Auxiliary material for
1
2
3
Calculation of the mixing ratio of wastewater effluents leakage
4
to pristine water sources by the weighted average of multiple
5
tracer approach
6
Guy Gasser1,2, Irena Pankratov2, Sara Elhanany2, Hillel Glazman3, and Ovadia Lev*1
7
8
9
1
Laboratory of Environmental Chemistry, Casali Institute of Applied Chemistry,
10
Institute of Chemistry, Edmond J. Safra Campus, The Hebrew University of
11
Jerusalem, Jerusalem
12
2
Israel Water Authority, Bet Dagan, Israel
13
3
Israel Nature and Parks Authority, Israel
14
Experimental Details
15
Chemicals. All reference compounds were of high purity (>98%). Carbamazepine
16
was purchased from Sigma-Aldrich and Acesulfame K from Fluka). ACS –d4 was
17
purchased from the TRC, Canada. CBZ – d10 was purchased from the C/D/N Isotopes
18
Ltd, Pointe-Claire, Canada. Caffeine and caffeine
19
Aldrich. Ammonium acetate (purity >98%) and chloride standard as NaCl was
20
purchased from Merck. Individual stock solutions were prepared by dissolving the
21
compounds in HPLC-grade methanol. ACN, formic acid and hydrochloric acid (37%)
22
were supplied by Sigma-Aldrich. Purity of all organic solvents was higher than
23
99.8%. The nitrogen used for drying the solid-phase cartridges and for evaporation of
24
solvents was of 99.995% purity from Maxima, Israel. Ultrapure water was provided
25
by Millipore laboratory water purification system.
26
13
C3 were purchased from Sigma-
Quality assurance of analytical procedures
27
The laboratory of the National Water Authority of Israel operates according to ISO
28
17025 guidelines. The quantitation of tracers included routine QA procedures that
29
ware delineated in EPA method 1694, including verification of zero signal in the field
30
blanks. The recovery of all tracers from spiked blank spring water exceeded 70%
31
with less than 10% relative standard deviation. These characteristics were much
32
superior to the QA provisions specified in the EPA 1694 method. Acesulfame is not
33
included in EPA method 1694 but its recovery and RSD provisions withstood the
34
high quality assurance specified above . The data in the "Justification for grab
35
sampling" section of the SI demonstrates the high precision achieved by our analytical
36
procedure.
37
Chloride, nitrate and sulfate were determined by a Dionex ion Chromatograph
38
according to EPA method 300.1. Sodium, potassium, calcium, and magnesium were
39
analysed by Varian 720 ICP-OES according to EPA method 6010.C.
40
Justification for Grab Sampling
41
In order to confirm that grab sampling gives valid results in this particular study area
42
we have conducted 6 consecutive samplings of one representative spring and the
43
effluents of one wastewater treatment plant in the researched area. Table S1 shows the
44
raw results of the consecutive sampling. The diurnal variation of the two tracers
45
clearly demonstrates that the relative standard deviation, RSD of the two tracers in the
46
spring source were <3% and <9.5% of the mean for CBZ and ACS respectively. In
47
the wastewater treatment plant the respective RSD were 10% and 8 % respectively.
48
This proved that it is not imperative to sample the different springs and water sources
49
by composite sampling, which made our work much easier.
50
51
52
Table A1: Justification for grab sampling: Diurnal sampling of a representative
wastewater reservoir and the Zuf spring in the studied area.
Time
Date
7:00
12.10.12
11:30
12.10.12
16:00
12.10.12
23:30
12.10.12
8:00
13.10.12
12:00
13.10.12
Average
Standard deviation
53
54
Ga'aton Reservoir
CBZ,
ACS,
(ng/L)
(ng/L)
2200
28000
2137
28300
2087
25200
1645
30000
2000
27800
1880
32000
1992
28500
203
2290
Zuf
CBZ,
(ng/L)
10.2
9.8
10.4
10.6
10.5
10.1
10.3
0.3
ACS,
(ng/L)
150
143
162
152
184
172
161
15
Auxiliary water quality parameters in the studied sites
Table A2 Concentrations of tracers and major ions in the target springs and in the Baloa sinkhole. (Locations of the different sites are depicted
in Figure 1).
Sampling
Na+
K+
Mg2+
Ca2+
SO42HCO3ClNO3CBZ
ACS
Caffeine
Location
Date
(mg/L) (mg/L)
(mg/L)
(mg/L)
(mg/L)
(mg/L)
(mg/L)
(mg/L) (ng/L) (ng/L)
(ng/L)
10.12.06
27.0
18.4
33.0
105.6
49.7
22.03.10
19.1
1.9
23.7
144.8
10.3
29.4
24.0
95.4
25.04.10
22.1
2.5
25.1
106.1
71.8
29.05.11
20.1
1.2
23.6
102.6
9.8
434.0
27.1
25.1
24.0
360
Ziv
11.09.11
19.2
2.2
28.4
112.8
9.5
437.0
29.8
24.4
21.0
160
50
16.01.12
18.3
1.8
17.9
105.8
12.4
382.0
23.5
27.2
15.0
180
80
26.03.12
17.4
1.3
20.9
111.2
11.0
419.0
26.6
24.7
27.0
230
10
09.05.12
18.2
1.7
24.9
105.8
9.1
399.0
25.7
24.8
83.0
400
20
22.03.10
18.2
1.7
29.3
81.7
11.3
32.8
14.5
ND
25.04.10
22.0
1.6
32.8
88.0
ND
29.05.11
21.7
1.1
27.9
76.8
10.7
380.0
30.5
13.0
2.0
ND
Hardalit
11.09.11
19.0
1.5
34.4
90.3
9.8
416.0
32.1
11.2
ND
ND
ND
16.01.12
19.3
2.1
26.7
79.0
12.5
364.0
25.2
17.0
2.0
ND
ND
26.03.12
18.4
1.7
27.2
81.2
11.7
364.0
30.3
17.6
29.0
150
ND
09.05.12
19.1
1.4
28.7
78.6
10.0
359.0
29.1
13.5
3.0
137
ND
22.03.10
15.2
1.9
29.1
98.1
14.8
25.9
25.9
15.0
25.04.10
18.7
2.0
29.8
95.0
17.0
29.05.11
20.7
1.7
27.5
95.1
14.8
428.0
26.9
22.8
29.0
640
Gia
11.09.11
16.1
2.2
30.7
98.5
11.2
414.0
25.1
23.8
18.0
200
ND
16.01.12
17.1
2.4
23.0
98.4
16.9
386.0
24.2
33.4
15.0
120
ND
26.03.12
17.5
1.7
27.4
102.7
18.7
414.0
27.0
29.1
25.0
170
ND
09.05.12
16.9
1.8
29.0
97.9
13.1
411.0
24.1
24.3
14.0
150
ND
Shefa
10.12.06
14.4
3.3
30.1
92.0
5.8
31.6
22.03.10
25.04.10
29.05.11
11.09.11
16.01.12
26.03.12
09.05.12
22.03.10
25.04.10
29.05.11
Zuf
11.09.11
16.01.12
26.03.12
09.05.12
22.03.10
25.04.10
29.05.11
Ga'aton
11.09.11
16.01.12
26.03.12
09.05.12
10.12.06
09.01.07
11.09.11
Baloa
16.01.12
26.03.12
09.05.12
ND- below detection limit.
14.9
18.8
20.7
15.8
17.1
17.7
17.2
15.3
18.5
20.9
15.4
16.7
17.9
16.9
14.8
18.8
20.6
15.8
17.1
17.7
16.6
114.7
1.8
2.0
1.7
2.1
2.3
1.7
2.3
1.8
2.0
1.7
2.2
2.2
1.8
1.8
1.9
2.1
1.8
2.3
2.0
1.8
1.9
88.0
28.6
29.9
27.4
30.5
23.0
27.6
29.1
29.3
29.7
27.6
29.7
22.4
28.2
29.0
28.7
30.0
27.0
30.1
22.0
26.9
28.9
43.7
96.0
95.7
94.7
97.8
98.9
103.1
97.2
97.7
94.3
95.5
96.1
97.1
106.1
97.3
97.5
97.1
95.9
97.4
99.0
105.2
98.0
102.8
88.8
26.7
26.9
29.1
10.4
8.9
6.0
8.0
39.7
25.8
32.8
32.3
92.2
68.0
76.8
79.4
14.3
25.4
25.6
14.7
11.1
16.9
17.7
13.2
14.8
429.0
418.0
382.0
420.0
412.0
27.0
24.8
23.4
25.6
26.9
26.3
22.6
23.5
33.2
27.4
23.7
26.3
14.5
11.1
15.7
18.7
18.2
15.0
422.0
401.0
372.0
414.0
408.0
26.6
25.0
22.4
26.7
30.2
25.7
22.3
23.6
30.6
28.7
24.3
27.2
15.0
11.4
17.6
19.5
13.5
1.4
16.1
21.5
23.5
19.7
1.4
446.0
409.0
375.0
418.0
405.0
26.7
24.7
24.1
27.2
26.3
140.8
67.9
106.9
27.9
35.4
35.3
22.5
23.7
35.1
30.5
25.4
18.6
3.4
<0.25
9.0
4.4
<0.25
515.0
378.0
416.0
446.0
17.0
16.2
37.4
17.0
11.0
27.0
15.0
18.0
16.0
25.5
18.0
16.0
26.0
15.0
20.0
18.1
26.0
17.0
8.0
35.0
20.0
650.0
500.0
100.0
760.0
680
150
110
120
400
ND
ND
ND
ND
580
200
150
220
360
ND
ND
ND
ND
420
170
75
230
280
ND
ND
ND
ND
10000
18000
8600
11000
2500
500
100
120
Table A3: Concentration of potential wastewater tracers in wastewater effluents in
the vicinity of the target springs.
-
-
Cl
(mg/L)
NO3
(mg/L)
CBZ
(ng/L)
ACS
(ng/L)
Caffeine
(ng/L)
Bet Jann - effluents
117
<0.25
775
22500
4000
Naharia - effluents
179
19.1
2300
30000
5000
Ga'aton reservoir
160
31.5
1870
33000
18000
Average
152
25.3
1650
28500
9000
Standard deviation
31.9
8.8
788
5410
7810
Location
Table A4: Concentration of potential wastewater tracers in nearby springs that are
not influenced by wastewater effluent.
.
-
Sampling
Date
Cl
(mg/L)
Hotem
22.07.12
Tamir
-
(mg/L)
CBZ
(ng/L)
ACS
(ng/L)
Caffeine
(ng/L)
17.3
2.2
ND
ND
ND
22.07.12
29.6
7.6
ND
ND
ND
Keren 3
22.07.12
23.0
10.1
ND
ND
ND
Keren 5
22.07.12
20.8
9.9
ND
ND
ND
Average
22.7
7.4
0
0
0
Standard deviation
5.2
3.7
Location
NO3
ND corresponds to less than 0.1, 10 and 10 ng/L for CBZ, ACS and Caffeine,
respectively. ND is taken as 0 for the calculation of the average value.
Calculated Mixing Ratios
Table A5: Mixing ratios, their standard deviations and relative standard deviations at
different springs and a heavily contaminated site based on CBZ.
Location
Ziv
Hardalit
Gia
Shefa
Zuf
Ga’aton
Sampling
Date
22.03.10
25.04.10
29.05.11
11.09.11
16.01.12
26.03.12
09.05.12
22.03.10
25.04.10
29.05.11
11.09.11
16.01.12
26.03.12
09.05.12
22.03.10
25.04.10
29.05.11
11.09.11
16.01.12
26.03.12
09.05.12
22.03.10
25.04.10
29.05.11
11.09.11
16.01.12
26.03.12
09.05.12
22.03.10
25.04.10
29.05.11
11.09.11
16.01.12
26.03.12
09.05.12
22.03.10
25.04.10
Mixing ratio
based on CBZ,
M.R.
5.8
4.4
1.5
1.3
0.9
1.6
5.0
N.D
N.D
0.1
N.D
0.1
1.8
0.2
0.9
1.0
1.9
1.1
0.9
1.5
0.8
1.0
1.0
2.3
1.0
0.7
1.6
0.9
1.1
1.0
1.5
1.1
1.0
1.5
0.6
1.2
1.1
Absolute
uncertainty level,
(M.R.) (ΔE), %
3.4
2.9
2.2
2.1
2.1
2.2
3.1
0.6
0.6
1.0
0.6
0.4
0.6
1.0
0.6
0.6
0.8
0.5
0.7
0.7
1.2
0.7
0.6
1.0
0.7
0.5
0.5
0.7
0.5
0.5
0.8
0.3
0.8
0.7
29.05.11
1.6
0.9
11.09.11
1.0
0.7
16.01.12
0.5
0.6
26.03.12
2.1
1.1
09.05.12
1.2
0.8
22.03.10
25.04.10
29.05.11
Baloa
11.09.11
39
26
16.01.12
30
18
26.03.12
6.1
18
09.05.12
46
28
Calculations are based on [ [CBZ]b=0; Δ[CBZ] b=0.1; [CBZ]ef=1,650 ; Δ[CBZ]ef=788
ng/L.
Table A6: Mixing ratios, their standard deviations and relative standard deviations at
the various springs and a heavily contaminated site based on ACS.
Location
Ziv
Hardalit
Gia
Shefa
Zuf
Ga’aton
Sampling
Date
22.03.10
25.04.10
29.05.11
11.09.11
16.01.12
26.03.12
09.05.12
22.03.10
25.04.10
29.05.11
11.09.11
16.01.12
26.03.12
09.05.12
22.03.10
25.04.10
29.05.11
11.09.11
16.01.12
26.03.12
09.05.12
22.03.10
25.04.10
29.05.11
11.09.11
16.01.12
26.03.12
09.05.12
22.03.10
25.04.10
29.05.11
11.09.11
16.01.12
26.03.12
09.05.12
22.03.10
25.04.10
29.05.11
11.09.11
Mixing ratio
based on ACS,
M.R.
Absolute
uncertainty level,
(M.R.) (ΔE), %
1.3
0.6
0.6
0.8
1.4
0.5
0.4
0.4
0.4
0.5
N.D
N.D
N.D
0.5
0.5
0.3
0.3
2.2
0.7
0.4
0.6
0.5
0.9
0.8
0.8
0.8
0.8
2.4
0.5
0.4
0.4
1.4
1.0
0.9
0.9
0.9
0.9
2.0
0.7
0.5
0.8
0.6
0.4
0.2
0.2
0.2
0.2
1.5
0.6
0.6
0.5
16.01.12
0.3
0.5
26.03.12
0.8
0.5
09.05.12
1.0
0.5
22.03.10
25.04.10
29.05.11
Baloa
11.09.11
35
16
16.01.12
63
19
26.03.12
30
16
09.05.12
39
16
Calculations are based on [ACS]b=0; Δ [ACS]b, =10 ; [ACS]ef= 28,500; Δ[ACS]ef, =
5,410 ng/L.
Table A7: Mixing ratios, their standard deviations, and relative standard deviations
at different springs and a heavily contaminated site based on chloride. Negative
values were retained though they are not physically feasible.
.
Mixing ratio
Absolute
Sampling
Location
uncertainty
level,
based on Cl ,
Date
(M.R.) (ΔE), %
M.R.
22.03.10
5.2
9.1
25.04.10
29.05.11
3.4
7.9
11.09.11
5.5
7.9
Ziv
16.01.12
0.6
7.9
26.03.12
3.6
7.9
09.05.12
2.3
7.3
22.03.10
7.8
4.7
25.04.10
29.05.11
6.1
4.6
Hardalit
11.09.11
7.2
4.6
16.01.12
1.9
4.5
26.03.12
5.9
4.6
09.05.12
4.9
4.5
22.03.10
2.5
4.1
25.04.10
29.05.11
3.2
4.1
Gia
11.09.11
1.8
4.1
16.01.12
1.1
4.1
26.03.12
3.1
4.1
09.05.12
1.1
4.1
22.03.10
6.9
4.5
25.04.10
29.05.11
2.1
3.8
Shefa
11.09.11
3.3
4.5
16.01.12
1.6
4.5
26.03.12
0.5
2.7
09.05.12
2.2
4.5
22.03.10
2.8
2.8
25.04.10
29.05.11
3.0
6.4
Zuf
11.09.11
1.8
6.4
16.01.12
-0.2
6.4
26.03.12
3.0
6.4
09.05.12
3.1
4.4
22.03.10
2.3
4.1
Ga’aton
25.04.10
29.05.11
3.1
4.1
11.09.11
1.5
4.1
16.01.12
1.1
4.1
26.03.12
3.5
3.5
09.05.12
2.8
4.0
22.03.10
25.04.10
29.05.11
Baloa
11.09.11
65
39
16.01.12
4.1
36
26.03.12
9.9
36
09.05.12
9.8
36
Calculations are based on [Cl-]b=22.7; Δ[Cl-]b,=5.2; [Cl-]ef=152 ; Δ[Cl-]ef=31.9 mg/L.
Table A8: Mixing ratios, their standard deviations and relative standard deviations at
different springs and a heavily contaminated site (Baloa) based on weighted average
of CBZ and ACS.
Location
Ziv
Hardalit
Gia
Shefa
Zuf
Ga’aton
Baloa
Mixing ratio based
on the two tracers,
̅̅̅̅̅̅̅
𝑀. 𝑅. , %
Absolute
uncertainty level,
̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅
(𝑀. 𝑅. )(𝛥𝐸) , %
Relative
uncertainty level,
̅̅̅̅̅̅̅
(𝛥𝐸) , %
1.3
0.6
0.6
0.9
1.5
0.03
N.D
0.03
2.1
0.4
2.0
0.94
0.74
1.0
0.7
2.3
0.8
0.6
1.0
1.2
1.9
0.8
0.6
0.9
0.6
1.5
0.7
0.6
1.1
1.0
36
46
20
41
0.5
0.4
0.4
0.4
0.5
0.3
38
72
66
44
33
1046
0.3
0.3
0.3
0.6
0.5
0.5
0.6
0.4
0.8
0.6
0.5
0.6
0.6
0.4
0.2
0.2
0.2
0.2
0.5
0.4
0.4
0.5
0.4
14
13
12
14
1048
15
72
32
52
61
54
60
33
69
91
66
51
20
28
33
28
31
32
55
62
45
41
38
20
60
35
Calculations are based on [ACS]b=[CBZ]b=0; Δ[CBZ]b=0.1 ng/L; Δ[ACS]b=10 ng/L;
[ACS]ef= 28,500 ng/L; [CBZ]ef=1,650 ng/L; Δ[CBZ]ef=788 ng/L; Δ[ACS]ef= 5,410
ng/L.
Table A9: Mixing ratios, their standard deviations, and relative standard deviations
at different springs and a heavily contaminated site based on the weighted averages
of CBZ, ACS and chloride
Location
Ziv
Hardalit
Gia
Shefa
Zuf
Ga’aton
Baloa
Mixing ratio
based on the three
̅̅̅̅̅̅̅̅
tracers, 𝑀.
𝑅. , %
Absolute
uncertainty level,
̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅
(𝑀. 𝑅. )(𝛥𝐸) , %
Relative
uncertainty level,
̅̅̅̅̅̅̅
(𝛥𝐸) , %
1.3
0.6
0.6
0.9
1.5
0.01
0.01
0.1
2.1
0.4
2.1
0.96
0.76
1.1
0.76
2.4
0.8
0.6
1.0
1.2
1.9
0.8
0.6
0.9
0.6
1.6
0.7
0.6
1.1
1.1
40
40
19
37
0.5
0.4
0.4
0.4
0.5
0.3
0.3
0.6
0.3
0.3
0.6
0.5
0.5
0.6
0.4
0.8
0.6
0.5
0.6
0.6
0.4
0.2
0.2
0.2
0.2
0.5
0.4
0.4
0.5
0.4
13
12
11
13
38
70
66
44
33
512
1165
236
15
68
31
51
60
51
59
32
69
91
66
51
20
28
33
28
31
31
55
62
44
40
33
31
61
37
Calculations are based on [ACS]b=[CBZ]b=0; [Cl-]b=22.7 mg/L; Δ[CBZ]b=0.1 ng/L; Δ[ACS] b =10
ng/L; Δ[Cl-]b-=5.2 mg/L ; [ACS]ef= 28,500 ng/L; [CBZ]ef=1650 ng/L; [Cl-]ef=152 mg/L; Δ[CBZ] ef
=788 ng/L; Δ[ACS]ef = 5,410 ng/L; Δ[Cl-]ef=31.9 mg/L.
Table A10: Comparison of the predicted mixing ratios obtained by two methods for
the estimation of the uncertainty level associated with [X]i: 1. Repeated sampling at
different seasons (RS-DS). Estimation based on the standard deviation of analyses
that involve sampling at different seasons by different samplers and different
sampling equipment. 2. Repeated sampling on the same date (RS-SD): Estimation of
the uncertainty level is based on the standard deviation of analyses that were
conducted by the same samplers during the same 24 hours. The conservative RS-DS
estimation was used in the text of this article
Location- Sampling
Zuf
Date
CBZ
Location
22.03.10
25.04.10
29.05.11
11.09.11
16.01.12
26.03.12
09.05.12
Average
Sampling
Date
Mixing ratio
Absolute
Mixing ratio
Absolute
based on CBZ
uncertainty based on CBZ, uncertainty
(RS-DS),
level (RS-DS),
(RS-SD),
level (RS-SD),
(𝑀.
)(𝛥𝐸),%
(𝑀.
𝑀. 𝑅., %
𝑅.
𝑀. 𝑅.,%
𝑅. )(𝛥𝐸),%
1.1
0.5
1.1
0.6
1.0
0.5
1.0
0.5
1.5
0.7
1.5
0.8
1.1
0.5
1.1
0.6
1.0
0.5
1.0
0.5
1.5
0.8
1.6
0.8
0.6
0.3
0.6
0.4
1.1
0.54
1.1
0.6
Mixing ratio
Absolute
Mixing ratio
Absolute
based on ACS,
uncertainty based on ACS, uncertainty
(RS-DS),
level,
(RS-SD),
level,
(RS-DS),
(RS-SD),
𝑀. 𝑅. ,%
𝑀. 𝑅. ,%
(𝑀. 𝑅. )(𝛥𝐸),%
(𝑀. 𝑅. )(𝛥𝐸),%
22.03.10
25.04.10
29.05.11
2.0
0.4
2.0
ACS
11.09.11
0.7
0.2
0.7
16.01.12
0.5
0.2
0.5
26.03.12
0.8
0.2
0.8
09.05.12
0.6
0.2
0.6
Average
0.92
0.29
0.94
Location- Sampling
Absolute
Mixing ratio
Relative
Zuf
Date
based on the two uncertainty
uncertainty
level,
tracers, (RS-DS),
level,(RS-DS),
(RS-DS),
̅̅̅̅̅̅̅̅
̅̅̅̅̅̅̅
𝑀. 𝑅. , %
(𝛥𝐸),%
̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅
(𝑀. 𝑅. )(𝛥𝐸),%
29.05.11
1.9
0.4
20
11.09.11
0.8
0.2
28
CBZ &
16.01.12
0.6
0.2
33
ACS
26.03.12
0.9
0.2
28
09.05.12
0.6
0.2
31
Average
0.96
0.24
28
0.1
0.1
0.1
0.1
0.1
0.1
Location - Sampling
Mixing ratio
Absolute
Relative
Zuf
Date
based on the two uncertainty
uncertainty
tracers,
level,
level, (RS-DS),
̅̅̅̅̅̅̅
(RS-SD),
(RS-SD),
(𝛥𝐸),%
̅̅̅̅̅̅̅̅
̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅
𝑀. 𝑅. , %
(𝑀. 𝑅. )(𝛥𝐸), %
29.05.11
2.1
0.1
4.7
11.09.11
0.7
0.1
10
CBZ &
16.01.12
0.6
0.1
14
ACS
26.03.12
0.8
0.1
9.2
09.05.12
0.6
0.1
14
Average
0.93
0.13
15.5
Calculations are based on [ACS]b=[CBZ]b=0; Δ[CBZ]b=0.1 ng/L; Δ[ACS]b=10 ng/L;
[ACS]ef= 28,500 ng/L; [CBZ]ef=1,650 ng/L; Δ[CBZ]ef=788 ng/L; Δ[ACS]ef= 5,410
ng/L.
Figure A1: Upper two frames: Graphical presentation of Table A7. Mixing ratios,
their standard deviations at different springs and a heavily contaminated site based
on chloride tracer. Negative values were not retained. Bottom frame: Visual
presentation of the Mixing Ratios at the Baloa sinkhole based on CBZ, ACS, Cl-, two
organic tracers and all three tracers.