Efficiency and bacterial diversity of an improved anaerobic baffled reactor for the remediation of wastewater from alkaline-surfactant-polymer (ASP) flooding technology.

Alkaline-surfactant-polymer (ASP) flooding technology is used to maximize crude oil recovery. However, the extensive use of alkaline materials makes it difficult to treat the water used. Here, an improved multi-zone anaerobic baffled reactor (ABR) using FeSO4 as electron acceptor was employed to treat the wastewater from ASP flooding technology, and the effects on major pollutants (hydrolyzed polyacrylamide, petroleum substances, surfactants suspended solids) and associated parameters (chemical oxygen demand, viscosity) were evaluated. Gas chromatography-mass spectrometry (GC-MS) was used to follow the degradation and evolution of organic compounds while high-throughput DNA sequencing was used to determine the bacterial diversity in the ABR. The results obtained after 90 d of operation showed decreases in all parameters measured and the highest mean removal rates were obtained for petroleum substances (98.8%) and suspended solids (77.0%). Amounts of petroleum substances in the ABR effluent could meet the requirements of a national standard for oilfield reinjection water. GC-MS analysis showed that a wide range of chemicals (e.g. aromatic hydrocarbons, esters, alcohols, ketones) could be sequentially removed from the influent by each zone of ABR. The high-throughput DNA sequencing showed that the bacteria Micropruina, Saccharibacteria and Synergistaceae were involved in the degradation of pollutants in the anaerobic and anoxic reaction zones, while Rhodobacteraceae and Aliihoeflea were the main functional microorganisms in the aerobic reaction zones. The results demonstrated that the improved ABR reactor had the potential for the treatment of wastewater from ASP flooding technology.

Handheld UV fluorescence spectrophotometer device for the classification and analysis of petroleum oil samples.

Oil spills can be environmentally devastating and result in unintended economic and social consequences. An important element of the concerted effort to respond to spills includes the ability to rapidly classify and characterize oil spill samples, preferably on-site. An easy-to-use, handheld sensor is developed and demonstrated in this work, capable of classifying oil spills rapidly on-site. Our device uses the computational power and affordability of a Raspberry Pi microcontroller and a Pi camera, coupled with three ultraviolet light emitting diodes (UV-LEDs), a diffraction grating, and collimation slit, in order to collect a large data set of UV fluorescence fingerprints from various oil samples. Based on a 160-sample (in 5x replicates each with slightly varied dilutions) database this platform is able to classify oil samples into four broad categories: crude oil, heavy fuel oil, light fuel oil, and lubricating oil. The device uses principal component analysis (PCA) to reduce spectral dimensionality (1203 features) and support vector machine (SVM) for classification with 95% accuracy. The device is also able to predict some physiochemical properties, specifically saturate, aromatic, resin, and asphaltene percentages (SARA) based off linear relationships between different principal components (PCs) and the percentages of these residues. Sample preparation for our device is also straightforward and appropriate for field deployment, requiring little more than a Pasteur pipette and not being affected by dilution factors. These properties make our device a valuable field-deployable tool for oil sample analysis.

A GHS-consistent approach to health hazard classification of petroleum substances, a class of UVCB substances.

The process streams refined from petroleum crude oil for use in petroleum products are among those designated by USEPA as UVCB substances (unknown or variable composition, complex reaction products and biological materials). They are identified on global chemical inventories with unique Chemical Abstract Services (CAS) numbers and names. The chemical complexity of most petroleum substances presents challenges when evaluating their hazards and can result in differing evaluations due to the varying level of hazardous constituents and differences in national chemical control regulations. Global efforts to harmonize the identification of chemical hazards are aimed at promoting the use of consistent hazard evaluation criteria. This paper discusses a systematic approach for the health hazard evaluation of petroleum substances using chemical categories and the United Nations (UN) Globally Harmonized System (GHS) of classification and labeling. Also described are historical efforts to characterize the hazard of these substances and how they led to the development of categories, the identification of potentially hazardous constituents which should be considered, and a summary of the toxicology of the major petroleum product groups. The use of these categories can increase the utility of existing data, provide better informed hazard evaluations, and reduce the amount of animal testing required.

Chemometric analysis of gas chromatography with flame ionisation detection chromatograms: a novel method for classification of petroleum products.

Most oil characterisation procedures are time consuming, labour intensive and utilise only part of the acquired chemical information. Oil spill fingerprinting with multivariate data processing represents a fast and objective evaluation procedure, where the entire chromatographic profile is used. Methods for oil classification should be robust towards changes imposed on the spill fingerprint by short-term weathering, i.e. dissolution and evaporation processes in the hours following a spill. We propose a methodology for the classification of petroleum products. The method consists of: chemical analysis; data clean-up by baseline removal, retention time alignment and normalisation; recognition of oil type by classification followed by initial source characterisation. A classification model based on principal components and quadratic discrimination robust towards the effect of short-term weathering was established. The method was tested successfully on real spill and source samples.

Classification and source determination of medium petroleum distillates by chemometric and artificial neural networks: a self organizing feature approach.

Three different medium petroleum distillate (MPD) products (white spirit, paint brush cleaner, and lamp oil) were purchased from commercial stores in Glasgow, Scotland. Samples of 10, 25, 50, 75, 90, and 95% evaporated product were prepared, resulting in 56 samples in total which were analyzed using gas chromatography-mass spectrometry. Data sets from the chromatographic patterns were examined and preprocessed for unsupervised multivariate analyses using principal component analysis (PCA), hierarchical cluster analysis (HCA), and a self organizing feature map (SOFM) artificial neural network. It was revealed that data sets comprised of higher boiling point hydrocarbon compounds provided a good means for the classification of the samples and successfully linked highly weathered samples back to their unevaporated counterpart in every case. The classification abilities of SOFM were further tested and validated for their predictive abilities where one set of weather data in each case was withdrawn from the sample set and used as a test set of the retrained network. This revealed SOFM to be an outstanding mechanism for sample discrimination and linkage over the more conventional PCA and HCA methods often suggested for such data analysis. SOFM also has the advantage of providing additional information through the evaluation of component planes facilitating the investigation of underlying variables that account for the classification.

Biosurfactant production by Rhodococcus erythropolis and its application to oil removal

The influence of different nutrients on biosurfactant production by Rhodococcus erythropolis was investigated. Increasing the concentration of phosphate buffer from 30 up through 150 mmol/L stimulated an increase in biosurfactant production, which reached a maximum concentration of 285 mg/L in shaken flasks. Statistical analysis showed that glycerol, NaNO3,MgSO4 and yeast extract had significant effects on production. The results were confirmed in a batchwise bioreactor, and semi-growth-associated production was detected. Reduction in the surface tension, which indicates the presence of biosurfactant, reached a value of 38 mN/m at the end of 35 hours. Use of the produced biosurfactant for washing crude oil-contaminated soil showed that 2 and 4 times the critical micellar concentration (CMC) were able to remove 97 and 99 percent of the oil, respectively, after 1 month of impregnation.

Discrimination of petroleum fluorescence spectra.

This paper presents studies of the total spectra (fluorescence-excitation matrix) of petroleum with regard to the utilization of fluorescence for determining petroleum pollutants. Thorough testing of one group, comprising almost forty lubricating oils in the form of their hexane solutions, points out their discrimination.

Classification of weathered petroleum oils by multi-way analysis of gas chromatography-mass spectrometry data using PARAFAC2 parallel factor analysis.

The application of multi-way parallel factor analysis (PARAFAC2) is described for the classification of different kinds of petroleum oils using GC-MS. Oils were subjected to controlled weathering for 2, 7 and 15 days and PARAFAC2 was applied to the three-way GC-MS data set (MSxGCxsample). The classification patterns visualized in scores plots and it was shown that fitting multi-way PARAFAC2 model to the natural three-way structure of GC-MS data can lead to the successful classification of weathered oils. The shift of chromatographic peaks was tackled using the specific structure of the PARAFAC2 model. A new preprocessing of spectra followed by a novel use of analysis of variance (ANOVA)-least significant difference (LSD) variable selection method were proposed as a supervised pattern recognition tool to improve classification among the highly similar diesel oils. This lead to the identification of diagnostic compounds in the studied diesel oil samples.

Today's and tomorrow's bio-based bulk chemicals from white biotechnology: a techno-economic analysis.

Little information is yet available on the economic viability of the production of bio-based bulk chemicals and intermediates from white biotechnology (WB). This paper details a methodology to systematically evaluate the techno-economic prospects of present and future production routes of bio-based bulk chemicals produced with WB. Current and future technology routes are evaluated for 15 products assuming prices of fermentable sugar between 70 euro/t and 400 euro/t and crude oil prices of US $25/barrel and US $50/barrel. The results are compared to current technology routes of petrochemical equivalents. For current state-of-the-art WB processes and a crude oil price of US $25/barrel, WB-based ethanol, 1,3-propanediol, polytrimethylene terephthalate and succinic acid are economically viable. Only three WB products are economically not viable for future technology: acetic acid, ethylene and PLA. Future-technology ethylene and PLA become economically viable for a higher crude oil price (US $50/barrel). Production costs plus profits of WB products decrease by 20-50% when changing from current to future technology for a crude oil price of US $25 per barrel and across all sugar prices. Technological progress in WB can thus contribute significantly to improved economic viability of WB products. A large-scale introduction of WB-based production of economically viable bulk chemicals would therefore be desirable if the environmental impacts are smaller than those of current petrochemical production routes.

[Petroleum substances--human health hazards. I. Classification of petroleum substances on the list of dangerous substances and assessment of existing hazards]. / Pochodne ropy naftowej--zagrozenia dla zdrowia czlowieka. I. Klasyfikacja substancji ropopochodnych w wykazie substancji niebezpiecznych a ocena rzeczywistych zagrozen.

Complex products derived from petroleum are widely used as fuels, greases, solvents, and intermediates in many branches of industry. Petroleum exposure-related human health hazards, observed in occupationally exposed people and in the general population, are a serious sanitary problem. Complex and variable composition of individual petroleum products makes the actual assessment of human health hazards difficult. Potential hazards, and resulting classification of individual petroleum substance groups, are discussed in the presented work. This should prove to be helpful to work safety and hygiene services as well as to supervising institutions, mainly the sanitary inspection, in a proper assessment of the hazards, and consequently in taking appropriate preventive actions. In Part I., general issues concerning the hazard assessment and legal aspects of petroleum substances classification are presented. In Part. II., individual groups of petroleum substances are discussed with respect to health hazards, resulting from both physicochemical properties and toxicity, and their classification based on this analysis is suggested.

Characterization and source of oil contamination on the beaches and seabird corpses, Sable Island, Nova Scotia, 1996-2005.

During April 1996-May 2005, 2343 oiled seabird corpses were recorded in beach surveys conducted on Sable Island, Nova Scotia. One hundred eighty-three samples of oil were collected from the beaches and from the feathers of bird corpses. Gas chromatographic (GC/FID) analysis was used to identify generic oil type and likely marine source. During this period, at least 74 marine oil discharge events were probably responsible for beached pelagic tar and contamination of seabird corpses found on Sable Island, of which 77.0% were crude oils, 14.9% were fuel oils, and 8.1% were bilge oil mixtures. While fuel and bilge oils may be discharged by all vessel and platform types, crude oil discharges are associated with tanker operations. This study demonstrates that oiling of the sea from tankers remains a serious wildlife issue in the Northwest Atlantic.

Classification of highly similar crude oils using data sets from comprehensive two-dimensional gas chromatography and multivariate techniques.

Comprehensive two-dimensional gas chromatography (GCxGC) has proven to be an extremely powerful separation technique for the analysis of complex volatile mixtures. This separation power can be used to discriminate between highly similar samples. In this article we will describe the use of GCxGC for the discrimination of crude oils from different reservoirs within one oil field. These highly complex chromatograms contain about 6000 individual, quantified components. Unfortunately, small differences in most of these 6000 components characterize the difference between these reservoirs. For this reason, multivariate-analysis (MVA) techniques are required for finding chemical profiles describing the differences between the reservoirs. Unfortunately, such methods cannot discern between 'informative variables', or peaks describing differences between samples, and 'uninformative variables', or peaks not describing relevant differences. For this reason, variable selection techniques are required. A selection based on information between duplicate measurements was used. With this information, 292 peaks were used for building a discrimination model. Validation was performed using the ratio of the sum of distances between groups and the sum of distances within groups. This step resulted in the detection of an outlier, which could be traced to a production problem, which could be explained retrospectively.

Time-resolved fluorescence spectroscopic study of crude petroleum oils: influence of chemical composition.

The fluorescence of crude petroleum oils is sensitive to changes in chemical composition and many different fluorescence methods have been used to characterize crude oils. The use of fluorescence lifetimes to quantitatively characterize oil composition has practical advantages over steady-state measurements, but there have been comparatively few studies in which the lifetime behavior is correlated with gross chemical compositional data. In this study, the fluorescence lifetimes for a series of 23 crude petroleum oils with American Petroleum Institute (API) gravities of between 10 and 50 were measured at several emission wavelengths (450-785 nm) using a 380 nm light emitting diode (LED) excitation source. It was found that the intensity average fluorescence lifetime (tau) at any emission wave-length does not correlate well with either API gravity or aromatic concentration. However, it was found that tau is strongly negatively correlated with both the polar and sulfur concentrations and positively correlated with the corrected alkane concentration. This indicates that the fluorescence behavior of crude petroleum oils is governed primarily by the concentration of quenching species. All the strong lifetime-concentration correlations are nonlinear and show a high degree of scatter, especially for medium to light oils with API gravities of between 25 and 40. The degree of scatter is greatest for oils where the concentrations (wt %) of the polar fraction is approximately 10 +/- 4%, the asphaltene component is approximately 1 +/- 0.5%, and sulfur is 0.5 +/- 0.4%. This large degree of scatter precludes the use of average fluorescence lifetime data obtained with 380 nm excitation for the accurate prediction of the common chemical compositional parameters of crude petroleum oils.

Petroleomics: the next grand challenge for chemical analysis.

Ultrahigh-resolution Fourier transform ion cyclotron resonance mass spectrometry has recently revealed that petroleum crude oil contains heteroatom-containing (N,O,S) organic components having more than 20,000 distinct elemental compositions (C(c)H(h)N(n)O(o)S(s)). It is therefore now possible to contemplate the ultimate characterization of all of the chemical constituents of petroleum, along with their interactions and reactivity, a concept we denote as "petroleomics". Such knowledge has already proved capable of distinguishing petroleum and its distillates according to their geochemical origin and maturity, distillation cut, extraction method, catalytic processing, etc. The key features that have opened up this new field have been (a) ultrahigh-resolution FT-ICR mass analysis, specifically, the capability to resolve species differing in elemental composition by C(3) vs SH(4) (i.e., 0.0034 Da); (b) higher magnetic field to cover the whole mass range at once; (c) dynamic range extension by external mass filtering; and (d) plots of Kendrick mass defect vs nominal Kendrick mass as a means for sorting different compound "classes" (i.e., numbers of N, O, and S atoms), "types" (rings plus double bonds), and alkylation ((-CH(2))(n)) distributions, thereby extending to >900 Da the upper limit for unique assignment of elemental composition based on accurate mass measurement. The same methods are also being applied successfully to analysis of humic and fulvic acids, coals, and other complex natural mixtures, often without prior or on-line chromatographic separation.

European hazard classification advice for crude oil-derived lubricant base oils compared with the proposed mineral oil mist TLV.

The notice of intended change for the threshold limit value (TLV) for mineral oil mist contains a notation for human carcinogenicity. A description is provided of the current European regulatory approach used to distinguish between carcinogenic and non-carcinogenic mineral base oils on the basis of oil refining process and chemical marker information. This approach has proven effective in creating a market situation in the countries of the European Union where many customers require severely refined, non-carcinogenic oils. It is recommended that ACGIH consolidate the distinction between poorly and severely refined base oils in the recommended TLV for mineral oil mist and use different toxicological considerations to derive exposure control guidelines.

Chemical characterization of naturally weathered oil residues in arid terrestrial environment in Al-Alamein, Egypt.

The main objective of this study was to investigate compositional changes in a range of source- and weathering-dependent molecular parameters in oil residues in the arid terrestrial environment of Al-Alamein, Egypt. The results of aromatic hydrocarbon analysis demonstrated the stability of several aromatic hydrocarbon ratios in oil residues over a wide range of weathering and hydrocarbon concentrations. The ratios of C2-dibenzothiophenes/C2-phenanthrenes (C2-DBTs/C2-PHENs), C3-dibenzothiophenes/C3-phenanthrenes (C3-DBTs/C3-PHENs), C2-chrysenes/C1-chrysenes (C2-CHRYs/C1-CHRYs), and C2-dibenzothiophenes/C1-dibenzothiophenes (C2-DBTs/C1-DBTs) were nearly constant in oil residues of varying degrees of weathering. Biomarker ratios of hopanes and steranes were useful for source identification even for severely weathered oil residues. The data confirmed previous observations that C29 20S/(20S + 20R) and C29 betabeta/(betabeta+ alphaalpha) sterane epimer ratios, and C29/C30, C30 alphabeta(alphabeta + 3alpha), C31 22S/(22S + 22R) hopane ratios correlate well even after extensive weathering of spilled oils, although some exceptions were encountered for an extensively weathered surface sample. The data provided clear evidence of correlation between samples of the weathered oil residues and the possible source oil. Moreover, the results of biomarker compositions were in good agreement with weathering classification based on alkanes and aromatic hydrocarbons. In general, samples with lowest pregnane indices (PI) and tricyclic terpane indices (TriTI) showed the lowest concentrations of n-alkanes and alkylated polycyclic aromatic hydrocarbon (PAH) homologues, the highest weathering ratios (WRs), the highest values of unresolved complex mixture (UCM)/total resolved peak (TRP) ratios, and the highest ratios of C2 and C3-alkylated CHRYs to their counterparts in the PHEN and DBT series.

Correlation of systemic and developmental toxicities with chemical component classes of refinery streams.

Refinery streams are complex mixtures, but of a relatively few homologous series of hydrocarbons (paraffins, olefins, naphthenics, and aromatics). Studies were performed to determine if systemic and developmental toxicity were related to the presence and levels of certain classes of refinery stream components. We have performed systemic toxicology studies in the rat on 13 refinery streams: Clarified Slurry Oil, Coker Light Gas Oil, Distillate Aromatic Extract, Heavy Atmospheric Gas Oil, Heavy Coker Gas Oil (from three refineries), Heavy Vacuum Gas Oil, Light Catalytically Cracked Naphtha, Light Cycle Oil, Syntower Bottoms, Vacuum Tower Overhead, and Visbreaker Gas Oil. Rats were exposed via repeated dermal administration (daily) at several dose levels. Developmental toxicology studies were performed on these same streams with the following exceptions: only two Heavy Coker Gas Oils were tested and Visbreaker Gas Oil was not tested. End points for systemic toxicity (13-week) studies included skin irritation, body and organ weights, hematology, and serum chemistry; for developmental toxicity studies some of these same end points (excluding hematology) were considered, but they also included resorption and fetal body weight. In general, toxicity was correlated with concentrations of polycyclic aromatic compounds (PAC) composed of 3, 4, 5, 6, and/or 7 rings (decreased thymus weight, increased liver weight, aberrant hematology and serum chemistry, increased incidence of resorption, decreased fetal body weight), PAC containing nonbasic nitrogen heteroatoms (increased mortality, decreased body weight, decreased thymus weight, increased liver weight, decreased hemoglobin content and hematocrit level, decreased fetal body weight), and/or PAC containing sulfur heteroatoms (decreased red blood cell and platelet counts, increased sorbitol dehydrogenase.)(ABSTRACT TRUNCATED AT 250 WORDS)