&EPA
United States
Environmental Protection
Agency
Office of Acid Deposition,
Environmental Monitoring and
Quality Assurance
Washington DC 20460
EPA/600/4-88/025
August 1989
Research and Development
Eastern Lake
Survey Phase II
National Stream
Survey -Phase I
Processing Laboratory
Operations Report
-------
SUBREGIONS OF THE NATIONAL STREAM SURVEY-PHASE I
Northern
Appalachians (2Cn)
Valley and Ridge (2Bn)
Southern Blue Ridge (2As)
(Pilot Study)
Poconos/Catskills (ID)
NY\
Ozarks/Ouachitas (2D)
Mid-Atlantic
Coastal Plain (3B)
Southern Appalachians (2X)
-------
EPA 600/4-88/025
Eastern Lake Survey-Phase II
National Stream Survey-Phase I
Processing Laboratory Operations Report
A Contribution to the
National Acid Precipitation Assessment Program
U.S. Environmental Protection Agency
Office of Research and Development
Washington, D.C. 20460
Environmental Monitoring Systems Uboratory - Las v?fl»«'"lY,89114
Environmental Research Laboratory Corvallis, OR 97333
-------
Notice
recommeSion toudseenaS " ^""^^ Pf°dU°tS dO8S n0' «"*" endorsement or
Proper citation of this document is:
Enwonmental Protection Agency, Office of HeircS and '
-------
Abstract
The National Surface Water Survey was designed to characterize surface water chemistry-in
associated with the 1986 surveys.
processed and analyzed during the 1986 studies.
The centralized laboratory operation was successful. Samples were prepared for shipment
in this report to assist in the preparation of similar projects.
This report was submitted in partial fulfillment of contract 68-03-3249 by Lockheed Engineering
and lSnagePmenT SeSs Company. Inc., under the sponsorship of the U.S. Environmental
Protection Agency.
in
-------
-------
Contents
Page
Notice .!!
Abstract "!
Figures v!
Tables v!"
Acknowledgments IX
Abbreviations and Symbols x
1. Introduction '
2. Processing Laboratory Preparation 3
Organization ~
Laboratory Personnel 4
Training and Safety 4
Communications 5
3. Quality Assurance 6
Sample Batches 6
Data Requirements '
4. Daily Laboratory Procedures 9
Sample Organization 9
pH (Closed System) 12
Flow Injection Analysis Monomeric Aluminum Determination 15
Conductivity 18
Dissolved Inorganic Carbon 20
Aliquot Preparation 22
Extractable Aluminum 24
Color and Turbidity 26
Equipment Maintenance 28
Field Support 29
Snowpack 30
5. Results 32
Quality Control Check Sample Results 32
Natural Field Audit Sample Results 36
6. Conclusions and Recommendations 44
7. References 46
Appendices
A. Instrumentation, Equipment, and Supply Lists 48
B. Warehouse and Trailer Floor Plans 51
C. Personnel List 53
D. Processing Laboratory Data Forms, Aliquot Labels, and Sample Codes 55
-------
Figures
Number
Page
1. Flow of samples and data from the field through the processing laboratory. 10
2. Flowchart for pH determination 12
3. The pH difference between NSS-I field values and processing laboratory values 14
4. Flowchart for conductivity method 1g
5. Flowchart for dissolved inorganic carbon analysis 21
6. Aluminum extraction method flowchart
7. Flowchart for turbidity method
8. Frequency distributions of the pH quality control check sample results 33
9. Control chart for flow injection analysis-aluminum quality control check
sample (channel 1)
10. Control chart for flow injection analysis-aluminum quality control check
sample (channel 2) __
35
11. Control chart for 14.7-pS/cm conductivity control check sample (channel 2) 35
12. Control chart for 73.9-pS/cm conductivity control check sample 37
13. Control chart for 147.0-juS/cm conductivity control check sample 38
14. Control chart for dissolved inorganic carbon quality control check sample 39
15. pH natural field audit sample results versus observation 40
16. Dissolved inorganic carbon natural field audit sample results versus observation 41
17. Flow injection analysis-aluminum natural field audit sample results versus
batch ID
18. Conductivity natural field audit sample results versus batch ID 43
B-1. Trailer floor plan
B-2. Warehouse floor plan
O<£
VI
-------
Figures (Continued)
., . Page
Number
D-1. Forms 2 and 5 laboratory batch/QC field data form 55
co
D-2. Form 3 Sample shipping/receiving form
D-3. Standard sample aliquot labels
58
D-4. Special project aliquot labels
VII
-------
Tables
Number
Page
1. Outline of National Surface Water Surveys for 1986
2. Summary of the Laboratory Training Program for the National Surface Water Survey . . 5
3. Quality Assurance Outline for Processing Laboratory Analyses 7
4. Eastern Lake Survey-Phase II Summer Seasonal Study ^
5. Protocol for Simultaneous Use of Two pH Meters 13
6. Comparison of Intermeter Check Samples for Spring and Summer 1986 14
7. Flow Injection Analysis-Aluminum Procedure
16
8. Natural Field Audit Sample Results for Flow Injection Analysis-Aluminum 17
9. Aliquot Preparation ....
23
10. Processing Summary . . .
24
11. Equipment Maintenance .
28
12. Field Supplies . . .
29
13. Quality Control Check Sample Results
32
Check Sample Frequency Distributions
34
15. Natural Field Audit Sample Results
4o
A-1. Instrumentation
48
A-2. Equipment and Supplies
48
53
D-1. Sample Codes for Eastern Lake Survey-Phase II Summer Seasonal Study 59
D-2. Sample Codes for Eastern Lake Survey-Phase II Summer Seasonal Study 59
VIII
-------
Ackno wledgments
Analytical method information was provided by B. Dickes, D. Hillman, T. Lewis, R. Metcalf, and
D Peck. Statistical computer programs were designed by C. Hagley and D. Peck. Lillian Steely
Susie Reppke. and Suzanne Speiser provided word processing support. D. Chaloud, C. Hagley, and
D Peck offered constructive suggestions and comments about the entire document. Technical
editing was done by J Nicholson. G. Filbin (International Science and Technology, Inc., Reston,
Virginia) and M. Peden (Illinois State Water Survey, Champaign, Illinois) were the external reviewers
of this document.
IX
-------
Abbreviations and Symbols
Abbreviations
ACS
ASTM
BTU
CEC
CPR
DIG
ELS
ELS-I
ELS-II
EMSL-LV
EPA
FIA
FN
HOx
ID
Lockheed-EMSCO
MIBK
NBS
NLS
NSS
NSS-I
NSWS
NTU
PC units
PCV
QA
QC
QCCS
RD Pair
%RSD
RO
SVS-P
TD
WLS
- American Chemical Society
- American Society of Testing and Materials
- British thermal unit
- cation-exchange column
- cardiopulmonary resuscitation
- dissolved inorganic carbon
- Eastern Lake Survey
- Eastern Lake Survey-Phase I
- Eastern Lake Survey-Phase II
- Environmental Monitoring Systems Laboratory-Las Vegas
- Environmental Protection Agency
- flow injection analysis (or analyzer)
- natural field audit
- 8-hydroxyquinoline/sodium acetate reagent
- identification
- Lockheed Engineering and Management Services Company, Inc.
- methyl isobutyl ketone
- National Bureau of Standards
- National Lake Survey
- National Stream Survey
- National Stream Survey-Phase I
- National Surface Water Survey
- nephelometric turbidity units
- platinum-cobalt units
- pyrocatechol violet
- quality assurance
-- quality control
- quality control check sample (or sample)
- routine and duplicate sample pair
- percent relative standard deviation
- reverse osmosis
- Spring Variability Study-Pilot
- trailer duplicate sample
- Western Lake Survey
-------
Symbols
AC -- alternating current
amp ampere
'C -- degrees centigrade
g - gram
L -- liter
m - meter
M - molar
MQ-cm -- megaohm centimeter, resistivity unit
mg -- milligram, 10"3 g
mL - milliliter, 1Q-3 L
mm - millimeter, 10"3 m
n - number of observations
N -- normal
ppm - parts per million
psi - pounds per square inch
r* - coefficient of correlation
rpm - revolutions per minute
V - volts
w/v - weight to volume
X - mean
jug - microgram, 10"6 g
/j|_ -- microliter, 10'6 L
jum - micron, 10~6 m
juS/cm -- microsiemen per centimeter, conductivity unit
% - percentage
> - greater than
< - less than
|x| - absolute value of x
Ax ~ change in x
XI
-------
-------
Section 1
Introduction
The National Surface Water Survey
(NSWS) was conducted under the direction of
the U.S. Environmental Protection Agency
(EPA). The NSWS, as part of the National
Acid Precipitation Assessment Program's
Aquatic Effects Research Program, was de-
signed to characterize surface water chemistry
in regions of the United States believed to be
potentially sensitive to acidic deposition. The
NSWS was composed of the National Lake
Survey (NLS) and the National Stream Survey
(NSS). The NLS consisted of the Eastern Lake
Survey (ELS) and the Western Lake Survey
(WLS).
Phase I projects of the NSWS were
synoptic surveys designed to quantify the
chemistry of lakes and streams in areas of the
United States known to contain low alkalinity
waters. Phase II projects were designed to
determine temporal variability of chemical
characteristics of a subset of Phase I lakes
and streams. Pilot studies were conducted
prior to Phase I projects in order to test equip-
ment, logistics, and protocols.
The EPA's Environmental Monitoring
Systems Laboratory in Las Vegas, Nevada
(EMSL-LV), has been charged with the respon-
sibility for conducting NSWS field and pro-
cessing laboratory operations. Laboratory,
field sampling, managerial, and quality assur-
ance (QA) personnel were provided by Lock-
heed Engineering and Management Services
Company, Inc. (Lockheed-EMSCO).
This report discusses the Las Vegas
processing laboratory operations for the six
surveys conducted in 1986 (Table 1). The
Spring Variability Pilot Study (SVS-P) and the
Snowpack Study were done in conjunction with
ELS-Phase II (ELS-II). The objective of SVS-P
was to obtain data describing the spacial and
temporal variability of lake chemistry during
snowmelt. The Snowpack Study was con-
ducted in order to determine the relationship
between snowpack conditions and the extent
and severity of episodic lake acidification.
Table 1. Outline of National Surface Water Surveys
for 1986
Laboratory pro- Field operations
Survey cessing dates (1986) report reference
Spring
Variability
Pilot Study
Snowpack
Study
National
Stream
Survey-
Phase I
FEB 21-APR 3
MAR 20-22;
MAY 1-23
MAR 18-MAY 16
Hagley et al.,
in preparation
Eastern Lake
Survey-
Phase II:
Spring
Summer
Fall
MAR 25-MAY 4
JUL 24-AUG 12
OCT 9-NOV 15
Merritt and
Sheppe, in
preparation
The main function of the processing
laboratory was to prepare and preserve water
samples received from the field and to ship
the prepared aliquots to a contracted analyti-
cal laboratory for subsequent analyses. Dis-
solved inorganic carbon (DIG), pH, aluminum
(total monomeric and organically bound mono-
meric), true color, turbidity, and conductivity
were measured at the processing laboratory in
Las Vegas, Nevada. The analytical methods
used by the processing and contracted analyti-
cal laboratories are presented in Hillman et al.
(1986) and Kerfoot et al. (in preparation).
Changes in or modifications to these methods
-------
are discussed in this report. A list of instru-
mentation, equipment, and supplies used for
these procedures is provided in Appendix A.
QA plans for ELS-II (Engels et al., in prepara-
tion) and NSS-I (Drouse et al., 1986) were
prepared. Quality control (QC) procedures
were incorporated into all laboratory analyses.
-------
Section 2
Processing Laboratory Preparation
Organization
Laboratory Trailer Description
Six laboratory trailers were constructed
for Phase I of NLS. A field laboratory was
stationed at each field site in order to process
samples as soon as possible following collec-
tion. The field laboratory operations are de-
scribed in Morris et al. (1986). A trailer floor
plan is presented in Appendix B, Figure B-1.
The trailers were constructed according to the
following specifications:
Prototype trailer
tow-behind design
length 24 feet, width 8 feet, height
12.5 feet
Additional five trailers
gooseneck design with fifthwheel
hitch
length 31 feet, width 8 feet, height
12.7 feet
Work space and storage capacity of
each trailer
length 24 feet, width 7.5 feet, height
7.5 feet
storage capacity 480 cubic feet
(compartment storage)
counter space 18 linear feet
Trailer requirements
110 V and 220 V AC, single-phase
80-amp electrical power
minimum water pressure of 50 psi
access to sewer drain or leach field
Trailer equipment
laminar flow hood containing high
efficiency purification apparatus
filters (0.3-)L/m pore size) capable of
delivering Class 100 air
Millipore Milli-RO reverse osmosis
purification system, 95-L reservoir,
Millipore Milli-Q system capable of
delivering American Society for
Testing and Materials (ASTM) Type
I deionized water (ASTM, 1984)
two freezers, refrigerator/freezer
two heating/air-conditioning units
(5,000-BTU heating capacity and
13,200-BTU cooling capacity)
Trailer safety features
eye-wash station
first aid kit
two fire extinguishers
storage cabinet for flammable
solvents
vented cabinet for concentrated
acids
safety shower
Centralization of Laboratory
Operations
The results of two experiments (Burke
and Hillman, 1987, and M. A. Stapanian, per-
sonal communication) indicated that the maxi-
mum sample holding time before aliquot prep-
aration could be extended from 12 hours to 24
hours. This permitted centralization of pro-
cessing laboratory facilities at a warehouse in
Las Vegas. Samples were shipped from the
field overnight by a commercial courier service
and processed within 24 hours of collection.
Several factors influenced the decision to
centrally locate the laboratory trailers. The six
available trailers were inadequate to accom-
modate all field sites necessary for concurrent
stream and lake studies. In particular, the
NSS-I sampling schedule would have neces-
-------
sitated frequent trailer relocation efforts, each
move requiring two days of field time.
Housing the trailers in a single location pro-
vided an organized area for sample receipt and
supply shipment, and the protected location
provided a cleaner work environment than
when the trailers were stationed in the field,
unsheltered from weather conditions. Chemi-
cals were stored in fireproof cabinets in the
warehouse. A floorplan of the warehouse is
shown in Appendix B, Figure B-2. The pur-
chase of a flow injection analyzer (FIA) for
monomeric aluminum determination for each
trailer was not possible because of the ex-
pense of the instrument. One FIA was pur-
chased for the single location and was suffi-
cient to analyze all samples.
For the centralized laboratory operation,
each trailer was dedicated to one or two
procedures. For example, all extractable alumi-
num aliquots were prepared in one trailer for
all surveys (Section 4, Extractable Aluminum).
This process required the use of methyl iso-
butyl ketone (MIBK), a hazardous liquid. MIBK
was confined to a specially vented trailer,
minimizing the potential exposure to personnel
and localizing the storage of hazardous waste.
Laboratory Personnel
When the trailers were located in the
field, each laboratory was staffed by five
persons: a field laboratory coordinator, a
supervisor, and three analysts. For the cen-
tralized laboratory operations, the staff con-
sisted of a laboratory coordinator, one or two
supervisors, and from 6 to 18 analysts. Two
supervisors were required for the spring sur-
veys, one for the ELS-II summer seasonal
study, and the coordinator and supervisor
positions were combined for the ELS-II fall
seasonal study. A list of personnel who
worked in the processing laboratory during
1986 is presented in Appendix C, Table C-1.
The laboratory coordinator was responsible for
the overall operations at the processing labo-
ratory, including the daily organization of sam-
ples, the shipment of samples to the analytical
laboratories, and the completion of all data
forms (Appendix D). The laboratory supervisor
was responsible for the daily operations at the
processing laboratory. The supervisor ensured
that samples were handled in accordance with
approved methodologies and QA guidelines.
Other supervisory responsibilities included
laboratory safety, troubleshooting instrument
malfunctions, and reviewing the analytical
results. Analysts prepared aliquots for subse-
quent analytical laboratory analysis and per-
formed DIG, pH, FIA-aluminum, true color,
conductivity, and turbidity analyses (Section 4).
Depending on the number of samples received,
a number of analysts were assigned to each
procedure.
Training and Safety
Twenty-two individuals were trained at
the processing laboratory during five training
sessions conducted in the spring of 1986.
Shorter training sessions were conducted at
the start of summer and fall operations be-
cause all analysts were trained during previous
NSWS studies. Prior to 1986 laboratory opera-
tions, a draft methods manual was prepared.
Analysts were expected to be familiar with all
procedures outlined in this document.
Methods
The supervisors and analysts with pre-
vious NSWS experience conducted the training
programs. Training objectives are summarized
in Table 2. Laboratory procedures were taught
in modular form to small groups over a three-
day period. Instructors described and demon-
strated each method. The analysts achieved
competency during supervised practice ses-
sions. New analysts, hired after the start of
processing, were assigned to positions which
were understaffed. They received on-the-job
training which consisted of a day observing
the analysts during sample processing, fol-
lowed by a question and answer session. For
summer and fall training sessions, analysts
reviewed laboratory procedures and tested the
analytical instruments under the direction of
the laboratory supervisor.
Laboratory safety instruction included the
location and use of safety equipment and fire
exits, hazardous material handling and dis-
posal, and emergency procedures.
At the end of each training session, all
analysts completed a written examination
covering laboratory and safety procedures.
Analysts assigned to process extractable
aluminum aliquots (Section 4) prepared a
practice extraction to test their accuracy
-------
(percent recovery of a known aluminum stan-
dard). Before each processing period, the
supervisors conducted a practice run simulat-
ing an operational day.
Table 2. Summary of the Laboratory Training
Program for the National Surface Water
Survey
1. Employee orientation
2. Project orientation and overview
3. Laboratory operations discussion
4. Overview of laboratory safety, including cardiopul-
monary resuscitation, first aid, and respirator
fitting
5. Presentation of laboratory methods:
a. pH
b. Dissolved inorganic carbon
c. Flow injection analysis for monomeric aluminum
determination
d. Aluminum extraction using methyl isobutyl ke-
tone
e. Aliquot preparation
f. Conductivity
g. Turbidity
h. True color
6. Logbook entry procedure
7. Communications center responsibilities
8. Inventory control procedure
9. Waste disposal method
10. Quality assurance plan discussion
11. Simulation of daily operations
12. Medical surveillance
Health and safety requirements sched-
uled for completion during training included:
medical surveillance examinations, certification
in cardiopulmonary resuscitation (CPR) and
first aid, and respirator and safety glasses
fittings.
Discussion and Recommendations
The success of the modular training
program was based on two items. First, in-
struction was given to small groups or individ-
uals followed by closely supervised practice
time. Second, experienced analysts assisted
the supervisor with instructing new analysts.
This practice reinforced skills in previously
trained analysts and distributed the teaching
load.
The modular approach is most effective
within a designated training period before
samples arrive. In the spring, training time
was organized around the new laboratory
set-up and sample processing. The super-
visors trained new personnel as the schedule
permitted. First aid, CPR classes, and medical
surveillance examinations were not completed
until later dates. For summer and fall opera-
tions, all training objectives were completed
before samples arrived.
Efficiency of future training programs
could be improved in two ways. First, certi-
fication in first aid and CPR as a prerequisite
for employment would save both time and
money. Second, a slide or video presentation
detailing processing, analytical, and safety
procedures should be prepared and shown in
order to familiarize new analysts with methods
and equipment and to serve as a review for
experienced personnel.
Communications
All information transferred between the
laboratory and the field sites was routed
through a communications center in Las
Vegas. This central communications center
played an integral role in the success of the
concurrent surveys.
The responsibilities of the communica-
tions center included the following:
Informing the laboratory coordinator
of the projected sample load and of
any field sampling difficulties affecting
the laboratory.
Tracking sample shipments from a
field site to the processing laboratory.
Resolving sample identification prob-
lems and data discrepancies.
Tracking sample shipments from the
processing laboratory to the analytical
laboratories and notifying the latter of
any sample processing problems.
Relaying field supply requests to the
laboratory coordinator and ware-
house manager and tracking the
shipment of requested materials.
Recording daily field, processing lab-
oratory, and shipping activities in a
logbook.
-------
Section 3
Quality Assurance
Rigorous QA measures were followed to
maintain consistency in laboratory procedures.
Details of the QA plan are presented in Drous£
et al. (1986) and Engels et al. (in preparation).
Sample Batches
A sample batch consisted of all samples
processed on a given day for each survey.
Sample Types
Four types of water samples (routine,
duplicate, blank, and audit samples) were
processed and analyzed. Collection proce-
dures are presented in Merritt and Sheppe (in
preparation) and Hagley et al. (in preparation).
A routine sample consisted of a 4-L container
(Cubitainer), a bulk sample for aliquot prepara-
tion, and four 60-mL syringes, one each for
DIG, FIA-aluminum, pH, and preparation of the
extractable aluminum aliquot (Section 4). A
duplicate sample, a second sample collected
immediately following the collection of the
routine sample, included a Cubitainer and four
syringes and was treated in the same manner
as a routine sample. One routine-duplicate
pair (RD pair) was included with each batch of
samples. A blank sample included a
Cubitainer and two syringes (FIA-aluminum
and extractable aluminum). Two types of
blank samples, field and laboratory blank
samples, were processed and analyzed. Field
blank samples consisted of deionized water
sent from the laboratory to the field, run
through the sampling equipment, and returned
to the laboratory for processing. Laboratory
blank samples were deionized water samples
prepared at the laboratory and incorporated
into a sample batch for processing. An audit
sample is a solution with a known chemical
composition used to monitor the performance
of the processing and analytical laboratories.
Two categories of audit samples were used:
field and laboratory audit samples. Field audit
samples were received in 2-L bottles and were
prepared and analyzed at the processing
laboratory in the same manner as a routine
sample. These samples were ordered in
advance and were stored at the processing
laboratory at 4 *C. A field audit sample repre-
sented a sample known to be an audit by the
processing laboratory staff but having a com-
position unknown to the analysts. When
received at the analytical laboratory, the field
audit was of unknown sample type and com-
position (a double blind test). A laboratory
audit sample was received from an assigned
audit laboratory as a complete set of aliquots.
The laboratory audit sample was prepared by
the audit laboratory staff following the same
protocols used in the processing laboratory
(Table 9). Arriving the day they were required,
the laboratory audit samples were relabeled at
the processing laboratory and were incorporat-
ed into a sample batch by the laboratory
coordinator. The laboratory audit sample was
a double blind sample to analysts at the
analytical laboratory. A description of the
audit sample types was originally presented in
Morris et al. (1986). There were natural (well-
characterized, filtered, lake water) and syn-
thetic sample types of both field and labora-
tory audit samples. Radian Corporation
(Austin, Texas) prepared field and laboratory
audit samples for all surveys. In addition,
EMSL-LV prepared synthetic laboratory audit
samples used during the ELS-II fall seasonal
study. Synthetic rainwater samples prepared
by the National Bureau of Standards (NBS)
(Gaithersburg, Maryland) were also used as
laboratory audit samples during the ELS-II fall
seasonal study. Sample codes for all sample
types are shown in Appendix D, Table D-1.
-------
Data Requirements
Quality control check samples (QCCS)
were prepared daily for all methods (except
true color) to monitor the reliability of the
results. The type of QCCS used for each
method is presented in Table 3. A QCCS was
analyzed after a specified number of samples
were measured; and control limits were deter-
mined for each QCCS. Control charts for
selected QC solutions are presented in Section
5 of this report.
Agreement between routine and duplicate
field samples for processing laboratory para-
meters was determined daily. If the precision
requirements were not met, the pair was
reanalyzed at the processing laboratory. As a
check on processing laboratory instrument
precision, a sample was selected randomly
each day by the laboratory coordinator as the
trailer duplicate (TD) and was analyzed in
replicate. The RD pair and TD agreement
precision requirements are listed in Table 3.
For pH, the processing laboratory result
was required to agree with the field result
within 0.50 pH units for each lake sample, and
within 0.30 pH units for each stream sample.
If the results did not meet these criteria, the
sample was reanalyzed at the processing
laboratory. Field versus laboratory pH results
for NSS-I are discussed in Section 4.
For the FIA-aluminum procedure (Sec-
tion 4), the instrument detection limit was
determined to be 7.0 jug/L Al. The detection
limit was calculated as three times the
standard deviation of repetitive, nonconsecu-
tive measurements of a low aluminum stan-
dard (Kerfoot et al., in preparation). The
detection limit QCCS, a sample containing
aluminum at a concentration nearly three times
the detection limit (20 pg/L Al), was analyzed
once per batch. A non-acidified deionized
water blank was analyzed once at the begin-
ning and once at the end of the daily analysis.
When the 75 jug/L Al QCCS was analyzed with
the cation-exchange column (CEC) engaged,
Table 3. Quality Assurance Outline for Processing Uboratory Analyses
Parameter
pH
Flow injection
analysis-
monomeric
aluminum
determination
Quality control
check sample
1 x 10-* N Hs,SO4
75 fjg/L Al
Maximum quality control
check sample interval
spring summer/fall
5 10
10 10
Quality control check
sample limit
4.00 ± 0.10 pH units
75.0 ± 7.5 pg/L Al
75.0 ± 15.0 pg/L Al
(spring-channel 2)
Routine-duplicate
pair and trailer
duplicate precision
requirement
0.10 pH units
10%
20%
Conductivity
Dissolved
inorganic
carbon
Turbidity
Color
1 x 10'4 N KCI
5 x 10'4 N KCI
1 x 10'3 N KCI
2 mg/L C
5 nephelometric
turbidity units
(NTU)
None
10
10
10
NA
NA
NA
NA
10
10
NA
14.7 ± 1.5 pS/cm
73.9 ± 7.4 pS/cm
147.0 ± 14.7 pS/cm
2.000 ± 0.200 mg/L C
5.0 ± 0.5 NTU
NA
10%
10%
10%
10%
10%
5 platinum-
cobalt units
-------
the channel 2 (organically bound monomeric
aluminum) result was required to be within
20% of the blank value or the sample was
reanalyzed after identification of the cause for
the high result.
Analysis of a calibration blank (deionized
water) was required for the conductivity and
DIG procedures (Section 4). For the DIG
method, the daily calibration blank result was
required to be less than 0.100 mg/L C. Each
week 20 consecutive blank samples were
analyzed for DIG. The detection limit, which
was calculated as three times the standard
deviation of the blank sample results, was
required to be less than 0.100 mg/L C. For
conductivity measurements, the daily calibra-
tion blank result was required to be less than
0.9 pS/cm.
8
-------
Section 4
Daily Laboratory Procedures
Analysts organized supplies and equip-
ment, prepared reagents and standards, and
calibrated instruments before samples arrived
from the field sites. The laboratory coordina-
tor organized samples (by survey) into sample
batches, then distributed samples to the
analysts. After processing was complete,
analysts prepared samples for shipment to the
analytical laboratories. Samples were analy-
zed at the contracted analytical laboratories
within 48 hours to 28 days of collection based
on the holding times specified in Hillman et al.
(1986). The laboratory coordinator reviewed
the analytical results, completed the data
forms, and forwarded the forms to QA person-
nel. Laboratory personnel cleaned the facility
and prepared for the next day's operations.
The flow of samples, from collection through
processing, is illustrated in Figure 1.
Sample Organization
Methods
Samples were packed with frozen chemi-
cal refrigerant packs in shipping containers
(coolers). They were shipped by an overnight
courier or by a commercial airline to the pro-
cessing laboratory. Samples arrived at the
laboratory by 9:30 a.m. the day following
collection. When commercial airlines were
used, laboratory personnel claimed the ship-
ment at the airport. Due to cost and incon-
venience, commercial airlines were used only
when the overnight courier was not in opera-
tion (Sunday) or when the overnight courier
pick-up deadline was missed in the field (less
than five times).
Each shipping cooler contained from one
to three Cubitainers, the associated syringes,
frozen chemical refrigerant packs, and field
data forms. The syringes, sorted by site
identification number, were secured in plastic
containers. To organize the samples, the
laboratory coordinator (1) collected field data
forms, (2) measured each cooler temperature
to the nearest 0.1 *C with an NBS-traceable
thermometer by placing the thermometer
between the Cubitainers, (3) recorded site ID
number, sample type information (Section 3)
and sample temperature on sample log-in
sheet, (4) matched each Cubitainer with the
associated syringes by the site ID number and
sample type, (5) randomly assigned a sample
ID number to the sample and recorded batch
and sample ID numbers on each container and
on the sample log-in sheet, (6) incorporated
scheduled audit samples into batches, and (7)
distributed samples to analysts. The super-
visors and analysts prepared to process
samples during batch organization (Morris et
al., 1986; Hillman et al., 1986).
The coordinator reviewed the field data
forms and transcribed the sample ID and
temperature information from the sample log-in
sheet to the field data forms. A copy of the
sample log-in sheet was distributed to QA
personnel. The field data forms for ELS-II and
NSS-I are presented in Merritt and Sheppe (in
preparation) and Hagley et al. (in preparation),
respectively. Three copies of the four-part field
form were sent to the processing laboratory
for each sampled site. The white original and
yellow copy were sent to QA personnel and
the pink copy was retained at the processing
laboratory. A summary sheet, which was
distributed to each trailer, included the field pH
results, identification of the TD, RD pair, and
blank samples (Section 3), and any special
remarks concerning the sample (i.e., low
sample volume, broken syringe tip, no analysis
required, etc.). A copy of the summary sheet
was forwarded to QA personnel. After sample
-------
FIELD SITES
Quality Assurance Samples-
AUDIT LABORATORY
ROUTINE
SAMPLES
4 Syringes (60 mL)
1 Ciibitainer (4 L)
FIELD
BLANK
2 Syringes
1 Cubitainer
FIELD
DUPLICATE
4 Syringes
1 Cubitainer
AUDIT SAMPLES
FIELD
1 Container
(2L)
Shipped to Processing
Laboratory at 4 °C via
Overnight Courier
LABORATORY
7 Preserved
Aliquots
PROCESSING LABORATORY (Next Day)
Samples Organized
into Batch
Sample Processing
Information
Recorded on Field
Data Forms
Aluminum Extraction
Performed and
Aliquot Prepared
ALIQUOT PREPARATION
1. Filtration
2. Preservation
3. Storage at 4 °C
QUALITY ASSURANCE
Seven Aliquots Packed for
Shipment and Sent to
Analytical Laboratories
via Overnight Courier
-(Next Day)
Forms Sent to
Quality Assurance
.Staff
Figure 1. Flow of samples and data from the field through the processing laboratory.
10
-------
processing was completed, the coordinator
completed the three-page laboratory batch/QC
data form (Appendix D, Figure D-1). The white
original and pink copy of this form were sent
to QA personnel and the yellow copy remained
at the processing laboratory. A four-part
shipping/receiving form (Appendix D, Figure
D-2) was completed by the coordinator and
the copies were distributed as follows: white
original to QA personnel; yellow copy to the
sample management office (Alexandria,
Virginia); pink and gold copies to the analytical
laboratory.
During the ELS-II summer seasonal
study, field samplers collected a number of
special project samples, including preserved
hypolimnetic, triplicate, chlorophyll, and zoo-
plankton samples. The responsibilities of
processing laboratory personnel regarding
these samples are presented in Table 4.
Analysis of preserved hypolimnetic samples
provided data to study the potential loss of
dissolved iron and manganese from hypolim-
netic water samples due to exposure to oxy-
gen during normal routine sample collection.
Triplicate samples were collected for an inter-
laboratory bias experiment. Each day, pro-
cessing laboratory personnel prepared two
batches of aliquots from the triplicate
Cubitainer: the routine batch and the bias
experiment batch. Each batch (routine and
bias) was sent to a separate analytical labo-
ratory. Processing of the triplicate samples is
discussed later in this section (Aliquot Prep-
aration). Batch/QC data form sample codes
for the ELS-II summer seasonal study are
shown in Appendix D, Table D-2.
Discussion
The organization of samples into batches
during the spring required a great deal of time
due to the large number of samples received.
When more than 30 samples arrived on a
given day, two people organized the sample
batches. All sample information was verified
by checking sampling schedules and field data
forms. The communications center resolved
any sample identification discrepancies.
Table 4. Eastern Lake Survey-Phase II Summer Seasonal Study
Special Project Responsibilities
Sample
Description
Procedure
Preseved
Hypolimnetic
250-mL aliquot; preserved
with 0.2 mL HNO3
(concentrated)
1 Assign batch, sample ID numbers
2. Incorporate audit samples (Appendix D, Table D-2) into batch
3. Check pH of all samples
4. Record information in logbook
5. Prepare 15-mL split and blank sample
6. Ship samples to Environmental Monitoring Systems Laboratory,
Las Vegas, Nevada
Triplicate
4-L Cubitainer
1. Assign two batch and sample ID numbers to each Triplicate
Cubitainer
2. Prepare two batches of aliquots
3. Incorporate audit (Appendix D, Table D-2) and blank samples into
each batch
4. Ship each set to assigned analytical laboratory daily
Chlorophyll 10-mL vial containing filter
(0.8 pm pore size, polycar-
bonate)
1. Assign a batch and a sample ID number to each vial
2. Incorporate audit samples into batch. Natural audit samples from
Lake Mead, Nevada; standards prepared by Environmental Monitoring
Systems Laboratory, Cincinnati, Ohio)
3. Store at -20 *C
4. Record information in logbook
5. Ship samples to Fresh Water Institute of Winnipeg, Manitoba,
Canada weekly
Zooplankton
250-mL glass jar; pre-
served with formalin (4%)
1. Record information in logbook
2. Ship samples to Academy of
Pennsylvania at end of survey
Natural Sciences, Philadelphia,
11
-------
pH (Closed System)
Introduction
Samples were collected in syringes to
minimize the variation in pH as a result of CO
gas transfer between the sample and the
atmosphere (Burke and Hillman, 1987). The pH
was measured in an 8-mL sealed chamber
(Hillman et al., 1986) using an Orion model 611
pH/millivolt meter and an Orion Ross model
8104 combination electrode.
Methods
The pH procedure is documented in
Hillman et al. (1986) and is illustrated in
Figure 2. Samples were equilibrated to room
temperature. A 1 x 10'4 N H2SO4 solution was
used as a QCCS. QC requirements are pre-
sented in Section 3. The pH meter was stan-
dardized using NBS-traceable pH buffer solu-
tions (certified pH 4.00 ± 0.01 and pH 7 00 ±
0.01 at 25 *C). Specific modifications of the
pH method incorporated to increase measure-
ment efficiency included the following:
A protocol was developed for the use
of two pH meters for one batch when
the batch size was greater than 20
samples. A dilute pH 7 buffer solution
was prepared by placing 5.000 ± 0.001
g of concentrated NBS-traceable pH 7
buffer in 1 L of deionized water. The
dilute buffer, which has an empirically
derived value of 7.31 ± 0.07 pH units
(mean ± two standard deviations,
n = 49), was used as an intermeter
comparability check solution. Table 5
summarizes the steps and indicates
the time of initiation.
STANDARDIZATION
QCCS
WITHIN ± 0.1 pH ^N
UNITS OF THEORETICAL
VALUE
ENOUGH
OLUME REMAINING
IN PREVIOUSLY ANALYZE
SAMPLES TO
REANALYZE
QCCS
WITHIN 0.1 pH
UNITS
I PREVIOUS SAMPLES (FROM LAST ACCEPTABLE QCCSI
MUST BE REANALYZED AFTER ACCEPTABLE QCCS IS
RECORD QCCS VALUE IN
LOGBOOK AND NOTE
SAMPLE ID NUMBERS
ASSOCIATED WITH
UNACCEPTABLE QCCS.
Figure 2. Flowchart for pH determination.
12
-------
Table 5. Protocol for Simultaneous Use of Two pH Meters
Procedure
Season
Spring Summer Fall
1. Designate primary and secondary pH meter
2. Analyze first half of batch on primary meter and second half on secondary meter
3. Analyze the routine-duplicate pair on the same meter
4. Analyze a trailer duplicate on both meters
5. Use a natural audit sample as a comparability check of each batch on both meters
6. Use a dilute pH 7 buffer solution as comparability check with each pH 4 QCCS on both
meters
7. If check sample values do not agree within 0.05 pH units and recalibration does not
succeed, analyze all samples on primary meter
x x
x x
x x
x
x x
x
x
x
x
The maximum QCCS interval was
increased from one analysis every five
samples during the spring surveys to
one analysis every ten samples during
the summer and fall seasonal surveys.
A stable pH reading was redefined to
be a pH value that does not vary
more than 0.02 pH units in one direc-
tion during a one-minute interval for
the summer and fall surveys. A
two-minute interval was used for the
spring surveys.
Performance of the pH meter two-
point temperature calibration was
changed from daily intervals during
the spring surveys to weekly intervals
during the summer and fall surveys.
Results
Samples used as intermeter compara-
bility checks and their associated ranges and
between meter ApH values are listed in
Table 6. Natural field (FN) audit samples are
described in Section 3. The FN audit sample
pH difference (|ApH|) was greater than the
dilute pH 7 buffer results for a given analysis
day. The frequency of unacceptable QC
checks between meters (%|ApH| > 0.05 pH
units) was also greater for the FN audit
samples than for the dilute pH 7 buffer
samples (0-33% vs. 0%).
Figure 3 is a plot of the difference
between NSS-I field and processing laboratory
pH values. QA protocol required that these
measurements agree within 0.3 pH units
(NSS-I only). If they did not, the sample was
required to be reanalyzed at the processing
laboratory.
QCCS results are presented in Section 5
(Figure 8, and Tables 13 and 14). FN audit
sample results are presented in Figure 15 and
in Table 15.
Discussion
The time required for a sample to reach
a stable pH value varied from seven minutes
to two hours, although most samples reached
a stable pH in approximately 20 minutes.
During the spring surveys, as many as 90
samples were received daily, requiring the use
of two pH meters per batch. Analysts used
four meters and measured two batches simul-
taneously to decrease the total analysis time.
Batch sizes justified the use of two pH meters
during the summer seasonal study also.
The use of two pH meters per batch
required the development of a protocol to
address the question of comparability of the
results between meters. To verify intermeter
comparability, a QCCS which closely approxi-
mated the chemistry of NSWS samples was
desired. The FN audit samples listed in Table 6
13
-------
Table 6. Comparison of Intermeter Check Samples for Spring and Summer 1986
Sample Type
Date Used
1986
Observed Range
by pH electrode
|ApH|
by day
% |ApH|>
0.05 pH units
Spring
FN-8
FN-7
FN-6
MAR 20-MAR 26
MAR 27-APR 2
APR 15-APR 19
APR 1-APR 16
I
5.08-5.20
6.90-6.96
6.62-7.01
A
5.05-5.24
6.84-6.99
6.61-7.03
0.00-0.04
0.00-0.10
0.00-0.24
0%
7%
30%
20:1 pH 7
buffer
200:1 pH 7
buffer
JUL 24-JUL 26
JUL 28-JUL 29
JUL 26-JUL 29
JUL 30-AUG 8
6.61-6.85
5.00-5.20
7.28-7.29
7.26-7.38
6.59-6.83
5.05-5.18
7.28-7.29
7.24-7.37
0.00-0.19
0.02-0.05
0.00
0.00-0.05
33%
20%
0%
0%
1.2
-1.2-
BATCH NUMBER
Figure 3. The pH difference between NSS-I field values and processing laboratory values.
14
-------
served as the intermeter comparability check
during the spring surveys and initially during
the summer seasonal survey. These audit
samples proved unsatisfactory for several
reasons. First, agreement within 0.05 pH units
between meters was difficult to obtain due to
unexplained within audit sample variability
(Table 6). For example, in the summer survey
the FN sample collected from Seventh Lake
(FN-7) failed to meet criteria (% | ApH | > 0.05
pH units) 33% of the time. Failure to meet the
agreement criteria required recalibration of
meters and reanalysis of the previous samples
from the last acceptable intermeter compara-
bility check. Second, the time required for the
FN samples to reach equilibrium averaged
approximately 30 minutes. When routine field
samples were slow to stabilize, these com-
parability audit samples added considerable
analysis time. Third, the additional audit
samples were a cost factor.
During summer processing, a new inter-
meter check sample, a dilute pH 7 buffer
solution, was introduced. Initially a 20:1 dilu-
tion of the NBS-traceable pH 7 calibration
buffer solution was used, yielding acceptable
results. A 200:1 dilution was chosen later
because its ionic strength was closer to that
of the pH 4 QCCS and FN audit samples. The
200:1 dilution gave comparable readings on
two pH meters (0% failure to meet 0.05 pH
unit agreement criteria, Table 6). A mean value
of 7.31 ± 0.07 for this comparability check
sample was determined empirically based on
statistical analysis of the summer survey data.
The precision of the 1 x 10'4 N H2SO4
QCCS measurements during the spring surveys
is presented in Section 5, Figure 8 and Tables
13 and 14. The maximum interval among
QCCS measurements was increased from one
measurement every five samples to one meas-
urement every ten samples before summer
processing, based on consistent QCCS results
obtained in all previous surveys. The deviation
of the mean pH value (4.06 ± 0.05) from the
theoretical value (pH 4.00 ± 0.1) was probably
due to a larger error in the liquid junction
potential of the electrode than previous theo-
ries would predict (Metcalf, 1987). For future
surveys, we recommended that the value of
the QCCS be corrected from 4.00 ± 0.1 to 4.06
± 0.05 pH units. This change more accurately
reflects the apparent pH of the standard using
the system described. Statistical tests have
demonstrated the good precision of the Orion
Ross combination electrode (Metcalf, 1987).
A Hydrolab Surveyor II was used in the
field to measure the in situ pH during ELS-II
(Merritt and Sheppe, in preparation). Orion
Ross combination electrodes (model 8104) and
Beckman pHI-21 portable pH meters were used
for NSS-I field pH measurements (Hagley et
at., in preparation). The acceptance criteria
between field and laboratory pH measure-
ments were 0.50 pH units for ELS-II samples
and 0.30 pH units for NSS-I samples. Field pH
results from each survey were compared with
the laboratory results immediately following
analysis at the processing laboratory. If
agreement criteria were not met, the sample
was reanalyzed at the laboratory to verify the
pH value obtained at the laboratory. Com-
parison of the field and laboratory results
served as a check on the function of the
laboratory instrumentation and as an indicator
of field instrument operation. As demon-
strated in Figure 3, field versus laboratory pH
agreement is excellent and confirms two items.
First, the pH of samples in sealed syringes
was stable for at least 24 hours following field
collection. Second, the precision of the meas-
urements was high (r2 = 0.988) despite the
fact that pH meters made by different manu-
facturers were used for field and laboratory pH
measurements.
Flow Injection Analysis
Monomeric Aluminum
Determination
Introduction
The FIA-aluminum procedure is a com-
puter-controlled cplorimetric method used to
accurately and quickly measure the concentra-
tions of various dissolved monomeric alumi-
num fractions. The system is an automated
continuous flow system in which two sample
streams are measured concurrently. One
stream (channel 1) is analyzed directly for total
monomeric aluminum which includes inorganic
monomeric and organically bound monomeric
species. The second stream (channel 2) is
passed through a CEC containing Amberlite
120 resin which removes the inorganic mono-
meric aluminum fraction (Driscoll, 1984) meas-
uring only the organically bound monomeric
15
-------
species. This method permits the indirect
determination of the inorganic monomeric
aluminum fraction which has been related to
high fish mortality (Baker and Schofield, 1982).
Although extractable aluminum and total alumi-
num in an unfiltered sample also were meas-
ured by the analytical laboratories using graph-
ite furnace atomic absorption spectroscopy,
the FIA-aluminum method provided specific
information about inorganic monomeric alumi-
num, the species believed to be toxic to fish.
Methods
Samples were collected in the field in
sealed syringes and stored at 4 °C until analy-
sis. A sample was loaded from the syringe
through a syringe filter (acid-washed, 0.45-fjm
pore size) into the two FIA sample loops
(10-AA.). The sample first filled the channel 1
sample loop, then passed through the CEC to
fill the channel 2 sample loop. The two dis-
crete sample volumes were delivered to the
reaction manifold by separate carrier streams
of deionized water. A peristaltic pump was
used to deliver reagents that mixed with the
separate sample streams. A masking reagent
was added in order to eliminate iron inter-
ference. Pyrocatechol violet (PCV), which
forms a colored complex with aluminum, was
added to the streams, then a buffer solution
was added to adjust the reaction pH to 6.1 to
maximize color development. The sample
streams passed through separate colorimeter
flowcells which measured the absorbance of
the PCV-AI3+ complex at 580 nm. The meas-
ured absorbances were proportional to the
concentration of total monomeric aluminum
and organically bound monomeric aluminum
present in the sample. The absorbance peak
areas were converted to readings in jug/L Al
using a computer program. The FIA-aluminum
method is presented in Kerfoot et al. (in prep-
aration). The colorimeter, reaction manifold,
and software package were developed bv
LaChat/Quick Chem.
A synopsis of the FIA-aluminum method
is presented in Table 7. This working method
is documented in Henshaw et al. (in prepara-
tion). A 75-jug/L aluminum standard was
prepared from a certified 1000-mg/L aluminum
standard and used as a QCCS. A calibration
curve was calculated each day using 0 25
100, 200, and 350-^g/L Al standards that were
prepared from a separate certified 1000-mg/L
Al standard. A 20-jug/L Al detection limit
standard and a reagent blank sample
(deionized water) were analyzed each day. QC
requirements are presented in Section 3.
Table 7. Flow Injection Analysis-Aluminum Procedure
A. Precalibration
1. Prepare reagents, standards, and qualitv
control solutions.
2. Warm up system components; begin pumping
reagents until baseline is stable.
3. Initiate background computer program and
chart recorder.
4. Input sample information to computer
5. Adjust "ZERO" to 100 and "GAIN" to 4 00 for
each channel.
B. Calibration
1. Place sample inlet into first of the five stan-
dards (acidified blank, 25, 100, 200, 350-pg/L
Al standards). Analyze each standard two
times.
2. Turn switch to "CAL" position.
3. Start program.
4. Place sample inlet into second standard after
two injection cycles.
5. Calibration data is printed after the fifth
standard.
6. Obtain raw calibration data.
C. Samples
1. Analyze 75-/jg/L Al quality control check sample
(with and without the cation-exchange column)
high calibration standards, 600-A/g/L Al quality
control check sample, 20-pg/L Al detection limit
sample, and deionized water blank.
2. Place syringe pump in line and set pump on
"7 mL/min".
3. Place syringe with filter on syringe pump
4. Turn switch to "SAMPLE" position.
5. Initiate sample analysis.
6. Analyze 75-ijg/L Al quality control check sample
every 10 samples, once with cationexchange
column and once without cationexchange
column.
7. At completion of sample analysis, analyze 75-
pg/L Al quality control check standard, detec-
tion limit standard, and blank.
D. System Shut-down
1. Stop background program.
2. Obtain raw sample data.
3. Run deionized water and cleaning solution
through reagent lines.
4. Turn off system components.
Results
For the fall seasonal study, control limits
were determined for a natural audit sample
16
-------
(Big Moose Lake, Adirondack Mountains, New
York State) based on 14 calibrations by a
single operator. This sample was analyzed
daily to monitor the status of the CEC. The
statistical analysis is presented in Table 8, and
is based on 14 instrument calibrations. QCCS
control charts for the FIA-aluminum method
are presented in Section 5, Figures 9 and 10.
QCCS statistical results are presented in
Table 13. Natural field audit sample results
are presented in Figure 17 and Table 15.
Table 8. Natural Field Audit Sample Results for Flow
Injection Analysis-Aluminum
Total Al Organic Al
Channel 1 Channel 2
(yg/L Al) (/jg/L Al)
n
J7
36 36
147.7 44.5
Two
Standard
Deviations
Range
12.58
135.1-160.3
10.74
33.8-55.2
Discussion and Recommendations
Numerous problems delayed the develop-
ment of a workable FIA-aluminum method
before spring sample processing began. The
instrument was not received until mid-January.
Further development of the method available
was required. Previous applications of the
method included an acidified carrier stream
and sample acidification. For NSWS samples,
it was decided to use a deionized water carrier
and not to acidify the samples in order to
minimize changes in pH and, hence, in alumi-
num speciation.
The main instrumental problem involved
the CEC. During the spring surveys, the sam-
ple flow for channel 2 (organically bound
monomeric aluminum) was as follows: the
sample stream first filled the channel 2 sample
loop, passed through the CEC, then entered
the reaction manifold. It was necessary to
manually remove the CEC from the sample line
for the analysis of standards and QC solu-
tions, then replace the CEC for sample analy-
sis. This removal and replacement of the CEC
was time-consuming and often resulted in the
introduction of air into the sample analysis
line. Due to these problems with the CEC, the
QCCS limit was extended to 75.0 ± 15.0 /jg/L Al
for channel 2 during the spring surveys. The
channel 1 QCCS limit remained at 75.0 ± 7.5
Al.
The major sample-related problem was
the high aluminum concentrations measured
in NSS-I samples. This led to the development
of a high-range analysis procedure. High
calibration standards (500, 750, and 1000 jug/L
Al) were analyzed each day following the 0-350
jug/L Al calibration. A 600-pg/L Al standard
was analyzed as the high-range QCCS. If a
sample aluminum concentration was between
350 and 600 /jg/L Al the 600-/jg/L Al QCCS was
subsequently analyzed. If the high QCCS was
within 10% of its theoretical concentration, the
sample result was accepted. If the sample
aluminum concentration was between 600 and
1000 fjg/L Al or the high QCCS criteria were
not met, a high calibration curve was deter-
mined manually from a linear regression of
peak area versus concentration of the high
calibration standards (350, 500, 750, and 1000
/jg/L Al). An expanded calibration was per-
formed for samples with aluminum concentra-
tions exceeding 1 mg/L Al using standard
concentrations of 1.000, 2.000, and 3.500 mg/L
Al and a QCCS of 2.500 mg/L Al (±10% limit).
The gain settings were changed to 1.00. Any
sample aluminum concentration exceeding
3.500 mg/L Al was diluted with deionized water
which was adjusted to the sample pH by
titration with 0.001 N H2SO4 (Ultrex) until the
absorbance was on scale at a gain setting of
1.00 (Kerfoot et al., in preparation).
As a result of the instrument and
sample-related problems, the spring FIA-alumi-
num procedure required excessive processing
time and produced a backlog of 395 samples.
The backlogged samples were analyzed as
time permitted during the spring surveys with
the assistance of methods development per-
sonnel. The data were qualified (flagged)
because the samples were not analyzed within
the specified sample holding time of 24 hours.
The effects of holding time on aluminum
speciation have not been determined con-
clusively.
The methods development group cor-
rected the FIA problems prior to the summer
seasonal survey. During the spring surveys,
routine FIA calibration was done with alumi-
num standards ranging from 0-150 fJQ/L Al.
17
-------
Experimentation with the calibration showed
that it was linear to 1000 jug/L Al and that the
best precision and sensitivity could be
achieved by performing a calibration using
standards from 0-350 pg/L Al. By installing a
switch and placing the CEC before the channel
2 sample loop, the operator could control the
activation of the CEC easily. This reduced
both the possibility of air introduction and the
total analysis time considerably. Reagent
concentrations and flow rates were varied in
order to optimize the method. A pH meter and
strip chart recorder were added to monitor the
system. Additional QC data requirements
were introduced. Method revision details are
described in Kerfoot et al. (in preparation).
During the summer seasonal survey, the
FIA-aluminum analysis proceeded with minimal
difficulty. Highly turbid samples could not
pass through the syringe filter without intro-
ducing air into the sample injection line. Once
these samples were identified, they were
centrifuged (for 90 seconds at setting of 40
equal to 1500 rpm) and analyzed successfully.
For three days during the summer survey,
channel 2 did not function properly as
evidenced by the low values obtained for a
natural audit sample known to contain a
measurable concentration of organically bound
monomeric aluminum. This resulted in the
modification of the protocol to include the
routine analysis of this natural audit sample
collected from Big Moose Lake in New York
State (FN-8 for the summer survey and FN-10
for fall activities). The calculated ranges for
this internal QCCS (Table 8) were not imple-
mented as strict limits, but were used as a
guideline to monitor the status of both chan-
nels of the FIA
For each QCCS interval, the 75-A/g/L Al
QCCS was analyzed one time without the CEC
and one time with the CEC. The control charts
presented in Section 5, Figures 9 and 10
demonstrate the comparability between chan-
nel 1 and channel 2. Without the CEC
engaged, only total monomeric aluminum is
measured.
The successful development of a viable
method for monomeric aluminum determination
and a final data requirement plan (Section 3)
continued throughout the sample processing
period. Many protocol revisions were neces-
sary after completion of the spring surveys.
The continued development of the FIA-
aluminum method during sample processing
produced a reliable FIA method for ELS-II
summer and fall seasonal studies.
Conductivity
Introduction
Conductivity, defined as the ability of an
aqueous solution to carry an electric current,
can be roughly linearly correlated with the ionic
strength of a solution when the conductivity of
the sample is less than 100 /^S/cm (25 °C).
Processing laboratory conductivity measure-
ments were made only on NSS-I samples,
using a YSI Scientific model 32 conductivity
meter and a YSI model 3417 conductivity cell
with a theoretical cell constant of 1.00 cm'1.
Methods
The method adopted for conductivity
measurement was a modification of the proce-
dure described in Hillman et al. (1986). Sam-
ples were poured from the Cubitainer into two
50-mL centrifuge tubes (a rinse solution and a
measurement solution) and equilibrated to
room temperature. Three QC solutions were
used for conductivity measurements: a 1 x \*
N, 5 x 10'4 N, and 1 x 10'3 N KCI solutions
measuring 14.7, 73.9, and 147.0 L/S/cm, respec-
tively (theoretical values at 25 C). The stock
solution was a 1 N KCI solution prepared from
reagent grade KCI dried for 2 hours at 105 'C.
A 147.0 /;S/cm KCI standard (prepared from a
second 1 N KCI stock solution) was used as a
calibration standard. The conductivity of a
deionized blank sample was measured each
day. QC requirements are presented in Sec-
tion 3. Deviations were detected in the output
from the conductivity meter temperature com-
pensation circuitry. The automatic temperature
probe was not used. Measured conductivities
of the QC standards and deionized blank
sample were corrected to 25 °C using a tem-
perature correction factor table and a pocket
calculator. Figure 4 is a flowchart for the
conductivity procedure.
Results
QCCS control charts are presented in
Section 5, Figures 11, 12, and 13. The QCCS
18
-------
CONSULT CONDUCTIVITY
METER OR CONDUCTIVITY
PROBE OPERATIONS MANUAL
AND NOTIFY SUPERVISOR
FINAL CELL
CONSTANT CHECK
ANALYSIS
COMPLETE
) PREVIOUS SAMPLES (FROM LAST ACCEPTABLE QCCS)
MUST BE REANALYZED AFTER ACCEPTABLE QCCS
IS OBTAINED.
Figure 4. Flowchart for conductivity method.
19
-------
statistical results are presented in Table 13.
FN audit sample results are presented in
Figure 18 and Table 15.
Discussion and Recommendations
During the spring surveys, analysts were
trained as time permitted. This resulted in
some analysis inconsistencies. As analysts
became familiar with the revised method and
the instrument, these problems were resolved.
The conductivity cell used early in the
spring was determined to be faulty when the
blank sample and cell constant (KJ values
were reviewed. A replacement YSI conductivity
cell was substituted after Batch ID 2129
(Figure 18).
Several modifications in the available
procedure (Hillman et al., 1986) were necessary
for the successful measurement of conduc-
tivity. First, it was necessary to correct the
measured conductivity values to 25 *C using a
table of temperature correction factors. These
computations were necessary to evaluate the
accuracy of the QCCS and to monitor the cell
constant during analysis. In the future, it
would be more efficient to equilibrate all sam-
ples and standards to 25 °C in a water bath.
Second, the deionized water used to prepare
the calibration standard and QCCS contributed
to the overall conductivity and had to be
considered in calculating the actual K,. and
QCCS values. The following equations were
used:
K,
(K,,, X T) - (Bm x T)
Sc= (Sm x ^ x 7} - (Bm x T)
(1)
(2)
where
Bm = measured value of blank
(deionized water)
K,. = temperature-corrected cell con-
stant
!<, = measured value of calibration
standard
K, = theoretical value of calibration
standard at 25 "C
Sc = temperature and blank corrected
specific conductance of QCCS
Sm = measured value of QCCS
T = temperature correction factor
Dissolved Inorganic Carbon
Introduction
The DIG concentration of water samples
was measured for all surveys. DIG measure-
ments, in combination with pH measurements,
provide an indication of the relative buffering
capacity of aquatic systems. Samples were
collected in syringes to prevent CO2 exchange
between the sample and the atmosphere
(Burke and Hillman, 1987). A Dohrmann/Xertex
(DC-80) carbon analyzer was used for the
infrared spectrophotometric measurement of
DIG.
Methods
Sample syringes were stored at 4 °C
until DIG analysis. The DIG method is detailed
in Hillman et al. (1986). Samples were filtered
using disposable 0.45-jum pore size syringe
filters. A 2-mg/L C DIG standard was used as
a QCCS and a 10-mg/L C standard (prepared
from a separate stock solution) was used for
the calibration procedure. The stock solutions
were 1000-mg/L C solutions prepared from
reagent grade Na2CO3 dried at 110 °C for 2
hours. A deionized water blank was analyzed
each day. QC requirements are presented in
Section 3. Increasing the maximum QCCS
interval from one analysis every eight samples
to one analysis every ten samples before
summer processing was the only procedural
change. A DIG method flowchart is illustrated
in Figure 5.
Results
A control chart for the 2-mg/L C QCCS
is presented in Section 5, Figure 14. The
QCCS statistical results are presented in Table
13. FN audit sample results for DIG analysis
are presented in Table 15 and Figure 16.
Discussion and Recommendations
A batch of 20 samples required three
hours to analyze. With two to four batches
arriving each day during the spring surveys,
two carbon analyzers were run simultaneously.
Several batches were cross-checked using
both carbon analyzers, and the values were
found to be within 10% of each other. Each
20
-------
INITIAL
CALIBRATION
LINEARITY
HECK WITHIN RANGE?
2mg C L~l(1.8-2.2ms C L"1)
20mg C LM(18.0-22.Q
mg C L
MEASURE
CALIBRATION BLANK
IS IT<0.1mg C L"1 ?
(RUN UP TO
THREE TIMES)
RECORD QCCS VALUE
IN LOGBOOK
AND NOTE SAMPLE
ID NUMBERS ASSOCIATED
WITH
UNACCEPTABLE QCCS
YES
RECORD QCCS
AND BLANK VALUES
IN LOGBOOK
MEASURE
SAMPLES
IDENTIFY ON
PRINTOUT
A
'MEASURE:
QCCS
IS 2mg C L
IN RANGE?
ENOUG
OF
PREVIOUS ANALYZED
SAMPLES FOR
EANALYSIS
PREVIOUS SAMPLES (FROM LAST ACCEPTABLE QCCS)
MUST BE REANALYZED AFTER ACCEPTABLE QCCS
IS OBTAINED.
Figure 5. Flowchart for dissolved Inorganic carbon analysis.
21
-------
batch was analyzed using only one carbon
analyzer to minimize within batch variability
(i.e., a batch was never split and analyzed
using two instruments.)
Due to the long storage time before the
beginning of the laboratory operations in 1986,
several instruments had to be returned to the
manufacturer for servicing. Problems dis-
covered by the manufacturer included unoiled
air pumps, soiled permeation driers, and
plugged flow restrictors. Weekly and monthly
maintenance procedures were established
(Table 11). A complete check-out of each
instrument should be performed before labora-
tory operations begin, and a detailed main-
tenance record should be kept.
When the trailers were located in the
field, inside and outside gas regulators were
used to control carrier gas flow to the carbon
analyzers. It was convenient for analysts to
control the gas flow from within the trailer in
the field, but the extra fittings increased the
possibility of gas fluctuations. When gas leaks
were discovered, recalibration and reanalysis
of samples was necessary. The inside N2
regulators were removed when laboratory
operations were consolidated eliminating the
extra gas fittings.
During the spring surveys an area-wide
power failure interrupted the analysis of sam-
ples. Samples were processed the following
day and the data were qualified (flagged).
Reserve power units were installed in the
processing laboratory as a precaution against
loss of instrument memory and calibration in
the event of future power failures. The reserve
power units could maintain a minimal power
supply for one to three hours.
The decision to increase the maximum
QCCS analysis interval after spring processing
was based on the accuracy and precision of
the 2-mg/L C QCCS (Figure 14) and results
from all previous surveys.
Aliquot Preparation
Introduction
A set of seven aliquots was prepared
from each Cubitainer. The samples were
required to be processed within 24 hours from
the time of collection. The parameter to be
measured at the analytical laboratory (Table 9)
dictated how samples were prepared and
preserved at the processing laboratory.
Methods
A set of aliquots was prepared from
each Cubitainer bulk sample (Hillman et al.,
1986). The preparation techniques, order of
priority, and chemical parameters measured
at the analytical laboratory for each aliquot
are presented in Table 9. Analytical methods
used by the contracted analytical laboratories
and sample holding times are presented in
Hillman et al. (1986).
For ELS-II seasonal studies, an addition-
al split sample was prepared for trace metal
analysis by graphite furnace atomic absorption
spectrophotometry at Indiana University
(Bloomington, Indiana) under the direction of
Dr. J. White. The preparation of this split is
outlined in Table 9.
In preparation for shipment, each aliquot
was sealed with electrical tape and individually
placed in a plastic bag tied with a twist-tie.
All aliquots for each sample (except the extrac-
table aluminum aliquot) were placed in a
one-gallon Ziploc bag. Samples were shipped
in coolers with frozen chemical refrigerant
packs. Extractable aluminum aliquots were
shipped in a separate shipping cooler with
frozen chemical refrigerant packs. Details
regarding the shipment of extractable alumi-
num aliquots are discussed in the Extractable
Aluminum discussion of this section. The
sample shipping form (Appendix D, Figure D-2)
was completed and distributed as described in
the Sample Organization discussion of this
section.
The summer seasonal survey included
special projects particular to temperate lake
stratification conditions. The sample organiza-
tion and analyses of preserved hypolimnetic,
chlorophyll, and zooplankton samples are
discussed in the Sample Organization discus-
sion of this section and Table 4. Two addi-
tional split samples were prepared at the
processing laboratory during ELS-II, the sum-
mer seasonal study: a total nitrogen and
phosphorus sample and a triplicate sample.
22
-------
Table 9. Aliquot Preparation
Aliquot Processing
1 Acid, filtered
2 Acid, filtered
3 No acid, filtered
Container
volume
250 mL
15 mL
250 mL
Preservation
acid
HN03
None
None, no
headspace
Chemical parameters measured
Metals (Ca, Fe, K, Mg, Mn. Na)
Extractable Al
Cr, F, NO3-, SO42-, SiO2
order
4
3
2
4
5
Acid, filtered 125 mL H2SO4 Dissolved organic carbon, NH4+ 6
Unfiltered 500 mL None, no Acid/base neutralizing capacity, 1
headspace conductivity, dissolved inorganic
carbon, pH
6
ELS-II,
SVS-P
6
NSS-I
7
Split, ELS-II
Unfiltered
Acid, filtered
Unfiltered
Acid, filtered
125 mL
125 mL
125 mL
15 mL
H2S04
H2S04
HNO3
HN03
Total P
Total dissolved P
Total Al
Trace metals (Cd, Cu, Ni, Pb, Mn)
i
7
5
8
1. Total nitrogen and phosphorus split
Description: Unfiltered, 125-mL, H2SO4
preserved, stored in specially prepared
HCI-washed containers; shipped to
EMSL-LVthe following day. The samples
were analyzed using a colorimetric FIA
method.
2. Triplicate sample for interlaboratory bias
experiment
Description: One set of aliquots (1 and
3-7, listed in Table 9) shipped daily with
the routine batch; one set of half-sized
aliquots (1 and 3-7) shipped daily with
the bias batch to a separate analytical
laboratory.
Aliquot labels used for the 1986 surveys
are represented in Appendix D, Figures D-3 and
D-4.
Results
The batch series, total number of
batches, analytical laboratories used, and
sample types processed are listed in Table 10.
A total of 3,377 samples were processed.
Discussion and Recommendations
During the spring surveys, as many as
seven analysts were assigned to filtration; a
team of two analysts assumed all preservation
responsibilities. In subsequent surveys, the
batch sizes dictated that one to three analysts
were needed to filter samples. One additional
analyst was assigned to preserve the aliquots.
Each analyst assigned to filtration could
process a maximum of 15 samples per day.
Stream samples usually filtered slowly.
The use of two-stage filtration units might
speed up future large-scale operations. These
units, which employ a coarse filter in addition
to the fine filter that was used, would elim-
inate excessive filtration times.
During the spring surveys, three blank
samples were contaminated with nitric acid.
This was attributed to contamination between
acid-washed and non-acid-washed filtration
units. A plastic barrier was constructed and
used to separate acid and non-acid filtration
units in subsequent surveys.
23
-------
Table 10. Processing Summary
Batch series
Number of batches
Analytical
Laboratories*
Routine
Duplicate
Audit
Blank
Spring
Variability
Pilot
Study
3000
17
PBS & J,
Versar
128
18
27
30
National
Stream
Survey
Phase-I
2100
68
NY State,
Global
1,395
65
134
68
Eastern Lake Survey-Phasell-Seasonal Studies
Snowpack
Study
4000
20
EMSI
277
51
20
86
Spring
3500
29
PBS & J.
Versar
146
29
43
29
Summer
3600
17
PBS&J
295
31
44
25
Bias
Experiment-
Summer
3650
17
Versar,
PBS&J
26
.
20
2
Fall
3700
26
Versar
239
26
93
30
Total
203
1,662
434
247
395
48
388
aPBS & J = Post, Buckley, Schuh, and Jermigan, Inc (Orlando, Florida)
Versar (Alexandria, Virginia)
NY State = New York State Department of Health (Albany, New York)
Global = Global Geochemistry Corporation (Canoga Park, California)
EMSI = Environmental Monitoring Services, Inc. (Thousand Oaks, California)
For the first part of the spring surveys,
the aliquots were not always refrigerated for
one hour prior to the taping of the lids, which
was the procedure for the earlier surveys.
This was due to the high number of samples
encountered and the overnight courier deadline
of 3:30 p.m. each day. The analytical labora-
tories reported that a few of the aliquot bot-
tles had leaked during shipment. To alleviate
this problem, the aliquots were stored at 4 "C
for at least one hour before the lids were
taped, minimizing the expansion and contrac-
tion of the bottle seal.
Due to the uncertainty of the weather
conditions in the field, weekend sample pro-
cessing was frequently necessary. Because
the overnight courier did not operate at full
capacity on Sunday, samples processed on
Saturdays were held by the courier for Monday
delivery to the analytical laboratory. Samples
processed on Sunday were shipped on Mon-
day.
Extractable Aluminum
Introduction
An extractable aluminum procedure using
MIBK was used to determine aluminum con-
centrations in natural waters (Barnes, 1975).
Sample aliquots were filtered, mixed with an
8-hydroxyquinoline/sodium acetate reagent
(HOx), and buffered with ammonium acetate to
a pH of 8.3. At this pH, dissolved aluminum
species complexed with the HOx in solution.
These complexes were extracted from the
mixture by adding MIBK. The complex was
transferred to the organic layer by agitation,
then was removed by pipet. The prepared
aliquots were shipped daily to the analytical
laboratories for analysis by graphite furnace
atomic absorption spectroscopy.
Methods
Extractable aluminum samples were
collected in syringes by the field crews. The
syringes were held at 4 "C until preparation.
The method for extractable aluminum using
MIBK is presented in Figure 6. The prepara-
24
-------
OBTAIN SAMPLES,
RECORD
TIME AND DATE COLLECTED
IN LOGBOOK,
PLACE FILTER ON SYRINGE
WASH SOmLTUBE 3x
WITH 1-2 mL SAMPLE. FILTER
EXACTLY 25 mL OF SAMPLE
INTO TUBE
PLACE SAMPLES IN COOLER
TO KEEP COLD
ADD 10 mL MIBK
AND SHAKE VIGOROUSLY
FOR 10 SECONDS
CENTRIFUGE FOR
90 SECONDS,
DECANT TOP LAYER
AND PLACE IN
15 mL TUBE
PROCESSING
COMPLETE
ADD REAGENTS
1...3 DROPS PHENOL
2...5 ml HOx
3... 2 mL BUFFER
MEASURE AND RECORD
VOLUME IN LOGBOOK
AND ON LABEL
PREPARE
FOR SHIPPING
Figure 6. Aluminum extraction method flowchart.
25
-------
tion techniques and the priority of this aliquot
are presented in Table 9 (Aliquot 2). A cali-
brated photo ionization detector was used to
monitor organic vapor (MIBK) levels in the
trailer. Personnel who performed extractable
aluminum analyses were required to wear
respirators. Method changes for the 1986
surveys are described below:
Samples were filtered from the syringe
into 50-mL centrifuge tubes using acid-
washed syringe filters instead of
obtaining a portion of filtered samples
from aliquot 1.
Glacial acetic acid was used in place
of hydrochloric acid for the buffer
preparation.
Analysts wore two pairs of gloves
when handling MIBK as an added
safety precaution.
The extractable aluminum aliquots
were shipped to the analytical labora-
tory separately.
Discussion and Recommendations
Glacial acetic acid was substituted for
hydrochloric acid in the buffer solution because
chlorine and ammonia contamination was
detected by the analytical laboratories in the
blank samples. This was attributed to the
fuming characteristics of the buffer solution
during preparation using hydrochloric acid.
To guard against leakage during sample
shipment to the analytical laboratory, the
15-mL centrifuge tubes were taped lengthwise
with electrical tape. Special Styrofoam carriers
were fashioned to hold tubes upright during
shipment. These aliquots were packaged in a
separate cooler.
Analysts' technique was a major source
of variability in the recovery of extractable
aluminum. The performance of each analyst
was tested prior to the survey and the percent
recovery of spiked samples was reviewed.
When possible, one or two operators were
assigned to prepare this aliquot throughout a
survey.
Preparation (including acid-washing) of
20 syringe filters required one analyst approxi-
mately one hour. For previous surveys, a
filtered portion of sample was obtained during
the preparation of Aliquot 2 (Table 9) in order
to prepare the extractable aluminum aliquot.
This eliminates the need for filter preparation
and the additional filtration from the syringe.
Since the extractable aluminum aliquot would
be prepared from the Cubitainer bulk sample,
one less syringe per sample would be col-
lected in the field.
Though the extractable aluminum pro-
cedure proved a reliable method for measure-
ment of aluminum concentrations when pre-
pared by a single analyst, the FIA-aluminum
method provides more specific information
concerning particular aluminum species.
Because a reliable FIA-aluminum method has
been developed, we recommended that the
extractable aluminum method be eliminated.
Sole use of the FIA method provides specific
aluminum species data, reduces contract
laboratory costs, and substantially reduces the
volume and handling of hazardous waste in
the laboratory.
Color and Turbidity
Introduction
Color in natural waters has been closely
correlated to the amount of dissolved organic
carbon. Dissolved organic compounds may
act as chelators for metals such as aluminum.
True color was measured using a Hach CO-1
color determination kit, in which a color disc
was rotated over the blank until the color
matched the sample color. The results were
expressed as American Public Health
Administration platinum-cobalt (PC) units.
Turbidity, a measure of suspended or-
ganic and inorganic material in the water
column, affects light transmission. The neph-
elometer projects an optical beam through the
unf iltered sample contained in a special optical
cuvette. Particulate matter in the sample
scatters the light which is then measured with
a photodetector. The digital readout, in neph-
elometric turbidity units (NTU), is a measure of
the concentration of the particles in the
solution.
26
-------
Methods
Methods for true color and turbidity are
documented in Hillman et al. (1986). The
applicable range of the Hach color determina-
tion kit is 0-500 PC units. A number of NSS-I
samples had color values exceeding 500 PC
units and required the development of a high-
range color procedure. The analyst decanted
the sample and the deionized water blank to
the 5-mL mark on the color tube and added 5
mL of deionized water to the sample tube.
The sample and the deionized water were
mixed thoroughly, and the volume was reduced
to 5 mL using a disposable pipet. The color
value was read using the procedure for sam-
ples with color values between 100 and 500 PC
units. The value was multiplied by ten and
recorded with a comment on how the final
color value was determined.
Figure 7 illustrates the turbidity method.
A 5 NTU standard was used as a QCCS; a 10
NTU standard was used as a calibration
standard. The linearity of the nephelometer
was checked using 2, 5, and 20 NTU stan-
dards. The maximum QCCS interval was
increased from one analysis every eight sam-
ples (spring) to one analysis every ten sam-
ples (summer and fall).
A matrix-corrected dilution equation for
high turbidity (>200 NTU) samples was mod-
ified from Hillman et al. (1986). Analysts
poured 25-30 mL of filtered sample into a
cuvette and measured turbidity. Unfiltered
sample (5 mL) was added to a 50-mL centri-
fuge tube with 45 mL of filtered sample and
mixed thoroughly. Analysts poured 25-30 mL
of the diluted sample into a cuvette and the
turbidity was measured using the standard
"ZERO" THE
NEPHELOMETER
CHECK INSTRUMENT
OPERATION AND
STANDARD QUALITY
INITIAL CALIBRATION
10 NTU STANDARD
ARE
VALUES WITHIN
10% OF THEORETICAL
VALUES
LINEARITY CHECK
WITH 2.0,5.0 AND
20.0 NTU STANDARDS
RECORD VALUES
IN LOGBOOK AND RECORD
VALUE FOR 5.0 NTU QCCS
ANALYSIS COMPLETE
RECORD VALUE
IN LOGBOOK
ANALYZE SAMPLES
AND RECORD IN LOGBOOK
CHECK INSTRUMENT,
RECALIBRATE AND NOTE IN
LOGBOOK, REANALYZE ALL
SAMPLES BACK TO LAST
ACCEPTABLE QCCS
AFTER ACCEPTABLE QCCS
IS OBTAINED.
ANALYZE 5.0 NTU QCCS
AND RECORD IN LOGBOOK
CCEPTABL
VALUE ?
(5.0±0.5
TU
Figure 7. Flowchart for turbidity method.
27
-------
protocol. The final turbidity was calculated
using the following equation:
Actual
turbidity
10
Turbidity
of diluted sample
10
-9
Turbidity
of filtered sample
10
High-range samples were reanalyzed at the
end of the batch with the appropriate QCCS
measured before and after the high-range
samples. Samples with turbidity values rang-
ing from 20-50 NTU required the use of a 20-
NTU QCCS; sample values ranging from 51-175
NTU required the use of a 50-NTU QCCS;
values ranging from 176-199 NTU required the
use of a 175-NTU QCCS.
Discussion and Recommendations
High-range methodology for both the
color and turbidity procedures was developed.
The decision to increase the maximum
QCCS interval for turbidity before the summer
survey was based on the high precision of the
5-NTU QCCS during previous surveys. A
further extension of the maximum QCCS inter-
val to include an initial check, a mid-batch
check, and a final check independent of batch
size is recommended based on previous
results.
Equipment Maintenance
The laboratory staff performed regular
maintenance on all instruments and the water
systems one day per week.
Methods
Appendix A provides a list of
instruments, equipment, and supplies used by
the processing laboratory. A list of weekly
maintenance is presented in Table 11. All
maintenance procedures were recorded in
logbooks. Records for all refrigerators,
freezers, and water systems were kept in daily
logs.
A reverse osmosis (RO) system provided
Type I reagent grade water (ASTM, 1984) in
each trailer. Due to the poor quality of the Las
Vegas feedwater, these systems required
frequent upkeep. Cartridge replacement and
system maintenance were done as directed by
the water system instruction manuals. A
Milli-RO water purification system which in-
cluded the RO membrane was employed. A
polishing system (Milli-Q) was used to produce
the high quality water required for processing.
A complete water system was composed of
both a Milli-RO and a Milli-Q unit.
Table 11. Equipment Maintenance
General Weekly Maintenance-
Check balance, pipet, and Repipet calibrations.
Check inventory and restock trailers.
Change water in eyewash stations.
Check all emergency showers and fire extin-
guishers.
Replace prefilters of the water systems.
Method Weekly'Maintenance-
Turbidity - Repour all standards.
Filtration - Soak filtration units.
pH - Drain and refill electrodes.
DIG - Change all pump tubing.
- Refill tin scrubbers and reaction vessels.
- Prepare reagents and stock solutions.
- Check scrubber line cartridges.
- Perform detection limit check.
Extractable aluminum - Check organic vapor
meter calibration.
- Prepare reagents as
needed.
- Check calibration of
Repipets.
FIA-aluminum - Replace pump and Teflon
tubing.
- Clean flow cells and rotary
valves.
- Prepare reagents as needed.
- Download data files.3
- Perform detection limit check.8
" These items should be incorporated in the future but
were not done during these surveys.
Results
Analysis of the incoming feedwater supply
to the warehouse showed that the conductivity
was 1,072/L/S/cm and the hardness (as CaCOg)
was 336 mg/L.
Discussion and Recommendations
We recommend that a day be set aside
each week for scheduled maintenance only.
Changes in the sampling itinerary due to poor
weather conditions did not always permit a
scheduled maintenance day. Performing
maintenance while samples are being pro-
cessed should be avoided.
28
-------
Type I reagent water has a resistivity
value 16.67 MQ-cm (0.06 /jS/cm) (ASTM, 1984).
Large sample loads during the spring surveys
created a high demand on the water systems.
Individual cartridges had to be replaced fre-
quently. A system could process approximate-
ly 300 gallons of water with a resistivity value
of 18 MQ-cm before losing its purification
ability (approximately every two to three weeks
with daily use). During the reduced demand of
the summer survey, frequent (and expensive)
cartridge replacement was still necessary to
maintain operations because the one-year life
expectancy of the RO membranes was near
expiration. An unsuccessful attempt was
made to preserve the old RO membranes at
the completion of the ELS-II summer seasonal
study. New RO membranes were installed in
each system prior to the beginning of fall
sampling. The systems performed successful-
ly with minimal attention throughout the fall
seasonal study.
The instruction manual for the RO mem-
branes specified that the maximum conduc-
tivity of the feedwater should be no greater
than 833 /jS/cm. The Las Vegas feedwater
conductivity value was measured at 1,072
/L/S/cm. This feedwater supply analysis shows
that the Milli-Q ion-exchange cartridges were
working under great stress to produce accep-
table water. Instead of replacing all of the
cartridges associated with both systems, only
the Milli-RO prefilter and precarbon cartridges
and the Milli-Q ion-exchange cartridges were
replaced to obtain Type I water. This was a
successful, cost-saving measure that resulted
in minimal system "down time." It would be
most efficient to rent or purchase some type
of pretreatment system for either the incoming
water line feeding the warehouse or for each
trailer individually. Suggestions confirmed by
the manufacturer included the use of a water
softener or a large ion-exchange unit on the
feedwater supply. Demand on the water
systems, age of the RO membranes, and the
composition of the incoming water affected
the maintenance of the water systems.
Field Support
Introduction
Field support for NSWS sampling teams
was centralized by combining the laboratory
and warehouse operations. Field standards
for conductivity and pH were prepared and
shipped from the laboratory; field supplies
were shipped simultaneously from the ware-
house.
Methods
Standards and equipment were shipped
according to a prearranged schedule. The
communications center coordinated all ship-
ping requests. Table 12 provides a list of all
items shipped by the processing laboratory.
Table 12. Field Supplies
1 x 10'4. 5 x 10"*. 1 x 10'3 N KCI standards
1 x 10"* N H2SO4 QCCS, pH 4, pH 7 NBS buffer solutions
3 M KCI
Deionized water
Frozen chemical refrigerant packs
Syringe containers
pH electrodes
Syringe valves
Shipping containers (coolers)
Conductivity and pH standards were
prepared in 20-L carboy containers, then trans-
ferred to 4-L Cubitainers for shipping. Stan-
dards were packed in frozen chemical refrig-
erant packs and shipped in hard plastic
coolers. Standards and deionized water were
prepared as needed for the spring surveys. All
summer and fall seasonal study standards
were prepared before the survey began.
Laboratory personnel also prepared the
following items for the summer survey:
HCI-leached, 125-mL bottles for total
nitrogen and phosphorus samples
Deionized, water-leached, 2-L bottles
for chlorophyll samples
Deionized water-rinsed filters and
250-mL bottles spiked with HNO3 for
preserved hypolimnetic samples
Buffered formalin solution for
zooplankton samples
Chlorophyll audit samples prepared
from Lake Mead (Nevada)
Field audits for preserved hypolimnetic
and total nitrogen and phosphorus
samples
29
-------
Discussion and Recommendations
During the start-up phase of the spring
surveys, the large demand for field supplies
created a backlog of supply orders at the
laboratory. Development of a weekly shipping
schedule and additions to the laboratory staff
alleviated the problem. Laboratory personnel
assigned to supply the field teams operated
on a second shift (1300-2100 hours) to more
efficiently utilize laboratory space and available
water systems. For the summer and fall
operations, field standards were prepared
before sample processing began and were
refrigerated until needed.
Laboratory freezer space was limited.
Commercial freezer space was rented during
the spring surveys to freeze the large number
of cold packs necessary for shipping stan-
dards and samples.
Snowpack
Introduction
The snowpack survey was designed and
conducted by Dr. D. DeWalle of Pennsylvania
State University in conjunction with ELS-II.
The objectives of the survey were to determine
the relationship between snowpack conditions
and the extent and severity of episodic lake
acidification and to examine snowpack spacial
and temporal variation. Nine watersheds were
sampled one time each to study snowpack
spacial variability. Temporal variability sam-
pling was conducted on two watersheds for
a six-week period. The processing laboratory
staff measured pH and DIG and prepared
aliquots for shipment to an analytical
laboratory.
Methods
Snowpack sample processing differed
from lake and stream sample processing in
the following ways:
(1) Samples were equilibrated to room
temperature.
(2) pH aliquots were poured from melt
buckets into 50-mL centrifuge tubes and
measured in an open system (i.e., no pH
sample chamber).
(3) DIG sample syringes were drawn
from the melt buckets.
(4) Cubitainers were filled with the
remaining volume from the melt buckets.
Analysts prepared aliquots 1, 3, and 5 as
half-sized aliquots and aliquot 4. See Table 9
for aliquot descriptions.
(5) Two 50-mL trace metal split samples
were prepared, preserved with HNO3, and sent
to Dr. DeWalle (Pennsylvania State University)
for analysis.
Results
A tabulation of snowpack samples
processed is presented in Table 10.
Discussion and Recommendations
Snowpack samples were scheduled to be
processed before NSS-I samples arrived.
Delays in the start-up of the processing labo-
ratory resulted in a backlog of samples at
Pennsylvania State University. Three batches
were processed in March. QA personnel noted
that the samples had not been organized
properly (by sampling date) into batches
before shipment and required that all samples
be shipped to Las Vegas, stored in commercial
freezer space, and properly organized into
batches. Further processing was postponed
until May. Once the frozen samples arrived at
the processing laboratory, they were melted,
processed, and shipped within one day and
analyzed by the contracted analytical labora-
tory within the required holding time. The
effect of storage on the frozen samples was
not assessed.
Trial samples were shipped to Las Vegas
to test snowpack protocols. The plastic bags
containing the samples jeaked during the
melting procedure leaving inadequate sample
volume for processing and analysis. The
decision was made to ship samples to the
laboratory in plastic bags, then transfer the
samples to plastic buckets for melting.
Samples were processed in the following
priority order when sample volumes were low:
(1) pH, (2) DIG, (3) aliquots, and (4) splits.
30
-------
For a batch of 20 samples, two hours
were needed to wash 20 melting buckets; two
hours were needed to transfer the samples
from the plastic bags to the buckets; and
16-20 hours were required to melt the samples
for processing the following day. Sample
organization and aliquot preparation required
an additional two hours. Processing time was
minimal (two to three hours). The pH of the
snowpack samples stabilized quickly (within
five minutes) and samples filtered rapidly.
Snowpack sample processing was
delayed until the samples were sorted properly
and the NSS-I sample load stabilized. Once
these problems were resolved, the flow of
snowpack samples through the processing
laboratory proceeded without incident.
31
-------
Section 5
Results
Quality Control Check Sample
Results
Analysis of the pH QCCS is presented in
this section along with control charts for
FIA-aluminum, conductivity, and DIG QCCS
results. Table 13 summarizes the QCCS res-
ults. The verified results will be available in
future QA reports.
pH
Figure 8 is a frequency distribution
demonstrating the accuracy and precision of
the 1 x 10"* N H2SO4 QCCS based on 485
samples analyzed during the spring surveys of
1986. The mean pH value was 4.06, which
was within QCCS limits of 3.90 to 4.10 pH
units. The precision as two standard devia-
tions was ± 0.05 pH units. The statistical
comparability of electrodes used for these
measurements is given in Table 14 (Metcalf,
1987). A similar mean of 4.05 ± 0.04 (mean ±
two standard deviations) was obtained for the
ELS-II fall seasonal data (n = 52).
FIA-Aluminum
Figures 9 and 10 are control charts for
the 75-/jg/L Al QCCS for FIA-aluminum analy-
sis. Figure 9 depicts channel 1 results and
Figure 10 depicts channel 2 results. The CEC
is not engaged so channel 1 and channel 2
both measure total monomeric aluminum. The
control lines are drawn at values representing
±10% and ±20% of the mean. The statistical
results are summarized in Table 13.
Conductivity
Control charts for the conductivity QCCS
are presented in Figures 11 through 13. Three
Table 13. Quality Control Check Sample Results
Parameter
Survey
Quality control
check sample
Two standard
deviations
n
pH (pH units)
Flow injection
analysis-aluminum
channel 1 (/jg/L Al)
Flow injection
analysis-aluminum
channel 2 (pg/L Al)
Conductivity
(A/S/cm)
Dissolved inorganic
carbon (mg/L C)
Spring
Eastern Lake Survey-
Phase II (summer)
Eastern Lake Survey-
Phase II (summer)
National Stream
Survey-Phase I
Spring Variability
Pilot Study
1 x 10"*N Hj,SO4 4.06
75/ug/L Al 74.5
75pg/L Al
1 x 10'4N KCI
5 x 10"*N KCI
1 x 10'3N KCI
2 mg/L C
73.6
15.5
74.2
146.3
2.115
0.05
6.16
8.26
1.58
3.92
6.58
0.142
485
34
34
78
78
78
34
NOTE: These results have been calculated from the raw data which were input directly from the processing laboratory
Batch/QC data forms (Appendix D, Figure D-1).
32
-------
i
£
|
3 £ o - a
cro % o jy
P IS I
;H " 3 c
^a 2:2. s
S§
-5 *
* :
II
3 O
i !
« 3
S o
O 7
a
3
« « «
» 2 5
a I |
m tt ti
Is?
a
NUMBER OF OBSERVATIONS -*-
NUMBER OF OBSERVATIONS
FREQUENCY PERCENT
X
5
a
3"
5"
-------
Table 14. Descriptive Statistics of pH Quality Control Check Sample Frequency Distributions Grouped by Electrode
(MoTCflIf i i987/
Statistical variables All electrodes
Electrode A
Electrode I
Electrode J
Remaining electrodes
Standard Deviation
485
4.056
0.023
171
4.056
0.022
141
4.056
0.022
92
4.059
0.026
81
4.053
0.020
105 -
95 -
85 -
L 75
<
O)
3.
65 -
55 -
45 -
2 0 %
" w u 10%
o
O O O O
6 00° " ' ° x
°00 00 0 0
o o o o o
o o o
0%
20%
3600 3602 3604 3606 3608 3610 3612 3614 3616
BATCH ID
Figure 9. Control chart for flow Injection analysis-aluminum quality control check sample (channel 1). 75-uo/L
Al quality control check sample values versus Batch ID for the Eastern Lake Survey-Phase II (summer)
Percent difference (%) from the mean (x).
34
-------
105-1
95-
85-
75-
O)
a.
65-
55-
45-
20%
--10%
O O O
o o o o o o
-O O-
o
-o-
o o
o o
o o o o
o
o o
o
-10%
20%
I'i
3600 3602
T
I 1 1
3608 3610
3604 3606
BATCH ID
I 1 1
3612 3614
3616
Figure 10 Control chart for flow Injection analysis-aluminum quality control check sample (channel 2). 75-j/g/L
Al quality control check sample values versus Batch ID for the Eastern Lake Survey-Phase II (summer).
Percent difference (%) from the mean (x).
standards were used as QC solutions: 1 x
10'4, 5 x 10"4,and 1 x 10'3 N KCI solutions. The
control lines are drawn at values representing
±5%, ±10%, and ±20% of the mean for the low
conductivity standard and ±5% and ±10% of
the mean for the medium and high conductivity
standards. The statistical results are pre-
sented in Table 13.
DIC
Figure 14 is a control chart for the 2-
mg/L C DIC QCCS with control lines drawn at
values representing ±10% and ±20% of the
mean. The statistical results are presented in
Table 13.
35
-------
20-
18-
16-
E
o
V)
14-
12 -
10-
-O
O O O O
OO
O O
o
-o-o-
o
O
20%
o 10%
o o o o o o
' o o o o
o o o o-O O O O 5%
O OOO OO
O OO OOO OO OO OOO O
5%
10%
20%
1 I ' ' ' ' I ' ' ' ' I ' ' ' I I II'
2130 2135 2140 2145 2150
BATCH ID
T-|i i
2155
I I I I I
2160
1 I '
2165
Figure 11. Control chart for 14.7-//S/cm conductivity control check sample (channel 2). Low quality control check
sample values versus Batch ID for the National Stream Survey-Phase I. (Values corrected to 25 °C)
Percent difference (%) from the mean (x).
Natural Field Audit Sample
Results
Several FN audit sample types were
measured at the processing laboratory. These
samples were collected, filtered, homogenized,
and split into aliquots by Radian Corporation
(Austin, Texas). FN-6, FN-7, and FN-8 audit
samples were collected from Bagley Lake
(Cascade Mountains, Washington), Seventh
Lake (Adirondack Mountains, New York), and
Big Moose Lake (Adirondack Mountains, New
York). Sample codes are presented in Appen-
dix D, Table D-1.
36
-------
100-
e
o
(f)
3.
50-
i | I I I I
2135 2140
2145 2150
BATCH ID
2155
2160
2165
Figure 12. Control chart for 73.9-pS/cm conductivity control check sample. Medium quality control check sample
values versus Batch ID for the National Stream Survey-Phase I. (Values corrected to 25 *C). Percent
difference (%) from the mean (X).
Figures 15 and 16 are plots of the FN-7
and FN-8 audit sample results for pH and DIG
for all surveys except the Snowpack Study
(FN-7 was not used for NSS-I). FIA-aluminum
audit sample results (FN-7 and FN-8) for
ELS-II (fall) are presented in Figure 17. Table
15 includes summary statistics for the FN-7
and FN-8 samples analyzed for pH, FIA-
aluminum, and DIG.
A distribution of results for the FN-6
audit sample is shown in Figure 18. There
were 23 observations and the mean ± two
standard deviations value was 15.7 ± 5.16
/vS/cm. The faulty conductivity cell (discussed
in Section 4) was replaced with a functioning
cell before Batch 2130 was analyzed.
37
-------
180 -
175 -
170 -
165 ~
160 -
155 -
y 150 -
E
0 145 H
w
a.
140 -
135 -
130 -
125 -
120 -
o
o o
o o o
O O
O OO O O
O O O O
o o o
o o
O 00
o o
o o o ooo
OOO O
20%
10%
o
10%
20%
I i I i i ir|ii i i [ i i ii| i i i i[iiii| i i i i | i i ii[ i i
2130 2135 2140 2145 2150 2155 2160 2165
BATCH ID
Figure 13. Control chart for 147.0-pS/cm conductivity control check sample. High quality control check sample
values versus Batch ID for the National Stream Survey-Phase I. (Values corrected to 25 *C) Percent
difference (%) from the mean (x).
38
-------
O
O)
2.6 -
2.4 -
2.2
2.0 -
1.8 -
1.6-
20%
10%
O O
O O
O O
O O
O
O O
O
O O O
O
o
I
3000
1 1 1 1 r 1
3005 3010
BATCH ID
10%
20%
3015
Figure 14. Control chart for dissolved Inorganic carbon quality control check sample. 2-mg/L C quality control
check sample values versus Batch ID for the Spring Variability Pilot Study. Percent difference (%) from
the mean (X).
39
-------
I
a
7.4 -
7.0 -
6.6 -
6.2-1
5.8 -
5.4-
5.0-
4.6-
CD
DDrjrjD
D°
0= FN-7
O = FN-8
°°o o0o00ooc
16
' 1 1 ' I I I 1 1 I 1 1 1
21 26 31
I 1
1 I I I
36
1 1 1
41
1 I I I I
46
I I I I I I I I I I
56 61 66
OBSERVATION
Figure 15. pH natural field audit sample results versus observation. FN-7 and FN-8 results for three 1986 spring
surveys.
40
-------
2.5
2.0-r.i
'-I 1.5-
O
O)
E
1.0
0.5-.
n
a
o o°o
o o
D ° ° a C
D °a n
0 = FN-7
0=FN-8
' ' | ' ' ' ' I ' ' i t | i i i | i i r i | i i i | i i i i | i i i i | i
1 6 11 16 21 26 31 36 41
OBSERVATION
' I ' ' ' ' I ' ' ' ' I ' ' ' ' I '
46 51 56 61
66
Figure 16. Dissolved Inorganic carbon natural field audit sample results versus observation. FN-7 and FN-8 results
for three 1986 spring surveys.
41
-------
O)
a.
zzu
200-j
180-
160-
140-
120-
100-
80-
60-
40-
-
20-1
<
>0ooo0oo°
FN-8
FN-7
Q D ,-, [-1 n 1
I
|
* ' T 1 | 1 1 1 1 1 1
3701 3705 3707 3713 3718 3722
BATCH ID
60-
<
50-
I
-I 40-
<
g 30-
20-
(
10-
0
o
0
I
° FN~8 o
(
o
FN-7
\ o ° a a
° a i
0 °
1 1 ' - 1 ' I I | '
3701 3705 3707 3713
BATCH ID
3718 3722
Figure 17. Flow Injection analysis-aluminum natural field audit sample results versus batch ID. FN-7 and FN-8
results for the Eastern Lake Survey-Phase II (fall).
Upper: Total monomerlc aluminum (channel 1)
Lower: Organic monomerlc aluminum (channel 2)
42
-------
Table 15. Natural Field Audit Sample Results
pH
All surveys
except Snowpack
FN-7 X 6-83
Two Standard Deviations 0.22
n 33
FN-8 X 5.13
Two Standard Deviations 0.12
n 68
Flow injection
analysis-aluminum
ELS-II (fall) ELS-II (fall)
Aig/LAI pg/LAI
total monomeric organic monomeric
24.6
6.84
11
196.3
16.16
11
15.3
6.74
11
52.5
16.00
11
Dissolved
inorganic carbon
All surveys
except Snowpack
mg/L C
2.023
0.410
37
0.551
0.110
68
NOTE: These results have been calculated from the raw data which were input directly from the processing laboratory
Batch/QC data forms (Appendix D, Figure D-1).
28-
24-
20-
r- 16-
I
E
o
CO 12
3.
8-
4-
0
a a
D D D D D D °
1 1 1 1 1 1 1 1 1 r
2139 2151
BATCH ID
2100
1 <
2114
1
2130
2165
Figure 18. Conductivity natural field audit sample results versus batch ID. FN-6 results for the National Stream
Survey-Phase I. (Values corrected to 25 *C.)
43
-------
Section 6
Conclusions and Recommendations
The NSWS processing laboratory located
in Las Vegas, Nevada, successfully prepared
and analyzed 3,377 lake, stream, snowpack,
and special interest samples for the following
1986 surveys: Spring Variability Pilot Study
(SVS-P), Snowpack Study, National Stream
Survey-Phase I (NSS-I), and Eastern Lake
Survey-Phase II (ELS-II) spring, summer, and
fall seasonal studies. Samples were prepared
for shipment to the contracted analytical
laboratories within the specified sample hold-
ing time in all cases. No personal safety
incidents occurred during the laboratory opera-
tions.
It was difficult to maintain high quality in
the training programs while processing sam-
ples at the same time. We recommend that a
specific block of time be identified for training
only. Certification in first aid and CPR as a
prerequisite for employment would facilitate
the training program.
The mean of 485 pH QCCS measure-
ments during the spring was 4.06 ± 0.05 (mean
± two standard deviations), which differs from
the established value of 4.00 ± 0.1 pH units for
a 1 x 10'4 N H2SO4 solution (Metcalf, 1987). We
recommend that the acceptable value of the
QCCS be changed to reflect the apparent pH
of the standard using the system described.
The simultaneous use of two pH meters for
sample batches with more than 20 samples
was required in order to analyze the samples
within the allowable holding time. A new pH
protocol that utilized an additional standard
was developed to check the comparability of
the results obtained from different pH meters.
The use of this protocol should be continued.
For NSS-I samples, the determination of
conductivity was added as a processing
laboratory measurement. Modification of the
method included the addition of a temperature
correction factor and a low concentration
QCCS. These additions to the protocol proved
successful and we suggest that they be incor-
porated in future studies.
Aluminum concentrations were deter-
mined by extraction into MIBK followed by
atomic absorption spectrophotometry and by
FIA. With the development of a reliable FIA-
aluminum method, we recommend that the
hazardous-waste-producing extraction method
using MIBK be discontinued. A series of QC
checks were developed for the FIA-aluminum
protocol, including the use of a natural sample
used to monitor the status of the instrument.
The development of additional QC checks
provided valuable information during sample
analysis and these guidelines should be con-
tinued for future surveys.
The large sample loads in the spring (30
to 90 per day) required up to seven aliquot
preparation analysts. To increase efficiency, a
two-stage filtration apparatus which employs
a coarse prefilter is recommended, especially
for stream samples. Many NSS-I samples had
high turbidity or color values. This required the
development of high concentration measure-
ment procedures for turbidity and true color.
A day scheduled each week for instru-
ment maintenance only is recommended. In
the spring, instrument maintenance was per-
formed concurrently with sample processing
as time permitted. This was necessary due to
various changes in field sampling schedules.
For the summer and fall seasonal studies, a
day for instrument maintenance was available.
This significantly reduced the number of analy-
tical instrument malfunctions. This practice
should be adopted for any future efforts of
this type.
44
-------
The efficiency and quality of sample
processing was increased by conscientious
laboratory maintenance procedures and careful
checks on data reporting. The coordinator
reviewed the data forms each day. Preliminary
review of the processing laboratory QC solu-
tion and audit data results during the labora-
tory operations indicate that the data are of
acceptable quality. The development of daily
data review procedures for each method
reduced the chances of omissions and record-
ing errors.
45
-------
Section 7
References
American Society for Testing and Materials. 1984. Annual Book of ASTM Standards, Vol. 11.01,
Standard Specification for Reagent Water, D 1193-77 (reapproved 1983). ASTM, Philadelphia,
Pennsylvania.
Baker, J. P., and C. L Schof ield. 1982. Aluminum Toxicity to Fish in Acidic Waters. Wat. Air Soil
Pollut. 18:289-309.
Barnes, R. B. 1975. The Determination of Specific Forms of Aluminum in Natural Water. Chem.
Geol. 15:177-191.
Burke, E. M., and D. C. Hillman. 1987. Syringe Sample Holding Time Study. In Knapp, C. M., C. L.
Mayer, D. V. Peck, J. R. Baker, and G. J. Filbin. 1987. National Surface Water Survey, National
Stream Survey (Phase I-Pilot Survey) Field Operations Report. EPA-600/8-87-019. U.S.
Environmental Protection Agency, Las Vegas, Nevada.
Driscoll, C. T. 1984. A Procedure for the Fractionation of Aqueous Aluminum in Dilute Acidic
Waters. Int. J. Environ. Anal. Chem. 16:267-284.
Drous6, S. K., D. C. Hillman, L. W. Creelman, and S. J. Simon. 1986. (Phase I- Synoptic Chemistry),
Quality Assurance Plan National Surface Water Survey-Eastern Lake Survey.
EPA-600/4-86-008. U.S. Environmental Protection Agency, Las Vegas, Nevada.
Engels, J. L., T. E. Mitchell-Hall, S. K. Drous6, M. D. Best, and D. C. McDonald. In preparation.
National Surface Water Survey, Eastern Lake Survey (Phase II-Temporal Variability) Quality
Assurance Plan. U.S. Environmental Protection Agency, Las Vegas, Nevada.
Hagley, C. A., C. L. Mayer, and R. Hoenicke. In preparation. National Stream Survey-Phase I, Field
Operations Report. U.S. Environmental Protection Agency, Las Vegas, Nevada.
Henshaw, J. M., T. E. Lewis, E. M. Heithmar, and S. J. Simon. In press. The Pyrocatechol Violet
Colorimetric Determination of Monomeric Aluminum Species Using Flow Injection Analysis.
Int. J. Environ. Anal. Chem.
Hillman, D. C., J. F. Potter, S. J. Simon. 1986. National Surface Water Survey, Eastern Lake Survey
(Phase I-Synoptic Chemistry) Analytical Methods Manual. EPA-600/4-86-009, U.S.
Environmental Protection Agency, Las Vegas, Nevada.
Kerfoot, H. B., T. E. Lewis, D. C. Hillman, and M. L. Faber. In preparation. National Surface Water
Survey, Eastern Lake Survey (Phase II-Temporal Variability) Analytical Methods Manual. U.S.
Environmental Protection Agency, Las Vegas, Nevada.
Merritt, G. D., and V. A. Sheppe. In preparation. Eastern Lake Survey-Phase II Field Operations
Report. U.S. Environmental Protection Agency, Las Vegas, Nevada.
46
-------
Metcalf, R. C. 1987. The Accuracy of Ross pH Combination Electrodes in Dilute Surfuric Acid
Standards. The Analyst. 112:1573-1577.
Morris, F. A, D. V. Peck, M. B. Bonoff, and K. J. Cabbie. 1986. National Surface Water Survey,
Eastern Lake Survey (Phase I-Synoptic Chemistry) Field Operations Report. EPA 600/4-86-010.
U.S. Environmental Protection Agency, Las Vegas, Nevada.
47
-------
Appendix A
Instrumentation, Equipment, and Supply Lists
Table A-1. Instrumentation
Parameter
PH
Dissolved inorganic carbon
Flow injection analysis-aluminum
Turbidity
True color
Conductivity
Instrument
pH/millivolt meter
Combination electrode
Carbon analyzer
Infrared gas analyzer
Flow injection analyzer
Nephelometer
Color test kit
Conductivity meter
Conductivity cell
Manufacturer
Orion
Orion Ross
Dohrman/Xertex
Horiba
LaChat Quick Chem
Monitek
Hach
Yellow Springs Instruments
Model
611
S104BN. 8104
DC-80
PIR-2000
System IV
Colorimeter
21
CO-1
32
3401, 3417
Table A-2. Equipment and Supplies
Chemicals-Drv
Aquasorb
Baking soda
Hexamethylene tetramine
Hydroxylamine hydrochloride
8-hydroxyquinoline-99% purity
Ion-exchange resin (Amberlite IR-120 14-50 mesh)
Mallcosorb
1,10-phenantholine monohydrochloride
Potassium chloride (ultrapure)
Pyrocatechol violet
Sodium acetate (anhydrous, ultrapure)
Sodium carbonate (American Chemical Society [ACS] Primary Standard Grade)
Sodium chloride (ACS reagent grade)
Sodium hydroxide pellets
Tin metal
Chemicals-Liquid
Acetic acid, glacial (Baker Instra-analyzed, Ultrex)
Aluminum Stock Solution-1000 mg/L
Ammonium hydroxide-5M (Baker Instra-analyzed, Ultrex)
Bleach
Formalin
Hydrochloric acid-12 M (Baker Instra-analyzed)
Isopropyl alcohol
(continued)
48
-------
Table A-2. Continued
Chemicals-Liquid (continued)
Methyl isobutyl ketone (high performance liquid chromatography)
NBS traceable buffers: pH 4, pH 7
Nitric acid-12 M (Baker Instra-analyzed, Ultrex)
Phenol red-0.04% w/v
Phosphoric acid-85%
Potassium chloride-3 M
Sulfuric acid-18 M (Ultrex)
Sulfuric acid-0.1 N
Turbidity standards: 5, 10. 20, 50, 100, 200 NTU
Equipment and Supplies
Accessory part kits for carbon and flow injection analyzers
Analytical balance (Ohaus)
Centrifuge (Dynac)
Chemical refrigerant packs
Color viewing tubes (Hach)
Copier
Electric and water inputs
Emergency shower
Emergency spill kits (J. T. Baker)
Eye-wash station (Lab-Line)
Filtration units (Fisher Filtrator)
Fire extinguishers
Freezer
Hazardous waste containers: 1, 5-gallon
Heating/cooling system
Laminar flow hood-Class 100 air (Forma Scientific)
MIBK gas tank for calibration of the organic vapor meter
NBS thermometers
Nitrogen gas tanks (analytical grade)
Optical cuvettes
Organic vapor meter
Pipettes: 40-200, 200-1000 pL; 1-5 mL (Finnpipette)
Refrigerator
pH chambers-8-mL polyethylene
Portable pumps (Millipore)
Reagent bottles with 3-valve caps
Repipettes: 2, 5, 10-mL (Labindustries)
Respirators and cartridges (Survivair)
Reverse osmosis water purification system (Millipore)
Smoke detectors
Solvent storage cabinets
Vacuum pump
Water output
Weight set
Wet-dry vacuum
Water System Cartridges (Millipore)
Carbon
Ion-exchange
Millistak filter
Organic
Prefilter
Reverse osmosis membrane
Consumable Products
Aliquot labels
Ampules-10-mL
Beakers: 50-, 250-mL
BenchKote
Bottles-Nalgene amber wide-mouth: 125-, 250-mL (acid leached); 250-, 500-mL (deionized water leached)
(I-Chem)
(continued)
49
-------
Table A-2. Continued
Consumable Products (continued!
Capillary tubes
Centrifuge tubes: 15-, 50-mL (I-Chem)
Cubitainers: 1-, 5-gallon (I-Chem)
Data forms
Diskettes
Filters: glass fiber filters. 1.2-pm pore size (Whatman GFC); 25-mm diameter, 0.4-pm pore size (Nucleopore)-
47-mm, 0.45-A/m pore size (Gelman); syringe filters, 0.45-pm pore size (Acrodisc)
Filter holders-25-mm (Nucleopore)
Forceps-Teflon or plastic
Gloves-powder-free
Kimwipes
Laboratory coats and safety glasses
Laboratory glass and plasticware
Nitrogen gas (zero-grade)
Office supplies
Parafilm
pH paper-ranges: 1.8-3.8, 8.1-9.4 pH units
Pipette tips: 40-200, 200-1000-pL; 1-5-mL
Plastic bags: sandwich, trash, Ziploc
Shipping coolers: plastic, Styrofoam
Spatulas
Syringes-60-mL
Syringe valves (Luer-Lok)
Tape: duct, electrical, cellophane, strapping
Tubing: peristaltic pump, Teflon, Tygon
Wash bottles
Weighboats
50
-------
Appendix B
Warehouse and Trailer Floor Plans
REAR
r
-REFRIGERATOR
1
\
\
\
>-
/
/
1
'
^
oJ'
MIBK
r--«
\ '
00
ACIDS
Q
O
O
I
\
\
U
X
[siNKJ
L=J
\
\
s,
ACID/BASE SPILL KIT-v ''
j_A j '
«J
FIRST *
AID KIT^^r
'vENTRY
BASES
FRONT STORAGE AREA
^
/
t~*.
^MIBK EMERGENCY SHOWER^ \ l»""<;
\
X
FRONT
ACIDS - STORED BELOW HOOD AREA IN LAB
BASES - STORED IN COOLER IN FRONT STORAGE AREA OF LAB
1-GALLON BOTTLE STORED IN HOOD IN LAB
1-GALLON BOTTLE STORED IN CHEMICAL LOCKER IN REAR STORAGE AREA
X - FIRE EXTINGUISHER
O - N2 & CO2 COMPRESSED AIR TANKS
MIBK
- TEMPORARY STORAGE OF SOLID WASTE
I !- TEMPORARY STORAGE OF LIQUID WASTE
Figure B-1. Trailer floor plan.
51
-------
r\
FL
EZ:
FS
MIBK "^S
WASTE
AND
GAS
CYLINDER!
STORAGE
FS
₯
FL
FL
m
FS
J
4677
r
M - TRAILER MAIN CIRCUIT BREAKER
FL - LARGE FIRE EXTINGUISHER
FS - SMALL FIRE EXTINGUISHER
FS
FL
FL
I
FS
4675^
1
ACID AND BASE
STORAGE CABINETS"
-fi
FRONT OFFICE
Figure B-2. Warehouse floor plan.
52
-------
Appendix C
Personnel List
Table C-1. List of Personnel and Positions Held for the National Surface Water Survey Processing Laboratory
Operations
Season
Position Held
Name
Spring 1986
Communications
Warehouse manager
Warehouse assistant
Laboratory coordinator
Supervisor/analyst
Analyst
Jerry Dugas
John Nicholson
Valerie Sheppe
Jeffrey Love
Mark Sweeney
Deb Chaloud
Betsy Dickes
Molly Morison
Barney Akuna
John Alston
Lori Arent
Mary Balogh
Christina Borror
Hal Coleman
Robert Heine
Herb Herpolsheimer
Robert Hughes
Valerie Miller
James Nitterauer
Roxanne Parks
James Pendleton
Carla Schuman
Sally Snell
Carl Soong
Brenda Whitfield
Jeffrey Wolfe
Summer 1986
Communications
Warehouse manager
Laboratory coordinator
Supervisor/analyst
Analyst
Jerry Dugas
Dave Peck
Jeffrey Love
Deb Chaloud
Lori Arent
Betsy Dickes
Christina Borror
Elizabeth Hill
James Nitterauer
Carl Soong
Brenda Whitfield
(continued)
53
-------
Table C-1. Continued
Season Position Held Name
Fall 1986 Communications jerry Dugas
Warehouse manager Daron Perez
Laboratory coordinator/supervisor Lori Arent
Analyst Linda Drewes
Elizabeth Hill
Molly Morison
Dave Peck
Carl Soong
Brenda Whitfield
54
-------
Appendix D
Processing Laboratory Data Forms, Aliquot Labels,
and Sample Codes
BATCH/QC FIELD DATA FORM
D FORM 2 LAKES
OR
D FORM 5 STREAMS
Figure D-1. Forms 2 and 5 laboratory batch/QC field data form.
55
-------
NATIONAL SURFACE WATER SURVEY
SAMPLE MANAGEMENT OFFICE
P.O. BOX 818
ALEXANDRIA, VA 22314
NSWS RECEIVED BY .
FORM 3 IF INCOMPLETE IMMEDIATELY NOTIFY:
«..XT SAMPLE MANAGEMENT OFFICE
SHIPPING (703)557-2490
PAGE_
_OF_
FROM
(STATION ID)'
SAM PL
ID
01
02
03
0-1
05
06
07
08
09
10
1 1
12
13
14
1 5
16
1'
18
1 9
20
21
22
23
24
26
27
28
29
30
3 1
32
33
34
35
36
3"
38
39
40
TO
(LAB):
BATCH
ID
DATE PROCESSED
ALIQUOTS SHIPPED
(FOR STATION USE ONLY)
1
2
3
4
5
6
7
8
DATE SHIPPED DATE RECEIVED
AIR-BILL NO
SPLTS
SAMPLE CONDITION UPON LAB RECEIPT
(FOR LAB USE ONLY)
QUALIFIERS
^/ ALIQUOT SHIPPED
M ALIQUOT MISSING DUE TO DESTROYED SAMPLE
WHITE - FIELD COPV PINK - LAB COPY YELLOW - SMO COPY
GILL'S 1702) 362-2100
GOLD - LAB COPY FOR RETURN TO SMO
Figure D-2. Form 3 Sample shipping/receiving form.
56
-------
ALIQUOT 1
Filtered - 250 ml
Batch ID -
Sample ID
Date
Sampled -
Preservative:
HN03, 4 *C
Amount: mL
Parameters:
Ca, Mg, K, Na, Mn, Fe
ALIQUOT 2
Filtered -10 mL
Batch ID
Sample ID
Date
Sampled
Preservative:
MIBK - HQ, 4 *C
Amount: ml
Parameters:
Extractable Al
ALIQUOT 3
Filtered - 250 mL
Batch ID -
Sample ID
Date
Sampled -
Preservative:
4*C
Parameters;
Cl, F-.SO/, N03-, Si02
ALIQUOT 4
Filtered -125 mL
Batch ID -
Sample ID
Date
Sampled -
Preservative:
, 4 *C
Amount-
Parameters:
DOC, NH4+
mL
ALIQUOT 5
Unfiltered - 500 mL
Batch ID
Sample ID
Date
Sampled
Preservative:
4'C
Parameters: pH, Acidity,
Alkalinity, DIG,
Conductivity
ALIQUOT 6
Unfiltered -125 mL
Batch ID
Sample ID
Date
Sampled
Preservative:
Amount-
Parameters:
, 4 *C
mL
Total P
ALIQUOT 6
Filtered -125 mL
Batch ID -
Sample ID
Date
Sampled -
Preservative:
4 "C
Amount-
Parameters:
Total Soluble P
mL
ALIQUOT 7
Unfiltered -125 mL
Batch ID
Sample ID
Date
Sampled ___.
Preservative:
HNO3. 4 *C
Amount mL
Parameters:
Total Al
INDIANA
UNIVERSITY
LAKE SPLIT
Batch ID -
Sample ID
Date
Sampled -
Preservative:
Amount-
HNO3, 4 *C
-mL
Parameters:
Metals
Figure D-3. Standard sample aliquot label*.
57
-------
SNOW SPLIT
Filtered - 50 mL
Batch ID: ""
Sample ID:
Date Processed:
Preservative:
HNOa
Amount:
Parameters:
Metals
-ml
Lake ID-
Crew
Date Sampled -
Time Sampled-
Depth
Tow No,-
Batch ID
Sample ID
-meters
-of-
Preservative: Formalin
Parameters: Zooplankton
EMSL SPLIT
Unfiltered -125 mL
Batch ID
Sample ID
Date
Processed
Preservative:
4 *C
Amount-
Parameters;
Total N and P
mL
Lake ID
Crew-
-Sample Type
EMSL ANOXIC SPLIT
Aliquot 1A - Filtered -125 mL
Date Sampled-
Time
Sampled
Time
-Filtered-
Batch ID -
Sample ID
Preservative: HN03r 4 *C
Amount:-
Parameters: Fe, Mn
-mL
Lake ID-
Crew
Sample Type
Date Sampled
Volume Filtered
Batch ID
Sample ID
Time
-mL
Preservative: -20 *C
Parameter: Chlorophyll
Figure D-4. Special project aliquot labels.
58
-------
Table D-1. Sample Codes for Eastern Lake Survey-Phase II Summer Seasonal Study
Code Sample Type
R Routine lake sample
D Duplicate lake sample
B Field blank sample
jB Trailer blank sample
70 Trailer duplicate sample
g Triplicate sample
Radian Audit Sample
FN #-# Field natural audit
LN #-# Laboratory natural audit
FL #-# Field low synthetic audit
L|_ #-# Laboratory low synthetic audit
Radian ID number
Concentration lot number
EMSL-L V Audit Samples Eastern Lake Survey-Phase II (fall)
#LS# Concentration (1-6)
I Laboratory tracking number (1-34)
NBS-Traceable Rainwater Audit Samples
Eastern Lake Survey-Phase II (fall)
RWXX Laboratory tracking letter (A-F)
' Concentration (L or H)
Table D-2. Sample Codes for Eastern Lake Survey-Phase II Summer Seasonal Study
Split Codes Sample Type
A Preserved hypolimnetic (anoxic) sample
G Chlorophyll sample
p Total nitrogen and phosphorus split
S Triplicate sample
W White split
#2. Zooplankton tows
59
-------
-------
SUBREGIONS OF THE NATIONAL STREAM SURVEY-PHASE I
c
Northern
Appalachians (2Cn)
Valley and Ridge (2Bn)
Poconos/Catskills (ID)
Southern Blue Ridge (2As)
(Pilot Study)
Mid-Atlantic
Coastal Plain (3B)
Ozarks/Ouachitas (2D)
Southern Appalachians (2X)
------- |