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ADDITIONAL GEOLOGICAL INFORMATION

– GEOLOGY OF MARCELLUS SH ALE AND

OTHER PENNSYLVANIA SHALE FORMATIONSPA DEP TENORM S tudy Report

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- 1 Appendix A

Additional Geological Information

 Geology of Marcellus Shale and Other Pennsylvania Shale Formations

The following information is provided by Dr. Robert C. Smith II, retired geologist with the Pennsylvania Geological Survey. Dr. Smith has ex tensive knowledge of Pennsylvania geology

and has been a consultant for the DEP Bureau of Radiation Protection, Radon Division

, helping

with the understanding of Rn and geology. The information below is not part of the original scope of work for the TENORM study, but rather explanatory and supportive geology

information as it relates to TENORM issues.

The Lockatong f

ormation is primarily recognized only in the high population density Bucks and Montgomery c ounties in the Newark Basin of southeastern Pennsyl vania. Demographic concerns can be expected to inhibit natural gas development from the Lockatong in Pennsylvania and across the Delaware River in New Jersey. However, the Lockatong and its companion

Stockton f

ormation remain serious concerns for indoor Rn and locally for radiums in groundwater.

In addition to the above, in northwestern Pennsylvania the Rhinestreet Member of the West Falls

f ormation associated with the Belpre volcanic ash, and the Pipe Creek Member of the Java

f ormation associated with the Center Hill volcanic ash bed, are black shales having natural gas potential. (The association of black shales with volcanic ash beds is considered favorable for natural gas recovery but beyond the scope of this report. It is mentioned here only because

de velopment might migrate away from areas where the black shales are thickest or even most organic

- rich.) Therefore, they may yield TENORM issues; however, because they are recognized only at depth, they will not yield indoor Rn problems when undisturbed.

T wo samples of black shale and one of a high

- graded black shale sample containing major rounded phosphate nodules and barite veinlets were collected from the Shellsville Member of the Dauphin f

ormation of the Hamburg Sequence, Lebanon County. The shale is r eported to be of Ordovician age. Because the area has undergone multiple tectonic events, whatever natural gas potential there once was is now minimal. Those data are useful for understanding and projecting indoor Rn hotspots

, but are not discussed further herein because they are not expected to yield TENORM as drill cuttings or flowback fluids.

Antes Formation

The Antes f

ormation or, variously, Antes Member of the Reedsville f ormation , or “Utica of drillers,” was deposited at the end of an approximately 1 00 million

- year period of carbonate deposition on a continental shelf. Indeed, many marine black shales in Pennsylvania occur at the end of carbonate shelf deposition. The carbonate shelves were disrupted when a series of

volcanic island arcs collided with the coast of the continent of Laurentia, of which Pennsylvania

was an integral part. The island arcs themselves ranged in age from approximately 458 to

448 million years ago ( Ma ) and are believed to have struck Laurentia from the southeast to the

northwes t. They left volcanic ash bed debris across much of the eastern portion of the U.S. In Pennsylvania, the Upper Ordovician volcanic ash beds are best seen at the Union Furnace section, Huntingdon County (Smith, Way, and Berkheiser 1986)

, as whitish gray lay ers ofPA DEP TENORM S tudy Report

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- 2 volcanically derived smectite clays ranging in thickness from approximately 2 to 20 centimeters (cm). The fresh ash layers were probably about twice that thick when they first fell on the carbonate shelf, killing many carbonate

- based organisms in t he process.

The arc

- continent impact itself occurred during the Taconic Orogeny, which Wise et al. 2007

have dated at 450 Ma. The Antes f ormation black shales were then deposited over the drown carbonate shelf in restricted, reducing marine environments t hat permitted preservation of organic material. The volcanics in the newly elevated highlands may have provided some of the U as metastable volcanic glass devitrified over time. In the Ridge and Valley physiographic province (located to the east, southeast , and south of U.S. 220 in Cumberland Valley and its continuation to the northeast, Bald Eagle Valley and beyond), the Antes was thoroughly folded

and thrust

- faulted during the Alleghanian Orogeny at approximately 275 Ma, destroying reasonable hope of natu ral gas preservation in that province, but not removing the U. Such destruction is not surprising considering that it was Africa hitting Laurentia. However, beneath the plateau’s physiographic province much farther from the impact zone, Alleghanian folding and faulting were minimal and the natural gas reserves as well as the associated U remain largely intact. Erosion is generally agreed to have removed 4 kilometers (km) of sediment in the Ridge and Valley and perhaps a little less in the plateaus since the Alleghanian Orogeny (Smith 2003). The Antes itself is Upper Ordovician in age.

Mandata Formation

Like the Antes f

ormation , the Mandata f

ormation also formed following a period of carbonate deposition. In this case, however, the duration of carbonate depo sition was roughly an order of magnitude shorter and only included, from bottom up, the Silurian Wills Creek formation calcareous hypersaline shale; the Tonoloway f ormation sabka environment hypersaline; algal

laminate limestones; the Keyser f ormation lime stones; the thin, petroliferous

- smelling Coeymans; and thin, fossiliferous New Scotland f ormation cherty limestones. Following New Scotland deposition, carbonate formation ceased for a time and glauconite

- bearing marine phosphate nodules accumulated U from the new, black shale depositional environment which, like the Antes long before, received and preserved organic matter in a restricted marine

environment. Interestingly, the three Bald Hill Bentonites (volcanic ash beds) are found on the

New Scotland

- Mand ata contact. They were found in Pennsylvania by first being hypothesized to be present because of the carbonate to black shale environment change (Smith, Way, and Berkheiser 1988). Bald Hill Bentonite C has been dated at 417 Ma (Smith 2010, reporting work of J. Ramezani) and is the effective boundary between the Silurian and the Devonian in Pennsylvania. Where exposed in the Ridge and Valley, the high organic zone is several meters thick, but an easy natural gas bonus if one already has a deep bore hole for a primary target. The Mandata, like the Antes, Marcellus, and Burket, suffered the same thrust faulting and folding in the Ridge and Valley during the Alleghanian O rogeny. Likewise, conditions beneath the plateaus were far more tranquil. The organic

- rich zone may only be several meters thick. In those cases where horizontal drilling encounters the glauconitic phosphate nodule horizon, the distribution of U and its daughters can be expected to be inhomogeneous and associated with the slightly higher

- density phosphate nodule fragments that might concentrate during deposition

.PA DEP TENORM S tudy Report

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- 3 Marcellus Formation

Because it is the most important economically and presently the greatest source of TENORM via cuttings and flowback fluids, the Marcellus f ormation marine black sha le has already been

covered in some detail. For our purposes here, it need only be repeated that the Marcellus was deposited following the Onondaga f ormation Limestone and that Way and Smith provided monazites from Tioga Ash Bed B (Way and Smith 1986) for dating to Mary Roden

- Tice who, with Parrish and Miller (1989), obtained an age of 390 Ma ±0.5 Ma, for the lower portion of the

Marcellus f

ormation

. In many places, the organic

- rich portion is tens of meters thick. To reduce the TENORM burden of cuttings br ought to the surface, some operators may choose to do the horizontal drilling in the upper portion of the Onondaga f ormation just below the Marcellus. However, it is expected that flowback fluids from the Onondaga will be in communication with

the Marcellu s such that minimal correlation would be expected between TENORM levels in the cuttings and those in the flowback fluids.

It should also be noted here that properly collected and preserved flowback fluids will retain

much of their TENORM burden as receive d and analyzed by a laboratory. Bulk flowback fluids exposed to atmospheric oxygen will, however, transfer much of their burden to sludges and cuttings as bisulfide (HS - ) oxidizes to sulfate and ferrous iron oxidizes to ferrioxyhydroxides.

Both of these la tter processes are expected to nearly quantitatively remove radiums from

solution. Conversely, the onset of oxidation may initiate mechanisms that will mobilize U.

Burket Member of the Harrell Formation

The Burket Member black marine shale was deposited f ollowing the relatively inconspicuous Tully Limestone. The Harrell f ormation was named after Horrell Station, Blair County, documenting the fact that geology is, at times, an inexact science. The top of the Tully Limestone marks the boundary between the Mi ddle and Upper Devonian p eriods

. To date, no

volcanic ash beds have been verified in the transition. The organic

- rich portion of the Burket might only be several meters thick in the Ridge and Valley. Nevertheless, it presents an interesting secondary natur al gas target already being utilized.

Lockatong Formation

Unlike all of the Paleozoic

- age, marine black shales discussed above, the Lockatong is of much

younger, post

- Paleozoic Mesozoic Age, specifically formed in the much younger Triassic

S ystem. Further asserting its distinctive nature, it is not a marine deposit, but rather terrestrial, subaerial black, reduced shale deposited in a hypersaline lake. It is nearly always associated

with the oxidized Stockton f ormation and both are enriched in U at many lo cations in Bucks County in particular. Several mechanisms are recognized to have enriched the Lockatong and portions of the Stockton f ormation in U: reduction of the soluble hexavalent uranyl ion into the insoluble uranic ion in black shale, redox boundari es at Lockatong

- Stockton contacts (Christine

E. Turner

- Peterson 1980); reduction by fossil wood charcoal in the base of otherwise oxidized stream channels; and, possibly even roll fronts utilizing natural gas as a reductant. As a result, widespread indoor Rn is a problem in the Newark Basin, but much less so in the Gettysburg

Basin. Both the locally uraniferous Reading Prong to the north (Smith and Barnes 2013) and various granitic gneisses to the southeast provide more U into the Newark Basin than other

so urces provided into the more westerly Gettysburg Basin. Note also that the immense Cole’sPA DEP TENORM S tudy Report

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- 4 Hill U deposit near Gretna, Virginia, is located along the base of a Mesozoic basin and underlying gneisses.

As it was not deposited until millions of years after th e Taconic and Alleghanian orogenies, the Lockatong has obviously not had its natural gas and possible liquid hydrocarbon potential reduced by deformation. However, in place of those two orogenies, sediments in the Newark Basin have been locally baked into porcelain

- like hornfels by 201.509 Ma (±0.035 Ma) (Blackburn and others, 2013) contact metamorphism caused by the York Haven Diabase

, which is estimated to have intruded at 1,050°C (Smith 1973, Smith, Rose, and Lanning 1975). However, because the diabase i ntruded with a substantial hydraulic head which typically pushed it to within a kilometer or two of the surface during the latest Triassic, baking may not be overly severe at depth except near magma conduits, which supplied the presently observed diabase

s heets. Extremely widespread, more gentle heating has been observed (Smith and Faill 2000, Kohn and others 1993).

Discussion of Relative NORM Risks by Geologic Unit

Of the three principal naturally radioactive elements

– K, U, and Th

– only U appears to

c onstitute significant radiological concerns. Potassium is, for practical purposes

, low risk

— a relative non

- issue. It is largely present in relatively insoluble minerals such as muscovite, illite and potash feldspars, and therefore, does not constitute an e xcess nutrient issue.

Thorium is somewhat enriched in two of four Lockatong f ormation samples from the Newark

Basin

, but is unlikely to be extensively drilled soon for both demographic reasons and rather low natural gas current prices. Even in those Locka tong samples in which the Th is moderately high, it is likely to be present largely in insoluble and immobile minerals such as zircon, monazite

, and thorite (Smith, et al. 1989). For practical purposes, Th is also a non

- issue. The Th

- 232 series includes pr oblematic Ra

- 228 as one of its progeny, but the amount of Ra

- 228 or Ra

- 226, in solution, is more nearly controlled by reducing conditions and absence of “normal” geochemical processes in the natural host rock at the depths penetrated by horizontal drilling , and not by an anomalously high amount of Th in the host rock (Cecil, Smith, Reilly, and Rose 1987, and Dresel and Rose 2010). Due to the high energy of some abundant gamma rays from the Th

- 232 series, Th may actually be a distraction to TENORM monitoring at landfills.

T he U contents are elevated for all of the high organic sampled and analyzed geologic units. However, one Marcellus sample, MRCPA147 ( s ee Table A

- 1 ) , collected by R.C. Smith II and R. Lewis, not part of this TENORM study, was collected well above the high organic zone near the base and suggests that vertical cuttings above the Marcellus might not require the same special treatment and/or disposal as the cuttings from horizontal drilling in the high organic zone itself.

Reconnaissance monitor ing may be adequate for vertical cuttings. In a few cases, astute producers might choose to do horizontal drilling to recover natural gas from the Marcellus by drilling in the Onondaga formation just below the base of the Marcellus. Those cuttings, but not the flowback fluids that communicate between adjacent geologic formations such as the Onondaga, might also prove to be relatively innocuous.

The Burket Member of the Harrell f ormation appears to lose its high organic character and even

its distinct ident ity far to the southeast of the plateau. Therefore, it is unlikely to support worse than what, unfortunately, goes for normal Rn problems in Pennsylvania as one gets a county orPA DEP TENORM S tudy Report

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- 5 two away from the edge of the plateaus. However, sample BURKLP (collected by R

. C. Smith, II) suggests that the Burket may produce elevated indoor Rn levels in Lockport, Clinton County, and nearby areas. As found in the Marcellus shale samples from the TENORM study

, similar increased levels of radioactivity may also arise with horiz ontal drilling of the Burket in the Appalachian plateau.

Somewhat prior to the TENORM study, representative rock sampling and analyses of the high organic zones of surface exposures of the corresponding black shales in the Ridge and Valley physiographic p rovince were conducted by R. C. Smith, II, in order to interpret and project high

indoor Rn contents ( see Table A

- 1 )

. These samples were analyzed by Activation Laboratories, Ltd., Ancaster, Ontario

. Table A

- 1 is only a partial listing of the elements analy zed. These samples were collected by cutting channels normal to bedding and compositing the corresponding chips. The sampling sites included road cuts, railroad cuts, and active and abandoned quarries which had been exposed to the atmosphere for only a few decades. Even

so, the outer few inches of slightly weathered shale was wasted. Because these are surface samples, some oxidation of sulfides to sulfates has inevitably occurred, but significant

remobilization of reduced U and many heavy metals is unlikely

. Relatively few samples have been collected from the individual geologic units. However, based on the general lateral continuity of marine black shales and even their volcanic components, medians of the U content for each unit are believed to be predictiv e. Thus with these caveats in mind, from youngest to oldest, we obtained median U contents of the high organic zones of: Lockatong 26 ppm and associated Stockton 9 ppm, Burket nearest plateau 10 ppm, Marcellus 26 ppm, Mandata 9 ppm

, and Utica 9 ppm. These values are in comparison to median U contents of shales of 3.7 ppm (Rose, Hawkes, and Webb 1979).

Study of additional, previously unsampled Marcellus f ormation cores from the high organic zone in five deep holes spread across western, northwestern, and no rthern Pennsylvania is believed to

be warranted. This analysis is planned for near future work.

One may speculate :

1) The high organic zone on the Marcellus formation is likely to contain the highest radiometric burden of the natural gas targets in the plat eaus of Pennsylvania and to yield the largest volume of cuttings. If producers chose to drill horizontally within the underlying Onondaga formation limestone, the cutting burden may be reduced, but at the possible expense of a larger volume of noxious flow back fluids from the Onondaga.

2) Each of the other sampled target high

- organic zones is likely to have around 40 percent of the

burden of the Marcellus. Considering that typical shale contains 4 ppm U, perhaps this could be better conceptualized as about 28 percent of the excess burden.

3) If re gulations are proposed for Marcellus shale disposal, they should be more than adequate to cover cuttings from the Burket, Mandata

, and “Utica” geologic units. As there tends to be exceptions to uniformity of geologic un its over time and space, a reasonable geological engineering factor might be to design for two times the maximum observed U content in the Marcellus of 42 ppm U. That is, it might be prudent to design for a maximum of 84 ppm U. Conversely, one might reduce monitoring of non

- Marcellus sources by perhaps half with the proviso that adjustments will be made both ways as ad ditional data become available.PA DEP TENORM S tudy Report

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- 6 4) As noted above, both the Rhinestreet Member of the West Falls f ormation associated with the Belpre volcanic ash and the Pipe Creek Member of the Java f ormation associated with the Center Hill volcanic ash bed (Berg et al. 1993) are both black shales that have natural gas potential. Neither are known to outcrop at the surface in Pennsylvania nor were deep drill

c ores found to be available. Because of the association with volcanic ash beds, they are likely to contain moderately high U an d to be exploited commercially.

5) The Lockatong is not a marine, but rather a non

- marine black shale. It is associated with the

oxi dized Stockton f

ormation. Because marine black shales lacked access to oxygen, there are very few mechanisms that can remobilize U within the geologic units to create localized

extreme U enrichments. However, the Lockatong and associated Stockton had acces s to oxygen and have yielded a number of localized U occurrences of several types in Bucks and Montgomery c ounties in the Newark Basin of Pennsylvania as well as across the Delaware River in New Jersey. (Because of the immense Coles Hill U ore deposit at t he base of a Mesozoic basin near Gretna in Virginia, ore grade deposits cannot be ruled out.) Thus, it can reasonably be assumed that cuttings from the Lockatong will encounter not just laterally continuous zones of perhaps 5 to 10 ppm U, but also localize d zones of 50 to 100 ppm U. Further, zones of 500 to 1,000 ppm U would not be too surprising. Adding to the downside potential from a TENORM viewpoint, the adjacent Stockton sandstones and siltstones can be expected to be more porous and permeable with res pect to connate brines than black shale. Thus, their yield of flowback fluids may be large.

6) All horizontal rock cutting samples that have not already been analyzed by XRF should be analyzed. This analysis would be helpful to determine the elements of thei r lithology.

7) Study of additional, previously unsampled Marcellus f ormation cores from the high organic zone in five deep holes spread across western, northwestern, and northern Pennsylvania is

believed to be warranted. This analysis is planned for near fu ture work.

Relative Heavy Metal Contents of Selected Black Shales in Pennsylvania

Based on examination of the abridged table of geochemical analyses, the following comments are offered by oxide or element. Note the Lockatong and associated Stockton format ions in the Newark Basin and the Hamburg sequence in the Great Valley, while of great relevance for indoor Rn, are not discussed herein because they are not likely to y ield TENORM in the near

future.

Calcium oxide (CaO)

– The Mandata f ormation in surface outcrop at Everett presently contains only 0.06 percent CaO and the Marcellus f ormation at Frankstown likewise only 0.06 percent

. These low CaO contents suggest very limited acid neutralization capacity. Water soluble supergene sulfates built up as crusts on surface outcrops during droughts may permit bursts of acidic heavy metal

- laden water following dry periods and possibly even in early spring. Such effects might also occur at disposal sites if there are any comparable cuttings and water contents

that fl uctuate seasonally.

Phosphorous pentoxide (P 2 O 5 )

– It cannot be ruled out that under some circumstances polonium (Po

- 210) might concentrate in the phosphate mineral apatite or commonly associated glauconite.PA DEP TENORM S tudy Report

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- 7 Thus, in cuttings containing > 0.2 percent P 2 O 5 , Po

- 210 enrichment cannot be entirely ruled out due to unusual geochemical environments.

Sulfur (S) is enriched in at least some samples of each marine black shale. The highest S content
seems to be associated with the Antes f ormation (“Utica”). Acid and spontaneous combustion problems need to be considered for the Antes in particular.

Arsenic (As)

– The Antes, Mandata, Burket near the plateau, and especially the Marcellus are

enriched in As

. Some may be substituting for phosphorus in carbonate

- fluorapati te. In any case, cuttings from these black shales might yield soluble As compounds depending on the activity of electrons/activity of hydrogen ions (Eh/pH) environment of the disposal site.

Barium (Ba)

– Several of the marine black shales, and especially the Marcellus, contain high Ba.

Table A

- 1 shows two samples with very high concentrations of Ba

. Sample CSMPB (101,000 ppm Ba) is from the Hamburg sequence near Harpers Tavern, Lebanon County. This sample was collected from a single block of phosphate

- bari te bed. Very near this area some rocks have been collected containing 95 percent barite. Barite is b arium s ulfate (BaSO 4 )

, and this is the source of the very high Ba concentration. The other sample, M

- 1L (11,201 ppm Ba)

from the Stockton formation in the N ewark Basin (Bucks County), was near an area where barite

was mined.

M ost of this is likely present as the geologically old, insoluble mineral barite, BaSO4, and probably not of direct environmental concern. Conversely, reducing connate brine fluids prese nt at depth in black shale formations are expected to be enriched in soluble Ba 2+

. When the

bisulfide ( HS - ) and possibly hydrogen sulfide (H 2 S) present at depth within these same connate fluids reach the surface and are rapidly oxidized to sulfate SO4 2

- , r adiobarites enriched in Ra

- 226 and, to a lesser extent in Ra

- 228, will form as insoluble precipitates. In some ways this is beneficial as the process removes soluble radiums from the connate brines, but it likely will yield intense localized hot spots wher e they precipitate. At least these radiobarites will likely remain relatively insoluble. The same cannot be said for all of the sulfates resulting from surface

oxidation of HS and H 2 S. Moderately soluble sulfates of alkali and especially alkaline earths

m ay result. These resulting radiosulfates are likely to be resolubilized under a variety of changing Eh and pH conditions, not to mention simple dissolution by rainwater. The Ra burden they carry might be further concentrated downstream. If appropriate disp osal methods can be found, we cannot rule out the potential benefit of concentrating the radiums for specialized disposal rather than the older “solution by dilution” methods.

An additional complication with naturally reducing connate brines from black sh ale formations is

that the Fe 2+ (ferrous iron) present in the brines at depth oxidizes almost immediately upon contacting oxygen in the air. This results in the production of Fe 3+ (ferric iron) and the ultimate precipitation of ferric oxyhydroxides. These

, too

, may be beneficial in that the precipitates will adsorb radiums and perhaps some other progeny from solution. However, these non

- crystalline ferric oxyhydroxides tend to crystallize into stable minerals over time. These more stable

minerals lack the e xtreme surface area of the former and fail to adsorb most radionuclides. Translated loosely, radiums bound with “yellow boy” may be remobilized in landfills over time unless other geochemical traps are planned in advance.PA DEP TENORM S tudy Report

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- 8 Bromine (Br) seems to be concentr ated in nearly all Marcellus and Antes high organic samples. It cannot be ruled out that some of the Br is in soluble forms such as sodium bromide (NaBr) or potassium bromide (KBr) from connate brines. Connate brines from nearly all formations can be

expec ted to be high in chlorine (Cl) which might form complexes to solubilize metals such as

copper (Cu) and mercury (Hg) in particular. The flowback fluids should be assumed to be slightly enriched in Br until proven otherwise.

Cadmium (Cd) is strongly enrich ed in high organic Marcellus samples. It is a toxic metal in and

of itself. It may piggyback with relatively innocuous zinc and be insoluble as sulfide at depth but

become solubilized as a sulfate at the surface. High Cd in the presence of high S may be

tr oublesome.

Mercury (Hg) is less than the detection limit of 1 ppm in all of the black shale samples collected

to date. However, from the standpoint of heavy metal toxicity, not radionuclide, obtaining separate analyses having a lower detection limit might be appropriate. If organic and sulfide

- rich cuttings were to combust spontaneously or otherwise, vapors of Hg

, As

, and s elenium ( Se ) would be particularly hazardous. Occasional thermal imaging may be in order, or at least noting anomalously snow

- free or s teaming piles of cuttings.

Molybdenum (Mo) geochemistry is complex. Particularly in Marcellus high organic samples,

the forms and amounts of Mo should be monitored. Possibly additional analyses should be obtained by DEP’s Bureau of Laboratories (BOL) for the two Marcellus samples containing more than the upper limit of the normal working range, 100 ppm. M olybdenum mig ht become solubilized and then later precipitate in concentrated form with ferric oxyhydroxides. Because caution is needed to keep Mo out of the human and animal food chain, precipitates and the connate brines themselves should be occasionally checked for a possible Mo burden.

Nickel (Ni) is enriched in high organic Marcellus samples. Although possibly present in the

black shale as iron sulfid es such as pyrite or pyrrhotite where the Ni probably substitutes for iron, organometallic compounds cannot be ruled out. Whatever Ni is solubilized, it is likely to be adsorbed on ferric oxyhydroxides once they precipitate.

Lead (Pb)

– Although Pb is a w ell

- known heavy metal toxin, the levels in the sampled black shales do not appear to be of particular concern. In fact, the levels observed are typical of many shales and Pb is only included here because it is a traditional concern.

Selenium (Se) is stron gly enriched in two of the high organic Marcellus samples and is toxic if

enriched in the food chain for animals or humans. It is likely present within pyrite in the

Marcellus. If Marcellus cuttings were to spontaneously combust, Se would likely be out

- gas sed as vapors, which might yield vapor

- deposited solids in cooler crusts near the surface of the piles.

Thallium (Tl), a.k.a. “rat poison,” is enriched to more than 1 ppm in three of four high organic Marcellus samples, all three Antes samples, both Manda ta samples and the three higher organic Burket samples. It may be substituting for zinc iron sulfides and subject to mobility if pyrite

oxidizes.

Uranium (U)

– Because of its importance and centrality to TENORM issues, it has been

discussed in more detail in the body of the report.PA DEP TENORM S tudy Report

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- 9 Thorium (Th) in the sampled black shales is typically at background levels as expected. It will contribute to the high energy gamma flux, but is not recognized as being of serious concern. This is partly because much of it is l ikely present in insoluble, stable m inerals.

The conclusion to heavy metal contents of black shales in Pennsylvania is that, once again, procedures designed to handle heavy metals in the Marcellus f ormation should be more than adequate to handle TENORM fro m the other black shale units.

Reduced Rock and Fluid at Depth vs. Pote ntially Oxidized Disposal Sites

As mentioned in part, above, the Marcellus and other black shales of marine origin were formed,

buried

, and preserved in reducing environments. This per haps appears obvious from the presence of methane, but it is mobile in some geologic environments. Confirmation of the reducing environment comes from the presence of sulfide minerals such as pyrite and the fact that significant portions of alkaline earth elements such as Ba and Ra are soluble in the connate brines at depth. Measurements of Eh on freshly produced brines are difficult to measure but also support this. Thus, U once in a hexavalent, uranyl ion form in weathered rocks exposed to the atmosphere or in the metastable volcanic glass component of volcanic ashes, was reduced in situ in the deep, black shale basins. Once cuttings of black shales are brought to the surface, it is reasonable to assume that depending on the disposal environment, that some U might once again

become oxidized and mobile

, i.e., soluble. Soluble U is highly toxic.

Liming may seem like an obvious remedy to the acid

- generating potential of pyrite in shales and indeed it is probably a good thing that the lower contacts of black s hales tend to be interbedded with underlying limestones. However, one needs to plan carefully as the carbonate anion might increase the mobility of hexavalent U and carbonate soils accumulate radiums at depth.

Another issue to consider in the disposal of black shale cuttings is that the risk of spontaneous

combustion cannot be ruled out. This is especially true for pyritic cuttings. Spontaneous combustion of natural outcrops of the Late Devonian Huron Member of the Ohio shale has occurred near Monroeville, Ohio. Finer

- grained cuttings may be even more susceptible to

oxidation.

Disposal of flowback fluids is perhaps even more complex because they are so unstable as they

reach the surface. Bisulfide ( HS - ) present at depth can be expected to oxidize immediate ly to the

sulfate ion

, effectively removing the bulk of the alkaline earths from solution. Note, however, that the solubility product for Ra sulfate still allows for high amounts of Ra 2+ in solution, which is the divalent, soluble form of Ra

- 226. The secon d, almost instantaneous reaction is the

oxidation of soluble Fe +2 (ferrous iron) to ferrioxyhydroxides having large adsorption capacities for radiums and other toxic heavy metals. Unfortunately, this “yellow boy” is metastable. “Yellow boy” is an orangish precipitate associated with some old coal mines. It will change to lepidocrocite and then to goethite over time, neither of which have significant adsorption capacities relative to “yellow boy ; ” thus, in an unengineered site, radiums might once again

becom e soluble.

Likewise, toxic heavy metals sequestered in minerals that are stable at depth may not remain so

at the surface. Careful planning is obviously needed in designing TENORM disposal sites.PA DEP TENORM S tudy Report

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- 10 Bibliography

Berg, T. M., McInerney, M. K., Way, J. H., a nd D. B. MacLachlan. Stratigraphic correlation chart of Pennsylvania, Pennsylvania Geological Survey, 4thseries, General Geology Report G

75, third printing slightly revised, 1993.

Blackburn, T. J., Olsen, P. E., Bowring, S. A., McLean, N.M., Kent, D. V. John Puffer, Greg McHone, E. Troy Rasbury, and Mohammad Et

- Touhami. Zircon U

- Pb geochronology links the

End

- Triassic Extinction with the Central Atlantic Magmatic Province, Science, v. 340, p. 941

- 945, 2013.

Cecil, L. DeWayne, Smith, II, R. C., Reilly, M . A., and A. W. Rose. Radium

- 228 and

Radium

- 226 in ground water of the Chickies Formation, southeastern Pennsylvania, p. 437

- 447 in Barbara Graves, editor, Radon, radium, and other radioactivity in groundwater, Hydrogeology impact and application to indoor airborne contamination, Proceedings of the NWWA Conference April 7

- 9, Somerset, New Jersey, 1987.

Dresel, P. E. and A. W. Rose. Chemistry and origin of oil and gas well brines in western Pennsylvania, Pennsylvania Geological Survey, 4th series Open File Report OFOG 10

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2010.

Haluszczak, L. O., Rose, A. W., and L. R. Kump. Geochemical evaluation of flowback brine from Marcellus gas wells in Pennsylvania, USA, Applied Geochemistry, v. 28, p. 55

- 61, 2012.

Kohn, B. P., Wagner, M. E., Lutz, T. M., and G . Organist. Anomalous Mesozoic thermal regime, central Appalachians and piedmont: evidence from zircon and sphene fission

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- colored 7 1 /2' topographic maps, October 1989.PA DEP TENORM S tudy Report

– Appendix A Rev. 0

January 2015 A

- 11 Smith, II, R. C. and Barnes, J. H. Geology and Mineralogy of uranium and thorium in the Reading Prong of Berks, Lehigh, and Northampton Counties, Pennsylvania, Pennsylvania Geological Survey, 4th series, 177 p. and 1 pla te, 2013, but completed 1989.

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A

- 12 PA DEP TENORM Study Report

– Appendix A

Rev. 0 Table A

- 1. Rock Formation Samples Analysis

Sample Name and

Formation Location, County U Th K2O P2O5 As Ba Br S Tl V Analyte Symbol: Unit Symbol: ppm ppm % % ppm ppm ppm % ppm ppm Detection Limit: 0.01 0.05 0.01 0.01 1 1 0 .5 0.001 0.05 5 Analysis Method: FUS

- MS FUS

- MS FUS

- ICP FUS

- ICP INAA FUS

- ICP INAA TD

- ICP FUS

- MS FUS

- ICP

ANTES = "UTICA" Oak Hall, Centre County 14.8 11.1 2.32 0.25 32 309 3.1 4.41 0.50 111

ANTES = "UTICA" Reedsville, Mifflin County 9.08 10.7 3.04 0.15 3 5 960 2.2 2.23 1.42 138

ANTES = "UTCA" Antes Gap, Lycoming County 7.76 8.88 2.91 0.27 9 371 3.4 1.04 1.00 130

MARCELLUS Hares Valley, Huntingdon 23.1 10.8 2.51 0.08 50 645 4.6 2.81 2.14 500

MARCELLUS Frankstown, Blair 26.6 9.13 1.81 0.11 92 1060 9.2 0.919 9.58 596 Tioga Ash Bed F

in Marcellus Frankstown, Blair 42.3 37.0 1.70 0.11 49 1100 1.0 N.A. N.A. 260

MARCELLUS Selinsgrove Junction,

Northumb. 25.0 7.69 2.07 0.09 32 1232 4.4 3.08 0.65 399

MARCELLUS Wardville, Perry/Juniata

MARCELLUS S. Sunbury, Northumberland 3.23 13.1 3.41 0.10 8 860 2.2 0.761 0.96 134

MANDATA Everett, Bedford 7.71 11.9 4.31 0.26 28 319 2.3 0.182 1.93 177

MANDATA Hollidaysburg, Blair 10.4 9.00 4.21 0.43 19 837 3.7 1.22 1.25 159

HAMBURG Fredericksburg, Lebanon 10.9 7.50 2.66 0.60 18 392 3.3 0.008 0.72 346

HAMBURG Harpers Tavern, Lebanon 18.7 10.9 5.12 1.74 43 1972 2.4 0.062 1.66 756

HAMBURG Harpers Tavern, Lebanon 46.2 3.95 0.72 19.12 4 101100 < 0.5 0.341 0.29 62

BURKET Lockport, Clinton 12.9 10.6 4.05 0.22 32 733 4.1 0.893 2.60 348

BURKET Amity Hall, Perry 4.82 14.7 4.57 0.09 21 618 < 0.5 0.499 2.21 209

BURKET Newry, Blair 7.43 12.2 4.09 0.10 45 750 < 0.5 1.53 2.85 279

BURKET Grazierville, Blair 3.72 14.0 3.76 0.11 8 700 2.1 0.387 0.92 155

BURKET Liverpool, Perry 3.54 15.2 3.91 0.13 12 549 < 0.5 0.021 0.90 154
LOCKATONG,

Newark Basin Pipersville, Bucks 39.6 14.3 4.87 0.28 58 578 < 0.5 0.60 1.17 162 LOCKATONG,

Newark Basin Jamison, Bucks 26.9 19.6 4.17 0.41 94 683 < 0.5 0.516 1.18 122 LOCKATONG,

Newark Basin Tradesville, Bucks 25.1 35.3 4.57 0.66 7 735 < 0.5 0.162 1.71 176 LOCKATONG,

Newark Basin Danboro, Bucks 8.13 26.8 3.34 0.45 10 542 < 0.5 0.336 0.41 117

STOCKT ON,

Newark Basin Lumberville, Bucks 9.04 11.6 2.00 0.26 14 11210 < 0.5 0.191 0.51 101 STOCKTON,

Newark Basin Newtown, Bucks 25.5 16.0 0.89 0.15 < 1 296 < 0.5 0.007 0.58 38 STOCKTON,

Newark Basin Carversville, Bucks 5.21 16.7 4.40 0.15 4 810 < 0.5 0.007 1.14 131

Middle Ordovician Bentonite Union Furnace, Huntg./Blair 4.28 20.0 6.26 0.06 4 194 1.5 1.83 1.31 14

Middle Ordovician Bentonite Union Furnace, Huntg./Blair 4.31 22.8 6.25 0.06 8 280 1.3 0.86 0.80 16

Middle Ordovician Be ntonite Union Furnace, Huntg./Blair 7.95 31.3 5.15 0.15 7 227 1.1 0.38 1.07 33Table A

- 1. Rock Formation Samples Analysi s (Continued) January 2015

A

- 13 PA DEP TENORM Study Report

– Appendix A

Rev. 0 Sample Name and

Formation Location, County U Th K2O P2O5 As Ba Br S Tl V Analyte Symbol: Unit Symbol: ppm ppm % % ppm ppm ppm % ppm ppm Detection Limit: 0.01 0.05 0.01 0.01 1 1 0 .5 0.001 0.05 5 Analysis Method: FUS

- MS FUS

- MS FUS

- ICP FUS

- ICP INAA FUS

- ICP INAA TD

- ICP FUS

- MS FUS

- ICP

Middle Ordovician Bentonite Union Furnace, Huntg./Blair 5.10 17.4 3.81 0.14 13 229 1.8 0.17 0.67 46

Middle Ordovician Bentonite Union Furnace, Huntg./Blair 8.77 15.0 6.25 0.05 10 278 1.2 0.12 1.19 13

Middle Ordovician Bentonite Union Furnace, Huntg./Blair 7.44 25.3 5.50 0.07 10 345 <.5 0.67 0.89 18

Middle Ordovician Bentonite Union Furnace, Huntg./Blair 5.77 31.2 5.56 0.09 6 335 1.4 0.10 0.88 17