Selecting a reduced suite of diagnostic ratios calculated between petroleum biomarkers and polycyclic aromatic hydrocarbons to characterize a set of crude oils.

A set of 34 crude oils was analysed by GC-MS (SIM mode) and a suite of 28 diagnostic ratios (DR) calculated. They involved 18 ratios between biomarker molecules (hopanes, steranes, diasteranes and triaromatic steroids) and 10 quotients between polycyclic aromatic hydrocarbons. Three unsupervised pattern recognition techniques (i.e., principal components analysis, heatmap hierarchical cluster analysis and Kohonen neural networks) were employed to evaluate the final dataset and, thus, ascertain whether the crude oils grouped as a function of their geographical origin. In addition, an objective variable selection procedure based on Procrustes Rotation was undertaken to select a reduced set of DR that comprised for most of the information in the original data without loosing relevant information. A reduced set of four DR (namely; TA21, D2/P2, D3/P3 and B(a)F/4-Mpy) demonstrated to be sufficient to characterize the crude oils and the groups they formed.

Comparing the weathering patterns of six oils using 3-way generalized Procrustes rotation and matrix-augmentation principal components.

A case study is presented in which advanced chemical fingerprinting and data interpretation techniques are used to characterize and compare the weathering processes of six oil spillages made under controlled conditions (including the heavy oil released after the Prestige tanker sunk off the Galician coast-NW Spain on 2002). A tiered analytical approach using gas chromatography-flame ionization detection (GC-FID) and gas chromatography-mass spectrometry (GC-MS) was applied along with two different approaches for 3-way analyses; namely, generalized Procrustes rotation, and matrix-augmented principal components analysis. Results showed that the two 3-way chemometric techniques leaded to essentially the same conclusions when analyzing three sets of compounds fingerprinting the spilled hydrocarbons (aliphatic hydrocarbons, polycyclic aromatic hydrocarbons (PAHs) and a set of diagnostic ratios). A steady evolution on the weathering of the oils was observed with both techniques, but for the diagnostic ratios. The variables involved on the weathering were the lightest aliphatic hydrocarbons and a general combination of the PAHs, which differentiated mostly among the light and the heavy products (fuel oils).

Identification of petroleum hydrocarbons using a reduced number of PAHs selected by Procrustes rotation.

Identifying petroleum-related products released into the environment is a complex and difficult task. To achieve this, polycyclic aromatic hydrocarbons (PAHs) are of outstanding importance nowadays. Despite traditional quantitative fingerprinting uses straightforward univariate statistical analyses to differentiate among oils and to assess their sources, a multivariate strategy based on Procrustes rotation (PR) was applied in this paper. The aim of PR is to select a reduced subset of PAHs still capable of performing a satisfactory identification of petroleum-related hydrocarbons. PR selected two subsets of three (C(2)-naphthalene, C(2)-dibenzothiophene and C(2)-phenanthrene) and five (C(1)-decahidronaphthalene, naphthalene, C(2)-phenanthrene, C(3)-phenanthrene and C(2)-fluoranthene) PAHs for each of the two datasets studied here. The classification abilities of each subset of PAHs were tested using principal components analysis, hierarchical cluster analysis and Kohonen neural networks and it was demonstrated that they unraveled the same patterns as the overall set of PAHs.

Comparison of single-reflection near-infrared and attenuated total reflection mid-infrared spectroscopies to identify and monitor hydrocarbons spilled in the marine environment.

The capability of single-reflection near-IR (NIR) spectroscopy to differentiate, characterize and monitor the fate of a set of hydrocarbons spilled in the marine environment was compared with that of multiple-reflection horizontal attenuated total reflection mid-IR (ATR-MIR) spectroscopy. Multivariate pattern recognition techniques [principal component analysis (PCA), multivariate polynomial regression, cluster analysis and potential curves] were applied to unravel the major trends of the weathering processes of four generic types of crude oils and two heavy fuel oils spilled under controlled conditions for almost 4 months. A chemical interpretation of the NIR spectra related the weathering processes and the PCA loadings, which had not already been done in the literature. Weathering for both light and heavy products was characterized by a contrast among the linear aliphatic structures (more volatile and easy to degrade) and the branched and aromatic structures (more recalcitrant). Potential curves were applied to model each product and determine objectively whether unknown samples could be classified correctly. Polynomial regression on the PCA scores was employed to evaluate the time elapsed from the oil spillage to its sampling; this represents a new approach to assess the age of a hydrocarbon lump. In general, NIR spectroscopy yielded good results when light crude oils were studied, whereas ATR-MIR spectroscopy led to satisfactory results for both light and heavy products.

The comparison of two heavy fuel oils in composition and weathering pattern, based on IR, GC-FID and GC-MS analyses: application to the Prestige wreackage.

This paper compares the weathering patterns of two similar fuel oils: a fuel oil spilled after a ship accident (Prestige-Nassau, off the Galician coast -NW Spain-) and a fuel designed to cope with the numerous quests for samples to carry out scientific studies (IFO). Comparative studies were made to evaluate the capability of common fingerprinting analytical techniques to differentiate the fuels, as well as their capabilities to monitor their weathering. The two products were spilled under controlled conditions during ca. four months to assess how they evolved on time. Mid-IR spectrometry and gas chromatography (flame ionization and mass spectrometry detectors) were used. IR indexes related to total aromaticity, type of substituents (branched or linear chains) and degree of aromatic substitution reflected well the differences between the fuels during weathering. Regarding the chromatographic measurements, the n-alkanes became highly reduced for both fuel oils and it was found that the PAHs of the synthetic fuel (IFO) were more resistant to weathering. Regarding biomarkers, the different profiles of the steranes, diasteranes and triaromatic steroids allowed for a simple differentiation amongst the two products. The %D2/P2 ratio differentiated both products whereas the %N3/P2 one ordered the samples according to the extent of their weathering.

Identification of fuel samples from the Prestige wreckage by pattern recognition methods.

A set of 34 worldwide crude oils, 12 distilled products (kerosene, gas oils, and fuel oils) and 45 oil samples taken from several Galician beaches (NW Spain) after the wreckage of the Prestige tanker off the Galician coast was studied. Gas chromatography with flame ionization detection was combined with chemometric multivariate pattern recognition methods (principal components analysis, cluster analysis and Kohonen neural networks) to differentiate and characterize the Prestige fuel oil. All multivariate studies differentiated between several groups of crude oils, fuel oils, distilled products, and samples belonging to the Prestige's wreck and samples from other illegal discharges. In addition, a reduced set of 13 n-alkanes out of 36, were statistically selected by Procrustes Rotation to cope with the main patterns in the datasets. These variables retained the most important characteristics of the data set and lead to a fast and cheap analytical screening methodology.

Development of a web-based support system for both homogeneous and heterogeneous air quality control networks: process and product.

The Environmental Laboratories Automation Software System or PALMA (Spanish abbreviation) was developed by a multidisciplinary team in order to support the main tasks of heterogeneous air quality control networks. The software process for PALMA development, which can be perfectly applied to similar multidisciplinary projects, was (a) well-defined, (b) arranged between environmental technicians and informatics, (c) based on quality guides, and (d) clearly user-centred. Moreover, it introduces some interesting advantages with regard to the classical step-by-step approaches. PALMA is a web-based system that allows 'off-line' and automated telematic data acquisition from distributed inmission stations belonging not only to homogeneous but also to heterogeneous air quality control networks. It provides graphic and tabular representations for a comprehensive and centralised analysis of acquired data, and considers the daily work that is associated with such networks: validation of the acquired data, alerts with regard to (periodical) tasks (e.g., analysers verification), downloading of files with environmental information (e.g., dust forecasts), etc. The implantation of PALMA has provided qualitative and quantitative improvements in the work performed by the people in charge of the considered control network.

Development of a fast analytical tool to identify oil spillages employing infrared spectral indexes and pattern recognition techniques.

A fast analytical tool based on attenuated total reflectance mid-IR spectrometry is presented to evaluate the origin of spilled hydrocarbons and to monitor their fate on the environment. Ten spectral band ratios are employed in univariate and multivariate studies (principal components analysis, cluster analysis, density functions - potential curves - and Kohonen self organizing maps). Two indexes monitor typical photooxidation processes, five are related to aromatic characteristics and three study aliphatic and branched chains. The case study considered here comprises 45 samples taken on beaches (from 2002 to 2005) after the Prestige carrier accident off the Galician coast and 104 samples corresponding to weathering studies deployed for the Prestige's fuel, four typical crude oils and a fuel oil. The univariate studies yield insightful views on the gross chemical evolution whereas the multivariate studies allow for simple and straightforward elucidations on whether the unknown samples match the Prestige's fuel. Besides, a good differentiation on the weathering patterns of light and heavy products is obtained.

Spatial and temporal distribution of dissolved/dispersed aromatic hydrocarbons in seawater in the area affected by the Prestige oil spill.

Seawater samples collected at three depths from 68 stations along the Northern Spanish coast were analysed for dissolved/dispersed petroleum aromatic hydrocarbons by UV-fluorescence and for 25 individual compounds by GC-MS. Sampling was performed in December 2002, just after the Prestige oil spill, and in February-March and September 2003. Higher concentrations of total aromatic hydrocarbons were found at all depths in the samples collected during December 2002 off the Galicia coast, with levels ranging between 0.19 and 28.8 microg/L eq. oil (0.1-4.8 microg/L chrysene eq.). These values decreased in the following cruises, till <0.05-2.86 microg/L oil eq. (av. 0.23 microg/L chrysene eq.) in September 2003, possibly representing the background levels for the region. However, in the Cantabrian coast they were still high at the surface in the March cruise, probably by the late arrival of the fuel-oil to this area. Some coastal hot spots were also identified, with values up to 29.2 microg/L fuel-oil eq., close to river mouths and urban areas. The individual PAH distributions in the December 2002 sampling off-Galicia were dominated by alkyl-naphthalene derivatives, consistently with the pattern distribution shown by the fuel-oil water accommodated fraction. The higher concentrations were found in the subsurface samples along the Costa da Morte, the area most heavily affected by the spill (av. 0.46 microg/L Sigma16 PAHs). The rest of the samples collected in other areas exhibited lower concentrations and a more even distribution of 2-4 ring PAHs, that ranged from 0.09 to 0.37 microg/L (av. 0.15 microg/L Sigma16 PAHs), with decreasing trends offshore and downward the water column. In September 2003, the values were rather uniform, averaging 0.09 microg/L (Sigma16 PAHs).

Monitoring photooxidation of the Prestige's oil spill by attenuated total reflectance infrared spectroscopy.

The recent release of ca. 70,000 tonnes of a heavy fuel oil from the Prestige-Nassau carrier along the Spanish northern coast, mainly along Galicia, was monitored using attenuated total reflectance-mid IR spectrometry. The fuel was characterized and differentiated from 10 products commonly transported along the Galician coast (and their series of weathered samples) using factor analysis. The Prestige's fuel was weathered under natural conditions and under infrared radiation to study its evolution on time. A correlation was established using the 1690-1700 cm(-1) carbonyl peak, where from it was deduced that IR radiation weathered the product two times faster than natural conditions. The use of 10 weathering indexes was carried out to confirm the main patterns given by factor analysis and to seek out which main functional groups and structures increased or decreased during weathering. It was found that the carbonyl and sulphoxide indexes varied greatly, as well as the total aromaticity and long chains ones. The substitution-related indexes pointed out that highly substituted aromatic structures increased although the total amount of isolated CH groups in aromatic structures reached a plateau.

Screening the origin and weathering of oil slicks by attenuated total reflectance mid-IR spectrometry.

The combination of attenuated total reflectance-fourier transform mid-infrared spectrometry (ATR-FTMIR) and multivariate pattern recognition is presented as a fast and convenient methodology to ascertain the source product an oil slick comes from and to evaluate the extent of its weathering. Different types of hydrocarbons (including crude oils, several heavy distillates and the Prestige's heavy fuel oil) were spilled on metallic containers designed ad hoc and their fate monitored by ATR-FTMIR. Not only environmental conditions were considered for weathering but artificial IR- and UV-irradiation. Pattern-recognition studies revealed that the different hydrocarbons clustered at different locations on the score plots and that the samples corresponding to each oil became ordered according to the extent of their weathering. Among them, fuel oil samples coming from the recent disaster of the Prestige tanker off the Galician shoreline showed a distinctive behaviour. Comparison of natural-, IR- and UV-weathering of a crude oil showed that IR solar radiation can be important in oil-weathering, in addition to broadly-reported UV degradation.

Microwave-assisted extraction and ultrasonic slurry sampling procedures for cobalt determination in geological samples by electrothermal atomic absorption spectroscopy.

Slurry sampling is compared to microwave-assisted acid digestion for cobalt determination in soil/sediment samples by electrothermal atomic absorption spectrometry (ETAAS). Furnace temperature programs and appropriate amounts of three chemical modifiers were optimised in order to get the highest signals and good separations between the atomic and background signals. Using nitric acid (0.5% (v/v)) as liquid medium, no chemical modifier was needed. The detection limit, based on integrated absorbance, was 0.04mugg(-1) for digests and slurries. Within-batch precision and analytical recoveries were satisfactory for both procedures. Accuracy was tested by analysing a reference soil and a sediment from IRMM. The methods were further compared employing a set of roadside soils and estuarine sediments. As no significant differences (95% confidence) were found, practical analytical properties were suggested in order to select one of them.

Generation and mid-IR measurement of a gas-phase to predict security parameters of aviation jet fuel.

The worldwide use of kerosene as aviation jet fuel makes its safety considerations of most importance not only for aircraft security but for the workers' health (chronic and/or acute exposure). As most kerosene risks come from its vapours, this work focuses on predicting seven characteristics (flash point, freezing point, % of aromatics and four distillation points) which assess its potential hazards. Two experimental devices were implemented in order to, first, generate a kerosene vapour phase and, then, to measure its mid-IR spectrum. All the working conditions required to generate the gas phase were optimised either in a univariate or a multivariate (SIMPLEX) approach. Next, multivariate prediction models were deployed using partial least squares regression and it was found that both the average prediction errors and precision parameters were satisfactory, almost always well below the reference figures.

Slurry sampling for direct analysis of solid materials by electrothermal atomic absorption spectrometry (ETAAS). A literature review from 1990 to 2000.

The determination of trace metals in solid samples has traditionally been performed by acid digestion and subsequent measurement by a suitable instrumental technique. This dissolution step is time-consuming and it shows important drawbacks. For these reasons, in the past years many efforts have been focused on the direct analysis of solid samples. Among the developed methodologies, slurry sampling-electrothermal atomic absorption spectrometry combines the significant advantages of the solid and liquid sampling methods, and it can be already considered as a mature technique, that is widely utilized for metal determination in both organic and inorganic matrices, even for routine analysis. Accordingly, this work gives a retrospective view of the progresses of this technique during the past decade (1990-2000).

Evolution of invertase activity in honey over two years.

Invertase activity is a good parameter for evaluating honey freshness. Invertase activity evolution was determined on 57 fresh, unheated, commercially purchased Galician (northwestern Spain) floral honey samples. All honeys were stored in darkness at room temperature for up 24 months and analyzed each 6 months so as to determine the invertase activity evolution tendency for the first time. Invertase activity analysis was carried out according to Siegenthaler's method and in a simple assay, the latter showing a good precision (coefficient of variation between 0.35 and 0.66%). Initial invertase activity mean value was 163.9 (48.4-251.0) micromol of 4-nitrophenyl-alpha-D-glucopyranoside hydrolyzed/kg of honey/min. After application of the SPSS statistical package, the values of invertase activity showed five types of temporal behavior: exponential (56% of samples), linear (25% of samples), logarithmic (11% of samples), inverse (5% of samples), and quadratic (3% of samples). Linear regression equations were used to predict the invertase activity at 6, 12, 18, and 24 months from the initial Galician honeys' invertase activities; no statistical differences were found between experimental data and the activities calculated from the linear regression equations.

Chemical modifiers for direct determination of cobalt in coal combustion residues by ultrasonic slurry-sampling-ETAAS.

Five modifiers were tested for the direct determination of cobalt in coal fly ash and slag by ultrasonic slurry-sampling electrothermal atomic absorption spectrometry (USS-ETAAS). The furnace temperature programs and the appropriate amount for each modifier were optimized to get the highest signal and the best separation between the atomic and background signals. Nitric acid (0.5% v/v) was the most adequate chemical modifier for cobalt determination, selecting 1,450 degrees C and 2,100 degrees C as pyrolysis and atomization temperatures, respectively. This modifier also acts as liquid medium for the slurry simplifying the procedure. The remaining modifiers enhanced the background signal, totally overlapped with cobalt peak. The method optimized gave a limit of detection of 0.36 microg g(-1), a characteristic mass of 13 +/- 1 pg and an overall-method precision which is highly satisfactory (<7%, RSD). The method was validated by analyzing two certified coal fly ash materials, and satisfactory recoveries were obtained (83-90%) and no statistical differences were observed between the experimental and the certified cobalt concentrations. Additionally, certified sediment, soil and urban particulate matter were assayed; again good results were obtained. The developed methodology was used to determine cobalt in several coal combustion residues from five Spanish power plants.

Enzymatic Determination of Citric Acid in Honey by Using Polyvinylpolypyrrolidone Clarification.

To characterize honey types, a citric acid determination may be useful. A citric acid determination on honey was carried out with previous polyvinylpolypyrrolidone (PVPP) clarification followed by the Boehringer-Mannheim GmbH enzymatic test. The sample solution was prepared from 2 g of honey in 100 mL of Milli-Q water. A volume of 10 mL of this sample was clarified with PVPP stirring for 1 min and filtered. The enzymatic determination was measured spectrophotometrically at 340 nm, using citrate lyase, L-malate dehydrogenase, and L-lactate dehydrogenase. With these conditions, there were no observed interference effects. The proposed method improves precision [coefficient of variation (CV) between 0.26% and 1.60%] and recovery (between 98.0% and 100.9%) on the direct enzymatic analysis (% CV between 1.02 and 2.66 and recovery between 84.0% and 115.6%). Furthermore, the cost was reduced 70% using a microtest. The method was applied to 20 honeys of Galicia (northwestern Spain), and the results ranged between 44.2 and 827.0 mg of citric acid/kg of honey (mean = 192.9 mg/kg).

Prediction of FCC gasoline octane numbers using FT-MIR and PLS.

A method for predicting "octane numbers" (RON and MON) in fluid catalytic cracking (FCC) gasolines is proposed. Using FT-MIR and PLS, improvements have been obtained in sample throughput, reduced delay times, accuracy (repeatability and reproducibility), amounts of samples and reagents and environmental working conditions when compared with current standard methods. A total number of 140 daily production samples were taken; and from there, a learning group was prepared (44 samples); a validation set (96 samples) was prepared, as well. Sample spectra were recorded from 4000 to 600 cm(-1) at 4 cm(-1) intervals (traditional sealed NaCl cells). The PLS technique was used in its two variants (1 and 2-block). Both provided similar results. Their predictive characteristics are very good: SEP(RON)=0.38; SEP(MON)=0.40; repeatability <0.1 O.N.; reproducibility <0.3 O.N. (SEP=Standard Error of Prediction).

Cadmium analysis in soil by microwave acid digestion and graphite furnace atomic absorption spectrometry.

The need to determine micronutrients and toxic elements in soils has grown in recent years and cadmium is of special interest. A method has been developed for the determination of cadmium in soils based on a prior acid digestion of the samples with nitric acid in closed Teflon vessels, into a microwave over. The cadmium determination was carried out by graphite furnace atomic absorption spectrometry (GFAAS) with L'vov platform. Optimum operating conditions, analyte modifiers and matrix interferences have been investigated. The best matrix modifier was found to be ammonium dihydrogen phosphate. The interferences are greatly reduced under these operating conditions and calibration can be performed with simple aqueous solutions of the metal standard. The method is rapid and provides accurate and precise results that agree with certified values for two reference materials: BCR 141 (calcareous loam soil) and BCR 277 (estuarine sediment).

Nonacaricide Pesticide Residues in Honey: Analytical Methods and Levels Found.

A bibliographic review on honey pollution with pesticides is presented. This paper reviews the methods set up for determining pesticide residues in honey samples as well as the pesticide residue levels found in European countries.