Forensic Geochemistry - Exploration Technologies, Inc.

Forensic Geochemistry – The Key to Accurate Site Characterization By Victor T. Jones III, Patrick N. Agostino (Exploration Technologies, Inc., Houston, Texas) ABSTRACT The majority of environmental site investigations are conducted using a limited number of randomly placed boreholes and/or monitoring wells in an attempt to characterize the subsurface contamination. Although costs often dictate the approach and work plan executed during an investigation, the key to an accurate site characterization is the use of forensic geochemical techniques. A well formulated work plan including the use of forensic geochemical methods can accurately delineate subsurface contamination, and ultimately be more cost-effective. Surface geochemical techniques and high resolution capillary gas chromatography analyses can be used to map the locations, areal (horizontal) and vertical extents, and geometries of subsurface petroleum hydrocarbon contaminant plumes. Source areas, migration pathways and relative ages of products released on a site can also be determined. A case study is presented to demonstrate the value of various forensic geochemical techniques in the proper characterization of subsurface contamination. Previous environmental investigations conducted at a large refinery site, using randomly placed boreholes and monitoring wells, indicated a very large liquid crude oil contaminant plume along the south boundary of the facility. This plume was also projected to continue offsite into an adjacent residential area. When crude oil was discovered seeping into the adjacent bay, it was assumed the source was related to the south boundary plume. A surface geochemical soil vapor survey was initially conducted to delineate the areal extent of subsurface contaminant plumes on the facility. Over 3150 soil vapor samples were collected on a 30-meter (approximately 100-foot) grid encompassing 75% of the refinery. Soil vapor constituent (contoured) plume maps were constructed to determine the areal extent of different hydrocarbon compounds. Product type “signatures” were also determined using high resolution capillary gas chromatography (HRCGC) analyses performed on the soil vapor samples. High resolution soil vapor chromatograms showed several different petroleum products had been released on the refinery over a long period of time, and the contaminant plumes were discontinuous. Soil vapor plume maps were used to locate 105 monitoring wells. Sediment and fluid samples (groundwater and NAPL) collected from the monitoring wells were also analyzed using HRCGC. The HRCGC fingerprints from sediment and fluid samples confirmed that several distinct products had been lost at different portions of the refinery. The vertical distribution of contaminants was also determined from samples obtained/analyzed in the monitoring wells. Several wells contained more than one product type and/or a mixture of products at different stratigraphic intervals. Data obtained from the soil vapor survey and monitoring wells allowed for delineation of both the horizontal (areal) and vertical extent of specific contaminant plumes and localized “pods”. The HRCGC data, when integrated with the geology/hydrogeology, allowed for a better understanding of the distribution of individual crude oil and refined petroleum product pods. Chemical fingerprinting (HRCGC) of vapors, sediment and fluids was essential in the identification of distinct plumes/pods on the refinery. The “pods” containing crude oil appear to have a common (relatively early) origin. The recent releases included refined products (predominantly gasoline additives) mixed with older crude oil. Two “new” contaminant plumes were found along the south boundary, northeast of the area defined by previous studies. These plumes contain straight run gasoline and alkylation products. The results of this study indicate that earlier estimates of free product (NAPL) contamination were excessive. Using a forensic geochemical approach, an accurate assessment of the facility (and product volume) was performed. The source(s) of liquid contaminants seeping into the bay are local and unrelated to the south boundary contaminant plume, identified during previous studies. It was also determined that the adjacent residential area contains only minor subsurface contamination.

1.0 Introduction In 1959, a residential area located adjacent to the south boundary of the subject refinery was found to be impacted by petroleum hydrocarbons. Following the extension of the refinery boundary into the residential area in 1971, more than 225,000 barrels of liquid product were recovered from this impacted area within four years. Subsurface contamination on the facility was characterized to some extent in 1990 using a limited number of randomly placed boreholes and monitor wells. Data obtained from this study found liquid product, ranging up to 2 meters in thickness, over a large portion of the south boundary. Calculations of lost product volumes, based on a contour map constructed from data obtained from these monitor wells suggested that upwards of 900,000 barrels of product might be present within the impacted area. The depth to ground water ranges from one to over 14 meters below ground surface, and decreases towards the west and south. Potentiometric surface maps indicate groundwater flow is mainly towards the south boundary, although there is some component of flow towards the western boundary. In 1998, liquid phase hydrocarbons began to migrate into the bay near the southwest corner of the refinery. A series of closely-spaced monitor/recovery wells were installed along the southwest boundary in an attempt to prevent this plume from contaminating the bay. Because of the potential for westward flow, it was assumed that the south boundary contamination had somehow migrated to the bay. The current (subsequent) geological evaluation of the available borehole and monitor well data indicated a complex sequence of interbedded coquina, shale, and sand strata existed in the near subsurface environment. This sequence of sedimentary rocks, in general, strikes (trends) east-west and dips to the south. The sand strata appear to be poorly cemented, and the coquina strata contain vugular, cavernous, and solution channel porosity/permeability. The solution channel porosity, fractures, and caverns in the coquina appear to allow for high mobility of groundwater and liquid phase hydrocarbons, both horizontally and vertically. Porosity and permeability in the various strata (especially coquina) are usually discontinuous. Liquid product and dissolved phase contaminants migrate along zones of relatively high porosity and permeability controlled by the environments of deposition of the sand and carbonate strata. Within the coquina environment discontinuous lateral and vertical migration pathways exist. In order to design an effective remediation solution, a thorough assessment of the horizontal and vertical extents of the contamination was conducted utilizing a multi-phase work program. The program included: 1) the collection and analysis (“fingerprinting”) of fluid samples from existing monitor and recovery wells, 2) the delineation of the horizontal (using soil vapor surveys) and vertical (using boreholes and monitor wells) extent of the contamination, 3) a determination of the subsurface geology (using borehole data), 4) the mapping of migration pathways along which contaminants move through subsurface strata, and 5) a determination of the products released at the facility (historical information). 2.0 Fingerprinting of Fluid Samples from Existing Monitor Wells Liquid product and water samples were collected from 30 preexisting monitor wells. Selected chromatograms of the free product from sixteen (16) of these preexisting monitor wells on Plate 1 have been grouped into four subgroups and shown as Figures 1 to 4 for evaluation and comparison with one another and with the preexisting product thickness contour map generated from these wells. Results of this high resolution capillary gas chromatography analyses of liquid product samples from these monitor wells indicate the presence of several completely different products. The liquid products show varying levels of weathering, with some minimally (near the bay boundary) and some severely biodegraded (on the south boundary). Several samples also show subordinate amounts of other products, including gasoline range compounds, gasoline, diesel fuel oil, etc. Some of the wells appear to contain a straight run gasoline (a distillate cut with no blending of additional process streams). The crude oils are distinguished mainly by their relative isoprenoid concentrations. Essentially five crude oil types and four different gasoline types were identified from the high resolution capillary GC data. Although a discussion of this complexity is beyond the scope of this paper, a limited discussion regarding some of the major differences follows. For example, Monitor well SB-3 on the South Boundary is located in the heart of the existing product recovery system (see Plate 1, Figure 1), where approximately 300 BBLS/day are recovered from pits dug just to the west

of this well. This sample is a very biodegraded crude oil showing a large unresolved hump and a nearly complete lack of normal paraffins. This sample also contains a very subordinate quantity of cycloparaffins. SB-4 just to the east of SB-3 is dominated by alkylates such as 2,2,4-TMP (Trimethylpentane), which is not a natural component of unprocessed crude oils. This sample does contain a small quantity of the very weathered crude oil found in SB-3. Sample SB-2 to the west of SB-3 is dominated by cycloparaffins rather than alkylates, but does also contain a subordinate quantity of the very weathered crude oil which dominates SB-3. Sample SB-1, which lies completely outside of the product thickness contours on Plate 1 is dominated by a minimally degraded and different crude oil that obviously has nothing in common with the crude recovered from the SB-3 area. This sample also contains a small amount of gasoline. As shown by Figure 2, the product, which began to seep into the bay is a minimally degraded crude oil mixed with gasoline, similar to SB-1. Clearly, these Bay area samples cannot be derived from the South Boundary products, which have no gasoline and a much more weathered crude of a different origin. Samples B-2 and B-4 have the largest percentage of gasoline, with B-4 being about a 50/50 mix. Interestingly enough, B-1 is a different crude oil than either of the other two and contains no gasoline. Samples B-2 and B-4 suggest the possibility of two separate gasoline-type plumes. This suggestion is confirmed by the soil gas survey data. It is also very interesting to look at the samples on the South East Boundary, which were used to define the eastern portion of the contour thickness map. Samples SE-1 and SE-3, shown in Figure 3, are dominated by straight-run gasoline with a small amount of weathered crude, while SE-2 and SE-4 are dominated by cycloparaffins. SE-4 also contains some alkylates. All four of these samples contain a subordinate quantity of the weathered crude oil, but are certainly not a main source for the oil being recovered near SE-3. These product samples indicate that the product in the eastern portion of the refinery is not related to the product found on the South Boundary. Thus indicating that the product thickness contour map needs to redrawn with a separation between these areas. As shown by Figure 4, none of the samples analyzed from the Central areas inside of the refinery can provide sources for either the Bay or South Boundary areas. Sample C-1 and C-2 are both from alkylate streams, while C-3 is dominated by a gasoline and a small quantity of degraded crude oil which could be related to the South Boundary contamination, and C-4 is dominated by a moderately degraded crude oil (different from any of the other crudes) with a subordinate quantity of a different gasoline containing alkylates. The most important conclusion to be drawn from these high resolution capillary gas chromatograms is that the contour map of the product thickness which suggests one large plume is actually a combination of many different products. These products must be contained in separate localized pods that are not connected chemically. Most important, it shows that the oil contamination currently being recovered at the bay is not related to the oil being recovered along the south boundary or from any of the known areas of contamination located inside the refinery. The bay product is a mixture of a fairly fresh crude oil with some light finished gasoline, whereas the south boundary product is a very old and weathered crude oil. Product samples collected on the bay boundary appear to have common parent product sources, which contain minimally biodegraded topped crude oil (after distillation-gasoline range compounds have been removed) and varying amounts of gasoline. The gasoline product portion of these samples ranges from approximately equal (50/50) to the crude, to somewhat more than 50 percent of the sample. Although these samples contain a common gasoline type, varying levels of weathering are apparent. Sample B-4 contains the least weathered, common gasoline product, with the gasoline contribution dominant over the crude in this sample. This analysis of the pre-existing products indicates that new boundaries for these product contamination pods must be redefined by additional monitor wells. As discussed below, the best method for determining the location for these additional monitor wells is to conduct a soil vapor survey in order to determine the horizontal extent of the individual contaminated areas.

3.0 Soil Gas Survey A surface geochemical survey, consisting of over 3150 soil vapor samples was conducted over the refinery to delineate the areal extent of subsurface contaminant plumes on the facility. The soil vapor samples were collected at a depth of approximately one meter on a uniform staggered sampling grid containing approximately 30 meters between sampling locations. These samples were sent to Exploration Technologies, Inc.'s Houston, Texas, USA laboratory and analyzed by FID gas chromatography to determine C1-C4 (methane, ethane, propane, and butanes) and C5+ (pentane-xylenes+) hydrocarbons and CO2 concentrations. Experience over many years has demonstrated that this particular combination of light (C1-C4) and gasoline range vapors (C5+) coupled with the two biogenic gases (methane and carbon dioxide) provide the most cost effective soil gas components for locating leaks and their associated cones of dispersion formed as the liquid products seep into the ground and migrate away from the leak or spill. Vapors associated with migrating underground plumes of liquid products can be detected by their vapor plumes, which rise vertically from the subsurface contamination towards the surface. Previous surveys using the light hydrocarbons have shown that the methane/ethane, ethane/propane and the iso/normal butane ratios are often very useful because these light gases are contained as trace components in the original crude oils that are processed by the refinery. Oil and gas reservoirs normally exhibit methane/ethane values less than 10 for oil reservoirs, around 20 for gas condensates and values ranging from 20 up to 400 – 500 for very dry gas reservoirs, (Jones and Drozd, 1983, Jones et al., 2000). In contrast, coal gases and biogenic gases are the only natural gases, which have ratios generally exceeding 1,000 to 10,000, or even 100,000 to one. As discussed below, hydrocarbon contaminated sediments provide a special case of natural biogenic gas generation. Whenever product is introduced into the ground, the first reaction is an oxidation reaction in which aerobic bacteria convert hydrocarbons into CO2, hence the usefulness of CO2 for mapping hydrocarbon spills. Once the free oxygen is used up by these reactions, other microbes become active and start to consume the available oxygen bound in NO2 and then in SO2. When all available oxygen is consumed the system becomes anaerobic and the generation of anaerobic methane begins. This process is very important because the consumption of all available oxygen generally only occurs in very close proximity to the most contaminated sediments. Because of this process, methane is only generated mainly in the deepest and most contaminated sediments, and even though it is not an original portion of the spilled fuel, it becomes the most useful, single component one can measure in a soil gas survey. Extensive, previous surveys (Jones and Agostino, NGWA, 1998) have demonstrated that drilling on the centers of the methane anomalies provides the greatest potential for drilling in the center of the most contaminated sediments. This, of course, has the decided benefit of also finding the free products, which are usually the root source of the contaminated sediments. In the event that a new spill has occurred, methane, or its absence can also be useful. Whenever new spills occur, the local soil bacteria have not had an opportunity to acclimate to their new conditions. Bacteria generally require about 14 days to acclimate. The initial diagenesis process is always oxidation, which has to proceed first, before anaerobic degradation can begin. This means that there is very little methane present in a new spill, and that very little is generated during the first two weeks to a month. Once acclimated however, the process works very well, and within one or two additional months, the levels of biogenic methane can easily approach 200,000 ppm (20%). Very mature spills of degradable products, such as gasoline, can achieve soil gas methane levels as high as 60% to 70%. This biogenic methane drives the methane/ethane (C1/C2) ratio to very large values, which are very useful for distinguishing very old contamination plumes from very recent contamination events. In contrast to methane, ethane, propane and butanes (iso and normal) are never generated biogenically. Background values away from petrogenic sources are generally less than 10 ppb (< 0.010 ppm). These light gases always indicate the presence of some type of hydrocarbon fuel. Although ethane, propane and butane are mainly removed in the refinery and sold as separate products because of their value, their solubility in the crude oil (and in the processed products, such as gasoline, diesel, naphtha, etc.) keeps them from being removed entirely from the crude and processed products. Thus they still remain as very volatile tracers that allow the mapping of vapor trails associated with products, which may have leaked from the refinery facilities. Their main distinction as dissolved phase components is that they have an inverse relationship as compared to their occurrence in natural oil and gas reservoirs. In gasoline, normal butane is usually the largest in concentration,

followed by iso-butane, propane and then ethane. However, once exsolved from the liquid product, these light gases are always vapors at normal temperatures and pressures, and thus can be detected at some distance from the free product (because of their volatility). The C5+ (pentane-xylenes+) hydrocarbon analyses yield a quantitative measure of the concentration, by volume, of gasoline range petroleum product vapors present in near surface soils. These C5+ hydrocarbons dissipate more slowly than lighter fraction (C1-C4) compounds. Due to the large number of individual compounds present in gasolines, diesels, jet fuels, etc., this method uses a capillary column that requires a temperature programmed operation. This group of compounds provides very diagnostic product identifications. Laboratory results for all C1-C4 and C5+ hydrocarbons are measured in parts per million by volume (ppmv). Soil vapor constituent (contoured) plume maps were constructed to determine the areal extent of different hydrocarbon compounds. Color dot maps were also constructed for methane, ethane, propane, iso-butane, normal-butane, C5+ hydrocarbons and carbon dioxide to demonstrate the magnitude and compositional variations of the vapors detected at each sample site. The size of each dot represents the magnitude of each soil gas sample and the color of each dot shows the hydrocarbon compositions as defined by selected ratios. The methane/ethane ratio was used for the methane map, the ethane/propane compositional ratio was used for the ethane and propane maps, and the iso/normal butane ratio was used for the butane maps. The ethane/propane compositional ratio was also used for the C5+ and for the CO2 maps. The cuts for the compositions (colors) and magnitudes (dot size) are shown on the respective maps. The light gas ratios used on the color dot maps are controlled mainly by their parent products, although, they can change slightly (volatilize) during weathering and water washing in the environment along their migration pathway. Changes due to weathering and water washing are more pronounced for product exposed very near to the surface, but are usually second-order changes when compared to differences related to product compositional differences. Lower numerical ratios (for all three ratios) generally tend to indicate fresher products (that are closer to the release point), while the larger numerical ratios tend to increase as the products weather. This is generally true of all three of these independent ratios. Within these constraints, one can map these ratios in the soil gas data in order to determine if they form coherent spatial clusters of similar composition, thereby indicating control primarily by the subsurface contamination. Unlike soil gas surveys conducted only with field screening instruments, there are no false anomalies when these components are properly collected and analyzed using laboratory gas chromatography methods. These specific gases do not occur naturally and can only be sourced by a petroleum product. The presence of elevated levels of these components in the shallow soil gas indicates the presence of a shallow source at one meter in depth where they were measured. They will either represent a cone of dispersion from a local source (leak or spill) or they must represent a vapor trail from the migration pathway followed by subsurface contamination that underlies the soil gas site. When combined with continuous vertical measurements of the contamination within specific boreholes and monitor wells, it is possible to provide a three-dimensional picture of the contaminated sediments providing the migration pathways. The vertical distribution of the subsurface contamination can only be determined by analyzing the vertical distribution of the petroleum products from soil cores collected during drilling. It cannot be determined from only soil gas data alone. 4.0 Monitor Wells Locations for one hundred and five (105) monitor wells were selected based upon the soil vapor plume maps. Soil core samples were collected continuously from the ground surface to groundwater in all boreholes. Seventy-two of the 105 monitor wells (69%) encountered measurable levels of product ranging in thickness from 0.005 meters to as much as 1.87 meters. A revised product thickness map is shown on Plate 2 and a normal butane contour map is shown on Plate 3, which also contains an interpretative summary of the products found in the monitor wells. These monitor wells were used for sampling the dissolved phase and liquid phase (free product) hydrocarbons from the groundwater and rock strata and for fingerprinting the specific products found in the wells. The data obtained from these monitor wells also includes subsurface stratigraphy, depth to liquid product and/or groundwater and information on hydrocarbon contaminant concentrations of rock cuttings and cores collected

from various depths. The boreholes have been utilized to establish the vertical extent of petroleum contaminants in the subsurface strata at depth. The soil vapor surveys identified the horizontal limits, and monitor wells defined the vertical extent of the petroleum product contaminant plumes, and served as the basis for locating potential product recovery wells. These wells can be used to monitor and measure product, dissolved and vapor phase hydrocarbons during future remediation activities. There is no relationship between the values exhibited by the soil gases and the thickness, or abundance of free product at depth below the soil gas anomalies. The saturated vapor pressure associated with liquid free product is the same for a film (“sheen”) as for several meters of free product. The saturated vapor pressure is controlled by solubility of the specific gas in the liquid product. It will vary with temperature (similar to water vapor pressure with its associated liquid phase) but will not change in association with changes in the thickness of the liquid product. As noted above, these vertical changes in thickness or volume can only be ascertained by measurements made in monitor wells. The value of the soil gas data is to provide horizontal localization of the anomalous areas so that random drilling can be avoided. 5.0 Discussion and Results Surface geochemical methods were used to map the location of subsurface petroleum hydrocarbon plumes, their boundaries and areas where new releases have occurred. A total of over 3150 four-foot soil vapor samples were collected on a 30 meter grid spacing covering approximately 75% of the refinery area. Soil gas component contour maps were used to place/drill 105 monitor wells. Data from the soil gas surveys and wells allowed for delineation of both the horizontal and vertical extent of specific plumes and localized pods of subsurface contamination. High resolution capillary gas chromatography conducted on the vapor, residual, dissolved and free phase hydrocarbon contamination allowed for specific products to be identified. With this approach the hydrogeology could be better characterized; both crude oil and refined petroleum products were recognized and individual product pods were better defined. The Bay area where the finished gasoline/crude oil contamination occurs is clearly defined by the soil gas data. The origin of the two soil gas plumes is no longer a current source area. A steam-power generation plant is currently located where this plume originated, removing the potential for an active source. The contamination from this former source area has moved down gradient toward the bay, where seepage occurs at the outcrop. Monitor wells drilled on the soil gas anomalies confirmed the migration pathways and defined a current source area where this contamination has pooled. As shown in Plate 3, new boundaries defining the locations of known contamination pods have been defined along the south boundary using specific chemical fingerprints, which can distinguish the different pods of crude oil and/or refined products. The differences in the areal extents of the different contaminant plumes appear to be controlled by their location within different terraces, supplemented by variable stratigraphy, porosity, permeability and possibility fractures in the carbonate bedrock. These factors also account for the discontinuous lateral and vertical migration pathways. Most of the crude oil in these pods is very weathered and appears to have a common origin, suggesting a relationship with the earliest releases reported, which date back to the 1970’s. The newer refined products, mixed with the older crude, are mainly gasoline additives and intermediate products (not finished gasolines). Most of these newer pods are found on the second to youngest terrace, which appears to be partially controlling downdip migration. Two new contaminant plumes have been defined along the southeast boundary. One of these newly defined plumes contains straight run gasoline, and the second contains nearly pure alkylation products. Numerous cones of dispersion associated with areas containing leakages and/or spills of refined products are clearly defined by the soil gas plume maps. One of the most serious leak areas occurs in the main process area, where percent levels of various light gases were found in close proximity to an active leak defined by this survey. The thickness of the vadose zone in these areas has thus far reduced the impact to the ground water under these cones of dispersion. Mitigation of this active leak will reduce product loses and prevent future environmental problems. Left undiscovered and untreated, such leakage areas would become serious problems in the future.

The monitor wells installed in the adjacent town contained very little product contamination. Slightly elevated ground water elevations were defined in these offsite well which will serve to retard migration of free phase product from the south boundary of the refinery. No further action was required within the town. Using a non-random soil gas/monitor well grid approach, it was possible to determine specific fingerprints for the products found in the monitor wells and to ascertain that the large plume mapped by random drilling was actually made up of many separate product pods. Even more important, this technology has demonstrated that these earlier estimates for product contamination were excessive. New estimates based on the more accurate mapping of the facility suggest the actual volume of product in the subsurface probably ranges from 96,000 to 192,000 barrels for the entire refinery. Results of the reassessment defined the location of the contamination seeping into the bay. In addition, the data allowed for the determination that none of the contaminated areas found on the northern, upper terraces, or along the south boundary of the refinery are moving toward the bay. This study also showed that the adjacent town contains only minor contamination, and that further offsite contamination could be prevented with appropriate remedial action. 6.0 References Jones, V.T., and R.J. Drozd, 1983. Predictions of Oil or Gas Potential by Near-Surface Geochemistry, AAPG Bull., V. 67, pp 932-952. Jones, V.T., and P.N. Agostino, 1998. Case Studies of Anaerobic Methane Generation at a Variety of Hydrocarbon Fuel Contaminated Sites. NGWA Petroleum Hydrocarbons and Organic Chemicals in Ground Water: Prevention, Detection, and Remediation. Jones, V.T., Matthews, M.D., and D. Richers, 2000. Light Hydrocarbons in Petroleum and Natural Gas Exploration. Handbook of Exploration Geochemistry: Geochemical Remote Sensing of the SubSurface. Vol. 7, Chapter 5, Elsevier Science Publishers, Editor Martin Hale.

Authors Dr. Victor T. Jones, III, President, Exploration Technologies, Inc. has been actively involved in the research and development of surface geochemical techniques to both exploration and environmental applications for more than 27 years, initially at the Superior and Gulf Oil Companies, Woodward Clyde Oceaneering and at ETI. Dr. Jones has a Ph.D. in physics from Texas A&M University. Dr. Patrick N. Agostino, Vice President, Exploration Technologies, Inc. has more than 26 years of experience in the petroleum exploration and environmental industries. He has directed various baseline environmental studies on oil and gas producing properties, refinery and chemical facilities for the purpose of remediating and/or bringing such sites into compliance with regulatory agencies. Dr. Agostino has a Ph.D. in Geology from Renssealer Polytechnic Institute.

P-110

P-100

C-1

P-80

C-2 P-70

S-I-1 P-17

C-4

S-I-2

S-I-3

P-62

C-3

P-140 M-I-1

P-61

M-I-2 M-I-3 M-I-4 INC-1 M-I-5 M-I-6

B-1

SE-4

INC-2

M-I-7

SE-3

M-I-8 M-I-9 M-I-10 M-I-11

B-2

M-I-12 M-I-13 INC-3

P-60

P-16 P-15 P-14 P-13 P-12 P-11

B-3

1.5

INC-4

1.0

0.5

0

MW-6 B-1

P-10

B-4

P-30

B-2 P-31 P-32 P-40

T-50

SE-1

B-3 P-20

SE-2

SB-4 LEGEND SB-1

N

SB-2 SB-3

Monitor Well Soil Gas Sampling Location

0

100 SCALE - METERS

200 1.5

Product Thickness (1990)

Plate 1

P-110

P-100

C-1

P-80

C-2 P-70

S-I-1 P-17

C-4

S-I-2

S-I-3

P-62

C-3

P-140 M-I-1

P-61

M-I-2 M-I-3 M-I-4 INC-1 M-I-5 M-I-6

B-1

SE-4

INC-2

M-I-7

SE-3

M-I-8 M-I-9 M-I-10 M-I-11

B-2

M-I-12 M-I-13 INC-3

P-60

P-16 P-15 P-14 P-13 P-12 P-11

B-3

INC-4

MW-6 B-1

P-10 B-2

B-4

P-30

P-31 P-32 P-40

T-50

SE-1

B-3 P-20

SB-4 SB-1

N

0

100 SCALE - METERS

200

SB-2 SB-3

SE-2

PRODUCT THICKNESS (Meters)

> 1.0 0.7 - 1.0 0.4 - 0.7 0.1 - 0.4 NP - 0.1 Plate 2

PLATE 3. REFINERY SITE - HRGC/FID OF SELECTED FREE PRODUCT SAMPLES AND N-BUTANE CONCENTRATIONS MAP CRUDE TYPE DEFINITIONS CRUDE OIL TYPES ARE BASED ON RELATIVE ISOPRENOID CONCENTRATIONS TYPE I: All isoprenoid peaks approximately equal TYPE II: IP20 > IP19 > IP18 TYPE III: IP14 and IP15 dominate isoprenoids IP18, IP19, and IP20 approximately equal TYPE IV: IP13, IP14, IP15, IP16 > IP18, IP19, IP20 IP18, IP19, and IP20 approximately equal TYPE V: IP13, >> IP14, IP15, IP16 > IP18, IP19, IP20 IP18, IP19, and IP20 approximately equal C15 fraction much lower than Type I

PM-91 Y’-40

DOMINATE: Non degraded light oil that terminates at C20 Does not look like other crude types. Could be atmospheric distillate of crude oil Heavy ends not present

PM-99 E’’-27

PM-103 W’-41

PM-81 R’-45

PM-98 C’’-26 PM-95 L’’-8 N'-35PM-101 N'-35

11.215m

PM-88 A’’-27

Page1

11.215m J:\HPDATA\99-2113\PRODUCT\109837.01R

P-120

GASOLINE TYPE DEFINITIONS

PM-102 Q’-42

NC8

1000

TYPE II: TYPE III: TYPE IV:

MCH

900

Cycloparaffin dominate. Probably not finished gasoline. O-xylene > m-, p-xylenes Has alkylates, normal paraffins relatively low. Ethylbenzene > or = m-, p-xylenes Substantial alkylates, relatively high normal paraffins, m-, p-xylenes > o-xylene. Probably a finished gasoline

NC7

PM-97 H’’-8

FREE PRODUCT SAMPLES HIGH RESOLUTION FID GC

2MHp

800

LIGHT ENDS HEAVY ENDS CRUDE TYPE

NC18 1P20

NC19

NC20

IP13

IP15 NC14

PM-101 N’-35

NC16 IP18 NC17 IP19

Naph

2MNaph 1MNaph

IP16 NC15

NC13

NC12

NC11

1M3EtBz 1,3,5TMBz

IPBz

EtBz

1,2,4TMBz

NC10

NPBz

3MHp

PM-96 Q’-29 P-110

PM-83 R’-25

C4Bz

NC4

100

PM-77 R’-31

1,2,3TMBz Indane

3MHx MCP 3MP CP 2,3DMB

IC5

200

2,4DMP+2,2,3TMB Benzene

NC5

300

EtCP 2,5DMHx+2,2,3TMP 2,3,4TMP 2,3DMHx 2,2,5TMHx

2MP

400

CH 2MHx+2,3DMP t1,2DMCP 2,2,4TMP+DMCP(s)

500

c1,3DMCP t1,3DMCP

mV

PM-94 Q’-35

NC9 NC6

Toluene+2,3,3TMP

600

m+p-Xylenes o-Xylene

700

P-100 0

5

10

15

20

25

30

35

40

45

50

55

60

Minutes

J:\HPDATA\99-2113\PRODUCT\109837.01R

Printed on 3/15/2000 6:20

PM-104 B’-47

Entirely alkylate stream Heavy ends not present

PM-105 N’-23

SI-1, ~1:10 DCM

Page1

SI-1, ~1:10 DCM C:\HPDATA\99-2113\PRODUCT\103105.03R 1000

PM-100 O-59 900

PM-82 N’-11 800

PM-87 H’-20 PM-64 I’-16

700

2MHx+2,3DMP 2,2,4TMP+DMCP(s) 2,4DMP+2,2,3TMB

0

5

10

PM-58 P-39

PM-53 F’-11

PM-90 G-48

PM-40 Q-37

P-70

PM-73 E-86 PM-10 K-39

15

20

25

30

35

40

NC27 NC28 NC29 NC30 NC31 NC32 NC33 NC34 NC35

NC26

NC25

NC24

NC23

NC22

NC21

NC20

NC19

NC18 1P20

NC16 IP18 NC17 IP19

IP16 NC15

IP15 NC14

PM-60 F’-7 Naph NC12 IP13

100

PM-86 H-51 PM-57 P-42

PM-55 E’-14

PM-59 I’-6 PM-61 J’-4

2MNaph 1MNaph NC13

IC4 NC4 IC5 NC5 DCM Solvent CP 2,3DMB 2MP 3MP NC6 MCP Benzene CH

200

PM-76 S-39 PM-65 T-37

P-80

PM-70 S-35

NC11 C4Bz

300

PM-71 Y-28

PM-67 A’-24

BH-H’10

EtBz m+p-Xylenes

400

PM-84 Y-30

PM-93 F’-19 PM-45 H’-14 PM-50 I’-11

o-Xylene NC9 IPBz NPBz 1M3EtBz 1,3,5TMBz 1M2EtBz 1,2,4TMBz NC10 1,2,3TMBz Indane

500

3MHx c1,3DMCP t1,3DMCP t1,2DMCP NC7 MCH EtCP 2,5DMHx+2,2,3TMP 2,3,4TMP Toluene+2,3,3TMP 2MHp 2,3DMHx 3MHp 2,2,5TMHx NC8

mV

600

45

50

55

P-17 60

Minutes

C:\HPDATA\99-2113\PRODUCT\103105.03R

PM-72 E-48 PM-39 P-34

S-I-1

PM-92 D’-6

PM-43 F’-2

Printed on 9/3/1999 4:52:26 PM

PM-66 Z-11

PM-56 B’-7

S-I-2

PM-78 C’-5

PM-21 N-31 PM-89 E-39

S-I-3

PM-47 Y-5

M-I-2 M-I-3 M-I-4 INC-1 M-I-5 M-I-6

Page1

m+p-Xylenes

5

PM-42 R-4 BH-S-1

o-Xylene

P-60

(ppbv)

PM-22 Ñ-12

PM-04 E-20

PM-31 O-9

PM-07 Q-5 PM-05 Q-4

PM-02 F-24

PM-03 G-20

INC-4

PM-11 I-13

PM-36 L-9

> 20,000 2,000 - 20,000 600 - 2,000 300 - 600 100 - 300 < 100

PM-25 M-9 MW-6

PM-20 P-5 PM-32 N-8 B-1

PM-09 P-3

NC11

1M3EtBz

P-10 NC10

NC9

NC8

N-BUTANE CONCENTRATIONS

PM-79 B-7 PM-01 G-22

PM-35 K-15 PM-13 M-14

PM-24 Ñ-14

PM-16 R-6

PM-38 Q-3

EtBz

10

PM-18 J-18

PM-23 R-8

BH-U-4

P-15 P-14 P-13 P-12 P-11

PM-30 J-6

CAL-2

PM-06 O-4

PM-33 Ñ-5

PM-34 N-5

P-31

25

NC16

PM-29 G-7

PM-12 M-1

PM-75 II-6

45

50

NC33

NC25

NC26

NC24

40

NC27 NC28 NC29 NC30 NC31

NC23

NC18

NC19

1P20

35

PM-74 HH-7

P-20 NC21

NC17

30

NC20

B-3

IP18 IP19

NC12

NC13 NC14

IP13

IP16

IP15

1MNaph 2MNaph

Naph

20

T-50

PM-28 F-10 CAL-1

PM-08 Ñ-1 NC15

1,2,3TMBz

1,3,5TMBz 1M2EtBz

C4Bz

15

B-2 P-40 P-32

P-30

PM-15 K-2

50

0

PM-14 L-19

PM-19 M-17

P-16

NC22

NC4

100

PM-48 V-5

PM-41 U-3

INC-3

Indane

150

CP

2,3DMB

200

PM-27 I-24 BH-W-4

PM-69 T-9 PM-17 O-17

M-I-13

IPBz NPBz

NC6

2,2,4TMP+DMCP(s)

Toluene+2,3,3TMP

NC7 MCH

250

MCP 2,4DMP+2,2,3TMB Benzene CH 2MHx+2,3DMP 3MHx

3MP

300

PM-63 U-10

M-I-11

EtCP 2,5DMHx+2,2,3TMP 2,3,4TMP 2,3DMHx 2MHp 3MHp 2,2,5TMHx

350

c1,3DMCP t1,3DMCP t1,2DMCP

mV

400

PM-44 X-4

PM-51 W-2

1,2,4TMBz

IC5 NC5 2MP

450

P-61

PM-68 U-13 PM-46 Y-2

M-I-12

550

500

PM-52 X-7

M-I-8 M-I-9 M-I-10

600

PM-37 N-28

INC-2

PM-49 X-1

M-I-7

O-9, PM-31, 0.1ul J:\HPDATA\99-2113\PRODUCT\108054.01R 700

PM-26 Q-23

PM-62 X-9

P-140 M-I-1

O-9, PM-31, 0.1ul

650

P-62

BH-A’-5

PM-54 B’-2

DOMINATE: Gasoline Type IV SUBORDINATE: Minimally biodegraded crude oil CRUDE TYPE: I

55

60

Minutes

PM-80 EE-9


0

Printed on 12/1/99 4:14:57 PM

100

200 METROS

METROS

PM-85 BB-8

1000

Page1

B-2

B-7 PM-79 0.1ul B-7

C:\HPDATA\99-2113\PRODUCT\103123.01R 200

Page1

0.1ul J:\HPDATA\99-2113\PRODUCT\109823.01R

H-51 PM-86 ; H-51;

0.1ul

Page1

0.1ul J:\HPDATA\99-2113\PRODUCT\109826.01R

500 2,2,4TMP+DMCP(s)

200

B-2

2,2,4TMP+DMCP(s)

1,2,4TMBz

1100

m+p-Xylenes

220

Page1

NC11

240

J-18,PM-18 J-18,PM-18 J:\HPDATA\99-2113\PRODUCT\108032.03R 1200


1600 180

450

MCH

Page1

B-3, 0.1 ul

1400 1P20

B-3, 0.1 ul

160

400

900

IP16 NC15

IP18 NC17 IP19

NC11

Naph NC12 IP13

IP15 NC14

2MNaph 1MNaph NC13

1,2,4TMBz NC10 1,2,3TMBz Indane

2MHx+2,3DMP 2,4DMP+2,2,3TMB

2,5DMHx+2,2,3TMP Toluene+2,3,3TMP 2,3DMHx 2,2,5TMHx

MCH

3MHx c1,3DMCP t1,3DMCP t1,2DMCP NC7 EtCP 2,3,4TMP

2,3DMB 2MP 3MP NC6 MCP Benzene CH

IC5 NC5

CP

200

NC31 NC32 NC33 NC34 NC35

NC23

NC24

NC25 NC26

NC27 NC28

NC29 NC30

IP16

IP18 IP19

1P20

NC20

NC21

NC22

NC19

IP15 NC14

NC15

NC18

NC16

NC17

400

2MHp 3MHp NC8

mV 1,2,4TMBz

NC11 C4Bz

NC12 IP13 Naph

2MNaph 1MNaph NC13

600

NC10 1,2,3TMBz Indane

NC9 NPBz

o-Xylene EtBz m+p-Xylenes

MCP NC6

2MP 3MP

2MHx+2,3DMP c1,3DMCP t1,3DMCP t1,2DMCP 3MHx 2,2,4TMP+DMCP(s)

EtCP 2,5DMHx+2,2,3TMP 2,3,4TMP Toluene+2,3,3TMP 2,3DMHx 3MHp 2,2,5TMHx NC8

2,4DMP+2,2,3TMB Benzene CH

IC5 NC5 IC4 NC4

50

CP 2,3DMB

NC23

NC25

100

800

EtBz m+p-Xylenes o-Xylene NC9 IPBz NPBz 1M3EtBz

2MHp NC7

mV NC19

150

IPBz 1M3EtBz 1,3,5TMBz 1M2EtBz

IP19 IP18

1000

250

NC20

NC18

NC21

IP15

IP16

NC14

NC17

IP13

2MNaph

300

NC13

1MNaph

NC16

1,3,5TMBz

Naph NC12

o-Xylene m+p-Xylenes

NC9 IPBz

EtBz

2,2,4TMP+DMCP(s) MCH 2,5DMHx+2,2,3TMP 2,3,4TMP Toluene+2,3,3TMP 2,3DMHx 3MHp2MHp

20

NC26

NC25

1P20 NC19

NC20

NC21

NC22 NC23

IP15

IP16

IP18 IP19

NC15

NC18

NC14

NC16

NC17

C4Bz

2MNaph 1MNaph

Naph

Indane

IP13

NC9 IPBz 1M3EtBz 1,2,4TMBz

40

NC11C4Bz

mV 2,2,5TMHx

2MHp 3MHp NC8

MCH EtCP 2,5DMHx+2,2,3TMP

60

EtBz m+p-Xylenes

2,3DMB 2MP 3MP

100

MCP 2,4DMP+2,2,3TMB CH 2MHx+2,3DMP c1,3DMCP t1,3DMCP

NC24

NC25

NC26

200 NC27

NC22

300 NC23

NC18

NC19

NC20

1P20

IP18 IP19

400

1200

350

200 NC15

2,3,4TMP Toluene+2,3,3TMP 2,3DMHx

mV NC17

100

80

NC21

NC16

NC15

2MNaph IP13

Naph

C4Bz

IP16

IP15

500

1,2,4TMBz 1,2,3TMBz Indane

NC14

1M3EtBz 1,2,3TMBz

1M2EtBz

NC9

600

IC5

20

120

700

NC28 NC29 NC30 NC31 NC32 NC33 NC34 NC35

IC4 NC4 IC5 NC5 DCM Solvent CP 2,3DMB2MP 3MP

40

1MNaph

60

800

Indane

80

EtBz

100

NC6 MCP 2,4DMP+2,2,3TMB Benzene CH 2MHx+2,3DMP c1,3DMCP t1,3DMCP t1,2DMCP 3MHx 2,2,4TMP+DMCP(s) NC7 MCH EtCP2,5DMHx+2,2,3TMP 2,3,4TMP 2,3DMHx 2MHp 3MHp 2,2,5TMHx NC8

120

IPBz NPBz 1,3,5TMBz

mV

140

o-Xylene

Toluene+2,3,3TMP

160

140 NC13

NC10

NC12

180

0 0

5

10

15

20

25

30

35

40

45

50

55

60

0

5

10

Minutes


SUBORDINATE: Gasoline Type IV DOMINATE: Minimally biodegraded crude CRUDE TYPE: I

15

20

25

30

35

40

45

50

55

60

5

10

Minutes

Printed on 8/16/1999 5:10:32 PM


DOMINATE: Mostly alkylate stream SUBORDINATE: Severely degraded crude oil CRUDE TYPE: II

15

20

25

30

35

40

45

50

55

60

0

5

10

15

Minutes

Printed on 12/1/99 3:28:08 PM


20

25

30

35

40

45

50

55

60

0

5

10

15

Minutes

Printed on 9/3/1999 4:33:17 PM

VERY SUBORDINATE: Cycloparaffin rich DOMINATE: Entirely severely degraded crude (older) CRUDE TYPE: II


20

25

30

35

40

45

50

55

60

Minutes

Printed on 3/10/2000 3:17

DOMINATE: Straight run gasoline cut? (no alkylates) SUBORDINATE: Severely biodegraded crude or diesel fuel oil CRUDE TYPE: II


Printed on 3/10/2000 4:14

DOMINATE: Very weathered alkylate rich, cycloparaffin rich. Probably not finished gasoline Heavy ends not present

0

Not present 5 10

20

15 20 25 30 35

Entirely topped and severely biodegraded crude oil 40 45 50 300

250

200

150

10 100

50

Minutes 55 60

II 0 5 10

C:\HPDATA\99-2113\PRODUCT\103126.01R 15 20 25

30

30

35

35

40

40

NC25

350

25

NC20

650

20

NC21

90 NC25

NC21

NC14

1P20

o-Xylene

IP18 IP19

IP16

IP15

IP13

NPBz

NC9

NC19 NC20

NC18

NC16

NC15

2MNaph NC131MNaph

Naph

NC11 C4Bz


IPBz

1,3,5TMBz

200

NC19

SB-3 700

EtBz m+p-Xylenes

MCH

100

1P20

110 15

NC18

Page1

10

IP19


NC16 IP18

T-50 0

IP16

T-50 60

IP15 NC14

Minutes

NC15

55

2MNaph 1MNaph NC13

Printed on 8/16/1999 5:10:32 PM

IP13

50

20

EtCP 2,5DMHx+2,2,3TMP 2,3,4TMP Toluene+2,3,3TMP 2,3DMHx 2MHp 3MHp 2,2,5TMHx

80

NC11 C4Bz

40

CH 2MHx+2,3DMP 3MHx c1,3DMCP t1,3DMCP t1,2DMCP 2,2,4TMP+DMCP(s)

mV 120

Naph


60

EtBz m+p-Xylenes o-Xylene NC9 IPBz NPBz 1,3,5TMBz 1,2,4TMBz 1,2,3TMBz Indane

NC25

NC13

180

2MHp 3MHp

45 NC26

NC14

SB-1

MW-6, 0.1 ul C:\HPDATA\99-2113\PRODUCT\103126.01R 750 2,2,4TMP+DMCP(s)

C:\HPDATA\99-2113\PRODUCT\103119.01R NC27

NC22 NC23

NC20

NC19

NC18

NC17

NC16

NC15

2MNaph

NC11

1,2,4TMBz

Page1

MCH 2,5DMHx+2,2,3TMP 2,3,4TMP Toluene+2,3,3TMP 2,3DMHx 2,2,5TMHx

mV

40 NC24

NC21

1P20

IP18 IP19

IP16

IP15

1MNaph

NC12

NC10

m+p-Xylenes


EtCP

NC19

100

NC20

1P20

35

NC21

80 IP19

30

NC18

25

IP18

IP16

IP15

IP13

Naph

C4Bz

1,2,3TMBz

o-Xylene 1M3EtBz

B-3, 0.1 ul

MCP 2,4DMP+2,2,3TMB CH 2MHx+2,3DMP 3MHx c1,3DMCP t1,3DMCP t1,2DMCP

NC15

2MNaph

70

NC14

20

NC25

40 Indane

NC9

160

NC16

50 1MNaph

15

NC13

10

IP13

5

C4Bz

0

Naph

40

NC11

60 1M2EtBz

240


60 1,3,5TMBz

80 EtBz

120

IPBz NPBz 1,3,5TMBz

140

Toluene+2,3,3TMP

200

NPBz

o-Xylene

100

NC6 MCP 2,4DMP+2,2,3TMB Benzene CH 2MHx+2,3DMP c1,3DMCP t1,3DMCP t1,2DMCP 3MHx 2,2,4TMP+DMCP(s) NC7 MCH EtCP2,5DMHx+2,2,3TMP 2,3,4TMP 2,3DMHx 2MHp 3MHp 2,2,5TMHx NC8

220

IPBz NC9

20 IC4 NC4 IC5 NC5 DCM Solvent CP 2,3DMB2MP 3MP

mV

B-3, 0.1 ul

2,3DMB 2MP 3MP

30

m+p-Xylenes

mV

FIGURE 1. SOUTH BOUNDARY AREA P-20, 0.1 ul C:\HPDATA\99-2113\PRODUCT\103121.01R

P-20, 0.1 ul Page1

220

180

SB-2

160

140

C:\HPDATA\99-2113\PRODUCT\103121.01R Minutes

45

Printed on 9/3/1999 4:43:02 PM

45

50

50

55

MW-6, 0.1 ul

55

60

Page1

600

SB-4

550

500

450

400

Minutes

60

Printed on 8/16/1999 5:28:13 PM

MCH

0 5

100

50

10

C:\HPDATA\99-2113\PRODUCT\103113.01R m+p-Xylenes o-Xylene NC9

15 20 25 30 35 40 45 50 100

55 50

Minutes 60

Printed on 9/9/1999 2:21:23 PM 5 10

C:\HPDATA\99-2113\PRODUCT\103115.01R 15 20 25 30 35 40 NC24 45

NC27

45

50

NC33

40

NC25


NC28 NC29 NC30 NC31

NC21 NC22 NC23

NC19 NC20

35

NC26

NC17

30

1P20 NC18

IP18 IP19

NC15

25

NC16

Minutes

IP16

NC13

20

NC14

2MNaph

NC11

NC24 NC25

50

NC35

NC28 NC29 NC30 NC31 NC32 NC33

NC27

NC26

NC21

NC16

NC15

2MNaph

NC17 NC18 NC19 NC20

IP16

IP15

IP13

Naph

IP18 IP19 1P20

1,2,3TMBz

C4Bz

1MNaph

NC22 NC23

Indane

m+p-Xylenes

NC14

NC13

NC12

NC10

220

1MNaph

NC12

15

C4Bz

1,2,4TMBz

100

Naph

NC10

120

1M3EtBz

200

1,2,3TMBz

140 o-Xylene NC9

160

1M2EtBz

1,2,4TMBz

NC11

260

IP15

150

EtBz

280

IP13

200

IPBz NPBz 1,3,5TMBz

220

Indane

250

m+p-Xylenes

180

1M3EtBz

300

1M2EtBz

350

IPBz NPBz 1,3,5TMBz

400

NC8

B-3 2,2,4TMP+DMCP(s)

450

NC9

450 10

EtBz o-Xylene

NC7

Page1

MCH


2MHx+2,3DMP 3MHx

MI-13 5

2,5DMHx+2,2,3TMP 2,3,4TMP Toluene+2,3,3TMP 2,3DMHx 2MHp 3MHp 2,2,5TMHx

MI-13 60 NC6 MCP

40

CH 2MHx+2,3DMP 3MHx 2,2,4TMP+DMCP(s) NC7 MCH EtCP 2,5DMHx+2,2,3TMP 2,3,4TMP Toluene+2,3,3TMP 2,3DMHx 2MHp 3MHp 2,2,5TMHx NC8

60


55 2MP

80

EtCP

50

2,4DMP+2,2,3TMB Benzene CH

Printed on 9/3/1999 4:38:57 PM

NC6

20

MCP

B-1

3MP

IC5

Page1

2MP

mV

IP16

NC13


NC5

NC26 NC27

1P20

IP18 IP19

NC15

IP15 NC14

IP13 NC12 2MNaph

MI-2

DCM Solvent CP 2,3DMB

45

NC28

NC23 NC24 NC25

NC19 NC20

NC17 NC18

NC16

1MNaph

NC11

MI-2

NC4

mV

40

NC26



NC23 NC24

NC21 NC22

60

NC25

400

NC20

35

NC21

30

NC19

80

NC22

200 NC17

Naph

100

NC18

NC15

25

IP19

NC16

C4Bz

140

1P20

IP18

IP16

300 NC14

20

NC13

NC11

120

IP15

350 NC12

200

2MNaph

IP13

180

1MNaph

150 C4Bz

1M2EtBz 1,2,4TMBz 1,2,3TMBz NC10

mV 160

Naph

250 1,2,4TMBz NC10

15

1,2,3TMBz

20

Indane

40

NPBz 1,3,5TMBz 1M2EtBz

10

EtBz

5

IPBz

0

2,3,4TMP Toluene+2,3,3TMP 2,3DMHx 2MHp 3MHp 2,2,5TMHx NC8

mV

FIGURE 2. BAY AREA MI-6

MI-6 C:\HPDATA\99-2113\PRODUCT\103139.01R

Page1

300

240

B-2

Minutes

Printed on 9/3/1999 4:27:54 PM

55

P-13

55

60

P-13 C:\HPDATA\99-2113\PRODUCT\103115.01R

Page1

B-4

Minutes

60

Printed on 8/21/1999 1:16:58 PM

50 IC5 NC5

0 5 10

C:\HPDATA\99-2113\PRODUCT\103129.01R 15 NPBz 1M3EtBz 1,3,5TMBz 1M2EtBz 20 NC12 IP13

25 NC15

30 35 40 45 50 80

60

40

20

Minutes 55 60

Printed on 9/3/1999 4:48:22 PM 0 5 10

C:\HPDATA\99-2113\PRODUCT\103130.01R 15 20 25 30 35 NC20

35 40

40

NC25

NC21

NC18

NC16

NC15

NC13

Naph IP13

1P20

IP15 NC14

IP18 IP19

IP16

2MNaph 1MNaph

C4Bz

o-Xylene 1,3,5TMBz

60

NC21

NPBz

NC11

NC9

65

NC19

1P20

30

NC18

IP18 IP19

IP16

25

NC16

100

IP15 NC14

Minutes

NC15

120

IP13

200

20

2MNaph NC13 1MNaph

160

15

NC11 C4Bz

SE-3 10

Naph NC12

Page1

5 IPBz

30


50

NC10 1,2,3TMBz Indane

P-61, 0.1 ul C:\HPDATA\99-2113\PRODUCT\103129.01R 350 0 EtBz m+p-Xylenes

55

1,3,5TMBz 1,2,4TMBz

Printed on 8/16/1999 5:46:42 PM

NPBz 1M3EtBz 1M2EtBz

P-61, 0.1 ul 60

o-Xylene

55

IPBz


NC8

45

MCH

40

NC9

40

EtBz

15

m+p-Xylenes

20

2MHp

35

2,5DMHx+2,2,3TMP 2,3,4TMP 2,3DMHx 2,2,5TMHx 3MHp

25 2MHx+2,3DMP 3MHx t1,2DMCP NC7 EtCP 2,5DMHx+2,2,3TMP 2,3,4TMP 2,3DMHx 2MHp 3MHp 2,2,5TMHx

160

MCH

180

2,2,4TMP+DMCP(s)

SE-1

NC7

mV

Page1

EtCP

1P20

MCH


MCP 2,4DMP+2,2,3TMB Benzene CH 2MHx+2,3DMP 3MHx c1,3DMCP t1,3DMCP t1,2DMCP

NC25

NC20

NC19

IP18 IP19

IP16

o-Xylene 1,3,5TMBz 1,2,4TMBz

EtBz

2MHp

INC-4

2MP 3MP NC6

NC16

NC18

2MNaph 1MNaph IP15 NC14

NC15

NC13

Naph NC12 IP13

NC11C4Bz

NC10 Indane 1,2,3TMBz

NPBz 1M3EtBz 1M2EtBz

NC9

m+p-Xylenes IPBz

NC7

INC-4

CP2,3DMB

mV

35

IC5 NC5

NC20

300

NC19

1P20

IP19

30

NC18

IP16

25

NC16 IP18 NC17

IP15 NC14

20

2MNaph 1MNaph NC13

Naph

NC11

NC8 15

C4Bz

o-Xylene

1,2,4TMBz

NC9

10

NC10 Indane 1,2,3TMBz

IPBz

200

EtBz

5 EtCP 2,5DMHx+2,2,3TMP 2,3,4TMP Toluene+2,3,3TMP 2,3DMHx 3MHp 2,2,5TMHx NC8

CH 2MHx+2,3DMP3MHx c1,3DMCP t1,3DMCP t1,2DMCP 2,2,4TMP+DMCP(s)

140

m+p-Xylenes

250 2MHp

MCH

120

3MHp

NC7

80

2MHx+2,3DMP 3MHx 2,2,4TMP+DMCP(s)

NC6 MCP

mV 220

EtCP 2,5DMHx+2,2,3TMP 2,3,4TMP 2,3DMHx 2,2,5TMHx


2MP 3MP

100


150 NC6 MCP

0 CP 2,3DMB

NC5

20

CH

2MP

60


100 3MP

40

CP 2,3DMB

mV

FIGURE 3. SOUTH-EAST AREA P-60 3,34M, 0.1 ul

P-60 3,34M, 0.1 ul C:\HPDATA\99-2113\PRODUCT\103128.01R 70

Page1

240

200

SE-2

45

10

5

C:\HPDATA\99-2113\PRODUCT\103128.01R Minutes

45

Printed on 9/3/1999 4:47:11 PM

45

50

50

55

P-62

55

60


Page1

220

180

SE-4

140

Minutes

60

Printed on 9/3/1999 4:49:02 PM

50 NC4 IC5 NC5

200

100

0 5 10

C:\HPDATA\99-2113\PRODUCT\103132.01R 15 20 25 30 35 NC20

NC181P20

2MNaph

40 45 50 100

50

Minutes 55 60

Printed on 9/3/1999 4:58:54 PM 0 5 10

C:\HPDATA\99-2113\PRODUCT\103133.01R 15 20 25 30 35

NC18 1P20

NC20 40

NC23 NC24 45

NC26


45


NC27

40

NC25

300

NC21

35

NC22

30

NC19

NC13

25

NC16 IP18 NC17 IP19

NC14

Minutes

IP16 NC15

IP15

150

20

2MNaph 1MNaph

200

NC12

250

IP13

400 15

Naph

C-3 NC10

600

NC11

Page1

10

C4Bz


Indane

P-70 0

NPBz 1M3EtBz 1,3,5TMBz 1,2,4TMBz 1,2,3TMBz

P-70 60

1M2EtBz

55

NC9

50

IPBz

Printed on 9/3/1999 4:23:56 PM

NC8

45

o-Xylene

50

m+p-Xylenes

10

EtBz

NC11

1,2,4TMBz

NC9

EtBz m+p-Xylenes

100

2MHp 3MHp NC8

200 2,5DMHx+2,2,3TMP 2,3,4TMP Toluene+2,3,3TMP 2,3DMHx 2,2,5TMHx

2MHx+2,3DMP

P-17, ~1:10 DCM C:\HPDATA\99-2113\PRODUCT\103106.01R 350 2,2,4TMP+DMCP(s)

300

2MHp

40

MCH

C:\HPDATA\99-2113\PRODUCT\103131.01R 2,4DMP+2,2,3TMB

250

3MHx NC7 MCH

150

CH

C-1

3MP NC6 MCP

IC5

100

2,2,4TMP+DMCP(s)

35 2,3DMB

Page1

2MP

mV


NC5 DCM Solvent

NC20

NC18

NC14

2MNaph

2,2,4TMP+DMCP(s)

P-110

EtCP 2,5DMHx+2,2,3TMP 2,3,4TMP Toluene+2,3,3TMP 2,3DMHx 2,2,5TMHx 3MHp

NC7

NC9 1,2,4TMBz

2,3,4TMP

P-110

IC5 NC5 DCM Solvent CP 2,3DMB 2MP 3MP NC6 MCP 2,4DMP+2,2,3TMB Benzene CH 2MHx+2,3DMP 3MHx c1,3DMCP t1,3DMCP t1,2DMCP

mV

30

NC16 IP18 NC17IP19

1MNaph

25

IP16 NC15

IP15 NC14

NC13

Naph

20

NC12IP13

Indane 1,2,3TMBz

550 1,2,4TMBz

m+p-Xylenes

15

NC11 C4Bz

1M3EtBz

500

1M2EtBz

EtBz

10

o-Xylene

Toluene+2,3,3TMP

40

NC10

300 2MHx+2,3DMP

30

MCH 2,5DMHx+2,2,3TMP 2,3DMHx 2,2,5TMHx

50

Toluene+2,3,3TMP 2MHp

5 2,4DMP+2,2,3TMB

60

NC9

250 MCH

350

2,2,4TMP+DMCP(s)

IC5

80

IPBz NPBz

3MP NC6 MCP 2,4DMP+2,2,3TMB Benzene CH 2MHx+2,3DMP 3MHx c1,3DMCP t1,3DMCP t1,2DMCP NC7 EtCP2,5DMHx+2,2,3TMP 2,3,4TMP 2,3DMHx 3MHp 2,2,5TMHx NC8

0 2MP 3MP

NC5

mV 90

IC4 NC4

150 2MP

20

CP 2,3DMB

mV

FIGURE 4. CENTRAL AREA P-17, ~1:10 DCM Page1

C-2

70

Minutes

Printed on 8/18/1999 9:38:34 AM

50

50

55

P-80

55

60


Page1

350

C-4

450

Minutes

60

Printed on 9/3/1999 4:50:37 PM

FORENSIC GEOCHEMISTRY - THE KEY TO ACCURATE SITE CHARACTERIZATION Victor T. Jones, III, Patrick N. Agostino - Exploration Technologies, Inc.

C-1

C-1

C-2

C-2

C-4

C-4

C-3

C-3 SE-4

B-1

B-1

SE-3

B-2

B-2

B-3

B-3

B-4 SE-1

SE-2

100

B-4

METHANE CONCENTRATIONS > 20,000 5,000 - 20,000 100 - 5,000 30 - 100 15 - 30 < 15

N

SB-1

SE-3

SE-1

(ppmv)

SB-4

0

SE-4

SB-2 SB-3

200

SCALE - METERS

SE-2

(ppbv)

SB-4

> 5,000 2,000 - 5,000 1,000 - 2,000 800 - 1,000 500 - 800 < 500

N

SB-1 0

100

SB-2 SB-3

200

SCALE - METERS

Methane Magnitude Contour Map (ppmv)

ETHANE CONCENTRATIONS

Ethane Magnitude Contour Map (ppbv)

C-1

C-1

C-2

C-2

C-4

C-4

C-3

C-3 SE-4

B-1

B-1

SE-3

B-2

B-2

B-3

B-3

B-4 SE-1

SE-2

SB-4 SB-1 100

SE-3

B-4

PROPANE CONCENTRATIONS

SE-1

(ppbv)

> 8,000 4,000 - 8,000 1,000 - 4,000 500 - 1,000 300 - 500 < 300

N

0

SE-4

SB-2 SB-3

200

SCALE - METERS

SE-2

(ppbv)

SB-4

> 20,000 2,000 - 20,000 600 - 2,000 300 - 600 100 - 300 < 100

N

SB-1 0

100

SB-2 SB-3

200

SCALE - METERS

Propane Magnitude Contour Map (ppbv)

N-BUTANE CONCENTRATIONS

Normal Butane Magnitude Contour Map (ppbv)

C-1

C-1

C-2

C-2

C-4

C-4

C-3

C-3 SE-4

B-1

B-1

SE-3

B-2

B-2

B-3

B-3

B-4 SE-1 SB-4 N

SB-1 0

SE-4

100

SB-2 SB-3

200

SCALE - METERS

C5+ Magnitude Contour Map (ppmv)

SE-2

SE-3

B-4

C5+ CONCENTRATIONS

SE-1

(ppmv)

> 5,000 1,000 - 5,000 100 - 1,000 5 - 100 2-5 5.0 4.0 - 5.0 3.0 - 4.0 2.0 - 3.0 1.0 - 2.0 < 1.0

FORENSIC GEOCHEMISTRY - THE KEY TO ACCURATE SITE CHARACTERIZATION Victor T. Jones, III, Patrick N. Agostino - Exploration Technologies, Inc.

C-1

C-1

C-2

C-2

C-4

C-4

C-3

C-3 SE-4

B-1

B-1

SE-3

B-2

B-2

B-3

B-3

B-4

B-4 SE-1

SE-1

100

0

200

5000

10000

SB-1 0

Methane (ppm)

SCALE - METERS

Ethane/Propane

N

> 10,000 7,500 - 10,000 5,000 - 7,500 2,500 - 5,000 < 2,500

SB-2 SB-3

SE-2

SB-4

Methane/Ethane

N

SB-1

SE-3

SE-2

SB-4

0

SE-4

100

>5 3-5 2-3 1-2 5 3-5 2-3 1-2 0.5 0.4 - 0.5 0.3 - 0.4 0.2 - 0.3 < 0.2

SB-2 SB-3 0

200

50000

100000

N-Butane (ppb)

SCALE - METERS

Propane Interpretive Dot Map (ppbv)

Normal Butane Interpretive Dot Map (ppbv)

C-1

C-1

C-2

C-2

C-4

C-4

C-3

C-3 SE-4

B-1

B-1

SE-3

B-2

B-2

B-3

B-3

B-4

B-4 SE-1

SE-1

100

0

200

2000

C5+ (ppm)

SCALE - METERS

C5+ Interpretive Dot Map (ppmv)

4000

Ethane/Propane

N

>5 3-5 2-3 1-2 5 3-5 2-3 1-2