HomeMy WebLinkAboutNC0089109_Response to Notice_20221208 (3)r.
, ..,
env ironmenta , Inc. (864) 877-6942 . FAX (864) 877-6938
P.Q. Box 16414, Greenville, SC 29606 4 Craftsman Court, Greer, SC 29650
CHRONIC TOXICITY IDENTIFICATION EVALUATION
Facility: American Zinc Products
Sample ID: Effluent
ID # 62886 (Collected September 6, 2022)
Test Reviewed and Approved By:
October 2022
Robert W. Kelley, Lab Manager Patrick Timms, QA/QC
FL Certification #E87819
Test results presented in this report conform to all
requirements of NELAC, conducted under NELAC
Certification #E87819 Florida Dept. of Health.
Included results pertain only to provided samples.
SCDHEC Certification #23104
NCDENR Certification #022
Page 1 of 14
1.0 INTRODUCTION
Effluent samples of final effluent from the American Zinc Products (AZP) Mooresboro facility are tested
quarterly for toxicity using the Ceriodaphnia dubia Survival and Reproduction Test (Method 1002) -
North Carolina Pass/Fail modifications. A toxicity test set in early July 2022 indicated the presence of
slight chronic toxicity, with a 27% reduction in reproduction noted at the 0.9% IWC concentration (a test
failure). A pass/fail toxicity test with more than a 20% reduction in reproduction (and a significant t
value) is assessed as a failure under NCDENR protocols. For this test effluent was collected twice and
the samples were used sequentially during the test.
In order to investigate the cause of the toxicity failure, a sample of effluent concentrations was collected
on 9/6/22. Using this sample a series of treatments and toxicity tests (partial Toxicity Identification
Evaluation [TIE]) were conducted. Effluent treatments included EDTA chelation, Solid Phase Extraction,
and pH Adjustment. Treatment effectiveness was assessed through use of chronic multi -concentration
toxicity tests.
This report present the results of the partial chronic TIE.
TIE- AZP 1022 ETT
Page 2 of 14
2.0 SAMPLE COLLECTION
A grab sample of effluent was collected by AZP personnel as follows;
Sample ID Collection Date Sample Age at TIE
62886 Sep 6, 2022 1 day
3.0 SAMPLE TREATMENT
In a Phase I Tier I TIE a variety of treatments of the effluent are conducted, and each treated sample is
tested for toxicity. The relative effectiveness of each treatment, as compared to untreated effluent,
provides valuable information regarding the identity of the toxic chemical agent.
The treatments used in this TIE are summarized as follows:
Treatment Potential Toxicants Removed
Untreated Baseline
EDTA chelation cationic metals
C-18 SPE organics
Graduated pH ammonia, metals
Methodology for the individual treatments is discussed below by treatment. Both the treatments and the
subsequent toxicity tests were initiated on September 7, 2022.
TIE- AZP 1022 ETT
Page 3 of 14
3.1 EDTA Chelation
A 5.0 g/L stock solution of diSodium EDTA was prepared by adding 2.5 g of solid to 500 mL of DI
water. 2.0 mL of the stock solution was added to an 1000 mL aliquot of 5% effluent to give a final
concentration of 5.0 mg/L EDTA in the effluent. This was done for both samples and for a treated
control. The solutions were given 2 hours to equilibrate. After treatment the effluent was tested for
toxicity at 0.5, 0.9, 2.0, 5.0% concentration, using moderately hard synthetic freshwater (MHSF) for
dilution.
3.2 C-18 SPE Treatment
A 500 mL aliquot of a 5% effluent sample was filtered through an Oasis 6g HLB column using a
chemical metering pump. The column was preconditioned with 15 mL of methanol and 35 mL of DI
water. The first 50 of effluent to pass through the column was not used. A treated control was prepared in
the same manner After treatment the effluent was tested for toxicity at 0.5, 0.9, 2.0, 5.0% concentration,
using moderately hard synthetic freshwater (MHSF) for dilution.
3.3 Graduated pH
The goal of this treatment was to test the effluent for toxicity at a more acidic pH (6.5) and at a more
alkaline pH (8.5). Aliquots of each effluent were adjusted to the desired pH with each renewal.
TIE- AZP 1022 ETT
Page 4 of 14
4.0 TOXICITY TESTING METHODS
Toxicity testing was conducted using the Short -Term Methods for Estimating the Chronic Toxicity of
Effluents and Receiving Waters to Freshwater Organisms Method 1002 EPA-821-R-02-013, with
NCDNER modification for renewal only on test days 2 and 5, with corresponding reduced feeding. The
test organism was Ceriodaphnia dubia and the dilution water was Soft Synthetic Freshwater (SSF:
hardness 50 mg/L). Test organisms were fed daily with Selenastrum capricornutum and YAT. Each test
dilution was comprised of ten replicates of 1 test organism.
Ceriodaphnia dubia
1.Temperature: 25°C ± 1
2.Light: 100 ft-cd; 16 hr It/8 hr dk
3.Test Chamber Size: 30 mL plastic cup
4.Test Solution Volume: 15 mL
5.Renewal: Daily
6.Age of Test Organisms: <24 hours
7.No. of Neonates / Test Chamber 1
8.No. Replicates / Dilution 10
9.Feeding: Daily
10.Cleaning of Test Chambers: None
11.Aeration: None
12.Dilution Water SSF
13.Effluent Concentrations: 0, 0.5, 0.9, 2.0, 5.0%
14.Dilution Factor: NA
15.Test Duration: 7 days / 3 broods
TIE- AZP 1022 ETT
Page 5 of 14
5.0 RESULTS
5.1 Summary of Toxicity Testing of Treated Samples Results
Test results are summarized by treatment, as follows;
Date of Mortality By Test Concentration
Sample Control 0.5 0.9 2.0 5.0% Comments
Untreated Effluent 9/6 0.0% 0.0% 0.0% 0.0% 0.0% no effect on survival
EDTA Chelation 9/6 0.0% 0.0% 0.0% 0.0% 0.0%
C-18 SPE 9/6 0.0% 0.0% 0.0% 0.0% 0.0%
pH 6.5 9/6 0.0% 0.0% 0.0%
pH 8.5 9/6 0.0% 0.0% 0.0%
Date of Mortality By Test Concentration
Sample Control 0.5 0.9 2.0 5.0% Comments
Untreated Effluent 9/6 21.0 20.4 20.6 18.8 7.6 toxic at cons. of 5.0% and higher
EDTA Chelation 9/6 17.8 19.6 21.0 18.2 0.2 no effect
C-18 SPE 9/6 20.4 21.0 22.0 20.8 11.6 toxicity reduced
pH 6.5 9/6 14.2 18.0 18.2 no effect
pH 8.5 9/6 20.2 18.2 19.4 no effect
TIE- AZP 1022 ETT
Page 6 of 14
5.1.1 Untreated Effluent (Baseline Test)
The toxicity test on the sample as received indicated not toxicity at concentrations up to 2.0%, with
substantial toxicity at a 5.0% effluent concentration.
5.1.2 EDTA Chelation
EDTA chelation did not reduce the toxicity of the effluent sample, and in fact appeared to slightly
increase toxicity. This could be a result of a removal of ions which had a beneficial effect. The
ineffectiveness of EDTA indicates that the cause of toxicity was not a cationic metal such as copper,
zinc, nickel, or cadmium.
5.1.3 C-18 Solid Phase Extraction
C-18 Solid Phase Extraction treatment lessened toxicity at the 2.0 and 5% effluent concentrations. The
effectiveness of SPE treatment is consistent with a non -polar organic chemical as the cause of toxicity.
5.1.3 Graduated pH
Adjusting the pH of the effluent had no significant effect on the relative degree of toxicity.
TIE- AZP 1022 ETT
Page 7 of 14
6.0 DISCUSSION
• The results of EDTA Chelation treatment indicate that EDTA was not effective for reducing
toxicity. When EDTA is not effective it is an indication that toxicity is not due to cationic metals.
• The result of SPE treatment (reduction in toxicity) indicates that an organic chemical or polymer
which can be removed by SPE was the cause of toxicity in the effluent.
TIE- AZP 1022 ETT
Page 8 of 14
APPENDIX A
TIE Toxicity Test Bench Sheets
TIE- AZP 1022 ETT
Page 9 of 14
Test Day
1__ 2_ 3 4
5
6
7
8
ZGt3f—
raar7
it>�k5 �1A C1NE --
source
1 ep
+3+f
71
Li
control
-Client
American Zinc Pr. gg¢¢�
uuab-si
A
+3+6
,+2+5
10
19
.
, Sample ID
-PROCESS EFFLUEI
DS 8 26
8
S10 8-26
C
12
19
.
NPDES#
NCOo-89109
GG38 31
D
+4+7
,+46
13
24
. County
Rutherford
028-25
E
12
22
Month
9
F
NJA
0
Start & fed Date
0T-Sep-22
G
NJA
U
- Start & fed Time
02:40 PM
H
NJA
_ 0
Started ffi fed By
AM
NJA
0
.
Test Organism
eriodaphniadubia
J
NJA
0
Neo, born date
06-Sep-22
A
+3+7
..+3+5
13
Li.Neo,
born time
1700-2200
El
11
19
Test Type
NCCD
C
+3+5
`+4+7
1(0
_ 18
Dilution Water
1.1HSF
D
13
24
Units for Conc.
%
is 5
f
,+3+5
10
13
%3rd BR00D
F
NJA
0
Test vessels
30m1
G
NJA
0
Test volume
15m1
H
NJA
0
incubator#
1
1
NJA
0
J
NJA
0
20.4
A
+4+6
12
LL
El
3
+7+10
20
C
+3+7
`+3+7
12
22Test
method
EPA 821-R-02-013:1002
D
11
21
0 9
E
, +3+4
11
13
F
NJA
0
EXIT
G
NJA
0
NIA
0
H
1
NIA
_
0
ommen
J
NJA
020.6
y
A
+3+4
12
'IP
,
El
+3+6
10
19
C
4
,+7+9
20
` `
Control initemp
D
, +3+5
10
18
2
E
+4+6
8
18
F
NJA
_ 0
` `
G
NJA
_ 0
I.
H
NIA
_ 0
....
1
NJA
_ 0
NJA
0
18.8
,
J
A
2
2
4
B
3
4
7
C
4
8
12
D
1
+5+4
10
5
E
2
3
5
F
NJA
0
` `
G
NJA
0
H
NJA
0
1
NIA
0
iPiE
J
NJA
0
7.6 `
6
A
u
.
.
B
0
C
0
.
I.
D
0
0
E
0
..
F
0
.
.
G
0
H
0
1
J
0
0.0
JZ
AM
End Date
Renew
JC
JZ
JZ
JC
AM
JC
14-Sep- z
Fed
Time fed & renew
07:52 AM
02:04 PM
07:05 AM
07:05 AM
11:43 AM
11:26 AM
-.
11:46 AM
AM
Effluent New ternp.'C
Z4. !
Z4_J
Dead NIA -Lost or not used
Old temp. 'C
L5.1
Z5_f
25_Z
Control Itew temp. 'C
L4.5
Z4.4
TIE- AZP 1022
Page l0 of 14
ETT
Tes Day
1 2
3
4
5
6
7
8
Z8191—
rr:e•
. :4. r•
SDUIce
iep
+3+u
y
1'7
—Client
American Zinc Prod
rdrm
A
144 3:25
El
+2+6
9
17
: m p e 1
" 1 1 t
W93-26
C
+3+7
10
20
NPDES#
N00039109
GG23-31
D
+3+6
12
21
County
Rutherford
GG1483'
E
+2+5
7
14
Month
9
F
N/A
0
Start & fed Date
0T-Sep-22
G
NJA
6
Start &fed Time
02:46P1d
H
NJA
0
Started & fed By
AM
1
NJA
6
Test Organism
Ceriodaphnia dubia
J
NJA
01
eo, • orn •a a
1. ep 3,
A
+3+5
9
1 r
Neo, born time
1700-2200
El
+3+5
12
20..
Test Type
NCCD
+4+6
`+3+6
11
_ 21
`
Eslufon Water
IdHSF
C
D
10
19
Units for Conc,
95
,+3+7
11
21
.
%3rd BROOD
5r
E
F
N/A
0
Test easels
30 ml
G
N/A
0
Testrolume
15m1
H
NIA
0
Incubator#
1
1
NIA
0
•rzwr
Light
16VF,dk
J
NIA
0
_ 19.6
`
initial Temp°C
25
A
+3+6
'12
L'i
Selenastrum
0.05 ml
El
+4+5
'
10
19
YAT
0.65 ml
C
+3+6
`+4+7
13
22
Test method
EPA 821-R-02-013:1002
D
12
23
D.9
E
,+4+5
11
_ 20
F
NJA
_ 0
G
N/A
0
NJA
0
H
1
N/A
0
iviedri
.rumen.:
J
NJA
0
21.0
'
A
+3+8
5
lb
`
El
4
10
14
C
+3+6
`+3+5
11
20
Control rti temp
D
13
21
2
E
4
.+5+11
20
F
NJA
0
G
N/A
0
H
NIA
0
1
N/A
0
iC
J
NIA
0
13 18.2
A
0
0
u
9
0
0
0
C
0
0
- 0
D
0
0
0
5
E
0
1
1
F
NJA
0
G
NJA
0
H
NIA
0
J
NJA
0
0.2
A
u
B
0
C
- a
D
0
E
0
F
0
G
0
H
0
0
0
0.0
JZ
AM
End Date
Rene.,
Fed
JC
JZ
JZ
JC
AM
JC
I 14- iep-L2
Time fed & renew
07:53 AM
01:33 PM
0
01:09 PM
11:27 AM
1
01:14 PM AM
Effluent New ternp.'C
Z4.b
Z4_d
D e,ail WA -Lost or not used
Old temp. :C
Zb.1
Z5.1
Z5_Z
Z4.5
Z4.4
Control Neu temp. 'C
TIE- AZP 1022
Page 11 of 14
ETT
Tes Day
SEW ice
,ep
1 2 3 4 E. 6 7 8
illnr—
Laa1F
1 sl
+5+:.
1L
Lu
control
Client
American Zinc ProdL
rf 6-2a
A
+4+E.
`+3+5
11
_ 20
a
a Sample ID
-PRO CESS•-EFFLUEN
N48-25
B
W98-26
C
9
17
.
NPDES#
NC0089109
GG28-31
D
+4+7
10
21
. County
Rutherford
GG108-3'
E
+4+8
12
24
Month
0
F
NJA
0
Start & fed Date
UT-Sep-22
G
NJA
0
Start &fed Time
02:40PM
H
NJA
0
Started ffi fed By
AM
-Ceriodaphnia
I
NJA
0
Test Organism
dubia
-06-Sep-22
J
NJA
0
4-
Neo, born date
A
+3+5
`+4+7
10
idNeo.
born time
1700-2200
El
`+4+6
12
23
Test Type
NCCD
C
12
22
`
` Elution Water
1.IHSF
D
+4+7
11
22
Units for Conc.
%
4,5
E
,+2+5
13
20
.
. %3rd BROOD
F
NJA
0
Testvessels
30ml
G
N/A
_ 0
Test volume
15 ml
H
N)A
0
incubator#
`
1
N/A
0
Light
16U8dk
J
NJA
0
21.0
`
Initial Temp°C
`
25
A
+3+7
12
rl
Selenastrum
0.05 mI
+4+5
14
23
YAT
0.05 mI
B
C
+3+7
11
21
Test method
EPA 821-R-02-013:1002
D
+4+6
12
22
(,ci
E
,+3+7
12
22
F
N)A
0
EXIT
G
NJA
0
N)A
- 0
`
H
I
NJA
11
,vicar,
Comments
J
NJA
0
22.0
;
A
3
+7+9
_ l'd
1.
1.0
B
+3+6
`+4+7
13
_ 22
12
23
` Cantrel m, temp
D
+3+6
11
20
2
E
,+4+6
10
20
F
N)A
0
y
G
N/A
0
N/A
_ 0
H
NIA
0
J
NIA
0
20.8
A
3
10
13
,
3
8
11
B
C
3
+5+9
`
17
,
D
4
0
4
5
E
,+2+4
7
13
F
N)A
0
` `
`
G
N/A
0
H
N/A
0
N/A
0
NJA
0
11.6
J
A
u
• ,
,
B
0
C
0
, I.
I.
D
0
0
E
0
F
0
r ,
,
G
0
0
H
0
J
0
O.
JZ
AM
End Date
Renew
Fed
JC
JZ
JZ
JC
AM
JC
14- ep-22
Time Fed & renew
07:54 AM
01:48 PM
07:48 AM
07:49 AM
01:42 PM
11:30 AM
01:54 PM
AM
or not used
E" __rt New temp.-C
Z4.b
L4_
WA-Lost
0 _ :a-p.:C
L5.1
Z5_I
L52
Ca-rwl New temp. -C.
Z4.5
Z4.4
TIE- AZP 1022
Page 12 of 14
ETT
Test Day
1 2 3 4 5 b 7 8
La =
3h2k5 'pRh.
source
rep
I d
co
-Client
American Zinc Prod
U'I U t-.Za
A
+L+4
r
_
mpe
GG98-31
+ +
Al 8-26
C
4
0
4
NPDES#
NC0089109
46 8-25
D
3
+5+5
13
County
Rutherford
VJ88-26
E
+3+6
6
15
Month
9
F
NJA
0
Start & fed Date
UT-Sep-22
G
NJA
0
Start &fed Time
02:40PM
H
NJA
1
to e.. e.:y
I
NJA
0
Test Organism
Cenodaphnia dubia
J
NIA
0
Neo, born date
A
+3+5
11
Iy
Neo. born time
1700-2200
B
+4+5
12
21
Test Type
NCCD
C
+3+6
9
_ 18
Dilution Water
1.IHSF
D
4
7
11
Units for Conc,
95
0.9
E
+4+7
10
21
%3rd BROOD
F
N.I.A.
0
Test vessels
30m1
G
NJA
0
Test volume
15 m1
H
N%A
0
Incubator#
1
1
NJA
0
mum
Light
16IV8dk
J
NJA
0
18.0
Initial Temp °C
25
A
+3+6
10
id
e enas rum
1.1 m
17
YAT
0.05 m1
B
+3+5
9
C
+3+5
11
_ 19
lest method
EPA 821-R-02-013:1002
D
+3+5
9
17
2
E
+4+5
10
19
F
NIA
0
EXIT
G
NJA
0
-
_ 0
H
NIA
1
NJA
0
* -
Comments
J
NJA
0
18.2
A
u
`
B
0
C
_ 0
Control ini temp
D
0
E
0
.
.
F
NJA
_ 0
G
NJA
0
t ,
1
1
NJA
1
-
J
NJA
0
0.0
A
u
B
0
-
C
- 0
•
D
0
E
- 0
F
NIA
0
`
G
NJA
0
H
NIA
0
1
NJA
_ 0
* • -
0
0.0
J
NJA
A
u
B
0
C
0
.
. .
1
E
0
F
0
G
0
H
0
I
CI
J
0
Renew
JZ
AM
End Date
JC
JZ
JZ
JC
AM
JC
14-ep-LZ
Fad
Trre feed & renew
01:55 AM
02:30 PM
01:50 AM
01:51 AM
02:18 PM
11:28 AM
11:55 AM
AM
- o t New temp.'C
Z4. !
Z4. H
D e,ad NA -Lost or not used
L5.1
Z5-1
25-1
O '.._ New temp. 'C
L4.5
Z4-4
TIE- AZP 1022
Page 13 of 14
ETT
Test Day
1_ —2— 3 4
5 6 7 vial
T62886 pH 8.5
SOU ce
i ep
+3+5
1.1
is
. Po.
-Client
American Zinc Prod
in u t-LS
A
+4+6
10
20
Sample ID
PROCESti tH-LUEN
GG98-31
El
A10 8-26
C
4
+7+9
20
NPDES#
NC0O09109 .
468-25
D
4
. +7+10
21
County
Rutherford .
W88-26
E
.+3+6
12
21
Month
9 .
F
NJA
0
Start & fed Date
0T-Sep-22 .
NJA
U
Start & fed Time
02:40 PM
G
H
NJA
0
Started ffi fed
AMA
I
NJA
CI
es rganism
erio ap ma u LaJ
,
NJA
CI
Neo, born date
06-Sep-22
A
4
9
13
Neo. born time
1700-2200
E4
+3+5
,+3+6
11
19
Test Type
NCCD
C
10
_ 19
.
Dilution Water
MHSF .
D
3
+6+10
19
Units for Conc.
%
.+3+7
11
_ 21
.
%3rd BROOD
ii.9
E
F
NJA
_ 0
Test vessels
30ml ,
NJA
0
, Test volume
15m1
G
H
NJA
6
incubator#
1
NJA
0
J
NJA
0
18.2
A
.. +4+6
13
L3
El
+3+6
8
17
C
+4+5
10
19
Test method
EPA. 821-R-02-0131002
D
4
+5+9
18
2
E
.+4+7
9
20
.
F
NJA
0
}
EXIT
G
NJA
0
NIA
_
0
H
NA
_
0
ommen
J
NIA
0
19.4
i
A
u
J.
0
Q
C
_ 0
`
Control ini temp
D
0
a
E
o
F
NJA
_ 0
G
NJA
_ 0
,
H
NIA
_ 0
NJA
_ 0
NJA
0
0.0
+ ,
J
A
u
B
0
C
Cl
.
. .
D
0
is
E
- 0
.
. .
F
NJA
0
.
. .
G
NJA
0
H
NJA
0
I
NIA
0
i4it fC
J
NIA
0
0.0
A
u
.
. .
B
0
C
0
.
. .
D
0
0
E
a
..
F
0
.
. .
G
0
H
0
771
1
J
0
JZ
AM
End Date
Renew
JC
JZ
JZ
JC
AM
JC
14-Sep-ZZ
Fed
Time fed & renew
01:56 AM
02:13 PM
07:16 AM
01:16 AM
02:01 PM
11:20 AM
-.
01:05 PM
AM
Effluent New ternp.'C
Z4. !
Z4_J
Dead NIA -Lost or not used
OM temp. 'C
LS.L
Z5_I
2b_C
Control 14ew temp. 'C
L4.5
Z4.4
TIE- AZP 1022
Page 14 of 14
ETT