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Supplemental Information
Extraction of sediment associated polycyclic aromatic hydrocarbons
with granular activated carbon
M.I. Rakowska*.†, D. Kupryianchyk‡, T. Grotenhuis†, H.H.M. Rijnaarts†, A.A. Koelmans‡.§
†
Subdepartment of Environmental Technology. Department of Agrotechnology and Food
Science, Wageningen University, Wageningen, The Netherlands
‡
Aquatic Ecology and Water Quality Management Group. Department of Environmental
Sciences, Wageningen University, Wageningen, The Netherlands
§
IMARES – Institute for Marine Resources & Ecosystem Studies, Wageningen UR,
Ijmuiden, The Netherlands
Number of pages: 17
Number of additional text pages: 3
Number of Tables: 5
Numbers of Figures: 13
Determination of total petroleum hydrocarbons (TPH)
TPH extraction was performed according to NEN 5733 [1]. In short, 4 g (w.w.) sediment, 10
mL water and 50 mL acetone were cold extracted for 30 minutes at 175 strokes per minute,
followed by a second extraction with 25 mL of hexane. To the resulting extracts, 50 mL of
water was added. After phase separation a hexane subsample was analyzed for TPH, using a
HP 5890 Gas Chromatograph (GC) equipped with a SIM DIST column and Flame Ionization
Detector with nitrogen as the carrier gas. After 5 minutes at an initial temperature of 40 ˚C,
GC temperature increased at 10 ˚C per minute to a final temperature of 300 ˚C. Carbon
number fractions were determined using the retention times of a boiling point standard. TPH
is determined as the area between C10 and C40.
Solid phase extractions with Tenax and four types of GAC
Tenax extractions. As a reference, single-step 24 h solid-phase extractions (SPE) with Tenax,
were performed to determine the residual fractions of PAHs in Petroleum Harbor (PH)
sediment. The results served as control tests for the selection of the best performing GAC, and
allowed a direct comparison of GAC versus Tenax extraction efficiency. The single step SPE
method was adapted from [2, 3]. In short, the extractions were carried out in 50 mL separatory
funnels, which were filled with PH sediment (1.5 g dry matter), 40 mL of Mili-Q water
containing 100 mg/L NaN3 and 0.01M CaCl2, and 1.5 g of Tenax adsorbent. The separatory
funnels were shaken end-to-end at 160 strokes per minute for 24 h. After 24 h the sediment
suspension was separated from the sorbent, centrifuged and dried with Na2SO4 for
determination of residual concentration of PAHs remaining in the sediment after Tenax
extraction. The Tenax beads with preconcentrated PAHs and residual sediment samples were
extracted in hexane/acetone (1:1) with microwave assisted extraction (MAE). All
hexane/acetone extracts were primarly concentrated with a rotary evaporator, further reduced
to 1 mL under gentle stream of nitrogen and switched to acetonitrile for PAH analysis. For
details on the Microwave assisted procedure, the reader is referred to [4]. The Tenax
extractions were carried out in triplicate.
GAC extractions. A series of 4 types of granulated carbons (GAC 1240W, 840W, RB 3W and
RB 4W, kindly supplied by Norit, Amersfoort, The Netherlands) with varying particle size
range (0.450-1.70), (0.60-2.36), 3 and 4 mm respectively, were evaluated for their efficiency
in extracting PAHs from PH sediment. Single-step extractions of PAHs from sediment
samples with all GACs were performed in the same way as Tenax extraction, also using a 1:1
(w/w) sediment to sorbent ratio. Briefly, 50 mL brown colored bottles were filled with 1.5 g
(d.w.) sediment, 1.5 g GAC and aqueous NaN3 / CaCl2 solution, and shaken at 160 strokes per
minute for 24h. The sediment was separated from GAC by sieving (500 µm), centrifuged and
dried with Na2SO4 for determination of residual concentration of PAHs remaining in the
sediment after GAC extraction. The extractions with GAC were carried out in triplicate.
Further extraction steps and analysis were identical to that of the Tenax and sediment
samples. The residual fractions of the total amount of 13 EPA PAHs remaining in the
sediment after extraction were calculated by dividing the PAH quantity extracted, by the total
quantity of PAHs determined in PH sediment by Soxhlet extraction (see main text). The
lowest residual fraction of PAHs was found after extraction with GAC 1240W, which was
selected for further tests (Fig. 1 and Fig. S1).
Boehm titration
The acidic surface groups (carboxyl, lactone and phenolic) and the total quantity of basic
groups present on granular activated carbon (GAC 1240W) were determined with Boehm
titrations as described elsewhere [5-7]. Since the method is based on the assumption that
NaOH neutralizes carboxyl, lactone and phenolic groups, Na2CO3 neutralizes carboxyl and
lactone groups and NaHCO3 neutralizes carboxyl groups, the quantity of acid and basic
groups can be calculated. In short, to four 100 mL Erlenmeyer flasks containing 20 mL of
0.05N NaHCO3, NaOH, HCl and Na2CO3, ~0.2 g GAC was added. Additionally, two blank
bottles filled with 20 mL of 0.05N NaOH and 0.05N HCl were prepared. The bottles were
shaken end-to-end for 24 h, after which the solutions were filtrated using 0.2 µm cellulose
filters. The supernatants were titrated with the excess of base and acid with NaOH and HCl
respectively. The titrations were carried out with Metrohm 702 SM Titrino (NaOH) and
SCHOTT TitroLine easy (HCl).
Table S1. Characteristics of Petroleum Harbor sediment; concentrations of PAH in the
sediment, aqueous phase concentrations determined with POM-SPE and POM – water
partitioning coefficients
Compound
fluorene (FL)
phenanthrene (PHE)
anthracene (ANT)
fluoranthene (FLU)
pyrene (PYR)
benzo[a]anthracene (BaA)
chrysene (CHR)
benzo[b]fluoranthene (BbF)
benzo[k]fluoranthene (BkF)
benzo[a]pyrene (BaP)
dibenzo[a.h]anthracene (DBA)
benzo[g.h.i]perylene (BghiP)
indeno[1.2.3.c.d]pyrene (InP)
Σ13 EPA PAHs
TOC [%]
OC [%]
BC [%]
BC/TOC
TPH [%]
a
Log KOW
4.2a
4.6b
4.7c
5.2b
5.2b
5.9b
5.8b
6.0a
6.1c
6.1c
7.0b
6.9b
7.0b
Data taken from Maruya et al.[8]
Data reported by Jonker & Smedes [9]
c
Data from de Maagd et al. [10]
d
Data taken from Hawthorne et al. [11]
b
CSED,
CW,
mg/kg
µg/L
99.8 (6.5)
63.74 (7.42)
304.8 (16.9)
179.99 (15.78)
116.7 (5.3)
16.76 (1.71)
323.5 (14.6)
23.98 (2.01)
199.5 (5.9)
13.65 (1.16)
106.9 (9.2)
0.75 (0.07)
96.6 (11.4)
0.57 (0.07)
92.0 (11.9)
0.14 (0.02)
40.7 (4.1)
0.04 (0.01)
105.9 (15.3)
0.10 (0.01)
10.0 (3.2)
1.79*10-3 (3.65*10-4)
45.9 (4.4)
1.34*10-2 (1.43*10-3)
51.3 (4.2)
8.96*10-3 (1.55*10-3)
1604.3 (90.2)
4.46
2.61
1.85
0.415
0.54 (0.041)
Log KPOMd
3.83
4.20
4.30
4.56
4.57
5.46
5.43
5.80
5.97
5.96
6.30
6.09
6.26
Table S2. Chemical and physical characteristics of coal based granular activated carbons.
Data obtained from low temperature nitrogen adsorption isotherms and Boehm titrations
performed for the quantification of functional groups present on GAC surface.
GAC
Type
Particle
SBETa
SBJHb
Vtot (BET)c
size
(m2/g)
(m2/g)
(cm3/g)
Vtot
(BJH)
d
(cm3/g)
(mm)
Average
BJH
Carboxyl
Lactone
Phenolic
Basic
pore
Averag
(mmol/g)
(mmol/g)
(mmol/g)
(mmol/g)
width
e pore
wadse
radiusf
(nm)
(nm)
1240W
0.45-1.70
1112
113
0.607
0.129
2.182
2.283
0.019
0.016
0.020
0.083
830W
0.60-2.36
1112
113
0.607
0.129
2.182
2.283
0.030
0.014
0.026
0.099
RB3W
3
997
51
0.482
0.052
1.936
2.053
0.031
0.007
0.007
0.134
RB4W
4
1035
29
0.470
0.035
1.816
2.475
0.012
0.023
0.010
0.133
a
BET surface area
BJH adsorption cumulative surface area of pores between 1.0 and 25.0 nm radius
c
Single point adsorption total pore volume of pores less than 25.0 nm radius at p/p0=0.96107
d
BJH adsorption cumulative volume of pores between 1.0 and 25.0 nm radius
e
Adsorption average pore width (4V/A by BET)
f
BJH adsorption average pore radius (2V/A)
b
Table S3. Multiple comparisons, ANOVA (Tukey HSD, p < 0.05) between residual
fractions obtained after GAC extractions versus residual fractions after Tenax-SPE. The p
values are reported for 3, 4 and 5&6 ring PAHs.
24 h - SPE extraction
PAH
4 ring
0.001
0.000
0.000
0.000
5&6 ring
0.602
0.910
0.098
0.011
Tenax vs.
GAC 1240W
GAC 830W
RB 3W
RB 4W
3 ring
0.774
0.110
0.001
0.000
GAC 1240W vs.
Tenax
GAC 830W
RB 3W
RB 4W
0.774
0.018
0.000
0.000
0.001
0.002
0.000
0.000
0.602
0.218
0.010
0.001
GAC 830W vs.
Tenax
GAC 1240W
RB 3W
RB 4W
0.110
0.018
0.030
0.003
0.000
0.002
0.000
0.000
0.910
0.218
0.329
0.042
RB 3W vs.
Tenax
GAC 1240W
GAC 830W
RB 4W
0.001
0.000
0.030
0.550
0.000
0.000
0.000
0.142
0.098
0.010
0.329
0.641
RB 4W vs.
Tenax
GAC 1240W
GAC 830W
RB 3W
0.000
0.000
0.003
0.550
0.000
0.000
0.000
0.142
0.011
0.001
0.042
0.641
Table S4. Partitioning coefficients (LogKSED (SD)) for PAHs, in individual sediment – water equilibration systems, and mean LogKSED values.
LogKSED
Sediment
(d.w.) (g)
0.75
3.75
7.50
18.75
37.50
75.00
χ2(5)a
p
LogKSEDb
a
FL
PHE
ANT
FLU
PYR
BaA
CHR
BbF
BkF
BaP
DBA
BghiP
InP
3.28(0.03)
3.24(0.03)
3.17(0.03)
3.18(0.04)
3.14(0.03)
3.15(0.03)
13.838
0.017
3.20(0.05)
3.29(0.04)
3.25(0.03)
3.19(0.03)
3.20(0.03)
3.22(0.03)
3.22(0.02)
13.147
0.022
3.23(0.04)
3.86(0.05)
3.88(0.02)
3.77(0.02)
3.81(0.02)
3.86(0.02)
3.86(0.02)
11.941
0.036
3.84(0.04)
4.18(0.03)
4.18(0.03)
4.11(0.03)
4.12(0.02)
4.12(0.02)
4.13(0.02)
11.596
0.041
4.14(0.04)
4.22(0.04)
4.21(0.04)
4.14(0.02)
4.16(0.02)
4.16(0.03)
4.16(0.01)
11.037
0.051
4.18(0.04)
5.19(0.05)
5.20(0.05)
5.14(0.05)
5.11(0.04)
5.13(0.04)
5.13(0.04)
11.221
0.047
5.15(0.04)
5.26(0.07)
5.29(0.08)
5.18(0.05)
5.20(0.05)
5.20(0.05)
5.20(0.05)
12.360
0.030
5.23(0.04)
5.84(0.06)
5.90(0.15)
5.80(0.06)
5.81(0.06)
5.81(0.06)
5.81(0.06)
3.015
0.698
5.84(0.08)
6.00(0.10)
6.08(0.05)
5.96(0.06)
5.95(0.05)
5.93(0.04)
5.94(0.04)
11.566
0.041
5.99(0.07)
6.06(0.06)
6.04(0.07)
5.98(0.06)
6.00(0.07)
5.99(0.06)
6.00(0.06)
9.596
0.088
6.02(0.04)
6.81(0.16)
6.89(0.18)
6.70(0.15)
6.69(0.14)
6.70(0.14)
6.70(0.14)
10.235
0.069
6.77(0.11)
6.55(0.08)
6.59(0.07)
6.54(0.07)
6.54(0.04)
6.58(0.04)
6.52(0.04)
3.897
0.564
6.56(0.05)
6.90(0.08)
6.88(0.10)
6.77(0.04)
6.78(0.04)
6.75(0.04)
6.74(0.04)
12.154
0.033
6.82(0.09)
Kruskal – Wallis tests for significant differences between individual sediment-water equilibration systems.
Single mean values of sediment – water partitioning coefficients (LogKSED) with associated errors (SD, n=18) obtained from sediment - water equilibration tests,
without carbon amendment.
b
Table S5. Granular activated carbon – sediment partitioning coefficients (LogKMIX (SD)) for a series of PAHs.
LogKMIX
Sed
(d.w.)
(g)
0.75
3.75
7.50
18.75
37.50
75.00
GAC
(g)
FL
PHE
ANT
FLU
PYR
BaA
CHR
BbF
BkF
BaP
DBA
BghiP
0.75
0.75
0.75
0.75
0.75
0.75
6.42(0.06)
5.38(0.04)
5.10(0.12)
4.36(0.05)
3.78(0.04)
3.28(0.03)
6.16(0.10)
5.08(0.04)
4.94(0.04)
4.31(0.03)
3.93(0.04)
3.76(0.02)
6.35(0.07)
5.10(0.03)
4.93(0.03)
4.40(0.03)
4.13(0.03)
4.03(0.02)
5.99(0.08)
4.72(0.02)
4.71(0.02)
4.37(0.03)
4.25(0.02)
4.19(0.02)
5.89(0.09)
4.69(0.02)
4.57(0.02)
4.35(0.02)
4.26(0.01)
4.21(0.01)
6.55(0.09)
5.39(0.06)
5.40(0.07)
5.22(0.05)
5.18(0.04)
5.14(0.04)
6.55(0.11)
5.30(0.06)
5.36(0.06)
5.26(0.06)
5.23(0.05)
5.23(0.06)
7.00(0.14)
5.85(0.07)
5.91(0.06)
5.83(0.06)
5.81(0.06)
5.80(0.06)
7.12(0.09)
6.02(0.06)
6.08(0.05)
5.99(0.05)
5.96(0.05)
5.94(0.05)
6.96(0.13)
6.04(0.08)
6.09(0.07)
6.06(0.07)
6.02(0.07)
6.00(0.07)
7.91(0.28)
6.77(0.17)
6.79(0.16)
6.72(0.15)
6.68(0.14)
6.72(0.14)
7.51(0.08)
7.59(0.05)
7.83(0.05)
6.68(0.05)
6.65(0.04)
6.52(0.04)
InP
7.85(0.07)
6.80(0.05)
6.83(0.04)
6.81(0.04)
6.77(0.05)
6.74(0.04)
Figure S1. Industrial sieving unit for separation of GAC from high volume sediment slurries.
Figure S2. Separation of granular activated carbon from treated sediment. Picture shows detail of
sediment being sieved using the unit depicted in Figure S1.
Figure S3. Fast desorbing (in 24 h) fraction of total PAHs (13EPA PAH) in PH sediment as
determined with Tenax extraction and residual fraction of total PAHs in PH sediment as
determined with Tenax extraction (grey bars). Residual fractions of PAHs after extractions with
four types of GAC (black bars). Fast and residual Tenax-based fractions (grey bars) together make
up 100% of PAH present in the sediment.
Figure S4. Single sediment – water partitioning coefficients (LogKSED) obtained in this study as a
function of PAH LogKOW.
Figure S5. LogKMIX distribution coefficients at fGAC/fSED = 1 weight ratio as a function of LogKOW
(closed symbols) and sediment – water partitioning coefficients obtained from the individual
control system without carbon amendment (open symbols).
Figure S6. LogKMIX distribution coefficients at fGAC/fSED = 0.2 weight ratio as a function of
LogKOW (closed symbols) and sediment – water partitioning coefficients obtained from individual
control system without carbon amendment (open symbols).
Figure S7. LogKMIX distribution coefficients at fGAC/fSED = 0.1 weight ratio as a function of
LogKOW (closed symbols) and sediment – water partitioning coefficients obtained from individual
control system without carbon amendment (open symbols).
Figure S8. LogKMIX distribution coefficients at fGAC/fSED = 0.04 weight ratio as a function of
LogKOW (closed symbols) and sediment – water partitioning coefficients obtained from individual
control system without carbon amendment (open symbols).
Figure S9. LogKMIX distribution coefficients at fGAC/fSED = 0.02 weight ratio as a function of
LogKOW (closed symbols) and sediment – water partitioning coefficients obtained for individual
control system without carbon amendment (open symbols).
Figure S10. LogKMIX distribution coefficients at fGAC/fSED = 0.01 weight ratio as a function of
LogKOW (closed symbols) and sediment – water partitioning coefficients obtained from individual
control system without carbon amendment (open symbols).
Figure S11. Isotherms for sorption of PAHs to GAC in the presence of sediment.
Figure S12. Apparent sorption isotherms for (a) FL, (b) PHE, (c) ANT and (d) FLU. Open symbols
without lines represent experimentally determined values, closed symbols with dashed curves
indicate data obtained from fitting to Freundlich isotherm equation, and closed symbols with dotted
lines represent values obtained from fitting to Langmuir equation.
Figure
S13.
Freundlich
affinity
(pseudo-)equilibrium
constants
(LogKF,GAC)
(μg/kgGAC)/(μg/L)nF,GAC as a function of octanol-water partitioning coefficients for GAC in the
presence of PH sediment.
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