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    © All Rights Reserved
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    28 views18 pages

    Identification of Natural, Antropogenc and Petroleum Hydrocarbons in Aquatic Sediments

    Uploaded by

    Natalia Kovalova
    remediation Iatroscan control

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    © All Rights Reserved
    Download as PDF or read online from Scribd
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    66/4861 The Science of the Total Environment, 112 (1992) 203-219 203, Elsevier Science Publishers B.V., Amsterdam Identification of natural, anthropogenic and petroleum hydrocarbons in aquatic sediments* John K. Volkman", Daniel G. Holdsworth*, Glen P, Neill and H.J. Bavor Jr? “CSIRO Division of Oceanography, GPO Box 1538, Hobart, Tasmania 7001, Australia “University of Western Sydney, Hawkesbury Campus, Richmond, New South Wales 275: Australia (Received August Ist, 1990; accepted November 8th, 1990) ABSTRACT ‘Complex distributions of hydrocarbons occur in most aquatic sediments. Total concentrations can range from a few parts per million in non-polluted intertidal and oceanic areas to parts Per thousand in heavily contaminated estuarine, lake and near-shore environments. Tatroscan TLC-FID provides a quick assessment of the total hydrocarbon load, but capillary GC, HPLC and GC-MS are essential for obtaining detailed composition data from which information on possible sources can be derived. Alkenes from microalgae, such as n-C,. A-Ciy, and unusual C3s and Cyo isoprenoid alkenes, are often the most abundant single components in sedimentary hydrocarbon distributions. Some hydrocarbons are also produced from diagenetic transformation of functionalised lipids present in the sediment. Long-chain alkanes typical of plant waxes can be important constituents, even in marine sediments far from the coast. These distributions display a strong predominance of odd chain lengths, whereas alkane distributions in oils usually show little or no predominance of either odd or even chain lengths. However, the presence of this type of distribution in a sediment may not indicate petroleum contamination since biological sources for similar distributions are now recognised. Petroleum-derived residues are common in coastal and estuarine areas, particularly those near urban or industrial centers, This contamination is readily seen in capillary gas chromatograms of the alkanes as an unresolved complex mixture (UCM). The source of the oil can often be deduced from characteristic distributions of biomarker steranes. rearranged steranes, hopanes and methyl hopanes determined by capillary gas chromatography-mass spectrometry. Methyl hopanes are major polycyclic alkanes in oils from carbonate source rocks, such as those from the Middle East, but are uncommon in Australian oils. GC-MS fingerprinting techniques show that lubricating oils are a major source of hydrocarbon pollution in many estuaries and coastal areas around Australia, It has been estimated that natural oil seeps may also contribute as much as 10% of the hydrocarbons in the global marine environment. Examples Of this include major oil seepage in the Gulf of California and the widespread occurrence of bitumen strandings on South Australian beaches. Examples from marine and estuarine * This paper is based on work presented at the International Chemical Congress of Pacific Basin Societies held in December 1989 in Honolulu. The conference was sponsored by the Chemical Society of Japan, the Chemical Institute of Canada and the American Chemical Society. (0048-9697/92/805.00 © 1992 Elsevier Science Publishers B.V. Alll rights reserved 204 1K. VOLKMAN ET AL, environments around Australia are presented to illustrate the use of modern analytical techniques to identify, quantify and determine the origins of hydrocarbons in aquatic sediments INTRODUCTION There are many possible sources of hydrocarbons in sediments and thus their distributions vary greatly from one area to another. Biological sources include land plants, animals, bacteria, macroalgae and microalgae. Certain hydrocarbons such as phytenes, hopenes and sterenes are produced from bacterial and chemical degradation of naturally occurring lipids. Bush fires, sugar cane burn-off, vehicle exhausts and combustion products in factory emissions are also significant sources of hydrocarbons in some areas. Considerable amounts of petroleum products are discharged into the marine environment through runoff, industrial and sewerage effluents, storm water drains, shipping activities, spillages, etc, Natural oil seeps can also be important in some areas. Some of the hydrocarbons are taken up by the biota, another fraction is lost by evaporation, but much ends up in the sediments where it remains for years [1]. Significant compositional changes occur due to water washing, evaporation, chemical oxidation and biodegradation. Short- chain alkanes and simple aromatics are rapidly lost, but complex cyclic molecules such as steranes and hopanes are rarely affected and so are par- ticularly useful in correlation studies (2, 3]. It is commonly assumed that all volatile petroleum products are rapidly lost by evaporation. However, Connell [4] and Kagi et al. [5] showed that uptake and modification by the biota can also be important. The severity of oil pollution in a region can be measured from the amount of hydrocarbons found in surface sediments [6, 7]. The history of exposure can be determined from the changes in hydrocarbon concentrations with depth, after allowance is made for biodegradation and disturbances to the sediment by bioturbation and water movements [1]. Many methods have been proposed to measure the amount of petroleum in the marine environment [8]. Spectroscopic methods can provide a rapid answer, but all too often provide poor estimates and little indication of the source of the oil. Total hydrocarbons can be measured by thin-layer chromatography flame ionisation detection (TLC-FID; [9]) or by direct weighing. The amounts present may not provide a good index of the extent of contamination since contributions from biogenic hydrocarbons must also be considered. Capillary gas chromatography with its high sensitivity and resolving power is the method of choice for studying complex hydrocarbon distributions [10]. The presence of an unresolved complex mixture (UCM) of. hydrocarbons, seen as a hump in the chromatogram, can be used as a measure IDENTIFICATION OF NATURAL. ANTHROPOGENIC AND PETROLEUM HYDROCARBONS, 205 of gross pollution [11], but this is not sufficient to determine the source of pollution. Capillary gas chromatography-mass spectrometry has proven to be a particularly valuable technique for fingerprinting petroleum mixtures and for the identification of source-specific biomarkers (steranes, diasteranes and hopanes ete. [2, 3)) Although it is commonly assumed that petroleum hydrocarbons in sediments arise solely from pollution, it is possible that submarine oil seeps can be important in particular areas (e.g. [26~28]). One estimate suggests that oil seeps contribute 10% of the petroleum entering the marine environment [26]. The value of biomarkers for characterising petroleum residues was well illustrated by McKirdy et al. [28] who showed using GC-MS fingerprinting techniques that bitumens washed up on South Australian beaches could not have originated from pollution but must be due to off-shore oil seeps. There have been comparatively few studies of hydrocarbons in marine environments around Australia, and most have concentrated on a single class of compounds or addressed a specific example of chronic pollution. Several authors have studied the occurrence of polycyclic aromatic hydrocarbons [12-17]. Murray et al. [18] studied alkyl benzenes in Port Phillip Bay, Victoria, and Burns and Smith [19] presented data on total hydrocarbons. There have been several studies of biogenic hydrocarbons (e.g. [20-23]). Data on petroleum hydrocarbon concentrations in Cockburn Sound [24] and Victorian coastal waters [25] have been reported. Kerosene tainting of sea mullet in Queensland waters has been described by Connell [4]. In this paper we present data on the hydrocarbon compositions in selected environments around Australia to illustrate the range of aliphatic hydro- carbon distributions found in aquatic environments and highlight some of the compositional features that can be used to distinguish between natural and anthropogenic sources. EXPERIMENTAL Samples Surface sediment from Davies Reef (18°48’S) in the central section of the Great Barrier Reef 70 km ENE from Townsville, Queensland, Australia, were collected in precleaned glass jars using SCUBA in July 1984. The sediment consisted of coarse coral sands in an oxidising environment immediately under a coral bombe. The water depth was 4m. The sediment from Lizard Island (14°38’S) in the northern section of the Great Barrier Reef was collected in May 1985 and also consisted of coral sands. These environments are remote from the mainland and should be uncontaminated with petroleum 206 2K. VOLKMAN EF AL products. Our study was designed to determine baseline levels for hydro- carbons in these environments and to ascertain to what extent microbial Populations were able to degrade introduced petroleum hydrocarbons Surface sediments from the Derwent River and D’Entrecasteaux Channel near Hobart (45°50'S), the capital city of Tasmania, Australia, were collected using a grab sampler. Details are given by Volkman er al. [21]. These sediments provide useful models of the type of distributions to be expected in temperate and estuarine sediments that display light to heavy contamination with petroleum hydrocarbons. Sediments were extracted three times with chloroform-methanol (2:11 v/v) aided by sonication, The combined extracts were partitioned with purified water to remove salts and water-soluble material; lipids were recovered in the lower chloroform phase. The solvents were then removed under vacuum, and the lipids stored under nitrogen at ~20°C. The concentrations of total hydrocarbons and other major lipid classes were determined by analysing a portion of the total lipid extract with an Iatroscan Mk IIT TH-10 TLC-FID analyser (Iatron Laboratories, Japan), as described by Volkman et al. [9]. The sample was applied to S-III silica rods and developed in hexane-diethyl ether-acetic acid (60/17/0.5 v/v/v). Peak areas were quantified by DAPA software running on an IBM-XT computer, The automotive lubricating oil analysed was Castrol GTX. Its composition appears to be typical of most lubricating oils used in Australia, A small amount was applied to the silicic acid column and the hydrocarbons were isolated and examined as for the sediment samples. Analyses of hydrocarbons by capillary gas chromatography and gas chromatography-mass spectrometry Hydrocarbons were isolated from the total lipid extract by applying a Portion to a glass column containing silicic acid (3 g) and eluting with hexane and hexane-toluene (1:1 v/v). Each sample was analysed using a Shimadzu GC-9A gas chromatograph equipped with a FID, cool OCI-3 on-column injector (SGE, Australia) and 25m or 50m x 0.3mm i.d. methyl silicone capillary columns. Peak areas were quantified with a Shimadzu C-R3A combined computing integrator and plotter. GC-MS analyses of the hydrocarbons from the coral reef sediments were carried out using a VG 70/70 F magnetic sector instrument coupled to a Pye 204 gas chromatograph modified for capillary columns. Data were acquired using a VG 2000 data system. Other GC-MS analyses used an HP 5890 GC and 5790 MSD coupled by a direct capillary inlet. The non-polar column, injector and chromatography conditions were the same as those described above, except that helium was used as the carrier gas instead of hydrogen. IDENTIFICATION OF NATURAL. ANTHROPOGENIC AND PETROLEUM HYDROCARBONS 207 Electron impact mass spectra were acquired and processed with a 59970A Computer Workstation. Typical MSD operating conditions were. electron Fa lier, 2000 volts; transfer line, 310°C; an electron impact energy of 10 eV. 2.8 scans per second; mass range, 40-600 Da. Hydrocarbons were identified by comparison of mass specira with previous reports and by comparison of Fetention data with those obtained with standards obtained commercially or from donations. RESULTS AND DISCUSSION A number of indicators has been proposed for recognising petroleum hydrocarbons in sediments. These include: (i) high concentrations (> 100 ppm) of total hydrocarbons; (ii) C:,-Cyg n-alkanes having no odd over éven predominance; (iii) complex distributions; (iv) an unresolved complex mixture (“hump”” or “UCM”) in the gas chromatogram of the hydrocarbon Fraction: (v) thermally-mature stereoisomers of pristane and phytane: and (vi) biomarkers such as steranes and hopanes. The usefulness of each of these Parameters is examined below with reference to examples from our studies of hydrocarbons in environments around Australia Concentration of total hydrocarbons Total hydrocarbons are readily determined by weighing the hydrocarbon fraction obtained from the total extract by one of many available chromate, graphic procedures. However, accurate data can be difficult to obtain where the sample size is small. Also, elemental sulphur must be removed from the extract usually by treatment with activated copper. We have found that Jatroscan TLC-FID Provides a quick assessment of hydrocarbon content in the sub-microgram range. Care must be taken to exclude contributions from Wax esters and £-carotene, which can co-elute on the silica rods [9]: reproduc- ibility is about +8% Examples of TLC-FID chromatograms obtained from total extracts of the heavily polluted anaerobic sediments from the upper reaches of the River Derwent near Hobart are shown in Fig. 1. The total concentrations of hydrocarbons are very high (up to 4000 ppm dry wt). The river is also comaminated by effluent from a paper mill which contributes high loadings of fatty acids and triacylglycerols (Fig. 1), and with heavy metals from an electrolytic zine refinery. In these samples, hydrocarbons comprise a maior Part of the extractable organic matter (EOM), whereas the TLC-FID chro. matograms for the reef samples are more typical of unpolluted sediments in which hydrocarbons comprise < 1% of the EOM [9]. Total hydrocarbons in ihe coral sediments from Davies Reef and Lizard Island fall in the range 0.5-2 ug/g, which is similar to that found in unpolluted intertidal sediments 20). 208 DK. VOLKMAN EF AL. sire A sire Near Boyer Bridgewater Sediment Sediment pL pL | He | bel | (I i | i A 1 st | ber Il |" va i irral | Fray) Nolin Al La | SAA JW Op 1 OR 10 Fig. | latroscan TLC-FID ehvomatograns of the tot solvent extracts of sediments ffom the River Derwent near Boyer (site of 4 paper mill) and Bridgewater. 32 and 19km upstream respectively from Hobart, Tasmania. Total hydrocarbon concentrations are 4.6 and 3.4mgig dry wt Total hydrocarbon concentrations > 500 ppm, as found in the River Derwent, are clearly indicative of significant pollution. Concentrations in unpolluted intertidal and estuarine sediments may range from sub-ppm to ~ 10ppm (e.g. [20, 21). Concentrations may be two to three times higher where there are significant inputs of n-alkanes derived from higher plants. Organic-rich marine sediments may contain up to 100ppm total aliphatic hydrocarbons, but concentrations higher than this are usually due to Petroleum inputs. Values up to 1800 ppm have been reported in petroleum- contaminated surface sediments from the New York Bight [29]. Concen- trations from 4 to 350 ppm were found in Puget Sound sediments [30], and an average concentration of 11.7 ppm was recorded for silts and clays from the Gulf of Mexico [31]. The higher values were associated with polluted samples, From these data, it is clear that the concentration of hydrocarbons from biogenic sources may exceed that from pollutant sources where the total concentration is

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