Annual Report
on the
EPA Program for Long-Term Monitoring of
Surface Waters 1n the United States
NAPAP Project No. El-15
by
Charles F. Powers
and
Marvin 0. Allum
r.orvallis Environmental Research Laboratory
U.S. Environmental Protection Agency
200 S.W. 35th Street
Corvallis, Oregon 97333
March 1985

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TABLE OF CONTENTS
page
Overview and Objectives 		1
Quality Assurance 		13
The Lake and Stream Monitoring Program	17
Northern Rocky Mountains 		17
Upper Midwest	18
New England	29
Maine	29
Vermont	33
New York			34
Catskill Mountains	34
Adirondack Mountains	43
Appalachian-Piedmont Region ..... 		47
Laurel Ridge Area, Pennsylvania 		47
Sandhills Area, North Carolina 	 		50
Southern Blue Ridge Province 		50
Appendix I: Sampling and Analysis Protocol for Long-Term Chemical
Monitoring of Lakes and Streams Relative to Effects of Acidic
Deposition
Appendix II: Quality Assurance/Quality Control Procedures and Data as
Reported by Cooperating Agencies and Institutions
Appendix III: Data Quality Objectives: Long-Term Surface Water Monitoring
Appendix IV: Working Protocol for Sampling, Sample Analysis, and QA/QC for
the IJSEPA Long-Term Surface Water Monitoring Program
11

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LIST OF TABLES
£±9i
1.	FY84 EPA-Funded Long-Term Surface Water Monitoring Projects 	 2
2.	Mean 1982 Precipitation pH and Sulfate Deposition Measured Near the
Long-Term Surfacp Water Monitoring Sites 	 7
3.	Methods of Analysis	8
4.	Lakes Monitored in the Northern Rocky Mountains (Montana-Wyoming). . . 19
5.	Chemical Characteristics of Montana-Wyoming Lakes 	 20
6.	Lakes Monitored in the Upper Midwest (Minnesota, Wisconsin, Michigan)
Through Summer 1983 	 21
7.	Mean Chemical Characteristics of Upper Midwest Lakes (Minnesota,
1978-1983	)	 22
8.	Mean Chemical Characteristics of Upper Midwest Lakes (Wisconsin,
1979-1983	)	 23
9.	Mean Chemical Characteristics of Upper Midwest Lakes (Michigan,
1982-1983)	 24
10.	Mean Chemical Characteristics of tipper Midwest Streams	25
11.	Lakes Monitored 1n the Upper Midwest (Minnesota, Wisconsin, Michigan)
Beginning Fall 1983 	 26
12.	Chemical Characteristics of Upper Midwest Region Lakes, November 1983 27
13.	Lakes Monitored 1n Maine	30
14.	Chemical Characteristics of Maine Lakes 	 31
15.	Lakes Monitored 1n Vermont 	 35
16.	Chemical Characteristics of Vermont Lakes 	 .36
111

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17.	Streams Monitored 1n the Catsklll Mountains Area of New York	44
18.	Chemical Characteristics of Catski11 Mountains Streams 	 45
19.	Streams Monitored in the Laurel Ridge Area of Pennsylvania 	 48
20.	Chemical Characteristics of Laurel Ridge, Pennsylvania, Streams ... 49
21.	Streams Monitored in the Sandhills Area of North Carolina 	 51
22.	Chemical Characteristics of North Carolina Sandhills Streams 	 52
23.	Reservoirs Monitored 1n the Southern Appalachians (North Carolina,
Tennessee, Georgia) ..... 	 54
24.	Chemical Characteristics of Appalachian Reservoirs Selected for
Monitoring	55
25.	Chemical Characteristics of Southern Appalachian Reservoirs 	 56
iv

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LIST OF FIGURES
1. locations of Long-Term Lake and Stream Monitoring Sites • 		6
v

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Overview and Objectives
An EPA program for long-term monitoring of lakes and streams was Initiated
1n 1982 wlt.hln the NAPAP organizational framework. The Aquatic Effects Task
6roup (Task Group E) recognized that a national monitoring program would
Involve all the agencies comprising the Task Group. An ad hoc committee was
organized 1n July 1982 to develop a national program and a standardized
sampling/analysis protocol for chemical monitoring. The committee, with
representation from EPA, USGS, TVA, USDA-FS, USFWS, USNPS, and Brookhaven
National Laboratory, produced a draft protocol in January 1983 as the basis for
a national surface water chemistry monitoring effort. This document received
extensive peer review. The revised draft 1s included as Appendix I. At
present EPA supports lake or stream monitoring at 126 sites comprising eleven
sets of lakes or streams 1n twelve states. These are summarized in Table 1.
The existing long-term monitoring studies are expected to be subsumed by
Phase III of the NSWS, in which geographically representative lakes will be
selected for long-term study. Those lakes will be chosen on the basis of data
acquired during Phase I (survey) and Phase II (chemical and biological vari-
ability) and will be representative of the various geographical regions defined
1n Phase 1. The transition to Phase II will probably begin in FY86 after
results of Phase I are available. Most of the existing monitoring sites are
probably compatible with Phase III owing to their location 1n low alkalinity
regions and their positioning with respect to minimization of extraneous
effects which could compromise interpretations of observed changes or trends.
Such effects Include land use and recent land-use changes (timber harvest,
agriculture, residential, or recreational development, road building, mining),
local atmospheric or water pollution sources, and forest fires.
The objectives of the EPA long-term monitoring program are to:
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Table 1
FY84 EPA-Funded Long-Term Surface Hater Monitoring Projects
Location
Principal
Investigator
Agency
Sites
Type
Start
m
20
Montana-Wyoming
Gordon Pagenkopf
Montana State U.
11
lakes
Fall 1983
Upper Great Lakes
Region(MN, Ml, MI)
Patrick Brezonlk
U. of Minnesota
38
lakes
Fall 1982
56
Maine
Terry Haines
USFWS, U. of ME
6
lakes
Fall 1982
25*
Vermont
Wallace McLean
State of Vermont
36
lakes
Winter 1981
15**
New York
Peter Murdoch
USGS, Albany, NY
7
streams
Summer 1983
25
Pennsylvania
James Barker
USGS, Harrlsburg, PA
6
streams
Summer 1983
25
North Carolina
Kent Crawford
USGS, Raleigh, NC
5
streams
Summer 1983
25
Southern Blue Ridge
Province (NC, TN, GA)
Harvey 01em
TVA, Chatanooga, TN
5
12
streams
reservoirs
Fall 1983
Fall 1982
100**<
2U
Totals: 11 (3 in Upper Great Lakes, 2 In Southern Blue Ridge)
127 sites
FY84 Funding
$21 IK
* Includes work on development of methodology for monitoring fish populations.
** Partial support for FY83 and FY84. Additional support being requested for FY85.
*** Combined research/monitoring project; FY83 funding.

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(1)	detect and measure long-term trends in the chemistry of low-alkalinity
surface waters that are related to atmospheric deposition; and
(2)	compare the response of low alkalinity waters (a) over a geographic
gradient of H+ and sulfate deposition (b) 1n different major sensitive
geographic areas that receive comparable deposition.
Sites would be 1n locations where annual sulfate deposition averaged 0-10,
10-20, 20-30, and 30-40 kg/ha, with average volume-weighted precipitation pH
ranging from about 5.3 to 4.2. Sites would at the same time be chosen to
provide observations in geographically separate regions (e.g., New England and
the southern Appalachians) receiving comparable sulfate and hydrogen ion
deposition. Questions to be answered relative to Objective 2 are:
(1)	At what level(s) of sulfate and hydrogen-1on deposition do measurable
changes in lake or stream chemistry occur?
(2)	Do lakes or streams of comparable alkalinity located in different geo-
graphical regions respond the same to similar levels of sulfate and
hydrogen ion deposition?
In planning a program with these objectives, 1t was necessary to take into
consideration the distribution and reglonality of acidic deposition, which
occurs 1n all states east of the Mississippi River and to some degree in
certain areas of the West. Some areas receiving acidic deposition contain
lakes and/or streams of low alkalinity (hence, presumably sensitive to acidifi-
cation); 1n others, surface water alkallnltles are uniformly high, and acidifi-
cation from atmospheric deposition is not expected. Sensitive waters also
occur 1n areas where deposition 1s not now acidic, or where addle deposition
1s minimal. However, 1t cannot be assumed that such precipitation chemistries
will remain unchanged 1n the future.
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Although precipitation chemistry may be essentially uniform within a given
geographical area, not. all lakes or streams can be expected to respond identi-
cally. There are probably even greater uncertainties with respect to compar-
ability of response of surface waters between geographical areas. For example,
although average precipitation acidity and sulfate deposition 1n the southern
Appalachians and in New England fall within the same range, significant differ-
ences exist between those regions. New England was glaciated, but the southern
Appalachians were not; New England contains many hundreds of small natural
lakes, but southern Appalachian surface waters are characterized by streams and
artificial reservoirs; soils 1n New England are quite young, while those in the
South are much older. Low alkalinity waters occur 1n both regions, but there
1s evidence that the rate of response to acidifying forces may not be the same.
Present Indications are that results regarding the Influence of acid deposition
on low alkalinity waters cannot be extrapolated from one such region to another.
Monitoring sites were selected so as to best satisfy the objectives of the
program, that is, to detect trends relatable to effects of deposition, and to
compare responses of surface waters over deposition chemistry gradients and
between sensitive areas receiving comparable deposition. The first of these
two objectives requires sites 1n sensitive areas receiving acidic deposition,
as removed from disruptive anthropogenic Influences (land use, local pollution,
fire) as possible. The second objective requires, 1n addition, the selection
of sites from a variety of locations exposed to various degrees of precipita-
tion acidity. Accordingly, monitoring sites are situated where surface waters
are commonly less than 200 yeq/1 total alkalinity (ANC). The national and
regional alkalinity maps generated by EPA have assisted 1n the identification
of these locations. Areas selected for monitoring to date Include the Northern
Rocky Mountains; the Upper Midwest lake district (Minnesota, Wisconsin,
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Michigan); Maine; Vermont; the Catskill Mountains 1n southeastern New York; the
Allegheny Mountains of southwestern Pennsylvania; the southern Appalachians
(Southern Blue Ridge Province of North Carolina, Tennessee, and Georgia); and
the Sandhills of south-central North Carolina (Figure 1). These locations not
only provide a broad sampling of sensitive (low alkalinity) waters, hut lie
across a gradient of precipitation chemistry from essentially background
chemical concentrations 1n the northern Rockies to the acidic precipitation of
the East (see Table 2). Individual sites were selected to minimize disruptive
effects of past or future land use, local atmospheric pollution, forest fires,
logging, and fish management (see Appendix I). When possible, sites where
concurrent research will provide related data are chosen, and sites with good
historical data are preferred over those without, other factors being equal.
Accessibility is also carefully considered.
The rationale for the selection of the particular monitoring sites pres-
ently comprising the program was as follows. First, 1t was evident from the
geographic distribution of lakes, reservoirs, and streams 1n the United States
that natural lakes are the dominant resource of concern 1n the northern tier of
states (south to the limit of Pleistocene glaclatlon) and 1n the mountainous
West, hut are replaced by streams and reservoirs 1n the South. In comparing
this distribution with known distributions of low alkalinity waters and deposi-
tion chemistry, 1t became further evident that monitoring sites should be
Identified 1n the mountainous West, the upper Great Lakes region, the
Adirondacks, New England, and the Appalachians. Emphasis would be on lakes in
•11 areas except the Appalachians where the focus would be on streams and
reservolrs.
Proceeding on these premises, opportunities for Initiation of monitoring
were sought which (1) would provide lake, streamt or reservoir monitoring sites
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tel,1.ke.n"*t«W"nU0Hn,S,US'
U«t^5 of

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TABLE 2
MEAN 1982 PRECIPITATION PH AND SULFATE DEPOSITION MEASURED
HEAR THE LONG-TERM SURFACE WATER MONITORING SITES

Precipitation


Precipitation
Vol.-Wt.
S04 dep.,
Monitoring Project
Site
Lat. °H
Long. °W
Hon. Network
PH
kg/ha
Horthern Rocky Mts.
Headwaters, ID
46°38'
115°49'
HADP
5.40
1.2
(MT, WY)
Yellowstone
44°55'
110"25'
NADP
5.22
3.5

Hat. Park, WY





Upper Midwest
Fernberg, MH
47°57*
91°29*
NAOP
4.96
10.3
(MN, WI, MI)
Trout lake, WI
46°03'
89° 39'
NADP
4.68
19.4

Spooner, WI
45°49'
91°52'
NADP
4.92
12.0

Douglas Lake, HI
45°34'
86°41'
HADP
4.42
20.3
Maine
Acadia Park
44°22'
68°16l
HADP
4.46
25.0
Vermont
Bennington
42°52'
73°10'
HADP
4.36
20.1

West Dover1


State of
4.36
—

Concord1


Vermont
4.39
—

Mt. Mansfield1


II
4.42
—

Swanton1


II
4.52

Catskill Mts. (NY)2
Stillwell Lake
41°21'
74°02'
HADP
4.31
26.4
Knobit
42°23'
73°30'
HADP
4.40
16.2
Laurel Ridge (PA)3
Parsons, WV
39°05'
79°40'
NADP
4.31
40.1
Leading Ridge, PA
40°40'
77°56'
HADP
4.16
36.6
Southern Appalachians4
Elkmont, TH
35°40'
83°35'
HADP
4.66
21.7
(TH, GA, NC)
Walker Branch, TH
35°58*
84° 17'
HADP
4.33
36.9
Coweeta, NC
35°04'
83°26'
HADP
4.66
23.6
Sandhills (NC)3
Piedmont Station
35°42'
80°37
HADP
4.35
29.1
Clinton Station
35°01'
78°17*
HADP
4.53
21.2
1	Bulk event samples.
2	Weekly and event sites also operated by project.
3	Weekly site also operated by project.
4	Four weekly sites also operated by project.

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1n locations corresponding to the criteria for geographical location, low
alkalinity, and deposition chemistry and (?.) were sites where ongoing work
could be modified or adapted to EPA's monitoring needs (thereby precluding the
necessity of "starting from scratch"). Refer to Table 1 for a summary of
present monitoring projects.
In the Upper Great Lakes region, the EPA-Duluth laboratory, together with
universities and state agencies, had begun a broad scale survey of lakes in
1978. Three suhsets of these lakes plus six streams in upper Minnesota (in the
vicinity of the Boundary Waters Canoe Area and Voyageurs National Park);
northeast Wisconsin; and the eastern half of the Upper Peninsula of Michigan
were chosen for monitoring, with the work to be carried out by the University
of Minnesota-Duluth cooperatively with EPA-Duluth. Sampling for this program
was conducted in the fall of 1982 and the spring and summer of 1983. Reorien-
tation of the Duluth program necessitated continuation of work beyond the
summer of 1983 by a new contractor. Monitoring of 38 lakes was assumed in fall
1983 by the University of Minnesota at Minneapolis, with contractual assistance
from the Wisconsin Department of Natural Resources. The stream sites were
eliminated. The list of lakes was further modified to eliminate some
redundancy in lake characteristics, to reflect recent information on water
quality changes in some Wisconsin lakes, to eliminate some insensitive lakes
and lakes subject to watershed disturbance, and to provide a broader range of
lake coverage in Minnesota.
In Maine, the U.S. Fish and Wildlife Service at the University of Maine
had just recently completed an excellent survey of lakes of New England, and
had undertaken fisheries-related research on effects of acidic deposition. It
was logical to draw on their extensive expertise for the Northeast and to
expand the existing program to include long-term montoring. Accordingly,
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monitoring of six lakes in the Tunk Lakes area of southeast Maine was begun in
fall 1982. Included 1n this project is exploratory work on non-destructive
fish sampling as well as chemical monitoring.
The State of Vermont had Initiated lake monitoring on twenty lakes in
1981. Coverage was later expanded to 36 lakes with 24 sampled in alternate
years. EPA initiated partial funding of the Vermont effort in 1982.
The need for monitoring low alkalinity reservoirs in the Southeast had
been established. The Tennessee Valley Authority (TVA) possessed a large body
of chemical and other data on reservoirs of the region, and arrangements were
made for a survey by TVA of 54 reservoirs selected on the basis of the existing
data. Based on the results of that survey, 12 reservoirs were chosen for
long-term monitoring.
In the West, ongoing or planned long-term studies by the U.S. National
Park Service and the U.S. Geological Survey provided monitoring coverage in
Sequoia National Park, California, and Rocky Mountain National Park, Colorado.
Proposed studies by the Geological Survey in the northern Cascade Mountains in
Washington have been delayed, but work has been initiated by the National Park
Service in the Olympic Mountains in that state. The most obvious omission in
t.he West appeared to be the northern Rocky Mountains, and a cooperative agree-
ment was implemented with Montana State University for a survey and subsequent
monitoring of lakes in southwest Montana and northwestern Wyoming near
Yellowstone National Park. From results of the survey, eleven lakes were
chosen for monitoring. These are all high-elevation, low-alkalinity lakes.
As stated in the Task Group E protocol (Appendix I)» monitoring is more
complex for streams than for lakes because of the influence of discharge
coupled with season. Base flow tends to display uniform representative compo-
sition, but storm flow and snowmelt runoff may significantly alter stream
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chemistry. Proper stream monitoring, therefore, requires continuous recording
of flow and sampling over a complete range of discharge, including during and
following storm events and snowmelt.
Obviously, the high frequency of sampling required for streams presents a
serious budgetary problem in a monitoring program. A reasonable solution was
achieved through a cooperative approach with the U.S. Geological Survey. The
Survey had initiated or was planning watershed studies on a number of low
alkalinity streams in the East. A single stream in each watershed was gauged
and instrumented for automatic sampling during storm or snowmelt events.
Wet-dry deposition sampling was carried out at each site. EPA arranged to
provide additional funding at three sites (the Catskilis of southeastern New
York, the Alleghenies of southwestern Pennsylvania, and the Sandhills of North
Carolina) for sampling five or six additional streams on an approximately
monthly basis to provide more broadly based monitoring data. Event samples
from the primary stream would provide indications of the effect of storms and
snowmelt on stream chemistry, and monthly sampling would provide information on
seasonal variation and long-term change.
Stream studies were also undertaken with TVA, in which five streams in the
southern Appalachians have been instrumented for automatic storm event sampl-
ing. The project is funded jointly by Task Group E Objectives E-01 and £-02.
Weather-related delays in this project have precluded its inclusion in this
report.
In practically all cases, lakes or streams are clustered to facilitate
sampling and to minimize within-cluster variations in climate and deposition
patterns.
Each group of monitored lakes or streams must be sufficiently represented
by deposition chemistry monitoring sites to permit characterization of chemical
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loading. In most cases, one or more NADP sites are located in the monitoring
area (Table 2). An initial exception was the eastern end of the Upper Penin-
sula of Michigan, where the nearest deposition site was at Douglas Lake, about
65 km south and across Lake Michigan. EPA has now established an NADP site in
Chippewa County at Raco to provide representative deposition data for monitored
lakes 1n that region.
Sampling and analytical methodology have generally followed Task Group
protocols. Methodology is summarized, by project, in Table 3. Methodologies
were not always identical, and such cases are specifically noted. The use of
Technicon automated procedures for anions by the University of Minnesota and
the State of Vermont, and the Eriochrome-cyanine reduction procedure for
aluminum by Montana State University, are the most notable departures.
The authors thank Dan Michaels of Radian Corporation for his thoughtful
review of this report and his many helpful suggestions.
Quality Assurance
As used here, "quality assurance" (OA) refers to the total program for
assuring sample integrity and the reliability and utility of the data collected
during the long-term monitoring project (NAPAP Task El-15), including "quality
control" (QC); i.e., the control of collection, handling, storage, and analyses
of samples and data processing and storage.
The basic quality control document for the monitoring program has been the
Task Group E sampling and analysis protocol (Appendix I). That document
describes field sampling procedures and recommended analytical methodology, but
1n a more general fashion than does the National Surface Water Survey protocol.
Each cooperator was required to submit a quality assurance plan in accordance
with EPA requirements. Further, site visits to evaluate and audit procedures
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TABLE 3. METHODS OF ANALYSIS
Cooperator
Parameter*
Color
ANC
Ca, Mg, Na, K
S0fl, CI. NO,
A1
Maine (FWS)
apparent, Pt-Co
standards
Gran
titration
atomic absorp-
tion (AA)
ion chromato-
graphy (IC)
0.45 11 filtration, atomic
absorption (AA)
Minnesota (U.)
true, centrifuge; Pt-Co
standards
Gran
AA
autoanalyzer
(A)**
0.1 u filter, AA
Montana (St.U.)
true, centrifuge; Pt-Co
standards
Gran
AA
IC
0.45 i» filter, spectro-
photometer (Erlochrome-
cyanine R)
TVA
true, centrifuge; Pt-Co
standards
Gran
AA
IC
0.45 p filter, atomic
emission
USGS
none
Gran
AA
IC
0.1 u filter, AA
(chelation-extractIon)
Vermont (State)
true, 0.45 v filter;
Pt-Co standards
Gran
AA
A**
0.45 11 filter, AA
* Specific conductivity and pH are determined electrometrically by all cooperators.
** SO4-methyl thymol blue; CI-ferricyanide; N03-cadmium reduction (Minnesota cross-checked with 1on
chromatography).

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were made to the three USGS projects and the TVA project in 1984. Visits to
the remaining projects are planned for 1985. Further visits will be made on an
"as needed" basis.
OA has proven to be more of a problem during this first full year of
multi-agency sampling than any other aspect of the long-term monitoring pro-
gram. This can be attributed in part to communication with one cooperator
(Montana State University) and in larger part to a lack of flexibility in one
cooperating agency's OA reporting procedures (USGS-New York, North Carolina,
and Pennsylvania).
The first aspect of the OA problem, communication, became evident when we
reviewed the field data contained in the Montana State University annual
report. Our routine Check of ion balances indicated a probable error in cation
and/or anion analyses. When we called this to the attention of the cooperator,
we found that he was not aware of the potential problem because ion balances
were not being routinely calculated. Subsequently, he found some procedural
errors in the analyses of two cations and one anion, and some of the data were
corrected by re-analysis of existing samples (unfortunately, some earlier
samples had by then been discarded, and those data could not be corrected). We
have since reviewed with the cooperator the routine OA procedures we expect
(duplicate field samples, field banks, replicate analyses, spikes, and the
like, including ion balances). The initiation of an audit sample program (see
page 16) will result in improved communication relative to data quality.
Results of analyses of audit samples will be submitted to ERL-Corvallis three
times yearly, corresponding with the spring, summer, and fall sampling periods.
The larger part of the OA problem appears to be a result of the multi-
level procedures of the Geological Survey. Operationally, all of the parts of
an adequate OA plan are in place, but they are in different places; i.e., each
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Central Laboratory has Internal analytical quality assurance; each District has
OA for field determinations, sample collection and storage, etc.; and the
Quality of Water Branch, which 1s independent of the laboratories and the
Districts, provides audit samples to both labs and Districts and analyzes the
results. This segmentation, together with the routine reporting safeguards of
USGS (data evaluation, verification, multi-level review, and final approval),
while laudable, can result in considerable delay in the delivery of all pertin-
ent OA information even to an investigation within USGS, let alone to an
outside agency such as EPA. Note, for example, that all of the USGS analytical
data shown in this report are "provisional," because they have not yet been
verified, reviewed, and approved for publication by the Geological survey.
A lesser problem relating to USGS data, but one requiring resolution, is
the routine rounding of reported values to conform to USGS policy on analytical
data. Alkalinities less than 1000 mg/1, for example, are reported to the
nearest mg/1 (essentially _+ 20 yeq/1), and aluminum concentrations less than
100 ug/1 are reported to the nearest 10 pg/1. Such rounding may be acceptable
1n reporting data for, say, the Ohio River, but it is not acceptable for the
poorly-buffered, dilute waters being sampled 1n the long-term monitoring
program, for which data need to be reported to the nearest micro-equivalent per
1 iter.
Arrangements have been made with the USGS Central Laboratory at Denver for
analyses of National Surface Water Survey (NSWS) samples with provisions for
all of the quality assurance requirements of the NSWS, Including timely report-
ing of OA results. Beginning 1n October 1984, 1on/metals samples from our
cooperative stream monitoring projects with USGS are being sent to the Denver
lab for analysis along with the NSWS samples. This arrangement 1s particularly
advantageous from the standpoint of linkage with the NSWS and will provide
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continuity of analytical effort since it is probable that a majority of the
Project El-15 waters will be Included in the NSWS Phase III monitoring along
with the other waters selected on the bases of Phase I and II sampling.
A review of the quality assurance effort for the monitoring program was
conducted by Dr. Eugene Meier, director of quality assurance and quality
control for the National Survey. His specific recommendations and the present
status of their implementation follow:
Recommendation: Work with the data users to define the data quality objectives
necessary to observe the trends necessary to establish problems related to
acidic deposition.
Status: A set of data quality objectives has been developed. The document is
included here as Appendix III.
Recommendation: Document specific requirements for duplicates, blanks, and
data reporting requirements for this program. A statistician should
review the objectives and requirements of the program to provide a
reasonable estimate of the number of blanks, duplicates, audit samples,
etc. that should be required to define the numbers of each sample that are
required to adequately define the quality of the data. This document
should be provided to all program participants to assure that they
understand what is required.
Status: A draft sampling, analysis, and QA/QC protocol document has been
developed. This document has drawn extensively upon the "Methods Manual
for the National Surface Water Survey Project — Phase I." It is included
here as Appendix IV, but is still undergoing review.
Recommendation: Document procedures for performing onsite evaluation. These
evaluations should include both field and analytical laboratory sites.
The document should include an outline or form to be followed to assure
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that the basic information is obtained in a consistent manner for all
sites. The document should be provided to all participants to assure that
they are aware of what is expected and to expedite the evaluations.
Status: These procedures are being developed with the assistance of Jeffrey
Sprenger, ERL-Corvallis quality assurance specialist. Mr. Sprenger will
conduct onsite evaluations at Montana State University and the University
of Minnesota this spring.
Recommendation: Document and provide a formal data review process, along with
requirements for standard data reporting formats, to the program partici-
pants. This assures that everyone knows what data are required and how
they are to be reported and evaluated. Criteria specified in the methods
manual for the National Surface Water Survey will be utilized.
Status: We are working with Oak Ridge National Laboratory to implement a data
management procedure similar to, and closely modeled after, that developed
for NSWS. Standard data reorting forms have been developed and are being
provided to program participants.
All products are being reviewed by Dr. Meier.
The first set of audit ("round-robin") samples was sent to all cooperators
in October 1984. Audit samples suitable for the evaluation of analyses of
poorly-buffered waters have only recently become available from the Radian
Corporation, Austin, Texas through arrangements made by the NSWS. They will be
sent to all participants three times each year, coinciding with the spring,
summer, and fall sampling periods. This phase of our OA was delayed because
dilute audit samples that have been available from the RTP and the Denver US6S
laboratories either lack constituents of particular interest (e.g., alkalinity)
or the auditing labs do not perform analyses for those constituents. Simi-
larly, the audit samples available from MERL-Cinc1nnati have solute concentra-
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tions that are usually much greater than those in the dilute project waters,
and evaluations of accuracy of analyses based on such audit samples would not
be very meaningful.
The DA/OC procedures as reported by the various cooperators are presented
as Appendix II of this report. Results of the October audit sample analyses,
which are still being evaluated, are not included; they will be documented in
the next report. Preliminary analysis of the results is quite encouraging.
Except for an obvious problem with the ion chromatograph work at Montana State,
and what appears to be a calibration problem at a number of laboratories with
the atomic absorption procedure for total aluminum, results are for the most
part consistent and near the theoretical concentrations reported by Radian.
The Lake and Stream Monitoring Program
Northern Rocky Mountains
Montana-Wyoming
Principal Investigator: Gordon Pagenkopf, Department of Chemistry,
Montana State University, Bozeman, Montana 57917.
Twenty-six lakes were surveyed in southwestern Montana and northwestern
Wyoming in 1983. Eleven were selected for long-term monitoring beginning in
fall 1983. The criteria for selection were alkalinity and access; all were
pristine and essentially unimpacted. Those lakes are variously located in the
Beartooth Plateau, Crazy Mountains, Gallatin Range, Madison Range, and the
Ritterroot Range. Elevations range from 2682 to 2975 m. All lakes are in
alpine situations, with a number at or above timber line.
Precipitation quantity and chemistry are monitored by NADP stations at
Headwaters, Idaho, and at Yellowstone National Park (Table 2). The Headwaters
site, while relatively near the two westernmost lakes, is about 400 km west and
-17-

-------
north of the remaining nine. A planned NADP site at Bozeman (Montana State
University) would greatly improve coverage. Deposition chemistry from the two
existing sites indicates essentially background conditions: mean 1982 pH 5.40,
sulfate deposition 1.? kg/ha at Headwaters and 5.22 and 3.5 kg/ha, respec-
tively, at Yellowstone. Natural sulfur emissions in Yellowstone National Park
may partially account for the greater sulfate deposition there. The Northern
Rocky Mountain project appears to provide an excellent reference area where
sensitive waters are exposed to essentially background deposition chemistry.
Tables 4 and 5 present locational and water chemistry data for the eleven
Rocky Mountain lakes for 1984. Tin all chemistry data tables, the final
column, headed +/-, is the ratio of the sum of cations (Ca, Mg, Na, K) to the
sum of anions (SO^, NO3, CI)].
Upper Midwest
Mi nnesota-Wi sconsi n-Mi chi gan
Principal Investigator: Patrick Rrezonik, Department of Civil and Mineral
Engineering, University of Minnesota, Minneapolis, Minnesota 55455.
Extensive surveys of lakes and some streams in northern Minnesota,
Wisconsin, and Michigan were made by ERL-Duluth (EPA) and cooperating state
agencies beginning in 1978-79; subsets were monitored seasonally until summer
1983. The locational data and mean chemical characteristics of 37 lakes and
six streams monitored by ERL-Duluth through summer 1983 are given in Tables 6
through in. Data for individual years could not be presented in this report,
but should be available for subsequent analytical treatment. The present
University of Minnesota at Minneapolis-based project, comprising 38 lakes and
no streams, began with the fall 1983 sampling period. As pointed out earlier,
-18-

-------
TABLE 4
LAKES MONITORED IN YhE NORTHERN ROCKY MOUNTAINS (MONTANA, WYOMING)




Surface



Latitude
Longitude
Area
Elevation
State
Lake
(°N)
(°W)
(ha)
(tn)
Montana
Emerald
44°24'48"
110°55'33"
2.0
2682

Heather
45°24'35"
110°56'33"
2.0
2718

Blue
46°02'01"
110°17119"
1.6
(at tree





line)

Granite
46°02'06"
110°15'56"
1.2
(at tree





1 ine)

Triple
44°52'50"
111°25'57"
0.4
2755

Blue Danube
44°52'37"
111°26'17"
2.4
2761

Upper Twin
46o09'26"
114°29'45"
8.1
(tree line)

Carlton
46°41'01"
114°13'12"
— — —
• •
Wyomi ng
Island
44°57'01"
109°32'30"
•v30.0
2901
Little Bear
44°56'30"
109°31'02"
2.0
2911

Long
44°56'45"
109°30'31"
4.0
2975
-19-

-------
TABLE 5
CHEMICAL CHARACTERISTICS OF MONTANA-WYOMING LAKES



Color
Sp. Cond.












Temp.
(true)
(pS/cm
pH

— ueq'/l


A1
	
peq/1 —

Lake
Date
C°C)
(PCU)
3 25°C)
(field)
ANC
Ca
Mg
Na
K
Mfl/1
S04
CI N03
*/-
Emerald
7/84
11.8
6
26
7.23
201
85
40
27
15
4
6
<6 <4
0.81
Heather
7/84
13.0
3
20
6.94.
154
67
30
24
11
1
4
<6 <4
0.85
Blue
7/84
10.0
6
15
6.94
101
80
11
9
<1
13
10
12 <4
0.81
Granite Outlet
7/84
7.0
5
15
6.89
83
82
11
3
<1
2
10
9 <4
0.94
Granite
7/84
12.0
3
14
6.97
93
85
11
17
<1
4
10
<6 <4
1.00
Island
7/84
16.0
4
13
6.98
96
60
21
12
<1
4
<4
7 <4
0.90
Little Bear
7/84
17.0
9
14
7.12
123
62
25
12
<1
5
6
<6 <4
0.77
Long
7/84
17.0
7
16
7.12
113
69
22
12
—
33
6
<6 <4
—
Blue Danube
7/84
11.0
1
10
6.92
64
45
11
5
<1
<1
<4
<6 <4
0.97
Triple
7/84
12.0
4
15
6.93
108
78
16
10
1
11
4
9 <4
0.87
Upper Levin
7/84
18.0
2
7
6.47
48
28
5
7
<1
53
<4
<6 <4
0.83
Carlton
7/84
12.0
5
7
6.59
33
20
7
12
<1
13
10
<6 <4
0.91
Emerald
8/84
8.0
7
25
7.54
234
95
61
37
37
2
4
<6 <4
0.97
Heather
8/84
8.5
4
18
7.44
163
62
39
31
27
0
<4
<6 <4
0.97
Blue
8/84
11.0
5
14
7.09
107
95
11
8
<1
3
10
<6 <4
0.97
Granite Outlet
8/84
10.0
3
14
7.16
106
97
11
8
<1
2
10
<6 <4
0.99
Granite
8/84
11.0
1
14
7.20
108
97
11
6
<1
5
12
<6 <4
0.94
Island
8/84
10.0
4
12
7.33
87
59
25
11
<1
6
6
<6 <4
1.00
Little Bear
8/84
10.0
8
12
7.37
128
70
35
17
<1
8
4
<6 <4
0.92
Long
8/84
11.0
8
12
7.31
117
80
32
17
<1
9
6
<6 <4
1.05
Blue Danube
8/84
15.5
2
12
6.93
73
47
12
34
8
3
<4
20 <4
1.09
Triple
8/84
16.0
8
13
7.04
117
80
16
14
2
26
<4
<6 <4
0.97
Upper Levin
8/84
12.0
3
7
6.70
47
39
2
10
<1
25
<4
<6 <4
1.11
Carlton
8/84
11.0
4
7
6.55
33
22
5
16
<1
12
10
<6 <4
1.00

-------
the lakes are not all identical with those monitored by ERL-Duluth. Locational
and chemical data for these lakes appear in Tables 11 and 12.
Minnesota monitoring lakes are located in the northeastern area of the
state, primarily in or near Voyageur National Park and the Boundary Waters
Canoe Wilderness Area. This region contains numerous lakes, many of which have
soft, low alkalinity water. Soils are thin, and granitic rock outcroppings are
common, suggesting the watersheds have low capacity to neutralize acid deposi-
tion. Wisconsin lakes are located in the north-central area of the state,
primarily in Vilas, Oneida, and Lincoln counties. This region, which is one of
the richest lake districts in the world, has a great diversity of lake types,
but the majority have soft, low alkalinity waters. Soils in the region are a
thick glacial till high in sand and low in organic and clay content. Michigan
lakes are located in the eastern part of the Upper Peninsula, near the south-
eastern corner of Lake Superior. This region has a rather diverse geology, but
the monitored lakes generally are located in areas with resistant bedrock and
sandy soils.
Criteria for selection of the lakes were based on water chemistry, water-
shed characteristics, and geographic considerations. Selected lakes are low in
alkalinity but generally reflect chemical characteristics for the numerous
softwater lakes in the regions. Watersheds of the lakes are forested or mostly
forested and have little or no human habitation. Consequently, watershed
influences on pH/alkalinity trends should be minimal.
Five NADP stations provide deposition data for the Upper Midwest project
(Table ?). The 1982 data show a generally west to east gradient in both pH and
sulfate deposition. Highest average pH and lowest sulfate occurred at Fernberg
(pH 4.96, sulfate 10.3 kg/ha) and Spooner (pH 4.92, sulfate 12.0 kg/ha), the
westernmost sites. Acidity and sulfate were greater at Trout Lake, in east-
-21-

-------
TABLE 6
LAKES MONITORED IN THE UPPER MIDWEST (MINNESOTA,
WISCONSIN, MICHIGAN) THROUGH SUMMER 1983
Surface


Latitude
Longitude
Area
State
Lake
(°N)
(°W)
(ha)
Minnesota
Cruiser
48°29'54"
92°48'19"
48.0

Spring
48°22'22"
92°37'48"
90.1

Weir
48°29'47"
92°44'33"
26.2

Shoepack
48°30'13"
92°53'00"
126.2

Loiten
48°31l33"
92°55'24"
38.8

Locator
48°32,26"
93°00'13"
54.1

Franklin
48°18'00"
92°36'50"
60.9

Long
48°18'00"
92°42'32"
191.5

Columbus
45°50'15"
89°14'30"
269.0

Duck
45°22'50"
89°14'45"
49.0

Summi t
45°22'30"
89012,25"
112.0

Sunset
45°55'35"
89°20'15"
83.0
Wisconsin
Vandercook
45°58'55"
89°41'13"
40.0

Finley
45°54'40"
89°24100"
43.0

Greater Bass
45°21'17"
89°12'00"
99.7

Camp Ten
45°59'50"
89°23'05"
13.0

Elna
45°40'55"
89°34'05"
9.0

Sand
45°43128"
89°39'05"
25.0

Nichols
46°06'14"
89°41'20"
16.2

Luna
45°54'19"
88°57'35"
27.1

Smokey
45°05'47"
89°56'32"
250.0

McGrath
45°47'28"
89°38'37"
21.4

Sugar Camp
45°48'05"
89°18'25"
220.6
Michigan
Monocle
46°28,30"
84°38'45"
70.7
Johnson
46°25'30"
85°02'40"
16.1

Andrus
46°42'00"
85°02'25"
12.6

Kelly
46°26'i24"
85°23'43"
12.2

Murray
46°28'15"
85°42'05"
38.3

Bass
46°27'49"
85°42'58"
58.3

Buckeye
46°27'57"
85044'19"
48.1

Stuart
46°35'24"
85°30'35"
30.1

Chris Brown
46°37'34"
85°30'27"
24.2

Pretty
46°36'03"
85°39'35"
18.9

Camp 8 Mile
46°35'57"
85°40'12"
25.6

Cusino
46°27'16"
86°15'30"
53.2

Nevins
46°31'00"
86°14'35"
113.5

McNearny
46025'38"
84°57'30"
50.4
-22-

-------
TABLE 7
MEAN CHEMICAL CHARACTERISTICS OF UPPER MIDWEST LAKES
(Minnesota, 1978-1983)
Color Sp. Cond.
Lake
(apparent)
(PCU)
(pS/cm
0 25°C)
pH
(field)
ANC
Ca
peq/1 -
Mg
Na
K
A1
Mg/i
S04
peq/i
CI
N03
~/-
Cruiser
6
23
6.83
122
100
56
28
14
43
64
6
2
1.00
Spring
13
38
6.92
242
175
128
43
19
39
74
9
5
1.08
Weir
87
24
6.51
128
99
63
36
16
125
27
8
14
1.24
Shoepack
88
24
6.11
82
110
71
38
3
177
61
7
12
1.52
Loiten
23
30
6.69
129
131
93
34
17
77
98
9
4
1.16
Locator
37
29
6.61
118
128
87
43
15
93
91
11
7
1.24
Franklin
15
52
7.51
441
254
190
46
27
48
46
8
13
1.02
Long
72
22
7.63
859
582
359
55
24
55
84
10
19
1.13

-------
TABLE 8
MEAN CHEMICAL CHARACTERISTICS OF UPPER MIDWEST LAKES
(Wisconsin, 1979-1983)
Lake
Color
(apparent)
(PCU)
Sp. Cond.
(pS/cm
@ 25°C)
pH
(field)
ANC
Ca
|jeq/l -
Mg
Na
K
A1
mq/i
peq/l
S04 CI
no3
+/-
Columbus
422
41
7.05
269
241
147
48
21
52
46
22
8
1.34
Duck
81
23
5.39
7
71
40
27
13
129
100
22
5
1.22
Summit
192
24
4.85
-8
61
35
26
26
285
96
23
4
1.35
Sunset
4
16
6.25
26
64
22
18
7
47
84
10
3
0.98
Vandercook
12
16
6.09
17
67
26
17
9
38
87
7
8
1.06
Finley
9
20
6.77
81
78
47
26
9
49
72
10
6
1.02
Greater Bass
40
20
5.53
11
71
43
26
17
109
92
23
2
1.22
Camp Ten
5
20
6.19
53
79
41
21
8
78
91
6
2
1.08
Elna
19
16
6.40
52
59
29
18
12
42
54
6
4
1.09
Sand
5
27
5.01
-9
87
27
23
12
70
168
20
4
0.85
Nichols
14
14
5.76
16
57
22
11
10
68
73
6
6
1.18
Luna
5
20
5.54
5
72
29
14
10
51
116
10
3
1.00
Smoky
6
31
7.15
195
148
89
34
10
33
69
8
4
1.03
McGrath
7
17
5.22
-5
49
22
13
14
41
100
8
2
1.06
Sugar Camp
4
23
5.40
0
77
22
26
13
48
134
26
1
0.92

-------
TABLE 9
MEAN CHEMICAL CHARACTERISTICS OF UPPER MIDWEST LAKES
(Michigan, 1982-1983)
Lake
- Color
(apparent)
(PCU)
Sp. Cond.
(pS/cro
P 25°C)
PH
(field)
ANC
— peq/i -
Ca Mg
Na
K
A1
pg/i
S04
peq/1
CI
N03
~/-
Monocle
13
40
6.98
237
229
92
41
12
39
108
9
2
1.08
Johnson
6
23
4.82
-14
60
25
8
11
39
125
8
2
0.89
Andrus
18
21
5.52
6
74
27
23
12
55
127
9
2
0.91
Kelly
8
15
5.22
-5
77
30
9
9
25
82
7
1
1.62
Murray
20
14
5.77
32
46
22
10
9
64
50
7
2
1.13
Bass
14
23
6.57
114
109
46
16
12
35
68
7
11
0.95
Buckeye
14
28
6.68
129
150
63
19
15
45
92
9
6
1.04
Stuart
6
18
4.82
-17
28
21
7
10
48
82
6
3
0.89
Chris Brown
24
33
6.85
201
216
77
23
20
43
73
6
2
1.12
Pretty
13
18
6.40
60
86
26
17
10
44
71
8
3
0.95
Camp Eight
14
21
6.60
95
108
40
18
10
41
67
8
2
1.02
Cusino
22
15
5.32
0
58
22
9
7
68
82
7
3
1.11
Nevins
10
36
6.72
161
232
66
20
8
59
132
8
6
1.05
McNearney
3
33
4.44
-38
60
21
7
6
254
150
7
10
0.80

-------
TABLE 10
MEAN CHEMICAL CHARACTERISTICS OF UPPER MIDWEST STREAMS
Stream
Color
(apparent)
(PCU)
Sp. Cond.
(pS/cm
3 25°C)
pH 	 peq/1 -
(field) ANC Ca Mg
Na
K
A1
pg/i
S04
peq/1
C1
N03
*/-



Michigan (1982-1983)







Pine R.
127
126
7.50 1183 980 460
65
35
1182
152
21
15
1.18
T ahquamenon
R. 100
114
6.95 878 848 352
61
21
149
195
31
10
1.12



Minnesota (1979-1983)







Filson Cr.
154
39
6.21 238 161 190
47
13
225
64
11
31
1.37
Lester R.
75
105
7.55 791 589 391
132
33
963
85
54
11
1.05
Amity Cr.
63
157
7.68 937 789 492
332
37
995
130
195
12
1.25



Wisconsin (1982-1983)







Popple R.
87
126
7.54 1179 805 673
52
13
38
92
45
1
1.24

-------
TABLE 11
LAKES MONITORED IN THE UPPER MIDWEST (MINNESOTA,
WISCONSIN, MICHIGAN) BEGINNING FALL 1983




Surface


Latitude
Longitude
Area
State
Lake
(°N)
(°W)
(ha)
Hinnesota
Cruiser
48°29'54"
92°48'19"
48.0

Spri ng
48°22'22"
92°37'48"
90.1

Shoepack
48°30'13"
92°53'00"
126.2

Loiten
48°31'33"
92°55'24"
38.8

Locator
48°32'26"
93°00'13"
54.1

Franklin
48°18'00"
92°36'50"
60.9

Long
48°18'00"
92°42'32"
191.5

Chester
47°58,00"
90°03'00"
--

Crum
47°50'00"
93°25'00"
—

Moon
47°30'00"
93°30'00"
--

Five
46°07'00"
93°12'00"
• -
Wisconsin
Long
45°43106"
89°36'17"
40.0

Sunset
45°55'35"
89°20'15"
83.0

Clara
45°30'46"
89°34117"
34.0

Vandercook
45°58'55"
89°41'13"
40.0

Greater Bass
45°21'17"
89°12'00"
99.7

Sand
45°43128"
89°39'05"
25.0

Clear
45°21'15"
89°i3'i4"
35.0

Little Rock
45°59'50"
89°42'15"
	

Nichols
46°06'14"
89°41'20"
16.2

Luna
45°54'19"
88°57'35"
27.1

Camp Twelve
45°59'10"
89°22'20"
29.9

McGrath
45°47'28"
89°38'37"
21.4

Sugar Camp
45°48'05"
89°18'25"
220.6

Morgan
45°46'00"
88°33'00"
17.2
Michigan
Garlinghouse
46°17145"
84°33'30"
--
Monocle
46°28'30"
84°38'45"
70.7

Johnson
46°25'30"
85°02'40"
16.1

Kelly
46°26'24"
85°23'40"
12.2

Murray
46°28'15"
85°42'05"
38.3

Bass
46°27,49"
85°42'58"
58.3

Buckeye
46°27'57"
85°44'19"
48.1

Stuart
46°35'24"
85°30'35"
30.1

Chris Brown
46°37'34"
85°30'27"
24.2

Cusino
45°27'16"
86°15,30"
53.2

Nevins
46°31'00"
86°14'35"
113.5

McNearney
46°25'38"
84o57'30"
50.4

-------
TABLE 12
CHEMICAL CHARACTERISTICS OF UPPER MIDWEST REGION LAKES, November 1983
Lake
Tt«p.
CO
Color
(apparent)
(PCU)
Sp. Cond.
(pS/cti
« 25°C)
PH
(field)
ANC
yeq/1
Ca Mg
Na
K
A1
yfl/1
»«
lieq/1 —
CI N0a
~/-




Michia
in








Andrus
10.7
32
14
5.72
25
72
46
87
7
31
129
13 <1
1.27
Base
12.2
13
22
6.80
125
109
56
67
9
8
73
10 <1
1.16
Buckeye
8.4
16
22
7.03
164
166
73
73
13
5
96
9 <1
1.21
CtirU Brow
9.7
47
30
7.19
209
205
77
63
9
10
87
17 <1
1.13
Custnc
9.3
19
15
5.46
13
72
29
80
4
8
127
8 <2
1.25
Barling
6.9
30
23
4.54
-12
73
38
77
8
21
100
11 2
1.99
Johnson
9.8
5
22
4.74
2
67
41
38
9
5
131
8 <1
1.19
Kelly
12.6
8
20
5.23
14
63
27
90
5
5
90
10 <1
1.62
McNearney
12.1
4
28
4.50
-24
80
31
53
6
139
148
7 1
1.3G
Monocle
11.8
16
38
7.31
252
228
94
71
9
12
lie
13 <1
1.05
Murray
7.6
29
13
6.03
38
57
29
75
5
10
61
9 <1
1.54
Kevins
10.3
14
31
7.02
162
209
67
66
4
9
129
10 1
1.15
Stuart
9.9
21
14
4.95
2
50
30
72
7
10
81
8 1
1.85




Minnesota








Cruiser, 0.5 o
13.9
13
22
6.72
119
96
66
44
12
8
71
16 <1
l.oe
26.0 m
14.1
12
24
6.31
122
101
70
71
14
10
71
8 <1
1.27
Franklin
14.8
30
51
7.52
540
297
226
82
24
10
55
12 <1
1.04
Locator
14.2
73
29
6.50
172
127
94
120
13
41
98
18 <1
1.27
Loiten
14.5
49
29
6.61
169
126
95
120
15
29
100
65 <1
1.07
Long
14.7
91
94
7.43
950
554
425
111
24
28
86
21 <1
1.05
Shoepack
14.6
215
24
6.30
173
107
84
152
16
85
107
28 1
1.16
Spring
14.1
19
37
6.92
306
173
136
74
17
10
77
11 <1
1.02




Wisconsin








Camp Twelve
9.7
7
13
5.32
31
53
26
33
4
7
* 74
5 <1
1. 05
Clara
11.6
14
32
6.37
43
94
53
162
16
8
100
127 <1
1.20
Clear
11.2
40
16
5.06
NA*
62
39
72
9
28
96
16 <1
--
Greater Bass
12.0
38
19
5.8b
30
80
45
89
10
27
105
27 <1
1.3E
Long
NA
7
14
5.27**
10
56
28
56
7
8
81
14 <1
1.40
Luna
12.4
13
18
6.07
17
73
39
91
9
10
106
11 <1
1.56
McGrath
12.4
9
18
5.39
10
59
34
42
10
7
101
12 <1
2.16
Morgan
10.3
7
21
4.73
-3
72
51
55
9
25
147
6 <1
1.35
Nichols
12.6
28
15
5.94
34
74
37
121
4
9
87
9 <1
1.82
Sand
12.2
3
23
5.23
18
B4
45
47
11
9
144
17 1
1.04
Sugar Canp
12.7
3
21
5.62
23
81
35
•53
10
5
125
26 <1
1.03
Sunset
12.5
6
17
6.57
32
66
33
44
4
7
86
17 <1
1.09
Vandercook
12.4
3
23
5.23
18
84
45
47
11
4
88
8 <1
1.64
• Not available.
•* Field value NA; lab value shown.
-28-

-------
central Wisconsin (pH 4.68, sulfate 19.4 kg/ha), and greatest at Douglas Lake
near the Straits of Mackinac in Michigan (pH 4.42, sulfate 20.3 kg/ha). This
latter site, as previously noted, is not ideally situated for purposes of this
project; the recently activated Raco, Michigan, site is now providing data more
representative of the monitored lakes in Michigan.
New England
Maine
Principal Investigator: Terry A. Haines, U.S. Fish and Wildlife Service,
Department of Zoology, University of Maine, Orono, Maine 04469.
The six lakes selected for the monitoring program are located southeast of
Orono in Hancock County. Sampling was initiated in October 1982. All lakes
are underlain by the Tunk Lake Pluton, a medium grained horneblende-aegerine-
augite-perthite granite. The surficial material is almost exclusively granitic
and was probably locally derived. The soils are generally well drained
spodosols of the Hermon and Lyman series, formed in till. Soil thickness
ranges from 0 to >30 cm with a 3-10 cm organic mat.
The watersheds are entirely forested with mixed hard and softwood species.
Hardwood species include paper birch, oak, beech, and red maple; softwood
species are red spruce, fir, and white pine. There are a few seasonal dwell-
ings on Spring River Lake, and one seldom-used seasonal dwelling on Anderson
Pond. There 1s no other human habitation or disturbance in the watersheds.
The northern half of the Anderson Pond watershed burned about 1960, otherwise
the vegetation in all watersheds has been undisturbed for at least 50 years.
The NAPP site at Acadia National Park appears to provide precipitation
data most representative of the Maine study lakes. Average sulfate deposition
in 1982 was relatively high, 25 kg/ha, although lower than for a number of
-29-

-------
sites in the Catskill and Appalachian regions farther south (Table 2). Average
pH was 4.46. Locational and chemical data are given in Tables 13 and 14.
Vermont
Principal Investigator: Wallace McLean, Chief, Monitoring and Surveill-
ance, Water Quality Division, Department of Water Resources and Environmental
Engineering, State Office Building, Montpelier, Vermont 05602.
Thirty-six lakes presently comprise the Vermont long-term monitoring
program. Sampling began in 1981 with twenty lakes. At the present time,
twelve lakes are sampled every year, and the remaining 24 in alternate years.
Twenty-four lakes are thus sampled annually. Lakes primarily are small, with a
median surface area of 14 hectares and a median drainage area of 120 hectares.
Major geologic formations in Vermont have been mapped following the classifica-
tion of Norton. The drainages for twenty-nine of the study lakes lie primarily
over Type I bedrock which is highly sensitive to acidification. Four drainages
lie primarily over Type II bedrock which is moderately sensitive to acidifica-
tion. The drainages of the three remaining lakes are in well buffered areas.
All drainage basins are primarily forested, with vegetation characteris-
tics ranging from predominantly softwood to predominantly hardwood. Only in
the Hardwood Pond drainage basin was there historical evidence of agricultural
activity.
Thirty of the lakes have no permanent inlet. Thirty-three are headwater
lakes. Wheeler Pond, Holland Pond, and Somerset Reservoir have one or more
bodies of water within their drainage basin. All of the lakes appear to have
permanent outlets.
Cultural impact is generally light or non-existent in the drainage basins
of almost all thirty-six lakes. Given the logging history of Vermont, it can
-30-

-------
TABLE 13
LAKES MONITORED IN MAINE



Surface


Latitude
Longitude
Area
Elevation
Lake
(°N)
(°W)
(ha)
(n)
Anderson Pond
44°38,51"
68°03'33"
5
68
Little Long Lake
44°38'16"
68°04'42"
22
75
Mud Lake
44°38'00"
68°05'24"
1
104
Salmon Pond
44°37'53"
68°04'12"
4
94
Spring River Lake
44°37l10"
68°03'06"
285
60
Tilden Pond
44°37'04"
68°04'23"
15
72

-------
TABLE 11+
CHEMICAL CHARACTERISTICS OF MAINE LAKES
Lake
Date
Dtpth Top.
(¦•tars) (•«
Color
(apparent)
(PCU)
Sp. Cond.
(pS/CM
f 25°C)
P« 	
(field) ANC
Ca
Meq/1 —
Mg Na
— A1 — yeq/1
K MB/1 S0« CI
N03
~/-
Andersen
11/21/82
0.5
10
15
17
5.51
14
36
30
74
6
3
59
61
0
1.09


5.0
9
10

5.78
17
37
28
74
5
3
59
61
0
1.05

02/21/83
0.5
0
10
18
5.86
15
45
29
78
9
S
59
63
0
1.18


5.0
—
10
17
5.68
14
41
28
83
7
4
59
65
0
1.18
—
04/21/83
0.5
7
10
18
5.90
10
33
25
72
5
5
55
69
0
1.01


5.0
—
15
18
5.88
11
33
25
73
5
5
56
71
0
0.99

07/07/83
0.5
23
10
20
5.95
9
33
25
75
5
3
59
60
4
1.05


5.0
19
15
22
5.86
8
34
25
76
5
10
59
67
4
1.01

01/16/84
1.0
--
10
20
5.64
8
42
28
84
7
5
56
80
0
1.12


4.5
--
10
20
5.36
4
40
27
85
8
4
58
85
0
1.09
Little
05/01/82
0.5
6.5
5
19
5.15
3
44
30
89
7
11
79
81
0
1.04
Long

22.0
7
10
20
5.03
-11
44
30
77
7
11
79
83
0
1.03
08/08/82
0.5
21
10
20
5.70
4
44
27
90
6
3
78
85
0
1.00


22.0
8
10
17
5.17
11
47
28
90
6
12
81
81
0
0.99

11/21/82
0.5
7.5
10
14
5.60
9
44
29
87
6
6
80
76
0
1.01

02/21/83
22.0
8
15
13
5.8 2
8
44
29
91
6
6
78
84
0
1.00

0.5
1
15
20
5.51
4
48
27
10 2
7
11
85
88
0
1.04

04/21/83
22.0
5
15
13
5.65
12
51
27
100
7
6
83
84
0
1.03

0.5
. 7
10
22
5.32
-2
43
30
91
6
10
80
84
0
1.07

07/07/83
22.0
5
10
21
5.72
6
46
30
94
6
11
80
77
0
l.oe

0.5
23
10
23
5.56
0
42
28
89
6
9
78
86
0
1.02

01/16/84
22.0
6.5
10
29
5.42
9
47
30
94
7
8
79
88
0
1.01

1.0
—
10
24
5.12
-4
46
31
114
8
4
87
93
1
1.14

05/01/82
20.0
--
15
24
5.51
3
49
30
100
8
9
81
94
1
1.04
Mud
0.5
7
30
22
4.39
-24
24
24
67
5
37
96
57
0
1.04

08/08/82
14.0
6
40
24
4.41
-23
30
26
82
6
41
105
74
0
1.02

0.5
20
15
25
4.52
-28
27
22
82
5
34
98
68
0
1.00

11/21/82
14.0
—
35
26
4.48
-32
28
25
91
6
48
108
79
0
0.98

0.5
8
25
19
4.60
-27
31
28
102
12
53
107
91
0
1.00


14.0
5
35
20
4.61
-27
30
29
97
6
54
107
86
0
0.97

02/21/83
0.5
6
25
20
4.52
-27
35
35
110
6
46
108
117
0
0.96


14.0
--
30
—
4.65
-22
37
34
105
7
46
no
103
0
0.96

04/21/83
0.5
6
30
31
4.52
-30
29
27
87
6
42
94
85
0
1.00


14.0
5
30
31
4.57
-29
30
30
92
6
45
100
90
0
0.97

07/07/83
0.5
22
15
27
4.64
-22
27
24
87
4
30
104
77
0
0.91


14.0
4
25
33
4.57
-31
28
28
89
6
40
105
94
2
0.89

01/16/84
1.0
--
30
34
4.45
-32
33
30
101
10
46
97
116
0
0.99


14.0
—
35
32
4.48
-31
33
29
94
10
46
92
102
1
1.02
Salaon
05/01/82
0.5
8
20
18
6.11
38
62
30
79
7
3
50
75
3
1.09


9.0
7
20
—
5.82
37
66
31
79
7
3
51
70
3
1.14

08/08/82
0.5
21
20
20
6.42
30
67
29
85
8
2
52
76
0
1.20


9.0
—
25
—
5.52
67
71
31
80
7
4
49
75
0
0.99

11/21/82
0.5
55
15
12
6.57
54
71
32
88
9
3
55
73
0
1.10


9.0
55
20
12
6.52
74
74
32
85
7
3
57
71
2
0.97

02/21/83
0.5
0
25
19
6.25
57
78
30
91
9
7
55
71
0
1.14


9.0
4
25
20
5.91
60
80
30
94
7
2
55
73
0
1.12

04/21/83
0.5
6
20
21
6.54
47
65
31
87
6
3
54
69
0
1.11


9.0
5
20
—
6.48
53
71
32
83
6
3
50
72
0
1.10

07/07/83
0.5
22
20
22
6.55
59
60
30
84
6
3
53
72
0
0.99


9.0
7.5
25
—
5.66
73
88
34
168
7
3
51
81
0
1.45

01/16/84
1.0
—
25
24
6.10
38
73
33
93
8
1
57
84
2
1.14


9.5
--
20
24
6.01
51
78
35
91
8
2
54
76
2
1.16
Spring
07/07/83
0.5
22.5
15
21
6.22
15
52
31
117
7
4
71
102
3
1.10
tivar

5.0
18.5
15
27
6.19
14
53
31
119
8
4
72
109
3
1.07

01/16/84
1.0
—
15
30
S.82
11
64
37
145
8
S
79
147
1
1.07


7.3
•*
20
30
6.01
20
68
36
142
8
2
78
156
1
1.00
(continued)
-32-

-------
CHEMICAL CHARACTERISTICS OF MAINE LAKES (continued)
Color Sp. Cond.
Depth Temp, (apparent) (yS/cm pH 		 AT — peq/1 —
Lake Date (meters) (°C) (PCU) « 25°C) (field) ANC Ca Mg Na K pg/1 S04 CI H03 ~/-
Til den 05/01/82
0.5
7
20
17
5.79
32
57
29
85
6
6
54
69
0
1.14
08/08/82
9.0
7
25
19
5.84
26
57
29
84
6
6
54
76
0
1.13
0.5
21
10
13
6.50
41
57
28
88
6
2
58
73
0
1.04
11/21/82
9.0
--
25
--
5.74
77
68
31
88
7
6
50
70
0
0.98
0.5
6
15
15
6.47
39
63
31
92
6
2
62
69
0
1.13
02/21/83
9.0
6
15
15
6.47
35
61
31
94
6
3
62
70
0
1.15
0.5
1
15
—
6.28
45
69
34
102
7
3
62
86
0
1.10
04/21/83
9.0
4
20
--
6.18
51
70
34
103
7
5
62
83
0
1.09
0.5
7
25
18
6.49
39
60
30
90
5
5
56
76
0
1.08
07/07/83
9.0
6
20
18
6.39
42
62
30
91
5
10
57
78
0
1.06
0.5
23.5
15
22
6.82
37
55
28
93
6
5
58
76
0
1.06
01/16/84
9.0
8
20
27
6.00
56
67
33
100
8
3
60
82
0
1.05
1.0
—
30
22
6.06
32
67
34
102
7
5
66
107
2
1.01

7.3
••
20
24
6.18
37
70
34
107
9
4
61
81
0
1.23
-33-

-------
be assumed that virtually all of the basins have been subject to siIvicultural
perturbations to some degree within the last 150 years. Several of the ponds
are on the Long Trail and thus are subject to relatively light recreational use
by hikers. Five of the lakes, Sunset Lake, Somerset Reservoir, Lake Ninevah,
Little Averill Pond, and Lake Mansfield, have dams and are subject to potential
water level regulation. Somerset Reservoir serves a hydroelectric facility and
1s subject to seasonal water level fluctuations. Ten of the ponds have light
seasonal camp development in the immediate basin. Permanent residences along
the shoreline are found at Cole Pond.
Precipitation quantity and pH were measured at four locations for the full
twelve months of 1983. Data from nine other sites were incomplete for the
calendar year. Precipitation was collected in bulk deposition collectors and
the pH measured on an event basis. Annual weighted averages of rainfall pH
were calculated for the four locations.
Precipitation pH (Weighted
Station	Amount (cm)	Average)
West Dover	159	4.36
Concord	121	4.39
Mt. Mansfield	141	4.42
Swanton	104	4.52
The weighted-average pH of the precipitation for these four sites was 4.41
with an average rainfall of 131 cm/year. Average pH for 1982 from the
Bennington NADP site was 4.36 (Table 2), in good agreement with the above 1983
data. Average sulfate deposition as measured at Bennington in 1982 was 20.1
kg/ha, about 5 kg less than at Acadia Park in Maine.
Locational and chemical data for Vermont lakes are presented in Tables 15
and 16.
-34-

-------
TABLE 15
LAKES MONITORED IN VERMONT



Surface


Latitude
Longitude
Area
Elevation
Lake
(°N)
(°W)
(ha)
(m)
Beaver Pond
45°00'30"
71°56'30"
16
468
Beebe Pond
43°03'
73°03'
4
710
Big Mud Pond
43°18'
72°53'
6
790
Big Muddy Pond
44°45'
72°36'
8
427
Bourn Pond
43°06'
73°001
20
778
Branch Pond
43°05'
73°01'
14
802
Cole Pond
43°09'
72°48'
17
363
Cow Mountain Pond
44°37'
71°40'
4
630
Forester Pond
43°05'
72°52'
4
641
Griffith Lake
43°21'
72°53'
7
793
Grout Pond
43°03'
72°57'
35
679
Hardwood Pond
44°28'
72°30'
18
479
•Haystack Pond
42°55'
72°53'
11
910
Holland Pond
44°59'
71°56'
135
436
Howe Pond
42°47'
72°59'
20
587
Kettle Pond
44°18'
72°19'
42
440
Levi Pond
44°16'
72°141
9
498
Lily Pond
43°14'
72°49'
8
454
Little Pond (Winhall)
43°08'
72°58'
4
753
Little Pond (Woodford)
42°46'
73°05'
6
793
Little Averill Pond
44°57'
71°43'
196
531
Little Rock Pond
43°22'
72°541
8
565
Lake Mansfield
44°28'
72°49'
14
348
Moses Pond
43°20'
72°481
5
686
Lake Ninevah
43°28'
72°45'
96
535
Osmore Pond
44°18'
72°16'
20
448
Pidgeon Pond
44°15'
72°20'
29
596
Somerset Reservoir
43°00'
72°56'
647
651
South Pond
42°51'
72°431
28
503
Stamford Pond
42°49'
73°03'
5
726
Sterling Pond
44°35'
72°45'
5
917
Stratton Pond
43°06'
72°58'
18
779
Sucker Pond
42°48'
73°07'
20
691
Sunset Lake
42°55'
72°41'
38
418
Unknown Pond
44°55'
71°50'
8
720
Wheeler Pond
44°43'
71°39'
28
314
-35-

-------
TABLE 16
CHEMICAL CHARACTERISTICS OF VERMONT LAKES


Color
Sp. Cond.











Lake Date
Temp.
(true)
(pS/cm
pH

— peq/1 -


A1
— ueq/1
	

CC)
(PCU)
9 25°C)
(field)
ANC
Ca
Mg
N>
K
tig/)
S04
CI

*/¦
(•aver Fond 02/23/61
—
—
50
5.62
38
160
35



146
14


04/23/81
—
—
32
6.03
64
190
51



133

6

06/24/81
--
--
26
6.34
42
170
35



135
--
5
• •
07/22/81
--
—
28
6.38
70
175
35



114
--
3

08/19/61
--
--
28
6.09
98
190
39



142

4

10/15/81
••
--
28
6.11
54
155
34



129
—
1
--
02/03/82
1
—
24
5.90
72
180
35



125

2

06/22/82
18
46
29
6.07
56
144
30
--
--
• •
116
--
2

08/04/82
22
66
26
6.11
58
149
30
10
14
..
110
14
1
1.11
10/14/82
12
43
22
6.53
69
169
33
26
7
--
110
12
<1
1.23
Betbe Fond 05/13/82
16
75
23
4.97
-6
54
29


mm
106

3
_ _
07/14/82
24
102
29
4.86
-5
49
28
29
7
--
117
--
<1
--
08/1B/82
20
101
20
5.22
20
56
30
29
7
--
118
17
1
0.78
11/05/82
13
89
22
5.40
8
59
33
34
9
--
113
17
1
0.97
02/16/83
1
>•
28
4.82
-9
70
37
41
13
350
142
15
6
1.07
05/13/83
11
85
20
4.79
-16
50
30
25
6
380
110
16
4
0.99
06/23/83
25
77
28
4.86
-8
50
30
27
6
440
119
17
2
0.93
08/30/63
23
59
20
4.91
-7
50
31
30
9
190
115
14
<1
1.02
01/11/83
7
65
22
5.10
0
50
31
33
10
300
116
6
1
1.01
Big Muddy 02/18/81
--
-•
45
5.49
70
165
37



137
17
..
--
Pond 04/28/81
—
—
27
6.11
36
145
42



112
—
1
--
06/02/61
—
--
21
6.89
38
140
34



137
--
2
--
07/03/81
—
--
22
6.52
46
155
105



135
—
<1
--
08/24/81
--
—
20
6.48
52
165
35



135
—
<1
--
10/02/61
—
—
25
6.54
56
170
35



139
--
<1
--
02/16/82
1

39
6.10
138
210
39



67
..
1
..
05/21/82
IB
26
23
6.46
56
144
29



111
—
2
--
06/14/82
16
28
25
6.09
46
141
30
--
--
—
116
--
<1
--
07/29/82
21
32
24
6.45
63
156
33
10
5
--
lis
21
<2
1.00
10/19/82
9
42
26
6.71
73
171
34
11
16

116
12
<1
1.14
BSc Mud 02/10/82
1
..
35
4.48
20
90
35



144

6
--
Pond 06/30/82
19
107
19
4.90
5
62
27



111
--
<1
--
01/26/83
1
59
25
5.36
38
120
41
28
11
410
162
25
2
o.ee
05/25/83
16
65
16
4.97
-5
70
25
16
9
300
106
14
<1
1.09
08/07/83
19
131
20
5.03
1
70
30
22
7
380
146
13
<1
0.80
09/01/83
20
71
30
4.79
-14
105
40
18
7
220
165
10
2
0.94
11/03/83
6
56
30
5.03
-1
125
44
25
9
370
189
7
<1
1.06
Bourne Pond 08/17/82
21
58
16
5.23
4
38
27
22
7
-•
90
11
1
0.89
11/09/62
6
60
10
5.52
5
52
32
13
11

105
10
1
0.69
02/16/83
1
40
27
4.85
-1
70
39
35
14
260
152
16
3
1.01
05/26/83
16
37
15
5.17
-5
45
27
23
9
260
83
13
1
1.14
07/07/63
21
40
16
4.96
-6
35
27
27
10
160
98
13
<1
0.99
08/31/83
21
30
16
4.92
-6
35
29
25
10
110
100
11
<1
1.00
11/02/83
5
28
16
5.26
2
40
27
26
11
110
98
6
<1
0.98
Branch Pond 04/30/61
--
--
22
4.22
..
100
36
—
..
..
142
20
5
--
06/10/81
—
—
18
4.62
-20
50
27



125
--
4
--
07/08/81
--
--
20
4.73
-16
40
27



127
—
3
--
08/05/81
--
—
24
4.41
-18
45
26



127
—
2
--
09/02/61
—
—
17
4.59
-16
45
26



117
--
1
--
10/22/81
--
--
24
4.64
-15
45
26



127
--
1
--
01/30/82
1
--
27
4.50
-13
50
31



162

13

05/13/82
15
B4
23
4.50
-12
48
36
--
--
—
98
--
3

07/14/82
23
96
27
4.66
-18
34
21
20
11
--
105
--
1
--
0B/19/B2
20
B8
19
4. BO
-11
36
24
21
8

103
12
2
0.90
11/05/82
10
90
IB
4.95
-5
45
24
23
12
"
100
14
1
1.00
(continuec)
36-

-------
CHEMICAL CHARACTERISTICS OF VERMONT LAKES (continued)



Color
Sp. Cond.











Uki

Te«p.
(true)
(mS/ck
pH

M*q/1 ¦


A1
— uea/1
_

Date
(•C)
(PC0)
• 25#C)
(field)
ANC
Ca
Mg
N<
K
yg/1
S0«
CI
no3
¦»/-
•ranch Pond 02/16/83
1
65
28
4.56
-25
60
28
30
11
360
158
17
4
0.BB
(cant.)
OS/26/83
15
£7
17
4.86
-10
40
23
23
13
320
98
14
3
0.97

07/07/83
21
71
21
4.64
-20
45
26
22
11
260
112
14
1
1.00

08/31/83
21
70
19
4.66
-17
35
22
23
10
140
104
9
<1
0.99

11/02/83
5
48
18
4.81
-6
40
21
24
11
190
115
6
<1
0.93
Colt Pond
02/02/83
1
7
30
5.77
50
120
59
70
20
40
152
57
1
1.03

04/28/83
15
12
25
6.22
44
95
47
69
16
70
119
54
<1
1.05

07/06/83
22
33
27
6.33
35
95
47
65
17
80
125
49
<1
1.07

08/30/83
24
15
27
6.31
42
90
52
67
18
30
125
51
<1
1.04

11/01/83
7
9
29
6.38
43
100
48
73
18
20
135
41
<1
1.09
Cow
02/23/81
—
—
46
5.70
134
100
76



137
10
• •
..
Mountain
05/01/81
—
—
26
6.31
110
150
69



117

2
--
Fond
06/23/81
—
--
24
6.76
110
145
67



171

<1
--

07/21/B1
--
--
25
6.38
84
145
67



110
—
<1
--

¦ 08/18/81
—
—
29
6.42
100
150
66



127
--
<1
--

10/14/81

••
32
6.32
122
145
66



119
—
<1
--

02/16/82
1
• •
36
6.02
130
150
86



77

3
_ _

05/14/82
15
66
31
6.13
104
139
63



10B
..
2
--

06/09/82
19
70
32
6.34
106
131
58
--

--
107

<1


08/03/82
20
86
31
6.28
136
140
63
17
20
--
110
15
<1
0. 92
Foretter
05/05/82
1
--
24
4.94
-9
41
20



85
	
2
	
Pond
06/29/82
23
29
24
4.69
-13
52
19



114

1


08/24/82
21
29
20
4.81
-10
54
18
37
4
--
99
3:
<1
C 99

10/06/82
15
32
ie
4.30
-30
52
16
36
4
—
101
30
<1
1.24
Griffith
01/21/82
1
--
33
5.16
44
130
46



150
..
3
..
Lake
05/12/82
14
75
23
5.46
20
104
32



96
--
3
«

07/01/82
16
84
16
5.69
29
140
31



107
--
<1
--

08/26/82
18
56
18
6.03
25
80
34
17
8
—
97
15
1
1.01

10/05/82
15
47
18
6.20
40
104
34
19
10
--
101
12
<1
1.05
Grout Pond
06/29/82
19
40
17
6.29
32
70
31
_ _
• •

82

1
--

08/17/82
22
32
18
6,42
32
66
30
23
12
—
8 2
12
<1
1.03

11/03/82
11
31
20
6.40
41
79
34
27
14
—
72
14
<1
1.21

02/15/83
1
7
21
6.08
45
90
38
28
14
40
106
14
<1
1.03

05/25/83
16
15
16
5.97
19
75
31
25
12
¦ 90
90
14
10
l.oe

07/07/83
22
28
18
5.99
20
70
31
30
7
60
98
14
<1
1.05

08/30/83
22
15
18
5.99
22
70
33
25
13
30
92
12
2
1.10

11/01/83
6
10
19
6.30
35
75
30
26
13
20
87
6
<1
1.12
Hardwood
01/28/82
1
--
22
5.64
42
105
47



121
—
1
--
Pond
05/13/82
14
45
22
6.44
38
96
40



99
—
10
--

06/15/82
18
42
27
6.22
27
86
37
—
~
--
101
—
<1
--

06/05/82
23
55
20
6.09
26
86
54
15
6
—
102
14
<1
1.13

10/01/82
16
50
18
--
19
90
41
21
4
--
100
14
<1
1.17

01/26/83
1
27
28
5.66
34
110
48
24
5
80
127
19
1
1.03

05/20/83
12
24
17
6.10
28
90
37
20
4
60
106
13
<1
1.03

07/01/83
22
43
19
5.72
26
65
39
15
4
SO
112
11
<1
0.95

09/06/83
24
70
20
5.78
36
80
42
21
7
100
117
12
<1
0.91

11/09/83
6
25
20
6.02
21
90
38
20
4
70
117
10
<1
1.03
Haystack
03/05/81
--
--
31
4.17

55
19



100
21


Pond
04/29/81
--
-»
29
4.47
-30
40
21



92
—
b
--

06/17/81
--
—
15
4.58
-29
45
21



90
--
4
--

07/15/81
--
—
17
4.63
-15
50
21



87
--
4
--

08/12/81
--
--
18
4.55
-18
45
21



90
--
4
--

10/28/81
--
--
18
4.92
10
45
21



90
—
3
--
(continuea)
-37-

-------
CHEMICAL CHARACTERISTICS OF VERMONT LAKES (continued)
Lake
Date
lamp.
CC)
Color
(true)
(PCU)
Sp. Cortd.
(yS/c*
» 25°C)
pH
(fHeld)
ANC
— »
-------
CHEMICAL CHARACTERISTICS OF VERMONT LAKES (continued)



Color
Sp. Cond.











Lake
Date
Teap.
(true)
(yS/cm
pH

— peq/1 -


A1
— ueo/1
_

CC)
(PCU)
• 25'C)
(field)
ANC
Ca
Mfl
Na
K
Hfl/1
*>«
CI
no3
~/-
Levi Pond
01/25/83
1
37
28
5.33
20
105
29
37
10
160
139
22
1
0.99
(cont.)
05/16/83
10
59
18
5.23
4
80
23
31
8
160
121
16
<1
1.01

06/27/83
21
S8
20
5.12
3
70
23
30
8
150
131
11
1
0.90

08/15/83
22
40
22
5.08
-4
80
24
30
8
110
129
13
<1
1.06

10/17/83
12
35
18
5.18
-3
75
25
33
8
80
125
6
<1
1.13
Lily Pond
03/05/81
—
—
14
5.10
6
40
27



87
28



04/15/81
—
—
17
6.05
38
B0
45



37
—
<1
--

06/10/81
—
—
18
6.51
10
80
46



115
—
<1
	

07/08/81
--
—
20
6.40
42
85
54



112
—
4
--

08/05/81
—
—
25
6.30
54
100
46



106
—
<1
--

10/21/81

--
27
6.19
66
80
48



102
--
<1
--

01/21/82
1
--
36
6.05
110
100
54



121
..
1


05/14/82
16
27
21
6.38
38
66
37



104
--
<1
--

06/29/82
23
35
20
6.28
38
70
40
--
--
—
104
—
<1
--

08/24/82
22
36
20
6.56
70
66
44
38
13
—
103
16
<1
0.85

10/06/82
15
36
20
6.15
54
41
45
43
17
--
94
15
<1
0.90

01/25/83
1
9
25
5.88
74
95
52
50
20
100
117
23
1
1.01

05/18/83
15
9
18
6.17
23
75
39
36
13
60
117
16
<1
1.04

06/30/83
23
23
21
6.05
31
75
43
42
14
40
121
13
<1
1.05

08/30/83
24
18
23
6.14
42
80
47
43
19
30
115
16
<1
1.09

11/01/83
6
20
24
6.36
60
75
45
44
19
20
110
6
<1
1.04
Little
02/23/81
--
..
49
6.54
104
160
43



121
10
• •
—
Averill
04/24/81
--
—
32
6.44
110
160
45



115
--
6
--
Pond
06/23/81
—
«
23
7.05
126
160
44



127
—
3
—

07/21/81
—
--
31
6.95
94
160
45



94
—
2
--

08/18/81
—
--
26
6.91
100
170
44



112
--
2
••

10/14/81
—
--
31
6.83
110
165
46



112
—•
1
••

02/04/82
1
..
33
6.56
128
200
51



110
—
6
--

05/29/82
14
40
32
6.95
105
156
44



103
—
2


06/21/82
17
32
32
7.10
117
159
43



103
--
2
--

08/03/82
20
29
29
7.26
121
—
--
--
--
--
110
8
1
--

10/13/82
13
29
26
7.08
123
150
44
34
7
-•
102
10
<1
1.00

02/01/83
1
5
25
6.47
120
180
46
34
8
30
112
15
2
1.06

06/01/83
11
6
25
6.96
114
120
43
32
7
30
96
11
2
0.91

07/12/83
20
9
28
6.91
118
170
41
32
7
30
110
B
<1
1.06

08/18/83
22
5
28
6.47
126
160
44
34
6
40
104
9
2
1.02

10/20/83
10
10
26
6.81
128
165
43
35
7
20
106
6
<1
1.04
Little Pond
03/06/81
..
..
25
4.75
--
55
21



98
20
--
--
(Woodford)
04/24/81
—
—
27
4.98
-10
70
31



115
--
11
--

06/18/81
--
—
16
4.98
-3
70
29



125
--
5
--

07/16/81
—
—
19
5.39
8
70
27



121
--
2
--

08/12/81
--
«
21
4.98
-2
70
25



125
--
1
--

10/28/81
--
—
20
5.05
-5
65
26



142
--
3


01/28/82
1

35
5.16
19
70
33



133
-•
4
..

05/19/82
18
20
22
5.35
2
61
25



96
—
6
—

07/07/82
22
26
23
4.96
-3
60
22
—
--

122
—
2
—

08/12/82
22
25
18
5.16
-3
54
22
26
8
—
116
4
1
0.97

11/11/82
5
28
18
5.51
6
69
26
34
14

134
8
3
0.95

02/10/83
1
3
22
4.86
3
80
28
31
15
590
129
14
11
0.99

05/12/83
9
10
20
4.75
-10
60
20
22
13
360
112
14
7
1.00

06/22/83
25
3
27
5.0B
-5
60
22
26
16
180
121
12
2
0.96

08/23/83
21
5
19
5.22
-2
60
26
30
14
90
122
11
1
1.01

10/27/83
4
7
17
5.77
6
60
26
35
13
70
121
6
1
1.00
(continued)
-39-
-------
CHEMICAL CHARACTERISTICS OF VERMONT LAKES (continued)



Color
Sp. Cond.













Tmp.
(true)
(pS/cn
PH

	 ueq/1 •


A1
— iiea/1


Late
Pate
CO
(PCU)
t 25*C)
(field)
ANC
Ca
Mg
Na
K
MO/1
S04
CI
no3
*/-
little >oi»d 01/21/82
1
—
34
5.04
82
115
49



85

12
__
(Vinhall)
05/18/82
22
33
20
5.76
14
83
31
«»•
* m

65
mm
11
• •

07/13/82
23
49
24
6.15
33
66
30
24
9
--
68
—
2
• •

08/18/82
22
56
17
6.38
40
65
30
27
9
—
60
13
1
1.15

11/03/82
13
62
19
6.30
72
75
29
28
12
—
71
16
2
0.89

02/17/83
1
17
29
5.76
66
130
44
35
14
140
106
14
10
1.14

05/24/83
17
22
16
5.59
13
75
26
21
10
210
75
13
5
1.25

07/06/83
21
43
17
5.86
19
70
27
—
11
70
89
15
<1


08/31/83
21
48
17
5.93
34
70
26
27
11
60
77
13
<1
1.08

11/10/83
6
42
19
6.18
37
70
23
27
12
70
77
14
1
1.02
Little Rock
07/01/82
19
32
29
6.87
137
138
17
..
..
..
112
--
<1
..
Pond
06/25/82
20
29
30
7.02
152
132
110
18
8
—
112
15
<1
0.96

10/07/82
15
29
30
7.00
160
150
113
21
12
—
111
14
<1
l.Ofl

01/27/83
1
6
30
6.80
162
150
115
20
13
50
119
19
<1
0.99

05/25/83
14
11
25
6.75
112
125
99
19
11
180
106
15
1
1.09

07/08/83
21
19
30
6.87
130
125
99
22
12
120
125
15
<1
0.96

09/01/83
21
10
30
7.06
134
140
107
16
11
240
117
11
<1
1.05

11/03/83
7
17
35
6.84
172
150
115
19
12
60
110
6
<1
1.03
Lake
02/27/81
• _
--
49
5.85
6
175
39



139
15
--
--
Mansfield
04/17/81
--
—
27
6.21
50
195
45



123
—
14
--

06/05/81
	
--
31
6.36
54
195
49



81
—
10
--

07/30/81
	
--
26
6.78
136
220
49



127
—
3
--

08/28/B1
—
--
27
6.16
64
200
40



146
--
4
—

10/01/81
—

26
6.57
72
195
41



162
--
5


02/02/83
1
17
46
6.26
202
274
59
20
9
BP
169
17
5
0 92

05/20/83
12
10
23
6.34
56
155
34
11
6
110
133
11
4
1.01

07/01/83
22
31
30
6.44
116
130
40
16
6
80
142
8
<1
0.73

09/06/83
24
59
32
6.60
146
190
43
16
7
80
127
8
1
0.91

11/09/83
6
32
30
6.60
76
160
37
20
6
140
156
11
2
0.99
Motes fond
03/05/81
--
--
24
4.63
..
65
40



133
18
--
--

04/29/81
—
—
10
4.99
-16
50
32



112
--
<1
--

06/10/81

—
14
4.91
-5
60
31



121
--
<1
--

07/08/81
--
--
15
5.11
-1
55
31



110
—
<1
--

08/05/81
..
--
22
4.29
-17
50
30



112
--
<1
—

10/21/81
••
--
24
4.59
-25
55
35



121
--
<1
——

01/21/82
1
..
27
5.18
58
65
39



117
--
2
--

05/14/82
15
55
21
4.86
-5
49
26



98
--
<1


06/29/82
23
106
17
5.25
6
61
27
—
--
--
116
--
2
—

08/24/82
19
87
15
5.00
5
45
29
20
2
—
92
14
--
0.95

10/06/82
15
70
16
5.15
-2
49
32
20
3

112
13
<1
0.89
Lake
03/04/81
_ _

25
5.99
52
105
44



127
30
--
--
fhnevab
04/24/81
—
--
26
6.30
54
115
62



125
--
5


06/10/81
—
—
19
6.42
56
115
48



106
--
<1
--

07/07/81
—
--
46
6.75
36
110
33



112
--
<1
--

08/04/81
--
--
26
6.65
70
130
44



110
—
<1
—

10/21/81
—
7-
20
6.50
70
120
50



110
—
<1
- -

01/27/83
i
9
26
6.50
102
140
53
36
21
30
112
23
1
1.05

06/07/83
17
16
22
6.57
56
105
41
29
17
SO
108
18
<1
1.05

06/30/83
22
26
24
6.75
62
110
43
37
17
40
108
17
1
1.10

09/07/83
23
54
24
6.77
65
115
49
31
17
20
106
15
<1
1.13

11/10/83
6
17
25
6.82
71
115
45
31
18
10
121
16
<1
1.00
Otaore Pond 02/01/83
1
17
29
6.74
215
240
52
83
15
50
135
33
<1
1.02

06/03/83
15
17
20
6.72
80
125
30
123
10
50
121
17
<1
1.32

06/26/83
20
32
26
7.00
102
135
34
54
10
40
125
17
<1
0.95

08/17/83
23
30
32
7.24
153
180
37
68
11
40
112
16
<1
1.05

10/18/83
11
20
22
7.40
144
165
39
74
12
40
117
7
<1
1.08
(continued)
-40-
-------
CHEMICAL CHARACTERISTICS OF VERMONT LAKES (continued)



Color
Sp. Cond.













Te*p.
(true)
(pS/cm
pH

ueq/1 -


A1
— uea/1


Lake
Date
(•C)
(PCU)
• 25"C)
(field)
AMC
Ca
Mg
Na
K
pg/1
S0«
CI
no3
*/•
Pigeon font
1 02/17/81
--
—
38
5.55
140
215
49



142
25



04/22/61
—
--
34
6.40
90
180
44



135

5


06/03/81
• m
m m
27
6.64
76
165
42



137
m m
4


07/10/81
--
--
30
7.02
96
180
46



133

1
	

10/07/81
•-
--
28
6.60
88
180
42



142
	
1
--

01/26/63
1
11
32
6.51
143
200
41
44
8
60
125
16
1
1.02

05/17/63
10
48
25
6.50
86
160
35
35
7
120
123
15
2
1.05

06/2B/B3
20
30
27
6.84
89
160
35
45
7
100
129
16
<3
1.06

06/17/83
22
30
26
6.75
97
170
35
49
6
40
127
13
<1
1-10

10/18/83
12
13
22
6.63
97
160
38
22
8
10
131
6
<1
0.97
Somerset
03/06/81
..

26
4.95
5
85
35



115
20


Retervoir
04/14/81
—
--
25
5.32
9
80
36



46
—
9
--

06/17/81
—
--
15
5.63
10
80
34



106
--
7
--

07/14/81
—
—
23
5.73
6
80
35



29
—
6
--

06/11/81
--
—
20
5.82
10
B0
35



112
--
5
--

10/27/81
--
--
20
5.44
19
70
33



119

5


01/28/82
1

32
5.47
15
75
38



106
--
8
«

05/13/82
15
55
21
5.46
13
76
33



102
--
5
--

07/08/82
20
43
19
5.56
10
69
30
--
--
--
103
—
4
--

06/12/82
22
43
19
5.91
15
75
30
25
12
—
96
6
<1
1.19

11/09/82
6
63
18
5.67
24
77
31
27
13
•-
113
11
3
o. se
Soutfi Pond
03/04/81

..
21
5.66
28
100
39



125
22
--
--

04/14/81
--
—
17
6.22
32
90
39



40
--
3
--

06/18/B1
—
--
16
6.48
32
95
39



119
—
<1
--

07/15/81

--
21
6.31
24
100
39



112
--
<1
-*

06/12/81
—
--
22
6.38
38
100
39


%
117
—
<1


10/29/81

--
21
6.27
38
95
39



no
-•
<1
~ ¦

01/27/82
1

32
6.05
48
100
41



115
—
1
—

05/06/82
10
41
24
6.27
45
100
37



90
--
1


07/06/82
22
21
21
6.53
33
90
36
—
—
—
'108
--
<1


08/11/82
23
23
23
6.47
45
105
39
34
e
--
103
19
<1
i.ii

11/08/62
9
31
22
6.47
43
106
40
34
9

115

<1
—

02/10/63
1
1
24
6.20
44
104
42
36
10
80
123
24
<1
ic:

05/11/83
12
39
18
6.24
26
80
33
32
7
50
108
20
<1
0.9?

06/21/83
25
9
27
6.20
23
84
35
32
7
SO
115
19
<1
1.01

08/23/63
21
--
21
6.50
25
90
39
33
8
90
115
20
4
1.04

10/25/83
10
7
20
6.17
31
90
37
35
e
••
117
6
<1
1.10
SUmford
01/27/82
1
..
36
5.52
46
100
36



121
--
6
—
Pond
07/08/82
22
49
20
5.33
7
64
26
--
--
—
lie
--
2
--

08/10/82
24
43
20
5.49
16
70
27
33
5
—
109
7
<1
1.02

11/10/82
3
55
21
5.69
26
91
35
47
10
••
131
15
3
1.04

02/09/83
1
5
26
5.51
11
100
35
41
15
2S0
135
17
11
1.10

05/12/63
9
33
20
4.97
-1
70
25
32
12
300
112
16
8
1.10

06/22/63
25
18
29
5.26
3
65
26
33
10
190
123
14
3
0.94

06/23/63
21
21
20
5.67
10
60
31
40
9
80
121
14
<1
0.97

10/26/83
4
43
18
5.96
34
80
34
48
12
130
108
6
1
1.17
Sterling
02/19/82
1
—
39
5.89
78
110
92
—
—
m •
144
..
4
..
Pond
06/24/82
13
79
19
5.88
39
83
120
--
--
--
88
—
5
—

06/05/62
19
64
20
5.92
53
85
39
20
11
--
87
13
2
1.00

10/01/82
13
95
20
••
84
100
70
10
5
—
61
14
<1
1.03
Stratton
05/16/82
17
37
20
6.03
36
91
32



78

4

Pond
07/13/82
23
32
24
6.23
17
64
31
24
14
--
95
..
<1


08/18/62
22
29
18
5.86
15
63
33
24
5
--
101
11
1
0.9B

11/03/82
10
32
20
5.90
14
79
35
27
12
--
107
15
<1
1.12
(continued)
-41-
-------
CHEMICAL CHARACTERISTICS OF VERMONT LAKES (continued)



















Color
Sp. Cond.












Pate
leap.
(true)
(pS/cn
pH

— peq/1 -


A1
— uea/1
,

Ul»
<*C)
(PCU)
• 25*C)
(field)
ANC
Ca
Mfl
Na
K
MB/1
so«
CI
no3
*/¦
Stratton
02/17/83
1
15
21
5.70
28
65
38
32
14
300
121
12
3
1.03
Pond
(cont.)
05/24/83
15
17
16
5.97
18
75
28
23
12
120
79
13
3
1.44
06/07/83
22
25
18
6.10
16
70
29
27
11
60
96
13
<1
1.10

08/31/83
22
17
16
6.65
36
70
30
25
12
20
77
11
<1
1.10

11/02/83
6
20
15
6.22
27
65
26
25
11
60
71
6
<1
1.22
Sucker Pond 03/05/81
--

25
5.63
34
125
42



127
16

	

04/30/81
—
-«
21
5.79
46
115
41



115
—
4
--

06/16/81
--
--
18
7.15
98
125
42



127




07/16/81
--
-»
26
6.77
66
125
44



106
—
<1


08/13/81
--
--
22
6.84
76
115
44



104
--
<1
--

10/28/81
••

25
6.73
60
120
44



110

<1


02/09/83
1
11
29
6.16
95
150
50
39
15
90
127
16
4
1. 05

05/13/83
10
42
21
6.69
52
105
36
30
12
60
106
16
2
1.05

06/23/83
24
31
29
6.56
61
110
37
35
16
70
112
16
<1
1.05

08/24/83
21
35
23
6.81
78
110
41
33
14
20
112
13
<1
0.96

10/27/83
4
12
22
6.93
80
110
43
35
14
20
104
6
<1
1.06
Sunset Lake
03/04/81
--

23
5.60
18
75
32



106
34
—


04/14/81
—
—
16
6.25
14
75
32



33
--
1
--

06/19/81
--
--
16
6.35
26
80
32



94
—
<1


07/15/81
--
—
18
6.41
24
85
32



96
--
<1
--

08/13/81
—
—
20
6.20
24
80
32



94
--
<1
—

10/29/81
--
-•
19
6.07
30
80
32



92

<1


01/28/82
1

27
5.90
36
70
35
—
..

89
—
<1
--

OB/03/82
24
20
20
6.22
30
72
31
36
6

91
19
<1
1.04

11/08/82
9
23
22
6.28
32
86
33
35
7
--
96

2
—

03/03/83
--
0
20
6.26
61
120
38
38
7
120

22
1
—

05/11/83
12
23
17
6.11
15
100
30
35
5
40
98
22
1
1.25

06/21/83
25
0
25
6.14
15
70
31
35
5
40
104
21
<1
1.01

08/23/83
10
3
20
6.18
17
75
30
35
6
30
104
21
<1
1.03

10/25/83
10
3
18
5.96
14
75
30
37
6
40
106
6
<1
1.17
Unknown
06/21/82
16
51
22
5.67
18
92
30
..
--
--
107
..
3
--
Pond
08/17/82
20
51
21
5.76
18
106
32
12
12
--
117
12
<1
1.10
(Avery'»
10/13/82
10
72
19
6.06
28
104
31
24
6
—
126
12
1
0.96
Gore
















02/03/83
1
44
25
5.62
31
140
35
28
7
330
156
21
3
1.00

06/02/83
11
39
18
5.42
8
90
25
18
10
180
115
13
3
1.05

07/14/83
19
—
20
6.11
14
95
30
21
9
250
135
9
<1
0.98

08/19/83
21
20
28
6.16
28
95
30
24
8
220
129
10
<1
0. 94

10/21/83
5
50
20
5.94
36
165
38
27
8
110
129
6
<1
1.39
Wheeler
02/01/83
1
87
31
5.92
99
170
50
S2
15
240
160
21
2
1.02
Pond
06/01/83
14
73
26
6.13
71
145
41
43
16
180
135
16
1
1.10

07/13/83
22
77
30
6.31
94
150
45
46
16
160
152
16
<1
o.9e

08/18/83
22
50
31
6.17
105
150
47
54
16
150
142
16
<1
1.02

10/20/83
10
97
30
6.46
132
175
51
62
18
180
133
6
<1
1.13
-42-
-------
New York
CatskiU Mountains
Principal Investigator: Peter Murdoch, U.S. Geological Survey, P.O. Box
1350, Albany, New York 12201.
The IJSGS report on the Catskill sites, with the exception of the tabulated
stream chemistry data, was not received in time for inclusion in this report.
The area is important economically, containing some of the premier trout
streams of the northeastern United States. Average precipitation pH in 1982 at
the Stillwell Lake NADP site, about 65 km south, was 4.31; average sulfate
deposition was 26.4 kg/ha. At the Knobit site, about 100 km northeast, these
values for 1982 were 4.40 and 16.2, respectively. Precipitation quantity and
chemistry monitoring on both weekly and event bases are funded and implemented
by USGS at the Catskill study sites, but data are not available at this time.
Locational and water chemistry data for the Catskill streams appear in
Tables 17 and 18. Data provided by the Geological Survey for this report are
provisional and subject to revision by that agency.
Adirondack Mountains
A monitoring study of twelve Adirondack lakes was initiated in October
1983 through an agreement with the State University of New York at Oswego. A
move by the principal investigator soon after, however, necessitated termina-
tion of the project. A proposal from Syracuse (New York) University for
monitoring sixteen Adirondack lakes is expected to be funded early in FY85.
Data from the October 1983 study will be included with those from the new
project in the next annual report.
Average 1982 deposition data from the Huntington Wildlife NADP site in
Essex County reflect a pH of 4.38 and sulfate deposition of 24.1 kg/ha.
-43-
-------
TABLE 17
STREAMS MONITORED IN THE CATSKILL MOUNTAINS AREA OF NEW YORK



Drainage


Latitude
Longitude
Area
Flow Range
Stream
(°N)
(°W)
(ha)
(m3/sec)
Biscuit Brook
41°59'34"
74°30'11"
9.8
0.04-16.34
Pigeon Brook
41°59'13"
74°30'11"
6.9
0.02- 3.12
High Falls Brook
41058'33"
74031'19"
7.1
0.02- 5.95
Woodland Creek
42°02'22"
74°20'01"

0.04-12.80
Rondout Creek
41°56'12"
74°22'35"
14.2
0.10- 7.80
Beaverkill River
42°01'02"
74°34'55"
20.9
0.10- 2.66
East Branch Neversink River
41°57'48"
72°27'19"
34.4
0.37-13.59
44
-------
TABLE 18
CHEMICAL CHARACTERISTICS OF CATSKIlL MOUNTAINS STREAMS


Flow


















Sp. Cond.














aage
Tmp.
(yS/en
P*

ueq/1 •


A1
— ueo/1


StfM
Date
¦•/see ht (ft) (*C)
t 25*C)
(field)
ANC
Ca
Hg
Na
K
MB/1
»«
CI
HO,
~/-
•itcuit
04/10/83
0.57*
0.97
4.5
25
5.6
9
125
40
22
6
210
126
13
26
1.10
•rook
04/10/63
2.92*
1.65
5.0
22
5.4
8
125
40
9
7
150
114
10
24
1.16

04/11/63
1.02
1.20
5.0
23
5.7
10
13D
50
48
9
180
125
15
29
1.32

04/11/83
1.36
1 34
5.0
23
5.6
6
110
40
17
7
190
121
18
47
0.91

05/19/83
0.20
0.63
6.5
29
6.2
17
130
44
17
6
100
149
15
11
1.03

07/08/83
0.09
0.51
14.2
27
6.6
--
145
58
30
5
30
160
22
19
--

08/12/83
0.51
1.00
—
26
6.3
23
155
54
22
7
90
148
16
31
1.09

08/15/83
0.04
0.32
14.0
26
6.4
23
145
50
26
5
60
163
20
27
0.97

10/06/63
0.10
0.53
—
30
6.4
31
145
SB
30
12
20
146
29
11
1.13

11/02/63
0.03
0.45
5.0
25
6.4
36
145
58
35
6
20
159
31
6
1.04

11/10/83
0.05
0.38
7.5
29
6.4
36
145
60
26
6
20
156
32
11
1.01

11/10/83
0.07
0.44
6.5
28
6.3
34
145
61
26
7
20
154
29
11
1.05

11/11/83
o.os
0.51
--
30
6.6
-4
150
56
35
7
20
159
30
13
1.24

11/11/83
0.19
0.52
9.0
30
6.4
42
145
59
30
8
--
151
29
12
1.03

11/16/83
0.2 2
0.85
5.0
30
6.5
30
165
52
22
7
70
153
29
18
1.07

11/30/83
0.49
0.96
3.5
28
6.1
12
145
54
26
5
60
154
22
15
1.13

12/13/83
3.37
2.02
—
22
5.1
-12
115
38
17
7
230
120
15
20
1.19

12/14/83
2.44
1.70
5.0
23
5.6
2
115
41
22
6
210
139
16
19
1.06

01/12/84
0.12
0.61
0.0
28
6.5
32
155
56
22
5
30
156
21
23
1.03

€2/01/84
0.16
0.65
0.0
30
6.2
16
145
58
22
5
50
155
19
24
1.07

03/06/84
0.45
0.85
0.5
29
6.1
14
130
50
17
5
10
152
20
24
0.96

03/21/84
0.42
—
1.5
25
6.0
16
125
47
17
5
30
137
16
24
0.99

03/21/84
0.79
—
1.0
26
5.9
16
125
46
17
5
50
134
17
27
0.99

03/28/84
0.29
0.81
1.5
29
6.3
20
130
46
17
5
50
143
18
16
1.01

04/03/84
0.32
0.84
1.5
23
5.2
21
90
34
13
7
200
100
11
26
0.91

04/03/84
0.32
0.84
4.5
32
6.2
22
230
49
17
5
SO
142
16
14
1.04

04/04/84
0.37
0.66
2.0
26
6.2
24
125
SO
17
5
Bb
141
16
16
1.00

04/05/84
0.42
0.94
2.5
27
6.2
20
130
45
17
5
60
136
16
17
1.03

04/05/84
16.34
2.61
2.0
26
4.9
-12
80
31
13
9
220
100
10
30
1.04

04/06/84
2.52
—
2.5
24
5.2
2
100
34
17
7
220
117
14
26
1.03

04/06/84
6.57
2.14
2.0
26
5.0
-4
90
31
13
7
210
109
10
29
1.02

04/10/84
0.53
1.02
3.5
21
5.9
4
115
40
13
5
70
145
16
18
0.95

04/17/84
1.53
1.52
5.5
20
5.4
2
105
36
13
6
140
131
11
16
1.02

05/30/64
4.33
1.94
8.5
20
5.3
4
90
35
63
6

122
6
9
1.04

06/12/84
0.16
—
—
24
6.4
24
115
42
13
--
to*
142
15
11
--

07/20/84
0.10 .
--
--
30
6.5
32









E.
08/15/63
0.35
0.74
16.0
22
5.0
-4
80
55
22
5'
60
152
19
19
0.91
Branch
11/02/63
0.37
0.60
—
22
5.1
0
75
61
17
6
160
138
23
13
0.96
Wever-
11/16/63
1.67
1.37
5.0
27
5.1
-12
65
55
17
7
240
140
24
17
0.95
cink
12/14/83
12.74
2.62
5.0
25
4.5
-32
60
36
17
7
420
115
16
19
2.02

02/01/84
0.57
0.94
0
29
5.2
-2
90
63
26
6
160
147
19
31
0.97

03/06/84
1.05
1.45
0.5
32
5.1
-6
80
55
17
6
160
140
19
27
0.69

03/21/64
1.23
1.20
1.0
24
5.1
-6
75
57
17
6
140
134
19
26
0.91

03/21/84
2.55
1.53
1.0
24
4.9
-12
75
S3
17
6
160
133
16
29
0.91

04/03/64
0.86
1.09
1.0
31
5.2
4
BO
57
17
6
160
138
17
25
0.90

04/05/84
S3.6
3.64
1.5
26
4.5
-20
50
31
13
9
360
S8
11
27
1.07

04/05/84
110.4
S.30
1.5
28
4.5
-27
44
25
9
12
320
80
7
29
1.05

04/06/64
S.63
2.39
2.0
26
4.6
-17
55
33
13
6
320
107
11
25
0.94

04/17/84
7.08
2.17
3.5
24
4.6
-24
55
40
13
6
w
123
12
19
0.90

05/30/84
13.59
2.67
6.5
26
4.6
-26
5D
34
13
7
••
112
9
9
0.99

06/13/64
0.66
-»
--
mm
5.1
—
70
49
17
6
••
136
15
11
—

07/20/84



21
5.1
-6
••
"•

mm
mm

--
--
*•
Hgeon
04/11/63
0.02
--
5.0
23
6.0
16
130
41
30
6
140
125
12
23
1.18
Brook
06/15/63
0.03
—
14.5
33
6.6
70
195
55
26
S
60
165
19
24
1.01

11/02/83
0.02
—
6.0
30
6.6
90
200
60
30
7
<10
160
30
6
1.04

12/14/83
1.64
--
5.0
22
5.6
6
115
44
17
6
200
126
16
IB
1,06
* When two or »ore observations were Mde on the tame date (usually during a runoff event}, data
corresponding with the lowest and highest Instantaneous flows are given here.
(continued)
•45-
-------
CHEMICAL CHARACTERISTICS OF CATSKILL MOUNTAINS STREAMS (continued)


Flow

















Sp. Cond.













gage
Teap.
(mS/c»
PH

ueo/1 ¦


A1
— peq/1
—

Stroaa
Date
¦r/sec ht (ft) (»C)
f 25*C)
(field)
ANC
Ca
"0
Na
K
»ig/l
so.
CI
H03
*/-
Pigeon
02/01/84
0.08
0.0
29
6.5
50
1B0
50
22
S
SO
157
19
23
1.03
•rook
04/03/84
0.20
4.5
30
65
40
155
42
17
5
80
139
16
12
1.06
(cent.)
04/05/84
1.25
2.0
23
5.8
16
105
31
13
6
150
100
12
18
1.06

O4/0S/84
3.12
1.5
25
5.2
0
100
31
13
9
200
100
10
30
1.14

04/06/84
0.68
3.0
25
5.5
6
110
31
13
6
150
115
11
26
1.01

04/17/84
0.92
5.5
19
5.8
16
115
33
13
6
100
133
12
17
0.94

05/30/84
0.68
8.5
18
5.7
16
105
28
13
6
--
119
8
7
1.01

06/12/84
0.16
—
25
6.7
46
140
42
17
5
—
145
17
10
0.94

07/20/84
0.07
--
28
6.8
51
—
—
--
—
—
••
••


High-
08/1S/83
0.03
14.5
38
7.1
136
265
54
30
5
60
169
17
25
1.02
tails
11/03/83
0.02
6.0
35
7.1
179
280
68
30
8
<10
158
23
9
1.05
Brook
12/14/83
1.39
5.0
21
5.9
13
145
33
17
6
120
129
17
18
1.14

02/01/84
0.10
0.0
39
6.8
97
235
57
22
5
30
162
18
26
1.05

04/03/84
0.21
4.0
36
6.7
70
190
47
13
5
40
144
16
14
1.05

04/05/84
5.95
2.0
26
5.2
-1
110
27
13
8
190
106
10
30
1.12

04/17/84
1.08
5.5
23
5.9
22
145
31
30
8
70
126
32
18
1.06

06/13/84
0.16
—
—
6.9
84
195
42
22
6
—
146
20
12
1.01

07/20/84
0.07
--
33
7.2
114









Woodland 08/15/83
0.04
15.0
28
6.5
12
120
64
26
5
60
147
21
31
1.04
Crock
11/01/83
0.07
7.5
27
6.3
26
110
74
30
8
10
145
22
13
1.08

12/15/83
2.63
5.5
15
6.5
11
115
63
22
7
10
125
22
29
1.31

02/02/84
0.17
0.0
33
6.2
20
115
70
26
6
30
142
21
29
1.02

04/02/84
0.54
5.0
25
6.7
24
130
67
22
6
50
133
22
19
1.04

04/16/84
12.8
4.5
20
6.1
14
90
50
13
7
20
110
12
22
1.01

06/12/84
0.22
11.5
23
6.4
28
105
54
17
7

131
16
14
0.97

07/17/84
0.08
--
23
6.4
27









Roundout 08/16/63
0.10
13.0
27
6.2
24
120
62
30
7
50
146
20
26
1.01
Crock
11/01/63
0.14
4.5
28
6.0
12
100
60
22
9
50
146
22
13
0.99

12/14/83
3.96
5.0
26
4.7
-24
70
37
22
9
390
: 112
16
21
1.06

02/02/84
0.31
0.0
31
5.6
-2
100
61
26
6
130
146
18
30
1.01

04/03/84
0.76
4.0
28
5.4
6
90
55
17
7
30
135
16
24
0.96

04/17/84
1.90
5.5
24
4.8
-10
70
39
13
7
290
133
13
23
0.86

05/30/84
7.82
9.0
25
4.7
-18
60
32
13
8
—
122
8
13
0.93

06/11/84
0.48
15.5
23
5.2
4
85
46
17
6
—
138
13
14
0.91

07/17/84
0.06
—
24
5.5
2
--
--
—
••
—
••
••
••
""
Beaver-
11/03/83
0.10

36
7.0
140
260
47
22
7
<10
152
20
21
1.01
kill
12/15/83
2.66
4.0
23
6.1
26
180
35
13
5
60
139
15
23
1.15
River
01/31/84
0.19
0.0
37
6.6
82
240
51
17
5
20
156
17
34
1.08

04/02/84
0.57
4.0
34
6.5
80
220
43
13
5
60
146
16
22
1.06

04/16/84
28.3
4.5
20
5.8
16
130
25
9
7
130
112
9
26
1.05

06/13/84
0.37
14.5
36
7.6
110
210
42
13
5
--
145
12
14
0.96

07/19/84
0.10
—
34
7.2
134
--
—
--
--
--
—
—
••
••
-46-
-------
Appalachian-Piedmont Region
Laurel Ridge Area, Allegheny Mountains. Pennsylvania
Principal Investigator: James Barker, U.S. Geological Survey, P.O. Box
1107, Harrisburg, Pennsylvania 17108.
This project was initiated in August 1983 on six low alkalinity streams in
southwest Pennsylvania (Laurel Ridge). Unanticipated clearcutting in the
watershed of Gross Run has necessitated the elimination of that stream as of
July 19R4. The region is underlain by sandstone formations, with sandy and
silty loam soils. A reconnaissance of the entire Laurel Ridge area preceded
selection of the monitored streams. The watersheds are not pristine but are
probably as near an undisturbed condition as can be found in that part of the
United States.
There are no NADP precipitation sites in the immediate vicinity of Laurel
Ridge. The Geological Survey, however, operates a wet-dry sampler, following
NADP procedures, at the Ben's Creek sampling site. Data for 1982 from the
Parsons, West Virginia, NADP site (Table ?.), approximately 112 km to the south,
show an average pH of 4.31 and sulfate deposition of 40.1 kg/ha (a very high
value). Average 1982 values for pH and sulfate deposition from the Leading
Ridge, Pennsylvania, NADP site (Table 2), about 100 km east of Laurel Ridge,
are 4.16 and 36.6 kg/ha, respectively. Data from the Ben's Creek station for
the period September 1983-June 1984 show weekly pH values ranging between 3.9
and 4.7. Averages and deposition values are not yet available.
Locational and chemical data for the Laurel Ridge streams appear in Tables
19 and ?0. As noted previously, these are Geological Survey data which must be
considered provisional and subject to revision, according to USGS procedure and
policy.
-47-
-------
TABLE 19
STREAMS MONITORED IN THE LAUREL RIDGE AREA OF PENNSYLVANIA
Stream
Latitude
(°N)
Longitude
(°W)
Drainage
Area
(ha)
Flow Range
(m3/sec)
South Fork Bens Creek
40o13'41M
79°02,49"
8.5
0.01-0.51
North Fork Bens Creek
40°16'21"
78°58'43"
8.9
0.01-0.40
North Branch Quenahoning
40°06'38"
79°08'04"
6.9
<0.01-0.62
Creek




Gross Run
40°01'55"
79°13'30"
3.0
<0.01-0.60
Cole Run
39°58'00"
79°17'25"
3.2
<0.01-0.26
Garys Run
39°58'25"
79°17'51"
3.4
<0.01-0.26
48
-------
TABLE 20
CHEMICAL CHARACTERISTICS OF LAUREL RIDGE, PENNSYLVANIA, STREAMS




Sp. Cond.













Flow
Temp.
(yS/cm
PH

— oeq/1


A1
	1
yeq/1
—

Strew
Date
¦rVsec
CO
§ 25°C)
(field)
ANC
Ca
Mg
Na
K
MQ/1
»«
CI
N03
~/-
N. Fork
08/02/83
0.01
18.0
46
6.1
21
185
82
91
14
80
169
166
11
0.96
ton* Cr»*k
09/13/83
0.05
16.0
46
E.3
35
205
91
113
15
10
189
141
9
1.13

10/18/83
0.01
10.0
44
6.3
52
165
82
74
9
60
179
24
4
1.35

11/16/83
0.34
5.0
46
5.7
17
205
91
61
19
70
250
82
10
1.05

12/20/83
0.19
1.0
44
5.0
••
90
53
22
13
460
208
37
8
--

01/17/84
0.03
0.5
45
6.0
41
175
81
87
16
60
192
121
5
1.00

02/23/84
--
3.0
46
5.5
-2
165
62
70
17
120
206
110
--
"

03/29/84
0.40
3.5
44
5.4
-3
165
61
61
16
210
229
76
--
--

04/24/84
0.37
6.5
44
5.6
•9
170
82
44
16
110
2oe
79
--
--
North
08/02/83
0.004
19.0
33
4.6
••
75
46
22
12
300
181
31
4

Branch
09/13/83
0.03
16.5
34
4.6
--
60
59
48
17
220
183
37
--

Quum honing 10/18/83
0.003
10.0
34
4.8
--
80
59
39
20
240
189
31
<1

Crtek
11/16/83
0.40
7.0
47
4.7
—
245
90
57
20
40
250
39
13


12/20/83
0.10
0.0
39
4.5
--
175
77
78
17
80
200
102



01/18/84
0.03
0.5
36
4.7
*.
90
60
26
10
580
204
31
6


02/23/84
0.20
3.0
40
4.6
—
90
53
22
13
690
229
31
--


03/29/84
0.62
2.5
41
4.6
•-
90
51
22
12
840
229
24
—


04/26/84
0.31
5.5
40
4.6
••
90
53
17
13
750
208
26
—

Grots Run
08/03/83
0.001
17.5
33
4.5
--
75
49
17
13
400
183
27
3


09/14/83
0.001
14.0
32
4.5
—
70
48
35
13
320
163
31
2


10/19/83
0.02
10.0
44
4.7
--
105
55
30
24
650
229
37
4


11/23/83
0.12
7.5
41
4.6
--
125
73
35
16
730
271
39
—


01/18/84
0.02
0.5
36
4.6
••
75
45
22
10
80
196
31
5


02/22/84
0.09
3.0
39
4.6
--
60
45
22
11
740
200
26
--


03/28/84
0.13
4.5
36
4.6
--
75
45
17
12
730 »
200
21
—


04/25/84
0.16
6.0
38
4.6
•-
75
44
13
11
780
200
22
~ -

Gary's Run
08/03/83
0.005
16.0
29
6.4
60
120
91
26
12
80
158
31
6
C.9&
09/14/83
0.002
14.0
32
6.8
47
120
82
39
11
20
148
24
5
1.12

10/19/83
0.01
9.0
31
6.1
28
120
91
30
28
70
167
28
5
l.ie

11/22/83
0.16
7.0
38
5.0
•1
115
72
30
15
600
229
31
11
c.e&

01/19/84
0.008
0.0
11
5.8
30
115
91
22
11
110
183
29
7
0.96

02/22/84
0.09
3.0
32
5.3
2
105
82
17
13
450
198
25
—
--

03/28/84
0.15
4.5
32
5.2
•6
100
79
13
12
400
204
21
--
--

04/25/84
0.26
5.5
34
4.9
—
95
72
13
12
610
208
19

—
Cole Run
08/03/63
0.001
17.5
32
4.6
--
80
60
17
12
320
194
27
3


09/14/63
0.001
16.0
28
4.5
—
85
63
30
12
250
200
25
3


10/19/83
0.03
10.0
44
4.8
—
125
91
30
41
420
271
50
1


11/22/83
0.13
7.0
41
4.7

100
45
26
12
850
250
31



01/19/84
0.003
0.0
32
4.8

80
55
30
9
440
198
26
3


02/22/84
0.11
3.0
36
4.6
--
80
53
26
10
720
208
25
—


03/28/84
0.14
4.5
36
4.7
—
80
53
13
9
680
208
23
--


04/25/84
0.26
5.5
37
4.6
--
••
••
••
••

"
*•


S. Fork
08/02/83
0.01
18.0
46
6.3
134
230
91
30
20
80
144
31
7
i:?
l«na Cr*tk
09/13/83
0.02
17:5
50
7.0
223
304 115
70
26
10
171
31
10
1.18

10/20/63
0.01
8.5
58
7.0
218
344
140
48
5
20
229
37
4
1.12

21/27/83
0.18
6.5
46
6.5
50
309
132
65
26
90
354
42
10
1.17

12/21/83
0.16
2.5
34
6.3
—
160
79
35
19
30
164
39
18


01/17/84
0.07
1.5
39
6.5
167
190
82
26
17
30
171
31
13
0.76

02/21/84
0.57
7.0
36
6.0
21
150
80
22
19
SO
179
28
—
-*

03/27/84
0.45
9.0
36
6.3
24
150
81
17
18
20
175
25
—


04/24/84
0.51
8.5
34
6.2
28
155
82
17
17
20
173
25
--
--
-49-
-------
Sandhills Area, North Carolina
Principal Investigator: Kent Crawford, U.S. Geological Survey, P.O. Box
2857, Raleigh, North Carolina 27602.
The USGS report on the Sandhills sites, with the exception of the tabu-
lated data, was not received in time for inclusion in this report. The project
began 1n September 1983 on five streams in the Sandhills Region of south-
central North Carolina. The area is characterized by deep highly-sandy soils
covered predominantly by pine and scrub oak. Waters tend to be colored and of
low pH.
NADP sites at Piedmont Station (about 100 km west-northwest) and at
Clinton Station (about 100 km east) (Table 2) bracket the study area. In
addition, the Geological Survey initiated an NADP site at Jordan Creek in
October 1983. Average 19R? pH and sulfate deposition at Piedmont Station were
4.35 and 29.1 kg/ha, respectively, and at Clinton Station 4.53 and 21.2.
Average weekly pH values from the Jordan Creek station ranged from 3.97 to 6.90
between October 1983 and June 1984.
Locational and chemical data for the Sandhills streams are given in Tables
21 and 22. Again, these USGS data are provisional and subject to revision.
Southern Blue Ridge Province (Tennessee, North Carolina, Georgia)
Principal Investigator: Harvey Olem, Tennessee Valley Authority, 248 401
Building, Chattanooga, Tennessee 37401.
Fifty-four reservoirs were surveyed by TVA in 1982-83 in this southern
Appalachian region. Twelve were selected for long-term monitoring to provide
a range of alkalinity, color, elevation, surface area, and drainage area.
Because of the absence of natural lakes in most of the Southeast, reservoirs
are predominant and important components of the aquatic environment and economy.
-50-
-------
TABLE 21
STREAMS MONITORED IN THE SANDHILLS AREA OF NORTH CAROLINA
Stream
Latitude
(°N)
Longitude
(°W)
Surface
Area
(ha)
Elevation
(m)
Suck Creek
SB^O'l?"
79°33'57"
*1.9
<0.01-0.07
Mill Creek
35°09'23"
79°22'04"
•vO. 5
<0.01-0.01
White Cedar Branch
35°05,45"
79°34'58"
1.1
0.01-0.02
Joe's Creek
35°04'49"
79°35'58"
*1. 3
0.01-0.03
Deep Creek

79°32'45"
0.6
<0.01-0.01
Jordan Creek
34°58'12"
79p31'34"
•^0.3
0.01-0.03
51
-------
TABLE 22
CHEMICAL CHARACTERISTICS OF NORTH CAROLINA SANDHILLS STREAMS


Inst.

Sp. Cond.











Flow
Taap.
(pS/cn
pH
	 ueq/1 -


A1
— pep/1 -

Strew
Date
(•Vsec)
co
• 25eC)
(field)
ANC Ca
Hfl
Na
K
MQ/1
so«
CI
N03
Suck CrMk
10/24/83
0.03
--
24
4.3
• » •«.
..
..

..
..


Tributary
11/14/83
0.03
—
25
5.8
— 80
107
130
33
30
200
76
1

12/19/83
1.20
••
26
4.5
- 39
54
83
20
120
98
70
1

01/23/84
2.30
—
20
5.2
" 26
52
61
15
120
73
59
1

02/13/84
1.10
—
17
5.7
-- 30
55
61
15
70
73
61


04/09/84
2.20
—
18
5.7
— 24
46
52
16
80
58
42
—

06/04/84
0.58
••
17
5.8
— 26
41
57
14
30
49
55
--
Mill CrMk
09/21/83
0.09
-•
11
4.2








Tributary
10/24/83
0.09
—
30
4.2
— —
—
—
—
—
--
--
--

11/15/83
0.11
—
17
4.5
— 11
26
63
6
80
19
102
1

12/21/83
0.10
••
16
4.4
— 8
21
78
4
110
17
98
1

01/25/84
0.25
--
18
4.5
— 8
28
78
4
110
23
105
1

02/15/84
0.29

19
4.5
- 12
28
87
7
160
33
107
--

04/11/84
0.29
—
19
4.5
— 9
24
78
4
80
29
73
«

06/06/84
0.21
••
16
4.5
" 10
25
74
3
90
17
86

Jordan Creek
09/20/83
0.25

13
3.6









10/25/83
0.29
--
28
3.6
-- —
—
--
--
--
—
—
--

11/16/83
0.30
—
19
3.4
- 7
21
44
3
80
27
44
1

12/20/83
0.33
••
16
4.4
— 6
10
49
6
80
19
41
••

01/24/84
0.33
—
18
4.5
— 4
10
39
5
70
25
40
1

02/14/84
1.20
—
42
4.0
-- 18
42
39
10
420
50
32
--

04/10/84
0.72
—
22
4.4
- 8
15
39
4
130
37
32
-•

06/05/84
0.36
•-
15
4.5
-- 6
12
35
2
i
10
i
16
42
~ —
White Cedar Br.
09/22/83
0.44

6
3.7









10/25/83
0.35
-•
IB
4.2
-- --
--
--

--
--
•"»


11/15/83
0.46
..
11
4.2
— 9
22
57
6
50
12
45
5

12/20/83
0.47
—
15
4.3
— 9
17
61
5
70
12
49
5

01/24/84
0.53
—
18
4.5
-- 7
18
52
6
70
15
45
5

02/14/84
0.61
—
20
4.5
- 12
28
52
7
230
27
42


04/10/84
0.77
—
15
4.5
- 10
19
46
6
20
21
35
--

06/05/84
0.57
--
14
4.6
-- 7
15
46
3
10
12
44

Joes Brook
09/20/83
0.56

12
3.7









10/25/83
0.53
—
12
' 4.3
— -*
••
- •
--
—-
••
~-
••

11/15/83
0.56

12
4.3
-- 9
17
44
4
80
17
46
1

12/20/83
0.51
—
25
4.2
— 8
14
44
5
100
21
45
1

01/24/84
0.59
..
12
4.4
— 7
19
39
4
90
25
43
1

02/14/84
1.20
--
24
4.4
.. 22
39
44
7
350
46
38
--

04/10/84
1.10
--
17
4.5
- 11
18
39
5
120
35
32
--

06/05/84
0.96
--
14
4.4
-- 12
21
35
4
60
25
32

Deep Creek
09/21/83
0.13
_¦
24
3.7








Tributary
10/24/83
0.16
—
42
3.8
-- --
--
-•
—
—
-•

~ "
11/14/83
0.10
--
17
4.3
- 6
11
39
2
90
17
46
1

12/19/83
0.28
—
24
4.2
— 8
12
S2
6
190
21
45
1

01/23/84
0.39

23
4.0
- 5
14
48
7
170
25
43
--

02/13/84
0.24
—
20
4.3
— 4
13
39
3
180
49
36


04/09/84
0.41
--
21
4.3
- 6
15
35
3
150
35
32
	

06/04/84
0.21
—
20
4.3
- 5
13
35
3
110
25
32
--
-52-
-------
The Southern Blue Ridge Province is located in the eastern portion of the
Tennessee Valley and includes sections of Georgia, North Carolina, Tennessee,
and Virginia. The IJnaka Mountains, Iron Mountains, and Great Smoky Mountains
straddle the North Carolina-Tennessee border on the western front and the Blue
Ridge Mountains lie along the Basin Divide on the eastern front. The region
contains two major groups of geological formations: crystalline rocks of
Precambrian age consisting mainly of gneisses and schists cut by later series
of granites, pegmatites, and basic intrusives; and highly-metamorphosed sedi-
mentary rocks of the Cambrian period, principally slates, quartzites, conglom-
erates, sandstones, graywacks, and marble. Neither of these formations render
significant buffering capacity to area surface waters.
The 1982 average pH and sulfate deposition values for the three NADP sites
representing the reservoir monitoring area (Table 2) were: Elkmont, Tennessee
-- pH 4.66, sulfate 21.7 kg/ha; Walker Branch, Tennessee -- pH 4.33, sulfate
36.9 kg/ha; and Coweeta, North Carolina -- pH 4.66, sulfate 23.6 kg/ha. Data
from the four TVA precipitation sites will be available for future reports.
Locational and chemical data for the twelve monitored reservoirs are given
in Tables 23 and 24. Chemical data for all 54 survey reservoirs appear in
Table ?5.
-53-
-------
TABLE 23
RESERVOIRS MONITORED IN THE SOUTHERN APPALACHIANS
(NORTH CAROLINA, TENNESSEE, GEORGIA)
Surface


Latitude
Longitude
Area
Elevation
State
Lake
(°N)
(°W)
(ha)
(m)
Georgia
Blue Ridge
34°52'54"
84016'47"
1332
515

Winfield Scott
34°44'25"
83°58'28"
6
875
North
Chatuge
35°01'01"
83°47130"
2854
587
Carolina
Ravenel (Cull
R.) 35°04'55"
83°09'56"
5
1177

Santeetlah
35°22'37"
83°52'34"
1154
591

Wolf Creek
35°16105"
82°58'10"
2
1073

Logan
35°25'14"
82°55'32"
39
887

Mars Hill
35°56'44"
82°29'39"
2
1158

Thunder
35°07'57"
82°39'46"
20
899
Tennessee
Miller
36°10'42"
82°09'23"
3
1097

Price
36°08'18"
81°43'55"
15
1030

Watauga
36°19'12"
82°07'31"
2603
597
-54-
-------
TABLE 24
CHEMICAL CHARACTERISTICS OF SOUTHERN APPALACHIAN RESERVOIRS SELECTED FOR MONITORING
Sp. Cond.	peq/1	peq/1 Color
Reservoir
Date
Temp.
(°C)
(pS/cm
0 25°C)
PH
(field)
ANC
Ca
Mg
Na
K
A1
pg/1
S04
CI
no3
(true)
(PCU)
+/-
Blue Ridge
10/82
19.7
15
6.00
150
50
39
44
15
<50
25
25
2
3
0.73

04/83
11.1
13*
6.10
100
44
37
41
14
<50
25
25
4
6
0.88
Chatuge
10/82
19.0
15
5.90
130
70
53
48
16
<50
27
31
3
4
0.98

04/83
11.2
13
6.40
100
55
46
52
16
<50
27
28
6
6
1.05
Winfield Scott
10/82
14.5
19
6.10
150
80
59
48
17
<50
27
28
6
12
0.95
Ravenal (Culla.
10/82
11.7
21
5.90
80
85
45
44
25
<50
67
45
4
90
1.02
R)
04/83
8.5
19
6.20
70
80
39
52
10
<50
56
48
8
31
0.99
Santeetlah
10/82
19.2
20
6.00
100
80
39
36
13
<50
31
20
4
5
1.08

04/83
10.4
13*
6.60
80
60
35
52
12
<50
29
20
5
2
1.19
Wolf Creek
04/83
4.9
18
5.80
110
26
20
29
8
<50
17
18
3
3
0.60
Logan
04/83
13.5
22
5.52
50
38
30
33
10
<50
25
14
11
4
1.10
Mars Hill
10/82
13.1
21
5.85
110
70
42
44
13
<50
25
20
2
23
1.08

04/83
6.1
17
5.06
70
60
32
39
12
<50
17
17
18
6
1.17
Thunder
04/83
11.5
13
4.65
20
12
12
27
5
<50
33
17
<1
23
0.80
Miller
10/82
10.6
28
6.01
180
130
33
57
13
<50
29
20
2
50
1.01
Price
10/82
9.5
23
6.37
120
85
35
52
14
<50
31
37
1
32
1.00
Watauga
10/82
17.1
73
6.67
500
344
296
91
36
<50
108
73
40
2
1.06
(0.5 meters)















Watauga
10/82
8.7
76
6.23
510
344
296
91
36
<50
108
76
40
2
1.04
(40 meters)
* Field value missing; lab value shown.
-------
TABLE 25
CHEMICAL CHARACTERISTICS OF SOUTHERN APPALACHIAN RESERVOIRS
ftetervoir
Data
Tee*.
CO
ApalacMa
10/82
IB. 4
lltit Ridge
10/82
19.7

04/83
11.1
CtMUpt
10/82
19.0

04/83
11.2
NIwiih
10/82
19.6

04/83
12.0
Vlnfield
10/62
14.5
Scott


Nottely
10/82
19.8
Woody
10/62
13.2
Brush Creek
04/83
9.0
Caldervood
10/82
17.1
Cheoah
10/62
17.5
Chilowee
10/82
17.1

04/83
10.9
Cliffside
10/62
13.4
Club
04/83
8.5
Fall* Branch
04/83
11.5
Fontana
10/82
20.3
Higdon
04/83
9.0
Sequoyah
10/82
13.4
Mi rror
10/82
12.9
Moor* No. 1
10/82
12.3
Moore No. 2
10/82
11.7
Nantahela
10/62
18.3

04/83
10.4
Queen*
10/62
16.1

04/63
10.5
Havana 1
10/82
11.7
(Culla. R.)
04/83
8.5
Ravenal
04/83
8.0
(Mill Cr.)


Santeetlah
10/82
19.2

04/83
10.4
Thorpe
10/82
16.9

04/83
10.2
Unnaaitd
04/83
20.0
(Allans Br.)


Watkins Cr.
04/83
6.5
Webb
04/83
9.0
Wolf Creek
04/83
4.9
Assembly
04/83
17.1
Banks
10/82
15.6
Boot
04/83
10.3
Burnett
04/63
13.1
Deer Park
04/63
14.6
Flat Top
10/62
12.5
Jeffen
10/82
13.9
Arrowhead
10/82
13.0
Junalutka
04/83
9.3
Uflan
04/83
13.5
Long
10/82
13.9
Mrs Hill
10/B2
13.1

04/83
6.1
Baylor
04/83
15.4
Thunder
04/63
11.5
Unnaaed
04/83
15.4
(N. Toe R.)


Miller
10/82
10.6
*rtee
10/82
9.5
lipthin
10/82
11.3
Slat Pond
10/62
7.3
Unnaaed
10/62
8.4
(Lance Cr.)


Sp. Cond.
(pS/cn
• 25*C)
»
15
13*
15
13
25
19
19
25
20
19
20
20
25
43
10
23
39
20
11
18
19
20
20
12
12
23
18
21
19
15
20
13*
15
15
26
6*
10
ie
26
15
16
25
31
20
23
16
49
22
13
£1
17
62
13
37
28
23
33
28
28
PH
(field)
ANC
— Meq/1
Ca Mg
Na
K
At
8/1
»«
Meq/1
CI
NO,
Color
(true)
(PCU)
*/-
6.20
160
110
63
57
20
50
42
34
13
2
1.00
6.00
150
50
39
44
15
50
25
25
2
3
0.73
6.10
100
44
37
41
14
50
25
25
4
6
0.88
5.90
130
70
S3
48
16
50
27
31
3
4
0.98
6.40
100
55
46
52
16
50
27
28
6
6
1.05
6.10
160
110
63
61
17
50
44
31
8
2
1.03
6.60
120
90
53
52
13
50
35
56
11
6
0.94
6.10
150
80
59
48
17
50
27
26
6
12
0.95
5.90
130
85
57
87
23
50
40
62
2
7
1.08
6.10
130
70
50
57
61
50
31
51
7
17
1.09
6.20
10
6
17
30
8
50
21
23
2
9
1.09
5.80
150
85
50
48
14
50
37
25
9
2
0.89
5.70
150
90
52
48
14
50
33
23
8
2
0.95
5.90
150
105
54
52
15
50
50
25
10
2
0.96
6.60
120
85
46
52
15
50
40
23
7
6
1.05
5.90
40
24
21
32
10
50
19
20
<1
33
1.10
6.30
80
90
41
63
37
50
50
79
21
37
1.09
6.60
160
95
61
52
14
50
23
25
3
9
1.05
5.90
120
75
44
61
14
50
35
23
7
4
1.05
6.30
60
39
26
41
8
50
21
28
19
8
0.89
6.00
70
75
33
61
19
50
42
46
7
50
1.13
5.90
90
110
73
48
15
50
46
56
6
50
1.23
6.10
170
95
73
46
15
50
35
23
<1
16
1.01
6.00
130
90
72
46
13
50
29
23
1
9
1.22
6.00
90
55
39
32
9
50
21
17
1
5
1.05
6.15
60
43
32
31
8
50
19
17
1
3
1.18
6.30
240
165
67
44
14
50
27
17
1
5
1.02
6.50
140
80
42
33
9
50
23
14
<1
3
0.93
5.90
80
B5
45
44
25
50
67
.45
4
90
1.02
6.20
70
80
39
52
10
50
56
46
8
31
0.99
6.00
30
26
26
39
8
50
42
34
3
14
0.94
6.00
100
80
39
36
13
50
31
20
4
5
1.08
6.60
80
60
35
52
12
50
29
20
5
2
1.19
6.00
70
55
26
48
12
50
21
39
1
6
l.oe
5.90
60
45
26
52
11
50
25
34
10
6
1.04
6.80
150
105
61
74
59
50
42
37
33
14
1.14
5.10
30
12
18
20
5
50
21
14
1
2
0.83
5.80
20
21
18
27
6
50
25
20
5
14
1.03
5.80
110
26
20
29
8
50
17
8
3
3
0.60
6.42
110
75
27
57
10
50
27
23
<1
6
1.06
5.40
70
22
15
52
12
50
9
23
<1
26
0.99
5.52
40
9
11
38
6
50
17
17
<1
3
0.86
6.10
60
48
36
32
9
50
40
20
14
1
0.93
6.21
130
70
77
61
11
50
37
31
1
6
1.10
5.87
130
48
29
57
15
50
12
25
1
23
0.89
5.65
180
80
15
74
19
50
19
37
<1
12
0.80
5.03
60
41
22
36
12
50
27
20
<1
55
1.04
6.80
200
145
197
87
22
50
167
51
37
11
0.99
5.52
50
38
30
33
10
50
25
14
11
4
1.10
4.91
60
33
14
42
10
50
12
23
<1
20
1.04
5.85
110
70
42
44
13
so
25
20
2
23
1.08
5.06
70
60
32
39
12
50
17
17
16
6
1.17
7.58
360
225
206
100
25
50
B5
B6
14
6
1.00
4.65
20
12
12
27
5
50
33
17
<1
23
0.80
6.09
200
110
107
70
13
50
33
37
3
6
1.10
6.01
180
130
33
57
13
50
29
20
2
50
1.01
6.37
120
85
35
52
14
50
31
37
1
32
1.00
6.02
230
150
53
78
17
50
29
25
<1
25
1.05
5.98
100
105
36
65
13
50
23
76
2
37
1.09
6.28
200
90
77
52
15
50
15
39
<1
34
0.92
(continued)
-------
CHEMICAL CHARACTERISTICS OF SOUTHERN APPALACHIAN RESERVOIRS (continued)



Sp. Cond.










Color



Teap.
(mS/ct.
PH

ueq/1 -


AT
—
m*q/i
—¦
(true)

R»*ervo1r
Date
CO
f 25*C)
(field)
ANC
Ca
"0
Na
K
Mfl/1
»4
CI
H03
(PCU)
*/-
Unnaaed
10/62
7.7
22
5.49
20
38
19
70
6
<50
42
79
1
42
0.95
(loom Fk.)
04/63
15.9
27
5.35
30
46
23
67
7
<50
29
104
4
8
0.98
Uppar Lance
Cr.
Watauga
10/62
6.4
26
6.23
120
65
47
57
18
<50
25
45
1
34
1.0B
10/62
17.1
73
6.67
500
344
296
91
36
<50
108
73
40
2
1. OB
(O.S aeterc)















Matauga
10/62
6.7
76
6.23
510
344
296
91
36
<50
108
76
40
2
1.04
(40 Mter»)















Wilbur
10/82
9.3
78
6.74
560
394
313
67
33
<50
121
71
40
3
1.04
* F1«1d value ¦Using; lab value shown.
-57-
-------
Appendix I. Sampling and Analysis Protocol for Long-Term Chemical
Monitoring of Lakes and Streams Relative to Effects of Acidic
Deposition.
(Note: For the EPA Long-Term Surface Water Monitoring Program,
this protocol has been replaced by the "Working Protocol" presented
as Appendix IV).
-------
NOTICE
This document Is a preliminary dr«";
It has not been formally released by
the u.S.E.P.A. and should ret aJ ***•
stage be construed to represent Agency
policy. It is being circulated for
comment on technical accuracy and
policy implications.
SAMPLING AND ANALYSIS PROTOCOL FOR LONG-TERM
CHEMICAL MONITORING OF LAKES AND STREAMS
RELATIVE TO EFFECTS OF ACIDIC DEPOSITION
prepared for
The Aquatic Effects Task Group
Interagency Task Force on Acid Precipitation
Revised March 1984
The program for long-term monitoring of the nation's surface waters had
its inception in July 1982, when an ad hoc committee from NAPAP Task Group E
(Aquatic Effects of Acid Precipitation) was organized to scope out a national
program and develop a standardized sampling/analysis protocol for chemical
monitoring. The committee, with representation from EPA, USGS, TVA, USDA-FS,
USFWS, USNPS, and Brookhaven National Laboratory, produced a draft protocol in
January 1983 entitled "Sampling and Analysis Protocol for Chemical Character-
istics of Lakes and Streams Sensitive to Acidic Deposition." The draft
document was circulated widely for peer review. The present revision has been
guided by the many thoughtful and helpful comments which were received. In
addition, the recent development of the "Methods Manual for the National
Surface Water Survey -- Phase I" (Hillman et ah, undated), has provided
further guidance. This revision attempts to achieve compatibility with the
survey protocol to the extent possible.
This monitoring protocol addresses measurements to be made, selection of
study sites (Appendix B), sampling protocols, sample storage and preservation,
analytical methods, quality assurance, and data management. Consideration of
these topics is limited here to studies of water chemistry only. We recognize
also the need for concurrent biological studies in long-term monitoring
programs where the primary objective is detection of ecosystem change.
Approaches to biological monitoring in lakes and streams were considered at an
1
-------
EPA-sponsored workshop, and work on a protocol is being pursued by another
group.
Those primarily responsible for the content of the original version of
the protocol were Owen Bricker, U.S. Geological Survey; George Hendrey,
Brookhaven National Laboratory; Raymond Herrmann, U.S. National Park Service;
Vance Kennedy, U.S. Geological Survey; Harvey Olem, Tennessee Valley
Authority; Charles Powers, U.S Environmental Protection Agency; Arthur
Schipper, U.S. Department of Agriculture ~ Forest Service; and Kent
Schreiber, U.S. Fish and Wildlife Service.
We thank the many other persons who contributed their expertise during
the evolution of this protocol, and those who provided reviews.
I. Measurements
A. Fundamental Variables
The variables to be measured depend in part on the objectives
of the study. For general monitoring, the following measurements
provide sufficient characterization of stream or lake water quality
for assessment of sensitivity and changes related to acidification:
These "core" measurements provide documentation of the status of a
stream or lake. Buffering capacity and acidity are determined by
measurement of pH, alkalinity, and conductivity. Presence of color
may indicate natural acidity (as well as possible interferences in
sulfate determination), and presence of naturally-occurring
chelators. Measurement of the major ions provides data for modeling
exercises, cation-anion balance calculations, and indication of
strong acids.
Aluminum is the metal of greatest concern because of its role
as a toxicant and buffer. General agreement does not exist as to
the form of aluminum most appropriate for measurement in monitoring
and survey programs. Choices include total aluminum, total soluble
aluminum, and extractable aluminum. Total aluminum is a gross
measurement that includes both dissolved and particulate forms, a
PH
total alkalinity
specific conductance
temperature
true color
Ca, Mg, Na, K, A1
S04, N03> CI
secchi disc transparency (lakes)
2
-------
great deal of which is non-reactive. Dissolved aluminum entails
filtration, ideally through a 0.1 |jm filter to retain the maximum
amount of particulate material, which can be extremely difficult in
some waters. Determination of extractable aluminum does not require
that degree of filtration, and yields a useful approximation of the
quantity of reactive aluminum present. Procedures for determination
of both the total soluble and extractable forms are given in this
document.
B. Additional Variables
It was the opinion of a number of the contributors to this
document that long-term monitoring studies should include additional
measurements to provide an understanding of the processes involved
in observed changes and to facilitate relation of those changes in
water chemistry to observed effects on biota. These measurements
largely focus on metals and metals chemistry. The recommended
additions are:
(Note: all metals determinations are for the dissolved forms; see
Section III).
These additional measurements, together with the core set, were
considered to constitute a minimal group for evaluation of geo-
chemical kinetics and toxicity at extended study sites. Information
on aluminum together with silica is necessary to understand silicate
mineral weathering and precipitation processes. There is some
evidence that manganese may be toxic to biota at levels observed in
acidified waters. Both dissolution and precipitation of iron and
manganese oxides may have significant effects on the concentrations
of other metals. Fluoride, phosphate, and DOC are important in
complexing aluminum and hence affect its action as a toxic agent.
These additions add to the complexity and expense of a monitor-
ing program and would have to be carefully justified in terms of the
use for which the data were intended. Process studies imply use of
Mn
Fe
Si02
F
Total P (dissolved)
DOC (dissolved organic carbon)
ammonia
weak and strong acidity
3
-------
calibrated watersheds, with development of input-output budgets;
monitoring sites do not have to be this elaborate. Systematic
measurement of the core variables can yield useful information on
changes in lakes and streams related to acidic deposition. The
additional variables allow investigation and interpretation of the
processes associated with these changes, but are not necessary for
detection of the change itself. Consequently, some monitoring
efforts will include all or some of the additional protocol, while
others will consist of the core measurements only. Programs
following the latter course would be able to add collection of
additional information in the event that biotic effects, for
example, began to appear.
II. Selection of Study Sites (see Appendix B)
A.	A detailed written description of each site is required. This
should include catchment area, bedrock geology and soil class(es) of
the watershed, stream order, mean annual discharge of stream, size
of lake or pond (area, depth, volume), residence time of lake or
pond (if known), whether seepage or f1ow-through, altitude of site,
general existing land use in watershed, and available historical
data on land use and water quality. In the field, any recent
changes in land use should be noted, together with an estimate of
percent of bedrock exposure in the watershed, and descriptions of
any other features such as pollution sources, old mine workings, and
nearby emission sources. (Such features, of course, would probably
eliminate the site as a monitoring location). Detailed geologic and
soils maps should be made for extended study sites, if such maps are
not otherwise available. Meteorological features should also be
noted, including mean annual precipitation, percent precipitation as
snowfall, evaporation and transpiration, and air temperature.
B.	Lake Monitoring
Each long-term lake monitoring project will consist of a set of
lakes located in the same geographical area, in geologically similar
conditions, exposed to essentially the same precipitation regime.
They should be "headwater" lakes, selected to provide a range of
4
-------
DRAFT
alkalinity values representative of the area, with average total
alkalinity values less than 200 peq/1. Lakes in the 200-500 peq/1
alkalinity range, while less sensitive, should be included for
comparison with those of lower alkalinities. This can be particu-
larly important with respect to fish populations, where decreases in
numbers could result from causes other than acidification.
C. Stream Monitoring
Monitoring is more complex for streams than for lakes because
of the influence of discharge and season. Base flow tends to
display uniform, representative composition, but storm flow and
snowmelt runoff may significantly alter stream chemistry. Some
recent observations have shown severe pH depressions in streams
following storm events, after which conditions return to base flow
conditions. Proper stream monitoring, therefore, requires contin-
uous recording of flow and sampling over a complete range of
discharge. This should include sampling during and following storm
events and snowmelt. This may necessitate the use of automated
sampling equipment, the occurrence of meteorological events often
being difficult or impossible to anticipate sufficiently far ahead
of time to permit adequate manual sampling.
III. Sampling and Analysis
A. Streams
1. General
Sampling will be confined to headwaters. No attempt is
made here to specify order of stream; selection should be a
function of the particular area of interest. Large streams and
rivers are poor sites because the effects of acidic deposition
are frequently masked downstream by the mixing of waters from
various tributaries and by other riverine processes.
As previously pointed out, the chemistry of streams is
strongly influenced by discharge and season. Base flow usually
displays the most uniform composition and represents water that
has had maximum interaction with watershed materials. For
survey purposes, sampling of base flow may be adequate, but in
5
-------
monitoring samples should also be taken during events (storm,
snowmelt) to provide information on changes in stream chemistry
as a function of discharge and of season. A range of flows and
seasons should be sampled.
Samp!ing
Streams should be sampled according to the following
procedures (which apply to grab sampling only, not automatic
sampling):
(a)	Measure or estimate stream discharge at time of sampling,
and note whether rising or falling.
(b)	Collect sufficient sample for requirements listed below
from mid-depth of main flow channel. Rinse container
thoroughly three times with stream water before taking
sample.
(c)	Pour appropriate amount of sample into plastic beaker for
£H measurement.
(d)	Record temperature and measure jgH in the field as soon
after sampling as possible.
(e)	Obtain sample for anion analysis (including S04, N03, CI):
Rinse a 250 ml (acid washed and distilled water rinsed)
polyethylene bottle (see Section IV) three times with
sample water which has been filtered directly into the
sample bottle (discarding each rinse). Then fill to 250
ml with filtered sample. Use a 0.45 [jm pore size membrane
filter (e.g., Nucleopore polycarbonate). If filtration
cannot be done in the field, samples should be iced or
refrigerated immediately and filtered in the laboratory as
soon as possible. A good portable unit for filtering
samples at field sites is described by Kennedy et al.
(1976).
(f)	Obtain sample(s) for metals analyses (including Ca, Mg,
Na, K: Filter 100 ml of sample into an acid-washed
plastic bottle after rinsing by passing 100 ml of sample
through filter and discarding (three times). Add 1 ml
ampoule of concentrated ultrapure nitric acid to the
6
-------
sample. Ice or refrigerate. For dissolved A1, Mn, and Fe
a 0.1 pm pore size filter is recommended to achieve the
greatest possible degree of separation of particulate and
dissolved material. (In reporting results, always specify
filter size, brand, and model number).
(g)	PROVISIONAL. Obtain samples for extractable aluminum
(reference: Hillman et al_.). In the field:
(1)	Filter about 60 ml of sample through a 0.45 pm
polycarbonate filter.
(2)	Rinse a clean plastic 50 ml graduated centrifuge tube
with three 10 ml portions of the filtered sample,
then fill to the 25.0 ml mark.
(3)	Add 2-3 drops phenol-red indicator and 5.0 ml of
8-hydroxy-quinoline sodium acetate reagent.
(4)	Add 2.0 ml of the NH4/NH3 buffer. This should adjust
the pH to 8.3 and the solution should turn red. If
it does not turn red, rapidly adjust the pH by
dropwise addition of 1 M NH40H until the solution
changes color to red. Add 6.0 ml of methyl isobutyl
ketone (MIBK), cap, and shake vigorously for 7-10
seconds using a rapid, end-to-end motion (note:
successful extraction depends on good agitation).
(5)	Allow the phases to separate (10-15 seconds), then
remove the MIBK layer with a 1 ml micropipet,
transfer to a 10 ml centrifuge tube, and cap tightly.
See Appendix A for preparation of extractable aluminum
reagents.
(h)	Sample blanks should be included with every tenth field
sample, both acidified and non-acidified, using high
quality deionized water (conductivity <0.1 ymho/cm). For
blanks to accompany acidified samples, prepare one
acidified deionized water sample and one non-acidified
deionized water sample. The total number of blanks of
each type should be £ 3 for any given "set" of samples.
7
-------
B. Lakes
1. General
DRAFT
Lakes should be sampled near their deepest points at least
20 m from shore. If the water column is not thermally strati-
fied, one sample should be collected approximately one-half
meter beneath the water surface. If the water body is strati-
fied, one sample should be collected approximately one-half
meter beneath the water surface and a second half-way between
the thermocline and the lake bottom. A plastic closing
sampling device of the Van Dorn type should be used to obtain
samples at depth; do not use a metal sampler. A means for
measuring subsurface temperature is necessary to locate the
thermocline; this requires an instrument capable of _in situ
measurement, such as a thermistor equipped with a sufficiently
long lead. Samples should be collected from the sampling
device in plastic bottles treated according to the procedure
described in Sections III-A and V-A. Near-surface samples can
be taken by simply dipping the plastic bottle directly into the
lake (taking care not to sample the surface film).
Minimum sampling intervals for lakes are (1) prior to
summer stratification (for ice-covered lakes, the period of
snowmelt runoff); (2) during summer stratification; and (3)
during the completely mixed conditions following summer
stratification (fall overturn). Spring sampling of northern
lakes during snow-melt is not an easy task. Access to lakes
can be difficult, and proper timing is uncertain. However,
data from Adirondack lakes show that the period of pH and
alkalinity depression during snowmelt may last for approxi-
mately two weeks, increasing the probability of obtaining data
during that event. The importance of this period in the
acidification history of lakes emphasizes the desirability of
its inclusion in the sampling schedule.
2. Sampling
Follow steps c - g under "Stream Sampling" (Section
III-A-2) for processing of samples.
8
-------
DRAFT
IV.	Sample Containers	pel^f*0'
Linear polyethylene bottles with (jrilJHHF-caps are recommended.
Because of the very dilute waters being considered here, and the conse-
quent enhancement of contamination problems, acid rinsing of all bottles
used for major ion chemistry samples, as well as for metals samples, is
required. All plasticware will be rinsed three times with deionized
water, rinsed three times with 3N HN03 (prepared from Ultrex HN03), then
rinsed six times with deionized water. Let stand for 48 hours with
deionized water. Empty and refill with deionized water; keep filled
until use in field, preferably refrigerated in the dark. Check 10
percent of the containers for adequacy of rinsing by measuring the
conductivity; it should be < 2 nmho/cm. If any containers fail the
check, rerinse all and retest 5 percent.
V.	Sample Preservation and Maximum Holding Times (Reference: USEPA, 1979;
Hillman et al.)
A.	Refrigeration at 4°C is the only recommended method of perservation
for the following constituents. (Maximum allowable holding time
appears in parentheses.) For present purposes, icing must be
considered equivalent to 4°C refrigeration.
specific conductance (14 days)
color (48 hr)
pH (no approved holding time; sample should be analyzed in the
field as quickly as possible)
alkalinity (14 days)
extractable aluminum (7 days)
sulfate (28 days) lor,-de O f cWs)
silica (28 days)	'
nitrate-nitrogen (7 days)
B.	Refrigeration at 4°C plus acidiication with sulfuric acid to pH < 2
is recommended for the following constituents.
calcium (6 months)
magnesium (6 months)
sodium (6 months)
potassium (6 months)
total dissolved phosphorus (28 days)*
9
-------
ammonium (28 days)*
VI. Analytical Procedures (Core Measurements)
A.	Temperature and pH must be measured immediately upon sampling. (pH
may also be air-equilibrated and measured a second time in the
laboratory; see below.)
B.	pH
1. Field Measurement
pH should be measured to ± 0.02 units using a high quality
pH meter with an expanded or digital scale. A good electrode
is the Corning No. 476182 glass combination. The electrode
should be calibrated in the field in pH 4 and 7 buffer solu-
tions and checked with a sulfuric acid solution with a theoret-
ical pH of 4 (5 x 10-s molar H2S04). Rinse probe copiously
with sample or distilled water and immerse in sample. Do not
stir. The electrode should remain in the sample until there is
no discernable drift in the pH reading, but no longer than 15
minutes. Upon completion of measurement, recheck pH of acid
solution, rinse, and calibrate with buffer. Perform in
replicate.
2. Laboratory (Air-Equilibrated) Measurement
For normalization of pH values obtained by various participat-
ing investigators, air-equilibrated pH measurements should be
obtained in the laboratory. Equilibration is achieved by bubbling
samples with standard air containing 300 ppm C02 for 20 minutes
while stirring on a magnetic stirrer. Use an acid-washed fritted
glass diffuser for dispersal of air in the sample. Measure pH
immediately following equilibration, following procedure in B-l
(above).
* USGS and NPS preserve with HgCl3.
10
-------
DRAFT
3.	Specific Conductance (pmho/cm at 25°C)
Measured in the laboratory on a wheatstone bridge type
conductivity meter. After calibration and prior to measuring
the first sample, measure the conductance of a standard with a
theoretical or certified conductance of about 50 pmho/cm
(0.0005 M KC1 has a conductance of 73.90 pmho/cm at 25°C). It
must be prepared from a stock solution which is different from
that from which the calibration standard is prepared. If the
measured conductivity does not lie within ± 10 percent of the
certified value, then restandardize the meter and cell and
repeat the measurement.
Remeasure the conductance of the standard at least every
10 samples. If the measured value does not lie within ± 10
percent of the certified value, restandardize the meter and
cell, repeat step 1, then reanalyze the previous 10 samples
(reference: Hillman et aK ).
4.	True color. Comparison of centrifuged sample with platinum-
cobalt color standards. (Reference: USEPA, 1979)
5.	Total alkalinity. Titration with 0.020 N H2S04 using Gran plot
calculations. Fixed endpoint titration is not acceptable.
(References: Gran, 1950, 1952; Golterman and Clymo, 1969;
Zimmerman and Harvey, 1978-1979)
6.	Calcium, magnesum, sodium, and potassium. Atomic absorption
spectrometry, direct aspiration. (Reference: USEPA, 1979)
7.	Sulfate, chloride, nitrate. Ion chromatography.
8.	Phosphorus. Colorimetric, automated, block digestor AAII
(USEPA, 1979), or USGS colorimetric, phosphomolybdate, auto-
mated (Hillman et aTL).
9.	Ammonia. Colorimetric, automated phenate (USEPA, 1979).
10. Kjeldahl nitrogen. Colorimetric, automated phenate (USEPA,
1979).
VII. Quality Assurance
Quality assurance and quality control procedures regularly followed
by each of the participating agencies will be a regular part of that
agency's monitoring program. All projects supported by EPA that collect
11
-------
FT
environmental data are required to submit a QA/QC plan addressing the
following points:
1.	The intended use of the data and the associated acceptance criteria
for data quality;
2.	Description of how precision, accuracy, representativeness, com-
pleteness, and comparability will be assessed;
3.	Procedures for selection of samples or sampling sites and collection
or preparation of samples;
4.	Procedures for sample handling, identification, preservation,
transportation, and storage;
5.	Description of measurement methods or test procedures with statement
of how the performance characteristics are determined if methods are
non-standard;
6.	Standard QA/QC procedures to be followed;
7.	Data reduction and reporting procedures, including description of
statistics used.
Comparability of results among various monitoring projects requires the
use of audit samples distributed by a central, independent laboratory.
The EPA monitoring program will follow procedures developed by the
National Surface Water Survey for an audit sample program. Samples with
known concentrations of the core variable, representative of the concen-
tration ranges normally encountered, will be supplied to each project
about three times each year. Results will be compiled and cross-checked
by EPA to determine comparablity of chemical results across the program.
VIII.Data Management
Each supporting agency is responsible for its own sample collection
and analysis, data analysis, data management, and data storage. Data may
be delivered to STORET, WATSTORE, ACID (Brookhaven National Laboratory)
or other data bases, providing that the data are of a routine survey or
monitoring nature which does not preclude their release. EPA will employ
the Oak Ridge National Laboratory ADDNET data base (Acid Deposition
Assessment Data Network) as a repository for monitoring data, beginning
in FY85. Annual reports will be prepared by the Principal Investigators
responsible for the monitoring projects.
12
-------
Additional Information
Requests for additional information or	copies of	this document
should be forwarded to Charles F. Powers,	U.S.E.P.A.,	Environmental
Research Laboratory, 200 S.W. 35th Street,	Corvallis,	Oregon 97333.
AF
13
-------
REFERENCES
American Public Health Association, American Water Works Association, Water
Pollution Control Federation. 1975. Standard methods for the examina-
tion of water and wastewater. 14th Edition. APHA, Washington, O.C.
Golterman, J. L., and R. S. Clymo. 1969. Methods for chemical analysis of
fresh waters. IBP Handbook No. 8, International Biological Program,
Blackwell Scientific Publishers, Oxford and Edinburgh.
Gran, G. 1950. Determination of the equivalence point in potentiometric
titrations. Acta Chem. Scan. 4:559-577.
	. 1952. Determination of the equivalence point in potentiometric
titrations. Part 2. Analyst 77:661-671.
Hillman, D. C., F. A. Morris. J. F. Potter, K. J. Cabbie, and S. J. Simon,
(undated). Methods manual for the National Surface Water Survey Project
— Phase I. Environmental Programs, Lockheed-EMSCO Contract No. 68-03-
3050 with USEPA/EMSL, Las Vegas, Nevada. Unpublished report.
Kennedy, V. C., E. A. Jenne, and J. M. Burchard. 1976. Backflushing filters
for field processing of water samples prior to trace-element analysis.
U.S. Geological Survey, Water Resources Investigations, Open-File Report
76-126. 12 p.
U.S. Environmental Protection Agency. 1979. Methods for chemical analysis of
water and wastes. Environmental Monitoring and Support Laboratory,
Office of Research and Development, USEPA, Cincinnati. EPA-600/4-79-020.
Zimmerman, A. P., and H. H. Harvey. 1978-1979. Final report on sensitivity
to acidification of waters of Ontario and neighboring states. University
of Toronto. 136 p.
14
-------
APPENDIX A

T
EXTRACTABLE ALUMINUM REAGENTS
A.	2.5 M HC1 — Dilute 208 ml 12 M Ultrex HC1 to 1 liter with deionized
water.
B.	1 M NH40H — Dilute 20 ml 5 M NH40H to 100 ml with deionized water.
C.	5 M NH4OH -- Approximate concentration of Ultrex NH40H.
D.	NH4/NH3 Buffer Solution -- Adjust the pH of 21 ml 5 M NH40H to 8.3 with
2.5 M HC1 (determine pH by testing a drop with Whatman pH paper (it
should take about 30-35 ml), add an additional 32 ml of 5 M NH40H, then
dilute to 100 ml.
E.	8-Hydroxyquinoline Solution -- Dissolved 5 g 8-hydroxyquinoline in 12.5
ml glacial acetic acid, then dilute to 500 ml.
F.	1.0 M Sodium Acetate — Dissolve 8.20 g sodium acetate in deionized water
and dilute to 100 ml.
G.	8-Hydroxyquinoline Sodium Acetate Reagent (HQX Reagent) — Mix in order,
10 ml 1.0 M NaOAc, 50 ml deionized water, and 10 ml 8-hydroxyquinol ine
solution. This solution must be prepared daily.
H.	Phenol-red indicator — 0.04%.
15
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APPENDIX B
CRITERIA FOR SELECTION OF LONG-TERM MONITORING SITES
A.	The criteria for site selection must be consistent with the objectives of
the monitoring program, which are:
1.	Determine, within a sensitive region, the response (if any) of the
chemistry and biology of lakes or of streams representing a range of
alkalinity values.
2.	Compare, between different sensitive regions, the response (if any)
of lakes and streams of similar sensitivities when those different
regions receive similar hydrogen ion or sulfate loading.
3.	Compare the chemistry of lakes and streams from a variety of regions
which exhibit various degrees of precipitation quantity and acidity.
It is important to recognize that it may not always be possible to
locate monitoring sites which satisfy all the suggested requirements
which follow; the need for flexibility must be recognized. The objective
is to choose situations in which any observed chemical or biological
change could most reasonably be attributed to effects of atmospheric
deposition; within these guidelines, the best possible efforts should be
made to achieve this. Specialized objectives of individual agencies may
act to modify certain criteria.
B.	Criteria for Selecting Monitoring Sites
1. Selection of Region
(a) Geographic Location
(1)	Should be a "sensitive" region with surface waters
commonly less than 200 peq/1 total alkalinity, since such
conditions would be the most likely to produce detectable
effects. The national alkalinity map (EPA-600-D-82-333)
is useful in locating such regions.
(2)	Major representative national sensitive regions will be
included: New England-New York, Appalachians, Upper
Midwest, Rockies, Cascades, Sierra Nevadas.
16
-------
(b)	Atmospheric H+ and S02 Loading
(1) Deposition gradients should be adequately represented;
both geographically separate sensitive regions with
similar loadings, and sensitive regions with different
loadings should be sampled. A region selected for
monitoring should receive precipitation as uniform with
respect to chemistry and quantity as possible, to
facilitate comparisons of effects at monitoring sites
within regions and of effects between regions. Areas with
local effects on weather patterns should be avoided.
(c)	Selected areas should not have a history of recent land use
changes, nor any prospects of future changes.
(d)	The region must afford remote sites, unaffected by past human
use, and which can be protected against future disruptive use.
(e)	There can be no local atmospheric pollution sources.
(f)	Sites must be accessible at key times of year, including snow
melt-ice out period.
(g)	There should be no recent history of forest fires, logging,
chemical spraying or treatment, or fish management.
(h)	If possible, choose sites where concurrent research will
provide related data.
2. Selection of Lakes or Streams Within an Approved Area
(a) Following selection of a suitable sensitive area, a set of
lakes and/or streams is selected for long-term monitoring. A
group of water bodies (rather than a single site) is monitored
because of expected lack of uniformity of response in both
chemical and biological parameters. Lakes or streams situated
close together may behave quite differently under the same
precipitation regime. Variation can occur between lakes or
streams with respect to seasonal averages, yearly averages,
diel response, year to year, etc.
The following criteria apply to selection of lakes or
streams within an approved region.
(1) Watershed Characteristics
(a) Location — headwaters only.
17
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(b) Size — Lakes: 100 mi2 or less, preferably 50 mi2 or
(c)	Minimal Human Disturbance
(d)	No Local Air or Water Pollution Sources
(2)	Accessibility. Should be able to transport equipment to
lake or stream on foot during non-winter seasons.
(3)	Average total alkalinity 200 peq/1 or less, except for a
few higher alkalinity lakes or streams (if present) as
reference points.
(4)	When other factors are equal, lakes for which historical
data are available will be chosen.
(5)	Sites should be located on "protected" land, which will
not be logged, developed, farmed, or managed for any other
purposes.
(6)	Elevation should be considered, where appropriate, to give
a representative range of heights above sea level.
(7)	There should be an NTN site, or its equivalent, repre-
sentative of the study site.
3. Where monitoring projects include "process" studies, measurements on
ground water, as well as surface waters, should be included. Most
of the foregoing site selection criteria would apply to ground water
monitoring.
less.
Streams: headwater streams with small
watersheds.
FT
18
-------
Appendix II. Quality Assurance/Quality Control Procedures and Data
as Reported by Cooperating Agencies and Institutions.
-------
Montana State University
-------
Surface Water Analysis Assessment
Gordon K. Pagenkopf
Department of Chemistry
Montana State University
July 1984
Die following presents data and assessment of the analytical
parameters currently being utilized to analyze the surface water samples.
The fourteen parameters include: temperature, pfi, specific conductance/
color, Na, K, Ca, Mg, Al, HJ4+, HOO3-, S042~, a" and NO3- T*ma>rature;
typical values fall in the 0° to 20° centigrade range. The
reproducibility of the measurement utilizing thermometers is ±0.5°C.
Both field and laboratory pH meters are standardized; pH = 4.00 and
7.00 at 25.0°C Ofce electrodes (e.g. Altex) are effective at low ionic
strength and a reproducibility of 0.02 units is obtainable provided there
is not temperature variation. Field calibration and measurement are
conducted at temperatures other than 25.0°C and thus a corresponding
adjustment needs to be made to report the value for 25.0°C
Specific Conductance: The specific conductance instrument is calibrated
with 1.0 x 1(T* m KC1. The conductance values are converted to the
25.0°C specific conductance values using the 0.010 H KC1 data.
Color: The color is obtained by comparison to the platinum-cobatores-
chloride standard. The waters have low concentrations of colorful
molecules and thus the standard curve goes from 0 to 10 units. The pH is
monitored but in general does not vary. The experimental variability is
± 1 color unit.
1
-------
Ca. Ma. Ua and £: These metals are determined using atomic absorption
spectrophotometry. The results of representative triplicate analysis are
summarized in the following table. Ihe range represents the average
deviation from the mean.
Metal	Sample msZl	Analysis isZl
Ca	6.00	5.96 ± 0.09
3.00	2.64 ± 0.02
Ng	4.00	3.99 ± 0.01
2.00	1.94 ± 0.02
Na	4.00	3.78 ± 0.02
2.00	1.94 ± 0.03
K	1.00	0.96 ± 0.01
0.50	0.48 ± 0.01
Aluminum: a spectrophotometry procedure (Eriochrome Cyanine R Method)
is utilized as described in Standard Methods; triplicate analysis was
conducted.
¦OaiB|p1» uy/l	AnalytHa. ug/1
6.00	6.34 ± 0.08
12.00	12.96 ± 0.08
Ammonia; A spectrophotometry procedure (phenate method) is utilized;
triplicate analysis.
Sampler ueqv/1	Analysis, ueqv/1
0.20	0.24 ± 0.02
0.40	0.46 ± 0.03
2
-------
Bicarbonate: This is determined by Gran Plot, triplic^j^analysis.
Samplei^g^	Analysis,
60.0	63.4 ±3.0
£1", ND3~. S0^2~; These were determined utilizing ion chromatography,
triplicate analysis.
CI":
SamDle. ma/1
Analysis, jngZl

2.0
2.14 ± 0.49

4.0
3.97 ± 0.34
NO3":
Sampler w/1
Analysis, mg/I

2.0
2.17 ± 0.23

4.0
3.86 ± 0.33
S042-;
Sample, ma/1
Analysis, jngZl

2.0
2.02 ± 0.29

4.0
4.15 ± 1.01
3
-------
University of Minnesota
-------
Besults
The fall 1983 survey of cluster lakes In the Upper Great lakes
states began November 1, when seven lakes were sampled in Minne-
sota. The 13 Michigan lakes were sampled between November 3 and
5# and 11 of the 13 Wisconsin lakes were sampled between November
6 and 8* Stormy weather delayed sampling the remaining two lakes
(Long and Camp Twelve) until November 14. Total loe cover.condi-
tions were narrowly averted on Camp Twelve Lake; extnsive shore
loe was broken through to obtain the samples.
Only one lake (Cruiser, MN) was not well-mixed at the time of
sampling. Temperature was decreased, oxygen partially depleted
and conductivity slightly elevated below 15 a. A bottom sample
was oolleeted at this lake. Profiles of temperature, dissolved
oxygen, and conductivity for all otheiv lakes indicated uniform
oondltions throughout the water oolumnfr'except for readings just
off the bottom. Dissolved oxygen oonoentrations generally were
near saturation.
Field data are summarized for each state duster and for the
entire data set in Table 3* The Seeehl disk was visible at the
bottom in nine lakes: four in Michigan and five in Wisconsin.
"Field" measurements of pH and conductivity were made eaoh day
Immediately on return from the field (maximum elapsed time 10 h),
without bringing the samples to room temperature.
Besults for physical and ohemloal analyses on the duster lakes
samples oolleeted in fall 1983 are oompiled in Table 4. Because
the results represent only one point in time, little oan 'be said
regarding environmental interpretation of the results, and ob-
viously it is premature to disouss temporal trends. Table 5
presents results for pH, alkalinity and oonduotlvlty on the lakes
for fall 1982 (sampling by ERL-D) and mean values for all pre-
vious data on the lakes (from previous ERL-D studies). In gen-
eral, previous results compare favorably with those from fall
1983. One exoeptlon was noted in the oase of Lake Vanderoook
(B232), whloh had a higher alkalinity In fall 1983* Baw data
from this titration were reoheoked, and the result reported is
oorreot for the sample. We will oontinue to olosely monitor data
from this lake In ensuing sampling periods to determine whether
the change is real or the sample was nonrepresentatlve.
Besults from the quality assurance program are summarised in
Tables 6-9. Duplicate samples were obtained on three lakes as
part of the fall 1983 aampling, and results for the pairs of
samples are listed in Table 6. (Besults for these lakes reported
in Table 4 are averages of the sample duplicates.) In .general,
sample duplicates compare quite favorably, exoept for parameters
near the analytical deteotlon limits (ammonium and SBF) and for
sodium, for whloh there seems to be a contamination problem of
unresolved origin.. Analytical duplicates are very good in all
cases; representative results are summarised in Table 7. These
results represent pairs of analyses performed on the same sample
bottle during the same analytical run. In all oases analytical
9
-------
duplicates agree within a few peroent.
Subs of oatlona and anlone (In ueq/L) are listed In Table 8.
along with the difference between oatlon and anion equivalents.
Fairly large differences were noted in some oases. These differ-
enoes may result fron several factors, and reasons for Individual
oases oannot be delineated at thla time. In brief, the differ-
enoes aay refleot (1) the presenoe of other lnorganlo oatlons
and/or anions In the samples besides the ones Included in the
summations, (11) analytical errors, (ill) differential contamina-
tion problems between anion bottles and oatlon (metal) bottles,
and (Iv) presence of organlo oolor in varying concentrations,
which contributes an unmeasured amount of anionic equivalents to
samples. Based on analysis of potential causes, it appears that
analytical errors per ae are not the major cause for the observed
differences. Analytical precision was high, and good agreement
was obtained with EP1 quality control samples (see Table 9)*
Sample contamination likely is a partial factor; some sample
"blanks" (Table 9) were high for some parameters (Ca^* and Ha*)
contributing to the general over-abundance of oatlons. We traoed
some of the problem of high blanks to distilled water from the
DRR lab and have replaoed this with DM deionized water In 1984
samplings. Blank problems also may be caused by the filters used
for the various samples; we are currently evaluating the need for
prevashlng of all filters used in the sampling scheme. At least
part of the differences between cation and anion equivalents
stems from the occurrence of organic oolor in many of the lake
samples. A correlation between color and the difference between
cation and anion equivalents explained about 50% of the varianoe
In the data.
Ve recently received a voluminous printout of all data from the
lake sampling program conducted at ERL-D since 1979# and we
expect to reoelve a tape of the data in the near future.
Consequently, we will be able to compare results from the present
monitoring program with previous monitoring data in the next
report and determine whether any trends or Inconsistencies exist.
Interpretation of the results wll become increasingly more
mealngful and assignment of causes to apparent outllera will
become easier as the temporal record on the lakes inoreases.
18
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Table 6. Results for sample duplicates taken from three lakes In fall 1983.
SNUM
U456
U456
U627
U627
R301
R301
I
LAKE I
NAME t
lasaassea |
GARLING	I
GARLING	I
NEVINS	I
NEVINS	I
GREATER	I
GREATER	I
(DNR)
pH
I 4.54
I 4.54
7.01
7.03
5.04
5.85
pH
4.58
4.51
6.95
6.94
5.81
5.75
(DNR)
EC 25
(umho/c
:ses ssss ssss
24.1
24.1
29.5.
2B.9
18.2
18.0
EC 325C COLOR ALK C» Mg Na	K
(umho/c (pcu) (ueq/1)(mg/1) (mg/1) tmg/1> (mg/1)
BssaasBBBBuuBBBesBeaaBaeaatasaaBameacanBVsas
23.0
23.0
30.4
31.4
19.9
18.8
29
31
14
14
39
37
-6
-17
151
172
32
27
1.24
1.29
3.B6
3.96
1.44
1.3?
0.47
0.45
0.80
0.82
0.54
0.56
1.25
2.32
1.74
1.28
2.37
1.71
0.33
0.32
0.17
0. IB
0.40
0.43


I



SNUM
LAKE
1 S04
CI
N03
N02

NAME
1 (mg/1)
(mg/1)
(ug/1)
(ug/1
KaaaftesasBaaa
I laaBBaaa
MB8sat*s*e
easseaa
•sasat
U456
GARLING
1 4.77
0.46
126
ND
U456
GARLING
1 4.84
0.33
114
ND
U627
NEVINS
1 6.18
0.35
32
ND
U627
NEVINS
I 6. IB
0.37
39
ND
R301
GREATER
1 5.02
0.90
9
ND
R301
GREATER
1 5. OB
1.03
12
ND

¦«faaaaaa
aBasass
sssssaasaes
VBssa:
NH4 P04 F Si 02 A1
jq/1) (ua/1) (ma/1) (ma/1) (ua/1)
55
20
19
2
20
12
1
3
2
1
1
4
0.05
0.04
0.03
0.05
0.03
0.04
0.10
0. 12
0. 18
0.18
0.42
0.36
21.
20.
8.
10.
27.
26.
Mn
(ug/1)
Mneaatai
25.5
24.2
0.2
0.4
0.7
0.7
Fe
(ug/1
tasesaa
20.
22.
5.
7.
100.
87.
DOC
) (mg/1)
7
2
4
0
O
9
7.6
5.5
10.7
6.5
7.2
4.5

-------
Table 7. REPRESENTATIVE RESULTS FDR LAB DUPLICATES
FOR CLUSTER LAKES FALL 19B3 SAMPLES:
SNUM
I Ca
Mg
Na
K
S04

ii
ii
ii
ii
ii
ii
it
ii
u
========
=========

======
SI
I 2.55
1.13
1.60
0.73
4.42

i 2.53
1. 14
1.59
0.74
4.48
S2
i 4.56
1.65
3.02
0.68
3. 19

! 4.56
1.64
3.02
0.69
3. 19
S3
1 1.27
5.16
2.53
0.66
4.57

i 1.29
4.90
2.51
0.67
4.57
S4
t 1.32
1.16
2.47
0.56
3.58

1 1.32
1.16
2.49
0.56
3.70
S5
1 1.07
1.02
1.78
1.00
4.06

I 1.07
1.02
1.7B
1.02
4.06
P04
3. 1
3.0
1.8
1.9
O. 3
0.3
0.3
0.3
15
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Table 8. Sums of cation and anion equivalents
and differences between sums for the
fall 1983 cluster lakes samples


, TOTAL
TOTAL

SNUM
LAKE
"CATIONS
ANIONS
C-A

NAME
(meq/1)
(m»q/l)

R2C=SS==CSESB
mi strsss&sass
BStBSSSS

B300
CRUISER
0.21B5
0.20B0
0.0105
B300
CRUISER
0.2557
0.2028
0.0529
B303
SPRING
0.3998
0.3941
0.0056
B30B
SHOEPAC
0.3594
0.3104
0.04B9
B312
LOITEN
0.3575
0.3356
0.0218
B313
LOCATOR
0.3541
0.2908
0.0633
B504
FRANKLI
0.6314
0.6098
0.0215
B505
LONG
1.1144
1.0596
0.0548
U456
GARLING
0.1966
0.1022
0.0943
U474
MONDCLE
0.4014
0.3850
0.0163
U501
JOHNSON
0.1545
0.1420
0.0124
US02
ANDRUS
0.2109
0.1691
0.0418
U553
KELLY
0.1847
0.1154
0.0692
U555
MURRAY
0.1651
0.1103
0.0548
U556
BASS
0.2402
0.20B8
0.0313
U557
BUCKEYE
0.3241
0.2712
0.0529
U565
STUART
0.1593
0.0921
0.0672
U567
CHRIS BR
0.3545
0.3152
0.0392
U625
CUSINO
0.1853
0.1171
0.0681
U627
NEVINS
0.3459
0.3023
0.0436
U717
McNEARN
0.1713
0.1323
0.0390
R033
LONG
0.1468
0.1064
0.0403
R033
LONG
0
0.015
-0.015
R0B6
SUNSET
0.1466
0.1356
0.0110
R146
CLARA
0.3251
0.2717
0.0533
R232
VANDERC
0.1522
0.2002
-0.047
R301
GREATER
0.2250
0.163B
0.0611
R434
SAND
0.1870
0.1808
0.0062
R473
CLEAR
0.1807
0.113B
0.0668
R513
NICHOLS
0.2366
0.1325
0.1040
R701
LUNA
0.2127
0.1353
0.0773
RB03
C TWELVE
0.1171
0. 1110
0.0060
RB17
McGRATH
0.1457
0.1245
0.0212
RB25
SUGAR C
0.1775
0.1746
0.0028
RB61
MORGAN
0.1866
0.1510
0.0356
esse
==-===—=*
SB SSSSSSS
SS&BSSS

-------
Table 9. Results for "blank bottles" and EPA quality control reference sample for fall 1983
cluster lakes analyses
5NUM
i 1
LAKE I,
pH !
COLOR
ALK Ca
Mg
Na
K
S04
CI
N03
N02
NH4

NAME 1;
(pcu)
ft '
(ueq/1)(mg/1)
(mg/1)
(mg/1)
(mg/1)
(mg/1)
(mg/1)
(ug/1)
(ug/1)
(ug/1)
=====
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0.00
0.00
0.00
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0.35
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32
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T.V.EPAQC* 1
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0.81
1.80
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5.70

0.82
1.77
4.79
0.99
7.13
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T.V. ¦ "true value" as reported by EPA; lab « our result
-------
Appendix A
Analytical Methods
Parameter
Alkalinity
Color
Conductance
Cations (major)
Chloride
Anrnonium
Nitrate plus nitrite
Soluble reactive P
Silica
Fluoride
Dissolved organic carbon
Fe, Mn, A1
Chlorophyll
Turbidity
Sulfate
Method
Gran titration with 0.020 N HgSO^
Absorbance at 420 r*n compared to Pt-Co std.
Wheatstone bridge conductivity meter standardized
with 0.0100 M KC1
Flame atomic absorption spectrophotometry (AAS)
Automated ferricyanlde method with cross-
comparison to 1on chromatography
Automated Indophenol (Solorzano) method
Automated cadmium reductlon/diazotizatlon method
Automated ascorbic acid/molybdate method
Automated oxalic acid/molybdate procedure
Ion selective electrode
Photochemical procedure with Barnstead/Syburon
carbon analyzer
Flame AAS
Flame-less AAS for Al^ automated colorlmetric
method for monomeric A1
Acetone/DMSO extraction and spectrophotometry
Hach turbidimeter with formazin standards
Aut6mated methyl thymol blue procedure vlth
cross-comparison to Ion chromatography (changed
to ion chromatography as primary method in 1984)
19
-------
USFWS, University of Maine
-------
2
METHODS
The six lakes selected for the monitoring program are located in
Township T10SD, Hancock County, Maine (Table 1 and Figure 1). Individual
bathymetric maps of each lake are presented in Appendix 1. All lakes are
underlain by the Tunk Lake Pluton, a medium grained
hornblende-aegerine-augite-perthite granite. The surficial material is
almost exclusively granitic and was probably locally derived. The soils
are generally well-drained spodosols of the Hermon and Lyman series, formed
in till. Soils thickness ranges from 0 to >30 cm with a 3-10 cm organic
mat.
The watersheds are entirely forested with mixed hard and softwood
species. Hardwood species include paper birch, oak, beech, and red maple;
softwood species are red spruce, fir, and white pine. There are a few
seasonal dwellings on Spring River Lake, and one seldom-used seasonal
dwelling on Anderson Pond. There is no other human habitation or
disturbance in the watersheds. The northern half of the Anderson Pond
watershed burned about 1960, otherwise the vegetation in all watersheds has
been undisturbed for at least 50 years.
Each lake was sampled three times: spring overturn, summer
stratification, and fall overturn. An inflatable raft was anchored over
the deepest portion of the lake. Water samples were collected from 0.1 m
depth directly into acid-washed, distilled water rinsed and soaked linear
polyethylene bottles. A second sample was collected about 1 m above the
bottom with a clear plastic Van Dorn type water sampler and transferred to
bottles. Each sample consisted of a set of three bottles: one 500 ml, one
250 ml, and one 60 ml that contained 0.6 ml 1+1 HNOj- Water temperature
was measured immediately with a pocket thermometer. The samples were then
-------
3
carried to the road, placed in an ice chest, and transported to Orono (ca 1
hr drive).
Upon arrival at the laboratory the 250 ml sample was split into two
subsamples. One fraction was frozen for future anion analysis. The other
fraction was pressure filtered (0.40p Nucleopore polycarbonate filter).
Half of the filtered fraction was frozen for future anion analysis, and
half was acidified with nitric acid (1 ml 1+1 HNO^ per 100 ml), and stored
at room temperature, along with the unfiltered acidified sample, for future
cation analysis.
The 500 ml sample was warmed to room temperature and used for pH,
alkalinity, specific conductance, and color analyses. The pH was measured
with two different meters (Fisher model 107, Cole-Parmer Digi Sense)
equipped with Beckman Altex Futura liquid-filled combination electrodes and
recorded separately. Alkalinity was also determined in replicate by
inflection-point titration (Stumm and Morgan 1981) using the two different
meters. The pH meters were standardized against pH 7.00 and 4.01 NBS
certified buffers and checked against 5 x 10"5 M H2SO4 (theoretical pH
4.00).
Specific conductance was measured in replicate (Markson model 10
meter). The meter was standardized with the internal standard before each
reading. Color was determined in replicate by comparison of unfiltered
sample with platinum cobalt standard solution (La Motte Chemical Co.,
Chestertown, MD).
The cations sodium, potassium, iron, and zinc were measured by
air-acetylene flame atomic absorption spectrophotometry (Perkin-Elmer model
703). Calcium and magnesium were determined by nitrous oxide-acetylene
flame AAS, and aluminum and manganese by graphite furnace AAS. The
instrument was calibrated according to manufacturer
-------
4
specifications. Every tenth sample was analyzed in duplicate, and a
standard was included with every 10 samples.
Chloride, nitrate, sulfate, and fluoride were mesured using an ion
chromatograph (Dionex model 16). The instrument was calibrated at the
start of each run with 5 standards, and standards were rerun at the end of
a batch of 10 samples.
The accuracy of analytical instruments was verified by analysis of
U.S. Environmental Protection Agency Water Pollution Quality Control
Samples for Trace Elements and Minerals and spiked samples. Precision and
bias were assessed by analysis of known standards, and replicate analysis
of known standards and unknown samples.
Fish were collected once, at fall overturn, by use of a light weight
trap net, minnow traps, and an experimental gill net. Because of the
remoteness of the lakes standard trap nets could not be used. In
consultation with a professional net designer (Sterling Marine Products,
Montclair, NJ) we arrived at a light weight, portable trap net design
(Figure 2). Two nets were to be manufactured, one with 1/2 in. square mesh
and one with 1/4 in. square mesh. Only the 1/2 in. mesh net was
delivered, and that deviated from specifications. Preliminary testing was
not possible because the net was not delivered until October, 1983.
We decided to use the trap net we received in conjunction with our
standard netting protocol to establish the efficiency of the trap net. The
standard protocol included one experimental nylon monofilament gill net
(four 50 ft. by 6 ft. sections of square mesh sizes 1/2 in., 3/4 in., 1
in., 1 1/4 in.), and four standard 1/4 in. square mesh galvenized wire
minnow traps. The gill net was set perpendicular to the shore of the lake
with the small mesh end next to the shore. The net covered both the
littoral zone and deeper water. The minnow traps were placed in a variety
-------
5
of littoral areas. The trap net was set perpendicular to shore with the
lead attached to the lake shore. It was set at least 100 m from the gill
net in a similar area. The nets were set in late afternoon and lifted in
mid-morning the following day.
All fish caught were identified to species by at least two trained
fisheries scientists. The number of fish species captured was small and
most species were easily identifiable. Only a few minnow species were
difficult to identify, especially for very small individuals. Accordingly,
a few small individuals were identified only to genus. Identifiable
individuals were weighed (nearest gram) and measured (nearest mm), and
scales were removed from individuals larger than 10 cm. If more than 25
individuals of one species were captured, only the first 25 were weighed,
measured, and scale sampled. As many fish as possible were returned to the
lake alive.
-------
6
RESULTS AND DISCUSSION
Quality Assurance
The analysis of EPA Water Pollution Quality Control Samples and spiked
samples (Table 2) indicates that the measurement systems used are accurate.
Bias was generally less than ±5%. The bias for potassium sample #2 was
9.18% but this concentration (46.5 mg/1) is far higher than our normal
operating range. Potassium concentrations in our samples never exceeded 1
mg/1. the bias for aluminum results based on the EPA true value was high
for sample#4 and 5. However, other laboratories reported values similar
to ours. Bias calculated using the mean value reported by other
laboratories rather than the "true value" were less than ±5%. This
suggests that the quality control samples are contaminated, probably by
aluminum leached from the glass ampules. This is not a problem for the
high aluminum concentration in sample #6. Bias was also somewhat high for
iron (-10.0%) and zinc (-7.31%). These elements were present at very low
concentrations.
The standard deviation and precision of replicate analyses of randomly
selected samples (Table 3) also are generally quite low. Precision is
poorest for iron, zinc, and manganese, all of which are present only at low
concentrations. Precision is variable for aluminum, ranging up to ±16%,
but the average is less than ±10%. Precision for other factors is
generally less than ±5%.
Water Chemistry
The water chemistry data are presented in Appendix 2. Samples are
identified by lake name, depth (surface or depth in meters), and date of
collection. Filtered samples are denoted by an asterisk following depth.
-------
10
Table 2. Results from analysis of EPA Water Pollution Quality Control
samples.
Factor	EPA Sample True	Laboratory Results
(Units)	Number	Value	Value	Bias
pH
1
5.70
5.64
-1.05%
(units)
2
7.80
7.75
-0.64*
alkalinity
1
74.7
72.4
-3.08%
(mg/1 as CaCC^)
2
21.7
21.2
-2.30%
calcium
1
40.6
42.0
3.45%
(mg/i)
2
5.3
5.2
-1.89%
magnesium
1
8.4
8.7
3.57%
(mg/1)
2
1.8
1.8
0
potassium
1
9.8
10.7
9.18%
(mg/i)
2
2.1
2.1
0
sodium
1
46.5
47.7
2.58%
(mg/1)
2
8.2
8.5
3.66%
aluminum
4
60
79
31.66%
(pg/1)
4
83a
79
-4.82%
5
450
479
6.44%

5
460a
479
4.13%

6
800
826
3.25%

6
819a
826
0.85%
manganese
_b
26
25
-4.23%
(wg/i)




iron
_b
0.13
0.12
-10.0 %
(mg/1)




zinc
_b
26
24
-7.31%
(ng/1)
aMean value from reporting laboratories.
^Recovery from 10 spiked samples.
-------
11
Table 3. Results from replicate analysis of randomly selected
samples.
	Laboratory Results	
Factor	N	Mean Standard Precision
(units)	Deviation
Calcium
(mg/1)
magnesium
(mg/1)
potassium
(mg/1)
sodium
(mg/1)
aluminum
(ug/1)
manganese
(vg/D
7
0.67
0.009
± 2.69%
7
1.29
0.010
± 1.55%
3
1.32
0.010
± 1.52%
7
1.98
0.026
± 2.63%
8
0.97
0.007
± 1.44%
10
0.85
0.007
± 1.65%
5
0.90
0.010
± 2.22%
7
0.32
0.004
± 2.50%
7
0.43
0.005
± 2.33%
3
0.33
0.006
± 3.64%
7
0.44
0.005
± 2.27%
8
0.41
0.003
± 1.46%
10
0.45
0.003
± 1.33%
5
0.40
0.002
± 1.00%
7
0.25
0.005
± 4.00%
7
0.36
0.005
± 2.78%
3
0.26
0.006
± 4.62%
7
0.36
0.001
± 0.72%
8
0.27
0.007
± 5.19%
10
0.22
0
± 0
5
0.25
0.006
± 4.80%
7
2.46
0.015
± 1.22%
7
3.05
0.027
± 1.77%
3
2.32
0.020
± 1.72%
7
2.95
0.030
± 2.03%
8
2.41
0.029
± 2.41%
10
2.53
0.018
± 1.42%
5
2.31
0.020
± 1.73%
7
432
14.6
± 6.76%
7
251
8.6
± 6.85%
3
93
2.5
± 5.38%
7
88
5.4
±12.27%
7
45
2.6
±11.56%
6
287
6.6
± 4.60%
7
24
2.0
±16.67%
7
23
1.49
±12.96%
7
8
0.69
±17.25%
3
9
0.57
±12.67%
7
38
3.08
±16.21%
8
16
1.01
±12.63%
10
0
1.44
-
-------
12
Table 3 continued.
iron
(mg/1)
zinc
(ug/1)
pH
(units)
alkalinity
(yeq/1)
5
14
0.71
±10.14%
7
0.04
0.012
±60.0 %
7
0.14
0.012
±17.14%
3
0
0
0
7
0.01
0
0
8
0.01
0.004
±80.0 %
10
0.04
0.015
±75.0 %
7
13
1.50
±23.1 %
7
35
0.075
± 0.43%
3
0
1.52
-
7
27
0.090
± 0.67%
8
0
0.019
-
10
10
1.20
±24.0 %
5
12
1.30
±21.67%
5
50
1.78
± 7.12%
4
0
0
0
2
6.24
0.014
± 0.45%
2
5.64
0
0
2
5.68
0.007
± 0.25%
2
4.54
0
0
2
4.46
0
0
2
6.52
0.028
± 0.86%
4
5.65
0.059
± 2.09%
2
6.62
0.007
± 0.21%
4
13
1.30
±20.0 %
2
8
0.21
± 5.25%
2
54
0.21
± 0.78%
2
-26
0.56
± 4.26%
2
12
0.57
± 9.83%
2
44
0.71
± 3.25%
3
-3
0.56
±36.13%
2
33
0.07
± 0.43%
-------
State of Vermont
-------
ACID RAIN LAKES
SAMPLING DUPLICATES
Conductance	pH	Ca	Mg	Na	K	Diss. A1
Lake	(vmhos/cm)	(standard units)	(mg/1)	(mg/l)	(mg/1)	(mg/1)	(ug/1)
Little Hock
30
30
6.81
6.79
3.06
2.92
1.45
1.39
0.460
0.460
0.495
0.495
0.052
0.047
Cow Mt.
30
28
5.89
5.99
3.43
3.36
0.833
0.833
0.914
0.894
0.513
0.503
0.104
0.095
Unkrwwn
24
26
5.60
5.64
2.84
2.80
0.435
0.427
0.647
0.635
0.292
0.295
0.326
0.326
Scraerset
22
20
5.63
5.62
1.68
1.70
0.425
0.428
0.679
0.681
0.534
0.536
0.161
0.205
Sunset
16
17
6.12
6.10
1.58
2.38
0.375
0.373
0.795
0.803
0.209
0.216
0.048
0.033
Beebe
20
20
4.78
4.80
1.00
0.98
0.325
0.325
0.577
0.577
0.392
0.326
0.382
0.386
Strattcn
16
16
6.01
5.92
1.55
1.45
0.341
0.343
0.556
0.530
0.459
0.432
0.108
0.115
Little
27
27
5.10
5.05
1.16
1.18
0.267
0.267
0.601
0.605
0.653
0.568
0.143
0.208
Mansfield
30
30
6.46
6.43
2.60
2.67
0.490
0.498
0.355
0.355
0.310
0.307
0.070
0.095
Grout.
18
18
6.06
5.92
1.37
1.39
0.378
0.382
0.660
0.720
0.273
0.273
0.055
0.057
Oanore
32
32
7.24
7.24
3.60
3.56
0.452
0.444
1.68
1.45
0.443
0.436
0.025
0.031
Little
19
19
5.23
5.21
1.16
1.15
0.309
0.302
0.712
0.710
0.564
0.530
0.082
0.100
Branch
19
19
4.66
4.67
0.725
0.765
0.272
0.274
0.510
0.520
0.393
0.393
0.135
0.137
Little Averill
26
26
6.76
6.86
3.31
3.36
0.524
0.524
0.803
0.800
0.287
0.287
0.018
0.020
Sunset
18
18
5.96
5.96
1.47
1.49
0.363
0.365
0.870
0.898
0.225
0.225
0.038
0
Grout
19
19
6.32
6.29
1.54
1.48
0.363
0.363
0.592
0.586
0.501
0.501
0.018
0.026
Cole
29
29
6.37
6.40
1.98
1.96
0.585
0.585
1.67
1.70
0.691
0.695
0.024
0.022
Hardwood
20
20
6.03
6.02
1.84
1.82
0.465
0.465
0.456
0.462
0.170
0.158
0.095
0.053
S
0.
60
0.0396

0.139

0.0104

0.0406

0.0196

0.0173

n (pairs)
18

18

18

18

18

18

18

95% C.I.
±1.
26
±0.083

±0.291

+0.0218

+0.085

±0.0412

+0.0364

-------
ACID RAIN LAKES
SAMPLING DUPLICATES
Color (Spectro) Color (Visual)	Alkalinity	N02~N03	S04	CI	TP
Lake	(Pt-Co, units)	(Pt-Co, units)	(mj/1)	(mg/1)	(irej/1)	(mg/1)	(mg/1)
Little Hock
6
6
10
10
8.16
8.07
0.018
0.029
5.71
5.72
0.67
0.69
0.009
0.007
Cow Mountain
46
46
40
40
6.74
7.09
0.081
0.077
6.14
6.28
0.68
0.67
0.018
0.024
Unknown
44
44
40
40
1.54
1.56
0.172
0.166
7.43
7.61
0.71
0.75
0.005
0.003
Somerset
37
37
20
20
0.94
0.84
0.184
0.194
5.49
5.50
0.63
0.62
0.024
0.011
Sunset
23
23
10
10
0.75
0.71
0.044
0.067
4.69
4.72
0.78
0.77
0.005
0.007
Beebe
85
85
30
30
-0.91
-0.94
0.217
0.216
5.19
5.32
0.58
0.56
0.013
0.012
Strattcn
17
—
10
10
0.92
0.90
0.206
0.205
3.78
3.75
0.47
0.45
0.012
0.013
Little
25
25
0
0
-0.22
-0.25
0.141
0.145
5.76
5.74
0.44
0.44
0.008
0.007
Mansfield
31
31
20
20
5.85
5.70
0.023
< 0.020
6.83
6.86
0.29
0.28
0.009
0.010
Grout
28
28
10
10
0.99
1.01
< 0.020
< 0.020
4.69
4.74
0.49
0.49
0.007
0.008
Osnore
30
30
20
20
7.36
7.94
< 0.020
< 0.020
5.38
5.38
0.63
0.66
0.030
0.026
Little
0
0
0
0
-0.19
-0.03
0.056
0.044
5.90
5.92
0.42
0.38
0.016
0.014
Branch
30
30
30
30
-0.84
-0.83
<0.020
<0.020
5.01
5.10
0.34
0.31
0.014
0.015
Little Averill
10
10
0
0
6.50
6.31
< 0.020
<0.020
5.12
4.99
< 0.20*
<0.20*
0.008
0.008
Sunset
3
3
0
0
0.72
0.69
< 0.020
<0.020
5.08
5.06
0.22*
0.21*
0.008
0.009
Grout
10
10
10
10
1.75
1.76
<0.020
<0.020
4.23
4.20
<0.20*
<0.20*
0.006
0.008
Cole
11
11
0
0
2.18
2.15
< 0.020
< 0.020
6.31
6.76
1.72
1.21
0.007
0.006
Hardwood
25
25
10
10
1.05
1.02
<0.020
<0.020
5.59
5.55
0.35
0.35
0.017
0.019
S
0

0

0.126

0.0073

0.092

0.094

0.0026

n (pairs)
17

18

18

9

18

15

18

95% C.I.
0

0

±0.264

+0.0166

+0.193

±0.201

±0.0056

* = value may be in error
-------
ACID RAIN LAKES
SPIKED SAMPLES


N02-N03


S°4


CI



(mg/1)


(mg/1)


(mg/1)


Lake
Spiked

lake
Spiked

lake
Spiked


Value
Value
% R
Value
Value
% R
Value
Value
% R
Big NLid
0.10
1.02
101
7.8
9.84
74.8
0.88
2.60
94.6
Holland
0.07
1.01
103
6.7
9.29
95.0
0.62
2.14
83.6
Little
0.59
1.38
86.9
5.1
7.80
99.0
0.49
2.21
94.6
Cole
0.02
0.237
95.5
5.7
7.69
73.0
1.9
3.56
91.3
^heeler
lily
0.06
0.272
93.3
6.5
8.60
77.0
0.58
2.23
90.8
<0.02
0.201
—
5.8
8.52
99.7
0.46
2.06
88
Unknown
<0.02
0.219
—
6.2
8.44
82.1
0.34
2.05
94.1
Stamford
0.03
0.212
80.1
5.8
8.08
83.6
0.50
2.60
115.5
Osnore
< 0.02
0.208
—
5.6
8.07
90.6
^ 0.26*
1.76
—
Sucker
<0.02
0.238
—
5.0
7.35
86.2
<0.020* 1.50
—
* = value may be in error
Ca	Mg	Na
(mg/1)	(mg/1)	(mg/1)
lake Spiked	Lake Spiked	lake Spiked
Value Value	% R Value Value	% R Value Value % R
2.4
3.18
78
0.50
0.642
71.0
0.64
1.05
82.0
4.2
5.05
85
0.52
0.667
73.5
0.77
1.12
70.0
2.6
3.4
80
0.53
0.658
64.0
0.80
1.12
64.0
1.9
2.85
95
0.57
0.693
61.5
1.59
1.89
60.0
2.9
3.85
95
0.50
0.650
75.0
0.99
1.40
82.0
1.5
2.38
88
0.52
0.692
86.0
0.97
1.40
86.0
1.9
2.70
80
0.37
0.530
80.0
0.56
0.899
67.8
1.2
2.10
90
0.38
0.537
78.5
0.93
1.35
84.0
3.3
3.90
60
0.48
0.625
72.5
1.69
2.12
86.0
2.2
2.99
79
0.52
0.650
65.0
0.80
1.19
78.0

K


(mg/1)

Lake
Spiked

Value
Value
% R
0.44
0.793
88.3
0.27
0.640
92.5
0.54
0.890
87.5
0.61
0.946
84.0
0.62
0.932
78.0
0.54
0.835
73.8
0.31
0.701
97.8
0.36
0.757
99.3
0.45
0.823
93.3
0.54
0.884
87.3
-------
ACID RAIN LAKES
SPIKES OF NANOPURE WATER
NCL-NO
<4/1)
so4
(mg/1)
CI
(mg/1)
Ca
(mg/1)
Mg
(mg/1)
Na
(mg/1)
K
(mg/1)
—
2.61
1.94
.975
.206
.475
.395
—
2.82
1.79
1.05
.202
.527
.400
—
2.62
2.05
1.03
.192
.534
.458
—
3.36
1.81
1.02
.197
.497
.396
—
—
1.78
.830
.197
.502
.396
.250
2.58
.28
1.05
.200
.503
.418
.251
3.24
2.01
1.10
.208
.810
.656
.217
2.62
1.70
.983
.203
.520
.407
.250
2.63
1.61
1.02
.204
.861
.400
.087
2.69
1.74
.912
.201
.655
.415
.231
2.77
1.63
.975
.223
.500
.412
.854
2.45
1.64
1.03
.197
.860
.408
.231
5.73
1.74
1.06
.220
.540
.415
.159
2.49
1.57
1.10
.209
.514
.424
.189
2.67
1.44
1.03
.201
.514
.386
.216
2.51
1.73
.90
.196
.525
.403
.196
2.51
1.67
.963
.201
.489
.397
Estimated 0.227	2.73	1.82	1.00 0.20 0.50 0.40
Value
-------
USGS, Albany, New York
-------
f'»* T,, T".	. J
Table 5.--Quality-control data on field'^lkalidURu fafi
measurements by Gran's Plot*
[Data in peq/L]


Measure-
Measure-
Measure-

Date
PH
ment 1
ment 2
ment 3
Average



Biscuit Brook


5-17-83
6.21
17
—
—
17
8-15-83
6.32
23
—
—
23
10-06-83
6.37
31
—
—
31
11-02-83
6.36
36
36
—
36
11-11-83
6.43
42
42
42
42
11-16-83
6.47
32
28
—
30
11-30-83
6.13
12
12
"
12
12-13-83
5.14
-12
—
——
-12
12-14-83
5.61
0
4
—
2
1-12-84
6.54
32
—

32
2-01-84
6.16
20
12
	
16
2-06-84
6.12
14.8
—
—
14.8
3-28-84
6.25
20
20
—
20
4-03-84
6.14
24
20
——
22
4-10-84
5.92
4
4
•mm*
4
4-17-84
5.41
2
—
	
2
5-30-84
5.30
4
4
	
4
6-12-84
6.41
24
—
——
24
7-20-84
6.49
32
32

32



Beaverkill Creek


11-03-83
6.99
140
140
	
140
12-15-83
6.13
26
26
——
26
1-31-84
6.61
80
84
—
82
4-02-84
6.81
80
78

79
4-16-84
5.83
16
16

16
6-13-84
6.97
110
110
	
110
7-19-84
7.15
114
«¦»
"
114



Woodland Creek


8-15-83
6.41
32
—
—
32
11-01-83
6.31
32
24
24
26.7
12-15-83
6.24
10
12
——
11
2-02-84
6.18
20
20
——
20
4-02-84
6.35
20
28
—
24
4-16-84
6.10
14
14
—
14
6-12-84
6.45
28
28
—
28
7-19-84
6.43
27.2
27.2
—
27.2
-------
Table 5Quality-control data ori fie
measurements by Gran's Plot
[Data in iJeq/L]
flt' tefcHfr fr fcia
std


Measure-
Measure-
Measure-

Date
pH
ment 1
ment 2
ment 3
Average



Rondout Creek


8-16-83
6.25
2.4

__
24.4
11-01-83
6.06
9.6
10.4
16.0
12.0
12-14-83
4.65
-24
-24
—
-24.0
2-02-84
5.5
0
-4
—
-2.0
4-03-84
5.39
4
8
—
6.0
4-17-84
4.83
-9.2
-9.2
—
-9.2
5-30-84
4.74
-18
-18
—
-10.0
6-11-84
5.24
4
4
—
4.0
7-11-84
5.45
2
2
—
2.0



High Falls Brook


8-15-83
7.05
136
—
—
136
11-03-83
7.07
178.8
178.8
—
178.8
12-14-83
5.92
12.0
12.8
12.0
12.3
2-01-84
6.77
92.0
102.0
—
97.0
4-03-84
6.75
68
72
——
70.0
4-05-84
5.24
-4.0
+2.0
	
-1.0
4-17-84
5.98
20
24
	
22.0
6-13-84
6.92
80
88
	
84.0
7-20-84
7.17
114
114
—
114.0



Pigeon Brook


4-11-83
6.04
16
—
	
16
8-15-83
6.58
6.92
—
——
6.92
11-02-83
6.78
90
90
	
90
12-14-83
5.55
6
6
	
6
2-01-84
6.49
50
50

50
4-03-84
6.52
40
40
	
40
4-05-84
5.84
12
20
——
16
4-05-84
5.21
0
0
	
0
4-06-84
5.49
5.6
5.6
"
5.6
4-17-84
5.77
16
16

16
5-30-84
5.73
16
16
	
16
6-12-84
6.68
46
46
	
46
7-20-84
6.78
46
56
56
53
-------
Table 5.--Quality-control data 
-------
USGS, Harrisburg, Pennsylvania
-------
GENERAL CLIMATOLOGICAL INFORMATION
The Laurel Ridge area of southwestern Pennsylvania is under the general
influence of a continental climate and prevailing westerly winds. Precipitation
averages 46 inches per year and is well distributed between the growing and
non-growing seasons. There are an average of 35 thunderstorms each year.
Average snow accumulation is 66 inches with 102 days per year of snow cover.
The period of ice cover is approximately October 1 to May 1.
NOAA meteriological stations relevent to the study area are located at
Johnstown, Boswell, Somerset, and Laurel Mt. Village. A Pennsylvania Department
of Environmental Resources/Penn State University (PaDER/PSU) Atmospheric
Deposition Monitoring Network site is maintained at Laurel Hill State Park (fig.
1). The nearest National Atmospheric Deposition Program (NADP) site is located
approximately 65 miles to the northeast at Leading Ridge, Penn State University
Forest Experiment Station in northern Huntingdon County.
METHODS
Sampling Procedures and Frequency
Sampling of the six study sites is accomplished within a two day period
every month. Discharge, temperature, pH, and specific conductance of each
stream is determined at the site. Samples are collected in polyethylene bottles
and kept chilled until they are taken back to the field laboratory at the South
Fork Bens Creek (primary site). Since the streams are small and well mixed it
was found that a transect and use of a calibrated hand held sampler was not
necessary. Therefore, a dip sample at about mid—stream has been employed
throughout the study. Within two hours of collection, the samples are analyzed
for alkalinity and acidity.
/3
-------
The site with the most attention is the primary site. Every week the stream
is sampled for pH and specific conductance. Significant storms are sampled with
an ISCO* automatic water-quality sampler. This sampler is pre-programmed to
take samples at various time intervals upon an rise in stage. A total of
twenty-four samples can be taken during a storm period. Immediately, at the
completion of the sampling sequence, the samples are tested for pH and specific
conductance. Then among the twenty-four samples about ten are selected from the
rise and recession of the event for analysis at the USGS Central Analytical
Laboratory. The primary site is also the precipitation monitoring site. Every
Tuesday at 9:00 A.M. the wet bucket of the precipitation collector is removed
and its contents analyzed for pH, specific conductance and volume. Provided
there is enough sample available, the prescribed laboratory schedule Is used
for analysis at the USGS Central Analytical Laboratory. Precipitation sampling
for this study closely follows the protocol established by the National
Atmospheric Deposition Program.
Consistency in storage and preservation technique is as important as the
actual sampling technique. Therefore all storage bottles and fixing agents are
supplied by the USGS Central Analytical Laboratory. Precipitation and stream
samples are both preserved for a laboratory schedule 291. Stream samples have
an added schedule 353. Under schedule 291 collected samples are divided into
three areas of concern: (1) dissolved metals determiniatlon, (2) ion deter-
mination, (3) raw analysis for pH, specific conductance, and alkalinity.
Schedule 353 is concerned with nutrient analysis and dissolved organic carbon
(DOC) content.
* "Use of the brand name ISCO in this report is for identificatlon purposes
only and does not consitlute endorsement by the U.S. Geological Survey."
Sample Storage and Preservation
-------
Sample processing is completed at the primary site within two hours of
collection. All filtering apparatus is washed and rinsed with distilled water
between filter changes and sample sites. A 40-ml portion of distilled water is
passed through each membrane prior to use. Samples to be analyzed for dissolved
metals are filtered through a 0.1 micron MFS* cellulose nitrate membrane filter
directly into acid rinsed bottles. Dissolved-metals samples are each treated
with a 1-ml ampule of ultra—pure nitric acid. Nutrient analysis samples are
filtered through a 0.45 micron cellulose nitrate membrane filter directly into
amber polyethylene bottles. The nutrient samples are each treated with a 185 mg
tablet of mercuric chloride and chilled to 4 degrees centigrade for shipping.
DOC samples are filtered through a 0.45 micron silver membrane filter using a
pressurized Gelman* stainless steel filter assembly accompanied by a cylinder of
high grade nitrogen. The DOC samples are transferred directly from the filter
assembly into pre-sterilized 100-ml glass bottles and chilled to 4 degrees cen-
tigrade for shipping. Raw unfiltered stream or precipitation samples are also
sent for analysis to fulfill concern number three.
-------
Analytical Procedure
Field
Water Quality Instruments
Temperature.—Temperature is measured with a NBS* certified mercury ther-
mometer on an aliquot of the collected sample as a precursor to measurement of
pH and specific conductance.
Specific Conductance.— Specific conductance is measured on an aliquot of
the collected sample prior to measurement of pH. The instrument used is a
Beckman RB-5* with a cell constant of 0.1. Prior to use the cell is rinsed with
distilled water and shaken dry. The cell is checked against a standard KCL
solution of the appropriate value (<50 pmhos) prior to measurement. The cell
constant is reconfirmed each month during calibration using a Beckman Model
CEL-RB1-Y8F* laboratory standard cell.
pH.—The pH meter is an Orion model 399A* equipped with a Ross Combination
Electrode which is specifically designed for use in low ionic strength solu-
tions. Electrodes are generally replaced every six months and quality assurance
checks are made three times a year. The pH meter is calibrated before each use
by means of a carbon dioxide buffer preparation (Hydrolab Corporation, 1982).
This method provides a low ionic strength solution similar to that of the stream
and precipitation samples being studied.

-------
Event Sampler,—Storm events are sampled at the primary site using an ISGO*
water-quality sampler. This instrument is pre-programmed to collect samples at
specific time intervals upon its initiation at the first increase in stream
stage. A range of samples are generally taken over the complete period of the
storm event. All sample bottles within the 1SC0 are open to the atmosphere
until the completion of the cycle. Concurrent analysis of stream samples taken
during the operation of the ISCO and the subsequent analysis of samples at the
completion of its sequence have shown data to be consistent.
Precipitation Instruments.—This study follows the National Atmospheric
Deposition Program (NADP) guidelines for the collection and handling of precipi-
tation samples with the exception of the laboratory analysis which is completed
at the USGS Analytical Laboratory.
The precipitation collector is a Wet/Dry Geotech Environmental Equipment
Model 0600*. Several problems developed with this equipment during the first
year of data collection which made it necessary to collect bulk samples in
lieu of event samples. Winter operation of the Geotech equipment has proven
very inconsistent. The sampler is equipped with two polyethylene buckets that
are rinsed with distilled water between samples. A thorough acid rinse will be
implemented into the cleaning process as soon as supplies become available.
Rainfall is recorded by a Belfort* weighing bucket type gage. This recorder
is equipped with an event marker to indicate the initiation of the Geotech model
0600 wet/dry collector. A National Weather Service standard rain gage is
roughly ten meters from the Belfort recorder. This gage gives the total inches
of precipitation that has occurred during the span of a week and it can be used to
check the accuracy of the Belfort. The entire precipitation monitoring station
is fenced in and placed approximately 100 meters from the stream.
-------
Surface-water Instruments.—All study sites are measured for discharge at
the time of sampling. Either a standard AA or a pygmy current meter Is used
depending on flow conditions. The five synoptic sites are measured on an
instantaneous basis only. There are no staff gages or reference marks at any of
these sites. The primary site is fully instrumented with a manometer stage
indicator, Stevens graphic recorder, and an Analytical Digital Recorder. The
manometer is integrated via a selonoid switch with the ISCO water-quality
sampler. During a storm event the ISCO will initiate an increase in stage of
the manometer for a short period to mark the sample time and stage on the
graphic recorder. All surface water data are processed at the Pittsburgh
Subdlstrict Office of the U.S. Geological Survey.
LABORATORY
Laboratory analytical methods are Indicated in table 2.
Table 2.—(caption on next page) belongs near here
-------
QUALITY ASSURANCE/QUALITY CONTROL
The ultimate goal of any sampling technique is to collect representative
samples free of contamination and to preserve their integrity for analysis. The
techniques followed to attain or approach this goal are described in papers by
Topol and Ozdemir (in press) and the Aquatic Effects Task Force Groups of the Interagency
Task Force on Acid Precipitation, 1983. Laboratory quality assurance/quality
control procedures followed by the U.S. Geological Survey Central Laboratory
are detailed by Friedman and Erdmann, 1982.
All sample containers are linear polyethylene with polyseal caps. Sample
bottles are rinsed three times with high quality deionized water (conductivity
<0.1 umhos/cm), filled with distilled water, and let stand for several hours
prior to use. The bottles are then rinsed three times with sample water.
Acidified and nonacidified sample blanks are submitted each month with the
regular samples. As this program was initiated in June 1984, there are no data
to report.
MONITORING DATA
Data collection was initiated in August 1983 at the six headwater streams and
one precipitation site listed in table 1. Monitoring data include monthly base
flow water quality at all six streams, storm sampling at the primary site,
weekly precipitation water quality, and continuous streamflow measurement at the
primary site.
This report presents streamflow and precipitation data collected during the
first nine months of operation. More recent data have not been reported by the
central laboratory. Because the data have not been verified, they should be
considered provisional at this time.
11
-------
USGS, Raleigh, North Carolina
-------
Analytical Procedures
Analytical procedures are outlined in table 3. Most analyses are
performed using standard procedures. However, samples for aluminum, iron,
and manganese are filtered through 0.1 um filters in the field. Aluminum is
extracted in the lab with methyl isobutyl ketone (MIBK) after chelation with
8-hydroxyquinoline and prior to analysis by atomic absorption spectrometry.
Alkalinity is determined in the field using the Gran plot technique.
Acidity also will be determined in the field begining in FY 1985. Six
constituents, bromide, chloride, fluoride, nitrate, phosphate, and sulfate,
are analyzed by ion chromatography.
QA/QC INFORMATION AND DATA
Quality-assurance and quality-control measures have been addressed
previously in three separate documents. Those documents were from the
Project Chief (Kent Crawford) to the EPA Project Officer (Charles Powers) on
February 2, 198M and August 27, 1984, and from the Project Chief to Owen
Bricker (USGS research program) on August 30, 1984. Each of these documents
is reproduced and appended to this report (Attachment 2). Published
references that detail quality control practices and results and that have
previously been sent to the EPA Project Officer are not included with this
report. A more recent quality-assurance report from the USGS Central
Laboratories than the one previously sent is also attached (Attachment 3).
This report covers the period January 1 - march 31, 1984.
QA/QC data from blanks and duplicates submitted in association with the
August, 1984 sampling are not yet available.
12
-------
Table 3.—Analysis techniques for parameters Included In the Sandhills project
Constituent	Parameter Lab Method	Detection	Field	Technique	Reference
Cr»d* Code Number	Limit	Treatment
Dlrwolvrd
nluminum
Dissolved
calcium
Pln.nolvod
Iron
n I .inol*o um)
Fl1 tor
(0.15 um)
Flltor
(0.*rt um)
Chelate with 8-hydroxyquinolinet
extract with methyl iaobutyl
ketone (MIBK), determine
aluminum by A,A..*>.«
Add lanthanum chloride
to mask interference,
determine by A.A.S.
A.A..5.
Add lanthanum chloride,
A.A.S.
A.A.S.
A.A.S.
A.A.S.
I.C.«
I.C.
T .C.
I.C.
I .c.
SkouRstad and
others, 1979
(p. w
SkouRstad and
others, 1979
(p. 107)
SkouRatad and
other*, 1079
(p. 151)
SkouRStad and
others, 1979
(p. 177)
SkouRftad and
others, 1979
(p. 187)
SknuRM.ad and
others, 1979
(p. 229)
SkouRStad and
others, 1Q79
(p. 255)
Fishman and
Pyen, 1979
Fiahman and
Pyen, 1979
Fi.ihman and
Pyen, 1979
Fishman and
Pyen, 1979
Flahman and
Pyon, 1970
-------
Table 3.— Analysis techniques for parameters Included In the Sandhills project—Continued
Constituent
Parameter Lah Method
Code Code Number
Detection
Limit
Field
Treatment
Technique
Reference
Plsr*o1ved
sulfate
P|sjwlve<1
slllra
Tr»t^ 1
aridity
f Inb)
Total
alkalinity
(laM
pil (lah)
Spec If Ic
conductance
(lah)
Dissolved
ammonia
nltrofien
Plssolved
orthophonphate
phosphorus
Plssolved
organic
carbon
009*15	538
009*>5	56	1-2700-78
71B2S	1	1-1020-78
QO'iOO	70	1-2020-78
00003	68	1-2587-79
90095 69	1-2701-81
00608	830
00671	828
00681	113	0-0002-78
0.1 ms/L
0.1 dr/L
1.0 mg/L
(as CaCO^
1.0 mg/L.
(as CaCO^)
0.002 mg/L
0.001 mg/L
0.1 ihr/L
Filter
(0.M5 urn)
Filter
(0.15 um)
Chill
Chill
0.1 pH units Chill
1.0 umho/cm Chill
Filter
(0.U5 um)
Filter
(0.M5 um)
Filter
(0.15 urn)
chill
I.C.
Reduce sample to lens than
pU 2.5, add ammonium molyhdate,
A.A.S
Automated electrometrlc
titration to pH 8.3
Automated electrometrlc
titration to pH *.5
Automated electrometry,
glass electrode
Wheatstone bridge,
automated
Sal. hypochlorite,
automated colorlmetry
Phosphomolybdate addition,
automated colorlmetry
Wet oxidation In carbon
analyzer, measurement of
carbon dioxide
Flshman and
Pyen, 1979
Skougstad and
others, 1979
(p. 197)
Skougstad and
others, 1979
(p. 515
Skougst^d and
others, 1979
(p. 519)
~icougnt4d and
others, 1979
(p. SM3)
SkouRst^d and
others, 1979
(p. 5*5)
Goerlltz and
Brown, 1972
(p. *)
•A.A.S, = Atomic Ahnorptirvn Spectrometry
••I.C. s ton Chromatography
-------
Tennessee Valley Authority
-------
A-l
Laboratory Quality Assurance Program for the Project:
Long-Term Monitoring of Reservoirs in the Southern Appalachians
1.0	OBJECTIVES
The objective of the quality assurance program was to assure that valid and
reliable analytical data were reported and to assess the accuracy and precision
of the values generated so that accurate interpretation could be made.
2.0	SCOPE
The program covered the analytical activities affecting the data generated
by the laboratory for the subject project.
3.0	REFERENCES
3.1	"Preparation of Sample Containers," NRS-LB-AS-3.1, Laboratory Branch, Division
of Natural Resource Services, Tennessee Valley Authority, April 1980.
3.2	"Performing Intra!aboratory Quality Control Analyses," NRS-LB-AS-3.9, Laboratory
Branch, Division of Natural Resource Services, Tennessee Valley Authority,
May 1980.
3.3	"Preparing Worksheets and Forms," NRS-LB-AS-3.6, Laboratory Branch, Division
of Natural Resource Services, Tennessee Valley Authority, March 1930.
3.4	"Performing Routine Analysis," NRS-LB-QAP-3.1, Laboratory Branch, Division
of Natural Resource Services, Tennessee Valley Authority, March 1980.
3.5	"Methods of Chemical Analysis of Water and Wastes," Environmental Protection
Agency, Cincinnati, Ohio (1979).
3.6	"Recording, Checking, and Approving Analytical Data," NRS-LB-AS-3,10,
Laboratory Branch, Division of Natural Resource Services, Tennessee Valley
Authority, June 1980.
3.7	"Preparing Reports of Results," NRS-LB-AS-3.12, Laboratory Branch, Division
of Natural Resource Services, Tennessee Valley Authority, June 1980.
3.8	"Conductance, pH, Strong and Weak Acidity," NRS-LB-AP-10.377.1.
3.9	"Acid Titration of Polar Snow," Legrand, et. al., Anal. Chem., 1982, 54,
1336-1339.
3.10	"Metals by Atomic Emission," NRS-LB-AP-30.200.2.
3.11	"Multiparameter Analysis of Rainwater by Ion Chromatography," NRS-LB-AP-10.200.1.
-------
A-2
4.0	ABBREVIATIONS AND DEFINITIONS
4.1	LB--Tennessee Valley Authority's Laboratory Branch
4.2	PJL--Project Leader of Laboratory Branch
4.3	PM--Project Manager
5.	0	PROCEDURES AND RESPONSIBILITIES
5.1	Sample Collection and Receiving (A flowchart displaying these steps is
given in Attachment 1.)
5.1.1	A maintenance program which involved periodic inspection, servicing,
and calibration of field equipment was utilized.
5.1.2	Sample containers were cleaned and labeled. Each batch of containers was
checked by randomly selecting several sample containers for quality control
analyses (reference 3.1). Containers were filled with deionized water
and container contents were analyzed for the required parameters.
5.1.3	Samples were collected and preserved as described in reference 3.1. All
samples were identified using a unique numbering system.
5.1.3.1 Filtration blanks were collected for nonfilterable (dissolved) anions and
cations and shipped to the LB for analysis.
5.1.4	Samples were recieved by the LB and all necessary information regarding
the samples was recorded.
5.1.5	The PL checked all samples and records for any irregularities.
5.1.6	The PL notified the PM of any irregularity regarding the samples.
5.1.7	The PL resolved all problems or questions before the samples were released
for analysis.
5.1.8	The PL prepared laboratory worksheets (reference 3.3) and submitted the samples
and worksheets to their proper locations.
5.2	Laboratory Analysis and Data Reporting (A flowchart displaying these steps
is given in Attachment 2.)
5.2.1	Samples and appropriate blanks were analyzed for the parameters listed in
Attachment 3. Analytical references, description of methodology, and detection
limits for the analytical procedures are also listed in Attachment 3.
5.2.2	Where possible, the LB Intralaboratory Quality Control Program (reference 3.2)
was followed by analyzing 10 percent of the samples in duplicate and spiking
10 percent of the samples.
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A-3
5.2.3	All analytical data were recorded in laboratory notebooks (reference 3.6),
calculations checked, analysis approved, and results forwarded to the PL.
5.2.4	Results from the accuracy and precision quality control samples were reviewed
by the PL. If a result was outside the control limits, the sample was
resubmitted for anlaysis.
5.2.5	If any data indicated a problem, the PL took corrective action.
5.2.6	Data were tabulated, reviewed, and approved by the PL.
5.2.7	Data were keypunched and stored in the STORET data system.
5.2.8	Completed printouts of data were forwarded to the PM for review and approval.
6.0	QUALITY CONTROL METHODS
6.1	Blanks
6.1.1	Filtration blanks were prepared by field personnel, submitted to laboratory,
and were analyzed to determine the adequacy of the filtration manipulation
as well as the cleanliness of the dissolved anion/cation sample container
(250 mL-LPE bottle). Membrane fjltr^gsofjdeionized water were analyzed
for the dissolved specTeT of fluoride, chloride, phosphate, nitrate, sulfate,
sodium, potassium, calcium, magnesium, and aluminim. Sixteen filtration
blanks were prepared, submitted, and analyzed.
6.1.2	Container blanks for unfiltered parameters were performed to check the
adequacy of the 1-quart cubitainer as a sample container, Unfiltered
parameters included pH, true and apparent color, conductance, strong and
weak acidity, and alkalinity. Virgin 1-quart cubitainers were used as
containers for unfiltered sample aliquots.
6.2	Evaluation of Precision
6.2.1 Precision data were generated by analyzing actual samples	in duplicate.
Difference between the two observed values was multiplied	by 0.89 to approxi-
mate the standard deviation (SD). The standard deviation	divided by the mean
of the duplicate values and multiplied by 100 yielded the	relative standard
deviation (RSD) in percent. RSD values were used to assess the adequacy of
precision observations.
6.3	Evaluation of Accuracy
6.3.1 Accuracy data were generated-b.y fortifying actual samples with known amounts'
of analyte, analyzing the spiked aliquot, ana calculating the percent recovery.
Bias values in percent were obtained by subtracting 100 from the percent
recovery. Bias values were used to assess the adequacy of accuracy
observations.
6.3.2 _Accuracy data were also generated by analysis of control solutions. Control
solutions are stable, synthetic working solutions of known concentration
that are analyzed after the calibration or optimalization of an analytical
procedure. Bias values obtained from these observations were also used
to assess the adequacy of accuracy.
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A-4
7.	0	RESULTS AND DISCUSSION
7.1	Blanks
7.1.1	Filtration blanks confirmed the acceptability of the membrane filtration
process for dissolved components. Filtration blank values also established
the adequacy of the 250-mL LPE bottle as a sample container. Results of
filtration blank analyses are described in Attachment 4. All values for
fluoride, phosphate, and aluminum parameters were less than detectable
concentrations. Detected concentrations of chloride, nitrate, sulfate,
calcium, and magnesium were within expected and acceptable ranges. Two
observations of potassium, 0.10 and 0.12 mg/L, were of a marginal magnitude;
however, these two values did not raise the mean concentration above the
detection limit of 0.01 mg/L. Only the mean concentration of the sodium
parameter was greater than the detection limit of the analytical procedure.
Detection limit for the sodium method was 0.01 mg/L. The observed mean
concentration of 0.01 mg/L matched the detection limit of 0.01 mg/L. A
single observation of sodium, at the 0.13 mg/L level, served to raise the
mean concentration to the detection limit.
7.1.2	Container for the unfiltered parameters was the standard 1-quart cubitainer.
Eight deionized water blank samples were prepared, submitted, and analyzed.
Results of the analyses are detailed in Attachment 5. All observations of
unfiltered parameters were within or below expected values. Previously
accumulated quality control data for the 1-quart cubitainer had also
demonstrated its contaminant-free reliability.
7.2	Precision Observations
7.2.1 Relative standard deviation (RSD) values for all parameters were excellent.
See Attachment 6 for details of the precision observations. Average RSD
values ranged from a low of 0.2 percent for pH and conductance parameters
to a high of only 3.7 percent for fluoride determinations.
7.3	Accuracy Observations
7.3.1	Spiked or fortified data.
7.3.1.1 Bias values for anion and cation parameters are detailed in Attachment 7.
All average bias values were acceptable. Values ranged from -7.5 percent
for sulfate to 12 percent for chloride. Bias values for anions were generally
greater because of the very low spike concentrations used to fortify the
sample aliquots. Conductance, pH, color, acidity, and alkalinity parameters
were not assessed for accuracy by spiking with known concentrations of analytes.
7.3.2	Control solution data-anion parameters.
7.3.2.1 .Bias values for dissolved anion parameters are detailed in Attachment 8.
All average bias values were acceptable. Values ranged from -0.3 percent
to 2.6 percent for fluoride.
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A-5
8.	0	CONCLUSIONS
8.1	Overall accuracy and precision of data generated during the 1982-1983
phases of the project were adequate and within the interpretative
requirements of the study.
8.2	Preparation of sample containers and filtration manipulations were
satisfactory.
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A-6
Attachment 1
Sample Collection and Receiving
Sampli ng
Equipment
Cleaned
Equipment
Calibrated
Sample
Containers
Prepared
V
Field
B1anks
Collected

Samples
Received and
Logged in
Laboratory
V
Any
Irreaularities
with Samples
or Field
Sheets?
V
No
-> Yes
Field
Measurements
Hade
y
Project Leader Willi
Prepare Worksheets j
and Submit Samples j
for Analysis j
Samples
Collected
Identifi ed
Preserved and
Shipped
Project Leader
Will
Contact Project
Manager and
Resolve
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A-7
Attachment 2
Laboratory Analysis and Data Reporting
Samples and
B1anks
Analyzed
Duplicates and
Spikes
Analyzed
J
Accuracy and
Precision Results
Acceptable
-
Yes
Data Recorded
Checked, Approved
By PL
J Completed Data
j	to
| Data Processing
-j
Data Key ,
Punched, Verified.
' and Stored in j
j STORET
j	,	—1
y
r	—	]
Completed Printoutsl
of Data {
Forwarded to __ j
Project Manager' i
___
No
Samples
Resubmitted
for Reanalysis
Review and
Approve Final
Printout of Data
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A-8
Attachment 3
Analytical Methodology
Parameter
pH
Acidity (weak and strong)
Alkalinity
Calcium, dissolved
Magnesium, dissolved
Sodium, dissolved
Potassium, dissolved
Aluminum, dissolved
Fluoride, dissolved'
Chloride, dissolved
Phosphate, dissolved
Nitrate, dissolved
Sulfate, dissolved
Color, True, and Apparent
Reference
3.8
3.8
3.9
3.5, Method 215.1
3.5, Method 242.1
3.5, Method 273.1
3.5, Method 258.1
3.10
3.11
3.1
3.1
3.1
3.11
3.5, Method 110.2
Method Description
Electrometric
Titrimetry, Gran's plot
Titrimetry, Gran's plot
Atomic absorption -
direct aspiration
Atomic absorption -
direct aspiration
Atomic absorption -
direct aspiration
Atomic absorption -
direct aspiration
Atomic emission
Ion Chromatography
Ion Chromatography
Ion chromatography
Ion Chromatography
Ion Chromatography
Chloroplatinate, visual
Minimum
Detectable
Concentration
N/A
10 ueq H+/L
10 veq H+/L
0.05 mg/L
0.01 mg/L
0.01 mg/L
0.01 mg/L
0.05 mg/L
0.02 mg/L
0.10 mg/L
0.04 mg/L
0.04 mg/L
0.10 mg/L
1 unit
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Attachment 4
Results of Container Blanks for Dissolved Parameters
(250 mL-LPE Bottle)
Dissolved
Parameter
Number of
Observations
Number of
Observations
Less Than
Detection
Limit
Range of
Values (mg/L)
Average
Concentration
(mg/L)
Fluoride
16
16
all were <0.02
<0.02
Chloride
16
9
<0.1 to 0.3
<0.1
Phosphate
16
16
all were <0.04
<0.04
Nitrate
16
10
<0.04 to 0.09
<0.04
Sulfate
16
13
<0.1 to 0.5
<0.1
Calci um
16
14
<0.05 to 0.09
<0.05
Magnesium
16
9
<0.01 to 0.02
<0.01
Sodium
16
12
<0.01 to 0.13
0.01
Potassium
16
13
<0.01 to 0.12
<0.01
Aluminum
16
16
all were <.05
<0.05
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A-10
Attachment 5
Results of Container Blanks for Unfiltered Parameters
(1-Quart Cubitainer)
Unfiltered
Parameter
PH
Acidity, strong
Acidity, weak
Alkalinity
Conductance
Color, true
Color, apparent
Number of
Observation
8
8
8
8
8
0
0
Range of Values
6.48 - 5.21 units
All <10 yeq H+/L
30 - 60 yeq H+/L
All <10 yeq H+/L
1.4 - 2.8 ymhos/cm
Average
Concentration
5.62
<10
40
<10
2.0
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A-11
Attachment 6
Results of Precision Observations
meter
Or, true
^or, apparent
idity, strong
idity, weak
ikalinity
Onductance
fluoride
Chloride
Phosphate
Nitrate
Sulfate
Calcium
Magnesium
Sodi um
Potassium
A1uminum
Number of
Duplicate
Analyses
2
3
8
2*
2
2
2
6
6
6
6
6
1**
2**
3
3
7
Range of
RSD Values (%)
0.1 - 0.3
0.0 - 15.4
0.0 - 10.4
0.0
0.0
0.1
0.0
0.0
0.0
0.0
0.0
5.0
1.9
0.2
17.7
1.9
2.9
15.4
2.2
2.1
2.4
0.0
0.0
0.0
0.6
3.0
2.8
Average
RSD (%)
0.2
3.4
1.6
2.5
1.0
0.2
3.7
0.8
0.7
2.8
0.8
2.1
2.4
0.3
1.8
0.8
*A11 observations were less than minimum detectable concentration.
**Lost record for all 1982 raw data.
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A-12
Attachment 7
Results of Accuracy Observations
Number of Concentration

Accuracy
of Spike
Range of
Averat
Parameter
Observation
(mg/L)
Bias (%)
Bias i
Fluori de
4
0.098
-12 to +30
7.8
Chloride
4
0.49
-2 to +39
12.
Phosphate
4
0.49
-10 to 0.0
-3.
Nitrate
4
0.49
0.0 to 16
7.5
Sulfate
4
0.98
-11 to -3
-7.5
Calcium
1*
2.0
4.0
4.0
Magnesium
1*
0.2
4.0
4.0
Sodium
3
2.0
+1.0 to 2.0
2.0
Potassium
3
0.2
-2.0 to +2.0
1.0
A1uminum
7
0.5
-3 to +7.0
2.0
*Lost record for all 1982 raw data.
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A-13
Attachment 8
Results of Accuracy Observations - Control Solution
Data for Dissolved Anions
Number of Concentration Range of	Average
Parameter Observations	mg/L		Bias {%)	Bias (%) Bias (%)
Fluoride
5
0.10
0.0 to 40
12


5
0.20
0.0 to -17
-3.4
2.6

5
0.40
0.0 to -2
-0.8

Chloride
5
0.5
-5.0 to 20
5.8


5
1.0
-8.0 to 2.0
1.6
2.4

5
2.0
0.0
0.0

Phosphate
3
0.20
-10 to 10
0.0


4
0.40
-15 to -2
-5.2
-0.3

5
0.80
-2.0 to 9.0
4.4

Nitrate
5
0.20
-10 to 4.9
-1.8


5
0.50
-2.0 to 5.0
3.0
0.4

5
2.0
-2.0 to 2.0
0.0

Sulfate
5
1.0
-2.0 to 20
5.4


5
5.0
-2.0 to 0.0
-1.5
1.7

5
10.
0.0 to 2.0
1.2

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Appendix III. Data Quality Objectives: Long-Term Surface Water
Monitoring Program,
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3/15/85
DATA QUALITY OBJECTIVES: LONG-TERM SURFACE WATER MONITORING PROGRAM
Stage I. Initial Input by EPA Senior Management and Task Group E
The program for the long-term monitoring of the nation's surface waters
had its inception in a request from EPA Headquarters in June 1982 to plan,
develop, and implement a program to quantify the effects of current deposition
levels on sensitive aquatic ecosystems. Reduction of precursor emissions has
been urged as a means of curtailing the rate of deposition of acidic materials.
In order to determine acceptable loadings, however, it is first necessary to
quantify current effects over a range of loading rates and geographical
regions. To evaluate the overall effect of emission controls, one must know:
(1) the response of lakes and streams of similar sensitivity to various
deposition rates; (2) the differences in response of lakes and streams of
differing degrees of sensitivity to a given deposition rate; and (3) whether
there are regional differences in the way sensitive lakes and streams respond
to various deposition rates.
This task was undertaken within the NAPAP organizational framework. An ad
hoc committee was organized in July 1982 within Task Group E to consider
approaches to monitoring and develop a standardized sampling/analysis protocol.
The committee, with representation from EPA, USGS, TVA, USDA-FS, USFWS, USNPS,
and Brookhaven National Laboratory, produced a draft protocol in January 1983
as the basis for a national surface water chemistry monitoring effort. This
document received extensive peer and inhouse review and has served as the basis
for the EPA lake and stream monitoring program.
1
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Stage II. Clarification of the Problem
A program was developed by EPA to monitor the quality of lakes and streams
in regions of low alkalinity to determine whether detectable changes in water
chemistry are occurring in those regions and, if so, whether they can be
related to atmospheric inputs. In planning this program, it was necessary to
take Into consideration certain factors concerning the distribution and
regionality of acidic deposition, which is known to occur in all states east of
the Mississippi River but is much less uniformly distributed in the West. Some
regions receiving acidic deposition contain lakes and/or streams of low alka-
linity (hence, presumably sensitive to acidification); in other regions,
surface water alkalinities are uniformly high and acidification from atmo-
spheric deposition is not expected. Sensitive waters also occur in regions not
now receiving acidic deposition, or where acidic deposition is minimal, but it
cannot be assumed that precipitation chemistries in those regions will remain
unchanged in the future. There is evidence from studies in, for example, the
Adirondacks, Maine and Vermont, and the Muskoka-Haliburton region of Ontario
that decreases in alkalinity (hence, acidification) have occurred in some North
American lakes. There is also evidence that alkalinity may actually be
increasing in the Northeast in response to decreases in sulfate emissions.
Although precipitation chemistry may be essentially uniform within a given
geographical region, we know that not all lakes or streams can be expected to
respond identically. There are probably even greater uncertainties with
respect to comparability of response of surface waters between regions. For
example, although average precipitation pH and SO4 deposition in the southern
Appalachians and in New England fall within the same range (pH, 4.4-4.2; SO4,
20-30 kg/ha/yr), significant differences exist between those regions. New
England was glaciated and the southern Appalachians were not; New England
2
-------
contains many hundreds of small natural lakes, but southern Appalachian surface
waters are characterized by streams and artificial reservoirs; soils in New
England are quite young, while those in the South are much older, on the order
of millions of years. Low alkalinity waters occur in both regions, but there
1s no good reason to expect that the effects of acidic deposition on aquatic
systems in the two regions would be the same. Based on present knowledge,
results probably should not be extrapolated from one region to another.
Objecti ves
The objectives of the long-term surface water monitoring program are:
1.	detect and measure long-term trends in the chemistry of low alkalinity
surface waters that are related to atmospheric deposition; and
2.	compare the response of low alkalinity waters (1) over a geographic
gradient of H+ and sulfate deposition and (b) in different major sensitive
geographic areas that receive comparable deposition.
Sites would be in locations where annual sulfate deposition averaged 0-10,
10-20, 20-30, and 30-40 kg/ha, with average volume-weighted pH ranging from
about 5.3 to 4.2. Sites would at the same time be chosen to provide observa-
tions in geographically separate regions (e.g., New England and the southern
Appalachians) receiving comparable sulfate and hydrogen ion deposition.
Questions to be answered relative to Objective 2 are:
1.	At what level(s) of sulfate and hydrogen ion deposition do measurable
changes in lake or stream chemistry occur?
2.	Do lakes or streams of comparable alkalinity located in different geo-
graphical regions respond the same to similar levels of sulfate and
hydrogen ion deposition?
3
-------
Stage III. Development of Conceptual Approach
Monitoring sites were selected so as to best satisfy the objectives of the
program, that is, to detect trends relatable to effects of deposition, and to
compare responses of surface waters over deposition chemistry gradients and
between sensitive areas receiving comparable deposition. The first of these
two objectives requires sites in sensitive areas receiving acidic deposition,
as removed from disruptive anthropogenic influences (land use, local pollution,
fire) as possible. The second objective requires, in addition, the selection
of sites from a variety of locations exposed to various degrees of precipita-
tion acidity. Accordingly, monitoring sites are situated where surface waters
are commonly less than 200 yeq/1 total alkalinity (ANC). The national and
regional alkalinity maps generated by EPA have assisted in the identification
of these locations. Areas selected for monitoring to date include the Northern
Rocky Mountains; the Upper Midwest lake district (Minnesota, Wisconsin,
Michigan); Maine; Vermont; the Adirondack Mountains of New York; the Catskill
Mountains in southeastern New York; the Allegheny Mountains of southwestern
Pennsylvania; the southern Appalachians (Southern Blue Ridge Province of North
Carolina, Tennessee, and Georgia); and the Sandhills of south-central North
Carolina. These locations not only provide a broad sampling of low alkalinity
waters, but lie across a gradient of precipitation chemistry from essentially
background chemical concentrations in the northern Rockies to the acidic
precipitation of the East. Individual sites were selected to minimize dis-
ruptive effects of past or future land use, local atmospheric pollution, forest
fires, logging, and fish management. When possible, sites where concurrent
research will provide related data are chosen, and sites with good historical
data are preferred over those without, other factors being equal. Access-
ibility 1s also carefully considered.
4
-------
The rationale for the selection of the particular monitoring sites pres-
ently comprising the program was as follows. First, it was evident from the
geographic distribution of lakes, reservoirs, and streams in the United States
that natural lakes are the dominant resource of concern in the northern tier of
states (south to the limit of Pleistocene glaciation) and in the mountainous
West, but are replaced by streams and reservoirs in the South. In comparing
this distribution with known distributions of low alkalinity waters and deposi-
tion chemistry, it became further evident that monitoring sites should be
identified in the mountainous West, the upper Great Lakes region, the
Adirondacks, New England, and the Appalachians. Emphasis would be on lakes in
all areas except the Appalachians where the focus would be on streams and
reservoi rs.
Proceeding on these premises, opportunities for initiation of monitoring
were sought which (1) would provide lake, stream, or reservoir monitoring sites
in locations corresponding to the criteria for geographical location, low
alkalinity, and deposition chemistry and (2) were sites where ongoing work
could be modified or adapted to EPA's monitoring needs.
In the Upper Great Lakes region, the EPA-Duluth laboratory, together with
universities and state agencies, had begun a broad scale survey of lakes in
1978. Three subsets of these lakes plus six streams in upper Minnesota (in the
vicinity of the Boundary Waters Canoe Area and Voyageurs National Park), in
northeast Wisconsin, and in the eastern half of the Upper Peninsula of Michigan
were chosen for monitoring, with the work to be carried out by the University
of Minnesota-Duluth cooperatively with EPA-Duluth. Sampling for this program
was conducted in the fall of 1982 and the spring and summer of 1983. Subse-
quent reorientation of the Duluth program necessitated continuation of work
beyond the summer of 1983 by a new contractor. Monitoring of 38 lakes was
5
-------
assumed in fall 1983 by the University of Minnesota at Minneapolis, with
contractual assistance from the Wisconsin Department of Natural Resources. The
11st of monitored waters was modified to eliminate stream sites because it was
recognized that meaningful data could not be obtained for trend analysis on
flowing systems 1n a monitoring program limited to three sampling dates per
year. The list of lakes was further modified to eliminate some redundancy in
lake characteristics, to reflect recent information on water quality changes in
some Wisconsin lakes, to eliminate some insensitive lakes and lakes subject to
watershed disturbance, and to provide a broader range of lake coverage in
Minnesota.
In Maine, the U.S. Fish and Wildlife Service at the University of Maine
had just recently completed an excellent survey of lakes of New England, and
hart undertaken fisheries-related research on effects of acidic deposition. It
was logical to draw on their extensive expertise for the Northeast and to
expand their existing program to include long-term montoring. Accordingly,
monitoring of six lakes in the Tunk Lakes area of southeast Maine was begun in
fall 1982. Included in this project is exploratory work on non-destructive
fish sampling as well as chemical monitoring.
The State of Vermont had initiated lake monitoring on twenty lakes in
1981. Coverage was later expanded to 36 lakes with 24 sampled in alternate
years. EPA initiated partial funding of the Vermont effort in 1982.
The need for monitoring low alkalinity reservoirs 1n the Southeast had
been established. The Tennessee Valley Authority (TVA) possessed a large body
of chemical and other data on reservoirs of the region, and arrangements were
made for a survey by TVA of 54 reservoirs selected on the basis of the existing
data. Based on the results of that survey, 12 reservoirs were chosen for
long-term monitoring.
6
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In the West, ongoing or planned long-term studies by the U.S. National
Park Service and the U.S. Geological Survey provided monitoring coverage in
Sequoia National Park, California, and Rocky Mountain National Park, Colorado.
Proposed studies by the Geological Survey in the northern Cascade Mountains in
Washington have been delayed, but work has been initiated by the National Park
Service in the Olympic Mountains in that state. The most obvious omission in
the West appeared to be the northern Rocky Mountains, and a cooperative agree-
ment was implemented with Montana State University for a survey and subsequent
monitoring of lakes in southwest Montana and northwestern Wyoming near
Yellowstone National Park. From results of the survey, eleven lakes were
chosen for monitoring. These are all high-elevation, low-alkalinity lakes.
Monitoring is more complex for streams than for lakes because of the
influence of discharge coupled with season. Base flow tends to display uniforn
representative composition, but storm flow and snowmelt runoff may signifi-
cantly alter stream chemistry. Proper stream monitoring, therefore, requires
continuous recording of flow and sampling over a complete range of discharge,
including during and following storm events and snowmelt.
Obviously, the high frequency of sampling required for streams presents a
serious budgetary problem in a monitoring program. A reasonable solution was
achieved through a cooperative approach with the U.S. Geological Survey. The
Survey had initiated or was planning watershed studies on a number of low
alkalinity streams in the East. A single stream in each watershed was gauged
and instrumented for automatic sampling during storm or snowmelt events.
Wet-dry deposition sampling was carried out at each site. EPA arranged to
provide additional funding at three sites (the Catskills of southeastern New
York, the Alleghenies of southwestern Pennsylvania, and the Sandhills of North
Carolina) for sampling five or six additional streams on an approximately
7
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monthly basis to provide more broadly based monitoring data. Event samples
from the primary stream would provide indications of the effect of storms and
snowmelt on stream chemistry, and monthly sampling would provide information on
seasonal variation and long-term change.
Stream studies were also undertaken with TVA, in which five streams in the
southern Appalachians have been instrumented for automatic storm event sampl-
ing. The project is funded jointly by Task Group E Objectives E-01 and E-02.
In practically all cases, lakes or streams are clustered to facilitate
sampling and to minimize within-cluster variations in climate and deposition
patterns.
Each group of monitored lakes or streams must be sufficiently represented
by deposition chemistry monitoring sites to permit characterization of chemical
loading. In most cases, one or more NADP sites are located in the monitoring
area.
8
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SLMMARY
Data Quality Objectives; Long-Term
Surface Water Monitoring Program
Monitoring Objectives:
1.	Detect and measure long-term trends in the chemistry of low-alkalinity
surface waters that are related to atmospheric deposition.
2.	Compare the response of low-alkalinity waters
a.	Over a geographic gradient of hydrogen ion and sulfate deposition
b.	In different major sensitive geographic areas that receive comparable
deposition.
3.	Monitoring data will be used to establish baselines with which future
observations can be compared, to calculate time trends in significant
chemical variables, and to determine the frequency and severity of chemical
changes accompanying hydrologic events.
Data Collection Approach:
° Monitoring sites are located in sensitive (low alkalinity) regions
receiving acidic deposition, as removed from disruptive anthropogenic
influences as possible. (See site summary, Table 1).
0 Sites are selected from a variety of locations exposed to various degrees
of hydrogen ion and sulfate loading.
0 Areas selected for monitoring include the northern Rocky Mountains, the
Upper Midwest, the Adirondack Mountains, Maine and Vermont, the Catskill
9
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Mountains (southeast New York), the Allegheny Mountains (southwest
Pennsylvania), the southern Appalachians, and the south-central North
Carolina Sandhills.
0 Emphasis is on lakes in the glaciated Northeast, Upper Midwest, and
mountainous West, and on reservoirs in the Southeast where natural lakes
are virtually absent. Streams are monitored in New York, Pennsylvania,
North Carolina, and the southern Appalachians.
° NADP/NTN or other precipitation monitoring stations are located in each
area of surface water monitoring to provide characterization of atmospheric
chemical wet loading.
° Lakes are sampled three times annually: following ice-out, during summer
thermal stratification, and during fall overturn. The southeastern
reservoirs do not freeze and are sampled quarterly.
° Lakes and reservoirs are sampled at a single location 0.5-1.0 m below the
surface when not thermally stratified. When stratified, a second sample
is obtained 1-2 meters from the lake bottom, providing representative
samples of epilimnetic and hypolinmetic water.
° Streams are sampled seasonally over a range of flows, from base-flow to
high runoff conditions.
0 Lake and stream sampling are in accordance with EPA-prescribed protocols.
Data Quality Objectives:
1. Precision and accuracy
Determine whether long-term trends 1n the chemistry of low-alkalinity
lakes, streams, and reservoirs are occurring. Trends are defined as sustained
10
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year-to-year increases or decreases in the concentrations of any of the
following variables at the stated confidence intervals:
pH (_+ 0.1 units)
alkalinity (_+ 1U%)
Z Ca, Mg, Na, K (+ b%)
S04 (+ b%)
NO3 (+ 10%)
Z SO4, NO3, CI (+ 10%)
Table 2 sets forth the required minimum analytical detection limits.
2.	Representativeness
Collect data of sufficient quality to characterize individual lakes,
streams, or reservoirs in terms of each characteristic measured and to generate
distributions within lake, stream, or reservoir sets for each measured charac-
teristic. Monitored sets of water bodies are located nationally to provide
sampling coverage of low alkalinity (< 200 yeq/1) waters over the existing
range of deposition of sulfate and hydrogen ions.
3.	Completeness
The quantity and temporal distribution of data must assure adequate
measurement of seasonal patterns of water chemistry to permit comparison of
conditions from year to year.
4.	Comparability
A standard sampling and analysis protocol prescribes the procedures used
by each sampling team and analytical laboratory. Data will be calculated and
11
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reported in the same units. Audit samples are analyzed three times each year
to determine comparability of results among investigators.
12
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Table 1
FY84 EPA-Funded Long-Term Surface Water Monitoring Projects
Location
Principal
Investigator
Agency
Sites
Type
Start
Montana-Wyoming
Gordon Pagenkopf
Montana State U.
11
lakes
Fall 1983
Upper Great Lakes
Region(MN, HI, MI)
Patrick Brezonik
U. of Minnesota
38
lakes
Fall 1982
Maine
Terry Haines
USFWS, U. of ME
6
lakes
Fall 1982
Vermont
Wallace McLean
State of Vermont
36
lakes
Winter 1981
New York
Peter Murdoch
USGS, Albany, NY
7
streams
Summer 1983
New York
Charles Driscoll
Syracuse University
17
lakes
Spring 198i>
Pennsylvania
James Barker
USGS, Harrisburg, PA
6
streams
Summer 1983
North Carolina
Kent Crawford
USGS, Raleigh, NC
b
streams
Summer 1983
Southern Blue Ridge
Province (NC, TN, GA)
Harvey 01 em
TVA, Chattanooga, TN
5
12
streams
reservoirs
Fall 1983
Fall 1982
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Table 2. Required Minimum Analytical Detection Limits, Expected Ranges, and
Intralaboratory Relative Precision. (Adapted from National Surface
Water Survey protocol).
Parameter (a)
Units
Required
Detection
Limit
Expected
Range
Intralab Relati ve
Precision Goal
1%) (b)
Acidity
yeq/1
5
10-150
10
Alkalinity (ANC)
yeq/1
5
0-1000
10
Al, Extractable
mg/1
0.005
0.005-1.0
10(A1>0.01),20(A1<0.01)
Al, Total
mg/1
0.005
0.005-1.0
10(A1>0.01),20(A1<0.01)
Ca
yeq/1
0.01
0.5-20
5
Cl-
yeq/1
0.01
0.2-10
5
Color
ALPH units
0
0-200
+5(c)
DIC
my/1
0.05
0.1-15
10
DOC
mg/1
0.1
0.1-50
5(DOC>5),10(DOC<5)
F-
yeq/1
0.005
0.01-0.2
5
Fe
ueq/1
0.01
0.01-5
10
K
yeq/1
0.01
0.1-1
5
My
yeq/1
0.01
0.1-7
b
Mn
yeq/1
0.01
0.01-5
10
Na
yeq/1
0.01
0.5-7
5
nh4
yeq/1
0.01
0.01-2
5
no3
yeq/1
0.005
0.01-5
10
pH, field
pH units
-
4-7
+0.1(c)
pH, lab
pH units
-
4-7
+0.05(c)
Secchi Disk
meters
•


Si02
mg/1
0.05
2-25
5
so42-
yeq/1
0.05
1-20
5
Specific Conductance yS/cm
(d)
1-100C
1 1
Total P
yeq/1
0.002
0.005-0.07
' 10(P>0.01),20(P<0.01)
(a) Dissolved ions and metals are being determined, except where noted.
(b)	Unless otherwise noted, this 1s the relative precision at concentrations
above about 10 times instrumental detection limits.
(c)	Absolute precision goal in terms of applicable units.
(d)	Blank must be <1.0 yS/cm.
14
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Appendix IV. Working Protocol for Sampling, Sample Analysis, and
CA/QC for the USEPA Long-Term Surface Water Monitoring Program.
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3/15/85
WORKING PROTOCOL FOR SAMPLING, SAMPLE ANALYSIS, AND QA/QC
FOR THE USEPA LONG-TERM SURFACE WATER MONITORING PROGRAM
Introduction
An EPA program for long-term monitoring of lakes and streams was initiated
in 1982 within the NAPAP organizational framework. An ad hoc committee, with
representation from USEPA, USGS, TVA, USDA-FS, USFWS, USNPS, and Brookhaven
National Laboratory, developed a draft sampling and analysis protocol to
standardize monitoring efforts among the member Task Group E agencies. This
document, with periodic reviews and updates, has served as the standard
protocol for the EPA surface water monitoring program since its inception.
In 1984 EPA initiated the National Surface Water Survey (NSWS). This
three-phase program is scheduled to culminate in the selection of geographic-
ally representative lakes for long-term monitoring in the east, upper midwest,
and mountainous west. This third phase of NSWS is expected to subsume the
existing long-term monitoring program. Most of the existing sites are probably
compatible with Phase III owing to their location in low alkalinity regions and
their positioning with respect to minimization of extraneous effects that could
compromise interpretations of observed changes or trends.
The methods manual developed for NSWS (Hlllman et al_.) has been used,
together with the Task Group E sampling and analysis protocol document, to
produce the present "working protocol" for the long-term monitoring program.
Laboratory analytical methodology, detection limits, and QA/QC procedures are
more adequately and precisely specified; site selection criteria are not
1
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included. The objective has been to align the long-term monitoring methodology
with that of NSWS, without undue disruption of existing monitoring procedures.
The present document replaces the Task Group E protocol (Aquatic Effects Task
Group, March 1984 revised) as the procedural document for the EPA monitoring
program. Participating agencies and institutions must be able to demonstrate
their use of these or equivalent sampling, analysis, and QA/QC procedures.
Audits will be conducted to determine compliances with these procedures.
This document recognizes that U.S. Geological Survey protocols used in
their stream research and monitoring program are not necessarily identical with
those set forth here. By prior agreement with the EPA project officer, USGS
protocols are acceptable 1n the existing cooperative EPA-USGS stream studies.
Differences are few, and are noted where appropriate in this document. The
USGS laboratory at Denver, where samples from the cooperative studies are
analyzed, is a participant in the NSWS. Therefore, there should be no differ-
ences in laboratory analytical methodology.
1.0 Collection of Samples in the Field
1.1 Lakes
Lakes should be sampled near their deepest points (at least 20 m
from shore if possible). If the water column is not thermal ly
stratified, one sample should be collected approximately one-half
meter beneath the water surface. If the water body is stratified,
one sample should be collected approximately one-half meter beneath
the water surface and a second one or two meters above bottom. These
two samples should not be mixed or composited. A plastic closing
sampling device of the Van Dorn type should be used to obtain samples
at depth; do not use a metal sampler. Samples should be collected
2
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from the sampling device in plastic bottles that have been treated as
described in 3.0. (See 6.1 regarding replicate samples.)
1.2	Streams
Samples are obtained by hand as near mid-stream as possible,
using a properly cleaned and rinsed plastic container of appropriate
size. (See 6.1 regarding replicate samples.) Keep hand away from
mouth of container, and minimize the number of persons handling
samples.
1.3	Carefully record any observed conditions that might affect analysis
or interpretation of samples in field notes or sampling log.
1.4	Key project personnel who are responsible for sample integrity must
be identified.
2.D Measurements
A set of "core" measurements are specified for the EPA monitoring
program. These measurements, which are considered to provide sufficient
characterization of stream or lake water quality for assessment of
sensitivity and changes related to acidification, are:
pH (field and laboratory air-equilibrated)
total alkalinity
specific conductance
temperature
Secchi disc transparency (lakes)
true color
3
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major cations (Ca, Mg, Na, K)
major anions (SO4, NO3, CI)
total aluminum (filtered).
Additional measurements, including titrated acidity, DIC, DOC, F*, Fe, Mn,
NH4, Si02» and total P, are being made by NSWS; some of these analyses,
while not required, are also being made by some cooperators in the
monitoring program.
Care must be taken to assure that the highest quality deionized water
is used throughout all stages of sampling and analysis. Specific conduct-
ance of such water should not exceed 1.0 yS/cm.
3.0 Sample Containers
3.1	Type
Containers should be composed of high density linear poly-
ethylene, with polypropylene caps (do not use polyseal caps).
3.2	Cleaning of Plastic Containers
3.2.1	Containers to be used for pH, acidity, alkalinity, and anion
determinations will be rinsed three times with deionized
water, filled with deionized water and allowed to stand for 48
hours, then emptied and sealed in clean plastic bags until
used in the field.
3.2.2	Sample containers for cations and metals will be rinsed three
times with deionized water, rinsed three times with 3N HNO3
(prepared from Baker Instra-Analyzed HNO3 or equivalent), then
rinsed six times with deionized water. They will then be
filled with deionized water and allowed to stand for 48 hours.
4
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They are then emptied, capped, and placed in clean plastic
bags.
3.2.3 After the initial cleaning, 5 percent of the containers will
be checked by filling with deionized water, capping, and
slowly rotating the container so water touches all surfaces.
Check conductivity; if greater than 1 yS/cm in any of the
checked containers, rerinse all containers and retest 5
percent.
4.0 Sample Filtration
4.1	For anion analysis (including SO4, NO3, CI): Rinse a cleaned 250 ml
bottle three times with sample water which has been filtered directly
into the sample bottle {discarding each rinse). Then fill to 250 ml
with filtered sample. Use a 0.45 um pore size membrane filter (e.g.,
Nucleopore polycarbonate). Ice or refrigerate. A good portable unit
for filtering samples at field sites is described by Kennedy et al.,
1976.
4.2	For metals and cation analyses (including Ca, Mg, Na, K): Filter 100
ml of sample into an acid-washed bottle (see 3.2.2) after rinsing
three times by passing 100 ml of sample through a 0.45 Mm filter and
discarding each rinse. Add a 1-ml ampoule of concentrated ultrapure
nitric acid (Baker Ultrex or equivalent) to the sample. Ice or
refrigerate.
5
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4.2.1 U.S. Geological Survey presently uses 0.1 um filters for A1,
Fe, and Mn in their stream work. (They are conducting
comparisons of various pore sizes.)
4.3 Samples for pH, alkalinity, specific conductance, and true color are
not filtered.
Sample Preservation and Maximum Holding Times
5.1	Refrigeration at 4°C is the only recommended method of preservation
for the following constituents. (Maximum allowable holding times
appear in parentheses.) For present purposes, icing must be consid-
ered equivalent to 4°C refrigeration.
specific conductance (14 days)
color (48 h£)
pH (no approved holding time; field sample should be analyzed
immediately, and air-equilibrated laboratory samples as
soon as possible)
alkalinity (14 days, according to NSWS protocol)
sulfate (28 days)
chloride (28 days)
silica (28 days)
nitrate-nitrogen (7 days)
5.2	Refrigeration at 4°C plus acidification with nitric acid to pH < 2 is
recommended for the following constituents:
calcium (6 months)
magnesium (6 months)
6
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sodium (6 months)
potassium (6 months)
aluminum (6 months)
5.3 Labels on all containers should include sufficient information to
permit tracing the sample back to point and time of collection.
QA/OC Samples: Lakes
Replicate samples, filtration blanks, and container blanks (total of
four additional samples) are to be obtained one time for approximately
every ten lakes sampled, as described below in Sections 6.1, 6.2, and 6.3.
These are minimum requirements. For each project, this results in the
following:
No. of Rep/Blank Sets
	Project	 Per Sampling	Interval*	Per Year
Montana State University	1	3
University of Minnesota	3 (1/state)	9
University of Maine	1	3
Vermont	2	8
Syracuse University	2	8
TVA	1	4
* Sampling Intervals are:
Minnesota, Maine — spring, summer, fall
Montana -- July, August, September (approximately)
Vermont, TVA -- spring, summer, fall, winter
Syracuse -- quarterly (17 lakes are sampled monthly; 2 rep/blank sets
per quarter)
7
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6.1	Replicate Samples
Obtain a replicate sample by repeating step 1.1 or 1.2. These
replicate samples are analyzed to determine the adequacy of the
sampling process in obtaining a representative sample of the lake or
stream at a particular point in time.
6.2	Filtration Blanks
Prepare two filtration blanks by filtration of deionized water
into properly cleaned (1) anion container (3.2.1) and (2) cation
container (3.2.2). Analysis of the filtrate for the appropriate ions
determines the adequacy of the filtration process and the cleanliness
of the sample containers.
6.3	Container Blanks
Prepare one unfiltered container blank by filling a properly
cleaned container (see 3.2.1) with deionized water. Analysis of this
sample for pH, alkalinity, specific conductance, and strong/weak
acidity (if applicable) provides a check on the adequacy of the
container.
6.4	EPA-USGS Cooperative Stream Monitoring Projects
Replicate samples, filtration blanks, and container blanks will
be taken at the primary (intensive) stream site each time that site
is sampled. In addition, replicates will be obtained on two satel-
lite streams three times yearly under low, intermediate, and high
flow conditions.
8
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7.0 Measurement Methods
7.1 pH
7.1.1	Field measurement. Measure as soon after collection as
possible. pH should be measured to _+ 0.02 units using a high
quality pH meter with an expanded or digital scale. A good
electrode is the Corning No. 476182 glass combination. The
electrode should be calibrated in the field 1n pH 4 and 7
buffer solutions and checked with a sulfuric acid solution
with a theoretical pH of 4 (5 x 10"® molar I^SO^). Rinse probe
copiously with sample or deionized water and immerse in
sample. Do not stir. The electrode should remain in the
sample until there is no discernable drift in the pH reading,
but no longer than 15 minutes. At least 10 percent of samples
must be measured in replicate. Upon completion of measurement
of a sample batch, recheck pH of acid solution.
7.1.2	Laboratory (air-equilibrated) measurement. For normalization
of pH values obtained by various participating investigators,
air-equilibrated pH measurements should be obtained in the
laboratory. Equilibration is achieved by bubbling samples
with standard air containing 300 ppm CO2 for 20 minutes while
stirring on a magnetic stirrer. Use an acid-washed (see
3.2,2) fritted glass diffuser for dispersal of air in the
sample. Measure pH immediately following equilibration,
following procedure 1n Section 7.1.1. At least 10 percent of
samples must be measured in replicate. (Ref: Hillman et al.)
9
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7.2	Specific Conductance (yS/cm at 25°C). Measured in the laboratory
using a wheatstone bridge type conductivity meter. See Section 8.2
for calibration and QA/QC instructions. (Ref: Hillman et a]_.)
7.3	True color. Comparison of centrifuged sample with platinum-cobalt
color standards. (Ref: USEPA, 1979).
7.4	Total alkalinity. Titration with 0.020 N H2SO4 using Gran plot
calculations. Fixed endpoint titration is not acceptable. (Ref:
Gran, 1950, 1952; Golterman and Clymo, 1969; Zimmerman and Harvey,
1978-1979; Hillman et al.)
7.5	Calcium, magnesium, sodium, and potassium. Atomic absorption
spectrometry, direct aspiration. (Ref: USEPA, 1979).
7.6	Sulfate, chloride, nitrate. Ion chromatography. (Ref: Hillman et
al.)
7.7	Aluminum, total filtered. Graphite furnace atomic absorption (EPA
Method 202.2). (Ref: Hillman et al_; USEPA 1979).
7.8	Phosphorus, total. Colorimetric, automated, block digestor AAII
(USEPA, 1979), or USGS colorimetric, phosphomolybdate, automated
(Hillman £t_ al.).
7.9	Ammonium. Colorimetric, automated phenate (USEPA, 1979).
7.10	Kjeldahl nitrogen. Colorimetric, automated phenate (USEPA, 1979).
7.11	Table 1 states desired minimum analytical detection limits and
within-laboratory relative precision goals.
Quality Control Procedures
Procedures normally followed by participants in the long-term
monitoring program should be continued. The intent of this section is to
ensure the common use of standardized quality control procedures for
10
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Table 1. Required minimum analytical detection limits and within-laboratory
relative precision (note reporting units). (NOTE: Some listed
measurements may not apply to the existing long-term montoring
program. See 2.0.)
Parameter (a)
Units
Requi red
Detection
Limit
Intralab Relative
Precision Goal (%) (b)
Acidity
yeq/1
5
10
Alkalinity
yeq/1
5
10
A1, Total
mg/1
0.005
10 0.01), 20 (AK0.01)
Ca
veq/1
0.5
5
ci-
yeq/1
0.3
5
Color
ALPH units
0
+ 5 (c)
DIC
mg/1
0.05
10
DOC
mg/1
0.1
5 (D0C>5), 10 (D0C<5)
F"
yeq/1
0.3
5
Fe
mg/1
0.01
10
K
yeq/1
0.3
5
Mg
yeq/1
0.8
5
Mn
mg/1
0.01
10
Na
yeq/1
0.4
5
nh4
yeq/1
0.6
5
no3
yeq/1
0.1
10
pH, field
pH units
«.
+ 0.1 (c)
pH, lab
pH units
-
+ 0.05 (c)
Si02
mg/1
0.05
5
S042'
yeq/1
1.0
5
Specific
yS/cm
(<0
1
Conductance



Total P
mg/1
0.002
10 (P>0.01), 20 (P<0.01)
(a)	Dissolved ions and metals are determined, except where noted.
(b)	Unless otherwise noted, this is the relative precision at concentrations
above about 10 times instrumental detection limits.
(c)	Absolute precision goal in terms of applicable units.
(d)	Blank must be <1.0 yS/cm.
-------
comparability of results. Any of the procedures given here that are not
now being followed by cooperating agencies or institutions should be added
to their QA/OC programs.
8.1 Precision and Accuracy
8.1.1 Precision
8.1.1.1	Definition: Precision is a measure of agreement
among individual measurements of the same property,
under prescribed similar conditions. In this program
we recognize (1) intra!aboratory and (2) sampling and
analysis precision.
8.1.1.2	Intralaboratory Precision
Intra laboratory precision is determined by
analyzing an individual sample in replicate. This
should be done for at least one sample per batch for
each variable being measured. The difference between
the two resultant values is multiplied by 0.89 to
approximate the standard deviation. The standard
deviation divided by the mean of the duplicate values
and multiplied by 100 yields the relative standard
deviation (RSD) in percent. The RSD is an opera-
tional statistic (also called the coefficient of
variation) Indicating the dispersion of a set of
replicate mesurements as a percentage of the mean
value. In reporting precision for a given variable,
12
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show the number of replicate analyses, range of RSD
values, and average RSD.
8.1.1.3 Sampling and Analysis Precision
Sampling precision cannot be estimated directly.
However, the precision in the combined sampling and
analysis procedure can be estimated from the analysis
of the replicate samples taken in the field (see
6.1). Then the sampling variance can be estimated by
subtracting the analytical variance obtained in
8.1.1.2. The precision in the combined sampling and
analysis operation is estimated by applying the same
methodology described for intralaboratory precision
(8.1.1.2).
8.1.2 Accuracy
8.1.2.1 Definition: Accuracy is a measure of the closeness
of an individual measurement or an average of a
number of measurements to the true value. Accuracy
includes both precision and recovery and can be
expressed as a percent recovery or percent bias
interval.
8.1.2.2 Evaluation of Accuracy
Two approaches are specified:
13
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8.1.2.2.1	Fortify an actual sample with a known
amount of material, analyze the fortified
(spiked) sample, and calculate the percent
recovery. This should be done for at
least one sample per batch for each
variable being measured. In reporting
accuracy for a given variable, show the
number of spiked analyses, concentration
of spike, range of bias (+ and - percent),
and average bias (+ or - percent).
8.1.2.2.2	Audit samples are provided three times
each year by an independent contractor.
Analysis results are compared with the
known concentrations to determine (1)
intra!aboratory bias and (2) comparability
of measurements among the various monitor-
ing projects.
Cautions Regarding Specific Conductance and Alkalinity
8.2.1 Specific Conductance
After calibration and prior to measuring the first sample,
measure the conductance of a QC standard. The standard should
have a theoretical or certified conductance of about 50 uS/cm
(0.0005000 M KC1 has a conductance of 73.90 yS/cm at 25°C).
It must be prepared from a stock solution that is different
from that from which the calibration standard is prepared. If
14
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the measured conductivity is not within 1 percent of the
certified value, then restandardize the meter and cell and
repeat the measurement.
Remeasure the conductance of the QC standard at least
once every 10 samples.
One sample per batch must be measured in duplicate.
8.2.2 Alkalinity
At least 10 percent of alkalinity titrations must be run
in replicate. Agreement must be +_ 10 percent or less. If
not, run a third determination.
Further Procedural Checks
Once each variable in a sample has been determined, there are
several procedures which must be followed to check the correctness of
the analyses. These are outlined below.
8.3.1 Cation-Anion Balance
Theoretically, the sum of equivalents of anions equals
the sum of equivalents of cations 1n a sample. In practice,
this rarely occurs due to analytical variability and ions
which are present but not measured. For each sample, the sums
of the measured anion and cation equivalents, total ion
strength, and ion percent difference are calculated as
follows:
15
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Z anions = [CT] + [F-] + [N03"] + [S042"] + [HCO3-] + [CO32-]
Z cations ¦ [Na+] + [K+] + [Ca2+] + [Mg2+] + [NH^] + [H+]
z anions - z cations
% Ion Difference = 	x 100
z anions + z cations
Total ion strength = E anions + Z cations
7	+
[Omission of F", CO3 , and NH4 will not significantly affect
results. Alkalinity plus H+ (calculated from pH) may be used
for HCO3".]
All concentrations are expressed as microequivalents/
liter (ueq/1). Table 2 lists factors for converting mg/1
to peq/1 for each of the parameters.
Samples which have a poor ion balance may have to be
reanalyzed. Table 3 lists the reanalysis criteria.
8.3.2 Specific Conductance Balance
An estimate of the specific conductance of a sample can
be calculated by summing the equivalent conductance values for
each measured ion at infinite dilution.
The calculated conductance is determined by multiplying
the concentration of each 1on (1n yeq/1) by the appropriate
factor (F) in Table 4.
The calculated conductance for the entire sample is
obtained from the relationship,
16
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I (F x Cone, in yeq/1)
Calculated Conductance = 	
1000
The percent difference between measured conductance and
calculated conductance is given by
Calculated - Measured
% Conductance Difference = 	 x 100
Measured
Samples which have percent conductance differences
exceeding the limits listed in Table 3 may have to be
reanalyzed.
Table 2. Factors to convert mg/1 to yeq/1.

Factor
Ion
(yeq/1 per mg/1)
Ca2+
49.9
ci-
28.2
co32-
33.3
F"
52.6
K+
25.6
Mg2+
82.3
Na+
43.5
nh4+
55.4
no3-
16.1
so42-
20.8
Alkalinity
20.0
(as CaC03)

17
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Table 3. Chemical reanalysis criteria.
A.	Cation-Anion Balance
Total Ion Strength (peq/1)	% Ion Difference*
<50	> +_ 60
> 50 < 100	> + 30
>_ 100	> + 15
B.	Calculated vs. Measured Conductance
Measured Conductance (yS/cm)	% Conductance Difference*
<5	>50
> 5 < 30	>30
~> 30	> 20
* If the percent difference exceeds these values, the sample is
reanalyzed. When reanalysis is indicated, the data for each para-
meter are examined for possible analytical error. Any suspect
parameters are then reanalyzed and the above percent differences
recalculated.
Table 4,
Conductance factors (F) of ions.3

Ion*5
Conductance
(uS/cm at 25°C)
per ueq/1
1000
Ionb
Conductance
(uS/cm at 25°C)
per ueq/1
IMS-
Ca2+
59.5
no3-
71.4
Mg2+
53.1
Cl-
76.3
Na+
50.1
S042"
79.8
K+
73.5
hco3"
44.5
H+
350.0
0H-
198.0
nh4+
73.4


a From Mclnnes, 1961.
b H+ and OH- calculated as: [H+] ¦ 10~PH x 106 ueq/1.
18
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Hillman, D.C., F. A. Morris, J. F. Potter, and S. J. Simon (undated). Methods
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Zimmerman, A. P., and H. H. Harvey. 1978-1979. Final report on sensitivity to
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20
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Annual Report
on the
EPA Program for Long-Term Monitoring of
Surface Waters 1n the United States
NAPAP Project No. El-15
by
Charles F. Powers
and
Marvin 0. All urn
CorvalUs Environmental Research Laboratory
U.S. Environmental Protection Agency
200 S.W. 35th Street
Corvallis, Oregon 97333
March 1985
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