Document K6oned8qqj91o8XV8vN6eerYx
AR226-2733
1
The miracles o f science
Study Title ADSORPTION-DESORPTION SCREENING STUDIES OF
AMMONIUM PERFLUOROOCTANOATE Author
William R. Berti Report Completed
May 2000 Performing Laboratory E. I. du Pont de Nemours and Company Environmental and Microbiological Sciences & Engineering Corporate Center for Engineering Research Central Research & Development Glasgow, Building 300, P.O. Box 6101 " Newark, DE 19714-6101 Report No. EMSE-053-00
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DuPont EMSE Report No. 053-00 GENERAL INFORM ATION Material Tested: Ammonium perfluorooctanoate Svnonyms/Codes: APFO, C-8, FC-143 DuPont Notebook No.: E98312 Sponsor: Robert Pinchot
' E I du Pont de Nemours and Company BARLML CRP-711/2210-B
Study Initiated / Completed: September 1999 / May 2000
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DuPont EMSE Report No. 053-00
ADSORPTION-DESORPTION SCREENING STUDIES OF ` AMMONIUM PERFLUOROOCTANOATE
SUMMARY
Five of nine materials appeared to adsorb a significant amount (greater than 25% of APFO added) at one or more concentrations of APFO. For four of the five matenals to which APFO significantly adsorbed, most of the adsorbed APFO appeared not to desorb after 2 washings at one or more concentrations of added APFO.
Study Conducted by: Kristi Barnett Research Technician, EMS&E
(date)
Study Conducted by: Jack DeCarolis Staff Biologist, EMS&E
(date)
Study Conducted by:
George Fisher Research Technician
(date)
Study Conducted by: Bogdan Szostek, Ph.D. Research Scientist, Haskell Lab
(date)
Report Prepared by: William R. Berti, Ph.D. Senior Research Biologist, EMS&E
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DuPont EMSE Report No. 053-00
INTRODUCTION AND PURPOSE
APFO adsorption/desorption screening studies were performed on several test materials, including two clays, a washed sand, peat moss, and an agricultural soil from Delaware, USA. The adsorption/desorption screening studies were also performed using two surface soils and two sediments from the Ohio River collected in the vicinity of the DuPont Washington Works plant near Parkersburg, West Virginia.
The adsorption/desorption procedure used in this study was adapted from a method developed by the Office of Prevention, Pesticides and Toxic Substances (OPPTS), United States Environmental Protection Agency for use in the testing of pesticides and toxic substances, and the development o f test data (1). Our objectives were to develop an adsorption/desorption protocol and analytical procedure for APFO. As part of this objective, we screened a variety of test materials for their APFO adsorption/desorption characteristics.
MATERIALS AND METHODS
Test Materials
The Kaolin (KGa-2) and Montmorillonite (SAz-1) are Clay Mineral Society "Source Clays" and were obtained from the curator of the sample collection in the Department of Geology at the University of Missouri, Columbia. Additional information on these and other Source Clays has been published (2). The Quikrete All-Purpose sand and Scotts sphagnum peat moss were purchased locally at a builders' supply store (Home Depot). The Sassafras soil is a surface (0 to 15 cm) soil collected from an agricultural field in Delaware, USA. The Garden Area soil and East Wood soil were surface soils collected from the DuPont Washington Works plant. The Upstream sediment was obtained from the bank of the Ohio River upstream of the DuPont Washington Works NPDES permitted outfall, and the Downstream sedment was from downstream of the outfall. The two soil and sediment sample from the vicinity Washington Works were collected in the fall of 1999.
Physical and chemical properties of the less than 2-mm size fractions of the soils, sediments, clays, sand, and peat moss used in this study are listed in Tables 1 and 2. Except for the clays, all samples were screened through a 2-mm ( 10 mesh) stainless steel sieve in preparation for the absorption/desorption screening test. Furthermore, the sand was washed using DI water-through 2-ram and-50-um stainless steel sieves. Material retained on the 50 um sieve was used in the study. The sand, soils, and sediments used in the studies were air-dried prior to use in the studies. Data calculations, however, were based on oven-dry weights o f the samples. Oven-dry weights were determined after drying a subsample of material in an oven at 105C for a minimum of 24 h.
The pH o f the sample were determined in a 1:1 test material to water. Percent organic matter was determined using the loss on ignition method.
Screening Test: Adsorption Studies
.
The adsorption test was performed in duplicate on each material. A blank containing 0.01M CaCl, solution with test materials and no APFO and a single control at each APFO concentration but no material were also included. Each material was equilibrated with the aqueous phase of a solution of the test chemical at 5.0, 0.5 and 0.05 mg L"1. prepared in 0.01 M
CaCl2
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DuPont EMSE Report No. 053-00
Sterile 50 mL Coming polypropylene centrifuge tubes were used as the test vessels. One part air-dried material (4.0 gfwas weighed and 5 part test solution (20 mL) was decanted into a centrifuge tube, except the control tube. The centrifuge tubes were secured on an end-over-end mixer and agitated at about 30 rpm for 24 hours. Samples were centrifuged for 20 minutes using a RT6000B Sorvall centrifuge at 4000 x g and then filtered through a 0.2 pm nylon syringe filter into a new centrifuge tube. The volume of aqueous supernatant was measured and refrigerated at about 5C until analyzed for the parent compound using an LC-MS. The blank and the control tubes were subjected to the same steps as the test systems, including filtering.
Screening Test: Desorption Studies
To each solid phase (pellet) was added a fresh volume of 0.01M CaCL solution without the test chemical equal to that added in the adsorption test, 20 mL. The sample was mixed, centrifuged, filtered, stored, and analyses as was done in the adsorption studies. This desorption step was repeated a second time, resulting in two washings that were analyzed separately.
Calculations
Data calculations included: 1. The percent o f APFO adsorbed, A:
A = (G - Ce x Vo)/G x 100 = x/G x 100 2. The percent of APFO which is desorbed, D:
D = [(Cl + C2)V - (Vo - V)Ce]/x x 100 3. The percent of APFO which is not desorbed, R:
R = [G -(C e + C l+ C2)V]/x x 100 4. The adsorption coefficient, K':
K' = (x/m)/Ce 5. The adsorption coefficient calculated as a function of the organic carbon content of the test
material, K'oc: K'oc = K (100/percent organic carbon)
Where: 1. m = dry weight of soil employed (g) 2. Ce = concentration of APFO remaining in solution (V) in the adsorption step (pg L'*1234567) 3. Cl = concentration of APFO in solution in the first wash (pg L 1) 4. C2 = concentration of APFO in solution in the second wash (pg L'1) 5. Vo = original volume o f solution employed (mL) 6. V = volume o f solution obtained after the adsorption step (mL) 7. G = quantity of material recovered from the soilless control (pg)
RESULTS AND DISCUSSION
Of the nine materials tested, five of them (peat moss, Upstream sediment, East Wood
soil, Garden Area soil, and Kaolin Clay) exhibited significant adsorption (greater than 25% of
APFO added) at one or more of the added concentrations of APFO. Peat moss alone, however,
adsorbed a significant amount at all three concentrations of added APFO; 50, 500, and 5,000 pg
APFO/L. Kaolin clay adsorbed a significant amount of APFO at 500 and 5,000 pg APFO/L. The
Garden Area soil collected at Washington Works also adsorbed significant amounts o f APFO at
500 pg APFO/L. Upstream sediments from the Ohio River and East Wood soil adsorbed a
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DuPont EMSE Report No. 053-00 significant amount of APFO at 50 pg APFO/L only. Sand, MontmoriHonite clay, Downstream sediment, and Sassafras soil did not adsorb a significant amount of APFO at any concentration ot the added APFO.
Once adsorbed on peat moss, most of the APFO (>76%) did not desorb after two washings with a solution of 0.01 M CaCl,. For the Kaolin clay, most the APFO adsorbed when added at 5 000 pg APFO/L desorbed with washing (>60%). At APFO added at 500 pg APFO/L, however, m average of 98% did not desorb from the Kaolin clay after two washings. The East Wood soil, which adsorbed 46% of the APFO added at 50 pg APFO/L desorbed only about 2 /For the Garden Area soil 57% of the APFO desorbed when adsorbed from the 500 pg APFO/L solution. No measurable desoiption of APFO from the Upstream sediment after two washings was observed when the APFO was added at 50 pg APFO/L.
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DuPont EMSE Report No. 053-00
ADSORPTION-DESORPTION SCREENING STUDIES OF AMMONIUM PERFLUOROOCTANOATE
TABLE 1. Physical properties of test materials,
Test material
Moi ture com entf
----------
i
Test Material Dry Wt., Sand Silt Clay m
g %%%
Sand Feat moss Kaolin clay Montmonllonite Sassatfass soil
-------- trP
A7 ---------07.^78
--------- IP ---------
East Wood soil
14
Garden Area soil
9T4
Upstream sediment
T3
Downstream sediment --------- 9 3 ---------
43 r m ~ 0
21 W TUT " ND"
4.0 0 0 100
33_797
0 Toir
-yy-H 19 10
33 " zIF"1 4 15 377 37 42 21 3.5 9 30 ll 377 b9 T T ~ 10
Organic M atter
%
ND -- ND ND
1
1.6 2.9 1.5 0.6
Organic Carboni
%
nd nd
pjB
nd
0.58
33 1.68 7R7 CT33
f Based on drying at 105C for a minimum of 24 h. j Estimated from percent organic matter. ND is not determined.
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DuPont EMSE Report No. 053-00
TABLE 2. Chemical properties of test materials.
Test material
pHf CEC}
Exchangeable cations, meq/100g
m eq/1 UUg Cm
Mg
Na
K
H
Sand Peat moss
Kaolin clay Montmorillomte Sassaffass soli
515 "ND1.... ND
377 -- ND
ND
CC
-----33----- ND
7Tb 1 T2 . ND'
..b .T .... 2.8
2.10.
ND ND ND ND ND ND ND .....ND 731 "'0701
ND ND ND ND n d ND ND ND 77ZT
East Wood soil Garden Area soil Upstream sediment
575 -----"^T
.T .7 .... 771
-----
7
^
"47T9- -- 0751
74
`" 5783 1.15 -- 701
6.08 (J.86 0.27
0715 7T8 0.15
571
nun
74
Downstream ....6:9".. 579
4.54 T9
0710 U.U9 7
sediment
"1:1 test material to water. Cation Exchange'Capacity.
Exchangeable cations in milliequivalents/100 g test material determined by a modified ammonium acetate method.
TJND is not determined.
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DuPont EMSE Report No. 053-00
TABLE 3. Absorption/desorption screening test data.
Test material
Nominal
APFO Originai solution concentration volume, Vo
Volume oi solution after adsorption step,
V
APFO in solution after adsorption step, APFO in first
Ce i wash, Cl
APFO in second wash, C2
Sand
p ig i-1
mL
-------(T0
2D
-------0D3------- --------- 20D
0.8 20D -------- 5--------- --------- 20D
mL
--------- TOD --------- T8D --------- f gD --------- TOD
/'g L ~l
Z779E+OI OOE+OZ 4.98E+02 3.8UE+U3
^ '
JIgTT1
NI5 RD f^D ND
Vg L-1
ND ND ND ND
Peat moss
-------ODO -------D5 --------0-5.5
2D ZOD --------- ZOD 2D
18.0
--------- TOD
--------- TOD --------- R D
^
4.00E+O1 7.98E+00
G.55E+UI 9.62B+02
: ;
:
O.UOE+UU O.OOE+OU 4.U7E+01 5D7E+OZ
0D0E+0 O.UUE+UU 2,62b+UI 3.37E+02
Kaolin clay
-------ODO --------- ZOD
-------0D3-------
ZOD
---------------0- 53 --------
-----------------
ZOD ZOD
--------- IOD TSD
--------- TOD --------- n ro
1.65E+0O 3.83E+-U1 37Z7E+OZ TDZE+03
r-
ODOE+OO
3.31E+01 4.52E+0Z
.UE+U NA
/.lb t+UU 3.82E+02
Montmoril Ionite -------ODO
-------0D3 03
---------5
ZOD --------- TOD
--------- ZOD
--------- rsD
--------- ZOD
18.0
--------- ZOD--------- --------- T8D
4.45E+01 4.68E+U1 3.80E+02 3.69E+03
0D0ET00 TTO
6.25E+-01 sjD
0.0E+0U ND
8.0UE+UU ND
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TABLE 3 (cont'd) Test material
Volume ol
Nominal
solution after
APFO Original solution adsorption step,
concentration volume, Vo
V
APFO in solution after adsorption
step, Ce
----- p g F
mL
mL
pg L 1
Sassatrass soil
X ------ CT5 ------- 3 -------- 5
--------- 2X --------- 2D --------- 2(10 --------- 2X
---------T O
---------rx o
---------nor-
---------T O
-------- 0.0E+ 4.33E+01 4.35E+U2 J.63E+03
East Wood soil
------ TJ------ ---------2X
------ CT3 ------- 03 -------- 5
---------2T5 ---------2X ---------2X
-------- T O rxu 17.8
---------T O
-------- 7.5E-2 1.18E+1 3.98E+2 4.78E+03
Carden Area soil
------ F ------ 703 ------- [j3 -------- 3
--------- 2 --------- 2X
2U.U --------- 22)
---------T O ---------rx u
1X5 ---------I7D
-------- 1.15ET1
2.5 )E+0l
^ 2. /6E+2 3.68E+U3
Upstream sediment
-------- -------- 5
-------5 ------ 5
--------- ZD ---------2X ---------2X --------- 2X
---------TX ---------IX ---------TX5
TX
-------- .0E+ 139E+I 4.12E+02 4.36E+3
APFO in first APFO in second
wash, Cl
wash, C2
pgT7
------- m NO NO ND
------- p.,gr, L[m---------------- m -------- xNrUn ---------
----- -- jNerUn---------
------ ---sINrrUn-------- -
0.E+ 1.63E+UU 733E+01 7.44E+2
.0E+ -----7UT.TUT7UTbTX+7UT7UT--------- 11.nyUoLb'+jJYuIi ----- 11.4nibn+iU\>2\-----
6.93E+ 1.24E+01 1.19E+U2 1.09E+U3
-----2.60E+ -----3T."377UTTbT+TUTTU71 t----- jDr.mUT3bTrxrUm1 ----- n3. n/ymby+>Uz
0.E+UU X5E-01 /.1 1E+Ul 7.71E+02
-----0.00E+ -----uA.uA uMbL-Hijmu---------z1. \1Ul\ 1b7+XU711i----i----- 1i .n/Vi\wb+nuvz)
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TABLE 3 (cont'd) Test material
Volume ot
Nominal
solution after
AFFO Originai solution adsorption step,
concentration volume, Vo
V
APFO in solution after adsorption
step, Ce
Downstream sediment --------50
-------5U ------ 5D
Sassatrass soil
-- um
------ TJ5
------- 3 -------- 5
mL
--------- 2m}
ZT 20.0 ----- ZD
" " ZJ
--------- zun
--------- ZTJ --------- zo n
mL
--------- rg 3
TO
' " T8TT
TO
ro --------"-t o
fig L '1
O.O0E+00 i .yoE+ui 4.58E+02 3.34E+03
U.OOE+OO 2.04E+01 ~ 4.94E+UZ 5.25L+03
APFO in first APFO in second
wash, Cl
wash, C2
----------- r=i-------
V g L '1
O.OE+0 U.OoE+00 4.63L+01 5.72E+0Z
O.OOH+OO 0.00E+00 9.83E+00 6.64E+U1
.00E+ 4AUE-01 5.32E+1 8.40E+02
.UH+0U U.0UL+0U 1.1UE+01 9.64E+01
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DuPont EMSE Report No. 053-00
gOf! 0,*
< w
N(B
a. h
%OT
TABLE 4. Adsorption/desorption screening test calculations.
Test material
APFO
Nominal recovered from
APFO
the soilless
concentration control, G
Adsorption
X
x/m or Cs
Material Adsorbed,
A
Adsorbed material desorbed,
D
Adsorbed material not desorbed, R
Adsorption coefficient,
IC
coefficient as a function of
organic carbon, K'oc
msl ' ;
Mg
Mg Mg'g --
%
%
%
Sand
------ (TOO------ o-------------------
------ 035------ ------ 0305
-------0 3 -------- 5
-------OHO 8i
-537b -o r -1.40E-OT 0 ---- RD
-1.88E+01T -4.71E-0T 3 TO
NU
3.5H-2. 8.77E-03- 0
RD
.06H-U1)' 135t+00" 7
ND
ND -5.(JlL-03~ ND| NL) --TTTTTTTn ------- RD ND Ni) ND -- A 1\A L17---------"RD
Feat moss '
------ ono
U
------ 0H3 ------ 0305
0 3 0310---------------- ----------------- ---------------S3------------------ 5 ------------------- ------------------
^ 7.99E-01 -3.77E-OT //VALUE!
7.37H-01' 3 .47E-0r 82
'8.68E+0" TOOE+OOj 6.38K+01 3.01E+01...
87 77
//VALUED~~SVALUTO- //VALUED"
NU
-1 1U2 -- *a-t,'J>auu rni--- ------ "RD
T2 00 --g n\ v w )-- "RD(j j i.v^ u 4 1---------------
23 -- --n u i ; r v )
----------------- j q p )
//
Kaolin Clay
0H0--------------
---------------
0
0H5 0305--------------
--------------- --------------
--------------
0 3 OHO---------------- ---------------- ---------------S3------------------ j ------------------ ------------------
-3.3E-2 ' -8.31E-0T WAEUET 0------------- --
1.30K-1- 3.26E-02" 3.45E3 0 " 8.68E-0T
13 33
RD 2
2.2E+01- 5.70E-I0" l i
l
-//VALUE!- //VALUE!-
tfVALUb! 7171-- <J L 1 L 1 -- ------------------sjX 5
9o
RD-- Tz , . T/ Jr Lt /n* Und -- ------------------
39 " RD-- ^ l \ i \ U V I " --------------
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Montmorillomte
OHO--------------
--------------------o -------------------
035 ------ 0305
-------03------- -------TOO
--------5--------
8J
-8.0UH-01 ' -2.40-UT VALUED //VALUE!"
-3H0b-Or -1.05L-OX -4 //VALUE!
2.38E+0" 6.44E-01 24
21
9.15E+00- 2.47E+00" 11 #VALUb!
//VALUED //VALUED"
NU
ffVALUb! 9
--
T J ML1(\A \1m/nv\ri-:/~ivTJi---------
RD
ffVALUb! 1--7, 1<UI\A-----------RD-------
Sassatrass Soil
------- 0H0--------------- o-------- ".0H+OO"'HHOE+OO" 3 VLUET ------- 0H3------------- 0305----- 2.05H-0r 7.48E-03" i
3 -------- OHO ' "T3 0 E+00" "3.28H-OT 1J 5 "33.... 1.04E+01" 2.63L+U1) 1/
RD ------ R RD NL) NL) ND RD ND
-- //D1V/!...------SEDTV701 1-----THTEH2----
/. /Ub-U4 4-----1 til'/V]------ n ^1: zrr------- T73EHT
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DuPont EMSE Report No. 053-00
TABLE 4 (cont'd)
Adsorption
Test material
NcoomncineanltrAaPtioFnO
AfrPoFmOthreecsoovilelersesd control, G
X
Material Adsorbed, x/mor Cs A
Adsorbed material desoDrbed,
Adsorbed Adsorption
mdeastoerrbiaeldn,oRt
coefficient, K'
coefficient asa function of
organKic'occarbon,
MgL`l
Mg Mg Mg/g ---- %---- ----- %----- %
.bast WoodSoil
-----0150----- -------0------- " 130E-03" -4.26E-04 " ?UIV70!. #mv/oi ' mivm\ SDTV701
----- 0153--------- 03-----
----- Tm -----------ron------
1.H6E-01. 6.35E-02 ----45---2.14E+00 "7.93E-9T---- pg----
2 29
87 5.39E-03. 39 2.00E-03
5 ------go------ '1.17E+00. .1.I21A00' -6 152 313 2.34E704..
DJV/0! 5.81E-01 2.1Sb-01 23ZE702
GardenAreaSoil -----0150----- -------o------- -2.3lb-0l loon-ur DiV/0! -64
164
----- 0153--------- 03-----
----- 0322----------roi------
-9.15E-02' *'4.i8H+00"'
-7.15E-03' OOE+OO"'
-------r^rs-------
---7-25T742
-
2725 34
------ 5------ ----- oo------ 2.32H+01 T.50E+00' 18
55
9
UpstreamSediment ------ o------ ------- 0------- O.OOE+OO' DDOFEXT value!" 'VALUE!'" WATDE!-
50 ----- 01422----- 1.05E-01. 4.2.il:.-U2"---- 27---- -11
90
500 ------ror------ 1.86E+00 "OTEOH- ---- 15---- 66
17
-----5000"---- ------go------ 9.32E+00' 3.2JE-I-0U 3 84 782
-5.47E-03" -2.70E-04" 4.72E;03 2.O4E-03
LVALUE! O.OUb+UO ' O.OOE+OO. 7.64E-OT-
-3.2ib-Ol -1.bOb-02 2.81E-01 1.2113-01 VALUE! O.UOb+OO O.OOE+OO 8.78E-02
DownstreamSediment
------ 0-----50
----- 500-----
------- o----------- 0322----------no------
.0700E+002J5E-02.9301)1'"
'""0"2.4U..0H'4E0E+E0-0:1025T' ------V--A-g7LUE!.
'VALUET -81
---- 5-----
VALUE!'" VALUE! TOO ..l.l 5E-UT" 34 9.75E-U4
5000 ------go------ -I'.40K+Ul -2.29E+00 ----723---- 13
239 .-4X1E:04~
VALUE! 3.30b-0t 2.8Ub-Ul -1.1EE-01
SassatrassSoil
-----0150----- ------- o-- : DiOOH+OO O.OOE+OO- LVALUE! "WALUET VALUE!"' VALUE!.
-----0135----- ----- 05422--------- 03----- ------no------
135E-02- 1.46E-02 2.17E-01 "" nsEU'r --
6 o--
-- -^44
84 7.35E-04. 7201 ' 2.43E7U4
5 go -8.2SE+00 1.2OE+00 -17 307 72430 2.24H-04..
VALUE! 1.27E-01 4.19E702 3.86E-02
f ND = Not determined.
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DuPont EMSE Report No. 053-00 FIGURE 1. Adsorption isoline of APFO onto Sand, Peat moss. Kaolin clay, Monlmorillonite clay, and Sassafras soil.
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DuPont EMSE Report No. 053-00 FIGURE 2: Adsorption isoline of APFO onto East Wood soil, Garden Area soil, Upstream sediment, and downstream sediments.
0 1000 2000 3000 4000 5000 6000 Ce, ug C-8 L'1
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DuPont EMSE Report No. 053-00 Reference: 1 US EPA. 1998. Fate, transport and transformation test guidelines: OPPTS 835.1220 sediment
and soil adsorption/desorption isotherm. United State Environmental Protection Agency Office of Prevention, Pesticides, and Toxic Substances. EPA712-C-98-048. January 1998 2 Olphen, H.V., and JJ. Fripiat (eds.). 1979. Data handbook for clay materials and other nonmctallic minerals Pergamon Press. New York 346 pp.
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