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Chemosphere
journal homepage: www.elsevier.com/locate/chemosphere
Environmental and Life Sciences Graduate Program, Trent University, ON, Canada
Chemistry Department, Trent University, ON, Canada
h i g h l i g h t s
g r a p h i c a l a b s t r a c t
DOM
DOM??
DGT assembly
with binding gel
a r t i c l e
i n f o
Article history:
Received 26 March 2014
Received in revised form 27 June 2014
Accepted 4 July 2014
Diffusive Gel
Prefilter
a b s t r a c t
In situ measurements of labile metal species using diffusive gradients in thin lms (DGT) passive
samplers are based on the diffusion rates of individual species. Although most studies have dealt with
chemically isolated humic substances, the diffusion of dissolved organic matter (DOM) across the hydrogel is not well understood. In this study, the diffusion coefcient (D) and molecular weight (MW) of 11
aquatic DOM and 4 humic substances (HS) were determined. Natural, unaltered aquatic DOM was capable of diffusing across the diffusive gel membrane with D values ranging from 2.48 106 to
5.31 106 cm2 s1. Humic substances had diffusion coefcient values ranging from 3.48 106 to
6.05 106 cm2 s1, congruent with previous studies. Molecular weight of aquatic DOM and HS samples
(5001750 Da) measured using asymmetrical ow eld-ow fractionation (AF4) strongly inuenced D,
with larger molecular weight DOM having lower D values. No noticeable changes in DOM size properties
were observed during the diffusion process, suggesting that DOM remains intact following diffusion
across the diffusive gel. The inuence of molecular weight on DOM mobility will assist in further understanding and development of the DGT technique and the uptake and mobility of contaminants associated
with DOM in aquatic environments.
2014 Elsevier Ltd. All rights reserved.
1. Introduction
Corresponding author. Tel.: +1 (705) 748 1011; fax: +1 (705) 748 1625.
E-mail address: celinegueguen@trentu.ca (C. Guguen).
http://dx.doi.org/10.1016/j.chemosphere.2014.07.013
0045-6535/ 2014 Elsevier Ltd. All rights reserved.
499
500
using 0.02 M NaOH. The HEPES buffer was chosen in order to maintain a constant pH throughout the duration of the experiment,
minimizing the inuence of pH variation on D (Lead et al., 2003).
In the aquatic DOM experiments, the receiving solution was
0.01 M NaNO3 adjusted to pH 7.1 and river conductivity using
0.02 M NaOH and Milli-Q water (Millipore; >18 O) to reect properties similar to those of natural waters. The aquatic DOM source
solutions had a pH of 7.06 0.34 (n = 12). No signicant differences
in pH and conductivities were observed between the solutions on
either side of the diffusion cells in all experiments (ANOVA;
p < 0.05). The same pH was chosen for both natural DOM and HS
to avoid any pH dependency (Lead et al., 2003; Scally et al., 2006).
Approximately 30 mL of solution were collected from both the
source and receiving compartments of the diffusive cell every
24 h for ve to six consecutive days (t = 0, 24, 48, 72, 96, 120 and
144 h). Longer periods of time (24 h) were used than previously
described in other studies (Scally et al., 2006; Furukawa and
Takahashi, 2008) in order to increase the concentration of diffused
DOM between time intervals and thus increase accuracy in calculating slopes. Samples were stored in 40 mL pre-combusted, amber
glass vials at 4 C and analyzed within 7 d. All experiments were
performed at room temperature and maintained at 23 C 0.4 C.
The diffusion coefcients were corrected to 25 C using the method
adapted from Zhang and Davison (1995) and Scally et al. (2006). All
diffusion coefcients experiments were conducted in duplicate
except for A14, R1R2, R6 and NAFA, due to tearing of the gel
membrane. With the amount of pressure placed on the gel membrane with it being secured between two planes of plexi-glass, it
was fragile and could rupture easily with increases in stirrer speed
and water turbulence. D values for A12 could not be measured
due to full rupturing of the gel membrane, however, initial MW
was measured for these samples and included in the MW results
for A14. R5 was used test the preservation of DOM MW as it
diffused across the gel membrane over time; no D values were
available for R5.
0.9
0.8
The absorbance spectra of both source and receiving compartments were measured using a Shimadzu UV 2550 spectrophotometer equipped with a 10-cm quartz cell. Absorbance values
between 250 and 700 nm were blank corrected using Milli-Q water
(Millipore; >18 O). Light scattering was also subtracted from each
sample using the average absorbance between 650 and 700 nm
from the blank. The dissolved organic carbon (DOC) concentrations
were estimated based on absorbance measured at two wavelengths 254 and 270 nm using a two-component model (Tipping
et al., 2009; Carter et al., 2012). The presence of a non-absorbing
component was also included in the DOC estimate (Carter et al.,
2012).
The diffusion coefcients D were calculated for each type of
DOM using the equation adapted from Scally et al. (2006):
0.7
0.6
0.5
0.4
0
20
40
60
80
100
120
140
160
Time [hr]
Fig. 1. Examples of the linear increase of diffused dissolved organic carbon vs.
elapsed time (s R1, d R6; NSRHA; r2 = 0.99, 0.96, and 0.99 respectively). Slope of
line created using SigmaPlot (11.0) linear line of best t.
501
Sample name
MW (Da)
D (cm2 s1)
A1
A2
A3
A4
R1
R2
R3
R3
R4
R4
R5
R6
R7
R7
SRFA
SRHA
SRHA
NAFA
NAHA
NAHA
507 18
544 37
721 52
973 21
1198 19
920 140
989 54
1065 54
865 18
891 18
1110 55
1482 130
1710 27
1748 27
1089 105
1490 0
1490 0
961 50
1405 8
1394 8
N/A N/A
N/A N/A
5.04E-06 1.65E-07
3.13E-06 3.05E-07
3.83E-06 7.27E-08
4.72E-06 4.66E-08
4.14E-06 7.70E-08
4.16E-06 6.05E-07
5.30E-06 4.93E-07
5.31E-06 2.13E-07
N/A N/A
2.94E-06 1.48E-07
2.94E-06 1.32E-07
2.48E-06 9.02E-08
4.78E-06 4.65E-07
5.96E-06 1.29E-07
6.05E-06 3.86E-08
4.28E-06 3.05E-06
3.71E-06 1.30E-07
3.48E-06 3.66E-08
Fig. 2. Range of (A) D and (B) MW values for aquatic DOM (Algae n = 2 and 4, respectively; River/wetland outlets n = 9 and 9, respectively) and humic substances (FA n = 2 and
4, respectively and HA n = 4 and 4, respectively) found in this study.
1600
6000
1400
4000
1200
Void
Peak
MW [Da]
Absorbance [mAU]
5000
3000
2000
1000
800
600
400
1000
200
0
0
6
10
12
14
16
18
20
Time [min]
Fig. 3. Fractograms of A3 (black) and R5 (gray) in the source compartment. Note:
the void peak as indicated by the arrows consists of a small, unfocused material and
appears immediately following elution of the material from the AF4 membrane.
A3
R5
Fig. 4. Time series of MW in the receiving cells at 28 h (black), 49 h (dark gray) and
149 h (light gray) for A3 and R5. The average MW in the source compartment
(white) is provided as comparison. Error bars represent standard deviation
(>100 Da) (n = 2). Note: no MW at 28 h for A3 is available due to very weak signal
(i.e. small amount of material diffused across the gel).
Dg 2
2D
For example, copper with a D of 6.23 106 cm2 s1 would take
approximately 17 min to travel across a gel thickness of 0.08 cm
while DOM would take between 21 and 36 min for the slowest
and the fastest diffusion rates reported here (A2 and R7, respectively; Fig. 2A) to travel across the gel. Although DOM diffuses
more slowly than free metals, it is likely that it will signicantly
diffuse across the gel with a typical DGT deployment time of few
days.
4.2. Relationship between diffusion coefcient and molecular weight
The dependence of the D values on molecular weight of natural
DOM is depicted in Fig. 5. The natural DOM (circles) and HS sam-
7e-6
6e-6
D [cm2.s-1]
502
5e-6
4e-6
3e-6
2e-6
600
800
1000
1200
1400
1600
1800
MW [Da]
Fig. 5. Correlation between D and MW (plain proposed model; dotted Bufes
model (1988)) using natural DOM (circles) HS (squares) were not used in tting the
exponential decay model. The model developed in this study used the exponential
decay function tting line in SigmaPlot (11.0) with r2 = 0.75, ANOVA; p < 0.05.
Acknowledgements
This study would not have been possible without the assistance
of Chad Cuss and Antoine Perroud and their sample analysis,
expertise and knowledge of instrumentation. Acknowledgments
are also made towards two anonymous reviewers and editor of
Chemosphere for their comments as well as NSERC and Canada
Research Chair program for their nancial support to this project.
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