QAPP Page 1
DRAFT INTERIM QUALITY ASSURANCE PROJECT PLAN
GREAT LAKES SURVEY STUDIES OF LAKES MICHIGAN
HURON, ERIE, ONTARIO, AND SUPERIOR
APRIL 1992 THROUGH FEBRUARY 1993
U.S. ENVIRONMENTAL PROTECTION AGENCY
GREAT LAKES NATIONAL PROGRAM OFFICE
SURVEILLANCE AND RESEARCH STAFF (SRS)
230 SOUTH DEARBORN STREET
CHICAGO, ILLINOIS 60604
PREPARED BY
MARVIN PALMER
GLENN WARREN
GREAT LAKES NATIONAL PROGRAM OFFICE
APPROVED:
CHIEF SCIENTIST
ASCI PROJECT OFFICER
CHIEF, SRS
QUALITY ASSURANCE OFFICER
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Great Lakes National Program Office
Great Lakes Studies
Survey Plan
Lakes Michigan, Huron, Erie, Ontario, and Superior
Limnology Program April 1992-February
1992
Survey DatesApril, August
Region Lakes Michigan,
Huron, Erie, Ontario
and Superior
Vessel R/V Lake Guardian
Master Captain R. Ingram
Agency United States
Environmental
Protection Agency
Chief Scientist Dr. G.J. Warren
Chief Chemist Mr. M.F. Palmer
Chief Biologist Dr. P.E. Bertram
Date of Issue March
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Table of Contents
Page
1.0 Project Description 4
2.0 Project Organization and Responsibility 21
3.0 QA Objectives 24
4.0 Sampling Procedures 27
5.0 Sample Custody 46
6.0 Calibration Procedures 47
7.0 Analytical Procedures 48
8.0 Data Reduction, Validation, and Reporting 49
9.0 Internal QC Procedures 51
10.0 Performance and System Audits 52
11.0 Preventative Maintenance 53
12.0 Specific Routine Procedures to be used to Assess 54
Data Precision, Accuracy, and Completeness of
Specific Measurement Parameters Involved
13.0 Corrective Action 55
14.0 Quality Assurance Reports to Management 56
Appendix 1. Analytical Procedures
Appendix 2. A User Manual of Laboratory Automation
Program
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1.0 PROJECT DESCRIPTION
1.1 Relevance of Water Quality Monitoring Program
Great Lakes water quality monitoring i3 needed to measure and
evaluate indicators of Great Lakes Ecosystem Health.
Monitoring surveys are conducted to sample biological, chemical
and physical parameters which lead to an understanding of the
current state of the ecosystem. As an integral part of Great
Lakes EMAP, data from the water quality surveys will contribute
to the evaluation of the state of the environment on a regional
and national basis. The long-term data record compiled by
GLNPO from past surveys allows an evaluation of the degree of
success of past regulatory actions. In a historical context,
the water quality surveys provide data to evaluate the degree
to which the objectives of the Canada - U.S. 1978 Great Lakes
Water Quality Agreement are being achieved, particularly
relating to phosphorus. This program will conduct limited
surveillance of Lakes Michigan, Huron, Erie, Ontario, and
Superior.
1.2 Purpose
The purpose of this surveillance program is to collect
biological, chemical and physical water quality data for use in
evaluating the ecosystem health of the Great Lakes, and to
establish a long term information data base on water quality
changes in the Lakes.
1.3 Survey Outline
Limnology Program Cruise Outline
Survey Approximate Date
1 April Spring conditions - pre stratification
2 August(tentative) Stratified period
The spring survey is important in assessing the initial
conditions in nutrient levels and their annual variance from
year to year. A summer survey will measure conditions during
a biologically active period under thermally stratified
conditions.
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1.4. Project Schedule
The R/V Lake Guardian is scheduled for approximately 35 davs of
24-hour operations. Expected sampling time, runnino
between stations, waste disposal and reprovisionini, Vh9
with fuel and supplies will vary depending on wind w*v!
availability of services when the ship i^in por? ' '
The plan is to complete a transit of the track
sa, .
segment of the sampling is 25 days: Lake Superior expectlS
tune, including transit is approximately 14 day. This is based
on 11 knots sailing speed, 1 to 4 hour sLpling time «n
station, 24 hours to transit interconnecting channels 24 hou?S
between lakes to complete analytical work, 12 to 24' hours to
refuel and reprovision the R/V Lake GnurHi/n two to three
per survey. Additional days estimated at 25% of saiUna
may be needed due to adverse weather conditions aillng
1.5. Vessel
The R/V Lake Guardian is a former offah^r-a «,- 1
vessel built by Halter Marine?™ ss Poin? MS in i
ship's dimensions are: length 1 180' , be^'- 40' , draft 1
, - , raft l
displaced tonnage - 850 tons. Propulsion is twin aJ
enclosed in Kort nozzles and driven by 12uO hp CaterDiU
dxesel engines. Cruising speed is 1 /knots, Lngl S ^J
miles.
1.6. Station Selection
The locations of the stations in the four lakes (Tables 1-1 to
1-5 and Figures 1-1 to 1-5) are selected from sites within
homogeneous areas of the lakes. These sites are also part of
the Great Lakes International Surveillance Program. Additional
stations in Lake Michigan, and the stations to be sampled in
Lake Superior are those from the EMAP base grid. EMAP stations
will be the permanent stations for Lake Superior.
Determination of future (post 1992) stations for the lower four
lakes is dependent on the evaluation of GLNPO/EMAP grid
comparison.
Experience on Lake Michigan, Lake Erie, Lake Huron and Lake
Ontario shows that spatial variation in open lake waters,
(beyond 13 KM from shore, and in deep water > 30M in depth) is
not great compared to nearshore spatial variation.
Core stations have been selected in each major lake basin:
Southern Lake Michigan station 18, mid-Lake Michigan station
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27, Northern Lake Michigan station 41, Northern Lake Huron
stations 43 and 45, Southern Lake Huron stations 15 and 93,
Western Lake Erie station 91, Central Lake Erie station 78,'
Eastern Lake Erie station 15, Western Lake Ontario station 33
and Eastern Lake Ontario station 55.
The core stations represent the deepest points within the basin
amongst the selected stations. At regular depths, the thermal
and chemical structure will be monitored in detail to better
characterize the vertical conditions during the survey.
1.7 Dry Run & Shakedown Cruise
A dry run of the ship laboratory will be performed prior to the
ship leaving port. At this time the scientific crew will
install the analytical equipment. Contract personnel will
demonstrate QC proficiency by analyzing check standards after
calibrating the analytical instruments using set standards and
demonstrating each analytical system is in control (for out of
control situations see section 13). A series of stations from
Saginaw Bay (Table 1-6 - Figure 1-6) will be used for shakedown
purposes. Water samples will be taken at these stations, and
the water analyzed for all usual water quality parameters.
1.8 Site & Depth Selection
Loran C will be used for navigation in locating the stations
and in recording drift of the ship while nominally "on
station." Radar will be used as the primary system for
determining position. In the event that the Loran C and Radar
indicate different positions, the Radar will be used to
position the vessel and readings from the Loran C will be
recorded until the discrepancy can be corrected.
Tables 1-6A through 1-11A give approximate depths for chemical
sampling during unstratified (isothermal conditions) and Tables
1-6B through 1-1 IB give approximate depths for chemical
sampling during stratified conditions for Lake Michigan, Lake
Huron, Lake Erie, Lake Ontario, and Saginaw Bay, respectively.
For Lakes Michigan, Huron, Ontario, and Superior, unstratified
or isothermal sampling depths for normal stations are surface
(1M) mid-depth, and 2 meters from the bottom (B-2)!
Unstratified sampling depths for Lake Erie are surface (1M)
mid-depth, and 1 meter from the bottom (B-l). Samples at core
stations will be more frequent through the water column.
During stratified conditions, sampling depths for normal
stations in Lakes Michigan, Huron, Ontario, and Superior are
surface (1M), lower epilimnion 1 meter above the knee (LE),
thermocline (T), upper hypolimnion 1M below the knee (UH), B-
10, and B-2. Where water depth is sufficient, samples will
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also be taken at 100M and 200M. For Lake Erie, sampling depths
during stratified conditions are surface (1M), mid-epilimnion
(ME), lower epilimnion 1M above the knee (LE), thermocline (T),
upper hypolimnion 1M below the knee (UH), mid-hypolimnion (MH),
and 1 meter from bottom (B-l).
Phytoplankton will be from a composite of equal volumes from
depths of 1, 5, 10, and 20 meters hereafter referred to as the
"integrated sample" for all stations. (See discussion on
phytoplankton for more details.) When regular sampling depths
do not fall within 3 meters of integrated sample depths,
samples will be collected at the appropriate depths for use in
the composite or "integrated" samples only.
Zooplankton sampling shall be vertical tows from B-2 to the
surface, and from 20M to the surface.
Station
Latitude/Longitude
Table 1-1
Lake Michigan Plan
Approx. Depth Eat. So. of Samples
(ml Unstratified/Stratified
Distance
Between
Sites HCM1
Straits of Mackinac to Milwaukee
1
2
3
4
S
6
7
8
9
10
11
47
41C
40
32
34
27C
23
19
18C
17
11
B4AF Stations
1
2
3
4
5
6
7
8
9
10
11
12
780400
781000
781200
781400
781600
781800
812300
812500
812700
812900
813100
813300
45
44
44
44
44
43
43
42
42
42
42
10
44
45
08
05
36
08
44
44
44
23
42
12
36
24
24
00
00
00
00
00
00
86
86
86
87
86
86
87
86
87
87
87
22
43
58
14
46
55
00
35
00
25
00
30
18
00
00
00
00
00
00
00
00
00
45
44
43
43
42
42
45
45
44
44
43
43
35
11
43
14
46
18
29
00
32
04
36
08
44
37
31
24
15
04
33
27
20
11
01
48
86
86
86
86
87
87
86
86
86
87
87
87
03
29
41
53
05
17
31
44
56
09
21
33
55
31
57
11
11
58
00
48
22
42
48
41
186
250
160
159
160
112
88
92
161
100
128
101
110
92
110
156
97
92
190
180
135
135
135
Total
4
13
1
1
TT
55
19
70
38
52
58
37
42
62
60
C designates core stations
Total
48
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Station No.
L. Huron
Latitude/Longitude
QAPP Page 8
Table 1-2
Lake Huron Plan
Approx. Depth Eat. No. of Sample!
("1 Unatratified/Stratified
Distance
Between
Sites (KM)
Port Huron to Strait* of Macklnac
61
54
S3
48
45C
37
38
32
27
93C
15C
12
9
6
C designates Core Stations
45
45
45
45
45
44
44
44
44
44
44
43
43
43
45
31
27
16
08
45
44
27
11
06
00
S3
38
28
00
00
00
42
12
42
24
12
54
00
00
24
00
00
83
83
82
82
82
82
82
82
82
82
82
82
82
82
55
25
54
27
59
47
03
20
30
07
21
03
13
00
00
00
54
06
00
00
36
30
12
00
00
24
00
00
120
91
119
115
110
73
137
73
SO
91
68
86
57
46
10
10
10
10
11
10
10
10
10
11
11
10
10
10
47
41
31
S3
45
27
39
31
31
25
27
32
26
Total 77
102
Station *
Latitude/Longitude
Table 1-3
Lake Erie Plan
Approx. Depth
Est. No. of Samples
Unstratified/Stratified
Detroit to Port Colburn
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
61
60
59
58
91C
92
43
42
73
36
37
38
78C
32
31
30
63
15C
10
9
41
41
41
41
41
41
41
41
41
41
42
42
42
42
42
42
42
42
42
42
56
S3
43
41
50
57
47
57
58
56
06
16
07
04
IS
25
25
31
40
32
48
30
36
06
27
00
18
54
40
06
36
54
00
54
12
48
00
00
48
18
83
83
83
82
82
82
81
82
81
81
81
81
81
81
81
81
79
79
79
79
02
11
09
56
SS
41
56
02
45
28
34
40
IS
00
06
12
48
S3
41
37
42
48
00
00
00
12
42
30
25
42
30
18
00
42
24
18
00
36
30
00
10
9.5
10
11.5
10.5
11
23
22
24
23
24
22
23
22
21
21
45
60
32
47
Total
12
4
4_
94
Port Colburn to Detroit
Reverse of above station order
C designates Core Stations
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Station t
QAPP Page 9
Latitude/Longitude
Table 1-4
Lake Ontario Plan
Approx. Depth
-LEL
Eat. No. of Sample*
Unatratifled/Stratified
1
2
3
4
5
6
7
8
12
25
33C
41
49
(3
60C
55
43
43
43
43
43
43
43
43
30
31
35
43
46
43
34
26
12
00
48
00
18
54
48
36
79
79
78
78
77
77
77
77
Port
21
04
48
01
26
01
12
26
t Heller
12
48
06
36
18
00
00
18
to Rochester
98
133
131
122
SO
82
133
183
Total
1
i;
4
4i
10
11
12
11
10
10
t 12
\ 11
» 97
C designates Core Station*
Table 1-5
Lake Superior Plan
Station
779800
811500
811700
843800
844000
875900
876100
876300
909000
909400
942500
942700
976400
976600
1010700
1010900
1011100
1045600
1080700
Distance
Approx. Depth Eat. No. of Sanple* Between
Latitude/Longitude (ml Unstratif led/Stratified Site* /KMi
46
47
46
47
46
48
48
47
48
47
48
47
48
47
48
47
49
47
47
59
21
53
IS
46
33
04
36
26
30
20
51
13
44
06
37
09
30
22
35
38
40
33
29
31
27
21
12
51,
37
22
47
27
41
17
52
52
13
85
85
85
84
86
86
86
86
87
86
87
88
88
88
89
89
89
90
90
09
37
51
20
33
22
35
49
OS
32
49
02
32
44
15
27
39
09
51
40
14
05
54
20
37
29
04
10
46
31
31
40
IS
37
47
43
07
14
130
185
160
185
130
165
185
284
175
130
230
250
ISO
210
185
185
205
135
190
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Table 1-6
Lake Huron
Saginaw Bay Plan
Station t Approx. Depth Eat. No. of Samples
Station * Latitude/Longitude fm) Unatrat If led/Stratified
1 43 52 30 83 40 00 3
2 44 07 30 83 20 00 3
Any scheduled depth between 5 and 30 Deter* will be altered to determine
conditions during the stratified period if it is within 3 neters of the
themocline depth.
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Table 1-6A
Lake Michigan Sampling Depths (Unatratifled)
(April, October, February, March)
Station i Surface
Estimated Sampling
Depths in Meters
Mid-depth
Maxima Number
B-10 8-2 of Samples*
11
17
18*
19
23
27*
32
34
40
41*
47
780400
781000
781200
781400
781600
781800
812300
812SOO
812700
812900
813100
813300
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
64
SO
5,10,20,30
46
64
5,10,20,30
79
80
80
5, 10, 20, 30
92
lit
90
,40,50,100 151
82
118
,40,50 102
.5 149
ISO
150
,40,50,100,200 240
.5 175
Otb*r Depths To to
on Station
126
98
159
90
126
110
157
158
158
248
183
D«t«rmin«d
5
5
11
5
5
10
5
5
5
12
5
5
5
5
5
5
5
5
5
5
5
5
5
•Core stations are 18, 27, 41.
•fin each basin, a station and depth will be randonly selected for field duplicate
•anpliog (2 Nlskin sanples taken fron the sane depth). A second station will be
randonly selected for field blank analysis. These field quality control samples'will
result la three duplicates and three field blanks for analysis. A laboratory split
(duplicate) of a sample fron a randonly chosen depth will be analyzed at each station.
An integrated sample is included in sanple total.
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Table 1-6B
Lake Michigan Sampling Depthi (Stratified)
August
Estimated Sampling Depths in Meters
Ma x Lnuai
Number
Station * Surface Thenocline B-10 B-2 of Samples*
11 1 LE,T,UH 100 118 126 8
17 1 LE,T,UH 90 98 7
18* 1 5,(10 or LE),(20 or T),(30 or UH),40,50 100 151 159 11
19 1 LE,T,UH 82 90 7
23 1 LE,T,UH 100 118 126 8
27« 1 5,(10 or LE),(20 or T),(30 or UH),40,50 102 110 10
32 1 LE,T,tJH 100 149 157 8
34 1 LE.T.UH 100 ISO 158 8
40 1 LE,T,UH 100 ISO 158 12
41* 1 5,(10 or LE),(20 or T),(30 or UH),40,50 100,200 240 248 13
47 1 LE,T,UH 100 175 183 8
•Core stations are 18, 27, and 41. Any regularly scheduled depth at a core station
closest to a themocline depth sample will be replaced by the appropriate thennocline
depth sample. Any regularly scheduled B-10 depth sample within 3 Deters of a
themocline depth sample will be omitted.
++In each basin, a station and depth will be randomly selected for field duplicate
sampling (2 N is tin samples taken froa the sane depth). A second station will be
randomly selected for field blank analysis. These field quality control samples will
result in three duplicates and three field blanks for analysis. A laboratory split
(duplicate) of a sanple frcn a randomly chosen depth will be analyzed at each station.
An integrated sanple is included in sample total.
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Table 1-7A
Lake Huron Sampling Depths (Unstratifled)
(April, October, February, March)
Station
Surface
Mid-depth
B-10
B-2
Maximum Number
of Samples*
6
9
12
1S«
27
32
37
38
45*
48
S3
54
61
93«
1
1
1
1
1
1
1
1
1
1
1
1
1
1
23
28
43
5,10,20
25
36
36
68
5,10
57
45
59
21
45
.5
,30,40,50
.5
.5
.5
,20,30,40,50
.5
.5
.5
36
47
78
58
40
63
63
127
100
105
109
81
110
81
44
55
84
66
48
71
71
135
108
113
117
89
118
89
5
5
5
10
s
5
5
5
10
5
5
5
5
5
•Core stations are IS, 45 and 93.
++In each basin, a station and depth will be randomly selected for field duplicate
sampling (2 Niskin samples taken from the sane depth). A second station will be
randomly selected for field blank analysis. These field quality control samples will
result in three duplicates and three field blanks for analysis. A laboratory split
(duplicate) of a sample frcn a randomly chosen depth will be analyzed at each station.
An integrated sample is included in sample total.
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Table 1-7B
Lake Huron Sampling Depths (Stratified)
August
Maximum Number
Station 0 Surface Thermocline B-10 B-2
6
9
12
15«
27
32
37
38
45*
49
S3
54
61
93*
1
1
1
1
1
1
1
1
1
1
1
1
1
1
LE,T,UH
LE.T.UH
LZ.T.UH
5,{10,LE),(20,T),(30,UH) 40,50
LZ,T,UH
LE,T,UH
LE,T,UH
LE,T,UH
5,(10,LE),(20,T), (30, UH) 40,50
LE,T,UH
LE,T,UH
LE.T.UH
LE,T,UH
5,(10,LE),(20,T), (30.UH) 40,50
36
47
78
58
40
63
63
127
100
105
109
81
110
81
44
55
84
66
48
71
71
135
108
113
117
89
118
89
10
10
10
11
10
10
10
10
11
10
10
10
10
11
•Core stations are 15, 45, and 93. Any regularly scheduled depth at a core station
closes to a thermocline depth sample will be replaced by the appropriate thernocline
depth sample. Any regularly scheduled B-10 depth sample within 3 neterB of a
thernocline depth sample will be onitted. Total nujnber of samples between 1M and 100M
will be six samples.
+At randon stations a depth will be randomly selected for quality control work
consisting of a duplicate Niskin bottle sampling, and a field blank. An integrated
sanple is included in sample total. At each station a lab split of a randomly chosen
depth will be done. Total number of field duplicates and field blanks will result
in two analysis each run in Lake Huron. Over the entire survey the total number of
field duplicates and field blanks will result in four analysis for each in Lake
Huron. There will be at least one field duplicate and one field blank per run in
each basin.
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QAPP Page 15
Table 1-8A
Lake Erie Sampling Depths (Unstratlfied)
April, October, February, March)
Estimated Sampling Depths In Meter*
MaxlmuB Number
Station * Surface Mid-depth B-10 B-l of Samplea +
09
10
15*
30
31
32
36
37
38
42
43
58
59
60
61
63
73
78*
91«
92
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
20
20
5,10,20,30,40
10.5
10.5
11
11.5
12
11
11
11.5
5.5
4.5
5
5
20
12
5,10
5
5
38 46
31
51 59
20
20
21
22
23
21
21
22
10.5
9
8.5
9
36 44
23
22
9.5
10
5
5
9
5
5
5
5
5
5
5
5
5
5
5
5
5
5
6
5
5
•Core stations are IS, 91, and 78
++In each basin, a station and depth will be randomly selected for field duplicate
sampling (2 Siskin samples taken froa the sane depth). A second station will be
randomly selected for field blank analysis. These field quality control samples will
result in three duplicates and three field blanks for analysis for each run (a total
of six each for the entire survey). A laboratory split (duplicate) of a sanple frcn
a randomly chosen depth will be analyzed at each station. An integrated sample is
included in sample total.
-------
QAPP Page 16
Station t
Table 1-8B
Lake Erie Sampling Depth* (Stratified)
(August)
Estimated Sampling Depths in Meters
Surface
Thermocline
B-l
Maximum Kumber
of Samples*
09
10
15*
30
31
32
36
37
38
42
43
58
59
60
61
63
73
78*
91*
92
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
HE
ME
5,
ME
ME
ME
ME
ME
ME
ME
ME
ME
ME
ME
ME
ME
ME
ME
i
t
1
f
9
t
9
t
9
f
t
.
t
t
t
t
t
9
LE
LE
0,
LE
LE
LE
LE
LE
LE
LE
LE
LE
LE
LE
LE
LE
LE
LE
,T
,T
20
,T
,T
,T
,T
,T
,T
,T
,f
,T
,T
,T
,T
,T
,T
5
5
,T
t
9
t
t
t
t
t
t
t
t
t
9
9
9
9
9
9
9
1
UH
UH
30
UH
UH
UH
UH
UH
UH
UH
UH
UH
UH
UH
UH
UH
UH
10
UH
,MH
,MH
,40
,MH
,MH
,MH
,MH
,MH
,MH
,MH
,MH
,MH
,MH
,MH
,MH
,MH
,MH
,Mfl
46
31
59
20
20
21
22
23
21
21 (
22 t
10.5 I
9 f
8.5 (
9 I
44 t
23 {
22 :
9.5 4
10 8
1
J
1
(
1
1
1
1
•Core stations are IS, 91, and 78. Any regularly scheduled depth at a core station
closest to a thennocllne depth sample will be replaced by the appropriate theraocline
depth sample. If thermal structure is configured such that there is less than 3M
between sample depths, keep sample depths at LE,T,DH.
•fin each basin, a station and depth will be randomly selected for field duplicate
sampling (2 Niskin samples taken froa the same depth). A second station will be
randomly selected for field blank analysis. These field quality control samples will
result in three duplicates and three field blanks for analysis for each run (a total
of six each for the entire survey). A laboratory split (duplicate) of a sample from
a randomly chosen depth will be analyzed at each station. An integrated sample is
included in sample total.
-------
QAPP Page 17
Table 1-9A
Lake Ontario Sampling Depth* (Unstratlfled)
(April, October, February March)
Estimated Sampling Depth* In Meter*
Maximum Number
Station* Surface Mid-depth B-10 B-J of Sample*
12
25
33*
41
49
55*
60
63
1
1
1
1
1
1
1
1
49
66
5,10,20,
61
25
5,10,20,
66.
41
30,40,50,100
30,40,50,100
5
88
123
121
112
40
173
123
72
96
131
129
120
41
181
131
80
3
5
11
5
5
11
5
5
•Core stations are 33 and 55.
•fin each basin, a station and depth will be randomly selected for field duplicate
sampling (2 Niakin samples taken froa the sane depth). A second station will be
randomly selected for field blank analysis. These field quality control samples will
result in three duplicates and three field blanks for analysis. A labotatory split
(duplicate) of a sample from a randomly chosen depth will be analyzed at each station.
An integrated sample is Included in sample total.
-------
QAPP Page 18
Table 1-9B
Lake Ontario Sampling Depth* (Stratified)
(August)
Estimated Sampling Depth* in Meter*
Maximum Number
Station i Surface Thenrocline B-10 B-2 of Samples*
12
25
33*
41
49
55*
60
63
1
1
1
1
1
1
1
1
LE,T,UH
LE,T,UH
5,(10,LE),(20,T),(30,UH)40,50,100
LE,T,UH
LE,T,UH
5.(10.LE),(20,T),(30,UH)40,50,100
LE,T,DH
LE,T,UH
68
123
121
112
40
173
123
72
96
131
129
120
48
101
131
• 0
10
10
12
10
10
12
10
10
•Core stations are 33 and 55. Any regularly scheduled depth at a core • tat ion closest
to a themocline depth sample will be replaced by the appropriate thermocline depth
sample. Any regularly scheduled B-10 depth sample vithin 3 neter* of a themocline depth
sample will be omitted. The total number of samples between 1M and 100H will be six
samples.
•fin each basin, a station and depth will be randomly selected for field duplicate sampling
(2 Hiskin samples taken frcn the same depth). A second station will be randomly selected
for field blank analysis. These field quality control samples will result in three
duplicates and three field blank* for analysis. A labotatory split (duplicate) of a sample
from a randomly chosen depth will be analyzed at each station. An integrated sample is
included in sample total.
-------
QAPP Page 19
Station t
Table 10-A
Lake Superior Sampling Depth* (Unstratifled)
(April)
Sampling Depths in Meters
Surface
B-10
B-2
MajcLmum Number
of Samples
779800
811500
811700
843800
844000
875900
876100
876300
909000
909400
942500
942700
976400
976600
1010700
1010900
1011100
1045600
1080700
Other Sampling Depths to b«
D*t*rmin*d During Sampling
Station *
Table 10-B
Lake Superior Sampling Depths (Stratified)
Surface
Themoeline
B-10
B-2
Maxima Number
of Samples*
779800
811500
811700
843800
844000
875900
876100
876300
909000
909400
942500
942700
976400
976600
1010700
1010900
1011100
1045600
1080700
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
-------
QAPP Page 20
Table 11-A
Saginaw Bay Sampling Depths (Unatratlfied)
(April)
Sampling Depths in Meters
Maximum Number
Station * Surface B-10 B-2 of Samples
1 1
2 1
Table 11-8
Saginav Bar Sampling Depths (Stratified)
Maximum Number
Station * Surface Thermocline B-IO B-2 of Samples*
1 1
2 1
Any regularly scheduled depth between the surface and B-2 sample within 3 meters of a
thernocline sample depth will be dropped in favor or the therrocline sample depth. There
are no I sample at these stations. A duplicate Nisken bottle sample and a field blank
sample will be taken. A lab split will be done at each station at a randomly selected
depth.
-------
QAPP Page 21
2.0 PROJECT ORGANIZATION AND RESPONSIBILITY
Project planning and operation requires close cooperation
between GLNPO, CRL, and Contractor's personnel. GLNPO will
designate an EPA supervisor for each survey, who will be the
official point of contact for survey planning activities, as
well as for shipboard supervision of one shift. GLNPO will
provide supervision for each shift, Contractor will designate
a Biology Supervisor, a Chemistry Supervisor and a Survey
Supervisor. Contractor's Survey Supervisory role may include
one of the other supervisory roles. Figure 2-la illustrates
the administrative reporting lines of communication for the
parties involved in the operation, while figure 2-lb
illustrates the scientific lines of communication.
Quality control responsibility rests with each analyst.
Quality control overview of chemical analyses is the
responsibility of the Contractor's chemistry supervisor.
Coordination of corrective action will involve the GLNPO survey
supervisor when sampling activities may need to be interrupted.
Corrective action if a back log of chemistry samples develops
is addressed in section 13.
Spill clean up is the responsibility of each analyst if
quantity is less than one pint. Spills of larger quantities
should be reported immediately to Contractor's shift supervisor
personnel and EPA shift supervisor personnel. Spill clean up
personnel shall take corrective action to contain spill or
vapors or evacuate lab. Situation shall be reported to the
ship's bridge. In addition to the above lab personnel, the
spill clean up team includes ship personnel who will be
activated in case of major spill. This includes two ship
personnel trained in the use of self-contained breathing
resperators and the electronic technician.
-------
Figure 2-1 a
Contract Administration
Lines of Reporting
EPA's Contract
Officer for ASd
EPA's Contract Officer
for Seaward Services
AScI Project
Manager
CRLAScI
Project Officer
GLNPO Seaward
Service Project
Officer
AScI Survey
Supervisor
AScI Chief
Biologist
Seaward Service
Marine
Manager
GLNPO Survey
Supervisor/
Chief Scientist
Ship's Master
AScI Chief
Chemist
1
Biology Staff
1
Electronic
Technician
Ship's Crew
Chemistry Staff
/
-------
Figure 2-1 b
Scientific Communication
ASd Chief
Biologist
Biology Staff
AScI Survey
Supervisor
EPA Chief
Biologist
-------
QAPP Page 24
3 .0 OA OBJECTIVES FOR MEASUREMENT DATA IN TERMS OF PRECISION.
ACCURACY. COMPLETENESS. REPRESENTATIVENESS AND COMPARABILITY
3.1 Precision - A measure of mutual agreement among multiple
measurements of the same property, usually under prescribed
similar conditions. Precision can be evaluated from duplicate
analyses and expressed as the mean difference or more commonly
as the standard deviation or variance (the square of the
standard deviation) of the differences, either absolute or
relative. 3.1
3.2 Accuracy - The degree of agreement between a measurement (or an
average of measurements of the same thing) , and the amount
actually present. Since the amount actually present in real
samples is not generally known, the evaluation of accuracy is
performed from spike recovery data. The differences between
the two samples(the original sample and the spiked sample) can
be calculated from the known amount added, with a high degree
of precision, and the interferences present in the normal
sample (in contrast to the lack of interfering substances in
standards) are present in the original sample and the spiked
sample. Therefore, if the procedure is generating accurate
results on real samples, the result from the spiked sample
should be nearly equal to the result from the original sample
plus the spike. The average difference should be numerically
equal to the average difference between duplicate analyses.
For those parameters capable of being evaluated, the accuracy
goal is an average spike recovery of 90 to 110 percent.
3.3 Completeness - A measure of the amount of valid data obtained
from a measurement system compared to the amount that was
expected to be obtained under correct normal conditions. Our
completeness goal for physical parameters is 100% and for
chemical analyses is 95%.
3.4 Representativeness - Expresses the degree to which data
accurately and precisely represent characteristics of a
population, parameter variations at a sampling point, a process
condition, or an environmental condition. Representativeness
with respect to the present study is a measure of the parameter
variation at a sampling point and is evaluated by collecting
random duplicate samples.
3.5 Comparability - Express the confidence with which one data set
can be compared to another. The comparability of the cruise
data with previous cruise data is maintained by maintaining the
same procedures as much as is reasonable. When a procedure or
an instrument is changed, a comparison is made to verify that
-------
QAPP Page 25
the data is identical or more precise or accurate.
3.3 Completeness - A measure of the amount of valid data obtained
from a measurement system compared to the amount that was
expected to be obtained under optimal conditions.
3.4 Representativeness - Expresses the degree to which data
accurately and precisely represent characteristics of a
population, parameter variations at a sampling point, a process
condition, or an environmental condition.
3.5 Comparability - Express the confidence with which one data set
can be compared to another.
-------
QAPP Page 26
Table 3-1. OA OBJECTIVES FOR MEASUREMENT DATA IN TERMS OF PRECISION, ACCURACY
COMPLETENESS, REPRESENTATIVENESS AND COMPARABILITY
PERCTSION COAL
From Duplicate Analysis
COMPLETENESS
PARAMETER |x, -x,| diff ACCURACY GOAL GOAL
or 8X whichever is larger
Air Temperature
Wind Speed
Wind Direction
Seech i Depth
Wave Height
Water Temperature
Optical Transmit tance
Turbidity
Specific Conductance
PH
Total Alkalinity
Total Ammonia Nitrogen
Total Kjeldahl Nitrogen
Dissolved Nitrate & Nitrite
Total Phosphorus
Dissolved Orthophosphate
Total Chloride
Total Sulfate
Total Dissolved Phosphorus
Dissolved Reactive Silica
Participate Organic Carbon
Dissolved Organic Carbon
Na
K
Ca
*9
Dissolved Oxygen
Phytoplankton
Zooplankton
Aerobic Heterotrophs
Chlorophyll "a"
* 0.5°C
i 1 nautical mph
i 10°
i .5m
t .5m
t .1°C
0.12 .18
.5uS .5uS
.2SU .6SU
,6mg/L 0.8mg/L
.5ppb O.Sppb
20ppb 22ppb
3ppb 3ppb
.6ppb Ippb
.6ppb Ippb
.2ppm 0.5ppm
.3ppn O.Sppn
.6pcb I.Opcb
5ppb &ppb
< ( + Zs)
not established
-
t .2 ppm 0.6ppn
see method varies
with algae type
not established
not established
RPD < 7X
t 0.buC 100X
t (1 nautical mph * 20X)
times measured value)
t 10°
t (.2 m + 20X
times measured value)
t (.3 m + 30X
times measured value)
t 0.5°C
t 5X
t (0.1 + 10X
times measured value)
(control std.) x t 3s)
(control std.) x t 3s)
(control std.) x t 3s)
(control std.) x t 3s)
(control std.) x t 3s)
(control std.) x t 3s)
(control std.) x l 3s)
(control std.) x t 3s)
(control std.) x t 3s)
(control std.) x t 3s)
(control std.) x t 3s)
(control std.) x t 3s)
(control std.) x t 3s)
not established
x i 2s
x t 2s
x t 2s
x t 2s
i 0.5 mg/L or t 10X
times measured value
NA
NA
NA
± 10X or t .3 ug/L
whichever is greater
100X
lOOX
100X
100X
100X
95X
95X
95 X
95X
95X
95X
955!
95X
95X
95X
95X
95X
95X
95X
95X
95X
95X
v5X
95X
95X
95X
95X
95X
95X
95X
NA = Not Applicable
RPO = Relative Percent Difference
- difference between duplicates (lab splits)
= average difference between lab splits
""=" *- -x-
n where xi and x
m=1 are duplicate
samples
-------
, -••/
/.'/•"' '
£/„
I • • / u • ,. //»
Figure 4-1b. Integrated Sample Flowchart , ft' LJ~ L/^i
Integrated (Composite) Sample / f^ /
1 Gallon Cubitainer
960ml 100ml 125ml 125ml
Poryethylene | Polyethylene Polyethylene
| 47 mm Glass i i '
1 l ^t/*\fc ^lr^£kf p*lltOf 1
^»yJ^J yl J i 1 ^^wl t II Iwl -- ^ -^ — ^ • f*^f 'jjmn.1 t_IK. 1^^
Phytoplankton Filter 300ml/L .
Acidify TKN 1 1
HCI Technicon Ca.Mg.Na K
| ICAP AA
POC
500 ml Filter (
Poryethylene ^artc
47mm
FiHer 250ml MemJ
Gelman Ml
Glass Fiber
Filter Filtr
125m
Add MgCO3
Store in
90% Acetone
I NCLNCLS
Chlorophyll a ^ «•
Phaeo. a Tecl
Fluorometer
300ml, 125
>riu3 Polyet
.45um
>rane
ter
Tech
ate
poly
JiO2TDP,SRP,DOC.
inicon
I
125ml
Poryethylene
ci,so4
Technicon
1
Primary Productivity Samples
1 i 1
ml 20ml 100ml 100ml 500ml
hylene I I
CI,SO4 pH Total Specific
P Technicon Meter Alkalinity Conductance
nicon Titration Wheatstone
Bridge
N£
NH,
i
100ml
Turbidity
iphelometer
-------
Figure 4-1 a. Sample Processing Flowchart - 81 Niskin Samples
. 8L Niskin
V l
I
Water Temp. 96C
)ml 60ml 12!
>ml 125ml 125
ml 1 ga
lion Sur
face 500
ml
Surface only polyethylene BOD polyethylene polyethylene polyethylene Cubitainer &B10 polyethylene
or graduate
Surf, 5, 1i
1 ge
3.&20 m Cl
Tec
illon no
Cubitainer Titration
integrated
I
.25mlH|O4 .625mlHNO0
SO4 300 ml/L 50(
hnicon
TKN
Technicon
r
Dml/L
i
sample I I
Ca.Mg.Na
ICAP
•^v-'
"
K
AA
.,.». L-f-t"
I
2 L plastic
container Filter 250ml
i Gelman
Millepore Glass Fiber
Ap20,47mm F rter
Glass Fiber
Fil!flr Add MgCO,
I Store in
Petr'idish 10 ml. 90%
i Acetone
Total
Suspended
Solids _._,
i__ .it ^
1
Filter 300ml,
Sartorius
47mm, .45um
Filter
1
Filtrate
125ml poly
I
I I
125ml 100ml 100ml
|
TP pl
I
H Total
Technicon Meter Alkalinity
/ W'j L Titration
* Jf
I
500ml
i
Specific
Conductance
Wheatstone
Bridge
100ml
Turbidity
Nephelometer
I
NQ..NO ,SiO .TDP.SRP.DOC.NH.
2 2 _ . . 3
Technicon
Chlorophyll a
Phaeo. a
Fluorometer
-------
QAPP Page 30
sample bottle and preservative dispenser. Dissolved oxygen samples
are "set up" immediately. This involves filling the bottle to
overflowing, allowing overflowing to continue 5 seconds before
adding, in series, the first two reagents, allowing the floe to
settle, mixing and allowing floe to settle again. D.O. samples are
then completed in the main laboratory.
4 . 3 Sampling Equipment
4.3.1 Rosette Sampler - General Oceanics Model 1015-12-8 with EBT
guideline Model 8705
A 12-bottle Rosette sampler system (General Oceanics Model 1015-
12-8) will be used to collect water sample. A submersible bottle
mounting array enables an operator to remotely actuate a sequence
of up to 11 water sampling bottles. This system consists of an
EBT (Guideline Model 8705) attached to the twelfth bottle position
of the array, an A-frame, 1000 feet of multi-conductor cable, and
a 5HP variable speed winch. The bottles can be sequentially
closed remotely from the deck of the vessel while the array is
submerged at the various sampling depths. The Rosette will
accommodate any of the General Oceanics rigid PVC 1010 Niskin
sampling bottles up to the 8 liter size.
The Guildline EBT is factory calibrated, so that the only way that
erroneous values can be obtained are through improper placement of
the suppression, zero, volts/unit controls, or the Recorder
controls. A variable zero control for the depth (pressure) is
necessary to compensate for atmospheric pressure variability. The
zero control for temperature should not be manipulated once it is
,/ properly set with an ice water bath prior to the cruise (Guideline
manual). Temperature will be plotted along the horizontal axis at
/X 50 ft/in, to 500 ft. at which point the scale will be shifted to
125 ft/in. After the samples are collected and the Rosette is
brought on board by use of the A-frame, the samples are
distributed to the various sample storage bottles while the Niskin
bottles remain attached to the Rosette.
-------
QAPP Page 31
4.3.2 x,y Plotter-Hewlett Packard Model 7046A
Since the selection for sampling depths is influenced by the
temperature-depth profile (Tables 1-6A to 1-10B), the temperature
vs. depth graph is recorded by an x,y plotter (Hewlett Packard
Model 7046A) as the Rosette is lowered to the bottom. Collection
of the samples (close the Niskin bottles) is done primarily as the
Rosette is raised to the surface. Care should be taken to assure
that the Hewlett Packard recorder vernier controls (on the range
selector switches) are set on the cal position, and that the
suppression controls on the Guideline console are set at zero.
4.3.3 Microbiology Samplers
Microbiological samples are to be collected by means of a
hydrographic winch, with 5/32 in. 5x7 stranded stainless steel
aircraft cable, terminated with a 50 Ib. steel weight. In the
event of a failure of the Rosette system^water quality samples
will be taken using this system. At depths less than 100-m,
ZoBell microbiology samples are triggered at the designated depths
by General Oceanics bronze messengers Model M1009MG. At depths
greater than 100-m, General Oceanics "butterfly" or "chopstick"
samplers are used, triggered in the same way.
The samplers and messengers are designed so that each sampler the
descending messenger encounters causes that sampler to release a
messenger to close the subsequent sampler. This sequence
continues until the lowest sampler is encountered. Sterile pre-
evacuated 250 ml ZoBell bottles (APHA, 1975) are used for
microbiology samples collection.
As the bottle handler attaches the Niskin bottle or ZoBell sampler
for the bottom sample, the winch operator sets the depth on the
metering wheel to coincide with the sampling depth. The winch
operator then lowers the cable until the metering wheel indicates
the next sampling depth. The cable is then stopped and the second
Niskin or ZoBell sampler is attached to the cable along with a
messenger.
This sequence continues until all sampling depths are represented.
Then the winch operator lowers the cable until the metering wheel
indicates minus two meters (or however high the bottle handler is
above the surface of the water). A messenger is attached to the
cable and released by the bottle handler. By touching the cable,
the bottle handler can feel an impact as each messenger triggers
its intended sampler. When all samples are triggered, the bottle
handler signals the winch operator to raise the cable until the
upper bottle can be retrieved and placed in a carrying container
for transfer to the microbiology laboratory.
-------
QAPP Page 32
4 .4 Sampling Protocol
4.4.1 Depth Control
The depth at which samples will be collected is determined by a
pressure transducer on the Rosette sampler. To assure that the
controls on the depth measuring equipment are properly set, the
bottom sounding will be compared to the Rosette sample reading at
each station. The Rosette winch operator obtains a depth sounding
from the bridge and writes this on the chart under observations
and marks the chart at the appropriate location on the depth axis
edge. The Rosette sampler will then be raised. Three minutes
will pass to allow the sampler to drift away from the disturbed
area before the B-2 sample is taken. The Rosette sampler will be
lowered to B-2 and the sample taken.
A duplicate sample will be taken prior to the B-2 sample.
Additional time intervals of three minutes are allowed to elapse
prior to taking the thermocline sample and the lower epilimnion
sample. These intervals provide time f&r water equilibration
within the Niskins.
The knees of the EBT temperature depth trace will be determined by
trisecting the angle between the epilimnion and mesolimnion
temperature traces (upper knee) and the angle between the
mesolimnion and hypolimnion temperature traces(lower knee). The
upper knee is the upper 1/3 angle intercept, the lower knee is the
lower 1/3 angle intercept. The lower epilinmlon sample is one
meter above the upper knee. The upper hypolimnion sample is one
meter below the lower knee.
4.4.2 Sequence of Sampling Events (Some events may be done
simultaneously and event order will be subject to conditions)
Visual and physical station observations recorded;
Air temperature, wind speed, aesthetics, wind direction, depth,
and wave height
a) Run EBT down to define the temperature profile and determine
the thermocline location during stratified situations
b) Examine the EBT profile obtained in 4.4.2.a. Select sampling
depths according to depth selection (Sec.1.8 and Sec. 4.4.1)
c) Trigger sample bottle at correct depths, while verifying the
temperature profile
-------
QAPP Page 33
d) Split Rosette Nlskin samples into the required sample
bottles/preservatives. (See Figures 4-1A and 4-1B for details)
A composite 20m sample is taken for phytoplankton, chlorophyll
a, pheophytin, DOC and POC by compositing Niskin samples at 1,
5, 10 and 20 meters.
e) Send ZoBell sampler down to collect microbiological samples at
the same depths as determined in 4.4.2.b.
f) Conduct the 20 meter and B-2 vertical tows for zooplankton
samples, rinse net and pour into 500 ml. polyethylene bottles
with 10-15 ml club soda and 5% formalin as preservatives.
4.4.3 Nutrient Sample Filtration
Dissolved nutrient samples will be prepared by vacuum filtration
(< 7 psi) of an aliquot from the PEC for onboard analyses within
an hour of sample collection. A 47 mm diameter 0.45 urn membrane
filter (Sartorius) held in a polycarbonate filter holder (Gelman
magnetic) with a polypropylene filter flask prewashed with 100 to
200 ml of demineralized water or sample water will be used. New
125 ml polyethylene sample bottles with linerless closures will be
rinsed once with filtered sample prior to filling.
The aliquot for total dissolved phosphorus will be transferred to
the digestion tube as soon as possible. The remainder of the
processed sample water will be used for the other dissolved
nutrient samples.
4.4.4. Suspended Solids Filtration
Samples for suspended solids (up to 2 liters) are taken from the
surface and the B-10 Niskin bottles. Vacuum filtration (<= 7psi)
through a 47mm millpore AP 20 glass fiber filter is performed
within two hours of sampling. One field blank or lab blank is
filtered for every four stations and one duplicate analysis is
performed every four stations.
4.4.5 POC Filtration
Whatmann GFF 47-mm glass fiber filters are used to collect the
particulates from the integrated sample at each station for POC
analysis. For every four stations a field blank or lab blank will
be filtered and a duplicate analysis will be performed.
4.5 QC Samples
4.5.1 Blanks
Field blanks will be collected in every basin during a survey.
for a total of 20 stations See Tables 1-6A to 1-10-B for details.
-------
QAPP Page 34
Field blanks are collected exactly as the samples except they are
taken from the deionized water tap instead of the Niskin bottle
spigot. Field blanks are used to measure the level of
contamination introduced by the sampling procedure but are not
used to adjust or correct sample values.
Lab blanks will be taken directly from the reagent water source,
a wash bottle or some other dedicated reagent water bottle.
4.5.2 Replicates
At 20 randomly selected stations, a depth is randomly selected to
be sampled and analyzed in duplicate to evaluate sampling
analytical variability.
A duplicate sample will be taken by firing a Niskin bottle at the
designated depth as the Rosette sampler is being lowered to the
bottom. This will be labeled "Duplicate." The primary sample is
then collected as the sampler is raised to the surface as
previously described. At another depth the primary sample from
the QC depth will also be analyzed in duplicate in the laboratory
(lab split) for each station.
Duplicate EBT profiles are not made using the Rosette sampler.
However, the surface Niskin temperature is measured using a
mercury thermometer and compared with the EBT profile at the
surface depth. The Rosette temperature probe is calibrated using
an ice water bath.
4.6 Sample Collection and Analysis
4.6.0 Brief Analytical Protocol
A list of parameters analyzed may be found in Table 4-1. Detailed
analytical methods are in Section 7.
4.6.1 Air Temperature
Air temperature will be determined by use of the Maxi-Min.
Temperature System RMS-Technology Inc. which wil be read to the
nearest 0.1°C.
4.6.2 Wind Speed and Direction
Wind speed and direction readings from a permanently mounted
Danforth Marine type Wind Direction and Speed Indicator or a Wind
Speed and Wind Direction Meterological Meter Model F will be taken
and recorded while the vessel is stopped to the nearest 1° (to the
right of true north). Wind direction is accurate to ± 10°. The
reading of speed will be estimated to the nearest nautical mile
per hour and stored as miles per hour.
-------
Page 33
Table 4-1
Parameter List
Parameter
Air Temperature
Wind Speed
Hind Direction
Secchi Depth Have
Height
Hater Temperature
Optical Transnittance
Turbiditv
Uliuolveo oxygen
Specific Conductance
PH
Total Alkalinity
Dissolved Amnonia N
Total Kjeldahl N
Dl». Nitrate* Nitrate N
Total Phosphorus
Total Dissolved P
Dissolved Ortho - P
Chloride
Total Sulfate
Din. Reactive Silica
Total Suspended Solids
Aerobic Beterotrophs
Chlorophyll a
Pbaeopbytin a
Aeithetlc-vhere
applicable
Phytoplankton
Xooplankton
Prinary Prod. Parameters
Particulate Organic C
Diisolved Organic C
Sodium
Potanltm
Calcium
Magnesias
STORET
00020
00035
00040
00078
70222
00010
00074
00076
00300
0009S
00040
00410
00608
00625
00631
00665
00666
00671
00940
00945
01140
00530
31749
32209
32213
00929
00937
00916
00927
Cruise
All
ugust
Stations
All
•
•
Selected
All
Depth
ATI
Continuous
All
Surf, BIO
All
•
•
Integrated
Integrated
Selected
All
•
All
•
•
•
Sample
Shaded fron sun
Onsite Measure
•
•
•
Niskin,EBT,CTD
CTD
Niskln - PEC
- 125 PE
- 125 PE(S)
- 125 PE
or 125 PE
- 125 PE
- 125 PE
- 125 PE
Zobell Sampler
Hi s kin - PEC
•
Niskin-960PE(L)
*6net-SOOPE(C)
Niskin - 125 PE
(N)
\
' 'J
v - tS
*i&
nc
CTD
PEC
PE
(S)
(H)
(C) -
Conductivity-Temperature-Depth (Sea Bird)
Polyethylene Cubitainer, 4 liter
Polyethylene, preceding number indicates voluae in nllliliters
lnl/1 concentrated sulfuric acid added as preservative
5nl/l concentrated nitric acid added as preservative
8-10 el/1 Acid Lugols preservative
Club soda, 5% fomalin
4.6.3 Secchi Disc Depth
Secchi Disc Depth will be estimated at each station on all cruises
by use of a 30 cm, all-white Secchi disc. Secchi disc depths will
be recorded to the nearest 0.5 meters.
4.6.4 Wave Height
Average wave height (valley to crest distance)' and wave direction
will be estimated at each station by the senior crew member on the
bridge. Wave heights will be recorded to the nearest 0.5 ft.
-------
OM>P Page 36
4.6.5 Water Temperature
EBT temperature will be verified by uses of a mercury thermometer
readable to 0.1 C (ASTM no. 90C). The thermometer shaft will be
immersed in the full surface Niskin bottle or in the 960 ml plastic
sajnple bottle. Readings will be estimated to the nearest 0.1 C.
EBT temperature trace data will be used for in situ temperature
readings for all sampling depths. The Niskin sampling bottles used
on the Rosette (fSxay* be fitted with Reversing Thermometer Assemblies
(one on every otHer bottle) to use as a check on the EBT temperature
probe readout. \
4.6.6 Water Temperature and Light Transmission Profiles
Temperature vertical profiles may be determined from surface to
bottom with the Sea Bird CTD.
The turbidity sensor uses a transmissometer technique of light
attenuation. The sensor utilizes a constant LED light source and
calibrated photosensor separated by a 25 centimeter path length.
The attenuation of the light source by the turbid water is measured.
The measurement is indicated in terms of percent transmission, or
alternatively as an attenuation coefficient.
4.6.7 Turbidity
Turbidity will be measured with a Turner Turbidimeter. The
turbidimeter will be calibrated before analysis of each set of
samples using a standard within the anticipated range of turbidity.
All turbidity samples will be heated to 25 C to avoid condensation
on the sample cuvet. Readings on the 0-1 range will be recorded to
the nearest 0.01 unit and readings from 1-20 range will be recorded
to the nearest 0.1 unit. These reading are done after conductivity
is determined (see 4.6.9) A portion of the conductivity sample is
transferred to the curvette for turbidity measurement since the
sample is already at 25 C
4.6.8 Dissolved Oxygen
Dissolved oxygen will be measured on water samples from all depths
in Lake Erie and at the bottom depth in all other lakes, at each
station on each survey. Analyses will be made by the azide
modification of the Winkler test (EPA, 1974). The dissolved oxygen
sample aliquot is obtained by inserting an 8 to 10 inch length of
flexible plastic Tygon tubing connected to the Niskin bottle outlet
plug to the bottom of a 60 ml glass BOD bottle. Flow will be
regulated by the outlet plug so as to minimize turbulence and
mixture of oxygen with the sample.
-------
0&PP Page 37
In addition, dissolved oxygen will be measured during the cast of
the Sea Bird CTD with the built-in polarographic electrode.
4.6.9 Specific Conductance
Specific conductance will be determined using a YSI Model 35
conductivity bridge and a conductivity cell (YSI 3401 or YSE 3403,
K = 1.0). An immersion heater (such as is used for heating a cup of
water for instant coffee), connected to a manually operated switch,
will be used to heat the sample in a 250 ml polypropylene beaker to
25.0 C. The temperature will be monitored with a mercury
thermometer (ASTM 90C) with 0.1 C divisions. Rapid stirring will be
accomplished with an immersion glass paddle attached to a small
electric motor. The apparatus will be standardized daily against a
standard KC1 solution according to the equation of Lind et al.
(1959).
Conductivity will also be measured during the cast of the Sea Bird
CTD. Raw conductivity measurements will be converted to specific
conductance using empirically derived formulas.
4.6.10 £H
pH analyses will be made by electrometric measurement. pH meters
will be standardized with pH 7.0 and 10.0 buffers, to bracket the pH
of lake water. A combination Ross electrode with a platinum
internal electrode element will be used. The pH measurement is
taken by placing the pH probe in the water remaining in the
conductivity sample (4.6.9) after the turbidity curvette (4.6.7) has
been filled.
Measurements of pH will also be made during Sea Bird CTD casts.
4.6.11 Total Alkalinity as CaCO,
Total alkalinity will be determined by titration to pH 4.5 with 0.02
NH2SO4. The pH neter (Cole Farmer Model 5997), with Ross combination
electrode, will be standardized daily with pB 4.0 and 7.0 buffers.
The acid will be standardized against a standard Na,CO, solution.
4.6.12 Dissolved Ammonia Nitrogen
Dissolved ammonia nitrogen analyses will be performed with a
Technicon Autoanalyzer System II using a modification of Technicon's
industrial method 154-7IW/Tentative (Van Slyke and Hillen, 1933).
The pump tube rates will be as follows: sample 0.80 ml/min,
complexing agent 0.42 ml/minf alkaline phenol 0.23 ml/min,
hypochlorite 0.16 ml/min, nitroprusside 0.23 ml/min, and flow cell
1.00 ml/min. The ammonia determinations will be performed on board
as soon as possible, but always within 8 hours of sample collection.
Samples will be maintained at 4 C until analyzed.
-------
OAPP Page 31
4.6.13 Total Kleldahl Nitrogen
Total Kjeldahl nitrogen samples will be preserved for no longer than
90 calendar days by the addition of 0.40 ml of H,SO« (310 ml/L) to
each 125 ml. Preservative will be added to samples within 30
minutes of sample collection. Analyses will be made by an
"ultramicro semiautomated" method (Jirka et al., 1976), in which a
10 ml sample is digested with a solution of K,S04, and HgO in a
thermostated 370 C block digestor. After cooling and dilution with
water, the sample neutralization and ammonia determination
(Berthelot Reaction) are accomplished on a Technicon Autoanalyzer
System II.
4.6.14 Dissolved Nitrate and Nitrite Nitrogen
A Technicon Autoanalyzer will be used with Technicons industrial
method no. 158-71W (Armstrong et al., 1967; Grasshoff, 1969; FWPCA,
1969). In this procedure, nitrate is reduced to nitrite, in a
copper cadmium column, which is then reacted with sulfanilamlde and
N-1-napthylethylenediamine dihydrochloride to form a reddish purple
azo dye. Nitrate and nitrite analyses will be performed within 48
hours of collection.
4.6.15 Total Phosphorus and Total Dissolved Phosphorus
Conversion of the various forms of phosphorus to orthophosphate is
by an adaptation of the acid persulfate digestion method (Gales et
al., 1966). Screw cap tubes containing samples and digestion
solution will be heated in an autoclave at 15 psi (121 C) for 30
min. After cooling, the resulting orthophosphate is determined by
the Technicon Autoanalyzer system II and Technicons industrial
method 155-71W (Murphy and Riley, 1962).
The sample storage bottle for total phosphorus will be agitated
before sampling. Samples will be transferred to digestion tubes as
soon as possible after sample collection.
4.6.16 Dissolved Orthophosphate
Samples will be analyzed for orthophosphate using a Technicon
Autoanalyzer System II and Technicon 's industrial method 155-7 1W
(Murphy and Riley, 1962). This is the single reagent ascorbic acid
reduction method in which a phosphomolybdenum blue complex is
measured photometrically at 880 mn. Analyses will be performed on
the filtered sample.
4.6.17 Chloride
A Technicon Autoanalyzer System II will be used with Technicon 's
industrial method No. 99-70W (Zall et al., 1956; O'Brien, 1962). In
this method chloride i'on displaces mercury from mercuric thiocyanate
-------
Page 39
forming unionized soluble mercuric chloride. The released
thiocyanate reacts with ferric ion to form intensely colored ferric
thiocyanate which is determined photometrically. Raw water samples,
will be stored non-refrigerated in 125 ml or 250 ml polyethylene
bottles with plastic closures.
4.6.18 Sulfate
Samples will be analyzed for sulfate with a Technicon Autoanalyzer
using Technicon's industrial method 118-71W (Lazrus et al., 1965).
In this procedure the sample is first passed through a
cation-exchange column to remove interfering cations. The sample is
then mixed with an equimolar solution of Bad, and methylthymol blue
(MTB). Sulfate reacts with Ba reducing the amount of Ba available
to react with MTB. The free MTB is then measured photometrically.
Raw water samples will be stored nonrefrigerated in 125 ml or 250 ml
polyethylene bottles with plastic closures.
4.6.19 Dissolved (Reactive 1 Silica
A Technicon Autoanalyzer System II is used with Technicon's
industrial method No. 186-72W/Tentative (Technicon, 1973). This
method is based on the chemical reduction of a silicomolybdate in
acid solution to "molybdenum blue" by ascorbic acid. Oxalic acid is
added to eliminate interference from phosphorus. Analyses will be
performed on the filtered samples.
4.6.20 Microbiology Parameters
Direct Observation of Bacteria by DAPI
DAPI is a highly specific stain for DMA and can be used to
separate bacteria from non-living particles. By observing
the nuclear material organisms, an estimate can be made of
the number of organisms per unit volume of water. An aliquot
of water collected with a nonmetallic sampling device is
transferred into a sterile glass vial and preserved with
glutaraldehyde. The sample is then exposed to DAPI, filtered
onto a black membrane filter which has been treated to
suppress autofluorescence, and then mounted on a microscope
slide. A compound microscope equipped with an
epifluorescence attachment is used to observe the filter.
Random fields are counted and the resultant number is used in
calculations to obtain a value in cells/unit volume.
Direct observation of bacteria by DAPI will be performed for
all water samples in parallel with analyses for aerobic
heterotrophs.
Aerobic Heterotrophs
-------
Page 40
Aerobic heterotrophic bacterial densities will be determined
at several depths at all stations on all cruises by the
membrane filtration technique, using Bacto Plate Count agar
with aerobic incubation at 20'C +/- . 5*C for 48 hours (APHA,
1971). Counts will be made with aid of a 10-power
stereomicroscope. Counts will be made in accordance with
Standard Methods. (APHA, 1975) except that total plate count
agar plates, presolidifled in petri dishes, type 50 x 15 nan,
will be used in place of pour plates.
4.6.21 Chlorophyll "a" and Pheophytin
Samples for chlorophyll analysis (100 ml to 500 ml) will be taken
from all depths at all stations and from the integrated or composite
sample and will be filtered at <7" of Hg vacuum along with 1 to 2 ml
of MgCOj suspension (10 gm/1) usually within 30 minutes of sample
collection. In some instances filtration may be delayed for as long
as 2 hours. The filter (Gelman - Glass Fiber Filter type AE) will
be retained in a capped glass tube containing 10 ml of 90% acetone
at -10 C in the dark for up to 30 days prior to completion of the
analysis. The tubes will be treated in an ultrasonic bath for 20
minutes and then allowed to steep for a minimum of 24 hours prior to
fluorometric analysis with a fluorometer (Strickland and Parsons,
1972) .
In situ chlorophyll a. measurements will also be made during Sea Bird
casts.
4.6.22 Aesthetics
Reports of any unusual visual conditions that exist at any station
will be made. Conditions such as floating algae, detritus, dead
fish, oil, unusual water color, or other abnormal conditions will be
recorded in the field observations.
4.6.23 Phytoplankton
Phytoplankton samples will be collected from all stations on the
regularly scheduled cruises as well as at master stations on
supplemental cruises. The samples will be representative of the
upper 20 meters of the water column and will be collected as
follows: whole water will be collected by Niskin bottle from 1, 5,
10, and 20 meters.
Approximately 960 ml of sample from each depth (1, 5, 10, and 20
meters) will be mixed in a one-gallon cubitainer. Approximately 960
ml of the mixed sample will be transferred to a 960 ml bottle and
immediately preserved with 10 ml of modified Lugol's solution for
phytoplankton analysis. The remaining volume in the cubitainer will
be designated the "Integrated Sample" and will be used for chemical
analysis.
-------
QAPP P«qe 41
At CRL diatoms will be cleaned with 30% H,O, plus KaCr207 and mounted
in Hydrax. At least 500 frustrulea per sample will be enumerated
and identified at 1250X. Other algal forms will be identified and
enumerated at 500X using a modification of the Utennohl (1958)
method.
Bio volume 3 will be determined for each sample by assigning an
appropriate geometric shape and making the necessary measurement for
the volume calculation. A minimum of 10 individuals of each common
species will be measured in each sample. Less common organisms will
be measured when they occur.
4.6.24 Zooplankton
Samples for crustacean zooplankton will be collected by vertical
tow. Zooplankton tows will be made from B-2 meters to the surface
and from 20 m to the surface at each station using a 62 micron mesh
plankton net with a 0.5 meter mouth opening. At master stations,
duplicate tows will be taken for evaluation of the
representativeness of the tows collection of the zooplankton
assemblages volume of water sampled for each tow will be determined
by recording the before and after tow reading of a flow meter
mounted in the mouth of the plankton net.
Following collection, the plankton net shall be hosed down (from the
outside onlyl) to wash organisms adhering to the side of the net
into the collection cup. The contents of the cup shall be rinsed
twice with distilled or potable water and the washings added to the
sample bottle. Ten to fifteen ml of the narcotizing agent (club
soda) shall be added to each sample.
The bottle shall be inverted two or three times to assure mixing and
then allowed to stand 10 or 20 minutes for narcotization to take
effect. Samples will then be preserved with 5% formalin (10 ml
concentrated formalin/250 ml sample). Each sample will be labeled
with the regular station number and the depth at which the tow was
begun. An entry will be made on the zooplankton field sheet
indicating station number, date time, depth at which the tow was
begun and the before and after tow flow meter reading, as well as
wire angle during the tow.
4.6.25 Particulate Organic Carbon
Particulate matter from a sample of variable volume is collected on
a 47 mm glass fiber filter (Whatman GF/P) which has been pretreated
by firing at 500 C. The material is washed with 0.1 NHC1 acid to
remove inorganic carbon, and the 47 mm filter is folded in quarters
and placed in a petrie dish. The petrie dish and filter are stored
in a freezer. The entire filter is later subjected to elemental
carbon analysis at CRL.
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Page 42
4.6.26 Dissolved Organic Carbon
Organic carbon will be determined on all filtered samples at all
stations using a Technicon Autoanalyzer System II and Technicon's
industrial method No. 451-76W. In this method, the acidified sample
is purged with COj-free gas and then subjected to short wave UV
radiation to convert carbon compounds to C02. The generated CO, is
measured with a nondispersive CO, detector.
4.6.27 Sodium, Potassium, Calcium, Magnesium
Sample are to be analyzed at CRL using flame Atomic Adsorption AA
for potassium and Inductively Coupled Plasma analysis for sodium,
calcium, and magnesium. Samples are preserved with .625 ml of 1/1
nitric acid per 125 ml of sample.
4.6.28 Primary Productivity Parameters
Samples for analysis of primary productivity will be collected at
selected sites in parallel with those for phytoplankton enumeration:
during the summer survey a separate sample from the M3 depth will be
taken for analysis also. Approximately 4L of composited water
sample will be collected into a darkened carboy or cubitainer, and
the carboy placed immediately in a light-tight insulated chest for
transportation to the shipboard laboratory. The water sample will
be transferred to 300 ml incubation bottles and inoculated with a
known quantity of bicarbonate substrate which is labeled with the
radiotracer"C. Samples from the same water source are incubated at
temperatures approximating ambient, at various light intensities for
2 to 4 hours, after which the algal cells are separated from the
water by filtration.
The filters are inmersed in a scintillation cocktail and returned to
CRL for counting in a liquid scintillation counter. Because the
measured radio activity of each filter will be proportional to the
quantity of carbon fixed by the algae into organic material, the
metabolic activity of the algae community can be established.
Calculation of the productivity parameters also require information
about the total inorganic carbon available in the incubation vessel,
the length of time of incubation, the chlorophyll content of the
incubated sample and the specific activity of the radiotracer.
4.6.29 Suspended Solids
Samples for analyses of suspended solids will be collected in
separate containers marked for surface (1M) and bottom (BIO). A
weighed filter contained within a petri dish will be used to collect
suspended materials from up to 2 liters of sample. Filtration at
<7" of Hg psi vacuum will be done within 30 minutes of sample
collection. The filter (47mm Millepore AP20 glass fiber filter) on
-------
Page 43
the spring/summer survey will be weighed at CRL after drying at
105 C for a minimum of 1 hour. The Millepore AP20 filters will be
replaced by Whatman GFF filters beginning Summer 1992.
4.7 Holding Times
Maximum holding times, preservation or storage methods, and ship
board operational storage methods and holding times are displayed in
Table 4-2.
-------
OAPP Page 44
TABLE 4-2. SAMPLE PRESERVATION AND HOLDING TIMES
Turbidity
D.O.
Specific Cond.
PH
Alkalinity
NH,-N*
TTOJ
N0,-N0,« TOP
TP
SRP«
Cl
SO,
SiO,«
POC
DOC*
Na,K,Mg, Ca
Aerobic hetero-
tropha
Sample
filtration
Max.
Holding TLme
Unpreserved
unstable
Perform ASAP
24 hr.
24 hr.
24 hr.
unstable
indefinite
indefinite
indefinite
48 hr.
ASAP
ASAP
Preservative/
Storage Method
Refrig. 4 C
None
Refrig. 4 C
None
Refrig. 4 C
1 ml H,SO,/1
and Refrig. 4 C
1 ml B.SO./1
1 ml B,S04/1
in filtered eanple
(orange label)
1 nl H,SO,/1
in unfiltered sanple
(yellow label)
Refrig. 4 C
None
None
None
1 nl B,SO,/1
1 nl HNO./l
Refrig. 4 C
None
Max.
Holding Tine
Preserved
48 hr (1)
8 hr (1)
28 days(l)
2 hr (1)
14 days(l)
28 daya(l)
90 days(2)
28 days( 1)
90 days(2)
28 days(l)
90 days(2)
28 days(l)
90 days (2)
48 br. (1)
28 days(l)
28 days(l)
28 days(l)
not es tab.
28 days(l)
90 days(2)
6 no. (1)
not es tab.
Operational
Storage Method I
Holding Time Limits
2 hr.
lat 2 reagent! liredlately
Add Acid within 8 or.
Titrate within 30 min.
of acid addition
2 hr.
2 hr.
2 hr.
48 hr. (4 C)
At CRL < 90 days
At CRL < 90 days
48 hr. (4 C)
At CRL < 90 days
At CRL < 90 days
48 hr.
indefinite
indefinite
48 hr. (4 C)
At CRL not estab.
48 hr.
At CRL < 90 days
« hr. (4 C)
1 hr.
(1) EPA 40 CFR, Part 136 Holding Tine.
(2) Recommendation of EPA CRL. Although there are no data to indicate that
this type of sample is unstable, a 90-day holding tine is reconmended.
-------
QAPP Page 45
4 . 8 Analysis Priority Ranking
If it appears that onboard holding tijne goals will not be reached,
the AScI Chemistry Supervisor and the EPA Survey Supervisor will
be notified. The EPA Survey Supervisor will assign priority to
backlog analysis. Suggested priorizations are listed in Table 4.3.
Sample collection will be interrupted until the back log is
reduced so that on board holding times are met.
Suggested order of biological analysis is:
1) aerobic heterotrophs
2) productivity
3) chlorophyll
4) DAPI, sample preservation
Table 4-3. Prioritization and Preservation of Chemistry Saxiples
PRIORITY
1
2
2'
3'
3'
4'
S
PARAMETER
physical teats,
turbidity, DO,
Cond . , pH ,
alk., All
filtration
SRP
KB,
NO, + NO,
TOP, DOC
TP
POC, TKN, Na,
K, Ca, Mg
OPERATIONAL
MAXIMUM HOLDING
TIME
Perfom ASAP
48 hr.
48 hr.
48 hr.
48 hr.
48 hr.
Analyzed at CRL
PRESERVATIVE/
STORAGE
None
4*C/Iced
4«C/Iced
4*C/Iced
4*C/Iced
1 nl H,SO,/L
Analyzed at CRL
COMMENTS
Unstable
Unstable
TKN samples nay be
used but AVOID
CONTAMINATION
•
Filter immediately
TKN samples nay be
used
Analyzed at CRL
Within these restrictions, backlogged samples vill be analyzed on the
Guardian on a * first-in-first-out* schedule.
•When these samples are returned to the CRL, they will be analyzed within
90 days of the collection date.
-------
QAPP Paga 46
5.0 SAMPLE CUSTODY
Chain-of-custody procedures do not apply for lake samples. None
of the lake data is intended to be used for litigation.
Prior to each survey, numbered sample bottle labels will be
printed by computer. The sample bottle label will contain the
following information:
CRL sample number (see below)
Lake
Station number
Survey date
Preservation used
Parameter to be measured
QC sample depth
CRL sample numbers are of the following format:
Primary samples (n)(n) G (a) (n) (n) S (n) (n)
Integrated G I
Duplicate G D
Field Blank G R
Duplicate Analysis G C
Spike G X
Laboratory Blank G B
where (n) indicates a number and (a) indicates a letter. The
first 2 numeric spaces are used to designate the fiscal year. The
second letter (a) specifies the lake (A = Michigan, B = Huron, C
= Erie, D = Connecting Channels, E = Ontario), and the remaining
numeric spaces indicate series and sample number.
Labels will be color coded to indicate the preservation used, and
to identify filtered samples ie. Yellow for Sulfuric acid (total
nutrient), Orange for Sulfuric Acid (total dissolved nutrients),
Green for Nitric acid (metals), and white for unpreserved.
/Prior to arrival at a sampling station, those station labels will
be segregated and applied to the sampling bottles. When sample
bottling and preservation are completed, a record of the numbers
on the labels used will be made on analysis request sheets.
All on-board results will be recorded in data files on floppy
diskettes on the on-board Intel computer. Back-up diskettes will
be updated at the end of each shift. Master sheets will also be
available for data recording as needed (samples attached) (Figures
5-1A to 5-1C). Physical parameters will be recorded on similar
sheets (sample attached) (Figure 5-2). Results generated at the
CRL will be reported on CRL data forms.
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QAPP Page 47
6.0 Calibration Procedures and Frequency
INSTRUMENT
REFERENCE OP
CALIBRATION
PROCEDURE
CALIBRATION STANDARD
PREQUENC
y
EBT Guildline Model 8705
Maxi-Min Temp. System, RMS
Technology, Inc
Danforth Marine Indicator -
Wind Speed and Direction,
Meteorological Meter Model
P
Secchi Disk
Turner Turbidimeter
YSI Model 35 Conductivity
Bridge
Jenco 6071 pH Meter
Cole Partner 5997 pH Meter
Technicon - NH3
Technicon - TKN
Technicon - TP & TOP
Technicon - N02-N03
Technicon - DRP
Technicon - Cl
Technicon - S0«
Technicon - Si02
Technicon - DOC
Turner Dual Mono.
Spectrofluorometer
ICP - Ca, Na, Mg
AA - K
Factory Calibrated
Factory Calibrated
None Required
Instrument Manual
Instrument Manual
Instrument Manual
Instrument Manual
Technicon Manual
Technicon Manual
Technicon Manual
Technicon Manual
Technicon Manual
Technicon Manual
Technicon Manual
Technicon Manual
Technicon Manual
Instrument Manual
CRL Method
CRL Method
Formazin
Shunts
Buffers pH 7 and pH
10
Buffers pH 4 and pH
7
4 Cone. NH
-------
Page 41
7.0 ANALYTICAL PROCEDURES
Methods for the following analytical procedures may be found in
Appendix 1.
7.1 R/V Lake Guardian Methods Manual: Shipboard Analyses
Contents;
1) GLNPO SOP Dissolved Nutrients Filtration
2) GLNPO SOP Total Alkalinity Titration
3) G1NPO SOP Ammonia Nitrogen
4) GLNPO SOP Chloride
5) GLNPO SOP Dissolved Organic Carbon
6) GLNOP SOP Chlorophyll "a" and Pheophytin "a"
7) GLNPO SOP Specific Conductance
8) GLNPO SOP Nitrate and Nitrite Nitrogen
10) GLNPO SOP Dissolved Oxygen, Winkler Titration
11) GLNPO SOP Electometric pH
12) GLNPO SOP Soluble Reactive Phosphorus (Orthophosphate)
13) GLNPO SOP Total and Total Dissolved Phosphorus
14) GLNPO SOP Soluble Reactive Silica
15) GLNPO SOP Standards and Spikes preparation (autoanalyzers)
16) GLNPO SOP Sulfate
17) GLNPO SOP Suspended Solids
18) GLNPO SOP Technicon Operation
19) GLNPO SOP Turbidity
20) Methodology for Aerobic Heterotrophs, Total Coliforms, Fecal
Coliforms, Fecal Streptococci
21) Method for Determining Primary Production Parameters using
Carbon 14 Radiotracer
22) GLNPO SOP Quality Control Schedule
7.2 Other Analytical Procedures
SOP for Total Kjeldahl Nitrogen
SOP for Analysis of Particulate Organic Carbon in Lake
Contents;
1) CRL
2) CRL
Water
3) Proposed Method for Direct Observation of Bacteria by DAPI
4) CRL SOP for the Analysis of Phytoplankton
5) CRL SOP for the analysis of Zooplankton
6) CRL: The Determination of Calcium, Magnesium, Potassium and
Sodium in water by Flame AA
7) CRL: The Determination of Total Calcium, Magnesium, Potassium
and Sodium in Water By I CAP
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8.0 DATA REDUCTION. VALIDATION & REPORTING
8.1 Calculations and Units
All calculations used to reduce raw data to its final form are
presented in each analytical method. Units are also specified in
each method.
8 .2 Raw Data
All shipboard generated strip charts, bench records, and computer
printouts will be kept in a folder, indexed by station, until the
remaining samples eg. Metals, TKNs and reruns are transferred to
the CRL. A master folder will be prepared to hold all sample
information and additional data as it is generated, reviewed and
approved. All raw data will be assembled and indexed by parameter
by lake and by survey leg. Analogue charts and digital conversion
printouts will be stapled together. Each parameter will be put in
a manilla folder and given to GLNPO.
8.3 Data Validation
All data generated will go through the same review process
required by the AScI QA Project Plan. This entails the following
(Figure 8-1): No data, whether generated on board or in the
laboratory will be released to GLNPO without this review.
8.4 Out of Control Criteria
All QC audit results falling outside the statistically established
control limits (see method or Table 3-1) are outliers, the
analytical system should not generate data on any real samples
until it has been determined whether the outlier is a normal low
probability result or the system is out of control. If the
outlier is a simply a low probability result in an otherwise
properly operating system, then the samples and QC audit results
should be retained. If the system is out of control, then the
associated samples and QC audit results should be discarded, and
the system brought into a properly operating mode prior to
rerunning the subject samples.
GLNPO will provide control limits based upon more than fifteen
years of previous experience using trained personnel aboard the RV
Simons. Current numerical limits will be recorded in the system
log for each method. The contractor QC coordinator will evaluate
the variance and means for each audit by cruise. This will
provide a basis for revisions to the GLNPO control limits.
8 . 5 Computer Support
User documentation for A/D transfer of data and down loading of
concentrations is found in appendix 2.
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Figure 8-1. Dala and QC Review
ANALYST
i. conduct analysis
ii. determine rf QC meets limits
iii. initiate corrective action if needed
iv. initial data
CONTRACTOR'S TEAM CHIEF
i. review QC results
ii. check appropriateness & effectiveness
of any corrective action
iii. review data for completeness
iv. sign data transmittal form
| CONTRACTOR'S QC COORDINATOR"
i. review QC results
ii. update statistical QC limits, if needed
iii. sign data transmittal form
CRL TEAM LEADER
i. check method & limit adherence
ii. sign data transmittal form
CRL SECTION CHIEF
i. sign data
transmittal form
GLNPO PROJECT
COORDINATOR
i. update backlog
ii. sign data
transmittal form
CRL DATA MGMT
COORDINATOR
i. update computer log
ii. file master folder
•ICRL QC COORDINATOR!
i. tally biases/flags
ii. sign data
transmittal form
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9.0 INTERNAL QC CHECKS AND FREQUENCY
9.1 Type & Frequency of Audits
Each method delineates the exact type,frequency & limit for each
audit. Unless otherwise indicated a pair of control standards, a
laboratory blank and a duplicate analysis will be run with each
group of samples from one or two non-master stations.
9.1.1 High Control and the Low Control standards are dilutions of the
particlular analyte in reagent water selected such that their
values fall at the upper and lower end of the range of values
normally found in the lake water or the range used for the
analysis.
9.1.2 Laboratory reagent blanks are prepared from reagent water and are
processed like aliquots removed from the sample storage bottle.
Laboratory blanks do not go through the filtering operation nor
sample storage bottles.
9.1.3 Duplicate analysis is performed at the conclusion of an analytical
run and the regular analysis of the same sample is performed at
the usual position within the run. For filtered samples, the
filtering is considered a part of the analysis. Separate sample
storage bottles are used for the regular filtered sample and the
duplicate analysis filtered sample.
9.1.4 Spiked samples are prepared from aliquots from the sample storage
bottle and a concentrate traceable to the calibration standard
concentrates. For filtered samples, one sample storage bottle is
used for the filtered sample, and another for the filtered sample
for the spiked sample preparation.
9.1.5 Between Shift Duplicate Analysis - Optional. The last sample run
on the shift will be reanalyzed by the next shift to check inter
analyst precision.
9.2 Recording and plotting of QC Data
Analysts will make every attempt to make maximum effective use of
QC data. Specific steps toward this end include prompt recording
of AQC results in the system log and plotting that data on the
appropriate control charts. Implementation for each survey will
include the following steps.
9.2.1 Preparation of system log books and control charts. Prior to the
survey, the lab contractor's QC Coordinator will be responsible
for assuring that the system logs are available and current.
He/she will assure that the control charts, covering low check
standards, high check standards, duplicate analyses, spike
recovery, duplicate samples, field blanks and laboratory reagent
blanks are available with the proper limits. The limits used will
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be those obtained from GLNPO.
A sample control chart is attached (Figure 9-1) . Each parameter
will have at least one control chart constructed for an associated
audit (i.e., spike recovery, control standard value).
9.2.2 Responsibility for Charting. Each analyst will maintain the logs
and control charts for their assigned parameters on an ongoing
basis. Each analyst will regularly evaluate whether the
analytical system is in control. Each analyst will report actual
or suspected impending out-of-control situations to the contractor
shift supervisor. Corrective action for beyond-limit situations
are discussed in section 13.0. Charts are to include the date the
point was generated, the associated station number and notations
of extraordinary situations. On the Hi, Lo, and Blk control
charts, entries should be made to indicate the preparation of new
batches of control standards and calibration standards and the
calibration points.
9.2.3 Training. All analysts participating in the survey will receive
training in the use of the logs and charts before the survey by
the contractor's QC coordinator.
9.3 Field Audits
Duplicate samples and field blanks will be collected at random
depths and stations at the rate of one each for lake basin.
9.3.1 Field Blank. Reagent water from the ship's distilled water tap
will be dispensed into the sample storage bottle and handled
exactly like the associated samples.
9.3.2 Duplicate Samples. The duplicate sample Niskin bottle is
triggered as the EBT/Rosette is deployed(on descent). The
regular sample Niskin bottle for the duplicate is triggered as the
EBT/Rosette is retrieved(on ascent).
10.0 PERFORMANCE AND SYSTEM AUDITS AND FREQUENCY
10.1 Training and Certification
The survey scientists provided by the Contractor will be trained
at the Central Regional Laboratory (CRL). All instrumentation
will be assembled and tested at the CRL before it is sent to the
R/V Lake Guardian for each Survey. Testing will consist of
checking all control standards on the assembled systems to (l)
verify proper concentration, and (2) demonstrate that all
analytical systems to be used on the RV Simons are capable of
running within the limits required using the current standards and
reagents.
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10.2 Dry Run
After the equipment is installed on the R/V Lake Guardian, the
Contractor's QC Coordinator will accompany the Contractor's survey
staff while they test all equipment prior to beginning the survey.
At that time, the QC Coordinator will evaluate the autoanalyzer
systems and advise the GLNPO survey supervisor of the status of
the equipment and personnel readiness.
10.3 Performance Evaluation
Periodically, Round Robin samples from the IJC will be analyzed.
These results will be reported to the Data Quality Work Group.
Upper Great Lakes reference group QC samples will also be obtained
from the QAO by the Contractor's QC Coordinator to evaluate
accuracy in an actual lake matrix. These samples are .used to
evaluate the comparability of the data to other data generators,
not to set accuracy and precision limits.
11.0 PREVENTIVE MAINTENANCE/SCHEDULE
After each survey, all on board instruments will be inspected for
worn parts or erratic behavior as indicated by QC results.
An on board back up recorder, sampler, colorimeter, pump,
manifold, tubing supply and small replacement parts will be kept.
Contractor Survey coordinator will maintain an inventory on this
equipment.
To prevent equipment misuses, the lab Contractor will assure that
its employees follow all operational procedures for each
instrument utilized. All personnel will be "checked-out" on an
instrument by either their direct supervisor or another
knowledgeable individual, as directed by the EPA Project Officer.
Preventative maintenance is necessary to keep analytical
instruments and other equipment in good working condition and to
decrease the amount of major repairs and downtime. Most
analytical instrument and equipment manuals have a section dealing
with preventive maintenance. These sections will be read by each
person operating the equipment. All preventative maintenance
performed will be noted in the system logbook.
The lab contractor will maintain the system logbooks on each
instrument used. All calibration procedures performed on the
instrument and a record of all maintenance(including installation
of new pump tubes) performed will be documented. The Contractor's
Project Manager or the QC Coordinator will inspect these logbooks
after each survey to determine the instrument's condition and
performance. Any failure/breakdowns will be reported immediately
to both the Contractor's Project Manager and the EPA Project
Officer. This action will be the responsibility of the individual
operating the instrument when such an event occurs.
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The laboratory contractor will operate within all established CRL
Quality Assurance procedures for equipment, glassware and
reagents. Parts that need periodic replacement will be requested
at a rate to ensure that parts are always on hand.
The lab contractor will have at least one employee attend each CRL
Safety Meeting to ensure that all safety concerns are addressed
promptly.
12.0 SPECIFIC ROUTINE PROCEDURES TO BE USED TO ASSESS DATA PRECISION.
ACCURACY, AND COMPLETENESS OF SPECIFIC MEASUREMENT PARAMETERS
INVOLVED
12.1 Precision
The precision will be evaluated by performing duplicate analyses,
and expressed as the standard deviation of duplicates. This is
the square root of the sum of the squares of the differences, the
sum being divided by the total number of pairs. If a
determination requires dilution of the sample in order to bring it
into the working range of the SOP, then the precision statement is
applicable only to the diluted sample. The control charts are
plotted using the result from the duplicate analysis minus the
result from the regular analysis.
12.2 Accuracy
The accuracy of the determinations will be derived from the mean
difference between the spiked sample results and the original
sample results. The average spike recovery will be calculated at
the conclusion of the cruise, but the individual spike recovery
results will be obtained as soon as possible and plotted so as to
eliminate or reveal any operator error while the details of the
analytical session may still be recalled. The control chart
should have the same limits as the duplicate analysis control
charts, or possibly higher by 2% of the amount the spike increases
the concentration. The value plotted is the spiked sample result
minus the result from the original sample corrected for the spike,
or the error in absolute recovery.
% recovery = 100 * ((R + 1) * CX - R * CS)/X
where CX = analytical result of spiked sample
CS = analytical result of original sample
R = (volume of sample before spike)/(vol of spike)
X = concentration of spike
absolute recovery = CX -CS
error in absolute recovery = CX - (X + CS * R)/(l + R)
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12.3 Completeness
Completeness for most analyses should be 100% since the samples
are available for reanalysis in the event that the analytical
procedure goes out of control for some reason. To maintain a high
completeness for those parameters with a limited shelf life, the
procedure must either be maintained in control or the capability
for corrective action must be such as to allow the samples to be
reanalyzed within the alloted time limit if 100% completeness is
to be maintained. For each parameter the completeness equals:
completeness = number of analyses in control / number planned
12.4 Representativeness
Representativeness of sampling is evaluated by analysis of
duplicate samples, and is represented by the standard
deviation of duplicates.
12.5 Comparability
Comparability is not assessed on a regular basis by GLNPO.
Comparability with previous cruises is maintained by using the
same analytical procedures, traceable to Standard Methods and EPA
methods of analysis. Periodically GLNPO participates in round
robin studies by the IJC.
13.0 CORRECTIVE ACTION
Any indication that a system is out of control will be brought
immediately to the attention of the Contractor's shift superviser
by the analyst. If an audit is beyond the prescribed limits, the
analyst will first determine that an error was not made in sample
placement or calculations. The next step is to run two of more of
the offending audits using the original standardization. If the
procedure is still suspect, and the offending audit is a check
standard or spike, then fresh working check standards or spike
material will be prepared and analyzes performed using the
original standardization. For further direction, see the flow
chart figure 13-1. The flow chart is an aid to the analyst, not
a restriction. If information is available that would indicate a
speedier resolution of the problem, it should be pursued.
Regardless of the course of action, there are three possibilities;
1. the procedure is declared to have been in control, in which
case the original samples, and QC audit results are accepted, 2.
the procedure is determined to be out of control, in which case,
modifications are made to correct the situation, and a hard copy
of the original data along with an explanation of the problem and
its resolution is placed in the system log. The original samples
are then rerun and the new results of the samples and QC audits
replace the original data. 3. if it is inconclusive whether the
system was in control or not, but it is operating properly at the
present, then continue as in 2 above.
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Feedback to the employees and suggestions for corrective actions
will be the supervisor's responsibility. In the event that the
only way that the procedure can be brought under control is by a
procedure modification, this must be reported to the Contractors
QC Coordinator and Contractor's Survey Supervisor. Documentation
will be in the form of a written variance to the establish
procedure. Written documentation will be presented to,
Contractor's project officer and to EPA's survey supervisor and
project officer.
Contractor's Survey Coordinator and EPA's Survey Supervisor can
stop the analysis if the system cannot be brought into control.
If a back log of samples develops such that it can not be cleared
within the sample time controls if additional samples are taken,
then the collection of samples will be interrupted until the back
log is cleared. The recommendation to halt sampling will be made
by Contractor's Survey Coordinator. The decision to stop sampling
will be made by EPA's Survey supervisor or shift supervisor.
14.0 QUALITY ASSURANCE REPORTS TO MANAGEMENT
After each survey, the contractor's Biology and Chemistry
supervisors will compile a summary of the survey output, technical
problems, corrective actions and QC results. The Contractor's QC
Coordinator will evaluate the overall level of quality based on
these reports and offer suggestions for improvement on the next
survey in a formal report. This report will be reviewed by the
Contractor's Project Manager who will provide a copy to the EPA
Project Officer and the Contractor's Corporate QAO. An annual
summary report will be submitted by the Contractor's QC
Coordinator discussing the success and problems of the QA program,
including the open lake surveys. The report will be sent to the
EPA Project Office.
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APPENDIX 1
7.0 ANALYTICAL PROCEDURES
Great Lakes Survey Studies
USEPA Great Lakes National Program Office
APPENDIX 2
A User Manual of Laboratory Automation Program
FOR REFERENCE
Do Not Take From This Room
U S Environmental Protection Agency
Pfigion 5, Library (PL-12J)
' 7 West Jackson Boulevard, 12th Floor
Chicago, IL 60604-3590
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