Chemosphere 73 (2008) 1258–1264

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Chemosphere
j o u r n a l h o m e p a g e : w w w . e l s e v i e r. c o m / l o c a t e / ch e m o s p h e r e

Comparison of GC–MS and FTIR methods for quantifying naphthenic acids

in water samples
Angela C. Scott, Rozlyn F. Young, Phillip M. Fedorak *
Depart­ment of Bio­log­ic­ al Sci­ences, Uni­ver­sity of Alberta, Ed­mon­ton, Alberta, Can­ada T6G 2E9

a r t i c l e i n f o a b s t r a c t

Article history: The extrac­tion of bitu­men from the oil sands in Can­ada releases toxic naph­thenic acids into the pro­cess-
Received 4 April 2008 affected waters. The devel­op­ment of an ideal ana­lyt­i­cal method for quan­ti­fy­ing naph­thenic acids (gen­eral
Received in revised form 8 July 2008 for­mula CnH2n + ZO2) has been impeded by the com­plex­ity of these mix­tures and the chal­lenges of dif­fer­
Accepted 10 July 2008
en­ti­at­ing naph­thenic acids from other nat­u­rally-occur­ring organic acids. The oil sands indus­try stan­dard
Available online 26 August 2008

FTIR method was com­pared with a newly-devel­oped GC–MS method. Naph­thenic acids con­cen­tra­tions
were mea­sured in extracts of sur­face and ground waters from loca­tions within the vicin­ity of and away
from the oil sands depos­its and in extracts of pro­cess-affected waters. In all but one case, FTIR mea­sure­
Key­words:
Oil sands
ments of naph­thenic acids con­cen­tra­tions were greater than those deter­mined by GC–MS. The detec­tion
Ana­lyt­i­cal meth­ods limit of the GC–MS method was 0.01 mg L¡1 com­pared to 1 mg L¡1 for the FTIR method. The results indi­
Tail­ings water cated that the GC–MS method is more selec­tive for naph­thenic acids, and that the FTIR method over­es­ti­
Alberta mates their con­cen­tra­tions.
© 2008 Else­vier Ltd. All rights reserved.

1. Intro­duc­tion dis­charge OSPW to receiv­ing water. Thus, huge tail­ings ponds have
been devel­oped to hold and clar­ify OSPW, allow­ing a portion of
In north­east­ern Alberta, Can­ada, there are vast depos­its of oil the water to be recy­cled in the extrac­tion pro­cess. Ulti­mately the
sands that are now con­sid­ered to be the world’s sec­ond larg­est OSPW will be dis­charged to receiv­ing waters or reclaimed as sus­
reserve of petro­leum. Many inter­na­tional oil com­pa­nies are invest­ tain­able eco­sys­tems. Con­se­quently, there is con­sid­er­able inter­est
ing and devel­op­ing this valu­able resource. These depos­its con­tain in under­stand­ing the tox­ic­ity of the OSPW.
a bio­de­grad­ed, vis­cous, tar-like mate­rial, known as bitu­men, which MacK­in­non and Boer­ger (1986) reported that the “main toxic
is asso­ci­ated with clay and sand par­ti­cles. There are cur­rently two com­po­nents have been ten­ta­tively iden­ti­fied in the polar acidic
meth­ods used to recover this energy sup­ply. The first method frac­tion of the dis­solved organic mat­ter.” The mate­ri­als in the polar
involves sur­face min­ing to remove oil sands from the ground, and acidic frac­tion are referred to as “naph­thenic acids”. The cur­rent
bitu­men is recov­ered using an alka­line hot water extrac­tion pro­ indus­try stan­dard method for quan­ti­fy­ing “naph­thenic acids”
cess (Sch­ramm et al., 2000). The sec­ond method is known as steam involves a dichlo­ro­meth­ane (DCM) extrac­tion of an acid­i­fied water
assisted grav­ity drain­age (SAGD, But­ler, 2001) in which par­al­lel hor­ sam­ple, con­cen­trat­ing the extract and then mea­sur­ing the absor­
i­zon­tal wells are drilled into the oil sands deposit. Steam is injected bance that is char­ac­ter­is­tic for car­box­ylic acids by Fou­rier trans­
into the upper hor­i­zon­tal well and released into the deposit to form infra­red (FTIR) spec­tros­copy (Ji­vraj et al., 1995; Ho­lo­wenko
reduce the vis­cos­ity of the bitu­men. The fluid bitu­men drains to et al., 2001).
the lower hor­i­zon­tal well where the bitu­men and co-pro­duced The def­i­ni­tion of naph­thenic acids is vague. Loch­te and ­Litt­mann
water from the condensed steam are col­lected. Water recov­ered (1955) defined naph­thenic acids as “car­box­ylic acids con­tain­ing
from the alka­line hot water extrac­tion, called oil sands pro­cess one or more ali­cy­clic rings”, and the exam­ples that they gave were
water (OSPW), is con­tained within tail­ings stor­age ponds for reuse mono­car­box­ylic acids. Sim­i­larly, Hunt (1979) defines naph­thenic
in the extrac­tion pro­cess. The major­ity of the water recov­ered from acids as “petro­leum acids con­tain­ing naph­thene or cyclo­par­af ­fi n
the SAGD pro­cess is recy­cled. struc­ture”. Bri­ent et al. (1995) described naph­thenic acids by the
OS­PWs are toxic to aquatic organ­isms (MacK­in­non and Boer­ gen­eral for­mula CnH2n+ZO2, where n rep­re­sents the num­ber of car­
ger, 1986; Nix and Mar­tin, 1992) and oil sands com­pa­nies can­not bon atoms in the mol­e­cule and Z spec­i­fies hydro­gen defi­ciency in
the case of cyclic naph­thenic acids. This for­mula implies the pres­
ence of one car­boxyl group, and the gen­eral for­mula has been used
* Cor­re­spond­ing author. Tel.: +1 780 492 3670; fax: +1 780 492 9234. widely in mass spec­trom­e­try stud­ies to char­ac­ter­ize naph­thenic
E-mail address: phil.fe­do­rak@ual­ber­ta.ca (P.M. Fedorak). acids from var­i­ous sources (see Cle­mente and Fe­do­rak, 2005 for

0045-6535/$ - see front matter © 2008 Else­vier Ltd. All rights reserved.
doi:10.1016/j.chemosphere.2008.07.024
 A.C. Scott et al. / Chemosphere 73 (2008) 1258–1264 1259

review; Ba­tai­neh et al., 2006; Lo et al., 2006). In other stud­ies, ful­vic acids (2 mg L¡1) or Mer­i­chem naph­thenic acids (0.1 mg L¡1).
naph­thenic acids are con­sid­ered to have more than one car­boxyl Su­wan­nee River ful­vic acids ref­er­ence mate­rial (cat no. 1R101F)
group. For exam­ple Smith et al. (2007) and Lutn­aes et al. (2007) was pur­chased from the Inter­na­tional Humic Sub­stances Soci­ety
described tet­ra­ac­ids that form cal­cium naph­th­e­nate pre­cip­i­tates (Uni­ver­sity of Min­ne­sota, St. Paul, MN). Com­mer­cial refined naph­
dur­ing crude oil pro­duc­tion. In this paper, we con­sider naph­thenic thenic acids were pro­vided by Mer­i­chem Chem­i­cals and Refin­ery
acids to be those com­pounds that fit the for­mula CnH2n+ZO2, and we Ser­vices LLC (Hous­ton, TX).
refer to the polar acidic frac­tion mea­sured by FTIR as “naph­thenic Free fatty acids and naph­thenic acids were extracted from
acids” (i.e. in quo­ta­tion marks). water sam­ples using a mod­i­fied method of Mer­lin et al. (2007).
Qual­i­ta­tive or quan­ti­ta­tive anal­y­ses of naph­thenic acids pres­ Briefly, 10 lg of 9-flu­o­ren­e­carb­oxy­lic acid (9-FCA; Sigma–Aldrich,
ent chal­lenges that have yet to be solved. Because of the vast array Mil­wau­kee, WI.) dis­solved in dichlo­ro­meth­ane (DCM; HPLC
of iso­mers for each value of n and Z in the for­mula CnH2n+ZO2, and grade, Fisher, Fair Lawn, NJ) was added as a sur­ro­gate stan­dard
the inabil­ity to sep­a­rate or iden­tify indi­vid­ual naph­thenic acids, to 1 L of water sam­ple or 1 L of diluted sam­ple. This solu­tion
the exact chem­i­cal make-up of a naph­thenic acids sam­ple has not was acid­i­fied to pH 2 with con­cen­trated HCl and 150 g NaCl was
been deter­mined. Sev­eral ana­lyt­ic­ al meth­ods have been used to dis­solved into the sam­ple. The water sam­ple was then extracted
esti­mate the total con­cen­tra­tion of naph­thenic acids in a sam­ple. with three 60-mL por­tions of chlo­ro­form (HPLC grade, Fisher).
Exam­ples of these meth­ods are: (a) FTIR anal­y­sis of the absorp­tion The free car­box­ylic acids were recov­ered by extract­ing the chlo­
inten­sity of the car­boxyl group in the sol­vent extract of an aque­ ro­form phase with three 10-mL por­tions of an alka­line aque­ous
ous sam­ple (Ji­vraj et al., 1995; Ho­lo­wenko et al., 2001), (b) deriv­a­ solu­tion con­tain­ing 4% (w v¡1) Na2CO3 (pH 11.6). The free car­box­
ti­za­tion of the car­boxyl group fol­lowed by high per­for­mance liquid ylic acids were recov­ered from the alka­line solu­tion by acid­i­fy­ing
chro­ma­tog­ra­phy (Yen et al., 2004) or gas chro­ma­tog­ra­phy (Jones with con­cen­trated HCl to pH 2 and extract­ing three times with
et al., 2001) and inte­gra­tion of the result­ing hump of unre­solved 10-mL por­tions of DCM. The com­bined DCM extracts were dried
naph­thenic acids, and (c) pre-con­cen­tra­tion of acids from ­aque­ous under nitro­gen and the res­i­due was trans­ferred to a 2-mL glass
sam­ples fol­lowed by neg­at­ ive-ion elec­tro­spray mass ­anal­y­ses, vial using fresh DCM. The extracts were again taken to dry­ness
mon­i­tor­ing the areas (inten­sity) of selected ions (Head­ley et al., under nitro­gen and then stored at ¡20 °C until deriv­a­ti­za­tion for
2002). GC–MS anal­y­sis.
Mer­lin et al. (2007) described a gas chro­ma­tog­ra­phy–mass
spec­trom­e­try (GC–MS) method to detect naph­thenic acids in 2.2. Deriv­a­ti­za­tion and quan­ti­fi­ca­tion of naph­thenic acids by GC–MS
aque­ous sam­ples. Chlo­ro­form extracts from acid­i­fied sam­ples
were deriv­a­tized to yield t-butyl­di­meth­yl­si­lyl esters of naph­thenic The extracted naph­thenic acids were deriv­a­tized based on the
acids. Recon­structed ion chro­mato­grams for m/z = 267, cor­re­spond­ pro­to­col of Cle­mente et al. (2004) using the N-methyl-N-(t-butyl­di­
ing to the t-butyl­di­meth­yl­si­lyl esters of the C13H22O2-iso­mers (i.e. meth­yl­si­lyl)tri­flu­o­ro­ac­e­ta­mide (MTBSTFA) reagent, which con­tains
n = 13 and Z = ¡4 in the for­mula CnH2n+ZO2) gave a hump that was 1% t-bu­tyl­dim­eth­yl­si­lyl­chlo­ride (Lot 04115TC, Sigma, St. Louis, MO).
indic­a­tive of the pres­ence of naph­thenic acids. Young et al. (2007) The naph­thenic acids were dis­solved in 50 lL of DCM and mixed
used the same approach and GC–MS method to detect naph­thenic with 50 lL of MTBSTFA. The solu­tion was then incu­bated at 60 °C
acids in fish that were exposed to com­mer­cial naph­thenic acids or for 20 min, dried under nitro­gen, and the res­i­due was dis­solved in
OSPW. Despite the high back­ground of nat­u­rally-occur­ring fatty 500 lL of DCM. The t-butyl­di­meth­yl­si­lyl deriv­a­tives were ana­lyzed
acids in fish, mon­i­tor­ing spe­cif­i­cally for the m/z = 267 ion proved by GC–MS as fol­lows.
to be very selec­tive for naph­thenic acids. More recently, Young The instru­ment used was an Ag­i­lent 6890N GC with a model
et al. (2008) devel­oped a GC–MS method to esti­mate the con­cen­ 5973 inert mass selec­tive detec­tor. A 30-m HP-5MS cap­il­lary col­
tra­tions of naph­thenic acids in fish. We have com­bined pro­ce­dures umn (Ag­i­lent) was used with He as the car­rier gas. The GC tem­
from the reports of Mer­lin et al. (2007) and Young et al. (2008) per­a­ture pro­gram was 100 °C for 3 min, 8 °C min¡1 to 300 °C, and,
to develop a method to esti­mate naph­thenic acids con­cen­tra­tions finally, hold­ing at 300 °C for 5 min. The injec­tion port tem­per­a­ture
in aque­ous sam­ples. The results from the newly-adapted GC–MS was 250 °C and the instru­ment was run in sin­gle ion mon­i­tor­ing
method were com­pared to the results for “naph­thenic acids” (SIM) mode for m/z = 267. The dwell time was 100 ms and the
­anal­y­ses by FTIR. res­o­lu­tion was low (peak width 0.7–0.9 amu). Sam­ples (2 lL) of
deriv­a­tized NAs were injected in splitless mode with the splitless
time 2 min. The sur­ro­gate stan­dard, 9-FCA, was cho­sen because
2. Mate­ri­als and meth­ods it yielded a major ion with m/z = 267, and it had a reten­tion time
of about 21 min. The total area of the unre­solved “hump”, cor­re­
2.1. Sources and prep­ar­ a­tion of water sam­ples spond­ing to the t-butyl­di­meth­yl­si­lyl esters of C13H22O2-iso­mers,
elut­ing between approx­i­mately 15.5 and 20.5 min was inte­grated
For this study, water sam­ples were col­lected from 18 loca­ and the area of the 9-FCA peak was also deter­mined. The ratio of
tions within Alberta, Can­ada. These included sam­ples of waters the “hump” area to 9-FCA peak area was then cal­cu­lated and com­
from seven oil sands tail­ings ponds, two SAGD oper­a­tions, six pared to val­ues from a cal­i­bra­tion plot.
riv­ers in the vicin­ity of the oil sands depos­its includ­ing one A cal­i­bra­tion plot for GC–MS was prepared with com­mer­cial
loca­tion upstream of the oil sands oper­a­tions (at Fort McMur­ naph­thenic acids as fol­lows. A con­cen­trated stock solu­tion of
ray), in addi­tion to sam­ples from one river and two domes­tic Mer­i­chem naph­thenic acids was made by dis­solv­ing the acids in
wells located sev­eral hun­dred kilo­me­ters south­west of the oil 100 mM NaOH. The stock solu­tion was then diluted with North Sas­
sands. katch­e­wan River water to yield cal­i­bra­tion stan­dards with con­cen­
Tail­ings pond sam­ples that con­tained sus­pended sol­ids were tra­tions rang­ing from 0 to 0.5 mg naph­thenic acids L¡1 in a final
clar­i­fied by adjust­ing the pH to »10.5 with 2 M NaOH and cen­tri­ vol­ume of 1 L. Each 1-L stan­dard solu­tion was extracted using the
fug­ing at 15000g for 20 min. The super­na­tant was recov­ered and pro­to­col described in Sec­tion 2.1. The recov­ered naph­thenic acids
ana­lyzed. Water sam­ples that were pre­dicted to have naph­thenic were deriv­a­tized and ana­lyzed as described above. The ratio of the
acids con­cen­tra­tions >0.5 mg L¡1 were diluted with dou­bly dis­ unre­solved hump area to the 9-FCA peak area was then plot­ted
tilled H2O to a final con­cen­tra­tion <0.5 mg L¡1 prior to extrac­tion against naph­thenic acids con­cen­tra­tion to gen­er­ate a cal­i­bra­tion
and anal­y­sis by GC–MS or FTIR. Selected sam­ples were spiked with plot.
1260 A.C. Scott et al. / Chemosphere 73 (2008) 1258–1264

2.3. Extrac­tion of free fatty acids and naph­thenic acids from water 3. Results and dis­cus­sion
sam­ples for FTIR
Cur­rently there is no abso­lute ana­lyt­i­cal method for the deter­
In the absence of 9-FCA, each 1-L portion of a water sam­ple mi­na­tion of naph­thenic acids in envi­ron­men­tal sam­ples because
was acid­i­fied to pH 2 with con­cen­trated HCl, then 150 g NaCl was there is no pro­ce­dure that can sep­a­rate each com­pound in a naph­
dis­solved into the sam­ple. Each sam­ple was then extracted with thenic acids mix­ture. Fur­ther­more, authen­tic stan­dards of each
three 60-mL por­tions of chlo­ro­form. The free car­box­ylic acids were of these com­pounds are not avail­able. Thus, for the esti­ma­tion of
recov­ered by extract­ing the chlo­ro­form phase with three 10-mL naph­thenic acids con­cen­tra­tions in aque­ous sam­ples, it is assumed
por­tions of an alka­line aque­ous solu­tion con­tain­ing 4% (w v¡1) (1) that a com­mer­cial mix­ture used to cal­i­brate the method is rep­
Na2CO3 (pH 11.6). Then the free car­box­ylic acids were recov­ered re­sen­ta­tive of the naph­thenic acids in the mix­ture being ana­lyzed,
from the alka­line solu­tion by acid­i­fy­ing with con­cen­trated HCl to (2) that the sol­vent extrac­tion effi­ciency is high and con­sis­tent, and
pH 2 and extract­ing three times with 10-mL por­tions of DCM. The (3) that the response fac­tor of the detec­tor being used is the same
com­bined DCM extracts were dried under nitro­gen and the res­i­due for all of the com­pounds in the mix­ture. In addi­tion, if a deriv­a­ti­za­
was trans­ferred to a glass vial using fresh DCM. The dis­solved car­ tion reac­tion is used, it is assumed that the effi­ciency of the deriv­a­
box­ylic acids were again dried under nitro­gen and then dis­solved ti­za­tion is the same for all com­pounds in the com­mer­cial mix­ture
in 5 mL DCM and stored at 4 °C prior to anal­y­sis of the DCM solu­ used to cal­i­brate the method and for all of the com­pounds in the
tions by FTIR as described below. sam­ple being ana­lyzed. In the indus­trial stan­dard FTIR method,
naph­thenic acids from Kodak (East­man Kodak Com­pany, Roches­
2.4. FTIR quan­ti­fi­ca­tion of naph­thenic acids ter, NY) are typ­i­cally used for cal­i­bra­tion (Ji­vraj et al., 1995; Ho­lo­
wenko et al., 2001). How­ever, Scott et al. (2005) dem­on­strated that
FTIR quan­ti­fic­ a­tion of naph­thenic acids was done by the the esti­mated naph­thenic acids con­cen­tra­tion in two OS­PWs was
­ na­lyt­i­cal and Instru­men­ta­tion Lab­o­ra­tory (Depart­ment of Chem­
A influ­enced by which com­mer­cial naph­thenic acids prep­a­ra­tion
is­try, Uni­ver­sity of Alberta) using the method devel­oped by Ji­vraj was used for cal­i­bra­tion of an HPLC method. For our study, Mer­i­
et al. (1995). The instru­ment was a Thermo Nico­let Magna 760 chem refined naph­thenic acids were used to cal­i­brate the FTIR and
FTIR oper­ated in trans­mis­sion mode. Om­nic Soft­ware (ver­sion 7.1) GC–MS meth­ods.
was used to acquire and pro­cess the spec­tra. The base­line used In their liquid or solid states, most car­box­ylic acids exist as
for the peak height mea­sure­ments was from 1900 to 1513 cm¡1. a dimer due to hydro­gen bond­ing between neigh­bor­ing COOH
The absor­bances at 1743 and 1705 cm¡1 were summed. For each groups (Lin-Vien et al., 1991). The dimer gives a sin­gle, sharp,
spec­trum, 64 co-added scans were obtained. The sol­vent (DCM) intense CO stretch band near 1700 cm¡1. For exam­ple, cast film FTIR
back­ground used for all spec­tra was obtained using 64 scans. anal­y­sis of the Mer­i­chem naph­thenic acids gives a strong band at
The spec­tral res­ol­ u­tion was 4 cm¡1 and the spec­tral range was 1708 cm¡1 (data not shown). How­ever, in dilute solu­tions, an equi­
4000–400 cm¡1. The path­length of the var­ia ­ ble path­length liquid lib­rium exists between mono­mers and hydro­gen-bonded dimers.
cell was 3.0 mm. The bench was purged con­tin­u­ously with dry N2 The mono­mer CO stretch band is at a higher fre­quency than that
and was allowed to re-estab­lish the purge for 3 min after a sam­ of the dimer. In our dilute DCM solu­tions of naph­thenic acids, the
ple was placed within the sam­ple com­part­ment and before the mono­mer absorbs at 1743 cm¡1 whereas the dimer absorbs at
spec­trum was obtained. 1705 cm¡1 (Fig. 1). In the prep­a­ra­tion of cal­i­bra­tion plots for the
Naph­thenic acids in sam­ples were quan­ti­fied based on com­ FTIR anal­y­ses, the peak heights at 1743 cm¡1 and 1705 cm¡1 are
par­i­son to a cal­i­bra­tion plot prepared as fol­lows: a con­cen­trated summed (Ji­vraj et al., 1995; Ho­lo­wenko et al., 2001) to account for
stock solu­tion of Mer­i­chem naph­thenic acids was made by dis­ the con­tri­bu­tions of both the mono­mers and the dimers pres­ent
solv­ing the acids in DCM. Ali­quots of the stock solu­tion were then at equi­lib­rium.
diluted with DCM to yield cal­ib ­ ra­tion stan­dards with con­cen­tra­ When apply­ing our cal­i­bra­tion plots for the GC–MS anal­y­
tions rang­ing from 0 to 300 mg naph­thenic acids L¡1 in a final ses of naph­thenic acids, it was also assumed that quan­ti­fy­ing the
vol­ume of 5 mL DCM. The stan­dards were ana­lyzed in the same C13H22O2-iso­mers would be rep­re­sen­ta­tive of all of the iso­mer
man­ner described above and the peak heights at 1743 cm¡1 (for clas­ses of naph­thenic acids from the oil sands. For this to be true,
mono­mers) and 1705 cm¡1 (for hydro­gen-bonded dimers) were the pro­por­tion of the C13H22O2-iso­mers in the Mer­i­chem mix­ture
summed and graphed ver­sus naph­thenic acids con­cen­tra­tions in used for the cal­i­bra­tion plot should be the same as the pro­por­
the stan­dards. tion of C13H22O2-iso­mers in the oil sands naph­thenic acids. From
data pre­sented by Ba­tai­neh et al. (2006), we cal­cu­lated that the
2.5. Anal­y­ses of free fatty acids in river water sam­ples

The method used for the extrac­tion of naph­thenic acids also

0.16 T
extracts nat­u­rally-occur­ring free fatty acids from water sam­ples.
Preliminary GC–MS anal­y­ses of the deriv­at­ ized extracts from M
0.12
Absorbance

some river water sam­ples showed the pres­ence of free fatty acids.
Do­deca­noic (C12), tet­ra­deca­noic (C14), hexa­deca­noic (C16), and oleic
0.08 S
(C18:1) acids were pur­chased from Sigma–Aldrich, and octa­de­ca­noic
(C18) acid was pur­chased from BDH Chem­i­cal Ltd. (Poole, England). 0.04 R
Cal­i­bra­tion plots were prepared by de­riv­atiz­ing these stan­dards
with MTBSTFA. The deriv­a­tized extracts of the river water sam­ples 0.00
obtained from sites within the oil sands region (exclud­ing the Fort 1850 1800 1750 1700 1650
McMur­ray site) were then rean­al­ yzed by GC–MS using full scan Wavenumber (cm -1)
mode. Peak inten­si­ties cor­re­spond­ing to these fatty acids were
com­pared with the cal­i­bra­tion plot to deter­mine their con­cen­tra­ Fig. 1. FTIR spec­tra of extracts from tail­ings water (T) from com­pany C, Mer­i­chem
naph­thenic acids (M), SAGD water (S) from com­pany C, and Ath­aba­sca River water
tion in the waters. In cases where fatty acids eluted with an unre­ (R) from near two oil sands com­pa­nies. In the dilute DCM solu­tions ana­lyzed by
solved com­plex mix­ture, the base­line was adjusted to inte­grate FTIR, the mono­mers of the car­box­ylic acids absorb at 1743 cm¡1 and the hydro­gen-
only the fatty acid peaks. bonded dimers absorb at 1705 cm¡1.
 A.C. Scott et al. / Chemosphere 73 (2008) 1258–1264 1261

C13H22O2-iso­mers com­prise 8.6% of the naph­thenic acids in the Table 1

Mer­i­chem prep­a­ra­tion. Han et al. (2008) ana­lyzed a water sam­ple Results from GC–MS and FTIR anal­y­ses of sam­ples from sur­face and ground waters
col­lected from loca­tions that are dis­tant from the oil sands oper­a­tions
from the West In-Pit at Syn­crude Can­ada Ltd. (one of the oil sands
com­pa­nies), and our cal­cu­la­tions with their data showed that the Sam­ple Naph­thenic acids “Naph­thenic acids” Ratio: FTIR/
by GC–MS (mg L¡1) by FTIR (mg L¡1) GC–MS
C13H22O2-iso­mers accounted for 7.9% of the com­pounds with the
for­mula CnH2n+ZO2. Although only a lim­ited amount of HPLC-QTOF/ North Sas­katch­e­wan <0.01 0.14 >14
Rivera
MS data is avail­able in the lit­er­at­ ure, it indi­cates that the C13H22O2-
N. Sas­katch­e­wan <0.01 0.20 >20
iso­mers com­prise about 8% of the total naph­thenic acids in both River + 2 mg FAs L¡1
the Mer­i­chem prep­a­ra­tion and the West In-Pit waters. Thus, cal­ N. Sas­katch­e­wan 0.10 0.18 1.8
i­bra­tion plots gen­er­ated from the Mer­ic­ hem prep­ar­ a­tion should River + 0.1 mg MNAs L¡1
be suit­able for esti­mat­ing the con­cen­tra­tions of naph­thenic acids Ath­aba­sca Riverb <0.01 0.29 ± 0.08c >29
Ath­aba­sca River + 2 mg <0.01 0.20 >20
from oil sands sources. FAs L¡1
If the true pro­por­tion of the C13H22O2-iso­mers in the sam­ple Ath­aba­sca River + 0.1 mg 0.11 0.33 3
is <8%, the GC–MS method will under­es­ti­mate the con­cen­tra­tion MNAs L¡1
of naph­thenic acids, and if the true pro­por­tion of the C13H22O2- Domes­tic well #12d 0.13 ± 0.05c 0.99 ± 0.3c 7.6
Well #12 + 0.1 mg 0.31 1.2 3.8
iso­mers in the sam­ple is >8%, the GC–MS method will over­es­ti­
MNAs L¡1
mate the con­cen­tra­tion of naph­thenic acids. In essence, if the Domes­tic well #13d 0.025 ± 0.007c 0.3 12
true pro­por­tion of C13H22O2-iso­mers was known, a more accu­rate Well #13 + 0.1 mg 0.12 0.33 2.6
esti­ma­tion of the naph­thenic acids con­cen­tra­tion could be made MNAs L¡1
by mul­ti­ply­ing the con­cen­tra­tion deter­mined based on the Mer­i­ Some sam­ples were spiked with Mer­ic­ hem naph­thenic acids (MNAs) or ref­er­ence
chem naph­thenic acids by the ratio of 8% divided by the true per­ ful­vic acids (FAs) before extrac­tion and anal­y­sis.
a
At Ed­mon­ton – about 450 km away from the oil sands oper­a­tions.
cent­age of C13H22O2-iso­mers. For exam­ple, if the con­cen­tra­tion of b
At Fort McMur­ray – about 30 km upstream of oil sands oper­a­tions.
naph­thenic acids was mea­sured to be 100 mg L¡1 by the GC–MS c
Mean of three rep­li­cates ± one stan­dard devi­a­tion.
method, and the true per­cent­age of C13H22O2-iso­mers was 10%, a d
Near Ed­mon­ton – described by Mer­lin et al. (2007).
bet­ter esti­mate of the con­cen­tra­tion would be 80 mg L¡1.
Deter­min­ing the true per­cent­age of C13H22O2-iso­mers can­not
be done using the GC–MS method described in this paper, as was
dem­on­strated by Ba­tai­neh et al. (2006). High res­o­lu­tion MS anal­y­ con­cen­tra­tion deter­mined by FTIR anal­y­ses (Table 1). The addi­tion
ses, used by Ba­tai­neh et al. (2006), would be required to deter­mine of 0.1 mg of com­mer­cial naph­thenic acids L¡1 to these two river
the per­cent­age of C13H22O2-iso­mers. The dis­cus­sion pre­sented in water sam­ples yielded 0.04 mg L¡1 increases in the “naph­thenic
the pre­ced­ing par­a­graph is pro­vided to give a sense of the uncer­ acids” con­cen­tra­tions, based on FTIR (Table 1), equiv­a­lent to 40%
tainty in the anal­y­ses using the Mer­i­chem naph­thenic acids as stan­ of the expected increases.
dards, and assum­ing that the C13H22O2-iso­mers make up 8% of the Based on GC–MS anal­y­ses, Mer­lin et al. (2007) detected naph­
sam­ples exam­ined in this study. thenic acids in waters from two domes­tic wells near Ed­mon­ton.
These wells were sam­pled and ana­lyzed dur­ing the cur­rent study
3.1. Anal­y­ses of water sam­ples from loca­tions dis­tant from the oil in order to esti­mate the naph­thenic acids con­cen­tra­tion. GC–MS
sands anal­y­ses of trip­li­cate sam­ples of the water from well #12 gave
a mean naph­thenic acids con­cen­tra­tion of 0.13 mg L¡1 with a
Preliminary GC–MS SIM (m/z = 267) anal­y­sis of North Sas­katch­ stan­dard devi­a­tion of 0.05 mg L¡1 (Table 1). Sim­i­larly, for water
e­wan River water showed no dis­cern­able hump cor­re­spond­ing to from well #13, the mean and stan­dard devi­a­tion were 0.025 and
naph­thenic acids. Thus, var­i­ous con­cen­tra­tions of Mer­ic­ hem naph­ 0.007 mg L¡1, respec­tively (Table 1). Spik­ing these sam­ples with
thenic acids (0–0.5 mg L¡1) were added to water from this source 0.1 mg of Mer­i­chem acids L¡1 increased the con­cen­tra­tions deter­
to pre­pare a cal­i­bra­tion plot for GC–MS. These deriv­at­ ized stan­ mined by GC–MS by 0.18 mg L¡1 for well #12, and 0.095 mg L¡1 for
dards were ana­lyzed each time a set of extracted sam­ples was ana­ well #13. These increases were 180% and 95%, respec­tively, of the
lyzed, and the seven-point cal­i­bra­tion was lin­ear, giv­ing R2 val­ues expected val­ues.
>0.99. The limit of detec­tion with the GC–MS method was approx­i­ The “naph­thenic acids” con­cen­tra­tions in the well waters deter­
mately 0.01 mg naph­thenic acids L¡1 when a 1-L water sam­ple was mined by FTIR were again higher than those mea­sured by GC–MS
extracted. (Table 1). By FTIR the con­cen­tra­tions were 0.99 and 0.3 mg L¡1
GC–MS anal­y­ses of extracts of North Sas­katch­e­wan River for wells #12 and #13, respec­tively. Spik­ing these sam­ples with
water and the Ath­aba­sca River water (col­lected at Fort McMur­ 0.1 mg of Mer­i­chem acids L¡1 increased the “naph­thenic acids”
ray, upstream of the oil sands oper­a­tions) gave naph­thenic acids con­cen­tra­tions by 0.21 mg L¡1 for well #12, and 0.03 mg L¡1 for
con­cen­tra­tions of <0.1 mg L¡1 (Table 1). When 1-L sam­ples of well #13, which were 210% and 30%, respec­tively, of the expected
these waters were spiked with 2 mg of ful­vic acids, there was val­ues.
no increase in the naph­thenic acids con­cen­tra­tion based on Based on the results from the four sam­ples that were spiked
GC–MS anal­y­ses (Table 1). How­ever, when 1-L sam­ples of these with 0.1 mg Mer­i­chem naph­thenic acids L¡1 (Table 1), the median
waters were spiked with 0.1 mg of Mer­i­chem naph­thenic acids, recov­ery by the GC–MS method was 105%, with a range of 95–180%.
the GC–MS anal­y­ses gave results of 0.10 and 0.11 mg naph­thenic This was supe­rior to the FTIR method which gave a median recov­
acids L¡1 for the North Sas­katch­e­wan and Ath­aba­sca River waters, ery of 49%, with a range of 30–210%.
respec­tively (Table 1). These were 100% and 110% of the expected In each case shown in Table 1, the FTIR method gave higher con­
­val­ues. cen­tra­tions than the GC–MS method, as illus­trated by the ratio of
The con­cen­tra­tions of “naph­thenic acids” mea­sured by the FTIR FTIR/GC–MS con­cen­tra­tions. Because the GC–MS method detected
method were higher than the con­cen­tra­tions mea­sured by GC–MS. no naph­thenic acids in the North Sas­katch­e­wan River or Ath­aba­
For exam­ple, the val­ues from FTIR were 0.14 and 0.28 mg L¡1 in the sca River water sam­ples, the ratios are reported as >14 and >28,
waters from the North Sas­katch­e­wan and Ath­aba­sca Riv­ers, respec­ respec­tively. How­ever, when these sam­ples were spiked with a
tively (Table 1). Spik­ing 1-L por­tions of these river waters with 2 g mea­sur­able amount of Mer­i­chem naph­thenic acids, these ratios
of ful­vic acids gave no marked change to the “naph­thenic acids” were decreased to 1.8 and 3, respec­tively.
1262 A.C. Scott et al. / Chemosphere 73 (2008) 1258–1264

Table 2 Table 3
Results from GC–MS and FTIR anal­y­ses of sam­ples from the Ath­aba­sca River and its Results from GC–MS and FTIR anal­y­ses of water sam­ples from sources at four oil
trib­u­tar­ies in the area of the oil sands depos­its sands com­pa­nies (A to D)

Sam­ple Total free fatty Naph­thenic “Naph­thenic Ratio: FTIR/ Sam­ple Naph­thenic acids “Naph­thenic Ratio: FTIR/
acidsa (mg L¡1) acids by GC–MS acids” by FTIR GC–MS by GC–MS (mg L¡1) acids” by FTIR GC–MS
(mg L¡1) (mg L¡1) (mg L¡1)
Ath­aba­sca 0.003 <0.01 0.26 >26 A – fresh water res­er­voir 0.099 ± 0.045a 0.53 ± 0.06a 5.4
Riverb A – tail­ings pond I 17 45 2.6
Jack­pine 0.002 <0.01 0.43 >43 A – tail­ings pond II 6.4 25 3.9
Creek A – aged tail­ings water 2.9 11 3.8
Ells River 0.005 <0.01 0.45 >45 B – tail­ings pond (2004)b 4.0 17 4.2
Mus­keg River 0.004 0.014 0.57 40 B – tail­ings pond (2007)b 12 34 2.8
Mac­kay River 0.012 <0.01 0.55 >54 C – CT pondc 4.9 18 3.7
a
Sum of the C12, C14, C16, C18, and C18:1 fatty acids. C – tail­ings pond 53 ± 15a 78 ± 1.5a 1.5
b
Sam­ple taken down­stream of two oil sands pro­cess­ing plants. C – SAGD 21 120 5.7
D – SAGD 110 ± 57d 100 0.91
a
Mean of three rep­li­cates ± one stan­dard devi­a­tion.
b
3.2. Anal­y­ses of nat­ur­ al water sam­ples from loca­tions near the oil Sam­ples from the same tail­ings pond taken in dif­fer­ent years.
c
sands CT = con­sol­i­dated or com­pos­ite tail­ings.
d
Mean of two rep­li­cates ± one stan­dard devi­a­tion.

Many riv­ers and creeks flow through the area of the oil sands
depos­its. In some cases, the oil sands are exposed in the river extrac­tion pro­cess. The mean con­cen­tra­tions were 0.099 mg L¡1 by
banks, and sus­cep­ti­ble to ero­sion and dis­so­lu­tion of mate­ri­als from GC–MS and 0.53 mg L¡1 by FTIR. The lat­ter value is in the range of
the oil sands into the river (Head­ley et al., 2001). Five nat­u­ral flow­ “naph­thenic acids” found in sur­face waters in the vicin­ity of the oil
ing waters were sam­pled from var­i­ous loca­tions within the region sands (Table 2).
of the oil sands depos­its, upstream of cur­rent min­ing oper­a­tions The “naph­thenic acids” con­cen­tra­tions deter­mined by FTIR
(Young et al., 2008). Extracts of these sam­ples were ana­lyzed by ranged from 11 to 110 mg L¡1 in all of the sam­pled tail­ings waters
GC–MS and FTIR (Table 2). Naph­thenic acids con­cen­tra­tions in four and the SAGD waters (Table 3). These val­ues are con­sis­tent with
of the sam­ples were below the limit of detec­tion by the GC–MS pre­vi­ous val­ues based on FTIR of tail­ings waters (Cle­mente and
method. That is, no hump from ions with m/z = 267 was detected in Fe­do­rak, 2005). Both the GC–MS and FTIR meth­ods showed that
the extracts of these four sam­ples. the low­est con­cen­tra­tion was found in an aged tail­ings water sam­
FTIR anal­y­ses of extracts of the same five sam­ples mea­sured ple. Sch­ramm et al. (2000) also reported that “naph­thenic acids”
“naph­thenic acids” con­cen­tra­tions between 0.26 and 0.57 mg L¡1 con­cen­tra­tions decreased with nat­u­ral aging. The high­est con­
(Table 2), based on the absorp­tion of car­boxyl groups. These con­ cen­tra­tions from FTIR anal­y­ses were found in the SAGD waters.
cen­tra­tions fell within the range of about 0.1–0.9 mg L¡1 reported Although Jen­nings and Sha­ikh (2007) observed organic acids and
by Sch­ramm et al. (2000) who quan­ti­fied the “naph­thenic acids” salts of organic acids in heat exchang­ers used in the SAGD pro­cess,
in eleven Ath­aba­sca River water sam­ples col­lected from 100 km to our knowl­edge, this is the first report of “naph­thenic acids” con­
upstream of Fort McMur­ray to the delta of Lake Ath­aba­sca. Thus, cen­tra­tions in SAGD waters.
although our extrac­tion method was dif­fer­ent than the oil sands In all but one case, the GC–MS method yielded lower con­cen­tra­
indus­try stan­dard method (Ji­vraj et al., 1995; Ho­lo­wenko et al., tions than the FTIR method (Table 3), and the ratios of FTIR/GC–MS
2001), the “naph­thenic acids” con­cen­tra­tions in Table 2 agree with con­cen­tra­tions were all <5.7 (Table 3). These ratios were mark­edly
the results of Sch­ramm et al. (2000). As was observed with the lower than those for the river water sam­ples (Tables 1 and 2), sug­
river waters in Table 1, the FTIR method gave higher con­cen­tra­ gest­ing that the use of this ratio is a good indi­ca­tor of the pres­ence
tions than the GC–MS method (Table 2). The ratios of FTIR/GC–MS of com­pounds with the for­mula CnH2n+ZO2.
con­cen­tra­tions were >26 (Table 2).
GC–MS anal­y­ses were done to quan­tify the five most abun­dant 3.4. The future of OSPW and ana­lyt­ic­ al chal­lenges
free fatty acids in waters from the sam­ples listed in Table 2, as well
as in sam­ples from the North Sas­katch­e­wan River and the Ath­aba­ After the indus­trial activ­i­ties in the oil sands region con­clude,
sca River (upstream of the oil sands oper­a­tions). The total con­cen­ the envi­ron­ment that has been dis­turbed by the min­ing and extrac­
tra­tions of these free fatty acids ranged from 0.001 mg L¡1 in both tion pro­cesses must be reclaimed. As part of the rec­la­ma­tion, the
the Ath­aba­sca River (upstream of the oil sands oper­a­tions) and tox­ic­ity of OSPW must be mit­i­gated and the con­tents of the vast
the North Sas­katch­e­wan River, to 0.012 mg L¡1 in the Mac­kay River tail­ings ponds must be able to sup­port via­ble eco­sys­tems. Even­
sam­ple. Data on free fatty acid con­tent in fresh waters is scarce, tu­ally, these waters may be released to nat­u­ral water-courses in
how­ever Fat­oki and Ver­non (1989) reported free fatty acids con­cen­ the region. The “naph­thenic acids” con­tent of OSPW is the major
tra­tion between 0.022 and 0.165 mg L¡1 in sam­ples from three riv­ com­po­nent asso­ci­ated with tox­ic­ity (Nero et al., 2006; Peters et al.,
ers in the United King­dom. The con­cen­tra­tions that we found were 2007). How­ever, there are still major chal­lenges in under­stand­ing
lower than those reported by Fat­oki and Ver­non (1989). The free the make-up of “naph­thenic acids” and their tox­ic­ity. For exam­ple,
fatty acids con­cen­tra­tions in Table 2 rep­re­sent only 0.4–2.2% of Ba­tai­neh et al. (2006) dem­on­strated the pres­ence of hydroxy-naph­
the “naph­thenic acids” that could be detected by the FTIR method. thenic acids in OSPW using cap­il­lary HPLC/QTOF-MS and GC-high
Thus, these nat­u­rally-occur­ring free fatty acids are not major com­ res­o­lu­tion MS. In addi­tion to the reac­tive hydro­gen atom on the
po­nents of the “naph­thenic acids” in these sur­face water sam­ples. car­boxyl group, hydroxy-naph­thenic acids have a reac­tive hydro­
gen atom on the hydroxyl group. Both of these reac­tive hydro­gen
3.3. Anal­y­ses of water sam­ples from oil sands com­pa­nies atoms react with MTBSTFA yield­ing a di(t-butyl­di­meth­yl­si­lyl)
ester. Cle­mente et al. (2004) illus­trated how the pres­ence of this
Ten water sam­ples were col­lected from four oil sands com­ sec­ond reac­tive hydro­gen atom leads to a 130-amu increase in the
pa­nies, and Table 3 sum­ma­rizes the GC–MS and FTIR anal­y­ses of molec­u­lar mass as a result of the addi­tion of the sec­ond t-butyl­di­
these sam­ples. The low­est con­cen­tra­tions were found in a fresh meth­yl­si­lyl group. GC-low res­o­lu­tion MS (as used in the cur­rent
water res­er­voir that is used to col­lect and store water for use in the study) can­not dis­tin­guish between di(t-butyl­di­meth­yl­si­lyl) esters
 A.C. Scott et al. / Chemosphere 73 (2008) 1258–1264 1263

of hydroxy-naph­thenic acids and the mono t-butyl­di­meth­yl­si­lyl were actu­ally in the river water sam­ples (i.e. in sam­ples spiked
esters of higher molec­u­lar mass naph­thenic acids. For instance, with Mer­i­chem naph­thenic acids) the ratios fell to 1.8 and 3 (Table
after deriv­a­ti­za­tion with MTBSTFA, the di(t-butyl­di­meth­yl­si­lyl) 1). These were closer to the range of ratios (0.91–5.7) observed
esters hydroxy-naph­thenic acids with n = 13 and Z = ¡4, can­not with OSPW sam­ples (Table 3).
be dis­tin­guished from the t-butyl­di­meth­yl­si­lyl esters naph­thenic The devel­op­ment and val­i­da­tion of ana­lyt­i­cal meth­ods for
acids with n = 24 and Z = 0 using GC-low res­ol­ u­tion MS (Cle­mente study­ing naph­thenic acids con­tin­ues to be a for­mi­da­ble chal­lenge.
et al., 2004). GC-high res­o­lu­tion MS can dis­tin­guish between The results pre­sented in this paper show that the FTIR method is
MTBSTFA-deriv­a­tized hydroxy-naph­thenic acids and MTBSTFA- rea­son­able for the anal­y­sis of OSPW, but it appears to over­es­ti­mate
deriv­a­tized naph­thenic acids (Ba­tai­neh et al., 2006). Hydroxy- the naph­thenic acids in river waters. This will pres­ent a major prob­
naph­thenic acids con­tain three oxy­gen atoms and fit the for­mula lem for mon­i­tor­ing or reg­u­lat­ing naph­thenic acids con­cen­tra­tions
CnH2n+ZO3, rather than CnH2n+ZO2. These can be dis­tin­guished by in nat­u­ral water sys­tems. Although the GC–MS method described
cap­il­lary HPLC/QTOF-MS (Ba­tai­neh et al., 2006) or by neg­a­tive-ion here has its lim­i­ta­tions, the spec­i­fic­ity of the method makes it more
elec­tro­spray high-field Fou­rier trans­form ion cyclo­tron res­o­nance suit­able than the FTIR method for mea­sur­ing naph­thenic acids in
mass spec­trom­e­try (Qian et al., 2001). nat­u­ral water sys­tems. None­the­less, the ideal method for char­ac­ter­
The hydroxy-naph­thenic acids are mea­sured as “naph­thenic iz­ing and quan­ti­fy­ing the toxic organic acids in OSPW and nearby
acids” by the FTIR method, but are not quan­ti­fied by our more river waters remains to be devel­oped.
selec­tive GC–MS method that mon­i­tors the m/z = 267 ions. The dif­
fer­ences between the results from the GC–MS and the FTIR method Acknowl­edge­ments
shown in Table 3 are likely due, in part, to hydroxy-naph­thenic
acids. At pres­ent, there is no ana­lyt­i­cal method avail­able to spe­cif­i­ Fund­ing was pro­vided by the Cana­dian Water Net­work and
cally quan­tify the hydroxy-naph­thenic acids, nor is there any infor­ NSERC. We thank W. Mof­fat for the FTIR anal­y­ses and valu­able dis­
ma­tion on whether the hydroxy-naph­thenic acids are more or less cus­sions dur­ing the prep­a­ra­tion of the man­u­script. We also thank
toxic to aquatic life than naph­thenic acids. J. Hop­ping for pro­vid­ing the Ath­aba­sca River water (Fort McMur­ray
OSPW con­tains a myr­iad of com­pounds, includ­ing poly­cy­clic sam­ple), and D. Coy and S. Ebert for pro­vid­ing the domes­tic well
aro­matic hydro­car­bons. How­ever, because naph­thenic acids are water sam­ples. We also acknowl­edge the will­ing­ness of oil sands
much more water sol­u­ble than hydro­car­bons, these acids are excel­ com­pa­nies to sup­ply sam­ples of OSPW and we thank F. Kuz­mic for
lent indi­ca­tors of OSPW seep­age into waters courses. It is now col­lect­ing river sam­ples in the oil sands area.
clear that reg­ul­ a­tory agen­cies will stip­u­late that naph­thenic acids
be mon­i­tored as a key indi­ca­tor of OSPW in receiv­ing waters near Ref­er­ences
the oil sands oper­a­tions. Thus, an accu­rate, sen­si­tive, and spe­cific
method for ana­lyz­ing naph­thenic acids must be devel­oped. Ba­tai­neh, M., Scott, A.C., Fe­do­rak, P.M., Mar­tin, J.W., 2006. Cap­il­lary HPLC/QTOF-MS
Some of the cur­rent tail­ings ponds are adja­cent to riv­ers and for char­ac­ter­iz­ing com­plex naph­thenic acids mix­tures and their micro­bial trans­
for­ma­tions. Anal. Chem. 78, 8354–8361.
there is a pos­si­bil­ity of OSPW seep­age into the riv­ers. Thus, many Bri­ent, J.A., Wess­ner, P.J., Doyle, M.N., 1995. Naph­thenic acids. In: Kro­sch­witz, J.I.
of the riv­ers in the oil sands region are mon­i­tored for “naph­thenic (Ed.), Ency­clo­pe­dia of Chem­i­cal Tech­nol­ogy., fourth ed. John Wiley & Sons, New
acids” using the FTIR method (RAMP, 2007). A sam­ple size of only York, pp. 1017–1029.
But­ler, R., 2001. Appli­ca­tion of SAGD, related pro­cesses grow­ing in Can­ada. Oil Gas
50 mL is used by com­mer­cial lab­o­ra­to­ries for this anal­y­sis, and the J. 99 (20), 74–78.
detec­tion limit is 1 mg L¡1. Thus, most of the “naph­thenic acids” Cle­mente, J.S., Fe­do­rak, P.M., 2005. A review of the occur­rence, anal­y­ses, tox­ic­ity,
con­cen­tra­tions reported by RAMP (2007) are given as <1 mg L¡1. and bio­deg­ra­da­tion of naph­thenic acids. Che­mo­sphere 60, 585–600.
Cle­mente, J.S., MacK­in­non, M.D., Fe­do­rak, P.M., 2004. Aer­o­bic bio­deg­ra­da­tion of
The 1-L sam­ples of river waters used in this study per­mit­ted a two com­mer­cial naph­thenic acids prep­a­ra­tions. Envi­ron. Sci. Tech­nol. 38,
bet­ter esti­mate of the “naph­thenic acids” con­cen­tra­tions (Table 1009–1016.
2) and, even with this large sam­ple vol­ume, no naph­thenic acids Fat­oki, O.S., Ver­non, F., 1989. Deter­mi­na­tion of free fatty acid con­tent of pol­luted
and unpol­luted waters. Water Res. 23, 123–125.
were detected four of the five waters sam­ples ana­lyzed by GC–MS Han, X., Scott, A.C., Fe­do­rak, P.M., Ba­tai­neh, M., Mar­tin, J.W., 2008. Influ­ence of
(Table 2). molec­u­lar struc­ture on the bio­de­grad­abil­ity of naph­thenic acids. Envi­ron. Sci.
Fig. 1 com­pares the FTIR spec­tra of extracts from sam­ples of tail­ Tech­nol. 42, 1290–1295.
Head­ley, J.V., Akre, C., Con­ly, F.M., Peru, K.M., Dick­son, L.C., 2001. Preliminary char­ac­
ings water and SAGD water with those of Mer­ic­ hem acids and the
ter­iza­tion and source assess­ment of PAHs in trib­u­tary sed­i­ments of the Ath­aba­
Ath­aba­sca River (col­lected down­stream of two oil sands pro­cess­ sca River, Can­ada. Envi­ron. Foren­sics 2, 335–345.
ing plants). The spec­tra for the tail­ings and SAGD waters clearly Head­ley, J.V., Peru, K.M., McMar­tin, D.W., Win­kler, M., 2002. Deter­mi­na­tion of dis­
show peak absor­bances at 1743 and 1705 cm¡1, which are char­ac­ solved naph­thenic acids in nat­u­ral waters by using neg­a­tive-ion elec­tro­spray
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