EPA ATTACHMENT NO. LE
Derivation of a Colorado State Manganese Table Value Standard
For The Protection of Aquatic Life
William A. Stubblefield and James R. Hockett
ENSR Corporation; 4303 West LaPorte Ave.; Fort Collins, Colorado 80521
July 2000
2
ABSTRACT
Manganese is a common constituent of fresh waters, often present at concentrations in the
mg/L range. Increases in the ambient concentrations of manganese above naturally occurring
activities,
levels in
FeCeiVindS666riiSOaFfreas
well as non-point discharges
giirfr6Mresulting
-061fit'Sblifcfrom
-e-tfitthardb-natural
runoff
-§ frtriffrifiin
mineralized
-g-a-ritt
areas.smelting--
?
Previously, little information was available regarding the acute and chronic toxicity of
manganese to aquatic organisms. National ambient water quality criteria (AWQC) do not exist
for manganese and in some instances, states have relied upon limited data in establishing
water quality compliance limits. Through the effort presented herein, we have attempted to
assemble all of the available freshwater aquatic toxicity data for manganese and, using the
USEPA's procedures for deriving AWQC [USEPA 1985], propose revised values for Colorado's
existing Table Value Standard (TVS) that reflects our current scientific understanding of
manganese toxicity.
Acute toxicity data were available for twelve freshwater species and median lethal
concentrations (LC50) ranged from a low of 5,322 pg/L for the rainbow trout to a high of
274,431 pg/L for the toad,
Bufo boreas
(data normalized to a hardness of 50 mg/L as CaCO3
for comparative purposes). Manganese acute toxicity decreases with increasing water
hardness; the slope for this relationship is 0.3331. Chronic toxicity data were available for six
species of fish and aquatic invertebrates. Hardness normalized (i.e.., 50 mg/L as CaCO3)
chronic effects concentrations for all of the tested species were remarkably consistent, ranging
from 1,859 pg/L for rainbow trout to 4,246 pg/L for
Daphnia magna.
Manganese chronic
'toxicity decreases also with increasing water hardness; the slope for this relationship is 0.2706.
Using the EC10 as the endpoint for evaluating chronic toxicity, the final acute-to-chronic ratio
(ACR) for manganese is 3.6196.
National AWQC consist of two values: the criterion maximum concentration (CMC, acute) and
the criterion continuous concentration (CCC, chronic). Using USEPA procedures for deriving
AWQC [USEPA 1985] the following equations were developed. These equations describe
manganese concentrations that should be protective of aquatic life in Colorado's waters:
CMC
TVS(at
hardness)
—
e 0.3331[In
hardness]
+6.4676
CCC
TVS(at
hardness)
=
e
0.3331[In
hardness]+
5.8743
Based on the above equations, at hardnesses of 50, 100, and 200 mg/L as CaCO
3
the criteria
continuous concentrations (CCC) of manganese are 1310, 1650, and 2078 pg/L, respectively,
and the criteria maximum concentrations (CMC) are 2370, 2985, and 3761 pg/L, respectively.
3
Introduction
Manganese is ubiquitously distributed throughout surface soils, aquatic sediments,
ground waters, and surface waters of the United States. Concentrations in fresh waters vary
....
? •?
_
widely, ranging from below detection to several hundred milligrams per liter [National Academy
of Science 1973]. Manganese often is elevated in surface waters near metal mining operations,
as it is a common constituent of point source discharges from mining and smelting activities, as •
well as from non-point discharges resulting from natural runoff in mineralized areas. In
Colorado, manganese concentrations in surface waters also vary widely, from a few pg/L to
several mg/L.
Prior to this effort, few acute or chronic toxicity studies have been reported with
manganese and no USEPA national ambient water quality criteria (AWQC) have been
promulgated. To derive enforceable standards, several states have relied on the
recommendation of McKee and Wolf [1963] and adopted a manganese standard of 1,000 pg/L
for the protection of aquatic life. This value is based on little toxicity data and does not consider
potential modifying factors such as water hardness. Previously, Colorado had a Table Value
Standard (TVS) of 1,000 pg/L. This value results from a recommendation from the Colorado
Division of Wildlife [Davies and Goett[ 1976], but again is based on limited toxicity data. In
1997, the Colorado Water Control Commission accepted a joint proposal from Climax
Molybdenum and the Colorado Division of Wildlife that proposed a revised manganese Table
Value Standard that considered a greatly increased database of acute and chronic toxicity data
for manganese, as well as the relationship between manganese toxicity and water hardness.
The chronic TVS is based on the following equation:
TVTVS ?
hardness)
0.5434(In
hardness)t4.7850
Since that time additional acute and chronic toxicity tests have been conducted, e.g.,
Davies and Brinkman [1998]. The current effort is intended to revise the existing Table Value
Standard, based on the most current toxicity data, so that it can be used throughout the waters
of Colorado for minimizing potential environmental risk to Colorado's aquatic species resulting
from manganese exposure. Toxicity test data considered in this evaluation were obtained from
the open literature and from studies conducted in both the Colorado Division of Wildlife's
4
toxicology laboratory and ENSR's laboratory. In addition, a search of the USEPA's
environmental toxicity database, AQUIRE, was conducted to identify additional data. This
report summarizes the results of acute and chronic toxicity tests conducted with a variety of
freshwater aquatic species; a detailed discussion of the test procedures and study results is
available in the individual study reports.
Acute and chronic toxicity data
Acute data
The acute toxicity of manganese to a variety of aquatic organisms is presented in Table
1. Among the twelve species represented .in the database, genus geometric mean acute values
ranged from a low of 5,322 pg/L for the rainbow trout to a high of 274,431 pg/L for the toad,
Bufo boreas(at
a hardness of 50 mg/L). As indicated in Table 2 below, possible age sensitivity
differences were noted in tests conducted with rainbow trout, brook trout and fathead minnows,
with older organisms being less sensitive to the acute toxic effects of manganese. Because of
this, only data for younger organisms were retained for subsequent calculation of the proposed
TVS to ensure conservatism.
Table 2. Comparison of manganese acute toxicity as a function of organism size.
Species
?
LC50 (pg/L)
?
LC50 (pg/L) Source
age/size
?
age/size
Rainbow trout?
14,500
?
30,000?
Davies [1980]
62 mm?121 mm
Fathead minnow?
8,557? 197,315
?
ENSR [1996]
<7 d
? 101 d
Brook trout? 3,606? 73,300?
ENSR [1994, 1996]
87 d? 150 d
All within species tests were conducted at a similar water hardness.
Table 1. Summary of acute toxicity data for manganese with fish and aquatic invertebrates.
Species
Genus geometric
mean LC50 (Ng
Mn/L)1
LC50 (Ng Mn/L)
Water
hardness (as
CaCO3)
Organism Age/Size
Rainbow trout
(Oncorhynchus
mykiss)
Hyalella azteca
5,322
6,631
2,008 (1,697-2,377)
2,490 (2,070-3,008)
5320
,?
(3,110-5,970)
,?
,
11,149 (10,038-12,464)
4,830 (4,180-5,580)
14,500 (8,500-24,800)
30,000 (19,000-47,300)2
116,000 (90,600-148,500)2
2,910 (2,600-3,230)
3
3,170 (2,900 - 3,470)
16,200 (1,400 - 18,700)
6,630 (4,893-9,018)
10,169 (8,548-11,717)
44
48
90
170
37.5
36
36
304
100
27.6
147.8
96
94
33d
24.5 mm, 0.123 g, 50 d
23.4 mm, 0.094 g, 50 d
23.5 mm, 0.097 g, 50 d
42 nirn
62 mm
121 mm
201 mm
embryo-larval
41 mm, 0.601 g, 70 d
41 mm, 0.590 g, 70 d
2-3 mm
2-3 mm .
- Source
ENS( [1990]4
ENS [1994]4
ENS [1994]4
ENS [1994]4
Davits and
Brinkman [1994]
Davies
ii
[1980]
Davies [1980]
Davies
il
[1980]
Bird et al. [1979]
Davies
.11
and
Brin man
1
[1998]
Davits and
Brin tt'an
[1998]
ENS [1996]4
ENS' [1996b]
Species
Genus geometric
mean LC50 (pg
Mn/L)1
LC50 (pg Mn/L)
Water
hardness (as
CaCO3)
Organism Age/Size
Source
Brook trout
(Salvelinus
fontinalis)
Fathead minnow
(Pimehales
promelas)
7,483
9,301
73,300 (48,250-111,340)2
3,606 (2,320-4,400)?
• ••
5,120 (4,600-5,700)
27,500 (23400-31,600)
3,542 (2,967-4,228)
6,232 (5,680-6,830)
9,346 (8,029-10,879)
15,826 (12,311-20,344)
. 10,302 (9,182-11,621)
17,279 (15,232-19,408)
27,440 (24,742-31,269)
>45,000
8,557 (7,188-10,187)
197,315 (99,951-389,522)2
28
48
31.3
148.1
26
50
100
200
48
92
176
396
28
28
74 mm, 5.2 g, 150 d
26 mm, 0.168 g, 87 d
37 mm, 0.405 g, 70 d
37 mm, 0.418 g, 70 d
<7 d
<7 d
<7 d
<7 d
<7 d
<7 d
<7 d
<7 d
<7 d
0.4 g, 101 d
E
B
E
Ei
E
E
E
E
ENISR
Davies
B
linkman
Davies
ENSR
ENSR
ENSR
Ek1SR
JSR [1996a]
[1994]
and
[1998]
and
inkman [1998]
[1992a]
,?
[1992a]
)
I
[1992a]
[1992a]
SR [1990]°
SR [1990]'
SR [1990]°
SR [1990]°
SR [1996]"
SR [1996]°
7
Species
Genus geometric
mean LC50 (pg
Mn/L)1
LC50 (pg Mn/L)
Water
hardness (as
CaCO3)
Organism Age/Size
Daphnia magna
10,150
9,800
45
12
h
Brown trout
(Salmo
trutta)
11,715
15,973 (7,464-36,484)
48
23.3 mm, 0.103 g, 115 d
3,770
37.5
138 mm
49,900 (43,600-57,400)
454
116 mm
Ceriodaphnia dubia
15,395
8,757 (7,330-10,470)
26
<24 h
12,513 (11,480-13,630)
50
<24 h
20,495 (17,865-23,513)
100
<24
h
25,480
(22,600-28,730) 200
<24 h
15,641 (14,073-17,437)
48
<24 h
28,849 (25,108-34,419)
176
<24
h
>45,000
396
<24
h
23,456 (20,734-26,552)
92
<24
h
Mussel
(Anodonta
imbecillus)•
30,954
36,200
80
6-8 d
Source
Biesilger and
Chri tensen
i
[1972]
ENS
i
[1994]
i
Davi
iIs
and
Brin man [1994]
Davies
. N
and
Brinkman
it
[1995]
ENSR [1992b]
li
ENSR [1992b]
ENSR [1992b]
ENENSF
SR
[1992b
ENS
]
i [1990]4
ENS
i
[1990]4
i
ENSR [1990]4
ENS [1990]4
Wade,
I
Hudson, and
McK nney [1989]
8
Species
Genus geometric
mean LC50 (pg
Mn/L)1
LC50 (pg Mn/L)
Water
hardness (as
CaCO3)
Organism Age/Size
Source
Longfin dace
78,890
130,000 (100,000-169,000)
224
43 mm
L wis [1978]
(A
gosia
chrysogaster)
Northern squawfish
83,766
130,465 (36,063--)
347
Juvenile
rleau and Bartosz
(Ptychocheilus
[
1982]
oregonensis)
189,482 (145,410-330,001)
316
'
Post-larval
eleau and Bartosz
[ 1982]
Chironomus tentans
263,811
327,832 (218,452-611,066)
96
11 d
NSR [1996c]
1
Bufo boreus
274,431
339,842 (312,300-369,820)
95
tadpole
NSR [1996d]4
'Values adjusted to a hardness of 50 mg/L (as CaCO
3)
using a hardness:toxicity slope factor of 0.7432.
2 Data not included in the reference value calculation due to a concern regarding sensitivity of older test organisms.
3
Data not included in the reference value calculation due insufficient data documentation and non-standard test procedures.
ENSR unpublished in-house data. Study raw data are available.
is
Typically, within-species LC50 values were consistent (differing by less than a factor of 10—
following elimination of high values
thought to reflect age/size related
?
1000000
differences suggest greater
variation (> than a factor of 100).
A clear relationship between
manganese acute toxicity and
water hardness was noted (Fig. 1).
When all of the available acute
toxicity data are considered, the
water hardness:toxicity slope was
shown to be 0.3331 (r2=0.56); this
slope was used in the derivation of
the TVS.
100000
O
0.)
10000
•
?
0
■
■■
■
■
■ ■
2
is
II.
1?
■ ■
IF
%
•
•
?•
•
■
■
?
.
% • •
ill
1000
9
sensitivity), while among species
1000
10?
100
Hardness (mg/L as CaCO3)
Figure 1.
Relationship between water hardness and manganese
acute toxicity (all species).
Chronic/Short-term chronic toxicity
tests
The available chronic toxicity test data are summarized in Table 3'. Data are available
for six test species,
Daphnia magna, Ceriodaphnia dubia,
brown trout, brook trout, rainbow trout
and fathead minnows. Test results suggest that both fish and invertebrate species are similarly
sensitive to the chronic toxic effects of manganese. Geometric mean genus chronic effects
values (normalized to a hardness of 50 mg/L as CaCO
3)
for all of the tested species were
remarkably consistent, ranging from 1,859 pg/L for rainbow trout to 4,246 pg/L for
Daphnia
magna.
Both short-term chronic (i.e., 7 d) and early-life-stage (ca. 35 d) toxicity tests were
conducted with fathead minnows. Results from these studies were similar, with the 7-d test
EC20 values (normalized to a hardness of 50 mg/L) being 0.57 to 1.8 times that determined
.?
1
Data presented for chronic toxicity tests are based on a calculation of the 20% and 10% Effect
Concentration (EC20 and EC10). This approach is based on regression analysis using a log-logistic model.
The selection of this approach was based on its recent use by USEPA in analyzing data for the revision of
the ambient water quality criteria document for ammonia (USEPA 1998).
1
0
Table 3. Summary of chronic toxicity data for manganese with fish and aquatic invertebrates.
Species
Genus geometric
mean chronic
value (pg Mn/L)1
Effect Concentration (pg Mn/L)2
Water
hardness
(as CaCO3)
Test type
1
.
Source
Rainbow trout
Brook trout
1,859
1,962
EC20: 1,398 (967-2,022)
EC10: 1,201 (765-1,887)
NOEC: 760
EC20: 4,259 (3,703-4,898)
EC10: 3,477 (2,961-4,082)
NOEC: 3,390
LOEC: 1,5
.303
NOEC: 770
LOEC: 1,0003
NOEC: <1000
EC20: 2,104 (1,379-3,209)
EC10: 1,699 (1,033-2,795)
NOEC: 550
EC20: 3,695 (2,846-4,796)
EC10: 2,826 (2,060-3,875)
29
151
34
5
32
156
Early-life-stage
Early-life-stage
33d
Early-life-stage
Early-life-stage
Early-life-stage
Daviedand
[1998]
Davies
[1998]
Goettl land
Lewis [1978]
Davies
[1998]
Davies
[1998]
Brinkman
and Brinkman
Davies [1978]
and Brinkman
and Brinkman
NOEC: 3,530
11
Species
?
Genus geometric
?
Effect Concentration (pg Mn/L)2
Water
?
Test type
?
Source
mean chronic
?
hardness
Fathead minnow
value (pg
3,444Mn/L)
?
1?(as
EC20: 2,550 (2,074-3,135)CaCO3)
?
30?
Early-life-stage
?
ENSR [1996e]
(2,289)4?EC10:
2,289 (1,806-2,902)
NOEC: 1,410 [based on
survival]
EC20: 1,338 (641-2,792)
?
26?
Short-term chronic ENSR [1992d]
EC10: 1,152 (932-2,696)
NOEC: 980
EC20: 5,490 (NC)
?
50?
Short-term chronic ENSR [1992d]
EC10: 5,183 (NC)
NOEC: 5,040
EC20: 5,120 (3,758-6,974)
?
100?
Short-term chronic ENSR [1992d]
EC10: 4,397 (3,022-6,399)
NOEC: 4,560
EC20: 13,152 (10,093-17,140)
?
200?
Short-term chronic ENSR [1992d]
EC10: 11,614 (8570-15,776)
NOEC: 7,860
EC20: 3,417 (3,091-3,777)
EC10: 3,164 (2,818-3,552)
NOEC: 4,700
46?
Short-term chronic ENSR [1989b]
12
Species
?
•
Genus geometric
mean chronic
value (pg Mn/L)1
Effect Concentration (pg Mn/L) 2
Water
hardness
(as CaCO3)
Test type
Source
Brown trout
3,719
EC20: 4,705 (NC)
31
Early-life-stage
Stubblefield et al. [1997]
EC10: 4,330 (NC)
NOEC: 3,940
EC20: 5,148 (4,179-6,342)
152
Early-life-stage
Stubblefield et al. [1997]
EC10: 4,133 (3,249-5,257)
NOEC: 2,780
EC20: 8,209 (7,110-9,478)
450
Early-life-stage
Stubblefield
et al. [1997]
EC10: 7,365 (6,227-8,710)
NOEC: 4,550
Ceriodaphnia dubia
3,820
EC20: 3,314 (2,630-4,175)
26
7-d chronic
ENSR [1992c]
EC10: 2,922 (2,237-3,819)
NOEC: 1,980
EC20: 4,885
(4,225-5,649)
50
7-d chronic
ENSR [1992c]
EC10: 4,370
(3,698-5,165)
NOEC: 2,010
EC20: 6,052 (4,349-8,422)
100
7-d chronic
ENSR
•1992c]
EC10: 5,281 (3,607-7,732)
NOEC: 4,460
13
Species
?
Genus geometric?
Effect Concentration (pg Mn/L)
2 Water?
Test type
?
Source
mean chronic
?
hardness
value (pg Mn/L) 1
?(as
EC20: 7,809 (6,317-9,654)CaCO3)
?
200?
7-d chronic.
?
ENSR [1992c]
EC10: 6,910 (5,430-8,792)
?
I
NOEC: 7,540
EC20: 3,317 (2;692-4,089)?
46?
7-d chronic
?
ENSR [1989a]
EC10: 2,731 (2,105-3,544)
NOEC: 2,900
t1
Daphnia magna
?
4,246
?
16% repro impair.: 4,100
?
45
?
3 wk
?
Biesinger and
Christensen [1972]
'Genus geometric mean values are based on EC10 values and have been adjusted to a hardness of 50 mg/L (as CaCO 3) using the pooled acute slope (0.3331)
to allow interspecies comparison—individual study values are reported as presented, i.e., not hardness adjusted.
2
EC20 and EC10 values based on biomass endpoint for fish tests except where noted.
3
Data not included in the reference value calculation due to insufficient data documentation and/or non-standard test procedures.
Genus geometric mean chronic value reported for the fathead minnow includes results for 7-d short-term chronic toxicity tests. This value, however, was not
used in the derivation of the fathead minnow acute-chronic ratio because the short-term test is not recognized by the USEPA as an acceptable chronic test for
criteria derivation purposes. The value used in deriving the acute-chronic ratio is provided in parenthesis and is
,
based only on the fathead early life stage test
which is a USEPA recognized chronic test.
NC - Confidence intervals could not be calculated.
■
■
■•
■
■
i?
•
I.
■
ti
■
14
from the early-life-stage study. Because of the similarity between the results for the two test
types, all test data were included in evaluating the effect of water hardness on manganese
chronic toxicity. However,
because the short-term chronic
test is not recognized by the US
EPA as an acceptable chronic
toxicity test for purposes of
criterion development only the
C
results from the early life stage
?
2
test were included in deriving
?
10000
the fathead acute-chronic ratio
presented in Table 4.
As was noted in the
acute toxicity tests, water
hardness and manganese
1000
chronic toxicity was inversely
?
10
correlated (Fig. 2). Manganese
?
Water hardness (mg/L: as CaCO3)
chronic toxicity decreased with
Figure 2.
Relationship between water hardness and manganese
increasing water hardness at a chronic toxicity (all species).
slope of 0.2706 (r2=0.70).
TVS Derivation
Typically, surface water pollutant concentrations are regulated by state water quality
standards, often derived from U.S. Environmental Protection Agency (USEPA) national ambient
water quality criteria (AWQC). These criteria apply nationally to all freshwater and marine
surface water bodies and are recommended as maximum chemical concentrations below which
adverse effects to aquatic life and their uses are not expected to occur. However, a national
criterion has not yet been promulgated for manganese. Several states have relied on the
recommendation of McKee and Wolf [1963], thereby adopting a manganese standard of
1,000
pg/L.
Colora
do has adopted the same value, i.e., 1,000 pg/L, based on a recommendation
from the Colorado Division of Wildlife (CDOW) [Davies and Goettl 1976]. Both the McKee and
Wolf
100
?
1000
15
Table 4. Summary of acute-chronic ratio data used for manganese final chronic value calculation.
Species
Water
Hardness --
(as CaCO3)
LC50 (pg
EC10(pg
Mn/L)-
Acute/Chronic
ratio-(ACR)–
Genus
mean ACR
Fathead minnow
30
8,557
2,289
3.7383
3.7383
Ceriodaphnia dubia
26
8,757
2,922
2.9969
50
12,513
4,370
2.8634
100
20,495
5,281
3.8809
200
25,480
6,910
3.6874
48
15,641.
2,731.
5.7272
3.7103
Daphnia magna
45
9,800
4,100
2.3902
2.3902
Brown trout
48/31
15,973
4,330
3.6889
3.6889
Brook trout
31
5,120
1,699
3.0135
150
27,500
2,826
9.7311
5.4156
•?
Rainbow trout
28
3,170
1,201
2.6395
150
1.6,200
3,477
4.6592
3.5064
Geometric mean ACR
3.6196
16
and the CDOW recommendations are based on limited toxicity data and do not consider toxicity
modifying factors such as water hardness.
Calculation of proposed TVS
Acute equation:
Calculation of a national numeric AWQC for a given chemical requires
empirical data from both acute and chronic toxicity tests. The minimum database requirements
stipulate that acceptable acute toxicity data must be available for one species of freshwater
animal in at least eight different families as described below:
•
the family
Salmonidae
in the class
Osteichthyes;
•
a second family of fish in the class
Osteichthyes
(preferably a warm water
species);
•
a third family in the phylum
Chordata
(may be.a.fish, amphibian, etc.);
•
a planktonic crustacean (e.g., cladoceran, copepod);
a benthic crustacean (e.g. ostracod, isopod, amphipod, crayfish);
•
an insect (e.g., mayfly, caddisfly, midge);
•
a family in a phylum other than
Arthropoda
or
Chordata (e.g., Rotifera,
Mollusca);
•
a family in any order of insect or any phylum not already represented.
The current database for manganese satisfies the minimum database requirements for acute
data. A Final Acute Value (FAV) is calculated from the acute testing database as the
concentration of the material corresponding to a cumulative probability of effect of 0.05 [USEPA
1988]. Table 1 presents all of the acute toxicity data and associated species mean acute
values (SMAV) used in deriving the FAV for manganese Using these cummulative probability
calculations (USEPA 1985), the FAV for manganese, at a hardness of 50 mg/L, was
determined to be 4,740 pg/L (Appendix A). To calculate the proposed TVS, and in accordance
with the AWQC 'derivation procedures, the FAV is divided by two and this value (i.e., 2,370) is
used in deriving the final acute equation (discussed in a later section).
Chronic equation:
In addition to the acute toxicity data requirements previously discussed,
freshwater chronic toxicity data are required so that chronic toxicity can be assessed for at least
three different families as described below:
•
at least one family is represented by a fish species;
at least one family is represented by an invertebrate species;
17
•
?
at least one family is represented by an acutely sensitive freshwater species.
The current chronic database for manganese satisfies the minimum database requirements.
A variety of procedures exist for calculating chronic AWQC, and these are discussed in
the A1NQC derivation bibcedilir g IUSEPA-
1 985]. -
The final Chronic value (FCV) may be d-e-rive-d----
similarly to the FAV, if sufficient chronic test data are available; however, insufficient data are
available for manganese. Alternatively, an acute-chronic ratio (ACR) is calculated to generalize
the relationship between measured acute and chronic toxicity values. Thus, for those species
for which chronic toxicity tests have been conducted, the mean ratio of chemical concentrations
associated with acute and chronic effects (final ACR) is determined. The FCV is calculated by
dividing the FAV by the final ACR. Implicit in generalizing the FCV from the final ACR is the
assumption that the relationship between acutely toxic and chronically toxic concentrations of a
given chemical is similar for the various species tested.
Table 4 presents the results of acute and chronic toxicity tests used in calculating the
final ACR. All studies were conducted in the same laboratories and in waters of similar
hardness. Geometric mean genus ACRs varied from 2.3902 to 5.4156;.the geometric mean
ACR was 3.6196. The final chronic value (FCV) is the quotient of the 'FAV and the final ACR;
using the geometric mean ACR of 3.6196, the FCV for manganese was determined to be 1,310
pg/L.
Evaluation of the water hardness:toxicity relationship for the available chronic data
confirms the relationship previously observed with the acute toxicity data; the slope for this
relationship was 0.2706 (r2=0.70;
Appendix A).. However, this value was not employed for
subsequent TVS calculations; rather, because the acute and chronic slopes did not differ
substantially (0.3331 vs. 0.2931), the acute slope was used in subsequent derivations. This is
the approach recommended by the USEPA particularly when an ACR approach is employed
(USEPA 1985).
Toxicity data also are required for a freshwater plant species (either an alga or vascular
plant). Plant toxicity values are not available for manganese; however, manganese has been
identified as an essential nutrient for plant growth and is recommended for incorporation in algal
growth media at concentrations approximating the previously discussed FCV [ASTM 1997].
Therefore, it is anticipated that the proposed TVS would be protective of exposed aquatic
plants; however, additional data would be necessary to verify this assumption.
Materials
. for which maximum permissible tissue concentrations are available (e.g.,
mercury), require additional testing to determine the bioconcentration potential of the material
18
and to calculate a Final Residue Value (FRV) for concentrations in tissue. No such value exists
for Mn, therefore, bioconcentration data are not required for AWQC derivation. Nonetheless,
Rouleau et al. [1995] found that brown trout rapidly accumulated manganese to whole body
steady-state concentrations by a factor of approximately 19. Manganese was found to
sequester in specific tissues such that liver and viscera (minus liver and kidney) contained the
highest manganese concentrations, while gills, kidneys, epidermal muscle, skin, fins, and bones
contained lesser concentrations. Tissue concentrations do not appear to accumulate to levels
that would represent a substantial risk to predatory organisms..
TVS values
A national AWQC consists of two concentrations: the criterion maximum concentration
(CMC, calculated as one-half the final acute value) and the criterion continuous concentration
(CCC, calculated as the lowest of the final chronic value, final plant value, final residue value, or
final chronic equation, if applicable). These values may be thought of as the acute and chronic
criteria, respectively. The criterion is defined by USEPA guidelines (USEPA 1985) as follows:
"except where a locally important species is very sensitive, aquatic organisms and their uses
should not be affected unacceptably if the 4-day average concentration of the material of
interest does not exceed the Criteria. Continuous Concentration (CCC) more than once every 3
years, on the average, and if the 1-hour average concentration does not exceed the Criteria
Maximum Concentration (CMC) more than once every 3 years, on the average."
Based upon USEPA procedures for deriving AWQC [USEPA 1985] and using the results of the
toxicity tests described, the following equations describing TVS values were developed (see
Appenix A for calculations:
CMC
TVS(at
hardness)
= e
0.3331[1n haniness]+6.4676
CCC
TvS(at
hardness)— e
0
.
3331[In hardness)+5.8743
Based on the preceding equations, the following table provides example values for the
proposed TVS at four water hardness levels .
Table 5. Proposed acute and chronic manganese Table Value
Standards over a range of water hardness.
Water hardness
CMC TVS (pg/L)
?
CCC TVS (pg/L)
50
2,370
1,310
100
2,986
1,650
200
3,760
2,078
400
4,738
2,618
19
20
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21
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•
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22
.. „
Appendix A
TVS Calculation Spreadsheets
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