United States Environmental Protection Agency
CBP/TRS 6/87
August 1987
Results of Comparative
Studies of Preservation
Techniques for Nutrient
Analysis on Water Samples
m
Chesapeake
Bay
Program
-------
RESULTS OF COMPARATIVE STUDIES OF PRESERVATION TECHNIQUES
FOR NUTRIENT ANALYSIS ON WATER "SAMPLES
A Report
To
The Environmental Protection Agency
Chesapeake Bay Liaison Office
410 Severn Avenue
Annapolis, Maryland 21403
by
Betty A. Salley
Julie G. Bradshaw
Bruce J. Neilson
Nutrient Analysis Laboratory
Division of Physical Oceanography
Virginia Institute of Marine Science/School of Marine Science
The College of William and Mary in Virginia
Gloucester Point, Virginia 23062
September .24, 1986
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ACKNOWLEDGEMENTS
This study would not have been possible without the endeavors of
the personnel in the Nutrient Analysis Laboratory at the Virginia
Institute of Marine Science. Julie Kemp ton, Nancy Courtney, Donald
McCall, and William Jones III performed the multitude of laboratory
analyses necessary"for this study.
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TABLE OF CONTENTS
INTRODUCTION 1
Sampling 1
Sample Processing 2
Sample Treatments 4
METHODS 6
Analytical Techniques 6
Statistical Methods 6
RESULTS 9
General 9
Nitrite 10
Nitrate-Nitrite 11
Ammonia. ............12
Total Kjeldahl Nitrogen 12
Orthophosphate 13
Total Dissolved Phosphorus 13
Total Phosphorus 14
Suspended Solids 14
Silica .... .......... 15
DISCUSSION 25
The Data Sets 26
CONCLUSIONS 32
REFERENCES 33
APPENDICES
Appendix A: Raw Data
Appendix B: Graphical Summaries of Raw Data
Appendix C: Results of Statistical Analyses
Appendix D: Laboratory Methods
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INTRODUCTION
Two generally accepted methods to handle water samples for
nutrient analyses which also have been approved by the U.S.
Environmental Protection Agency are: (1) to analyse the samples within
24 hours* or if this is not possible, (2) to analyse the samples
within EPA recommended holding times. In addition, the holding times
for some nutrient analyses can be extended by the addition of preserv-
atives. Personnel constraints often preclude immediate analyses, but
the addition of foreign substances (preservatives) can introduce con-
tamination and cause other problems. The purpose of this study was to
assess a third method, freezing, as a sample preservation alternative.
In this study, five different treatments (including two freezing
treatments) were investigated. Four water samples were analysed for
nine water quality constituents:
Prthophosphate (OP) .
Total dissolved phosphorus (TOP)
Total phosphorus (TP)
Nitrite - (N02)
Nitrate-Nitrite (N023)
Ammonia (NH3)
Total Kjeldahl Nitrogen (TKN)
Silica (Si)
Suspended solids (SS)
Sampling
Sampling was done on April 30, 1986. Four stations (two on the
James River and two on the York River) were sampled in order to give a
diverse salinity range. The James River stations were 31.85 (James
1) and 50.19 (James 2) kilometers upstream from the river mouth and
the York River stations were at 0.00 (York 1) and 19.21 (York 2)
kilometers from the Bay. The Chesapeake Bay Program designations for
these stations are LE5.2, LE5.1, WE4.2 and LEA.2, respectively. All
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four stations have been monitored for a number of years. All samples
Hera collected within an hour of each other and the samples were back
in the laboratory within two hours of the last sample taken. Five
carboys of water were collected at each station. Each sample was taken
with a submersible pump at a depth of ten feet.
processng
Concentrations for certain nutrients, particularly at the York
Ri.ver stations, were low; therefore, the samples were spiked in order
t'.iat concentrations be above the lowest standard used for those
analyses. The carboys for each station were poured into a large vat
with a valve at the bottom, the additional nutrients wera added (see
Table 1), and the combined sample stirred with a paddle while aliquots
were taken off. A carboy of each sample was withdrawn and given to
personnel of the Maryland Office of Environmental Protection to
process for particulate analyses.
Table 1. Approximate spike values (in mg/1)
for each station.
STATION
JAMES 1
JAMES 2
YORK 1
YOIK 2
N02
0.005
0.005
0.005
0.050
NH3
0.010
0.100
OP
___
0.020
0.100
It was known from historical data that the concentrations of dis-
solved nutrients at the York River stations would be low. Except for
the N02 concentrations, the James River stations have had values above
the lowest -standards used in the analyses. Unfortunately, concentra-
tions at the James stations were lower than in previous years,
particularly in NH3, and concentrations were less than 0.010 mg/1, the
lowest standard. The OP for the station York 1 also was below the
lowest standard of 0*010 mg/1. The values for these analyses for
Chese stations are in the data files, but the numbers are lower than
generally reported. The mean concentrations for the four stations and
mine constituents are shown in Table 2., The salinity
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range was not as large as planned. The severe drought resulted in the
salt water intrusion being further upriver than usual.
Table 2". Mean concentration of samples (in mg/1) after spiking
Salinity concentration is in ppt.
ANALYSES
SALINITY
N02
N023
NH3
TO
SI
TP
TDP
OP
TSS
JAMES 1
13.5
0.010
0.180
0.002
0.365
0.660
0.065
0.020
0.010
16
STATIONS
JAMES 2
6.4
0.007
0.270
0.002
0.445
1.270
0.110
0.025
0.015
38
YORK 1
18.5
0.010
0.110
0.013
0.470
0.035
0.030
0.015
0.005
7
YOtK 2
17.7
0.055
0.080
0.080
0.550
0.065
0.135
0.090
0.080
20
The handling of the samples when they arrived in the laboratory
was pre-orchestrated. First, samples for all the treatments and for
all the analyses were to be processed and stored.' In addition, the
zero day samples were to be analysed as well. Given the intense work
load on the first day there was a strong possibility for mishandling.
This did occur with one sample for one treatment for two constituents.
The sample for holding time from the York 2 station for NH3 and N023
did not have H2S04 added for preservation. This was not discovered
until the time came to run the analyses and the pH was to be adjusted.
There was also the odd replicate lost and this is indicated in the
data files with '-. '. Some of the replicate values were suspect
and in normal sample handling, these samples would have been rerun.
For this study, the values were kept in the data file because there
was no attempt to identify and remove outliers.
As previously mentioned, a carboy of each sample was provided to
the personnel from Maryland's Office of Evironmental Protection for
processing for particulate analyses. The Virginia Institute of Marine
Science portions were processed according to Table 3. In addition to
samples for analysis in the Nutrient Analysis Lab, samples for TOC/DOC
analyses were provided to Old Dominion.University.
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Table 3. Processing schema for the Nutrient Analysis Lab
SAMPLE
FILTERED I NOT FILTERED
OP TOP NH3 N02 N023 SI TO TP TSS
Sample Treatments
Each water quality constituent analysed received five treatments*
I''irst, samples were analysed on the day they were taken (Day 0) in or-
der to have a reference ("true") value to which to compare the other
treatments. Second, the samples were analysed the following day (Day
l)c This was in accordance with our normal laboratory treatment of
samples. Third, the samples were held for the EPA recommended time
span with any necessary preservation (HT). Any storage time in the
previous treatments was done at 4 degrees centigrade. The fourth and
fifth treatments were conducted to test the effect of freezing on the
samples. The samples were frozen at -20 degrees centigrade and, after
seven days for the fourth treatment, thawed at room temperature (25
degrees centigrade) and then analysed. The fifth treatment was the
same except the samples remained in the freezer for 28 days (FB).
These treatments are summarized in Table 4. It was predetermined
that thawing would take approximately 12 hours. The samples to be run
were removed from the freezer the evening before analysis. In accord-
ance with findings by MacDonald and McLaughlin (1982) that reactive
silicate concentration is a function of thaw time for low salinity
samples that have been filtered, silica samples were given an addi-
tional 12 hours after thawing to counter any freezing effect and the
bottles were shaken particularly well before being analysed.
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Table 4. Treatments investigated on each of the five days when
samples were analysed.
DAY
ANALYSES
28
N02
N023
NH3
TKN
SI
TP
TDP
OP
TSS
Treatments: X
N
HT
FA.
FB
X N HT
X N
X N
X N
X N
X N
X N
X N HT
X N
"TRUE VALUE" - Immediate
NORMAL PROCESSING TIME
EPA HOLDING TIME (* PH'
7 DAYS FROZEN
28 DAYS FROZEN
FA
FA
FA
FA
FA
FA
FA
FA
HT/FA
analysis
ED TO 2N
FB
HT*/FB
HT*/FB
HT*/FB
HT/FB
HT*/FB
HT*/FB
FB
FB
WITH H2S04)
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METHODS
Analytical Techniques
Ammonia, nitrite, nitrate-nitrite, and silica were analysed
using the Technicon Autoanalyzer 11 according to Technicon
methodology. Orthophosphate, total dissolved phosphorus, total phos-
phorus, total Kjeldahl nitrogen, and suspended solids were determined
manually using EPA's, "Methods for Chemical Analysis of Water and
Wastes".
Statistical Methods
Statistical techniques were employed to test whether the dif-
ferent treatments (i.e. laboratory analysis at Day 0, Day 1, after an
analysis-specific holding time, at 7 days after freezing, and at 28
days after freezing) produced different results. Each water quality
constituent (i.e. nitrite, nitrate-nitrite, ammonia, total Kjeldahl
nitrogen, orthophosphate, total phosphorus, total dissolved phos-
phorus, silica, and suspended solids) was tested individually, as .was
each sampling station. In addition to hand calculations, the
computer-based statistical packages SPSS (Nie, 1975) and SFSSX (SPSS
Inc., 1986) were used for statistical'analyses. In general, the null
hypotheses tested by statistical procedures stated that the treatments
produced equal results and were tested at alpha-0.05. Tables of
results show the probability of getting test statistics at least as
large as those calculated if the null hypothesis was indeed true. The
null hypothesis was typically rejected when this probability fell
below the chosen alpha level. When the probability was greater than
the alpha level* the null hypothesis was accepted, and equality of
treatments was concluded*
A series of paired t-tests was used to test differences between
the control (Day 0) and each other treatment* Specifically, the null
hypothesis stated that the mean difference between the control group
(Day 0) and each other treatment was zero. Results of the paired t-
tests are shown in Appendix C, Table Cl.
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The paired t-test was thought to be an appropriate test because
of the relatedness of samples: within each station, each sample
analyzed was originally split from one large sample rather than
originating as an independent sample. However, in order to determine
whether the control population is different from the treatment to
which it is compared, the paired t-test calculates the difference be-
tween observed values for each case and determines whether the mean of
these differences is significantly different from zero. For this
study, the replicates were the cases to be considered, but replicate
number 1 of the control group (Day 0) was not actually any more re-
lated to replicate 1 of the Day 1 group than it was to replicate 2 or
3, and so on, of the Day 1 group.- Therefore, the pairings used for
calculation of differences between treatments seem rather artificial
and the meaningfulness of the results of the paired t-test is
questionable. In addition, the stated null hypothesis suggests that
the use of a multisample technique such as analysis of variance would
be more appropriate than multiple use of the t-test, a two-sample
technique.
One-way analysis of variance was used to test the hypothesis
that the population means for each treatment, including Day 0, were
equal. Two-way analysis of variance, with sampling station as the
second factor, was determined inappropriate for two reasons: artifi-
cial variation between stations was produced when samples from some
stations were spiked prior to analysis and other samples were not, and
testing of the station effect was not relevant to the study
objectives. Results of the one-way analysis of variance are shown in
Table C2.
Once a significant difference between treatment means was es-
tablished with analysis of variance, multiple comparisons procedures
were employed to determine which treatments were different.
Dunnett's multiple comparisons procedure (Zar, 1984) was used
to compare the control (Day 0) mean to each other treatment mean,
testing the hypothesis that the control mean did not differ sig-
nificantly from the other treatment means. Results of this procedure
at alpha=0.05 and alpha=0.01 are shown in Table C3.
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A second multiple comparisons procedure which seemed useful was
Scheffe's multiple contrasts procedure, which compared the average of
the means of the currently acceptable treatments (Day 0, Day 1, and
Holding Time) with each of the freezing treatments. Specifically, the
null hypothesis that was tested stated that the mean of the accepted
treatment means (the composite control) was equal to the mean of the
chosen freezing treatment. Results of this procedure are shown in
Table C4.
It was also thought to be of interest not only to investigate
differences between the control and other treatments, but also to in-
vestigate differences between all treatments* This was accomplished
with Tukey's multiple comparisons procedure, testing the hypothesis
that for each comparison, the two means compared were equal. Results
are shown in Table C5.
The parametric analysis of variance and multiple comparisons
techniques utilized assume that data are normally distributed and that
treatment variances are equal. These assumptions appear to have been
violated for some data groups in this study, as shown by the
Kolmogorov-Smirriov test of normality (Table C6) and Bartlett's test of
homogeneity of variances (Table C7). Although analysis of variance
and the multiple comparisons procedures are thought to be rather
robust to departures from the .assumptions, nonparametric analysis of
variance and multiple comparisons, which test means of value rankings
rather than means of the values themselves, have also been included.
The rank means used for nonparametric tests are shown in Table C8.
Results of the Kruskal-Wallis nonparametric analysis of variance,
testing the hypothesis that all treatments are equal, are shown in
Table C9. Results of Dunn's nonparametric multiple comparisons tech-
nique, comparing all combinations of treatments to determine where
differences exist, are shown in Table CIO.
It is realized that computing multiple statistics from the same
data can be considered poor technique. However, statisticians do not
always agree on which statistics are appropriate for a given
situation. Therefore, several statistics are provided so that the
reader may choose the test deemed appropriate.
-8-
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RESULTS
General
Appendix A contains raw data arranged by water quality con-
stituent and includes means, standard deviations, minima, and maxima
for each station (Tables Al through A9).
Appendix B contains figures summarizing the results of the
study* Figures Bl through B9 (one figure per water quality
constituent) are plots of mean concentration vs. treatment, with each
station's results shown as a separate line on each graph. These
figures show the greater magnitude of differences between stations
relative to differences between treatments.
In Figures BIO through B45, the mean concentrations vs. treat-
ments for each of the stations are plotted on separate graphs, and
standard deviations from the mean concentrations are added to the
graphs to show the variability within each data group. The treatments
were arranged on the X-axis to illustrate how the EPA-approved treat-
ments (Day 0, Day 1, and Holding Time) compared with each, other'as.
well as how the freezing treatments compared with the "control" (Day
0) . The control is situated in the middle of the X-axis, with Day 1
and Holding Time treatments running to the left, and Day 7(frozen) and
Day 28(frozen) treatments running to the right. In theory, the varia-
tion in constituent concentrations described by the left half of the
graphs is acceptable to EPA. For the freezing treatments (the right
half of the graphs) to be accepted as being equivalent to the cur-
rently accepted treatments, they should fall, within the range of
variability described by the left half of the graph. This appeared to
be. the case for most of the analyses, with exception of silica and
possibly some of the nitrate-nitrite, orthophosphate, and total phos-
phorus results.
The results will be described by water quality constituent.
Results of the first analysis (nitrite) will be described in detail,
and the remaining results will be described more generally. Results
of statistical analyses for each constituent are summarized in
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tables at the end of this section. Results of statistical procedures
are also organized by statistical analysis in Appendix C.
Nitrite
Nitrite concentrations were generally higher at Day 0 than at
an)' other time, fell at Day 1 and fell again at the Holding Time
(Figures BIO through B13) . The data from frozen samples seemed to
generally fall within the range defined by data from the approved
treatments (Day 0, Day 1, Holding Time), and variability of the frozen
daf.a did not appear to be greater than variability of the approved
treatments.
Results of statistical analyses are shown in Table 5. The
paired t-test showed significant differences between the control (Day
0) and all other treatments except Day 1 at stations James 1 and York
1. For reasons mentioned in the Statistical Methods section, the t-
test results should be viewed with caution.
The parametric ANOVA results showed that all treatment means
could not be considered equal for any of the sampling stations. Using
Dunnett's multiple comparisons then to determine where differences ex-
isted between the control (Day 0) and the other treatments,
significant differences were found between the control mean and all
other treatment means, except for Day 1 at stations James 1 and York
1. Although the differences between means"were statistically sig-
nificant, examination of the treatment means showed that the actual
difference between means in many cases was less than 0.001 mg/1, which
wtis the smallest difference detectable by the equipment used for this
s<:udy. Many of the statistically significant differences were there-
fore not practically significant. It is interesting to note that the
treatment most different from the control was consistently the Holding
Tfime treatment. In all cases, the frozen samples were more similar to
the control than the Holding Time samples.
Scheffe's multiple contrasts procedure showed statistically
significant differences between the mean of the means of accepted
treatments (Day 0, Day 1 and Holding Time) and all freezing sample
means except the Day 28( frozen) sample at James 2 and York 1. But
these differences were in all cases, except the York 2 Day 7(frozen)
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sample, smaller than the smallest difference detectable by the
laboratory equipment used, and were therefore not measurably
different.
Tukey's multiple comparisons also showed many significant dif-
ferences between treatment means. Means that were not significantly
different included Day 0 and Day 1 at stations James 1 and York 1, the
two frozen samples at James 1 and York 1, Holding Time and the 7 day
frozen sample at James 2, and the 28 day frozen sample and Day 1 at
James 2. Again, however, these differences were often smaller than the
smallest difference detectable with available analysis equipment.
The Kolmogorov-Smirnov test for normal distribution indicated
that within each treatment at each station, the nitrite data were not
normally distributed, so it may be prudent to examine the results of
the nonparametric techniques. The Kruskal-Wallis nonparametric ANOVA
indicated that the treatments were not all equal at any of the
stations. Dunn's nonparametric multiple comparisons showed fewer sig-
nificant differences between treatments than Tukey's multiple
comparisons, with additional similarities including Day 0 and the 28
day frozen sample at all stations except James 1, Holding Time and the
7 day frozen sample at all stations, Day 0 and Day 1 at all stations,
and the 28 day frozen sample with various combinations of the other
treatments at different stations.
Nitrate-nitrite
An examination of Figures B14 through B17 showed that in
general, Holding Time and Day 28(frozen) data seemed to be more vari-
able than data for the other treatments. Nitrate-nitrite
concentrations in the frozen samples tended to be slightly lower than
the range defined by the approved treatments.
Results of statistical analyses are shown in Table 6. For
nitrate-nitrite the frozen samples were not generally similar to the
control. At James 1, Day 28(frozen) was different from all other
treatments. At York 2, however, Day 0 was different from all other
treatments. At York 1, Day 28( frozen) was different from all treat-
ments except Day 7(frozen). At James 2, Day 7(frozen) was different
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from Day 0 and Holding Time. Unlike the nitrite data, all statisti-
cally significant differences between treatment means were also
measurable differences.
Although the nitrate-nitrite data appeared to be normally dis-
tributed, the variances of the treatment means were not equal, so use
of the nonparametrie statistics may be desired* These results were
very similar to the parametric statistics results*
Aumonia
Figures B18 through B21 show that except at York 2, ammonia
concentrations in the frozen samples generally fell within the range
defined by the approved treatments. Holding Time data appeared to be
more variable than other treatment data*
Results of statistical analyses are shown in Table 7. None of
the statistical methods found any differences between any treatments
at the James stations.
At York 1* the primary differences seemed to exist between Day
1 and the other treatments. At York 2, Day 28(frozen) was the only
treatment different from the other treatments.
1'otal Kjeldahl Nitrogen
Total Kjeldahl nitrogen concentrations seemed to be more vari-
able than other constituent concentrations. Except at James 1, the
frozen sample data seemed to fall within the range defined by the data
from approved treatments (Figures B22-B25). Compared to other treat-
ments. Day 28(frozen) and Holding Time were generally less variable.
Results of statistical analyses are shown in Table 8. In
general, all treatments were shown to be equal at James 2 and the two
York stations. At James 1, the control (Day 0) was similar only to
Day 28(frozen), while the composite coritrol (Day 0, Day 1, Holding
Time) was similar to both freezing treatments. Comparisons of other
treatments found Day 28(frozen) to be different from Day /(frozen) and
Holding Time.
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Orthophosphate
Frozen sample data did not consistently fall within the range
defined by the data from approved treatments; at James 1 frozen or-
thophosphate concentrations were higher and at York 2 frozen
orthophosphate concentrations were lower (Figures B26-B29).
Results of statistical analyses are shown in Table 9. The
statistical methods showed many differences between treatments.
However, as with the nitrite results, many of the differences between
treatment means, although statistically significant, were not
measurably different with the available lab equipment. This lack of
measurable difference between means occurred at James 1 (where the
smallest mean, Day 1, was 0.0105 mg/1, and the largest mean, Day
28(frozen), was 0.0115 mg/1) and York 1 (Day 1 mean, 0.0042 mg/1;
holding time mean, 0.0052 mg/1). In addition, the only treatment mean
measurably different from the control (Day 0) at James 2 was the
Holding Time treatment. Scheffe's contrasts showed that Day
28( frozen) was statistically significantly different from the com-
posite control at the James stations and York 2. However, the actual
difference at James 1 was not measurable.
Total Dissolved Phosphorus
Frozen concentrations did not quite fall within the range
defined by concentrations from approved treatments (Figures B30-B33) .
At York 2, total dissolved phosphorus concentrations were higher than
at other stations, and differences between treatments seemed more evi-
dent than at other stations.
Results of statistical analyses are shown in Table 10. In
general, the different treatments did not produce significantly dif-
ferent results at the James stations or York 1. At York 2, however,
all treatments except Day 1 were different from the control and dif-
ferent from each other. The composite control was different only from
Day 28(frozen).
The James stations and York 1 data were not normally
distributed; York 2 data were normally distributed and had equal
variances. It might be wise to use the nonparametric tests in the
case of the James stations and York 1. Those tests showed differences
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between Day 1 and other treatments at James 2, between Holding Time
and other treatments at York 1* No differences existed between the
control and the freezing treatments for nonparametric comparisons.
Total Phosphorus
Examination of Figures B34-B37 revealed that total phosphorus
concentrations from frozen samples did not fall completely within the
range defined by the approved treatments*
Results of statistical analyses are shown in Table 11* The
different treatments seemed to produce different results for the total
phosphorus data. At James 1, the control was different from Day 1 and
Day 7(frozen), while at James 2, the control was different from all
other treatments. At York 1, the control was different from both
freezing treatments, and at York 2, the control was slightly different
from Holding Time. The composite control was similar to both freezing
treatments at James 2 and York 1, but was different from both at James
1 and York 2.
The total phosphorus data seemed to be nearly normally dis-
tributed, but had unequal variances. Nonparametric statistics showed
differences between treatments similar to those found in the
parametric statistics.
Suspended Solids
Figures B38-B41 show that frozen sample concentrations did not
generally fall within the range defined by the approved treatments.
Results of statistical analyses are shown in Table 12. The
control differed from Day 1 at James 1 and the York stations; it dif-
fered from Day 7(frozen) at James 2 and York 1; it differed from Day
28(frozen) at York 2. The composite control did not differ from
either freezing treatment at any station.
Suspended solids data appeared to be normally distributed, but
variances were not homogeneous. Nonparametric statistics indicated
that Day 0 differed from Day 1 at James 1, from Day 7(frozen) at James
2 and York 1, and from Day 28(frozen) at York 2.
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Silica
Figures B42-B45 show that frozen sample silica concentrations
were generally not similar to other treatments. At the James sta-
tions, frozen sample concentrations were much lower than other
treatment concentrations. At York 2, the Day 7(frozen) sample con-
centration was much higher than other treatment concentrations.
Results of statistical analyses are shown in Table 13. There
appears to be quite a bit of statistically significant variation be-
tween treatments for the silica data. The control was different from
Day 28(frozen) at all stations, from Day 7(frozen) at all except York
1, and from Holding Time at all except York 2. The composite control
was different from both freezing treatments at all stations. In all
cases i statistically significant differences between means were also
measurable differences.
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Table 5. Results of Statistical Analyses: Nitrite
TEST
TREATMENT James 1
STATION
James 2 York. 1
York 2
Paired
t-test
Day 1
Hold Time
Day 7-frz
Day 28-frz
NS
<.001
<.001
<.001
One-way
Analysis
of
Variance
<.0001
.002
<.001
<.00l
.018
<.0001
NS
<.001
<.001
.005
<.0001
<.001
<.001
<.001
<.001
<.0001
Dunno fit's Day 1
Multiple Hold Time
Comparisons Day 7-frz
Day 28-frz
Scheffe's
Multiple
Contrasts
Day 7-frz
Day 28-frz
**
**#
**
**#
**£
**
**
**#
**
**#
**#
**
**
**
**
**
**#
Kruskal-WalULs
Nonparametric
ANOVA
<.0001
<.0001
<.0001
<.0001
DO Dl HT D7f DO Dl HT D7f DO Dl HT D7f DO Dl HT
Tukeiy's
Multiple
Comparisons
Dunn's
Non-
parametric
Multiple
Comparisons
Day 1
Hold Time * *
D7-frz *# *# *
D28-frz * *# *
Day 1 .
Hold Time * *
D7-frz * * .
D28-frz * * .
* *#
* *# .
*# . * *
*
k
*
*
*#
*
*
*
*
*
*
*
*
Probability of getting test statistic at least as large as
that calculated if null hypothesis true is shown.
* = significant difference between means (alpha=0.05)
** *" significant difference between means (alpha^O.Ol)
, or NS = no significant difference between means (alpha=0.05)
# = difference is not measurable
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Table 6. Results of Statistical Analyses: Nitrate-Nitrite
STATION
TEST
Paired
t-test
One-way
Analysis
of
Variance
Dunne tt's
Multiple
Comparisons
Scheffe's
Multiple
Contrasts
TREATMENT James 1
Day 1 NS
Hold Time NS
Day 7-frz .025
Day 28-frz .003
.0001
Day 1
Hold Time
Day 7-frz
Day 28-frz **
Day 7-frz .
Day 28-frz **
James 2
NS
NS
<.001
NS
.0011
**
*
**
York 1
NS
NS
.005
<.001
.0015
**
.
**
York 2
.001
m
<.001
.002
<.0001
**
m
**
**
**
*
Kruskal-Wallis
Nonparametric
ANOVA
.0003
.0001
.0025
.0001
DO Dl HT D7f DO Dl HT D7f DO Dl HT D7f DO Dl HT D7f
Tukey's Day 1 . . *
Multiple Hold Time .. . . .. mm
Comparisons D7-frz ... *.* ... *.m
D28-frz **** .... ***. *.m.
Dunn's
Non-
parametric
Multiple
Comparisons
Day 1
Hold Time
D7-frz
D28-frz
* *
* *
m m
* .
* .
m
m
Probability of getting test statistic at least as large as that
calculated if null hypothesis true is shown.
* = significant difference between means (alpha=0.05)
** = significant difference between means (alpha=0.01)
or NS - no significant difference between means (alpha=0.05)
m = missing data group
-17-
-------
TEST
Table 7. Results of Statistical Analyses: Ammonia
TREATMENT James 1
STATION
James 2 York 1
York 2
Paired
t-eest
One-way
Analysis
of
Variance
Dunne tt's
Multiple
Day 1
Hold Time
Day 7-frz
Day 28-frz
Day 1
Hold Time
NS
NS
NS
NS
NS
NS
NS
NS
NS
NS
o
.035 NS
NS m
.022 NS
NS <.001
.0003 <.0001
*
. m
Comparisons Day 7-frz
Day 28-frz
Seheffe's
Multiple
Contrasts
Day 7-frz
Day 28-frz
**
**
Kruskal-Wallis
Nonparametric
ANCVA
NS
NS
.0003
<.0001
DO Dl HT D7f DO Dl HT D7f DO Dl HT D7f DO Dl HT D7f
Tukey's Day 1
Multiple Hold Time . . » . * mm
Comparisons D7-frz ... ... .*. . m
D28-frz .* * * m *
Duna's Day 1 . * .
Ho:i- Hold Time .. .* .mm
parametric D7-frz ... ... . * . ..m
Multiple D28-frz .... .... .... * * m
>arisons
Probability of getting test statistic at least as large as that
calculated if null hypothesis true is shown.
* B significant difference between means (alpha=0<>05)
** = significant difference between means (alpha=0.01)
o or NS = no significant difference between means (alpha=0.05)
- = no variance in data group
Q = missing data group
$ = difference is not measurable
-18-
-------
Table 8.- Results of Statistical Analyses: Total Kjeldahl Nitrogen
STATION
TEST TREATMENT James 1 James 2 York 1 York 2
Paired
t-test
One-way
Analysis
of
Variance
Dunnett's
Multiple"
Day 1
Hold Time
Day 7-frz
Day 28-frz
Day 1
Hold Time
.005
.001
.020
NS
<.0001
*
**
.046
NS
NS
NS
NS
*
NS
NS
NS
NS
NS
NS
NS
NS
NS
NS
Comparisons Day 7-frz ** ...
Day 28-frz . ...
Scheffe's Day 7-frz .. ...
Multiple Day 28-frz . ...
Contrasts
Kruskal-Wallis <.0001 NS NS .0118
Nonparametric
ANOVA
DO Dl HT D7f DO Dl HT D7f DO Dl HT D7f DO Dl HT D7f
Tukey's Day 1 *
Multiple Hold Time *
Comparisons D7-frz *
Procedure D28-frz
Dunn's Day 1
Non- Hold Time *
parametric D7-frz *
Multiple D28-frz
Comparisons
Probability of getting test statistic at least as large as that
calculated if null hypothesis true is shown.
* = significant difference between means (alpha=0.05)
** = significant difference between means (alpha=0.01)
. or NS = no significant difference between means (alpha=0.05)
-19-
-------
Table 9. Results of Statistical Analyses: Orthophosphate
TEST
TREATMENT James 1
STATION
James 2 York 1
York 2
Paisei
t-test
One-vay
Analysis of
Varieince
Day 1
Hold Time
Day 7-frz
Day 28-frz
NS
NS
NS
.0001
.020
.002
NS
.014
<.0001
Durmast's Day 1
Multiple Hold Time
Comparisons Day 7-frz
Day 28-frz
ScheEfe's
Multiple
Contrasts
Day 7-frz
Day 28-frz
**#
**#
**
**
.0001
**#
.
.014
.005
NS
<.001
<.0001
**
**
*
**
Knuskal-Wallis
Noaparametric
ANOVA
.0001
<.0001
.0001
<.0001
DO Dl HT D7f DO Dl HT D7f DO Dl HT D7f DO Dl HT D7 £
Tuktiy's Day 1 . *#
Multiple Hold Time . . * . . *# * .
Comparisons D7-frz ... ... .*#. ..*
D28-frz *#*#*#. . * * * .**.-. * * * *
Dunn's
Non-
parametric
Multiple
Comparisons
Day 1
Hold Time
D7-frz
D28-frz
* *
. *
* it
Probability of getting test statistic at least as large as that
calculated if null hypothesis is true is shown.
* = significant difference between means (alpha=0.05)
**: ° significant difference between means (alpha=0.01)
,; or NS ° no significant difference between means (alpha=0.05)
= no variance in data group
# = difference is not measurable
-20-
-------
Table 10. -Results of Statistical Analyses: Total Dissolved Phosphorus
TEST
TREATMENT James 1
STATION
James 2 York 1
York 2
Paired
t-test
One-way
Analysis of
Variance
Day 1
Hold Time
Day 7-frz
Day 28-frz
NS
NS
NS
NS
NS
.003
NS
NS
NS
.0012
NS
NS
NS
NS
NS
NS
<.001
<.001
<.001
<.0001
Dunnett's Day 1
Multiple Hold Time
Comparisons Day 7-frz
Day 28-frz
Scheffe's
Multiple
Contrasts
Day 7-frz
Day 28-frz
**
**
**
**
**
Kruskal-Wallis
Nonparametric
ANOVA
.0025
<.0001
<.0001
<.0001
Tukey's Day 1
Multiple Hold Time
Comparisons D7-frz
D28-frz
DO Dl HT D7f DO Dl HT D7f DO Dl HT D7f DO Dl HT D7f
* . .
* * *
«**
" « TCXrt
* * * *
'A * n«*nn
Dunn's
Non-
parametric
Multiole
Day 1
Hold Time
D7-frz
D28-frz
. * .
*
. *
. *
Comparisons
Probability of getting test statistic at least as large as that
calculated if null hypothesis true is shown.
* ° significant difference between means (alpha=0.05)
** » significant difference between means (alpha=0.01)
. or NS = no significant difference between means (alpha=0.05)
-21-
-------
Table-11. Results of Statistical Analyses: Total Phosphorus
STATION
TEST TREATMENT James 1 James 2 York 1 York 2
Paired
t-test
One-wiiy
Analysis of
Variance
Dunne tt' s
Multiple
Comparisons
Scheffe's
Multiple
Contraufts
Day 1
Hold Time
Day 7-frz
Day 28-frz
Day 1
Hold Time
Day 7-frz
Day 28-frz
Day 7-frz
Day 28-frz
NS
NS
<.001
<.001
.002
**
**
*
<.001
<.001
<.001
<.001
C.0001
**
**
**
**
**
**
NS
.033
<.001
<.001
<.0001
e
*
**
**
**
**
NS
.009
NS
.023
.0001
e
*
»
*
Kruskal-Wallis <.0001 <.0001 <.0001 <.0001
Nonpare,raetric
ANOVA
DO Dl HT D7f DO Dl HT D7f DO Dl HT D7 f DO Dl HT D7f
Tukey's Day 1 * * . .
Multiple Hold Time . * * . . . . *
Comparisons D7-frz * . * * *** ...
D28-frz .... **** **** ..*.
Dunn's Day 1 * * .
Non- Hold Time . * . . . *
parametric D7-frz * . * *.. *** ...
Multiple D28-frz ..... *.*. .**. ..*.
Comparisons
Probability of getting test statistic at least as large as that
calculated if null hypothesis true is shown.
* ° significant difference between means (alpha=0.05)
** = significant difference between means (alpha=0.01)
. or NS = no significant difference between means (alpha=0.05)
-22-
-------
TEST
Table -12. Results of Statistical Analyses: Suspended Solids
TREATMENT James 1
STATION
James 2 York 1
York 2
Paired
t-test
One-way
Analysis -of
Variance
Day 1
Hold Time
Day 7-frz
Day 28-frz
.002
NS
NS
NS
.0078
.021
.006
.006
NS
.0259
NS
NS
NS
NS
.0091
NS
NS
NS
.018
.0057
Dunnett's Day 1
Multiple Hold Time
Comparisons Day 7-frz
Day 28-frz
Scheffe's
Multiple
Contrasts
Day 7-frz
Day 28-frz
Kruskal-Wallis
Nonparametrie
ANOVA
.0037
**
.0128
*
.
**
.0028
**
**
.0069
DO Dl HT D7f DO Dl HT D7 f DO Dl HT D7 f DO Dl HT D7 f
Tukey's Day 1 *
Multiple Hold Time .
Comparisons D7-frz .
D28-frz
Dunn's
Non-
parametric
Multiple
Comparisons
Day 1 *
Hold Time .
D7-frz
D28-frz
Probability of getting test statistic at least as large as that
calculated if null hypothesis true is shown.
* = significant difference between means (alpha=0.05)
** = significant difference between means (alpha=0.01)
. or NS = no significant difference between means (alpha=0.05)
-23-
-------
Table 13. Results of Statistical Analyses: Silica
TEST
TREATMENT James 1
STATION
James 2 York 1
York 2
Paired
t-test
One-way
Analysis of
Variance
Day 1
Hold Time
Day 7-frz
Day 28-frz
<.001
<.001
<.001
<.001
<.0001
NS
<.001
<.001
<.001
<.0001
NS
.008
.018
<.001
<.0001
NS
NS
<.001
<.001
<.0001
Dunnett's Day 1
Multiple Hold Time
Comparisons Day 7-frz
**
**
**
Scheffe's
Multiple
Contrasts
Day 28-frz **
Day 7-frz **
Day 28-frz **
**
**
**
**
**
**
.
**
**
**
**
**
**
**
Kruskul-Wallis
Nonparametrie
ANOVA
<.0001
<.0001
<.0001
<.0001
DO Dl HT D7f DO Dl HT D7f DO Dl HT D7f DO Dl HT D7f
Tukey's Day 1 * ; .
Multiple Hold Time * * * * * * . .
Comparisons D7-frz
D28-frz
* * *
* * * *
* * *
* * * *
. *
* *
* * *'
* * * *
Dunn's
Non-
parametric
Multiple
Comparisons.
Day 1
Hold Time
D7-frz
D28-frz
. *
* * .
* * *
* * *
* * *
Probability of getting test statistic at least as large as that
calculated if null hypothesis true is shown.
* = significant difference between means (alpha=0.05)
** = significant difference between means (alpha=0.01)
. or NS = no significant difference between means (alpha=0.05)
-24-
-------
DISCUSSION
The statistical parameters which are of importance are the mean
and the variance of the various populations sampled (each combination
of station, treatment, and water quality constituent). Power statis-
tics were used in the design of this study to choose the number of
replicates that would allow detection of a difference between sample
means that is equal to or greater than the standard deviation for the
procedure with a 95% confidence level for avoiding type I errors
(alpha = 0.05) and a 90% confidence level for avoiding type II errors
(beta =» 0.10). Stated somewhat differently, the number of replica-
tions was chosen to be large so that the estimates of the statistical
parameters would be good and small differences between sample means
could be detected with a relatively large degree of certainty. In
general, this objective has been met.
It is one thing to be able to detect small differences during
special studies and quite another to be able to make similar distinc-
tions during the routine operations of a laboratory. For that reason,
it seems appropriate to compare the differences between sample means
for the various treatments with the variations typically observed in
routine lab operations. Therefore, the differences between the means
for each treatment and the mean for Day 0 have been listed in Table 14
for each water constituent. Also included in the table is the lowest
standard used in each analysis, the number of replicates, and the con-
trol limit for daily laboratory quality control for precision in each
analysis. The control limit is determined from 20 duplicates for a
particular analysis. The limit is calculated by using an EPA recom-
mended method of multiplying the mean o'f the differences in the
duplicates by 3.27. Any duplicates in daily measurements that are
greater in difference than this number indicate the procedure is out
of control and the samples must be rerun after the problem has been
corrected. The control limit is an in-house measure of daily
variability within a procedure. It is not a measure of the
variability in the same procedure performed at another time. This
time variability is caused by recalibratibn of standards, different
-25-
-------
baselines or blanks, different reagents, and sometimes different
technicians.
The !3ata Sets
A data point was omitted only when it was known that it was in
error or if the replicate or sample were lost. There has been no at-
tempt: to remove possible outliers. The raw data is listed in Appendix
A. 15 a low are presented, on an analysis by analysis basis, comments
about the raw data. It is to be noted from Table 14 that in most
case:) the difference in mean of each treatment from the mean for Day 0
is loss than the control limits for precision in the laboratory.
Nitrite - The nitrite data set is complete. Reference to Table
1 shows that all four stations were spiked with N02 to insure values
abovt: the lowest standard. The differences between the Day 0 mean and
each of the freezing treatment means for stations James 1, James 2,
and York 1 are roughly equal to the control limit for precision. The
mean differences between Day 0 mean and other treatment means for York
2 were several .times the control limit. This was the station with the
highest spike value.
Nitrate-Nitrite - The sample for York 2 station for holding
time for this analysis was not preserved with H2S04. This was dis-
covered when the samples were being brought to a pH of 7 to be run.
The samples were run out of curiosity but the values were about half
the value of Day 0.
A replicate was lost in the James 2/Day 1 set* This set had read
off scale and had to be diluted. One of the replicates had not been
correctly diluted.
All stations included the spiking done with nitrite. All dif-
ferences between treatment means and day 0 mean were within the
control limits for precision except James I/Day 28( frozen) and James
2/Dey 7(frozen).
-26-
-------
TABLE 14
DIFFERENCE IN MEAN OF EACH TREATMENT
FROM MEAN FOR DAY 0
(Concentrations in mg/l)
STATION
NITRITE Jl J2 Yl Y2
Replicates = 13
Lowest Standard = 0.005
Upper Control Limit = 0.001
DAY 1 0.0001 0.0007 0.0002 -0.0020
HT 0.0022 6.0017 0.0017 0.0099
FREEZE 7 0.0009 0.0017 0.0010 0.0042
FREEZE 28 0.0011 0.0005 0.0007 0.0034
NITRATE - NITRITE
Replicates - 13
Lowest Standard = 0.010
Upper Control Limit = 0.007
DAY 1 0.0002
HT -0.0008
FREEZE 7 -0.0021
FREEZE 28 0.0084
0.0011
-0.0039
0.0105
0 .0020
0.0005
0.0008
0.0018
0 .0044
0.0028
_.
0.0051
. 0.0040
AMMONIA
Replicates = 13
Lowest Standard = 0.010
Upper Control Limit = 0.007
DAY 1 0.0019 -0.0011 0.0029
HT 0.0015 -0.0014 -0.0013
FREEZE 7 0.0015 -0.0007 -0.0026
FREEZE 28 0.0001 -0.0010 0.0012
0.0008
0.0020
0.0129
TOTAL KJELDAHL NITROGEN
Replicates = 8
Lowest Standard = 0.025
Upper Control Limit = 0.050
DAY 1
HT
FREEZE 7
FREEZE 28
-0.0456
-0.0876
-0.0796
-0.0125
0.0448
0.0086
0.0172
0.0298
0.0286
0.0262
0.0218
-0.0033
-0.0424
-0.0323
0.0244
0.0202
-27-
-------
TABLE 14
(Continued)
DIFFERENCE IN MEAN OF EACH TREATMENT
FROM MEAN FOR DAY 0
(Concentration in mg/1)
STATION
SILICA Jl J2 Yl Y2
Replicates = 13
Lowest Standard = 0.056
Upper Control Limit = 0.010
DAY 1 -0.0137 0.0030 0.0015 -0.0015
HT 0.0092 0.0126 -0.0037 -0.0006
FREEZE 7 0.0142 0.0552 -0.0024 -0.1275
FREEZE 28 0.0697 0.1776 -0.0058 -0.0229
TOTAL SUSPENDED SOLIDS
Replicates = 10
Lower Limit = 4
Upper Control Limit = 12
DAY 1
HT
FREEZE 7
FREEZE 28
ORTHOPHOSPHATE
Replicates = 13
Lowest Standard - 0.010
Upper Control Limit = 0.003
DAY 1 0.0004
HT 0.0000
FREEZE 7 -0.0001
FREEZE 28 -0.0006
TOTAL DISSOLVED PHOSPHORUS
Replicates =13
Lowest Standard » 0.010
Upper Control Limit
DAY 1
HT
FREEZE 7
FREEZE 28
TOTAL PHOSPHORUS
Replicates = 13
Lowest Standard - 0.010
Upper Control Limit = 0.005
DAY 1 0.0035
HT 0.0002
FREEZE 7 0.0037
FREEZE 28 0.0022
2.2
1.0
1.2
-0.6
2.8
2.7
3.9
1.3
2.2
0.4
2.8
1.3
1.7
0.7
0.8
1.9
0.0008
0.0015
0.0008
-0.0008
0.0008
-0.0002
0.0002
0 .0000
-0.0008
-0.0017
0.0002
0.0024
0.005
-0.0004
-0.0013
-0.0040
-0 .0003
0.0029
-0.0013
-0.0004
0.0012
0.0008
-0.0015
0.0006
0.0004
0.0005
-0.0048
-0.0027
0.0052
0.0258
0.0224
0.0235
0 .0333
0.0010
0.0011
-0.0070
-0 .0037
0.0016
-0.0020
0.0000
0.0019
-28-
-------
Ammonia - The sample for York 2 station for holding time was
the same as the nitrate-nitrite and suffered the same problem; no
H2S04 was added to the sample for preservative.
James I/Day 0, is missing a data point because one of the repli-
cates was not analysed.
The two York River stations were spiked in order to read above
the lowest standard. The data for the James stations were much lower
in value than expected. This data was so low in ammonia as to be of
doubtful statistical value. All differences between treatment means
and Day 0 mean were within the control limit for precision except the
York 2/Day 28(frozen) sample.
Total Kjeldahl Hitrogen - The one missing data point in the
James I/frozen 7 days data set was due to a broken flask. The data
reflect the ammonia spikes in the York River samples. One data point
in the York 2/Day one set is questionable (0.801), but there was no
known reason for this anomalous value. All differences between treat-
ment means and Day 0 mean were within the control limit for precision
except James I/holding time and James I/Day 7.
Silica - Silica was not spiked and the values for York 1 were
below the lowest standard. The data sets are all complete. The data
in York 2/Day 7(frozen), is more than twice the value of the other
treatments. A possible cause is that insufficient time after thawing
was allowed, but that is uncertain. Sample means for James I/Day
28(frozen), James 2/Day 28(frozen), and York 2/Day 7(frozen) have a
greater difference from Day 0 than the control limit for precision.
Total Suspended Solids - Except for the James 2 station, the
total suspended solid concentrations were low. The data for two
replicates were lost due to filters being torn after filtering. None
of the treatment means showed a difference from Day 0 mean greater
than the control limit for precision.
Orthophosphate - This data set is complete. Low values were
expected in the York River and these samples were spiked. The values
-29-
-------
for York 1 were still below the lowest standard. It has been observed
that when adding phosphate to a large container of water, the amount
measured is always less than the amount originally added. This could
be due to biological activity or adsorption onto the walls of the
container. This was not taken into account in determining the amount
of phosphate added* None of the treatment means showed a difference
from Day 0 mean greater than the control limit for precision.
Total Dissolved Phosphorus - This data set is complete. The
York River values reflect the spiking of the samples for
orthophosphate. None of the treatment means showed a difference from
Day 0 mean greater than the control limit for precision.
Total P hop horns - This data set is complete. The York River
values reflect the spiking of the samples for orthophosphate. The
value for James 2/Day 0* is about 20% higher than the other
treatments. It is possible that the container was contaminated, but
this is uncertain. All other treatment means have a difference from
Day 0 mean less than the control limit for precision.
-30-
-------
CONCLUSIONS
This study was designed with power statistics so that the number
of replicates (13) was sufficient to detect small differences between
treatments* The volume of water required and the equipment limited
the replicates in TSS and TKN analyses (10 and 8 respectively).
The difference between treatments was measurable and statisti-
cally significant in a number of cases. The difference between the
immediate analysis and the frozen samples was generally less than the
daily control limits in the laboratory for precision. Therefore* in
our opinion, the difference was not a practical one.
An additional source of variability was created by performing
the analyses on different days. Performing an analysis at another
time introduces new calibration standards, possible new reagents, new
baselines or blanks, and sometimes different technicians. This
variability has not been quantified, but its magnitude is expected to
be similar to that of interlaboratory variability.
Except for silica, freezing had ho practical effect on the con-
centration levels measured in the laboratory. Freezing is known to
cause difficulties for silica measurements; for 3 out of 4 stations in
this study the difference between treatment means was greater than the
control limit for precision. It is suggested that samples to be
analysed for this constituent not be frozen as a method of preserva-
tion, particularly in estuaries and fresh water.
Although the differences in means between immediate analysis and
either of the freezing treatments was statistically significant, that
difference generally was less than the laboratory control limit for
precision. The difference between means may have been greater than
the control limit for one out of the four samples, but this was also'
true for the EPA - recommended treatments.
The procedure for total suspended solids requires a large volume
of water. When a large number of replicates are being processed, the
volume required is incredible. The results of this study suggest that
freezing does not affect the measurements. However, given the 7 day
holding time, there usually is no need to freeze these samples.
-31-
-------
REFERENCES
MacDonald, R.W. and F.A. McLaughlin (1982) "The effect of storage by
freezing on dissolved inorganic phosphate, nitrate and reactive
silicate for samples from coastal and estuarine waters"* Water
Research 16:95-104.
Nie, Norman H. (1975) SPSS: Statistical Package for the Social
Sciences. 2nd ed. 675pp. McGraw-Hill Book Co. NY.
SPSS Inc. (1986) SPSSX User's Guide. 2nd ed. 988 pp. McGraw-Hill Book
Co. NY.
Standard Methods for the Examination of Water and Wastewater (1975)
14th ed. 1193pp. American Public Health Association.
Washington,DC.
Strickland, J.D.H. and T.R. Parsons (1972) A Practical Handbook of
Seawater Analysis. Fisheries Research Board of Canada. Bulletin
167.
Technicon Industrial Method No. 186-72W, Silicates in Water and
Seawater, (1973). Technicon Instruments Corp. Ardsley, NY.
U.S. Environmental Protection Agency. (1979) Methods for" Chemical
Analysis of Water and Wastes. National Environmental Research
Center. Cincinnati, OH.
Zar, Jerrold H. (1984) Biostatistical Analysis. 2nd ed. 718pp.
Prentice-Hall, Inc. Englewood Cliffs,. NJ.
-32-
-------
APPENDICES
A. Raw Data
B. Graphical Summaries of Raw Data
C. Results of Statistical Analyses
D. Laboratory Methods
APPENDIX A
Raw Data
CONTENTS:
Table Al. Nitrite Data for Freezing Study
Table A2. Nitrate-Nitrite Data for Freezing Study
Table A3. Ammonia Data for. Freezing Study
Table A4. Total Kjeldahl Nitrogen Data for Freezing Study
Table A5. Silica Data for Freezing Study
table A6. Total Suspended Solids Data for Freezing Study
Table A7. Orthophosphate Data for Freezing Study
Table A8. Total Dissolved Phosphorus Data for Freezing Study
Table A9. Total Phosphorus Data for Freezing Study
-------
TABLE A.I NITRITE DATA FOR FREEZING STUDY
(concentration in mg/1)
STATION
'JAMES 1'
MIN
MAX
MEAN
STDEV
'JAMES 2'
MIN
MAX
MEAN
STDEV
DAY ZERO
.010
.010
.010
.010
.010
.010
.010
.010
.010
.010
.010
.010
.010
.010
.010
.010
.000
.007
.007
.007
.008
.008
.008
.008
.007
.007
.007
.008
.007
.008
.007
.008
.007
.001
DAY ONE
.010
.010
.009
.010
.010
.010
.010
.010
.010
.010
.010
.010
.010
.009
^.010
'.010
.000
.006
.007
.006
.006
.007
.007
.007
.007
.007
.007
.007
.007
.007
.006
.007
.007
.000
HOLDING
TIME
.008
.007
.007
.008
.008
.008
.008
.008
.008
.008
.008
.008
.008
.007
.008
.008
..000
.006
.005
.006
.006
.006
.006
.006
.005
.006
.006
.006
.006
.006
.005
.006
.006
.000
FROZEN
7 DAYS
.009
.009
.009
.009
.009
.009
.009
.009
.009
.009
.009
.009
.009
.009
.009
.009
.000
.005
.005
.005
.006
.006
.006
.006
.006
.006
.006
.006
.006
.006
.005
.006
.006
.000
FROZEN
28 DAYS
.009
.009
.009
.009
.009
.009
.009
.009
.009
.009
.009
.008
.009
.008
.009
.009
.000
.007
.007
.007
.007
.007
.007
.007
.007
.007
.007
.007
.007
.007
.007
.007
.007
.000
-------
TABLE A.I NITRITE DATA FOR FREEZING STUDY
(continued-) (concentration in mg/1)
STATION DAY ZERO DAY ONE HOLDING FROZEN FROZEN
TIME 7 DAYS 28 DAYS
"YORK 1'
HIN
11AX
iJTDEV
-YORK 2'
.011
.011
.011
.011
.011
.011
.011
.011
.011
.011
.011
.011
.011
.011
.011
.011
.000
.011
.010
.011
.010
.011
.011
.011
.011
.011
.011
.011
.011
.011
.010
.011
.011
..000
.009
.009
.009
.009
.009
.009
.009
.009
.009
.010
.010
.010
.010
.009
.010
.009
.000
.010
.010
.010
.010
.010
.010
.010
.010
.010
.010
.010
.010
.010
.010
.010
.010
.000
.010
.010
.010
.010
.010
.010
.010
.010
.011
.011
.011
.010
.011
.010
.011
.010
.000
11IN
I1AX
MEAN
IJTDEV
.054
.054
.054
.055
.055
.055
.054
.054
.055
.055
.054
.054
.055
.054
.055
.054
.001
.055
.056
.058
.056
.056
.056
.056
.058
.057
.058
.056
.056
.056
.055
.058
.056
.001
.044
.044
.044
.045
.044
.044
.044
.045
.045
.045
.046
.045
.045
.044
.046
.045
.001
.050
.050
.0'51
.050
.050
.050
.051
.050
.051
.050
.050
.050
.051
.050
.051
.050
.000
.051
.051
.051
.051
.052
.051
.051
.051
.051
.051
.051
.051
.051
.051
.052
.051
.000
-------
TABLE A.2 NITRITE-NITRATE DATA FOR FREEZING STUDY
(concentration in mg/1)
STATION
'JAMES 1'
MIN
MAX
MEAN
STDEV
'JAMES 2'
MIN
MAX
MEAN
STDEV
DAY ZERO
.177
.179
.176
.176
.181
.182
.184
.177
.182
.181
.177
.181
.182
.176
.184
.180
.003
. .265
.269
.266
.264
.263
.263
.261
.276
.276
.274
.267
.272
.272
.261
.276
.268
.005
DAY ONE
.174
.181
.178
.182
.180
.179
.179
.179
.179
.179
.182
.180
.180
.174
.182
.179
.002
.261
.270
.271
.268
.263
.268
.268
.268
.262
.270
.266
.268
*~~
.261
.271
.267
.003
HOLDING
TIME
.196
.162
.166
.183
.184
.180
.180
.182
.184
.184
.180
.182
.182
.162
.196
.180
.008
.249
.256
.270
.274
.274
.274
.274
.305
.277
.273
.269
.269
.275
.249
.305
.272
.013
FROZEN
7 DAYS
.178
.179
.183
.183
.183
.181
.184
.183
.181
.182
.181
.181
.183
.178
.184
.182
.002
.251
.257
.261
.263
.257
.258
.256
.258
.258
.258
.258
.261
.256
.251
.263
.258
.003
FROZEN
28 DAYS
.178
.180
.171
.178
.171
.166
.185
.173
.166
.163
.156
.164
.174
.156
.185
.171
.008
.242
.286
.273
.261
.266
.272
.281
.274
.267
.254
.266
.260
.260
.242
.286
.266
.012
-------
TJ\BLE A.2 NITRITE-NITRATE DATA FOR FREEZING STUDY
(continued) (concentration in mg/1)
STATION
'YORK 1'
:MEAN
STDEV
'YORK 2'
WIN
MAX
MEAN
STDEV
DAY ZERO
.108
.113
.110
.110
.110
.109
.110
.109
.111
.109
.107
.110
.109
.107
.113
.110
.001
.073
.076
.079
.080
.079
.081
.082
.082
.080
.081
.082
.080
.076
.073
.082
.079
.003
DAY ONE
.102
.107
.108
.110
.111
.111
.110
.108
.111
.111
.110
.108
.111
.102
.111
.109
.003
.074
.074
.076
.076
.080
.077
.077
.077
.077
.077
.076
.077
.076
.074
.080
.076
.002
HOLDING
TIME
.108
.102
.105
.109
.104
.108
.115
.118
.111
.111
.105
.112
.106
.102
.118
.109
.005
"
»*»
~-
~" ""
""""
~
^
~
~~~
~~"
~~
""
.
M
M
M
H
FROZEN
7 DAYS
.104
.108
.108
.107
.108
.109
.110
.106
.108
.109
.108
.108
.109
.104
.110
' .108
.002
.074
.075
.075
.073
.074
.074
.074
.074
.074
.074
.074
.074
.075
.073
.075
.074
.001
FROZEN
28 DAYS
.102
.102
.104
.105
.110
.106
.104
.108
.105
.102
.105
.111
.103
.102
.111
.105
.003
.070
.072
.081
.079
.079
.072
.076
.079
.075
.071
.073
.077
.075
.070
.081
.075
.004
-------
TABLE A.3 AMMONIA DATA FOR FREEZING STUDY
(concentration in mg/1)
STATION DAY ZERO DAY ONE HOLDING FROZEN FROZEN
TIME 7 DAYS 28 DAYS
'JAMES 1'
MIN
MAX
MEAN
STDEV
'JAMES 2'
.002
.001
.002
.002
.003
.015
~
.002
.005
.005
.008
.007
.009
.001
.015
.005
.004
.001
.003
.003
.004
.005
.008
.003
.004
.001
.003
. .003
.000
.003
.000
.008
. .003
.002
.005
.005
.005
.007
.007
.002
.002
.002
.002
.000
.002
.003
.003
.000
.007
.003
.002
.009
.001
.007
.004
.005
.006
.004
.003
.001
.000
.000 .
.000
.007
.000
.009
.004
.003
.006
.002
.002
.000
.003
.005
.004
.007
.006
.004
.009
.009
.007
.000
.009
.005
.003
MIN
MAX
MEAN
STDEV
.002
.001
.001
.002
.001
.002
.000
.002
.000
.000
.001
.002
.006
.000
.006
.002
.002
.002
.002
.000
.003
.005
.002
.001
.002
.004
.007
.002
.002
.002
.000
.007
.003
.002
.010
.008
.004
.003
.003
.000
.003
.003
.002
.000
.000
.002
.000
.000
.010
.003
.003
.007
.004
.002
.002
.004
.002
.002
.001
.001
.001
.001
.001
.001
.001
.007
.002
.002
.000
.003
.006
.002
.000
.004
.001
.005
.003
.003
.003
.003
.000
.000
.006
.003
.002
-------
TABLE A.3 AMMONIA DATA FOR FREEZING STUDY
(continued) (concentration in mg/1)
STATION DAY ZERO DAY ONE HOLDING FROZEN FROZEN
TIME 7 DAYS 28 DAYS
'YORK 1'
.014
.014
.014
.012
.012
.012
.012
.012
.014
.014
.014
.014
.014
.012
.014
.013
.001
.008
.008
.008
.009
.011
.010
.010
.021
t
.009
.010
.010
.010
.008
.021
.010
.003
.022
.018
.018
.020
.015
.014
.013
.013
.011
.010
.015
.012
.008
.008
.022
.015
.004
.021
.017
.017
.020
.021
.016
.012
.012
.017
.013
.012
.014
.014
.012
.021
.016
.003
.009
.010
.009
.010
.013
.013
.013
.013
.014
.014
.009
.015
.014
.009
.015
.012
.002
MIN
MAX
MEAN
STDEV
'YORK 2'
.070 .079 . .085 .068
.072 .075 . .079 .064
.075 .080 . .075 .065
.077 .079 . .079 .067
.080 .081 . .079 .069
.083 .080 . .077 .065
.084 .081 . .080 .068
.100 .081 . .080 .067
.084 .080 . .076 .069
.087 .084 . .079 .068
.081 .080 . .079 .067
.080 .081 . .079 .071
.079 .080 . .079 .076
MIN .070 .075 M .075 .064
MAX .100 .084 M .085 .076
MEAN .081 .080 M .079 .068
STDEV .008 .002 M .002 .003
-------
TABLE A.4 TOTAL KJELDAHL NITROGEN DATA FOR FREEZING STUDY
(concentration in mg/1)
STATION DAY ZERO DAY ONE HOLDING FROZEN FROZEN
TIME 7 DAYS 28 DAYS
'JAMES 1*
.375 - .415 .402 .389 .376
MIN
MAX
MEAN
STDEV
.257
.340
.367
.360
.370
.365
.378
.257
.378
.351
.040
.359
.421
.405
.405
.405
.390
.377
.359
.421
.397
.021
.437
.444
.411
, .446
.462
.445
.466
.402
.466
.439
.022
.451
.400
.415
.387
.434
.515
""
.387
.515
.427
.045
.380
.368
.357
.336
.380
.346
.369
.336
.380
.364
.016
'JAMES 2'
MIN
MAX
MEAN
STDEV
.396
.365
.516
.438
.416
.460
.446
.441
.365
.516
.435
.045
.422
.277
.440
.448
.388
.327
.418
.399
.277
.448
.390
.059
.405
.449
.483
.419
.391
.423
.412
.427
.391
.483
.426
.029
.417
.475
.453
.402
.389
.396
.399
.409
.389
.475
.417
.030
.399
.429
.432
.424
.371
.392
.399
.393
.371
.432
.405
.021
-------
TABLE A.4 TOTAL KJELDAHL NITROGEN DATA FOR FREEZING STUDY
(continued) (concentration in mg/1)
STATION DAY ZERO DAY ONE HOLDING FROZEN FROZEN
TIME 7 DAYS 28 DAYS
"YOHK 1
MIN
14AX
MAN
3TDEV
'YORK 2'
.493
.408
.606
.450
.450
.432
.435
.436
.408
.606
.464
.062
.524
.383
.432
.420
.411 .
.443
.438
.430
.383
.524
.435
.041
.422
.464
.433
.416
.421
.488
.416
.440
.416
.488
.437
.026
.407
.509
.427
.440
.424
.431
.462
.435
.407
.509
.442
.031
.459
.479
.475
.464
.455
.473
.455
.476
.455
.479
.467
.010
MIN
MAX
MEAN
STDEV
.521
.425
.520
.533
.550
.571
.574
.567
.425
.574
.533
.049
.530
.423
.534
.556
.635
.801
.564
.557
.423
.801
.575
.108
.542
.574
.572
.584
.548
.558
.574
.567
.542
.584
.565
.014
.465
.507
.487
.485
.500
.542
.552
.528
.465
.552
.508
.030
.539
.562
.554
.544
.545
.543
.558
.578
.539
.578
.553
.013
-------
TABLE A.5
SILICA DATA FOR FREEZING STUDY
(concentration in mg/1)
STATION
'JAMES 1'
MIN
MAX
MEAN
STDEV
'JAMES 2'
- ".
MIN
MAX
MEAN
STDEV
DAY ZERO
.654
.666
.659
.666
.659
.666
.666
.659
.659
.659
.666
.659
.654
.654
.666
.661
.005
1.272
1.277
1.277
1.272
1.277
1.283
1.283
1.283
1.274
1.272
1.272
1.267
1.267
1.267
1.283
1.275
.006
DAY ONE
.671
.671
.673
.673
.678
.678
.678
.678
.678
.673
.673
.673
.673
.671
.678
.675
.003
1.271
1.278
1.271
1.271
1.271
1.271
1.278
1.271
1.271
1.271
1.271
1.271
1.271
1.271
1.278
1.272
.003
HOLDING
TIME
.650
.653
.650
.653
.648
.653
.653
.653
.650
.653
.653
.650
.653
.648
.653
.652
.002
1.247
1.259
1.264
1.267
1.272
1.259
1.259
1.267
1.267
1.267
1.267
1.259
1.259
1.247
1.272
1.263
.006
FROZEN
7 DAYS
.645
.645
.645
.645
.647
.645
.645
.647
.649
.645
.651
.649
.649
.645
.651
.647
.002
1.205
1.210
1.215
1.235
1.221
1.227
1.232
1.218
1.218
1.218
1.221
1.218
1.221
1.205
1.235
1.220
.008
FROZEN
28 DAYS
.588
.590
.594
.594
.594
.594
.588
.594
.594
.594
.588
.585
.588
.585
.594
.591
.003
1.079
1.096
1.091
1.091
1.096
1.091
1.105
1.096
1.108
1.101
1.113
1.101
1.100
1.079
1.113
1.098
.009
-------
TABLE A.5 SILICA DATA FOR FREEZING STUDY
(continued)- (concentration in mg/1)
STATION DAY ZERO DAY ONE HOLDING FROZEN FROZEN
TIME 7 DAYS 28 DAYS
"YOIK 1*
MIN
MAX
MEAN
STDEV
"YOFK 2'
.035
.035
.035
.035
.035
.035
.035
.035
.035
.035
.042
.028
.028
.028
.042
.034
.003
.036
.031
.026
.036
.033
.029
.024
.036
.031
.029
.040
.040
.038
.024
.040
.033
.005
.038
.042
.038
.038
.038
.036
.038 -
.042
.038
.036
.036
.038
.038
.036
.042
.038
.002
.038
.038
.038
.038
.038
.038
.038
.038
.038
.038
.034
.033
.033
.033
.038
.037
.002
.041
.046
.043
.041
.039
.039
.039
.039
.039
.041
.039
.039
.039
.039
.046
.040
.002
MIN
MAX
MEAN
STDEV
.067
.067
.067
.067
.067
.060
.060
.060
.067
.060
.060
.060
.060
.060
.067
.063
.004
.064
.087
.064
.059
.059
.064
.064
.061
.059
.068
.064
.064
.064
.059
.087
.065
.007
.063
.063
.063
.063
.063
.063
.067
.063
.070
.063
.063
.063
.063
.063
.070
.064
.002
.189
.185
.189
.194
.194
.189
.194
.189
.189
.189
.190
.199
.189
.185
.199
.191
.004
.087
.084
.082
.082
.087
.093
.080
.087
.093
.084
.080
.087
.093
.080
.093
.086
.005
-------
TABLE A.6
TOTAL SUSPENDED SOLIDS DATA FOR FREEZING STUDY
(concentration in mg/1)
STATION
'JAMES 1
MIN
MAX
MEAN
STDEV
'JAMES 2
DAY ZERO DAY ONE
MIN
MAX
MEAN
STDEV
15.000
15.000
15.000
17.000
17.000
17.000
13.000
15.000
16.000
17.000
13.000
17.000
15.700
1.337
37.000
38.000
39.000
39.000
37.000
37.000
38.000
37.000
38.000
39.000
37.000
39.000
37.900
.876
14.000
15.000
13.000
13.000
13.000
13 .000
13.000
13.000
14.000
14.000
13.000
15.000
13.500
.707
34.000
28.000
36.000
37.000
37.000
38.000
33.000
35.000
34.000
39.000
28.000
39.000
35.100
3.143
HOLDING
TIME
14.000
14.000
17.000
14.000
15.000
15.000
14.000
15.000
15.000
14.000
14.000
17.000
14.700
.949
36.000
31 .000
38.000
36.000
36.000
30.000
37.000
36.000
35.000
37.000
30.000
38.000
35.200
2.616
FROZEN
7 DAYS
16.000
15.000
14.000
14.000
13.000
15.000
14.000
15.000
15.000
14.000
13.000
16.000
14.500
.850
32.000
31.000
30.000
35.000
30.000
39.000
35.000
38.000
35.000
35.000
30.000
39.000
34.000
3.162
FROZEN
28 DAYS
16.000
14.000
14.000
14.000
18.000
18.000
19.000
21.000
11.000
"""
11.000
21.000
16.111
3.140
33.000
34.000
37.000
39.000
37.000
40.000
31.000
41 .000
37.000
37.000
31.000
41 .000
36.600
3.134
-------
TABLE A.6
(continued)
TOTAL SUSPENDED SOLIDS DATA FOR FREEZING STUDY
(concentration in mg/1)
STATION
'YORK I"
MIN
MAX
MEAN
STDEV
'YORK 2'
MIN
MAX
MEAN
STDEV
DAY ZERO
6.000
7.000
6.000
5.000
7.000
16.000
7.000
7.000
10.000
8.000
5.000
16.000
7.900
3.143
17.000
17.000
20 .000
22.000
20 .000
19.000
19.000
21 .000
19.000
19.000
17 .000
22 .000
19.300
1.567
DAY ONE
6.000
6.000
6.000
6.000
7.000
5.000
5.000
5.000
7.000
4.000
4.000
7.000
5.700
.949
19.000
18.000
18.000
16.000
17.000
18.000
19.000
17.000
18.000
16.000
16.000
19.000
17.600
1.075
HOLDING
TIME
6.000
8.000
10.000
10.000
7.000
7.000
6.000
7.000
6.000
8.000
6.000
10.000
7.500
1.509
20.000
19.000
19.000
21 .000
19.000
18.000
17.000
18.000
18.000
17.000
17.000
21 .000
18.600
1.265
FROZEN
7 DAYS
7.000
6.000
5.000
6.000
5.000
2.000
4.000
6.000
6 .000
4.000
2.000
7.000
5.100
1.449
18.000
19.000
19.000
18.000
19.000
19.000
19.000
19.000
19.000
16.000
16.000
19.000
18.500
.972
FROZEN
28 DAYS
6.000
8.000
7.000
9.000
7.000
5.000
6.000
8.000
3.000
7.000
3.000
9.000
6.600
1.713
17.000
18.000
18.000
18.000
17.000
18.000
18.000
16.000
17.000
""~
16.000
18.000
17.444
.726
-------
TABLE A.7 ORTHOPHOSPHATE DATA FOR FREEZING STUDY
(concentration in mg/1)
STATION
'JAMES 1'
MIN
MAX
MEAN
STDEV
'JAMES 2'
MIN
MAX
MEAN
STDEV
DAY ZERO
.011
.011
.011
.011
.011
.011
.010
.011
.011
.011
.011
.011
. .011 .
.010
.011
.011
.000
.013
.016
.013
.013
.013
.013
.013
.013
.015
.015
.015
.015
.015
.013
.016
.014
.001
DAY ONE
.009
.011
.011
.009
.011
.011
.011
.011
.011
.009
.011
.011
.011
.009
.011
.011
.001
.013
.013
.013
.013
.013
.013
.013
.013
.013
.015
.013
.013
.013
.013
.015
.013
.001
HOLDING
TIME
.011
.011
.011
.011
.010
.011
.011
.011
.011
.011
.011
.011
.011
.010
.011
.011
.000
.013
.013
.013
.013
.011
.013
.011
.013
.011
.013
.013
.013
.013
.011
.013
.013
.001
FROZEN
7 DAYS
.011
.011
.011
.011
.011
.011
.011
.011
.011
.011
.011
.011
.011
.011
.011
.011
.000
.014
.012
.014
.014
.012
.012
.014
.014
.014
.012
.012
.014
.014
.012
.014
.013
.001
FROZEN
28 DAYS
.012
.012
.012
.012
.012
.012
.011
.011
.012
.011
.011
.011
.011
.011
.012
.012
.001
.015
.015
.015
.014
.015
.015
.014
.015
.015
.015
.015
.015
.015
.014
.015
.015
.000
-------
TABLE A.7 ORTHOPHOSPHATE DATA FOR FREEZING STUDY
(continued) (concentration in mg/1)
STATION DAY ZERO DAY ONE HOLDING FROZEN FROZEN
TIME 7 DAYS 28 DAYS
"YORK 1'
MIN
MAX
MEAN
STDEV
'YORK 2'
.005
.005
.005
.005
.005
.005
.005
.005
.005
.005
.005
.005
.005
.005
.005
.005
.000-
.004
.004
.004
.004
.004
.004
.004
.004
.006
.004
.004
.004
.004
.004
.006
.004
.001
.005
.005
.005
.005
.005
.006
.005
.005
.006
.005
.005
.005
.006
.005
.006
.005
.000
.004
.004
.006
.004
.004
.004
.004
.004
.006
.006
.006
.006
.004
.004
.006
.005
.001
.005
.005
.005
.005
.005
.005
.005
.005
.005
.005
.005
.005
.005
.005
.005
.005
.000
MIN
MAX
MEAN
STDEV
.076
.076
.078
.078
.078
.076
.076
.078
.078
.078
.078
.078
.078
.076
.078
.077
.001
.078
.078
.078
.078
.078
.078
.079
.078
.078
.078
.079
.079
.078
.078
.079
.078
.000
.079
.079
.079
.079
.080
.080
.080
.079
.080
.080
.075
.079
.079
.075
.080
.079
.001
.076
.076
.076
.078
.078
.076
.078
.076
.078
.078
.078
.078
.078
.076
.078
.077
.001
.071
.075
.075
.073
.076
.075
.076
.076
.078
.075
.073
.076
.076
.071
.078
.075
.002
-------
TABLE A.8 TOTAL DISSOLVED PHOSPHORUS DATA FOR FREEZING STUDY
(concentration in mg/1)
STATION
'JAMES 1'
MIN
MAX
MEAN
STDEV
'JAMES 2'
MIN
MAX
MEAN
STDEV
DAY ZERO
.025
.022
.022
.022
.022
.027
.022
.025
.022
.022
.022
.022
.022
.022
.027
.023
.002
.029
.022
.022
.022
.022
.025
.022
.029
.022
.025
.022
.022
.022
.022
.029
.024
.003
DAY ONE
.022
.020
.022
.051
.020
.022
.022
.020
.020
.022
.020
.020
.020
.020
.051
.023
.008
.020
.022
.022
.022
.020
.020
.020
.022
.020
.020
.020
.020
.020
.020
.022
.021
.001
HOLDING
TIME
.022
.022
.022
.022
.041
.022
.022
.022
.022
.024
.024
.024
.024
.022
.041
. .024
.005
.024
.024
.024
.026
.024
.024
.024
.024
.024
.024
.026
.026
.028
.024
.028
.025
.001
FROZEN
7 DAYS
.025
.033
.029
.027
.023
.021
.021
.023
.050
.025
.023
.025
.023
.021
.050
' .027
.008
.023
.025
.023
.023
.023
.027
.023
.023
.027
.023
.023
.023
.025
.023
.027
.024
.002
FROZEN
28 DAYS
.024
.024
.022
.020
.024
.022
.020
.028
.022
.022
.022
.022
.028
.020
.028
.023
.003
.036
.020
.020
.020
.020
.020
.022
.020
.022
.020
.020
.024
.026
.020
.036
.022
.005
-------
TMLE A.8 TOTAL DISSOLVED PHOSPHORUS DATA FOR FREEZING STUDY
(continued) (concentration in mg/1)
STATION DAY ZERO DAY ONE HOLDING FROZEN FROZEN
TIME 7 DAYS 28 DAYS
"YORK 1*
WIN
MAX
MEAN
STDEV
.012
.012
.012
.012
.012
.014
.014
.012
.012
.027
.012
.014
.012
.012
.027
.014
.004
.012
.012
.012
.012
.012
.014
.012
.012
.012
.012
..018
.012
.014
.012
.018
.013
.002
.020
.015
.015
.013
.015
.015
.015
.015
.013
.015
.015
.015
.015
.013
.020
.015
.002
.012
.010
.012
.014
.012
.012
.012
.012
.012
.010
.012
.012
.027
.010
. .027
.013
.004
.012
.012
.014
.012
.012
.012
.014
.014
.014
.014
.014
.012
.016
.012
.016
.013
.001
2'
MIS
MM
MILAN
STDEV
.090
.090
.090
.092
.092
.092
.090
.090
.092
.090
.094
.092
.090
.090
.094
.091
.001
.092
.090
.090
.090
.090
.092
.092
.090
.096
.088
.088
.090
.090
.088
.096
.091
.002
.096
.096
.096
.096
.096
.098
.098
.096
.094
.096
.094
.098
.092
.092
.098
.096
.002
.092
.092
.092
.094
.094
.094
.092
.094
.096
.094
.100
.092
.094
.092
.100
.094
.002
.085
.087
.087
.087
.085
.085
.085
.089
.085
.083
.085
.087
.087
.083
.089
.086
.002
-------
TABLE A.9 TOTAL PHOSPHORUS DATA FOR FREEZING STUDY
(concentration in mg/1)
STATION DAY ZERO DAY ONE HOLDING FROZEN FROZEN
TIME 7 DAYS 28 DAYS
'JAMES 1'
MIN
MAX
MEAN
STDEV
'JAMES 2'
.063
.065
.063
.065
.065
.065
.065
.065
.065
.065
.063
.065
.067
.063
.067
.065
.001
.057
.059
.059
.059
.061
.081
.059
.061
.059
.059
.059
.061
.061
.057
.081
.061
.006
.065
.063
.067
.063
.065
.063
.065
.065
.067
.063
.065
.063
.065
.063
.067
.065
.001
.060
.060
.062
.062
.062
.062
.062
.060
.060
.062
.058
.062
.061
.058
.062
.061
.001
.063
.063
.063
.063
.063
.061
.061
.061
.063
.063
.063
.063
.063
.061
.063
.063
.001
MIN
MAX
MEAN
STDEV
.100
.102
.100
.106
.108
.106
.108
.108
.108
.110
.106
.108
.108
.100
.110
.106
.003
.081
.079
.081
.081
.077
.083
.081
.079
.079
.081
.079
.081
.081
.077
.083
.080
.002
.082
.082
.084
.094
.082
.082
.083
.084
.082
.086
.080
.080
.086
.080
.094
.084
.004
.081
.081
.081
.079
.079
.077 '
.111
.081
.081
.081
.079
.081
.081
.077
.111
.083
.009
.071
.069
.071
.077
.071
.071
.069
.073
.069
.087
.077
.071
.069
.069
.087
.073
.005
-------
TABL15 A. 9 TOTAL
(continued)
STATION DAY ZERO
"fOKK. 1'
.026
.026
.026
.026
.031
.029
.029
.031
.029
.031
.029
. .029
.029
KIN .026
KM .031
K1EAN .029
STDEV .002
'^OFK 2'
.133
.133
.135
.135
.135
.133
.135
.133
.139
.133
.133
.131
.137
MIN .131
MAX .139
MSAN .134
13TDEV .002
PHOSPHORUS DATA FOR FREEZING
(concentration in ng/1)
DAY ONE
.026
.026
.026
.028
.026
.026
.026
.028
.028
.026
.036
.028
.028
.026
.036
.028
.003
.132
.130
.132
.141
.130
.132
.132
.135
.132
.132
.132
.132
.132
.130
.141
.133
.003
HOLDING
TIME
.026
.026
.028
.026
.028
.028
.028
.026
.028
.028
.028
.028
.028
.026
.028
.027
.001
.135
.135
.137
.135
.139
.137
.137
.135
.137
.137
.135
.137
.135
.135
.139
.136
.001
FROZEN
7 DAYS
.041
.033
.035
.035
.035
.035
.037
.037
.033
.035
.035
.035
.035
.033
.041
.035
.002
.128
.134
.136
.134
.136
.136
.132
.134
.134
.136
.136
.134
.134
,128
.136
.134
.002
STUDY
FROZEN
28 DAYS
.030
.030
.034
.030
.032
.032
.030
.040
.032
.032
.032
.032
.032
.030
.040
.032
.003
.130
.134
.134
.132
.132
.130
.134
.134
.130
.132
.132
.132
.134
.130
.134
.132
.002
-------
Appendix B
Graphical Summaries of Raw Data
Figures B1-B9 Mean Concentration vs. Treatment by Station/Salinity
Figures B10-B45 Concentration (mean* standard deviation, observations)
vs Treatment
-------
c
o
0)
0.06
Figure B1. Comparison of mean
nitrite concentrations by
treatment, station and salinity
18 0.04
o
L_
-4-
C
-------
c
o
o
0.30
0.25-
o
z 0.20n
c
0)
o
c
o
0.15-
0.10-
0.05-
Rgure B2. Comparison of mean
nitrite+nitrate concentrations by
treatment^ station and salinity
-B-
-CJ
-X-
-B-
HT
D1
DO ' D7f D28f
Stction/'Salinity
A Jcmes2/6.44 ppt
X Jomcjl/13.47 ppt
O York2/t7.72 ppt
a York 1/18 4 6 ppt
-------
c
o
c
(D
O
C
o
O
(D
0.10-1
0.08-
0.06-
0.04-
0.02-
0.00-
Rgure B3. Comparison of tnecn
ammonia concentrations by
treatment, stjtion and ^aliniL.
HT
D1 DO D7r D28t
Treatment
Station/Salinity
ii Jomea2/6.44- ppt
x Jcmes1/13.47 ppt
a York2/T7.72 ppt
Q York 1/18.4 6 ppt
-------
0.60
O.bb-
0.50-1
c
CD
O
O
O
p-
i__
O
CL
0.45-
0.40-
0.35
irp R/i. Prv-nrviricjon ot
-w4i s^> k_/ i x^v>/i i >>-^ . i.. ^-^,
-J '
total Kjeldahl N. cc^ncentrations by
treatment, station and salinity
D1 DO D7f
Treatment
D23f
Station/Salinity
A Jcmgd2/C.4 4 ppt
X Jomga 1/13.47 opt
a York2/t7.?2 opt
a Yorkl'l3.46p-jt
-------
c
.0
'-+->
o
+-J
c
-------
0.10
0.08-
c
o
0.06-
o
c
o
c
o
0>
0.04-
0.02-
0.00-
Figure B6. Comparison of mean
total dissolved P. concentrations by
treatment, station and sdhitv
HT
D1 DO' D7f D28f
Treatment
Station/Salinity
A Jw-nna32/6.44 opt
X Jnmcal M3.4? ppt
3 YcT'"2/17.72 ppt
3 Yorkl/18.4 6 ppt
-------
0.15
c
0.10
£ 0.05
o.oo-
Rgure B7. Comparison of mean
total phosphorus concentrations by
treatment, station and 'salinity
x
Hf
D1 00.
Tre> itment
D7f D28f
Station/Salinity
A James2/6.44 ppt
X JamesVl3.47 ppt
D York2/t7.72 ppt
H YorkVl8.46 ppt
-------
40
Rgure B8/Comparison of mean
suspended solids concentrations by
treatment, station and salinity
o
c
CD
O
o
c
o
0)
20-
10 -I
0
--B
Station/Salinity
ppt
X Jomesl/13.47 ppt
D York2/t772 ppt
B Yorkl/18.46 ppt
HT
D1
DO
D7f D28f
ro ^ f --^ .o p f
il v^VJ Li ! , V/l ! v
-------
1.5
Rgure B9. Comparison of mean
silica concentrations by
treatment, station and salinity
o
1-
c
0)
o
c
o
o
c
D
-------
I
T
0.011
0.010-
P 0.009
1
9
° 0.008-
0.007
Rgure B10. Comparison of nitrite
concentrations by treatment
at James 1
A Mean
X +1 SidDov
X -1 StdDev
O Observations*
'9 9,
9.0
S
"
5.
Rgure Bit Comparison of nitrite
concentrations by treatment
at James 2
(. Note: -13 ODifttMiorfll (.'or treatment:
circle may represent >\ observation)
A Mean
X +1 StdDev
X -1 StdDev
O Observations*
( Note: ~13 oHsv t>V treatment:
circle may represent >1 observation)
O.C
cn
§
.b
I
O
O
0.011-
0.010-
0.009-
0.008-
Rgure B12. Comparison of nitrite
concentrations by treatment
at York 1
DO D7f D28f
Hf D1
( Solo- ~|3 oosv«HaV.o'M tV treatment:
circle may repreaont >1 observation)
A Mean
X +1 StdDov
X -1 StdDev '
O Observations*
0.060
0.
Rgure B13. Comparison of nitrite
concentrations by treatment
at York 2
A Mean
X +1 StdDev
X -1 StdDev
O Observations*
( Note: -13 oBJTSrttflldrrJ |>V treatment:
circle may represent >T observation)
-------
figure B14. Comparison of nitrite+nitrate
concentrations by treatment
at James 1
Rgure B15. Comparison of nitrite+nitrate
concentrations by treatment
at James 2
u.^xi-
O.iS-
<-^
cn
£
vi> 0 18-
C.
O
-b
§j 0.17-
o
o
o
0.16-
0.15 -
O
\
Q \ " ]
A --.in H '
g J
-^o "*
*^
o
o
o
"_ _fl^"^xx_
j _*5\ ^^*x. n
-*^^ D^^S ^5
^ \\R
\
\o
B
o
Hf D1 DO D7f D28f
H.JZ-
s-*. 0.30-
*0i
.^^
c
o
'g 0.28-
1
O
A Mean U 0.26-
X +1 StdDov
X -1 StdDov
O Observations*
09A»
.^^
O
X ii
jL^ "\»_ -*
^^
^- ^H
u^^-"^^ W '
O
o
0
o
V
k /8
\S*-'^X'^ B
^- ($
o
o
A Maan
X +1 StdDev
X -1 StdDev
O Observations*
HT D1 DO D7f D28f
( Note: O oBs^rvaiionlf p»r treatment: (* Note: ~13 oosirvatlona per treatment:
Ffgure B16. Comparison of nitrite+ritrate Rgure B17. Comparison of nitrite+nitrate
concentrations by treatment concentrations by treatment
at York 1 at York 2
^ 0.115-
D>
v&
^-^^
O
'-*= 0.110-
D
L_
s
O
0
° 0.105-
0 lOO
o
0
V
^^x«^ (
° "^^-i<^-
7* f -
O O "\
o <
g_ A ' !
o o ^
Q^-' (
O ^x
°
0 0
k^, 0
' "^^^vS °
' ^^""^S^^^v
\ >
o \ o
\
HT D1 DO D7f D28f
.
^
CT 0.080-
&
g
Ii3
O
Q)
g 0.075-
O
A Mean °
X +1 StdDev
X -1 StdDov
O Observations*
OCTTfl
.UA U
1
/ (
O / (
/
/^
/
o/
a *
O ^r i
X^
o
1
I
\
'\
I \
\
L \ O
\\ /
\ \ /
W °
x^6
1 (3^^ O
"^
0
A Moan
X +1 StciDav
X -1 StdOav
0 Obs-M-vaHon,.
HP D1 DO D7F D28F
(» Note: 13 oDse'rvcitioria por (treatment* , (* ?Co4c: *-j3 ODaSrvallona p«r treatment:
-------
Rgure B18. Comparison of ammonia
concentrations by treatment
at James 1
^
g* 0.010-
3=*
g
*-»
-+-*
§
c 0.005-
<3
OfirtA
.uuu -
o
/
\ ° /'
0 \ / '
v /
^^^~^^ ° s'
o e» <
O (
^ 'Q . .
5\ o o
) N^'-'^'^O
0 O
K^^^ O Jl
^~\^--o
) O 0
/*
" x^
A Mean
X +1 StdDev
X -1 StdDev
O Observations*
HT D1 DO D7f D28f
( Note: ~13 oBSrvin!ar?i' p>r treatment:
circle may represent >1 observation)
Rgure B20. Comparison of ammonia
concentrations by treatment
at York 1 .
.Uc3 H
^-* 0.020-
^
£
Q
'g 0.015-
§
0
° 0.010-
Of)f\C
.UUD "
o
o
o
x
°\
\
i \ ^
°o\ A
Q ^VO .^^ /
X ^tr f
as^ 5 /
\ o /
O * O /
\x'
0
o
A^
/ \
/ ° \
c/°\ ^
J_.^-§x Nj
\
"^
o
A Mean
X +1 StdDev
X -1 StdDev '
O Observations*
HT. D1 DO D7f D28f
( Note: --13 oBs\ abiarvation)
Rgure B21. Comparison of ammonia
concentrations by treatment
at York 2
A Mean
X +\ StdDov
X -1 StdDev
O Observations*
A Mean
X +1 StdDev
X -1 StdDev
O Observations*
(. Note: -13 oBorrbr treatment:
circle may represent >\ observation)
-------
o
0.2-
Rgure B22. Con^on'son of totd KjddoN N.
concentrations by treatment
at James 'I
circle may represent >1 opsorvation)
Rgure B24. Comparison of totd Kjddahl N.
concentrations by treatment
at York 1
( Note- ~3 oBiok, treatment
circle ma/ repfe»i.-nt irt obaorvation)
A Mean
X +1 StdDov
X -1 StdDov
O Observations*
Mean
X 4-1 StdDev
X -1 StdDov
O Observations*
0.55
(8
0.25-
0.9
0.4-
Rgure B23. Comparison of totd Kjddohl N.
concentrations by treatment
at James 2
D1
DO D7f D28f
(. Mote: ~A oiK?r9S(?38rlL treatment;
(.ircltt may represent M oosorvation)
Rgure B25, Conrpa-ison of totd KjddaN N.
concentrations by treatment
at York 2
( Mate: ~d jffieYV&lro'rH'jJer treatment:
circle may r«pr«aent«» oo»etvgt»on)
Mean
X +1 StdDev
X -1 StdDev
O Observations*
Meal i
X +1 StdDov
X -1 StdDev
O Observations*
-------
Rgure B26. Comparison of orthophosphate
concentrations by treatment
at James 1
Rgu-e B27. Comparison of orthophosphate
concentrations by treatment
at James 2
..-s' 0.012-
cn
J.
O
=6 °°"-
i_
-4-'
1
o
0 0.010-
0.009-
X Vx
O O (
^^^\ ^^
^
\ /'
\ /
v .
f
/
\ /x
I -~^3si"'^---^ °
/ "^
s
)
t
1 i
u.u 10 -
.^ 0.016-
cn
J.
O
'-g 0.014-
£
a>
o
c
a Mean ° 0.012-
X +1 StdOev
X 1 StdDov
O Observations* .
0.010-
<
**
0 -^ <
je^
^ ^
^^
o ^^-^o <
A^^ X
^
r^
S
^//
0 /^I
^^//
^ /
^
I |
A Mean
X +1 StdDev
X ;;1_Sto2ov__ .
O Observations*
Hr D1 DO D7f D28f HT D1 DO D7f D28f
'(« ^olc: "-13 oD3%rval.orty per treatment: . ( Note: *-l3 oosirvations per treatment;
Figure B28. Comparison of orthophosphate Figure B29. Comparison of orthophosphate
concentrations by treatment concentrations by treatment
? at York 1 at York 2
i / .U-
6.0-
E
-=* b.O-
g
*^
p
JD
| "-
O
0
3.0-
X
\
0 x\0
X
\
°\ ^
^\/ /
0 1
\
X
A
/\
/ \
*T~~~--~ -^r*
\ -A ' /
\ /
V
HT D1 DO D7f D28f
\J.\JU*J ~
^
£? 0.080-
^ '
O
"6
C 0.075-
O
A Mean °
X +1 StdOev
X -1 StdDev
O Observations*
Ofrrf\
.U/U -
x^
^^^
o ^^
6~-~-^.^ O V\
^ft -^ (
. t
1
o
. -~*-
r o \ o
: NN
> --.^ o \, o
vo
^
o
A Mean
X +1 StdDev
X -1 StdDov
O Observations*
Hf D1 DO D7F D28F
(» "Jote- ~i3 oBjT'RlMdrr/Vtr lieatment: ( Note- ~|3 ors^ftln!3rrJl>>r treatment:
-------
Rgure B30. Comparison of totd dissolved P.
concentrations by treatment
at James 1
Figure B31. Comparison of totd dissolved P.
concentrations by treatment
at James 2
u.uo -
0.05-
^
C7*
-=- 0.04-
§
-w
O
4s
g 0.03-
u
§
o
0.02-
OiTl-
-U 1
O
0
^<
o 8 i
*\ ° xx
"^-^
o
&
/o\
t/jB^^y
" 5- 8
HT D1 DO D7f D28f
u.u^o-
.
0.035-
^
.rj»
^^ 0.030-
s
=8
J3
£ 0-025-
AMean ^RWQP/])»r treatment:
Rgure B32. Comparison of totd dissolved P. Rgure B33. Comparison of totd dissolved P.
concentrations by treatment concentrations by treatment
at York 1 at York 2
.\jj\j
0.025-
a>
-=" 0.020-
c
g
"o
L.
ID 0.015-
U
§
O
0.010-
Onns -
-U U J
c
o
f)
° S
'^""s*^ j^^
*^^ '
^\ 0 (
"""-»-,
o
*c
^X o
0 ^
1 6 *
I O «
r ° "^
^~* ")s^
HT D1 DO D7f D28f
W. IWW
. 0.095-
cn
'
C
o
'-g 0.090-
L_
s
u
A Mean . ° 0.085-
X -1-1 StdDav
~~*~~
X -1 StdDev
O Observations*
a
\\°
V\ '
0 \ \0 I
\ \
\ ° ^
\*-***^1*^1*
0
,XA
l .s Q \ \
S^ Jxx*\ \ \
^* \ \ \
J- \\\
\ \ \ ^
\\A
^
o
A Mean
X -M StdDev
-~ . __^
X -1 StdDov
0 Observations*
HT D1 DO D7F D28F
( Note- J3 oBairvffl^ans ptr treatntent: . (* Mote: *-O oDs^rvcryorrJ per treatment:
-------
0.09
I
p
1
0.08-
0.07-
0.06-
0.05
Rgure B34. Comparison of totd .phosphorus
concentrations by treatment
at James 1
( Noto: ~13 oiwb' troalm.nl:
circlft may represent >1 observation)
Mean
X +1 StdDev
X -1 StdDev
O Observations*
0.12
0.06
Figure B35. Comparison of totd phosphorus
concentrations by treatment
at James 2
( Note: ~13 ovinir treatment:
circle may represent >1 observation)
A Mean
X +1 SldDev
X -1 StdDev
O Observations*
0.045
0.040-
^
CTi
O
O
O
0.035-
0.030-
0.025-
0.020-
Rgure B36. Comparison of totd phosphorus
concentrations by treatment
at York 1
HT D1 DO D7f D28f
(« Mole- -13
circle mav r
A Mean
X +1 StdDev
X -1 SldOev
O Observations*
CT
O
I
O
o
Rgure B37. Comparison of totd phosphorus
concentrations by treatment
at York 2
HF D1 DO D7F D28F
treatment:
A Mean
X +1 StdDev
X -1 StdDev
O Observations*
(. Note: -13 oBamtbr treatmini:
i irt-la mav rttr*rti*ant
-------
10-
Figure B38. Comparison of suspended solids
concentrations by treatment
at James I
( Note: ~|0 :iBf*r-4o'l!oln-J fix treatment:
4.ircl« may repreyant M observation)
Figure B40. Comparison of suspended soids
concentrations by treatment
at York 1
A Mean
X +1 StdDev
X -1 StdDev
o Observations*
=> 15-
..
en
£
c
o
'g 10-
»^_
1
u
c
o
0 5-
-
<
/
/'
>J -
*<^'^<
»\^^^ '
""""-- 3 5
o
HF D1 D
i * JT-Q /-% \ »
'(* Mote -10 aJsWy
'\
' \
\ O
\ -^
'\ ^^2
^-^1
-~- ^-'JJ
"^-5^'
o
o
3 D7f D28f
T^T^nl"
\tifj pur trcattiicnt
A Mean
X +1 StdDev
- - - ' " " "
X 1 StdDev
O Observations*
25
IS
Rgure B39. Comparison of suspended solids
concentrations by treatment
at James 2
( Note: -10 oBSatfiir tnatmant:
circlo may r«preaant >1 observation)
Rgure B41. Compcrison of suspended soGds
concentrations by treatment
at York 2
A Mean
X -H StdDev
X -1 StdDov
O Observations*
A Mean
X +1 SldDov
X 1 StdDev
O Observations*
( Note: ~10 oyinjfcr \i eotmenl:
circle tnav represent >] observation)
-------
0.68
o.sa
0.050
0.020-
Rgure B42. Comparison of silica
concentrations by treatment
at James 1
( Note: -13 owi*' treatment:
circle may represent M observation)
Rgure B44. Comparison of silica
concentrations by treatment
at York 1
HT D1 DO D7f D28f
(« Note- -13
A Mean
X +1 StdDev
X -1 StdDev
O Observations*
A Mean
X +1 StdDev
X -1 StdDov
O Obiorvationx*
1.05
0.20
0.05
Rgure B43. Comparison of silica
concentrations by treatment
at James 2
(t Note:*-t3 o:'p>r treatment:
circle may represent >1 observation)
fTgure 845. Comparison of silica
concentrations by treatment
at York 2
A Mean
X +1 StdDev
X 1 StdDov
O Observations*
treatment:
(. Mote: -13 otrrjbr treatment:
A Mean
X 4-1 StaDov
X 1 StdDev
O Observations*
-------
Appendix C
Results of Statistical Analyses
CONTENTS:
Table Cl. Faired t-test
Table C2. Parametric One-way Analysis of Variance
Table C3. Dunnett's Parametric Multiple Comparisons
Table CA. Scheffe's Parametric Multiple Contrasts
Table C5. Tukey's Parametric Multiple Comparisons
Table C6. Kolmogorov-Smirnov Test for Normality
Table C7. Bartlett's Test for Homogeneity of Variances
Table C8. Rank Means Used for Nonparametric Tests
Table C9. Kruskal-Wallis Nonparametric One-way ANOVA
Table CIO. Dunn's Nonparametric Multiple Comparisons
Abbreviations used:
N02 Nitrite-Nitrogen
N023 Nitrate-Nitrite-Nitrogen
NH3 Ammonia Nitrogen
TKN Total Kje'ldahl Nitrogen
OP Orthophosphate
TP Total Phosphorus
TDP Total Dissolved Phosphorus
SS Suspended Solids
SI Silica
DO Day 0 treatment (control)
Dl Day 1 treatment
HT Holding Time treatment
D7f or D7frz Day 7 (frozen) treatment
D28f or D28frz Day 28 (frozen) treatment
-------
Table Cl. Paired t-test
Null hypothesis: Control (Day 0) mean equals treatment mean.
ANALYSIS TREATMENT
OP
TDP
TP
N02
N023
NH3
TKN
Silica
SS
STATION
James 1 James 2 York 1
York 2
Day 1
Hold time
Day 7-frz
Day 28-frz
Day 1
Hold time
Day 7-frz
Day 28-frz
Day 1
Hold time
Day 7-frz
Day 28-frz
Day 1
Hold time
Day 7-frz
Day 28-frz
Day 1
Hold time
Day 7-frz
Day 28-frz
Day 1
Hold time
Day 7-frz
Day 28-frz
Day 1
Hold time
Day 7-frz
Day 28-frz
Day 1
Hold time
Day 7-frz
Day 28-frz
Day 1
Hold time
Day 7-frz
Day 28-frz
NS
NS
NS
NS
NS
NS
NS
NS .
NS
<.001
<.001
___
_
NS
NS
.025
.003
NS
NS
NS
NS
.005
.001
.020
NS
<.001
<.001
<.001
<.001
.002
NS
NS
NS
.020
.002
NS
.014
.003
NS
NS
NS
<.001
<.001
<.001
<.001
.002
<.001
<.001
NS
NS
<.001
NS
NS .
NS
. NS
NS
.046
NS
NS
NS
NS
<.001
<.001
<.001
.021
.006
.006
NS
_
NS
NS
NS
NS
NS
.033
<.001
<.001
___
-
NS
NS
.005
<.001
.035
NS
.022
NS
NS
NS
NS
NS
NS
.008
.018
<.001
NS:
NS
NS
NS
.014
.005
NS
<.001
NS
<.001
<.001
<.001
NS
.009
NS
.023
<.001
<.001
<.001
.001
(m)
<.001
.002
NS
(m)
NS
<.001
NS
NS
NS
NS
NS
NS
<.001
<.001
NS
NS
NS
.018
Probability of getting test statistic (t) at least as large as that
calculated if null hypothesis is true is shown.
NS = no significant difference between means (alpha=0.05)
= no variance in data group
(m) - missing data group
-------
Table C2. Parametric Oneway Analysis of Variance
Null hypothesis: Treatment means are equal.
STATION
ANALYSIS
N02
N023
NH3
TKN
OP
TOP
TP
SS
SI
James 1
<.0001
.0001
NS
<.0001
.0001
NS
.002
.0078
<.0001
James 2
<.0001
.0011
NS
NS
<.0001
.0012
<.0001
.0259
<.0001
York 1
<.0001
.0015
.0003
NS
.0001
NS
<.0001
.0091
<.0001
York 2
<.0001
<.0001
<.0001
NS
<.0001
<.0001
.0001
.0057
<.0001
Probability of getting test statistic (F) at least as large
as that calculated if null hypothesis is true is shown.
NS=no significant difference between means (alpha=0.05)
-------
Table C3. Dunnett's Test for Comparing Control Mean (Day 0)
to Treatment Means
Null hypothesis: Control mean equals treatment mean
STATION
ANALYSIS TREATMENT James 1 James 2 York 1 York 2
N02
N023
NH3
OP
TDP
TP
SS
SI
Day 1
Hold Time
Day 7-frz
Day 28-frz
Day 1
Hold Time
Day 7-frz
Day 28-frz
Day 1
Hold Time
Day 7-frz
Day 28-frz
Day 1
Hold Time
Day 7-frz
Day 28-frz
Day 1
Hold Time
Day 7-frz
Day 28-frz
Day 1
Hold Time
Day 7-frz
Day 28-frz
Day 1
Hold Time
Day 7-frz
Day 28-frz
Day 1
Hold Time
Day 7-frz
Day 28-frz
Day 1
Hold Time
Day 7-frz
Day 28-frz
**
**#
**
**
*
*
**
**
**#
**
**
*
**
**
**
**
**
**#
**
**#
**.
*
*#
**
*# '
**
**
**
**
**
**
**
**
**
**
** **
**# **
**# **
. **
. m
. **
** **
*
. m
*
**
*
»
**# .
. **
*
**
«
**
**
**
*
*
** .
** ,
** .
. **
** .
. **
** **
* = significant difference between means (alpha=0.05)
** = significant difference between means (alpha=0.01)
. = no significant difference between means
m = missing data group
# = difference is not measurable
-------
Table C4. Scheffe's Multiple Contrasts Procedure
Null hypothesis: Mean of Day 0, Day 1* and Hold time means equals
freezing treatment mean*
STATION
ANALYSIS TREATMENT James 1 James 2 York 1 York 2
N02
N023
NH3
TKN
OP
TOP
TP
SS
SI
Day 7-frz *# *#
Day 28-frz **#
Day 7-frz . **
Day 28-frz **
Day 7-frz
Day 28-frz
Day 7-frz . .
Day 28-frz
Day 7-frz .
Day 28-frz **# **
Day 7-frz
Day 28-frz . .
Day 7-frz . **
Day 28-frz . **
Day 7-frz
Day 28-frz
Day 7-frz ** **
Day 28-frz ** **
*# **
**#
9 1ric
** *
*
*# **
**
**
** .
**
9
*-k 4*
** **
*=signif icant difference between means (alpha=0.05)
**=significant difference between means (alpha=0.01)
,=no significant difference between means
#=difference is not measurable
-------
Table C5. Tukey's Multiple Comparisons Procedure
Null hypothesis: Treatment means are equal
STATION
TREATMENT
James 1 James 2 York 1 York 2
ANALYSIS TREATMENT DO Dl HT D7f DO Dl HT D7f DO Dl HT D7f DO Dl HT D7f
N02 Day 1 *# . *
Hold Time * * * *# * * * *
D7-frz *# *f * * *# . *#*#*# * * *
D28-frz * *# * . *# . * * *#*#*#. * * * *#
N023 Day 1 . . *
Hold Time .. . . . . mm
D7-frz ... *.* ... *.m
D28-frz * * * * .... ***. *.m0
NH3 Day 1 .
Hold Time . . . * mm
D7-frz ... ... . * . . . m
D28-frz .... .... ...* * * m *
OP Day 1 . *#
Hold Time .. *. .*# *.
. D7-frz ... ... . *# . . .- *
D28-frz *#*#*#. . * * * . *# . . * * * *
TK.N Day 1 - *
Hold Time * . . . ...
D7-frz * . . ... ... ...
D28-frz . . * *
TOP Day 1 . .. *
Hold Time . . . * . . * *
D7-frz ... .*. ... ***
D28-frz ****
TP Day 1 * * . "-.'
Hold Time . * * . .' . . *
D7-frz *.* *.. *** ...
D28-frz .... **** **** ..*.
SS Day 1 * . . *
Hold Time . . . .
D7-frz ... * . . * . . ...
D28-frz . * * ...
SI Day 1 *
Hold Time * * * * * * . . '
D7-frz *** *** .*. ***
D28-frz **** **** **.. ****
*=significant difference between means(alpha=0.05)
=no significant difference between means c
m=missing data group
#=difference is not measurable
-------
Table C6. Kolmogorov-Smirnov Test for Normality
Null Hypothesis: Data are normally distributed.
ANALYSIS TREATMENT James 1
N02
N023
NH3
TKN
SS
SI
OP
TOP
TP
Day 0
Day 1
Hold Time
Day 7-frz
Day 28-frz
Day 0
Day 1
Hold Time
Day 7-frz
Day 28-frz
Day 0
Day 1
Hold Time
Day 7-frz
Day 28-frz
.001
.003
.001
NS
NS
NS
NS
NS
NS
NS
NS
NS
NS
(All treatments &
(All treatments &
Day 0
Day 1
Hold Time
Day 7-frz
Day 28-frz
Day 0
Day 1
Hold Time
Day 7-frz
Day 28-frz
Day 0
Day 1
Hold Time
Day 7-frz
Day 28-frz
Day 0
Day 1
Hold Time
Day 7-frz
Day 28-frz
NS
NS
.045
NS
NS.
.001
.006
.001
NS
.008
.005
.017
NS
NS
.048
.015
NS
NS
.006
NS
.006
.003
.006
NS
NS
NS
NS
NS
NS
NS
NS
NS
NS
stations NS)
stations NS)
NS
.003
NS
NS
NS
NS
.001
.006
.037
.003 "
.025
.016
.023
.022
NS
NS
NS
NS
.004
NS
STATION
James 2 York 1
.003
.016
.016
NS
NS
NS
NS
NS
.037
NS
NS
NS
NS
.026
NS
.048
.007
NS
.001
.006
.037
.042
.013
.013
.014
NS
NS
NS
.016
NS
NS
York 2
NS
NS
NS
.016
.001
NS
NS
m
.048
NS
NS
NS
m
NS
NS
NS
.043
.003
NS
NS
.016
.006
.031
.037
NS
NS
NS
NS
NS
NS
NS
.015
NS
NS
NS
Probability of getting test statistic at least as large as that
calculated if null hypothesis true is shown.
NS = deviation from non-normality is not significant (alpha=0.05)
__.. = data group has no variance
m missing data group
-------
Table C7. Bartlett's Test for Homogeneity of Variance
Null hypothesis: Variances are equal.
STATION
ANALYSIS
N02
N023
NH3
TO
OP
TDP
TP
SS
si .
James 1
NS
<.001
NS
.046
<.001
<.001
<.001
<.001
.016
James 2
NS
<.001
<.001
NS
.003
<.001
<.001
.011
.004
York 1
NS
<.001
<.001
.001
.011
<.001
.015
.008
.001
York 2
.009
<.001
<.001
<.001
.001
NS
NS
NS
.002
Probability of getting test statistic" at least as large as
that calculated if null hypothesis true is shown.
NS = deviation from homogeneity is not signif icant(alpha=0 .05)
-------
Table C8. Rank means used for nonparametric tests
STATION
ANALYSIS TREATMENT James 1 James 2 York 1 York 2
N02
N023
NH3
TKN
OP
TOP
TP
SS
SI
Day 0
Day 1
Hold Time
Day 7-frz
Day 28-frz
Day 0
Day 1
Hold time
Day 7-frz
Day 28-frz
Day 0
Day 1
Hold time
Day 7-frz
Day 28-frz
Day 0
Day 1
Hold time
Day 7-frz
Day 28-frz
Day 0
Day 1
Hold time
Day 7-frz
Day 28-frz
Day 0
Day 1
Hold time
Day 7-frz
Day 28-frz
Day 0
Day 1
Hold time
Day 7-frz
Day 28-frz
Day 0
Day 1
Hold time
Day 7-frz
Day 28-frz
Day 0
Day 1
Hold time
Day 7-frz
Day 28-frz
53.00
51.04
7.42
27.50
26.04
32.58
29.81
42.42
45.31
14.88
34.83
27.69
33.27
29.08
37.81
8.63
21.94
32.38
27.93
10.13
29.88
25.08
29.88
32.00
48.15
32.73
17.69
35.62
45.96
33.00
50.88
13.69
49.04
18.50
32.88
34.05
11.50
25.20
23.65
31.22
46.00
59.00
32.38
20.62
7.00
52.81
38.27
15.27
14.15
44.50
38.27
34.58
45.04
11.88
32.88
22.65
37.15
35.92
32.12
37.15
25.69
16.56
24.00
19.88
16.38
38.92
25.54
18.15
28.46
53.92
35.31
13.92
50.23
43.15
22.38
58.00
26.62
41.19
29.19
10.00
37.70
21.90
21.40
17.10
29.40
55.08
48.38
34.54
20.00
7.00
51.50
47.19
10.69
23.50
32.12
43.04
41.12
34.92
28.96
16.96
35.38
14.13
38.88
45.42
27.27
22.50
15.06
16.50
17.75
30.69
38.50
14.38
43.69
29.92
38.50
28.73
26.62
53.31
22.12
34.23
26.92
17.65
18.04
57.15
45.23
32.60
17.90
34.40
14.10
28.50
18.77
20.50
38.81
31.69
55.23
46.23
58.77
7.00
21.85
31.15
40.19
29.42
m
14.31
22.08
34.54
36.08
m
27.88
7.50
18.69
22.75
29.19
9.06
22.81
30.04
40.88-
54.58
28.42
11.08
29.85
27.00
55.42
45.58
7.15
35.58
19.46
52.88
37.31
19.77
34.65
17.60
27.85
29.20
14.67
19.00
21.77
19.85
59.00
45.38
m = missing data group
-------
Table C9. Kruskal-Wallis Nonparametric
Oneway Analysis of Variance
Null hypothesis: Mean ranks are equal
ANALYSIS STATION
James 1 James 2 York 1 York 2
<.0001 <.0001
.0025 .0001
.0003 <.0001
NS .0118
.0001 <.0001
<.0001 <.0001
<.0001 <.0001
.0028 .0069
<.0001 <.0001
Probability of getting test statistic at least as large
as that calculated if null hypothesis true is shown.
NS=No significant difference between mean ranks(alpha=0.05)
Test statistic (chi-squared) is corrected for ties in rank.
N02
N023
NH3
TKN
OP
TDP
TP
SS
SI
<.0001
.0003
NS
<.0001
.0001
.0025
<.0001
.0037
<.0001
<.0001
.0001
NS
NS
<.0001
<.0001
<.0001
.0128
<.0001
-------
Table CIO. Dunn's Nonparametric Multiple Comparisons Procedure
Null hypothesis: Mean ranks are equal*
STATION
TREATMENT
James 1 James 2 York 1 York 2
ANALYSIS TREATMENT DO Dl HT D7f DO Dl HT D7f DO Dl HT D7f DO Dl HT D7f
N02
K023
NH3
CP
IDP
!3S
Day 1 .
Hold Time * * * *
D7-frz * * . * * .
D28-frz * * . . . . * *
Day 1 »
Hold Time . . .
D7-frz ... * * *
D28-frz . . * * ... *
Day 1 .
Hold Time . . .
D7-frz ... ...
D28-frz
Day 1
Hold Time . . . .
D7-frz ... ...
D28-frz . * . . . * * *
Day 1
Hold Time * . . .
D7-frz * . . ...
D28-frz . . * * ....
Day 1 *
Hold Time . . *
D7-frz . * . . * .
D28-frz * .
Day 1 * *
Hold Time . * .
D7-frz * . * * . .
D28-frz .... * . * .
Day 1 *
Hold Time . . . .
D7-frz ... * . .
D28-frz . * . . ....
Day 1
Hold Time . * .
D7-frz * * . * * .
D28-frz * * * . * * * .
* .
* * * *
* * . * * .
. . * . * * .
mm
t> a » o m
**«c * m o
. * mm
. * . . . m
* * m *
*
. * * .
. . . . . . *
. * . . . * * .
4
. . . . . *
*
* * * *
. . * ...
. . . . * . * *
. *
* * * ...
* * *
t -x -x m «»K«
* . * ...
* *
* 4 * ft tC ff
**.* ***.
'^significant difference between mean ranks(alpha=0.05)
»=no significant difference between mean ranks
ra=missing data group
-------
APPENDIX D
LABORATORY METHODS
Analysis:
Storet number:
References:
Brief:
Modification:
Anmonia, dissolved
00608
1. U.S. EPA (1979) Methods for Chemical
Analysis of Water and Wastes, Method
350.1.
2. Standard Methods for the Examination of
Water and Wastewater (1975) 14th Edition,
p. 616, Method 604.
An automated phenate method. Alkaline Phenol
and hyp-chlorite react with ammonia to form
indophenol blue which is intensified with
sodium nitroprusside and measured
colorimetrieally.
None
Analysis:
Storet number:
References:
Brief:
Nitrate-Nitrite, dissolved
00631
1. U.S. EPA (1979) Methods for Chemical
Analysis of Water and Wastes, Method
353.2.
2. Standard Methods for the Examination of
Water and Wastewater (1975) 14th Edition,
pp. 620-624, Method 605.
3. Strickland and Parsons (1972) A Practical
Handbook of Seawater Analysis, pp. 127-
130.
4. Technicon Industrial Method No. 100-70W
(1973) Nitrate and Nitrite in Water and
Wastewater.
An automated method where nitrate is reduced
to nitrite by a copper-cadmium column, and
determined by diazotization with sulfamilamide
and coupling with N-(l-naphtyl)-
ethylenediamine dihydrochloride to form
an azo dye which is measured colorimetrically.
Modification:
None
-------
Analysis:
Storet number:
References:
Brief:
Modification:
Total Kjeldahl Nitrogen
00625
1. U.S. EPA (1979) Methods for Chemical
Analysis of Water and Wastes, Method
351.3, Method 350.1.
2. Standard Methods for the Examination of
Water and Wastewater (1975) 14th Edition,
p. 437, Method 421.
The sample is digested using heat, cone.
sulfuric acid, mercuric sulfate (catalyst).
The residue is diluted and made alkaline with
a hydroxide thiosulfate solution. The ammonia
is distilled into boric acid solution and read
by automated phenate colorimetry.
Use of automated phenate procedure to read
resulting ammonia.
Analysis:
Storet number;
References:
Brief:
Total Phosphorus
00665
1. U.S. EPA. (1979) Methods for.Chemical
Analysis of Water and Wastes, Method
365.2.
2. Standard Methods for the Examination of
Water and Wastewater (1975) 14th Edition,
p. 476, pp. 481-482, Method 425C.111,
Method 425E.
An acid persulfate digestion, with, the
liberated orthophosphate determined by single
reagent, blue-colored complex ascorbic acid
reduction and measured colorimetrically.
Modification:
None
-------
Analysis:
Storet number:
References:
Brief:
Modification:
Residue* Tdtal non-filterable
00530
1. U.S. EPA (1979) Methods for Chemical
Analysis of Water and Wastes; Method
160.2.
2. Standard Methods for the Examination of
Water and Wastewater (1975) 14th Edition,
p. 94, Method 208D.
A mixed sample is filtered through a glass
fiber filter and filter is dried to constant
weight at 103-105 degrees C.
None
Analysis:
Storet number:
References:
Brief:
Silicates, dissolved
None
1. Technicon Industrial Method No. 186-72W
(1973) "Silicates-in Water and Seawater".
2. Strickland and Parsons, A Practical
Handbook of Seawater Analysis (1972) pp.
. 139-140.
An automated procedure based on the reduction
of a silicomolybdate in acidic solution to
molybdenum by blue ascorbic acid. Oxalic acid
eliminates interference from phosphates.
Modification:
None
-------
Analysis:
Storet number:
References:
Urief:
Modification:
Nitrite, dissolved
00630
1. U.S. EPA. (1979) Methods for Chemical
Analysis of Water and Wastes Method 353.2.
2. Standard Methods for the Examination of
Water and Wastewater (1975) 14th Edition,
pp. 620-624, Method 605.
3. Strickland and Parsons (1972) A Practical
Handbook of Seawater Analysis, pp. 127-
130.
An automated method where nitrite is
determined by diazotizing with Sulfanilamide
and coupling with N-(1-naphthy 1) -
ethylenediamine dihydrochloride to form an azo
dye which is measured colorimetrically.
None
Analysis:
Jlfcoret number:
References: . .
U.S. Environmental Protection Agency
Room 2404 PM-211-A
401 M Street, S.W.
Washington, DC 20460
Brief:
Orthophosphate
00671
1. U.S. EPA (1979) Methods for Chemical
Analysis of Water and Wastes, Method
365.2.
2. Standard Method for the Examination of
Water and Wastewater (1975) 14th Edition,
pp. 481-482.
Orthophosphate is determined by single reagent
reaction of antimony phospho-molybdate complex
reduced to a blue-colored complex by ascorbic
acid and measured colorimetrically.
Modification:
None
------- |