Suitability of using diffusive gradients in thin films (DGT) to study metal bioavailability in mine tailings: possibilities and constraints
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Environ Sci Pollut Res (2010) 17:657–664 DOI 10.1007/s11356-009-0254-x 6.1 • ANALYTICAL AND BIO-ANALYTICAL METHODS FOR QUANTIFYING PERSISTENT CHEMICALS Suitability of using diffusive gradients in thin films (DGT) to study metal bioavailability in mine tailings: possibilities and constraints Héctor Miguel Conesa & Rainer Schulin & Bernd Nowack Received: 25 May 2009 / Accepted: 23 September 2009 / Published online: 9 October 2009 # Springer-Verlag 2009 Abstract 90%) and controlled temperature conditions (night 16°C Background, aim, and scope Diffusive gradients in thin and day 23°C). Pots were irrigated with deionized water to films (DGT) have been recognized as a suitable tool to field capacity, and then two different experiments were assess in situ metal bioavailability in soils. Mine tailings performed: (a) allowing free drainage and (b) maintaining have some singular characteristics such as high heavy-metal the water saturation. In addition, we tested DGT devices in concentrations, low pH, or absence of water retention solutions at pH3 with similar properties to the soil solution capacity that may compromise the correct application of this measured in the acid tailing. Eluted Zn, Cd, Pb, and Cu technique whose applicability is known to be pH dependent. from the chelating resins were measured using inductively The goal of this study was to determine the response of DGT coupled plasma–optical emission spectrometer (ICP–OES; devices in heavy-metal-polluted mine tailings with different Vista-MPX Varian). pH. In addition some experiments were performed in order Results and discussion The metal concentrations taken up to determine the effect of acidic pH and dissolved ions on the by the DGT devices were affected by the different pH binding properties of the chelating resin. values of the tailings. The highest metal concentrations Materials and methods We tested DGT devices on three measured with DGT (CDGT) were obtained in the pH3 different mine tailings: acid pH3, acid tailing limed to pH treatments (both saturated and free drainage). Significant 5.5, and neutral pH7.2. The tailings showed high metal differences for CDGT were observed between water- concentrations, e.g., 7,000 mg kg−1 Pb, 9,000 mg kg−1 Zn, saturated and free drainage treatments in the acid pH3 and 380 mg kg−1 Cu. Diffusive and Chelex resin gels were tailing. When limed pH5.5 tailing and neutral pH7 tailing prepared according to previously published methods. Two were considered, these differences were lower and not chelating resins and diffusive gels thicknesses (0.4 and significant. In pH3 tailings low values for CDGT/Csoil solution 0.7 mm) were tested. Four DGT devices of each type were were obtained (
658 Environ Sci Pollut Res (2010) 17:657–664
Conclusions The use of DGT in mining soils can be a heavy metal concentrations, low pH, or absence of water
promising tool to study bioavailable metals concentrations retention capacity that may compromise the correct appli-
in mine tailings but it has to be used carefully under acidic cation of this technique. DGT is limited to the pH range of
pH. Competition with other cations that are present at very five to nine for most of the metals and from two to 11 for
high concentrations may hinder the accumulation of metals Cu (INAP 2002), and does not work under dry conditions
by the chelating resins, which should be tested under the (studies at field capacity conditions are necessary), and also
conditions of the particular mine tailing. saturation of the chelating resin may occur at high metal
concentrations. Some previous studies have focused on acid
Keywords DGT . Mine tailings . Acid pH . mine drainage samples, using a correction factor when pH
Metal bioavailability was low (Sondergaard 2007). In this sense much more work
has to be carried out to improve the use of DGT in mining
soils since saturation conditions and the presence of high
1 Background, aim, and scope concentrations of different ions may affect the binding
properties of the chelating resin.
The assessment of metal toxicity in soils and sediments is The goal of this study was to determine the response of
considered an important issue in heavy-metal-polluted DGT devices in heavy-metal-polluted mine tailings with
ecosystems. Traditionally, these studies have been based different pH. In addition some studies were done in order to
on the determination of the total concentration, avoiding determine the effect of acidic pH and dissolved ions on the
aspects related with the speciation or bioavailability binding properties of the chelating resin.
(McGrath et al. 1999; Degryse et al. 2003). However, in
the last decades the majority of researchers that work in the
field of soil contamination have assumed that using total 2 Materials and methods
metal concentrations in environmental risk assessment
studies is not a suitable tool, because a large fraction of 2.1 Soil analyses
the total metal content is not bioavailable (Zhang et al.
2001). In this sense speciation studies using weak extrac- The soil was sampled from two mine tailings (“Belleza”
tants have been proposed as a more accurate tool (Planquart and “El Gorguel”) situated in Southeast Spain. Both tailings
et al. 1999). These procedures represent a better approach were extensively characterized by Conesa et al. (2006) and
to the environmental behavior of metals, but still they are have pH values of 3 and 7, respectively, and high metal
limited since they are generally applied on disturbed soil concentrations, e.g., 7,900 mg kg−1 Pb, 7,700 mg kg−1 Zn,
samples that have been previously dried and thus metal and 530 mg kg−1 Cu for acid pH tailing and 5,600 mg kg−1
speciation has been affected (Wang et al. 2002), and there is Pb, 12,000 mg kg−1 Zn, and 94 mg kg−1 Cu for neutral pH
a separation of the solid phase from the soil solution (that tailing. Tailing samples were taken from the upper 40 cm of
may affect the physical–chemical equilibrium; Zhang et al. 15 separate soil pits that were dug at regular intervals, at
1998). In this sense and in order to avoid these problems, least 8 m apart, on each tailing pile. All samples of a tailing
the technique diffusive gradient in thin films (DGT) was were mixed to give one homogenized composite sample per
proposed to study in situ the bioavailability of metals in mine tailing. The composite samples were air-dried, sieved
soils. This technique has been applied successfully in toEnviron Sci Pollut Res (2010) 17:657–664 659
Table 1 Soil solution composi-
tion according to Conesa et al. Parameter Tailing
(2007a, 2007b)
Acid (N=5) Acid limed (N=3) Neutral (N=8)
pH 2.9 (660 Environ Sci Pollut Res (2010) 17:657–664
Values between parentheses are standard deviations. Significant differences were calculated for each metal, both thicknesses and the same pH at PEnviron Sci Pollut Res (2010) 17:657–664 661
Table 3 Ratios CDGT/CSS for the three mine tailings measured for the three mine tailings after 24-h contact time under free drainage and water
saturation for two DGT devices thicknesses
Tailing pH and water Zn Cu Pb Cd
conditions
0.4-mm 0.7-mm 0.4-mm 0.7-mm 0.4-mm 0.7-mm 0.4-mm 0.7-mm
DGT DGT DGT DGT DGT DGT DGT DGT
Acid pH3 free drainage 0.002 0.002 0.011 0.013 0.04 0.073 0.001 0.002
pH3 water saturation 0.008 0.014 0.055 0.056 0.013 0.042 0.006 0.011
Acid limed pH5.5 free drainage 0.045 0.191 n.a. n.a. n.a. n.a. n.a. n.a.
pH5.5 water saturation 0.373 0.391 n.a. n.a. n.a. n.a. n.a. n.a.
Neutral pH7 free drainage 0.596 0.319 n.a. n.a. n.a. n.a. n.a. n.a.
pH7 water saturation 0.681 0.936 n.a. n.a. n.a. n.a. n.a. n.a.
0.4-mm DGT DGT devices assembled by a 0.4-mm resin gel and a 0.4-mm diffusive gel, 0.7-mm DGT DGT devices assembled by a 0.7-mm resin
gel and a 0.7-mm diffusive gel, n.a. not available (soil solution concentration below detection limit)
different solutions at pH 3. A typical saturation-type The 0.7-mm-thick resin gel contains 1.75 times the amount
behavior is observed: a first section with linear character- of resin of a 0.4-mm-thick resin gel.
istics, a second one where the slope changes, and a third More Zn was accumulated in the resin gel in the ZnSO4
one that indicates the saturation of the resin. As expected, treatment compared to the solutions with Na2SO4 and
0.4-mm DGT devices reached saturation before the 0.7 mm CaSO4, indicating an effect of Na and Ca on the Zn
ones. Also the quantities accumulated in the chelating resin binding. This magnitude of the Zn binding followed the
varied as a function of the thickness of the DGT devices. order ZnSO4 >ZnSO4 +CaSO4 +MgSO4 >ZnSO4 +Na2SO4.
For the ZnSO4 treatment the saturation for the 0.4-mm In order to calculate the reduction in binding metals by
DGT devices was reached after 150 min (at 500–1,500µg), DGT devices, we used R′ as the ratio CDGT/Csolution, with
whereas for the 0.7-mm DGT ones, this occurred after Csolution being the Zn concentration (2,000 mg L−1) in the
180 min (at 1,800–2,200µg). Resin gel layers of 0.7-mm “mimicking” solutions. The average ratios CDGT/Csolution
DGT devices accumulated on average 380–450 μg more Zn for the non-saturated state (≤150 min immersed for 0.4-mm
than the ones of 0.4-mm DGT devices in all three solutions. DGT devices; ≤180 min for 0.7-mm DGT devices) enabled
Fig. 1 Micrograms of Zn accu- µg Zn
mulated in the resin gel for two 3000
DGT device thicknesses (0.4
and 0.7 mm) and three solution
compositions: ZnSO4
(2,000 mg L−1 ZnSO4), ZnSO4 + 2500
Na2SO4 (2,000 mg L−1 ZnSO4
and 30,000 mg L−1 Na2SO4),
ZnSO4 +CaSO4 +MgSO4
2000
(2,000 mg L−1 ZnSO4,
100 mg L−1 CaSO4, and
3,000 mg L−1 MgSO4)
0.4 mm - ZnSO4
0.4 mm - ZnSO4 + Na2SO4
1500
0.4 mm - ZnSO4 + CaSO4 + MgSO4
0.7 mm - ZnSO4
0.7 mm - ZnSO4 + Na2SO4
1000 0.7 mm - ZnSO4 + CaSO4 + MgSO4
500
0
0 50 100 150 200 250 300 350 400 450 500
Time (minutes)662 Environ Sci Pollut Res (2010) 17:657–664
the calculation of a correction factor that relates the Zn calculate CDGT. However, taking the correction factor for
concentration in the DGT to the Zn in solution (Table 4). Zn into account does not yield a very big increase in the
These ratios were more dependent on the two thicknesses ratio and still values below 0.05 are obtained.
of the DGT devices employed than on the different The 0.4-mm DGT devices in the mine tailing under
competing ions: For 0.4-mm DGT devices, the ratios were water saturation were already saturated with respect to Zn
0.50 for the ZnSO4 treatment, 0.38 for ZnSO4 +Na2SO4 (>500µg), and the results from the DGT devices cannot be
treatment, and 0.43 for ZnSO4 + CaSO4 + MgSO4, and used under these conditions. The ratios shown in Table 3 at
significant differences only occurred between ZnSO4 and pH3 for 0.4-mm DGT devices under water saturation are
ZnSO4 +Na2SO4 treatments. For the 0.7-mm DGT devices, thus minimal values; the true values are definitely higher.
lower ratios were obtained: 0.36 for the ZnSO4 treatment, However, 0.7-mm DGT devices reached saturation at
0.23 for the ZnSO4 +Na2SO4 treatment, and 0.27 for the around 1,800 μg accumulated Zn, and thus, the results in
ZnSO4 +CaSO4 +MgSO4. If we compare the same reagents this case were not supposed to be affected.
and different thicknesses, statistical differences were According to Gimpel et al. (2001) Zn can be measured
obtained in all the cases. by DGT down to pH3.5; at lower pHs Zn showed low
affinity for Chelex resin. However, other metals such as Cu
could be still measured by DGT at pH2.0. In other cases, as
4 Discussion for example for Cd, there is a reduction of the binding
capability at pH5 did not show DGT measurements is in the range between 5 and 10
good correlations with soil solution results: The Zn (Zhang and Davison 1995; Gimpel et al. 2001). Therefore,
concentration in the soil solution at pH5.5 was two-fold the limits of the application of DGT measurements are
higher than at pH7, while the CDGT values were in the same strongly pH dependent (Garmo et al. 2003). This is
range (except for 0.4-mm DGT devices at free drainage). In especially relevant for studies conducted in extremely acid
solutions with pH3 mimicking the soil solution composi- environments as it is the case of mine wastes or acid mine
tion of the tailings, a loss of the binding capacity of the drainage waters.
chelating resin of 50–60% and 60–80% for Zn using 0.7- The ratios CDGT/CSS indicate the magnitude of the metal
and 0.4-mm DGT devices, respectively, was observed resupply from the solid phase to the soil solution. Small
(Table 4). As a consequence 0.7-mm DGT devices had ratios (Environ Sci Pollut Res (2010) 17:657–664 663
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