Prepared in cooperation with

New York State Energy Research and Development Authority

Natural Occurrence of ethane in !roundwater of South"
#entral New York State$Systematic Evaluation of a
!laciated Region %y &ydrogeologic Setting
By Paul M. Heisig and Tia-Marie Scott
Scientific Investigations Report 201!""""
'(S( Department of the )nterior
'(S( !eological Survey
1
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S#$$% &'('$$) Secretary
'(S( !eological Survey
Su*ette M. +i,-all) #cting .irector
/.S. 0eological Survey) Reston) 1irginia2 201
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Suggested citation2
Heisig) P.M.) and Scott) Tia-Marie) 201) 8atural occurence of ,et4ane in ground7ater of sout4-central 8e7 %or9
State5syste,atic evaluation of a glaciated region -y 4ydrogeologic
setting2 /.S. 0eological Survey Scientific Investigations Report 201!::::) ::) "" p.)
4ttp2;;pu-s.usgs.gov;sir;201;::::;.
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2
<ontents
#-stract..........................................................................................................................................................................=
#-stract..........................................................................................................................................................................=
Introduction.....................................................................................................................................................................=
Introduction.....................................................................................................................................................................=
Regional 0eology.......................................................................................................................................................=
Study #rea..................................................................................................................................................................=
Hydrogeology .........................................................................................................................................................=
Met4ane >ccurrence in t4e Su-surface.................................................................................................................=
Met4ane in 0round7ater........................................................................................................................................?
Purpose and Scope....................................................................................................................................................?
Met4ods..........................................................................................................................................................................?
Met4ods..........................................................................................................................................................................?
Hydrogeologic <lassification of (ells in t4e Study #rea...........................................................................................?
Ta-le 1. Hydrogeologic setting classification in t4e study area) sout4-central 8e7 %or9. ...........................................?
1alleys and /plands...............................................................................................................................................?
<onfined <onditions...............................................................................................................................................?
#dditional <lassification of 1alley Settings.............................................................................................................6
Monitoring-(ell 8et7or9 <riteria...............................................................................................................................6
Ta-le 2. Su,,ary of c4aracterisitics of sa,pled 7ells) -y ,a@or 4ydrogeologic setting) sout4 -central 8e7 %or9.
A1alley 7ells 7ere co,pleted in sand and gravel or -edroc9B in sand and gravel 7ells) over-urden t4ic9ness is t4at
of glacial deposits a-ove t4e -otto, of t4e 7ell Cfinis4ed as open pipe) not screenedD. Bedroc9 penetration is *ero
in sand and gravel 7ellsE................................................................................................................................................6
3
$a-oratory #nalysis of (ater Sa,ples......................................................................................................................6
Sa,pling Met4ods......................................................................................................................................................6
Fuality!<ontrol Sa,ples............................................................................................................................................6
Reston <4lorofluorocar-on $a-oratory #nalyses...................................................................................................G
<o,parison of Isotec4 and Reston <4lorofluorocar-on $a-oratory #nalyses......................................................G
Blan9 #nalyses ......................................................................................................................................................G
Statistical Met4ods.....................................................................................................................................................G
Met4ane >ccurrence in 0round7ater............................................................................................................................G
Met4ane >ccurrence in 0round7ater............................................................................................................................G
Met4ane <oncentrations and Hydrogeologic Setting................................................................................................G
Ta-le . Hydrogeologic classification of 7ells sa,pled) 7it4 eac4 class color coded -y percentage of sa,ples 7it4
,et4ane concentrations greater t4an or eHual to2 #. 0.1 ,illigra,s per liter) B. I ,illigra,s per liter) and <. 10
,illigra,s per liter in sout4-central 8e7 %or9) 2012. AJ) greater t4an or eHual toB K) greater t4anB ,g;$ ),illigra,s
per literB L) percentB C"D) nu,-er of sa,plesE.............................................................................................................10
Met4ane <oncentrations and 3ield-<4aracteristic Measure,ents ........................................................................10
Met4ane <oncentrations and (ell <o,pletion .......................................................................................................10
/se of Isotopic .ata to #ssess Met4ane SourceCsD................................................................................................10
<onceptual Model of Met4ane >ccurrence in Sout4!<entral 8e7 %or9.....................................................................10
<onceptual Model of Met4ane >ccurrence in Sout4!<entral 8e7 %or9.....................................................................10
$i,itations of .ata ...................................................................................................................................................11
.ata 8eeds...............................................................................................................................................................11
Significance of 3indings ..........................................................................................................................................12
Su,,ary and <onclusions..........................................................................................................................................12
4
Su,,ary and <onclusions..........................................................................................................................................12
#c9no7ledge,ents......................................................................................................................................................12
#c9no7ledge,ents......................................................................................................................................................12
References <ited.........................................................................................................................................................12
References <ited.........................................................................................................................................................12
*igures
Tables
5
Conversion Factors
Inch/Pound to SI
ultiply +y ,o o%tain
$engt4
foot (ft) 0.3048 meter (m)
mile (mi) 1.609 kilometer (km)
#rea
!u"re mile (mi
2
) 2.590 !u"re kilometer (km
2
)
1olu,e
#"llon (#"l) 3.$85 liter (%)
Temperature in degrees Celsius (C) may be converted to degrees Fahrenheit (F)
as follows:
F=(1!"C)#$%
&ertical coordinate information is referenced to the 'orth (merican &ertical )atum
of 1*!! ('(&) !!)
+ori,ontal coordinate information is referenced to the 'orth (merican )atum of
1*!$ ('() !$)
-levation. as used in this report. refers to distance above the vertical datum
/peci0c conductance is given in microsiemens per centimeter at %1 degrees
Celsius (2/3cm at %1 C)
Concentrations of chemical constituents in water are given either in milligrams per
liter (mg34) or micrograms per liter (2g34)
A%%reviations
CFC Chloro5uorocarbon
'67/ 'ational 6ater 7nformation /ystem
'684 'ational 6ater 9uality 4aboratory
6
:/;/ :/ ;eological /urvey
&<C &olatile organic carbon
$
Natural Occurrence of ethane in !roundwater of South"
#entral New York State$Systematic Evaluation of a
!laciated Region %y &ydrogeologic Setting
By Paul M. Heisig and Tia-Marie Scott
A%stract
& ur'e( of meth"ne in #round)"ter )" undert"ken to document n"tur"l meth"ne occurrence
on the *"i h(dro#eolo#ic ettin# )ithin " #l"ci"ted 1+810,!u"re,mile "re" of outh,centr"l -e) .ork
"lon# the Penn(l'"ni" *order. Si/t(,i/ )ell )ere "m0led durin# the ummer of 2012. &ll )ell )ere
"t le"t 1 mile from "n( kno)n #" )ell ("cti'e+ e/0lor"tor(+ or "*"ndoned). 1eult indic"te tron#
0oiti'e "nd ne#"ti'e "oci"tion *et)een h(dro#eolo#ic ettin# "nd meth"ne occurrence. 2he
h(dro#eolo#ic ettin# cl"e "re *"ed on to0o#r"0hic 0oition ('"lle( "nd u0l"nd)+ confinement or
non,confinement of #round)"ter *( #l"ci"l de0oit+ )ell com0letion in fr"ctured *edrock or "nd "nd
#r"'el+ "nd h(dro#eolo#ic u*c"te#orie. 3nl( dometic )ell "nd imil"r 0ur0oed u00l( )ell )ith
)ell,contruction "nd lo# inform"tion )ere elected for cl"ific"tion. 4ield )"ter,!u"lit( ch"r"cteritic
(05+ 0ecific conduct"nce+ diol'ed o/(#en+ "nd tem0er"ture) )ere me"ured "t e"ch )ell+ "nd
"m0le )ere collected "nd "n"l(6ed for diol'ed #"e+ includin# meth"ne "nd hort,ch"in
8
h(droc"r*on. 7"r*on "nd h(dro#en ioto0ic r"tio of meth"ne )ere me"ured in 21 "m0le th"t h"d "t
le"t 0.3 milli#r"m 0er liter (m#/%) meth"ne.
1eult of "m0lin# indic"te th"t n"tur"l occurrence of meth"ne in #round)"ter of the re#ion i
common8#re"ter th"n or e!u"l to 0.001 m#/% in $8 0ercent of the #round)"ter "m0le.
7oncentr"tion of meth"ne r"n#ed o'er fi'e order of m"#nitude. 9eth"ne concentr"tion "t )hich
monitorin# or miti#"tion "re indic"ted (#re"ter th"n or e!u"l to 10 m#/%) )ere me"ured in 15 0ercent
of the "m0le. 9eth"ne concentr"tion #re"ter th"n 0.1 m#/% )ere "oci"ted )ith 0ecific
h(dro#eolo#ic ettin#. :ell com0leted in *edrock )ithin '"lle( "nd under confined #round)"ter
condition )ere mot cloel( "oci"ted )ith the hi#het meth"ne concentr"tion. 4ift(,e'en 0ercent of
'"lle( )ell h"d #re"ter th"n or e!u"l to 0.1 m#/% meth"ne+ )here" onl( 10 0ercent of u0l"nd )ell
e!u"led or e/ceeded th"t concentr"tion. Ioto0ic i#n"ture differed *et)een thee #rou0 " )ell.
9eth"ne in '"lle( )ell )" 0redomin"ntl( thermo#enic in ori#in+ likel( " " reult of cloe 'ertic"l
0ro/imit( to underl(in# meth"ne,*e"rin# "line #round)"ter "nd *rine "nd 0oi*l( " " reult of
enh"nced *edrock fr"cture 0erme"*ilit( *ene"th '"lle( th"t 0ro'ide "n "'enue for u0)"rd #"
mi#r"tion. Ioto0ic i#n"ture of meth"ne from four u0l"nd )ell "m0le indic"ted " micro*i"l ori#in
(c"r*on,dio/ide reduction) )ith one "m0le 0oi*l( "ltered *( micro*i"l meth"ne o/id"tion. :"ter
"m0le from )ell in " '"lle( ettin# th"t indic"te " mi/ of thermo#enic "nd micro*i"l meth"ne reflect
the cloe 0ro/imit( of re#ion"l #round)"ter flo) "nd underl(in# "line )"ter "nd *rine in '"lle( "re".
2he micro*i"l meth"ne i likel( 0roduced *( *"cteri" th"t utili6e c"r*on dio/ide or form"tion"l or#"nic
m"tter in hi#hl( reducin# en'ironment )ithin the u*re#ion"l #round)"ter flo) (tem. 2hi
ch"r"cteri6"tion of #round)"ter meth"ne ho) the im0ort"nce of u*urf"ce inform"tion
(h(dro#eolo#(+ )ell contruction) in undert"ndin# n"tur"l meth"ne occurrence "nd 0ro'ide "n initi"l
conce0tu"l fr"me)ork th"t c"n *e utili6ed in in'eti#"tion of tr"( #" in outh;centr"l -e) .ork.
9
)ntroduction
2he de'elo0ment of technolo#( for hi#h,'olume h(dr"ulic fr"cturin# in hori6ont"l #" "nd oil
)ell h" m"de lo),0erme"*ilit( *l"ck h"le unit )ithin l"r#e "re" of the northern &00"l"chi"n <"in
(=ener"li6ed north;outh ection )ith *edrock form"tion in outh,centr"l -e) .ork (from :illi"m+
2010> modified from -e) .ork St"te 9ueum+ 2009).) into "re" "ttr"cti'e for n"tur"l,#" 0roduction.
:ide0re"d de'elo0ment of thee reource+ includin# drillin#+ e/tr"ction+ tr"n0ort 'i" 0i0eline+ "nd
under#round tor"#e+ h" cre"ted the 0oi*ilit( of in"d'ertent introduction of n"tur"l #" (0rim"ril(
meth"ne) into the u*urf"ce en'ironment. 5itoric"ll(+ in thee "me "re"+ n"tur"l #" h" *een
re0orted in dometic )ell )"ter "t " minorit( of )ell> recent d"t" on 0redrillin# )ell,"m0lin# of )"ter
)ell from northe"tern Penn(l'"ni" confirm thi "nd ho) " )ide0re"d ditri*ution of meth"ne "t
concentr"tion #re"ter th"n or e!u"l to 0.1 milli#r"m 0er liter (m#/%) (9olofk( "nd other+ 2011).
2hee findin# indic"te th"t+ 0rior to h"le,#" drillin# in " re#ion+ " (tem"tic undert"ndin# of the
n"tur"l occurrence of diol'ed meth"ne in #round)"ter (0ecific"ll( dometic )ell) c"n *e ueful
)hen meth"ne concentr"tion in #round)"ter "re of concern.
Pre'iou )ork on diol'ed meth"ne occurrence in #round)"ter in the re#ion h" focued
0rim"ril( on the de0th of )"ter )ell+ the #ener"l *edrock unit t"00ed+ "nd the to0o#r"0hic loc"tion.
2hee de0iction "re un"*le to e/0l"in the )ide r"n#e of #round)"ter chemic"l ch"r"cteritic "nd
meth"ne concentr"tion o*er'ed 0"rtl( *ec"ue the( l"ck inform"tion on the u*urf"ce #l"ci"l #eolo#(
"nd det"iled inform"tion on )ell com0letion "nd )ell lo#+ uch " the thickne of *edrock 0enetr"ted.
2hi tud(+ conducted in coo0er"tion )ith the -e) .ork St"te ?ner#( 1ee"rch "nd @e'elo0ment
&uthorit(+ "ddree thoe need *( "m0lin# )ell )ith )ell,com0letion inform"tion th"t h" *een 0ut
into the l"r#er conte/t of h(dro#eolo#ic ettin# "cro the l"ndc"0e. 5(dro#eolo#ic ettin#
10
encom0"e to0o#r"0hic 0oition+ the "!uifer the )ell i com0leted in+ *edrock t(0e+ #l"ci"l de0oit
t(0e "nd thicknee+ "nd )hether or not the #round)"ter i confined *( #l"ci"l de0oit.
Regional !eology
In outh,centr"l -e) .ork+ " #entl( outh)"rd di00in# e!uence of ediment"r( *edrock of
7"m*ri"n throu#h @e'oni"n "#e o'erlie Prec"m*ri"n,"#e cr(t"lline *"ement rock (=ener"li6ed
north;outh ection )ith *edrock form"tion in outh,centr"l -e) .ork (from :illi"m+ 2010> modified
from -e) .ork St"te 9ueum+ 2009).> 1ick"rd "nd 4iher+ 19$0> 4iher "nd other+ 19$0). -"tur"l #"
h" *een re0orted in m"n( of the ediment"r( unit (ee fi#. 2 in A"00el "nd -(trom+ 2012). :ith
de'elo0ment of the hi#h,'olume h(dr"ulic,fr"cturin# techni!ue+ the or#"nic,rich 9"rcellu Sh"le of
@e'oni"n "#e "nd Btic" Sh"le of 3rdo'ici"n "#e h"'e *ecome "re" of interet in outh,centr"l -e)
.ork St"te (7olem"n "nd other+ 2011> Airch*"um "nd other+ 2012). 2he 9"rcellu Sh"le i the
h"llo)er of the t)o unit "nd i 4+000 to 5+000 feet (ft) *elo) l"nd urf"ce+ re"chin# it m"/imum
de0th in -e) .ork ne"r the -e) .ork;Penn(l'"ni" *order> it *ecome h"llo)er north)"rd 60 to $0
mile until it cro0 out "t l"nd urf"ce (ee :illi"m+ 2010> fi#. 1).
0enerali*ed nort4!sout4 section 7it4 -edroc9 for,ations in sout4-central 8e7 %or9 Cfro, (illia,s) 2010B ,odified
fro, 8e7 %or9 State Museu,) 200GD.
<edrock i o'erl"in *( '"ri"*le thicknee of #l"ci"l de0oit ; drift ; 0redomin"ntl( till in the
u0l"nd "nd tr"tified de0oit in the '"lle( (9uller "nd 7"d)ell+ 1986> 7"d)ell "nd @ineen+ 198$>
9"c-ih "nd 1"nd"ll+ 1982). 2ill i "n unorted mi/ture of ediment de0oited *( #l"cier th"t i
t(0ic"ll( of lo) 0erme"*ilit( )ith thicknee r"n#in# u0 to "*out 250 ft. 2ill i commonl( thin or
"*ent on hillto0 or hilllo0e f"cin# north;northe"t (the direction th"t f"ced "d'"ncin# #l"cier) "nd
thicket on the o00oite ide of hill (7o"te+ 1966). Str"tified drift )" de0oited *( #l"ci"l melt)"ter
11
"nd r"n#e from fine "nd+ ilt+ "nd cl"( de0oited in 0ro#l"ci"l l"ke to "nd "nd #r"'el in melt)"ter
ch"nnel )ithin "nd ne"r meltin# ice or do)n'"lle( from the ice in outh)"rd,dr"inin# '"lle(.
Study Area
2he tud( "re" (2o0o#r"0hic ele'"tion of the tud( "re"+ outh,centr"l -e) .ork "nd 'icinit(.)
co'er 1+810 !u"re mile (mi
2
) "nd encom0"e "ll or 0"rt of fi'e -e) .ork countie (7hemun#+ 2io#"+
<roome+ 7hen"n#o+ "nd @el")"re) "dC"cent to northe"tern Penn(l'"ni" (2o0o#r"0hic ele'"tion of
the tud( "re"+ outh,centr"l -e) .ork "nd 'icinit(.). 2hi "re" i conidered f"'or"*le for 9"rcellu
Sh"le #" reource> etim"ted drillin# de0th to the *"e of the 9"rcellu Sh"le r"n#e from le th"n
3+000 feet in north,centr"l 7hemun# 7ount( to more th"n 5+000 ft "lon# the Penn(l'"ni" *order in
outhe"tern <roome 7ount( (:ri#httone+ 2009). 2he tud( "re" i underl"in 0redomin"ntl( *( cl"tic
ediment"r( e!uence ("ndtone+ ilttone+ h"le+ )ith onl( minor c"r*on"te rock) of the :et 4"ll
"nd Son(e" =rou0 (=ener"li6ed north;outh ection )ith *edrock form"tion in outh,centr"l -e)
.ork (from :illi"m+ 2010> modified from -e) .ork St"te 9ueum+ 2009).). 2he northern *ound"r( of
the tud( "re" i defined " either the northern m"00ed e/tent of the Son(e" =rou0 or the northern
*ound"r( of e"ch count( in the tud( "re"+ )hiche'er i f"rthet outh. 2hi *ound"r( )" elected to
"'oid *edrock cont"inin# i#nific"nt c"r*on"te unit+ uch " the 2ull( %imetone+ )hich )ould h"'e
introduced )"ter,chemitr( '"ri"tion "oci"ted )ith diolution of c"r*on"te rock. 2he e"tern
*ound"r( i defined " *ein# Cut )et of the 7"nnon'ille 1eer'oir+ )hich 0ro'ide 0"rt of -e) .ork
7it(D )"ter u00l(. 5i#h,'olume h(dr"ulic,fr"cturin# #" )ell )ill not *e 0ermitted )ithin the -e)
.ork 7it( )"terhed 0er the -e) .ork St"te @e0"rtment of ?n'ironment"l 7oner'"tionD (-.S@?7)
Se0tem*er 2011 @r"ft Su00lement"l =eneric ?n'ironment"l Im0"ct St"tement+ 7h"0ter 3;Section 3.2.4
Prohi*ited %oc"tion (htt0E//))).dec.n(.#o'/ener#(/$53$0.html).
Topograp4ic elevations of t4e study area) sout4-central 8e7 %or9 and vicinity.
12
Hydrogeology
5(dro#eolo#( of the tud( "re" include freh #round)"ter flo) (tem in the tr"tified drift in
l"r#e '"lle( "nd in fr"ctured *edrock throu#hout the "re". 4reh)"ter flo) (tem o'erlie ne"rl(
t"#n"nt "line )"ter or *rine in the northern &00"l"chi"n <"in (Poth+ 1962> :illi"m+ 2010> 5eii#+
1999> :illi"m "nd other+ 1998> Schiner "nd ="ll"her+ 19$9> :unch+ 1993> 5o0kin+ 1966). 2he l"ck
of "00reci"*le flo) of the "line )"ter "nd *rine h" *een "ttri*uted to l"ck of " dri'in# force for flo)+
it hi#h denit( "nd occurrence *ene"th the freh)"ter flo) (tem+ it loc"l 0oint of dich"r#e (Poth+
1962)+ "nd the #ener"l decre"e in fr"cture 0erme"*ilit( )ith de0th. &cti'e freh #round)"ter flo)
(tem "re #ener"ll( 'ie)ed " h"'in# fluhed out 0re,e/itin# "line )"ter "nd *rine (Poth+ 1962+
1963). 2he 0oition of the freh)"ter/"line,)"ter (or *rine) tr"nition in '"lle( "nd u0l"nd "re"+
ho)e'er+ i 0oorl( defined *ec"ue of limited d"t" "nd uncert"intie introduced *( flo) in )ell*ore. In
l"r#er '"lle(+ the de0th to "line )"ter h" *een re0orted from le th"n 100 ft to " fe) hundred feet
*elo) the '"lle( floor (:unch+ 1993> 5eii#+ 1999> Poth+ 1963> :illi"m+ 2010). & recent )ell drilled
)ithin the Su!ueh"nn" 1i'er '"lle( "t <in#h"mton+ -...+ 0enetr"ted " "line )"ter,*e"rin# fr"cture "t
320 ft *elo) l"nd urf"ce "nd 2$4 ft into *edrock F:ell <9 504+ B.S. =eolo#ic"l Sur'e( (BS=S)
-"tion"l :"ter Inform"tion S(tem (-:IS) d"t"*"e> http://waterdata.usgs.gov/nwisG. @e0th to "line
)"ter or *rine in u0l"nd "re" i l"r#el( undefined. 2he tr"nition *et)een freh)"ter "nd "line )"ter
or *rine in fr"ctured *edrock m"( *e h"r08" fr"cture cont"inin# )"ter )ith hi#h "linit( (H. 5.
:illi"m+ BS=S+ or"l commun.+ 2012> 5eii# "nd Anuton+ 199$)8or #r"du"l (5o0kin+ 1966).
9"c-ih "nd 1"nd"ll (1982) conce0tu"li6e "nd cl"if( the h(dro#eolo#ic fr"me)ork of
tr"tified,drift "!uifer "cro the Su!ueh"nn" 1i'er <"in in -e) .ork+ )hich encom0"e mot of
the tud( "re"+ "nd 1"nd"ll (2001) 0ro'ide " com0reheni'e fr"me)ork for tr"tified,drift "!uifer
"ement )ith decri0tion of condition+ *( re#ion+ for the #l"ci"ted northe"tern Bnited St"te. 9ore
13
det"iled tr"tified,drift "!uifer m"00in# h" *een undert"ken in the tud( "re" ince the e"rl( 1980 (for
e/"m0le+ 5olocek "nd other+ 1982> 9iller "nd other+ 1982> 1e(nold "nd ="rr(+ 1990> 1e(nold+
2003> 9iller "nd Pitm"n+ 2012> "nd 5eii#+ 2012). In #ener"l+ #round)"ter flo) in '"lle( mo'e from
the '"lle( )"ll to)"rd the tre"m or ri'er. 2hi flo) i mot r"0id in h"llo) unconfined 0erme"*le
de0oit in h(dr"ulic connection )ith the tre"m "nd lo)et in dee0er '"lle( "nd "nd #r"'el or
*edrock+ 0"rticul"rl( if there i "n inter'enin# confinin# unit.
2he 0rim"r( ource of #round)"ter to )ell in u0l"nd "re" i fr"ctured *edrock (for e/"m0le+
5eii#+ 2012). 4e) h(dro#eolo#ic tudie in the &00"l"chi"n <"in in -e) .ork h"'e focued on
u0l"nd;hillide flo) (tem. 5eii# (1998) conce0tu"li6e #round)"ter flo) in hillide in the
northern 7"tkill 9ount"in from #eo0h(ic"l lo# "nd #round)"ter,le'el me"urement from " m"ll
num*er of hillide )ell (5eii# "nd Anuton+ 199$) "nd from det"iled hillide tudie in the ?"tern
Aentuck( 7o"lfield (Ai00 "nd other+ 1983> 9inn+ 1993> :unch+ 1993).
Met4ane >ccurrence in t4e Su-surface
In "re" underl"in *( #",*e"rin# *edrock+ )ide0re"d u0)"rd mi#r"tion (microee0"#e) of
h(droc"r*on to o'erl(in# #round)"ter "nd oil h" *een reco#ni6ed (7h"fin+ 1994> @irect
=eochemic"l+ 2004). In )etern -e) .ork+ "nom"loul( hi#h meth"ne concentr"tion "nd h(droc"r*on
r"tio (eth"ne/ethene+ meth"ne/eth"ne) in oil #" h"'e *een ued to identif( f"ult "nd " " 0ro0ectin#
tool for n"tur"l,#" reer'oir (4ount"in "nd H"co*i+ 2000> @irect =eochemic"l+ 2004). 2hee tudie
ho) re#ion"l h(droc"r*on microee0"#e )ith ee0"#e r"te loc"ll( enh"nced *( f"ultin# "nd
fr"cturin#. B0)"rd ee0"#e c"n *e curt"iled *( c"00in# or confinin# unit (7h"fin+1994)+ )hich m"(
include *edrock tr"t" in )hich fr"cture "re motl( cloed or+ in #l"ci"ted "re"+ o'erl(in# #l"ci"l,drift
de0oit of lo) 0erme"*ilit(.
14
Met4ane in 0round7ater
Pre,1990 d"t" on meth"ne in #round)"ter from outh,centr"l -e) .ork "re limited "nd
!u"lit"ti'e+ collected from homeo)ner durin# )"ter,)ell in'entorie (for e/"m0le+ 1"nd"ll+ 19$2).
:illi"m (2010) com0iled #" "nd "lt)"ter occurrence d"t" from thee 0re,1990 tudie "nd from #",
)ell lo# from the ?m0ire St"te 3il "nd =" Inform"tion S(tem d"t"*"e
(http://esogis.nysm.nysed.gov/ ). 2he occurrence of #" "nd "lt)"ter )" mot common in '"lle( "re"+
*ut mot of the in'entoried )"ter )ell )ere in '"lle( o the e/tent of #" "nd "lt)"ter in u0l"nd "re"
)" not )ell ch"r"cteri6ed durin# thi 0eriod.
&n"l(e of diol'ed #" in #round)"ter th"t include meth"ne "n"l(i *ec"me more common
in the 1990 *ec"ue diol'ed #" concentr"tion )ere re!uired for chlorofluoroc"r*on #round)"ter
"#e,d"tin# techni!ue (A"00el "nd -(trom+ 2012). Interet in meth"ne rel"ted to h"le,#" reource
de'elo0ment reulted in the "ddition (in 2009) of diol'ed #" to the uite of "n"l(te "n"l(6ed in the
#round)"ter "m0le "nnu"ll( collected *( BS=S in coo0er"tion )ith the -e) .ork St"te @e0"rtment
of ?n'ironment"l 7oner'"tion (-(trom+ 2012> ee htt0E//n(.)"ter.u#.#o'/0roCect/305*/). A"00el
"nd -(trom (2012) com0iled d"t"et of reult of "n"l(e for )"ter "m0le from -e) .ork "nd
0reented " m"0 "nd t"titic of concentr"tion *( #eolo#ic form"tion. 9eth"ne occurrence "t lo)
concentr"tion (0.001 to 1 m#/%) i )ide0re"d+ *ut hi#her concentr"tion "re l"r#el( 0reent in *edrock
)ell com0leted in ediment"r( *edrock.
1ecent tudie of meth"ne in #round)"ter "oci"ted )ith 9"rcellu Sh"le #" drillin# include 3*orn
"nd other (2011) "nd 9olofk( "nd other (2011+ 2013). 3*orn "nd other (2011) "m0led 51 *edrock
)ell in northe"tern Penn(l'"ni" "nd 9 in 3te#o 7ount(+ -e) .ork+ "nd me"ured diol'ed #"
concentr"tion of meth"ne "nd hi#her,ch"in h(droc"r*on+ "nd c"r*on "nd h(dro#en ioto0e r"tio of
meth"ne. :ell de0th+ *edrock form"tion+ "nd 0ro/imit( to "cti'e #" )ell )ere recorded. :"ter
15
collected from )ell )ithin 1 kilometer (km) of "cti'e #" )ell (ome )ithin "n "re" of kno)n
meth"ne cont"min"tion) "ccounted for "ll *ut one meth"ne concentr"tion #re"ter th"n 10 m#/%. Ioto0ic
i#n"ture of meth"ne indic"ted " thermo#enic ori#in (inter0reted " conitent )ith 9iddle @e'oni"n
or older tr"t" includin# the 9"rcellu Sh"le) for )ell ne"r "cti'e #",)ell "re" "nd " mi/ed
thermo#enic,micro*i"l ource for thoe outide e/tr"ction "re". 9olofk( "nd other (2011> 2013)
re0ort reult of more th"n 1+$00 0re,h"le,#",drillin# "n"l(e for meth"ne in dometic )ell,)"ter
"m0le in Su!uh"nn" 7ount(+ northe"tern Penn(l'"ni". 2he( found (1) detect"*le meth"ne (#re"ter
th"n 0.0001 m#/%) in $8 0ercent of the )ell+ (2) i#nific"ntl( hi#her meth"ne concentr"tion in lo)l"nd
'"lle( "re" th"n in u0l"nd "re"+ "nd (3) no rel"tion of meth"ne concentr"tion to 0ro/imit( of e/itin#
#" )ell. 9olofk( "nd other (2011> 2013) inter0reted Su!ueh"nn" 7ount(+ P".+ meth"ne ioto0ic
reult from 3*orn "nd other (2011) " conitent )ith " meth"ne ource of 0redomin"ntl( B00er
@e'oni"n tr"t" ("*o'e the 9"rcellu Sh"le).
Purpose and Scope
2hi re0ort document the reult of " ur'e( of meth"ne in #round)"ter from )"ter )ell of
outh,centr"l -e).ork conducted from l"te Hune throu#h e"rl( &u#ut 2012 th"t utili6ed det"iled )ell,
contruction d"t" to "i#n " h(dro#eolo#ic ettin# cl"ific"tion for e"ch )ell th"t )" "m0led.
S"m0lin# method "re decri*ed+ "nd "m0le loc"tion "re m"00ed. @"t" on concentr"tion "nd ioto0ic
i#n"ture of meth"ne "nd other h(droc"r*on "re t"*ul"ted "lon# )ith )"ter,!u"lit( field ch"r"ctritic+
)ell,contruction ch"r"cteritic+ ele'"tion+ "nd h(dro#eolo#ic ettin#. =r"0h "nd 0lot ho) the r"n#e
of meth"ne concentr"tion me"ured+ t"titic"l com0"rion of meth"ne concentr"tion *( h(dro#eolo#ic
ettin#+ com0"rion of meth"ne )ith )"ter,!u"lit( field ch"r"cteritic+ "nd ioto0ic i#n"ture of
meth"ne. & conce0tu"l di"#r"m of meth"ne occurrence )ithin the re#ion )ith reference to
h(dro#eolo#ic ettin# i 0reented "nd decri*ed.
16
ethods
9ethod include h(dro#eolo#ic cl"ific"tion "nd election of )ell for the monitorin# net)ork+
l"*or"tor( "n"l(i+ )"ter "m0lin#+ !u"lit( control+ "nd t"titic"l "n"l(i.
&ydrogeologic #lassification of -ells in the Study Area
?'idence from 0re'iou )ork indic"te th"t meth"ne occurrence in #round)"ter i "ffected *(
the h(dro#eolo#ic ettin#8to0o#r"0hic 0oition of the flo) (tem "nd )hether or not the #round)"ter
i confined *( #l"ci"l de0oit (l"cutrine de0oit or till> 9iller "nd Pittm"n+ 2012> 5eii#+ 2012).
I"lle( "re likel( f"'or"*le for meth"ne occurrence for multi0le re"onE '"lle( re0reent. I"lle( "re
"re" of (1) m"/imum loc"l inciion (eroion) into *edrock tr"t"+ (2) cloet 0ro/imit( to underl(in#
meth"ne,*e"rin# "line )"ter or *rine+ "nd (3) loc"ll( )e"k (fr"ctured "nd 0oi*l( f"ulted) *edrock
)ith 0reum"*l( more 0erme"*ilit( th"n urroundin# u0l"nd+ thu enh"ncin# u0)"rd ee0"#e of
meth"ne. 7onfinement *( either unconolid"ted de0oit or *edrock of lo) 0erme"*ilit( c"n tr"0 the
u0)"rd ee0"#e of h(droc"r*on. 2hu+ deline"tion of '"lle( "nd u0l"nd "nd determin"tion of
confined or unconfined #round)"ter condition "re the *"i of the cl"ific"tion ued herein (t"*le 1).
,a%le .( Hydrogeologic setting classification in t4e study area) sout4-central 8e7 %or9.
1alleys and /plands
I"lle( "re conce0tu"ll( the locu of #round)"ter dich"r#e to urf"ce )"ter+ motl( throu#h
h"llo)+ 0erme"*le de0oit under unconfined condition. <ene"th thee de0oit+ confinin# unit "re
common0l"ce )ith l"cutrine fine "nd+ ilt+ "nd cl"( in l"r#e lo)l"nd '"lle( "nd till in n"rro) u0l"nd
'"lle(. =round)"ter circul"tion in "nd "nd #r"'el "nd fr"ctured *edrock *ene"th confinin# unit i
likel( lo)er "nd more retricted th"n under h"llo) unconfined condition. 2he de0th of "cti'e
1$
circul"tion "nd the tr"nition from freh to "line )"ter i h"llo)et *ene"th '"lle( (0ro*"*l( "*out or
le th"n 300 ft into *edrock).
B0l"nd hillide "nd hillto0 "re" "re 0rim"ril( #round)"ter,rech"r#e "re"+ "nd mot
#round)"ter flo) i likel( )ithin the u00er 100,300 ft of fr"ctured *edrock (5eii# (1998)> Ai00 "nd
other (1983). =round)"ter flo) i rel"ti'el( r"0id *ene"th hi#h,#r"dient hilllo0e )ith little till co'er+
)hich reult in #round)"ter )ith rel"ti'el( lo) miner"l content. Sh"llo) fr"cture t(0ic"ll( "re
un"tur"ted durin# dr( 0eriod "nd re"tur"te in re0one to rech"r#e of r"inf"ll or no)melt. :here till
co'er i thick "nd confine *edrock+ 0"rticul"rl( on lo)er hilllo0e or in till h"do) (7o"te+ 1966)+
e"on"l ch"n#e in "tur"tion m"( *e muted+ "nd #round)"ter flo) r"te m"( *e reduced. =round)"ter
flo) in u0l"nd con'er#e do)nlo0e to)"rd '"lle( "re". @ee0 do)n)"rd flo) in u0l"nd *edrock i
"lo lo) "nd retricted. 2he de0th of "cti'e circul"tion "nd the tr"nition from freh)"ter to *rine i
l"r#el( undocumented. :ell in the u0l"nd "re" "re "lmot e/clui'el( com0leted in fr"ctured
*edrock+ "nd re0ort of )"ter )ith hi#h "linit( "re r"re. 2he dee0et freh)"ter 0enetr"ted *( #" )ell
in the u0l"nd i re0orted to *e "*out 800 feet *elo) l"nd urf"ce (:illi"m+ 2010).
I"lle( "nd u0l"nd "re" )ere deline"ted )ith the o*Cecti'e of differenti"tin# )ell *(
#round)"ter flo) re#ime+ " decri*ed "*o'e. 7once0tu"ll(+ " J'"lle(K )ell i loc"ted on the '"lle(
floor or on immedi"tel( "dC"cent hillide "nd com0leted *elo) the ele'"tion of the '"lle( tre"m or
ri'er+ either in "nd "nd #r"'el or *edrock. &n Ju0l"ndK )ell i loc"ted on " hillide or hillto0 "nd i
com0leted "lmot e/clui'el( in *edrock )ith the *ottom of the )ell "t "n ele'"tion t(0ic"ll( hi#her
th"n the "dC"cent '"lle( tre"m or ri'er.
2he 0ecific of definin# '"lle(+ )ith the rem"inin# l"nd urf"ce " u0l"nd+ follo) "nd i
illutr"ted in fi#ure 3. 4irt+ " (nthetic tre"m net)ork )" #ener"ted from " lid"r di#it"l ele'"tion
model (@?9). 2he lon#itudin"l e/tent of tre"m th"t define '"lle( )" defined *( " dr"in"#e "re" of
18
"t le"t 0.58 mi
2
(1.5 million m
2
)+ tre"m,e#ment lo0e of le th"n 2.$5 0ercent+ "nd loc"l relief of
#re"ter th"n 150,200 ft. 2he )idth of '"lle( )" defined " the l"nd "re" 'ertic"ll( $5 ft or le "*o'e
the '"lle( tre"m in m"ll '"lle( )ith limited tr"tified #l"ci"l de0oit. 2he "me definition )" ued
in l"r#e '"lle( )ith tr"tified #l"ci"l de0oit+ e/ce0t )here thick #l"ci"l de0oit rie #re"ter th"n $5
feet "*o'e the '"lle( tre"m8in thoe re"che+ the '"lle( e/tent )" defined )here re#ul"r '"lle(
hillide lo0e *e#in (?rrorE 1eference ource not found).
Sc4e,atic diagra, defining #) valley areas and B-<) 7idt4s2 #) 1alley linear e:tent defined in ,ap vie7. .igital
elevation ,odel generated strea, courses Cdas4ed and solid -lue linesD 7it4 drainage areas greater t4an or eHual
to 0.I6 sHuare ,iles C1.I ,illion sHuare ,etersD. Solid -lue lines indicate valley-defining strea, courses Cstrea,-
seg,ent slopes of less t4an 2.?I percent and local relief greater t4an appro:i,ately 200 feetD. .as4ed strea,
courses do not ,eet criteria and are not defined as valleys. B) $and area 7it4in ?I feet a-ove t4e valley strea, in
s,all valleys 7it4 li,ited stratified glacial deposits. <) $arge valleys 7it4 stratified glacial deposits are defined in a
,anner si,ilar to t4at of s,all valleys) e:cept 74ere t4ic9 glacial deposits rise greater t4an ?I feet a-ove t4e valley
strea,. 1alley e:tent is defined 74ere regular valley 4illside slopes -egin. CK) greater t4anB M) appro:i,atelyD
<onfined <onditions
7onfinement *( #l"ci"l,drift de0oit of #round)"ter t"00ed *( )ell )" "ddreed on " )ell,
*(,)ell or loc"l *"i+ " com0reheni'e deline"tion "cro the tud( "re" )" *e(ond the co0e of thi
tud( "nd the "'"il"*ilit( of d"t". &lthou#h it i reco#ni6ed th"t non,fr"ctured *edrock )ith little
0rim"r( 0erme"*ilit( "ct " " confinin# unit+ cl"ific"tion of confined or unconfined condition )"
*"ed on the t(0e of #l"ci"l,drift de0oit o'erl(in# *edrock. 2he confinement condition of
#round)"ter in u0l"nd "nd '"lle( "re" )" determined *( different criteri" *ec"ue of the difference
in the t(0e "nd ditri*ution of #l"ci"l,drift de0oit. B0l"nd "re" t(0ic"ll( h"'e " in#le t(0e of
#l"ci"l,drift de0oit "nd confinin# unit (till) th"t 0"rti"ll( o'erlie *edrock. =l"ci"l,drift de0oit in
19
'"lle( "re" "re more '"ried "nd conit of tr"tified m"teri"l th"t r"n#e from 0erme"*le ice,cont"ct
"nd out)"h "nd "nd #r"'el to rel"ti'el( im0erme"*le (confinin#) l"cutrine fine "nd+ ilt+ "nd cl"(.
2ill i "lo " confinin# unit in ome '"lle( "re"+ t(0ic"ll( Cut "*o'e *edrock+ )here 0reent.
7onfined "nd unconfined condition in u0l"nd ettin# )ere defined throu#h "n"l(i of lid"r
(%i#ht @etection "nd 1"n#in#) im"#er( "nd )ell,lo# d"t". 7om0"rion of thee d"t" indic"te th"t till
co'er i thin or loc"ll( dicontinuou )here Jt"ir,te0K ediment"r( *edrock tructure i 'ii*le on
lid"r im"#er( "nd rel"ti'el( thick )here thi 0"ttern i o*cured. 2he t"ir,te0 outcro0 0"ttern in thee
#entl( di00in# tr"t" reflect the difference in *edrock reit"nce to eroionE "ndtone "re mot
reit"nt+ "nd h"le "nd ilttone "re le"t reit"nt. In thee "re" till thickne c"n '"r( )idel( from
"*ent (unconfined) on the outer ed#e of " Jt"ir tre"dK to 0erh"0 ten of feet ('er( loc"ll( confined) on
inner 0"rt of the tre"d8thu+ unconfined on the )hole. In li#ht of thee o'er"ll unconfined condition+
till thicknee of 30 ft or le (or le th"n or e!u"l to 30 ft of c"in# ued) )ere conidered unconfined
ettin#+ "nd till thicknee of "t le"t 45 ft (#re"ter th"n or e!u"l to 60 ft of c"in#) )ere conidered
confined. :ell th"t h"d #re"ter th"n 30 ft "nd le th"n 45 ft of till thickne )ere of uncert"in
confinement "nd thu omitted from )ell election.
@etermin"tion of confinement condition in '"lle( "re" re!uired )ell lo# *ec"ue of the
tr"tified "nd untr"tified n"ture of the #l"ci"l,drift de0oit )ithin " limited "re"l e/tent. 7onfined
condition )ere defined *( " tot"l of 15 ft or more of fine,#r"ined de0oit (t(0ic"ll( l"cutrine
de0oit+ le commonl( till) "*o'e the to0 of creen+ o0en end+ or o0en *edrock )ell*ore. Bnconfined
condition )ere defined " le th"n 15 ft of fine,#r"ined de0oit.
#dditional <lassification of 1alley Settings
I"lle( confined "nd unconfined ettin# )ere u*di'ided on the *"i of (1) "!uifer m"teri"l8
"nd "nd #r"'el or *edrock+ (2) "nd "nd #r"'el )ell o'er unconfined *edrock or "nd "nd #r"'el )ell
20
o'er confined *edrock+ "nd (3) confined *edrock )ell in u0l"nd I,h"0ed '"lle( "nd lo)l"nd B,
h"0ed '"lle(.
I"lle( confined "nd unconfined )ell )ere u*di'ided *( the "!uifer in )hich " )ell )"
com0leted8"nd "nd #r"'el or *edrock8*ec"ue 0enetr"tion of *edrock "nd #re"ter de0th )ithin
'"lle( #round)"ter flo) (tem )ere conidered 0otenti"l f"ctor in meth"ne occurrence. I"lle(
unconfined )ell com0leted in "nd "nd #r"'el )ere 0redomin"ntl( "nd "nd #r"'el o'er *edrock
(unconfined *edrock). & m"ll u*et of )ell )" com0leted in "nd "nd #r"'el *ut loc"ll( iol"ted
from *edrock *( "n underl(in# confinin# unit. 2he 0reence of "n inter'enin# confinin# unit could
0otenti"ll( 0re'ent u0)"rd h(droc"r*on ee0"#e from re"chin# the unconfined "nd "nd #r"'el.
7onfined '"lle( )ell com0leted in *edrock )ere u*di'ided into lo)l"nd "nd u0l"nd
c"te#orie. %o)l"nd '"lle( "re defined *( tre"m or ri'er *elo) the 1+100,ft ele'"tion+ "nd u0l"nd
'"lle( "re defined *( tre"m "t #re"ter th"n or e!u"l to the 1+100,ft ele'"tion. %o)l"nd '"lle( cont"in
tr"tified drift "nd h"'e rel"ti'el( fl"t '"lle( *ottom (B,h"0ed '"lle()+ )here" u0l"nd '"lle( "re
n"rro)+ t(0ic"ll( cont"inin# ome "llu'ium th"t o'erlie till (I,h"0ed '"lle().
onitoring"-ell Network #riteria
2he )ell net)ork )" dei#ned to e'"lu"te concentr"tion of n"tur"ll( occurrin# meth"ne
concentr"tion in #round)"ter from the immedi"te #round)"ter en'ironment of the "m0lin# 0oint.
:ell )ithin " one,mile r"diu of "n( kno)n current or former #" )ell in the tud( "re" or "lon# the
Penn(l'"ni" *order )ere e/cluded from conider"tion for "m0lin# to "'oid 0otenti"l effect from
current or hitoric #" )ell (%oc"tion of "m0led )"ter )ell "nd former or e/itin# #" )ell )ith 1,
mile *uffer+ "nd deline"tion of '"lle( "re"+ in outh,centr"l -e) .ork "nd Penn(l'"ni".). 9ot of the
#" )ell "re in 7hemun# 7ount( (e0eci"ll() "nd 2io#" 7ount(+ reultin# in fe)er c"ndid"te )"ter
)ell in thee "re". -e) .ork #" )ell )ere identified *( uin# the ?m0ire St"te 3il "nd ="
21
Inform"tion S(tem d"t"*"e (http://esogis.nysm.nysed.gov/ ) "nd the -e) .ork St"te @e0"rtment of
?n'ironment"l 7oner'"tion 3il "nd =" d"t"*"e (htt0E//))).dec.n(.#o'/cfm//e/t"00/="3il/)+ *oth
of )hich include currentl( 0roducin# )ell+ 0lu##ed )ell+ detro(ed )ell+ or other c"00ed+ non,
0roducin# tet )ell. Penn(l'"ni" )ell )ere identified *( uin# the St"teD online #",)ell d"t"*"e
(htt0E//))).0ort"l.t"te.0".u/0ort"l/er'er.0t/communit(/oilL"ndL#"Lre0ort/2029$). %o), to
moder"te,(ieldin# )"ter )ell (re0orted (ield of 2;80 #"llon 0er minute)+ ued motl( for houehold
or li'etock u00l(+ )ere "m0led+ "nd hi#h,(ieldin# 0u*lic u00l( or indutri"l,u00l( )ell )ere
"'oided to enure th"t #round)"ter from " rel"ti'el( loc"li6ed ource )" *ein# "m0led. 9"n( hi#h,
(ieldin# )"ter )ell deri'e " u*t"nti"l 0"rt of their (ield throu#h induced infiltr"tion from urf"ce,
)"ter *odie "nd do not reflect loc"l #round)"ter condition. :ell of t(0ic"l de0th "nd )ell
contruction )ere "m0led> de0th of u0l"nd )ell r"n#ed from 100 to 350 ft+ )here" de0th of '"lle(
)ell r"n#ed from 28 to 225 ft. &ll )ell com0leted in "nd "nd #r"'el )ere finihed )ith "n o0en,
ended c"in#> creen "re r"rel( ued for dometic )ell. <edrock )ell "re c"ed "*out 10 feet into
*edrock+ "nd the rem"inin# )ell i "n o0en hole throu#h the rock.
2he initi"l t"r#et for the num*er of )ell in the net)ork )" 60 )ith 15 )ell in e"ch of the four
m"Cor h(dro#eolo#ic ettin# cl"e ('"lle( confined+ '"lle( unconfined+ u0l"nd confined+ "nd u0l"nd
unconfined). 2he 0rim"r( ource of inform"tion on )ell )ith lo# "nd contruction d"t" )" the -e)
.ork St"te @e0"rtment of ?n'ironment"l 7oner'"tion :"ter :ell Permit d"t"*"e
(htt0E//))).dec.n(.#o'/l"nd/3331$.html). &*out 2+500 )ell from thi d"t"*"e "re )ithin the tud(
"re". Some )ell "*out 0.25 mi north (outide) of the Son(e" =rou0 *ound"r( in 7hen"n#o 7ount(
)ere included in the 0ool of 0otenti"l )ell *ec"ue of co"re c"le of the #eolo#( m"0 (1E250+000
c"le). 2hi d"t"et )" edited *( remo'in# (1) )ell )ithin 1 mile of " #" )ell+ (2) u0l"nd )ell
)ithin 1 mile of '"lle( *ottom (in the ori#in"l cl"ific"tion+ thee "re" )ere conidered tr"nition"l
22
*et)een u0l"nd "nd '"lle()+ "nd (3) )ell )ith incom0lete *"ic contruction d"t" or un,inter0ret"*le
)ell lo#. B0l"nd )ell c"ed *et)een 30 "nd 60 ft )ere omitted *ec"ue of uncert"in confinement
condition+ " dicued under h(dro#eolo#ic ettin#. I"lle( )ell th"t )ere h"llo) )ith no definition
of underl(in# #eolo#( from drillerD lo# "t ne"r*( )ell "lo )ere omitted. B0l"nd )ell )ere
0rim"ril( c"te#ori6ed *( c"in# len#th or+ for ome )ell+ *( direct re0ort of till thickne. I"lle( )ell
)ere c"te#ori6ed indi'idu"ll( *( )ell lo# or *( e/itin# urfici"l m"00in#. 2he reultin# 0ool of
0otenti"l )ell conited of 336 u0l"nd unconfined )ell+ 332 u0l"nd confined )ell+ 210 '"lle(
confined )ell+ "nd 135 '"lle( unconfined )ell. %etter e/0l"inin# the tud(+ "lon# )ith )ell
!uetionn"ire+ )ere ent to )ell o)ner "ddree from the -.S@?7 )ell 0ermit "lon# )ith )ell
!uetionn"re. 2he net)ork )" de'elo0ed from 0oiti'e )ell,o)ner re0one "nd !uetionn"ire
reult+ includin# "ccei*ilit( "nd "cce to r") )ell )"ter. 2he net)ork conited of 66 )ell ()ith
one u0l"nd )ell of uncert"in confinement)+ 53 com0leted in *edrock "nd 13 com0leted in "nd "nd
#r"'el. 2here )ere 28 )ell in <roome 7ount(+ 19 )ell in 2io#" 7ount(+ 11 )ell in 7hemun# 7ount(+
$ )ell in 7hen"n#o 7ount(+ "nd 1 )ell in @el")"re 7ount( (%oc"tion of "m0led )"ter )ell "nd
former or e/itin# #" )ell )ith 1,mile *uffer+ "nd deline"tion of '"lle( "re"+ in outh,centr"l -e)
.ork "nd Penn(l'"ni".). @ecri0tion of )ell "re 0reented in "00endi/ 1+ "nd elected )ell
ch"r"cteritic "mon# m"Cor h(dro#eolo#ic ettin# "re umm"ri6ed in t"*le 2.
$ocations of sa,pled 7ater 7ells and for,er or e:isting gas 7ells 7it4 1-,ile -uffers) and delineation of valley
areas) in sout4-central 8e7 %or9 and Pennsylvania.
,a%le /( Su,,ary of c4aracterisitics of sa,pled 7ells) -y ,a@or 4ydrogeologic setting) sout4 -central 8e7 %or9.
A1alley 7ells 7ere co,pleted in sand and gravel or -edroc9B in sand and gravel 7ells) over-urden t4ic9ness is
t4at of glacial deposits a-ove t4e -otto, of t4e 7ell Cfinis4ed as open pipe) not screenedD. Bedroc9 penetration
is *ero in sand and gravel 7ellsE.
23
0a%oratory Analysis of -ater Samples
&ll "m0le )ere "n"l(6ed *( Iotech %"*or"torie+ Inc.+ (here"fter Iotech) in 7h"m0"i#n+
Illinoi. IotechD -=,2 diol'ed #" "n"l(tic"l chedule )" ued ("00endi/ 2)+ )hich include the
mol"r 0ercent of e"ch diol'ed #" ("r#on (&r)+ o/(#en (32)+ c"r*on dio/ide (732)+ nitro#en (-2)+
c"r*on mono/ide (73)+ meth"ne (754 or 71)+ eth"ne (7256 or 72)+ "nd lo)er,ch"in h(droc"r*on u0 to
0ent"ne (75) "nd the he/"ne (76) "nd lon#er ch"in fr"ction)+ the concentr"tion (milli#r"m 0er liter) of
meth"ne "nd eth"ne+ "nd if ufficient "m0le+ the c"r*on "nd h(dro#en ioto0e r"tio of meth"ne "nd the
c"r*on ioto0e r"tio of eth"ne. Iotech ue " modified 'erion of B.S ?n'ironment"l Protection
&#enc(D 1SA,1$5 method+ " #" chrom"to#r"0h( he"d0"ce e!uili*rium techni!ue+ for "n"l(i of
diol'ed #"e in )"ter "m0le. Ioto0e r"tio "n"l(e "re *( either offline 0re0"r"tion )ith du"l inlet
I19S or online =7,7,I19S. 5(dro#en t"*le ioto0e d"t" re0orted rel"ti'e to Iienn" St"nd"rd 9e"n
3ce"n :"ter (IS93:) "nd c"r*on t"*le ioto0e d"t" re0orted rel"ti'e to Iienn" Pee@ee <elemnite
(IP@<).
9eth"ne "nd other diol'ed #"e (c"r*on dio/ide+ nitro#en+ o/(#en+ "nd "r#on) )ere "n"l(6ed
in i/ "m0le *( the BS=S 1eton 7hlorofluoroc"r*on (747) %"*or"tor( ("00endi/e 2;3) *( #"
chrom"to#r"0h(. 2he "r#on+ nitro#en+ "nd o/(#en "re !u"ntified *( therm"l conducti'it( detector.
9eth"ne "nd c"r*on dio/ide "re e0"r"ted "nd 0"ed throu#h " nickel meth"ni6er "nd me"ured )ith "
4l"me Ioni6"tion @etector (<uen*er# "nd other (1998)> htt0E//)"ter.u#.#o'/l"*/diol'ed,
#"/l"*/"n"l(tic"lL0rocedure/). 2hee "m0le )ere "n"l(6ed *( *oth l"*or"torie o th"t " com0"rion
could *e m"de of the reult from *oth method. Bntil the 0reent tud(+ "ll diol'ed meth"ne
#round)"ter d"t" #ener"ted in -e) .ork St"te *( the BS=S h"d *een "n"l(6ed uin# the 747
l"*or"tor(> in order to com0"re the reult of the 0reent tud( )ith reult of 0re'iou tudie of
24
meth"ne occurrence in #round)"ter (ee A"00el "nd -(trom+ 2012)+ it )" nece"r( to h"'e meth"ne
d"t" #ener"ted *( *oth l"*or"torie.
Sampling ethods
S"m0le )ere collected "ccordin# to t"nd"rd BS=S "m0lin# method (B.S. =eolo#ic"l
Sur'e(+ '"rioul( d"ted) )ith ome modific"tion " " reult of )ell+ 0lum*in#+ "nd "ccei*ilit(
condition in the tud( "re". -e"rl( "ll )ell "m0led )ere ued re#ul"rl( "nd thu re#ul"rl( 0ur#ed.
9ot )ell )ere com0leted " o0en hole in fr"ctured *edrock+ "nd in the "uthorD e/0erience )ith
re#ion"l )ell*ore+ "cti'e flo) )ithin uch )ell*ore i common0l"ce. 2herefore+ t"*ili6"tion of field
)"ter,!u"lit( ch"r"cteritic )" the criterion ued to determine "de!u"te )ell 0ur#in#.
&ll )"ter "m0le "n"l(6ed for diol'ed #" )ere collected uin# the 0um0 0erm"nentl(
int"lled in the )ell. :"ter )" collected from " t"0 " cloe to the )ell " fe"i*le+ *efore the 0reure
t"nk )here 0oi*le+ "nd *efore "n( )"ter,tre"tment (tem. S"m0le )ere collected uin# one or more
10,ft len#th of 2eflon tu*in# "tt"ched to " 0i#ot. :ell )ere 0ur#ed "t 0um0in# r"te on the order of
2;5 #"llon 0er minute (#"l/min)+ "nd field ch"r"cteritic ()"ter tem0er"ture+ 05+ 0ecific conduct"nce+
"nd diol'ed o/(#en concentr"tion) )ere recorded "t re#ul"r inter'"l. 4ield )"ter;!u"lit(
ch"r"cteritic )ere me"ured )ith " multi;0"r"meter meter th"t recei'ed 1 to 2 #"l/min of dich"r#e
)"ter. Be of " flo),throu#h cell for field,ch"r"cteritic me"urement )" modified )hen "ccumul"tion
of #" *u**le )" e/cei'e "nd interfered )ith field,ch"r"cteritic me"urement. 2o minimi6e *u**le
"ccumul"tion+ the dich"r#e line )" tr"00ed to the field,ch"r"cteritic 0ro*e "nd 0l"ced in " *e"ker (to
retrict freh dich"r#e ne"r the 0ro*e) th"t )" then 0l"ced in the *ottom of " 5,#"llon *ucket th"t
recei'ed the dich"r#e )"ter. 2hi 0rocedure "lo er'ed to kee0 the dich"r#e )"ter "nd field 0ro*e
cloe to "m*ient #round)"ter tem0er"ture durin# ummer field )ork. 2em0er"ture of the dich"r#e
25
)"ter "nd 0reure "t the )ell,(tem 0reure #"#e )ere monitored to 'erif( th"t the )ell )" c(clin#
on "nd off "t re#ul"r inter'"l uch th"t the "m0le )" " re0reent"ti'e of )ell )"ter " 0oi*le.
S"m0lin# *e#"n "fter "t le"t t)o+ *ut t(0ic"ll( "ll four+ of the field ch"r"cteritic h"d met
t"*ili6"tion criteri" (B.S. =eolo#ic"l Sur'e(+ '"rioul( d"ted). &ll "m0le )ere collected "fter "t le"t
20 minute of 0ur#in#. @urin# )ell 0ur#in#+ recent )"ter ue *( the )ell o)ner )" noted+ "nd the )ell
loc"tion )" ketched on " m"0 "nd 'erified )ith " #lo*"l 0oitionin# (tem (=PS) me"urement of
l"titude "nd lon#itude.
@iol'ed,#" "m0le )ere collected throu#h " m"nifold (tem "tt"ched to the end of the
2eflon tu*in# (http://www.isotechlabs.com/customersupport/samplingprocedures/IsoBagSM.pdf) th"t
conited of " 0reure #"#e+ " 0ur#e '"l'e th"t "llo)ed dich"r#e to continue to )"te+ "nd " "m0lin#
'"l'e th"t "llo)ed reduced flo) for "m0lin# 0ur0oe. @urin# "m0le collection+ *"ck 0reure )" 0ut
on the )ell,)"ter dich"r#e *( 0"rti"ll( cloin# *oth '"l'e to minimi6e de#"in# in the 2eflon tu*in#
u0 to the "m0le,line '"l'e. <"ck 0reure r"n#ed from "*out 5 to 25 0ound 0er !u"re inch+
de0endin# on the "m0le. @urin# "m0le collection+ the flo) r"te in the "m0le line )" "dCuted to
"*out 0.5 #"l/min. ?ffer'ecent "m0le )ere collected in Io<"#M (Iotech %"*or"torie+ Inc.) )hich
"re e'"cu"ted fle/i*le 0l"tic *"# ()ith *iocide c"0ule) )ith " '"l'e th"t connect to the "m0le line to
0re'ent lo of #" durin# "m0le collection
(http://www.isotechlabs.com/customersupport/samplingprocedures/IsoBagSM.pdf). S"m0le )ith little
or no effer'ecence )ere collected throu#h the "me m"nifold+ com0letel( fillin#+ from the *ottom+ the
1,liter 0ol(eth(lene tere0hth"l"te *ottle e0tum c"0 )ith *iocide c"0ule "nd then fillin# the e!ui'"lent
of t)o more *ottle 'olume )hile the *ottle )" u*mer#ed in the *ottom of " full 5,#"llon *ucket
(Iotech %"*or"torie+ Inc.+
http://www.isotechlabs.com/customersupport/samplingprocedures/DGbottle.pdf> 747 l"*or"tor(
26
http://water.usgs.gov/lab/dissolvedgas/sampling/). &ll "m0le "n"l(6ed *( the 747 l"*or"tor( )ere
collected in 125,milliliter (m%) #l" erum *ottle uin# the "me fillin# method re#"rdle of the
0reence or "*ence of effer'ecence.2he 2eflon tu*in#+ 0i#ot,"tt"chment e!ui0ment+ "nd m"nifold
)ere initi"ll( cle"ned in the l"*or"tor( 0rior to field )ork )ith " dilute %i!uino/ olution+ follo)ed *(
t"0 )"ter "nd deioni6ed )"ter. In the field+ the "m0le tu*in# "nd m"nifold )ere fluhed )ith 1 liter of
deioni6ed )"ter "fter e"ch "m0le )" collected. :"ter "m0le )ere collected in *ottle 0ro'ided *(
e"ch "n"l(6in# l"*or"tor(.
4ollo)in# "m0le collection+ "ll "m0le )ere chilled to 4 de#re 7eliu (N7) or le. Iotech
"m0le )ere hi00ed o'erni#ht+ "t the end of e"ch "m0lin# d"( "nd 747 l"*or"tor( "m0le )ere
hi00ed o'erni#ht "t the end of e"ch "m0lin# )eek.
1uality2#ontrol Samples
In "ddition to the 66 #round)"ter "m0le+ re0lic"te "m0le "nd field *l"nk "m0le )ere
collected. 1e0lic"te difference )ere com0uted for three different t(0e of com0"rionE (1) re0lic"te
reult )ith "m0le reult from Iotech+ (2) re0lic"te reult )ith "m0le reult from the 747
l"*or"tor( "nd (3) Iotech reult )ith 747 l"*or"tor( reult.Iotech &n"l(e
@icuion *elo) #ener"ll( focu on the mot im0ort"nt com0ound or me"urement> thee
include concentr"tion in milli#r"m 0er liter (m#/%) of meth"ne+ h(dro#en (O@) "nd c"r*on (O
13
7)
ioto0e r"tio of meth"ne+ "nd c"r*on (O
13
7) ioto0e r"tio of eth"ne ("00endi/ 4). In #ener"l+ reult of
com0"rion of other contituent (uch " &r+ 32+ 732+ -2+ 71+ "nd 72+ throu#h 76P) "re limited to thoe
contituent )ith fi'e or more com0"rion (&r+ 32+ 732+ -2). Percent difference for Iotech reult i
defined " the difference *et)een concentr"tion for t)o "m0le di'ided *( the me"n concentr"tion.
-ine re0lic"te "m0le )ere "n"l(6ed *( the Iotech l"*or"tor(> concentr"tion )ere #re"ter th"n
the detection limit for ei#ht of thee "m0le. Percent difference in meth"ne concentr"tion )ere
2$
#ener"ll( lo) ( (medi"n $.85 0ercent) for the ei#ht 0"ir of Iotech l"*or"tor( re0lic"te "m0le> 0ercent
difference r"n#ed from 0 to 19 0ercent+ indic"tin# #ood re0roduci*ilit(. 9eth"ne concentr"tion for
thee "m0le )ere #ener"ll( hi#h )ith "ll concentr"tion #re"ter th"n 1 m#/%. 2he ei#ht re0lic"te )ith
meth"ne detection included t)o re0lic"te in *ottle (0ercent difference r"n#in# from 0 to 8.$
0ercent)> three re0lic"te in *"# (0ercent difference r"n#in# from 0 to $.3 0ercent)> "nd three cont"iner
re0lic"te+ one in " *ottle "nd one in " *"# (0ercent difference r"n#in# from 15 to 19 0ercent). <ottle
concentr"tion )ere hi#her th"n corre0ondin# *"# concentr"tion in "ll three "m0le.
1e0lic"te difference for concentr"tion in the he"d0"ce of "m0le for other contituent )ere
lo)+ #ener"ll( le th"n 10 0ercent. 2he medi"n 0ercent difference for eth"ne+ detected in more th"n fi'e
"m0le+ )" 2.44 0ercent+ "nd medi"n difference in h(dro#en (O@) "nd c"r*on (O
13
7) ioto0e r"tio of
meth"ne )ere le th"n 1 0ercent. & l"r#e difference )" found for the "m0le from )ell 79856
*et)een h(dro#en ioto0e r"tio (O@) in re0lic"te (,6 "nd ,1$.4+ r"tio difference+ re0ecti'el().
1e0lic"te difference for four other #"e (&r+ 32+ 732+ "nd -2) )ere "ll #ener"ll( lo)+ )ith
medi"n difference r"n#in# from le th"n 1 to 11 0ercent. ?th"ne "lo h"d lo) re0lic"te difference
)ith medi"n r"n#in# from 0 to 8 0ercent.
Reston <4lorofluorocar-on $a-oratory #nalyses
Si/ "m0le "nd their re0lic"te )ere "n"l(6ed *( the 747 l"*or"tor( ("00endi/ 3)> of thee+
meth"ne )" detected in four "m0le "nd their re0lic"te. &ll i/ "m0le cont"ined concentr"tion of
the rem"inin# four diol'ed #"e "n"l(6ed (&r+ 32+ 732+ "nd -2). Percent difference for 747
l"*or"tor( reult )" defined " the difference *et)een concentr"tion in t)o "m0le di'ided *( the
me"n concentr"tion. Percent difference for the meth"ne re0lic"te )ere "ll le th"n $ 0ercent+ )ith "
medi"n of 4.5 0ercent. 9edi"n 0ercent difference for the other diol'ed #"e )ere le th"n 9
0ercent.
28
<o,parison of Isotec4 and Reston <4lorofluorocar-on $a-oratory #nalyses
&ll *ut one of the fi'e Iotech "m0le )ith " corre0ondin# 747 l"*or"tor( "m0le )ere
re0lic"te "m0le+ reultin# in four "m0le )ith four concentr"tion com0"rion *et)een the t)o
l"*or"tor( reult "nd one "m0le )ith t)o concentr"tion com0"rion. 2he Iotech l"*or"tor( "m0le
)ith onl( one reult h"d " 'er( lo) meth"ne concentr"tion (Q0.001 m#/%)> the corre0ondin# 747
l"*or"tor( "m0le h"d non,detection. 2hi com0"rion i not included in the "n"l(i. &ll the
com0"rion of the 747 l"*or"tor( meth"ne d"t" )ith the Iotech l"*or"tor( d"t" for concentr"tion
#re"ter th"n 0.01 m#/% ho)ed th"t the 747 l"*or"tor( h"d conitentl( hi#her concentr"tion th"n the
Iotech l"*or"tor(. 4or thee com0"rion+ 0ercent difference )" c"lcul"ted " the concentr"tion of the
Iotech l"*or"tor( reult minu th"t of the 747 l"*or"tor( reult di'ided *( the "'er"#e concentr"tion of
*oth reult. @ifference in concentr"tion r"n#ed from " minimum of 9 0ercent hi#her to 41 0ercent
hi#her for the 747 l"*or"tor( concentr"tion com0"red to thoe from the Iotech l"*or"tor( )ith "
medi"n of 19 0ercent hi#her concentr"tion for 747 l"*or"tor( reult. <ec"ue concentr"tion for the
Iotech l"*or"tor( "m0le in thi com0"rion r"n#e from 1.9 to 12 m#/%+ thee reult m"( not "00l( to
lo)er concentr"tion.
Blan9 #nalyses
2)o field *l"nk )ere included in the "n"l(e to "e 0otenti"l meth"ne cont"min"tion in the
field. 2he t)o *l"nk "m0le )ere collected uin# 'ol"tile or#"nic c"r*on (I37) #r"de+ nitro#en 0ur#ed
or#"nic free )"ter o*t"ined from the BS=S -"tion"l :"ter Ru"lit( %"*or"tor( (-:R%) "nd )ere
0roceed imil"r to field "m0le. 3ne of the field *l"nk "m0le h"d " non,detection for meth"ne+
)here" the other "m0le h"d " detection "t 0.00019 m#/%. &lthou#h thi re0orted concentr"tion of
meth"ne i 'er( lo)+ in order to 0re'ent "n( f"le 0oiti'e re0ortin# for meth"ne concentr"tion in field
"m0le+ "ll meth"ne concentr"tion "t or le th"n 0.001 m#/% (5 time the *l"nk concentr"tion) )ere
29
tre"ted " non,detect. 2hi reulted in the cenorin# of 14 concentr"tion *ut h"d no m"Cor effect on the
inter0ret"tion of meth"ne d"t" #i'en the 'er( lo) concentr"tion in thee "m0le (ee 3rdered meth"ne
concentr"tion in "m0le from 65 )ell in outh,centr"l -e) .ork+ color,coded *( h(dro#eolo#ic
ettin#. (m#/%+ milli#r"m 0er liter> Q+ le th"n> S+ #re"ter th"n or e!u"l to) for ditri*ution "mon#
ettin#).
Statistical ethods
-on,0"r"metric t"titic )ere ued in thi tud( to com0"re meth"ne concentr"tion *et)een
different )ell t(0e. -on,0"r"metric t"titic "re "00ro0ri"te for ue )ith d"t" (uch " thoe in thi
tud() th"t "re not norm"ll( ditri*uted (5elel "nd 5irch+ 2002)+ "nd r"nked d"t" )ere ued in thi
tud( to "e t"titic"l difference *et)een different #rou0. In #ener"l+ com0"rion of meth"ne d"t"
*et)een different #rou0 of )ell )ere firt teted uin# the 2uke( tet to "e )hether there )ere "n(
i#nific"nt difference *et)een medi"n concentr"tion for "n( of the )ell #rou0. If thi "n"l(i
indic"ted "n( i#nific"nt difference in medi"n concentr"tion+ " Aruk"l,:"ll"ce tet (p,'"lue le th"n
0.05) )" ued to "e )hich medi"n concentr"tion differed "mon# the #rou0.
ethane Occurrence in !roundwater
@"t" on field ch"r"cteritic "nd #"e from Iotech l"*or"tor( "n"l(e of "m0le collected
from 66 )ell "re lited in "00endi/ 4. 9e"ur"*le meth"ne in the "m0led #round)"ter )"
common0l"ce> concentr"tion #re"ter th"n or e!u"l to 0.001 m#/% )ere 0reent in $8 0ercent of "m0le
(3rdered meth"ne concentr"tion in "m0le from 65 )ell in outh,centr"l -e) .ork+ color,coded *(
h(dro#eolo#ic ettin#. (m#/%+ milli#r"m 0er liter> Q+ le th"n> S+ #re"ter th"n or e!u"l to)). 2he
concentr"tion r"n#e e/tended o'er 5 order of m"#nitude. -ine 0ercent of meth"ne concentr"tion
r"n#ed from 10 to le th"n 28 m#/%+ the r"n#e in )hich 0eriodic monitorin# i indic"ted (?ltchl"#er
30
"nd other+ 2001). Si/ 0ercent e!u"led or e/ceeded 28 m#/%+ )hich i the olu*ilit( of meth"ne "t
"tmo0heric 0reure "nd conidered "n e/0loi'it( h"6"rd> miti#"tion i indic"ted "t thi concentr"tion
(?ltchl"#er "nd other+ 2001). 2he m"/imum concentr"tion )" 55 m#/%.
?th"ne )" 0reent in 14 "m0le "t concentr"tion of 0.0001 to 0.04$ m#/%+ "nd thoe "me
"m0le h"d meth"ne concentr"tion from 0.2 to 55 m#/%. ?thene )" detected in one "m0le. -o other
h(droc"r*on e/ceeded he"d0"ce 'olume 0ercent"#e of 0.001. 2he meth"ne to eth"ne m" r"tio in
the "m0le )ith the hi#het meth"ne "nd eth"ne concentr"tion )" 1+1$0+ )hich i indic"ti'e of " Jdr(
#"K (Schoell+ 1980).
>rdered ,et4ane concentrations in sa,ples fro, =I 7ells in sout4-central 8e7 %or9) color-coded -y
4ydrogeologic setting. C,g;$) ,illigra,s per literB N) less t4anB J) greater t4an or eHual toD
ethane #oncentrations and &ydrogeologic Setting
2he o'er"ll ditri*ution of meth"ne concentr"tion i "oci"ted )ith h(dro#eolo#ic ettin#
(3rdered meth"ne concentr"tion in "m0le from 65 )ell in outh,centr"l -e) .ork+ color,coded *(
h(dro#eolo#ic ettin#. (m#/%+ milli#r"m 0er liter> Q+ le th"n> S+ #re"ter th"n or e!u"l to)). 9eth"ne
concentr"tion #re"ter th"n or e!u"l to 0.1+ 5+ "nd 10 m#/% )ere #ener"ll( "oci"ted )ith )ell
com0leted in the confined '"lle( ettin# or unconfined '"lle( ettin#+ if com0leted in *edrock. 2he
lo)et meth"ne concentr"tion+ le th"n 0.1 m#/%+ )ere #ener"ll( "oci"ted )ith unconfined u0l"nd
*edrock "nd unconfined '"lle( "nd "nd #r"'el ettin#.
St"titic"l com0"rion (Aruk"l,:"lli tet) of meth"ne concentr"tion "mon# )"ter "m0le
from the firt t)o tier of h(dro#eolo#ic ettin# from t"*le 1 (to0o#r"0hic 0oition "nd confinement)
indic"te th"t the hi#het concentr"tion of meth"ne #ener"ll( occur in '"lle( "nd confined ettin#.
1eult of the tet for t"titic"l difference "mon# ettin# "re de0icted )ith *o/0lot in @itri*ution
of meth"ne concentr"tion in "m0le from outh,centr"l -e) .ork )"ter )ell+ 2012+ *(
31
h(dro#eolo#ic ettin#+ for &+ )ell cl"ified *( to0o#r"0hic 0oition "nd )hether or not confined *(
#l"ci"l drift de0oit "nd <+ '"lle( ettin# )ell *( )ell,com0letion in "nd "nd #r"'el or *edrock.
St"titic"l com0"rion doe not include confined "nd "nd #r"'el due to m"ll num*er of "m0le (nT3)
in thi c"te#or(. &;<. 2hee d"t" indic"te th"t *oth '"lle( ettin# "nd confinement )ere im0ort"nt
f"ctor in #round)"ter meth"ne occurrence. 2he '"lle( confined ettin# "m0le e/hi*ited the hi#het
meth"ne concentr"tion "nd )ere t"titic"ll( different (p,'"lue le th"n 0.05) from the other three
ettin#. I"lle( unconfined "nd u0l"nd confined ettin# h"d the ne/t hi#het meth"ne concentr"tion
"nd )ere not t"titic"ll( different from one "nother. 2he u0l"nd unconfined ettin# h"d the lo)et
meth"ne concentr"tion "nd )" t"titic"ll( different from the u0l"nd confined ettin# *ut not
t"titic"ll( different from '"lle( unconfined ettin#.
.istri-ution of ,et4ane concentrations in sa,ples fro, sout4-central 8e7 %or9 7ater 7ells) 2012) -y
4ydrogeologic setting) for #) 7ells classified -y topograp4ic position and 74et4er or not confined -y glacial drift
deposits and B) valley setting 7ells -y 7ell-co,pletion in sand and gravel or -edroc9. Statistical co,parison does
not include confined sand and gravel due to s,all nu,-er of sa,ples CnOD in t4is category.
9eth"ne concentr"tion from the third tier of h(dro#eolo#ic ettin# in t"*le 1 ("!uifer) "re
ho)n in (@itri*ution of meth"ne concentr"tion in "m0le from outh,centr"l -e) .ork )"ter )ell+
2012+ *( h(dro#eolo#ic ettin#+ for &+ )ell cl"ified *( to0o#r"0hic 0oition "nd )hether or not
confined *( #l"ci"l drift de0oit "nd <+ '"lle( ettin# )ell *( )ell,com0letion in "nd "nd #r"'el or
*edrock. St"titic"l com0"rion doe not include confined "nd "nd #r"'el due to m"ll num*er of
"m0le (nT3) in thi c"te#or(. <). 2he h(dro#eolo#ic u*c"te#orie )ere limited to the '"lle( ettin#>
the u*c"te#orie )ere "lo teted for t"titic"l difference. <edrock "nd "nd "nd #r"'el "!uifer
ettin# confined *( #l"ci"l de0oit e/hi*ited hi#h meth"ne concentr"tion+ )hich "re conitent )ith
the "ccumul"tion of u0)"rd ee0"#e *elo) confinin# unit "nd rel"ti'el( lo) #round)"ter flo).
32
<edrock unconfined *( #l"ci"l de0oit "lo e/hi*ited hi#h meth"ne concentr"tion th"t )ere not
t"titic"ll( different from thoe for confined *edrock. =round)"ter flo) )ithin *edrock in '"lle( i
likel( rel"ti'el( lo)+ "nd *edrock itelf 0ro'ide '"ri"*le de#ree of confinement. 2hee reult im0l(
th"t the '"lle( *edrock ettin# i tron#l( "oci"ted )ith meth"ne occurrence.
9eth"ne concentr"tion in unconfined "nd "nd #r"'el )ere t"titic"ll( lo)er th"n
concentr"tion for the other '"lle( #rou0 (@itri*ution of meth"ne concentr"tion in "m0le from
outh,centr"l -e) .ork )"ter )ell+ 2012+ *( h(dro#eolo#ic ettin#+ for &+ )ell cl"ified *(
to0o#r"0hic 0oition "nd )hether or not confined *( #l"ci"l drift de0oit "nd <+ '"lle( ettin# )ell *(
)ell,com0letion in "nd "nd #r"'el or *edrock. St"titic"l com0"rion doe not include confined "nd
"nd #r"'el due to m"ll num*er of "m0le (nT3) in thi c"te#or(. <). 2hi c"te#or( include )ell
com0leted in "nd "nd #r"'el "*o'e *edrock "nd ome )ell com0leted in "nd "nd #r"'el "*o'e "
confinin# l"(er o'er *edrock. 2he lo) concentr"tion "re conitent )ith the conce0tu"li6"tion th"t
h"llo)+ rel"ti'el( f"t unconfined #round)"ter flo) re#ime h"'e hort reidence time 0rior to
dich"r#e th"t limit e/0oure time for meth"ne "ccumul"tion "nd "llo) dii0"tion of u0)"rd meth"ne
ee0"#e to the "tmo0here or micro*i"l o/id"tion of meth"ne. 7onfinin# unit *ene"th )ell com0leted
in "nd "nd #r"'el limit the u0)"rd ee0"#e of meth"ne from *edrock.
2he 0"ttern of meth"ne occurrence *( h(dro#eolo#ic ettin# "cro " r"n#e of minimum
concentr"tion (0.1+ 5+ "nd 10 m#/%) "re conitent "t the #re"ter th"n 0.1 "nd 5 m#/% le'el (t"*le 3&;
<) "nd encom0" thermo#enic "nd micro*i"l ori#in in *oth '"lle( "nd confined *edrock u0l"nd
ettin#. 9eth"ne concentr"tion of 10 m#/% or #re"ter+ ho)e'er+ )ere limited to '"lle( ettin#
(e/cludin# the '"lle( unconfined "nd "nd #r"'el ettin#). 2he hi#het concentr"tion (#re"ter th"n or
e!u"l to 28 m#/%) "re found onl( in confined *edrock "!uifer in '"lle( (noted in t"*le 37).
33
,a%le 3( Hydrogeologic classification of 7ells sa,pled) 7it4 eac4 class color coded -y percentage of sa,ples
7it4 ,et4ane concentrations greater t4an or eHual to2 #. 0.1 ,illigra,s per liter) B. I ,illigra,s per liter) and
<. 10 ,illigra,s per liter in sout4-central 8e7 %or9) 2012. AJ) greater t4an or eHual toB K) greater t4anB ,g;$
),illigra,s per literB L) percentB C"D) nu,-er of sa,plesE
ethane #oncentrations and *ield"#haracteristic easurements
4ield me"urement m"de durin# "m0lin# 0ro'ide " #ener"l )"ter,chemitr( conte/t for
meth"ne concentr"tion. =round)"ter "m0le from )ell com0leted in *edrock "re " com0oite of
)"ter from one or more 0roducin# fr"cture() )ith 0otenti"ll( different )"ter chemitr(. <edrock )ell
th"t 0enetr"te conider"*le *edrock thicknee (t(0ic"ll( le in '"lle( th"n in u0l"nd) likel( deri'e
mot of their (ield from h"llo)er fr"cture+ *ut it i 0oi*le th"t ome )ell deri'e mot of their (ield
from dee0er fr"cture. 2hu+ field ch"r"cteritic "nd meth"ne concentr"tion likel( do not re0reent "
in#le #round)"ter chemitr(+ unle the )ell deri'e it (ield from " in#le fr"cture. -e'erthele+
#ener"l trend "re e'ident. 9eth"ne occurrence in #round)"ter flo) (tem re0reent hi#hl( reducin#
redo/ condition under )hich the "*ence of diol'ed o/(#en "nd the 0reence of h(dro#en ulfide
)ould *e e/0ected. 5o)e'er+ if meth"ne h" mi#r"ted u0)"rd from *ene"th the "cti'e #round)"ter
flo) (tem+ meth"ne occurrence "nd redo/ condition m"( not *e conitent. In "m0le )ith meth"ne
concentr"tion of 0.5 m#/% or #re"ter+ the concentr"tion of diol'ed o/(#en )" 0.2 m#/% or le in "ll
*ut one "m0le+ "nd h(dro#en ulfide )" detected in "ll *ut one "m0le.
05 "nd 0ecific conduct"nce t(0ic"ll( incre"e )ith time in non,c"r*on"te #round)"ter flo)
(tem *ut re"ch their hi#het '"lue in )ell th"t t"0 tr"nition"l )"ter of incre"in# "linit( )ith
de0th *et)een the freh)"ter flo) (tem "nd underl(in# *rine (5eii#+ 1999> fi#. 34). 2hi tr"nition
6one likel( re0reent incom0lete fluhin# of 0re,e/itin# *rine *( the freh)"ter flo) (tem
34
(Poth+1963). 2hu+ com0"rion of meth"ne concentr"tion to 05 "nd 0ecific conduct"nce *( '"lle( "nd
u0l"nd ettin# (9eth"ne concentr"tion in rel"tion to 05 "nd 0ecific conduct"nce in '"lle( "nd u0l"nd
"re". -ote difference in meth"ne "nd 0ecific conduct"nce c"le *et)een u0l"nd "nd '"lle( "re".) c"n
*e ueful in undert"ndin# meth"ne occurrence.
Met4ane concentrations in relation to pH and specific conductance in valley and upland areas. 8ote difference in
,et4ane and specific conductance scales -et7een upland and valley areas.
9eth"ne concentr"tion #ener"ll( correl"ted )ith 05 in u0l"nd "nd '"lle( ettin# "t 05 of $.$
"nd "*o'e> in '"lle( "re"+ "ll meth"ne concentr"tion e/ceeded 1 m#/% "t 05 8.0 "nd #re"ter (9eth"ne
concentr"tion in rel"tion to 05 "nd 0ecific conduct"nce in '"lle( "nd u0l"nd "re". -ote difference in
meth"ne "nd 0ecific conduct"nce c"le *et)een u0l"nd "nd '"lle( "re".). 2hi im0lie th"t meth"ne
occurrence "t concentr"tion #re"ter th"n 1 m#/% i "oci"ted )ith older+ motl( "no/ic #round)"ter+
r"ther th"n recent #round)"ter. 3ne e/ce0tion to thi "oci"tion )" " "m0le from " '"lle( confined
ettin# )ith " meth"ne concentr"tion of 9.6 m#/% "nd " 05 of $.4 (the )"ter )" "no/ic8diol'ed
o/(#en )" 0.1 m#/%). 2hi could *e the reult of hi#h u0)"rd ee0"#e r"te of meth"ne into (oun#er
confined #round)"ter "t thi loc"le.
S0ecific conduct"nce #ener"ll( correl"ted )ith meth"ne concentr"tion *ut onl( "t the hi#het
end of the 0ecific,conduct"nce r"n#e. In '"lle( "re"+ ho)e'er+ hi#h meth"ne concentr"tion c"n "lo
occur "t rel"ti'el( lo) 0ecific conduct"nce (340;5$0 microiemen 0er centimeter (US/cm)> "t 25N7>
9eth"ne concentr"tion in rel"tion to 05 "nd 0ecific conduct"nce in '"lle( "nd u0l"nd "re". -ote
difference in meth"ne "nd 0ecific conduct"nce c"le *et)een u0l"nd "nd '"lle( "re".). 2hree of four
meth"ne concentr"tion #re"ter th"n 0.1 m#/% in u0l"nd "re" corre0ond to 0ecific conduct"nce of
#re"ter th"n $50 US/cm "t 25N7. 2he one u0l"nd unconfined "m0le )ith hi#h 0ecific conduct"nce "nd
no meth"ne 0oi*l( indic"te " non,n"tur"l ource of the diol'ed olid+ )hich "re ele'"ted "*o'e
35
*"ck#round le'el (uch " ro"d "lt or e0tic ()"ter oftener) le"ch"te). In '"lle( "re"+ "ll "m0le
)ith 0ecific conduct"nce #re"ter th"n 6$5 US/cm "t 25N7 h"d meth"ne concentr"tion #re"ter th"n 1
m#/%. <elo) 6$5 US/cm "t 25N7+ 0ecific conduct"nce )" not " ueful indic"tor of meth"ne
occurrence *ec"ue meth"ne concentr"tion r"n#ed )idel( "cro the r"n#e of 0ecific conduct"nce
'"lue.
ethane #oncentrations and -ell #ompletion
:ell com0letion det"il (*edrock 0enetr"tion+ ele'"tion of )ell *ottom+ "nd confinin#,unit
thickne) )ere com0iled to illutr"te difference "nd imil"ritie "mon# m"Cor h(dro#eolo#ic ettin#
"nd to e'"lu"te )hether thee ch"r"cteritic mi#ht *e "oci"ted )ith #round)"ter meth"ne occurrence.
& com0"rion of )ell com0letion ch"r"cteritic )ith meth"ne occurrence indic"ted th"t indi'idu"ll(+
ch"r"cteritic "re not o*'ioul( "oci"ted. 2he thickne of *edrock 0enetr"ted "nd the ele'"tion of the
*ottom of *edrock )ell )ere 0lotted in rel"tion to the four m"Cor h(dro#eolo#ic ettin# (@itri*ution
of ch"r"cteritic of )ell com0leted in *edrock h(dro#eolo#ic ettin# in outh,centr"l -e) .orkE &+
<edrock thickne 0enetr"ted *( )ell "nd <+ ele'"tion of the *ottom of *edrock )ell. )+ "nd the
thickne of confinin# unit "nd the ele'"tion of )ell *ottom in confined *edrock '"lle( )ell )ere
0lotted in rel"tion to meth"ne concentr"tion (@itri*ution of ch"r"cteritic of )ell com0leted in
*edrock h(dro#eolo#ic ettin# in outh,centr"l -e) .orkE &+ <edrock thickne 0enetr"ted *( )ell
"nd <+ ele'"tion of the *ottom of *edrock )ell. > "00endi/ 5). 2he thickne of *edrock 0enetr"ted
)" hi#het in u0l"nd unconfined *edrock )ell+ )hich h"'e the lo)et meth"ne concentr"tion. 2hi
indic"te th"t the thickne of *edrock 0enetr"tion (*edrock urf"ce "re") *( itelf i not " critic"l f"ctor
for meth"ne occurrence> '"lle( *edrock )ell )ith much le *edrock 0enetr"tion h"'e the hi#het
meth"ne concentr"tion. 2he ele'"tion of the *ottom of *edrock )ell in rel"tion to m"Cor
h(dro#eolo#ic ettin# eenti"ll( reflect to0o#r"0h(8the lo)et ele'"tion of *edrock 0enetr"tion "re
36
"oci"ted )ith confined '"lle( *edrock )ell. & com0"rion of meth"ne concentr"tion )ith confinin#
unit thickne in '"lle( confined ettin# found no o*'iou rel"tion nor did " com0"rion of meth"ne
concentr"tion )ith the ele'"tion of the *ottom of confined *edrock '"lle( )ell ("00endi/ 5).
.istri-ution of c4aracteristics of 7ells co,pleted in -edroc9 4ydrogeologic settings in sout4-central 8e7 %or92 #)
Bedroc9 t4ic9ness penetrated -y 7ells and B) elevations of t4e -otto, of -edroc9 7ells.
'se of )sotopic Data to Assess ethane Source4s5
Ioto0ic r"tio of c"r*on (O
13
7 ) "nd h(dro#en (O@) in meth"ne )ere me"ured in 24 "m0le
)ith "t le"t 0.3 m#/% of meth"ne. 1eult "re 0lotted on "n ioto0e cro0lot in fi#ure 9 )ith the m"Cor
meth"ne ource "re"E (1) micro*i"l meth"ne 0roduction *( ferment"tion+ (2) micro*i"l meth"ne
0roduction *( c"r*on dio/ide reduction+ "nd (3) thermo#enic meth"ne 0roduction (ource "re" e/tent
from 1e'e6 "nd other+ 2012). 2he thermo#enic u*,"re" ch"r"cteritic of 9"rcellu Sh"le #"
"m0le "re "lo included for reference8northe"tern Penn(l'"ni" from 9olofk( "nd other (2011)>
north;centr"l/northe"tern Penn(l'"ni" from &. <"ld""re+ ?75?%3- &00lied =eocience
7onultin#+ )ritten commun.+ 2013> "nd Steu*en 7ount(+ -...+ (ne"r the )etern *ound"r( of the tud(
"re") from (3*orn "nd 9cIntoh (2010). 2he 24 "m0le indic"te incre"in# therm"l m"turit( from
)et to e"t. &rro) "re included in fi#ure 9 to indic"te the direction of incre"in# therm"l m"turit( "nd
the #ener"l effect of meth"ne o/id"tion on ioto0ic r"tio (7olem"n "nd other+ 1981). 2)o "m0le "re
not ho)n in fi#ure 9 *ec"ue the( 0lot outide of the t"nd"rd cro0lot c"le. 2he "m0le reult )ere
re,'erified *( the l"*or"tor(. 2he( )ere e/ceedin#l( Jhe"'(K in O@ (,6+ ;89 0er mil) "nd le o in O
13
7
(,3$.$+;3$.2 0er mil). 2hee "m0le m"( re0reent meth"ne #"e th"t h"'e under#one u*t"nti"l
3$
o/id"tion (7olem"n "nd other+ 1981). 5o)e'er+ *oth "m0le )ere from confined '"lle( ettin# "nd
cont"ined 'irtu"ll( no o/(#en (0.1 m#/%)
Sta-le-isotopic co,position of car-on C<D and 4ydrogen Cdeuteriu,B .D in ,et4ane C<H
P
D in 7ater-7ell sa,ples
fro, sout4-central 8e7 %or9. Met4ane isotope ratio source fields fro, Reves* and ot4ers C2012D) unless noted
ot4er7ise. 8u,-er ne:t to eac4 point is ,et4ane concentration) in ,illigra,s per liter.
9eth"ne )" 0redomin"ntl( of thermo#enic ori#in in '"lle(,ettin# "m0le "nd 0redomin"ntl(
of micro*i"l ori#in (c"r*on dio/ide reduction) in u0l"nd,ettin# "m0le. 4ourteen '"lle(,ettin#
"m0le 0lotted )ithin the lo),m"turit( end of the thermo#enic ource field+ "nd t)o "m0le 0lotted "
" mi/ of thermo#enic "nd micro*i"l ource of meth"ne. 2he mi/ed "m0le h"d the hi#het meth"ne
concentr"tion (55 "nd 32 m#/%) "nd mi#ht *e inter0reted " either e/tremel( lo),m"turit( thermo#enic
in ome thermo#enic ource,"re" deline"tion (Schoell+ 1980> 3*orn "nd other+ 2011) or " " mi/ of
c"r*on dio/ide reduction, "nd ferment"tion,ourced meth"ne. 4erment"tion i mot commonl(
"oci"ted )ith ne"r,urf"ce 0rocee ()etl"nd "nd l"ndfill) *ut h" "lo *een documented in h"llo)
"nd dee0 #round)"ter flo) (tem (5"nen "nd other+ 2001> Ieto "nd other+ 2004). 2hree of four
u0l"nd,ettin# meth"ne "m0le 0lotted )ithin or on the *ound"r( of the micro*i"l (c"r*on dio/ide
reduction) field (St"*le,ioto0ic com0oition of c"r*on (7) "nd h(dro#en (deuterium> @) in meth"ne
(754) in )"ter,)ell "m0le from outh,centr"l -e) .ork. 9eth"ne ioto0e r"tio ource field from
1e'e6 "nd other (2012)+ unle noted other)ie. -um*er ne/t to e"ch 0oint i meth"ne concentr"tion+
in milli#r"m 0er liter.). 2he fourth u0l"nd,ettin# "m0le "nd one '"lle(,confined ettin# "m0le )ith
lo) meth"ne concentr"tion (0.34+ "nd 0.38 m#/%+ re0ecti'el(> St"*le,ioto0ic com0oition of c"r*on
(7) "nd h(dro#en (deuterium> @) in meth"ne (754) in )"ter,)ell "m0le from outh,centr"l -e)
.ork. 9eth"ne ioto0e r"tio ource field from 1e'e6 "nd other (2012)+ unle noted other)ie.
-um*er ne/t to e"ch 0oint i meth"ne concentr"tion+ in milli#r"m 0er liter.) h"'e le ne#"ti'e O@ th"n
38
the other micro*i"l, or thermo#enic,ourced "m0le+ )hich m"( indic"te th"t ome de#ree of micro*i"l
o/id"tion of meth"ne h" "ltered the ioto0ic r"tio (7olem"n "nd other+ 1981). -o "m0le 0lotted
)ithin the thermo#enic"ll( m"ture 9"rcellu Sh"le #",ource "re" for northe"tern or north;centr"l
Penn(l'"ni" (St"*le,ioto0ic com0oition of c"r*on (7) "nd h(dro#en (deuterium> @) in meth"ne
(754) in )"ter,)ell "m0le from outh,centr"l -e) .ork. 9eth"ne ioto0e r"tio ource field from
1e'e6 "nd other (2012)+ unle noted other)ie. -um*er ne/t to e"ch 0oint i meth"ne concentr"tion+
in milli#r"m 0er liter.) "nd "ll "m0le )ere ch"r"cteri6ed *( O
13
7 r"tio of le th"n ,40 0er mil.
2he "m0le th"t 0lot )ithin or ne"r the micro*i"l c"r*on dio/ide reduction ource field )ere from
u0l"nd ettin# (three confined+ one of uncert"in confinement) "nd )ere )idel( 0"ced "cro the tud(
"re". 2he "oci"tion i not"*le+ " no u0l"nd meth"ne "m0le 0lotted )ithin the thermo#enic ource
"re". 2he onl( other "m0le )ithin the c"r*on dio/ide reduction ource field )" from " '"lle( confined
*edrock ettin#. 9eth"ne deri'ed from thi micro*i"l 0"th)"( h" *een documented in m"n( ettin#+
uch " #l"ci"l ediment "nd P"leo6oic *edrock in Illinoi (7olem"n "nd other+ 1988) "nd or#"nic,rich
h"le in 9ichi#"n (9"rtini "nd other+ 1996). Simil"r micro*i"l #" h" *een identified outh "nd )et
of the tud( "re" in north;centr"l Penn(l'"ni" (1e'e6 "nd other+ 2012). S0"ti"l trend
(#eo#r"0hic"ll( north;outh or e"t;)et) of ioto0ic i#n"ture "re not e'ident "cro the tud( "re".
#onceptual odel of ethane Occurrence in South#entral New York
2he difference in #round)"ter meth"ne occurrence "mon# the h(dro#eolo#ic ettin# cl"e
(t"*le 3) indic"te th"t thi cl"ific"tion (tem 0ro'ide " *"i for undert"ndin# )here #round)"ter
meth"ne (in )ell) m"( *e 0reent n"tur"ll( "t !u"ntitie #re"ter th"n tr"ce concentr"tion. Settin# )ith
"t le"t one meth"ne detection #re"ter th"n or e!u"l to 0.1 m#/% or 5 m#/% (t"*le 3&;<) include "ll
'"lle( ettin#+ e/ce0t unconfined "nd "nd #r"'el+ "nd the u0l"nd confined *edrock ettin#. 9eth"ne
concentr"tion #re"ter th"n or e!u"l to 10 m#/% (t"*le 37) "re e/clui'el( found in '"lle( ettin#8
39
unconfined or confined *edrock "nd confined "nd "nd #r"'el. 7oncentr"tion "t or #re"ter th"n or e!u"l
to 28 m#/% )ere 0reent onl( in "m0le from confined *edrock )ithin '"lle(. 2hee ettin# "re
dicued *elo) )ithin the conte/t of #round)"ter flo)+ *"ic chemitr( (field ch"r"cteritic)+ "nd
meth"ne ioto0ic d"t" "nd "re illutr"ted conce0tu"ll( in 7once0tu"l di"#r"m of thermo#enic "nd
micro*i"l meth"ne occurrence "t )"ter )ell in outh,centr"l -e) .ork. :ell "re ho)n in different
h(dro#eolo#ic ettin# "nd in rel"tion to the (freh) #round)"ter flo) (tem "nd the tr"nition to
underl(in# *rine. 2he (m*ol (V)indic"te likel( meth"ne 0reence "nd the color (#reen or 0ur0le)
indic"te meth"ne ource. -o (m*ol indic"te tr"ce or "*ent meth"ne in #round)"ter "m0le.+ "
chem"tic h(dro#eolo#ic ection. 2hi conce0tu"li6"tion of meth"ne occurrence i *"ed on " limited
d"t"et "nd+ " uch+ i conidered 0relimin"r( "nd m"( *e u*Cect to tetin# " "ddition"l d"t" "re
collected in the re#ion.
<onceptual diagra, of t4er,ogenic and ,icro-ial ,et4ane occurrence at 7ater 7ells in sout4-central 8e7 %or9.
(ells are s4o7n in different 4ydrogeologic settings and in relation to t4e Cfres4D ground7ater flo7 syste, and t4e
transition to underlying -rine. T4e sy,-ol CMDindicates li9ely ,et4ane presence and t4e color Cgreen or purpleD
indicates ,et4ane source. 8o sy,-ol indicates trace or a-sent ,et4ane in ground7ater sa,ples.
2he meth"ne concentr"tion "nd ioto0ic d"t" c"n *e inte#r"ted )ith h(dro#eolo#ic ettin#+ *"ic
chemitr(+ undert"ndin# of #round)"ter flo) (tem+ "nd )ell*ore,flo) condition to e/0l"in n"tur"l
meth"ne occurrence in the #round)"ter from dometic )ell in outh;centr"l -e) .ork (7once0tu"l
di"#r"m of thermo#enic "nd micro*i"l meth"ne occurrence "t )"ter )ell in outh,centr"l -e) .ork.
:ell "re ho)n in different h(dro#eolo#ic ettin# "nd in rel"tion to the (freh) #round)"ter flo)
(tem "nd the tr"nition to underl(in# *rine. 2he (m*ol (V)indic"te likel( meth"ne 0reence "nd the
color (#reen or 0ur0le) indic"te meth"ne ource. -o (m*ol indic"te tr"ce or "*ent meth"ne in
#round)"ter "m0le.). :ide0re"d occurrence of thermo#enic meth"ne in *edrock )ell in '"lle( "re"
40
likel( reult from the cloe 'ertic"l 0ro/imit( to underl(in# meth"ne,*e"rin# tr"nition"l "line
#round)"ter "nd *rine "nd 0oi*le enh"nced fr"cture 0erme"*ilit(+ )here" the limited occurrence in
confined *edrock of u0l"nd "re" reult from " micro*i"l ource (c"r*on dio/ide reduction) th"t
re0reent hi#hl( reducin# #round)"ter condition )ithin dee0er+ lo) #round)"ter flo) 0"th of the
u*re#ion"l flo) (tem. Some )"ter from u0l"nd )ell )ith lo) meth"ne concentr"tion m"(
re0reent " mi/ture of micro*i"l "nd thermo#enic meth"ne. 2he con'er#ence of #round)"ter dich"r#e
in '"lle( "re" reult in ome '"lle(,"re" meth"ne "m0le )ith " micro*i"l ource or 0oi*l( " mi/ of
meth"ne ource (0redomin"ntl( thermo#enic). :ithin thi fr"me)ork+ confinement "00e"r to enh"nce
the "ccumul"tion of meth"ne.
Valleys and uplands
2he tron# "oci"tion of meth"ne ("nd more "line #round)"ter) from )ell in '"lle( ettin# i
conitent )ith hitoric"l inform"tion (:illi"m+ 2010) "nd )ith the reult of 9olofk( "nd other
(2011+ 2013) "nd :"rner "nd other (2012). 9eth"ne "t concentr"tion of concern F#re"ter th"n or e!u"l
to 10 m#/%> B.S. 3ffice of Surf"ce 9inin# recommend"tion in ?ltchl"#er "nd other (2001)G )ere
e/clui'el( from )ell )ithin the '"lle( ettin#> of the 1$ "m0le )ith "t le"t 1 m#/% of meth"ne+ "ll
*ut one )ere from " '"lle( ettin#.
In l"r#e (lo)l"nd) '"lle(+ freh)"ter flo) (tem "re #ener"ll( thin (7once0tu"l di"#r"m of
thermo#enic "nd micro*i"l meth"ne occurrence "t )"ter )ell in outh,centr"l -e) .ork. :ell "re
ho)n in different h(dro#eolo#ic ettin# "nd in rel"tion to the (freh) #round)"ter flo) (tem "nd the
tr"nition to underl(in# *rine. 2he (m*ol (V)indic"te likel( meth"ne 0reence "nd the color (#reen or
0ur0le) indic"te meth"ne ource. -o (m*ol indic"te tr"ce or "*ent meth"ne in #round)"ter "m0le.)
+ "nd thu+ )ell "re in cloe 0ro/imit( to underl(in# tr"nition"l "line )"ter "nd dee0er *rine+ )hich
"re likel( ch"r#ed )ith meth"ne+ th"t i re0reent"ti'e of the either loc"l *edrock or the u0)"rd meth"ne
41
ee0"#e r"te from underl(in# ource rock (7once0tu"l di"#r"m of thermo#enic "nd micro*i"l meth"ne
occurrence "t )"ter )ell in outh,centr"l -e) .ork. :ell "re ho)n in different h(dro#eolo#ic
ettin# "nd in rel"tion to the (freh) #round)"ter flo) (tem "nd the tr"nition to underl(in# *rine.
2he (m*ol (V)indic"te likel( meth"ne 0reence "nd the color (#reen or 0ur0le) indic"te meth"ne
ource. -o (m*ol indic"te tr"ce or "*ent meth"ne in #round)"ter "m0le.). 9eth"ne "oci"ted )ith
mot *rine in the re#ion i likel( of thermo#enic ori#in+ " indic"ted *( meth"ne ioto0ic d"t" from
n"tur"l #" "m0le from underl(in# tr"t" (3*orn "nd other+ 2011> 9olofk( "nd other+ 2011).
=round)"ter "m0le )ith ele'"ted meth"ne ("*o'e *"ck#round le'el) in thee '"lle( h"'e hi#h 05
(t(0ic"ll( #re"ter th"n $.$) "nd 0ecific conduct"nce (#re"ter th"n "*out $$0 US/cm "t 25N7) th"t reflect
lon# #round)"ter reidence time "nd likel( ome mi/in# )ith+ or diffuion from+ reidu"l "line )"ter
or *rine in *edrock incom0letel( fluhed *( freh)"ter circul"tion (7once0tu"l di"#r"m of thermo#enic
"nd micro*i"l meth"ne occurrence "t )"ter )ell in outh,centr"l -e) .ork. :ell "re ho)n in
different h(dro#eolo#ic ettin# "nd in rel"tion to the (freh) #round)"ter flo) (tem "nd the tr"nition
to underl(in# *rine. 2he (m*ol (V)indic"te likel( meth"ne 0reence "nd the color (#reen or 0ur0le)
indic"te meth"ne ource. -o (m*ol indic"te tr"ce or "*ent meth"ne in #round)"ter "m0le.). In
outh,centr"l -e) .ork+ :illi"m (2010) document thin freh)"ter 6one *ene"th '"lle( "nd thicker
freh)"ter 6one in u0l"nd. &lo mot re0orted meth"ne "nd "lt)"ter occurrence re0orted in th"t
tud( )ere from )ell in '"lle(. 2he "line 0rin# )"ter "t S"lt S0rin# St"te P"rk in Penn(l'"ni"
(outh of the tud( "re") i ch"r#ed )ith meth"ne (9olofk( "nd other+ 2011) "nd re0reent " mi/ture
of freh)"ter "nd le th"n $ 0ercent *rine (:"rner "nd other+ 2012). S"m0lin# of " dee0 corehole in
"n u0l"nd ettin# in north,centr"l Penn(l'"ni" indic"te the 0reence of ele'"ted meth"ne of
thermo#enic ori#in "oci"ted )ith "line,)"ter or *rine,*e"rin# fr"cture t"rtin# "t 915 ft *elo) l"nd
urf"ce ("t le"t 30+000 US/cm "t 25N7> 1ier "nd other+ 2013).
42
2he "oci"tion of '"lle( )ith hi#h meth"ne concentr"tion "nd " thermo#enic ource i
conitent )ith the conce0t th"t #re"ter fr"cture 0erme"*ilit( of *edrock underl(in# thee "re" 0ro'ide
enh"ncement of u0)"rd ee0"#e of meth"ne. I"lle( e/it *ec"ue of ome inherent )e"kne in
*edrock> '"lle( orient"tion commonl( reflect ome com*in"tion of the direction of #l"ci"l ice "d'"nce
"nd re#ion"l Coint+ line"ment+ or f"ult orient"tion. H"co*i (2002) re0ort th"t field in0ection of
line"ment com*ined )ith "n"l(i of u*urf"ce d"t" indic"te th"t m"n( "re dee0,e"ted f"ult th"t m"(
e/tend throu#h the entire ediment"r( e!uence into the *"ement rock (=ener"li6ed north;outh
ection )ith *edrock form"tion in outh,centr"l -e) .ork (from :illi"m+ 2010> modified from -e)
.ork St"te 9ueum+ 2009).). 2he de0th to )hich the f"ultin# mi#ht "ffect *edrock fr"cture 0erme"*ilit(
i not kno)n+ *ut enh"nced 0erme"*ilit( to e'en " rel"ti'el( h"llo) de0th )ould *e " contri*utin#
f"ctor for incre"ed u0)"rd ee0"#e of meth"ne.
2he u0)"rd h(dr"ulic,he"d #r"dient )ithin '"lle(+ )hich "re "re" of dich"r#e+ trend in the
"me direction " ee0"#e of meth"ne> "t " minimum+ u0)"rd #round)"ter flo) )ould not *e "n
im0ediment to u0)"rd meth"ne ee0"#e. ?nh"nced meth"ne ee0"#e in fr"ctured *edrock *ene"th
'"lle( i conitent )ith the 0reence of meth"ne in *oth confined "nd unconfined '"lle( )ell th"t "re
com0leted in *edrock. &lo+ u0l"nd confined '"lle( ettin# "t ele'"tion of #re"ter th"n 1+100 ft "nd
confined *( till )ere ne"rl( " f"'or"*le for thermo#enic meth"ne "ccumul"tion " lo)l"nd confined
'"lle( ettin# (t"*le 3) *ut )ere ch"r"cteri6ed *( motl( lo) 0ecific conduct"nce. 2hi i
conce0tu"ll( conitent )ith enh"nced fr"cture 0erme"*ilit( th"t "llo) u0)"rd ee0"#e of diol'ed
#"e uch " meth"ne+ *ut not the "line )"ter. 2he 'ertic"l dit"nce of )ell "*o'e tr"nition"l "line
)"ter "nd underl(in# *rine (7once0tu"l di"#r"m of thermo#enic "nd micro*i"l meth"ne occurrence "t
)"ter )ell in outh,centr"l -e) .ork. :ell "re ho)n in different h(dro#eolo#ic ettin# "nd in
rel"tion to the (freh) #round)"ter flo) (tem "nd the tr"nition to underl(in# *rine. 2he (m*ol
43
(V)indic"te likel( meth"ne 0reence "nd the color (#reen or 0ur0le) indic"te meth"ne ource. -o
(m*ol indic"te tr"ce or "*ent meth"ne in #round)"ter "m0le.) "00e"r to *e #re"ter in u0l"nd
'"lle( th"n in lo)l"nd '"lle(.
9eth"ne in m"n( "m0le from '"lle(,"re" )ell i thermo#enic"ll( ourced+ *ut one "m0le
indic"te " micro*i"l ource. &lo+ t)o "m0le )ith meth"ne *elo) the lo),m"turit( end of the
thermo#enic field m"( re0reent mi/in# of thermo#enic "nd micro*i"l meth"ne (St"*le,ioto0ic
com0oition of c"r*on (7) "nd h(dro#en (deuterium> @) in meth"ne (754) in )"ter,)ell "m0le from
outh,centr"l -e) .ork. 9eth"ne ioto0e r"tio ource field from 1e'e6 "nd other (2012)+ unle
noted other)ie. -um*er ne/t to e"ch 0oint i meth"ne concentr"tion+ in milli#r"m 0er liter.). 2hee
"m0le could indic"te th"t old #round)"ter from the u*re#ion"l flo) (tem (from the urroundin#
u0l"nd) )ith micro*i"ll( ourced meth"ne h" mi/ed )ith u0)"rd ee0"#e of thermo#enic meth"ne
from *ene"th '"lle(. B0l"nd 0reum"*l( conit of more com0etent+ le fr"ctured rock th"n '"lle(+
"nd unconfined )ell com0leted in thee "re" 0enetr"te the #re"tet thicknee of *edrock
(@itri*ution of ch"r"cteritic of )ell com0leted in *edrock h(dro#eolo#ic ettin# in outh,centr"l
-e) .orkE &+ <edrock thickne 0enetr"ted *( )ell "nd <+ ele'"tion of the *ottom of *edrock )ell. +
7once0tu"l di"#r"m of thermo#enic "nd micro*i"l meth"ne occurrence "t )"ter )ell in outh,centr"l
-e) .ork. :ell "re ho)n in different h(dro#eolo#ic ettin# "nd in rel"tion to the (freh)
#round)"ter flo) (tem "nd the tr"nition to underl(in# *rine. 2he (m*ol (V)indic"te likel( meth"ne
0reence "nd the color (#reen or 0ur0le) indic"te meth"ne ource. -o (m*ol indic"te tr"ce or "*ent
meth"ne in #round)"ter "m0le.)> de0ite the l"r#e thickne of 0enetr"ted *edrock+ meth"ne
concentr"tion "re "t tr"ce le'el or "*ent. 3ne re"on for thi o*er'"tion i th"t the 0redomin"nt
#round)"ter flo) direction in unconfined u0l"nd (rech"r#e "re") i do)n)"rd "nd do)nlo0e. 2hi
rel"ti'el( f"t flo) )ould "ct to entr"in "nd remo'e u0)"rdl( ee0in# meth"ne. Hut " im0ort"ntl(+ "
44
ch"r"cteritic of )ell drilled in uch "re" i the r"0id initi"tion of do)n)"rd flo) )ithin the )ell*ore
itelf )hen more th"n one 0roducin# fr"cture i interected *( the )ell*ore (5eii#+ 1999 ()ith )ell
lo# in 5eii# "nd Anuton+ 199$) "nd re#ion,)ide drillin# re0ort of loe in h(dr"ulic he"d
(decre"in# )"ter le'el) durin# drillin# of )ell in hillide "nd hillto0 "re").). 2hu+ under non,
0um0in# condition+ "m*ient do)n)"rd flo) in )ell*ore "ct to fluh the )ell )ith rel"ti'el( recent+
o/(#en"ted rech"r#e )"ter. 2hee do)n)"rd flo) r"te (fr"ction of " #"llon to #"llon 0er minute+
de0endin# on fr"cture 0erme"*ilit( "nd h(dr"ulic,he"d difference) eem likel( to #re"tl( e/ceed "n(
u0)"rd ee0"#e r"te of meth"ne. 7olem"n "nd other (1988) decri*e #round)"ter flo) " the 0rim"r(
mech"nim of micro*i"l #" mo'ement in Illinoi #round)"ter> 0reum"*l(+ do)n)"rd flo)in#+
meth"ne,free #round)"ter in the tud( "re" m"( o'ercome u0)"rd ee0"#e of meth"ne from underl(in#
ource. 2he "cceler"ted do)n)"rd flo) of o/(#en"ted )"ter in )ell*ore "lo reult in the
introduction of thi )"ter into *edrock fr"cture in )h"t m"( h"'e ori#in"ll( *een " reducin#
#round)"ter en'ironment. 2he introduction of o/(#en"ted )"ter in thi en'ironment "nd u*e!uent
micro*i"l o/id"tion of meth"ne m"( "lo "ccount for t)o "m0le th"t 0lot "*o'e the c"r*on,dio/ide
reduction "re" (St"*le,ioto0ic com0oition of c"r*on (7) "nd h(dro#en (deuterium> @) in meth"ne
(754) in )"ter,)ell "m0le from outh,centr"l -e) .ork. 9eth"ne ioto0e r"tio ource field from
1e'e6 "nd other (2012)+ unle noted other)ie. -um*er ne/t to e"ch 0oint i meth"ne concentr"tion+
in milli#r"m 0er liter.).
9ot u0l"nd )ell "re likel( com0leted much f"rther "*o'e tr"nition"l "line )"ter "nd *rine
th"n '"lle( )ell (7once0tu"l di"#r"m of thermo#enic "nd micro*i"l meth"ne occurrence "t )"ter )ell
in outh,centr"l -e) .ork. :ell "re ho)n in different h(dro#eolo#ic ettin# "nd in rel"tion to the
(freh) #round)"ter flo) (tem "nd the tr"nition to underl(in# *rine. 2he (m*ol (V)indic"te likel(
meth"ne 0reence "nd the color (#reen or 0ur0le) indic"te meth"ne ource. -o (m*ol indic"te tr"ce
45
or "*ent meth"ne in #round)"ter "m0le.) "nd thu "re likel( f"rther remo'ed from thermo#enic
meth"ne. 2he h"0e+ de0th+ "nd h"r0ne of the tr"nition 6one *ene"th u0l"nd i l"r#el( undefined+
*ut limited e'idence 0oint to " urf"ce ome)here *et)een " u*dued reflection of to0o#r"0h( "nd "
rel"ti'el( fl"t urf"ce (7once0tu"l di"#r"m of thermo#enic "nd micro*i"l meth"ne occurrence "t )"ter
)ell in outh,centr"l -e) .ork. :ell "re ho)n in different h(dro#eolo#ic ettin# "nd in rel"tion to
the (freh) #round)"ter flo) (tem "nd the tr"nition to underl(in# *rine. 2he (m*ol (V)indic"te
likel( meth"ne 0reence "nd the color (#reen or 0ur0le) indic"te meth"ne ource. -o (m*ol indic"te
tr"ce or "*ent meth"ne in #round)"ter "m0le.) "t de0th of #re"ter th"n or e!u"l to 300 ft *elo) l"nd
urf"ce. 2he micro*i"ll( ourced u0l"nd "m0le in St"*le,ioto0ic com0oition of c"r*on (7) "nd
h(dro#en (deuterium> @) in meth"ne (754) in )"ter,)ell "m0le from outh,centr"l -e) .ork.
9eth"ne ioto0e r"tio ource field from 1e'e6 "nd other (2012)+ unle noted other)ie. -um*er
ne/t to e"ch 0oint i meth"ne concentr"tion+ in milli#r"m 0er liter. re0reent "t le"t one 0oint )here
the u00ermot tr"nition 6one de0th i "00ro/im"ted> the )ell (<91589) from )hich the "m0le )"
collected i ho)n chem"tic"ll( in 7once0tu"l di"#r"m of thermo#enic "nd micro*i"l meth"ne
occurrence "t )"ter )ell in outh,centr"l -e) .ork. :ell "re ho)n in different h(dro#eolo#ic
ettin# "nd in rel"tion to the (freh) #round)"ter flo) (tem "nd the tr"nition to underl(in# *rine.
2he (m*ol (V)indic"te likel( meth"ne 0reence "nd the color (#reen or 0ur0le) indic"te meth"ne
ource. -o (m*ol indic"te tr"ce or "*ent meth"ne in #round)"ter "m0le.. 2hi )ell 0enetr"ted the
#re"tet thickne of *edrock "mon# confined u0l"nd )ell (295 ft) "nd h"d the hi#het meth"ne
concentr"tion (9.3 m#/%)+ 05 (9.2)+ "nd 0ecific conduct"nce (1+041 US/cm "t 25N7) of "ll u0l"nd )ell
"m0led.
Confinement by glacial-drift deposits
46
In "ddition to to0o#r"0hic 0oition+ confinement of #round)"ter i "lo "oci"ted )ith
"ccumul"tion of meth"ne. ?le'en of the 13 "m0le th"t e/ceeded 5 m#/% of meth"ne )ere from
confined ettin#. 2en )ere from '"lle( ettin#+ "nd one )" from the u0l"nd ettin#. =round)"ter
flo) *ene"th confinin# unit under n"tur"l condition i t(0ic"ll( much lo)er th"n h"llo) unconfined
flo) th"t dich"r#e to urf"ce )"ter or flo) do)n hi#h,#r"dient hilllo0e *ec"ue dich"r#e h" to
0" throu#h or circum'ent the confinin# unit. 2hi older+ confined #round)"ter i ch"r"cteri6ed *(
rel"ti'el( hi#h 05 )here meth"ne i 0reent "t #re"ter th"n 0.1 m#/%+ )ith fe) e/ce0tion (9eth"ne
concentr"tion in rel"tion to 05 "nd 0ecific conduct"nce in '"lle( "nd u0l"nd "re". -ote difference in
meth"ne "nd 0ecific conduct"nce c"le *et)een u0l"nd "nd '"lle( "re".).
S0ecific,conduct"nce '"lue in confined ettin# "00e"r to indic"te 0erh"0 t)o cen"rio of
meth"ne occurrence under confined condition. In the firt cen"rio+ hi#h 0ecific,conduct"nce '"lue
(from "*out $50 to 2+405 US/cm "t 25N7> 9eth"ne concentr"tion in rel"tion to 05 "nd 0ecific
conduct"nce in '"lle( "nd u0l"nd "re". -ote difference in meth"ne "nd 0ecific conduct"nce c"le
*et)een u0l"nd "nd '"lle( "re".) in *oth u0l"nd "nd '"lle( confined ettin# corre0ond to meth"ne
concentr"tion #re"ter th"n 0.1 m#/%. 2he hi#h 0ecific,conduct"nce '"lue "re inter0reted "
re0reentin# motl( freh #round)"ter lo)l( circul"tin# throu#h *edrock th"t h"'e *een incom0letel(
fluhed of "line )"ter or 0erh"0 mi/in# )ithin the )ell*ore of freh)"ter "nd " "line )"ter from "
fr"cture ne"r the *ottom of the )ell*ore. & dicued "*o'e+ thi underl(in# "line )"ter i inter0reted
" cont"inin# ele'"ted diol'ed meth"ne.
2he econd cen"rio conit of ele'"ted meth"ne in #round)"ter )ith lo)er 0ecific
conduct"nce ("*out 400;$00 US/cm "t 25N7). 2hi indic"te u0)"rd meth"ne ee0"#e+ e0"r"te from
underl(in# tr"nition"l "line )"ter or *rine+ "nd "ccumul"tion )ithin the confined ettin# (7once0tu"l
di"#r"m of thermo#enic "nd micro*i"l meth"ne occurrence "t )"ter )ell in outh,centr"l -e) .ork.
4$
:ell "re ho)n in different h(dro#eolo#ic ettin# "nd in rel"tion to the (freh) #round)"ter flo)
(tem "nd the tr"nition to underl(in# *rine. 2he (m*ol (V)indic"te likel( meth"ne 0reence "nd the
color (#reen or 0ur0le) indic"te meth"ne ource. -o (m*ol indic"te tr"ce or "*ent meth"ne in
#round)"ter "m0le.). 2he u0l"nd confined '"lle( ettin# "re "n e/"m0le of thi cen"rio (for
e/"m0le+ ee )ell 2I 660 d"t"> "00endi/e 1 "nd 4) .
2he l"ck of ele'"ted meth"ne in unconfined '"lle( "nd "nd #r"'el ettin# i conitent )ith
rel"ti'el( f"t #round)"ter mo'ement to)"rd dich"r#e 0oint "t urf"ce,)"ter *odie (limited time for
"ccumul"tion)+ the l"ck of " e"l to tr"0 the meth"ne *efore it dii0"te to the "tmo0here+ "nd ele'"ted
diol'ed o/(#en concentr"tion th"t u00ort remo'"l of meth"ne *( micro*i"l o/id"tion. 2hree of the
"m0le )ithin thi #rou0 re0reented "nd,"nd,#r"'el )ell com0leted "*o'e " confinin# unit o'er
*edrock+ )hich i 0ro*"*l( the ettin# le"t likel( in )hich to find meth"ne *ec"ue u0)"rd ee0"#e
from *edrock i e"led *elo) *( the inter'enin# confinin# unit.
0imitations of Data
2he reult of thi tud(+ *"ed on )"ter "m0le collected from 66 )ell in the 1+810,mi
2
tud(
"re"+ 0ro'ide " 0relimin"r( undert"ndin# of meth"ne occurrence in #round)"ter of outh;centr"l -e)
.ork+ )hich could *e teted )ith u*e!uent d"t" collected in the re#ion. 2he ditri*ution of
#round)"ter meth"ne re0orted here i re0reent"ti'e of the de0th r"n#e of t(0ic"l )"ter,u00l( )ell in
the tud( "re" *ut m"( not *e re0reent"ti'e of other de0th in the #round)"ter flo) (tem
(7once0tu"l di"#r"m of thermo#enic "nd micro*i"l meth"ne occurrence "t )"ter )ell in outh,centr"l
-e) .ork. :ell "re ho)n in different h(dro#eolo#ic ettin# "nd in rel"tion to the (freh)
#round)"ter flo) (tem "nd the tr"nition to underl(in# *rine. 2he (m*ol (V)indic"te likel( meth"ne
0reence "nd the color (#reen or 0ur0le) indic"te meth"ne ource. -o (m*ol indic"te tr"ce or "*ent
meth"ne in #round)"ter "m0le.). 4or e/"m0le+ one c"n en'iion "t(0ic"l (unuu"ll( dee0) u0l"nd
48
)ell interectin# old #round)"ter )ith much hi#her meth"ne concentr"tion (0erh"0 of thermo#enic
ori#in) "nd hi#her 0ecific,conduct"nce '"lue th"n thoe re0orted here.
2he tud( dei#n focued on " u*et of )ell th"t e/cluded )ell )ithin 1 mi of #" )ell
("cti'e or "*"ndoned) "nd )ell th"t could not *e cl"ified )ith ome cert"int(. 2he )ell not cl"ified
include thoe on the )"ll of mot m"Cor '"lle( (initi"ll( uncert"in to0o#r"0hic 0oition) "nd u0l"nd
)ell )ith o'er*urden *et)een "*out 30 "nd 45 ft (uncert"in confinement).
2he reult of thi tud( re0reent " n"0hot of meth"ne concentr"tion re0reent"ti'e of "
rel"ti'el( dr( ummer 0eriod. & " diol'ed #"+ meth"ne concentr"tion m"( *e "ffected *( ch"n#e in
0reure+ uch " e"on"l #round)"ter,le'el '"ri"tion+ "tmo0heric,0reure fluctu"tion+ "nd
0um0in# c(cle of the )ell or the 0reure t"nk (tem. 2hu+ different meth"ne reult from different
"m0lin# condition "re 0oi*le+ "nd the tud( reult m"( *e on the hi#h end of likel( "nnu"l '"ri"tion
*ec"ue of lo) #round)"ter le'el durin# the ummer "m0lin# 0eriod.
@ometic 0lum*in# (tem )ith 0reure t"nk m"( "llo) ome de#ree of #" diffuion "nd+
there*(+ "ffect me"ured concentr"tion. S"m0le,collection method (*ottle or *"#+ *ottle i6e) m"( "lo
"ffect me"ured meth"ne concentr"tion.
2he inter0ret"tion 0reented here "re ome)h"t limited *( the e/tent of chemic"l "n"l(i
"'"il"*le for thi tud(. 7om0lete chemic"l "nd ioto0ic "n"l(e of )"ter "m0le c"n 0ro'ide
"ddition"l e'idence of mi/in#+ rel"ti'e #round)"ter "#e (#round)"ter e'olution "lon# flo) 0"th)+ "nd
meth"ne ource. Ioto0ic "n"l(i of h(dro#en (O@) in the )"ter molecule "nd c"r*on (O
13
7) in
diol'ed inor#"nic c"r*on in )"ter "m0le c"n 0ro'ide "ddition"l e'idence for inter0ret"tion of
meth"ne ource (1e'e6 "nd other+ 2012+ for e/"m0le).
49
Data Needs
2he inter0ret"tion of n"tur"l meth"ne occurrence 0reented here c"n *e ued " " fr"me)ork for
"ein# re0ort of tr"( #"+ *ut "ddition"l meth"ne ioto0ic d"t" from u0l"nd )ell "re needed to
'erif( the micro*i"l ource of meth"ne in thi 0"rt of the flo) (tem. %ine"ment+ fr"cture+ "nd f"ult+
uch " identified in H"co*i (2002)+ )ere not e'"lu"ted " 0"rt of thi "m0le ur'e( *e(ond the "umed
"oci"tion )ith '"lle(. 1e#ion"l line"ment "lo cro u0l"nd "re"+ "nd m"n( h"'e *een 'erified "
f"ult *( H"co*i (2002). 4ount"in "nd H"co*i (2002) identified ome f"ult *( meth"ne detection in
o'erl(in# oil+ o th"t it i 0oi*le th"t ome u0l"nd "re" m"( h"'e meth"ne #re"ter th"n tr"ce le'el
th"t m"( *e of thermo#enic r"ther th"n micro*i"l ori#in. & meth"ne ur'e( "lon# "n identified f"ult or
fr"cture intentific"tion dom"in (" line"r trike,defined trend of cloel( 0"ced fr"cture+ H"co*i+ 2002)
could *e teted for 0otenti"ll( ele'"ted meth"ne "cro u0l"nd "re".
Su*urf"ce d"t" on the de0th of the freh #round)"ter "nd the n"ture of the tr"nition to "line
)"ter "nd *rine "lon# )ith #eochemic"l d"t"+ includin# d"t" on diol'ed #"e+ "re needed "cro
u0l"nd "nd '"lle( "re". & future cot,effecti'e "00ro"ch could in'ol'e d"t" collection durin# the e"rl(
0h"e of "n( #",)ell drillin#.
Significance of *indings
2hi tud( "d'"nce the re#ion"l undert"ndin# of meth"ne occurrence in outh;centr"l -e)
.ork St"te *( utili6in# det"iled h(dro#eolo#( (in " #l"ci"ted re#ion) "nd the 0ecific of )ell
com0letion. 2he tud( confirm the "oci"tion of '"lle( ettin# )ith meth"ne occurrence ho)n *(
9olofk( "nd other (2011) in northe"tern Penn(l'"ni" "nd identifie 0ecific h(dro#eolo#ic
ch"r"cteritic (confinement+ com0letion of unconfined '"lle( )ell in *edrock) )ithin )hich
#round)"ter i likel( to cont"in meth"ne #re"ter th"n tr"ce le'el. 9eth"ne ioto0ic d"t" indic"te th"t
meth"ne of thermo#enic ori#in i t(0ic"ll( 0redomin"nt in )ell )"ter from '"lle( "re" "nd th"t limited
50
"nd lo)er concentr"tion of meth"ne in u0l"nd "re" )ell "re of either micro*i"l ori#in (0rim"ril(
c"r*on dio/ide reduction) or " mi/ of micro*i"l "nd thermo#enic ori#in. 2he occurrence of thermo#enic
meth"ne in '"lle( i inter0reted " the u0)"rd ee0"#e of diol'ed #"+ likel( due to their cloe
'ertic"l 0ro/imit( to underl(in# meth"ne,*e"rin# "line #round)"ter "nd *rine "nd 0oi*l( throu#h
enh"nced fr"cture 0erme"*ilit( in *edrock. 9eth"ne of micro*i"l ori#in i #ener"ted )ithin the
u*re#ion"l flo) (tem " #round)"ter *ecome 0ro#rei'el( more reducin#. 2hi meth"ne m"( mi/
)ith thermo#enic meth"ne " #round)"ter flo) con'er#e to)"rd '"lle(.
2he "oci"tion of meth"ne )ith older #round)"ter (hi#h 05+ hi#h 0ecific conduct"nce) i
m"de+ "nd " conce0tu"l di"#r"m of meth"ne occurrence i 0reented from inter0ret"tion of thee reult+
field;ch"r"cteritic me"urement+ 0re'iou )ork+ "nd "n undert"ndin# of #round)"ter flo) (tem in
the northern &00"l"chi"n <"in.
4rom " 0r"ctic"l 0er0ecti'e+ thi undert"ndin# of meth"ne occurrence "nd ori#in 0ro'ide
)"ter,reource m"n"#er "nd the 0u*lic )ith " fr"me of reference for initi"l e'"lu"tion of future
!uetion rel"ted to tr"( #"+ 0"rticul"rl( if hi#h,'olume h(dr"ulic fr"cturin# de'elo0ment of h"le #"
0roceed in -e) .ork St"te. 4or e/"m0le+ u0l"nd unconfined )ell "nd '"lle( unconfined "nd "nd
#r"'el )ell )ere ch"r"cteri6ed *( tr"ce meth"ne concentr"tion> therefore+ re0ort of ele'"ted meth"ne
in uch ettin# )ould *e conidered unuu"l "nd not e/0ected to occur n"tur"ll(. 1e0ort of ele'"ted
meth"ne in '"lle( )ell th"t "re confined "nd com0leted in *edrock could )ell *e )ithin the re"lm of
n"tur"l occurrence. 2he difference in meth"ne ori#in *et)een u0l"nd "nd '"lle( "re"+ " indic"ted *(
the ioto0ic ch"r"cteri6"tion 0reented here+ m"( re0reent " ueful tool for 0uttin# meth"ne occurrence
in conte/t. 2he reult of thi tud( "re from " rel"ti'el( m"ll 0o0ul"tion of )"ter,)ell "m0le "nd "re
thu u*Cect to future refinement " "ddition"l d"t" "re collected in the re#ion.
51
=round)"ter meth"ne occurrence "nd ori#in identified in thi tud( "re conitent )ith re#ion"l
reult for -e) .ork "nd northe"t Penn(l'"ni". A"00el "nd -(trom (2012) re0ort th"t )ithin -e)
.ork St"te+ #round)"ter meth"ne (#re"ter th"n 0.001 m#/%) mot fre!uentl( h" occurred )ithin
ediment"r( *edrock+ "nd 0ecific"ll( )" 0reent in $4 to $$ 0ercent of "m0le from 9iddle
3rdo'ici"n to B00er @e'oni"n,"#e *edrock )ith "oci"ted *l"ck h"le> in the 0reent tud(+ meth"ne
)" detected "t #re"ter th"n 0.001 m#/% in $$ 0ercent of *edrock #round)"ter "m0le. 2he lo),
m"turit( thermo#enic ori#in indic"ted for m"n( of the "m0le in thi tud( h" "lo *een indic"ted for
"m0le from northe"t "nd north;centr"l Penn(l'"ni" (1e'e6 "nd other+ 2012> @.:. 1ier+ B.S.
=eolo#ic"l Sur'e(+ )ritten commun.+ 2013> 9olofk( "nd other+ 2011> 3*orn "nd other+ 2011)+
"cro centr"l -e) .ork in outhe"tern 7hen"n#o 7ount( (R. Nyahay+ )ritten commun.+W 2012W)+ "nd
outh;centr"l @el")"re 7ount( to " f"r e"t " S"r"to#" 7ount(+ -e) .ork (:.9. A"00el+ B.S.
=eolo#ic"l Sur'e(+ )ritten commun.+ 2012). 9icro*i"l (c"r*on dio/ide reduction) "nd mi/ed,ori#in
meth"ne identified in thi tud( )ere "lo identified in north;centr"l Penn(l'"ni" (1e'e6 "nd other+
2012).
Summary and #onclusions
& 66,)ell ur'e( of n"tur"l meth"ne occurrence in #round)"ter )" c"rried out durin# the
ummer of 2012 to "ddre " l"ck of inform"tion for outh;centr"l -e) .ork. 2he tud( "re"
encom0"e "*out 1+810 !u"re mile "nd include "ll or 0"rt of <roome+ 2io#"+ 7hemun#+ 7hen"n#o+
"nd @el")"re 7ountie. :"ter )ell )ithin " one,mile r"diu of kno)n #" )ell ("cti'e+ e/0lor"tor(+ or
"*"ndoned) )ere e/cluded from the ur'e(. 2he )ell,election "00ro"ch focued on h(dro#eolo#ic
ch"r"cteritic of the "re" th"t mi#ht "ffect "ccumul"tion of meth"ne from either in itu #ener"tion or
u0)"rd ee0"#e from underl(in# ource rock. 2he cl"ific"tion included to0o#r"0hic 0oition ('"lle(
"nd u0l"nd+ )hich rel"te to 0oition )ithin the #round)"ter flo) (tem)+ confinement or non,
52
confinement of #round)"ter *( #l"ci"l,drift de0oit+ )ell com0letion ch"r"cteritic+ "nd loc"l
#eolo#ic ch"r"cteritic.
2he election criteri" for )ell for "m0lin# re!uired )ell,contruction "nd )ell,lo# d"t" for
u*e!uent cl"ific"tion. I"lle( "nd u0l"nd ettin# )ere defined *( #ener"tin# " (nthetic tre"m
net)ork from ele'"tion d"t" uin# criteri" for the t"rt of tre"m th"t omitted m"ll u0l"nd tre"m. &
m"/imum lo0e criterion )" ued to further 0"re do)n the net)ork. 2he )idth of '"lle( )ere
defined " the "re" )ithin $5 feet (ft) ele'"tion "*o'e the loc"l tre"m+ *ut '"lle( )ere loc"ll( edited to
(1) remo'e m"ll tre"m )ith i#nific"nt re"che )ithin l"r#e '"lle(+ (2) incre"e '"lle( )idth to
re#ul"r '"lle( )"ll contour in '"lle( e#ment choked )ith #l"ci"l de0oit th"t h"d *een dee0l(
incied *( the '"lle( tre"m or ri'er or (3) trunc"te he"d)"ter tre"m in rel"ti'el( fl"t (hi#h 0l"te"u)
u0l"nd "re" )ith little tre"m inciion (m"ll loc"l relief).
4ield ch"r"cteritic (05+ 0ecific conduct"nce+ diol'ed o/(#en+ "nd tem0er"ture) )ere
me"ured "t e"ch )ell+ "nd "m0le )ere collected "nd "n"l(6ed for diol'ed #"e+ includin# meth"ne
"nd lo)er,ch"in h(droc"r*on. 7"r*on "nd h(dro#en ioto0ic r"tio of meth"ne )ere me"ured in 24
"m0le )ith "t le"t 0.3 milli#r"m 0er liter (m#/%) of meth"ne.
1eult of "m0lin# indic"te th"t n"tur"l occurrence of meth"ne in #round)"ter in the re#ion i
common (#re"ter th"n or e!u"l to 0.1 milli#r"m 0er liter (m#/%) in 35 0ercent of "m0le) *ut i
"oci"ted )ith 0ecific h(dro#eolo#ic ettin#. :ell com0leted in *edrock )ithin '"lle( "nd )ith
confined #round)"ter condition )ere mot cloel( "oci"ted )ith meth"ne occurrence. 4ift(,e'en
0ercent of '"lle( )ell h"d #re"ter th"n or e!u"l to 0.1 m#/% meth"ne+ )here" onl( 10 0ercent of
u0l"nd )ell e!u"led or e/ceeded th"t '"lue. Ioto0ic i#n"ture differed *et)een thee #rou0 " )ell.
9eth"ne in '"lle( )ell )" 0redomin"ntl( thermo#enic in ori#in+ likel( due to cloe 'ertic"l 0ro/imit(
to underl(in# meth"ne,*e"rin# "line #round)"ter "nd *rine "nd 0oi*l( from enh"nced *edrock,
53
fr"cture 0erme"*ilit( *ene"th '"lle( th"t 0ro'ide "n "'enue for u0)"rd ee0"#e of diol'ed meth"ne.
Ioto0ic i#n"ture of the fe) u0l"nd )ell "m0le )ith ufficient meth"ne indic"ted " micro*i"l ori#in
(c"r*on dio/ide reduction) or micro*i"ll( 0roduced meth"ne th"t h"d under#one mi/in# )ith
thermo#enic meth"ne+ or o/id"tion. 9ot u0l"nd )ell "re likel( com0leted much f"rther "*o'e
tr"nition"l "line )"ter "nd *rine th"n '"lle( )ell (7once0tu"l di"#r"m of thermo#enic "nd micro*i"l
meth"ne occurrence "t )"ter )ell in outh,centr"l -e) .ork. :ell "re ho)n in different
h(dro#eolo#ic ettin# "nd in rel"tion to the (freh) #round)"ter flo) (tem "nd the tr"nition to
underl(in# *rine. 2he (m*ol (V)indic"te likel( meth"ne 0reence "nd the color (#reen or 0ur0le)
indic"te meth"ne ource. -o (m*ol indic"te tr"ce or "*ent meth"ne in #round)"ter "m0le.) "nd
thu likel( f"rther remo'ed from thermo#enic meth"ne. 2he micro*i"l meth"ne i inter0reted " *ein#
0roduced *( *"cteri" th"t utili6e c"r*on dio/ide or form"tion"l or#"nic m"tter in hi#hl( reducin#
en'ironment )ithin the u*re#ion"l #round)"ter flo) (tem. 2hi meth"ne i entr"ined )ith
#round)"ter flo)+ )here" thermo#enic meth"ne in '"lle( "re" l"r#el( im0lie u0)"rd ee0"#e of
diol'ed #" "nd not "line )"ter chemitr(. 2hi ch"r"cteri6"tion of #round)"ter meth"ne 0ro'ide "
conce0tu"l fr"me)ork th"t c"n *e utili6ed in in'eti#"tion of tr"( #" in outh,centr"l -e) .ork+ "nd
the undert"ndin# of meth"ne occurrence c"n *e refined " "ddition"l d"t" "re collected.
Acknowledgements
2he "uthor e/tend th"nk "nd "00reci"tion to "ll )ell o)ner )ho took time to fill out )ell
ur'e( "nd to thoe )ho #"'e 0ermiion "nd f"cilit"ted "m0lin# of their )ell+ )hich )" critic"l to
the tud(. 2h"nk "re "lo e/tended to B.S. =eolo#ic"l Sur'e( 0eronnel )hoe )ork u00orted the
tud(. ?li6"*eth -(trom "ited )ith "m0lin# "nd "m0lin# e!ui0ment in the field+ includin# the
field me"urement of meth"ne. 1ich"rd 1e(nold "nd 7"rol(n I"n &lt(ne "lo "ited )ith field
"m0lin#+ "nd P"trick Philli0 0re0"red t"titic"l "nd !u"lit(,"ur"nce "n"l(e. 9"rt(n Smith "nd
54
@ou#l" 4reeh"fer 0ro'ided #eo#r"0hic inform"tion (tem u00ort th"t included 0rocein# of lid"r
im"#er( "nd #ener"tion "nd 0rocein# of tre"m net)ork "nd to0o#r"0hic inform"tion th"t f"cilit"ted
the definition of '"lle( "re".
References #ited
<uen*er#+ ?.+ Plummer+ %.-.+ <"rtholom"(+ 1.7.+ "nd :"(l"nd+ H.?.+ 1998+ 7hlorofluoroc"r*on+
ulfur he/"fluoride+ "nd diol'ed 0erm"nent #"e in #round )"ter from elected ite in "nd ne"r the
Id"ho -"tion"l ?n#ineerin# "nd ?n'ironment"l %"*or"tor(+ Id"ho+ 1994;9$E B.S. =eolo#ic"l Sur'e(
30en,4ile 1e0ort 98;2$4+ $2 0.
7"d)ell+ @.5.+ "nd @ineen+ 1.H.+ 198$+ Surfici"l #eolo#ic m"0 of -e) .ork85udon,9oh")k SheetE
-e) .ork St"te 9ueum =eolo#ic"l Sur'e(+ 9"0 "nd 7h"rt Serie no. 40+ 1E250+000.
7h"fin+ @.2.+ 1994+ Source "nd mi#r"tion 0"th)"( of n"tur"l #" in ne"r,urf"ce #round )"ter *ene"th
the &nim" 1i'er I"lle(+ 7olor"do "nd -e) 9e/icoE B.S. =eolo#ic"l Sur'e( :"ter,1eource
In'eti#"tion 1e0ort 94;4006+ 56 0.
7o"te+ @.1.+ 1966+ =l"ci"ted &00"l"chi"n Pl"te"u8till h"do) on hillE Science+ '. 152+ 0. 161$;
1619.
7olem"n+ @.@.+ 1i"tti+ H.<.+ "nd Schoell+ 9"rtin+ 1981+ 4r"ctio"ntion of c"r*on "nd h(dro#en ioto0e
*( meth"ne,o/idi6in# *"cteri"E =eochimic" et 7omochimic" &ct"+ '. 45+ 0. 1033;103$.
7olem"n+ @.@.+ %iu+ 7h"o,%i+ "nd 1ile(+ A.9.+ 1988+ 9icro*i"l meth"ne in the h"llo) P"leo6oic
ediment "nd #l"ci"l de0oit of Illinoi+ B.S.&.E 7hemic"l =eolo#(+ '.$1+ 0. 23;40.
7olem"n+ H. %.+ 9ilici+ 1.7.+ 7ook+ 2.&.+ 7h"r0entier+ 1.1.+ Airh*"um+ 9.&.+ Alett+ 2.1.+ Poll"tro+
1.9.+ "nd Schenk+ 7.H.+ 2011+ &ement of undico'ered oil "nd #" reource of the de'oni"n
m"rcellu h"le of the "00"l"chi"n *"in 0ro'ince+ 2011E B.S. =eolo#ic"l Sur'e( 4"ct Sheet 2011;
3092+ 2 0.+ htt0E//0u*.u#.#o'/f/2011/3092/.
55
@irect =eochemic"l+ 2004+ &00lic"tion of 0eci"li6ed urf"ce #eochemic"l tetin# to define 0roducti'e
"nd f"ulted "re" rel"ted to h(drotherm"l dolomite #" 0roduction in the &00"l"chi"n <"in of -e)
.orkE 7ontr"ct &#reement 8168E -e) .ork St"te ?ner#( 1ee"rch "nd @e'elo0ment &uthorit(+ 19 0.
@reel+ P.?.+ "nd 1oe+ &.:.+ 2010+ 7hemitr( "nd ori#in of oil "nd #" )ell *rine in )etern
Penn(l'"ni"E Penn(l'"ni" =eolo#ic"l Sur'e(+ 4th er.E 30en,4ile 1e0ort 343= 10,01.0+ 48 0.
?ltchl"#er+ A.A.+ 5")kin+ H.:.+ ?hler+ :.7.+ "nd <"ld""re+ 4red+ 2001+ 2echnic"l me"ure for the
in'eti#"tion "nd miti#"tion of fu#iti'e meth"ne h"6"rd in "re" of co"l minin#E B.S. @e0"rtment of
the Interior+ 3ffice of Surf"ce 9inin# 1ecl"m"tion "nd ?nforcement+ 125 0.+ "cceed H"nu"r( 9+
2012 "t htt0E//))). techtr"nfer.omre.#o'/-229"inSite/%i*r"r(/h*m"nu"l/ meth"ne/meth"ne.0df.
4iher+ @.:.+ I"chen+ ..:.+ "nd 1ick"rd+ %.I.+ 19$0+ =eolo#ic m"0 of -e) .ork+ 5udon;9oh")k
heetE -e) .ork St"te 9ueum "nd Science Ser'ice+ 9"0 "nd 7h"rt Serie no. 15+ 1E250+000.
4oter+ H.<.+ 1980+ 4reh "nd "line #round)"ter of :et Iir#ini"E :et Iir#ini" =eolo#ic"l "nd
?conomic Sur'e( 9"0 :I,12+ 2 0l"te.
4ount"in+ H.7.+ "nd H"co*i+ 1.@.+ 2000+ @etection of *uried f"ult "nd fr"cture uin# oil #" "n"l(iE
?n'ironment"l "nd ?n#ineerin# =eocience+ '.II+ no. 3+ 0. 201;208.
5"nen+ %.A.+ H"ko*en+ 1"mu+ "nd Potm"+ @ieke+ 2001+ 9eth"no#enei in " h"llo) "nd( "!uifer+
1omo+ @enm"rkE =eochimic" et 7omochimic" &ct"+ '.65+ no. 1$+ 0. 2925;2935.
5eii#+ P.9.+ "nd Anuton+ A.@.+ 199$+ <orehole #eo0h(ic"l d"t" from *edrock )ell "t :indh"m+
-e) .orkE B.S. =eolo#ic"l Sur'e( 30en,4ile 1e0ort 9$;42+ 24 0.
5eii#+ P.9.+ 1999+ :"ter reource of the <"t"'i" Aill *"in "t :indh"m+ =reene 7ount(+ -e) .orkE
B.S. =eolo#ic"l Sur'e( :"ter,1eource In'eti#"tion 1e0ort 98,4036+ 96 0.
56
5eii#+ P.9.+ 2012+ 5(dro#eolo#( of the Su!ueh"nn" 1i'er '"lle(,fill "!uifer (tem "nd "dC"cent
"re" in e"tern <roome "nd outhe"tern 7hen"n#o 7ountie+ -e) .orkE B.S. =eolo#ic"l Sur'e(
Scientific In'eti#"tion 1e0ort 2012;5282+ 21 0. 1 0l"te.
5elel+ @.1.+ "nd 1. 9. 5irch+ 2002+ St"titic"l method in )"ter reourceE B.S. =eolo#ic"l Sur'e(
2echni!ue of :"ter 1eource In'eti#"tion+ *ook 4+ ch"0. &3+. 522 0.
5olecek+ 2.H.+ 1"nd"ll+ &.@.+ <elli+ H.%.+ "nd &llen+ 1.I.+ 1982+ =eoh(drolo#( of the '"lle(,fill "!uifer
in the ?ndicott;,Hohnon 7it( "re"+ <roome 7ount(+ -e) .orkE B.S. =eolo#ic"l Sur'e( 30en,4ile
1e0ort 82;268+ 5 heet+ c"le 1E24+000.
5o0kin+ 5.2.+ 1966+ 2he freh,"line )"ter interf"ce in Aentuck(E Aentuck( =eolo#ic"l Sur'e( 1e0ort+
19 0.+ 1 0l"te.
Iotech %"*or"torie+ Inc.+ 2012+ Intrument"tion+ "cceed H"nu"r( 6+ 2012+ "t htt0E//iotechl"*.com/.
H"co*i+ 1.@.+ 2002+ <"ement f"ult "nd eimicit( in the &00"l"chi"n <"in of -e) .ork St"teE
2ectono0h(ic+ '. 353+ 0. $5;113
A"00el+ :.9.+ "nd -(trom+ ?.&.+ 2012+ @iol'ed meth"ne in -e) .ork #round)"ter+ 199982011E
B.S. =eolo#ic"l Sur'e( 30en,4ile 1e0ort 2012;1162+ 6 0.+ http://pubs.usgs.gov/of/!"#!/##$!.
Ai00+ H.&.+ %")rence+ 4.:.+ "nd @in#er+ H.S.+ 1983+ &conce0tu"l model of #round,)"ter flo) in the
?"tern Aentuck( 7o"lfield+ in =r"'e+ @.5.+ ed.+ S(m0oium on Surf"ce 9inin#+ 5(drolo#(+
Sedimentolo#(+ "nd 1ecl"m"tionE %e/in#ton+ A(.+ Bni'erit( of Aentuck(+ -o'em*er 2$;@ecem*er
2+ 1983+ 0. 543;548.
Airch*"um+ 9.&.+ Schenk+ 7.H.+ 7ook+ 2.&.+ 1(der+ 1.2.+ 7h"r0entier+ 1.1.+ Alett+ 2.1.+ =")irth+ S.<.+
2enn(on+ 9.?.+ "nd :hidden+ A.H.+ 2012+ &ement of undico'ered oil "nd #" reource of the
3rdo'ici"n Btic" Sh"le of the &00"l"chi"n <"in Pro'ince+ 2012E B.S. =eolo#ic"l Sur'e( 4"ct Sheet
2012;3116+ 6 0.+ htt0E//0u*.u#.#o'/f/2012/3116/.
5$
9"c-ih+ 1.@.+ "nd 1"nd"ll+ &.@.+ 1982+ Stratified%drift a&uifers in the Sus&uehanna 'iver basin( )ew
*or+: -e) .ork St"te @e0"rtment of ?n'ironment"l 7oner'"tion <ulletin $5+ 68 0.
9"rtini+ &.9.+ <ud"i+ H.9.+ :"lter+ %.9.+ "nd Schoell+ 9"rtin+ 1996+ 9icro*i"l #ener"tion of economic
"ccumul"tion of meth"ne )ithin " h"llo) or#"nic,rich h"leE -"ture+ '. 383+ 0. 155;158.
9iller+ 2.S.+ 1"nd"ll+ &.@.+ <elli+ H.%.+ "nd &llen+ 1.I.+ 1982+ =eoh(drolo#( of the '"lle(,fill "!uifer in
the ?lmir" "re"+ 7hemun# 7ount(+ -e) .orkE B.S. =eolo#ic"l Sur'e( 30en,4ile 1e0ort 82;110+ $
heet+ c"le 1E24+000.
9iller+ 2.S.+ "nd Pitm"n+ %.H.+ 2012+ 5(dro#eolo#( of the tr"tified,drift "!uifer in the 7"(ut" 7reek
"nd 7"t"tonk 7reek '"lle( in 0"rt of 2om0kin+ Schu(ler+ 7hemun#+ "nd 2io#" 7ountie+ -e)
.orkE B.S. =eolo#ic"l Sur'e( Scientific In'eti#"tion 1e0ort 2012;512$+ 44 0. 3 0l
9inn+ S.&.+ 1993+ 7once0tu"l model of loc"l "nd re#ion"l flo) in the ?"tern Aentuck( 7o"lfieldE
Aentuck( =eolo#ic"l Sur'e(+ 2hei Serie 6+ Serie XI+ 194 0.
9olofk(+ %.+ 7onnor+ H.+ :(lie+ &.+ "nd :"#ner+ 2.+ 2011+ 9eth"ne in Penn(l'"ni" )"ter )ell
unrel"ted to 9"rcellu h"le fr"cturin#E 3il "nd =" Hourn"l+ '. 109+ no. 49+ 12 0.+ "cceed H"nu"r(
23+ 2012 "t htt0E//))).o#C.com/1/'ol,109/iue,49/e/0lor"tion,de'elo0ment/meth"ne,in,
0enn(l'"ni",)"ter,full.html.
9olofk(+ %.+ 7onnor+ H.+ :(lie+ &.+ :"#ner+ 2.+ "nd 4"rh"t+ S. A.+ 2013+ ?'"lu"tion of meth"ne ource
in #round)"ter in northe"tern Penn(l'"ni"E =round)"ter+ '.51+ no. 3+ 0. 333;349.
9uller+ ?.5.+ "nd 7"d)ell+ @.5.+ 1986+ Surfici"l #eolo#ic m"0 of -e) .ork84in#er %"ke SheetE -e)
.ork St"te 9ueum;=eolo#ic"l Sur'e(+ 9"0 "nd 7h"rt Serie no. 40+ 1E250+000.
-e) .ork St"te 9ueum 1eer'oir 7h"r"cteri6"tion =rou0+ 2009+ Schem"tic north,outh cro ection
4in#er %"ke 1e#ion of -e) .ork St"teE &l*"n(+ -...+ -e) .ork St"te 9ueum 1eer'oir
7h"r"cteri6"tion =rou0.
58
-(trom+ ?.&.+ 2012+ =round)"ter !u"lit( in the @el")"re "nd St. %")rence 1i'er <"in+ -e) .ork+
2010E B.S. =eolo#ic"l Sur'e( 30en,4ile 1e0ort 2011;1320+ 58 0.+ htt0E//0u*.
u#.#o'/of/2011/1320/.
3*orn+ S.=.+ "nd 9cIntoh+ H.7.+ 2010+ 7hemic"l "nd ioto0ic tr"cer of the contri*ution of micro*i"l
#" in @e'oni"n or#"nic,rich h"le "nd reer'oir "ndtone+ northern &00"l"ch"in <"inE &00lied
=eochemitr(+ '. 25+ 0. 456;4$1.
3*orn+ S.=.+ &'ner+ Ien#oh+ :"rner+ -.1.+ "nd H"ckon+ 1.<.+ 2011+ 9eth"ne cont"min"tion of
drinkin# )"ter "ccom0"n(in# #",)ell drillin# "nd h(dr"ulic fr"cturin#E Proceedin# of the -"tion"l
&c"dem( of Science+ ))).0n".or#/c#i/doi/10.10$3/0n".1100682108+ 5 0.
Poth+ 7.:.+ 1962+ 2he occurrence of *rine in )etern Penn(l'"ni"E Penn(l'"ni" 2o0o#r"0hic "nd
=eolo#ic Sur'e( <ulletin 9 4$+ 53 0.
Poth+ 7.:.+ 1963+ =eolo#( "nd h(drolo#( of the 9ercer Ru"dr"n#le+ 9ercer+ %")rence+ "nd <utler
7ountie+ Penn(l'"ni"E Penn(l'"ni" 2o0o#r"0hic "nd =eolo#ic Sur'e( :"ter 1eorurce 1e0ort 16+
149 0.
1"nd"ll+ &.@.+ 19$2+ 1ecord of )ell "nd tet *orin# in the Su!ueh"nn" 1i'er *"in+ -e) .orkE -e)
.ork St"te @e0"rtment of ?n'ironment"l 7oner'"tion <ulletin 69+ 92 0.
1"nd"ll+ &.@.+ 2001+ ,ydrogeologic framewor+ of stratified%drift a&uifers in the glaciated northeastern
-nited States: B.S. =eolo#ic"l Sur'e( Profeion"l P"0er 1415,<+ 1$9 0.+ 1 0l.
1edd(+ H.?.+ "nd 1ien+ &.H.+ 2012+ =round)"ter !u"lit( in the B00er Su!ueh"nn" 1i'er <"in+ -e)
.ork+ 2009E B.S. =eolo#ic"l Sur'e( 30en,4ile 1e0ort 2012;1045+ 29 0.+
htt0E//0u*.u#.#o'/of/2012/1045/.
59
1e'e6+ A.9.+ <reen+ A.H.+ <"ld""re+ &.H.+ "nd <urru+ 1.7.+ 2012+ 7"r*on "nd h(dro#en ioto0ic
e'idence for the ori#in of com*uti*le #"e in )"ter,u00l( )ell in north,centr"l Penn(l'"ni"E
&00lied =eochemitr(+ '. 2$+ 0. 361;3$5.
1e(nold+ 1.H. "nd ="rr(+ H.@.+ 1990+ 5(dro#eolo#( of the '"lle(,fill "!uifer "t 3)e#o+ 2io#" 7ount(+
-e) .orkE B.S. =eolo#ic"l Sur'e( :"ter,1eource In'eti#"tion 1e0ort 89;4000+ 8 heet+ c"le
1E24000.
1e(nold+ 1.H.+ 2003+ 5(dro#eolo#( of the :"'erl(,S"(re "re" in 2io#" "nd 7hemun# 7ountie+ -e)
.ork "nd <r"dford 7ount(+ Penn(l'"ni"E B.S. =eolo#ic"l Sur'e( 30en,4ile 1e0ort 02;284+ 6 heet+
c"le 1E24+000+ 1 7@,139.
1ick"rd+ %.I.+ "nd 4iher+ @.:.+ 19$0+ =eolo#ic m"0 of -e) .ork+ 4in#er %"ke heetE -e) .ork St"te
9ueum "nd Science Ser'ice+ 9"0 "nd 7h"rt Serie no. 15+ 1E250+000.
1ier+ @. :.+ :illi"m+ H. 5.+ 5"nd+ A. %.+ <ehr+ 1oe,&nn"+ "nd 9"rko)ki+ &. A.+ 2013+
=eoh(drolo#ic "nd )"ter,!u"lit( ch"r"cteri6"tion of " fr"ctured,*edrock tet hole in "n "re" of
9"rcellu Sh"le #" de'elo0ment+ <r"dford 7ount(+ Penn(l'"ni"E Penn(l'"ni" =eolo#ic"l Sur'e(+
4th er.+ 30en,4ile 9icell"neou 1e0ort 349I 13,01.0+ 480.
Schiner+ =.1.+ "nd ="ll"her+ H.2.+ 19$9+ =eolo#( "nd #round)"ter reource of )etern 7r")ford
7ount(+ Penn(l'"ni"E Penn(l'"ni" =eolo#ic"l Sur'e( :"ter 1eource 1e0ort 46+ 50 0.
Schoell+ 9"rtin+ 1980+ 2he h(dro#en "nd c"r*on ioto0ic com0oition of meth"ne from n"tur"l #"e of
'"riou ori#inE =eochimic" et 7omochimic" &ct"+ '. 44+ 0. 649;661.
Schoell+ 9"rtin+ 1983+ =enetic ch"r"cteri6"tion of n"tur"l #"eE 2he &meric"n &oci"tion of
Petroleum =eolo#it <ulletin+ '. 6$+ no. 12+ 0. 2225;2238.
Sed"m+ &.7.+ "nd Stein+ 1.<.+ 19$0+ S"line #round,)"ter reource of 3hioE B.S. =eolo#ic"l Sur'e(
5(drolo#ic In'eti#"tion &tl" 5&;366+ 2 0l.
60
B.S. =eolo#ic"l Sur'e(+ '"rioul( d"ted+ -"tion"l field m"nu"l for the collection of )"ter,!u"lit( d"t"E
B.S. =eolo#ic"l Sur'e( 2echni!ue of :"ter,1eource In'eti#"tion+ *ook 9+ ch"0. &1;&9+
http://pubs.water.usgs.gov/twri./.
Ieto+ It'"n+ 4uto+ It'"n+ 5or'"th+ It'"n+ "nd S6"nto+ Yu6"+ 2004+ %"te "nd dee0 fermenti'e
meth"no#enei " reflected in the 5,7,3,S ioto0( of the meth"ne,)"ter (tem in dee0 "!uifer of
the P"nnoni"n <"in (S? 5un#"r()E 3r#"nic =eochemitr(+ '. 35+ 0. $13;$23.
:"rner+ -.1.+ H"ckon+ 1.<.+ @"rr"h+ 2.5.+ 3*orn+ S.=.+ @o)n+ &dri"n+ Yh"o+ A"i#u"n#+ 2012+
=eochemic"l e'idence for 0oi*le n"tur"l mi#r"tion of 9"rcellu 4orm"tion *rine to h"llo)
"!uifer in Penn(l'"ni"E Proceedin# of the -"tion"l &c"dem( of Science '. 109+ no. 30 0. 11961;
11966.
:illi"m+ H.5.+ 2010+ ?'"lu"tion of )ell lo# for determinin# the 0reence of freh)"ter+ "lt)"ter+ "nd
#" "*o'e the 9"rcellu Sh"le in 7hemun#+ 2io#"+ "nd <roome 7ountie+ -e) .orkE B.S. =eolo#ic"l
Sur'e( Scientific In'eti#"tion 1e0ort 2010;5224+ 2$ 0.+ htt0E//0u*.u#.#o'/ir/2010/5224/.
:illi"m+ H.:.+ 2"(lor+ %.?.+ "nd %o) @.H.+ 1998+ 5(dro#eolo#( "nd #round)"ter !u"lit( of the
#l"ci"ted '"lle( of <r"dford+ 2io#"+ "nd Potter 7ountie+ Penn(l'"ni"E Penn(l'"ni" =eolo#ic"l
Sur'e( :"ter 1eource 1e0ort 68+ 89 0.
:unch+ @.1.+1993+ =round,)"ter #eochemitr( "nd it rel"tionhi0 to the flo) (tem "t "n unmined
ite in the ?"tern Aentuck( 7o"l 4ieldE Aentuck( =eolo#ic"l Sur'e(+ 2hei Serie 5+ Serie XI+ 128
0.
61