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METHODS FOR THE ASSESSMENT OF AQUEOUS
ORGANIC MATERIALS
David W. Schnare Russel 1 F. Christman F rede r i c K, Pfaender
Department o f Environmental Sciences & Engineer ing U n i v e r s i t y o f Nor th Ca ro l i na a t Chapel H i l l
Chapel H i 11, Nor th Caro l i n a 27514
The work upon which t h i s p u b l i c a t i o n i s based was supported i n p a r t by funds p rov ided by t he O f f i c e o f Water Research and Technology, U. S. Department o f t h e I n t e r i o r , Washington, D. C., th rough t h e Water Resources Research I n s t i t u t e of The U n i v e r s i t y o f Nor th Caro l ina , as au tho r i zed by t h e Water Research and Development A c t o f 1978.
P r o j e c t No. A-087-NC
Agreement No. 14-34-0001-7070
DISCLAIMER STATEMEIVT
Contents o f t h i s publication do not necessarily r e f l e c t the views and pol ic ies of the Off ice of Water Research and Technology, U. S. Department of the In ter ior , nor does mention of trade names or commercial products cons t i tu te t h e i r endorse- ment or recommendation for use by the U. S. Government.
TABLE OF CONTENTS
Page
ABSTRACT ......................................................... i i i ACKNOWLEDGEMENTS ................................................ i v
LIST OF FIGURES ................................................. v
LIST OF TABLES ................................................... v i
SUMMARY AND CONCLUSIONS ......................................... v i i
................................................. RECOMMENDATIONS i x
INTRODUCTION .................................................... 1
SECTION ONE . W Discuss ion o f Cur ren t A n a l y t i c a l P rac t i ces ...... 3
Detec t ion Technologies ..................................... 3 E x t r a c t i o n Schemes ......................................... 9 D i f f e r e n t i a t i o n by S ize and Weight ......................... 21 ......................... Concentrat ion Methods ... ......... 22 F r a c t i o n a t i o n Schemes ...................................... 25 Summary .................................................... 32
SECTION TWO . M a t e r i a l s and Methods ............................. 33
Experimental Design ........................................ 33 Equipment and M a t e r i a l s .................................... 33 Experimental Procedures .................................... 46 Caro l ina Method ............................................ 50
SECTION THREE . Resul ts and Discuss ion .......................... 55
E x t r a c t i o n o f So lu tes f rom Water ........................... 55 Desorpt ion o f Solutes f rom the Resin ....................... 61 Concentrat ion o f Solutes by Sol ven t Evaporat ion ............ 65
REFERENCES ...................................................... 74
APPENDIX A
A Top ica l B ib l i og raphy ..................................... 70
ABSTRACT
Methods f o r t he Assessment o f Aqueous Organic Ma te r i a l s
XAD res ins have been evaluated w i t h a range o f known organic compounds
f o r poss ib le use i n a f r a c t i o n a t i o n method in tended t o comprehensively
analyze the organic contaminants present i n water. Among the parameters
i nves t i ga ted are the e f f e c t s on the e x t r a c t i o n e f f i c i ency of s o l u t e
p o l a r i t y , f l o w r a t e , pH, e l u t i o n so lven t , and the conta iner i n which the
e x t r a c t i o n and e l u t i o n a re c a r r i e d out . These s tud ies p rov ide a bas is f o r
a suggested procedure us ing XAD res ins t h a t can be r a p i d and e f f i c i e n t f o r
i s o l a t i n g a wide range o f mon-vo la t i le contaminants from water.
Using t h i s method, h igh recover ies a l l o w i s o l a t i o n and recovery of
organics i n i t i a l l y present i n sub p a r t per b i l l i o n concentrat ions. Futher-
more, water samples can be ex t rac ted i n t he f i e l d . E x t r a c t i o n o f water and
e l u t i o n o f the r e s i n can take p lace i n a s i n g l e vessel, which e l im ina tes
many handl ing and concent ra t ion problems a t tendant w i t h carbon adsorp t ion
methods. The batch desorpt ion c h a r a c t e r i s t i c a l lows f o r g rea te r recover ies,
and s p i k i n g o f the desorp t ion so l ven t can prov ide an i n t e r n a l standard
which a ids accurate and reproduc ib le quant i t a t i o n , two s i g n i f i c a n t improve-
ments over o t h e r suggested r e s i n methods. This method prov ides a s o l u t i o n
o f n o n - v o l a t i l e organics i n concentrat ions necessary f o r GLC o r GC/MS
i d e n t i f i c a t i o n and quant i t a t i o n .
iii
Acknowledgements
The research data presented i n t h i s r e p o r t i s based on t h e d i sse r ta -
t i o n o f David W. Schnare submit ted as p a r t i a l f u l f i l l m e n t o f t h e requ i re -
ments o f the MSPH degree i n t h e Department o f Environmental Sciences and
Engineering. This work was conducted under t he d i r e c t i o n o f D r . R. F.
Christman. Dr. Schnare i s p resen t l y associated w i t h t he Environmental
P ro tec t i on Agencies O f f i c e o f D r i nk ing Water i n Washington, D.C.
LIST OF FIGURES
Page
F igure 2-1 : Flow o f Organic So lu tes Through t he A n a l y t i c a l Procedures . . . . . . . . . . . . . . . . . . . . 3 4
4 5
47
F igure 2-2: The Schnare Tube . . . . . . . . . . . . . . . F igure 2-3: Scale Drawing of Junk Apparatus . . . . . . . .
F igure 3-1: Leakage vs. Loading f o r an 80 x 11.5 rnm XAD-2 Resin Column . . . . . . . . . . . . . . . . .
LIST OF TABLES Page
Tab1 e 1 . 1 : Approximate Sol ute/Sol vent Requirements f o r Various Methods o f Ana lys is . . . . . . . . . . . . . . 10
Table 1-2: Reported L i q u i d . L i q u i d E x t r a c t i o n Methods . . . . . . 13-14
Table 1-3: Recovery Data f o r Adsorbents 19-20 . . . . . . . . . . . . . . . Table 1-4: Reported Concentrat ion Techniques . . . . . . . . . . . 24
Table 1-5: I n v e s t i g a t i o n s Using Acid F r a c t i o n a t i o n . . . . . . . . 28
Table 1-6: L i q u i d Chromatography I n v e s t i g a t i o n s of Natura l Waters . . . . . . . . . . . . . . . . . . . . . . . 29
Table 1-7: Gas Chromatographic Separat ion and Detec t ion of Organic Ma te r i a l i n Water . . . . . . . . . . . . . . . 31
Table 2-1 : Gas Chromatographic Parameters . . . . . . . . . . . . . 41
Table 3-1 : Capacity o f the XAD-2 Resin t o Organic Solutes on an 80 x 11.5 mn Bed . . . . . . . . . . . . . . . . . . . . 57
Table 3-2: The E f f e c t o f Flow Rate on Recovery E f f i c i e n c y . . . . . 60
Table 3-3: Recovery E f f i c i e n c y w i t h Respect t o E l u t i o n Time and Mode o f Contact . . . . . . . . . . . . . . . . . . 63
Table 3-4: Recovery E f f i c i e n c y w i t h Respect t o Aromatic versus A l i p h a t i c Solutes . . . . . . . . . . . . . . . . . . . 64
Table 3-5: Recovery E f f i c i e n c y f o r m-Xylene w i t h Respect t o s o l v e n t s . . . . . . . . . . . . . . . . . . . . . . 66
Table 3-6: Recovery E f f i c i e n c y o f Ether Desorpt ion w i t h Respect t o P o l a r i t y and S o l u b i l i t y . . . . . . . . . . . . . . . 67
Table 3-7: Recovery E f f i c i e n c y o f Three XAD Resin Methods . . . . . 69
SUMMARY AND CONCLUSIONS
The f o l l o w i n g conclusions have been drawn from the i n v e s t i g a t i o n and
regard the f i v e quest ions de l i nea ted i n sec t i on two.
1. The Caro l ina Method i s an improvement over carbon adsorp t ion and
o the r r e s i n techniques due t o -- i n s i t u desorpt ion, reduc t i on o f r e s i n hand-
l i n g , and i n t e r n a l s tandard iza t ion which a l lows f o r reproduc ib le quan t i t a -
t i o n .
2 , With respect t o p rev ious l y pub1 ished methods, t he Caro l i na Method
appears t o be more comprehensive and q u a n t i t a t i v e .
3. Using the Schnare Tube, and XAD-2 r es in , t he Carol i n a Method w i 11
e x t r a c t from water h igh propor t ions o f exper imenta l l y d isso lved organ ic
compounds of w ide l y d i f f e r i n g p o l a r i t i e s and conf igura t ions a t p a r t pe r
b i l l i o n concentrat ions w i t h a 10 ml/min f l o w r a t e and under favorab le pH
cond i t ions .
4. The batch desorp t ion technique which d i f f e r e n t i a t e s the Caro l i na
Method from o the r e x i s t i n g r e s i n procedures increases recovery e f f i c i e n c i e s .
Flow r a t e s of approximately 10 ml/min a1 low very s t rong b ind ing o f some
n e u t r a l so lutes, e s p e c i a l l y a l i p h a t i c compounds, which may be p a r t i a l l y
m i t i g a t e d by so l ven t se lec t i on .
5. Losses due t o u l t r a - c o l d d r y i n g techniques and concent ra t ion by
so lven t evaporat ion can be accounted f o r through use o f an i n t e r n a l standard.
6. A1 1 organ ic so lu tes appear t o be adsorbed t o some ex ten t , b u t f l o w
r a t e o f loading, e l u t i n g so l ven t and method of e l u t i o n are impor tan t con-
s i de ra t i ons i n determin ing the amount t h a t i s u l t i m a t e l y recovered.
7. To do q u a n t i t a t i v e work i t i s necessary t o know r e s i n capaci t y
and recovery e f f i c i e n c y f o r each s p e c i f i c compound o r c l ass o f compounds
you are a t tempt ing t o i d e n t i f y .
8. The technique can be very use fu l when the o b j e c t i v e i s t o quan t i -
t a t e known compounds, where recovery experiments can be done, and f l o w and
e l u t i o n parameters op t im ize so t h a t recover ies are known. For compounds
where t h i s i n fo rma t i on i s no t ava i l ab le , t h e concent ra t ion found represents
a minimum environmental l e v e l , b u t the ac tua l amount by which t h i s under-
est imates the r e a l concent ra t ion i s n o t known. Experimental da ta suggest
t h a t t he underestimates would be no more than by a f a c t o r o f 2-5.
m s -r L 0 C, .I--
s 0 E C, s 4 C, 3 I-- - 0 a 0 6,
V) r: 8 -r C, 4 U ..- P
Q a rrJ
r .r V) aJ L
n z s 0
-C U L 4 w V) aJ L
a, L 3 C, 3
L L
Ti-
Ghri stman and H r u t f i o r d (1973) are rep resen ta t i ve o f t h e many i nves t i - ga tors t h a t have commented on the bas ic purpose o f research i n t o the poss i -
b l e hea l t h and environmental r i s k s t h a t may e x i s t i n n a t u r a l waters. They
s ta te : "The ab i 1 i t y o f p ro fess iona l panels t o recomnend water qua1 i ty
c r i t e r i a f o r p u b l i c water supp l ies i s severe ly l i m i t e d by a l ack o f s u f f i -
c i e n t l y comprehensive i n fo rma t i on on p o t e n t i
des i rab le cons t i tuents. 'I
One o f t h e p r i n c i p a l ob jec t i ves o f the
prov ide methods t h a t can be used t o assess t
a1 l y dangerous o r o therw ise un-
research presented here was t o
he types o f p o t e n t i a l l y harmful
organic cons t i t uen ts t h a t might be present i n water supp l ies and waste water.
The purpose o f t h i s work was t o begin eva lua t i on o f a method designed t o
p rov ide some knowledge about t he e n t i r e range o f organic compounds present
i n water, and i n what amounts. No s i n g l e method f o r t h i s purpose c u r r e n t l y
has been accepted. Several workers have r e f e r r e d t o the need f o r a method
o f t h i s type. Middleton (1973) : "Techniques f o r i d e n t i f y i n g i n d i v i d u a l
compounds a t low concentrat ions are becoming soph is t i ca ted , b u t no simple
and inexpensive method i s y e t a v a i l a b l e f o r r o u t i n e use. " T a r d i f f and
Deinzer (1973) : "There i s re1 a t i v e l y 1 i t t l e i n fo rma t i on about t h e i d e n t i t y
of organic compounds i n t he environment, p a r t i c u l a r l y i n d r i n k i n g water.
I n those cases where i d e n t i t i e s of some agents are known, t h e i r concentra-
t i o n s are not . " Ongerth -- e t a1. (1973): " I n an e f f o r t t o g a i n some i n s i g h t
i n t o the na ture of these s t a b l e organic residues, a d e t a i l e d review was made
of t h e l i t e r a t u r e . These e f fo r t s produce the d i s q u i e t i n g in fo rmat ion t h a t
very l i t t l e work has been done to identify these organic constituents in
treated sewage or i n water supply sources and even less has been done to
determine the related health effects . . . . [Tlhe 1 i terature indicated only
six references i n which major e f for t s were made to i so la te and identify the
constituents in specific organic fractions i n water supply sources."
Robeck (in: Christman and Hputfiord, 1973) : "Of course, knowing the
occurrence of a chemical in water implies there i s an analytical method for
quantifying the substance. In r ea l i ty , however, especially with organics,
there i s no quick, reasonable way to measure certain c~mpounds.~~ Andelman
( in: - Christman and Hrutfiord, 1973): "The s t a t e of knowledge about the
incidence ... of organic matter i n drinking water can generally be character-
ized as most unsatisfactory, i f not alarming."
To construct and t e s t an analytical procedure requires knowledge of
existing technologies. The f i r s t section of th i s report will review what
has been done. Section two will describe the procedure selected, and
section three will discuss the resul ts . The underlying goal of th i s work
i s to construct and evaluate a method designed to extract, fractionate and
concentrate organic contaminants of water using known compounds represen-
ta t ive of those expected to be present in the environment.
Sect ion I
Discussion o f Current A n a l y t i c a l Prac t ices
The nature o f organic ma te r i a l i n water ranges from very simple hydro-
carbons t o very complex syn the t i c and na tu ra l polymers. A n a l y t i c a l pro-
cedures designed t o i d e n t i f y these compounds began appearing i n the sc ien-
t i f i c l i t e r a t u r e very e a r l y i n the techno log ica l e ra ( S a v i l l e , 1917).
The basis o f the a n a l y t i c a l procedures discussed i n t h i s sec t i on l i e s
i n the c a p a b i l i t y t o de tec t organic molecules. The s e n s i t i v i t y of the de-
t e c t i o n methods create requirements f o r ex t rac t i on , concentrat ion, and i n
s m e cases f r a c t i o n a t i o n of the organic compounds i n i t i a l l y present i n water.
A review o f t he a v a i l a b l e de tec t i on methods w i l l p rov ide a framework f o r
d iscussion o f the ex t rac t i on , concentrat ion and f r a c t i o n a t i a n procedures
ava i lab le .
Detect ion Techno1 ogies
Detect ion o f a chemical compound i s always a measurement o f some
charac ter i s t i c o f the compound. E f the c h a r a c t e r i s t i c i s h i g h l y s p e c i f i c
t o the compound, de tec t i on w i l l prov ide i n fo rma t ion of h igh q u a l i t a t i v e
value and i n some cases pe rm i t p o s i t i v e i d e n t i f i c a t i o n of the compound.
Requirements imposed by de tec tor s e n s i t i v i t y and s p e c i f i c i t y determine what
p repara t ive technologies must be used. Many detec t ion technologies are
avai l a b l e t o the i n v e s t i g a t o r i n t e r e s t e d i n organic contaminants o f water.
Thei r cu r ren t uses and 1 i m i t a t i o n s are described be1 ow.
CCE - CAE - OCA : The weight o f the carbon compounds adsorbed and
e the r o r a lcohol ex t rac ted i s determined g r a v i m e t r i c a l l y and repor ted t o
the nearest t e n t h o f a gram f o r carbon chloroform e x t r a c t (CCE) , carbon
a lcohol e x t r a c t (CAE), and organics-carbon adsorbable (0-CA). Th is method
prov ides very l i t t l e i n fo rma t i on about the nature o f t he organics ex t rac ted
s ince i t i s in tended as an i n d i c a t i o n o f t o t a l organics. EPA i s con t i nu ing
an i n v e s t i g a t i o n on the va lue o f these methods, and t h e i r most recen t f i nd -
ings were pub1 ished i n May 1975. For t he c u r r e n t method (0-CA) see Buelow
e t . a., 1973. -
Tota l Organic Carbon: Th is method d i f f e r e n t i a t e s organi c carbon f rom
ino rgan i c carbon. Malcom a. - a1. , (1971 ) have developed a s tandard ized method
f o r r o u t i n e sampling us ing commercial ly ava i l ab
i s 0.1 mg pe r l i t e r w i t h o u t p r i o r concent ra t ion
on1 ine , inst ream apparatus f o r i n d u s t r i a l use.
l e equipment. S e n s i t i v i t y
. Cohen has developed an
Manj i n v e s t i g a t o r s have
used s i m i l a r methods f o r mon i to r i ng of e f f luen ts (Bunch -- e t a l . , 1961;
Murtaugh and Bunch, 1965; Pa lu te r , 1973) or f o r determin ing breakthrough o f
carbon o r r e s i n beds ( T i l swor th , 1974). A r i n (1974) g ives an excel l e n t
review o f these methods f o r r o u t i n e mon i to r ing .
T i t r a t i o n / I n d i c a t o r Methods: These procedures i n v o l v e a s p e c i f i c
chemical phenonmenon such as oxygen use, p ro ton t rans fer , o r deco lo ra t i on
o f an i n d i c a t o r upon reduc t i on o f t he organic ma te r i a l t o another chemical
form. The f i v e day BOD t e s t i s i n t h i s category. Tsuchida and Matsura
(1974) suggest observat ion o f the l oss o f KMr04 c o l o r o f a low pH s o l u t i o n
f o r use as a simple method. Keiser (1928) measured t h e c h l o r i n e demand
assumed t o be from the organic con ten t o f t he water.
The t i t r a t i o n method measures res idua l c h l o r i n e content . Skopintsev and
Kry l ova (1955) describes the standard dichromate method, one t h a t reduces
organic carbon. Color o f the r e s u l t a n t s o l u t i o n i s measured. Each of
these t e s t s may be diminished i n accuracy and value due t o i n t e r f e r i n g
ma te r ia l s . These methods may have value f o r s p e c i f i c app l i ca t i ons and
r o u t i n e moni tor ing, b u t reveal l i t t l e o r no th ing about t he nature o f the
organic cons t i tuents measured.
Voltammetry: Voltammetry can be used t o de tec t organic contaminat ion.
Afghan e t . a l . (1975) r e p o r t t h a t i n a t w i n c e l l p o t e n t i a l sweep apparatus
he was ab le t o de tec t nanogram q u a n t i t i e s of carbonyl compounds. No pre-
concent ra t ion o r separat ion was requi red. The value o f t h i s work, l i k e
o ther gross parameter methods, i s 1 i m i t ed by i t s i n a b i l i t y t o comprehensive-
l y i d e n t i f y organic contaminants. I t has some value as a mon i to r ing tech-
nique.
Energy absorpt ion and emission: As e a r l y as 1910, D iener t (1910) used
emission spectrometry t o i n v e s t i g a t e the na ture o f f l uo rescen t substances
I n surface water. Ochi and Okaichi (1973) used a s i m i l a r procedure t o
charac ter ize sea water. I n 1974, Gaevaya and Khesina (1974) were ab le t o
d i f f e r e n t i a t e f i f t e e n p o l y c y c l i c aromatic hydrocarbons i n octane a t 0.1 ppm
l e v e l s . However, Gaevaya's methods a re r e l a t i v e l y i nsens i t i ve , due t o com-
pound inter ference, the bas ic weakness of a l l spectrometr ic methods. To
ensure exactness i n i d e n t i f i c a t i o n , the compounds under i n v e s t i g a t i o n must
be i s o l a t e d p r i o r t o the spectrometry. For f luorescent compounds t h i s i s
t y p i c a l l y done by t h i n-1 ayer chromatography (TLC) (Segura and Gotto, 1974).
An analog of emission spectrometry i s absorp t ion spectrometry, The adsorp-
5
t i o n spectrum of co lo red waters was used by Skopintsev and Kry lova (1955)
t o i n v e s t i g a t e humic acids. Datsko (1944) attempted t o develop the method
fo r q u a n t i t a t i v e work i n 1940. Both repor ted l ess than s a t i s f a c t o r y re -
su l t s due t o the many d t f f e r e n t and i n t e r f e r i n g compounds t h a t w i 11 absorb
i n the v i s i b l e band.
Mrkva (1969) abandoned the v i s i b l e spectrum f o r t he U l t r a v i o l e t (UV)
i n an attempt t o f i n d a more d i s c r i m i n a t i n g phenomenon. Analyzing a t t h ree
s p e c i f i c wavelengths, he unsuccessfu l ly attempted t o d i s t i n g u i s h var ious
humic ac ids. Huhn (1974) used s i m i l a r methods whi l e i n v e s t i g a t i n g
l i p o p h i l i c substances i n the recharge o f groundwater. UV spectrometry,
l i k e the v i s i b l e methods, i s a nonspec i f i c method. Balch -- e t a l . (1975)
has used t h i s technique f o r general moni tor ing. Operat ing qua1 i t a t i v e l y
when on l y one compound i s present, UV i s the de tec tor o f choice f o r h igh
pressure l i q u i d chromatography. I n such a system both q u a l i t a t i v e and
q u a n t i t a t i v e data can be recorded (Knox, 1975). There are, however, organic
compounds t h a t do n o t absorb w e l l i n the UV o r v i s i b l e spectrum. T u r b i d i t y
measurements should be inc luded i n t h i s subsect ion because they are of ten
conducted on the same inst rument upon which absorbance i s measured. Lee
and Wal den (1 970) used t u r b i d i t y t o charac ter ize kerosene i n e f f l u e n t s a f t e r
lengthy prepara t ive work. They repor ted s e n s i t i v i t i e s o f 10 t o 100 ppm.
M a l l e v i a l l e (1974) moved t o the i n f r a r e d energy band ( I R ) when i n v e s t i -
ga t i ng the carbon t e t r a c h l o r i d e e x t r a c t s o f sur face water a t t he th ree wave-
lengths t h a t a re c h a r a c t e r i s t i c o f alkanes, thereby at tempt ing t o develop
a method f o r the measurement o f hydrocarbons. Simard -- e t a l . (1951) a l so
working i n carbon t e t r a c h l ~ r i d e , i nves t i ga ted phenol s by concent ra t ing t h e i r
attention a t the appropriate wavelength for C-OH absorption. Frisch and
Kunin (1960) and Ungar (1962) both used the fu l l IR band t o attempt to
characterize the organics that were fouling the anion exchange resins in
water treatment systems. J e l t s and Dem Tonkelaar (1972) compared gas
chromatography and infrared spectrometry for the determination of mineral
oi 1 in water. They favored T R because i t identified exactly the presence of
mineral oi 1 , and because of the relative non-volati l i ty of mineral oi 1.
Obremski (1974) analysed specific compounds such as dieldrin and aldr in a t
ug levels by IR. He did not describe how he separated one from the other.
If both were present, there would be extensive interference.
Quantitation by IR spectrometric detection i s subject to interference
just as i s vis ible and U V spectrometric methods. The solution to th is pro-
blem i s similar to the solution for U V work, pretreatment by chromatographic
procedure. For IR, gas chromatography lends i tsel f we1 1 . The interfering
solvent and solutes are we1 l separated, and IR work i s easi ly adapted to
the gas phase. In 1971 Brown - e t ,- a l . (1971) reported success w l t h both
support coated open tubular (SCOT) and packed column methods. In 1975
Katlafsky and Dietrich (1975) constructed and evaluated an online GC/IR tha t
required 200 ug of compound to produce a spectrum suff icient t o identify
the compound. With 20 ug functional groups could be ident i f ied, This i s
a sizable amount of material and concentration of 20 to 200 times i s re-
quired f a r identification of materials present a t ppb levels i n waters.
GLC Detectors: The most sensitve detection technology i s tha t used
w i t h GLC. Three basic detectors are in use, and are described in detail i n
the sc ien t i f ic l i t e ra tu re (McNair and Bonelli, 1969). Most sensi t ive,
electron capture detectors a re able t o de tec t 0.1 picogram quant i t i es of
electron trapping compounds such as ha1 ogens, carbonyls and oxidized nitro-
gen compounds. Flame ionizat-ion detectors can de tec t 20 picograms of a l i -
phatic compounds. Thermal conductivity detectors can detect 10 micrograms
of most compounds. The detectors cannot d i f f e r en t i a t e between s imilar com-
pounds so a r e useful only a f t e r gas chromatography has been used t o sepa-
r a t e the consti tuents t o be ident i f ied .
Mass Spectroscopy: Mass spectroscopy (MS) i s perhaps the best current
detection technique. The spectrum of the unknown compound can be pr inted,
te levised, or transmited to a computer f o r comparison with spectra of known
compounds. I t has been suggested t h a t research on and practical applica-
t ion of such methods a re primary and paramount(Christman and Hrutfiord 1973;
Middleton, 1973). Hi t e s and Biemann (1972) and Arpino -- e t a1 . (1974) a l so
suggest HPLC/MS, b u t the major impetus has been i n the GC/MS area. These
expensive methods have been used primarily fo r research, a1 though use f o r
routine analysis has become more comnon in recent years ,
Early work on organics in water by MS was published by Melpolder et
a l . in 1953. Using hydrogen s t r ipping techniques, they examined the v o l a t i l e
f ract ion of organic contaminants in surface waters. In 1973, Burnham et
a1 . reported on two Iowa water supplies contaminated by t a s t e producing -
material , Evan's (1973) study of Clear Lake pollution by organics d i d make
use of a computer reference f i l e . Manka -- e t a l . (1974) characterized
organics in secondary eff luents by GC/MS/Computer, and Hellar -- e t a l . (1975)
reports on the future of routine monitoring with these methods. They suggest
t ha t a f i l e of about 50,000 compounds wi l l be available in the near future .
Table 1-1 provides a sumnary o f t he d iscussion above. As t he data i n d i -
cate, any compound t h a t i s present i n water i n concentrat ions o f l ess than
25 ppb w i l l r equ i re some form o f concentrat ion p r i o r t o de tec t ion . T f
s p e c i f i c i d e n t i f i c a t i o n of the compound i s essen t i a l , then e x t r a c t i o n from
water i s a l s o requi red, thereby necess i ta t i ng analyses by UV, I R , V isual
and Mass spectrophotometry, u s u a l l y preceded by l i q u i d , t h i n l a y e r o r gas
chromatography.
Ex t rac t i on Schemes
With several de tec t i on methods ava i l ab le , a t t e n t i o n should be tu rned
t o concentrat ion schemes which have been developed t o p rov ide the masses
o f organic so lu tes needed t o be w i t h i n the de tec t i on l i m i t s o f the a v a i l -
ab le instruments. Typ ica l ly, so lub i 1 i t y c h a r a c t e r i s t i c s a re exp lo i t ed , b u t
some concentrat ion procedures are based on o the r phys ica l p rope r t i es o f
organic so l utes ,
Gas-st r ipp ing: Gas-st r ipp ing has been used e f f e c t i v e l y t o concentrate
low weight organic compounds o f the C1 t o Cg range. Perras (1973) develop-
ed a po r tab le technique t h a t ex t rac ted alkanes from Cg t o C6. The EPA re -
cognized the v o l a t i l e s method as developed by Be1 l a r and L ichtenberg (1974),
who repor ted recover ies o f 90 t o 95% f o r C5 t o Cg compounds. This method
was ab le t o e x t r a c t compounds up t o the C15 range a t 27% recovery. B e l l a r
suggests the method fo r those compounds l ess than two percent so lub le i n
water and w i t h b o i l i n g po in t s l ess than 150°C. High e x t r a c t i o n e f f i c i e n c i e s
fo r such compounds a re common. Using such s t r i p p i n g methods, Webber and
Burks (1972) ex t rac ted 95% of the methane and 97% of the butadiene present
Table 1-1
APPROXIMATE SOLUTE/SOLVENT REQUIREMENTS FOR VARf OUS METHODS OF ANALYSIS
Maximum Sampl e Mln. Detectable Method Sensl t i v i ty Size Conc. Sol vent Ref.
GRAVf METRI C CCE/CAE 1 m!3
TITRATION
KMn04 2 Ug D i chromate 2 Ug
ELECTRODYNAMIC
Yo1 tammetry 25 ng E lec t rophores is -
OXYGEN DEMAND
BOD 100 ug
ABSORBANCE
TOC 15 ng T R 20 ug UV/VIS 20 ug
CHROMATOGRAPHY
GLC - EC 10 Pg GLC - FID 1 ng TLC 100 ng
MASS/ION RATIO Mass Spec. 50 ng
100%
0.1 ppm 0.1 ppm
25 P P ~ 50 PPm
100 ppm
1.5 ppm 20 pp th 10 PPm
10 P P ~ 1 PPm
0.2 ppm
50 PPm
N *
water water
water water
water
water N,NI* . N I
v o l a t i 1 e vo l a t i 1 e v o l a t i l e
N ,NI
*N = none, NI = n ~ n ~ i n t e r f e r i n g
a t 20-30 ppm l e v e l s . Mieure (1973) ex t rac ted up t o 93% of the ch lo ro fo rm
present i n prepared waters.
Commonly, t h i s method i s used p r t o r t o gas-chromatography, I n 1953,
Melpolder -- e t a1 , (1 953) used gas-s t r ipp ing techniques i n con junc t ion w i t h
GC and mass spectrometry t o i d e n t i f y v o l a t i l e ~ present i n concentrat ions o f
0,01 ppm. I'n 1960, F r i s c h and Kunim (1960) found 0.72 ppm v o l a t t l e s by
t n f r a r e d spectrophotometry used i n 1 i n e w i t h gas s t r i p p i n g . Ploder (1974)
used a i r - s t r i p p i n g and a SCOT column t o f i n d compounds present a t 0.1 ppm
l e v e l s . A i r - s t r i p p i n g i s a va luable ad junc t t o gas chromatography. Grob
(1973) was a b l e t o i d e n t i f y 63 compounds a t concentrat ions as low as 2 ppb.
However, many i n v e s t i g a t o r s f e e l t h a t i d e n t i f i c a t i o n of compounds present
a t such l e v e l s i s n o t q u a n t i t a t i v e . Desbaumes and Imhof f (1972) attempted
t o m i t i g a t e t h a t compla int by running c a l i b r a t i o n curves w i t h each s e r i e s
of ex t rac t i ons , However, when they repor ted 0.01 ppb concent ra t ions o f
hydrocarbons i n f i e l d samples, they s p e c i f i c a l l y withdrew t h e i r statement
o f conf idence i n the accuracy o f t h e i r q u a n t i t a t i o n methods.
The at tempt t o counteract t he s o l u b i l i t y o f v o l a t i l e s w i t h s t r i p p i n g
techniques appears t o be successful , as Mori t a -- e t a1 . (7974) were ab le t o
i d e n t i f y 25 compounds us ing t h i s procedure. However, comparison w i t h
approaches t h a t take advantage o f so lub i 1 i ty v e r i f y t h a t t h e s t r i p p i n g
method has i t s 1 i m i t s . Hewes, Smith and Davison (1974) found t h a t ex t rac-
t i o n can compete w i t h s t r i p p i n g a t low r e l a t i v e v o l a t i l i t i e s .
l i q u i d L i q u i d Ex t rac t i on : L i q u i d e x t r a c t i o n i s the o l d e s t and per-
haps the most w ide ly used e x t r a c t i v e t o o l a t t he i n v e s t i g a t o r s d isposal .
Two bas ic parameters determine the e f f i c i e n c y o f these methods, the cho ice
of so lvent and the e x t r a c t i o n apparatus.
Choice of so lvent e f f e c t i v e l y 1 i m i t s the ex t rac t i on , no ma t te r what
apparatus i s used. Far example, Goldberg -- e t a l . (1973) were ab le t o g e t
o n l y 4.80% o f the solute, 2-pentanol, from water us ing benzene. They repo r ted
the a b i l i t y t o ge t 110.35% o f i t out us ing trichlorotrifluoroethone. T h e i r
apparatus was a counter-current continuous f o u r stage e x t r a c t o r . Cooper and
Wheatstone (1973) were equa l l y successful by s e l e c t i n g methyl i sobuty l
ketone ( M I K ) f o r removal o f phenol from water. They repor ted 100% r e -
cover ies and suggested t h i s work fo r standard use.
The a t t r i b u t e s of a un i ve rsa l so lvent , use fu l i n a l l circumstances, i n -
clude: i m m i s c i b i l i t y w i t h water, p o l a r i t y s u f f i c i e n t f o r e x t r a c t i o n o f
ac ids, as w e l l as r e l a t i v e l y nonpolar a l i p h a t i c s and aromatics, and the
a b i l i t y n o t t o mask s o l u t e compounds du r ing detect ion. Although no s imple
compound has been found t h a t i s bes t i n a l l cases, some standard so lvents
a re i n use which approximate these requirements. For example, hexane has
been used f o r a l l types o f work from i d e n t i f i c a t i o n o f p e s t i c i d e s and PCB's,
t o d iese l and outboard motor o i l , hydrocarbons, l i g n o s u l f o n i c s and l i p o p h i l i c s
Ether i s o f t e n used f o r pes t ic ides , PCB's, and many o ther compounds, Chloro-
form i s the so lvent f o r the CCE method, and has been used f o r o the r work as
w e l l . Table 1-2 i s a sho r t l i s t o f i n v e s t i g a t i o n s w i t h data on solvents,
so lutes, recover ies and sample sizes. This l i s t i s a l s o a qu ick e n t r y i n t o
the l i t e r a t u r e on l i q u i d - l i q u i d ex t rac t i on .
There are two basic approaches t o e x t r a c t i o n w i t h l i q u i d solvents,
batch e x t r a c t i o n and continuous ex t rac t i on . The purpose o f both methods i s
t o mix the so lvent w i t h the sample water op t im iz ing t r a n s f e r o f organic
Table 1-2
REPORTED LIQUID - LIQUID EXTRACTION METHODS
Volumes Conc. Recovery Reference Date Sol vent Smpl /Slvnt Factor % Sol u te Method
Kawa hara 1967
Goldberg 1971
Kahn
Headington C3
Hoa k
Luessem
Bornef f
Cooper
Eichel berger
EPA
Harvey
Hughes
Je l t s
hexane hexane-benzene
hexane , benzene CCl4 C2C13F3
ether
benzene
M I K
l i q . butane
benzene
M I K
ether, hexane
t e t r a l
aceton
hexane
CC14
i n
i tri l e
40
Var. 75.6
Var . ----
25
---- 271 7
1
16.6
500
260
3 0
2 0
d i e l d r i n , endr i n
1 Oppm toluene, 2-pentanol
lppb a l d r i n
lOpprn o i l
1 OOpprn phenol
- -
1 Oppt PAH
lOOppb phenol
lOppb pest.
various
l p p t PCB's
toxaphene
lppm o i l
batch
mu l ti stage con t i nuous
continuous
batch
continuous
batch
batch
batch
batch
batch
batch
batch
batch
s U C, la n
aJ E aJ L h n C, P P 0 V)
I I I
Ln
h C
S 0 cu \ C
In
M
a, s aJ a u C w h L -(= 0 G - als E U
cu h m C
V) aJ C, . r I
so lu tes i n t o the so lvent according t o so lub i 1 i t y p r i n c i p l e s , The advantage
of a continuous e x t r a c t i o n device i s t h a t Par more water can be ex t rac ted
w i t h the same amount o f so lvent used i n most batch methods. The basic d i s -
advantage i s t h a t contac t t ime between so lvent and sample can be much less
than batch methods. Ni t h appropr ia te f l ow ra tes , t h i s disadvantage can
be overcome. However, l a rge volumes of sample water a re d i f f i c u l t t o t rans-
p o r t , and the glassware and a u x i l l a r y heat ing o r coo l i ng equipment requ i red
genera l l y p r o h i b i t f i e l d ex t rac t i on .
Solvent e x t r a c t i o n i s useful f o r two reasons, i t removes water from
the cha rac te r i za t i on process, and concentrates the organic solutes, an
essen t i a l f o r many de tec t i on techniques. The so l ven t volume i s u s u a l l y
f u r t h e r reduced from t h a t volume necessary f o r e x t r a c t i o n by evaporat ion
procedures which w i l l be d e a l t w i t h i n f u l l i n a subsequent sect ion. Con-
s ide r ing on l y the e x t r a c t i o n process, concentrat ion nea r l y always takes
place. One agency t h a t has placed great conf idence i n l i q u i d e x t r a c t i o n i s
the EPA. One l i t e r o f New Orleans d r i n k i n g water was ex t rac ted w i t h two m l
o f t e t r a 1 i n . However, the recover ies were n o t as h igh as obta ined us ing
the carbon adsorpt ion method (CAM), so there are no repor ted e f f i c i e n c i e s
(US-EPA, 1974). Another ambit ious method was repor ted by Bornef f and
Kunte (1969). They ex t rac ted 500 l i t e r s of water w i t h 18 l i t e r s o f benzene,
reproduc ib ly e x t r a c t i n g 10 p p t o f the po lynuc lear aromatic hydrocarbons
(PAH) present. Vei t h and Lee (1974) were ab le t o e x t r a c t PCB's a t s i m i l a r
concentrat ions w i t h 400 m l hexane and 1.6 l i t e r s o f sample water.
Two bas ic conclusions can be made regarding l i q u i d - l i q u i d ex t rac t i ons :
(1 ) proper so lvent se lec t i on s t r o n g l y in f luences e x t r a c t i o n e f f i c i e n c y ; and
(2) recovery of a p a r t i c u l a r so lu te can on ly be rough ly est imated unless
recovery e f f t c i e n c y i s de tem ined by i n v e s t i g q t i ~ n s w l t h t h a t so lu te .
Adsorpt ion: By 1916 water s p e c i a l i s t s had a l ready recognized and pub-
1 i shed conclus ions about the absorp t ive qua1 i t i e s of var ious adsorbents , i n p a r t i c u l a r w i t h respect t o c o l o r ma te r i a l s o f organic o r i g i n ( ~ a v i l l e ,
1917). I n 1940, Lemaire (1940) publ ished a rev iew of s y n t h e t i c adsorbents.
That rev iew d isc losed the pr imary research i n t e r e s t s as removal of organics
from water. Such work has cont inued (Luh and Baker, 1971 ; D u f o r t and Rud,
1972; Orhme and Mar t ino la , 1973; Ohtani , 1974; Shevchenko -- e t a1 . , 1974;
Love e t a1 . , 1975).
Removal o f organics from water by adsorp t ion onto var ious r e s i n s and
polymers does n o t o f necess i ty presume an a b i l i t y t o desorb them f rom the
adsorbent. Th i s presumption, if v a l i d , would a l l o w methods t o be designed
t o recover the ex t rac ted m a t e r i a l s f o r t h e purpose o f ana lys is .
I n August of 1951, Brause, Middleton and Walton (1951) descr ibed a
method f o r the e x t r a c t i o n and recovery o f organic m a t e r i a l s u s i ng carbon
adsorpt ion and e the r ex t rac t i on . I t was t h i s work t h a t has evolved i n t o
t he standard method f o r e x t r a c t i o n o f organics by adsorpt ion. The c u r r e n t
method (organics-carbon adsorbable, 0-CA) i s used by EPA, and i s f u l l y de-
sc r ibed by Buelow, e t a l . (1973).
Carbon adsorp t ion i s n o t w i t h o u t t echn i ca l weaknesses. I n 1962, Hoak
demonstrated t h a t desorp t ion was l e s s than q u a n t i t a t i v e , and t h a t compounds
may change chemica l l y w h i l e adsorbed. I n 1965, Booth, Eng l i sh and McDemott
( 1965) "conf irmed t h a t act ivated-carbon columns , even wi t h the g r e a t e s t
p r a c t i c a l con tac t t imes, do n o t adsorb a l l organic ma t te r present . " More
recen t l y , Pahl, A l len, Mayhan and Ber t rand (1973) publ ished a s e r i e s o f
a r t i c l e s which show t h a t there i s nQ reasonable method t h a t q u a n t i t a t i v e l y
desorbs a l l organics from carbon. The data on chemical reactivity o f
ac t t va ted carbon and poor desorpt ion capabi 17 ty when us ing 1 t I n s t i g a t e d
ser ious research i n t o o ther adsorbents.
The l o g t c a l replacement f o r carbon would be an organic s o l i d t h a t i s
no t reac t i ve , t h a t would adsorb as w e l l , and would desorb b e t t e r . Ton ex-
change res ins do n o t meet these c r i t e r i a , bu t h i s t o r i c a l l y were the nex t
adsorbent t o undergo in tense i nves t i ga t i on . The i n v e s t i g a t i o n was of s h o r t
du ra t i on as i t was found t h a t the neu t ra l compounds do no adsorb quan t i t a -
t i v e l y (F r i sch and Kunin, 1960) and the p o l a r ones do n o t desorb quan t i t a -
t i v e l y ( P e t r a r i v -- e t al . , 1969), even w i t h appropr ia te pH co r rec t i on . It i s
assumed t h a t those forces which encourage s o l u t i o n are n o t s t rong enough
t o compete w i t h the i o n i c forces o f d i ssoc ia ted ac ids and bases.
The pro1 i f e r a t i o n o f so l i d ma te r i a l s from a growing chemical and p las-
t i c s i ndus t r y have begun t o p rov ide candidates f o r a b e t t e r adsorbent.
Three groups have i nves t i ga ted polyurethane foam (Bedford, 1974; Gesser - e t
a., 1971 ; Musty and Nickless, 1974). They repor ted recover ies o f 95-100%
f o r pes t i c i des and PCB's w i t h appropr ia te pH cor rec t ions . There has n o t
been extensive f i e l d tes t i ng , however, and Bedford (1974) i n d i c a t e d t h a t
the foams f a i l r a p i d l y i n r e l a t i v e l y t u r b i d waters.
Tenax, a r e c e n t l y described adsorbent i s c h a r a c t e r i s t i c o f t h e na t i ona l
concern f o r removal and i d e n t i f i c a t i o n o f organics i n water. I t was
developed s p e c i f i c a l l y f o r t h a t purpose. Leoni -- e t a l . (1975), publ ished re -
cover ies of 90% and b e t t e r f o r pes t i c i des and PAH us ing t h l s r e g i s t e r e d
product. I t i s the second i n a growing generat ion o f commercially produced
adsorbents designed t o rep lace carbon. The f f r s t , aqd t h e one used i n t he
research undertaken by the author, i s an Amberl t t e product c a l l e d XAD r e s i n ?
There are var tous types of t h i s mac ro re t i cu la r res in , and the cha rac te r of
the one used t s discussed immedtately fo l lowtng Table 1-3. Recoveries us-
f ng XAD a re c o n t i n u a l l y repor ted as near 100% (Bastos -- e t a1 . , 1973;
Burnham e t a1 . , 1972, 1973; Kelsey and Mosgatel l i , 1973; Musty and Nick1 ess , 1974; R i l e y and Taylor , 1969).
An example o f a new d i r e c t i o n i n adsorbent development i s t h e work
Ah1 i n g and Jensen (1970) have done w i t h what has here to fo re been used as
gasmchromatographic s o l i d and l i q u i d phases. They used 10% carbowax and
30% undecane on Chromasorb W and repo r ted up t o 100% recover ies f o r p e s t i -
c ides and PCB's. Table 1-3 descr ibes some o f the l i t e r a t u r e on adsorbents.
XAD-2 Mac ro re t i cu la r Resin: The so l i d adsorbant used throughout t h i s
i n v e s t i g a t i o n i s the mac ro re t i cu la r r e s i n XAD-2, an
Rohm and Hass Company, Ph i lade lph ia , Pennsylvania.
styrene-divinylbenzene (DVB) co-polymer.
I n 1965 research w i t h t h i s r e s i n i n d i c a t e d an
Amberl i t e produc t o f
The r e s i n i s a po l y -
ncrease i n en t ropy f o r
the adsorp t ion o f organic so lu tes t o t h e copolymer (Schneider, -- e t a l . , 1965).
Schneider descr ibed ' i cebergs ' o f f a t t y ac ids i n water being broken up and
adsorbed by t h e r e s i n . The bes t source f o r in fo rmat ion about XAD-2, and
o ther s i m i l a r res ins , remains an a r t i c l e by Gustafson and Paleos (1971).
They suggest Van der Waal's fo rces as the impor tan t chemical phenomenon
exp la in ing adsorpt ion. It remains unc lear i f phys ica l s i z e o f organics
so lu tes a f f e c t s adsorp t ion s i g n i f i c a n t l y .
The copolymer i s formed i n t o spheroids o f va ry ing mesh s i ze . Each
Table 1-3 Continued
Sampl e Vol ume Conc . % Ref. Date Adsorbent Source Smpl/Slvnt Solvent Factor Recovery Solute
Leon i
Burnham
Harvey
Kami ku bo
Musty N 0
Richard
Ripley
Bas tos
Kel sey
Junk
EPA
Tenax
XAD2/7 XAD 2
XAD2
XAD1/2
XAD 4 XAD 2 XAD 8
XAD 2
XAD 1
XAD 2
XAD 2
XAD 2
drnk wtr
river grnd wtr
ocean
pure wtr II
II
r iver
ocean
Urine
Urine
pure wtr
XAD2,4,7,8 pure wtr
e the r
methanol e ther
acetoni t r i l e
methanol
hexlether I 1
I 1
acetoni tri 1 e
methanol
e ther
methanol
e ther
chloroform
1000 85-100 lppb pest , PAH
1000 97 .37ppb neutrals 10000 90 lppb var.
1 00 lOppt chlororg.
100 neutrals . 100 lppb PCB 45-71 11
28 11
=to l i q . extn lppb pest
100 pest . 81 -1 00 aci ds/bases
- chl orpromazi ne
100 var. org.
40- 90 var. org.
sphere I s 'open l a t t t c e d ! which prov ides f o r Very h igh surface area, com-
pared t o t r a d l t i o n a l c r y s t a l 1 i n e res ins .
D i f f e r e n t i a t i o n by Size and Weight
One approach t o t he ana l ys i s of organics i n water w I l l n o t P i t appro-
p r t a t e l y i n t o the proscr ibed sec t ions on ex t rac t i on , concentrat ion, f rac-
t i o n a t l o n and de tec t i on because i t invo lves a l l o f these processes. That
approach invo lves c e n t r i f u g a t i o n and f i l t r a t i o n . The terms c e n t r i f u g a t i o n
and f i l t r a t i o n each i n d i c a t e a c lass o f methods. C e n t r i f u g a t i o n can be
batch o r cont inuous f low; i t can be v a r i e d t o separate by weight and/or
s i z e down to , b u t no t u s u a l l y i nc lud ing , c o l l o i d a l s izes. T t can be used
alone o r i n a t r a i n i n c l u d i n g preceding f i 1 t r a t i o n devices. F l l t r a t i o n
t y p i c a l l y removes m a t e r i a l s o f 0.45 micron diameter o r g rea ter . Below -
0.45 microns, the t e r n u l t r a - f i l t r a t i o n i s usual l y app l ied . As g rea te r
s e l e c t i v i t y i s desired, t he i n v e s t i g a t o r begins t o encounter reverse
osmosis (RO) tbchniques and ge l permeation; and a t some p o i n t , o n l y gases
pass t h ~ o u g h the media (perevaporat ion) .
The u t i l i t y o f these methods depends t o a l a r g e degree upon the i n -
t e n t o f the researchers. I n v e s t i g a t i o n of secondary and pr imary e f f l u e n t s
have p u t major emphasis on d i f f e r e n t i a t i o n by s i z e o r weight (Groves, 1974;
R i c k e r t and Hunter, 1967; EPA, 1971 ). Charac ter iza t ion o f o rgan ics i n
e f f l uen ts has been conducted by c e n t r i f u g a t i o n (Rebhun and Manka, 1971),
reverse osmosis (Gurtz, 1967; Reuter, 1973), and ge l permeation (Chudoba
e t a l . , 1973; Manka e t a l . , 1974). T a r d i f f and Deizner (1973) used RO and --
perevaporat ion t o concentrate organics found i n d r i n k i n g water . H a l l and
Lee (1976), Varshal e t a l . , (1974) and M i g a l a t i l and Pushkarev (1973) i n -
vestigated ~ r g a n i c s i n natural wqters using RO and gel permeation.
There i s l i t t l e data on the efficiency of these methods. Yarshal
e t a1 . , (1 974) reported t h a t during fractionation by permeation techniques --
l ess than for ty percent of the organtcs were los t , Reuter (1973) indicated
that 150 mg/l total carbon permeated a RO apparatus designed to remove .
organics from primary effluent waters. This i s an inordinately large con-
centration i n a supposedly clean effluent and belies the inefficiency of
one RO apparatus.
A t best, these methods provide fractions that must be subjected to
further fractionation or extraction before being amenable to identifica-
tion of organic constituents. Reports have not been published on a compre-
hensive system of methods designed to get a l l components of the organic
fraction in waters. These methods do not specify much more than s i ze of
the components unless the methods are followed by more sensit ive detectors
Concentration Methods
Concentration usually takes place a t every step of a search for organ
in water, However, some steps are designed to do only the task of concen-
t ra t ion. This i s necessary because most organics are present i n natural
waters in low concentrations relative to the amounts needed by the detec-
tion methods.
Concentration genera1 ly exploits the character is t ic sol ubi 1 i ty and
volati 1 i ty of substances in solution. Plumb and Lee (1973) concentrated
organics by vacuum d i s t i l lation of raw waters. The assumption i s t h a t the
solubi l i ty of the organics i s so great that a t low temperatures and pres-
sures, the loss of mass from the d i s t i l l a t ion flask i s predominately water.
Some organic l o s s may occur through formation of azestropes, however the
success of vacuum d i s t i 11 a t i o n has been shown by Kuninobu and, Mori kawa (1974).
They d t s t l l l e d 300 m l water t r e a t e d w l t h 0.115 eq. Ca(OH)2 t o 50 m l and r e -
covered 99.995% of t he formaldehyde t h a t was placed t n s o l u t i o n .
For water samples con ta in ing l e s s so lub le organtcs , such recover ies
should n o t be expected. f n non -quan t i t a t i ve work Rebhun and Manka (1971)
and Katz e t a l . (1972) used t h i s method t o concentrate e f f l u e n t contaminants.
I n bo th cases, p r e c i p i t a t e s formed and were red isso lved i n an organic so lvent .
Other work o f t h i s nature i s i n d i c a t e d i n Table 1-4.
S i m i l a r methods o f concent ra t ion are used when organic compounds have
been concentrated i n organic so lvents. I n t h i s case, an a d d i t i o n a l
p roper ty a ids the process, General l y , organic so lven ts have lower bo i 1 i ng
p o i n t s than the so lu tes being i nves t i ga ted so 1 ower temperatures a re r e q u i r -
ed. This a l l ows simple d i s t i l l a t i o n , l eav ing the so lu tes i n t he o r i g i n a l
f l ask i n a concentrated form. Many methods and appara t i i have been develop-
ed t o e f f e c t such d i s t i l l a t i o n . The method o f choice, as descr ibed i n t h e
publ ished 0-CA method (Buelow -- e t a l . , 1973) and o t h e r work (Junk -- e t a l . ,
1974) i s use of the Kuderna-Danish (KD) evaporator. Developed i n a Denver
l a b i n 1951, i t has been used ex tens i ve l y , and i t s e f f i c i e n c y has been i n -
ves t i ga ted a t l eng th (Gurtz, 1967). Gunther e t a1 . , (1951) were ab le t o
concentrate p e s t i c i d e s i n s o l u t i o n by reducing volumes from 200 m l t o t h ree
m l w i t h recover ies of 80-84%. Goldberg -- e t a l . , (1973) found t h a t such r e -
cover ies a re n o t rou t i ne , and t h a t depending upon evaporat ion r a t e and
f i n a l volume, recover ies a r e from 26-72%. They suggested so l vent volume
reduc t i on t o o n l y 50111 from 500. Junk -- e t a l . (1974) found t h a t evapora-
Table 1-4
REPORTED CONCENTRAT FON TECHNTQUES
Conc. % Ref. Date Solvent Solutes Method Factor Recovered
P I umb
Ka t z
Rebhun
Kuni nobu
Muel 1 e r
Bunch
Black
Baker
Gunther
Go1 dberg
Junk
n a t w t r
e f f l u e n t
e f f l u e n t
pure w t r
pure w t r
e f f l u e n t
n a t w t r n a t w t r
pure w t r
org. so l .
org. so l .
org. so l .
var ious vac d i s t
var ious vac d l s t
var ious vac d i s t
formaldehyde d i s t i 1.
o rg ac ids evap
var ious vac evap
f u l v i cs evap f u l v i c s f reeze
var ious freeze
org. s u l f i t e KD*
var ious KD
var ious KD
- - -
6x
-
20x
151x 7 5x
var.
66x
1 ox
41 x
* KD = Kuderna-Danish
t i o n r a t e has no e f f e c t prqy ided i t i s matntqined w t t h i n t he range of 0.5
t o 2 ml/mtn, They d t d suggest t h a t t h e shape of the concentpatron vessel
i s c r i t k a l , and, ustng a specfa1 f l a s k constructed from a 50 m l round
bottom f l a s k and a tapered cen t r i f uge tube, obta ined recover ies o f no
l ess than 93% w h i l e concent ra t ing from 25 m l t o 0.6 ml ,
A second concent ra t ion technique 1s c r y s t a l 1 i z a t i o n . I n c u r r e n t work,
the so lven t i s f rozen out , l eav ing the so lu tes i n t he remaining water and
i n h igh concentrat ion. Black and Christman used t h i s method i n 1963,
f reez ing ou t water i n a l a r g e drum. Water volume was reduced from 40
ga l lons (151 L. ) t o one l i t e r . Recovery e f f i c i e n c i e s were n o t repor ted.
The American w i t h t he g rea tes t experience i n f reeze concent ra t ion i s
Robert Baker. He pub l i shed a se r i es o f f o u r papers e n t i t l e d "Trace Organic
Contaminant Concentrat ion by Freezing1' (Baker, 1967a; 1967b; 1969; 1970).
Using a r o t a t i n g f l a s k and cascade o r mu l t i s tage techniques, many l i t e r s
of water can be concentrated t o a f i n a l volume o f no l ess than 30 m l w i t h
recover ies o f up t o 100%. Factors t h a t i n t e r f e r e w i t h the process i n v o l v e
the presence o f inorgan ic s a l t s i n so lu t i on . No good s o l u t i o n t o t h a t
problem was i d e n t i f i e d .
F rac t i ona t i on Schemes
F rac t i ona t i on i s use fu l as i t f a c i l i t a t e s t h e de tec t i on process by
p e r m i t t i n g b e t t e r separat ion o f t he components present and removal o f i n t e r -
ferences. For example, 66 separate organic compounds were discovered i n
the New Orleans water supply i n a search conducted by EPA (1974). Most
of these compounds were i d e n t i f i e d by gas chromatography. No one column
can adequately separate a1 1 m a t e r i a l s present. However, i f , f o r example,
only acids were present, a column can be used so t ha t excel lent separation
of acids wil l occur. A dtstTnct separation i s important i f detection i s
fur ther reftned by mass spectrometry, infrared spectrometry, or UY spectro-
metry.
Acid Fractionation: The character of organtc compounds may be der
scribed by functfonal groups such as amines, carboxylic acids , e s t e r s and
so on. They may a l so be described by s t ructural charac te r i s t i cs , f o r ex-
ample a1 kanes, alkenes, alkynes, aromatics and so on. In acid f ract iona-
t ion procedures organics are divided in to strong acids , weak acids and
phenolics, neutra ls , weak bases, strong bases, and amphoterics. This i s
accomplished by pH adjustment and extraction. The c l a s s i c work on t h i s
method i s t h a t of Shriner and Fuson ( i n : - Malcolm -- e t a l . , 1971). The method
r e l i e s on the par t i t ioning of organic species between an acid o r a l k a l i i
water phase and an organic solvent phase. As pH i s varied the non-polar
(unionized) species dissolved in the organic solvent while the polar (ion-
ized) species remain in aqueous solution. Neutrals migrate in to the organic
solvent with very wide ranges of pH.
The appeal of t h i s method l i e s in i t s wide appl icabi l i ty . A pH adjust -
ment can be made pr ior t o the extraction of water, thereby causing se lec t ive
extraction (Bark -- e t a l . , 1972; Bunch -- e t a l . , 1961; Rebhun and Marka, 1971).
The adjustment can be done pr io r t o use of an adsorbent (Junk e t a l . , 1974).
A pH adjustment can faci 1 i t a t e se lec t ive desorption of adsorbents (Bastos
e t a l , 1973; Burnham e t a1 , 1972, 1973; Christman and Hrutfiord, 1973; Hoak, --
1962; Laqua, 1973; Tard
scribed, the f rac t iona t
i f f and Deizner, 1973). Or as Shrlner and Fuson de-
ion can be done a f t e r extractton o f waters o r ad-
sorbents (Kawahara e t a1. , 1967; Ma1 colln e t a1. , 1971).
An important c l a s s i f j c a t t o n system t h a t was developed p r i o r t o comon
use o f gas chromatography and mass spectrometers i nvo l ves the a c i d f r a c t i o n
of the above method. I n v e s t i g a t i o n s on the nature of c o l o r i n water r e -
s u l t e d i n t he determinat ion of the percentage o f organic m a t t e r i n each of
th ree subgroups w i t h i n the a c i d f r a c t i o n . These are known as the gener ic
groups f u l v i c ac ids, hymatomelanic ac ids and humic ac ids. Table 1-5 i s
a s h o r t 1 i s t i n g o f research t h a t has used the a c i d f r a c t i o n a t i o n method.
Chromatographic F rac t i ona t i on : Another method used t o separate
organic so lu tes i n t o groups o r i n d i v i d u a l components i s chromatography.
Four types o f chromatography a re i n wide use, gas, l i q u i d , h igh pressure-
l i q u i d , and t h i n - l a y e r . Each o f t he methods e x p l o i t compound s p e c i f i c
p a r t i t i o n c o e f f i c i e n t s between a c a r r i e r so l ven t o r gas and a s o l i d suppor t
coated w i t h a l i q u i d phase. P a r t i t i o n i n g may be on the bas is o f s o l u b i l i t y ,
adsorpt ion, molecular c o n f i g u r a t i o n and/or molecular weight.
L i q u i d chromatography (LC), and i t s successor, h igh pressure 1 i q u i d
chromatography (HPLC), a re va luab le f r a c t i o n a t i o n methods. However t h e de-
t e c t i o n techniques t y p i c a l l y used i n con junc t ion w i t h LC/HPLC a re n o t
spec i f i c . To improve s p e c i f i c i t y , Knox (1975) dep i c t s t he r o l e o f HPLC as
a p repa ra t i ve method f o r mass spec t ra l analys is . He repo r t s t h a t such
methods can separate 0.1 t o 1.0 mg s o l u t e pe r gram o f packing, and i s use-
f u l f o r separa t ion o f compounds o f g rea te r than 1000 malecular weight.
Both Knox and Saika (1970) have repor ted t h a t c e r t a i n organics adsorb s t rong-
l y onto some column packing m a t e r i a l s reducing the u t i l i t y of the method.
Because the c a r r i e r phase i s l i q u i d , pumps are r o u t i n e l y employed.
Table 1 ~ 5
Ref. Date Smple FraCti ~ n s vethod
Bastos 1973 Urlne acid-neutral , se lec t ive desorp'n of XAD base-neu t r a l w/HCl/ether then borax/HCC13
Laqua . 1973 drnk wtr a1 1 SF* f rac . of e the r ex t rac t of various adsorbents
Tardiff 1973 drnk wtr a l l se lec t ive desorp'n of XAD
Hoa k 1962 drnk wtr a1 1
Christman 1973 drnk wtr a1 1
SF frac . of e ther ex t r ac t of carbon
suggests se lec t ive desorp'n of XAD
Burnham 1972 d r n k wtr neutrals sel ec t ive desorp' n of XAD 2/acid +base discarded
Junk 1975 drnk wtr a1 1
Brause 1951 surf wtr a1 1
Kawahara 1967 surf wtr a l l
pH adjustment p r io r t o XAD adsorption
SF frac . of e ther ex t rac t of carbon
SF f rac . of e ther ex t rac t of carbon
Bark 1972 e f f luen t bases ex t r ac t ' n of pH adj. water
Rebhun 1971 eff luents a l l
Bunch 1961 e f f l u e n t s a l l
SF f rac . of e ther ex t rac t of vac. evap'd concentrate
SF f rac . of e ther ex t r ac t of vac. evap'd concentrate
Black 1963 colored wtr acids fulvic/hymatomelanic/humic
?SF = S h i n e r and Fuson
The pressure es tab l i shed t n t r ~ d u c e s f u r t h e r compl i c a t f ~ n s upon i n j e c t q r
design. f f used @tR a de tec to r as a charactepTzat ion apparatus, HPLC
tends t o have h igh background noise t o pumps and i n j e c t a r s (Ber ry and
Kargen, 19731, q l though recent devel o p e n t s t n f n j e c t o r qnd de tec to r de-
sf gn Rave e l trninated many of these d i f f i c u l t i e s . HPLC o f f e r s extremely
RSgR t h e o r e t i c a l separat ing c a p a b i l i t y which has l e d t o increased app l i ca-
t l o n of t h i s technique, Ohtani r o u t i n e l y separated xy lene isomers, a t ask
poss ib le a t h igh e f f i c i e n c y on l y by LC o r GLC. Lee and Chang (1975) de-
v i sed a scheme o f repeated chromatography w i t h a combination o f var ious
absorbents, s t a t i o n a r y phases and e l u ten ts . I t i s noteworthy t h a t they
fee l t h e i r methods a re too ted ious and long f o r general work. Table 1-6
l i s t s some o f the recent work i n LC and HPLC on organics i n water.
Table 1-6
LIQUID CHROMATOGRAPHY INVESTIGATIONS OF NATURAL WATERS
Ref. Date Method Support So lu te
C hu 1973 HPLC XAD 2 S tero ids , Phenols
Lee 1975 HPCC var ious F lavo r Compounds
J o l l y 1973 HPLC - Trace org. i n n a t waters
H i t e s 1972 LC - Org. compounds i n Charles R ive r
Koe h 1 1974 LC - 39 amino ac ids
Plumb 1973 LC sephadex Org, compounds i n na t waters
Zai ka 1970 LC po lys ty rene Org. compounds i n n a t waters
H a l l 1974 LC - Org. ma t te r t n Lake water
Ohtani 1974 LC z e o l i t e s xylene t n e f l u e n t s waters
Gas-1 i q u i d chromatography [GLC o r ($1 provides ma,rkedl y b e t t e r
separat ion cqpabfl f ty than standard, non pressur f zed, LC, and cornparable
t o HPLC, Sample s izes are reduced t o micro1 t t e r l e v e l s because de tec to rs
used w i t h GLC are capable o f responding t o nanogram and picogram q u a n t i t i e s
of s o l u t e mass, GLC i s most o f t e n l i m i t e d by the v o l a t i l i t y o f t he sample
compounds. Soph is t i ca t i on o f column design cont inues t o increase t h e
c a p a b i l i t y o f the technique. Urov -- e t a1 . (1974) repor ted the use of a
column which separated anthracene and phenanthene, two representa t ives of
the polynuclear aromatic hydrocarbon (PAH) fami ly t h a t are normal ly con-
s idered h igh b o i l e r s and u n l i k e l y t o v o l a t i l i z e . I n o ther cases where
v o l a t i l i t y i s low, d e r i v a t i v e s can be formed which a l l ow use o f GLC methods.
Table 1-7 i s a s h o r t compi la t ion o f repo r t s on organics i n water separated
and detected us ing the gas chromatograph. Note t h a t two bas ic e x t r a c t i o n
procedures a re used p r i o r t o gas chromatography, purg ing and so l ven t ex-
t r a c t i o n .
Th in- layer chromatography prov ides an a1 t e r n a t i v e t o GLC when h igh
b o i l e r s a re under i nves t i ga t i on . For example, Bornef f and Kunte (1 969)
developed a method fo r i d e n t i f i c a t i o n o f over f i f t e e n PAH. Th in- layer a l -
so prov ides a technique f o r r e p e t i t i v e t e s t i n g requirements. Thideman
(1974) has repor ted on coated f o i l s f o r the de tec t ion o f i n s e c t i c i d e s and
pes t ic ides . Atanus (1974) repor ted t h a t the Chicago Me t ropo l i t an San i ta ry
D i s t r i c t used a TLC method f o r d a i l y t e s t i n g o f waters containing hexane
solubles. Aly (1 968) suggests TLC fo r r o u t i n e i d e n t i f i c a t i o n o f phenols.
Although separat ion i s e x c e l l e n t f o r some compounds, the de tec t i on o f those
compounds f o l l o w i n g TLC i s n o t as s e n s i t i v e as those used w i t h HPLC of GLC,
Table 1 ~ 7
Ref,, , , , , €)It!. . , " , Source , , , , . , Solute Concentrattan Method
P l oder
Perras
M I eu re
Des baumes
Be1 l a r
Cooper
Goma
Jel t s
Kawa hara
Lamar
Muel 1 e r
Nurtaug h
Smi th
Van Hyssteen
Urov
1974 surf wtr
1973 ocean
1973 surf wtr
1972 effluent
1974 surf wtr
1973 effluent
1971 nat wtr
1972 nat wtr
1971 surf wtr
1963 surf wtr
1958 surf wtr
1967 eff 1 uent
1971 - 1970 pure wtr
1974 -
C#C13 Headspace purge
hydrocarbons Purge
HCC1 ,phenol Pu rge
hydrocarbons Purge
volati l es Pu We
phenol s MBK extr 'n
hydrocarbons surfacant emulsion
mineral o i l n i trobenzene ext r ' n
phenols, acids CAM ex t r ' n
acids butane ex t r ' n
acids ether ex t r ' n
s te ro ls hexane extv-' n
a1 i phati c ci ami nes - f a t ty acids none
anthracene -
and q u a n t i t a t t o n i s very d i f f i c u l t ~ i t h ~ u t r e m ~ v i n g the solutes from the
t h i n layers and sub jec t ing them t o add i t i ona l a n a l y t i c a l techniques.
Th is review po in ts o u t t h a t n o t enough 1s knawn about, n o r a re appro-
p r t a t e methods ava i l ab le f o r , the t d e n t i f i c a t i o n o f h igh molecular weight ,
organic compounds t h a t may be t n water - compounds t h a t a re assumed t o
cause c o l o r and f i 1 t e r clogging. However, f o r many compounds, e s p e c i a l l y
those being manufactured and deposited i n water resources, a l e g i t i m a t e
t r a i n o f processes may be constructed which a l lows accurate i d e n t i f i c a -
t i o n and quant i t a t i on.
Sectl'on T I
Experimental Design
The under ly ing goal o f t h i s work was t o develop and evaluate a
method designed t o ex t rac t , f r a c t i o n a t e and concentrate organic contami-
nants o f water us ing known compounds representa t ive o f those expected t o
be present i n the environment. Under i n v e s t i g a t i o n i s an XAD r e s i n pro-
cedure c o n s i s t i n g o f f i v e steps. F igure 2-1 i nd i ca tes the f l o w of the
organic so lu tes through t h i s procedure.
F ive quest ions requ i red i n v e s t i g a t i o n : (1 ) What i s t h e p o t e n t i a l o f
t h i s procedure f o r l a b and f i e l d a p p l i c a b i l i t y , f o r reduc t ion i n handl ing
o f l i q u i d s and so l i ds , and when there are l a r g e numbers of analyses?
(2) What i s the experimental assessment o f p rev ious l y publ ished methods
t h a t approximate t h i s new XAD procedure? (3) What i s the a b i l i t y o f t h i s
procedure t o e x t r a c t organic solutes, espec ia l l y w i t h respect t o the
vary ing nature of the so lu tes and the range o f poss ib le f l o w ra tes through
the r e s i n ? (4) What i s the a b i l i t y of a so lvent o r so lvent m ix tu re t o re -
move adsorbed organic so lu tes? (5 ) What i s the e f f e c t o f u l t r a - c o l d dry-
i n g techniques and concentrat ion by so lvent evaporat ion, and can losses
dur ing these steps be accounted f o r i n a systematic way?
The d e s c r i p t i o n of ma te r i a l s and equipment fo l lows, w i t h the descr ip-
t i o n of the experimental procedures concluding the sect ion.
Equipment and Ma te r ia l s
Macrore t icu la r Resin: XAD-2 res in , described i n sec t i on one, i s
shipped i n p l a s t i c g a l l o n b o t t l e s , and i s saturated w i t h water. New r e s i n
and used res in , kept separate, are s tored under water. As received the
r e s i n i s contaminated and must be cleaned before use. Both new and used
res ins are cleaned by a method cons is t ing o f a c i d and base washing,
fol lowed by a ser ies o f ex t rac t i ons (Soxhlet apparatus), us ing methanol,
acetone o r a c e t o n i t r i l e , and ether, i n t h a t order, and each fo r e i g h t
hours. The r e s i n i s then washed w i t h methanol under which i t i s s tored I n
ground glass stoppered f l a s k s , and r e f r i g e r a t e d . E lec t ron capture-GC has
detected some contaminants t h a t remain on used r e s i n i n s p i t e of the
c leaning procedure, and t h a t were ex t rac ted from the r e s i n w i t h the e ther
used i n the experiments. It i s unclear whether these cantaminants were
on the r e s i n o r i n the solvents. FID-GC d i d no t de tec t any contaminants
remaining on the r e s i n a f t e r c leaning us ing the above procedure. It i s
suggested t h a t any contaminants remaining on the r e s i n w i l l n o t i n t e r -
f e r e w i t h FID-GC charac ter iza t ion , bu t t h a t they can p o t e n t i a l l y a f fec t
the qua1 i t y o f GC/MS analys is . Since the contaminants on ly appear on used
res ins, new res ins may be a requirement f o r r o u t i n e uses. Add i t iona l work
may be requ i red t o produce a c leaning procedure capable o f removing a l l
contaminants from used res in , a1 though t h e procedure g iven above produces
a r e s i n adequate f o r most app l ica t ions . Only new res in , app rop r ia te l y
cleaned, was used i n the work described by t h i s repor t .
P r i o r t o use, the methanol, under which the r e s i n s are stored, must
be replaced by water. I t was discovered t h a t some e the r a l so remains on
the res in , and adding water q u i c k l y r e s u l t s i n the format ion o f a very
small e ther f r a c t i o n . The methanol and e ther are removed by washing 200
m l o f water through the r e s i n i n the experimental e x t r a c t i o n column w i t h
g r a v i t y . The e the r f r a c t i o n t h a t c o l l e c t s a t t he top of the column i s
f lushed o f f by g e n t l y over f i l l i n g the column w i t h water. Experimental
e x t r a c t i o n columns, once f i l l e d w i t h r e s i n and washed w i t h water, can be
s to red i n a sealed cond i t i on f o r reasonable per iods o f t ime, (up t o a
week) and may be c a r r i e d i n t o the f i e l d f o r on-s ight ex t rac t i on . Columns
t o be s to red f o r more than a day should be r e f r i g e r a t e d t o reduce the
p o s s i b i l i t y o f contaminat ion by m ic rob ia l ac t ion . Appendix A prov ides a
comprehensive t o p i c a l b ib1 iography o f the 1 i t e r a t u r e on XAD res ins .
Solvents: Three solvents a re used i n the procedures described below;
water, d i e t h y l e t h e r and acetone. Water, used t o d i sso l ve the organic
solutes, i s Chapel H i l l tap water t r e a t e d by a c t i v a t e d carbon f i l t r a t i o n
fo l lowed by c a t i o n i c and an ion ic exchange columns. The t reatment i s a
commercial product c a l l e d U l t rapure Water Systems, mainta ined by Hydro
Serv ice & Supplies, Inc. , Durham, N.C. There a re no d iscernable ha logenab
ed organic compounds present i n the waters as determined by EC-GC.
S e n s i t i v i t y o f t h a t de tec t i on system i s 10 ppb f o r ch lo ro form and a 1 u l
water i n j e c t i o n . Solvent e x t r a c t i o n o f one l i t e r o f water w i t h 200 ml
ether , reduced t o 1 ml by KD, i nd i ca ted the presence o f no compounds.
Detect ion was by FID-GC, s e n s i t i v e t o 10 ng o f 3,4-dimethoxy acetophenone
w i t h a 1 u l i n j e c t i o n . This suggests t h a t no d iscernable organic compounds
were present a t concentrat ions above 10 ppb. The pH o f the water, de te r -
mined by Fisher , ACCumet Model 420 D i g i t a l pH/ion meter averaged 6.91 w i t h
a standard dev ia t i on of 0.12 over a 10 month per iod.
D ie thy l e ther , (C2H5)20, was used as a desorpt ion solvent . I t i s re -
l a t i v e l y i n s o l u b l e i n water, d issolves organic compounds w i t h a wide range
of polar i t ies , i s readily volatilized, and does not freeze a t -70°C.
Absolute di ethyl ether (anhydrous) was purchased from ei ther Matheson
Coleman and Be1 1 Manufacturing Chemists or Ma1 linckrodt, Inc. The sol-
vent was red is t i l led in a glass apparatus a t a slow ra t e , and stored in
extracted tinned cans with teflon cap l iners . The d i s t i l l a t e tha t came
over from 34.6 -35.Z°C was retained. Purity was determined by FID-GC.
A t 80°C, w i t h an OW 101 column, only one peak i s recorded (74 sec.) . A t
225°C with a porapack QS column, four peaks are recorded a t 10,19,39 and
56 seconds. The major peak i s a t 39 seconds and contained onver ninety-
nine percent of the total peak area.
Pesticide quality acetone, (CH3COCH3) was used to dissolve and d i lu te
organic compounds prior to dissolution of them in purified water, and i s
used w i t h ether for desorption. The solvent was purchased from Matheson
in dark glass one gallon bottles w i t h teflon lined caps. Purity was
determined by FID-GC. A t 100°C, with an BV 101 column, one peak i s re-
corded a t f i f t y seconds,
Organic Solutes: Eleven organic compounds were used to evaluate
the extraction scheme. Two other organic compounds were used as internal
standards to determine efficiency of the freezing and concentrating step.
(1) Anthracene, C I 4 H l 0 , M.W. 178.23, a solid a t room temperature, was
purchased from Eastman Chemicals. Flat white crystals typically 2-1 5 mm
in diameter, the chemical was dissolved in ether and analyzed for purity
by FID-GC. On OV 101 a t 218°C one sharp peak was detected a t 345 seconds.
( 2 ) 3,4-Dlmethoxy-acetophenone , CIOH1 M.W. 180.20, a solid a t
room temperature, was purchased from Aldrich Chemical Co. Transparent
prisms of varying s i z e s , the c ry s t a l s tended t o aggregate i n to opaque
chunks. Puri ty was determined by FID-GC. A t 180°C w i t h OV 101 one sharp
peak was detected a t 352 seconds.
(3 ) Benthiazole, C7H5NS, M.W. 135.19, a l iquid a t room temperature,
was purchased from Aldrich. The pur i ty of the c l e a r l iqu id , having a
f a i n t almond odor, was determined by FID-GC. A t 150°C w i t h an OV 101
column, one very sharp peak was detected a t 230 seconds.
( 4 ) m-Xylene, C8H10, M.W. 106.17, a l iquid a t room temperature, was
purchased from Aldrich. The s l i g h t l y amber l iquid was d i s t i l l e d , and then
stored i n a g lass bo t t l e . The f ract ion from 136.5 - 137°C was c l ea r and
produced a l i g h t mothball odor. Puri ty was determined by FID-GC. Program-
ing a t 4"/rnin from 45°C t o llO°C w i t h an OV 101 column, three peaks were
observed a t 403, 688 and 724 'seconds. The second peak accounted f o r near- -
ly a l l of the peak area . Chromatography of 300 ng of the d i s t i l l a t e , in
e t he r , w i t h a porapack QS column a t 225OC, produced a s ing le peak a t 358
seconds.
(5) o-Xylene, C8tt l0, M.W. 106.17, a l iquid a t room temperature, was
purchased from Eastman Chemicals. The c l ea r l iqu id , s tored in a brown glass
bo t t l e , produced a s ing le peak by FID-GC w i t h a porapack QS column a t 225OC.
Retention time was 272 seconds.
(6 ) p-Xylene, C8Hl0 , M.W. 106.17 a l iquid a t room temperature, was
purchased from Eastman Chemicals. The c l ea r l iqu id , s tored i n a brown
glass bo t t l e , produced a s ing le peak by FID-GC w i t h a porapack QS column
a t 225°C. Retention time was 241 seconds.
(7 ) Toluene, C7H8, M.S. 92.13, a l iqu id a t room temperature, was pur-
chased from A l l i e d Chemicals. The c l e a r l i q u i d , s to red i n a brown b o t t l e ,
produced a s i n g l e sharp peak by FID-GC w i t h a Porapack Q column a t 215°C.
Retent ion t ime was 86 seconds.
(8) Ethy l Benzene, C8H10, M.W. 106.17, a l i q u i d a t room temperature,
was purchased from Aldr ich . The c l e a r l i q u i d , s to red i n a brown glass
b o t t l e , produced a s ing le sharp peak by FID-GC w i t h a Porapack Q column a t
215°C. Retent ion t ime was 160 seconds.
(9 ) Cumene, [i sopropyl benzene] CgH1 2, M. W. 120.20, was purchased
from Aldr ich . The c l e a r l i q u i d , s to red i n a brown glass b o t t l e , produced
a s ing le sharp peak by FID-GC w i t h a Porapack Q column a t 215°C. Reten-
t i o n t ime was 284 seconds. Cumene was used as an i n t e r n a l standard w i t h
the xylene isomers.
(10) 3-Methyl Butanoic Acid, [ i s o - v a l e r i c ac id] C5H1002, M.W. 102.13,
a l i q u i d having a pungent stench was purchased from Eastman. P u r i t y was
determined by FID-GC. A t 125°C w i t h a Porapack Q column, one sharp peak
was observed a t 400 seconds.
(11) n-Nonane CgHZ0, M.W. 128.26, a l i q u i d a t room temperature, was
obtained from Aldr ich . Used as an i n t e r n a l standard w i t h i s o v a l a r i c
acid, toluene, e t h y l benzene and cumene, the c l e a r l i q u i d was n o t red i s -
t i l l e d . A t 215"C, w i t h a porapack Q column, a sharp peak was observed a t
501 seconds. No i n t e r f e r i n g peaks were observed a t the r e t e n t i o n times
f o r the experimental compounds.
(1 2) n-Hexadecane, C16H34, M. W. 226.45, a 1 i q u i d a t room temperature,
was obtained from Aldr ich . Used as a so lu te and an i n t e r n a l standard w i t h
.; anthracene, 3,4-dimethoxy-acetophenone, and Benzothiazole, the c l e a r 1 i q u i d
was n o t r e d i s t i l l e d . A t each of the fo l low?ng temperatures, o n l y one peak
was observed, and no in te r fe rence peaks were observed a t the e l u t i o n s t imes
o f the compounds under i nves t i ga t i on : 150°C-603 sec. , 180°C-451 sec. ,
21 0°C-207 sec ,
(13) n-Octadecane, C18H38, M.W. 254.5, a s o l i d a t room temperature,
was obtaf ned from A ld r i ch . Used as an i n t e r n a l standard w i t h hexadecane,
the opaque s o l i d was no t pu r i f i ed . A t 210°C w i t h a OV 101 column, a s i n g l e
peak was observed a t 620 seconds.
Gas Chromatography: Determinations of concentrat ions of organic
so lu tes i n both water and e the r were determined by flame i o n i z a t i o n gas
chromatography (FID-GC) . A Perk i n Elmer Model 900 gas chromatograph
coupled t o an I n f o t r o n i c s e l e c t r o n i c d i g i t a l i n t e g r a t o r Model 208 and a
Westronics s t r i p c h a r t recorder was used t o de tec t organics present a t
p a r t per mi 11 i o n concentrat ions w i t h one micro1 i t e r i n j e c t i o n s . Table 2-1
i nd i ca tes t y p i c a l GC parameters and columns used throughout the exper i -
mentat ion.
S e n s i t i v i t y o f GC was determined fo r each s o l u t e by ana lys is o f an
e the r d i l u t i on ser ies o f au thent ic standard compounds. Accuracy was
determined fo r each s o l u t e a t the same t ime by repeated i n j e c t i o n s of
known amounts. Peak he igh t and i n t e g r a t o r p r i n t o u t s were used f o r quan t i t a -
t i o n by comparison w i t h the peak heights and p r i n t o u t s o f standard d i l u t i o n s
analysed a t the same time. This method, al though more t ime consuming, was
more r e l i a b l e than i f a c a l i b r a t i o n curve was used. This i s j u s t i f i e d be-
cause no one compound received enough a t t e n t i o n t o b u i l d an excep t i ona l l y
s tab le c a l i b r a t i o n curve, a t best, an even more t ime consuming procedure.
Table 2-1
GAS CHROMATOGRAPH1 C PA
Gas Chromatograph Column Temperature
In jector Temperature Mani f 01 d Temperature Detector Carrter Gas Carrier Flow Rate Hydrogen Pressure Air Pressure Operation Mode
Columns
Sol id Support Stat ionary Phase Column Ma t e r i a1 : Column Plugs Length Outside Diameter Inside Diameter Theoretical Pla tes ( N )
Benzothiazole dimethoxyacetophenone A n t hracene
I I Sol id Support Stat ionary Phase Column Material Column Plugs Length Outs i de D i ame t e r Inside Diameter Theoretical Pla tes (N)
iso-valer ic acid
I11 Sol id Support Stat ionary Phase Column Material Column Plugs Length Outside Diameter Inside Diameter Theoretical Pla tes (N)
m-Xylene
Perkin Elmer Model 900 Operated isothermally a t tempera- tu res from 150' t o 225T Ten degrees g rea te r than column Twenty degrees g rea te r than column Flame ionization Nitrogen (Zero Grade Gas) 45 ml/mi n 22 PSIG 30 PSIG Single Column (uncompensated
Chromasorb W , 60-80 mesh 10% ov-101 S ta in less Steel Si 1 ani zed G I a s s Wool 1 .8 m 3.17 mm 2.0 mm
1617 1129 3481
Porapack Q, 50-80 mesh None S ta in less Steel Si 1 ani zed Glass Wool 1.8 m 3.17 mm 2.0 mm
Porapack QS, 50-80 mesh None S ta in less Steel Silanized Glass Wool 1.8 m 3.17 mm 2.0 mm
455
Although r e t e n t i o n time, i n seconds, were der ived from the i n t e g r a t o r p r i n t -
out , q u a n t i t a t i o n was done by peak he igh t measurements. The peak he igh ts
were se lec ted over the i n t e g r a t o r on the bas i s o f dev ia t i on o f q u a n t i t a t i o n .
Using reference s o l u t i o n of xylene, standard dev ia t i on o f peak he igh ts was
determined t o be approximately f i v e percent o f a h a l f scale d e f l e c t i o n .
The var iance increased f o r smal ler de f l ec t i ons , so a t tenua t i on was ad jus t -
ed t o p rov ide l a r g e scale de f l ec t i ons .
Standard dev ia t i on of the i n t e g r a t o r p r i n t o u t was greater than t e n
percent f o r t he maximum s e n s i t i v i t y requ i red by the experimentat ion,
Retent ion t imes and detec tor response va r ied s l i g h t l y from day t o
day, b u t was m i t i g a t e d by the q u a n t i t a t i o n technique t h a t depended upon
standard d i l u t i o n ser ies i n j e c t i o n s i n teg ra ted w i t h experimental i n j e c t i o n s .
S e n s i t i v i t y o f the GC d i d n o t appear t o change over t h e pe r iod o f expe r i -
mentat ion w l t h the except ion of when the gas t r a i n was open f o r a p e r i o d
o f approximately a month. The detec tor was cleaned, and s e n s i t i v i t y r e -
turned,
The g lass i n j e c t o r l i n e r s were a c i d cleaned when they appeared d i r t y
upon v i sua l insepct ion. Leaks and contaminat ion of the column d i d n o t
appear t o occur, and were c o n t r o l l e d by c a r e f u l assembly o f the gas t r a i n
and adequate baking o u t of the columns before use. Columns t h a t remained
i n the GC f o r long per iods o f t ime were kept a t temperatures above t h a t
a t which they were operated, b u t below t h e i r maximum recommended l e v e l s .
Septums were replaced f requent ly , u s u a l l y upon gross l o s s o f s e n s i t i v i t y .
With the except ion o f when the detectors were cleaned, t h i s took car6 o f
any losses i n s e n s i t i v i t y . Septums were ex t rac ted w i t h acetone p r i o r t o
use, a p r a c t i c e t h a t began immediately a f t e r gross i n te r fe rence was caused
by an apparently clean and new septum. No problems were noticed af te r
th i s practice began. l'njection of pure ether or water was used to indi-
cate lack of column of septa contamination prior to quantitation of experi-
each sample
standard di
the samples
mental aliquots.
Approximately 1.0 micro1 i t e r of each sample, measured and recorded
accurately to 0.05 ul was injected onto the column. To insure accuracy,
was injected a t least twice. Typically, injections of the
lution that would most nearly approximate the peak heights of
were made af te r every three or four sample injections.
Equipment: The cold sink required for drying of the solvent prior
concentration i s an upright Kelvanator Series 100 Ultracold Freezer. The
temperature of the freezer i s maintained a t -70°C. The freezer i s opened
two to s ix times a day. Such frequent use allows ice formation on the
shelves and doors. A1 l flasks or containers placed into the cold sink
were covered with aluminum fo i l to prevent contamination.
A steam bath i s used t o evaporate the solvent during the concentration
step. A Fisher Thermix hot plate provided heat and a support for an eigh-
teen cm. diameter by 12 cm. deep copper steambath, w i t h concentric ring
cover. Heat to the evaporator was controlled by use of the concentric ring
cover. The hot plate was placed on maximum temperature and non re-adjusted.
Desorption of the solute occurs while the resin i s shaken w i t h ether
within the extraction glass column. The column, described below, i s shaken
by a Burrel Wrist-Action Shaker. This apparatus can be adjusted to shake
twelve tubes through a l l degrees from vert ic le t o horizontal. I t was used
in the horizontal position only.
Glassware: Various pieces o f standard l abo ra to ry glassware were used.
These vessels a re i nd i ca ted i n the experimental methods sect ion. One i t em
was designed and manufactured s p e c i f i c a l l y f o r the r e s i n work. The r e s i n
column has been designated the Schnare Tube, and was designed i n our
labora tory . Th is tube i s g lass and s t a i n l e s s s tee l mesh as i n d i c a t e d i n
f i g u r e 2-2. O f p a r t i c u l a r s ign i f i cance are the two capping arrangements.
As i n d i c a t e d i n the f igure , the tube can be capped w i t h pe r fo ra ted con-
nectors c o n s i s t i n g of t e f l o n washers and a per forated cap which seals the
washer onto the tube and around the connect ing tubing. The tube can a l s o
be closed completely w i t h so l i d caps and t e f l o n l i n e r s . The t e s t tubes
and capping apparatus are French products f rom Sov i re l . The s t a i n l e s s s t e e l
screen i s approximately 100 mesh. The Schnare tubes were constructed by
U n i v e r s i t y Glassware, Carrboro, North Carol ina.
While t h i s device prov ides a convenient method f o r doing the adsorp-
t i o n and e l u t i o n of organics from XAD res ins , many o ther column arrange-
ments are poss ib le t h a t should y i e l d comparable r e s u l t s . The most s i g n i f i -
cant cons idera t ion i s t o p rov ide adequate mix ing of t he r e s i n w i t h the
e l u t i n g so lvent t o achieve maximum removal of adsorbed organics from the
res in .
A l l glassware used was scrubbed w i t h h o t water and Alconox detergent,
r i nsed w i t h tap water, acetone, then carbon f i l t e r e d deionized water. A f t e r
d ra in ing , the glassware i s l e f t f o r a t l e a s t e i g h t hours i n an oven main-
ta ined a t 20Q°C. A f te r dry ing, vessels and tubes are capped w i t h aluminum
f o i l u n t i l used.
Figure 2-2
THE SCFF$ARJ3 TUBE
Experimental Procedures
S i x groups o f experiments were conducted i n l i n e w i t h t h e f i v e ques-
t i o n s p rev ious l y described: (1) t e s t i n g o f the XAD adsorp t ion method as
repo r ted by Junk e t a l . (1974), (2) t e s t i n g of the Caro l ina method as
developed by the authors, (3 ) de termina t ion of the load ing c a p a c i t i e s o f
the r e s i n , (4 ) de termina t ion o f t he i n f l u e n c e o f p o l a r i t y on recovery
e f f i c i e n c y , (5) determinat ion o f t he i n f l uence o f molecular c o n f i g u r a t i o n
on recovery e f f i c iency , and (6) de termina t ion of t he i n f l u e n c e o f so l ven t
s e l e c t i o n and con tac t t ime on desorpt ion e f f i c i e n c y .
Iowa Method: The Iowa method was used as repor ted by Junk -- e t a1 . (1974) w i t h one mod i f i ca t i on . An i n t e r n a l standard was used t o determine
e f f i c i ency o f the f r e e z i n g and concent ra t ion steps. Essent ia l l y , the
method fo l lows t h e f low diagram i n F igure 2-1 w i t h the except ion t h a t de-
s o r p t i o n i s n o t a ided by shaking o f the res in . F igure 2-3 i s a sca le draw-
i n g of the Junk apparatus. I t was cons t ruc ted i n our l a b o r a t o r y accord-
i n g t o 1 i t e r a t u r e s p e c i f i c a t i o n s .
The referenced a n a l y t i c a l procedure lacks some important comments
about anomolies o f the method. To insure t h a t t he re i s no confusion about
what was done w h i l e us ing the Iowa method, the fo l l ow ing notes p rov ide
clarification on the nature of the anomolies, and the steps taken t o over-
come them,
Column preparat ion: During column preparat ion, a methanol sa tu ra ted
column o f r e s i n i s doused w i t h water. The heat o f s o l u t i o n o f methanol i n
water i s s u f f i c i e n t l y h igh t o cause gas bubble formation i n and around the
beads o f the r e s i n . These evacuated po r t i ons o f t he column remain f r e e
Figure 2-3
Scale drawing of Junk apparatus ( 9 4 ) . A - pure inert gas pressure source; B - cap; C - 2 l i t e r reservoir; D - 24/40; E - silanized glass plugs; F - 0.6 cm I . D . x 10 cm column of XAD-2 20-60 mesh; G - PTFE stopcock.
of water no mat te r what amount i s f lushed downward through the column.
This i s an undesi rable cond i t i on s ince n o t a l l t he r e s i n i s being used, and
therefore the capac i ty of the r e s i n bed i s lowered. Fur ther , there may be
channelization of t he f low of l i q u i d through the column which m igh t qu ick-
l y m i t l g a t e the u t i l i t y of the column as the adsorpt ive sur face area o f t he
channel may be r a p i d l y f i l l e d . Two procedures can be used t o i nsu re a
sa tura ted column f ree o f gas fil l e d voids. The column may be tapped w i t h
a rubber t i p p e d s t i r i n g rod. This w i l l j a r gas bubbles f r e e from t h e i r
p o s i t i o n as the r e s i n beads rearrange themselves. This i s t ime consuming.
A second method i s quicker , b u t requ i res more e labora te preparat ion. A
back f lush ing o r upward f low of water through the column q u i c k l y f r e e s
trapped bubbles, The r a p i d reverse f low tends t o send the e n t i r e column
o f r e s i n o u t the top of the glassware, so a pumping motion impar t i ng pulses
of reversed f low water i s suggested, al though a very gen t l e reverse f l o w
f o r a longer t ime works as w e l l . Th is takes about one and one h a l f minutes
A f t e r the column i s completely saturated w i t h water, th ree 20 m l p o r t i o n s
o f pure water a re appl ied. A very uniform column, w i t h l a r g e beads on the
bottom i s the r e s u l t o f t h i s change i n procedure.
Sample preparat ion: The Iowa method suggests adding organic so lu tes
d i l u t e d w i t h e t h e r o r methanol. Adding e the r t o a r e s e r v o i r o f water
tends t o t rans fe r the organic so lu tes i n the water i n t o the e the r l a y e r
t h a t i s f l o a t i n g around on the top of the water. When attempted, i t was
found t h a t t he e ther f r a c t i o n never d i d reach the column, b u t was he ld up
a t the c o n s t r i c t i o n s o f the glassware. When the resevo i r was washed w i t h
water, the e the r f r a c t i o n r e f l o a t e d and again s e t t l e d on the w a l l s o f t he
glassware, Acetone was used t o aid dilution of the organic solutes in
water.
With simple injection of the solute into a calm reservoir, mixing
takes place very slowly. When anthracene was injected into the reservoir,
i t immediately came out of solution and gradually f e l l o u t onto the reser-
voir walls. Such an experimental procedure does not simulate natural
Waters containing dissolved organic compounds. Because of the construc-
tion of the apparatus, mixing of the reservoir could n o t be done.
Column Extraction: Extraction of the water was not different from
that described by Junk. However, washing the walls of the reservoir with
20 ml of pure water three times can only be done effectively i f the re-
servoir i s removed from the column and the water agitated within the
vessel. Removal of the reservoir a1 lows some of the organic material tha t
collected on the constrictions around the joint to drip off or evaporate.
When the reservoir i s l e f t in place, not even three washings will adequate-
ly wash the ent i re reservoir surface area.
Elution: Washing of the reservoir walls with two ten ml portions of
ether was found to be inadequate. Large crystals of anthracene were l e f t
on the walls of the reservoir a f t e r t h i s step. The assumption tha t ether
poured into a drained, b u t water saturated, column of XAD-2 resin will mix
well i s also invalid. A t no point did the ether flow past the f i r s t glass
wool plug, Furthermore, no more than two or three drops of the ether ever
passed through the column in less than ten minutes with the stopcock fu l ly
open. A nitrogen head had to be applied t o push the ether t h r o u g h the
column. Rarely d i d more than 10 ml of ether ever get collected, wlth or
without a nltrogen head.
Carol i n a Method
Column Preparat ion: The apparatus used f o r removing t r a c e organi cs
from water i s shown i n f i gu re 2-1 and 2-2. With the siphon and top tub-
i n g adaptor detached, the lower tub ing adaptor i n p lace and c losed o f f ,
p u r i f i e d water s u f f i c i e n t t o cover the mesh i s al lowed i n t o the column.
If the water does n o t move through the mesh, ten t o f i f t e e n pumping
squeezes on the lower tub ing w i l l f o r ce trapped a i r o u t o f the lower por-
t i o n of the rese rvo i r . P u r i f i e d XAD r e s i n i n a methanol s l u r r y i s added
u n t i l an 80 mrn column bed i s formed. An etched r i n g on the column i n d i c a t -
ed the proper he igh t . Add i t i on o f the r e s i n was f a c i l i t a t e d by use o f a
10 m l p i p e t w i t h t i p removed. Methanol i s al lowed t o d r a i n from the tube
u n t i l the l i q u i d reached the top o f the r e s i n bed. The r e s e r v o i r s iphon
(F igure 2-1 ) i s at tached l oose ly and p u r i f i e d water from the r e s e r v o i r i s
a l lowed t o fill the tube. The r e s e r v o i r siphon i s then f i r m l y at tached
and approximately 200 ml o f water i s al lowed t o f l ow through the column.
A t t h i s p o i n t two phenomena occur: (1 ) gas bubbles form i n the column,
and ( 2 ) an e t h e r bubble forms a t the top of the tube. The r e s e r v o i r s iphon
i s disconnected. Water i s al lowed t o g e n t l y en te r the tube from the
bottom thereby causing a backf lushing, c a r r y i n g away the e the r and a few
f l o a t i n g beads. With the cap s t i l l d isconnected,. the,resin bed i s g e n t l y
d i s tu rbed by a s w i r l i n g motion o f a s t i f f s t a i n l e s s s t e e l wi re. The mot ion
i s cont inued u n t i l the gas bubbles trapped i n the r e s i n column a re removed
and the r e s i n bed appears uniform. S u f f i c i e n t water i s in t roduced i n t o
the tube so as t o f i l l i t. The siphon i s reconnected and an a d d i t i o n a l
f i f t y m l water i s al lowed t o f low through the column. A t t h i s p o i n t t h e
column may be stored fo r a day or tws with both ends sealed by rubber t u b -
ing clamps. This preparative operation requires appr~ximately f ive minutes
per tube.
Sample preparation: The reservoir i s f i l l e d with suff ic ient purified
water to allow one l i t e r of water per extraction tube to be used, plus an
extra 500 ml of water to insure good siphoning. Acetone i s used to d i lu te
the organic solute into the water. A calibrated volume of the dissolved
organic solute i s injected into the reservoir. A magnetic s t i r r e r i s used
and adjusted throughout the extraction procedure to insure good mixing in
the reservoir, The reservoir i s allowed to mix for approximately f ive
minutes t o insure proper dissolution. In th i s study, the amounts of organic
compounds added varied from 50 to 300 ug/l i t e r (ppb). Additional pretreat-
ment of the water such as pH adjustment, or addition of s a l t , i s done
immediately a f t e r injection of the organic solute. In the case of the
organic acid tested during this work, approximately 10 rnl of concentrated
HC1 was added to b r i n g the pH to about two as determined by paper pH tape.
Column Extraction: Both pinch clamps are removed to allow gravity
flow of the prepared water through the column and into a graduated flask
or beaker. Flow rates vary s l ight ly as the level of the reservoir decreases,
and average one hundred rnl per minute. Slower flow rates can be maintain-
ed with the use of adjustable clamps a t the lower tubing adapter. After
one l i t e r of the water i s allowed to flow through the column, the flow i s
stopped and the column i s a1 lowed to drain.
Elution and Internal Standardization: The tube i s removed from the
siphon equipment, and both caps are removed while insuring tha t the tube
i s kept up r igh t . Excess water i s a l lowed t o f l ow i n t o the measuring
beaker i f a second e x t r a c t i o n i s t o be done. The r e s l n remains wetted.
A s o l i d cap and l i n e r i s p laced on the bottom o f the tube. A known amount
of an i n t e r n a l standard, d isso lved i n a known amount o f ether , i s added
as the i n i t i a l a l i q u o t of so lvent begins t o saturated the r e s i n . The r e s i n
bed w i l l con ta in many a i r pockets, some o f which are removed by gen t l e
s w i r l i n g w i t h a s t a i n l e s s s tee l w i re . The top cap and l i n e r i s t igh tened
down and the tube i s inver ted . The bottom cap (now on top) i s removed
and add i t i ona l e the r s u f f i c i e n t t o fill the tube i s added. The cap i s re -
placed and the tube i s shaken w i t h s u f f i c i e n t f o rce t o d is lodge t h e r e s i n
bed, so as t o f a c i l i t a t e good mix ing. The tube i s attached h o r i z o n t a l l y
t o a w r i s t a c t i o n shaker and al lowed t o shake f o r var ious chosen e l u t i o n
t imes. A f t e r shaking, the tube i s removed from the shaker and tapped
g e n t l y t o re fo rm the r e s i n bed. The tube i s i nve r ted and t h e bottom cap
removed. The tube i s r i g h t e d and the so lvent i s poured i n t o a small f l a s k
o f twenty t o f i f t y m l . capaci ty . The top cap i s removed and the remaining
so lvent f lows i n t o the small f l a s k . An a d d i t i o n a l t e n m l o f c lean e t h e r
i s poured i n t o the tube and al lowed t o d r a i n through the column i n t o t h e
c o l l e c t i o n f l a s k . I f a second e l u t i o n i s t o be done, the tube i s r e f i l l e d
w i t h so lvent and e lu ted again as described above.
Drying: The f l a s k i s covered w i t h aluminum f o i l and p laced i n t o an
u l t r a - c o l d f reezer (-70°C) f o r f i f t e e n minutes. An a1 i q u o t o f p u r i f i e d
e ther i s a l so p laced i n t o t h e f reezer . Upon removal, the d r i e d e l u t a n t
i s q u i c k l y poured i n t o a Kudurna-Danish evaporator through a s i l an i zed
glass wool p lug placed i n a g lass funnel. The i c e l e f t behind i s washed
w i t h a two t o th ree m l a l i q u o t o f the equa l l y c h i l l e d ether . Th i s i s re -
frozen, then i s added t o the I n i t i a l e l u t n n t . T y p i c a l l y , two t o f i v e ml
o f water i s removed by t h i s procedure.
Concentrat ion: The d r i e d e the r i s t r ans fe red t o a Kuderna-Danish
evaporator and i s then reduced i n volume t o one ml by g e n t l e heat ing
over a steam bath. Evaporat ion r a t e s are n o t c r i t i c a l because of t he i n -
t e r n a l standard, b u t the slower the evaporat ion r a t e , the g rea te r t h e
e f f i c i e n c y o f the concent ra t ion step. T y p i c a l l y , t he b o i l i n g of t he e t h e r
i s aided by a p o r c e l a i n b o i l i n g ch ip, b u t even t h a t a i d does n o t e l i m i n a t e
r e l a t i v e l y r a p i d bubbl ing when volumes are below th ree m l . The end p o i n t
o f t he concent ra t ion i s n o t e a s i l y observed due t o t h i s phenomenon. The
evaporator i s removed from t h e heat source when the re i s d e f i n i t e l y l e s s
than one m l l e f t i n the KD th imble. Rapid c o o l i n g o f t he evaporator occurs
upon removal o f t h e heat source and condensing e t h e r washes t h e w a l l s of
t he KD. The th imb le i s q u i c k l y removed from the evaporator when i t i s
f i l l e d t o one ml. A ground g lass stopper i s used t o cap the th imb le un-
t i l measurement o f t he s o l u t e by GLC. Chromatographic ana l ys i s i s u s u a l l y
done no l a t e r than one day a f t e r concentrat ion. F i n a l one ml a l i q u o t s a re
r e f r i g e r a t e d if an i n t e r v a l of more than a few minutes i s expected t o
elapse before c h a r a c t e r i z a t i o n by GLC.
Determinat ion of load ing capac i ty o f XAD r e s i n : Prepara t ion o f
the column and so lu tes i s done e x a c t l y as descr ibed i n the Caro l ina Method
above. Rather than determine the amount o f mass adsorbed by the column,
the amount of s o l u t e n o t adsorbed by t h e column was measured. A one m l
sample was drawn a t f i v e m l i n t e r v a l s . From t h a t column e f f l u e n t sample,
a one u l a l i q u o t was i n j e c t e d i n t o t h e GLC and the r e s u l t a n t peak r e f l e c t -
ed the concent ra t ion o f s o l u t e i n the column e f f l u e n t . Minimum concentra-
tions quantifiable were f ive percent of the in i t i a l concentration of the
prepared solute (prior to extraction by the resin column).
Anthracene was not tested since i t i s so insoluble i n water tha t a
saturated solution i s marginal 1y quantifiable without further concentra-
t i on, Otherwise, typical concentrations of the prepared waters were 100
mg per 1 i t e r (ppm).
Sect4 on Three
Results and Discussion
As the protocol i n Section two indicates, s ix evaluation actions will
describe the merits and weaknesses of the experimental work conducted.
Some of these evaluations such as ab i l i t y to adsorb, or ab i l i t y to desorb,
can be deal t with in d i s t inc t sections. Other evaluations must be carried
through each part of th i s section. For that reason, the resul ts of the
work undertaken by the authors will be compared with that of Junk e t a l .
(l974), Webb (l975), Musty and Nickless (l974), and Goldberg-et a l . (1973).
Of primary importance are three experimental phases of the work w i t h
the Carolina Method: (1 ) extraction of solutes from water, (2) desorption
of solutes from the resin, and ( 3 ) concentration of the solutes by solvent
evapora t i on.
(1) Extraction of solutes from water: The a b i l i t y of the XAD-2 macro-
re t icu lar resin to extract non-volati l e organic solutes from water has been
reported t o range from 100% t o less than 4% for widely differing compounds
(Junk -- e t a1 . , 1974; Webb, 1975). Junk e t a1 . (3974) has concluded: "These
porous polymer resins are completely effective i n extracing neutral organic
solutes from water. Many dissociated solutes are also extracted provided
the acidi ty of the water sample i s adjusted prior to the..extraction. No
significant improvements or detrimental effects can be defini te ly a t t r ibut -
ed to salting-out, flowrate variations, pore diameter, bead s ize, resin
bed volume, and mixtures vs. s i ngl e component contaminationsN.
To the contrary, Harvey (1973) reports that there i s an optimal bed
dimension, and that flow rates are significant. Webb (1975) also reports
that flow rate significantly influences extraction efficiency; and
fur ther , that the resin adsorbs the polar and aromatic portions of fuel
o i l , b u t n o t the al iphat ic hydrocarbons. Musty and Nickless (1974) also
report tha t flow rate exerts a significant influence on extraction e f f i -
ciency.
The significance of the bed dimension was n o t tested by th i s research.
The recommendation of Harvey (1973) for a column depth seven times the
diameter of the column was followed throughout. For the Schnare Tube,
the resin column i s 1.15 cm x 8.0 cm.
The capacity of the XAD-2 resin t o adsorb four non-volati
solutes i s indicated in Table 3-1. A 95% adsorption level (5%
occurs a t loading rates we1 1 in excess of that concentration n
l e organic
leakage)
orma 1 ly
found in natural or polluted water. In a l l cases, i t was possible t o p u t
a t l eas t three milligrams of solute onto one gram of resin with no more than
5% leakage. These capacities compare favorably with other reported data.
Rohm and Haas loaded phenol a t 73 mg/g resin w i t h a very low leak ra te ,
and Musty and Nickless (1974) loaded lindane a t 20 mglg resin with an
apparent s ix percent leak rate. Figure 3-1 indicates the nature of leak-
age through a column as loading increases for compounds of varying polarity.
A t s imilar flow rates , the resin adsorbs greater amounts of non-polar
solutes than polar or dissociated solutes, even when pH i s adjusted to
favorable condi t ions,
The ef fec t of two flow rates on adsorptive capacity was determined
with iso-valeric acid. Figure 3-1 indicates that a flow rate of 10 ml/rnin
Table 3-1
CAPACITY OF THE XAD-2 RESEN TO RETArN ORGANIC SOLUTES ON AN 80 X 11.5 mm BED
mg s o l u t e adsorbed p e r gram r e s i n , w i t h column leakage of:
Col umn Compound 5% 10% 20% 40% F l ow Rate
m-Xyl ene
Benzothi azo l e 29.5 36.6 43.3 59.8 100
3,4-Dimethoxy 68.6 7.5 10. - 100 acetophenone
f soval e r i c Acid* 2.19 3.4 4.7 - 100 8.4 12. 15. - 10
* pH o f wate r was ad jus ted t o approx imate ly pH = 2 p r i o r t o c o l urnn e x t r a c t i on
Flow Rate
I Isovalaric Acid (pH 7) 10 rnl/min 11 Isovalaric Acid (pH 2) 100 ml/min I11 3,4-dimethoxy
acetophenone (pH 7) 100 ml/min
IV Isovalaric Acid (pH 2) 10 ml/min V Benzothiazole (pH 7) 100 rnl/min VI m-Xylene (pH 7) 100 ml/min
mg solute/gram resin
Figure 3 d
LEAKAGE VS. LOADING FOR AN 80 x 11.5 mm XAD-2 RESIN COLUMN
w aJ L ce a E U
3 s a,
.r- U .r 'I- '4- aJ
E: 0 -r C, 0 (d L C, X a,
rn aJ V) m a, L U s -r
s st'-
E --. P
E 0 @.I
I 0 - C, 3 0 n m '4- 0
aJ C, m L
3 0 7
cc
5 L '4-
V) aJ C, 3 P 0 V)
% 0
h U s aJ .r- 0
%--
'I- '4- a,
s 0 -P- c, 3 2 L 0 V) al PI
'4- 0
C 0 .I-- C, U 6 3 '4-
m V) .r
>, F
m 5 C m 6, E: a L (d Q Q a aJ c LP
I a L 0 V) aJ PI
1, P aJ > -r C, U aJ 'I- rc aJ C, 0 s aJ L m 2, w r C,
C, a r C,
V) aJ C, m L
3 0
L
i5 7
t' m 2, 7
C, r m T-
C,
0 V)
n L O V) PI m 0 C,
C, s aJ .r U "7
'4- '4- 3 V)
aJ a 0 C,
rn % W Q) Q a m 2, C, .I?- U m Q m U
a, c I-
V) aJ C, ce L
B P
'I-
'4- 0
1, C, a, v- L m > m C, m M b a, C, m 3
Table 3-2
THE EFFECT OF FLOW' RATE ON RECOVERY EFFICIENCY
% Recovered -% Rec~ve red Compound @ 10 ml/min @ 100 m l / m i n
Neutra 1 Compounds
m-Xy? ene 19.4 40.8 i ncrease
o-Xyl ene 26.3 27.8
p- Xyl ene
To1 uene
E t h y l Benzene 63.8
Cumene 59.9
39.8 inc rease
81.9 increase
84.6 i ncrease
85.3 i ncrease
Po la r Compounds
Benzothi azole 87.5
3,4-Dimethoxy acetophenone 85.3
95.1 inc rease
62.6 decrease
~ s o v a l e r l c Ac id 79.0 42.3 decrease
applications i t i s c r i t i ca l that a large enough resin bed be used so column
capacity i s not exceeded.
( 2 ) Desorption of solutes from the resin: Since most compounds appear
ed, and an internal standard has Been included that accounts
for losses of solute mass during the concentration step, the recoveries that
a re observed can be presumed t o be direct ly ref lect ive of desorption e f f i -
ciency, when a1 1 other con i tions are favorable. Four factors were i n -
vestigated to determine the degree to which they affected desorption
efficiency, solvent selection, polarity of the solutes, a l iphat ic and
aromatic nature of the solutes, and batch or column desorption technique.
There i s some question as to the u t i l i t y of flow through column de-
sorption, versus batch desorption, in l igh t of the wetting characteristics
of XAD resins. Once a column i s water saturated, ether will not quickly
permeate the top of the column. In the procedure developed by Junk e t a l ,
(1974) a plug of glass wool covers the column. In our use of his method,
ether would not quickly saturate the plug, and was less able t o enter the
resin column. The ten minute period during which ether was to elute the
adsorbed organics i s in actuality only about one minute, the period of time
i t takes to force the ether through the column. A further problem in
column desorption i s the characteristic a i r pocketing tha t occurs when
immiscible, or miscible solvents are replaced by one another as column
elution i s attempted. Such pocketing indicates that there are numerous
areas of resin surface tha t are not brought into contact with the eluting
solvent. Finally, glass wool plugs apparently adsorb some of the solutes.
tdebb C1975) reports up to 15% of the organtc compounds extracted by solvent
methods adhere to a glass wool plug used as a drying agent. Musty and
Nickless (1974) r e p o r t up t o 32% o f i n s e c t i c i d e s s tud ied adhere t o g lass
and g lass wool Before they had an oppor tun i t y t o reach an XAD column. For
t h a t reason, g lass wool was abandoned i n the Carol ina Method. Fur ther ,
w r i s t a c t i o n shaking o f the column w h i l e covered by e l u t i n g so l ven t breaks
up the column and a1 lows we t t i ng of the e n t i r e r e s i n surface. Table 3-3
i nd i ca tes an improvement i n recover ies w i t h the batch-type e l u t i o n when
compared t o the column type e l u t i o n . For m-xylene t h i s accounted f o r an
increase i n recovery from 34.8% recovered by the Junk method t o 46.4% re-
covered by the Carol ina Method. An increase was a l so noted w i t h benzothia-
zole, b u t was not marked, as i n i t i a l recover ies were very high.
A second important c o n d i t i o n f o r s i g n i f i c a n t desorpt ion o f organic
so lu tes i s so l ven t se lec t ion . This i s most s i g n i f i c a n t f o r those so lu tes
t h a t p a r t i t i o n on t o XAD-2 from an organic solvent . Such so lu tes appear t o
be s t r a i g h t cha in hydrocarbons and small neu t ra l aromatic compounds. Table
3-4 i nd i ca tes t h a t normal s t ra igh t - cha in compounds adsorb very w e l l t o XAD-
2 res ins , and do not desorb w e l l a t a l l . S i m i l a r l y , t h e d l - s u b s t i t u t e d
benzenes, meta-,ortho- and para-xylene, appear t o desorb poo r l y f rom the
res in , This does no t seem t o be a func t i on o f p o l a r i t y as e t h y l benzene,
w i t h a d i p o l e moment very s i m i l a r t o o-xylene, i s recovered i n much l a r g e r
amounts. The a f f i n i t y o f t he r e s i n i s f u r t h e r described as s t rong fo r
small neu t ra l aromatic compounds and neu t ra l a1 i p h a t i c compounds as i ndi - cated i n Table 3-2. These f a c t o r s make the amount of any spec i f i c so lu te
t h a t w i l l be recovered by XAD-2 d i f f i c u l t t o p r e d i c t on the bas is of known
chemical c h a r a c t e r i s t i c s . To be ab le t o q u a n t i t a t e organic p o l l u t a n t s i t
i s necessary t o have recovery in format ion f o r each spec l f i c p o l l u t a n t t h a t
must be quan t i f i ed .
Table 3-3
RECOVERY EFFICIENCY WITH RESPECT TO ELUTION TIME AND MODE OF CONTACT
Mode of Compound Contact Time Contact Method % Recovered
m-Xyl ene 10 min quiescent Junk* 34.8 6 0 shaken Carol i na 46.4 6 0 mag s t i r batch 86.8
Benzothiazol e 10 qu i escent Junk 90.1 6 0 shaken Carol i n a 91.9 9 0 shaken Carol i na 95.1
* Junk r e f e r s t o t he Junk -- e t a l . (1974) method as used by the authors, and does no t r e f e r t o recovery e f f i c i e n c y repor ted by Junk
Table 3-4
RECOVERY EFFICIENCY WITH RESPECT TO AROMATIC VERSUS ALIPHATIC SOLUTES
% Recovered D ipo le Compound @ 10 ml/mln Moment Conf igura t ion
n-Hexadecane 12.0* - normal s t r a i g h t - c h a i n
m-Xy4ene 19.4 - d i - subs t i t u t e d (meta)
o- Xyl ene 26.3 0.62 d i - subs t i t u t ed (o r tho )
p- Xyl ene 27.4 0.0 d i - s u b s t i t u t e d (para)
To1 uene 56.5 0.36 mono-substi t u t e d (CH3)
E thy l Benzene 63.8 0.59 mono-su bs t i t u t e d (C2H5)
Cumene 60.3 - mono-substi t u t e d ( i sop ropy l )
* Less than 2% of the n-Hexadecane i n i ti a1 l y present i n t he sample water was found i n the column e f f l u e n t
Proper choice of solvent may mitigate th is very strong at t ract ion.
Table 3-5 shows the e f fec t of varytng the eluting solvent. Recovery of mm
xylene improved from 46.4% t o 72.3% by eluting with 50%aacetone/- 50% ether
rather than pure ether. I t was noted that wetting of the resin occurs more
quickly with the mixed solvents. However, when applied t o the Junk -- e t a l .
(1974) procedure, a i r pockets remained, A further complication with sol-
vents that are miscible in water, such as methanol, Is that they are d i f f i -
c u l t , t o dry, a prerequisite for solvent evaporation.
When considering the ent i re range of compounds that could be present
in water, the use of XAD-2 resin appears useful for recovering a high per-
centage of solutes present. Table 3-6 indicates t h a t with ether, and a t
slow flow rates that encourage high adsorption for most compounds, the polar
compounds are recovered a t re lat ively high levels. If ether i s replaced by
a solvent mixture (acetone/ether), recoveries of about 75% can be expected
for most classes of compounds, and polarity need not appreciably a f fec t re-
covery. The effective use of these resins requires attention to a l l the
variables discussed about, including flow rate , desorpti on solvent, and
method of sol vent/resin contact during desorption. The most c r i t i c a l
factor for achieving high recoveries appears to be the use of a solvent
system that permits maximum contact between the solvent and the surface of
the resin bead, .
(3 ) Concentration of solutes by solvent evaporation: In order to use
detection methods such as GLC/MS, the concentration of a compound must be
on the order of 50 uglml. Elution of s ~ l u t e s adsorbed on the resin resul ts
in an eluate c~ncentrat ion of about 2 ug/ml, compared t o an t n i t i a l water
RECOVERY EFFICIENCY FOR m-XY LENE WITH RESPECT TO SOLVENTS
Sol vent Contact t ime % Recovered
e t h e r
10% acetone/ 90% e the r
50% acetone/ 50% e t h e r
60 min 180
60 180
Table 3-6
RECOVERY EFFICIENCY OF ETHER DESORPTION WITH RESPECT TO POLARITY AND SOLUBILITY
% Recovered % Recovered D ipo le Compound @ 100ml/min @ lOml /m in Moment S o l u b i l i t y
Anthracene 71.8 - 0 i
p-Xylene 39.8 27.4 0
n- Hexadecane 11.7 12.0 - To1 uene 81.9 56.5 0.36
E t hy 1 Benzene 84.6 63.8 0.59 i
o-Xyl ene 27.8 26.3 0.62 i
Benzothiazole 95.1 87.5 - s s
Acetophenone, 62.6 85.3 - 3 ,bdimethoxy
concent ra t ion I n the p a r t per b i l l i o n range. Concentrat ion of the so lu tes
us ing the Kudurna-Dani sh (KD) technique t s s u f f i c i e n t t o i ncrease s o l u t e
concentrat ion t o requ i red l eve l s . There Is, however, some quest ion as t o
the reproduci b i 1 i ty and e f f i c i e n c y o f t h i s concentrat fan technique.
Goldberg e t a1 . (1973) recovered 66% of the to luene i n a ch lo ro form solu-
t i o n b u t recovered on l y 30% o f the to luene i n a carbon t e t r a c h l o r i d e so lu -
t i o n us ing KD techniques. Junk -- e t a l . (1974) designed a spec ia l concentra-
t i o n th imble f o r use w i t h the KD apparatus so as t o e l im ina te v a r i a t i o n i n
recovery e f f i c l e n c y f o r d i f f e r e n t compounds i n the same solvent .
The problems t h a t a r i s e from using the KD technique can be nea r l y
m i t i g a t e d by us ing an i n t e r n a l standard s f m i l a r t o the so lu tes under i n -
ves t i ga t i on . P r i o r t o desorpt ion o f the res in , an organic compound n o t
found i n waters, o r n o t expected t o be found i n waters, can be in t roduced
i n t o the e l u t i o n solvent i n known amounts. Q u a n t i t a t i o n o f t h i s compound
w i l l i n d i c a t e e f f i c i e n c y of the concentrat ion procedure as w e l l as account
f o r losses dur ing shaking o f the e x t r a c t i o n apparatus, t r a n s f e r o f e l u t i o n
solvent , and d ry ing o f the so lvent by f reezing. Table 3-7 i nd i ca tes the
r e p r o d u c i b i l i t y o f the Carol ina Method. The standard dev ia t i on o f r e -
covery e f f i c i e n c i e s was t y p i c a l l y l ess than th ree percent.
Table 3-7
RECOVERY EFFICIENCY OF THREE XAD RESIN METHODS
Compound Sol . Dlpole
Anthracene i
m-Xylene i
onXylene u2
p-Xylene
To1 uene
E thy1 Benzene
Cumene
Benmothiazole
3 ,4-Dimethoxy acetophenone
Iso-valeric Acid
n--Hexadecane
Carol t na Method
100ml /nl n 1 0ml l m t n % SD % sol vent
ether
ether 1 O%acetone 50%acetone
ether
ether
ether
ether
ether
ether
ether
ether
5O%aceton6
clunk Method 2Qn1 / m i n
a Reported in Junk e t a l . (1974)
Reported in Webb (1975)
APPENDIX A
A Topical Bi bl iography
Chemical and Theoretical Properties of XAD Resins
Gustafson, R. and Paleos, J., "Chapter Ten -Interactions responsible for the selective adsorption of organics on organic surfaces", Faust, S.B. and Hunter, J.V., ed., Organic Compounds in Aquatic Environments, Marcel Dekker, New York, 1971 , pp. 21 3-237.
Rohm and Haas Company, "Summary Bulletin Amberlite Polymeric Adsorbents", Rohm and Haas Research Division, Philadelphia, Pennsylvania.
Schneider, H., Kresheck, G. and Scheraga, H,, "Thermodynamic Parameters cfHydrophobic Bond Formation in a Model System", Journal of Physical Chemistry, Vol . 69, pp. 1310-1324, ( ~ p r . r
Isolation of Aqueous Organic Contaminants
Burnham, A*, Calder, G., Fritz, J.9 Junk, G., Svec, H. and Willis, Re, "IDentification and Estimation of Neutral Organic Contaminants in Potable Water", Analytical Chemistry,Vol . 44(1) , pp. 139-142, (Jan. 1972).
Burnham, A,, Calder, G., Fritz, H., Junk, G., Svec, H. and Vick, R., "Trace Organics in Water: Their Isolation and Identification", Journal of the American Water Works Association, Vol. 65, pp. 722- 725, (Nov. 1973).
Harvey, G., "Adsorption of Chlorinated Hydrocarbons from Seawater by a Cross1 ink1 ed Polymer", EPA-R2-73-177, U .S. Environmental Protection Agency, Washington, D.C., (Mar. 1973).
Junk, G., Richard, J., Grieser, M., Witiak, D., Witiak, Jay Arguello, m., Vick, R., Svec, H., Fritz, H. and Calder, G.3 "Use of Macro- reticular Resins in the Analysis of Water for Trace Organic Contaminants", Journal of Chromatography, Vol. 99, pp. 745-762, (1 974).
Musty, P. nd Nickless, G., "Use of Amverlite XAD-4 for Extraction and Recovery of Chlorinated Insecticides and Polychlorinated Biphenyls from Water", Journal of Chromatography, Vol . 89(2), pp. 185-1 90, (Feb. 1974).
Richard, J . and F r i t z , J. "Absorpt ion o f Ch lo r ina ted Pes t ic ides from River Water w i t h XAD-2 Resin", Talanta, Vol . 21, pp.91-93, (1974).
R i ley, J. , and Taylor, D., "The A n a l y t i c a l Concentrat ion of Traces o f rgan i c Ma te r i a l s from Sea Water w i t h Amber l i te XAD-1
Resin", Ana l y t i ca Chimica Acta, Vol. 46 pp. 307-309, (1969).
U. S. Envi ronmental P r o t e c t i o n Agency, " D r a f t A n a l y t i c a l Report, New Orleans Area Water Supply Study", Survei 1 lance and Analys is D i v i s i o n , Region V I , Dal las, Texas, (Oct. 1974).
Water Treatment
Kennedy, D., "Treatment of E f f luen t from Manufacture o f Ch lo r ina ted P res t i c i des w i t h a Synthe t ic Polymeric Adsorbent, Amver l i t e XAD-4", Env i rqmen ta l Science and Technoloav, Vo1. 7 (2 ) , pp. 138-141, (Feb. 1373).
Segar, G.A., "Macrore t i cu la r Resins - A S o l u t i o n t o Aqqressive Condi t ions" , Ef f l uen t and Water Treatment ~ o u r n a i ; Vol . 9(8) , pp. 433-438, (Aug. 1969).
Appl i c a t i o n s f o r B i o l o g i c a l Research
Elce, J .S., "Metabol ism o f a G l u tahione Conjugate o f 2-Hydroxyoestro- d io l -176 i n t h e Adu l t Male Rat", Biochemical Journal , Vol. 126, pp. 1067-1 071 , (Mar. 1972).
Kami kubo, T. and Narahara, H., "Adsorbents f o r Cor r ino ids , Nonionic, Nonpolar Synthe t ic High-Pol y e r s " , Japan Patent 38,058 (1970).
Kokubu, T., " I s o l a t i o n and I d e n t i f i c a t i o n o f a Renin I n h i b i t o r f rom Ox B i 1 e" , Biochemical Pharmacology, Vol . 21, pp. 209-217, (Jan. 1972).
Popjak, G., Edmond, J., C l i f f o r d , K., and Wi l l iams, V . , "Biosynthesis and S t ruc tu re o f a Mew Intermedia between Farnesyl Pyrophosphate and Squalene", Journal o f B i o l o g i c a l Chemistry , Vol . 244(7), pp. 1897-1 91 8, (Apr. 1969).
Scheider, W. and F u l l e r , J.K., "An E f f e c t i v e method f o r D e f a t t i n g Albumin us ing Resin Columns", B iochimical e t Biophysica Acta, Vol . 221 (2 ) , pp. 376-378, (Nov. 1970).
App l i ca t i ons t o Assessment and Treatment o f Human Drug Use.
Bastos, M., Jukofsky, D. and Mule, S., "Routine I d e n t i f i c a t i o n o f Drugs o f Abuse i n Human Ur ine 111 D i f f e r e n t i a l E l u t i o n o f t h e XAD-2 Resin", Journal of Chromatography, Vo. 81 (1 ) , pp. 93-98, (June 1973).
Chu, T.M., Bsawa, Y. and Rey oso, G., "Simple Assay for Urinary Estrogens in Non-pr cy", Clinical Chemistry, Vol. 17(5), pp. 438-439, (May 7
and Cawley, L ti on of Dehydroepiandro- esterone (DHW) Sul fat eroi d Conjugates from Urine by Amber1 ite", Clinical Biochemistry, Val. 4, pp. 287-296,
Fujimoto, J.M. and Wanq, R.I.H., "A Method of Idnetifying Narcotic . - - ~najgesics in ~umki Urine after Therapeutic Doses", and Appl ied Pharmacology, Vol . 16, pp. 186-193, (Jan
usette, A., "Steroid Excretion Patterns in Urine zed and Adrenalectomized Rats'', Biochimica et , Vol . 280, pp. 182-186, (Sept. 1972).
Hetland, L.V., Knowlton, D. and Couri, D., "A Aethod for the Detection of Drugs at Therapeutic Dosages in Human Urine using Adsorption Column Chromatography and Ti n-Layer Chromatograph", Cl inica Chimica Acta, Vol . 36, pp. 473-478, (Feb. 1992).
Kelsey, M. and Mosgatelli, E., "Gas-liquid Chromatographic Analysis of Phenolic and Non-phenolic Chlorpromazine Metabolites in the Urine of Chronic Schizophrenic Patients", Journal of Chromatography, Vol. 85(l) , pp. 65-74, (Oct . 1973).
Leung, F.Y. and Giffitsh, J., "A Chromatographic Method for Aldosterone Determination in Human Urine", Clinica Chimica Acta, Vol. 37, pp. 423-432, (Mar. 1972).
Rosenbaum, J., Winsten, S., Kromer, M., Moras, J. and Raja, R., "Resin Hemoperfusi on in the Treatment of Drug Intoxication", Transactions
, Vol. 16,
Rosenbaum, J., Kramer, M., Raja, R. and Boreyko, C., "Resin Hemoper- fusion: A New Treatment for Acute Drug Intoxication", New En land Journal of Medici ne, Vol . 284(16), pp. 874-877, (Apr. 1971 e
Rosenbaum, J. L., "The Use of Resin Hemoperfusion in the Treatment of Acute Drug Intoxication", Clinical Toxicology, Vol. 5(3), pp. 331- 335, (Fa1 1 1972).
Liquid Chromatography
Chu, Chi-Hong, "An Investigation of the Column Chromatographic Behavior of the Prous Support XAD-2: Separation of the Qrganic Bases, Phenols,
roids", dissertation presented at the University of Iowa, Ames, Iowa, in 1973, In partial fulfillment of the requirements for the degree of Doctor of Philosophy.
Fritz, J.W. and Beurman, D. R., "Chromatographic Separation of Molyb- denum Using an A1 iphatic a- hydroxy Oxime" , Analytical Chemistry, Vol . 44(4), pp. 692-694, (Apr . 1972).
Grieser, M. and Pietrzyk, D . 9 "Liquid Chromatography on a Porous Polystyrene-Divinyl benzene Support", Analytical Chemistry Vol . 45, pp. 1348-1353, (July 1973).
Scoggins, M.W. and Miller, J.W., "Rapid Separation Technique for Mono- and Disulfonic Acids", Analyticad Chemistry, Vol . 4O(7), pp. 155- 157, (June 1968).
Scoggins, M.W., "Analysis of Potassium Terphthalate-Benzoate Mixtures of Column Chromatography", Analytical Chemistry, Vol . 44(7), pp. 1285-1288, (June 1972).
Zaika, L., "Column Chromatography on Polystyrene Resin using Aqueous Systems", Journal of Chromatography, Vol . 49(2), pp. 222-229, (June 1970).
Applications in Physical Chemistry
Fritz, J.S. and Tateda, A., "Studies on the Anion Exchange Beahvior of Carboxyl ic Acids and Phenols", Analytical Chemistry, Vol . 40(14) pp. 2115-2119, (Dec. 1968).
Appl ications in Analytical Chemistry
Witiak, J., Junk, G., Calder, G., Fritz, J. and Svec, H., "A Simple Fraction Collector for CC", Journal of Organic Chemistry, Vol . 38(17), pp. 3066-3067, (Aug. 1973).
Review Article
Brusse, F.S., Furst, R. and Van Bennekom, W.P., "Amberlite XAD-2, een literatuuroverzicht", Pharaceutisch Weekblad, Vol. 109, pp. 921 -929, (1974). (Dutch) (Translation available from Schnare)
Webb, R.C., "Isolating Organic Water Pollutants: XAD Resins, Urethane Foams, Solvent Extractiont', EPA-660/4-75-003, U.S. EPA, Corvallis, Oregon, June, 1975.
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