ML20127H237
| ML20127H237 | |
| Person / Time | |
|---|---|
| Site: | West Valley Demonstration Project |
| Issue date: | 09/13/1984 |
| From: | Fakundiny R NEW YORK, STATE OF, NEW YORK, STATE UNIV. OF, ALBANY, NY |
| To: | Thomas Nicholson NRC OFFICE OF NUCLEAR REGULATORY RESEARCH (RES) |
| Shared Package | |
| ML20127B821 | List: |
| References | |
| FOIA-84-905 NUDOCS 8505210253 | |
| Download: ML20127H237 (2) | |
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na nm w mmes THE BICENTENNIAL OF THE BOARD OF REGENTS AND THE UNIVERSITY OF THE STATE OF NEW YORK ASSISTANT COMMISSIONER FOR MUSEUM, SCIENCE SERVICE AND HISTORICAL SERVICES THE NEW YORK STATE EDUCATION DEPARTMENT ALBANY, NEW YORK 12230 September 13, 1984 Mr. Thomas J. Nicholson Earth Science Branch Division of Health, Siting and Waste Management Office of Nuclear Regulatory Research U. S. Nuclear Regulatory Commission Washington, DC 30555
Dear Tom:
As per your request in the letter dated July 5, 1984 we have reviewed the contractor's draft report " Plan for Diagnosing the Solvent Contamination at the West Valley Facility Disposal Area," by Stephen E. Herbes and Roger B.
Clapp.
Overall, the proposal is well thought out and appears to be rather complete in scope.
We have a couple of comments for your consideration.
First, the proposal refers to the difficulty of using the existing monitoring wells to follow the kerosene contamination.
This is because the wells were i
designed to monitor and collect water samples.
- Secondly, the report continually refers to measuring water tables and j
following fluid flow from one water table to another within the till.
We cannot emphasize too much that the clay-rich silty till does not have hydrologic properties that allow for the collection of water in a manner that produces water tables.
At best, one can refer to various degrees of saturation of the l
material at different places.
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Mr. Nicholson Page Two September 13, 1984 Thank you for sharing this. proposal with us.
We continue to be interested in the progress of work at West
. Valley.
Best regards, 1
Robert H. Fakundiny State Geologist New York State Geological Survey Rm. 3140 Cultural Education Center Albany, NY 12230 REF:gf cc:
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AUG 3 01984 Project M-32 MEMORAtiDUM FOR:
Leland C. Rouse, Chief Advanced Fuel and Spent Licensing Branch Division of Fuel Cycle and Material Safety, 48.S5 Leon L. Beratan, Chief Earth Sciences Branch Division of Health, Siting and Waste !!anagement, RES
.FROM:
Winston Burkhardt Advanced Fuel and Spent Licensing Branch Division of Feel Cycle and Material Safety, 4tSS
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Thomas J. Nicholson Earth Sciences Branch Division of Health, Siting and Waste Management, RES
SUBJECT:
TRIP REPORT
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I Location:
Visit to U. S. Geological Survey' (USGS), Water Resources 1
Division (WRD), Ithaca, NY on August 2,1984 and to West Valley Nuclear Service Center (UVNSC), West Valley, ifY on August 3,1984 Attendees:
See attached i
Purpose:
To visit with USGS-WRD technical staff and review the hydrologic data base
.and maps. To conduct a field trip at the WVNSC area to assist in the development of a hydrogeologic characterization plan of the site.
Suma ry:
Preparatory to the field trip to the MVNSC area, a meeting was held with Bill Kappel, principal USGS investigator, at the USGS-URD office on August 2,1984 A number of geologic and hydrologic reports (both published and unpublished),
t raps and f igures were examined.
Pertinent ones were made available to Dr. Parizek, Pennsylve 11a State University.(PSU), for his use.
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. AUG 3 01984 Lelend C. onuse Leon L. Peratan The field trip on August 3,.1984, consisted of a geologic field exaninatien of a major. landslide feature on Ruttemilk Creek, WVNSC site. The exposed slide features and outcrops provided an excellent stratigraphic vertical-section of the glacial units in the WVHSC vicinity. The geologic observations allowed for an interpretative analysis of the glacial deposital environments and the related hydrogeologic framework at the site. Additional observations were nade of the area between Buttemilk Creek and Frank's Creek and along Frank's Creek.
T. Nicholson, R. Parizek and W. Kappel also' toured the remaining HVNSC site area and environs to observe the regional geology and relevant hydrologic features.
Additionally, the opportunity was taken to observe the solvent recovery operations at the Facility Disposal Area (IRC licensed), and examine recent water level and solvent recovery records. As of that date, only one well has remained dry; the rest have observable water levels. Pecords indicated that most of the original periphery wells and those within the disposal area have had a detectable solvent phase.
The solvent is recovered by using submersible pumps in these recovery wells and then it is pumped to a 6000 gallon tank. We have requested that DOE provide us with any available progress reports on activities being conducted in this area.
T prisinal s,1gned by W.Burkhardt Winston Burkhardt -
Advanced Fuel and Spent Fuel Licensing Branch Division of Fuel Cycle and Material Safety, NitSS ys/
Thomas J. Nicholson I
Earth Science Branch Division of Health, Siting and Waste Management, RES
Enclosures:
As stated cc:
Warren Rehfeldt, WMRP, hHSS Jacob Philip, ESB, RES I
LL A-17, A-18. A-19
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MEETING Attendees August 2,1984 USGS-WRD Office, Ithaca, NY i
NAME ORGANIZATION W. Burkhardt FCAF, PMSS, NRC T. Nich1 son ESB, RES, NRC
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W. Kappel USGS-WRD, Ithaca, NY R. Parizek Pennsylvania State University.
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i MEETING ATTENDEES j
August 3,1984 WVNSC, West Valley, NY NAME ORGANIZATION W. Burkhardt NRC T. Nicholson NRC R. Parizek Pennsylvania State University S. Herbes ORNL R. Clapp ORNL W. Hannum DOE, West Valley T. Adams DOE, Hest Valley H. Walter DOE, Germantown, MD E. Picasso Dames & Moore W. Kappel USGS-WRD, Ithaca, NY j
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SEP 111984 1
Project it.32
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pet'ORANDUM FOR:
Leland C. Rouse, Chief Advanced Fuel and Spent Fuel Licensing Branch Division of Fuel Cycle and Material Safety, teiSS W. Burkhardt, A. T. Clark, and N. Davison FROM:.
Advanced Fuel and Spent Fuel Licensing Branch Division of Fuel Cycle and Material Safety, NMSS l
MEETINGS WITH DOE AND WVHS AT HEST VALLEY-
SUBJECT:
we met with the Department of Energy (DOE) and On Septeder 12 and 13,1984, its ' prime contractor, West Valley Nuclear Services, Inc. (WVNS), at theTwo West Valley. Demonstration Project Office.
- 1) the WVHS developnent of a " safety strategy" consistent with DOE orders, and 2) the development of additional information related to operation and future use of the Facility Disposal Area (FDA). The meeting agenda and a list of attendees is attached.-
1 TOUR We toured the newly constructed Component Test Stand (CTS) early in the rt.orning of September 12 to avoid interference with construction activities.
No equipment has been installed, although the test melter shell is ovite The transfomer and the brick placing is.to start the week of September 17.It was stated that trenching to supply power to the melter has been received.
would begin soon for transfer piping between waste tanks and the CTS and the Equipment Decontamination Room.
Hydraulic testing has begun on the sludge mobilization test equipment-Kaolin clay located in a separate building east of the CTS.
There as an ersatz sludge for the tests in the one-sixth scale equipment.
is some~ optimism at the moment since laboratory tests with actual sludge have indicated that sludge washing will dissolve a significant fraction of the sludge, mostly sodium sulfate, reducing the mass to be moved for The present tests will use six slurry transfer pumps, non-articulated, transfer.
The tests will be used to detemine the but with 'a 360* azimuth pivot.
exact location for the six (or more) tank roof penetrations necessary for pump installation.
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MEETING ON SEPTEMER 12 p
Supernatant Treatment Ebasco is the Architect-Engineer designer for the supernatant treatment l
WMS has decided upon the IE-95 inorganic realite ion exchange process.
resin.to remove cesium and strontium from the supernatant. Since this process is still being developed, design aspects may change. However, the basic concept is to use the spare tank, 8D-1, for a process enclosure.
This is a considerable engineering task. Four ion exchange columns will be used, one off line at any time, with series flow through the other three such that the radioactivity in the effluent from the final (or third) column will be at least one thousandth of the inlet feed. Since columns
,are reused, the slight contamination present after resin discharge will limit the operational decontamination factor. The resins are theoretically capable of a DF in the range of 100,000.
It is presently planned to install a " false" bottom in 8D-1 to collect dis' charged resin in a pool of deionized water. _ The processing could begin in early 1986 and be completed six to twelve months later. The decontaminated supernatant would flow' to a converted tank in a cell in the old plant.
Since some of this information is somewhat~ uncertain, it is premature for us to review 1.t.
However, we should receive some infomation toward the end of this year and should expect a more formal, detailed review in the spring of 1985.
i Log In Eighty Four (LIEF)
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WVNS is still holding to the LIEF program.
In fact, some things have been
= accomplished three months ahead of schedule. We noted that we had an interest in the application of the quality assurance program to melter and feed tank fabrication. We were assured that this was being done. We i
indicated that we might monitor this aspect in some detail on a forthcoming visit.
i LLW Treatment The contractor plans to phase out all use of the Low Level Waste Treatment The unused cell in the old plant, 014, which was to have been used Plant.
for iodine treatment, is being converted to a low-level cement treatment It is hoped to start up that operation in April 1985. Lagoon operation.
No. I has been drained to Lagoon No. 2 and the bottom silt removed.
Eventually, all lagoons will be removed from service.
Pro. ject Plan The fourth revision of the Project Plan was available for our reading.
In a comparison of the Plan with the requirements of the Memorandum of Understanding These were noted to
' between DOE and NRC we noted several items lacking.
the DOE Project Director. Dr. Hannum agreed in general with the modifications n T m n revision vaii ne egoin avaii.oie for oor revie.
we suggesteo.
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3-SEP 211984 Leland C. Rouse "EETICG OD SEPTE:RER 13 y
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FACILITY DISPOSAL AREA (FDA) i Geolocy-Hydrology Review
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HYPS personnel provided a review of their conceptual geology-hydrology j
nodels. For the most part, these were excerpts frora various report that we 1
have already seen. They would use these concepts to develop pathway analyses required in their environnental reports.
Current Plans Wns will centinue monitoring and recovery of the contaminated kerosene using existing wells. They are launching a new program to characterize the shall' w-water hydrology associated with the facility disposal area.
o Their plans are not complete, but they are proceeding to locate positions for installation of additional wells which they hope to have in place by r.id-October 1934. These will be fully engineered wells including screen to cover depths of 5 to 20 feet.
Future Plans He were provided an advance ccpy of a proposal prepared by WVHS for correction of the kerosene nigration problem. They believe that the leakage is occurring from holes SH-10 nd SH-11 and propose to exhume the tanks buried in these holes, repackage the contents and properly dispose of them. They estimate that the cost will be around $1.4 million and that this will solve
-the problem. The proposal is being reviewed by DOE-Germantown and the Ioaho Operations Office.
Environmental Evaluation Coments We had previously been provided a copy of a WVHS prepared Environmental Evaluation of the FDA for our information. We took the opportunity at this time to provide verbal coments on the report. We were sdvised that they had been instructed to upgrade this report to a full Environmental Assessment.
Oak Ridge National Laboratory (ORNL) Reports We presented the status of the Task 1 report and expected schedule for the final version. We provided the ORNL outline for the Task 2 report for their review and coernent.
Field Inspections WNS is currently disposing of DAD waste in a FDA trench. This was open,
There during this visit and afforded the opportunity to take a look at it.
were sufficiently interesting features, i.e., cracks, to consider inspection Q
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L Subsequent to the visit we learned that a severe stom precluded taking the photos, and also, Dr. Perizek's schedule would not make it possible for him
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' *o see the current trench.
WNS agreed that it would be of mutual interest for Dr. Perizek to see and to examina a future trench. They will look into the safety problems that might be associated with such an inspection.
It was agreed that future contacts for pursuing this would be between Tom Hicholson and Bob Blickwedhl.
1 In a previous field visit, large surface cracks were observed in a field between Buttermilk Creek and the site fence boundary. We reinspected these cracks and now question whether these are caved-in mole tunnels or true cracks. This will be followed-up with Dr. Perizek.
Conclusions In our discussions, it was mutually agreed that a review of the current status of the geology-hydrology considerations by WVNS, ORNL, USGS and f#SGS would be best accomplished by a meeting of the interested parties in mid-October. DOE will make the arrangements for th'is meeting.
Origins! signed by i
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Origir.nl signed by A. m = ms Clark A. T. Clark OriginalSignedBy NonnanH.Daviscn W. Davison Advanced Fuel and Spent Fuel 1.icensing Branch Division of Fuel Cycle and Material Safety Distribution:
Original concurrence to be
Enclosures:
As stated Project M-32 returned to FBrown SS 396 NMSS R/F FCAF R/F PDR LPDRs NDavison WBurkha rdt ATClark RBoyle SCornell/GBeveridge Region I JRoth FBrown (LA FJ1e)
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MEETING AGENDA
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West Valley Demonstration Project September 12, 13, 1984 I.
Project Update (September 12)
II..
Safety Strategy and Project Plan (September 12)
A.
Relation of safety classifications to Quality Assurance B.
Need for accident analysis and use of consistant assumptions and techniques III.
Supernatant Treatment (September 12)
A.
Process information - DF factors expected B.
Safety aspects C.. Storage of proddet and taffinate IV.
Facility Disposal Area (September 13) f A.
Update on WVNS observations B.
Environmental Assessment-Project Waste disposal C.
ORNL reports s.
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PROPOSED NRC TECHNICAL REVIEW AGENDA Wednesday 5eptemoer 12 R. E. Steins 7:00 a.m.
Facility Tour J. ' A. Janes D. J. Stroud 8:30 Introduction / Project Update W. H. Hannum 9:30 Safety and Quality Assurance R. E. Lawrence Strategies J. V. Denero C. J. Roberts 10:30 Break 10:50 Safety and QA Strategies (Cont.)
noon Break for lunch 1:30 p.m.
Supernatant Treatment J. M. Pope Thursday 5eptemoer 13 8:30 NRC Licensed Disposal Area S. Marchetti Environmental Assessment DRNL Reports i
10:40 Break 11:00 Tour of NDA A. W. Mikkola h
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Neeting Attendees September 12, 1984 DOE NRC WVNS NYSERDA W. H. Hannum.
N. Davison.
J. Knabenshuh R. Spchberg S. Ketola A. T. Clark-R. E Lawrence J. Dempsey J. V. Denero C. J. Roberts J. M.-Pope D. Carl September 13, 1984 DOE NRC WVNS NYSERDA W. H. Hannum N. Davison C. J. Roberts R. Spohberg W. Burkhardt S. Marchetti J. Dempsey A. T. Clark
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V-Delineating Hydrocarbon Plumes Within Shallow Groundwater by Chromatographic f>eparation of Organic Volatiles Within overlying Soil Richard R. Parizek, Principal Investigator Professor of Hydrogeology, Geosciences Department Ginette Abdo, Graduate Student l-Department of Geosciences The Pennsylvania State University University Park, Pennsylvania 16802 Master of Science Thesis Proposal g
f or Ms. Ginette Abdo October 8, 1984 l.
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' Grour.dwater and surf ace water pollution caused by petroleum spills to the subsurf ace has become an increasing problem., Underground storage at retail gas-stations, pipeline leaks, bulk storage facilities and refineries are contributing to one of-the more serious and difficult problems we are faced to solve.
Contamination problems of this sort have presented health problems, explosions from gas vapors, property damage and contamination of potable water supplies. The potential future pollution problems resulting from these sources is very great judging from the number of storage facilities in use in the United States and the growing age of storage facilities of all sizes.
The movement of petroleum products in the subsurface is dictated by the viscosity of the product, the permeability of the soil, water saturation and other factors. As the product moves downward in the vadose zone, some of it becomes attenuated as it is held by soil particles and in the interstitial soil pores.
Some may be altered by microbiological activity or volatilized.
f Depending on the volume of the spill and the physical characteristics of the sediment, the product will continue to spread by capillary and gravitational forces until it reaches the water table.
Petroleum products being lighter in density than water, will spread along the water table surface or more accurately the capillary zone (Blake and Hall,1984) and above perched groundwater lenses and confining beds.
In~ order to fully assess the problems a spill of this nature can present, it is necessary to locate the source of the spill and to determine the extent of the contaminant plume. A thorough understanding of the hydrogeology of the spill area is essential in implementing a plan for the monitoring and recovery
'of the spilled product.
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To locate the pollutant source, tanks and pipelines are pressure tested and inventory and use recorcs are reviewed in an attempt t,o establish the location and magnitude of loss. Tanks and pipelines are dug up and inspected i
and trace elements are ol' ten analyzed for in hopes of locating unique sources
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of product. The conventional method of installation and sampling of well bores and monitoring wells is used to determine the extent of the contaminant Wells are initially drilled in the vicinity whcre the spill has been plume.
known to occur or adjacent to where pollutants were first detected.
Subsequent drilling is usually away from the initial discovery wells or springs until contaminants are no longer found. This is a costly method for problem assessment and uneconomical for smaller spill areas but is inevitable because site specific hydrogeological data are rarely available to assist in There is also a time factor involved between locating, these efforts.
drilling and sampling the developed well.
A hydrocarbon spill in Lancaster, Pennsylvania for example, was to be monitored and recovered by six wells that were drilled in the area. However, by the time the wells were finally t
completed it was discovered that the hydrocarbon had escaped from the soil and disappeared into the f ractured limestone, bedrock (Jef f Molnar, PA DER, pers.
These disadvantages associated often with well drilling on a grid has
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led us to propose what we hope will be an economical and time effective method The study is to be to help identify the serial extent of a contaminant plume.
used as a Master of Science thesis for Ms. Ginette Abdo, Graduate Student in the Department of Geosciences, The Pennsylvania State University, and is to be by the Mineral Conservation Section, College of Earth and f unded in part, Mineral Sciences, The Pennsylvania State University.
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NEW METHOD TO BE EMPLOYED i
Hydrocarbons give of f volatile compour.de as they propagate downward Soil through the soil zone and spread along the ground-water table interface.
gas sampling and measurement of these,yolatile compounds h'as been studied, as a method to supplement drilling in the determination of a contaminant plume (Lappala and Thompson,1983, Claucuum and others,1983). Sampling has been f
1 performed with organic vapor detectors also known as " gas sniffers".
j Instrumentation-is often expensive and several factors must be considered in determining the effectiveness of this method.
Vapors mast be present near the probe at the time of sampling in order to be detected. These vapors must also be sampled in a reasonable time period and the amount of vapor present in the soil must be detectable by the instrument selected. Fluctuating water tables, barometric pressure changes, soil water contents, amount ofj product lost.
. soil and rock discontinuing and other f actors all in the weather can greatly influence the presence of absence of volatile organic compounds in the subsurface at any location of interest and time of sampling. It is therefore
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questionable as to the effectiveness of the shallou soil gas sampling method as a reliable means of determining the extent of a contaminant plume.
The method we propose to evaluate if contamination is present within shallow ground-water aquifers and confining beds relies on the fact that volatile compounds are released from a wide range of crude petroleum and its by-products (Table 1).
A fraction of these volatile organic constituents should become adsorbed onto the soils overlying a spill site. Therefore, once
- an area has been exposed to a volatile compound, it's signature should be lef t on the soil for a prolonged period regardless of any f actors that might result In in the release or degradation of the volatile compounds from the system.
this sense, the soil should act to integrate the volatiles through time even
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though the soil atmosphere any not be enriched in these volatiles on any i
The soil should particular occasion when soil gas samples are being obtainpd.
act in a manner similar to a doseometer slowly integrating the occasional presence of the volatiles within the soil atmosphere.
The method was invented and patented by Edwin W. Biederman, Jr., and Bennie Heinze (1984). Dr. Biederman is now a professional engaged in technology transfer at The Pennsylvania State University.
The Biedermann Heinze Method was initially patented as a geochemical exploration method to determine the proximity of petroleum reservoirs by analysis of soil samples (United State Patent 3,149,068 Biederman et al., Sept. 15, 1964). Methods previously used in extracting organic constituents f rom soil samples to This determine the presence of petroleum reservoirs had not been effective.
was due to the f act that analysis of extracted organic constituents under ultra-voilet light had f ailed to determine petroleum constituents because of Green j
the presence of other organic constituents, which flouresee similarly.
plants, for example, or parts of plants containing chlorophyll will give very
,b strong flouresce if they are included in soil analyses.
The uniqueness of the Biedermann Heinze method is that it utilizes two dimensional chromatography in order to separate those constituents that are 4
mobile in a polar solvent (oxygenated organics) and thdse that a::e mobile in a non-polar solvent (petroleum constituents). Fluorescence is then checked under ultra-voilet light to determine if petroleum constituents are present in the soil sample.
The procedure is as follows:
l.
Traverse lines are laid out over a potential oil or gas reservoir.
In our case, a hydrocarbon spill contained in shallow groundwater.
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2.
A sampling depth is selected just deep enough to avoid living plant tissue and possible surface noise resulting from minor hydrocarbon spills.
3.
Up to 4 two gram soil samples are collected at each sampling station and placed in an air-tight container..
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4.
A two gram soil sample is first treated with a suitable solvent in order to extract the organic constituents.
We will use a 2 al. solution of a one to one ratio of alcohol and toluene to achieve the necessary extraction.
5.
A small amount of the extract (.01 al) is placed in the corner of chromatographic or filter paper and allowed to evaporate.
6.
A polar chromatographic solvent is introduced onto the absorbed Methanol will be used as the polar solvent to separate out the extract.
oxygenated organics.
7.
A non-polar carrier solvent, such as heptane, will then be introduced onto the absorbed material, in a direction perpendicular to the path of the polar solvent.
8.
A standard ultraviolet light can then be used to evaluate the t
presence of the petroleum constituents by flourescence.
9.
The concentration of a particular organic constituent is estimated by comparing the brightness of the color noted on the filter paper with a Solvents are predetermined standard of the pollutant being investigated.
mixed in known and varying proportions w1th the hydrocarbon under study and subjected to the same test _as the field unknown sample.
Figure 1 shows the various constituents found in the various corners of the filter paper using the above method, assuming the carrier solvents drove the extracted compounds the entire width of the filter paper.
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OBJECTIVE OF INVESTIGATION The main objective of this study is theref ore, (1) to, determine the 4
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ituents in the subsurface at
. presence or absence of various petroleum const product spill sites by analyzing the soil samples for volatile compounds; (2) determine if the Biedermann-Heinze method applied to petroleum exploration might be used to detect the presence of known petroleum product in shallow groundwater under varying soil and rock types, depth of polluted groundwater and age of spill; (3) determine if the technique is applicable under any season of the year; (4) determine the optimum depth of soil sampling to avoid surface noise caused by green plants and landuse activitics.
IMPLEMENTATION OF METHOD Once final site selection for suitable spill areas has been completed, a I-J.-
regularly spaced grid system will be set up over the area, in order to j.
implement the testing method at regular intervals. The grid system will be
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i determined by site size and the physical characteristics, such as geology,
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soils, and topography, of the area and by the presence of well defined pollutant plumes.
Soil samples will be taken at depth intervals of 1, 2, and 3 feet at each i
determined point. Four samples will be teken at each depth interval to give a C
more stable estimate of the hydrocarbon vapor that has attenuated onto the soil by averaging the four results. This approach was recommended by Dr.
Biedermann (personal communication). This will alco cut down on any ' noise' (influence of hydrocarbons on the soil resulting from sources such as I
highways, f arms, etc. ).
Points known to be outside the spill area will also be tested and act as l~
A comparison of the results from these samples and those taken a control.
within the spill area will be made.
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SUBSTUDIES Various substudies will be undertaken once it has been determined that petroleum constituents have been f ound in the soil samples.
(1) Af ter determining if there are petroleum constituents present in a soil: sample, we can take this one step further by quantifying the results. By determining the concentrations of the hydrocarbon vapors present in the soil samples, we will be able to make a predictive statement as to the amount of hydrocarbon that has come into ecntact with the soil hence, possibly also the amount that lies in the subsurface. This is accomplished by implementing the aforemantioned method on varying known concentrations of product and using these chromatograms as standards of reference.
By comparing the color intensities of the soil sample chromatograms against those of the standards we can obtain concentrations of the hydrocarbon vapors.
(2) Soil samples can also be taken during the different seasons of the year to determine if climatic differences will effect the results of r
sampling.
t (3) Varying concentrations of the hydrocarbon vspors, depending on the depth at which the sample was taken, will also be evaluated.
(4) The effectiveness of this method can also be analyzed by comparing the results of two or more spill sites, having similar and differed Evaluation can hydrogeological characteristics and hydrocarbon contaminant.
then be'made to determine if age of spill makes a difference on the findings.
(5) Adsorption of vapors onto soils is also dependent on the soil characteristics. A comparison of the different soil textural classes and their ability to absorb hydrocarbon vapors can also be evaluated.
(6) Concentrating the sampling efforts on features such as fracture traces, solution openings, areas around exposed bedrock outcrops and joint
9 sqts can allow us to aske predictive statements as to the importance of these features as pathways for contaminant movement.
SITE SELECTION We are currently in the process of selecting suitable sites in which to implement the aforementioned testing method and procedures. Site selection 1
criteria includes:
l (1) The presence of a relatively shallow water table (between 10-40 feet).
(2) Ideally, we would like a somewhat shallow, continuous soil cover.
Thicker soils in which fractures are present also would be suitable.
(3) The spill must be well documented, with at least several wells that have been drilled for monitoring purposes.
This will enable us to compare results that we might obtain from the experiment to those already obtained by conventional drilling. The thickness of product on groundwater, for example, may correlate with the strength of the volatiles noted in the overlying soil.
i (4) The spill should be of a relatively large size so that a range in soil and rock conditions can be studied.
At the present time, two spills have been identified that will be considered for preliminary testing.
Both have been investigated in detail by the Pennsyivania Department of Environmental Resources (DER).
Regional office personnel have expressed interest in this study, and have agreed to provide available hydrogeological and product spill data.
l Mechanicburg, Pennsylvania A mixture of refined products were found in the subsurface just east of Mechanicburg, Pennsylvania.
The area is underlain by carbonate rock in which a number of zones of f racture concentrations have been mapped. The spill was
10 first brought to the attention of the State Agencies in February,1969. As cf March, 1984, 219,675.5 gallons of petroleum products have been recovered (Mechanicsburg Area Product Salvage Report, PA DER). This is avery well documen',ed spill in which 45 wells were initially used for monitoring and
)
recovery purposes. Product varied in hickness above the water table and at depths below land surface.
At least several areas contained product that was purched through soil to landsurf ace in res;ponse to s rising water table variable soil thickness has been noted.
Harrisburg, Pennsylvania Service Oil Company, located in Harrisburg, Pennsylvania, reported a spill that occurred between January and February, 1977. Forty-six thousand gallons had been reported lost.
Sixteen wells were drilled to monitor the contamination. The area is underlain by intensely weathered carbonate rock l
(pinnacle weathering).
Rocks are exposed at the. surf ace in several points and the area is prone to sink development.
Further site investigation is also currently taking place in the Philadelphia-New Jersey-New York areas. Spil?s in these areas are likly to occur in glacial outwash or coastal pitio deposits that are likely to be more l
I nearly homogenous and isotopic when compared with the fracture carbonate aquifer examples at Hechanicsburg and Harrisburg, Pennsylvania.
West Valley, New York The West Valley area may be ideal for this demonstration because the hydrocarbon spill is at shallow depth, solvent occurs within fractured till, it has a spreading front that has been detected in a number of boreholes and would not require the placement of deep test wells to obtain soil samples.
Shallew soil samples most likely could not be contaminated by radionuclides
~
11
\\
making the study simplier. The site contains a relatively new spill that f
f could be monitored over a period of one year to see if the. concentration of solvent increases rather rapidly with time..The fractured nature of till and dry summer of 1984 should help to opey.up fractures by dessication processes.
'l Gas vapor should move within these fractures each time the water table rises and as barometric pressure changes.
A preliminary set of soil samples taken from above, and adjacent to the documented solvent could be run to sae if there is potential merit of the Biedermann-Heinze method.
Enclosed is a list of literature relevant to the thesis proposal.
It is by no means complete, as literature review is currently taking place.
References are cited on petroleum spills occurring in the subsurface to give the reader an insight o'n the mechanisms involved in subsurface leakage and an overview on the current state of affairs.
References on the subject of geochemical exploration are also enclosed
?
The j
because of the relevancy of the subject matter to that of the proposal.
technique we intend to use in the detection of contaminant plumes, as mentioned previously, was intended as a tool for geochemical exploration.
Geochemical prospecting for petroleum reservoirs by means of soil analysis has been employed since the early 1930's.
Early methods developed for geochemical exploration involved the analysis of interstitial soil gases for hydrocarbon constituents derived from the vertical migration of gases from the petroleum reservoir (Laubmeyer, 1933).
Developments by Horvitz (1939) and Rosaire (1940) involved analyzing adsorbed hydrocarbons directly on the soil itself.
Numerous field experiences by Horvitz and Rosaire confirmed the fact that this type of analysis yielded greater concentrations of hydrocarbons than analysis Smith and Ellis (1963), performed chromatographic analysis on of soil air.
hydrocarbons adsorbed on the soil. As o recult cf th2ir findirgs, th;y 8
n questioned the presence of hydrocarbons in soil due to e jetroleus source.
They felf the presence of hydrocarbons f rom a petroleum reservoir could be small and would be overshadowed by hydrocarbons from small amounts of r~
vegetation.
Horvitz (1972), using a hydrogen flame chromatograph to analyse
)
l the adsorbed hydrocarbons on soil, concluded that organic matter in the soil does not interfere with the applicction of hydrocarbon geochemistry to petroleum exploration.
To date, many techniques have been employed in geochemical prospecting, including analysis of 002 found in soils above a petroleum reservoir, to carbon isotope ratios from underlying hydrocarbon accumulations. Requested literature will give further insight into current methodology development.
Astresses bO O
e n
V V V _..
y Phasanthreae 1.3.7 trimethylasphthalene Anthraquinone g,
18 B.C-4%
Perylens Asenaphtheos Carbazole
/
/
/
\\
E 30 Acrnne Asc.aphthylene A
Dibenzothiophene N
M pg Pyrrole a
1seary m ulade CE,-s-s-CH
/s
/
Naphtherde acids y,g, C:!:d:
CnH o,
y Ooo exarnple:
Dibydropyrens oon Y
50 Cho!Ic acid I C-CR.
\\
/
CE.
Co-C a ParaEas
,,, cm drCs,ca. coon i
y UPPER RIGHT Tetrahydr pyrene 2 maphthol b/\\/
-on Bo-
-on
/
y leaphth,;, g Proscaterone coon ss C W,.
E. -
- t *.tcr:rp) Tete
=o CE.
70
/
6 b/\\/
2-caphthioc acid h/ /
-Coon is 0yy V
s Figure 1.
Petroleum compounds separated out on various portions of filter paper in the presence of solvents using the Biedermann-Hein:e method.
e Tatde 1: Classification of Crude Petrolaum and its Components 3088+
SoSieg fehus Aa.ge *C 498 8 Se les ASe Ice 25e sSe See 8M N
.e-FesselsesntM
[ini.ile llemvy itslue
-- ui.imai,--- -- nimane-- 4 can.
-- Petroleusn.-- -
c-.a-cn oas.,, a.id.,icesi ig oils --
8.ght breep hgbo beavy r
Asphaltenes -
Maame3
.e-.-Kernunes-o. e-t'inet uits lighs be,sey hyb,
. beeny I
.eNephshes
- Solid
~
I-N C4 andlewer., d'h" I.ieguid Cm C
C4 Cs Cs Ces Coe Paraffinic-Paraffinic Paraffinic-Naphthenic Naphthenis l'araffinic Naphah,nic-Naphtisenic Base halen Paraffenic (8 W)
Mised (Arosnatic)
Nephthenic (lleavy)
Asplialtic ss*-4f st-se*
2s*-as*
l'&^&
spa ne ceevisy o.s ss-o.soo o.s4o-o.su n.,ou-o.970
..,.....u.,,,,,,,,,,,,,,,,,,...e
. n,. g.
~.
g,,
From Crabbe and McBride, 1978) 6 6
e
' - - - - ~ -
13 t
REFERENCES American Petroleum Institute,1972, The Migration of Petroleum Products in a
Soil and Groundwater, Publication 4149: API, Washington, D.C.
United States Biedermann, E. W. and B. Heinze, 1964, Geochemical Exploration:
i Patent, 3,149,068, Sept. 15, 1964.
Blake, S. B. and R. A. Hall,1984, Monitoring Petroleum Spills with Wells:
Some Problems and Solutions. Fourth National Symposium and Exposition on Aquifer Restoration and Groundwater Monitoring, NWWA, Columbus, Ohio, pp. 20.
Journal of the Blair, Hunter,1980, Groundwater Pollution by Oil Products:
of Water Engineers and Scientists, 34, No. 6, pp. 557-569.
Instit.
Nichols Publishing Crabbe, D. and R. -McBride,1978, The World Energy Book:
Co., New York, pp. 259.
Dennis, David M.,1977, Effectively Recovering Oil Spills to Groundwater:
Proceedings of the 1977 Oil Spill Conference, March 8-10, 1977, API f
Institute, pp. 255-258.
Duf fy, J. J. and M. F. Mohtadi,1977, Subsurf ace Persistence of Crude Oil Oil Spill Conference Spilled on Land and Its Transport in Groundwater:
Proceedings, New Orleans, La., pp. 475-477.
Ground Water Age, Ferguson, D. P.,1979, Petroleum Contamination of Wells:
14, No. 1, pp. 67-74.
Fried, J. J., P. Muntzer and L. Zilliox,1979, Ground-Water Pollution by Transfer of Oil Hydrocarbon: Groundwater, 17, No. 6, pp. 586-594.
Hepple, Peter (ed.),1967, The Joint Problems of the Oil and Water Industries:
Elsevier Publishing Co., Amsterdam, 156 pp.
m
y n'
t Kamath, K. I., J. Pasini and B. J. Kush,1980, Contaminatics cf Froch Wator b
Aquifers by Oil Spills: in: Third Annual Madison Conference of Applied Research and Practice on Municipal and Industrial Waste, Sept. 10-12, pp. 174-186.
/-
Ground Water Kramer, William, H.,1982, Groundwater Pollution f rom Gasoline:
l Monitoring Review, Spring 1982, pp. 18-22.
[
Lappala, E. G. and G. M. Thompson, 1984, Detection of Ground-Water 9
Vadose Contamination by Shallow Soil Gas Sampling in the Vadcre Zone:
Zone Conference, NWWA, Columbus, Ohio, pp. 28.
Natis, John R., 1971,_ Petroleum Contamination of Ground Water in Maryland:
Groundwater, 9, No. 6, pp. 57-61.
McKee, J.
E., F. B. Laverty and R. Hertel, 1972, Gasoline in Groundwater:
Journal of the Water Poll. Control Fed., 44, No. 2, pp. 293-302.
Mechanicsburg Area Product Salvage Report, March 1984, Department of Environmental Resources, Harrisburg, Pennsylvania.
O'Connor, M.
J., 1981, Contamination of Groundwater by Hydrocarbons from a Refinery--A Case History: Proceedings of the 1981 011 Spill Conference, March 2-5, 1981, APl Institute, pp. 393-399.
Pf annkuch, H. O.,1983, Hydrocarbon Spills, Their Retention in the Subsurf ace 4
and Propogation into Shallow Aquifers: NTIS, DB-83-196477, 51 pp.
Service Oil Co., 1977-1984, Updated reports submitted by R. E. Wright and Associates, Department of Environmental Resources, Harrisburg, PA.
Slater, J. P., F. R. McLaren, D. Christenson and D. Dineen,1984, Sampling and Analysis of Soil f or Volatile Organic Compounds:
Methodology Vadose Zone Conf erence, NWWA Columbus, Ohio, pp. 37.
Development:
Williams, Dennis E. and D. G. Wilder, 1971, Gasoline Pollution of a Ground-Water Reservoir--A Case History:
Groundwater, 9, No. 6, pp. 50-56.
15
- , y., :,
REFERENCES:
GEOCHEMICAL EXPLORATION Duchscherer, W. 'J., Jr.,1980, Geochemical Methods of Prospecting for Hydro-i l
carbons: 011 and Gas Journal,' v. 78 No. 48, pp.194-208.
, Gottlieb, B. M. (editor), 1981, Unconventional Methods in Exploration for Petroleum and Natural Gas: Sout ern Methodist University, Dallas, 257 pp.
Borvitz,' L.,1939,' On Geochemical Prospecting: Geophysics, v. 4, pp. 210-228.
Borvitz, L.,'1945, Recent Developments in Geochnical Prospecting for Petroleum: Geophysics, v. 10, pp. 487-493.
Horvitr, L.,1972,-Vegetation and Geochemical Prospecting for Petroleum:
Am.
Assoc. Petroleum Geologists Bull., v. 56, No. 5, pp. 925-940.
Kartsev,- A. ' A., Z. A. Tabasaranskii, M. I. Subbota and G. A. Mogilevskii, 1959, Geochemical Methods of Prospecting and Exploration for Patroleum and Natural Gas: University of California Press, 347 pp.
Laubmeyer, G.,1933, A New Geophysical Prospecting Method, Especially for Deposits of Hydrocarbons: Petroleum, 29, No. 18, pp. 1-4.
McDermott, E.,1940, Geochemical Exploration (Soil Analysis):
Am. Assoc.
Petroleum Geologists Pall., v. 25. No. 5, pp. 859-881.
Rosaire, E. E.,1940, Geochemical Prospecting for Petroleum:
Am. Assoc.
Petroleum Geologists Bull., v. 24, No. 8, pp. 1400-1433.
Smith, G. H. and M. M. Ellis, 1963, Chromatographic Analysis of Gases from Soils and Vegetation Related to Geochemical Prospecting for Petroleum:
Am. Assoc. Petroleum Geologists Bull., v. 47, No. 11, pp. 1897-1903.
- Stegna, L., 1961, On the Principals of Geochemical Prospecting:
Geophysics,
- v. 26, No. 4, pp. 134-145.
ei
-<,+--%-
,m_
y s--:.gg-y
---,-,-,----,.7.-_3-.--,
,~
- REQUfj';7'D LITERATURE ;s0 DATE:
. Brown, S. W.,1981, Surf ace Detection of Free Hydrocarbon Microseepage from Am. Assoc. of Petroleum Subsurface Petroleum Accumulation, Case Study:
Geologists Bull., Abst., 65, No. 5.
Coggeshall et al., Oct. 16, 1956, Unitt'd States Patent, 2,767,320.
Durand, B.,1983, Present Trends in Organic Geochemistry in Research on Migration of Hydrocarbons:
in Advances in Organic Getchemistry,10, pp. 117-128.
Dyer, Rolla McIntyre,1983, Reservoir Identification by Chromatographic Special Publication--Kentucky Geological Survey, 6, pp. 32-36.
Methods:
Asso. of
. Hunt, J. M.,1981, Surf ace Geochemical Prospecting--Pro and Con, Am.
Petroleum Geologists Bull., Abst., 65, No. 5.
Larsen, Nov. 25, 1947, United States Patent, 2,431,487.
Winters, J. C.,1983, State of the Art of Organic Geochemistry in Petroleum in Advances in Organic Geochemistry, 10, pp. 3-6.
Exploration:
I 1977, Application and Yagodkin, V. V., S. G. Kulagin, and I. S. Sarkisyan, Significance of UV-Microscopy in Oil and Gas Prospecting Geochemistry:
Abstracts of Reports--International Congress on Organic Geochemistry, 8, pp. 47-49.
9
dimetto Abd3-
?;bfonasylv',nin Stato Univ rsity-Department cf Geo:ciencio
'343 E!aike Building
' Dniversity Park,PA 16802 (814) 863-0590-t
~
EDUCATION The Pennsylvania State University,-1A,9/83 - present.
M.S. Thesis Topic: See attached proposal-Advisor, Richard R. Parisek t Long Island' University, C.W. Post College, Long Island, New York October, 1981. Bachelor of Arts Degree with Honors in Geology and Environmental Science.
. HONORS Geology Student Award for academic excellence (C.W. Post College),
May, 1978 7-Phi Eta Society. October 1981' EMPLOYMENT EXPERIENCE f
Pennsylvania State University, University Park, PA 6/84'- present: Graduate Research Assistant.
Participation in a project for the abatement of acid nine drainage by application of limestone quarry waste. Responsibilities included supervising and assisting in the installation of suction lysimeters and piezameters. Routine sampling of soil water by suction ly-simeters.
j Participation in a project to restore a trout habitat effected by acid rain, Linn Run State Park, Ligonier, PA Assisted in a
' 24 pump test to determine aquifer characteristics.
1/84 - 5/84: Graduate teaching assistant.for introductory geology course.
'(
- f State College Borough (Water) Authority, Stcte College, PA_
Field collection of water level data from wells 7/84 - present:
in the State College area to determine effects from pumping of the Nixon Well Field.
New York Legislative Connission on Water Resources, Great Neck, New York 11/82 - 6/83: Volunteer work on a project to determine the extent of contamination plumes in aquifers that are generated by gasoline i
spills, oil and' landfills. Research involved the collection and analysis of data (Board of Health and Department of Environmental Conservation) in order to determine the location and extent of contamination.
ORGANIZATIONS l
National Water Well Association Geological Society of America y--'-ty-g
.y
F. t:rit;d 5ept. H,1964 F
1 2
An ther object tf the Invention is to provide a novel l
- J) method for detecting the presence of petroleum constito-3,149,068
=
s CEOCifD13CA1. EXPLORATION Edeln W. Biederman. Jr., sod Benole Helnae. Tulsa, ents in earth samples.
- ~"?~'
Okla., assignors to Cities Serdce Research and Develop.
It has now h fM the h pesence of petrh.1'"t'
" I
,,, y ment Coropany, New Yor1, N.Y, a conforation of New 5 constituents in earth samples may be determined with a w
Jersey high destee of accuracy by Srst applying chromatographic f.i ci,(. g No Drawing. Filed h1ar. 8,1961, Ser. No. 94,168 separation techniques to eeparate from the earth sample.. rgo.W *t 5 Claims. (CI. 210-31) those constit,uents which are not mobile in polar chromato. ' g.,,,,,,7
. graphic carr er solvents but which are mobile in}non-polar m
This invention relates to geochemical exploration and toTchrofirafographie earner solventsj The suorescence et 8"" W*,*
more particularly to the analysis of earth samples co ese consutuents is then checked to determine the pres.
determine the proximity of petroleum deposits.
nce of Sucrescent petroleum constituents in the earth Various geochemical methods have been suggested pre.
sample.
viously for determining the location of underground pe-Any suitable chromatographic technique may be used C>r.usf at e
troleum reservoirs. These methods are intended to detect II. In separating constituents of earth samples in accord. 'tiwn.a0: -
L the presence of petroleum constituentiin surface or under.
ance with tht persent invention. For instance, the sepa. Mer.. L-J -
=
ground formations in greater than normal quantity. Such ration scay be effected in a combination of chromato.pp4 m.s.
anomalics are taken as an indication of ths proximity of graphic columns packed with suitable chromatographic g;,n.
a petroleum reservoir or other concentration of petro-adsorption material such as cellulose, alumina sel, milica leum type hydrocarbons. Itis thus possible,bf detecting 20 gel,etc. While column chromatography or suitable com.
the presence of petroleum constituents in carth samples binations of other one dimensional chromatographic tech.
such as soil or rock samples, to ascertain the location and niques may be used, it is highly advantageous to utilize J. t.;rr...
?
proximity of petroleum deposits by correlating the relative tuo dimensional chromatography in obtaining the desired.,th 2 U.c E
amounts of petroleum constituents present in the earth separation of constituents from the earth samples. In two>m
samples with the locations from which the samples were 25 dimension:] chromatography, the sample being analyzed Of'd;
,M taken.
s5 placed on chromatographic adsorption material and-
"g,.r It has been suggested previously that the presence of driven in two different directions by two different carrie. ? '
?*.
c petroleum constituents in an earth sample may be detected solvents. Due to their different adsorption characteristics us *3 M.s-by exttmng organic constituents from the earth sample with respect to the adsorption material and solvents, the &",
f Tl m c'M r:r and then evaluating the fluorescence of the extract or a 30 various constituents of the sample are carried varying dis.
concentration thereof under ultraviolet light. These tances along the adsorption material in each direction
, 'f.
methods depend upon the known fluorescence of certain before being deposited thereon from solution with the petroleum constitutents, especially intermediate aromatics, carrier. While any suitable bed of chromatographic ad.
One such method is described in U.S. Patent 2.451.853.
sorption material may be used. the use of a relatively thin While methods of this type for determining the presence 35 laler of material is preferred. Special chromatographie of petroleum constituents by fluorescence of earth samples paper or ordinary filter paper is especially suitable for this*".*j,,. -
or concentrated extracts thereof have met with some de.
purpose. Two-dimensional chror..atography using a rela-
~
~
' gree of success, such methods have frequent 1v failed _tg tively thin layer of chromatographic adsorbtion materialf,"[l l'
- y_rovi.de the, desired inferrr ation.becaus.e_ithas_been im.
such as filter paper is preferred in practicing the present,,,,
I possibic to distinguish the fluorescence due to the desired 40 invention for two reasons. First, this technique requiresb 1.r,..,
, s-r -
petroleum constituents from fluorescence due~to other arr extremely small quantities of extract sample and can thus s anic constitt.ents.
~
~ ~ ~ - - - ' ~
be used to analyze small carth samples. This, of course.
k.g i' lighter aromatics normally found in petroleum, fluoresce well as analysis and storage of samples and completed While certain petroleum constituents, especia!!y the facilitates co!!ection and transportation :sf samples as
- .,. E *.
-,,M O', j strongly in the light blue range under ultraviolet radiation, 45 chromatograms.
In addition, this technique, especially numerous other organic compounds which do not neces-in the form described below,is very simple and readily j.
sarily indicate the presence of petroicum (although they adaptable to field conditions, requiring only a minimum p O.O o may also be present in petroleum) also fluoresce under of simple, rugged equipment and small quantities of sup.
f
+
9 rpc;*%c,c #-
suhraviolet light, some of them in the same color range.
plies.
J
- w.-
For instance, extracts of coals, coal.like materials and 50 In applying two dimensional chromategraphy to the c
.r -
chlorophylls all flooresce under ultraviolet light but are not praetice of a preferred embodiment of the present inven.M. *C, i.
v.y
. f anindication of the presence of petroleum. More specifi.
tion. the earth sample being analyzed is first treated withr,....a i
g('
cally, anthracene type materials fluoresce with a light blue suitable solvent to extract organic constituents including +r e, -
J.-
color and are readily extracted from soft coal and anthra-the desired petroleum conrtituents therefrom. This ex J.
.e s cite. Where the anthracene is oxygenated and ocents as 55 tract is then deposited on chromato;raphic adsorption -., r-anthraquinone,it also fluoresces blue. Organic acids and material such as ordinary filter paper and the solvent is... *** "
F cresols likewise contribute tr.be overall fluorescence of -~ preferably at least partially evaporated. A polar chrod * ' C carth samples. Crude oil-
., wever, contain much less malographic carrier solvent is then introduced into the ad..# -
W-of these materials than di scales, especially oil barren
- sorption material and passes therethrough by adsorprion. 6 V,'
~
h shales. If a sufficiently strug sohent is used to extract C0 Constituents rnobile in the polar carrier sohent are thuf::'
P' substantially all of the desired petroleum constituents, separated from the deposited extract and moved along ther -
then any of these undesirable fluorescent of;2nic con-adsorpiton material in the direction taken by the carrier.O " ' ~
~
stnuents present in the sample will be extracted along A non polar carrier sohent is then introduced into the ad-
~
r with the desired petroleum constituents. Presiously sorption material so as to pass throu;b the adsorpion ma. E
- known methods for determining the presence of petto. C3 terialin a direction perpendicular to the path of the polar s, i u U
_L leum constituents by fluorescence of carth samples or ex.
soh ect. The non. polar schem thus moses constituents ~- '
tra:ts therefrom have been unable to discriminate between of the deposited estract which are mobile in the non polar
-: **' ?
the sarious types of fluorescent materials mentioned solvent alor; the adsorption material in the direction of above.
movement of the non. polar solvent. The fluorescence of
)
It is an object of the present invention to provide an *0 any of the thus separated constituents of the earth sample r-icvrosed method of geochemical exploration to deter-mal ther. te est. lusted by suitable means such as the use mine the proximity of petroleum deposits.
of a st:r.dard t.hraviolet 1;ght. It should be understood a-er e
p 2
M
WV "
aorption material la a Cr~PD nos para 0M and prefer.
Iowing description of various constituents found in various
- j.,,
ably perpendic,sar to the direction of movement of the corners of squares of Alter paper following analys*a of the Arst solvent. While k order in chich the polar and non 5 type described tbove is based on the assTmption that suffi-I',
polar solvents are employed is not critical, it has been cient quiltities af carrier solvents are utilized to cive the
[
found Cat somewhat sharper separations of various con-majority of such compounds which are mobile la the par-stituents are obtained when the polar solvent is used Arst ticular solvent involved substantially the entire width of and the use of a polar carrier solvent followed by a non.
the Alter paper. If the analysis is carried out in this fasb.
's 1
polar carrier solvent as described above is, therefore,10 loo the various constituents will be grouped substantially r"
preferred.
at the corners of the Alter paper. The following com-o i
As a matter of convenience in using the two dimen.
pounds are t> pica! of those which wi!! be found at the alonal chromatographic techniques described above and various corners of the Alter paper when the required j
1 in discussing the results obtained with such t.chniques it chromatographic separation has been accomplished in the has been found desirable to deposit the extracted organic 15 arbitrary manner described above using methanol as the constituents of the earth sample on the corner of a square polar carrier solvent and heptane as the non. polar carrier.
or rectangular piece of Alter paper and arbitrarily refarfo UPPER LEFT
.i the various, portions of the Elter paper with reference Anthracene to the position of the filter paper when the deposited ex.
tract is in the lower right hand corner thereof. This prac. 20
,A l
tice will be followed berein.
1
. 4 14 A wide variety of organic solvents are suitable for ex.
J.-
O tracting organic constituents from carth samples in the
'd., " '
practice of the present invention. It is preferred, how.
Phenanthrene f.'
ever, to use solvents sufficiently strong to insure that all of 25 6bl4NIO t
the desired fluorescent petroleum constituents are ex.
tracted from the sample. If all these constituents are not pqrci #. g g*
II extracted, the quantitative analytical results will, of courte, p gp cht be somewhat in error. To insure that substantially all of y
the constituents are extracted, the organic solvent used is 30 l
preferably one which is sufficiently strong to dissolve asphahic material. These may be referred to as strong a
organic solvents. For this purpose asphahic material l
may be defined as hydrocarbon material which is not solu-Acenaphthene ble in pentane. Suitable strong solvents include, for in-35
/N A H
stance, benzene, toluene, x)lene, carbon te:rachloride, di.
C ethyl ether, ethyl acetate, etc. or combinations of these g
g with polar solvents such as isopropyl aJcohol or acetone.
%A/
8"M Iitewise, any suitable polar and non-pc!ar carrier sol.
D vents may be used in practicing the present invention. In 40 h))
order to cause all of the desired constituents to migrate Acenaphthylene
,,Y' without having an excessive amount of the relatively U
Y' heavier asphaltic material migrate, it is preferred that both the polar an! non-polar carriers be relatively weak carriers which are not sufficiently strong to cause migra-es Be:
[
tion of asphahic material as defined above. These may
/
i be refe to as weak polar and non-polar carrier a'
_pise of overly strong carrier solvents tends to r
i i
reause migration of asphahic material which then masks Pyrene Na, k l
.the presence of the desirable constituents, especially the 50
.J' lighter aromatics. Suitable weak polar carrier solvents in-
- W clude. for instance. methanol, ethanol, acetone or mixtures of these with sma!! amounts of water.
.MM Duitable non-polar carrier solvents include. for instance,
/
/
h straight cbc.in hydrocarbons having at least 5 carbon 55
,t atoms, branched chain paraffins, cycloparaffins, etc.
Among the polar carrier solvents methanoi has been found especially suitable while among the non-poler car-Dibydropyrene e
a.
rier solvents hexane, heptane and octane have been found especially suitable.
CD C -(
When organic constituents extracted from carth sam-y ples are deposited on the corner of a sheet of fiher paper y
as described above and the polar carrier solvent is intro-
%Af s.n4 duced by placing the lower edge of the filter paper in the solvent so as to cause the same to move upwardly through C5 h
the fiber paper and the nontolar carrier solvent is then A/
l h@j introduced by placing the right hand edge of the filter Tetrahydropyrene paper in the non polar carrier solvent so thit it ene to r
fik the lef t across the filter paper,% desired fluores:ent AA 3.nz
.p1 peirn cens-ttttnts v.hich are mocile in the non-polar 70 solvent but irr.rnobile in the polar sohent v.ill be found
'l 8
i 9J 1
(along_the leecr ce nf th-har rove nr ehre- -: ;rari.
6A//
It is chious that the distan:e from the original deposit g,
at which th:se consti:uents mi!! be found de;:nds t:pon j
)
1:
,)
the ameent an.! cen:entration cf th: cerr.:t scuent u:i. is N/N/
g
,, w. v...w
.g f
at
- g (
.L.ew.=*
p =y
.n. +h.[, N 1-2.*Q E b.,.dO [-jag O.bO- $ N d U
.~.
.~.
.'.b
~..
u.
b-.2:8.. ::* *'"$.C'""".~ D *2 * 'h"I ~~"
g ti
.'yL
~ ~ ~ ~ ~ ^
c i.
3,149,068 6- * ;
5 6
t 2.naphthioc acid
/
IJ h u P)T888 coon was the AA par.
Quinoline b e!
/gj\\/
' sh.
I a
ially 10
/.
{
rom-yy tthe I.
aired Decalin, C.His Anthraquinone i
- j w$
^^
vv 1,3,7 trimethy! naphthalene g
Ea BaC-Carbazole O
-cm u
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Earth sampics from the follow'ng rock formations were constitue:ts chich are mobile in a weak non-polar chro.
g-also cnalyard as described tbove.
matographic carrier solvent and immobile in a weak polar chromatographic carrier solvelt from a) carth sample j
y A,,
y ties 3 i.
es.i.
containing the same which comprises contacting the earth 5 sample with a strong organic solvent to extract organic Pale n we...
'rew.
constituents including the desired petroleum constituents rcrs4en sen A.ndres...
e tenien....
De therefrom, depositing thus extracted organic constituents ge.....
bI**~~~.""'.".."nan.~.~
N-.
- SI on chromatographic adsorption material, and treating thus go.
deposited organic material with a weak po!ar and a non.
w ume_
se g....
E.".*****. DI 10 polar carrier solvent by Arst passing one of said carrier Fenm rWe~~~.~~;.'""." So*** I'.~".
d D e......... can res..
Permian....
De-solvents in one direction through the adsorption material N:*............Z NE
$~....
DI Ao thereby separate fractions of the organic constituents
~
Do. -
cocrotie Twen cur...
Kanas mobile in such carrier and then passing the second of N:"*".".~~.**"~. En$na UE""
N~~.~..'
SI said carriers through the chromatographic adsorption cressemons....~
haewry....
trine Rtrer_ wyomtos.15 material in a direction non parallel to the path of the first of said carriers to thereby separate fractions mobile In each case the extracts from these earth samples fluo-in said second carrier.
resced strongly while analysis in accordance with the
- 3. The method according to cla'un 2 in which the or.,
present invention disclosed that the flucrescent material genic solvent is a mixture of isopropyl alcohol and ace.
8 was actually composed partty of fluorescent petroleum 20 tone, the polar solvent is methanol and the non. polar constituents and partly of fuorescent constituents not in-solvent is beptane.
dicating the pretence of petroleum. This was in accord.
- 4. The method for separating fluorescent petroleum ance with known facts cineerning these ' formations. In constituents which are mobile in a weak non-polar chro.
the case of these earth sunples mere examination for flu-matographic canier solvent and immobile in a weak polar crescence correctly indicated the presence of petroleum 25 chromatographic carrier solvent from an earth sample constituents but gave completely erroneous information cantaining the same which comprises contacting the carth concerning the relative quantities of such constituents sample with a strong organic solvent to extract organic since, except by the application of the pretent invention, constituents including the desired petroleum constituents it was impossiole to determine how much of the fluores.
therefrom, depesiting thus extracted organic constituents,
cence was attributable to peticleum constituents and how 30 on chromatographic adsorption material, and treating much to non. petroleum indicating constituents.
thus deposited organic material with a weak polar and a l
i The above examples iridica:e clearly that the process of weal non. polar carrier by first passing one of said car.
the present inventien is capabic of distinguishing between riers in one direction through the adsorption material to those fluorescent constituents of earth samples which in-thereby separate fractions of the organic constituents mo.
dicate the presence of petroleum and those fluorescent 35 bile in such carrier and then passing the second of said 1
constituents which may or may not be present in petro-carriers through the chromatographic adsorption mate-leum but which do not necessarily indicate the. presence of rial in a direction generally perpendicular to the path of petroleum.
the first of said carriers to thereby separate from said While the invention has been described above in con-first fractions the se fractions mobile in said second carrier.
nection with certain preferred embodiments thereof, it 40
- 5. The method of determining the presence of fluo-
~,
e will be understood by those skilled in the art that various rescent petroleum constiments in an earth satnple contain-changes and modi 5 cations may be made without depart-ing the same and other fluorescent organic constituents ing from the spirit and scope of the invention and it is which comprises contacting the earth sample with a strong l
Intended to cover all such changes and modiScations in organic solvent to extract organic constituents including the appended claims.
45 the desired petroleum constituents and other undesired We claim:
fluorescent constituents therefrom, depositing thus ex-
- 1. A geochemical exploration method for determining tracted organic constituents on chromatographic adsorp.
the proximity cf an underground petroleum reservoir tion material, passing a weak polar chromatographic car-which comprises collecting carth samples from various tier solvent through said adsorption material in one direc-locations in an exploration zone, similarly and separately 60 tion to thereby separate from the deposited organic con-treating said samples by contacting them with strong or-
. stituents fractions mobile in said polar carrier, passing ganic solvent to extract organic constituents including a weak non-polar chromatographic carrier solvent through desired petro! cum constituents therefrom, chromatograph-said adsorptien material in a dkection generally perpen-ically fractionating each sample to separate therefrom flu
- dicular to the path of the polar carrier to thereby sepa-crescent petroleum constituents mobile in a weak non-55 rate fractions mobile in the non. polar carrier and subject-polar carrier solvent and immobile in a weak polar carrier ing thus separated fractions to ultraviolet radiation.
solvent, subjecting thus separated constituents to utraviolet I
t radiation and correlating the relative fluorescence of the References Cited in the file of this patent flucrescent petroleum constituents separated from each UNITED STATES PATENTS sarnple with the locations from which such samples were CO I
taken.
2A31,487 Larsen............... Nov. 25, 1947 I
- 2. The method for separating fluorescent petroleum 2.767,320 Coggeshall et al......... Oct. 16, 1956
/!OVdV" Task 2 Report Outline: Research Plan for Investigating Radionuclide Migration at the West Valley Facility Disposal Area 1.
Executive Summary II.
Introduction III.
Source Characterization A, Present Knowledge
- 1. Summarized by Hurt (1984): evaluation of hull and irradiated fuel rod nuclide inventories.
Estimations ci 137Cs, 90Sr, 60Co, and transuranics probably accurate within 2-to 4-fold.
- 2. Hurt's estimates of fission product inventories dependent upon Pu recovery figures, which are highly variable; assumption of similar recoveries is questionable.
- 3. No evaluation of 1 291 or 99Tc levels in irradiated fuel rod assemblies; likely to be both quantitatively significant and highly mobile.
B. Additional Studies Needed
- 1. More complete estituation of nuclide inventory in irradiated fuel based on NFS records and known fuel burnup rates.
- 2. Identification and quantitation of all radionuclide-containing solvent in FDA burial pits (stipulated in Task 1 report).
- 3. Sampling of burial hulls not recommended for soarce characterization variability of hull nuclide concentrations, but may be necessary for leaching studies (see Section II).
IV.
Waste Form Leaching A. Present Knowledge 3,60Co, 137Cs,
- 1. Physical characterization of form of H
90Sr, transuranics in hulls outlined by F4urt (1984).
- 2. Virtually no information available on leaching of nuclides out of hulls or cladding.
- 3. Considerable body of information available from Swedish and U.S. investigators (primarily PNL and LANL) on leach rates of nuclides from irradiated fuel.
a) Due to migration within fuel assembly, 137Cs leaches I9 i; up to 10% of relatively rapidly, as does inventory may be leached within weeks.
. y L
6 2
b) 90 r leaches 30-fold more rapidly (0.12/yr) than S
most.other fission products.
c). Uranium and Pu dissolution rates are less than 0.001%/yr.
d) Leaching of all nuclides considerably slower under reducing conditions; ef fects of pH and complexing ions present in groundwater have been investigated.
B* Additional Information Needed
- 1. Determination of present status of hull cannisters
-(saturated vs dry) by test borings into representative hull burial pits.
- 2. Determination of leach rates of radionuclides from chop-leach treated hulls (obtained either from other sources or by exhumation at FDA). Laboratory studies should include effects of water pH, D.O. content, and presence of groundwater complexing constituents.
- 3. Determination of groundwater composition and oxidizing /
reducing capacity within burial pits (water may be quite different than within till due to rapid inf.iltration through cap). Wil1 require test borings into representative hull
~
burial pits.
l c
- 4. Assessment of radionuclide migration rates through concrete containment of NPR fuel rods, based on known rates of water
,(
infiltration through concrete and attenuating effect of alkaline material.
- 5. Laboratory studies on possible enhancement of extraction of radionuclides frca hulls by buried kerosene-TBP solvent (recovered from burial pits SH-10/11).
V.
Radionuclide Mob!11ty A. Present Knowledge
- 1. Site-specific monitoring of present extent of nuclide migration, a) Extensive monitoring for nuclides in cores and groundwater adjacent to and beneath NYS burial 3H trenches indicate downward movement of only (Im) dvring the past decade.
1,y 3
b) Cores and pore water from USGS boreholes around FDA show uniform distribution of 3H through
, eathered zone, possibly indicating movement by w
shallow subsurface pathway from burial pits.
137Cs in FDA surface; may c) Ubiquitous presence of be.due to original burial practices or airborne contamination rather than aqueous mobilization.
- 2. Studies on Euclide Form a) Surface water studies indicate association of nuclides with fine particles, as would be expected from earlier studies at a number of sites (eg. ORNL Trench 7 study).
b) No extant data on chemical / physical form of nuclides in groundwater samples at West Valley.
B. Additional Studies Needed
- 1. Evaluation of form and concentrations of radionuclides in burial pits.
a) Cores from several test borings into hull burial pits should be analy' zed for nuclides to determine vertical extent of migration at present.
b) Burial pit water samples should be analyzed for nuclide I
concentration, speciation (redox state, free vs. complexed),
and extent of particle} association.
Additional water analyses should be determined to assist in radionuclide species characterization (Section IV.B.3).
Nuclide 99Tc and 1 29,
1 analyses should include
- 2. Determination of Nuclide Mobilization Parameters a) Laboratory eclumn experiments to assess rates of nuclide mobility through both weathered and unweathered till. 'Should employ groundwater of same composition as that at West Valley, with nuclide
" spikes" added under both oxidizing and reducing conditions.
b) Determination of nuclide Kd values from West Valley groundwater onto lacustrine material under natural conditions of redox and pH.
1
)
J
7-j c
l 4
c) Laboratory experiments on potential for alteration of f
nuclide sorption onto weathered til1~due to presence or
. prior presence of kerosene-TBP solvent (as stipulated in Task 1 Report).
d) Laboratory experiments to determine extent of nuclide sorption by till material along fractures in weathered till layer.
- 3. Monitoring a) Emplacement of monitoring wells within unsaturated weathered till (0-3m) around FDA.
Sample collection on flow-weighted basis (i.e. most frequent during apring thaw and storm infiltration), and analysis for both soluble and particle-associated nuclides.
b) Collection of samples annually from lacustrine unit through existing USGS wells, and analysis for nuclides.
VI.
S.te eohydrology - Subsurface Hydrologic Transport A.
Introduction:
Main Issues B. Near-Surface Versus Deep Flow
- 1. Solvent movement indicates that near-surface route may be important; experience at the NY State commercial site.
C. Operational Division of the Problem: Water-Budget Versus Mechanistic Analysis.
- 1. What are the'aurface, interflow, and base flow components; What are the groundwater pathways?
D. Overview of Regional Geology (Provided by Parisek)
- 1. Cross-sections of geology.
- 2. Critical review of Sec. 2.3, Albanese et al. (1982).
- 3. List of key qualitative (quantitative, too?) questions to be answered.
E. Water-Budget Analysis
- 1. Importance - provide information on infiltration, ET, recharge for subsurface flow analyses.
5
- 2. Past Work. Prudic,19 79 7, draf t pp. 26-27 provides overview of streamflow. See also Boothroyd et al.1979; Ragan et al.1979.
- 3. Cooperation between NYSGS and USGS p. 43, Albanese et al,19 82.
Stream flow data collected at B1 near burial-ground, including stage, discharge and suspended sediment.
Record is available for 6/19/81, 9/28/81, to 12/7/81, 3/7/82 to Lapses due to freezing and channel slumping.
- 4. Precipitation data was recorded at 3 Belford ' gages. Find out interval of record, status of data. Estimated snowfall input for snowstorm of 4/3-7/1982. May need methodology for routine measurement of snow ( Albanese,1982).
- 5. Continued monitor / data reduction of precipitation /s.treamflow is needed.
- 6. Infiltration Studies. Recommend field work 50 determinations with double-ring infiltrometer ($1000 equip., 1.5/12 PY, 5 days in field). Consider tests at negative pressures to assess role of cracks in flow regime.
- 7. Biological Components. Relate grass standing crop to interception storage.
Develop method to assess e
interception easily. Measure root depth and density distribution. Determine ET rate for at least 1 growing season (cost for ET work:
$6000 equip., 3/12 PY).
(
- 8. Data Analysis. Do hydrograph separation to assess flow components.
Run water-budget models to assess recharge rates for subsurface flow.
F. Near-Surface Flow
- 1. Review past work, especially observations of soil cracks at test trenches, inadequacies of past modeling, and information inferred from solvent movement.
- 2. Quantification of near-surface soil hydraulic properties.
Perform in situ drainage test for conductivity-wetness-pressure relationships. Design / perform a macro-scale pump-in test for large-scale saturated hydraulic conductivity.
Emphasize the experimental aspects of latter task.
- 3. Consider the use of remote sensing, i.e., thermal scanning as a means to identify wet spots where possible recharge or seepage occurs.
Possible location of buried materials.
... -, N6 :
-1 6
- 4. Thermal exploration of flowing tributaries to determine
- seeps.
- 5. Investigate the status of existing burial holes. Test borings in selected trenches to determine.if "bathtubbing" has occurred.
- 6. Monitor tensiometer networks to determine patterns of~
unsaturated flow, rates of drainage.
- 7. Place wells in near surface with continuous monitoring.
G.' Deep Subsurface Flow
- 1. Review past work, especially the modeling of Prudie and assessments of Bergeron and Kappel.
- 2. Dating of groundwater.
Age of water recovered from the near surface, middle of laver and lacustrine sands would yield indication of deep recharge.
Explore suitable methods.
- 3. Consider further pump tests.
Assess the significance of unsaturated conditions at depth.
H. Role of Computer Modeling s
- 1. Discuss past modeling.
Design model to examine near-surface flows. Dynamic simulation.
- 2. Model 2-dimensional cross-section of the deeper system.
Review available models.- Examine conditions which could yield observed unsaturated conditions.
- 3. Where deemed important, couple solute transport /
absorption model-for radionuclide movement.
I.~ Possible Role of Remote Sensing
- 1. Discuss the analysis of available dats; the possible use of remote sensing for long-term assurance of trench-cap integrity.
1 VII.
Site Geohydrology - Erosion Hazard l
A. Review of past work. Two nick points in gulley within Frank's Creek are advancing up-gradient at 9-15 f t/yr (Boothroyd et al.,19 82).
Potential for land sliding and sheet erosion will be discussed.
6
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B. Utility of a monitoring system based on precision surveying.
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C. Review of possible remedial techniques.
Contact DeBoer at NYSERDA regarding state activities in slope
?
stabilization.
{
VIII. Conclusions and Reconsnendations IX. References 4
op go Bf e
a