Fingerprinting of petroleum hydrocarbons (PHC) and other biogenic organic compounds (BOC) in oil-contaminated and background soil samples.

Total petroleum hydrocarbons (TPH) or petroleum hydrocarbons (PHC) are one of the most widespread soil contaminants in Canada, the United States and many other countries worldwide. Clean-up of PHC-contaminated soils costs the Canadian economy hundreds of millions of dollars annually. In Canada, most PHC-contaminated site evaluations are based on the methods developed by the Canadian Council of the Ministers of the Environment (CCME). However, the CCME method does not differentiate PHC from BOC (the naturally occurring biogenic organic compounds), which are co-extracted with petroleum hydrocarbons in soil samples. Consequently, this could lead to overestimation of PHC levels in soil samples. In some cases, biogenic interferences can even exceed regulatory levels (300 µg g(-1) for coarse soils and 1300 µg g(-1) for fine soils for Fraction 3, C(16)-C(34) range, in the CCME Soil Quality Level). Resulting false exceedances can trigger unnecessary and costly cleanup or remediation measures. Therefore, it is critically important to develop new protocols to characterize and quantitatively differentiate PHC and BOC in contaminated soils. The ultimate objective of this PERD (Program of Energy Research and Development) project is to correct the misconception that all detectable hydrocarbons should be regulated as toxic petroleum hydrocarbons. During 2009-2010, soil and plant samples were collected from over forty oil-contaminated and paired background sites in various provinces. The silica gel column cleanup procedure was applied to effectively remove all target BOC from the oil-contaminated sample extracts. Furthermore, a reliable GC-MS method in combination with the derivatization technique, developed in this laboratory, was used for identification and characterization of various biogenic sterols and other major biogenic compounds in these oil-contaminated samples. Both PHC and BOC in these samples were quantitatively determined. This paper reports the characterization results of this set of 21 samples. In general, the presence of petroleum-characteristic alkylated PAH homologues and biomarkers can be used as unambiguous indicators of the contamination of oil and petroleum product hydrocarbons; while the absence of petroleum-characteristic alkylated PAH homologues and biomarkers and the presence of abundant BOC can be used as unambiguous indicators of the predominance of natural organic compounds in soil samples.

Assessment of the environmental risk of long-chain aliphatic alcohols.

An environmental assessment of long-chain alcohols (LCOH) has recently been conducted under the OECD SIDS High Production Volume (HPV) Program via the Global International Council of Chemical Associations (ICCA) Aliphatic Alcohols Consortium. LCOH are used primarily as intermediates, as a precursor to alcohol-based surfactants and as alcohol per se in a wide variety of consumer product applications. Global production volume is approximately 1.58 million metric tonnes. The OECD HPV assessment covers linear to slightly branched LCOH ranging from 6 to 22 alkyl carbons (C). LCOH biodegrade exceptionally rapidly in the environment (half-lives on the order of minutes); however, due to continuous use and distribution to wastewater treatment systems, partitioning properties, biodegradation of alcohol-based surfactants, and natural alcohol sources, LCOH are universally detected in wastewater effluents. An environmental risk assessment of LCOH is presented here by focusing on the most prevalent and toxic members of the linear alcohols, specifically, from C(12-15). The assessment includes environmental monitoring data for these chain lengths in final effluents of representative wastewater treatment plants and covers all uses of alcohol (i.e., the use of alcohol as a substance and as an intermediate for the manufacturing of alcohol-based surfactants). The 90th percentile effluent discharge concentration of 1.979microg/L (C(12)-C(15)) was determined for wastewater treatment plants in 7 countries. Chronic aquatic toxicity studies with Daphnia magna demonstrated that between C(13) and C(15) LCOH solubility became a factor and that the structure-activity relationship was characterized by a toxicity maximum between C(13) and C(14). Above C(14) the LCOH was less toxic and become un-testable due to insolubility. Risk quotients based on a toxic units (TU) approach were determined for various scenarios of exposure and effects extrapolation. The global average TU ranged from 0.048 to 0.467 depending on the scenario employed suggesting a low risk to the environment. The fact that environmental exposure calculations include large fractions of naturally derived alcohol from animal, plant, and microbially mediated biotransformations further supports a conclusion of low risk.

Occurrence of volatile organic compounds (VOCs) in Liverpool Bay, Irish Sea.

Surface seawater samples were collected in the Irish Sea and Liverpool Bay area from the R.V. Prince Madog during the period of 25-31 of March 2006. VOCs were purged with nitrogen, pre-concentrated on a SPME fibre and analysed immediately on a GC-MS. Target compounds quantified were halogenated (0.2-1400 ng L(-1)), BTEXs and mono-aromatics (1.5-2900 ng L(-1)), aliphatic hydrocarbons and others (0.6-15,800 ng L(-1)). Day and night sampling was performed at a single station and suggested that factors such as sunlight and tide affect the presence of many of these compounds. Sample variability was high due to the variable weather conditions at the station. Poor correlations were found between marine phytopigments and selected VOCs. Principal component analysis (PCA) analysis showed that chlorinated compounds such as 1,2-dichloroethane, 1,1,1-trichloroethane, trichloroethene, tetrachloroethene and carbon tetrachloride, predominantly from anthropogenic sources, originated from the River Mersey. Other brominated and iodinated compounds quantified were more likely to be from biogenic sources including novel marine compounds such as 2-chloropropane, 1-bromoethane and 1-chlorobutane.

Effects of ionic strength on the production of short chain volatile hydrocarbons by Dunaliella salina (Teodoresco).

The effect of ionic strength on the production of short chain volatile hydrocarbons was studied in cultures of Dunaliella salina. Axenic cultures of D. salina were grown at three different ionic strengths 0.5, 2 and 3 M of NaCl in Johnson (J/1) culture medium [Journal of Bacteriology 95 (1968) 1461] under the following laboratory growth conditions: a 12:12 h photoperiod, 300 micromolm(-2)s(-1) of photosynthetic active radiation (PAR) provided by a fluorescent lamp of 40 W combined with a 100 W incandescent lamp at 20 +/- 1 degrees C at pH 7.5. C1 to C5 hydrocarbons were detected using a head space technique and GC-FID. Cell numbers and growth rate was greatest at 2 M NaCl 4.3 x 10(6) cellml(-1) after a 15 days period of culture. Maximum hydrocarbon production was measured in the concentration of 0.5 NaCl with lower production rates in the more concentrated solutions. The principal hydrocarbon was pentane at 0.5 M but was ethane in 2 and 3 M solutions. Production rates for individual compounds ranged between 0.13 and 22 x 10(-15) microgCcell(-1)h(-1). It is suggested that the ability to produce and release volatile organic compounds of D. salina is related to osmotic conditions established by the ionic strength of growth solution.

Tracing sewage in the marine environment: altered signatures in Concepción Bay, Chile.

Lipid biomarkers are now widely used to trace organic matter in the marine environment. Selected compounds and ratios can be used to identify sources or processes. However, in a study of a particularly contaminated area, the expected signatures were not found (Mudge and Seguel, Bol. Soc. Chil. Quím. 42 (1997) 5). This site has been re-examined to determine why they were absent. The concentrations of sterols, fatty acids and alcohol biomarkers of 10 sediment cores from Concepción Bay, Chile, were quantified by capillary gas chromatography-mass spectrometry. The data obtained from 34 fatty acids, 28 fatty alcohols (C12-C30) and 32 sterols from the target study area, indicated that fatty acids from Concepción Bay sediments were the most abundant lipids (range 1.6-307 microg g(-1) dry wt) followed by sterols (range 0.02-25.3 microg g(-1) drywt). The sewage markers 5beta-coprostanol and epi-coprostanol were found in the areas close to the Penco-Lirquen disposal pipe. High bacterial activity was also present as indicated by the cholestanol, 18:1omega7, iso, anteiso and branched fatty acids and enhanced odd/even ratios of fatty alcohol biomarkers. The sediments from the centre of Concepción Bay had a greater marine/algal input characterized by brassicasterol and the marine fatty acids (20:4omega6, 20: 5omega3 22: 6omega3). The terrestrial contribution was mainly characterized by beta-sitosterol, C22-C26 fatty acids and confirmed by short/long chain ratio of the fatty alcohols. The distribution of these two markers indicates that the terrestrial matter passing through the sewage system is deficient in short chain fatty alcohols. The epi-coprostanol/coprostanol versus coprostanol/cholesterol plots also indicated selected removal of the stanols leaving apparently high cholesterol concentrations.