Unresolved Complex Mixture Research Articles

Identification of weathered multiple petroleum products in contaminated soils by characterizing unresolved complex mixture hump in gas chromatograph data

A new method for identifying the petroleum products in contaminated soils is presented, which characterizes the unresolved complex mixture (UCM) hump in the baseline of gas chromatograph (GC) data. The UCM hump identified in soil data was fitted to the Gaussian function, and characterized according to the time for the maximum point (TUCM) and the width of the hump (w). Experimental results showed that a UCM hump should be clearly observed in soils when contaminated with petroleum, and that soils contaminated with kerosene, diesel, or some lubricating oils estimated herein should present different characteristic values of TUCM and w. Even though the environmental weathering of contaminated soils under evaporative conditions might cause variations in these characteristic values, they converged to specific constants depending on the product. The method could also differentiate between multiple petroleum contaminants in soil. Feasibility was evaluated using soils from a military oil storage site that was closed in 1970. The soil contaminants identified by the proposed method corresponded to the historical storage records, suggesting that the UCM hump characterization method could have strong potential in environmental forensics for differentiating products in petroleum-contaminated soils.

Toxicity of organic compounds from unresolved complex mixtures (UCMs) to primary fish hepatocytes

Many environmental matrices contaminated with organic pollutants derived from crude oil or degraded petroleum contain mixtures so complex that they are typically unresolved by conventional analytical techniques such as gas chromatography. The resulting chromatographic features have become known as ‘humps’ or unresolved complex mixtures (UCMs). These UCMs often dominate the organic contaminants of polluted environmental samples: for example, in oil sands produced water up to 150mgL−1 of ‘naphthenic acids’ appear as UCMs when examined by gas chromatography as the esters. In oil-contaminated mussels, aromatic hydrocarbon UCMs may comprise almost all of the total toxic hydrocarbons, with over 7000μgg−1 dry weight reported in some samples. Over the last 25 years, efforts to resolve and thus identify, or at least to produce average structures, for some UCM components, have proved fruitful. Numerous non-polar UCM hydrocarbons and more polar UCM acids have been identified, then synthesised or purchased from commercial suppliers. As UCMs have been proposed to represent a risk to aquatic organisms, the need for assessment of the ecotoxicological effects and characterisation of the mode of action (MoA) of these environmental pollutants has arisen. In the present study, several chemicals with structures typical of those found in some UCMs, were assessed for their potential to disrupt membrane integrity, inhibit metabolic activity, activate the aryl hydrocarbon receptor (AhR), and activate the estrogen receptor (ER) in primary rainbow trout hepatocytes (Oncorhynchus mykiss). These endpoints were determined in order to screen for common toxic modes of action (MoA) in this diverse group of chemicals. The results from the in vitro screening indicated that of the endpoints tested, the predominant toxic MoA was cytotoxicity. EC50 values for cytotoxicity were obtained for 16 compounds and ranged from 77μM–24mM, whereof aliphatic monocyclic acids, monoaromatic acids, polycyclic monoaromatic acids and alkylnaphthalenes were the most toxic. The observed cytotoxicity of the chemicals correlated well with the hydrophobicity (LogKOW) suggesting that the toxicity was predominantly due to a non-specific MoA. Interestingly, two compounds induced the ER-mediated production of vitellogenin (Vtg) and six compounds induced the AhR-mediated Ethoxyresorufin-O-deethylase (EROD) enzymatic activity to >20% of the positive control; by doing so suggesting that they may act as ER or AhR agonists in fish. The heterogeneous group of ‘UCM compounds’ tested exhibited multiple MoA that may potentially cause adverse effects in fish. Additional studies to determine if these compounds may cause adverse effects in vivo at environmentally relevant concentrations, are warranted to identify if such compounds are indeed of potential environmental concern.

Effects of deep CO2 on petroleum and thermal alteration: The case of the Huangqiao oil and gas field

The CO2-rich natural gas from the Huangqiao oil and gas field of the Subei Basin is produced along with crude oil. The CO2 content, ranging from 80.56% to 99.30% and the 3He/4He ratio of 0.94×10−6 to 4.67×10−6, indicates that this includes a substantial fraction of mantle-derived CO2 in the Huangqiao region. Although the positive carbon isotopic series of alkane gases (i.e., δ13C1<δ13C2<δ13C3) supports that the gaseous alkanes at the Huangqiao region are biogenic gas, some of the abiogenic CH4 is contributed to the natural gas, including the mantle-derived CH4, and the water-rock interaction generated CH4 by based on the relationships of CO2/3He vs R/Ra and CH4/3He vs R/Ra of the components of crust and mantle end members.The crude oil of the Huangqiao region is light or condensate oil, with low densities of 0.7933–0.8255g/cm3. Saturated hydrocarbons comprise 90.06%–97.37% the crude oil, while the aromatic, non-hydrocarbon and asphaltene fractions are very small. The n-alkanes range from C13 to C34, with highest abundances at C16 and C17. The gas chromatogram of the crude oil shows an unresolved hump or unresolved complex mixture (UCM) distribution of a complete n-alkane series, non-odd/even predominance, and major n-alkane peaks on the highest positions of the UCM distribution. This may indicate that deep mantle-derived CO2 fluid extracted and accumulated the oil now found in the reservoirs or source rocks.

Hydrocarbon composition and concentrations in the Gulf of Mexico sediments in the 3 years following the Macondo well blowout

In April of 2010, the Macondo well blowout in the northern Gulf of Mexico resulted in an unprecedented release of oil into the water column at a depth of approximately 1500 m. A time series of surface and subsurface sediment samples were collected to the northwest of the well from 2010 to 2013 for molecular biomarker and bulk carbon isotopic analyses. While no clear trend was observed in subsurface sediments, surface sediments (0–3 cm) showed a clear pattern with total concentrations of n-alkanes, unresolved complex mixture (UCM), and petroleum biomarkers (terpanes, hopanes, steranes) increasing from May to September 2010, peaking in late November 2010, and strongly decreasing in the subsequent years. The peak in hydrocarbon concentrations were corroborated by higher organic carbon contents, more depleted Δ14C values and biomarker ratios similar to those of the initial MC252 crude oil reported in the literature. These results indicate that at least part of oil discharged from the accident sedimented to the seafloor in subsequent months, resulting in an apparent accumulation of hydrocarbons on the seabed by the end of 2010. Sediment resuspension and transport or biodegradation may account for the decrease in sedimented oil quantities in the years following the Macondo well spill.

Mercury, n-alkane and unresolved complex mixture hydrocarbon pollution in surface sediment across the rural–urban–estuarine continuum of the River Clyde, Scotland, UK

ABSTRACTSurface sediments (n=85) from a 160-km river-estuarine transect of the Clyde, UK, were analysed for total mercury (Hg), saturated hydrocarbons and unresolved complex mixtures (UCMs) of hydrocarbons. Results show that sediment-Hg concentration ranges from 0.01 to 1.38mgkg–1 (mean 0.20mgkg–1) and a spatial trend in Hg-content low–high–low–high, from freshwater source, to Glasgow, to estuary, is evident. In summary, sediment-Hg content is low in the upper Clyde (mean of 0.05Hg mgkg–1), whereas sediments from the Clyde in urbanised Glasgow have higher Hg concentrations (0.04 to 1.26mgkg–1; mean 0.45mgkg–1), and the inner estuary sediments contain less Hg (mean 0.06mgkg–1). The highest mean sediment Hg (0.65mgkg–1) found in the outer estuary is attributed to historical anthropogenic activities. A significant positive Spearman correlation between Hg and total organic carbon is observed throughout the river estuary (0.86; P&lt;0.001). Comparison with Marine Scotland guidelines suggests that no sites exceed the 1.5mgkg–1 criterion (Action Level 2); 22 fall between 0.25 and 1.5mgkg–1 dry wt. (Action Level 1) and 63 are of no immediate concern (&lt;0.25mgkg–1 dry wt.). Saturated (n-alkane) hydrocarbons in the upper Clyde are of natural terrestrial origin. By contrast, the urbanised Glasgow reaches and outer estuary are characterised by pronounced and potentially toxic UCM concentrations in sediments (380–914mg/kg and 103–247mgkg–1, respectively), suggesting anthropogenic inputs such as biodegraded crude oil, sewage discharge and/or urban run-off.

Occurrence, source and ecological assessment of baseline hydrocarbons in the intertidal marine sediments along the shoreline of Douglas Channel to Hecate Strait in British Columbia

The occurrence, source and ecological assessment of baseline hydrocarbons in the intertidal zone along the northern British shoreline were evaluated based on analyzing total petroleum hydrocarbons (TPH), n-alkanes, petroleum related biomarkers such as terpanes and steranes, and polycyclic aromatic hydrocarbons (PAHs) including non-alkylated and alkylated homologues (APAHs). The TPH levels, n-alkanes, petroleum biomarkers and PAHs in all the sampling sites, except for Masset Harbor/York Point at Gil Island were low, without obvious unresolved complex mixture (UCM) and petroleum contamination input. Specifically, n-alkanes showed a major terrestrial plants input; PAHs with abundant non-alkylated PAHs but minor APAHs showed a major pyrogenic input. However, obvious petroleum-derived hydrocarbons have impacted Masset Harbor. A historical petroleum input was found in York Point at Gil Island, due to the presence of the low level of petroleum biomarkers. Ecological assessment of 13 non-alkylated PAHs in Masset Harbor indicated no potential toxicity to the benthic organisms.

The origin of aliphatic hydrocarbons in olive oil.

There are many substances that can interfere with olive oil quality. Some of them are well characterized, but many others have an unknown origin. Saturated hydrocarbons make an extraordinary complex family of numerous molecules, some of them present naturally in vegetable oils. When major natural saturated hydrocarbons are analyzed by standard chromatographic methods, this complex mixture of saturated hydrocarbons appears as a hump in the chromatogram and is commonly named as unresolved complex mixture (UCM), whose origin remains unknown. In this work we studied the occurrence and the origin of aliphatic saturated hydrocarbons in olive oil. Hydrocarbons were analyzed in olive oil and along the industrial process of oil extraction. We also analyzed n-alkanes and the UCM fraction of hydrocarbons in leaf, fruit and oil from different varieties and different locations, and we also analyzed the soils at these locations. We conclude that the hydrocarbons present in olive oil do not necessarily have their origin in a contamination during olive oil elaboration; they seem to have a natural origin, as a result of olive tree metabolism and/or as the result of an intake and accumulation by the olive tree directly from the environment during its entire life cycle. © 2017 Society of Chemical Industry.

GEOCHEMICAL CHARACTERISTICS OF THE SKRUGARD OIL DISCOVERY, BARENTS SEA, ARCTIC NORWAY: A “PALAEO‐BIODEGRADED – GAS REACTIVATED” HYDROCARBON ACCUMULATION

This paper investigates the filling history of the Skrugard and Havis structures of the Johan Castberg field in the Polheim Sub‐Platform and Bjørnøyrenna Fault Complex, Barents Sea (Arctic Norway). Oil and gas occurs in the Early Jurassic and Middle Jurassic Nordmela and Stø Formations at Johan Castberg, and both free oil and bitumen are interpreted to be sourced from the Upper Jurassic Hekkingen Formation (Kimmeridge Formation equivalent). The geochemical characteristics of the petroleum from Skrugard and Havis, including the GOR, API and facies and maturity signatures, can be understood within a complex fill history which includes a palaeo oil charge, Tertiary uplift (&gt;2 km), dismigration, in‐reservoir biodegradation, and late‐stage refill with gas.The API and GOR of the Skrugard oil are 31° and 60m3/m3, respectively. The petroleum is geochemically similar to that in the nearby Havis structure, to that in the Snøhvit region to the south of the Loppa High, and also to the petroleum recorded as traces in well 7219/9‐1, approximately 16 km SW of Johan Castberg field. However, the petroleum differs from the oil in the Alta well 7120/2‐1, located in the southern part of the Loppa High, illustrating the complexity of the regional petroleum systems. The Skrugard oil is of medium maturity (ca. 0.8–0.9% Rc), and is significantly biodegraded despite being gas‐saturated. Evidence for biodegradation includes the reduced concentrations of C10‐C25 n‐alkanes and the presence of a prominent unresolved complex mixture (UCM) in gas chromatogram traces. However non‐biodegraded C4‐C8 range hydrocarbons are also present in the reservoir. This suggests a recent charge of gas/condensate into the structure which therefore contains a mixture of palaeo‐degraded and unaltered petroleum.Oil‐type inclusions within authigenic quartz and feldspar from reservoir sandstones at Skrugard were analysed. The results indicate that the structure (present‐day depth 1276–1395m) underwent Tertiary uplift by ca. 2–3km following an earlier phase of oil emplacement. The presence of the oil type inclusions, both in the current gas zone (Stø Formation) and in the oil zone (Stø and Nordmela Formations), indicates that the positions of the oil‐water and gas‐oil contacts have changed over time. This is consistent with a recent gas charge to the upper part of the reservoir, and also with the gas being at dew point. These observations are supported by analyses of core extracts which show an increasing bitumen content towards the OWC, and the oil‐type bitumen in the present‐day gas zone.A charge history model for the Skrugard structure is proposed which integrates both the observations concerning the petroleum inclusions and the biodegraded oil together with observations of seismically‐monitored gas fluxes along the rim of the Loppa High. Improved understanding of the Skrugard structure and its filling history will assist exploration in similar settings in other parts of the Barents Sea and worldwide, particularly where multiple source rocks and a multi‐stage charge history have controlled reservoir filling.

Source and Toxicological Assessment of Polycyclic Aromatic Hydrocarbons in Sediments from Imo River, Southeastern Nigeria

ABSTRACTPolycyclic aromatic hydrocarbons (PAHs) in sediments from the Imo River were analyzed to characterize their sources and assess their toxicity potential. The total PAH concentrations ranged from 409.43 to 41,198 ng/g dw with standard deviation of 4,796 ± 1,941. This wide variation reflects a localized contamination in the study area. The inadequacy in the use of traditional isomeric ratios for PAHs source characterization in sediment from tropical environments with shallow water depth of < 10 m was highlighted. A more robust principal component analysis coupled with n-alkanes unresolved complex mixture profiles approach to apportioned specific chemical signatures to samples was proposed. This approach differentiated stations that were heavily—from those that were mildly—impacted by oil and discriminated among stations that were influenced by pyrogenic sources. Effect range low (ERL) and effect range median (ERM) as well as risk quotients (RQwcs) revealed that only naphthalene, flourene, dibenzo(a,h)anthracene and low molecular weight PAHs were implicated with ERL and ERM exceeding the US National Oceanic and Atmospheric Administration's limit of concern and RQwcs > 1, as compounds of concern. The maximum toxicity equivalency value of 179.81 ng/g TEQscarc measured for the illegal petroleum refinery site indicated that this site requires some control measure and remedial action.

Transformation of diesel range hydrocarbons by inorganic double salts

Ability of double salts: Ammonium cobalt (ll) sulphate hexahydrate (NH 4 ) 2 Co (SO 4 ) 2 .6H 2 O and Potassium aluminium sulphate dodecahydrate KAl(SO 4 ) 2 .12H 2 O to degrade diesel range hydrocabons (DRH) were investigated by treating a sample of diesel with the double salts at elevated temperature of 200 o C. The degradation or otherwise of the hydrocarbons in the treated and untreated diesel samples were determined using Gas chromatography (GC). The results showed that the double salts were able to alter the hydrocarbon fingerprint of the diesel sample as the C 11 -C 14 aliphatic hydrocarbons were drastically reduced and the C 16 -C 36 range of hydrocarbons experienced noticeable increase. The hump for unresolved complex mixtures was retained in all the chromatograms, showing that the salts were unable to alter the oxygenated compounds in the diesel sample. Keywords: Diesel, double salt, Hydrocarbons, Gas Chromatography

Lipid Biomarker Analysis of Suspended Particulate Matter from the Great Kwa River, SE Nigeria: Origins and Environmental Implications of Biogenic and Anthropogenic Organic Compounds

Biomarkers found in natural waters, sediments, soils, fossils, crude oil, and coal can be unambiguously linked to specific precursors biosynthesized by biota. Petroleum and its refinery products carry their biomarker information into the environment when they are released by pollution. Lipid biomarkers can be used to assess the environmental status of an ecosystem and the degree to which it has been influenced by biogenic and anthropogenic inputs. The marine ecosystem of the southeastern Niger Delta of Nigeria is receiving new attention due to increased human and industrial development and the consequent potential health effects. Suspended particulate matter (SPM) from the Great Kwa River was characterized using biomarkers to assess such pollution. The total organic carbon contents of SPM from the river at low and high tide was 12–50% (avg 34.75%) and 16–28% (avg 24.25%), respectively. The lipid biomarkers identified using gas chromatography–mass spectrometry were mainly n-alkanes, n-alkan-2-ones, triterpenoids and minor amounts of aromatic compounds. The n-alkanes ranged from C 17 to C 35, with an odd/even predominance and C max > 27, indicating a mixed origin from higher plant wax, biodegraded detritus, and petroleum. The n-alkan-2-ones in most samples ranged from C 16 to C 33, with C max = 31, also supporting an input from vascular plants dominating the riparian zone along the river. The triterpenoids, mainly taraxerone, taraxerol, α- and β-amyrins, and friedelin, also derived from higher plants (angiosperms). Minor amounts of aromatic hydrocarbon derivatives from α- and β-amyrins were present and are likely the result of different diagenetic processes. The presence of trace fossil fuel-derived hopanes with an unresolved complex mixture of branched and cyclic hydrocarbons supported a minor petroleum product input to the SPM of the Great Kwa River.

Extraction optimization and pixel-based chemometric analysis of semi-volatile organic compounds in groundwater

Combined dual extraction steps provided high enrichment factors and separation of peaks from unresolved complex mixtures in groundwaters. For the first time, pixel-based analysis of summed extracted ion chromatograms (sEIC's) was used for the characterization of semi-VOCs.

Identifying the source of petroleum pollution in sediment cores of southwest of the Caspian Sea using chemical fingerprinting of aliphatic and alicyclic hydrocarbons

In this study, the concentration and sources of aliphatic and petroleum markers were investigated in 105 samples of Anzali, Rezvanshahr and Astara cores from the southwest of Caspian Sea. Petroleum importation was diagnosed as a main source in most depths of cores by the results of unresolved complex mixture, carbon preference index and hopanes and steranes. From the chemical diagnostic parameters, petroleum inputs in sediment of cores were determined to be different during years and the sources of hydrocarbons in some sections differed than Anzali and Turkmenistan and Azerbaijan oils. Diagenic ratios in most sediments of upper and middle sections in Astara core were determined to be highly similar to those of Azerbaijan oil, while the presence of Turkmenistan and Anzali oils were detected in a few sections of Anzali and Rezvanshahr cores and only five layers of downer section in Anzali core, respectively.

MOLECULAR DIAGNOSTIC RATIOS TO ASSESS THE APPORTIONMENT OF PETROLEUM HYDROCARBONS CONTAMINANTION IN MARINE SEDIMENT

As maritime fulcrum nation, in Indonesia, marine environmental analytical chemistry field is still under developed. So that why, this review paper aims to provide basic understanding of the use some molecular diagnostic indices using n-alkanes indexes and polycyclic aromatic hydrocarbons (PAHs) diagnostic ratios to estimate the source of apportionment of the hydrocarbons contamination and origin. The n-alkane chromatograms were then used to characterize the predominance of petrogenic or biogenic either terrestrial or aquatic. Furthermore, characterization allowed to discriminate riverine versus marine input. The occurrence of a broad unresolved complex mixture can be an evidence of biodegraded petroleum residues. For aromatic compounds, the prevalence of petrogenic, pyrolitic, and combustion-derived can be easily plotted by using isomers ratio calculation. This paper thus provides useful information on the hydrocarbon contamination origin, especially in marine sediments. Further researches should be undertaken in order to validate the use of molecular diagnostic ratio with isotopic approach.

Determination of hydrocarbons transported by urban runoff in sediments of São Gonçalo Channel (Pelotas – RS, Brazil)

A high concentration of hydrocarbons in the environment is indicative of pollution. To evaluate the effect of hydrocarbons transported by urban runoff, the present study analyzed total petroleum hydrocarbons (TPHs), aliphatic hydrocarbons (AHs), unresolved complex mixture (UCM), and n-alkanes of the sediments of the canal that cross the urban area of Pelotas, Rio Grande do Sul, Brazil. The carbon preference index (CPI), terrigenous/aquatic ratio (TAR), and pristane/phytane ratio were determined. The TPH content ranged from 177,043.7μg·kg−1±13.4% to 5,892,667.0μg·kg−1±5.9%. The total aliphatic content ranged from 116,268.8μg·kg−1±11.1% to 2,393,592.6μg·kg−1±7.7%, indicating chronic contamination of n-alkanes petrogenic and biogenic sources. The levels of hydrocarbons (TPH, AHs, and n-alkanes) were considered relatively high, confirming the effect of urban runoff on the drainage system of cities and their consequent effect on the estuarine region of Patos Lagoon and other water resources.

Biodegradation and possible source of Silurian and Carboniferous reservoir bitumens from the Halahatang sub-depression, Tarim Basin, NW China

Five core samples comprising three Silurian and two Carboniferous bituminous sandstones from the Halahatang sub-depression (Tarim Basin, NW China) were studied to determine the nature and extent of microbial alteration and possible source(s) of the reservoir bitumens. A total of twelve Ordovician crude oil samples from this sub-depression were also examined for comparative purposes. Co-occurrence of a series of 25-norhopanes (NHs) (C28–C34), variable amounts of chromatographically unresolved complex mixture (UCM), and diminished concentrations of n-alkanes below ca. C20 in saturated hydrocarbon fractions of the Silurian and Carboniferous bitumens indicates that they are mixtures of heavily biodegraded oil from a former charge and slightly biodegraded oil from a later charge. The presence of C28–C34 25-NHs suggests a biodegradation level of at least PM 6 for these bitumen samples. Nevertheless, minor differences in terpane and sterane distributions between the Silurian and Carboniferous bitumen samples were observed which can be attributed to small variations in biodegradation levels. Values for the 25-NH ratio (Peters et al., 1996), gammacerane/(gammacerane + C30 hopane), C28 25-NH/C29 hopane and C29 25-NH/C30 hopane ratios indicate slightly higher levels of microbial alteration for the Silurian bitumens compared to the Carboniferous bitumens, although caution must be exercised when comparing the biodegradation intensities using molecular parameters. The Ordovician crude oil samples appear to be more severely biodegraded than the Silurian and Carboniferous bitumens, as evidenced by higher concentrations of tricyclic terpanes relative to hopanes, and pregnanes and diasteranes relative to the regular steranes, although thermal maturity effects cannot be ruled out. Geochemical correlation studies were successfully applied based on carbon isotopes and biomarkers including tricyclic terpanes and triaromatic steroids which are highly resistant to severe biodegradation (PM 6). Bulk isotopic compositions, distribution patterns and certain ratios of these biomarkers indicate that the Ordovician crude oils and the Silurian and Carboniferous bitumens originated from a single source. They were probably derived from Middle–Upper Ordovician source rocks.

Bioremediation of diesel and lubricant oil-contaminated soils using enhanced landfarming system

Lubricant and diesel oil-polluted sites are difficult to remediate because they have less volatile and biodegradable characteristics. The goal of this research was to evaluate the potential of applying an enhanced landfarming to bioremediate soils polluted by lubricant and diesel. Microcosm study was performed to evaluate the optimal treatment conditions with the addition of different additives (nutrients, addition of activated sludge from oil-refining wastewater facility, compost, TPH-degrading bacteria, and fern chips) to enhance total petroleum hydrocarbon (TPH) removal. To simulate the aerobic landfarming biosystem, air in the microcosm headspace was replaced once a week. Results demonstrate that the additives of activated sludge and compost could result in the increase in soil microbial populations and raise TPH degradation efficiency (up to 83% of TPH removal with 175 days of incubation) with initial (TPH = 4100 mg/kg). The first-order TPH degradation rate reached 0.01 1/d in microcosms with additive of activated sludge (mass ratio of soil to inocula = 50:1). The soil microbial communities were determined by nucleotide sequence analyses and 16S rRNA-based denatured gradient gel electrophoresis. Thirty-four specific TPH-degrading bacteria were detected in microcosm soils. Chromatograph analyses demonstrate that resolved peaks were more biodegradable than unresolved complex mixture. Results indicate that more aggressive remedial measures are required to enhance the TPH biodegradation, which included the increase of (1) microbial population or TPH-degrading bacteria, (2) biodegradable carbon sources, (3) nutrient content, and (4) soil permeability.

Achieving a Near-Theoretical Maximum in Peak Capacity Gain for the Forensic Analysis of Ignitable Liquids Using GC×GC-TOFMS

At present, gas chromatography–quadrupole mass spectrometry (GC-qMS) is considered the gold standard amongst analytical techniques for fire debris analysis in forensic laboratories worldwide, specifically for the detection and classification of ignitable liquids. Due to the highly complex and unpredictable nature of fire debris, traditional one-dimensional GC-qMS often produces chromatograms that display an unresolved complex mixture containing only trace levels of the ignitable liquid among numerous background pyrolysis products that interfere with pattern recognition necessary to verify the presence and identification of the ignitable liquid. To combat these challenges, this study presents a method optimized to achieve a near-theoretical maximum in peak capacity gain using comprehensive two-dimensional gas chromatography (GC×GC) coupled to time-of-flight mass spectrometry (TOFMS) for the forensic analysis of petroleum-based ignitable liquids. An overall peak capacity gain of ~9.3 was achieved, which is only ~17% below the system’s theoretical maximum of ~11.2. In addition, through the preservation of efficient separation in the first dimension and optimal stationary phase selection in the second dimension, the presented method demonstrated improved resolution, enhanced sensitivity, increased peak detectability and structured chromatograms well-suited for the rapid classification of ignitable liquids. As a result, the method generated extremely detailed fingerprints of petroleum-based ignitable liquids including gasoline, kerosene, mineral spirits and diesel fuel. The resultant data was also shown to be amenable to chromatographic alignment and multivariate statistical analysis for future evaluation of chemometric models for the rapid, objective and automated classification of ignitable liquids in fire debris extracts.

Anthropogenic and biogenic hydrocarbons in soils and vegetation from the South Shetland Islands (Antarctica)

Two Antarctic expeditions (in 2009 and 2011) were carried out to assess the local and remote anthropogenic sources of aliphatic and aromatic hydrocarbons, as well as potential biogenic hydrocarbons. Polycyclic aromatic hydrocarbons (PAHs), n-alkanes, biomarkers such as phytane (Ph) and pristane (Pr), and the aliphatic unresolved complex mixture (UCM), were analysed in soil and vegetation samples collected at Deception, Livingston, Barrientos and Penguin Islands (South Shetland Islands, Antarctica). Overall, the patterns of n-alkanes in lichens, mosses and grass were dominated by odd-over-even carbon number alkanes. Mosses and vascular plants showed high abundances of n-C21 to n-C35, while lichens also showed high abundances of n-C17 and n-C19. The lipid content was an important factor controlling the concentrations of n-alkanes in Antarctic vegetation (r2=0.28–0.53, p-level<0.05). n-C12 to n-C35 n-alkanes were analysed in soils with a predominance of odd C number n-alkanes (n-C25, n-C27, n-C29, and n-C31), especially in the background soils not influenced by anthropogenic sources. The large values for the carbon predominance index (CPI) and the correlations between odd alkanes and some PAHs suggest the potential biogenic sources of these hydrocarbons in Antarctica. Unresolved complex mixture and CPI values ~1 detected at soils collected at intertidal areas and within the perimeter of Juan Carlos research station, further supported the evidence that even a small settlement (20 persons during the austral summer) can affect the loading of aliphatic and aromatic hydrocarbons in nearby soils. Nevertheless, the assessment of Pr/n-C17 and Ph/n-C18 ratios showed that hydrocarbon degradation is occurring in these soils.

Identification of sources of tar balls deposited along the Southwest Caspian Coast, Iran using fingerprinting techniques

In 2012, a significant number of tar balls occurred along the Southwest coasts of the Caspian Sea (Iran). Several oil fields of Turkmenistan, Azerbaijan and Iran might be sources of oil spills and lead to the formation of these tar balls. For source identification, 6 tar ball samples were collected from the Southwest beaches of the Caspian Sea and subjected to fingerprint analysis based on the distribution of the source-specific biomarkers of pentacyclic tri-terpanes and steranes. Comparing the diagenic ratios revealed that the tar balls were chemically similar and originated from the same source. Results of double ratio plots (e.g., C29/C30 versus ∑C31–C35/C30 and C28 αββ/(C27 αββ+C29 αββ) versus C29 αββ/(C27 αββ+C28 αββ)) in the tar balls and oils from Iran, Turkmenistan and Azerbaijan indicated that the tar balls might be the result of spills from Turkmenistan oil. Moreover, principle component analysis (PCA) using biomarker ratios on the tar balls and 20 crude oil samples from different wells of Azerbaijan, Iran and Turkmenistan oils showed that the tar balls collected at the Southwest beaches are highly similar to the Turkmenistan oil but one of the Azerbaijan oils (from Bahar field oils) was found to be also slightly close to the tar balls. The weathering characterizations based on the presence of UCM (unresolved complex mixture) and low/high molecular weight ratios (L/H) of alkanes and PAHs indicated the tar ball samples have been significantly influenced by natural weathering processes such as evaporation, photo-degradation and biodegradation. This is the first study of its kind in Iran to use fingerprinting for source identification of tar balls.