A ricin forensic profiling approach based on a complex set of biomarkers.

A forensic method for the retrospective determination of preparation methods used for illicit ricin toxin production was developed. The method was based on a complex set of biomarkers, including carbohydrates, fatty acids, seed storage proteins, in combination with data on ricin and Ricinus communis agglutinin. The analyses were performed on samples prepared from four castor bean plant (R.

Part 2: Forensic attribution profiling of Russian VX in food using liquid chromatography-mass spectrometry.

This work is part two of a three-part series in this issue of a Sweden-United States collaborative effort towards the understanding of the chemical attribution signatures of Russian VX (VR) in synthesized samples and complex food matrices. In this study, we describe the sourcing of VR present in food based on chemical analysis of attribution signatures by liquid chromatography-tandem mass spectrometry (LC-MS/MS) combined with multivariate data analysis. Analytical data was acquired from seven different foods spiked with VR batches that were synthesized via six different routes in two separate laboratories.

Identification of RIP-II toxins by affinity enrichment, enzymatic digestion and LC-MS.

Type 2 ribosome-inactivating protein toxins (RIP-II toxins) were enriched and purified prior to enzymatic digestion and LC-MS analysis. The enrichment of the RIP-II family of plant proteins, such as ricin, abrin, viscumin, and volkensin was based on their affinity for galactosyl moieties. A macroporous chromatographic material was modified with a galactose-terminated substituent and packed into miniaturized columns that were used in a chromatographic system to achieve up to 1000-fold toxin enrichment.

Deamidation in ricin studied by capillary zone electrophoresis- and liquid chromatography-mass spectrometry.

Deamidation in ricin, a toxin present in castor beans from the plant Ricinus communis, was investigated using capillary zone electrophoresis (CZE) and liquid chromatography coupled to high resolution mass spectrometry. Potential sites for deamidation, converting asparagine (Asn) into aspartic or isoaspartic acid (Asp or isoAsp), were identified in silico based on the protein sequence motifs and tertiary structure. In parallel, CZE- and LC-MS-based screening were performed on the digested toxin to detect deamidated peptides.

Direct derivatization and gas chromatography-tandem mass spectrometry identification of nerve agent biomarkers in urine samples.

Rapid determination of nerve agent biomarkers at low-ppb levels in urine samples was achieved by direct derivatization and sample analysis using gas chromatography-tandem mass spectrometry. The studied biomarkers were alkylphosphonic acids (APAs), as they are specific hydrolysis products of organophosphorus nerve agents that can be used to verify nerve agent exposure. The sample preparation technique employed involves rapid direct derivatization (5min) of acidified urine samples (25μL) using a highly fluorinated phenyldiazomethane reagent [1-(diazomethyl)-3,5-bis(trifluoromethyl)benzene].

A concept study on identification and attribution profiling of chemical threat agents using liquid chromatography-mass spectrometry applied to Amanita toxins in food.

Accidental or deliberate poisoning of food is of great national and international concern. Detecting and identifying potentially toxic agents in food is challenging due to their large chemical diversity and the complexity range of food matrices. A methodology is presented whereby toxic agents are identified and further characterized using a two-step approach.

Determination of S-2-(N,N-diisopropylaminoethyl)- and S-2-(N,N-diethylaminoethyl) methylphosphonothiolate, nerve agent markers, in water samples using strong anion-exchange disk extraction, in vial trimethylsilylation, and gas chromatography-mass spectrometry analysis.

Since the establishment of the Chemical Weapons Convention in 1997, the development of analytical methods for unambiguous identification of large numbers of chemicals related to chemical warfare agents has attracted increased interest. The analytically challenging, zwitterionic S-2-(N,N-diisopropylaminoethyl) methylphosphonothiolate (EA-2192), a highly toxic degradation marker of the nerve agent VX, has been reported to resist trimethylsilylation or to result in an unacceptably high limit of detection in GC-MS analysis. In the present study, the problem is demonstrated to be associated with the presence of salt, which hinders trimethysilylation.

An isomer-specific high-energy collision-induced dissociation MS/MS database for forensic applications: a proof-of-concept on chemical warfare agent markers.

Spectra database search has become the most popular technique for the identification of unknown chemicals, minimizing the need for authentic reference chemicals. In the present study, an isomer-specific high-energy collision-induced dissociation (CID) MS/MS spectra database of 12 isomeric O-hexyl methylphosphonic acids (degradation markers of nerve agents) was created. Phosphonate anions were produced by the electrospray ionization of phosphonic acids or negative-ion chemical ionization of their fluorinated derivatives and were analysed in a hybrid magnetic-sector-time-of-flight tandem mass spectrometer.

Direct derivatization and rapid GC-MS screening of nerve agent markers in aqueous samples.

A rapid screening and identification method based on derivatization and gas chromatography mass spectrometry (GC-MS) has been developed for the detection of alkylphosphonic acids (APAs), the degradation products of organophosphorus nerve agents. The novel method described involves rapid (5 min) and direct derivatization of 25 microL aqueous sample using highly fluorinated phenyldiazomethane reagents (e.g.

Combination of solid phase extraction and in vial solid phase derivatization using a strong anion exchange disk for the determination of nerve agent markers.

Alkylphosphonic acids (APAs) are degradation products and chemical markers of organophosphorous (OP) nerve agents (chemical warfare agents). Anion exchange disk-based solid phase extraction (SPE) has been combined with in vial solid phase derivatization (SPD) and GC-MS analysis for the determination of APAs in aqueous samples. The optimization of critical method parameters, such as the SPD reaction, was achieved using statistical experimental design and multivariate data analysis.

De novo sequencing of RCB-1 to -3: peptide biomarkers from the castor bean plant Ricinus communis.

Ricinus communis (also know as the castor bean plant) whose forbears escaped from suburban gardens or commercial cultivation grow wild in many countries. In temperate and tropical climates seeds will develop to maturity, and plants may be perennial. In Australia these plants have become widespread and are regarded as noxious weeds in many localities.

Solution structure of poly(ethylene) glycol-conjugated hemoglobin revealed by small-angle X-ray scattering: implications for a new oxygen therapeutic.

Developing protein therapeutics has posed challenges due to short circulating times and toxicities. Recent advances using poly(ethylene) glycol (PEG) conjugation have improved their performance. A PEG-conjugated hemoglobin (Hb), Hemospan, is in clinical trials as an oxygen therapeutic.

Solvent-assisted trypsin digestion of ricin for forensic identification by LC-ESI MS/MS.

The castor bean plant (Ricinus communis) is used in large quantities for oil production and is also a common ornamental garden plant. However, the beans contain 1-3% of the highly toxic protein ricin, a type II ribosome-inactivating protein that is covered by the Chemical Weapons Convention, and there have been a number of reports concerning the use, or alleged use, of the toxin in terrorist and criminal activities. In the study reported here, we investigated the potential utility of organic solvent-assisted trypsin digestion of crude extracts containing the closely related toxins ricin or abrin to prepare samples for peptide analysis by liquid chromatography combined with electrospray ionization quadrupole time-of-flight tandem mass spectrometry.

PCDD/F in source-sorted waste fractions and emissions from their co-combustion with reed canary-grass.

The dry combustible fraction of source-sorted household waste, including material that would otherwise be recycled, was mixed with the energy crop reed canary-grass (Phalaris arundinacea L.), and combusted as briquettes in 150 and 600 kW biofuel-boilers without advanced cleaning systems. The source-sorted waste was further sorted and characterized according to its material and chemical contents.

Gas chromatography-mass spectrometry determination of the pentafluorobenzoyl derivative of methylhydrazine in false morel (Gyromitra esculenta) as a monitor for the content of the toxin gyromitrin.

The main toxic compound found in false morel (Gyromitra esculenta) is acetaldehyde-N-methyl-N-formylhydrazone (gyromitrin). This paper describes a method of determining the total hydrazones content based on acid hydrolysis of gyromitrin and other related hydrazones in air-dried false morel followed by derivatisation of methylhydrazine with pentafluorobenzoyl chloride. The derivative, tris-pentafluorobenzoyl methylhydrazine (tris-PFB-MH) is analyzed by gas chromatography-mass spectrometry.

Emissions of polychlorinated dibenzodioxins and dibenzofurans and polychlorinated biphenyls from uncontrolled burning of garden and domestic waste (backyard burning).

To assess emissions of dioxins (chlorinated dibenzodioxins and dibenzofurans) and PCB from uncontrolled domestic combustion of waste ("backyard burning"), test combustions in barrels and open fires were monitored. The waste fuels used were garden waste, paper, paper and plastic packaging, refuse-derived fuel (RDF), PVC, and electronic scrap. Combustions including PVC and electronic scrap emitted several orders of magnitude more dioxins than the other waste fuels.

Emissions from small-scale energy production using co-combustion of biofuel and the dry fraction of household waste.

In sparsely populated rural areas, recycling of household waste might not always be the most environmentally advantageous solution due to the total amount of transport involved. In this study, an alternative approach to recycling has been tested using efficient small-scale biofuel boilers for co-combustion of biofuel and high-energy waste. The dry combustible fraction of source-sorted household waste was mixed with the energy crop reed canary-grass (Phalaris Arundinacea L.

Forensic identification of neat ricin and of ricin from crude castor bean extracts by mass spectrometry.

The protein toxin ricin, which originates from the seeds of Ricinus communis plants, has been the subject of increased interest, due to its potential terrorist use. Exceptionally, this toxin is also subject to the Chemical Weapons Convention. In this paper, it is shown that mass spectrometry can be used to unambiguously verify the presence of ricin in crude toxin preparations.

An experimental comparison of a kinetic model for the reaction of alpha-pinene and Delta(3)-carene with ozone and nitrogen oxides.

Unlabelled: A kinetic model was compiled to simulate reactions of the monoterpenes, alpha-pinene and Delta(3)-carene, with O(3), NO(2) and NO. The influence of different initial settings of O(3), NO(2) and NO on the monoterpene reaction was evaluated. At initial levels of 75 p.

Emissions of aldehydes and ketones from a two-stroke engine using ethanol and ethanol-blended gasoline as fuel.

Besides aliphatic gasoline, ethanol-blended gasoline intended for use in small utility engines was recently introduced on the Swedish market. For small utility engines, little data is available showing the effects of these fuels on exhaust emissions, especially concerning aldehydes and ketones (carbonyls). The objective of the present investigation was to study carbonyl emissions and regulated emissions from a two-stroke chain saw engine using ethanol, gasoline, and ethanol-blended gasoline as fuel (0%, 15%, 50%, 85%, and 100% ethanol).