PB86-183928
Evaluation of Site-Specific Criteria for
Copper and Zinc: An Integration of Metal
Addition Toxicity, Effluent and Receiving
Water Toxicity, and Ecological Survey Data
(U.S.) Environmental Research Lab.-Duluth, MN
Apr 86
I
•f Conmerce
WenruUon Service
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EPA/600/3-86/026
April 1986
Evaluation of Site-Specific Criteria for Copper and Zinc:
An Integration of Metal Addition Toxicity, Effluent and Receiving Water
Toxicity, and'Ecological Survey Data.
by
Anthony R. Carlson3, Henry Nelson*5, and Dean Hammermeisterc
a U.S. EPA, Environmental Research Laboratory, Duluth, MN
b Science Applications, International Corporation, McLean, VA
c University of Wisconsin-Superior, Superior, WI
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TECHNICAL REPORT DATA
I'Pteau rtad Intiructior.s on iht rtvent before completing)
1. REPORT NO.
EPA/600/3-86/026
ECIPIENT-S ACCESSION NO.
P88f> 1839 28/AS
•.REPORT DATE
April 1986
4. TITLE AND SUBTITLE
Evaluation of Site-Specific Criteria for Copper and
Zinc: A:i Integration of Metal Addition Toxicity, Ef f lu«j*tfERFORMiNG ORGANIZATION CODE
and Receiving Water Toxicity, and Ecological Survey Datja
'• ^ntftony R. Carlson*, Henry Nelson, Dean E. Hammermeistc
. PERFORMING ORGANIZATION REPORT NO.
9. PERFORMING ORGANIZATION NAME AND ADDRESS
U.S. Environmental Protection Agency
Environmental Research Laboratory-Duluth
6201 Congdon Boulevard
Duluth, MN 55804
10. PROGRAM ELEMENT NO.
11. CONTRACT/GRANT NO.
12. SPONSORING AGENCY NAME AND ADDRESS
U.S. Environmental Protection Agency
Environmental Research Laboratory-Duluth
6201 Congdon Boulevard
Duluth, MN 55804
13. TYPE OF REPORT AND PERIOD COVERED
14. SPONSORING AGENCY CODE
EPA-600/3
15. SUPPLEMENTARY NOTES
16. ABSTRACT
Comparative laboratory toxicity tests using daphnids Ceriodaphnia dybia and
fathead minnows ?imephale8 promelas were conducted to establish and evaluate
relationships between the toxicity of domestic and industrial effluents
containing copper and zinc, toxicity of the effluents in Naugatuck River,
Connecticut receiving water, toxicity of each metal added to the receiving
water and a reference water, and receiving water ecological survey data.
The relationships were used to determine if site-specific water quality
criteria for copper and zinc derived according to U.S. Environmental Protection
Agency (U.S. EPA) guidelines were protective of aquatic life under complexed
ambient conditioi ^ caused by point source effluents.
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Unclassified
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NOTlCli
This document has been reviewed in accordance with
U.S. linvironmc-ntal Protection Agency policy and
approved for publication. Mention of trade names
or commercial products does not constitute endorse-
ment or recommendation for use.
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INTRODUCTION
The physical and/or chemical characteristics of water in a natural
system may alter the biological availability and/or toxicity of materials
such as copper and zinc. Guidelines for deriving site-specific water quality
criteria for the protection of aquatic life and its uses [1,2] which take
these factors into account (hereafter referred to as the site-specific
guidelines) have.been provided by the U.S. Environment a 1 Protection Agency
(U.S. EPA). One guideline approach is to simply test a prescribed number of
resident species in site water to meet minimum data requirements from which a
site criterion is calculated. Another approach is to test sensitive
"indicator or surrogate species" from the same population in both clean
reference water, hereafter referred co as laboratory water, and sice water at
the same time under similar condit-ions except for water characteristics. The
ratio of the site water toxicity value/lab water toxicity value is used to
modify the national criteria value to a site-specific value. Both of these
criteria derivation approaches are based on the assumptions: (I) that
differences in the toxxcity values of a specific material determined in
laboratory water and site water may be attributed to chemical (e.g.,
complexing ligands) and/or physical (e.g., adsorption) factors that alter the
biological availability and/or toxicity of a material and (2) that selected
test species directly integrate differences in the biological availability
and/or toxicity of the material and provide a direct measure of the capacity
of a site water to increase or decrease toxicity values relative to values
obtained in laboratory water.
Single chemical criteria address effects of pollutants on aquaeic life
in the absence of other pollutants in the wacer column, a condition which
seldom occurs. A chemical of interest is usually one component of many
1
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components in 'an effluent which may affecc che chemicals biological
availability and/or toxicity. The objective of chis research projecc was co
determine if site-specific water quality criteria derived for copper and zinc
using che indicator scecies procedure were protective of aquatic life under
complexed ambient conditions caused by point source effluents.-
The research objective was approached by conducting comparative aquatic
toxicity tests to establish toxicity relationships for the metals of interest
between a reference water, a relatively unpolluted upstream river water,
downstream waters containing effluents and expected to contain the metals of
interest in excess of national water quality criteria, and ecological survey
data.
This study on derivation and effectiveness of site-specific criteria was
integrated with a larger receiving and effluent water study of Mount er al.
{3} designed to investigate the use of laboratory effluent toxicity tests to
predict ambient stream toxicity impacts at a multiple discharge site on a
mediua-size river system. The study area extended from Tomngton to
Ansonia, Connecticut and encompassed 50 kilometers (30 miles) of the
Naugatuck River atid included both domestic and industrial waste discharges.
The industries are mostly small metal refinishing facilities that discharge
wastes into tributaries. ''\
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MATERIALS AND METHODS
River, tributary, and effluent sampling
Mount et al. [3] established twelve Naugatuck River sampling stations
above and below the Torrington (TRN), Thomaston (THM), Waterbury (WTB), and
Naugatuck (NOT) sewage treatment plant (STP) discharges and Gulf Stream (GS),
Steele Brook (SB), Great Brook (CB), and Mad River (M) tributaries to the
river (Figure 1). The STPs and tributaries which were considered point
source effluents were also sampled. Sampling station 1 was locateJ r»r> the
west branch of the Naugatuck (N) upstream from all point source discharges
and was used as the control and dilution water source. Most water samples
collected were 24 hour composite samples with sampling done every 15 minutes.
Station 1 samples were daily grab samples. Daily grab samples were taken
from station 3 on 23, 24 and 27 August 1983, station 4 on 28 August 1983,
station 9 on 24 August 1983, and station 10 on 23 August 1983. Stations 6
and 7 were composites of four grab samples of equal volume taken at six hour
intervals over a 24 hour period. On the day of collection subsamples of test
waters were used in coxicity tests and the rest stored at 6 C for later use.
The tests were conducted in a mobile laboratory located on site. Subsamples
were also transported to an off-site laboratory for use in effluent dilution
toxicity tests.
Toxicity testing
Water sampling commenced on 22 August 1983 and receiving water toxicity
tests of up to seven days duration started the next day by Mount et al. (3).
Daphnids Ceriodaphnia dubia and larval fathead minnows Piroephales promelas
from laboratory cultures were used as the test species. For comparative
purpose (this study), Ceriodaphnia dubia were exposed in seven day tests to
copper and zinc additions to station 1 water collected on 26 August 1984,
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These two test species and a resident daphnid Scaphrolebaris sp. were also
exposed to copper and zinc added to Lake Superior water (reference) and wacer
samples collected on 31 August 1983 from river stations 1, 4A, 5, 6, 7 in
acute toxicity tests. These stations were selected for testing based on the
completed and ongoing receiving water toxicity tests. Additional acute
Coxicity tests were conducted with water collected from station 1 on 5
September 1983 and transported within 48 hr to the U.S. EPA Environmental
Research Laboratory at Duluth, Minnesota and stored at 6 C prior to use.
The daphnids used in the seven day tests were placed one animal to each
of ten 30-ml plastic cups for each effluent concentration, receiving water
sample, or metal addition sample tested. Fifteen ml of the test water was
placed in each cup and a daphnid, less than 4 hr old, was added. One drop of
water containing 250 ,jg yeast was added daily. Each daphnid was moved on day
2 and 4 of the test to a new cup containing 15 ml volume of water obtained
from the stored sample. When young were present, they were counted and
discarded. Toxicxty endpoints measured were effects on survival and young
production of original'y exposed females. For additional details of the test
procedure used see Mount and Norber? (4).
The laboratory stock of Ceriodaphnia dubia used were from the U.S. EPA
Environmental Research Laboratory, Duluth, Minnesota, culture unit which is
maintained in Lake Superior water. Cravid females had been placed in water
from station 1 on 22 October 1983 from which young were drawn for testing.
Some females were also maintained in Lake Superior water from which young
were drawn for use in tests in this water.
Adult Scaphrolebaris sp. were collected from station 5 and maintained in
station 1 water for approximately 1 or 2 days prior co use in che acute
toxicity tests with copper. Collections were made from shallow areas on the
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edge of the river where there was no apparenc current. Algae mats containing
the daphnids were scooped into plastic pails and transferred to the mobile
laboratory. Like animals were selected for testing by their behavior.
The on-site copper and zinc acute toxicity rests were conducted using
the laboratory stock daphnids «4-hr-old), site collected daphnids (adults),
and fathead minnows «24-hr-old) from the U.S. EPA Environmental Research
Laboratory, Duluth culture unit. Ten or twenty animals were tested at each
of 5 concentrations and a control. A one to three dilution factor was used.
Five daphnids were placed into duplicate test containers at each treatment.
The daphnids tested in w/iter collected on 31 September 1983 were placed in 30
ml plastic cups containing 15 ml of water and exposed for 48 hr under static
water conditions. Class beakers containing 30 ml of water were used in the
off-site tests conducted with water collected on 5 September 1983. A one to
two dilution factor was, used. The daphnids used in these tests were <24 hr
old. Ten fathead minnows were placed in 1,000 ml polyethylene (PE) test
chambers containing 700 ml of water collected on 31 August 1983 and exposed
for 96 hr under static water conditions. Duplicate test chambers were used
for each copper and zinc concentration and type of test water. Also, an
additional test chamber containing the test water but no organisms, was s>et
up for each copper concentration and type of test water, so that electrode
determinations of free copper (Cu**) activities could be made. Duplicate
500 ml glass beakers containing 180 ml of water and a one to two dilution
factor were used in the fachead minnow «24 hr old) tests of water collected
on 5 September 1983.
Physical and chemical
Test temperature in the mobile laboratory ranged between 22 and 28 C
over the on-site test period. The recorded temperature changes were gradual
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and associated with diurnal ambient temperature fluctuations and should not
have been a problem. Test temperatures in the toxicity tests using water
collected on 5 September 1983 ranged between 24 and 25 C. All water samples
used in testing were scored in 20 liter'PE containers. Subsamples were
analyzed for pH, alkalinity, total hardness, turbidicy, conductivity, nitrite
and chlorine content within 12 hours of subsampling. Samples were kept in an
air-condicioned laboratory to prevent overheating. Conductivity, nitrite,
and chlorine measurements were not made every day. Dissolved oxygen
concentrations were at or near air-saturation concentrations at the beginning
of each test or after a water change. Dissolved oxygen concentrations of
water in selected treatments from ail tests were measured at the end of a
test or just before a water change in order to estinate minimum occurring
concentrations. U.S. EPA approved procedures (5) were used for all analysis.
Sub samples were preserved for analysis of ammonia, nitrate, non-filterable
residue and total organic carbon (TOG) following U.S. EPA appoved procedures
[5]. Ammonia and nitrate samples were taken daily by filling 250 ml PE
bottles, adding 400 ul of concentrated sulfuric acid and placing the samples
in coolers containing ice. Nonfilterable residue samples (180 ml) and total
organic carbon samples (250 ml) were placed on ice and frozen upon arrival at
the University of Wisconsin-Superior laboratory.
Subsamples of all test waters were preserved for later total acid
exchangeable (non-filtered) and dissolved (filtered, 0.45 ^) metal analysis.
A 25 ml portion of subsample, both non-filtered and filtered, were stored in
PE or polypropylene (PP) bottles. A set of subsamples collected on 29 August
1983 were preserved for later total recoverable metal analyses [5] for use in
comparison to acid exchangeable (total recoverable procedure minus the
digestive process) metal values.
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U.S. EPA approved procedures [5] were used for sampling, flame and
flaraeless atomic absorption specCrophotometry (AA) and inductively coupled
plasma-atomic absorption emissions spectrometer (ICPAES) analysis of water
samples for metals. For quality control assessment, spikes and reference
,»- '.
samples ;ere developed at the time of AA analysis. Percentage recovery and
standard deviations of spiked samples for copper (N=27) and zinc (N=12) were'
101.2 +_ 3. 7 and 102.5 ^ 6.4, respectively.
Generally, copper AA measurements were made on all water samples
collected. The samples analyzed by AA for zinc-were those collected on the
23, 24, 26, 29 and 31 of August 1983. ICPAES analysis was performed on the
26 and 31 August samples and a reference water sample.
The free copper (Cu*^) activities were determined in water from the
test chambers without organisms within the first 24 hours of the beginning of
each fathead minnow acute toxicity test. Additional free copper activities
were also determined in water from the exposure chambers with organisms after
the termination of the tests. However, due to time*limitations, free copper
determinations after the termination of the tests were performed only in
water from exposure chambers bracketing the LC50 point.
The free copper determinations were performed as follows. Water from a
given exposure chamber was poured into a 500 oil polyethylene bottle to the
top of the bottle, and then closed to the atmosphere with a screw
polyethylene top into which a cupric ion selective electrode, double junction
reference electrode and pH electrode had been previously tightly fitted. The
sample was closed to the atmosphere with minimal head space, to prevent CC>2
exchange and the associated pH changes from occurring during the stirring
required for the free copper determinations. The sample was then stirred
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wich a Teflon bar, and mV readings were recorded until they leveled off .co
changes of no more than 0.1 mV in a 5 minute period. For additional
procedural details see Nelson et al. [6]. '
the copper and zinc exposure stock solutions were prepared using Fisher
reagent grade copper-chloride and zinc-chloride dissolved in deiomzed water.
Statistical procedures
The trimmed Spearman-Karber Method (7) was used for estimating median
lethal concantration (LCSOs) or effect concentrations (EC50&). The EC50
values calculated were based on the total number of dead fish plus fish with
impaired mobility observed at each test concentration. One way analysis of
variance and Dunnett's procedure [8] for comparing all treatments with a
control (P=0.95) was used to identify significant differences in endpoincs
measured in the seven day daphnid tests.
For discussion purpose no observed effect concentrations (NOECs) were
used. A NOEC is defined as che highest concentration of an effluent jr metal
in a toxicity test that does not cause an observable adverse effect. _
Biological surveys
In conjunction with the receiving water and effluent toxicity tests of
Mount et al. [3], an ecological survey including the quantitative assessment
of the periphytic, zooplankton, benthic macroinvertebrate, and fish
communities were conducted at each water sampling station. Only the selected
results of the ecological survey, germane to determining if the sice-specific
water quality criteria derived for copper and zinc were protective of aquatic
life, will be presented in this paper.
Quality Assurance
Coordination of various studies was completed by the authors. Details
of sampling, transfer of samples,.storage of samples, specific sampling
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sites, date? of collections and measurements to be made on each sample were
delineated. We were responsible for all quality assurance related decisions
onsite or in the laboratory.
All instruments were calibrated by methods provided by the manufactur-
ers. Methods in the referenced published reports were followed.
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RESULTS AND DISCUSSION
Physical and chemical
The physical and chemical measurements (Table 1) made, on Naugatuck River
wacer samples and point source effluent samples collected between 23 and 29
August 1983 demonstrate that the river is a multi-sffluent complexed system
containing the metals of interest (Table 2). Copper and zinc concentrations
were relatively low in station 1 wacer samples when compared to water samples
collected downstream which contained elevated concentrations of copper and
zinc that were directly attributable to the concentrations in the effluents
(Table 2). The impacts of the effluents on water quality are also evident in
the hardness, turbidity, total suspended solids, total organic carbon,
conductivity, nitrite, nitrate, and ammonia measurements which differed
between station 1 and ail other stations (Table 1). Data for selected
physical and chemical parameters measured on water collected from station 1,
4A, 5, 6, and 7 on 31 August 1983 (Table 3) and from station 1 on 5 September
1983 for use in the copper and zinc addition toxicity tests were within the
ranges obtained during the above seven day period for respective sampling
stations.
Life cycle - Metal addition tests
Copper toxicity — Ceriodaphnia survival and youn$ production were not
affected by copper added to station 1 water at total copper concentrations
ranging from 3 to 12 pg/1 when compared to the control (Table 4). Compared
to the control, a 62.72 reduction in survival and 972 reduction in the mean
number of voung per original female daphnid exposed occurred at the 32 ^ig/l
total copper exposure. None survived to produce young at the 91 pg/1 total
copper exposure. A 48 hr LC50 of 44 ;jg/l total copper with a 955! confidence
interval of 34-57 pg/1 were calculated from-the data.
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Zinc coxicicy — Ceriodaphnia survival and young production were not
affected at total zinc concentrations ranging from 7 to 102 ug/I total zinc
in station 1 water when compared Co the controls (Table 5). Four days after
the test was started, it was evident that the 102 >Jg/l zinc exposure was not
toxic. At this time two additional treatments of 273 >jg/l total zinc were
added. All of the test animals died within 48 hrs at ttv.s treatment. These
data were used to calculate a 48 hr LC50 of 163 jjg/J for total zinc.
Acute toxicity tests
The estimated total and dissolved copper 48 hr LC50s for Ceriodaphnia
determined in reference and station 1 water were essentially the same (Table
6). These values are indicative of a similar copper biological availability
and/or toxicity in each water sample. Decreased biological availability
and/or toxicity of copper was evident in the LC50 values for station 4A, 3, 6
and 7. These downstream total and dissolved copper LC50 values ranged from
3.2 to 7.1 and 2.6 to 4.6 times, respectively, greater than the station I
LC50 value. Such increases in total and dissolved copper LC50 values are not
surprising, since the binding capacity for copper of waters containing
treated domestic sewage are generally much greater than that of similar
waters containing less or no treated sewage (9).
The results of the concurrent acute toxicity tests in which the
laboratory reared and field collected daphnid species were both exposed in
replicate copper concentrations in reference water and water collected from
stations 4A, 5, 6, and 7 on 31 August 1983 indicate that they were of near
equal sensitivity to copper (Table 6). The total and dissolved copper LC50
values for the laboratory reared daphnids differed from the field collected
daphnid LC50 values at most by a factor of 1.3.
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Although the fathead minnow larvae were less sensitive to copper than
the daphnids, a trend of decreased copper biological availability and/or
coxicity between station 1 and stations 4A, 5, 6, and 7 was also evident in
the fathead minnow 96-hr total and dissolved LC50 data (Table 7). The
station 1 total and dissolved copper LC50 values, however, were 3.1 to 3.3
times greater than the reference water LC50 and indicative of a difference in
biological availability and/or toxicity between these test waters.
The LC50s and EC50s for fathead minnows in terms of total, dissolved and
free copper for the different site waters (Table 7) are based on measurements
of water samples collected at the beginning of each test. In going from the
Lake Superior water to the relatively clean station 1 water to the waters
carrying increasing effluent loads (stations 4A, 5, 6, 7), the LC50 values in
terms of not only total and dissolved copper, but also the free copper,
generally increase. The proportional increases in the free copper LC50
values are often also substantial. That indicates that the decrease in
copper toxicity downstream is not just due to an increase in the binding
capacity of the water due to municipal sewage effluents, since if that was
the case, the increases in Che free copper LC50 values (if any} would be much
smaller. Therefore, there appear to be factors introduced downstream which
cannot only bind copper, but reduce the toxicity of the non-bound
bioavailable fraction. One of those factors may be hardness since hardness
values increase monotonically (36 to 90 yg/l) in going downstream from
station 1 to station 7 (Table 7). However, with this increase in hardness,
only a 2.4 fold decrease in toxicity would have been expected at station 7
based on the hardness correction factor used in the National Criteria
Document for Copper [10].
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la contrast to the LC50 values, the EC50 values in terms of total,
dissolved, and free copper (Table 7) remain relatively constant in going from
the station 1 water to the various waters downstream (stations 5, 6, 7). The
only major anomaly is the free copper EC50 for the station 4A water. The
free copper EC50 value in station 4A water is lower than in station 1 water.
This anomaly may have been at least partially due to possible errors in the
initial determinations of the free copper activities in station 6A test
waters. If the free copper LC50 value for the 4A test water is based on
measurements at the end of the test, it is similar to that determined 1:1
station 1 water. The relative constancy of EC50 values compared to the
increasing LC50 values going downstream may possibly be due to some kinetics
effect that decreases the bioavailable fraction during the duration of the 96
hour tests.
The above postulate is based on the following reasoning. During a 96
hour test, the exposure of an organism to a given chemical at the gill
membrane is given hy
/96 hr
Total Exposure ^/ Q(t)CBAp(t)dt
where
Q(t) = flow of water across the gills as a function of time
Cjj£p(t) * concentration of the bioavailable fraction of the chemical
It should require less total exposure for an organism to develop and to
exhibit mobility impairment than for 1C to be killed. If the kinetics of
binding are slow enough such chat the exposure of the organism is sufficient
to cause mobility impairment before a substantial reduction in the.
bioavailable fraction occurs, but fast enough to lower the bioavailable
fraction of the chemical substantially before lethal amounts of exposure
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occur, the ECSOs should be less dependent upon Che binding capacity of the
wacer than che LCSOs.
The postulate is supported by free copper deternunations in waters
bracketing the LC50 point after the termination of the tests. The free
copper concentration should be ac-lease somewhac proportional to che
bioavailable fraction. The free copper concentration in scacion 5 and
station 6 test waters which bracket the LC50 point decreased by close co SOX
and 252, respectively, by the end of the test. Those are the two waters
which show the largest increase in LC50 values from .those upstream. The
lower of the two free copper concentrations in station 1 water which
bracketed the LC50 decreased by 482 while the higher concentration increased
by 24%. The decrease in the lower concentration supports the postulate while
the increase in the higher concentration, although unexplained, neither
supports nor detracts from the postulate.
Substantial periphyton growths were observed in all of the fathead
minnow test chambers at the end of the tests in stations 4A, 5, 6, and 7 test
waters. Periphyton growth can cause pH and dissolved oxygen fluctuations
during the tests which can affect the biological available copper and total
exposure of the organisms. Evidence of such fluctuations can be seen in che
final pH and dissolved oxygen measurements (Table 8). These factors can
affect not only acute values in terms of the free copper, but also acute
values in terms of the total and dissolved coppe.-. However, during the first
24 hr of the fathead minnow exposures in station 1, 4A, 5, and 7 waters, when
periphyton effects on water quality are thought to have been minimal,
impaired mobility and/or mortality was observed resulting in 24 hr EC50
values identical to the 96 hr EC50 values presented in Table 7. For station
6, impaired mobility was not seen at 24 hr but was observed at 48 hr :
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resulting in EC50 values identical co that calculated for 96 hr. In
reference water tests, no impaired mobility of fathead minnows was observed
after 48 hr of exposure resulting in identical LC50 and EC50 values. The
total, dissolved, and free copper fathead minnow 48 hr LC50 and EC50 values
and 952 confidence intervals in parentheses were 94 (59-148), 91 (56-147),
and 3.5 (2-6) pg/1, respectively. From the above results it was concluded
that the EC50 values were more useful than the LC50 values for calculating
water effect ratios reflective of the differences in the biological
availability and/or toxicity between river water samples.
The total and dissolved zinc 48 hr LC50 values for Cerxodaphnia
determined in reference water and station 1 water differed by a factor of
only 1.1 indicating that zinc was of similar biological availability and/or
toxicity in each water (Table 9). Larger downstream LC50 values indicate
that zinc was less biologically available and/on toxic in the downstream test
waters.
The fathead minnow 96 hr zinc LC50 and EC50 values (Table 10) indicate
that zinc added to station 1 water was slightly more biologically available
and/or toxic than in reference water. Compared to station 1 LC50 values,
downstream values were greater at most by a factor of 3.5. These factors
reflect a general trend of decreased zinc biological availability and/or
toxicity at the. downstream stations similar to that observed for the
daphnids. The stepwise increase in fathead minnow toxicity values from
upstream to downstream appear to reflect increases in water hardness, a
factor known to affect zinc toxicity. For example with the 36 to 90 yg/1
water hardness increase (Table 3) from station 1 to station 7, a two fold
increase in toxicity values occurred and would have been expected based on
the hardness correction factor for zinc toxicity used in the national
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criteria document for zinc (llj. This zinc-hardness relationship indicates
that the domestic and industrial effluents within this river reach from
station 1 to station 7 had little or no effect:on zinc bioavailability and/or
toxicity other than their contribution to water hardness.
The total copper LC50 values derived from the,Ceriodaphnia 48 hr acute
toxicity tests in which the organisms were not fed differed by two fold from
the 48 hr LC50 values derived from the seven day metal addition tests in
which the organisms were fed. The addition of yeast may have contributed to
a reduction in the bioavailability and/or toxicity of copper. No such
difference was apparent between zinc LC50 values determined in station 1
water under fed and unfed conditions.
Receiving water toxicity
Generally, the total copper LC50 values for Ceriodaphnia are reflective
of the presence or absence of receiving water toxicity to this species
(Figures 2A and 2B) . For example, the total copper LC50 values were not
exceeded by the mean of the total copper concentrations measured in the river
water samples from stations 1, 4A, and 5 which were not toxic whereas the
L.C50 values were essentially the same as the mean of the total copper
concentration measured for the water samples from station 6 and 7 which were
intermittently toxic in the mass balance toxicity tests of Mount et al. [3].
Such a relationship was not evident for the total zinc LC50 values because
the mean zinc concentration of the samples were all lower than the zinc LC50
values (Figure 3).
Reduced biological availability and/or toxicity of copper in downstream
Naugatuck River water can be inferred from the results of the seven day
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copper addition (Table 4) and mass balance coxixicy test 13] conducced with
Ceriodaphnia using water collected on 26 August 1983. Except for water
quality characteristics these tests were conducted under similar conditions.
For stations 2 through 5 (Figures 4A and 4B) water samples, total copper
concentrations ranged from 9 to 21 ug/l and survival and young production
were similar to that obtained in the controls in the metal addition tests.
For the station 6 water sample total copper concentration was 97 ug/l
survival and young production were slightly reduced when compared to that in
the upstream water samples. At most, these reductions in survival and
reproduction are indicative of chronic toxicity. In the copper addition test
performed in station 1 water (Table 4), reduction in survival and young
production indicative of chronic toxicity were observed at the 32 .jg/1 total
copper concentration. The different total copper concentrations associated
with these survival and reproduction endpoints are thought to be reflective
of differences in copper biological availability and/or toxicicy caused by
differences in the physical and chemical characteristics between station 5
and station 1 waters.
The differences in toxicicy (reflected as effects on Cenodaphnia
survival and young production) in the mass balance toxicity tests (3) between
downstream water samples collected on 26 August 1983 appear to be correlated
with relative increases, and decreases in copper concentration (Figures 4A and
45). For exanple, station 6 water contained 97 ^ig/1 total copper and was, at
most, chronically toxic to Cenodaphnia. Station 7 water contained 146 >jg/l
total copper and was acutely toxic. Station 8 water contained 201 ;ig/l total
copper and was more acutely toxic than station 7 water. Station 9 water
17
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contained less total copper (114 mg/1) than scacion 8 and was chronically
coxic. Station 10 water contained even less copper (67 >jg/l) and was not
coxic.
Total copper concentrations associated with toxicity endpoints measured
in the Ceriodaphnia mass balance toxicity tests [3] indicate that the
bioavailability and/or toxicity of copper fluctuated through time. For
example, for station 6, total copper concentrations of the seven samples
tested ranged from 77 to 108 ;jg/l. The water sample containing the hignest
total copper concentration (108 yg/1) was collected on the first sampling day
and correlates with the most severe toxic effects observed in the tests of
water samples from this station (Figures 5A and 5B). In this water 95X of
the test organisms survived for 48 hr but all were dead within 96 hr of
exposure and no young were produced. Less severe effects were evident in the
tests using water collected from this station on the second, third, and
fourth day of the sampling period in which total copper concentrations, ranged
from 82-100 vig/1. Oaphnid survival after 48 hr of exposure in these waters
ranged from 70 to 802 and toxicity was reflected by low young production when
compared to young production in waters collected on the fifth, sixth, and
seventh day of the sampling period. Daphnid survival and young production ui
these latter collected water samples were not affected at total copper
concentrations ranging from 77-99 iJg/l. The differences in coxic response
observed for the daphnids between these two groups of station 6 water
samples, with practically identical ranges of total copper concentrations,
indicate that the biological availability and/or toxicity of the copper also
differed. Such differences are also evident in the station 7 data. The
total copper concentration in scacion 7 water samples ranged from 87 to 177
;jg/l. Water samples collected on the first and second day of sampling
18
-------
(Figures 6A and 6B) were essentially identical in total copper concentration
(124 and 122 ug/1), however, the water collected on the first day was not
acutely toxic, 80Z of the daphnids survived for 48 hr and survival decreased
to 50t by the end of the test resulting in relatively low young production
whereas effects on daphnid survival and young production were more severe in
the water collected on the second day. This water was acutely toxic and no
young were produced. Test waters collected on the next three sampling days
were also acutely toxic. For these waters total copper concentrations ranged
from 122 to 166 ug/1. No daphnids exposed to these samples survived to
produce young. The water collected on the sixth sampling day contained 68
ug/1 total copper. Copper concentration was affected by dilution from runoff
from heavy rain-fall in the upstream watershed. In this water sample, 70
percent of the organisms were alive after 48 hr of exposure and were still
alive at the end of the test. Young production was relatively high when
compared to that produced in previously collected water samples. The water
*
collected on the seventh sampling day contained 157 ug/1 total copper but was
not toxic. Ninety percent of the daphnids were alive after 48 hr exposure,
802 survived to the end of the test and produced young. In this water the
total copper concentration was higher than in the toxic water samples
collected throughout the first four days of the sampling period. The lack of
toxic response is indicative of lessened copper biological availability
and/or toxicity and correlates with a marked increase in turbidity.
Turbidity measurements ranged from 2.3 to 3.2 N.T.U. for the preceding six
water samples and was 10.9 N.T.U. on the seventh day.
The severity of toxic effects on Ceriodaphnia survival and young
production measured in the mass balance tests (3] of station 6, 7, 8, and 9
19
-------
water samples are correlated with mean cocal copper concencrations. For
station 5, mean survival was 932 afcer 48 hr of exposure and che grand mean
number of young produced by the end of the seven day test period was 16.2.
The marked increase from 16 to 93 .jg/1 in mean total copper concentration
between station 5 and 6 water samples correlates with a 25% reduction in the
mean number of young produced compared to station 5 (Figures 2A and 28). The
sequentially higher mean total copper concentrations of 139 and 185 ug/l for
station 7 and 8 water samples correlate with a 55 and 842 reduction in
survival and 67 and 99? reduction in young produced, respectively, when
compared to station 5. Compared to station 8, the mean total copper
concentration decrease to 112 ug/l for station 9 correlates with increases in
survival and the number of young produced. For this station, 48 hr survival
of the daphnids was similar to that obtained in station 5 water but the mean
number of young produced was 622 less.
For station 10, contrasting results were observed. The mean copper
concentration for station 10 water (80 ug/l) was less than for station 9 (112
jg/1). The mean number of young produced in station 10 water was greater
than in station 9 water as would be expected due to the lower mean copper
concentration in station 10 water. However, the mean survival in station 10
water was 262 lower Chan in station 9 water. Thus with che mean total copper
concentration decrease from station 9 to 10, mean survival did not increase
as expected. The mortality which lowered the mean survival value occurred on
24 and 25 August 1983 and has been attributed to slug doses of effluent from
the Naugatuck STP which also are thought to have ki>.led the fathead minnows
in receiving water and effluent toxicicy tests (3). This effluent contained
very little copper. The copper concentration of the effluent samples were 11
and 12 jg/l on the above dates.
20
-------
The total cupper concentration of station 1, 4A, 5, 6, and 7 water
samples, that were not toxic in. the fathead minnow impact toxicity tests of
Mount et al. (3], were all less than the total copper EC50 values determined
usin? water collected from the respective sampling stations at a later date
(Figure 7A). Station 8 water was toxic to the fish. Toxicity was evident as
a marked reduction in survival and growth when compared to that obtained in
upstream water samples (Figure 7B). This toxicity correlates with a mean
total copper concentration of 185 >Jg/l and range of 161 to 284 >jg/1 for the
seven water samples used in the test. The high concentration of this range
is essentially the same as the 24 hr EC50 of 282 yg/1 copper determined in
the acute toxicity test in which copper was added to station 7 water. The
mean total copper concentration of the station 7 water samples was 139 yg/I
and is representative of copper concentration 2 kilometers upstream from
station 8.
The toxicity observed at station 8 was associated with the copper added
to the system from the Mid River tributary located between stations 7 and 8.
Station 9 water samples which were not toxic also contained less copper than
the station 8 water samples. The mean total copper concentration for this
station was 112 >»g/l. Reduction of river copper concentration to this level
was associated with the dilution of the river water by the Waterbury ST?
effluent located between stations 8 and 9. This effluent averaged 38.42 of
the river flow after mixing for the period 22-26 August 1983 [3]. It can be
inferred from this information that Che presence (station 8) or absence
(station 7) of Mad River copper in the river system correlates with the
presence or absence of toxicity, and also that toxicity and total copper
concentrations were reduced by dilution with the Waterbury STP effluent. For
station 10 water samples mean total copper concentrations decreased compared
21
-------
to station 9, however, toxicicy occurred (Figure 6A and 68). This toxicity
i.s thought due .to unidentified organic toxicants in the Naugatuck STP
effluent which contained only a mean concentration of 11 (N=A) ug/l total
copper but was axtremely coxic (1002 mortality was observed ac a 1% effluent
concentration) to fathead minnows in the effiuent dilution test [3j. Because
of this toxic source, metal concentration and toxicity correlation were not
attempted at station 10, 11 and 12, The highest total zinc concentration
measured in the water samples used in the above fathead minnow impact
toxicity tests .was 162 (Jg/l. This concentration was measured in station 8
water and was 5 times.less than total zinc LC50 determined in the acute
toxicity test in which zinc was added to station 7 water (Figure 3). Overall
these data indicate that the toxicity of station 8 water samples (to fathead
minnows) was at least partially, if not all, caused by copper.
Effluent toxicity -- The acute (48 hr LC50) and chronic toxicity (NOEC)
values determined for Ceriodaphnia in the off-sice effluent dilution tests
(3), conducted using water samples collected on 26 August 1983, appear to be
directly attributable to copper concentration when compared to the results
from the copper addition toxicity test in station 1 water. In all of chese
tests station 1 water collected on this date was used as dilution water.
Although the 48 hr LC50 values for Gulf Stream, Great Brook, Steel Brook,
/
station 8, and Thomaston STP water samples ranged from 1.6 to 53 percent
effluent (v/v), total copper concentrations calculated from these values
differed only slightly and ranged from 27 to 46 pg/1 (Table 11). These
copper concentrations are essentially the same or similar tc the 44 .jg/1
total copper LC50 value determined from the seven day copper addition test.
Likewise, for four of these tests, the NOEC values ranged from 1 to 30
percent effluent (v/v) whereas the total copper concentration calculated from
22
-------
these values were essentially che same and ranged from 18 to 21 vig/1. These
copper concentrations all fall between the no observed effect concentration
(NOEC) and the lowest effect concentration range of 12 to 32 (jg/1 determined
in the copper addition test (Table 4). For two tests NOEC of 6 ug/1 were
calculated and the lowest effect copper concentrations exceeded the copper
addition NOEC of 12 ug/1. The total zinc concentrations calculated from che
percent effluent LC50 and NOEC values ranged from 8 to 69 pg/1 (Table 11).
These zvnc concentrations are all less than the NOEC of 102 ^g/l determined
in the zinc addition test (Table 5). These relatively low concentrations of.
zinc indicate that zinc was not contributing to the acute and chronic
toxicity endpoints measured in the effluent dilution tests, however, zinc and
other detected metals (Table 12) and unknown components of the water samples
tested may have contributed to Coxic effects observed at the higher effluent
concentrations. Overall, these results indicate that the toxic response of
the daphnids observed at the lowest effect effluent concentrations were
partially due to copper if not caused by copper.
Copper concentrations associated with the daphnid effluent NOEC(s) of
water samples collected over the 7 day sampling period were highly variable
(Table 13). For example, the total copper concentration associated with the
Thomaston STP effluent NOEC(s) ranged from 4 to 143 ^g/1. Where effluent
copper NOEC(s) were markedly lower than the 12 jjg/1 NOEC determined in the
copper addition test, the toxicity measured at the lowest effect concentra-
tion was probably caused by some other material. W>-ure effluent copper
NOEC(s) exceeded this value by a large margin, raoi-t of the copper was
apparently bound to some other material and not biologically available to the
daphnids.
-------
Sice~specific water quality criteria
Criteria derivation— According co Che revised national guidelines (12]
a water criterion consists of two concentrations: the criterion continuous
concentration (CCC) and the criterion maximum concentration (CMC) (the CCC is
equivalent to the criterion average concentration of the former national
guidelines and the site-specific guidelines). The criterion is fcated as:
the procedures described in "Guidelines for Deriving Numerical National Water
Quality Criteria for the Protection of Aquatic Organisms and Their Uses"
indicate that, except possibly where there are multiple discharges, multiple
pollutants, or unusually stressful conditions or where a locally important
species is very sensitive (1) aquatic organisms should not be affected
unacceptably if the four-day average concentration of the material of
interest (copper and zinc in this case) does not exceed the CCC more than
once every three years on the average and if the one hour average
concentration does not exceed the CMC more than once every three years on the
average.
National water quality criteria for copper in this study are expressed
.• as total recoverable copper [10], In this study total acid exchangeable and
dissolved copper measurement were made on almost all of the samples used in
testing. For comparative purposes total acid exchangeable and total recover-
able measurements were also made on the 29 August 1983 water samples from
stations 1 through 12 (Table 14). For copper, in ail cases, the total acid
exchangeable concentration was essentially equal to or less than the total
recoverable concentration. These d^ta indicate that total acid exchangeable
copper concentrations of the Naugatuck River water equal to or above the
criteria concentrations are evidence of the copper criteria being exceeded.
National water quality criteria for zinc are expressed as total recoverable
24
-------
zinc [111. The total acid exchangeable and total recoverable zinc concentra-
tions measured in each of the above samples were essentially the same. Thus,
for zinc criteria evaluation, criteria concentrations equal to or exceeding
the total acid exchangeable zinc concentrations .are considered evidence of
the zinc criteria being exceeded.
In*order to derive specific water quality criteria using the indicator
species procedure of the site-specific guidelines, the resident species range
of sensitivity to the chemical of interest should be similar to that for the
species used to establish the national criteria. Species representatives of
the genus Daphnia have been identified in the national criteria documents for
copper [10] and zinc [11] as the most sensitive to each chemical based on
acute toxicity data and among the most sensitive based on chronic toxicity
data. Paphnia spp. also inhabit the Naugatuck River [3]. Because of this
similarity, it was assumed that the range of sensitivity of the resident
species of the Naugatuck River to copper and zinc was similar to that used to
establish national criteria for these metals. Furthermore, acute toxicity
values for copper determined in reference water with Ceriodaphnia and the
resident daphnids Scaphrolebaris (Tat'e 6) indicate they are of near equal
sensitivity to the Daphnia spp. cited in the copper national criteria
document.
Analysis of the copper LC50 data determined in site (station 1) and
laboratory (reference) waters indicate that there was very little if any
difference in the biological availability and/or toxicity of copper in these
waters. The water effect ratios (site water LC50 value/laboratory water LC50
value) calculated from the total copper LC50 values determined in tcsrs of
station 1 water (collected on 31 August 1983) and reference water were 1.0
and 3.4 for Ceriodaphnia and fathead minnows, respectively. For both
25
-------
species, tests in the site water and reference water were not conducted
concurrently and different batches of organisms were used. The larger
fathead minnow ratio may be reflective of experimental error and/or
differences in copper sensitivity between batches of fish tested. A
difference of three fold in total copper LC50 values has been previously
observed for different batches obtained from the same breeding stock used in
this study [6], In concurrent tests with each species using station 1 water
collected on 5 September 1983 and another reference water sample, similar
LC50 values for each species were obtained (Table 15). A 95% confidence
interval could not be calculated for the Ceriodaphnia 48 hr LC50 value (18
tjg/l) determined in this site water, however, the 24 hr LC50 value was 20
ug/l and its 95% confidence interval of 17-22 ug/1 overlaps the reference
water 24 and 48 hr LC50 value 95Z confidence intervals (which were equal)
indicating that these LC50 values are not significantly different. These
Ceriodaphnia 48 hr LC50 values for the two dilution waters are essentially
the same as chose determined in the previous tests (Table 6) indicating that
copper biological availability and/or toxicity remained relatively constant
between tests. From these data is was concluded that the copper water effect
ratio was 1.0.
The Ceriodaphnia and fathead minnow LC50 data obtained from concurrent
zinc acute toxicity tests in station 1 water and reference water were similar
(Table 9) resulting in water effect ratios of 1.0 and 0.7 respectively.
These ratios indicate that there was little if any difference in the
biological availability and/or toxicity of zinc in these waters.
According co the indicator species procedure of the site-specific
guidelines, if the LC50 values for each indicator species, determined in
relatively clean upstream site and laboratory (reference) water, are not
: 26
-------
different, then the national CMC concentration is the site-specific CMC. for
copper and zinc f.he site-specific CMC would be based on the water hardness of
the reference water used. The mean water hardness of the reference water
used in the copper acute coxicity tests was 47 pg/1. At this mean hardness
value, the national and site-specific CMC(s) are both 8.1 pg/1 copper [10).
For zinc, the water hardness of the reference water used in acute testing was
52 ug/l. At this water hardness the national and site-specific CMC(s) are
both 187 >jg/l total recoverable zinc [11]. Following the indicator species
of the site-specific guidelines, the site-specific CCC concentrations, for
both copper and zinc are the same as the national CCCs. These CCC(s) are 6.2
jjg/1 copper and 47 ug/l total recoverable zinc. The national CCC for zinc
(and thus the site-specific CCC) is not hardness dependent and would apply to
the whole river system.
Station specific criteria for copper were calculated using the geometric
mean of the water effect ratios (Table 16) determined from reference water
and stations 4A, 5, 6, and 7 acute toxicity data. For zinc, because there
was little or no evidence of effluent effect in the acute toxicity data from
the above stations, other than their contributions to water hardness, the
station specific zinc CMC(s) are considered the same as the national CMC
corrected for hardness. The station specific zinc CCC(s) are also considered
the same as the national CCC of 47 Mg/1 total recoverable zinc. Thus any
copper or zinc measurements above the CCC(s) are considered evidence of
criteria being exceeded.
Criteria evaluation— The site-spijcific and national water quality
criteria derived for copper were exceeded at all of the downstream Naugatuck
River sampling stations (Table 17). Total acid exchangeable copper concen-
trations exceeded the CMC(s) in one or more water samples collected at each
27
-------
scacion and were in excess of Che CCC(s) in all of the vater samples. The
differences between the criteria and cocal acid exchangeable copper concen-
trations for station 2 to 5 water samples were not great, however, more
marked differences occurred at the downstream stations (6 through 12).
The site-specific copper criterion based on a water effect ratio of 1
does not take into account the changes in physical and chemical water
characteristics caused by the combined input to the Naugatuck River from the
tributaries, industries, and STPs, however, station specific criteria for
stations AA, 5, 6, and 7 take these factors into account and are presented in
Table 17. The station specific copper criterion for stations 4A and 5 were
not exceeded whereas the station specific criterion for stations 6 and 7 were
both markedly exceeded.
The site-specific, station specific, and National Criteria derived for
zinc were not exceeded at Naugatuck River sampling station 1 through 5. The
total acid exchangeable zinc concentration, of the four water samples analyzed
for each station were less than the CCC of 47 ug/l zinc. This zinc CCC was
exceeded by the mean total acid exchangeable zinc concentrations calculated
for all of the remaining downstream sampling stations (6 through 12).
The results of the ecological survey [3] indicate that where the station
specific copper criteria were exceeded (station 6 and 7), the aquatic
community was markedly impacted. The total number and abundance of fish
species captured in the upstream sampling stations (Figure 8) were indicative
of an abundant and diverse fish community whereas those captured at station 6
and below were indicative of a severely stressed community. The difference
in the number and abundance of species between upstream stations are thought
to be primarily caused by habitat differences between stations. Influences
of the point source effluents were thought to be minimal. Periphyton
28
-------
community samples from scat ions 1 through 5 were generally highly diverse
when examined using a diversity index and indicative of good water quality
within this section of the river (Figure 9), however minor pollution effects
were evident in data for stations 2, 3, and 4. Periphyton in the downstream
stations (6 through 12) were of low to moderate diversity and indicative of
poor to moderate water quality. Macroinvertebrate data were examined using
the diversity index and a community loss index. Direct effects on the
benthos were attributed to the discherges from the Gulf Stream and Had River
tributaries, the Tomngton and Naugatuck STP (POTW) and the Thomaston dam.
Direct effects were not as apparent in the number of taxa and density data
(Figure 10). The data were interpreted as reflective of the presence of the
healthiest benthic community between station 1 through 5 and a lower quality
community from station 6 through 8 and the poorest quality community between
stations 9 through 12. The downstream trend of decreasing health of the
benthos was attributed to a combination of cumulative industrial wastes and
habitat differences related to increased flow. The density of the
predominant tricopterans in the samples (Figure 11) were reflective of a
marked difference in the density between the upstream (1 through 5) and
downstream stations (6 through 12). Zooplankton data were thought to be more
reflective of the presence of impoundments masking the detection of any STP
or tributary effects on abundance and composition.
29
-------
CONCLUSIONS
From Che results of this study, it was concluded that the national and
site specific water quality criteria derived for copper in the Naugatuck
River would be protective of the rivers aquatic life under low flow
conditions. This conclusion is based on the observation that a relatively
healthy aquatic community existed where these criteria were exceeded slightly
(stations 2 through 5). This was thought to be due to presence of effluent
copper which was complexed and in a non-toxic form. Furthermore, examination
of monthly water quality monitoring data 111] from October 1981 to August
1983 indicates that copper concentrations continually exceeded the national
and site-specific copper criteria at station 5. Over this period of time the
reported total recoverable copper concentrations averaged 17 +_ 1 standard
deviation of 6.4 and ranged from 8 to 36 ^g/1.
Station specific criteria for copper (site within a site criteria) for
stations 4A and 5 indicate that the site-specific and national criteria are
over-protective at these stations, however, wherfter or not the station
specific criteria are protective could not be discerned from the available
data. The only conclusion made is chat where the station specific criteria
were exceeded (stations 6 and 7), a markedly pollution impaired aquatic
community was evident.
It could not be determined whether or not the site-specific, station
specific, and national criteria for zinc were protective of the Naugacuck
River biota because these criteria were not exceeded in the upstream samples
(stations 1 through 5) where a relatively healthy aquacic community was
found. However, an impaired aquatic community was observed where the
criteria were exceeded (stations 6 and below).
30
-------
This study demonscrates chat numerical wacer quality criteria for copper,
if incorporated in water quality standards or National Pollution Discharge
Elimination System permits, could be used to protect Naugatuck River biota
from copper coxicicy. However, in some of the effluent dilution test* where
copper was a relatively low concentration and expected to be non-toxic,
effluent toxic icy was observed. This toxicity may have been due to
combinations of known and unidentified chemicals for which criteria are
lacking. In these cases, alternate standards based on effluent toxicity
limits such as recommended by the U.S. EPA [12] would be necessary to protect
the well-being of the river biota.
31
-------
ACKNOWLEDGMENTS
We thank Donald Mount for his cooperation and use of data obtained under
his direction and sll of the people associated'vith his study. We also thank
Scocc Heinritz and Dennis McCauley for conducting the on-site toxicity tests,
Duane Benoit and Vince Mattson for conducting the off-site toxicity tests,
and Donald Ruppe, Carol Lindberg, and John Poldoski for analytical chemistry
support.
32
-------
REFERENCES
1. Carlson, A.R., W.A. Brungs, G.A. Chapman and D.J. Hansen. 1984.
Guidelines for deriving numerical aquatic site-specific water quality
criteria by modifying national criteria. National Technical Information
Service, Springfield, VA. EPA-60Q/3-84-099. Order No. PB85-121101.
2. U.S. Environmental Protection Agency. 1983. Water Quality Standards
Handbook. Chapter 4. Guidelines'for deriving site-specific water
quality criteria. Office of Water Regulations and Standards, Washington,
DC 20460.
3. U.S. Environmental Protection Agency. 1985. Validity of effluent and
arabient toxicity tests for predicting biological impact, Naugatuck River,
Waterbury, Connecticut. D.I. Mount, T.J. Norberg-King and A.E. Steen,
eds. (in preparation).
4. Mount, D.I. and T.J. Norberg. ly84. A seven-day life-cycle cladoceran
toxicity test. Environ. Toxicol. Chem. 3: 425-434.
5. U.S. Environmental Protection Agency. 1979. Methods for chemical
analysis of water and wastes. EPA-600/4-79-020. U.S. EPA, Environmental
Monitoring and Support Laboratory, Cincinnati, Ort 45268.
6. Nelson, H., R. Erickson, D. Benoit, V. Mattson and J. Lindberg. 1985.
The effects of variable hardness, pH, alkalinity, suspended clay, and
humics on the chemical speciacion and aquatic coxicity of copper. U.S.
EPA, Environmental Research Laboratory, Duluth, MN (in preparation).
7. Hamilton, M.A., R.C. Russo and R'.V. Thurston. 1977. Trinmed
Spearman-Karber method for estimated median lethal concentrations in
toxicity bioassays. Environ. Sci. Technol. 7: 714-719. Correction 12:
417 (1978).
33
-------
3. Sceel, R.G.D. and J.H. Tome. I960. Principles and procedures of
scacistics wich special reference to the biological sciences.
McGraw-Hill, New York. 481 pp.
9. Morel, F., R. McDuff and J. Morgan. 1973. Interactions and chemostasis
in aquatic chemical systems: role of pH, pE, solubility, and
complexation. In P. Singer, ed., Trace Metals and Metal-Organic
Interactions in Natural Waters. Ann Arbor Science, Ann Arbor, MI 91973.
10. U.S. Environmental Protection Agency. 1984. Ambient water quality
criteria for copper. Draft 11/26/84. U.S. EPA, Environmental Research
Laboratories, Duluth, MN and Narragansett, RI.
11. U.S. Environmental Protection Agency. 1980. Ambient water quality
criteria for zinc. EPA-440/5-80-079. Office of Water Regulations and
Standards Oivision. Washington, DC 20460.
12. U.S. Environmental Protection Agency. 1985. Technical support document
for water quality-based toxic control. Office of Water, Washington, DC
20460.
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1,040-1.680
M*o*1a lotal OrqaMc
(NMj-N)* Orbonb
l.g/l) (*9/ll
12-46
18-36
62-800
29-64
6,200-11.200
MV3.200
49-205
6,200-44,000
140-510
21-61
44-280
34-216
-------
Table 2. Total acid exchangeable and dissolved copper and zinc concent rac ions iui w.i» ,
between 23 and 29 August 1983 from the Naugatuck River, STP effluents, and tributaries.
Water
Sample
1
2
CSI
3
TRN
4
4A
Tnrt
5
SB1
6
CB1
7
M5
8
WTB
9
NOT
10
11
12
Copper
Total
He an
0.9
11
81
12
38
19
13
vo
16
570
93
1,790
139
568
185
95
112
11
80
54
47.7
Range
0.7-1.1
9-20
58-120
7-17
21-60
16-21
11-14
60-140C
13-18
472-680
82-100
166-3,392
122-177
240-891
161-234
38-190c
100-146
9-12«
56-97
40-76
187-1,140
(US/I)"
Zinc (pg/l)b
Dissolved
Mean
0.8
9
51
8
28
13
9
91
11
101
50
1,350
63
160
83
63
55
4
39
29
168
flange
0.6-1.2
7-12
79-94
5-11
20-37
14-16C
8-12c
30-150C
10-15C
85-123
48-50c
187-2, 237C
46-86
70-273
60-102
25-89c
39-76c
l-8f
23-57c
16-36e
110-294 f
Total
Mean
6
17
145
21
57
29
18
114
23
548
89
656
88
374
162
114
92
66
55
60
112
Range
3-12
8-43
85-218
8-48
42-70 .
26-31
9-27
64-160
14-29
368-1,004
58-146
240-970
73-124
301-142
150-185
103-133
79-103
33-130d
64-89
36-77
62-192
Dissolved
Mean
6
7
47
13
27
11
14
110
11
\
103
30
652
46
239
127
81
46
46
35
29
81
Range
1-8
4-13
37-163
7-26
20-32
B-15
1-25
27-170
7-18d
54-150
23-44
262-922
38-54
130-260
110-144
47-102
35-54d
18-96d
25-53
18-37
42-92
a Mean and range based on N=7 unless otherwise noted.
' Mean and range based on N**4 unless otherwise noted.
c N-6
d M-3
e Ni«4
f N-5
-------
Table 3. Initial chemical and physical data for reference water (Lake Superior source) and Naugatuck River
water from ucacion 1, 4A, 5, 6, and 7 collected on .31 August 1983 and used in the acute coxicity tests.
Water
S.imple pll
Reference 7.7
I 7.5
4A 7.5
5 7.5
6 7.3
7 7.3
Hardness8
(mg/l)
52
36
55
68
82
90
Alkal initya
(mg/l)
55
38
42
40
40
43
Conduct ivity
(|j mhos/cm)
95
90
250
305
320
395
Turbidity
(NTU)
O.I
0.7
2.2
2.3
3.6
3.0
Total Residual
Chlorine
(ug/U
N0b
NO
NO
40
NO
NO
Nitrite
(Mg/D
<2
<2
150
140
130
120
a As CaC03
b NO = not detected at a limit of 5 -Jg/1
-------
Table 4. Young production and percentage survival of Ceriodaphnta (N=10) obtained from
CO
a seven day copper addle
ion toxic
icy test in
1983.
station 1 water
collected on
26 August
Copper Concentration (pe/1)
Nominal
100
33
11
3
1
0
Total
Measured9
91
32
12
4
3
<3
(Control)
Dissolved
Me. in
72b
27b
10C
5C
5C
<3b
Range
71-72
26-27
9-10
4-5
4-5
™
Young/Female
0
0.5d
8.1
13.1
11.8
14.5
Standard
Deviation
-
1.0
5.0
3.7
5.7
9.1
Pet cent age
Survival
Od
30d
80
V100
90
80C
a N = 1
b N = 2
c N = 3
d Significantly different than the controls (P = 0.95)
e Includes one male
-------
Table 5. Young produce ion anil percentage survival of daphnids Ceriodaphnia
(N=10) obtained from a seven day zinc test in station 1 water
collected on 26 August 1983.
Nomi nal
300
too
33
11
3.0
1.5
0.0
Zinc Concentration (u:f»/l)
Total Dissolved
Measured3 Mean Range Young/Female
273 292a - Od
102 94a - 10.1
47 38b 36-40 9.6
18 16C 14-17 9.5
7 9b 3-14 9.5
7 5b 4-5 14.7
5 11. la - 14.1
(Control)
Standard
Devi at ion
-
6.1
5.6
6.3
6.4
7.4
7.3
Percentage
Survival
Od
90
90
^90
80
90e
90e
a N = 1
b N - 2
c N - 3
*J Significantly different than the control (P = 0.95)
e Includes one male
-------
Table 6. Forty-eight hour acute coxicicy values and 95* confidence
intervals in parenthesis for daphnid species exposed to copper added co
reference water (Lake Superior source) and to Naugatuck River water from
stations 1, 4A, 5, 6, and 7.
Ceriodaphnia
Copper LC50 (jg/ 1 )
Water
Reference
1
4A
5
6
7
Total
19
(ll-31)a
20
(12-34)a
64
(51-80)
91
(81-101)
90
(87-93)
142
(77-193)*
Dissolved
18
(10-30)
19
(12-33)
51
(42-64)
78
(69-87)
57
(54-61)
88
(48-l46)a
Scaphrolebaris
Copper LC50 (ga/l)
Total
18
(17-20)
_
-
76
(46-126)*
97
(86-109)
121
(110-133)
138
(130-146)
Dissolved
17
(16-19)
w
-
61
(33-96)a
83
(74-94)
79
(72-88)
35
(31-90)
a These are concentrations bracketing the LC50. Confidence intervals
could not be calculated.
-------
Table 7. Ninety-six hour toxicicy values an998
7 689
(555-354)
Naui>at437
440
(373-518)
Kree
Copper
1.8
(1.0-3.2)
3.7
(3.1-4.3)
2.0
(1.1-3.7)
16.1
(12.0-21.7)
>20.1
14. H
(11.5-18.9)
Total
Copper
47
(35-64)
171
(153-196)
202
(126-320)a
229
(143-366)3
265
(181-389)3
282
(257-310)
, 6, and 7.
EC50 (ug/l)
Dissolved
Copper
45
(33-61)
156
(139-176)
153
(89-243)a
179
(117-275)3
164
(lll-241)a
187
(167-209)
Free
Copper
1.5
(0.9-2.6)
3.4
(2.6-4.4)
0.6
(O.l-2.7)a
\
3.3
(l.2-9.0)a
3.5
(1.5-8.2)3
3.0
(2.2-4.2)
a These are concentrations bracketing the EC50. Confidence intervals could not be calculated.
-------
Table 8. Final water chemisrry dacn for reference water (Lake Superior source) and Naugacuck Kivcr
water from stations 1, 4A, 5, 6, and 7 collected on 31 August 1983 and used in the acute toxiciiy
tests.
Fathead Minnow
Water
Reference
1
4A
5
6
7
Reference
1
4A
5
6
7
Final D.O
Control
7.7
7.b
9.4
9.9
8.7
9.2
7.2
7.5
12.2
9.1
8.4
8.8
.* (mg/D
Ran«jeD
7.4-8.3
7.4-7.6
9.4-12.4
8.2-11.4
8.3-13.2
7.6-11.2
7.2-7.3
7.4-7.6
8.4-12.2 ,
8.3-9.1
8.2-8.8
8.8-9.8
Final pH
Control Range*1
Copper Tests
7.1
7.2 7.0-7.2
8.5 8.5-9.4
8.2
7.7
7.9
Zinc Tests
7.2
7.4 6.9-7.4
9.2 8.4-9.2
7.2
7.6
7.8
Final D.O.
Control
\
8.0
7.6
7.5
7.6
7.8
- '
8.1
7.9
-
8.2
7.8
7.3
Daphnid
(mg/1) Final pH
Range Control Range0
7.9-8.1
_
_
7.6-8.1
7.6-8.1
7.6-7.8
8.1-8.2 7.3 7.2-7.3
7.9 7.0 6.8-7.0
_
8.0-8.2
7.7-7.8
7.0-7.6
a D.O. " dissolved oxygen
Between two or more treatments.
-------
Table 9. Forty-eighc hour acute toxicity values and 952
confidence intervals in parenthesis for Ceriodaphnia exposed
to zinc added co reference water (Lake Superior source) and
Naugatuck River water from stations 1, 5, 6, and 7.
Water
Zinc LC50
Qg/I)
Total
Dissolved
Lake Superior
1
5
ISO
U05-305)3
164b 149C
(128-217) (103-217)
222
(186-263)
366
(272-493)
255
(160-406)
169
(104-308)a
165b 145C
(126-217) (101-210)
194
(161-233)
234
(253-443)
232
(149-361)
3 These are concentrations bracketing the LC50. Confidence
intervals could not be calculated.
k The test was started on 1 September 1983 using water
collected on 31 August 1983.
c The test was started on 3 September 1983 using water
collected on 31 August 1983.
-------
Table 10. Ninecy-six hour acute coxicicy values for larval
fachead minnow Pimephales promelas exposed co zinc added co
reference
wacer (Lake Superior source)
from scacions 1, 4A, 5,
Wacer
Reference-
1
4A
5
6
7
Zinc LC50
Tocal
551
(450-677)
393
(308-501)
440
(190-1,018)*
556
(475-650)
655
(570-752)
807
(693-969)
(gg/1)
Dissolved
550
(451-672)
387
(307-489)
373
(156-893)3
527
(445-624)
576
(532-624)
742
(614-896)
and Naugacuck River wacer
6, and 7.
Zinc EC50 (
Tocal Di
551
(450-677)
188
(107-329)3
440
(190-l,018)a
556
(475-650)
621
(566-683)
659
(333-1, 070)a
Jg/l>
•solved
550
(451-672)
191
(111-328)3
373
(156-893)3
527
(445-624)
560
(390-1, 090)a
601
(361-1, 000)a
a These are concencracions brackecing che coxicicy value.
Confidence incervals could noc be calculated.
-------
Table 11. Ceriodaphnia effluent dilution toxicity test results determined in water
samples collected on 26 August 1983. Station 1 water was used as dilution
water in all tests.
Water
Gulf Stream
Tor ring ton STP
Thomas ton STP
Steel Brooke
Great Brooke
Station B
Acute
48 hr LCSO as
% Effluent
(v/v)
53.1
(30-100)b
MOO
44.8
(30-1 00 )b
6.9
(5.2-9.2)°
1.6
U-3)b
17.3
(I0-30)b
Toxicity
Total3
Copper
(ug/0
31
>42
27
46
29
34
Chronic Toxicity
Total3
Zinc
Og/1)
64
>53
29
69
13
27
NOEC as
2 Effluent
(v/v)
10
10
30
3
1
10
Total3
Copper
Og/n
6
6
20
\
20
18
21
Total3
Zinc
12
54
19
30
8
16
a Total copper and zinc concentrations were calculated from concentrations measured in
the undiluted effluent samples.
b These are concentrations bracketing the LCSOs. Confidence interval could not be
calculated.
c Ninety-five percent confidence interval.
-------
Table 12. Metals detected* Ug/l) using ICPAES analysis of water samples from
che Naugatuck River, several tributaries, STP effluents, and reference water.
Copper and zinc values in parenthesis were determined
using atomic absorption speccrophotometry.
Water
Sample
I
2
3
4
4A
5
6
7
8
9
10
11
12
CSl
SB
CBt
M5
TRS
THM
WTB
NGT
1
4A
5
6
7
Reference
Al
(5)b
NDC
NO
ND
83
228
64
98
77
528
114
90
61
ND
ND
310
161
94
45
109
ND
1,437
ND
58
568
198
178
ND
Cd
(5)
ND
ND
ND
ND
ND
ND .
ND
ND
ND
ND
ND
ND
ND
ND
23
ND
ND
ND
NO
ND
ND
ND
ND
ND
ND
ND
ND
Cr
(5)
26
ND
ND
ND
ND
ND
ND
ND
6
12
11
7
6
14
29
39
109
39
ND
ND
11
ND
31
ND
ND
ND
ND
ND
ND
Cu
(6)
August 1983 Samples
ND(1)
ND(9)
ND(IO)
20(21)
NDU3)
ND(13)
85(97)
126(142)
199(201)
108(114)
61(67)
45(50)
387(356)
52(57)
677(667) 1
1,858(1,773)
609(608)
35(42)
52(60)
124(131)
ND(9)
August 1983 Samples
ND(l)
ND(9)
ND(21)
66(68)
62(73)
Lake Suoerior
ND
Fe
(5)
'
267
173
384
520
480
167
299
323
490
409
429
470
244
514
,435
579
734
189
418
112
69
229
256
496
361
384
ND
Ni
(10)
ND
ND
ND
ND
ND
ND
ND
19
51
31
57
51
30
116
76
145
446
ND
ND
262
ND
ND
ND
ND
ND
ND
•NO
Zn
(5)
12(3)
ND(3)
15(18)
28(27)
ND(9)
ND(14)
152(146)
65(73)
166(158)
92(97)
56(68)
74(78)
99(98)
112(121)
1,000(1,004)
836(811)
339(342)
31(43)
51(64)
96(109)
19(33)
SD(3)
ND -
ND(27)
47(47)
65(44)
ND
* As, Ba, Hg, Pb, Sb, and Se were noc detected ac 30, 5, 30, 20, 20, and 30
Detection limic in
c ND • noc detected
46
-------
Table 13. Range of no observed effect concentrations determined from
Ceriodaphnia effluent dilution tests conducted using
water samples collected between 23 August 1983 and 29 August 1983.
Station 1 water was used as dilution water in all tests.
Effluent
Samples
Gulf Stream
Torrington STP
Thomaston STP
Steele Brooke
Great Brooke
Mad River
Station 8
No Observed
Percent Effluent
(v/v)
1-30
(7)b
3-] 00
(6)
3-100
(7)
1-3
(6)
1-10
(5)
3-30
(2)
10-30
(7)
Effect Concentration
Total Copper3
Cug/D
1-26
(7)
1-57
(6)
4-143
(7)
6-20
(6)
7-18
(5)
8-72
(2)
18-38
O)
Range
Total Zinc3
(wg/0
1-65
(4)
17-70
(4)
2-48
(4)
10-30
(4)
6-10
(4)
87
(1)
15-19
(4)
a Total copper and sine concentrations were calculated from concen-
trations measured in the undiluted samples.
The number of samples represented by the ranges are in parenthesis.
47
-------
Table 14. Comparison of cocal acid exchangeable and cocal recoverable
mecal concentrations of Naugacuck River samples collected on
29 Augusc 1983.
Scacion
1
2
3
4
4A
5
6
7
8
9
10
11
12
Copper
Toe a I Acid
Exchangeable
<1.5
15
15
19
17
15
89
142
221
97
82
42
180
(VJR/I)
Tocal
Recoverable
<0.5
15
14
18
14
16
102
159
247
117
108
49
208
Zinc
Tocal Acid
Exchangeable
-
17
24
13
15
30
73
123
223
113
111
37
103
(ug/1)
Total
Recoverable
0.7
21
28
16
15
26
76
122
207
110
102
44
102
48
-------
Table 15. Acute coxicicy values for Ceriodaphnia and
larval fachead minnows exposed co copper in
reference vacer (Lake Superior source) and Naugacuck
River water collected form station I on
5 Sepcember 1983.
War.er
Reference3
1 =
«
Ceriodaphnia
A3 hr LC50 (yg/1)
as cocal copper
17
(15-20)b
18
(!3-25)d
Fachead Minnow
96 hr LC50 Og/l)
as cocal copper
85
(64-112)b
95
<74-l22)b
a Dissolved copper measuremenc in two treatments
ranged from 100 co 102Z of che cocal copper
concentration.
b Ninety-five percent confidence incerval.
c Dissolved copper measuremenc in cwo treatments
ranged from 95 co 96Z of che cocal copper
concentration.
** k 95? confidence incerval could noc be calculated,
these are concentrations bracketing the LC50.
49
-------
Table 16. Water effect ratios for copper (site water LC50/lab water LC50).
The daphrud ratios are based on LCSO daca and the fish ratios are based on
EC50 d.-ita.
Geometric
Station Cenoo'aphnia Scaphrolebaris Fathead Minnow Mean
4A. 3,3 4.2 4.3 3.9
5 4.8 5.4 4.9 5.0
6 4.7 6.7 5.6 5.6
7 7.4 7.7 6.0 7.0
50
-------
Table 17. Naugatuck River copper concentrations and water quality criteria for
copper in PR/I.
Copper Criterion
River Mean Total Acid
National
Station Exchangeable Copper CMC
1
2
3
4
4A
•v. ••
5
6
7
8
9
10
11
12
1
11
12
19
13
16
93
139
185
112
80
54
427
7.4
9.2
10.8
11.3
10.3
13.1
13.3
15.0
15.7
14.9
17.6
17.6
16.7
CCC
5.1
6.5
7.5
7.8V
7.2
9.0
9.1
10.2
10.6
10.0
11.7
11.7
11.2
Site-Specific Station Specific
CMC
8.7
8.7
8.7
8.7
8.7
8.7
8.7
8.7
8.7
8.7
8.7
8.7
8.7
CCC
6.2
6.2
6.2
6.2
6.2
6.2
6.2
6.2
6.2
6.2
6.2
6.2
6.2
CMC CCC
8.7 6.2
-
\
-
34 24
44 31
49 35
61 43
_
-
-
-
-
a N - 7
b
Baaed on the mean of the total water hardness value for the seven daily water samples
-------
LIST OF FIGURES
Figure 1. Study area of Naugatuck River.
Figure 2. (A) Mean cocal copper concentrations of the ambient river water
saraples used in the Ceriodaphnia mass balance toxicity tests and
total copper LC50 values from the ac-;r.e toxicity tests. (B) Mean
48 hr survival and young production data for che Ceriodaphnia mass
balance toxicity tests [3].
Figure 3. Mean total zinc concentrations of the daily ambient river water
samples collected on the 23, 24, 26, and 29 August 1VJ3, and 48 hr
Ceriodaphnia LC50 and 96 hr LC50 fathead minnow values determined
in water samples collected on 31 August 1983.
Figure 4. (A) Total copper and zinc concentrations of ambient river water
samples collected on 26 August 1983. (B) Forty-eight hour
Ceriodaphnia survival and young production data from the mass
balance toxicity test of the river water samples collected on 26
s
August 1983 (3).
Figure 5. (A) Copper concentrations for station 6 river water samples
collected over the seven day sampling period. (B) Forty-eight
hour Ceriodaphnia survival and young production data from the mass
balance toxicity tests conducted with station 6 water samples [3J.
52
-------
Figure 6. (A) Copper concentrations for station 7 river water samples
collected over the 7 day sampling period. (B) Forty-eight hour
Ceriodaphnia survival and young production from the mass balance
conducted with station 7 water samples [3].
Figure 7. (A) Mean total copper concentration and ranges of total copper
concentrations of the river water samples used in the fathead
minnow impact toxicity tests, and total copper LC50 and EC50
values from acute toxicity tests. (B) Fathead minnow survival and
growth data from the ambient toxicity tests [3].
Figure 8. Abundance and number of species of fish captured from the
Naugatusk River, Connecticut [3].
Figure 9. Variation of periphyton diversity [3].
Figure 10. Comparison of benthic community parameters [3].
Figure 11. Trend in abundance of trichoptera and predominant
trichopteran genera in the Naugatuck River [3].
53
-------
Nl
Gulf Stream
-------
100
80
80
40
"
0 •
4 4 A A > A
COMQOAPHNIA
. .. 12
a Survnai
• Ytung
20*
to
I 2 3 4 4A 9 e r 8 9 10 II 12
NAUGATUCX «(VW STATIONS
Figure 2. (A) Mean cocal copper concencracions of che arabienc river wacer
samples used in che Ceriodaphnia mass balance coxicicy cescs and
cocal copper LC50 values from che acuce coxicicy.cescs. (8) Mean
48 hr survival and young produccion daca for che Ceriodaphnia mass
balance coxicicy cescs (3).
55
-------
Ul
600
S 600
o
M 40O
g
H 200
O
I
• Ambient Concentration
oDophnid LCSO
• Fathead LCSO
344A5 6 789101112
NAUGATUCK RIVER STATIONS
Figure 3. Mean total zinc concentrations of che daily ambient i »v..i water
samples collected on the 23. 24, 26, and 29 August 1983, and 48 hr"
Ceriodaphnia LC50 and 96 hr LCSO Cathead minnow values determined
in water samples collected on 31 August 1983.
-------
250r
I 2 34 4A 56789 10
100 r
125
I 2 34 4A 56789 10
NAUGATUCK RIVER STATIONS
Figure 4. (A) local copper and zinc concencracions ot' arobienc river uacsr
samples collected on 26 Augosc 1983. (8) Foccy-eighc hour
Ceriodaphnia survival and young production daca fron ch* mass
balance coxicicy cesc of che river wacer samples collecced on 26
Augus: 1933 [3J.
57
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STATION 6
290
2
I'80
2
2 100
• ToW
e OtuolvM
90
I 2
4 3
4
f
CEBtQaAPHMA
125
Figure 5. (A) Copper concentrations for scacion 6 river vacer samples
collected over the seven day sampling period. (B) Forty-eight
hour Ceriodaphnia survival and young production daca from che mass
balance coxicicy cescs conducted with station 6 water samples (3).
58
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STATION 7
-2 J 4 i
RqurtB
CgfflOOAPHNU
Figure 6. U> Copper concencracions for sc.cion 7 river wacer .«PU.
collecced over the 7 day sailing period. (B) Forty-eight hour
C.riodaohni. survival aad young production from che m*sa balance
conducted wich station 7 water samples [3].
59
-------
lOOOr
•FenxotfLCSO
(••gramr man)
i
8 9 10 II 12
FATHCAO MINNOW
T0.3
4* 9 *6 7 a 9 JO II 12
NAUOATUCXKIVCK STATIONS
Figure 7. (A) Mean cocal copper concencracion and ranges of cocal copper
concencracions of che river wacer samples used in che Cachead
minnow Lmpacc coxicicy cescs, and cocal copper LC50 and EC50
values from acuce coxicicy cescs. (B) Pachead minnow survival and
growch daca from che ambUnc coxicicy cescs (3).
60
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FISH
70
60
£ 50
8
a
Ul
40
30
20
10
Abundonct
: Number of Spacits
t STP
t Tributary
y w\-
I 2 ! 3 t 4 4At 5 t 6 t 7
i I I i !
STATIONS
! 9T
I I
20
IS UJ
&5
ft
10 £
5
03
5 ^
10 II 12
Figure 8. Abundance and number of species of fish captured trom the
Naugatuck River, Connecticut [3].
61
-------
PERIPHYTON
4.0
3.0
2.O
1.0
tsTP
* Tributary
O-
j i
I 2
] 3 t 4 4At 5 ] 6 t 7^ 8 J 9 MO II 12
I! i i § ! * i
STATIONS
Figure 9. Variation of penphyton diversity [3].
-------
BENTHOS
Olvtrsity
Community Loss
tSTP
* Tributary
I 2 t 3 t 4 4A| 5 t 6 .| 7 t 8 t 9 J 10 l'l
8
K»XX»r - Total Btntho
— Total Btnthos
•— Numbtr of Taxo
I100
75 <
x
I 2J3T4 4A|S| 6^ 7! 8[ 9HO II 12
STATIONS
Figure 10. Comparison of benthic communicy paramecers [3],
63
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.57000
7
2
2,000
IJOOO
200
100
20
10
5
I •
— Trfchopttre
* ThomostonDom
t STP
* Tributary
» I I I A I I I I
I I I
I 2T
5|6|7|6
r\
10 II 12
,_, ioo,ooor
w
e
^ 20,000
o 10.000
Chtumoiopsyche Lorvoe
——— Symphitopsyche Lorvoe
Hydropsychidoe
Early Instar
J
a
UJ
10
I 2 t3
(4 44t5re 7 8 TT
I 1 I i • I I
10 II 12
STATIONS
Figure 11. Trend in abundance of trichoptera and predominant
trichopteran genera in the Naugati ck River [3].
64
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