Abstract. The simultaneous determination of Zn2+, Cd2+, Cu2+, Pb2+ in acid mine drainage
(AMD) by differential pulse-anodic stripping voltammetrics (DPASV) with high sensitivity,
selectivity, and accuracy is difficult because of many influential factors in the waste-water.
This paper presents the results of studying supporting electrolyte for simultaneous
determination of these ions in AMD in Mao Khe, Quang Ninh province to serve the wastewater treatment process. The working electrode as a stationary mercury electrode, and a
platinum electrode and an Ag/AgCl/KCl (sat) electrode as the counter and reference
electrode, respectively were used. In the electrolyte background of 0.12 M KCl, a buffer
solution of 0.08 M NaAc, 0.08 M NH4Ac and 50 μL of 1 g/L Ga, and certain parameters
including a deposition potential of -1.15 V, deposition time of 90 s, sweeping rate at 0.015
V/s, pulse amplitude of 0.05 V, pulse time of 0,04 s, stirring rate at 2000 V/min, equilibration
time 10 s were applied. The method reached high repeatability. The limit of detection of Zn2+,
Cd2+, Pb2+, Cu2+ ions reached 0.216; 0.071; 0.107 and 0.202 ppb, respectively. The limit of
quantification reached 0.720; 0.237; 0.357 and 0.673 ppb, respectively.
11 trang |
Chia sẻ: thanhle95 | Lượt xem: 425 | Lượt tải: 0
Bạn đang xem nội dung tài liệu Study of supporting electrolytes of KCl-Acetate buffer - NH4Ac for simultaneous determination of Zn2+, Cd2+, Cu2+, Pb2+ in acid mine drainage in Mao Khe, Quang Ninh by anodic stripping voltammetry at hanging mercury-drop electrode, để tải tài liệu về máy bạn click vào nút DOWNLOAD ở trên
JOURNAL OF SCIENCE OF HNUE DOI: 10.18173/2354-1059.2016-0061
Natural Sci. 2016, Vol. 61, No. 9, pp. 93-103
This paper is available online at
93
STUDY OF SUPPORTING ELECTROLYTES OF KCl-ACETATE BUFFER - NH4Ac
FOR SIMULTANEOUS DETERMINATION OF Zn
2+
, Cd
2+
, Cu
2+
, Pb
2+
IN ACID MINE
DRAINAGE IN MAO KHE, QUANG NINH BY ANODIC STRIPPING VOLTAMMETRY
AT HANGING MERCURY-DROP ELECTRODE
Nguyen Hoang Nam
1
, Tran Thi Hong Van
2
and Nguyen Thi Thanh Huong
3
1
Faculty of Environment, Hanoi University of Mining and Geology
2
Faculty of Chemistry, Hanoi National University of Education
3
Faculty of Chemistry, Military Medical University
Abstract. The simultaneous determination of Zn
2+
, Cd
2+
, Cu
2+
, Pb
2+
in acid mine drainage
(AMD) by differential pulse-anodic stripping voltammetrics (DPASV) with high sensitivity,
selectivity, and accuracy is difficult because of many influential factors in the waste-water.
This paper presents the results of studying supporting electrolyte for simultaneous
determination of these ions in AMD in Mao Khe, Quang Ninh province to serve the waste-
water treatment process. The working electrode as a stationary mercury electrode, and a
platinum electrode and an Ag/AgCl/KCl (sat) electrode as the counter and reference
electrode, respectively were used. In the electrolyte background of 0.12 M KCl, a buffer
solution of 0.08 M NaAc, 0.08 M NH4Ac and 50 μL of 1 g/L Ga, and certain parameters
including a deposition potential of -1.15 V, deposition time of 90 s, sweeping rate at 0.015
V/s, pulse amplitude of 0.05 V, pulse time of 0,04 s, stirring rate at 2000 V/min, equilibration
time 10 s were applied. The method reached high repeatability. The limit of detection of Zn
2+
,
Cd
2+
, Pb
2+
, Cu
2+
ions reached 0.216; 0.071; 0.107 and 0.202 ppb, respectively. The limit of
quantification reached 0.720; 0.237; 0.357 and 0.673 ppb, respectively.
Keywords: Stripping methods, determination, heavy metal AMD, electrolyte, supporting.
1. Introduction
Toxic and persistent substances in the environment continuously increase, owing to mining
activities. In particular, the rapid diffusion of heavy metals as environmental contaminants has
called for attention to their determination at trace and ultra-trace levels [1]. In fact, such elements
tend to accumulate in all the aquatic matrices in the environment (suspended matter, sediment,
and biota [2]), resulting in a definite presence in the aquatic food chain, and ground water which is
dangerous for humans, as a consequence of the consumption of marine products.
Received November 24, 2016. Accepted December 5, 2016.
Contact Nguyen Hoang Nam, e-mail address: nguyenhoangnam@humg.edu.vn
Nguyen Hoang Nam, Tran Thi Hong Van and Nguyen Thi Thanh Huong
94
Together with numerous simple treatment procedures [3, 4], several methods described for
metal determination at low concentration, such as spectroscopy [5-7] and Voltam-metric [8]
techniques have been the most frequently employed. In particular, anodic as well as cathodic
stripping Voltammetry methods form a valid and effectual option for the multi-component
analysis of metals, since the high sensitivity of the Voltammetry method [8] can be associated
with considerable selectivity especially reached once the alternative electrolyte background
selected is suitable.
However, problems arise when determining directly and simultaneously various elements in
environmental samples, sediment samples, etc. There are many factors hindering the
determination process such as the voltammetric signals quite unrepeatedly and non-interferedly
relevant to hindering elements, with very high concentration ratios. Most authors solve such
problems by employing mathematical methods (chemo-metrics), which are often complicated and
difficult to follow or apply, or only determine one or two elements simultaneously. It remains
difficult to obtain the specification of 4 elements including: Zn, Cd, Pb, and Cu in environment
samples simultaneously. The present work suggests, instead, a simple and quick procedure
proving that voltammetric techniques with an appropriate electrolyte background are alternative to
the standard additional method, allowing the repeatability, as well as density of highly
voltammetric signals. This fact, especially once applied to samples of great interest, e.g.
environmental matrices, may certainly encourage the employment of the same voltammetric
techniques. The technique may also be applicable to cases of impossible simultaneous metal
determination is, owing to high concentration ratios, and simultaneous small peak potential differences.
2. Content
2.1. Materials and methods
2.1.1. Apparatus
Voltammetry measurements were carried out with a Metrohm (Switzerland) Model 757 VA
Computrace, employing a stationary mercury electrode as the working one, while an
Ag/AgCl/KCl (sat) electrode and a platinum wire used as the reference and counter electrode,
respectively. The Voltammetry cell was kept at 20.0 ± 0.5 °C. The solutions were de-aerated with
pure nitrogen for 15 minutes, prior to the measurements, then a nitrogen blanket was maintained
above the solution during the analysis. The solutions were de-aerated for 2 minutes, after each
standard addition.
All solutions were prepared with de-ionized water (Millipore, Milli Q), and all reagents
(Merck, Germany) were of ‘ultra-pure’ grade. KCl 3 M, acetic + sodium acetate solution buffer 1
M (pH = 4.75), ammonium acetate solution 1 M was prepared. Aqueous stock solutions of Cu
2+
,
Pb
2+
, Cd
2+
and Zn
2+
and Ga
3+
were prepared by dilution of the respective standard of 1 g/L
solutions (Merck, Germany). The Teflon Voltammetry cell was rinsed with ultra-pure
concentrated nitric acid to minimize potential contamination every day.
Study of supporting electrolytes of KCl-acetate buffer - NH4Ac for simultaneous determination
95
2.1.2. Sample preparation
Before the Voltammetry determinations, an examination sample was prepared from standard
solution of Zn
2+
, Cd
2+
, Pb
2+
, Cu
2+
10 mg/L by: taking 50 µL of standard solutions (Zn
2+
, Cd
2+
, Pb
2+
,
Cu
2+
) 10 mg/L, next pouring a determined volume of electrolyte solution in a 25-mL flask, then
adding ultrapure distilled water to the mark.
The AMD sample was taken in August 2016, from the positions of S1 (input), (S2.), and S3
(output) of a constructed wetland treatment system in Mao Khe, Quang Ninh. Before analyses,
samples were filtered by 0.45 µm membranes, then treated by micro-wave: take 100 μL of treated
sample, and 1 mL of 3 M KCl + 2 mL of 1 M acetate buffer + 2 mL of 1M NH4Ac + 50 μL of
1 g/L Ga all in a 25-mL flask, next norm it two times by distilled water, then put in electrolyser.
Proceed with recording differential pulse lines in conditions of table 1. Add a 20 μL standard
solution containing Zn
2+
concentration of 10 mg/L, Pb
2+
, Cd
2+
, and Cu
2+
(of 10 mg/L/each) twice
repeat measuring 3 times.
2.1.3. Optimal condition examination
Supporting electrolyte is examined from a standard solution and added various electrolytes of
various volumes to other optimal conditions such as: potential, sweep rate, Hg drop size, etc. as
shown in Table 1. Afterward, find the optimal condition to apply to reality [9].
Table 1. The optimal parameters used to determine Cd
2+
Cu
2+
, Pb
2+
, Zn
2+
simultaneously
Working electrode HMDE Deposition potential (V) -1.15
Measuring mode DP Deposition time (s) 90
Drop size 4 Equilibrium time (s) 10
Stirring rate 2000 (r/min) Pulse amplitude (V) 0.05
Blank purge time 100 s Pulse time (s) 0.04
Start Potential (V) -1.2 Voltage step time(s) 0.4
End potential (V) 0.0 Sweep rate (V/s) 0.015
2.2. Results and discussions
2.2.1. Examine choosing supporting electrolytes
To find the optimal electrolyte background for analysis, the examination of dependence of
maximal current intensity on different electrolyte backgrounds in fixed condition of parameters
has been proceeded. Pour 50 μL of standard solution (Cu2+, Pb2+, Zn2+, Cd2+) 10 mg/L into a 25-mL
flask, next add different electrolytes of various volumes of electrolyte solution (see Appendix 1), then
proceed recording 3 times repeated measurements of dissolving current intensity in conditions
stated in Table 1, take the average value and deviation of the repeated measurements.
* Supporting electrolyte of KCl
Result of measuring dissolving current intensity in various conditions of KCl supporting
electrolyte indicates that: in different concentrations of KCl, stripping current intensity Ip of ions
decreases in the follow of Ip(Zn) > Ip(Cd) > Ip(Pb) > Ip(Cu). When the concentration of KCl
Nguyen Hoang Nam, Tran Thi Hong Van and Nguyen Thi Thanh Huong
96
increases from 0.06 M to 0.5 M, the Ip value of Cd
2+
and Cu
2+
decreases regularly from 120 to 62 nA,
but slowly and insignificantly from 92 to 46 nA. At CKCl = 0.12 M, Ip of Zn
2+
reached maximum.
Once the electrolyte potential enrichment is greater, the enrichment of heavy metal ions on the
mercury drop has lower efficiency, resulting in a smaller dissolving current. When the
concentration of KCl increases, it is very efficient to determine Pb, however the repeatability is
low and in-appropriate for determining Cd
2+
and Cu
2+
. The study results show that, at CKCl = 0.12 M,
Ip of ions did not reach its maximum, while Ip of Zn did, with the highest repeatability (Figure 1).
Therefore, we can see that, in this condition of background solution, it is only suitable for
determining ion Pb
2+
and Zn
2+
, as a result, CKCl = 0.12 M is selected to proceed the next study.
Figure 1. Dissolving current intensity Ip of Zn
2+
, Cd
2+
, Pb
2+
, Cu
2+
(10 mg/L)
in supporting electrolyte of KCl (0.12 M)
* Supporting electrolyte of KCl + NaAC buffer
The result indicated that when changing acetate buffer concentration, the dissolving current
intensity changed as well. In general, in the same concentration of studied ions, the solution with a
presence of acetated ion lowed the dissolved current intensity in comparison to using only KCl
supporting electrolyte (see Appendix 1). However, the intensity of dissolved current of Zn
changed without any pattern, while that of Cd increased regularly. The Ip of Pb had atrend to
increase once the concentration of electrolyte increased, while that of Cu decreased with an almost
unchanged intensity starting from a concentration of buffer solution of NaAc at 0.08 M. Besides,
it had the higher repeatability of measurements and more balanced peaks than those with only KCl
(see Figure 2). The results also indicated that at the acetate concentration of CNaAc = 0.08 M, the
intensity of dissolved current of Zn and Pb was the biggest. Moreover, the measurements
witnessed the highest repeatability in the examined concentrations. The results showed that the
presence of acetate benefited the determination of Cu and Cd in the solution. Therefore, the
concentration of acetate buffer chosen was 0.08 M, and we used this fixed concentration to
examine the optimal one of NH4Ac.
Study of supporting electrolytes of KCl-acetate buffer - NH4Ac for simultaneous determination
97
Figure 2. Intensity of dissolve current Ip of Zn
2+
, Cd
2+
, Pb
2+
, Cu
2+
(10 mg/L)
in supporting electrolyte of KCl (0.12M)
* Supporting electrolyte of KCl + NaAc buffer and NH4Ac
The results of studying the effect of NH4Ac to dissolve current intensity of 4 aboved ions
indicates that the concentration of NH4Ac changes relating to its peak changes. In general, with
the presence of NH4Ac, the dissolving current Ip intensities of the 4 ions significantly increase and
were all higher than both the KCl-background condition and the mixture of KCl electrolyte
background with NaAc buffer, despite having the same concentration. Its value increase by 1.5
times compared to that of Ip using solution of KCl electrolyte background and NaAc buffer.
However, when the concentration of electrolyte background increases, the dissolving current
intensity has a different trend of decreasing insignificantly compared to other electrolytes having
very high repeatabilities. When the concentration of NH4Ac increase from 0.02 M to 0.08 M, the
dissolving current intensities of Zn, Cd, Pb, Cu (within the range of 0.06 M to 0.08 M) is very
stable having balanced peaks and high repeatabilities, despite at no maximum value. The peaks
have very high resemblances. Adding NH4Ac into the solution, on one hand, the concentration of
CH3COO
-
increases, while on the other hand, ion NH
4+
forms a a heavy metal ammine complex
which is discharged easier than any ones of Chloro, acetate, and aquo. It also strengthens ions
conductivity for peak to become balanced with ahigher repeatability. Therefore, the mixture of
electrolyte background of KCl (0.12 M) + NaAc buffer (0.08 M) and NH4Ac (0.08 M) is chosen
to examine the optimal concentration of Ga
3+
.
Figure 3. Dissolving current intensity Ip of Zn
2+
, Cd
2+
, Pb
2+
and Cu
2+
(10 mg/L)
in supporting electrolyte of KCl (0.12 M), acetate buffer (0.08 M) and NH4Ac (0.08 M)
Nguyen Hoang Nam, Tran Thi Hong Van and Nguyen Thi Thanh Huong
98
* Supporting electrolyte of KCl + NaAC buffer + NH4Ac and Ga
3+
In the presence of Ga
3+
, the peaks of all 4 metals are clear; intensities of stripping currents are
greater than those without Ga3+. Especially when the intensity of stripping current of Cu
increases tremendously, due to Ga
3+
hindering the forming institute of heavy metal on Hg drop.
Besides, it distances the peaks of Cd and Pb simultaneously even at the bottom of heavy metal
peaks, particularly in the cases of Cu and Cd. At an adequate content of Ga
3+
, the intensity of
dissolving current of heavy metals changed insignificantly without affecting the current intensity
itself. Also, the repeatability of the measurements is very high (Figure 4 and Appendix 1) the
sample analysis process showed an exceeding amount of Ga could be added to achieve best results.
Figure 4. Differential pulse anodic stripping voltammetry of 4 elements (10 mg/L)
in supporting electrolyte of KCl (0.12 M) + acetate buffer (0.08 M) + NH4Ac (0.08 M)
and 20 µL Ga
3+
(1 g/L)
As shown from the results, the simultaneous determination of all 4 ions has good Ip values in
all 4 supporting electrolytes, and the higheset one in electrolyte of KCl + acetate buffer + NH4Ac + Ga
3+
.
The examination processing samples was done many times to determine the repeatability of
the measurement. In this supporting electrolyte, the mixture gives the best repeatability result.
Therefore, to analyze Cu
2+
, Pb
2+
, Zn
2+
, Cd
2+
, the background mixture of KCl + acetate buffer + NH4Ac +
Ga is selected.
2.2.2. Assessment of repeatability, limit of detection and limit of quantification
* Assessment of repeatability
To assess the repeatability of the measurement, we proceeded to record the line of stripping
Volt - Ampere of Zn
2+
, Cd
2+
, Pb
2+
, Cu
2+
in a fixed concentration (0.025 mg/L), then repeated
multiple times in the same condition. The measurement conditions were stated in Table 1. The
results are shown in Table 2.
The results indicates that in the study condition, the error are very low, repeatability of
measurement is very high, this shows the electrolyte background is highly reliable and could be
applied very well to measure simultaneously 4 elements.
Study of supporting electrolytes of KCl-acetate buffer - NH4Ac for simultaneous determination
99
3. .S C
LOD
X
10. .S C
LOQ
X
Table 2. Results of assessment of measurement repeatability
Measure value of repeatability n
IP (nA)
Zn
2+
Cd
2+
Pb
2+
Cu
2+
1 275.08 215.17 151.06 121.00
2 276.98 215.79 150.73 120.34
3 275.30 215.54 151.09 120.98
4 276.05 215.65 150.98 121.06
5 276.35 215.69 150.78 120.34
6 275.98 215.27 150.88 121.03
7 274.67 215.28 151.03 120.45
8 275.09 215.65 151.08 120.65
9 274. 45 215.35 150.46 121.02
10 275.31 215.45 150.64 120.35
Average value 275.53 215.48 150.87 120.72
Standard deviation S 0.792 0.205 0.215 0.325
Average standard deviation
X
S
0.250 0.065 0.068 0.103
* Limit of detection (LOD) and limit of quantification (LOQ)
LOD as convention is considered to be the concentration of examining substance which gives
signal 3 times higher than standard deviation of background line. If the concentration of the
substance in sample is C then LOD is:
Limit of quantification (LOQ) is considered to be the lowest concentration of the analyzing
substance which the analysis system can quantify with the different analysis signal from quantify
with signal of blank sample or signal of background line, conventionally calculated by formula:
The study result indicates that the method Volt-ampere-stripping voltammetry with hanging
mercury-drop electrode, using electrolyte background of KCl (0.12M) + NaAc buffer (0.08 M) +
NH4Ac (0.08 M) and Ga (20 µg/L), has high sensitivity, repeatability and applicability for
analyses of quantifying traces.
The results of studying repeatability to calculate limit of detection of substances gives Table 3.
Nguyen Hoang Nam, Tran Thi Hong Van and Nguyen Thi Thanh Huong
100
Table 3. Results of LOD and LOQ
Zn
2+
Cd
2+
Pb
2+
Cu
2+
LOD (ppb) 0.216 0.071 0.107 0.202
LOQ (ppb) 0.720 0.237 0.357 0.673
2.2.3. Determine simultaneously 4 ions Zn
2+
, Cd
2+
, Pb
2+
and Cu
2+
in AMD in Mao Khe,
Quang Ninh
AMD sample has various metal ions depending on their mining types. In coal mines such as
Mao Khe, Quang Ninh, the content of Fe and Mn in waste-water is very high. Waste-water sample
after being micro-waved was measured directly without extracting hindering substances, enriching
the number of measurement repeatability of 3, using the standard additional methods to determine
the concentration of ions in sample. The results of direct simultaneous analyses of 4 ions Zn
2+
,
Cd
2+
, Pb
2+
and Cu
2+
are indicated in Table 4 and presented in Figures 5 - 7.
Table 4. Average value of Zn, Cd, Pb and Cu in samples
Samples
Adding
time
Ip (nA)
Zn
2+
Cd
2+
Pb
2+
Cu
2+
S1
0 43.72 1.08 18.01 4.13
1 292.75 46.67 90.82 28.01
2 489.61 98.00 161.38 58.34
S2
0 33.7 0.5234 15.01 3.02
1 255.23 41.69 81.08 27.26
2 445.61 85.70 142.25 57.23
S3
0 21.67 KPHĐ 10.45 1.12
1 203.05 56.98 82.17 28.67
2 424.28 94.12 142.96 56.78
Figure 5. Peak DP-ASV determines Zn
2+
, Cd
2+
, Pb
2+
, Cu
2+
in sample S1
Study of supporting electrolytes of KCl-acetate buffer - NH4Ac for simultaneous determination
101
Figure 6. Peak DP-ASV determines Zn
2+
, Cd
2+
, Pb
2+
, Cu
2+
in sample S2
Figure 7. Peak DP-ASV determines Zn
2+
, Cd
2+
, Pb
2+
, Cu
2+
in sample S3
Table 5. Results of determining simultaneously contents
of ion Zn, Cd, Pb and Cu in AMD samples
Samples
C (mg/L)
Zn
2+
Cd
2+
(*10
3
) Pb
2+
Cu
2+
S1 0.469 ± 0.003 2.538 ± 0.00 0.256 ± 0.001 0.113 ± 0.007
S2 0.354 ± 0.004 1.530 ± 0.00 0.211 ± 0.006 0.068 ± 0.001
S3 0.149 ± 0.001 0.00 ± 0.00 0.185 ± 0.001 0.036 ± 0.001
The results indicates that the measurement has high repeatability, sensitivity, and peak
bottom narrowly-balanced despite samples containing heavy metal are measured directly on spots
with many obstacles to repeatability, sensitivity, and reliability. Resulted with electrolyte
background, it could be widely used to analyze directly and simultaneously 4 ions Zn
2+
, Cd