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The rapid dispersion of new psychoactive substances (NPS) presents challenges to customs services and analytical laboratories, which are involved in their detection and characterization. When the seized material is limited in quantity or of a complex nature, or when the target substance is present in very small amounts, the need to use advanced analytical techniques, efficient workflows and chemo-informatics tools is essential for the complete identification and elucidation of these substances. The current work describes the application of such a workflow in the analysis of a single blotter paper, seized by Swedish customs, that led to the identification of a lysergic acid diethylamide (LSD) derivative, 1-butyl-lysergic acid diethylamide (1B-LSD). Such blotter paper generally contains an amount in the range of 30&ndash, 100 ug. This substance, which is closely related to 1-propionyl-lysergic acid diethylamide (1P-LSD), seems to have only recently reached the drug street market. Its identification was made possible by comprehensively combining gas chromatography with mass spectrometry detection (GC&ndash, MS), liquid chromatography coupled with high-resolution tandem MS (LC&ndash, HR-MS/MS), Orbitrap-MS and both 1D and 2D nuclear-magnetic-resonance (NMR) spectroscopy. All the obtained data have been managed, assessed, processed and evaluated using a chemo-informatics platform to produce the effective chemical and structural identification of 1B-LSD in the seized material.

Dialkyl diketene dimers are used as sizing agents in the manufacture of paper and board for food contact applications to increase wetting stability. Unbound residues can hydrolyze and decarboxylate into dialkylketones. These non-intentionally added substances (NIAS) have potential to migrate to fatty foods in contact with those packaging materials. In Germany, the Federal Institute for Risk Assessment (BfR) established a specific migration limit (SML) of 5 mg/kg for the transfer of these dialkylketones into foodstuffs. In order to investigate the differences between simulants and real foods, an analytical method was optimized for extraction and quantification of dialkylketones in edible oils and fatty foods by gas chromatography coupled with flame ionization detection (GC-FID), and additionally by gas chromatography with mass spectrometry (GC-MS), to confirm their identification and to quantify them in case of interferences. Dialkylketones are separated from the extracted fat by alkaline saponification of the triglycerides. Dialkylketones migration from paper-based food contact articles into organic solvents isooctane and dichloromethane, in olive and sunflower oils, and in fatty foods (croissants, Gouda, cheddar cheese, and salami was studied). As a result, it was found that the simulating tests, including the edible oil extraction tests, gave migration values that exceeded the SML largely, while the migration with the food samples were largely below the SML. Antía Lestido Cardama is grateful for her predoctoral grant “Programa de axudas á etapa predoutoral” da Xunta de Galicia (Consellería de Cultura, Educación e Ordenación Universitaria) SI

An extraction and determination method is shown for the analysis of dyes and solvents present in two types of ballpoint pen inks that are deposited onto paper. Ink extracts are analysed using a combination of gas chromatography with mass spectrometry (GC-MS), and high-pressure liquid chromatography with photodiode array detection (HPLC-DAD), within a single sample extraction procedure. Seventeen solvents and thirteen dyes contained in two Montblanc® inks (black and blue) were monitored for 45 months at monthly intervals, in order to determine variations in the concentrations of the compounds over time. We also studied the relative variations between different compounds and the generation of degradation products such as phenol. The concentration data obtained from these compounds during their exposure have been analysed and a multiple regression model is developed for each ink type that allows an estimate of the exposure time of the ink on paper with a maximum error of between 4 and 7 months.

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.

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 builds upon the work of a multiagency consortium tasked with determining cost-effective solutions for the effects of pulp mill effluents on fish reproduction. A laboratory fathead minnow egg production test and chemical characterization tools were used to benchmark 81 effluents from 20 mills across Canada, representing the major pulping, bleaching, and effluent treatment technologies. For Kraft and mechanical pulp mills, effluents containing less than 20 mg/L BOD5 were found to have the greatest probability of having no effects. Organic loading, expressed as the total detected solvent-extractable components by gas chromatography/mass spectrometry (GC/MS), also correlated with decreased egg laying. Exceptions were found for specific Kraft, mechanical, and sulfite mills, suggesting yet unidentified causative agents are involved. Recycled fiber mill effluents, tested for the first time, were found to have little potential for reproductive effects despite large variations in BOD5 and GC/MS profiles...

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

Photoinitiators are widely used to cure ink on packaging materials used in food applications such as cardboards for the packaging of dry foods. Conventional migration testing for long-term storage at ambient temperature with Tenax® was applied to paperboard for the following photoinitiators: benzophenone (BP), 4,4ʹ-bis(diethylamino)benzophenone (DEAB), 2-chloro-9H-thioxanthen-9-one (CTX), 1-chloro-4-propoxy-9H-thioxanthen-9-one (CPTX), 4-(dimethylamino)benzophenone (DMBP), 2-ethylanthraquinone (EA), 2-ethylhexyl-4-dimethylaminobenzoate (EDB), ethyl-4-dimethylaminobenzoate (EDMAB), 4-hydroxybenzophenone (4-HBP), 2-hydroxy-4-methoxybenzophenone (HMBP), 2-hydroxy-4ʹ-(2-hydroxyethoxy)-2-methylpropiophenone (HMMP), 2-isopropyl-9H-thioxanthen-9-one (ITX), 4-methylbenzophenone (MBP) and Michler’s ketone (MK). Test conditions (10 days at 60°C) were according to Regulation (EU) No. 10/2011 and showed different migration patterns for the different photoinitiators. The results were compared with the migration in cereals after a storage of 6 months at room temperature. The simulation with Tenax at 60°C overestimated actual migration in cereals up to a maximum of 92%. In addition, the effect of a lower contact temperature and the impact of the Tenax pore size were investigated. Analogous simulation performed with rice instead of Tenax resulted in insufficiently low migration rates, showing Tenax is a much stronger adsorbent than rice and cereals.

A análise de tintas e papéis é de grande interesse para a ciência e a interação tinta-papel é importante em vários níveis. A análise da tinta de um documento é extremamente importante para o estudo de diferentes aspectos, como adulterações e determinação da recentidade. Esses aspectos podem ser estudados analisando a tinta e o papel tanto fisicamente quanto quimicamente. Portanto, o desenvolvimento de uma técnica para a análise de tintas de caneta esferográfica e a determinação da recentidade de um documento é interessante para a Ciência Forense. No Brasil, cientistas forenses enfrentam todos os dias diversos casos que requerem a análise de tintas de caneta esferográfica, e não se tem nenhuma técnica onde a determinação da idade de uma tinta é possível. Os casos mais comuns onde há a necessidade da recentidade de um documento são fraudes em recibos de pagamento e de quitação de dívidas, preenchimento e assinatura de contratos, adulteração em documentos e em cheques. Neste trabalho, é discutida uma nova metodologia para a análise de tintas de canetas esferográficas e a sua utilização na determinação da recentidade de uma amostra de tinta de caneta esferográfica. Foram analisadas periodicamente amostras provenientes de diferentes países, como Estados Unidos, Canadá, Peru, Japão, Espanha e Grécia. Com os resultados obtidos, foram construídas curvas de degradação do solvente em função do tempo de preparo. Com as curvas, obtiveram-se as equações logarítmicas relativas. As equações propostas mostraram ser capazes de distinguir a idade relativa de uma tinta, com 20% de variação em relação ao valor teórico. Portanto, a principal conclusão deste trabalho é a metodologia proposta pode ser utilizada para determinar a idade relativa de uma tinta de caneta esferográfica. The analysis of inks and papers are of great interest to science and an understanding of the interaction between ink and paper is very important in mamy levels. The ink analysis from a document is extremely important to the study of several aspects such as adulteration and the age of the ink. These aspects could be studied by analysing the ink and paper both physically and chemically. The development of a technique to analyse ballpoint pen ink and to determine the age of a document by analysing the ink applied on a paper is very helpfull for every aspect of Forensic Science. In Brazil, Forensic Scientists face everyday many cases that require the ballpoint pen ink analysis, and there are no methods in which the determination of the ink age is possible. The most habitual cases which ink age analysis is requested are frauds in receipts, debt quittances, contract completions, signatures, adultered documents and checks. In this work, a new methodology of the ballpoint ink pen and its utilization to determine the age of a ballpoint ink sample will be discussed. Ballpoint pen ink samples from different countries such as the United States, Canada, Peru, Japan, Spain and Greece were periodically analysed. With the obtained results and according to the preparation time, curves of degradation of the solvent were built. The logarithmic equations from the curves were obtained too. The proposed equation has shown to be able to distinguish the relative age of the ballpoint ink with a variation of 20% from the theoretical value. Therefore, the main conclusion of this work is that the methodology proposed could be used to determine the relative age of a ballpoint ink pen.

This study combined chemical analysis and bioassays of paper mill effluents and their components in order to determine their antiestrogenic activity. The bioassay comprised a yeast two-hybrid assay incorporating the estrogen receptor alpha (hERalpha) and an hERalpha competitive enzyme-linked immunosorbent assay (ELISA). Samples were fractionated by solid phase extraction (SPE) with a C18 disk and a Florisil cartridge to obtain four fractions. The final fraction, eluted with methanol from the Florisil cartridge after pre-extraction by the C18 disk, was the most active in the two-hybrid assay, and its antiestrogenic potency, expressed as the equivalent concentration to 4-hydroxytamoxifen (OHT), was 277 nM. Seven resin acids had antiestrogenic activity in the active fraction as determined by gas chromatography/mass spectrometry (GC/MS), and their concentration levels ranged from 0.11 to 12 microg/L. All the resin acids exhibited greater activity than OHT; their activity relative to OHT ranged from 2.8- to 4.0-fold in the yeast two-hybrid assay. Based on the chemical analysis data and relative potency of resin acids from the yeast two-hybrid assay, the contribution ratio of resin acids accounted for 72% of the observed antiestrogenic activity of the extract. Furthermore, no resin acid showed any affinity for the estrogen receptor in the ELISA. This study showed that analysis combining the SPE method and the yeast two-hybrid assay is likely to be effective for the comprehensive monitoring of resin acids in paper mill industrial discharge areas.

In this study, a new sampling method called headspace mulberry paper bag micro solid phase extraction (HS-MPB-mu-SPE) combined to gas chromatography-mass spectrometry has been applied for the analysis of volatile aromas of liquid essential oils from Bulgarian rose and Provence lavender. The technique uses an adsorbent (Tenax TA) contained in a mulberry paper bag, minimal amount of organic solvent. Linearities for the six-points calibration curves were excellent. LOD values were in the rage from 0.38 ng mL(-1) to 0.77 ng mL(-1). Overall, precision and recovery were generally good. Phenethyl alcohol and citronellol were the main components in the essential oil from Bulgarian rose. Linalyl acetate and linalool were the most abundant components in the essential oils from true lavender or lavandin. Additionally, the relative extraction efficiencies of proposed method have been compared with HS-SPME. The overall extraction efficiency was evaluated by the relative concentration factors (CF) of the several characteristic components. CF values by HS-MPB-mu-SPE were lower than those by headspace solid phase microextraction (HS-SPME). The HS-MPB-mu-SPE method is very simple to use, inexpensive, rapid, requires small sample amounts and solvent consumption. In addition, this method allowed combining of extraction, enrichment, and clean-up in a single step. HS-MPB-mu-SPE and GC/MS is a promising technique for the characterization of volatile aroma compounds from liquid essential oils.

A gas chromatography-ion-trap tandem mass spectrometry procedure was developed for the determination of 2,6-diisopropylnaphthalene (DIPN) and n-dibutylphthalate (DBP) in domestic and imported paper packages and food sold in US marketplaces. The procedure involved ultrasonic extraction with dichloromethane, followed by analysis with the gas chromatography-ion-trap tandem mass spectrometry. Calibration curves for DIPN and DBP were achieved with concentrations ranging from 0.01 to 10 microg ml(-1) and the corresponding r(2) values were 0.9976 and 0.9956, respectively. In most of the fortified samples the recoveries were higher than 80% with a relative standard deviation (RSD)

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.

A study comparing recently available 100 x 3 mm id, 200 x 3 mm id monolithic reversed-phase columns with a 50 x 2.1 mm id, 1.8 microm particle packed reversed-phase columns was carried out to determine the most efficient approach (using traditional van Deemter analysis and a modern kinetic plot approach) for the rapid screening of samples for 16 illicit drugs and associated metabolites. A plot of column backpressure versus plate number (N) showed a significant advantage of using the monolithic phases, with the 20 cm monolithic column exhibiting a maximum 15,000 plates at a column backpressure of approximately 70 bar, compared to approximately 7000 plates at 150 bar for the 5 cm 1.8 microm particle packed column. Optimum linear velocities were found to be 0.40 mm s(-1), 0.52 mm s(-1) and 0.98 mm s(-1) for the three above columns, respectively. The 20 cm monolithic column was subsequently applied to the separation and determination of illicit drug contamination on Irish euro banknotes, using methanol extraction followed by LC-MS/MS. Method performance data showed that the new LC-MS/MS method was significantly more sensitive than previous GC-MS/MS based methods for this application, with detection limits in the pg note(-1) region, based upon a 20 microL standard injection. All of the notes examined tested positive for trace quantities of cocaine, with benzoylecgonine detected on 12 of the 45 notes sampled. Traces of heroin were also detected on three of the 45 notes.

A completely unexplored area of research is constituted by the impact of secondary substances of paper on the mechanism and kinetics of paper’s aging. Hence the interest in the adhesive substances used in the manufacturing technology of historical printing paper. The main goal of the experiment was the usage of selected chromatographic techniques to mark natural ingredients in the historic library materials and the products of their reactions as yet another element of the natural process of aging. Learning the data allowed to create basic mechanism of this process and its influence on the structural and mechanical parameters of the historical library material. Such knowledge makes the decision about the degree of conservator’s interference easier as well as allows to choose appropriate materials or neutral contemporary substitutes.

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.

Parchment, a biologically based material obtained from the processed hides of animals such as cattle and sheep, has been used for millennia as a writing medium. Although numerous studies have concentrated on the structure and degradation of collagen within parchment, little attention has been paid to noncollagenous components, such as lipids. In this study, we present the results of biochemical and structural analyses of historical and newly manufactured parchment to examine the potential role that lipid plays in parchment stability. The lipid fraction extracted from the parchments displayed different fatty acid compositions between historical and reference materials. Gas chromatography, small-angle X-ray scattering, and solid-state NMR were used to identify and investigate the lipid fraction from parchment samples and to study its contribution to collagen structure and degradation. We hypothesize that the origin of this lipid fraction is either intrinsic, attributable to incomplete fat removal in the manufacturing process, or extrinsic, attributable to microbiological attack on the proteinaceous component of parchments. Furthermore, we consider that the possible formation of protein-lipid complexes in parchment over the course of oxidative degradation may be mediated by reactive oxygen species formed by lipid peroxidation.

The capability of a polypropylene (PP) film barrier to prevent migration of residual contaminants from recycled paperboard into food simulants was studied. Anthracene, benzophenone, methyl stearate and pentachlorophenol were chosen as chemical surrogates to represent classes of contaminants likely to be found in recycled paper/paperboard. Each surrogate was spiked into a test specimen made of seven thin virgin paper layers at concentrations of 1-50 mg kg(-1). Test specimen were dried, stacked and sandwiched with PP films, laminated with PP film and then subjected to migration experiments using a compression cell maintained at 100 degrees C for 2 h. The concentration of the surrogates in the test specimen and in 95% ethanol, isopropanol and 10% ethanol food-simulating solvents was determined by gas chromatography with flame ionization and electron capture detection. The results show that although the concentrations of the surrogates in the food simulants decreased with an increase in PP film thickness, they were still high and generally resulted in dietary concentrations >0.5 microg kg(-1), the level that US Food and Drug Administration would equate with negligible risk for a contaminant migrating from food packaging. Only at the lowest spiking level (1 mg kg(-1) benzophenone) did migration from the paperboard through a 0.127-mm PP film result in a dietary concentration of

Solid-phase microextraction (SPME) combined with gas chromatography (GC) is optimized and applied to the analysis of street-cocaine samples followed by the field-testing of isolated chemicals using certified detector dogs. SPME proves to be a very sensitive and rapid method for isolating odor chemicals from street-cocaine samples. SPME-GC and activated charcoal strip (ACS)-SPME-GC signature profile methods are developed for the detection and quantitation of cocaine-odor chemicals, including the optimization of controllable variables such as fiber chemistry, extraction time, and desorption time. The volatile odor chemicals in representative illicit cocaine samples are identified and quantitated by the ACS-SPME-GC signature profile method and direct injection. Field tests with drug detector dogs show methyl benzoate to be the dominant signature odor chemical along with cocaine on U.S. currency at a threshold level of approximately 1-10 microg when spiked or when 10 ng/s methyl benzoate is diffused from polymer bottles, which is required in order to initiate an alert. No other substance studied initiated consistent responses by the drug dogs. The results indicate that the microgram levels of cocaine that have been reported on circulated U.S. currency are insufficient to signal an alert from law-enforcement trained drug detector dogs.

A rapid non-destructive sampling technique for the analysis of volatile organic compounds (VOCs) emitted by paper sheets is described. A capillary, which is connected to a microcolumn packed with Tenax TA, is inserted between two sheets at the centre of a paper stack encapsulated inside a PET/Al/PE composite foil. The other end of the microcolumn is connected to a gas-tight syringe and an appropriate volume of gaseous phase is aspirated. The microcolumn is then thermally desorbed in a modified GC inlet (modification is presented) and analysed by gas chromatography-mass spectrometry (GC-MS). In the chromatogram from the analysis of artificially aged paper sample 21 compounds were identified. Advantages of the method including the short sampling time (1 min), simplicity and economic aspect are discussed.

High molecular mass fractions of lignin and humic compounds in sediments and waters downstream of a pulp mill were characterized applying pyrolysis-gas chromatography-mass spectrometry. The results were compared to those obtained using reversed phase HPLC on the cupric oxide oxidation products. The chromatographic data of both pyrolysis and cupric oxide oxidation were also subjected to the principal component analysis (PCA). The sediment samples and fractions obtained by ultrafiltration of river water samples were freeze dried prior to characterization. The sediment samples were also extracted using 2 M sodium hydroxide solution. The extracts were ultrafiltrated, freeze dried and compared to the freeze dried original sediments using the procedures mentioned above. The amounts of HMMs obtained from the sediments ranged from 62 mg to 97 mg per one gram of sediment. Gel permeation chromatography was applied to samples obtained from sediments by extraction with tetrahydrofuran. The weight average molecular weights of these fractions were in the range of 1500–2300 amu.

In order to study the purity of recycled fibre‐based materials, products containing recycled fibre as well as recycled pulp were examined with regard to their chemical impurities, toxicity and microbiological quality. The study was carried out to clarify both qualitatively and quantitatively the variations in microbiological quality. The levels of several classes of chemical substances were analysed and semi‐volatile and volatile substances identified. The toxicity and mutagenicity of virgin fibre and recycled fibre materials were screened using the Photobacter toxicity test and the Ames Salmonella mutagenicity test. Preliminary chemical characterization of the mutagens was carried out. Identification of the compounds found in the mutagenic fractions was performed by gas chromatography/mass spectrometry (GC/MS). The concentration of various substances analysed was found to be low, although the variety of substances present appeared to be very broad. Preliminary chemical characterization revealed that some samples contained compounds known to have mutagenic or other toxic activity. Also, the recycled fibre pulps contained large amounts of various microbes, the microbial load consisting mainly of aerobic spore‐forming bacteria. The paper‐making process was found to clearly have reduced the total microbial counts.

This study reports on a method for determination of methanol in paper products by headspace gas chromatography (HS-GC). The method is based on the hydrolysis of the pulp or paper matrix, using a phosphoric acid solution (42.5%) as the medium at 120 °C in 5 h (excluding air contact) in order to release matrix-entrapped methanol, which is then determined by HS-GC. Data show that, under the given conditions of hydrolysis, no methanol was formed from the methoxyl groups in the material. Reproducibility tests of the method generated a relative standard deviation of

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.

The use of pyrolysis/gas chromatography/mass spectrometry (PY/GC/MS) to determine the molecular composition of lignocellulose is reviewed and the technique illustrated with applications on some novel systems. Constituents and structural arrangement of lignocellulosic polymers in plant cell wall are briefly described. The basic principles of pyrolysis and the main advantages and disadvantages of PY/GC/MS are discussed. PY/GC/MS analyses of (a) paper industry effluents, (b) agricultural by-products subjected to biological processes of delignification and (c) recycled paper are presented as examples of the amount of information that PY/GC/MS can provide on lignin classification and monitoring of delignification treatments as well as on the fingerprinting of lignocellulosic materials. The ion trap detector mass spectra of 56 pyrolysis products of lignocellulose, including compounds of phenolic, furanic and pyranic nature, are shown.

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.

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.

Pyrolysis-gas chromatography-mass spectrometry (Py-GC/MS) and Fourier transform infrared (FT-IR) spectroscopy were used for characterizing specks in cellulose pulp, polymeric materials and pitch formed during the cellulose extraction and paper production in the Brazilian mill. Three samples were analyzed and the pyrograms and infrared spectra obtained were compared. The results showed that the analytical pyrolysis more effectively differentiated between impurities (dirt specks) when compared to the infrared spectroscopy.

Nonylphenol is a recognized environmental contaminant, but it is unclear whether its occurrence in food arises only through environmental pathways or also during the processing or packaging of food, as there are reports that indicate that materials in contact with food such as rubber products and polyvinylchloride wraps can contain nonylphenol. A review of the literature has highlighted the scarcity of robust analytical methodology or data on the occurrence of nonylphenol in packaging materials. This paper describes a methodology for the determination of nonylphenol in a variety of packaging materials, which includes plastics, paper and rubber. The method uses either Soxhlet extraction or dissolution followed by solvent extraction (depending on the material type), followed by purification using adsorption chromatography. Procedures were internally standardized using 13C-labelled nonylphenol and the analytes were measured by gas chromatography-mass spectrometry. The method is validated and data relating to quality parameters such as limits of detection, recovery, precision and linearity of measurement are provided. Analysis of a range of 25 food-contact materials found nonylphenol at concentrations of 64-287 microg g(-1) in some polystyrene and polyvinylchloride samples. Far lower concentrations (0.03-1.4 microg g(-1)) were detected in the other materials. It is possible that occurrence at the higher levels has the potential for migration to food.

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.

A comprehensive gas chromatographic-high-resolution mass spectrometric (GC-HRMS)-based method was developed that permitted the simultaneous determination of 30 estrogenic endocrine-disrupting chemicals (EDCs) and related compounds, including surfactants, biogenic and synthetic steroids, fecal sterols, phytoestrogens, and plasticizers, in wastewater. Features of the method include low sample volume (~40 ml), optimized Florisil cleanup to minimize matrix interferences and optimized analyte derivatization to improve sensitivity via GC-HRMS. Detection limits were in the low- to mid-ng/L range, and recoveries were greater than 60% for most target analytes. This new method allows for high throughput analysis of many organic wastewater contaminants in a complex matrix with relative standard deviation of less than 15% for most measurable compounds. The applicability of the method was demonstrated by examining wastewater samples from different origins. Compounds such as di(2-ethylhexyl)phthalate, cholesterol, cholestanol, and other cholesterol derivatives were measured in much higher concentrations in untreated sewage and were reduced substantially in concentration by the treatment process. However, steroidal compounds, particularly estrone (E1), 17beta-estradiol (E2), and estriol (E3), as well as plant sterols (except stigmastanol), were greater in the treated municipal wastewater versus the untreated effluent. Plant and fungi sterols, stigmastanol and ergosterol, were found largely associated with bleached kraft mill effluent (BKME) as compared to the municipal effluents.

8 pages, 3 figures, 1 table.-- PMID: 17118260 [PubMed].-- Online version available Nov 20, 2006., Issue title: Air Pollution and Climate Change: A Global Overview of the Effects on Forest Vegetation., The efficiency of several lab scale treatments (aerobic, anaerobic and ozone or combination of these) was evaluated using two packaging board mill whitewaters. The effect of the different treatments on the elimination of the organic load, the chemical oxygen demand (COD) and the toxicity was tested as well as the relationship between these parameters. Biocides, phenolic compounds, surfactants, plasticiziers and wood extractives were identified in untreated and treated whitewaters by liquid chromatography coupled with mass spectrometry (LCeMS) or gas chromatography coupled with mass spectrometry (GCeMS). A strong dependency on the water type and treatment efficiency was observed, being the combination of anaerobic and aerobic treatments the best option to reduce the organic contaminants in these waters, although in some cases, the toxicity did not decrease. However, ozone as post-treatment permitted a further reduction of organic compounds, toxicity and COD., Aerobic and anaerobic treatments remove organic compounds in paper mill effluents but toxicity remains., This study has been supported by the EU Energy, Environmental and Sustainable Development Program (CLOSEDCYCLE, Contract No EVK1-2000-00749). The authors thank Riudesa factory (Catalonia, Spain) and Anox (Sweden) for supplying water samples and Merck for supplying the LC columns.

Instituto de Recursos Naturales y Agrobiología, CSIC, PO Box 1052, E-41080, Seville, Spain; Centro de Investigaciones Biológicas, CSIC, Ramiro de Maeztu 9, E-28040 Madrid, Spain; CIT, ENCE, Carretera de Campañó s/n, E-36157 Ribeiro Vao, Pontevedra, Spain, Free and conjugated sterols are among the main compounds responsible for pitch deposition in the manufacture of wood chemical pulps, making difficult the implementation of totally chlorine free bleaching (TCF) and closure of bleach plant circuits. In this work, the suitability of oxidative enzymes in efficiently removing sterols from eucalypt pulps is revealed. The enzymatic treatment was applied as an additional stage of an industrial-type TCF sequence for bleaching eucalypt kraft pulp. The pulp obtained after oxygen delignification was treated with a highredox potential and thermostable fungal laccase using 1-hydroxybenzotriazole as an enzyme mediator. This pulp was further submitted to chelation and peroxide stages and compared with a control TCF pulp obtained using chemical reagents. The composition of the lipophilic extractives in the pulps and the corresponding liquids after the different stages was analyzed by gas chromatography and gas chromatography-mass spectrometry. Free sitosterol and sitosterol esters and glucosides, the major lipophilic compounds in eucalypt pulps, were completely removed during the laccase-mediator treatment. Only some intermediate products from sitosterol oxidation remained after the laccase stage, as well as in the final pulp. Pulp brightness was also improved due to the simultaneous removal of lignin by the laccase-mediator treatment., This study has been funded by the Spanish projects AGL2002-393 and BIO2002-1166, the EU projects "New environmentally-sound methods for pitch control in different paper pulp manufacturing processes" (contract QLK5-99-1357) and "Fungal metalloenzymes oxidizing aromatic compounds of industrial interest" (contract QLK3-99-590), and two ENCE-CSIC contracts.

Contamination of foods with trimethyldiphenylmethanes is reported and the origin is shown to be migration from food packaging materials of which the use of recycled carbonless copy paper was found to be the major source. This chemical is one of the solvents used in the carbonless copy paper and its presence in food and the environment has not been previously identified. In this paper we have pursued previous studies on diisopropylnaphthalenes and hydrogenated terphenyls contamination from packaging and now report the identification of this new food contaminant and present evidence of its source. Solid foods such as egg pasta, barley coffee and rice were analysed by GC/MS and a mean concentration of 18 microg/kg of trimethyldiphenylmethanes was found. Extracts from carbonless copy paper were analysed by proton NMR to characterize the trimethyldiphenylmethanes. Since trimethyldiphenylmethanes are found in solid food together with diisopropylnaphthalenes, and considering their similar chemical character, they may follow the same migration pathway as one another.

In order to identify potential genotoxicant(s) in recycled paperboard, samples were fractionated using multiple liquid/liquid extraction, and gel permeation chromatography, and analysed by gas chromatography/mass spectrometry and liquid chromatography/mass spectrometry. The rec-assay was used as an indicator of genotoxicity. Genotoxicants in the recycled paperboard were identified as dehydroabietic acid (DHA) and abietic acid (AA). DHA and AA were detected in two out of five virgin products, and in all seven recycled products for food-contact use. Total amounts of DHA and AA were 240 and 990 microg/g in the virgin products and 200-990 microg/g in the recycled products. A good correlation was observed in the total amount of DHA and AA content determined in paper products and DNA-damaging activity. Moreover, genotoxic effects in paper products showed a good match with standard compounds, indicating that the genotoxic effects of these paper products was mostly attributable to DHA and AA.

Open-vessel focused microwave (FMW) extraction with a purely aqueous carbonate solution was used for the extraction of chlorophenols from various solid matrices. After SPE on C18-bonded silica, the analytes were determined as such by LC-UV or, as their acetyl derivatives, by GC-ECD. The FMW aqueous extraction is efficient and rapid and no organic solvents are used. PCP was detected in several solid samples, with recoveries of 101-115% (RSD, 2-4%) relative to Soxhlet extraction. Similar recoveries were obtained for the other chlorophenols for spiked samples.

A non-destructive, fast and environmentally friendly procedure has been developed for cocaine determination in euro bank notes. Cocaine was extracted with 15 ml methanol by vortex agitation during 5 min. The extract was evaporated and reconstituted in 0.5 ml methanol. GC-MS-MS analysis was performed using as precursor ion m/z 182.2, with an excitation energy voltage of 1.60 eV, being the product ions measured m/z 150.2 and 82.0. A limit of detection of 0.15 ng per note and a repeatability of 6%, established from the relative standard deviation, of a 1 ng ml(-1) level, were achieved. Recoveries of 101+/-2 and 98+/-3% were obtained for samples spiked with 100 and 10 microg respectively. Results show that all the euro bank notes measured (16 samples) were contaminated with cocaine in the range between 1.25 and 889 microg. Two different contamination levels, high level (150-889 microg) and low one (1.25-77 microg) were found and it could be related with the direct or indirect contact with the drug.

6 pages, 6 figures.-- PMID: 15782971 [PubMed].-- Printed version published Feb 18, 2005. A novel and simple method for the determination of active endocrine disrupter compounds (octylphenol OP, and nonylphenol NP) in paper using microwave-assisted extraction (MAE) and headspace solid-phase microextraction, coupled with gas chromatography–mass spectrometry has been developed. Parameters affecting the efficiency in the MAE process such as exposure time and extraction solvent were studied in order to determine operating conditions. The optimised method was linear over the range studied (1.25–125 μg kg−1 for OP and 9.50–950 μg kg−1 for NP) and showed good level of precision, with a RSD lower than 10% and detection limits at 0.10 and 4.56 μg kg−1 for OP and NP, respectively. The results obtained from six different types of paper revealed the presence of the target compounds in all samples analysed, at levels ranging between 3 and 211 μg kg−1. A Marie Curie Host Fellowship (HPMT-CT-2001-00393) and the EU Energy, Environmental and Sustainable Development Program (CLOSEDCYCLE) (Contract Number EVK1-CT-2000-00749) have supported this work.

The suitability of recycled paperboard packaging materials for direct food contact applications is a major area of investigation. Chemical contaminants (surrogates) partitioning between recycled paper packaging and foods may affect the safety and health of the consumer. The partition behavior of all possible organic compounds between cardboards and individual foodstuffs is difficult and too time consuming for being fully investigated. Therefore it may be more efficient to determine these partition coefficients indirectly through experimental determination of the partitioning behavior between cardboard samples and air. In this work, the behavior of organic pollutants present in a set of two paper and board samples intended to be in contact with foods was studied. Adsorption isotherms. have been plotted and partition coefficients between paper and air have been calculated as a basis for the estimation of their migration potential into food, Values of partition coefficients (K-paper/air) from 47 to 1207 were obtained at different temperatures. For the less volatile surrogates such as dibutyl phthalate and methyl stearate higher K-paper/air values were obtained. The adsorption curves showed that the more volatile substances are partitioning mainly in air phase and increasing the temperature from 70 to 100 degrees C their concentrations in air (C-air)have almost doubled. The analysis of surrogates was performed with a method based on solvent extraction and gas chromatographic-flame ionization detection (GC-FID) quantification. (c) 2005 Elsevier B.V. All rights reserved. Journal of Chromatography A

Instituto de Recursos Naturales y Agrobiología, CSIC, P.O. Box 1052, E-41080, Seville, Spain E-mail address: delrio@irnase.csic.es, The composition of pitch deposits occurring in pulp sheets and mill circuits during soda/anthraquinone pulping and elemental chlorine-free pulp bleaching of bast fibers of industrial hemp (Cannabis sativa) has been studied. Pitch deposits were extracted with acetone, and the extracts analyzed by gas chromatography (GC) and gas chromatography/mass spectrometry (GC/MS). Acetone extracts (15-25% of pitch deposits) were constituted by the defoamers used at the mill and by lipophilic extractives from hemp fibers. Acetone-insoluble residues (75-85% of pitch deposits) were analyzed by pyrolysis-GC/MS in the presence and absence of tetramethylammonium hydroxide. These residues were constituted by salts of fatty acids (arising from hemp fibers) with calcium, magnesium, aluminum and other cations that were identified in the deposits. It was concluded that inappropriate use of defoamer together with the presence of multivalent ions seemed to be among the causes of hemp extractives deposition in the pitch problems reported here., This study has been supported by the Spanish Ministerio de Ciencia y Tecnología (MCYT) and FEDER funds (projects 2FD97-0896-C02-02 and AGL2002-00393). A.G. acknowledges a "Ramón y Cajal" contract of the Spanish MCYT. We also thank CELESA (Tortosa, Spain) for providing the samples.

The purpose of this study was to evaluate photodegradabilities of the following new low-nitrogen chelating agents: N-bis[(carboxymethoxy)ethyl]glycine (compound 1), N-bis[(1,2-dicarboxyethoxy)ethyl]glycine (compound 2) and N-bis[(1,2-dicarboxyethoxy)ethyl]aspartic acid (compound 3). At first photodegradation of these chelating agents as uncomplexed Na-compound 1–3 and Cu(II) complexes were tested, both in lake and distilled water, by exposing them to near-UV region radiation at the range of 315–400 nm. Uncomplexed Na-compounds 2 and 3 were selected to sunlight exposure experiments carried out in lake and distilled water. Compound 3 was also tested in sunlight as Cu and Ca complexes in both solutions. Photodegradation of Na6-compound 3 in distilled water was studied by exposing it to radiation at the wavelength of 253.7 nm. Photodegradation products were analysed by means of GC-MS (gas chromatography with mass selective detector). The results demonstrated that compound 1 was quite photostable even as Cu complex while compounds 2 and 3 were found to be photodegradable. Over 90% reduction of compound 3 was achieved during one week and 80% reduction of compound 2 in two weeks' time when they were added as Na salt to lake water and exposed to sunlight. Compound 3 as Cu complex degraded totally in the sunlight in less than one week. In the case of compound 3, the degradation rate decreased depending on the counter cation in the order Cu > Na ⩾ Ca. The study demonstrated that photodegradation of Na6-compound 3 does not result in total mineralization of the compound. A photodegradation pathway for Na6-compound 3 is proposed.