Classification of local diesel fuels and simultaneous prediction of their physicochemical parameters using FTIR-ATR data and chemometrics.

Class identification and prediction of physicochemical variables of eight diesel fuel brands collected from several stations within the Atlanta metropolitan area in the State of Georgia were investigated using principal component analysis (PCA), partial least squares discriminant analysis (PLS2-DA), and partial least squares regression (PLSR) as modeling techniques. The fuels were from a common pipeline, therefore, assumed to have very similar characteristics. Ten FTIR-ATR spectra per fuel brand were collected over the 650 - 4000 cm-1 mid-infrared region, and the 80 x 3351 matrix was submitted to PCA to determine if there were any clusters. Following PCA, the 80 x 3351 matrix was split into a training matrix (56x3351) and a test matrix (24x3351). PLS2-DA models were built and evaluated for class identification using dummy variables (I,0) as input matrix. For physicochemical variable predictions, models were developed via PLSR using the FTIR-ATR spectra training matrix and physicochemical variables obtained from the Georgia Department of Agriculture Labs as input. Correlation coefficients of the eight fuels ranged from 0.9960 to 0.9998. PCA revealed all eight clusters of the diesel fuels, regardless of the tight correlation coefficients range. With a 1.0 ± 0.1 cut-off for fuel identification, the PLS2-DA models showed 100% correct predictions for four or five fuel brands, and 75% correct prediction for all eight fuel brands. PLSR predicted 100% correct physicochemical variables, with a RMSEP range of 0.019 to 1.132 for all 80 variables targeted.

Laser-Induced Breakdown Spectroscopy for the Rapid Characterization of Lead-Free Gunshot Residues.

This study investigated the use of laser-induced breakdown spectroscopy (LIBS) and scanning electron microscopy energy dispersive X-ray spectroscopy (SEM-EDX) as means of characterizing gunshot residue (GSR) originating from commercially available lead-free rounds. Data from two experiments are presented in this work. One experiment focused on identifying prominent analytical markers present in lead-free GSR by LIBS while the other applied SEM-EDX to determine the degree of evidence preservation after LIBS analysis. Samples of GSR were collected via tape-lift method from the hands of volunteer shooters and instrumental analyses were conducted in triplicate. As a result, the lead-free ammunition analyzed in this work generated GSRs comprising primarily Ba, Al, Si, and/or K. Trace amounts of Ti, Fe, and S were also apparent in some compositions. Through SEM-EDX analysis, a spheroidal geometry consistent with traditional lead-containing GSR was observed. Additionally, it was determined that evidence is preserved after LIBS analysis which supports the implementation of LIBS as a rapid preliminary screening method followed by confirmatory testing via SEM-EDX on the preserved evidence.

Antibacterial Activities of Wasabi against Escherichia coli O157:H7 and Staphylococcus aureus.

Escherichia coli O157:H7 and Staphylococcus aureus are two of the major pathogens frequently involved in foodborne outbreaks. Control of these pathogens in foods is essential to food safety. It is of great interest in the use of natural antimicrobial compounds present in edible plants to control foodborne pathogens as consumers prefer more natural "green" foods. Allyl isothiocyanate (AITC) is an antimicrobial compound naturally present in wasabi (Japanese horseradish) and several other edible plants. Although the antibacterial effects of pure AITC and wasabi extract (essential oil) against several bacteria have been reported, the antibacterial property of natural wasabi has not been well studied. This study investigated the antibacterial activities of wasabi as well as AITC against E. coli O157:H7 and S. aureus. Chemical analysis showed that AITC is the major isothiocyanate in wasabi. The AITC concentration in the wasabi powder used in this study was 5.91 ± 0.59 mg/g. The minimum inhibitory concentration (MIC) of wasabi against E. coli O157:H7 or S. aureus was 1% (or 10 mg/ml). Wasabi at 4% displayed higher bactericidal activity against S. aureus than against E. coli O157:H7. The MIC of AITC against either pathogen was between 10 and 100 µg/ml. AITC at 500 µg/ml was bactericidal against both pathogens while AITC at 1000 µg/ml eliminated E. coli O157:H7 much faster than S. aureus. The results from this study showed that wasabi has strong antibacterial property and has high potential to effectively control E. coli O157:H7 and S. aureus in foods. The antibacterial property along with its natural green color, unique flavor, and advantage to safeguard foods at the point of ingestion makes wasabi a promising natural edible antibacterial plant. The results from this study may be of significant interest to the food industry as they develop new and safe foods. These results may also stimulate more research to evaluate the antibacterial effect of wasabi against other foodborne pathogens and to explore other edible plants for their antimicrobial properties. To our knowledge, this is the first report on the antibacterial activity of wasabi in its natural form of consumption against E. coli O157:H7 and S. aureus.

Microextraction, capillary electrophoresis, and mass spectrometry for forensic analysis of azo and methine basic dyes from acrylic fibers.

Designed experiments based on a simplex mixture design were employed to explore the effects of three solvent components (water, formic acid, and aqueous acetic acid), extraction time, and extraction temperature for the automated microextraction of basic (cationic) dyes from acrylic fibers. Extractions were conducted by an automated liquid handling system, and dye extraction was evaluated using a UV/visible microplate reader. Highest extraction efficiency for two subclasses of basic dyes (methine and azo) from acrylic fibers was achieved with an extraction solvent containing 88% formic acid/12% water. Cationic dyes were analyzed by capillary electrophoresis using a 45 mM ammonium acetate buffer in acetonitrile-water at pH 4.7. The utility of microextraction combined with capillary electrophoresis-mass spectrometry for analysis of extracts from trace fibers was demonstrated by the detection and characterization of three basic dyes extracted from a 2-mm length of single acrylic fiber.

Forensic analysis of anthraquinone, azo, and metal complex acid dyes from nylon fibers by micro-extraction and capillary electrophoresis.

The extraction and separation of dyes present on textile fibers offers the possibility of enhanced discrimination between forensic trace fiber evidence. An automated liquid sample handling workstation was programmed to deliver varying solvent combinations to acid-dyed nylon samples, and the resulting extracts were analyzed by an ultraviolet/visible microplate reader to evaluate extraction efficiencies at different experimental conditions. Combinatorial experiments using three-component mixture designs varied three solvents (water, pyridine, and aqueous ammonia) and were employed at different extraction temperatures for various extraction durations. The extraction efficiency as a function of the three solvents (pyridine/ammonia/water) was modeled and used to define optimum conditions for the extraction of three subclasses of acid dyes (anthraquinone, azo, and metal complex) from nylon fibers. The capillary electrophoresis analysis of acid dye extracts is demonstrated using an electrolyte solution of 15 mM ammonium acetate in acetonitrile/water (40:60, v/v) at pH 9.3. Excellent separations and discriminating diode array spectra are obtained even for dyes of similar color.

Determining the lifetime of detectable amounts of gunshot residue on the hands of a shooter using laser-induced breakdown spectroscopy.

Laser-induced breakdown spectroscopy (LIBS) has been used to determine the period of time that a shooter will test positive for gunshot residue (GSR) after firing a revolver. Multiple rounds of primer were fired and samples collected at multiple hour intervals using an adhesive tape pressed against the skin. Samples were analyzed directly using a commercially available laser-induced breakdown spectrometer where barium emission (originating from barium nitrate in the primer) was observed. Population statistics were used to compare suspected GSR to a library of blank samples from which a threshold value was established. Statistically significant results, positive for GSR, are obtained 5.27 days after a firearm discharge using these techniques.

Speciation of chromium via laser-induced breakdown spectroscopy of ion exchange polymer membranes.

A new method for the speciation of ng/mL concentrations of Cr(III) and Cr(VI) solutions with analysis by laser-induced breakdown spectroscopy (LIBS) is reported. Speciation is achieved by pre-concentration of the chromium onto commercially available cation exchange polymer membranes. Chromium(III) is removed directly by cation exchange; chromium(VI) in the filtrate is reduced to Cr(III) and concentrated onto a second cation exchange membrane, affording independent measurement of both species. Large volumes of waters containing Cr(III) and Cr(VI) can be concentrated onto the membranes and directly analyzed by laser-induced breakdown spectroscopy. The estimated limit of detection corresponds to 500 ng of Cr on the membrane: if a solution volume of 1 L is used, then the detection limit corresponds to a solution concentration of 0.5 ng/mL. Excellent separation of the chromium species is attained. Results show that overall method efficiencies range from 94-116% and are independent of the matrix. The influence of pH has been measured, and although Cr(VI) converts to Cr(III) in acidic solutions, the total Cr recoveries are not appreciably influenced by pH over the range of natural waters (4 to 9). In addition, speciation was performed in the presence of a number of different cations and showed that the method is robust in many different and complex matrices.

Laser-induced breakdown spectroscopy for the detection of gunshot residues on the hands of a shooter.

Laser-induced breakdown spectroscopy (LIBS) has been used to determine whether the hands of a suspected gun user contain traces of gunshot residue. Samples are obtained by pressing adhesive tape against the skin of the suspect and analyzing the tape directly. When the suspect has fired multiple shots, or if the gun has not been cleaned, the gunshot residue provides a spectral signature that is readily apparent, but a person who has fired a single shot from a clean gun is not so easy to identify. The error rates associated with the LIBS identification of a subject who fired one shot from a clean gun have been evaluated by Monte Carlo simulation techniques, and criteria are proposed for defining a positive or a negative test result.