real packs made of the same packaging material containing six test foods and stored over 9 months. For the direct contact, simulation at 60°C overestimated the maximum migration of the saturated hydrocarbons in the real packs by 73%. Simulation reflected hardly any effect by the plastic films and resulted in an overestimation of the maximum migration into the real packs by a factor of 5.1 and 27 for the polyethylene and the polypropylene film, respectively. Analogous simulation was performed with polenta (corn semolina) instead of Tenax®. Three main causes for this deviation were identified: (i) at 60°C, migration reached beyond n-C₃₅, whereas it ends at about n-C₂₄ in reality. (ii) Tenax® is a far stronger adsorbent than foods, resulting in almost complete extraction. (iii) The significant barrier effect of polypropylene films at ambient temperature is lost at increased temperature. The suitability of such simulation for the prediction of long-term migration is questioned.

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 degrees C, but in only 1week at 40 degrees 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

So far the majority of the measurements of mineral oil saturated hydrocarbons (MOSH) and mineral oil aromatic hydrocarbons (MOAH) were obtained from on-line high performance liquid chromatography-gas chromatography-flame ionization detection (on-line HPLC-GC-FID). Since this technique is not available in many laboratories, an alternative method with more easily available tools has been developed. Preseparation on a small conventional liquid chromatographic column was optimized to achieve robust separation between the MOSH and the MOAH, but also to keep out the wax esters from the MOAH fraction. This was achieved by mixing a small portion of silica gel with silver nitrate into highly activated silica gel and by adding toluene into the eluent for the MOAH. Toluene was also added to the MOSH fraction to facilitate reconcentration and to serve as a keeper preventing loss of volatiles during solvent evaporation. A 50 μl volume was injected on-column into GC-FID to achieve a detection limit for MOSH and MOAH below 1 mg/kg in most foods.

This paper describes a new method for the rapid determination of the moisture content in paper materials. The method is based on multiple headspace extraction gas chromatography (MHE-GC) at a temperature above the boiling point of water, from which an integrated water loss from the tested sample due to evaporation can be measured and from which the moisture content in the sample can be determined. The results show that the new method has a good precision (with the relative standard deviation

Dimethyl sulfide (DMS) is one of the sulfurous pollutants present in the waste gas generated from the pulp and paper industry. DMS has environmental health implications; therefore, it is necessary to treat the waste gas containing DMS prior to discharge into the environment. A bench-scale biofilter was operated in the laboratory as well as in a pulp and paper industry for the treatment of DMS. Both the biofilters were packed with pre-sterilized wood chips and cow dung/compost of the same origin seeded with biomass developed from garden soil enriched with DMS. The biofilters were operated for the generation of process parameters, and the potential microorganisms isolated from both the biofilters have been purified and characterized for degradation of DMS. Further, these cultures were purified on a basal medium using DMS as a sole carbon source for the growth. Further, the purified cultures were characterized through standard fatty acid methyl esters (FAME)-gas chromatography method, and the isolates were found to be mesophilic, aerobic microbes. These microbes were identified as Bacillus sphaericus-GC subgroup F, Paenibacillus polymyxa, B. sphaericus-GC subgroup F, B. sphaericus-GC subgroup F, and Bacillus megaterium-GC subgroup A, respectively. The potential culture for degradation of DMS was identified as B. sphaericus by 16s rRNA molecular analysis.

Party plates made of recycled paperboard with a polyolefin film on the food contact surface (more often polypropylene than polyethylene) were tested for migration of mineral oil into various foods applying reasonable worst case conditions. The worst case was identified as a slice of fried meat placed onto the plate while hot and allowed to cool for 1 h. As it caused the acceptable daily intake (ADI) specified by the Joint FAO/WHO Expert Committee on Food Additives (JECFA) to be exceeded, it is concluded that recycled paperboard is generally acceptable for party plates only when separated from the food by a functional barrier. Migration data obtained with oil as simulant at 70°C was compared to the migration into foods. A contact time of 30 min was found to reasonably cover the worst case determined in food.

The synchronous fluorescence (SF) technique has been used in the identification of polycyclic aromatic hydrocarbons (PAHs) from air particulate sample in an urban environment of Delhi, Jawaharlal Nehru University. Suspended particulate matter samples of 24h duration were collected on glass fiber filter papers. PAHs were extracted from the filter papers using dichloromethane (DCM)+hexane with ultrasonication method. Qualitative measurements of the polycyclic aromatic hydrocarbons (PAHs) were carried out using the SF technique at various wavelength intervals (Deltalambda). Due to the difference in chemical structure, each PAH gives specific characteristic spectrum for each Deltalambda. Following PAHs were detected in our measurement: benz(a)anthracene (BaA), pyrene (Pyr), chrysene (Chry), fluoranthene (Flan), phenanthrene (Phen), and benz(ghi)perylene (BghiP). This is in agreement with our earlier work for determination of these PAHs using gas chromatography (GC). The seasonal variation of the PAHs was found to be maximum in winter and minimum during the monsoon.

Bisphenol A (BPA; 4,4'-(propane-2,2-diyl)diphenol), a suspected endocrine disruptor with weak estrogenic activity, is used in a variety of consumer products, including paper and cardboard products used as food contact materials. The present study compared four different gas chromatographic methods for the analysis of BPA in paper and cardboard food packages. Eighteen different food packages were extracted and BPA was determined using two different derivatisation reactions--trimethylsilylation with N,O-bis(trimethylsilyl) trifluoroacetamide (BSTFA) and halide alkylation with pentafluorobenzoyl chloride (PFBOCl)--and four different separation and detection techniques. The BSTFA derivatives were quantified with (1) GC-MS in single-ion monitoring (SIM) mode with electron ionisation (EI-GC-MS) and (2) GC-MS/MS in multiple reaction monitoring (MRM) mode using electron ionisation (EI-GC-MS/MS); while the PFBOCl derivatives were quantified with (3) GC-MS using electron ionisation (EI-GC-MS) as well as (4) GC-MS with negative chemical ionisation (NCI-GC-MS). All developed methods showed good linearity (R(2)0.9938), precision (CV4.5% for reproducibility; CV2.2% for repeatability) and sensitivity, with limits of detection (LODs) between 0.02 µg kg(-1) for the pentafluorobenzoyl derivatives measured with the NCI-GC-MS method and 6 µg kg(-1) for the pentafluorobenzoyl derivatives determined with EI-GC-MS. Levels of BPA in the samples were in agreement for all methods, ranging from values below the limit of quantitation (LOQ) to 11.9 mg kg(-1) paper. In a last step, the maximum potential migration into food products was calculated for all tested paper and cardboard samples, assuming a 'worst case' scenario of 100% migration.

1Instituto de Recursos Naturales y Agrobiología, CSIC, PO Box 1052, E-41080, Seville, Spain; and 2Centro de Investigaciones Biológicas, CSIC, Ramiro de Maeztu 9, E-28040 Madrid, Spain, Lipophilic extractives in wood and other lignocellulosic materials exert a negative impact in pulp and paper manufacturing causing the so-called pitch problems. In this work, the appropriateness of an enzymatic treatment using the laccase-mediator system for pitch biocontrol is evaluated. With this purpose, three pulp types representative for different raw materials and pulping processes - eucalypt kraft pulping, spruce thermomechanical pulping and flax soda-anthraquinone pulping - were treated with a high-redox potential laccase from the basidiomycete Pycnoporus cinnabarinus in the presence of 1-hydroxybenzotriazole as a redox mediator. The gas chromatography and gas chromatography/mass spectrometry analyses of the lipophilic extractives from the enzymatically-treated pulps revealed that the laccase-mediator treatment completely (or greatly) removed most of the pitch-causing lipophilic compounds present in the different pulps including: i) free and conjugated sitosterol in eucalypt paper pulp; ii) resin acids, sterol esters and triglycerides in spruce pulp; and iii) sterols and fatty alcohols in the flax pulp. Different amounts of free and conjugated 7-oxosterols were found as intermediate products in the oxidation of pulp sterols. Therefore, the laccase-mediator treatment is reported as an efficient method for removing pitch-causing lipophilic compounds from paper pulps obtained from hardwood, softwood and nonwoody plants., This study has been funded by the Spanish projects AGL2002-393 and BIO2002-1166, the EU projects QLK5-99-1357 and QLK3-99-590, and by ENCE-CSIC contracts.

A solid-phase microextraction (SPME) method has been developed for the determination of pentachlorophenol (PCP) in paper and board samples. The analytical procedure involves direct extraction of PCP from paper and board samples and determination by gas chromatography with electron capture detection (GC-ECD). Two kinds of commercially available fibres; 100 microm polydimethylsiloxane (PDMS), apolar, and 85 microm polyacrylate (PA), quite polar, were evaluated to determine the extraction efficiency of pentachlorophenol. Parameters affecting the extraction process, such as temperature and time, were studied. Moreover, time of desorption and the effect of addition of salt were also investigated. The optimized procedure was applied to the analysis of pentachlorophenol (PCP) in five samples of virgin and recycled paper and board. The PCP content was determined by GC-ECD. To evaluate the effectiveness of the proposed method, it was compared with conventional extraction method with liquid-liquid extraction and derivatization. Detection limit of 0.015 microg/g for PCP in paper was achieved with a RSD of 14%.

This paper uses countercurrent fermentation to anaerobically convert paper fines and industrial biosludge to carboxylate salts using a mixed culture of acid-forming microorganisms. Using the MixAlco process, the carboxylate salts can be thermally converted to ketones and hydrogenated into mixed alcohol fuels. Continuum particle distribution modeling (CPDM) correlated batch fermentation data to countercurrent fermentation data, allowing the prediction of product concentrations and conversions over a wide range of solid loading rates and liquid residence times. For 80% paper/20% biosludge, the predicted product concentrations agreed with the data within 7.7%. The predicted conversion agreed with the actual conversion within 27.8%. By correcting for varying selectivity, the predicted conversion agreed with the actual conversions within 15.2%. For 40% paper/60% biosludge, the predicted product concentrations agreed with the data within 9.6%. The predicted conversion agreed with the actual conversion within 28.3%. By correcting for varying selectivity, the predicted conversion agreed with the actual conversions within 15.4%. For both the 80/20 and 40/60 cases, CPDM predicts that 90% conversion is possible with a 20 g/l product concentration, 300 g/l substrate concentration, 16 day liquid residence time, and 2.5 g/(ld) solids loading rate. Before proceeding to an industrial plant, these predictions must be verified in a pilot plant.

Treatment of wheat straw with hot water at 80–95 °C for 0.5 h at pH 6.0–8.0 released 41.0–53.0% of the original lipophilic extractives. The chemical compositions of six lipophilic extractives were determined by GC on a medium-length high-temperature capillary column without derivatization, thus giving a method for direct determination of individual components of free fatty and resin acids, sterols, waxes, sterol esters, and triglycerides. The extracts contained 68.7–75.8% lipophilic substances, comprising mainly free fatty acids (25.8–48.4%), waxes (9.4–27.0%), sterols (4.1–8.0%), triglycerides (3.3–11.0%), and sterol esters (2.6–5.1%). Minor amounts of diglycerides (0.3–0.5%), resin acid (0.5–3.1%), and phenolic compounds (0.9–3.6%) were also quantitatively determined in the extractives.

The migration of five surrogate contaminants, anthracene, benzophenone, dimethyl phthalate, methyl stearate and pentachlorophenol, from paper and paperboard into water through a polyethylene (PE) coating layer was investigated. Virgin paper and paperboard coated with PE films of 0.012 and 0.030 mm thickness were spiked evenly with standard 1-ml solutions containing 5mg of each surrogate. The spiked papers were placed in contact with the PE coating layer at 10 and 24 degrees C for 21 days. The resulting surrogate migration through the PE layer into 100ml water was measured by an analytical method developed here that used gas chromatography equipped with a flame ionization detector. Non-polar surrogates of anthracene and methyl stearate did not show any significant migration. In the case of the thin layer coating of 0.012 mm, polar water-soluble contaminants of benzophenone, dimethyl phthalate and pentachlorophenol showed an equilibrated or maximized migration after 1 day, even at a refrigerated temperature of 10 degrees C. A thick PE coating of 0.030 mm thickness delayed the progress of contaminant migration, which was also slower at lower temperature. Our results indicate that polyethylene coatings should not be seen as a complete barrier against possible contaminants in paper packaging materials under chilled or ambient conditions. Several variables such as coating thickness, temperature and suspected contaminants need to be considered to control the possible contamination risk from recycled or printed paper.

The surface energies of various inorganic fillers including kaolin clay, titanium dioxide, and talc were examined using inverse gas chromatography (IGC). In an earlier investigation that examined calcium carbonate fillers, dehydration by heating under a dry nitrogen purge had a substantial influence on the apolar (gammaS(LW)) and polar (gammaS(AB)) components of surface energy as measured using IGC. Using the same approach, the influence of such conditioning on several inorganic fillers used in papermaking were determined using preconditioning IGC from 100 to 300 degrees C, and sequential isothermal analysis at 100 degrees C. Results from IGC analysis of titanium dioxides (rutile and anatase) were similar to precipitated calcium carbonate (PCC) for temperatures up to 200 degrees C. PCC was significantly more energetic after preconditioning at 300 degrees C, which may indicate the onset of significant thermal decomposition that titanium dioxides will not exhibit. Kaolin clay samples had relatively high apolar surface energy similar to that of the chalk samples. Calcination gave lower gammaS(LW) values that could not be accounted for by changes in the microporous structure. More likely the differences resulted from contamination of highly energetic surface sites with adsorbates other than water. Talc samples exhibited relatively high apolar surface energies that increased with preconditioning temperature. The results provided insight into the significance of water on the final adhesion properties of fillers in the sheet structure or coating layer.

Because of the lack of information about the possible transfer of toxic compounds from papers and boards to food, the overall cytotoxicity induced by six papers and 15 boards was investigated from water extracts prepared according to the European prestandard. Cytotoxicity measurements were based on RNA synthesis rate of human HeLa S3 cells. The tested virgin and recycled papers and boards were differentiated and classified according to their cytotoxicological quality, which ranged from absence of any cytotoxic effect to severe inhibition of RNA synthesis rate. The cytotoxicity level also varied according to the total amount of compounds detected by gas chromatography. No correlation was found between cytotoxicity and endotoxins contained in the samples. No significant difference in cytotoxicity was observed between the papers and boards produced from virgin fibres and from recycled fibres. Moreover, the products obtained from chemical pulp showed lower cytotoxicity than the products based on mechanical pulp. More generally, the cytotoxicological approach is promising for monitoring paper/board treatment-induced problems. Further work is required to assess a modified standard procedure for the preparation of water extracts specifically adapted to paper/board.

Building on breakthroughs recently made at kraft mills, a survey of mechanical pulp and paper mill effluents was undertaken to gain insights concerning potential effects on fish reproduction. Effluents from seven Canadian mills were characterized chemically for conventional parameters such as biochemical oxygen demand (BOD) and total suspended solids (TSS). Each sample was further subjected to solvent extraction followed by gas chromatographic separation for the determination of resin/fatty acids and for the estimation of a gas chromatography (GC) profile index. Each mill effluent was assessed for the potential to affect fish reproduction in the laboratory using a five day adult fathead minnow (Pimephales promelas) egg production bioassay with exposures to 100% effluent. The seven effluents were found to have substantial variation both in terms of chemical characterization and effects on fish reproduction. Temporal variations were also noted in effluent quality at mills sampled on different occasions. Similar to what has been observed for kraft mills, a general trend of greater reductions in egg production caused by effluents with greater BOD concentrations and GC profile indices was noted. Effluents with BOD > 25 mg/L and GC Profile indices >5.0 caused a complete cessation of egg production. At the same time, about half of the total effluents sampled had BOD < 25 mg/L and GC profile indices

A method for determining potentially health-relevant components in paperboard used for packaging dry foods as comprehensively as technically feasible was applied to a sample of recycled paperboard. The task was specified by a detection limit in food of 0.01 mg/kg, from which a detection limit of 0.1 mg/kg in paperboard was derived. Extracts from the paperboard were preseparated into seven fractions by high performance liquid chromatography (HPLC) and transferred on-line to gas chromatography with flame ionization detection (GC-FID). The chromatograms visualize the high complexity of the material that may migrate into foods at toxicologically potentially relevant concentrations. Since only a minority of the substances was also detectable in fresh fiber board, most must have originated from chemicals used in the paper and board fed into the recycling process. Significant variability between recycled paperboards of four manufacturers was observed because of varying feedstocks. Using comprehensive two-dimensional GC (GC × GC) with time of flight mass spectrometry (TOF-MS), more than 250 substances were counted that probably exceeded the detection limit and were probably of sufficient volatility for migration into dry food. It is concluded in three main messages to risk managers: (i) since most potential migrants have not been adequately evaluated, many not even identified, the safety required by Article 3 of EU Regulation 1935/2004 has not been ensured; (ii) the number of substances potentially migrating into food above 0.01 mg/kg is too large to realistically be brought under control; (iii) a barrier reducing the migration into food by a factor of 100 over the life time of a product would keep the migration of all except a few well known substances below 0.01 mg/kg in food.

Legislation on food contact materials, mainly focusing on food safety, requires the absence of potentially harmful substances in the migrate from packaging materials. For recycled paperboard with essentially unknown input this presupposes comprehensive analysis of all substances potentially migrating above the regulatory threshold. Present chemical analysis is strong in target analysis, but not in methodologies enabling comprehensive analysis of unknown mixtures at low detection limits. An attempt was made to analyze the potential migrants into dry foods as comprehensively as possible. The required detection limit was derived from the conventional regulatory European detection limit of 0.01 mg/kg in food, which was approximated by a detection limit in paperboard of 0.1mg/kg. Various obstacles had to be overcome and adjusted or even new tools were required. Compromises were unavoidable, which could have resulted in loss of relevant components. This paper points out facets of related analytical methodology, but also provides an analytical base for the information of regulators about the feasibility of the old legal requirements that substances endangering human health must not migrate into food.

Waste money bills (WMB) that are no longer legal tender are nonrecyclable and are generally useless. In this work, we used this cellulose-rich material for ethanol fermentation for the first time. Torrefaction of this nonlignocellulosic waste material was attempted to examine whether such material could benefit from this process as a conventional lignocellulosic material does. Effects of two important parameters, that is, residence times (20, 40, and 60 Min) and temperatures (140, 160, 180, 200, and 220°C), on the torrefaction yield were studied under an inert atmosphere. Glucose and ethanol yields were compared using a factorial experimental design. The highest glucose yield (81.59 mg/mL) was obtained with a torrefaction treatment consisting of 40 min at 180 °C, and it was increased 44.89% compared to untreated WMB. Based on ethanol feasibility studies conducted on WMB, this estimated quantity of glucose could be produced for subsequent fermentation to ethanol (38.92 mg/mL) and it was increased 47.92% compared to the untreated sample. The fermentation rate was also enhanced by adding 0.4 mM benzoic acid under anaerobic conditions. It is concluded that production of ethanol from WMB would reduce waste management costs and thus would be profitable.

In this work, a method for measuring polychlorinated biphenyls (PCBs) in contaminated solid waste was investigated. This waste includes paper that is used in electric transformers to insulate electric components. The PCBs in paper sample were extracted by supercritical fluid extraction and analyzed by gas chromatography-electron capture detection. The recoveries with this method (84–101%) were much higher than those with conventional water extraction (0.08–14%), and were comparable to those with conventional organic solvent extraction. Limit of detection was 0.0074 mg kg −1 and measurable up to 2.5 mg kg −1 for 0.5 g of paper sample. Data for real insulation paper by the proposed method agreed well with those by the conventional organic solvent extraction. Extraction from wood and concrete was also investigated and good performance was obtained as well as for paper samples. The supercritical fluid extraction is simpler, faster, and greener than conventional organic solvent extraction.

Retail samples of dry goods (bread, biscuits and breakfast cereals) packaged in waxed paper were examined for the presence of mineral hydrocarbon wax. Bread loaves contained up to 50 mg/kg of the wax (associated with the outer surfaces) and crackers up to 185 mg/kg. Mineral oil was found in bread samples, at up to 550 mg/kg and was dispersed throughout indicating its use in food processing machinery as the likely source. Retail confectionery products wrapped in waxed paper (containing 12-44% w/w) gave rise to levels of 12-1300 mg/kg mineral hydrocarbon in the individually wrapped sweets. Migration into boiled sweets was lowest at 10-130 mg/kg, whilst soft chews and toffee products contained 110-1300 mg/kg. The distribution of wax hydrocarbons (principally n-alkanes) in the confectionery coincided exactly with that for the paper wrapping, with a range of C23 to C33 (95% material) centred around C26. This indicated that the transfer to the food occurred largely by adhesion rather than by diffusion since the latter would be expected to favour preferential migration of the low molecular weight components. In simulated home-use experiments with waxed bags sold in the United States for domestic use, migration into sandwiches and cake amounted to 40 mg/kg (1% transfer of wax). Use of these waxed bags in the microwave oven (as recommended) gave rise to contamination of foods from 210 to 1650 mg/kg (up to 60% transfer of wax).

This study investigates factors affecting reproduction in fish exposed to pulp and paper mill effluents by comparing effluents from countries with varying levels of documented effects. To explore the hypothesis of wood as a common source of endocrine disrupting compounds, feedstocks from each country were analyzed. Analyses included in vitro assays for androgenic activity (binding to goldfish testis androgen receptors), estrogenic activity (yeast estrogen screen), and neurotransmitter enzyme inhibition (monoamine oxidase and glutamic acid decarboxylase). Chemical analyses included conventional extractives, known androgens, and gas chromatograph index (GCI) profiles. All effluents and wood contained androgenic activity, particularly in nonpolar fractions, although known androgens were undetected. Effluents with low suspended solids, having undergone conventional biotreatment had lower androgenic activities. Estrogenic activity was only associated with Brazilian effluents and undetected in wood. All effluents and wood inhibited neurotransmitter enzymes, predominantly in polar fractions. Kraft elemental chlorine free mills were associated with the greatest neurotransmitter inhibition. Effluent and wood GCI profiles were correlated with androgenic activity and neurotransmitter enzyme inhibition. Differences in feedstock bioactivities were not reflected in effluents, implying mill factors mitigate bioactive wood components. No differences in bioactivities could be discerned on the basis of country of origin, thus we predict effluents in regions lacking monitoring would affect fish reproduction and therefore recommend implementing such programs.

Mineral oil hydrocarbons are complex as well as varying mixtures and produce correspondingly complex chromatograms (on-line HPLC-GC-FID as described in Part 1): mostly humps of unresolved components are obtained, sometimes with sharp peaks on top. Chromatograms may also contain peaks of hydrocarbons from other sources which need to be subtracted from the mineral oil components. The review focuses on the interpretation and integration of chromatograms related to food contamination by mineral oil from paperboard boxes (off-set printing inks and recycled fibers), if possible distinguishing between various sources of mineral oil. Typical chromatograms are shown for relevant components and interferences as well as food samples encountered on the market. Details are pointed out which may provide relevant information. Integration is shown for examples of paperboard packaging materials as well as various foods. Finally the uncertainty of the analysis and limit of quantitation are discussed for specific examples. They primarily result from the interpretation of the chromatogram, manually placing the baseline and cuts for taking off extraneous components. Without previous enrichment, the limit of quantitation is between around 0.1 mg/kg for foods with a low fat content and 2.5 mg/kg for fats and oils. The measurement uncertainty can be kept clearly below 20% for most samples.

Paraffins from raw extracts of foods and packing materials were isolated by LC and directly transferred to GC, applying concurrent eluent evaporation and a loop-type interface. Paraffins from various packing materials have been characterized: sisal bags, cardboard boxes, plastic films, wax-coated paper and cardboard as well as paraffin coatings. Important food contamination was found for sisal bags, cardboard boxes, and wax-coated paper/cardboard. Contamination by paraffin coatings on cheese was surprisingly small.

The presence of cocaine on US paper currency has been known for a long time. Banknotes become contaminated during the exchange, storage, and abuse of cocaine. The analysis of cocaine on various denominations of US banknotes in the general circulation can provide law enforcement circles and forensic epidemiologists objective and timely information on epidemiology of illicit drug use and on how to differentiate money contaminated in the general circulation from banknotes used in drug transaction. A simple, nondestructive, and accurate capillary gas chromatographic method has been developed for the determination of cocaine on various denominations of US banknotes in this study. The method comprises a fast ultrasonic extraction using water as a solvent followed by a SPE cleanup process with a C(18) cartridge and capillary GC separation, identification, and quantification. This nondestructive analytical method has been successfully applied to determine the cocaine contamination in US paper currency of all denominations. Standard calibration curve was linear over the concentration range from the LOQ (2.00 ng/mL) to 100 microg/mL and the RSD less than 2.0%. Cocaine was detected in 67% of the circulated banknotes collected in Southeastern Massachusetts in amounts ranging from approximately 2 ng to 49.4 microg per note. On average, $5, 10, 20, and 50 denominations contain higher amounts of cocaine than $1 and 100 denominations of US banknotes.

E-mail: anagu@irnase.csic.es (A. Gutiérrez), Different model lipids—alkanes, fatty alcohols, fatty acids, resin acids, free sterols, sterol esters, and triglycerides—were treated with Pycnoporus cinnabarinus laccase in the presence of 1-hydroxybenzotriazole as mediator, and the products were analyzed by gas chromatography. The laccase alone decreased the concentration of some unsaturated lipids. However, the most extensive lipid modification was obtained with the laccase–mediator system. Unsaturated lipids were largely oxidized and the dominant products detected were epoxy and hydroxy fatty acids from fatty acids and free and esterified 7-ketosterols and steroid ketones from sterols and sterol esters. The former compounds suggested unsaturated lipid attack via the corresponding hydroperoxides. The enzymatic reaction on sterol esters largely depended on the nature of the fatty acyl moiety, i.e., oxidation of saturated fatty acid esters started at the sterol moiety, whereas the initial attack of unsaturated fatty acid esters was produced on the fatty acid double bonds. In contrast, saturated lipids were not modified, although some of them decreased when the laccase–mediator reactions were carried out in the presence of unsaturated lipids suggesting participation of lipid peroxidation radicals. These results are discussed in the context of enzymatic control of pitch to explain the removal of lipid mixtures during laccase–mediator treatment of different pulp types.