Petroleum Product Identification in Environmental Samples: Distribution Patterns of Fuel-Specific Homologous Series Yakov Galperin, Henry Camp Identification

of fuel-type in environmental samples (hydrocarbon fingerprinting) is one of the major objectives of forensic investigations conducted at many of the petroleumcontaminated sites throughout the country. Among analytical methods commonly used to identify fugitive refined petroleum products, are those that focus on hydrocarbon grouptype analysis, such as alkanes, polynuclear aromatic hydrocarbons (PAH) and the polycyclic alkanes, often referred to as biomarkers. These classic methods are included in the analytical arsenal of most laboratories conducting fuel fingerprinting. Basic principles of their application have been exhaustively examined in this column by Battelle researchers. Alkane distribution patters are routinely obtained using gas chromatography with flame ionization detection (GC/FID). For petroleum products that have not undergone noticeable biodegradation, this method provides an adequate procedure for fingerprinting and fuel recognition based on the n-alkane homologous series. However, GC/FID is significantly less useful for identification of other hydrocarbon groups, which is often necessary for petroleum product fingerprinting in weathered environmental samples. Conventional analytical methods for identification of isoprenoids, PAH and biomarkers which are commonly used in characterizing crude oil, are of limited utility for light and some middle distillate fuels. The serious limitations for the application of normal alkanes arises from the fact that upon release into the environment, refined petroleum products are subject to various weathering changes. In weathered products, most n-alkanes could be lost due to biological degradation, whereas distribution of the more recalcitrant isoprenoids and PAH may not provide conclusive information on the source or type of fugitive fuel. Recent investigations demonstrated that the cyclohexane homologous series of hydrocarbons also exhibits fuel-specific distribution patterns that allow for fingerprinting of weathered fugitive fuels. Fuel-specific distribution patterns Crude oil contains a wide range of hydrocarbons from light gases to heavy residue. At the refinery, crude oil is separated by distillation into three main products: naphtha, middle distillate and bottoms fraction. Naphtha is mainly used for motor gasoline and processed further for octane improvement. The middle distillate can actually be

separated into two categories consisting of kerosene range products (light-end) and diesel range products (heavy-end). The light-end products are used for specialty solvents (mineral spirits, stoddard solvent, etc), certain jet fuels and light diesel fuels (diesel #1). The heavy-end middle distillates are used for diesel fuels (diesel #2), some jet fuels and heating oils. Based on the systematic studies of different commercial and military fuels, it was determined that in addition to a well-known alkane pattern, cyclohexane homologous series also exhibit characteristic distribution patterns. Examples of alkane and alkylcyclohexane patterns for three common fuels are shown in Figures 1-3. The alkylcyclohexane distribution in gasoline (Figure 1) exhibits an asymmetric rapidly decreasing pattern from methylcyclohexane to heptylcyclohexane. Jet propulsion fuel Jet A (Figure 2) is characterized by a distribution pattern in the range from methylcyclohexane to decylcyclohexane with the maximum at butylcyclohexane. Diesel fuel exhibits alkylcyclohexane pattern from methylcyclohexane to tridecylcyclohexane with maximum at pentylcyclohexane (Figure 3). The range of hydrocarbons in each product is determined by its boiling range, whereas the distribution pattern reflects its application-specific formulation. Since the composition of modern fuels is controlled by stringent manufacturing specifications, the range and distribution pattern of each fuel varies only slightly, depending on the composition of crude oil feedstock and refining practices used in manufacture. Fuel-type characterization in weathered samples Distribution patterns shown demonstrate that alkylcyclohexane distribution patterns are as fuel-specific as are the alkane distributions. The main advantage in utilizing alkylcyclohexane patterns for hydrocarbon fuel recognition is that alicyclic compounds are more resistant to environmental alteration and could be detected in a sample even when most of the alkanes are degraded. Two case studies illustrating the application of alkylcyclohexane pattern recognition for weathered environmental samples are summarized below. Case 1. Shown in Figure 4 is an alkane distribution pattern in the product sample. The product lost most of n-alkanes due to weathering in the subsurface environment. The group of peaks identified on the chromatogram represents isoalkanes, whose distribution suggests the presence of diesel fuel. Because of the alkane reduction, it is not apparent if other middle distillate products are also present. However, evaluation of the alkylcyclohexane pattern confirms that the product consists entirely of diesel fuel. Case 2. Alkane distribution patterns of two samples collected at the same site are shown in Figure 5. Sample A have lost most of n-alkanes and appears to represent a severely weathered product, whereas a high abundance of n-alkanes in sample B attests to its relatively unaltered nature. A significant difference in the degree of product weathering does not allow evaluating their source relationship. However, a comparison of the alkylcyclohexane distributions (Figure 6) clearly indicates that both samples represent the same fuel-type.

Figure 1. Gasoline alkane (a) and alkylcyclohexane (b) distribution patterns

Response_ 09190036.D\FID1A 420000 400000 380000 360000 340000 320000 300000 280000 260000 240000 220000 200000 180000 160000 140000 120000 100000 80000 60000 40000 20000 0 5.00 10.0015.0020.0025.0030.0035.0040.0045.0050.0055.0060.0065.00 Time

(a)

100 90 80
Relative Abundance, %

70 60 50 40 30 20 10

(b)

Undecanylcyclohexane

Dodecanylcyclohexane

Pentylcyclohexane

Nonylcyclohexane

Propylcyclohexane

Hexylcyclohexane

Heptylcyclohexane

Decylcyclohexane

Butylcyclohexane

Octylcyclohexane

Ethylcyclohexane

Tridecanylcyclohexane

Methylcyclohexane

Figure 2. Jet A fuel alkane (a) and alkylcyclohexane (b) distribution patterns

Response_

n-C12
150000 140000 130000 120000 110000 100000 90000 80000 70000 60000 50000 40000 30000 20000 10000 0

09190041.D\FID2B

(a)

n-C16 n-C9
5.00 10.0015.0020.0025.0030.0035.0040.0045.0050.0055.0060.0065.00

Time

100 90 80
Relative Abundance, %

70 60 50 40 30 20 10

(b)

Undecanylcyclohexane

Dodecanylcyclohexane

Pentylcyclohexane

Nonylcyclohexane

Propylcyclohexane

Hexylcyclohexane

Heptylcyclohexane

Decylcyclohexane

Butylcyclohexane

Octylcyclohexane

Ethylcyclohexane

Tridecanylcyclohexane

Methylcyclohexane

Figure 3. Diesel fuel alkane (a) and alkylcyclohexane (b) distribution patterns
Response_ 09190044.D\FID1A

120000 110000 100000 90000 80000 70000 60000 50000 40000 30000 20000 10000 0

n-C14 (a)

n-C21 n-C9

5.00 10.0015.0020.0025.0030.0035.0040.0045.0050.0055.0060.0065.00 Time

100 90 80
Relative Abundance,%

(b)

70 60 50 40 30 20 10
Undecanylcyclohexane Dodecanylcyclohexane Pentylcyclohexane Nonylcyclohexane Propylcyclohexane Hexylcyclohexane Heptylcyclohexane Decylcyclohexane Butylcyclohexane Octylcyclohexane Ethylcyclohexane Tridecanylcyclohexane Methylcyclohexane

Figure 4. Product sample alkane (a) and alkylcyclohexane (b) distribution patterns
Abundance Ion 700000 650000 600000 550000 500000 450000 400000 350000 300000 250000 200000 150000 100000 50000 0 5.00 Time--> 10.00 15.00 20.00 25.00 30.00 35.00 40.00 85.00 (84.70 to 85.70): Y4504.D

Pr

i-C15 Ph i-C18 i-C15

(a)

100 90 80
Relative Abundance, %

(b)

70 60 50 40 30 20 10
Undecanylcyclohexane Dodecanylcyclohexane Pentylcyclohexane Nonylcyclohexane Propylcyclohexane Hexylcyclohexane Heptylcyclohexane Decylcyclohexane Butylcyclohexane Octylcyclohexane Ethylcyclohexane Tridecanylcyclohexane Methylcyclohexane

Figure 5. Product samples alkane distribution patterns

Abundance Ion 100000 95000 90000 85000 80000 75000 70000 65000 60000 55000 50000 45000 40000 35000 30000 25000 20000 15000 10000 5000 0 20.00 25.00 30.00 35.00 40.00 45.00 50.00 55.00 60.00 65.00 70.00 75.00 80.00 85.00 Time--> 85.00 (84.70 to 85.70): V4978.D

Sample A

Abundance Ion 70000 65000 60000 55000 50000 45000 40000 35000 30000 25000 20000 15000 10000 5000 0

n-C11
85.00 (84.70 to 85.70): V4687.D

Sample B

20.00 25.00 30.00 35.00 40.00 45.00 50.00 55.00 60.00 65.00 70.00 75.00 80.00 85.00 Time-->

Relative Abundance, %

Relative Abundance, %

100

100

10 0
Methylcyclohexane Ethylcyclohexane Propylcyclohexane Butylcyclohexane Pentylcyclohexane Hexylcyclohexane Heptylcyclohexane Octylcyclohexane Nonylcyclohexane

20

30

40

50

60

70

80

90

10

20

30

40

50

60

70

80

90

Methylcyclohexane

Ethylcyclohexane

Propylcyclohexane

Butylcyclohexane

Pentylcyclohexane

Hexylcyclohexane

Heptylcyclohexane

Octylcyclohexane

Nonylcyclohexane

Figure 6. Product samples alkylcyclohexane distribution patterns

Sample B

Sample A

Decylcyclohexane

Undecanylcyclohexane

Dodecanylcyclohexane

Tridecanylcyclohexane

0
Decylcyclohexane Undecanylcyclohexane Dodecanylcyclohexane Tridecanylcyclohexane