HomeMy WebLinkAboutNC0089109_Response to Notice_20221208 (2)• • ...environmental, 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 # 62597 (Collected July 29, 2022)
Test Reviewed and Approved By:
4(
August 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, additional samples were collected on 7/29/22,
including FA300@SP333. Using sample FA300@SP333, 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 0822 ETT
Page 2 of 14
2.0 SAMPLE COLLECTION
A grab sample of effluent AZP FA300@P333 was collected by AZP personnel as follows;
Sample ID Collection Date Sample Age at TIE
62597 Jul 29, 2022 19 days
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 August 17, 2022.
TIE- AZP 0822 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 0822 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 0822 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 7/29 0.0% 0.0% 0.0% 0.0% 0.0% no mortality effect
Untreated Effluent 8/17 0.0% 0.0% 0.0% 0.0% 20% no effect
EDTA Chelation 8/17 0.0% 0.0% 0.0% 20% 60% toxicity increased
C-18 SPE 8/17 0.0% 0.0% 0.0% 0.0% 0.0% toxicity reduced
pH 6.5 8/17 0.0% 0.0% 0.0% no effect
pH 8.5 8/17 0.0% 0.0% 10% 0.0% 40% 100% no effect
Date of Reproduction By Test Concentration
Sample Control 0.5 0.9 2.0 5.0% Comments
Untreated Effluent 7/29 20.8 18.3 15.1 10.3 0.3 toxic at concs. of 0.9% and higher
Untreated Effluent 8/17 20.9 19.0 17.2 12.0 2.0 toxicity reduced over time
EDTA Chelation 8/17 15.4 19.2 16.2 0.8 0.4 toxicity increased
C-18 SPE 8/17 12.0 15.4 16.0 11.8 toxicity reduced
pH 6.5 8/17 13.8 18.0 16.0 no effect
pH 8.5 8/17 16.6 15.6 no effect
TIE- AZP 0822 ETT
Page 6 of 14
5.1.1 Untreated Effluent
The original toxicity test on July 29 indicated a significant decrease in reproduction at effluent
concentrations of 0.9% and higher. It used a single effluent sample. When the same effluent sample was
tested again as the baseline for the TIE (on 8/17) toxicity appeared to have decreased slightly over time,
resulting in a decrease in reproduction of less than 20% at the IWC 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 even up to the 5% effluent concentration. 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 0822 ETT
Page 7 of 14
6.0 DISCUSSION
• Toxicity was noted to decrease slightly over time.
• 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 0822 ETT
Page 8 of 14
APPENDIX A
TIE Toxicity Test Bench Sheets
TIE- AZP 0822 ETT
Page 9 of 14
Tes Day
1 2 3 4 5 6 7 8
76r2r
Lang
It • • ' SEL
NE
source
rep
.3.1j21-1
n
3
+5+1u
'+6+12
I6
control
lient
American Zinc
rod�
C7S3
B
3
'+6+11
21
`
Sample @
PROCESS EFFLUEN
W63-5
C
3
20
NPDES#
NC0089109
013-4
D
3
_+8+9
- 20
.
County
Rutherford
V108-5
E
4
+8+12
24
Month
8
F
N/A
- 0
Start & fed Date
17-Aug-22
N/A
0
Start & fed Time
02:00PM
G
H
NIA
r
Started & fed By
AM
I
N/A
0
Test nismdate
Ceriod16-Au phnladuhia
J
NIA
0
`
or
Nea. horn date
16 Au}22
A
+2+7
14
Z.3
Neo, born time
1700-2200
B
`+4+5
13
- 22
Test Type
NCCD
C
3
.+7+10
20
Dilution Water
I.IHSF
D
3
6
9
Units for Conc.
%
0.5
E
3
`+7+11
21
, , ,
%3rd BROOD
F
NIA
0
Test vessels
30m1
G
N/A
0
Test volume
15m1
H
NIA
0
Incubator#
1
I
N/A
_ 0
Light
161U8dk
J
N/A
0
19.0
Initial Temp °C
25
L,
4
12
14
Selenastrurn
0.05 m1
B
3
+7+10
'
20
,
YAT
0.05 mI
C
2
+7+8
'
_ 17
Test method
EPA 821-R-02-013:1002
D
2
+3+11
21
4.9
E
4
8
- 12
F
NIA
0
EXITG
I
N/A
0
NIA
0
H
1
NIA
0
•T r rr[
.
Comments
J
NIA
0
17.2
A
2
11
1s
`
B
3
6
9
C
0
+5+7
'+2+9
12
: `
Control in i temp L
D
0
11
0
..+7+8
15
2
E
NIA
- 0
F
G
VIA
IF
fA
0
1
VIA
0
'view'
J
NIA
0
12.0
A
0
3
s
'
B
D
0
"
C
0
0
0
-
D
0
4
4
5
E
0
3
3
F
NIA
- 0
G
NIA
0
•
1
NIA
0
NIA
_
J
N/A
0
2.0
u
A
B
0
'
C
0
'
D
0
0
E
_ 0
.
F
0
G
0
'
H
0
I
0
j7412�R�
`
,Renew
J
0
0.O
JC
AM
End Date
Fed
JC
JC
JC
AM
AM
JC
L4-Aug-LG
1
10:12 AM
10:13 AM
10:31 AM
10:39 AM
07:45 AM
j
1138 AM
AM
Tm1e fed & renew
Effluent New temp. 'C
L4-I
L4-4
D=Des d NIA -Lost or not used
Old temp. 'C.
L5 _L
L5 _.1
L5.5
Z4.4
Z4.4
Control New temp. 'C
TIE- AZP 0822
Page l0 of 14
ETT
Tes Day
1 2 3
6 7 8
r[�Kc r��
um
control
I IT T
�mt�
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D
Caunty
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----
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It
1171M
tart & fed Date
7-Aug-22
t.
ULM
®
tart & fed Time
12:6U PM
1i
[O&M
---�
Started $ fed By
• M
1
Test Organism
eriod a phn ia du bia
J
NIA
Neo, born date
16-Aug-22
0.5
A
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13
Nea. born time
TOO-22GO
I
----WM
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Mal
1
Test Type
CCD
I.
.I
Mil
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hIHSF
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MM-_i
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It
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--
i
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r0ml
IULM-------®
1
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1Sml
bator#
161t18dk
I
-------�,ITg=-
11
Light
®®
Initial Temp °C
25
0.9
A
+3+5
12
�1
Selenastrum
1.65 ml
11
QOM
M-ALi
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I.05 ml
I.
tea-
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est method
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I_
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iii
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Ia
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-
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. N
--a -8 renew
T �
AM
01:0& PM
01:08 PM
0108 PM
00
11:00 AM
04:d6 AM
■
1150 AM AM
Effluent New temp.-C
L4_b
Z4.4
Dead N/A -Lost or not used
Old temp.:C
MVO-W-
-MEN
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-
-
-...
TIE- AZP 0822
Page 11 of 14
ETT
Tes Day
1 2 3 4 5
6
7
8
souice
1ep
len
American Zinc Prod
s J� u-a
AI
s
u
3
C7 3-5
B
2
0
2
m p e
W635
C
3
+5+8
16
NPDES#
NC0089109
013-4
D
2
0
2
County
Rutherford
V1O35
E
O
0
0
Month
8
F
N/A
0
`
` Start & fed Date
17-Aug-22
G
NJA
0
Start & fed Time
02:09 PM
H
NIA
O
`
` Started & fed By
AM
I
NIA
O
_
Test Organism
_ Carlo -daphnia cloths
J
N/A
Neo, born date
16-Aug-22
A
4
2
to
Nea. born time
170G-M90
B
4
+5+12
21
Test Type
NCCD
C
3
10
_ 13
Dilution Water
MHSF
D
0
5
5
Units for Conc.
%
0.5
E
4
11
_ 15
%3rd BROOD
F
N/A
0
`
` Test vessels
30 m1
G
N/A
0
Test volume
15 m1
H
N/A
0
Incubator#
1
I
N/A
0
Light
161ft&ik
J
N/A
0
_ 12.0
Initial Temp '',C
25
A
3
0
3
Selenastrum
0.05 ml
B
4
+5+9
13
YAT
0.05 mI
C
4
+6+7
17
Test method
EPA 821-R-02-013:1002
D
4
+8+10
22
~
0.9
E
4
+4+9
17
F
N/A
0
I EXIT
NIA
0
`
H
NIA
0
I
NIA
0
iviear1
ornments
J
NJA
0_
15.4
A
3
11
'I4
O
3
12
15
C
4
8
_ 12
Control initemp
D
4
+8+10
22
2
E
4
+4+9
17
F
NJA
0
` <
N/A
O
_
H
NJA
0
NIA
_ O
16.0
J
N/A
0
A
2
10
1L
O
3
+4+7
14
C
4
5
9
Ff
D
0
+5+7
12
5
E
0
+4+8
12
F
NIA
0
NIA
O
H
NJA
0
I
NIA
0
iviedri
J
NJA
0
11.8
A
u
O
0
C
- 0
D
0
0
E
0
F
0
O
H
O
J
0
Q.Q
Renew
JC
AM
End Date
Fed
JC
JC
JC
AM
A1,1
JC
L4-Aug-z1
Time fed & renew
08:12 AM
01:20 PM
01:20 PM
01:20 PM
11:22 AM
07:51 AM
01:14 PM I AM
Effluent New teap.'C
L4_b
Z4.4
IDead N/A -Lost or not used
Old temp. =C
Zb
Z5.4
2b.5
I
Control New temp. 'C
L4-b
Z4-4
TIE- AZP 0822
Page 12 of 14
ETT
Tea. Day
1 2 3
& 7 8
11
n' .
sarce
I ep
-IuJ u-a
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, 11k • r•
County
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imm
E
-----
+=.+10
_�
Month
U1
1171=
--
I
Start & fed Date
17-Aug-22
�r •
Start & fed Time
02:00 PM
H
A
0
Started ffi fed By
AM
I
N1A
3
Test Organism
Carlo -daphnia dubla
J
WA
0
Neo, born date
16-Aug-22
A
3
9
lr
Nea. born time
1700-2200
IZ
----laiM-
II
ICI
Test Type
NCCD
1.
EOM
MU
1
Dilution Water
MHSF
il.
amity
1
Units for Conc.
95
0.9
1-
----CZ=
iii
1
%3rd BROOD
IfiII
Test vessels
30m1
[ram-------��
Test volume
15mI
Incubator#
1
I
-------�
Nam
Light
16hl8dk
I®
18.0
Initial Temp °C
25
A
0
+F+I I
iii
Selenastrum
0.05 mi
L�
----i.1
Ill
Mi11
1
YAT
0.05 mi
I.
E1
MU
1
Test method
EPA 821-R-02-013:1002
11
iil
CUM
MU
1
2
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11
li
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0.0
0
A
I
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k 1
1.
F
0
G
0
H
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End Date
Fed
MEMMOMI0MOMMUMIO
MIMIGD7•
Time fed & renex
®®®II®1=1
SERLIZINAM
MVO
--�4
I
...t1=17T
.rrter-Ai7eTsur .
Effluent New ternp.'C-
Old temp. =C
I-�I-I-
WAN
-WAN
i■••
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-
-
i■••
■
TIE- AZP 0822
Page 13 of 14
ETT
Tes Day
1 2 3
& 7 8
n'
sarrce
I ep
oomro illrn
lithi
American Inc Prod
-I uL u n
Al
u
L
il.
ILI
M■■
itI.Irl7rfi 4ggIllaNI
W iMg.
����II1
�i
• • r -a•:
11k•• r•
LS t
uI
1
11
County
Rutherford
Month
8
■TAU:IMI.
----11
If
Ka=
--
i
Start & fed Date
17-Aug-22
1.11711M
Start & fed Time
02:00 PM
1
Started $ fed By
AM
'
1r
I
N1A
Test Organism
Carlo -daphnia dunia
J
WA
Neo, born date
16-Aug-22
A
3
Nea. born time
1700-2200
IZ
----liilDM—
II
MI
Test Type
NCCD
1.
..1
E.1
MU
1
Dilution Water
MHSF
r
+ +
1
1
Units for Conc.
95
0.9
E
4
+5+12
21
1
%3rd BROOD
F
JA
0
1
Testrressels
30m1
G
JA
D
1
Test volume
1Sml
H
JA
0
1
Incubator#
1
I
JA
D
Light
161f/Mdk
J
JA
0
Initial Temp°C
25
A
0
++3+12
ill.
1
Selenastrum
0.05 ml
L-----iI—
all
—
I
1
YAT
0.05mI
L.
.il—CM—MU
1
Test method
EPA 821-R-02-013:1002
I:.
����i.I
Ir4
ila
1
2
1-
a1
MU
1
Ia
!IL=
EXIT
El
It_
lill •_
—
Iifd:M
11WL1W
■
- ■
15.6
A
Ili
--------
Control ini templi
11.
1
UMW
0.0
A
.
Lim
I.
.
I.
.
a
1-li
MIMI
0.0
0
A
IZ
��������
®
1
F
0
G
0
H
0
I
0
J
0
0.0
Renew
JC
AM
End Date
Fed
MIMMOMMEEMMEMECEMMOM—!'L•alRD7�
Time fed & WWI'LEIBIZEMBEIZIEMEGIEILIELEMEMILIE11=1
0104 PM
.7--m
I
...f1=17T
.r/eR'3i7 mirm M
Effluent New ternp.'CM
Old temp. =C
—�J
WAN
'
—•••
Control Neu temp. -C
-
-
—•••
■
TIE- AZP 0822
Page 14 of 14
ETT