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Monitoring Heavy Metals in River Water Receiving Mine Water Discharge using the Diffusive Gradients
in Thin-‐film technique (DGT)
Trang HUYNH and Sue VINK The University of Queensland, Australia
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-‐ The Fitzroy River Basin (FRB) is the home to QLD’s major mining acKvity -‐ Since 2008-‐2009 wet season, the FRB catchment was subject to prolonged and intense periods of rainfall.
-‐ In order for the mines to operate water needs to be released from the mine-‐sites into the rivers.
-‐ Mining are permiUed to discharge mine water under condi2ons specified in EA issued under the EP Act 1994.
-‐ Water quality needs to be assessed based on QLD guidelines to protect the aqua2c biota of FRB.
-‐ Mul2ple grab samples analyses are required during and a@er mine water releases, this costly in term of both analyses and personnel Kme.
Background
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Research QuesDon: DGTs vs Grab samples
Can the in-‐situ and Kme-‐integrated Diffusive Gradients in Thin Films technique (DGT) replace the series gab samples to determine metal concentraKons in river water receiving mine water discharge?
(Modified from Lorax, 2002)
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tADgMC
d
DGTΔ
=Diffu
sive
gel
Res in gel
Δg
C
water M2+ diffusion
1 2 mm
CSOL
Filter Piston holder
M: measured mass
Δg: diffusive layer thickness
A: area of the exposure window
t: deployment Dme
D: diffusion coefficient
Principles of the DGT
ML
L M2+ M2+
M2+
M2+
M2+
M2+
M2+
M2+
M2+
M2+
(Zhang and Davison, 1995)
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• Allow solutes to pass easily • No reacKon with solutes • Defined thickness • Hydrophilic • Diffusion of metals similar to water
Diffusive Layer
ü Time integrated
ü Independent of pH, ionic strength
ü SpeciaKon (diffusion, reacKons)
ü Simple field deployment
ü MulKmedia
Key ProperDes of DGT
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Trials Purposes Laboratory trial (5-‐15/1 2015)
• High fluctuaDon of metal concentraKons in the water
• Simulated changes in concentraKons to mimic water condiKon fluctuaKon when river receiving mine water
Isaac River (29/1-‐13/2 2015)
• InsensiKve DGT trial: before, during and a@er the mine water released program at upstream and downstream of mine release points during release events
• Coincident with mine site water quality monitoring Recycle water dams (24/4-‐ 8/5 2015)
• This trial is represenKng a lower fluctuaDon condiKon in mine water chemistry and metal concentraKons
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Review of Metal/loid ConcentraDons monitoring data of river water (2/2010 to 5/2013)
Dissolved conc. (µg/L) Al As Cd Cr Cu Pb Ni Zn Mn Se
Min 1 0.001 0.0001 0.001 0.01 0.002 0.006 0.01 0 0.002 Max 127,000 76 232 331 537 820 31,000 4,670 7,730 5,000 Median 5,200 2 0.1 11 7 3 11 17 130 2.5 N 834 806 811 850 875 806 831 873 771 865 TV95% 55 24 0.2 10 1.4 3.4 11 8 1,900 11 N of Exceedance 785 1 338 432 824 331 394 646 5 54
% Exceedance 94 0 42 51 94 41 47 74 1 6
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Laboratory ValidaDon Experiment
Sample RaDonale and Experimental Design -‐ River water (the Mackenzie) were spiked with different levels of metals (As, Cd, Cu, Ni, Pb & Zn) to create 5 test waters
-‐ Water columns were diluted (by simulated rain waters) -‐ 12 grab samples per test water were collected for analysis -‐ 3 replicates per treatment and 7 replicates for in-‐house QA/QC
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Chemical ProperDes of Test Waters Parameters! Ranges!pH! 7.7 -‐ 8.2!EC (mS/cm)! 0.4 -‐ 0.5!TDS (mg/L)! 284 – 300!WH (mg/L CaCO3)!
100 – 112!SAR! 1.9 -‐ 2.0!Cl (mg/L)! 62 – 67!SO4
2-‐ (mg/L)! 14 – 22!TSS (mg/L)! 6 -‐ 45!
Metal/ metalloids
Ranges (µg/L) Total Dissolved
Al 44 – 380 1 – 26 As 0.5 – 81 2 – 71 Cd 1 – 56 1 – 45 Cr 0.1 -‐ 0.5 0.1 -‐ 0.12 Cu 2 – 195 2 – 102 Ni 3 – 42 3 – 23 Pb 0.2 – 71 5 – 8 Zn 43 – 94 2 – 37
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Laboratory ValidaDon Results
0
20
40
60
80
100
Cd (µ
g/L)
Grab sample dissolved conc. Labile DGT conc. Mean grab samples +SD Mean grab samples -‐SD Mean grab samples
0
40
80
120
1 2 3 4 5 6 7 8 9 10 11 12 Zn
(µg/L)
Times (12hrs interval)
0
40
80
120
1 2 3 4 5 6 7 8 9 10 11 12
Cu (µ
g/L)
Times (12hrs interval)
0
50
100
150
As (µ
g/L)
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Bioavailability of Copper in Water: DGT Measurements and MINTEQ Modelling
0 20 40 60 80
100 120 140
1 2 3 4 5 6 7 8 9 10 11 12
Cu (µ
g/L)
Times (12hrs interval)
Grab sample 0.45um
Mean grab samples
Labile DGT conc.
Modelling Inorganic Cu
Mean Modelling Inorganic Cu
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Decision tree for metal specia2on guideline (ANZECC, 2000)
Applica2on of DGT in ANZECC
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Field Trials – Isaac River, Central QLD
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Water Chemistry Isaac River Waters
Sampling sites/dates
Cherwell Creek Bridge (CCB)
Isaac River upstream Cherwell Creek (IRCC)
Isaac River Down Stream (IRDS)
Isaac River Highway Bridge (IRHB)
29/01 to 12/02/15 29/01 to 19/02/15 29/01 to 19/02/15 29/01 to 12/02/15
pH 7.8 7.7 8.1 7.9 8.0 8.1 7.9 8.0 8.1 8.1 8.0 7.5 7.8
EC (µS/cm) 553 995 613 442 373 404 445 2270 408 491 496 214 358
TSS (mg/L) 67 524 17 83 30 35 87 524 16 <1 103 784 <1
WH (mg/L CaCO3)
106 142 112 70 83 93 72 300 89 105 78 58 85
SAR 2 5 3 3 2 2 3 9 2 2 3 1 2
Cl (mg/L) 105 168 82 73 49 53 67 390 58 62 116 31 40
SO42-‐(mg/L) 44 123 59 18 12 13 18 333 17 23 23 5 7
DOC (mg/L) 7.5 7.1 5.4 6.2 10.4 5.0 6.2 6.7 4.7 4.5 6.1 6.0 4.4
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Field Trial Results: DGT vs Grab samples (Copper)
0.0
1.0
2.0
3.0
Cu (µ
g/L)
DGT CCB DGT-‐IRCC DGT-‐IRDS DGT-‐IRHB Grab CCB Grab IRCC Grab IRDS Grab IRHB Mean Grab CCB Mean Grab IRCC Mean Grab IRDS Mean-‐IRHB
LOR
0 1 2 3 4 5
CCB IRCC IRDS IRHB Cu (µ
g/L)
Grab-‐total Grab dissolved DGT ANZECC (TV 95%)
• The concentraDons of Cu measured by the DGT were significantly lower than total and dissolved Cu.
• The bioavailable Cu concentraDons at 4 sites are well above the lower of report value (LOR)
• High variaDon in total & dissolved Cu conc. during the trial.
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DGT vs Grab samples: Zinc
0
1
2
3
4
Zn (µg
/L)
DGT CCB DGT-‐IRCC DGT-‐IRDS DGT-‐IRHB Grab CCB Grab IRCC Grab IRDS Grab IRHB Mean Grab CCB Mean Grab IRCC Mean Grab IRDS Mean-‐IRHB
LOR
0
2
4
6
8
10
CCB IRCC IRDS IRHB
Zn (µ
g/L)
Grab-‐total Grab-‐dissolved DGT LOR
• Total Zn concentraDons in water were high, however most of dissolved Zn were below the LOR
• The bioavailable Zn measured by DGT were detected and well above the lower of report value (LOR)
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Water Chemistry of Recycle Water Dams
Sites Ranges pH 8.2 -‐ 9.2 EC (µS/cm) 8,000 – 11,000 TDS (mg/L) 5,450 -‐ 7,500 TSS (mg/L) 3 – 20 WH (as mg/L CaCO3)
900 – 980
SAR 20 – 35 Chloride (mg/L) 1,640 – 2,020 SO4
2-‐ (mg/L) 1,224 – 2,256 DOC (mg/L) 4.5 -‐ 12
Metal/ metalloids
Ranges Total (µg/L) Dissolved (µg/L)
Al 4 – 10 1 – 2 As 4 – 5 3 – 4 Cd BDL BDL Cr 0.1 – 0.4 0.1 – 0.4 Cu 0.4 – 0.6 0.3 – 0.5 Fe 7 – 22 4 – 6 Ni 2 – 9 2 -‐ 8 Zn BDL BDL
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Recycle water dams (Al & As)
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Recycle water dams (Co & Cu)
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EsDmated Cost Comparison* ConvenKonal grab sampling Unit Per Unit Total
Analysis (AUD) 4 65 260 Deloyment/sampling 4 60 240 Total 500 Time-‐integrated DGT sampling Unit Per Unit Total DGT unit (AUD) 1 25 25 Analysis (AUD) 1 65 65 Deloyment/sampling 2 120 240 Total 330 Cost saving (%) for 4 days deployment 34 *This es<ma<on based on 4 days water release and grab samples are taken everyday and price based on research rate
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Key Findings: Laboratory trial • The DGT measurement is comparable to the averaged concentraKon of 12 grab samples over the 7 days trial (except Cu).
• The labile concentraKons measured by the DGT were significantly lower, 13% and 23% respecKvely, than the measured total and dissolved Cu concentraKons.
• The bioavailable concentraKons of other metals including Cd, Ni and Zn ranged from 60% to 80% of the measured dissolved concentraKons.
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Key Findings: Field trials • The bioavailable concentraKons heavy metals in Isaac river water measured by the DGT were significantly lower than that of total and dissolved concentraKons.
• Cd in water at 4 study sites was not detected by both DGT and grab sampling.
• In some cases, As and Zn was not detected by grab sampling but was detected by the DGT at a low concentraKon and well above LOR.
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Mechanism of the CollaboraDon and Partnership
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Decision tree for metal specia2on guideline (ANZECC, 2000)
Recommenda2on and Future Work DGT measurement will replace 4 steps for assessing metal/loid toxicant in water in the ANZECC decision tree
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Thank You & Questions
Contact details: Dr. Trang Huynh [email protected] Dr. Sue Vink [email protected]
References: Reducing AnalyDcal and Water Quality Monitoring Costs using Diffusive Gradients in Thin Films (DGT) Technique (Project C23027 ACARP)