United States
Environmental
Protection Agency
Great Lakes
National Prograr
EPA905-R-97-012c
June 1 997
Lake Michigan Mass Balance Study
(LMMB) Methods Compendium
Volume 1: Sample Collection Techniques
•a*
Printed on P,.cyc/»d Pop
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FDA
United States Office of Water EPA-905-R-97-012a
Environmental Protection 4303 October 1997
Agency
Lake Michigan Mass Balance Study (LMMB)
Methods Compendium
Volume 1: Sample Collection Techniques
US EPA
MID-CONTINENT ECOLOGY DIVISION
LIBRARY
DULUTH, MM 55804
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Lake Michigan Mass Balance Study
(LMMB) Methods Compendium
Volume 1: Sample Collection Techniques
Printed on Pecyc/ed Pop«r
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Acknowledgments
This compendium was prepared under the direction of Louis Blume of the EPA Great Lakes National
Program Office. The compendium was prepared by DynCorp Environmental and Grace Analytical Lab.
Special thanks are extended to Dr. William Telliard and staff at EPA's Office of Water for technical
assistance and support of this project. The methods contained in this compendium were developed by the
following Principal Investigators (Pis) participating in the Lake Michigan Mass Balance (LMMB) Study:
Eric Crecelius, Ph.D., Battelle Marine Sciences Laboratory, Sequim, WA
David Edgington, Ph.D., Great Lakes Research Facility, Milwaukee, WI
Brian Eadie, Ph.D., NOAA, Ann Arbor, MI
Steven Eisenreich, Ph.D., Rutgers University, New Brunswick, NJ
John Gannon, Ph.D., USGS National Biological Survey, Ann Arbor, MI
Nathan Hawley, Ph.D., NOAA, Ann Arbor, MI
Bob Hesselberg, USGS National Biological Survey, Ann Arbor, MI
Ron Hites, Ph.D., Indiana University, Bloomington, IN
Mark Holey, Fish and Wildlife Service, Green Bay, WI
Alan Hoffman, U.S. EPA AREAL, Research Triangle Park, NC
Tom Holsen, Ph.D., Illinois Institute of Technology, Chicago, IL
Peter Hughes, United States Geological Survey, Madison, WI
Jim Hurley, Ph.D , University of Wisconsin, Madison, WI
Tom Johengen, Ph.D., NOAA, Ann Arbor, MI
Jerry Keeler, Ph.D., University of Michigan, Ann Arbor, MI
Robert Mason, Ph.D., University of Maryland, Solomons, MD
Mike Mullin, U.S. EPA Large Lakes Research Station, Grosse He, MI
Edward Nater, Ph.D., University of Minnesota, Minneapolis, MN
Jerome Nriagu, Ph.D., University of Michigan. Ann Arbor, MI
John Robbins, Ph.D., NOAA, Ann Arbor, Michigan
Ron Rossmann, Ph.D., EPA Large Lakes Research Station, Grosse He, MI
Martin Shafer, Ph.D., University of Wisconsin, Madison, WI
William Sonzogni, Ph.D., Wisconsin State Lab of Hygiene, Madison, WI
Clyde Sweet, Ph.D., Illinois State Water Survey, Champaign, IL
Deborah Swackhamer, Ph.D., University of Minnesota, Minneapolis, MN
Pat Van Hoof, Ph.D., NOAA, Ann Arbor, MI
Glenn Warren, Ph.D., U.S. EPA, GLNPO, Chicago, IL
Marvin Palmer, GLNPO, Chicago, IL
Disclaimer
This document describes sampling and analytical methods used by Pis participating in the LMMB Study.
Due to ihe nature and low concentrations ot pollutants monitored in the siikK. main of the methods used in
the LMMB Study represent state-of-the art techniques that will be refined further as new technology is
developed and as necessary to resolve matrix interferences. Therefore, the procedures described in this
compendium should be considered to accurately reflect procedures in use by the LMMB Study Pis at the
time of publication. Users of this document should recognize that these procedures are subject to change.
Users of this document also should recognize that these methods do not constitute "approved EPA methods'
for use in compliance monitoring programs. Publication of these methods is intended to assist users of
LMMB Study data and to provide a reference tool for researchers interested in building upon LMMB Study
findings. Mention of company names, trade names, or commercial products does not constitute
endorsement or recommendation lor use
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Foreword
The Lake Michigan Mass Budget/Mass Balance (LMMB) Study was initiated in late 1993 as part of the
Lakewide Management Plan (LaMP) for Lake Michigan. The Lake Michigan LaMP and the LMMB Study
were developed to meet requirements mandated by Section 118 of the Clean Water Act (CWA); Title III,
Section 112(m) of the Clean Air Act Amendments; and Annex 2 of the Great Lakes Water Quality
Agreement. Organizations participating in the development of these programs included: EPA Region 5,
the EPA Great Lakes National Program Office, the National Oceanic and Atmospheric Administration, the
U.S. Geological Survey, the U.S. Fish and Wildlife Service, the Michigan Department of Natural
Resources, the Wisconsin Department of Natural Resources, the Illinois Department of Natural Resources.
and the Indiana Department of Environmental Management. In general, the primary goal of the LaMP and
the LMMB Study is to develop a sound, scientific base of information with which to guide future toxic load
reduction efforts at the federal, state, and local levels.
This compendium describes the sampling and analytical methods used in the LMMB Study. For ease of
use, the compendium is organized into three volumes. Volume 1 describes sampling procedures used in the
study; Volumes 2 and 3 describe analytical procedures used by each PI. Because sampling apparatus and
techniques are generally geared towards specific matrices, Volume 1 is organized according to sample
matrix (e.g., air, water, sediment, tissue, etc). Volumes 2 and 3 are organized by pollutant type (e.g,
organics, metals, biologicals) because laboratories and instrumentation are typically set up to address
specific pollutants rather man specific matrices.
Each Principal Investigator (PI) was required to follow specific quality control requirements necessary to
meet data quality and measurement quality objectives for the LMMB Study. To assist users of this
document, Appendix A provides the measurement quality objectives (MQOs) established by each PI for
his/her sampling and analysis program.
Finally, EPA has made no attempt to standardize the procedures submitted by Pis for publication in this
compendium. Therefore, the methods provided in this document contain varying levels of detail. Appendix
B provides names, addresses and phone numbers for each PI and for each EPA Project Officer (PO).
Specific questions about the procedures used in the study should be directed to the appropriate PI or PO
listed in Appendix B.
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Table of Contents
Volume 1
Sample Collection Techniques
CHAPTER 1: AIR
LMMB 001 Standard Operating Procedure for Air Sampling for Semivolatile Organic
Contaminants Using the Organics High-Volume Sampler (Sweet, C.) 1-3
LMMB 002 Standard Operating Procedure for Precipitation Sampling Using XAD-2 and
MIC Collectors (Sweet, C.) 1-31
LMMB 003 Standard Operating Procedure for Air Sampling for Metals Using the
Dichotomous Sampler (Sweet, C.) 1-53
LMMB 004 Standard Operating Procedure for Sampling Trace Metals in Precipitation
Using Modified Aerochem Collectors (Vermette, S. and Sweet, C.) 1-71
LMMB 005 Metals Cleaning Procedures for Teflon Bottles and Rigid HOPE (Vermette, S.
and Sweet, C.) 1-87
LMMB 006 Standard Operating Procedure for Sampling of Vapor Phase Mercury (Keeler, G.
and Landis, M.) 1-91
LMMB 007 Standard Operating Procedure for Sampling of Mercury in Precipitation
(Keeler, G and Landis, M.) 1-107
LMMB 008 Standard Operating Procedure for Sampling of Particulate Phase Mercury
(Keeler, G. and Landis, M.) 1-123
LMMB 009 Standard Operating Procedure for Dry Deposition Sampling: Dry Deposition of
Atmospheric Particles (Paode, R. and Holsen, T.) 1-137
CHAPTER 2: WATER
LMMB 010 Standard Operating Procedure for Sample Collection of Atrazine and Atrazine
Metabolites (Eisenreich, S., Schottler, S., and Mines, N.) 1-159
LMMB 011 HOC Sampling Media Preparation and Handling; XAD-2 Resin and GF/F Filters
(Crecelius, E. and Lefkovitz, L.) 1-167
LMMB 012 Standard Operating Procedure for Site Selection and Sampling for Mercury in
Lakewater (Mason, R. and Sullivan, K.) 1-175
LMMB 013 Field Sampling Using the Rosette Sampler (Warren, G.) 1-185
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Table of Contents
LMMB 014 Standard Operating Procedure for the Sampling of Particulate-Phase and
Dissolved-Phase Organic Carbon in Great Lakes Waters (Grace Analytical Lab) . . 1-193
LMMB 015 Standard Operating Procedure for Chlorophyll-a Sampling Method: Field
Procedure (Grace Analytical Lab) 1-199
LMMB 016 Standard Operating Procedure for Primary Productivity Using 14C: Field
Procedure (Grace Analytical Lab) 1 -205
LMMB 017 USGS Field Operation Plan: Tributary Monitoring (USGS/Eisenreich, S.) 1-215
LMMB 018 Trace Metal and Mercury Sampling Methods for Lake Michigan Tributaries
(Shafer, M.) 1-221
CHAPTERS: SEDIMENT
LMMB 019 Standard Operating Procedure for Collection of Sediment Samples
(Edgington, D. and Robbins, J.) 1-239
LMMB 020 Trap Sample Splitting (wet): Use of Sediment Traps for the Measurement of
Particle and Associated Contaminant Fluxes (Eadie, B.) 1-245
CHAPTER 4: PLANKTON
LMMB 021 Standard Operating Procedure for Sampling Lake Michigan Lower Pelagic
Foodchain for PCBs, Nonachlor, and Mercury (Swackhamer, D.,
Trowbridge, A., and Nater, E.) 1-253
LMMB 022 Sampling Procedure for Collection of Benthic Invertebrates for Contaminant
Analysis (Warren, G.) 1-269
LMMB 023 Standard Operating Procedure for Phytoplankton Sample Collection and
Preservation (Grace Analytical Lab) 1-273
LMMB 024 Standard Operating Procedure for Zooplankton Sample Collection and
Preservation (Grace Analytical Lab) 1-277
CHAPTER 5: FISH
LMMB 025 Fish Processing Method (Hesselberg, R.) 1-285
LMMB 026 Quality Assurance Project Plan for Lake Trout and Forage Fish Sampling for
Diet Analysis and/or Contaminant Analysis (Brown, E. and Eck, G.) 1-291
LMMB 027 Quality Assurance Project Plan for Coho Sampling for Contaminant and Diet
Analysis (Holey, M. and Elliott, R.) 1.357
IV
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Table of Contents
Volume 2
Organic and Mercury Sample Analysis Techniques
CHAPTER 1: ORGANIC ANALYSIS
LMMB 028 Instrumental Analysis and Quantisation of Polycyclic Aromatic Hydrocarbons
and Atrazine: IADN Project (Cortes, D. and Brubaker, W.) 2-3
LMMB 029 Analysis of PCBs and Pesticides in Air and Precipitation Samples : IADN
Project - Gas Chromatography Procedure (Basu, I.) 2-23
LMMB 030 Analysis of PCBs, Pesticides, and PAHs in Air and Precipitation Samples:
IADN Project - Sample Preparation Procedure (Basu, I.) 2-61
LMMB 031 Analysis of PCBs, Pesticides, and PAHs in Air and Precipitation Samples:
Sample Preparation Procedures (Harlin, K. and Surratt, K.) 2-115
LMMB 032 Standard Operating Procedure for the Analysis of PAHs and Atrazine by
GC/lon Trap MS (Peters, C. and Harlin, K.) 2-165
LMMB 033 Standard Operating Procedure for the Analysis of PCBs and Organochlorine
Pesticides by GC-ECD (Harlin, K., Surratt, K., and Peters, C.) 2-189
LMMB 034 Standard Operating Procedure for Isolation, Extraction and Analysis of
Atrazine, DEA and DIA (Eisenreich, S., Schottler, S., and Hines, N.) 2-243
LMMB 035 Standard Operating Procedures for Semivolatile Organic Compounds in Dry
Deposition Samples (Eisenreich, S. and Franz, T.) 2-251
LMMB 036 Extraction and Cleanup of XAD-2 Resin Cartridges for Polychlorinated
Biphenyls and Trans-No;,achlor (Crecelius, E. and Lefkovitz, L.) 2-257
LMMB 037 Extraction and Cleanup of Glass Fiber Filters for Polychlorinated Biphenyls
and Trans-Nonachlor (Crecelius, E. and Lefkovitz, L.) 2-271
LMMB 038 PCB Congener Analysis of XAD-2 Resins and GFF Filters Using GC/ECD
(Crecelius, E. and Lefkovitz, L.) 2-285
LMMB 039 PCBs and Pesticides in Surface Water by XAD-2 Resin Extraction (Wisconsin
State Lab of Hygiene) 2-307
LMMB 040 Extraction and Cleanup of Sediments for Semivolatile Organics Following the
Internal Standard Method (Van Hoof, P. and Hsieh, J.) 2-325
LMMB 041 Analysis of Polychlorinated Biphenyls and Chlorinated Pesticides by Gas
Chromatography with Electron Capture Detection (Van Hoof, P. and Hsien, J.) .... 2-335
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Table of Contents
LMMB 042 Standard Operating Procedure for the Analysis of PCB Congeners by GC/ECD
and Trans-Nonachlor by GC/MS/ECNI (Swackhamer, D., Trowbridge, A.,
and Nater, E.) [[[ 2-347
LMMB 043 Extraction and Lipid Separation of Fish Samples for Contaminant Analysis and
Lipid Determination (Schmidt, L.) ........................................ 2-381
LMMB 044 Analysis of Total PCBs and PCB Congeners and Trans-nonachlor in Fish by Gas
Chromatography/Negative Chemical lonization Single Ion Mass Spectrometry
(Schmidt, L.) [[[ 2-389
CHAPTER 2: MERCURY ANALYSIS
LMMB 045 Standard Operating Procedure for Analysis of Vapor Phase Mercury (Keeler, G.
and Landis, M.) [[[ 2-403
LMMB 046 Standard Operating Procedure for Analysis of Mercury in Precipitation (Keeler, G.
and Landis, M.) [[[ 2-417
LMMB 047 Standard Operating Procedure for Analysis of Particulate Phase Mercury
(Keeler, G. and Landis, M.) ............................................ 2-431
LMMB 048 Standard Operating Procedure for Mercury Analysis (Mason, R. and Sullivan, K.) . . 2-445
LMMB 049 Total Mercury Analysis in Aqueous Samples (Hurley, J.) ..................... 2-453
LMMB 050 Standard Operating Procedure for Analysis of Sediment for Total Mercury Using
the Cold Vapor Technique with the Leeman Labs, Inc. Automated Mercury
System (Uscinowicz, T. and Rossmann, R.) ............................... 2-473
LMMB 051 Mercury in Plankton (Nater, E. and Cook, B.) .............................. 2-505
LMMB 052 Versatile Combustion-Amalgamation Technique for the Photometric
Determination of Mercury in Fish and Environmental Samples (Willford, W.,
Hesselberg, R., and Bergman, H.) ....................................... <^-51 1
LMMB 053
Analysis of Fish for Total Mercury (Nriagu, J.) .............................. 2-527
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Table of Contents
Volume 3
Metals, Conventionals, Radiochemistry, and Biomonitoring
Sample Analysis Techniques
CHAPTER 1: METALS
LMMB 054 Laboratory Methods for ICP-MS Analysis of Trace Metals in Precipitation (Talbot, J.
and Weiss, A.) 3-3
LMMB 055 Standard Operating Procedures for Preparation, Handling and Extraction of Dry
Deposition Plates: Dry Deposition of Atmospheric Particles (Paode, R. and
Holsen, T.) 3-25
LMMB 056 Standard Operating Procedure for EPA's LBL Energy Dispersive X-Ray
Fluorescence Spectrometry (Kellogg, R.) 3-43
LMMB 057 Analysis of Surface Waters for Trace Elements by Inductively-Coupled Plasma
Mass Spectrometry (Shafer, M. and Overdier, J.) 3-83
CHAPTER 2: CONVENTIONALS
LMMB 058 ESS Method 130.1: General Auto Analyzer Procedures (Wisconsin State Lab
of Hygiene) 3-127
LMMB 059 ESS Method 200.5: Determination of Inorganic Anions in Water by Ion
Chromatography (Wisconsin State Lab of Hygiene) 3-135
LMMB 060 ESS Method 140.4: Chloride - Automated Flow Injection Analysis (Wisconsin
State Lab of Hygiene) 3-145
LMMB 061 ESS Method 220.3: Ammonia Nitrogen and Nitrate + Nitrite Nitrogen,
Automated Flow Injection Analysis Method (Wisconsin State Lab of Hygiene) 3-153
LMMB 062 ESS Method 230.1: Total Phosphorus and Total Kjeldahl Nitrogen,
Semi-Automated Method (Wisconsin State Lab of Hygiene) 3-163
LMMB 063 ESS Method 310.1: Ortho-Phosphorus, Dissolved Automated, Ascorbic Acid
(Wisconsin State Lab of Hygiene) 3-173
LMMB 064 ESS Method 310.2: Phosphorus, Total, Low Level (Persulfate Digestion)
(Wisconsin State Lab of Hygiene) 3-179
LMMB 065 ESS Method 340.2: Total Suspended Solids, Mass Balance (Dried at
103-105 C) Volatile Suspended Solids (Ignited at 550 Cj (Wisconsin State Lab
of Hygiene) 3-187
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Table of Contents
LMMB 066 Outline of Standard Protocols for DOC Analyses (Shafer, M.) 3-193
LMMB 067 Outline of Standard Protocols for Particulate Organic Carbon (POC) Analyses
(Baldino, R.) 3-201
LMMB 068 ESS Method 360.2: Silica Dissolved, Automated, Colorimetric (Wisconsin State
Lab of Hygiene) 3-207
LMMB 069 ESS Method 360.3: Silica, Dissolved, Micro Level Automated, Colorimetric
(Wisconsin State Lab of Hygiene) 3-213
LMMB 070 ESS Method 370.2: Sulfates Colorimetric, Automated, Methylthymol Blue
(Wisconsin State Lab of Hygiene) 3-219
LMMB 071 ESS Method 370.3: Sulfates Colorimetric, Automated Flow Injection,
Methylthymol Blue (Wisconsin State Lab of Hygiene) 3-227
LMMB 072 Standard Operating Procedure for Chloride and Silica in Lake Water
(Lachat Method) (Grace Analytical Lab) 3-235
LMMB 073 Standard Operating Procedure for Dissolved Reactive Phosphorous
(Lachat Method) (Grace Analytical Lab) 3-247
LMMB 074 Standard Operating Procedure for Ammonia (Lachat Method)
(Grace Analytical Lab) 3-255
LMMB 075 Standard Operating Procedure for Nitrate, Nitrite (Lachat Method)
(Grace Analytical Lab) 3-263
LMMB 076 Standard Operating Procedure for Total Kjeldahl Nitrogen (Lachat Method)
(Grace Analytical Lab) 3-275
LMMB 077 Standard Operating Procedure for Total and Dissolved Phosphorous
(Lachat Method) (Grace Analytical Lab) 3-285
LMMB 078 Analysis of Total Suspended Particles (TSP) and Total Organic Carbon (TOC)
in Air Samples: Integrated Atmospheric Deposition Network (IADN) TSP/TOC
Procedure (Wassouf, M. and Basu, I.) 3-297
LMMB 079 Standard Operating Procedures for Determining Total Phosphorus, Available
Phosphorus, and Biogenic Silica Concentrations of Lake Michigan Sediments
and Sediment Trap Material (Johengen, T.) 3-305
LMMB 080 Standard Operating Procedure for Perkin Elmer CHN Analyzer (Model 2400)
(Eadie, B.) 3-313
LMMB 081
Quality Assurance Plan for the Use of Sediment Traps (Eadie, B.) 3-319
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Table of Contents
CHAPTER 3: RADIOCHEMISTRY
LMMB 082 Standard Operating Procedure for Primary Productivity Using MC: Laboratory
Procedures (Grace Analytical Lab) 3-327
LMMB 083 Protocol for Standard Analysis for Cesium-137 (Robbins, J. and Edgington, D.) ... 3-337
LMMB 084 Determination of the Activity of Lead-210 in Sediments and Soils (Edgington, D.
and Robbins, J.) 3-341
CHAPTER 4: BIOMONITORING
LMMB 085 Standard Operating Procedure for Chlorophyll-a and Pheophytin-a (Turner
Designs Method) (Grace Analytical Lab) 3-349
LMMB 086 ESS Method 150.1: Chlorophyll - Spectrophotometric (Wisconsin State Lab
of Hygiene) , 3-357
LMMB 087 Standard Operating Procedure for Phytoplankton Analysis (Grace Analytical Lab) . 3-365
LMMB 088 Standard Operating Procedure for Zooplankton Analysis (Grace Analytical Lab) . . . 3-395
LMMB 089 Quality Assurance Project Plan: Diet Analysis for Forage Fish (Davis, B. and
Savino, J.) 3-417
CHAPTER 5: SHIPBOARD MEASUREMENTS
LMMB 090 Standard Operating Procedure for GLNPO Turbidity: Nephelometric Method
(Palmer, M.) 3-443
LMMB 091 Standard Operating Procedure for GLNPO Total Alkalinity Titration (Palmer, M.) . . 3-451
LMMB 092 Standard Operating Procedure for Electrometric pH (Palmer, M.) 3-457
LMMB 093 Standard Operating Procedure for Meteorological Data Aboard the RV/Lake
Guardian (Palmer, M.) 3-463
LMMB 094 Standard Operating Procedure for GLNPO Specific Conductance: Conductivity
Bridge (Palmer, M.) 3-467
LMMB 095 Total Hardness Titration (Palmer, M.) 3-473
LMMB 096 Standard Operating Procedure for the Analysis of Dissolved-Phase Organic
Carbon in Great Lakes Waters (Grace Analytical Lab) 3-477
LMMB 097 Standard Operating Procedure for the Analysis of Particulate-Phase Organic
Carbon in Great Lakes Waters (Grace Analytical Lab) 3-485
LMMB 098 Standard Operating Procedure for the Sampling and Analysis of Total
Suspended Solids in Great Lakes Waters (Grace Analytical Lab) 3-499
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Volume 1
Chapter 1: Air
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Standard Operating Procedure for
Air Sampling for Semivolatile Organic
Contaminants Using the Organics
High-Volume Sampler
Clyde W. Sweet
Office of Air Quality
Illinois State Water Survey
2204 Griffith Drive
Champaign, 1161820
December 1993
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Standard Operating Procedure for Air Sampling for Semivolatile
Organic Contaminants Using the Organics High-Volume Sampler
1.0 Overview
This SOP is intended to provide a step by step procedure for collecting airborne suspended
particles on quartz fiber filters and airborne semivolatile organic contaminants on XAD-2 resin
cartridges using a High-Volume (Hi-Vol) sampler.
The data collected from analyses of 20.3 x 25.4 cm quartz filter., and XAD-2 cartridges from the
organics Hi-Vol samplers will be used primarily for the Lake Michigan Loading Study (LMLS)
and the Integrated Atmospheric Deposition Network (IADN) programs. Samples at the Sleeping
Bear Dunes site, which is part of the Integrated Atmospheric Deposition Network, were sampled
and analyzed by Indiana University. The sampling method is identical apart from a few minor
differences in QC samples. This site represents 10 % of the samples for this method. The
objectives of the programs are to determine the loadings of persistent toxic contaminants from the
atmosphere to the Great Lakes from both urban and regional sources. Sampling sites have been
strategically located around the Great Lakes basin to provide these estimates.
A modified Hi-Vol sampler is used for the collection of suspended particles and organic
contaminants in air. The modification consists of an aluminum cylinder behind the filter holding a
XAD-2 cartridge. Specific analytes of interest that will be collected from this sampler are listed in
Table I. The sampler operates for one 24-hour period every 12 days. Samples are collected
during the week following the installation of filters. Therefore, every other week, the sampler will
not contain filters or a cartridge, unless blanks are run.
The flow rate through the sampler is 34 cubic meters per hour. This interval is used because of the
need to collect about 800 cubic meters of air in order to get a reliable measurement of the target
contaminants at the remote sites in the network. Because of the low concentrations of target
compounds, the operator must follow this protocol carefully to insure sample integrity.
This sample will be collected by passing air through a 20.3 x 25.4 cm quartz filter and then
through an XAD-2 resin cartridge. The sampler inlet is a standard TSP shelter. The filters, which
are pre-cleaned and pre-weighed at the Illinois State Water Survey (iSWS), and the XAD-2
cartridge are shipped to the site, and returned to ISWS for anaKses The analytical methods are
documented in laboratory SOPs.
The following procedure is used by the field operator to maintain the organics Hi-Vol sampler, and
to remove and replace glass fiber filters and XAD-2 cartridges in a manner that will maintain
sample integrity. Dates of operation and sample collection will be provided in the monthly site
operation protocol. Generally one filter and cartridge sample will be collected every 12 days The
site must be visited each week to collect samples and set-up samplers for the next week's sample
collection. Any questions on the sampling methods or operation of equipment should be directed
to the follow ing mdi\ uhuU The Principal I in estimator will Iv the prime contact for all
methodological and general questions. The HP A Project Lead is the second contact if the
Principal Investigator cannot be contacted.
1-5
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SOP for Air Sampling for Semivolatile Organic Contaminants
Using the Organ/cs High-Volume Sampler
Volume 1, Chapter 1
Table 1. Elements/Contaminants to be Determine
on Glass Fiber Filters and XAD-2 Resin
Filter
Parameter
Glass fiber
Total suspended
particles
Organic Carbon
XAD-2
PCB Congeners
Chlorinated Pesticides
a-HCH
g-HCH
p,p' DDT and metabolites
HCB
Dieldrin
Alpha-chlordane
Gamma-chlordane
Trans-nonachlor
Atrazine
PAHs
acenaphlhylene
acenaphthene
fluorene
phenanthrene
anthracene
fluoranthene
pyrene
chrysene
benzo(a)anthracene
benzo(b)nuoranthene
benzo(k)fluoranthene
benzo(a)pyrene
indeno( 123cd)pyrene
dibenzo(a,h)anthracei:e
benzol ghi)per\lene
ix'tene
coronene
benzo(e)pyrene
1-6
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Volume 1, Chapter 1
SOP for Air Sampling for Semivolatile Organic Contaminants
Using the Organics High-Volume Sampler
Sampling Protocol and General Operations
Principal Investigator:
Clyde W. Sweet
Illinois State Water Survey
2204 Griffith Dr.
Champaign, IL61820
Project Lead:
Angela Bandemehr
USEPA/GLNPO
77 W. Jackson
Chicago, IL 60604
Equipment Operation and Maintenance
Paul Nelson
Illinois State Water Survey
Phone: 217-244-8719
Fax: 217-333-6540
Phone: 217-333-7191
Fax: 217-333-6540
Phone: 312-886-6858
Fax: 312-353-2018
Supplies and Packaging
Mike Snider
Illinois State Water Survey
Phone: 217-244-8716
2.0 Summary of Method
Site operators will visit the site weekly to check for proper functioning of equipment and to either
collect a sample or set-up the sample collector. Samples will be collected on the prescribed day.
If it is raining or snowing, or hazardous conditions prevail, samples may be collected later in the
day at the discretion of the site operator. If the sample can not be collected on the prescribed
sampling day, the Principal Investigator must be notified. The following sampling activities will
take place in the order listed.
1) Initial equipment inspection and testing.
2) Filter/cartridge removal and labeling.
3) Packaging filter/cartridge and sample report form for shipment.
4) Installation of a new filter/cartridge and setting flow rate.
5) Resetting the sampler timer.
6) Waste disposal and clean up.
7) Sample shipment
Steps 1 through 3, 6 and 7 will be conducted when the filters are changed and Steps 1 and 4
through 6 during collector set-up. Each of these steps will be detailed in the following sections.
1-7
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SOP for Air Sampling for Semivolatile Organic Contaminants
Using the Organics High-Volume Sampler Volume 1, Chapter j
3.0 Sample Handling and Preservation
Due to the expense of sampling and analyzing the quartz filters and XAD-2 cartridges, a limited
number of sites have been selected in order to achieve the goals of this study. Therefore, every
sample is important and represents a significant portion of that site's yearly estimate. Any
contamination through mishandling or lack of preservation could cause a bias in the program
estimates. The filter/cartridge should only be removed from, and installed into the holders in an
enclosed area. The cartridges should be at the same temperature as the holders to avoid a tight fit
due to thermal expansion.
Once in place, the filters should not be removed until the end of the sampling cycle (one 24-hour
sampling period over a 12-day period). Follow all procedures for filter removal, packaging and
shipment.
4.0 Interferences
Due to the nature of the chemicals being collected, all precautions should be taken to avoid
contamination of the sample and sampler during weekly visits and sample collection. The sampler
functions to collect samples of airborne particles that will be analyzed for the parameters list in
Table I. It is very important to avoid touching the filters and to prevent any dust or dirt from
contaminating the deposit on the filter. The surfaces on the organics hi-vol inlet should be
inspected each week and any dust or dirt wiped away with a damp cloth.
5.0 Safety
In any field operation, emphasis must be place on safety. Site operators must be aware of the
potential safety hazards to which they are subjected. Follow all safety protocols and equipment
guidelines, and be prepared for emergency situations. The site operator is responsible for his/her
safety from potential hazards including but not limited to:
5.1 Travel: When traveling to the site be sure to check on road conditions and weather
advisories. Carry1 emergency supplies (warm clothing, food, water) when
traveling in the winter. Always let someone know where you're goins and when
you expect to be back. Always carry a first aid kit.
5.2 Electrical: For obvious problems (fire, scorching, blown UINCM. aim u'T the power for the
circuit involved and notify ISWS. Never attempt electrical repairs other than
replacing fuses and circuit boards. Unplug the sampler before making
replacements. Be especially cautious if conditions arc \vet.
5.3 Insect pests: If you are allergic to insect stings, you should carry a kit prescribed by a
physician. Be especially cautious if nests or large numbers of stinging insects are
present. Notify ISWS of all problems.
1-8
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SOP for Air Sampling for Semivolatile Organic Contaminants
Volume 1, Chapter 1 Using the Organics High-Volume Sampler
6.0 Equipment and Supplies
Careful use, proper maintenance and cleaning extends the life of serviceable field equipment.
Permission should be obtained from the Principal Investigator to use anything other than the
equipment and supplies mentioned in this list (supplied by ISWS).
6.1 Serviceable Equipment
These items will stay at the site at all times.
-Modified Hi-Vol sampler for organics (pump and timer unit, inlet shelter)
-Filter holder with snap-on cover
-XAD-2 cartridge holder
-Fine forceps
6.2 Consumable Equipment
These items will be sent to the site operator in bulk or once every four weeks.
-Pre-weighed, numbered quartz fiber filters
-XAD-2 cartridges
-XAD-2 transport tins
-Teflon tape
-Black electrical tape
-Latex gloves
-Spare fuses
-Kimwipes
7.0 Calibration and Standardization
The Hi-Vol sampler will be checked quarterly against a standard orifice by ISWS personnel. A
magnehelic gauge provides a flow check before and after each sampling run.
7.1 Sampler Inlet
Each week check the condition of the sampler inlet and the quart/ fiber filter cover plate. Wipe up
any dust and dirt using a damp Kimwipe.
7.2 Timer and Pump Unit
Figure I shows the mechanical timer and Figure 2 shows the electronic timer. Each week check
the operation of the timer and pump. The following checks should be made:
I) The time of day should be correct to local time.
1\ The "Total Sampling Tune" should have advanced 24 \\«\\<* • I 440 minutes) from the
previous week, if a sample period was programmed dimn>j the preceding week.
1-9
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SOP for Air Sampling for Semivolatile Organic Contaminants
Using the Organics High-Volume Sampler
Volume 1, Chapter
Turn on the pump manually (see Section 8.1) and let it run for two minutes to determine
magnehelic reading.
TIME OF DAY
TRIPPERS
Figure 1. Mechanical Timer
1-10
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SOP for Air Sampling for Semivolatile Organic Contaminants
Volume 1, Chapter 1 Using the Organics High-Volume Sampler
8.0 Procedures
The following procedures will be discussed:
I) Initial Inspection.
2) Filter/cartridge removal and labeling.
3) Filter/cartridge packaging for shipment.
4) Installation of new filter/cartridge.
5) Setting the clock and sample timer.
6) Waste disposal/clean-up.
7) Sample shipment.
Steps I through 3, 6 and 7 will be conducted when the filters are changed (every two weeks) and
Steps I and 4 through 6 during collector set-up. Each of these steps will be detailed in the
following sections.
8.1 Initial Inspection (mechanical timer).
Note: This timer is on most of the Organics Hi-Vols.
Upon arrival at the site, make an initial inspection of the equipment to determine proper operation
for the week. This procedure is accomplished every week. When a sample is set up, this
procedure should be used to check final settings before leaving the site. Refer to Figure I for
timer details. Check the elapsed time counter reading on the lower left corner of the timer.
Record this number on the Data Reporting Form. The counter reads in hundredths of an hour.
The large red arrow should point to the correct day and time.
Turn on the sampler by moving the "Hand Trip" switch to the "On" position and note whether the
pump is running normally. After two minutes, record the value on the magnehelic on the Sample
data Sheet and the Weekly Site Visit Sheet. Turn the sampler off after two minutes.
This inspection, which should be entered into the Weekly Site Visit Sheet and the Sample Data
Sheet, will include:
I) General comments. Comments that might affect the sample collection that week, i.e., fire
in the area, wind storms, abnormal precipitation, vandalism, etc.
2) Equipment evaluation. Note any damage to equipment. If the sampler is not operating
properly, notify ISWS as soon as possible.
3) Magnehelic reading.
4) Total Sampling Time reading.
8.2 Initial Inspection (electronic timer).
Note: This timer is installed in most ot the TSP Hi-vols and sonic ul the orgamcs Hi-vols.
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SOP for Air Sampling for Semivolatile Organic Contaminants
Using the Organ!cs High-Volume Sampler Volume 1, Chapter 1
Upon arrival at the site, make an initial inspection of the equipment to determine proper operation
for the week. This procedure is accomplished every week. When a sample is set up, this
procedure should be used to check final settings before leaving the site. Refer to Figure 2 for
timer details. Check the timer to confirm that the following settings:
The "Power" switch should be "On"
• The "Set" switch should be on "Display"
• The "Displav" switch should be in "Time of the Day" position
• The "Sampler" switch should be in "Timer" position
• The "Sample After" should be on the setting required on the previous week.
The "Sample Every" switch should be on nine day setting.
The "SampleFor" switch should be on the 24 hour setting.
If, on the prior week, the sampler was set to collect a sample, the Total Sampling Time reading on
the timer should have advanced 1440 minutes. Check this reading and record it on the Data
Reporting Form.
Turn on the sampler by moving the "Sampler" switch to the "Opposition and note whether the
pump is running normally. After two minutes, record the value on the magnehelic on the Weekly
Site Visit Sheet and the Sample Data Sheet. Turn the sampler off after two minutes.
This inspection, which should be entered into the Weekly Site Visit Sheet and the Sample Data
Sheet, will include:
I) General comments. Comments that might affect the sample collection that week, i.e., fire
in the area, wind storms, abnormal precipitation, vandalism, etc.
2) Equipment evaluation. Note any damage to equipment. If the sampler is not operating
properly, notify ISWS as soon as possible.
3) Magnehelic reading.
4) Total Sampling Time reading.
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Volume 1, Chapter 1
SOP for Air Sampling for Semivolatile Organic Contaminants
Using the Organics High-Volume Sampler
Ff
•
SI
Dis£
•
Tir
1ST
•
,OW
3 1 di-
HOURS (set)
MINUTES (setl
DIS
Sample o
Start
Time ,
^LAY
Ef Time
of
mm Day
ner
SAMPLE SAt
AFTER E\
C
AC
POWt
SAMPLE
FOR
r
(
*r^m
0
Push
Total Sampling Time P 0
! ! I |
R
OF
Push
S
3N t:
M
, P
L
"F E
R
in
^J
1
out
Figure 2. Electronic Timer
1-13
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SOP for Air Sampling for Semivolatile Organic Contaminants
Using the Organics High-Volume Sampler Volume 1. Chapter^
8.3 Filter/Cartridge Removal and Labeling
At the end of a sampling cycle, the filter and cartridge are removed by the following procedure.
The quartz fiber filter should not be touched, and should be placed in aluminum foil as soon as
possible. The following procedures are accomplished only during the replacement of the
filter/cartridge.
8.3.1 Glass Fiber Filter Removal
I) Turn on the sampler manually and record the magnehelic gauge reading
after two minutes.
2) Lift the triangular hood of the sampler in order to extract the filter holder. The
filter is protected by a filter cover plate that exposes the filter during the sampling
period. This plate should be covering the filter. While unscrewing the filter
holder leave this piate down. Remove the filter holder from the sampler by
unscrewing the nuts on the comers of the holdei in a diagonal pattern. Let the
nuts fall to side, freeing the filter holder.
3) Lift the filter cover plate and remove the filter holder. Place the snap-on filter
cover over the filter holder to protect the filter from dust when transporting it to
the enclosure. Close the sampler hood and transport the filter holder to an
enclosed area.
4) Once in an enclosed area, remove the snap-on filter cover. Remove the quartz
fiber filter by unscrewing the outer casing of the filter holder which is held on by
nuts on the short sides of the filter holder.
5) Place latex gloves on. Remove the filter and fold it in half lengthwise
with the deposit side facing in. Wrap the filter securely in the same piece
of aluminum foil that the filter originally came in (the dull side of the foil
should face the filter). Attach a label on the outside of the aluminum foil
and place the filter in a zip-lock plastic bag.
8.3.2 XAD-2 Cartridge Removal
Refer to Figure 3.
I) Open the front door of the sampler, exposing the cartridge holder. To remove
holder, loosen the hand screw nut on the tnp of the ^ artnd_v holder. Once the top
has been completely loosened and off, proceed to unscrew the bottom nut. This
nut remains on the cartridge holder. Remove the cartridge holder and transport
the holder to an enclosed area.
2) Once inside the enclosure, turn the cartridge holder upside down in order to
remove the stainless steel cartridge containing the XAD-2 resin.
Wrap the XAD-2 cartridge in aluminum foil and place the resin cartridge into the
resin cartridge transport tin. Seal the tin by placing a piece of Teflon tape around
(he area uheiv ihe top aiul hcitoni meet. Co\er th:- . ;:ii Hack electrical tape.
Place a label on ihe im
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SOP for Air Sampling for Semivolatile Organic Contaminants
Volume 1, Chapter 1 Using the Organics High-Volume Sampler
8.3.3 Sample Labeling
All organics Hi-Vol air samples should be labeled using the same alphanumeric system.
The label includes:
The "Site ID" letter for the site,
The "Sample" which will be "H" for Hi-Vol samples and "T" forTSP samples.
The "Sample Type", designating either a routine sample (01), duplicate (02). or a QA
sample,
The "Matrix" designation, "F" for the glass fiber filter and "C" for the XAD-2 resin
cartridge and.
The "Date" of collection in a year-month-day format.
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SOP for Air Sampling for Semivolatile Organic Contaminants
Using the Organics High-Volume Sampler
Volume 1, Chapter 1
XAD CARTRIDGE
FLANGE
CARTRIDGE HOLDER
BOTTOM NUT
Figure 3. XAD-2 Cartridge and Cartridge Holder
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Volume 1, Chapter 1
SOP for Air Sampling for Semivolatile Organic Contaminants
Using the Organics High-Volume Sampler
An example label and the valid codes are listed below.
Hi-Vol Sample
Site Sample Samp.Type Matrix Year Month Day
Valid Codes
Site ID
Sample
U-Brule River S-Sleeping Beai Dunes H- Hi-Vol
C-Champaign B-Beaver Is. T- TSP
N-Manitowoc E-Eagle Harbor
W-Chiwaukee T-Sturgeon Point Matrix
V-South Haven I-Indiana Dunes
M-Muskegon J-IIT Chicago C- XAD Cartridge
L-Lake Guardian F- Filter
Sample Type
01- Routine Sample
02-Duplicate Sample
TB-Trip Blank
FB- Field Blank
Example: SH-OlC-930119 is the code for a routine organics Hi-Vol XAD-2 sample
collected at the Sleeping Bear Dunes site on January 19, 1993.
8.4 Filter Packaging for Shipment
The filter and cartridge should be shipped in a in a box with packing material. They may be
shipped together with other samples.
8.5 Installation of New Filter/Cartridge
At the start of a new sampling cycle, a new filter and cartridge should be installed. The monthly
site protocol will list the dates that installation of the filter and cartridge is to take place.
8.5.1 Quartz Fiber Filter Installation
1) Examine the filter holder It should be wiped clean with a damp (DI water) cloth
if necessary.
2) Place on a pair of latex gloves. Within the enclosure, unwrap one of the pre-
weighed and place it m the filter holder, numhcri'd w'
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SOP for Air Sampling for Semivolatile Organic Contaminants
Using the Organics High-Volume Sampler ^ Volume 1, Chapter 1
6) Place the filter holder nuts onto the filter holder and tighten diagonally. Place the
filter cover plate over the filter holder and close the sampler hood.
8.5.2 XAD-2 Cartridge Installation: Refer to Figure 3.
I ) Place on a pair of latex gloves. Within the enclosure, open a new resin cartridge
sampling tin and unwrap the aluminum foil.
2) Place the XAD-2 cartridge into the cartridge holder with the flange facing down.
Transport the cartridge holder to the sampler.
3) At the sampler, open the sampling door, make sure the orange o-ring at the bottom
of the cartridge holder is seated in the proper groove. Install the cartridge holder,
bottom end first, screwing the hand screw nut on the cartridge onto the threaded
pump device.
4) Make sure the orange o-ring at the top of the cartridge holder is in place and screw
the top of the cartridge holder into place by holding the cartridge holder steady
and using the hand screw nut to tighten onto the threaded end of the cartridge
holder.
5) Turn the sampler on. If the motor does not run smoothly, there may be a
leak. Retighten the fittings on the filter and cartridge holders. Once the
motor is running smoothly, record the magnehelic reading after two
minutes.
8.6 Setting the Clock and the Timer
8.6.1. Mechanical Timer
This procedure is used during sample set-up in samplers with mechanical timers. Refer to
Figure 1 for timer details.
1 i Turn the large ring clockwise so that the red pointer points to the correct day and
lime.
2) Attach the switch trippers to the timer ring. The .v//r
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SOP for Air Sampling for Semivolatile Organic Contaminants
Volume 1, Chapter 1 Using the Organics High-Volume Sampler
8.6.2 Electronic Timer
This procedure is used during sample set-up in samplers (TSP samplers and a few of the
organics Hi-vols) with electronic timers. Refer to Figure 2 for timer details.
I) Check whether the "Time of the Day" display is correct. Toggle to the "Sample
Start Time" and see if this reads "09.00" Record any deviations on the site log
and on the sample data sheet. To reset either setting, place the "Display" switch
to the proper setting and use the "Fast/Slow" toggle to make adjustments. The
"Time of the Day" should be the current time using military units. The "Sample
Start Time'' should be set to "09.00". The sample start time must be at least
30 minutes after the time of day and the function switch must be left in the "Time
of the Day'' position.
To set up the sample run:
2) Position the "Sample After" switch to the number of days to be skipped before the
start of the first sampling period. This position will change each week and will
need to be calculated from the sampling date specified in the monthly site
protocol. Position "0" will initiate sampling the first time the "Time of Day"
equals "Sample Start Time" For example if the present time is 10:00 and the
sample start time is 09:00 sampling will start 23 hours later. If position " I" is
selected, sampling will start one day + 23 hours later at 09:00.
3) The "Sample Every" switch sets the sampler to repeat the sampling cycle after the
indicated number of days. This switch should be left in the maximum position
(nine days) unless otherwise directed.
4) The "Sample For" switch sets the sampling time in hours and should be left at the
24-hour setting unless directed otherwise.
Note: Some of the samplers have positive detent switches rather than knobs.
These must be seated in the detent to control the sampler.
5) Set the "Sampler" switch to the "Timer" position. Finally, push the "Set" switch
down to the "Timer" position momentarily and release. This enters the new
sampling program. This initializes all timing functions. These steps must he done
last, after all other switches have been set.
6) Be sure to record the Total Sampling Time reading.
Check the timer to confirm that the following settings:
The "POWER" switch should be "ON"
The "SET" switch should be on "DISPLAY"
The "DISPLAY" switch should be in "TIMF OF H \Y" position
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SOP for Air Sampling for Semivolatile Organic Contaminants
Using the Organics High-Volume Sampler Volume 1, Chapter 1
The "SAMPLER" switch should be in "TIMER" position
• The "SAMPLE AFTER" should be on the setting required for the next
sampling period.
• The "SAMPLE EVERY" switch should be on nine day setting.
• The "SAMPLE FOR" switch should be on the 24 hour setting.
8.7 Waste Disposal and Clean-up
Waste may include materials used to clean the inlet and packaging materials. Dispose of these
properly.
8.8 Sample Shipping
Once they are properly packaged (8.4), send the samples, Sample Data Sheets, and the Weekly
Site Visit Sheet to the Principal Investigator. Keep a copy of the both Sheets in the site log book.
UPS 2nd day delivery is the preferred shipping method. U.S. Priority mail may also be used.
8.9 Quality Assurance Samples
Occasionally the protocol will require collection of quality assurance samples. Travel blanks are
filters that are shipped with regular sample filters and stored at the site during the collection
period. They should be returned to ISWS unopened after the specified period. Field blanks are
filters that are installed in the sampler during the sampling period. The sampler should be
unplugged or the silver tripper removed so that the sampler does not run. On samplers with
electronic timers, the "SAMPLER" switch is turned off so that the sampler does not run. These
samples should have a "TB" or "FB" in the sample code (Section 8.3.3). They are run to assess
overall contamination during periods when the cartridge and filter are installed in the sampler but
no air is being sampled. Specific instructions will be included in the shipping box for the
implementation requirements of these samples.
8.10 Equipment Maintenance and Trouble Shooting
The sampler is exposed to weather, and wind-blown dust and should be cleaned each
week by wiping dirty surfaces with a clean damp cloth.
The operation of the sampler should be checked each week. If the pump does not run or
there is a problem with the tinier displu\, consult the trouble shooting tiuide below and
contact ISWS. For more information, consult the site operator's manual or contact the
manufacturer, Andersen Samplers Inc., 4215 Wendell Dr., Atlanta, GA, 800-241-6898.
Table 3 includes some trouble shooting information.
On samplers with electronic timers, a flashing timer indicates that a power failure has
occurred. Reset the timer and notifv ISWS.
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Volume 1, Chapter 1
SOP for Air Sampling for Semivolatile Organic Contaminants
Using the Organics High-Volume Sampler
Table 3. Trouble shooting
SYMPTOM/CAUSE
Collector fails to operate
No power to instrument
Circuit breaker continues to break
Electrical short
Motor speed not steady
Air leak
Timing or programming error
"SAMPLER" switch not on "TIMED", or
"SAMPLE EVERY" not in proper position
"DISPLAY" switch not on "TIME OF DAY"
REMEDY
Check switches and power source.
Reset circuit breaker.
Instrument needs servicing
Tighten filter holder screws and
cartridge holder nuts
Check that the switches are in detents
and all instructions have been
followed (see Section 2.4.2)
Occasionally motor replacement may be necessary. Figure 4 gives a step-by step
description for removal of the old motor. Follow the sequence in reverse to install a new
motor. This diagram applies only to IADN master sites (Eagle Harbor, Sleeping Bear, and
Sturgeon Point).
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SOP for Air Sampling for Semivolatile Organic Contaminants
Using the Organics High-Volume Sampler
Volume 1, Chapter 1
Figure 4. Motor Installation
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SOP for Air Sampling for Semivolatile Organic Contaminants
Volume 1, Chapter 1 Using the Organics High-Volume Sampler
High-Volume Summary
This summary does not take the place of the detailed SOP and should be used strictly to reinforce the
procedure when in the field. Steps 1 through 3 will be conducted when the filters are changed, and
Steps 1, 4 and 5 during collector set-up.
1.0 Initial Inspection
Upon arrival at the site, make an initial inspection of the equipment to determine proper operation
for the week. This inspection will be entered into the Weekly Site Visit Sheet.
1.1 General comments. Comments that might affect the sample collection that week, i.e., fire in the
area, wind storms, abnormal precipitation, vandalism, etc.
1.2 Equipment evaluation. Note any damage to equipment. If the sampler is not operating properly,
notify 1SWS as soon as possible.
1.3 Clean sampler inlet.
1.4 Magnehelic reading.
1.5 Total Sampling Time reading.
2.0 Filter/Cartridge Removal and Labeling
2.1 Glass Fiber Filter Removal
2.1.1 Turn on the sampler and record the magnehelic reading after two minutes.
1.1.2 Lift the triangular hood of the sampler in order to extract the filter holder. The filter is
protected by a filter cover plate that exposes the filter during the sampling period. This
plate should be covering the filter. While unscrewing the filter holder leave this plate
down. Remove the filter holder from the sampler by unscrewing the nuts on the corners of
the holder in a diagonal pattern. Let the nuts fall to side, freeing the filter holder.
2.1.3 Lift the filter cover plate and remove the filter holder. Quickly place the snap-on filter
covering over the filter holder to protect the filter from dust when transporting it to the
enclosure. Close the filter hood and transport the filter holder to an enclosed area.
2.1.4 Once in an enclosed area, remove the snap-on filter cover. Remove the quartz fiber filter
b\ unscrewing the outer casing of ihe filter holder which is held on b) nuts on the short
sides of the filter holder.
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SOP for Air Sampling for Semivolatile Organic Contaminants
Using the Organics High-Volume Sampler Volume 1, Chapter 1
2.I.5 Place latex gloves on. Remove the filter and fold the filter in half lengthwise with the
deposit side facing in. Wrap the filter securely in the same piece of aluminum foil the
filter came with, attach a label to the aluminum foil, and place the filter in a zip-lock
plastic bag.
2.2 XAD-2 Cartridge Removal
2.2.1 Open the front door of the sampler, exposing the cartridge holder. To remove holder,
loosen the hand screw nut on the top of the cartridge holder. Once the top has been
completely loosened and off, proceed to unscrew the bottom nut. This nut remains on the
cartridge holder. Remove the cartridge holder and transport the holder to an enclosed
area.
2.2.2 Once inside the enclosure, turn the cartridge holder upside down in order to remove the
stainless steel cartridge containing the XAD-2 resin. Wrap the XAD-2 cartridge in
aluminum foil and place the resin cartridge into the resin cartridge transport tin. Seal the
tin by placing a piece of Teflon tape around the area where the top and bottom meet then
secure with electrical tape. Attach a label to the outside of the transport tin.
3.0 Filter Packaging for Shipment
The filter and cartridge should be shipped in a box with packing material. They may be shipped
together with other samples.
4.0 Installation of New Filter/Cartridge
At the start of a new sampling cycle, a new filter and cartridge should be installed. The monthly
site protocol lists the dates for installation and sampling.
4.1. Glass Fiber Filter Installation
4.1.1 Place on a pair of latex gloves. Within the enclosure, unwrap the aluminum foil from a
pre-weighed filter and place it in the filter holder, numbered side facing up. Save the
aluminum foil in a plastic bag.
4 1 2 Close the filter holder by tightening the screw nuts on either side of the holder.
4.1.3 Place the snap-on filter covering over the filter holder for transport to the Hi-vol sampler.
4.1.4 Lift up the sampler hood and the filter cover plate. Remo\e the snap-on filter covering
and place the filter holder into the proper position.
4.1.5 Place the filter holder nuts (1-4) onto the filter holder and tighten diagonally. Place the
filter cover plate over the filter holder and close the sampler hood.
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Volume 1, Chapter 1
SOP for Air Sampling for Semivolatile Organic Contaminants
Using the Organics High-Volume Sampler
4.2 XAD-2 Cartridge Installation
4.2.1 Within the enclosure, open a new resin cartridge sampling tin and unwrap the aluminum
foil.
4.2.2 Place the XAD-2 cartridge into the cartridge holder with the flange facing down.
Transport the cartridge holder to the sampler.
4.2.3 At the sampler, open the sampling door, make sure the bottom o-ring is properly seated,
and install the cartridge holder, bottom end first, screwing the hand screw nut on the
cartridge onto the threaded pump device.
4.2.4 Make sure the top o-ring is properly seated. Screw the top of the cartridge holder into
place by holding the cartridge holder steady and using the hand screw nut to tighten onto
the threaded end of the cartridge holder.
4.2.5 Turn on the sampler to check for leaks; record the magnehelic reading two minutes after
the motor is running smoothly.
5.0 Setting the Clock and the Timer
Mechanical timer. Turn the timer ring so that the red pointer points to the correct day and time.
Position the switch trippers so that the 5;7ver-colored tripper is at the start day and time and the
Black tripper at the end day and time specified in the site protocol. Make sure the thumb screws
face out and are hand-tightened so that the trippers are firmly attached to the rim of the ring. Be
sure to record the reading on the elapsed time counter.
For samplers with electronic timers refer to Section 8.6.2.
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Volume 1, Chapter 1
SOP for Air Sampling for Semivolatile Organic Contaminants
Using the Organics High-Volume Sampler
Appendix A
SAMPLE DATA SHEET
I. Station Name BRULE RIVER
3. Sample Start
Yr Mo Da Time
4. Sample Type Sample Codes
Precipitation Column UP -
2. Operator
End
Yr Mo Da Time
Total
Vol:
TSP/TOC
Sampler
Organics
High Volume
Sampler
Dichot Sampler
Filter UT -
Timer End
Timer Start
Set-up Date
Filter UH - F-
Cartridge UH - C-
Timer End
Timer Start
Codes UD-
Filter IDs: Fine
1st Timer end
start
2nd Timer end
start
3rd Timer end
start
4th Timer end
start
Rotameters
Rotameters
Rotameters
Rotameters
5. Comments on sample condition or site operation
Filter ID
Magnehelic End
Magnehelic Start _
days
Filter ID
Magnehelic End
Magnehelic Start
UD-
Coarse
(0
(C)
(C)
.(T)
.(T)
.(T)
.(T)
6. Date Shipped.
Receixed.
Yr Mo Da initials
Yr Mo Da initials
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Volume 1, Chapter 1
SOP for Air Sampling for Semivolatile Organic Contaminants
Using the Organics High-Volume Sampler
Appendix B
WEEKLY SITE VISIT SHEET
INSTRUCTIONS: Fill in all applicable space, enter general weather conditions (sunny, raining, etc.) and
approximate values for weather variables. Enter "OK" after OPERATION for each sampler tested if the
sampler is operating properly; if there is a problem, enter "X" and describe the problem at the bottom of the
page. For the Hi-Vols and Dichots, fill in the TIMER, MAGNEHELIC, or ROTAMETER (Coarse and Total)
readings in the appropriate spaces. For the MICs and metals AEROCHEM, enter the temperature inside the
sampler and the approximate volume in the overflow container (MIC only). For all samplers, indicate with
an "X" whether a sample was collected this week and if the sampler was set up for another run. Indicate with
an "OK" whether the wind vane is pointing in the proper direction and whether the anemometer is turning.
SITE
WEATHER
ORGANICS HFVOL#l
ORGANICS HIVOL #2
TSP HIVOL
DICHOT#l
DICHOT #2
MIC#1
MIC #2
METALS AEROCHEM
STANDARD AEROCHEM
MET SYSTEM
DATE
TIME
TEMP
OPERATION
WIND DIR_
TIMER
WINDSP
MAGN
Sample: Collected
OPERATION
Sample: Collected
OPERATION
Sample: Collected
OPERATION
Sample: Collected
OPERATION
Sample: Collected
OPERATION
Sample: Collected
OPERATION
Set up
TIMER
Set up _
TIMER
Set up _
MAGN
MAGN
TIMER
Set up _
C
TIMER
Set up _
TEMP_
Set up _
TEMP
T
VOL
VOL
Sample: Collected Setup
OPERATION TEMP
Sample: Collected Set up
OPERATION
Sample: Collected Setup
WIND VANE ANEMOMETER
PROBLEMS AND r,[-NHRAL OBSERVATION'S
OPERATOR
1-29
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Standard Operating Procedure for
Precipitation Sampling Using
XAD-2 and MIC Collectors
Clyde W. Sweet
Office of Air Quality
Illinois State Water Survey
2204 Griffith Drive
Champaign, IL 61820
December 1993
-------
Standard Operating Procedure for
Precipitation Sampling Using XAD-2 and MiC Collectors
1.0 Overview
This SOP is intended to provide a step by step procedure for collecting and replacing an XAD-2
column in an MIC-B sampler.
The data collected from analyses of XAD-2 columns from the MIC (Meteorological Instruments of
Canada) samplers will be used primarily for the Lake Michigan Loading Study (LMLS) and the
Integrated Atmospheric Deposition Network (IADN) programs. Samples at the Sleeping Bear
Dunes site, which is part of the Integrated Atmospheric Deposition Network, were sampled and
analyzed by Indiana University. The sampling method is identical apart from a few minor
differences in QC samples. This site represents 10 % of the samples for this method. The
objectives of the programs are to determine the loadings of persistent toxic contaminants from the
atmosphere to the Great Lakes from both urban and regional sources. Sampling sites have been
strategically located around the Great Lakes basin to provide these estimates.
The MIC sampler is used for the collection of toxic organic compounds (PCBs, pesticides, and
PAHs) in precipitation. Specific analytes of interest that will be collected from this sampler are
listed in Table 1. The sampler operates continuously for four weeks. This interval is used because
of the need to collect at least 5 L of precipitation (equivalent to about 1 inch of rainfall) in order to
get a reliable measurement of the target chemicals. Because of the low concentrations of target
compounds, the operator must follow this protocol carefully to insure sample integrity.
The sample will be collected by passing the precipitation through a column containing a 10 cm bed
of XAD-2 resin. The column is prepared at the Illinois State Water Survey (ISWS), shipped to the
site for exposure to the precipitation, and returned to ISWS for extraction and analysis of the
chemicals listed in Table 1. These methods are documented in laboratory SOPs.
The following procedure is used by the field operator to maintain the MIC sampler, and to remove
and replace XAD-2 columns in a manner that will improve sampler integrity. Although a sample
will be collected every four weeks, the collector must be checked each week to ensure proper
operation and to empty the overflow container if necessary. Any questions on the sampling
methods or operation of equipment should be directed to the following individuals The Principal
Investigator will be responsible for informing the Project Lead at U.S.EPA of changes in this
procedure and any problems that develop.
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SOP for Precipitation Sampling Using
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Volume 1, Chapter 1
Table 1. Analytes Analyzed from XAD-2 Column
Parameter
Specific
PCB Congeners
To be determined
Chlorinated Pesticides
a-HCH
g-HCH
p,p' DDT and metabolites
HCB
Dieldrin
Alpha-chlordane
Gamma-chlordane
Trans-nonachlor
Atrazine
PAHs
acenaphthalene
acenapthene
fluorene
phenanthrene
anthracene
fluoranthene
pyrene
chrysene
benzo(a)anthrene
benzo(b)fluoranthene
benzo(k)fluoranthene
benzo(a)pyrene
indeno(123cd)pyrene
dibenzo(a,h)anthracene
benzo(ghi)perylene
retene
coronene
benzo(e)pyrene
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SOP for Precipitation Sampling Using
Volume 1. Chapter 1 XAD-2 and MIC Collectors
Sampling Protocol and General Operations
Principal Investigator: Project Lead:
Clyde W. Sweet Angela Bandemehr
Illinois State Water Survey US Environmental Protection Agency
2204 Griffith Dr. Great Lakes National Program Office
Champaign, IL 61820 77 W. Jackson
Phone: 217-333-7191 Chicago, IL 60604
Fax: 217-333-6540 Phone: 312-886-6858
Equipment Operation and Maintenance: Supplies and Packaging:
Paul Nelson Mike Snider
Illinois State Water Survey Illinois State Water Survey
Phone: 217-244-8719 Phone: 217-244-8716
Fax: 217-333-6540
2.0 Summary of Method
Site operators will visit the site weekly to check for proper functioning of equipment and to ensure
that the overflow container is less than % full. Samples will be collected on the prescribed day at,
or as close to 10:00 a.m. local time as practical. If it is raining or snowing, or hazardous
conditions prevail, samples may be collected later in the day at the discretion of the site operator.
If the sample can not be collected on the prescribed sampling day, the Principal Investigator must
be notified. The following sampling activities will take place in the order listed.
1) Initial equipment inspection.
2) Check overflow container; measurement of precipitation volume if necessary.
3) Rinsing and cleaning of the precipitation collection surface with deionized (DI) water
(from ISWS).
4) XAD column removal and labeling.
5) Packaging XAD column and sample report form for shipment.
6) Cleaning collection surface with methanol (supplied by ISWS).
7) Installation of a new column and setting flow rate.
8) Waste disposal and clean up.
9) Sample shipment.
Steps 1 and 2 will be conducted weekly; Steps 1 through 7 will be conducted when an XAD-2
column is changed (every four weeks). Each of these steps will be detailed in the following
sections.
3.0 Sample Handling and Preservation
Due to the expense of sampling and analyzing the XAD-2 columns, a limited number of sites have
been selected in order to achieve the goals of this study. Therefore, even, sample is important and
represents a significant portion of thai site's searly estimate. An\ contamination through
mishandling or lack of preservation could cause a bias in the program estimates. The XAD-2
column should remain moist with the uater level between the top of the resin bed and the top of
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SOP for Precipitation Sampling Using
XAD-2 and MIC Collectors Volume 1, Chapter 1
the column. If the column is broken or dry on arrival, contact the Principal Investigator
immediately. If the column drys out during the sampling period, DI water should be added. This
must be noted in the site log and on the sample sheet. Before removal, DI water will be added to
the column.
Once in place, the column should be wrapped tightly in aluminum foil to exclude light and should
remain wrapped for removal and shipment. Follow all procedures for sample removal, packaging
and shipment.
4.0 Interferences
Due to the nature of the chemicals being collected, all precautions should be take to avoid
contamination of the sample and sampler during weekly visits and sample collection. The
sampler functions to collect precipitation samples. Therefore, the sample collection surface and
the XAD column should not be exposed more than is necessary. This will minimize
contamination from dry deposition of atmospheric particles. The sampler should be inspected
weekly to verify that the sealing pad is mating properly with the top of the :ampler. The XAD
columns should be plugged at both ends and sealed in a plastic bag as soon as they are removed
from the sampler.
Exposure of the XAD column to light can cause the degradation of some of the PAHs. Once
installed, the XAD column must remain wrapped in aluminum foil.
Heaters and fans are included in the sampler to avoid temperature extremes that might damage the
columns or degrade the samples. Proper maintenance of the heating unit is required, and it should
be checked weekly when temperatures below freezing are possible (see Section 6.2).
5.0 Safety
In any field operation, emphasis must be place on safety. Site operators must be aware of the
potential safety hazards to which they are subjected. Follow all safety protocols and equipment
guidelines, and be prepared for emergency situations. The site operator is responsible for his/her
safety from potential hazards including but not limited to:
Travel: When traveling to the site be sure to check on road conditions and weather
advisories. Curry emergency supplies (warm cK'thini:. food. \\ater) uhen
traveling in the winter. Always let someone know where you're going and when
you expect to be back. Always carry a first aid kit.
Electrical: For obvious problems (fire, scorching, blown fuses), turn off the power for the
circuit involved and notify ISWS. Unplug the sampler before replacing fuses and
circuit boards. Do not attempt other electrical repairs. Be especially cautious if
conditions are wet.
Insect [v-lv If \ou are allergic to m^ca Mings. \ou should carr\ a kit prescribed by a
physician. Be especialK cautious if nesls or large numbers of stinging insects are
present. Notify ISWS of all problems.
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SOP for Precipitation Sampling Using
Volume 1, Chapter 1 XAD-2 and MIC Collectors
Samp. Proc.: Never force glassware with unprotected hands. If the column arrives broken,
return it to ISWS. Do not attempt to remove the Teflon plugs.
Chemicals: Methanol is toxic and should not be ingested, inhaled, or come into contact with
bare skin.
6.0 Equipment and Supplies
Careful use, proper maintenance and cleaning extends the life of serviceable field equipment.
Permission should be obtained from the Principal Investigator to use anything other than the
equipment and supplies mentioned in these lists (supplied by ISWS).
6.1 Serviceable Equipment
These items will stay at the site at all times.
MIC Sampler (frame, motor, rain sensor, fan assembly)
Overflow tubing, funnel, and overflow container (25 L plastic carboy)
Space heater
Maximum/minimum thermometer
Graduated cylinders (2 L and 10 mL)
Precleaned Pyrex beaker (2 L)
Forceps
Teflon wash bottles (DI water and methanol)
Standard wash bottle (tap water)
Plastic bucket
Spare o-rings
Plastic bags
Teflon column outlet valve
Latex gloves
Log book
Report forms
Sample labels and marker
Kleen Guard coveralls
Kimwipes
A diagram of the MIC sampler and XAD column assembly is shown in Figure I. General
maintenance and trouble shooting are coxered in Section 9.0.
6.2 Consumable Equipment
These items will be shipped to the site operator every 4 weeks.
XAD columns and Teflon plugs
Glass fiber filter pieces
Sample jar
Test tube brush
Shipping box and packaging materials
Free/er packs (summer only)
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SOP for Precipitation Sampling Using
XAD-2 and MIC Collectors
Volume 1, Chapter 1
Modified M.I.C. Type B Collector
Retractable, /)
gasketed snow roof
Stainless steel.
catch basin
7g of XAD-2 resin
in 30-cm glass
column with glass x I
wool plugs at top
and bottom
VaJved teflon tube
coupling
Ram sensor
25 liter carboy
accumulates
column overflow
Weatherproof enccsure.
Temperature maintained
a! 15°C during winter
rr.cnths by a smaJI srace
heater
Overflow tubing
Figure 1. Schematic of the MIC Precipitation Collector
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Volume 1, Chapter 1
SOP for Precipitation Sampling Using
XAD-2 and MIC Collectors
7.0 Calibration and Standardization
7.1 Rain sensor
Each week check the operation of the MIC sampler. If it is dry, wet the sensor with DI water; the
cover should open immediately and close within five minutes if no additional wetting occurs.
Clean any accumulated dirt off the sensor. Do not allow the sampler to remain open any longer
than necessary. See Section 9.0 for more information.
7.2 Heater and Fan
The heater must operate properly in freezing temperatures to maintain proper operation of
Campling equipment. The heater should maintain a 5° + 10°C temperature in the sampling
enclosure. The heater will be calibrated at ISWS. When cold weather is expected, check that the
heater is operational by turning up the heater thermostat until the heater comes on; set this
thermostat at the calibration mark. During warm weather, make sure that the fan is operational by
turning down the fan thermostat; set this thermostat at the calibration mark. Reset the
maximum/minimum thermometer and record the temperatures each week.
8.0 Procedures
The following procedures will be discussed:
1) Initial equipment inspection
2) Measurement of precipitation volume in overflow containers
3) Rinsing precipitation collection surface
4) XAD column removal and labeling
5) XAD column packaging for shipment
6) Cleaning collector surface and funnel outlet
7) Installation of new column
8) Waste disposal/clean-up
9) Sample shipment
Steps 1 will be conducted weekly, Step 2 will be conducted as necessary, Steps 1 through 7 will all
be conducted every four weeks when the column is changed.
8.1 Initial Inspection
Upon arrival at the site, make an initial inspection of the equipment to determine proper operation
for the week. This inspection will be entered on the Weekly Site Visit Sheet and will include:
1) General comments. Comments that might affect the sample collection that week, i.e., fire
in the area, wind storms, abnormal precipitation, vandalism, etc. If it is raining or snowing
during the visit, note whether the sampler is open. If there is standing water in the funnel
see Section 8.2 or if the column has gone dry.
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SOP for Precipitation Sampling Using
XAD-2 and MIC Collectors Volume 1, Chapter 1
2) Equipment evaluation. Note any damage to equipment. Check operation of the rain
sensor if it's not raining (Section 6.1) and the heater or fan (Section 6.2). Check for
interferences (Section 3.0). Check the Teflon sealing pad on the cover of the MIC. If it is
loose, cracked, or holding water notify ISWS.
3) Record minimum/maximum temperature and reset thermometer.
8.2 Measurement of Precipitation Volume
This procedure will be done on a weekly basis if the overflow container is more than 3/4 full. It will
always be done when changing an XAD column. If possible do not perform this step during a
precipitation event, since this will affect the volume estimate.
If this step has to be done during an event, immediately replace the overflow container with the
plastic bucket; and record the amount of precipitation that passes through the column while the
water in the full container is being measured. Measure the volume in I L increments using the
large graduated cylinder. All measurements should be recorded in the Weekly Site Visit and
Sample Data Sheets.
If there is standing water in the collection funnel, check that water is flowing through the column.
If water is not flowing or flowing very slowly, close the valve on the column and remove it from
the funnel catching the precipitation in the pre-cleaned beaker. Check for debris blocking the
funnel outlet or the column outlet valve. Use the cleaning wire if necessary. Reconnect the
column, adjust the flow (Section 8.8), and allow the water collected in the beaker to pass through
the column. Return the beaker to ISWS for recleaning. If flow can not be restored, notify the
Principal Investigator.
If the column has gone dry, add DI water from the Teflon wash bottle and try to determine where
the leak is. Replace o-rings or tighten fittings as necessary Note this and the approximate volume
of DI water added on both the Weekly Site Visit Sheet and the Sample Data Sheet.
8.3 Rinsing the Precipitation Collection Surface
This procedure is carried out only during XAD column removal and replacement (every four
weeks). If possible, do not perform this step during a precipitation event. Wait until all
precipitation has drained from the collection funnel. Wear latex gloves at all times. If the system
is plugged, see Section 8.2.
If the sample must be collected during a rain event, wear Kleen Guard coveralls making sure that
all clothing extending over the collection surface is covered. If practicable, stand downwind of the
instrument. Do not lean over the collecting surface.
I) Squirt DI water onto the rain sensor to open the sampler. Turn off the switch on the front
of the sampler so that it remains open during the procedure.
-1 \\ .MI mi: Lue\ gloves (and t\ \e\ |,u kel it necessary), retinue an_s oh\ uuis debris (bird
dnippmgs. leaves, etc.) from the collection funnel. The presence of Johns should be noted
on the Data Sheet.
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SOP for Precipitation Sampling Using
Volume 1. Chapter 1 XAD-2 and MIC Collectors
3) Rinse the collection surface with about 200 mL of Dl'water (one wash bottle full) while
wiping with the piece of precleaned glass fiber filter sent with the monthly supplies. This
step removes adhering particles from the collection surface. Allow rinsings to pass
through the column until the water level is halfway between the top of the resin bed and
the top of the column (see Figure I). If the temperature is so cold that water freezes on
contact with the funnel, simply wipe of the collection surface with a dry piece of filter and
go to Step 4.
4) Turn off the column outlet valve to maintain the water level in the column.
5) Seal the filter used to clean the collection surface in the glass jar.
6) Be sure to turn the power switch on the front of the sampler back on. Proceed to
Section 8.4.
8.4 Column Removal and Labeling
The aluminum foil should remain on the column.
1) Unscrew the XAD column from the fitting at the base of the collection funnel. Cap the
column with a Teflon plug. Make sure the black o-ring is in place.
2) Remove the overflow tube while turning the column upside down. Remove the outlet valve
fitting and replace it with a Teflon plug. Make sure the black o-ring is in place.
3) Label the column (on the outside of the aluminum foil) and the glass sample jar containing
the filter wipe using the same ID number (see Section 8.5).
4) Place the column in a plastic bag and proceed to Section 8.6.
8.5 Labeling Codes
All precipitation samples should be labeled using the same alphanumeric system.
The "Site ID" letter for the site
• The "Sample" which will be "P" for precipitation samples
• The "Sample Type", designating either a routine sample (01), a duplicate (02), or a
QA sample, field blank or travel blank (FB, TB)
• The "Date" of collection (end date of sample period) in a ycar-nionth-day format
An example label and the valid codes are listed below.
Precipitation Sample
Site Sample Samp.Type Year Month Day
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SOP lor Precipitation Sampling Using
XAD-2 and MIC Collectors Volume 1, Chapter 1
Site ID
U-Brule River S-Sleeping Bear Dunes
C-Champaign B-Beaver Is.
N-Manitowoc E-Eagle Harbor
W-Chiwaukee T-Sturgeon Point
V-South Haven I-Indiana Dunes
M-Muskegon J-IIT Chicago
L-Lake Guardian
Sample Sample Type
P-Precipitation 01- Routine Sample
02- Duplicate sample
TB- Trip Blank
FB- Field Blank
Example: SP-02-930119 is the code for a duplicate precipitation sample collected at the
Sleeping Bear Dunes site on January 19, 1993. Both the column and the filter
wipe should be labeled with this code.
8.6 Column Packaging for Shipment
The columns should be packed in the shipping containers provided by ISWS. Noniiaily supplies
for each sampling period will come in these boxes and they can be reused to return the samples.
The columns and glass jars should be carefully packed using styrofoam "peanuts1' so that the
contents do not shift when the package is moved. During the winter (November through April),
the box should be clearly labeled "Do Not Freeze" so that the shipper does not store the packages
outside. During the summer (May to October), three pre-frozen freezer packs (supplied by ISWS)
and a reset max/min thermometer should be included in the package.
8.7 Cleaning Collector Surface and Funnel Outlet
Prior to installation of a new column, the collection surface and funnel outlet must be cleaned.
8.7.1 Put on a new pair of gloves.
8.7.2 Place the white plastic bucket under the funnel outlet.
8.7.3 Clean the collector surface by rinsing with 200 mL of pesticide-free methanol (supplied
b\ ISWS) with additional scrubbing with a clean Kimwipe if necessary. Clean the
funnel outlet using the test tube brush.
8.7.4 Follow with a rinse of 1 L of tap water from the plastic wash bottle.
8.7.5 Follow with a rinse of 200 mL of DI water from the Teflon \\ush bottle.
8.7.6 Rinse the funnel outlet fitting and o-ring with methanol and DI water.
8.7.7 Proceed to Section 8.8.
8.8 Installation of a New XAD Column
8.8.1 Remove the aluminum foil to make sure the XAD bed in the column has not separated and
is p.ickeil between the glass wool pines If it has separated, notify ISWS
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SOP for Precipitation Sampling Using
Volume 1, Chapter 1 XAD-2 and MIC Collectors
8.8.2 Replace the aluminum foil and remove the Teflon plug on the bottom (unmarked) of the
XAD column and replace it with the column outlet valve. Make sure the black o-ring is in
place. Wrap the plug in aluminum foil and put it in a clean plastic bag for reuse when
removing the cartridge.
8.8.3 Remove the top Teflon plug (marked red) and place it, wrapped in aluminum foil, in the
plastic bag. Rinse the funnel outlet fitting with methanol. Screw the top of the column
into the funnel outlet fitting. Make sure the black o-ring is in place.
8.8.4 Open the collector lid by moistening the rain sensor. Add about 50 mL of DI water to the
collection funnel (these steps may not be necessary if rain is falling). Make sure water is
flowing from the column outlet valve at the bottom of the column. Adjust the flow to
between 10 and 15 mL/min using the column outlet valve. Measure the flow using the
small graduated cylinder. Connect the outlet tube to the overflow container. The water
level should come to rest between the top of the resin bed and the top of the column.
8.8.5 Empty all water from the overflow container and make sure the column is wrapped with
aluminum foil.
8.9 Waste Disposal Clean-up
Waste may include materials (water, methanol) and glass fiber filter used to clean the collection
surface. Empty any leftover liquid from the Teflon wash bottles into the plastic bucket and seal
them in a plastic bag until the next column change. Return the test tube brush with the samples.
The water-methanol mixture in the plastic bucket is biodegradable and can be put down the drain.
8.10 Sample Shipping
Once they are properly packaged (Section 8.6), send the samples, Sample Data Sheets, and
Weekly Site Visit Sheet to the Principal Investigator. Keep a copy of both Sheets in the site log
book. UPS 2nd day delivery is the preferred shipping method. U.S. Priority mail may also be
used.
9.0 Quality Assurance Samples
Occasionally the protocol will require collection of quality assurance samples. Travel blanks are
columns that are shipped with regular sample columns and stored unopened in the sampler during
the collection period. They should be returned to ISWS unopened after the specified period. Field
blanks are columns that are connected to the sampler funnel during the sampling period. The
switch on the front of the sampler is turned off so that the sampler does not open and no rain
passes over the column. Field blanks should include a funnel rinse just like regular samples.
Travel blanks are run to assess the amount of sample contamination that occurs during shipment
and storage. Field blanks assess overall contamination including shipment, storage, and passive
contamination in the sampler during dry periods. These samples should have a "TB" or "FB" in
the sample code (Section 8.5).
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SOP for Precipitation Sampling Using
XAD-2 and MIC Collectors Volume 1, Chapter 1
10.0 Equipment Maintenance and Trouble Shooting
The rain sensor grids are exposed to weather, dust, dirt, and pollutants and must be kept clean to
avoid malfunctions. The grids should be cleaned every week by wiping the exposed side with a
damp sponge or cloth, using a mild detergent if necessary. If a detergent is used, be sure to wipe
off the grid thoroughly to ensure that a detergent film does not build up.
The operation of the sampler should be checked each week. If the cover is not seating properly on
either side or if the movement of the cover is not smooth, refer to the trouble-shooting guide
below. For more information, contact the manufacturer, MIC Co. 216 Duncan Rd, Richmond Hill,
Ontario, Canada, 416-889-6653.
Cause Remedy
Collector fails to operate
No power to instrument Check switches and power source
Blown fuse Replace fuse
Faulty sensor board Change sensor board
Faulty PC board Change PC board
Motor will not switch off
Limit switch and or cam
out of adjustment Readjust limit switch or cam
Limit switch broken Replace limit switch
MIC Healer jails to operate
Heater element burnt out Change sensor board
Faulty component on PC board Change PC board
Moving cover drops once it moves over top center
Loose set-screw on motor sprocket Tighten set-screw
Chain loose Tighten chain
Cover docs not return to funnel
Dirt on sensor board Clean sensor board
Heater on the sensor not operating See "Heater fails to operate"
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SOP for Precipitation Sampling Using
Volume 1, Chapter 1 XAD-2 and MIC Collectors
MIC Summary SOP
This summary does not take the place of the detailed SOP and should be used strictly to reinforce the
procedure when in the field. Steps I and 2 will be conducted weekly; Steps I through 7 will be conducted
when an XAD-2 sample is required (monthly).
1.0 Initial Equipment Inspection
Upon arrival at the site make an initial inspection of the equipment to determine proper operation
for the week. This inspection which will be entered into the site operator's weekly activity sheet
would include:
1.1 General Comments - Comments that might effect the sample collection activity that week.
1.2 Equipment Evaluation Determine whether the rain sensor and heater (see Section 6.1 and 6.2) or
other mechanical devices are operating properly. Check the Teflon sealing pad.
1.3 Record minimum/maximum temperature and reset thermometer.
2.0 Overflow Container Measurement for Precipitation Volume
2.1 Remove overflow tubing from overflow container. If precipitation is occurring, place overflow
tubing into spare overflow container.
2.2 Pour the contents of the overflow container into a graduated cylinder. Record each 1 L increment
and discard contents of cylinder. Repeat procedure until contents of overflow container are empty.
If the column is being changed, add any additional sample in the spare overflow container, reading
the final portion to the nearest 10 mL.
2.3 Record the total volume estimate on the Weekly Site Visit Sheet. If the container is less than
3/4 full, indicate an "N" in the appropriate space. If the visit is for removal and replacement of an
XAD-column, record the total from that week on the Weekly Site Visit Sheet, and record the total
(the summation of any weekly overflow measurement during the four-week sample collection
period) on the Sample Data Sheet.
3.0 Rinsing and Cleaning of Precipitation Collection Surface
This procedure occurs only during XAD-2 cartridge removal and replacement (monthly).
3.1 Squirt DI water onto the rain sensor to open sampling lid and turn off the power.
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SOP for Precipitation Sampling Using
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3.2 Wearing latex gloves (and Kleen Guard coveralls if necessary), remove debris from the collection
funnel. Rinse the collection surface with about 200 mL of DI water while scrubbing with a piece
of glass fiber filter to remove deposited particles. Allow rinsings to pass over the column until the
water level is between top of the column and the top of the resin bed (Figure 1). Close the column
outlet valve to maintain water level in column and remove the outlet tubing. If the temperature is
very cold, simply dry wipe with the filter.
3.3 Place glass fiber filter in sample jar.
4.0 XAD-2 Column Removal and Labeling
4.1 Unscrew the XAD-2 column from the collection funnel. Once removed, close the top with a
Teflon plug. Make sure black O-ring is in place.
4.2 Remove column outlet valve and replace with Teflon plug. Make sure black O-ring is in place.
4.3 Place the column, wrapped in aluminum foil, into a plastic sampling bag.
4.4 Label cartridge (on the outside the aluminum foil) and sample jar (containing glass fiber filter)
with the appropriate sample code (see Section 8.5). Place samples into shipping container for
protection.
5.0 XAD Column Packaging for Shipment
5.1 Carefully pack the columns in the shipping box with styrofoam "peanuts." Enclose a reset
max/min thermometer in the package and pre-frozen freezer packs (May through October only).
During the winter (November through April), label the outside of the package Do Not Freeze."
5.2 Ship to ISWS as soon as possible.
6.0 Cleaning Collector Surface and Funnel Outlet
6.1 Place new pair of gloves on.
6.2 Place the plastic bucket under funnel outlet.
6.3 Clean the collector surface by rinsing with 200 mL of pesticide-free methanol.
6.4 Follow with rinse of 1 L tap water. Scrub with a clean Kimwipe if necessary and use the test tube
brush to clean the funnel outlet.
6.5 Follow with 200 mL rinse of DI water. Discard contents of overflow Container #2.
6.6 Rinse funnel outlet with methanol.
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SOD for Precipitation Sampling Using
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7.0 Installation of New XAD-2 Column
7.1 Remove the Teflon plug from the bottom (unmarked) of the new column and attach the column
outlet valve. Make sure black o-rings are in place. Wrap the plug in aluminum foil and put it into
plastic bag until the column is removed.
7.2 Remove the top plug (marked with red and wrap it with aluminum foil and place it in the plastic
bag. Screw the top of the column into the funnel outlet. Make sure the black o-ring is in place.
7.3 Open collector lid by moistening rain sensor. Add about 50 mL DI water to the sample collection
surface. Open the column outlet valve and adjust the flow to between 10 and 15 mL/min. using
the small graduated cylinder to measure the volume. If it is raining, allow the rain to flow through
the system. Connect the column outlet to the overflow container using the overflow tubing.
7.4 Wrap the XAD-2 column tightly with aluminum foil.
7.5 Keep the Teflon plugs in a plastic bag within enclosure for next column removal.
8.0 Waste Disposal/Clean-up
Waste includes water, methanol, glass fiber filter, test tube brush used to clean the collector after
the XAD-2 column had been removed. Pour all liquids from wash bottles and bucket into the
spare overflow container, cap and dispose of properly. Enclose the DI and methanol wash bottles
in a plastic bag, and return the test tube scrub brush in the sample shipment to ISWS. The glass
fiber filter, gloves, and other trash can be properly disposed.
9.0 Sample Shipping
Once packaged properly (see Section 8.6 of detailed SOP) send the samples (XAD-2 column and
glass fiber filter from Sections 8.3 and 8.4 of detailed SOP), the Weekly Site Visit Sheet, the
Sample Data Sheets to ISWS.
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SOP for Precipitation Sampling Using
XAD-2 and MIC Collectors
\. Station Name
3. Sample Start _
4. Sample Type
Precipitation
TSP/TOC
Sampler
Organics
High Volume
Sampler
Dichot Sampler
Appendix A
SAMPLE DATA SHEET
BRULE RIVER
2. Operator
Yr Mo Da Time
Sample Codes
Column UP -
Filter
End
Yr Mo Da Time
UT -
Total
Vol:
Filter ID
Timer End
Timer Start
Set-up Date
Filter UH -
F-
Magnehelic End
Magnehelic Start
_, + days
Filter ID
Cartridge
Timer End _
Timer Start
UH -
C-
Magnehelic End
Magnehelic Start
Codes
UD-
UD-
Filter IDs: Fine
end
start
end
Rotameters
Rotameters
Coarse
(C)
(0
(T)
(T)
start
3rd Timer end
start
4th Timer end
stan
Rotameters
Rotameters
(C)
(C)
(T)
JT)
5. Comments on sample condition or site operation:
6. Date Shipped:
Yr Mo Da initials
Rcccued.
Yr Mo Da initials
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SOP for Precipitation Sampling Using
XAD-2 and MIC Collectors
Appendix B
WEEKLY SITE VISIT SHEET
INSTRUCTIONS: Fill in all applicable space, enter general weather conditions (sunny, raining, etc.) and
approximate values for weather variables. Enter "OK" after OPERATION for each sampler tested if the
sampler is operating properly; if there is a problem, enter "X" and describe the problem at the bottom of the
page. For the Hi-Vols and Dichots, fill in the TIMER, MAGNEHELIC, or ROTAMETER (Coarse and Total)
readings in the appropriate spaces. For the MICs and metals AEROCHEM, enter the temperature inside the
sampler and the approximate volume in the overflow container (MIC only). For all samplers, indicate with
an "X" whether a sample was collected this week and if the sampler was set up for another run. Indicate with
an "OK" whether the wind vane is pointing in the proper direction and whether the anemometer is tunning.
SITE
WEATHER
ORGANICSHIVOLtfl
ORGANICS HIVOL #2
TSP HIVOL
DICHOT#1
DICHOT #2
MIC#l
MIC #2
METALS AEROCHEM
STANDARD AEROCHEM
MET SYSTEM
PROBLEMS AND GENERAL OBSERVATIONS:
DATE
TEMP
OPERATION
Sample: Collected
OPERATION
Sample: Collected
OPERATION
Sample: Collected
OPERATION
Sample: Collected
OPERATION
Sample: Collected
OPERATION
Sample: Collected
OPERATION
Sample: Collected
OPERATION
Sample: Collected
OPERATION
Sample: Collected
WIND VANE
WIND DIR
TIMER
Set up
TIMER
Set up
TIMER
Set up
TIMER
Set up
TIMER
Set up
TEMP
Set up
TEMP
Set up
TEMP
Set up
Set up
ANEMOMETEI
TIME
WIND SP
MAGN
MAGN
MAGN
C
VOL
VOL
OPERATOR
1-51
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Standard Operating Procedure for
Air Sampling for Metals
Using the Dichotomous Sampler
Clyde W. Sweet
Office of Air Quality
Illinois State Water Survey
2204 Griffith Drive
Champaign, IL 61820
December 1993
-------
Standard Operating Procedure for
Air Sampling for Metals Using the Dichotomous Sampler
1.0 Overview
This SOP is intended to provide a step by step procedure for collecting samples of airborne
particles on Teflon filters for metals analysis using the dichotomous sampler.
The data collected from analyses of 37 mm Teflon filters from the dichotomous samplers will be
used primarily for the Lake Michigan Loading Study (LMLS) and the Integrated Atmospheric
Deposition Network (IADN) programs. Samples at the Sleeping Bear Dunes site, which is part of
the Integrated Atmospheric Deposition Network, were sampled and analyzed by Indiana
University. The sampling method is identical apart from a few minor differences in QC samples.
This site represents 10 % of the samples for this method. The objectives of the programs are to
determine the loadings of persistent toxic contaminants from the atmosphere to the Great Lakes
from both urban and regional sources. Sampling sites have been strategically located around the
Great Lakes basin to provide these estimates.
The dichotomous sampler is used for the collection of airborne particles for analysis of trace
elements. Specific analytes of interest that will be collected from this sampler are listed in Table 1.
The sampler operates for four 24-hour periods during each four-week sampling cycle. The flow
rate through the sampler is 1 cubic meter per hour. This interval is used because of the need to
collect about 100 cubic meters of air in order to get a reliable measurement of the target chemicals
at the remote sites in the network. Because of the low concentrations, the operator must follow
this protocol carefully to insure sample integrity.
The samples will be collected by passing air through a 37 mm Teflon filter. The sampler inlet is
mounted in a standard Hi-Vol shelter. The filters are pre-weighed at the Illinois State Water
Survey (ISWS), shipped to the site for collection of airborne particles, and returned to ISWS,
weighed, and shipped to the U.S.EPA labs in North Carolina for analysis of the trace elements
listed in Table 1 by X-ray fluorescence (XRF) methods. These methods are documented in
laboratory SOPs.
The following procedure is used by the field operator to maintain the dichotomous sampler, and to
remove and replace Teflon filters in a manner that will maintain sample integrity. Although a
single composite sample will be collected every four weeks, the collector must be checked and
reset each week to ensure proper operation and to collect samples on the prescribed sampling
periods. Any questions on the sampling methods or operation of equipment should be directed to
the following individuals. The Principal Investigator will be the prime contact for all
methodological and general questions. The EPA Project Lead is the second contact if the
Principal Investigator cannot be contacted.
1-55
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SOP for Air Sampling for Metals
Using the Dichotomous Sampler
Volume 1, Chapter 1
Sampling Protocol and General Operations
Principal Investigator:
Clyde W. Sweet
Illinois State Water Survey
2204 Griffith Dr.
Champaign, IL61820
phone: 21 7-333-7 1 91
Fax: 217-333-6540
Project Lead:
Angela Bandemehr
USEPA/GLNPO
77 W. Jackson
Chicago, IL 60604
phone: 312-886-6858
Fax: 312-353-2018
Equipment Operation and Maintenance
Paul Nelson
Illinois State Water Survey
phone: 217-244-8719
Fax: 217-333-6540
Supplies and Packaging
Mike Snider
Illinois State Water Survey
phone: 217-244-8716
Table 1. Trace Elements Determined on Teflon Filters
Aluminum
Potassium
Manganese
Zinc
Strontium
Silicon
Calcium
Iron
Arsenic
Tin
Phosphorus
Titanium
Cobalt
Selenium
Iodine
Sulfur
Vanadium
Nickel
Bromine
Cadmium
Chlorine
Chromium
Copper
Lead
2.0 Summary of Method
Site operators will visit the site weekly to check for proper functioning of equipment and to set the
sampler timer for the next prescribed sampling day. If it is raining or snowing, or hazardous
conditions prevail, samples may be collected later in the day at the discretion of the site operator.
If the sample can not be collected on the prescribed sampling day. the Principal Investigator must
be notified. The following sampling activities will take place in the order listed.
1) Initial equipment inspection and testing.
2) Resetting the sampler timer (weekly).
3) Changing the Teflon filters (every four weeks).
4) Filling out the Sample Data Sheet (weekly).
5) Packaging filters and sample report form for shipment.
6) Installation of a new filters and setting flow rate.
7) Waste disposal and clean up.
8) Sample shipment.
Steps 1. 2. and 4 will he conducted weekly; Steps 1 through S will he conducted when the filters
arc changed ic\er\ lour weeks) Kach of these steps will he detailed in the following sections.
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Volume 1, Chapter 1
SOP for Air Sampling for Metals
Using the Dichotomous Sampler
3.0 Sample Handling and Preservation
Due to the expense of sampling and analyzing the Teflon filters, a limited number of sites have
been selected in order to achieve the goals of this study. Therefore, every sample is important and
represents a significant portion of that site's yearly estimate. Any contamination through
mishandling or lack of preservation could cause a bias in the program estimates. The filters are
very fragile and should not be removed from the polypropylene filter holders. As the new filters
are being installed, if a hole is discovered, the filter should not be installed but returned to ISWS.
Once in place, the filters should not be removed until the end of the sampling cycle (four 24-hour
sampling periods over a four-week period). Follow all procedures for filter removal, packaging
and shipment.
4.0 Interferences
Due to the nature of the chemicals being collected, all precaution:; should be taken to avoid
contamination of the sample and sampler during weekly visits and sample collection. The sampler
functions to collect samples of airborne particles that will be analyzed for trace elements. It is very
important to avoid touching the filters and to prevent any dust or dirt from contaminating the
deposit on the filter. The surfaces on the inlet should be inspected each week and any dust or dirt
wiped away with a damp cloth.
5.0 Safety
In any field operation, emphasis must be place on safety. Site operators must be aware of the
potential safety hazards to which they are subjected. Follow all safety protocols and equipment
guidelines, and be prepared for emergency situations. The site operator is responsible for his/her
safety from potential hazards including but not limited to:
Travel: When traveling to the site be sure to check on road conditions and weather
advisories. Carry emergency supplies (warm clothing, food, water) when
traveling in the winter. Always let someone know where you're going and when
you expect to be back. Always carry a first aid kit.
Electrical: For obvious problems (fire, scorching, blown fuses), turn off the power for the
circuit involved and notify ISWS. Never attempt electrical repairs other than
replacing fuses and circuit boards. Unplug the sampler before any replacements
are made. Be especially cautious if conditions are wet.
Insect pests: If you are allergic to insect stings, you should carry a Lit prescribed by a
physician. Be especially cautious if nests or large numbers of stinging insects are
present. Notify ISWS of all problems.
1-57
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SOP for Air Sampling for Metals
Using the Dichotomous Sampler Volume 1, Chapter 1
6.0 Equipment and Supplies
Careful use, proper maintenance and cleaning extends the life of serviceable field equipment.
Permission should be obtained from the Principal Investigator to use anything other than the
equipment and supplies mentioned in this list (supplied by ISWS).
Serviceable Equipment
These items will stay at the site at all times.
Dichotomous sampler (pump and timer unit, inlet shelter).
Calibration filters in polypropylene holders.
Pre-weighed Teflon filters in polypropylene holders in snap-lock Petri dishes.
Kiinwipes.
Spare fuses.
7.0 Calibration and Standardization
The dichotomous sampler will be recalibrated quarterly against a mass flow meter by ISWS
personnel. New rotameter settings will be marked on the instrument and entered in the log book
along with the date of recalibration.
7.1 Sampler Inlet
Each week check the condition of the inlet surfaces. Wipe up any dust and dirt using a damp
(DI water) Kimwipe.
7.2 Timer and Pump Unit
Figure 1 shows the timer. Each week check the operation of the timer and pump. The following
checks should be made:
1) The time of day should be correct to the present local time.
2) The "Total Sampling Time" should have advanced 24 hours (1440 minutes) if a sample
period was programmed during the preceding week.
Turn on the pump manually and let it run for one or two minutes. When the filters are changed
every four weeks, reset the rotameter using the calibration filters (Section 8.4) before installing the
new clean filters.
1-58
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Volume 1, Chapter 1
SOP for Air Sampling for Metals
Using the Dichotomous Sampler
TIME OF DAY
TRIPPERS
Figure 1. Mechanical Tinier
1-59
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SOP for Air Sampling for Metals
Using the Dichotomous Sampler Volume 1, Chapter 1
8.0 Procedures
The following procedures will be discussed:
I) Initial Inspection.
2) Setting the clock and timer.
3) Filter removal and labeling.
4) Filter packaging for shipment.
5) Adjusting sampler flow rates.
6) Installation of new filters.
7) Setting the clock and timer.
8) Waste disposal/clean-up.
9) Sample shipment.
Steps 1 and 2 will be conducted weekly; Steps 1 through 8 will all be conducted every four weeks
when the filters are changed.
8.1 Initial Inspection
Upon arrival at the site, make an initial inspection of the equipment to determine proper operation
for the week. This procedure is accomplished every week. When a sample is set up, this
procedure should be used to check final settings before leaving the site. Refer to Figure 1 for
timer details. Check the elapsed time counter reading on the lower left corner of the timer.
Record this number on the Sample Data Sheet. The counter reads in hundredths of an hour or
minutes. The large red arrow should point to the correct day and time. Note any discrepancies on
the Sample Data Sheet. The switch trippers should be firmly attached to the timer rim with the
silver tripper at the last scheduled start time and the black tripper at the last scheduled stop time.
Turn on the sampler by moving the "Hand Trip" switch to the "On" position and note whether the
pump is running normally. After two minutes, record the value on the rotameters on the Sample
Data Sheet. Turn the sampler off after two minutes.
This inspection which should be entered onto the Weekly Site Visit Sheet and the Sample Data
Sheet will include:
1) General comments. Comments that might affect the sample collection that week, i.e., fire
in the area, wind storms, abnormal precipitation, vandalism, etc.
2) Equipment evaluation. Note any damage to equipment. If the sampler is not operating
properly, notify ISWS as soon as possible.
3) Rotameter reading.
4) Total Sampling Time reading.
S 2 Setting the Chick and Timer
It" :\ sampling period is scheduled for the next week but no filter change is required, set the clock
and timer at this point. Follow the instructions in Section 8.7.
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Volume 1, Chapter 1
SOP for Air Sampling for Metals
Using the Dichotomous Sampler
8.3 Filter Removal and Labeling
At the end of a sampling cycle, the filters are removed and replaced by the following procedure. It
is extremely important that the filters not be touched, and should be placed in the snap-lock Petri
dish as soon as possible. The following procedures are accomplished only during the replacement
of filters and not every week.
I) Remove the two Teflon filters by unscrewing the locking nut (Figure 2). The filters must
remain in their polypropylene holders. There will be a coarse particle filter in a yellow
holder and a fine particle filter in a white holder. Place the each filter and holder in a
separate snap-lock Petri dish for shipment. Be careful not to touch the filter.
2) Sample Labeling
All dichotomous (dichot) air samples should be Ibeled on the outside of the Petri dish
using the same alphanumeric system. The label includes:
The "Site ID" letter for the site,
• the "Sample" which will always be "D" for dichotomous samples,
• the "Sample Type", desisnating either a routine sample (01) or a QA sample (FB,
TB),
• the "Filter" size designation, a "C" for course or an "F" for fine, and
• the "Date" of collection in a year-month-day format.
An example label and the valid codes are listed below.
Dichotomous Sample
Site Sample Samp.Type Filter Year
Month
Day
Valid Codes
Site ID
D-Dichotomous
Sample Type
Ol - Routine Sample
FB- Field Blank
TB-Trip Blank
Filter
C-Coarse
F-Fine
U-Bmle River S-Sleeping Bear Dunes
C-Champaign B-Beaver Is.
N-Manitowoc E-Eagle Harbor
W-Chiwaukee T-Sturgeon Point
V-South Haven I-Indiana Dunes
M-Muskegon J-ITT Chicago
L-Lake Guardian
Example: SD-OlC-930119 is the code for a routine dichot coaise particle sample collected at the
Sleeping Bear Dunes site on Januar\ 19. 1993 (date filters are removed from the sampler).
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SOP for Air Sampling for Metals
Using the Dichotomous Sampler
Volume 1, Chapter 1
Figure 2. Schematic of the Dichotomous Sampler
1-62
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SOP for Air Sampling for Metals
Volume 1, Chapter 1 Using the Dichotomous Sampler
8.4 Filter Packaging for Shipment
The filters in labeled Petri dishes should be shipped in a padded envelope or in a box with packing
material. They may be shipped together with other samples.
8.5 Adjusting Sampler Flow Rates
8.5.1 Install the calibration filters (labeled side facing up) and tighten the locking nut (Figure 2).
8.5.2 Turn the sampler on using the hand trip switch (Figure 1) and allow it to warm up for at
least 10 minutes.
8.5.3 Set the rotameters on the instrument to the most recent calibration set points. These
should be marked on the instrument and entered into the site log. The set point on the
rotameter scale should be lined up with the center of the metal ball using the adjustment
knobs at the base of the rotameters. The rotameter on the left sets the flow to the coarse
particle filter and the one on the right sets total flow. If the ball is stuck or there is some
other problem with the rotameter, do not attempt to adjust it; but notify ISWS as soon as
possible.
8.5.4 Turn off sampler and remove calibration filters.
8.6 Installation of New Filters
At the start of a new sampling cycle (every four weeks), fresh filters should be installed after the
flow has been adjusted (Section 8.5).
8.6.1 Place new pre-weighed filters in their color-coded filter holders into the instrument. The
labels should face up and the holder color should match the color patch on the instrument
(yellow for the coarse position and white for the fine position). Once the filters are in
place, tighten the locking nut. Be careful not to touch the filters themselves.
8.6.2 Set the timer for the next sampling period as described in next section.
8.7 Setting the Clock and Timer
8.7.1 Turn the large ring (Figure 1) clockwise so that the red pointer points to the correct day
and time.
8.7.2 Attach the switch trippers to the timer ring (see Figure 1). The silver-colored -tripper
should be positioned at the start day and time and the black tripper on the end day and
time specified in the monthly site protocol. The trippers should be attached so that the
thumb screw is to the front. The screws should be hand tightened so that the trippers rest
firmly against the rim of the ring.
8.7.3 Be sure to record the elapsed time reading on both the Weekly Site Visit Sheet and the
Sample Data Sheet.
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SOP for Air Sampling lor Metals
Using the Dichotomous Sampler
Volume 1, Chapter 1
8.8 Waste Disposal Clean-up
Waste may include materials used to clean the inlet and packaging materials. Dispose of these
properly.
8.9 Sample Shipping
Once the\ are properly labeled and packaged (Sections 8.3 and 8.4), send the samples. Sample
Data Sheet, and Weekly Site Visit Sheet to the Principal Investigator. Keep a copy of both Sheets
in the site log book. UPS 2nd day delivery is the preferred shipping method. U.S. Priority mail
may also be used.
9.0 Quality Assurance Samples
Occasionally the protocol will require collection of quality assurance samples. Travel blanks are
filters that are shipped with regular sample filters and stored at the site during the collection
period. They should be returned to ISWS unopened after the specified period. Field blanks are
filters that are installed in the sampler during the sampling period. These samples are run to assess
contamination of the filters during periods when the sampler is not running. When field blanks are
run the sampler should be unplugged. These samples should have a "TB" or "FB" in the sample
code (Section 8.3). Specific instructions will be included in the Monthly Site Protocol with the
requirements for these samples.
10.0 Equipment Maintenance and Trouble Shooting
The sampler is exposed to weather, and wind-blown dust and should be cleaned each week by
wiping dirty surfaces with a clean damp cloth.
The operation of the sampler should be checked each week. If the pump does not run or there is a
problem with the timer display, consult the trouble shooting guide below and contact ISWS. For
more information, consult the site operator's manual or contact the manufacturer, Andersen
Samplers Inc., 4215 Wendell Dr., Atlanta, GA, 800-241-6898. Table 2 includes some trouble
shooting information.
Table 2. Trouble shooting
CAUSE
Collector fails to operate
No power to instrument
Circuit breaker continues to break
Electrical short
Operates for a short period then shuts off
Overloaded filter or plugged line
REMEDY
Check switches and power source. Reset circuit
breaker.
Instrument needs servicing
Check filters and lines.
Call ISWS.
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SOP for Air Sampling for Metals
Volume 1, Chapter 1 Using the Dichotomous Sampler
Dichot Air Sample Summary SOP
This summary does not take the place of the detailed SOP and should he used strictly to reinforce the
procedure when in the field. Steps I and 2 will be conducted weekly; Steps 1 through 8 will be conducted
when the filters are changed (every four weeks).
1.0 Initial Inspection
Upon arrival at the site make an initial inspection of the equipment to determine proper operation
for the week. This inspection which will be entered into the site operators weekly activity sheet
would include:
1.1 Comments on site and area conditions that might have affected the sample collection activity that
week.
1.2 Determine whether the pump is operating properly by turning it on and allowing it to operate for
two minutes. Record the rotameter and timer readings on the Sample Data Sheet and Weekly Site
Visit Sheet.
1.3 Wipe clean the surfaces on the inlet.
2.0 Setting Clock and Sample Timer
This is done when a 24-hour sampling period is scheduled for the coming week and no filter
change is required. Follow the procedure in Section 6.0.
3.0 Filter Removal and Labeling
3.1 Unscrew the locking nut (Figure 2) and remove the filters in their plastic holders being careful not
to touch the filter. Place each filter directly into its own snap-lock Petri dish.
3.2 Label the Petri dish with the appropriate code (see Section 8.3).
4.0 Filter Packaging for Shipment
Carefully pack the filters in padded containers. Ship to ISWS as soon as possible.
5.0 Adjust Flow Rates
5.1 Install calibration filters.
5.2 Turn the pump on and let it warm up for at least 10 minutes
5.3 Adjust the flous to the latest calibration set point usintr the adjustment knoh at the hniiom ot the
rotameters
5.4 Turn off the pump and remove the calibration filters
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SOP for Air Sampling for Metals
Using the Dichotomous Sampler Volume 1, Chapter 1
6.0 Installation of New Filters
6.1 Install new pre-weighed filters in the sampler. The labels on the filter holders should face up, and
the holder color (yellow for coarse and white for fine) should match the color code patches on the
sampler. Tighten the locking nut.
6.2 Attach the switch trippers to the timer ring (see Figure I). The Silver-colored tripper should be
positioned at the start day and time and the Black tripper on the end day and time specified in the
monthly site protocol. The trippers should be attached so that the thumb screw is to the front. The
screws should be hand tightened so that the trippers rest firmly against the rim of the ring.
7.0 Waste Disposal/Clean-up
Dispose of all trash properly.
8.0 Sample Shipping
Once packaged properly send the samples, the Weekly Site Visit Sheets for the month, the Sample
Reporting Forms to ISWS via UPS or Priority Mail.
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Volume 1, Chapter 1
SOP for Air Sampling for Metals
Using the Dichotomous Sampler
Appendix A
SAMPLE DATA SHEET
I. Station Name BRULE RIVER
3. Sample Start
Yr Mo Da Time
4. Sample Type Sample Codes
Precipitation Column UP -
2. Operator
End
Yr Mo Da Time
Total
Vol: L
TSP/TOC
Sampler
Organics
High Volume
Sampler
Dichot Sampler
Filter UT -
Timer End
Timer Start
Set-up Date
Filter UH -
Cartridge
Timer End
Timer Start
Codes UD-
F-
UH -
C-
Filter IDs: Fine
1st i imer end
start
2nd Timer end
start
3rd Timer end
start
4th Timer end
start
5. Comments on sample condition or site operation:
6. Date Shipped:
Rotameters
Rotameters
Rotameters
Rotameters
Filter ID
Magnehelic End
Magnehelic Start _
+ days
Filter ID
Magnehelic End
Magnehelic Start
UD-
Coarse
(C)
(O
(C)
.(C)
Received:
.(T)
(T)
(T)
.(T)
Yr Mo Da initials
Yr Mo Ua initial
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Volume 1, Chapter 1
SOP for Air Sampling for Metals
Using the Dichotomous Sampler
Appendix B
WEEKLY SITE VISIT SHEET
INSTRUCTIONS: Fill in all applicable space, enter general weather conditions (sunny, raining, etc.) and
approximate values for weather variables. Enter "OK" after OPERATION for each sampler tested if the
sampler is operating properly; if there is a problem, enter "X" and describe the problem at the bottom of the
page. For the Hi-Vols and Dichots, fill in the TIMER, MAGNEHELIC, or ROTAMETER (Coarse and Total)
readings in the appropriate spaces. For the MICs and metals AEROCHEM, enter the temperature inside the
sampler and the approximate volume in the overflow container (MIC only). For all samplers, indicate with
an "X" whether a sample was collected this week and if the sampler was set up for another run. Indicate with
an "OK" whether the wind vane is pointing in the proper direction and whether the anemometer is turning.
SITE
WEATHER
ORGANICSHIVOLtfl
ORGANICS HIVOL #2
TSP HIVOL
DICHOT #1
DICHOT #2
MIC#1
MIC #2
METALS AEROCHEM
STANDARD AEROCHEM
DATE
TEMP
OPERATION
MET SYSTEM
PROBLEMS AND GENERAL OBSERVATIONS:
TIME
WIND DIR_
TIMER
WINDSP.
MAGN
Sample: Collected Set up _
OPERATION TIMER
Sample: Collected Set up _
OPERATION TIMER
MAGN
MAGN
Sample: Collected Set up _
OPERATION TIMER .
Sample: Collected Set up _
OPERATION TIMER
T
Sample: Collected Set up
OPERATION TEMP
Sample: Collected Set up
OPERATION TEMP
Sample: Collected Set up
OPERATION TEMP
Sample: Collected Set up
OPERATION
Sample: Collected Set up
WIND VANE ANEMOMETER
VOL
VOL
OPERATOR
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Standard Operating Procedure for
Sampling Trace Metals in Precipitation
Using Modified Aerochem Collectors
Stephen J. Vermette and Clyde W. Sweet
Illinois State Water Survey
Office of Air Quality
2204 Griffith Drive
Champaign, IL 61820
December 1993
-------
Standard Operating Procedure for Sampling Trace Metals in
Precipitation Using Modified Aerochem Collectors
1.0 Overview
This SOP is intended to provide a step by step procedure for the proper collection of a
precipitation sample using a modified wet-only Aerochem Metric sampler. Procedures include
replacement of the Teflon sampling train and inspection and maintenance of the sampling
equipment.
Data collected from analysis of precipitation samples from the modified Aerochem samplers will
be primarily used for the Lake Michigan and Lake Superior Load Monitoring Program and for the
Integrated Atmospheric Deposition Network (IADN). Samples at the Sleeping Bear Dunes site,
which is part of the Integrated Atmospheric Deposition Network, were sampled and analyzed by
Indiana University. The sampling method is identical apart from a few minor differences in QC
samples. This site represents 10 % of the samples for this method. The data will be used to assess
the atmospheric loadings of trace metals to the Great Lakes.
The modified wet-only Aerochem sampler is used to collect weekly precipitation samples for trace
metals analysis. Wet-only deposition samplers are designed to open only during a precipitation
event in order to minimize contamination from dry deposition and blowing dust, etc. Due to the
very high susceptibility of precipitation samples to trace metal contamination, the procedures seek
to minimize operator contact with the sample and allow the sample to contact only Teflon surfaces.
The Teflon sampling train, which consists of a Teflon-coated funnel, Teflon tubing and Teflon
bottle, is shipped to the site each week by Buffalo State University (BUF). After a one week
collection period, the entire sampling train is returned to BUF for cleaning and analysis of the
precipitation sample. The trace metals listed in Table 1 will be analyzed by ICP/MS as detailed in
the laboratory SOP.
Any questions concerning sampling methods or operation of equipment should be directed to the
following individuals. The ISWS Contact will be the prime contact for all methodologies and
general operation questions. The EPA Project Lead is the second contact if the ISWS Contact
cannot be reached. Specific questions should be directed as indicated below.
ISWS- Contact Equipment Maintenance
Clyde Sweet Paul Nelson
Illinois State Water Survey Illinois State Water Survey
2204 Griffith Drive 2204 Griffith Drive
Champaign, IL 61820 Champaign. IL 61820
Phone: (217)333-7128 Phone: (217)244-8719
Fax: (217)333-6540 Fax: (217)333-6540
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SOP for Sampling Trace Metals in
Precipitation Using Modified Aerochem Collectors
Volume 1, Chapter 1
EPA Project Lead
Angela Bandemehr
USEPA/GLNPO (G-9J)
77 W Jackson Boulevard
Chicago, IL 60604
Phone: V312)886-6858
Fax: (312)353-2018
Protocol, Supplies, and Packaging
Kevin Cappo
Illinois State Water Survey
2204 Griffith Dr.
Champaign, IL 61820
Phone: (217)244-6128
Fax: (217)333-6540
Table 1. Analvtes from Modified Aerochem Metric Sampler
Parameters:
Aluminum
Cadmium
Copper
Manganese
Sodium
Titanium
Zinc
Arsenic
Chromium
Lead
Nickel
Selenium
Vanadium
2.0 Sampling Equipment Description
The Aerochem Metric (ACM) sampler is modified so that the sample will contact only Teflon
surfaces to minimize trace metals contamination. The precipitation will be caught in a Teflon-
coated aluminum funnel and stored in a 2 L Teflon bottle. The 2 L bottle can collect a volume
equivalent to 3 cm of precipitation. The funnel is fitted with a Teflon o-ring and Teflon fitting and
is connected to the bottle by Teflon tubing. The metal lid and pad are replaced with a polyethylene
lid and Teflon wrapped foam pad. A new polyethylene bag is inserted in the dry bucket each week
so that the lid will contact a clean surface. The arms of the ACM are Teflon coated and, at the
pivot points, are covered with plastic sleeves to prevent freezing in the winter. The base of the
ACM is enclosed with aluminum and insulated to control the temperature and minimize
contamination. A heater and fan inside the enclosure operate to regulate the winter temperature to
between 5 and 25 "C. In tiie winter, heat from the enclosure warms the funnel to melt any snow
caught by the collector. Summer temperature will be maintained at ambient temperature using the
fan.
3.0 Summary of Method
The sampling period, the time between bottle/funnel installation and removal, is one week. The
sampling tram \\ill he replaced each Tuesday at or about 10 00 am local time. If it is rainine or
snowing at collection time, the tram should he changed alter the precipitation stops, hut nn later
than midnight Tuesday Bottles/tunnels are sent to the lahoraton. even if no precipitation uas
collected. If the sample can not be collected on the prescribed sampling day, the ISWS Contact
must be notified. The following sampling activities will take place in the order listed.
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SOP for Sampling Trace Metals in
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I) Initial inspection
2) Removal of collection bottle
3) Replacement of polyethylene bag over the dry-side bucket
4) Removal of funnel
5) Replacement of sampling train (funnel/tubing/bottle in that order)
6) Sample shipment
7) Field log reporting and sample reporting form completion and submission
All steps will be conducted weekly and are detailed in Sections 9.1 through 9.8. Heavy
precipitation may cause the collection bottle to overflow. Changing the bottle during the week to
prevent overflow is discussed in Section 9.3.
4.0 Sample Handling and Preservation
Every sample is important and represents a significant portion of that site's yearly estimate. Any
contamination through mishandling could cause a bias in the program results. Plastic gloves
should be worn while removing, handling, and replacing the Teflon sampling train. (Do not use
latex gloves with powder.) All procedures for sample handling, packaging and shipping should be
followed.
5.0 Interferences
Ideally, the sampler should collect 100% of the precipitation. However, due to losses of
precipitation and/or mechanical malfunctions, not all of the precipitation is collected. The validity
of the sample is not based on the amount of precipitation collected but on the integrity of the
precipitation collected. The sampler should not remain open for periods greater that 30 minutes
after precipitation stops. Any sample exposed to dry deposition for greater than six hours during a
standard sampling period will be considered invalid and flagged as such.
Examples of other events which will result in invalid data are malfunctioning of the lid so that
continuous cycling occurs during a precipitation event, use of non-standard or modified
equipment, or inadequate documentation by operator. Data corresponding to these events will be
flagged appropriately.
Samples may also be contaminated by the site operator from water and/or other contaminants
entering the sampling train from hands or clothing. Plastic gloves must be worn during all contact
with the sampling tram. If the sample must be collected during a precipitation event, a T> vek
jacket should be worn and returned to the plastic pouch after completion of sampling.
Extreme temperatures may result in improper operation of the equipment. Freezing temperatures
may inhibit flow of precipitation through the funnel opening, while high temperatures may
enhance evaporation. A heater and fan are provided to regulate the temperature and should be
maintained and inspected weekly. A max-min thermometer is also provided inside the sampler
and should be recorded and reset weekly.
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SOP for Sampling Trace Metals in
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6.0 Safety
In any field operation, emphasis must be placed on safety. Site operators must be aware of the
potential safety hazards to which they are subjected. Follow all safety protocols and equipment
guidelines, and be prepared for emergency situations. The sites operator is responsible for his/her
safety from potential hazards including but not limited to:
Travel: When traveling to the site be sure to check on road conditions and weather
advisories. Carry emergency supplies (warm clothes, food, water) when traveling
in winter. Always let someone know where you are going and when you expect to
return. Always carry a first aid kit.
Electrical: For obvious problems (fire, scorching, continuously blowing fuses), turn off the
power of the circuit involved and notify IS WS. Never attempt electrical repairs
other than replacing fuses and circuit boards. Be sure to unplug the sampler
before changing fuses. Be especially cautious if conditions are wet.
Insects/pests: If you are allergic to insect stings, you should carry a kit prescribed by a
physician. Be especially cautious if nests or large numbers of stinging insects are
present. Notify ISWS of all problems.
7.0 Equipment and Supplies
Proper use, maintenance and cleaning will extend the life of serviceable equipment. The
equipment and supplies specified in these lists (supplied by ISWS) should be used at the site. Any
modifications or changes must be approved by the ISWS Contact.
7.1 Serviceable Equipment
These items will be maintained at the site at all times':
Modified Aerochem Metric wet/dry precipitation collector (Model 301)
Space heater
Maximum/minimum thermometer
One extra sampling train (Teflon bottle, tubing, and funnel) in packaging as sent by laboratory
One extra Teflon bottle in laboratory packaging
Jack to hold bottle in place
Overflow tray
Enclosure filter
Plastic gloves
Log book
Report forms
Tyvek jacket (in plastic bag)
Kimwipes
Squirt bottle lo \\et precipitation sensor
A diagram of the Aerochem Metric collector and Teflon sampling tram is shown in Figure I.
General maintenance and trouble shooting are covered in Section 1 1 0.
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Figure 1. Modified Aerochem Precipitation Sampler (Dry-side bucket not shown)
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SOP for Sampling Trace Metals in
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7.2 Consumable Equipment
These items will be shipped to the operator every week.
Sampling train (Tenon bottle and cap, tubing, and funnel in polyethylene bags)
Shipping box and packaging materials
8.0 Calibration and Standardization
8.1 Rain Sensor
The Aerochem Metric (ACM) sampler consists of a collection container which is covered by a
motor-activated lid. In a precipitation event a sensor activates a motor to move the lid off the
collector. Each week the sensor should be checked to ensure proper operation. The procedure for
this is covered under Section 1.4.4.
8.2 Heater and Fan
The heater must operate properly in freezing temperatures to maintain proper operation of
sampling equipment. The heater must maintain a 15° ± 10=C temperature in the sample
enclosure. The heater will be calibrated at ISWS. When cold weather is expected, check that the
heater is operational by turning up the heater thermostat until the heater comes on; set this
thermostat at the calibration mark. During the warm weather, make sure that the fan is operational
by turning down the fan thermostat; set this thermostat at the calibration mark. Reset the
maximum/minimum thermometer and record the temperatures each week.
9.0 Procedures
The site operator is responsible for maintenance of the site and for weekly sample collection,
submission and documentation. The site operator will conduct routine maintenance, request
needed supplies or parts in a timely manner, complete the weekl) data sheet and maintain the field
log book.
In order to ensure a representative wet deposition sample the following detailed procedures on the
removal and installation of the sampling train, documentation, and maintenance should be
implemented.
The following procedures should be adhered to each week:
1) Initial inspection
2) Removal of collection bottle
3) Replacement of polyethylene bag over dry-side bucket
4) Removal of funnel
5) Replacement of sampling train (funnel/tubing/bottle in that order)
6) Waste disposal and clean up
7) Sample shipment
8) Field log reporting ,ind sample reporting form completion
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SOP for Sampling Trace Metals in
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9.1 Reporting and Labeling
All observations should be recorded on the sample reporting form and in the site log book. All
entries should be made with a permanent ink marker. All times will be recorded in local time on
2400 hour clock. Labels are placed only on the sample bottles and only after the sample has been
collected.
9.2 Initial Inspection
Carrying a box containing the new sampling train (bottle, tube, and funnel) approach the collector
from downwind if possible.
9.2.1 Inspect the immediate site and surrounding area for any conditions which may affect the
integrity of the sample, i.e. fire in the area, wind storm, vandalism, etc. Note these in the
site log book and on sample reporting form. Also note if it is raining or snowing during
sample collection.
9.2.2 Inspect the equipment for any damage and to see that all connections are secure. Remove
any snow from top of lid. Operation of the rain sensor and lid will be checked during
Section 1.4.4. Check operation of the heater or fan. Check for interferences
(Section 1.1.3)
9.2.3 Record minimum and maximum temperatures from inside enclosure and reset
thermometer.
9.3 Removal of Bottle from the Previous Week
9.3.1 Put on a clean pair of plastic gloves.
9.3.2 Unscrew the bottle, lower the jack, and recap the exposed collection bottle with the stored
cap. (Last week the cap was placed in a plastic bag and stored in the enclosure. Do not
put the cap down inside the enclosure unless it is inside a bag.) Place capped bottle inside
a plastic bag. Put the label on the out side of the bag.
9.3.3 Remove the tube assembly and place in the plastic bag which was stored inside enclosure
last week.
9.3.4 Close door to enclosure, leaving used bottle and tubing in bags inside enclosure. Bottle
and tubing will be transferred to shipping box in Section 1.4.4.
9.4 Changing of Bottle for Overflow (During Sampling Period)
Heavy precipitation may result in bottle overflow. To prevent this the bottle may be changed
during the sampling period as follows:
9.4.1 Bring one of the extra Teflon bottles in polyethylene haes to field site.
9.4.2 Wearing polyethylene gloves, unscrew the bottle cap. Inucr ihe jack, and recap the
exposed collection bottle with the cap that was stored in the enclosure. Place the capped
bottle inside a plastic bag and leave inside enclosure until Tuesday sampling.
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9.4.3 Place the new bottle on the overflow dish. Place the cap inside a polyethylene bag. Raise
the jack to position the collection bottle so that Teflon tube is about '/2 inch into the
collection bottle. Screw on the cap which is part of the tubing assembly. Store the cap in
bag inside the enclosure for use at the end of the week.
9.4.4 Both bottles will be shipped to BUF at the end of the sampling period. Indicate on the
field report form and in the field notebook that two bottles were shipped.
9.5 Removal and Replacement of the Funnel
9.5.1 Replace the polyethylene bag in the dry side bucket and secure it with a bungee cord.
Discard the old bag.
9.5.2 Standing downwind of the sampler, apply enough DI water to the sensor grid for the lid to
remain open while changing funnels. Watch as the lid moves over. The lid should move
freely with little motor noise. Wipe the underside of the lid with a damp (DI) Kimwipe.
9.5.3 Without leaning over the funnel, note any contamination on the funnel and record this on
the site reporting form.
9.5.4 Using the bag as a second glove, remove the exposed funnel and place it in a polyethylene
bag.
9.5.5 Retrieve the new funnel from the shipping box and place the used funnel in the shipping
box in the same position.
9.5.6 Holding the new funnel through the bag, open the bag, and position the funnel on the wet-
side sampler. Do not touch the funnel except when using the bag as a second glove. After
the funnel has been properly seated, place the bag inside the enclosure for next week.
9.5.7 Blow any remaining water off the sensor, allowing the lid to close on the wet-side. After
the sensor plate has been open, check to see that the sensor plate is warm. Clean any
accumulated dirt off the sensor.
9.5.8 Check for a good seal between the lid and funnel.
9.6 Installation of Bottle and Tubing for Next Week
9.6.1 Open the sample enclosure. Put the used bottle and tubing in the shipping box and
retrieve the new bottle and tubing.
9.6.2 Copy the weight written on the top of the capped bottle into the log book and onto the
sample report form to be submitted next week. The dates of the new sampling period
should be included with the weight.
c) K j'h\ lene hag as a second iilovc.
remove the new tubing assembly from its bag and slip it i>nu> the bucket nipple from
inside the enclosure
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9.6.4 Remove the bottle from the bag and place on the overflow dish. Remove the cap and
place it inside a polyethylene bag. Raise the jack to position the collection bottle so that
the Teflon tube is about '/z inch into the collection bottle. Screw on the cap which is part
of the tubing assembly. Store the bottle cap in a bag inside the enclosure. Place the bags
for the bottle and funnel inside the enclosure for next week.
9.7 Waste Disposal and Clean up
Check the site for waste materials such as plastic gloves and Chem wipes prior to leaving site.
Take an inventory of equipment and consumables. Notify ISWS of any equipment need repair or
replacement of if any supplies are needed.
9.8 Sample Shipping
Once the bottle is detached from the funnel and capped it is not opened again by field personnel.
Ensure that sampling train is properly packaged in polyethylene bags and in proper locations in
shipping box. Send the contents to: Stephen Vermette, ESSE, Buffalo State University College,
1300 Elmwood Ave., Buffalo, NY 14222. Samples and the sample report form should be sent via
UPS or U.S. priority mail to the laboratory no later than the day after collection. Photocopy
paperwork so that a copy remains with the site operator. Notify ISWS if any equipment needs
repair or replacement or if any supplies are needed.
10.0 Quality Assurance Samples
Occasionally the protocol will require collection of quality assurance samples. Travel blanks are
bottles which are shipped with the regular sample trains and stored unopened in the enclosure
during the sample period. They should be returned to BUF unopened after the specified period.
The operator will receive a box labeled "system blank" which contains a new sampling train and
250 mL bottle containing DI water. The sampling train should be installed as usual; however, the
precipitation sensor is unplugged from the motor box so that the lid remains closed throughout the
sampling period. At the end of the sampling period (the following Tuesday), the operator should
reconnect the sensor and open the lid by wetting the sensor. The operator should then pour the DI
water from the 250 mL bottle into the funnel in circular motions, wetting the sides of the funnel.
The lid is then allowed to close. The sampling train is collected according to the procedures for
weekly samples, with the exception that the field sheet is labeled "system blank" and the 250 mL
bottle is returned
11.0 Equipment Maintenance
Site operators will maintain equipment in good working order at the original location. Site
operators should also maintain the area around the collector. An\ changes to site conditions
should be recorded and reported to ISWS. Modifications at the site or to its equipment must be
approved by the ISWS Contact. This includes placing other equipment in close proximity to the
existing samplers.
I I. I Check Power Supply
Check all power connections at each visit.
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II.2 Routine Cleaning
The housing and top of the lid should be washed periodically with water (distilled water is best)
and a clean sponge to remove any residues (i.e. bird feces or accumulated dirt). Also the sensor
grid should be scrubbed with a wetted toothbrush to remove accumulated minerals or other
contaminants.
11.3 Check Foam Pad Insert
The foam pad should maintain a good seal with the funnel. If there are any gaps blowing dust may
enter and contaminate the sample. Over time, the pad will tear and break down and may fall into
the sample and cause contamination. This has been the most common maintenance problem. The
pad should be replaced at least once a year.
11.4 Enclosure Filter
The enclosure filter is replaced at least once a year.
11.5 Troubleshooting
If the sampler fails to operate when you wet the sensor (lid does not move and motor does not
start) there may be an existing power failure. Check that all the line power connections are secure,
and that the fuses (found on the motor box) are good (check fuses with a volt meter or spare fuses,
as you can't always see that they are blown). A voltage meter or appliance (i.e. radio or light bulb)
can be used to check the power supply from the outlet.
If the sampler fails to operate when temperatures are below freezing (the lid does not move and
motor is running) the collector lid may be frozen to the bucket, or the support arm pivots may be
frozen to the housing, or the weight of snow on the collector lid may prevent the lid from opening.
Gently pull at the lid or lid arms to break the ice, or remove the snow from the collector lid. A
peaked roof and heating pads can be used to prevent freezing if this problem occurs often.
If the precipitation sampler fails to operator properly, aside from a power failure and freezing
there are three components which can fail: the sensor unit, the motor box (containing the drive
motor, fuses, and circuitry), or the clutch unit. Common signs of these failures are the continuous
cycling of the collector lid, the lid remains on the wet (even when the sensor is wet) or dry-side
bucket, or the collector lid stays open long after the precipitation e\ent ends. Signs of these
failures well be evident from the event recorder trace on the Belfort raingage drum chart.
1 1.5.1 Sensor Unit
When the sensor unit is faulty the following symptoms may be observed: The collector lid
oscillates non-stop between buckets, or remains on either the wet- or dry-side with the
motor running. A quick way to check if the sensor is faulty is to unplug it from the motor
box. If the collector lid moves to cover the wet bucket the sensor needs to be replaced.
V\ hen the sensors heater is lauli\ tlv lid stu\s o\er the dr\-side long after precipitation
stops and the sensor dries slowly. A faulty heater will not allow the sensor to evaporate
\\aler or melt snow, and the collector lid is not triiiuered to i_o\er the "\vet" bucket in a
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timely manner. This can be checked by feeling the sensor for heat. A properly operating
sensor will feel warm to the touch. If the sensor has cooled the heater probably has failed.
If this is the problem, the sensor should be replaced, even though the sensor may continue
to activate the lid as the sensor will dry through natural evaporation. If a replacement is
not available the sensor may still be used, although the sample may be more susceptible to
contamination from dry deposition. Note this on report forms and notify ISWS of the
need of a replacement sensor.
I 1.5.2 Motor Box Unit
When the motor box unit is faulty the collector lid oscillates non-stop between buckets. ,,r
rests on the wet- or dry-side without the motor running. If unplugging the sensor
(discussed in previous section) doesn't move the lid over to the wet bucket, or if the fuses
are found to be good, the motor box will require replacement or repair. ISWS should he
contacted. A diagram of the fuse arrangement in the motor box is shown in Figure 2.
11.5.3 Clutch Unit
When the clutch unit is faulty the motor will run but the lid mechanism will not move. In
this case the clutch needs to be examined for wear. To do this, remove the clutch arm bolt
to separate the clutch from the lid mechanism, and then loosen the thrust collar screw and
gently pry the clutch off the motor box. If the thrust collar indent or the clutch tooth
appear significantly worn then the clutch should be replaced. If they do not, the tension
spring needs to be stretched. To do this, move the tension plate away from the thrust
collar. The further away from the thrust collar the plate is pushed, the more tension is
produced. Note: the clutch spring should not be stretched so far as to "freeze" the clutch -
- it should still be able to pull away ("pop-out") from the motor box. If the clutch cannot
be repaired at the site, notify ISWS.
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Volume 1, Chapter 1
LM/LS Metals Network
L r,.T,D
o
7 Vj«
Figure 2. Aerochem Motor Box
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Appendix A
SAMPLE REPORTING FORM
I. STATION
Name
ID
D
3. SAMPLE INTERVAL
Start
End
yr/mo/day/hr(0000.0000
/DD "
yr/mo/day/hr
DP)
(0000-0000)
5. SAMPLE WEIGHT (laboratory use)
Collection Bottle & Sample
Collection Bottle [ | (__]
Sample Weight
Sample Volume
DD
irams
irams
'rams
-nL
Rain Gage Volume
-nL
7. REASON FOR BOTTLE CHANGE
End of Sampling Period
To Prevent Overflow
8. REMARKS
Did Bottle Overflow
2. OBSERVER
Name
Initials
4. SAMPLE TYPE
Wet-deposition | |
System-blank
6. SAMPLE APPEARANCE
Clear
Cloudy
Floating Material
Settled Out
Other
9. LABORATORY CUSTODY (laboratory use) Ultrapure
i
Sample Acidified Yes ( if yes. Date f\ \
\ /
Aliquots: Lab I.D. Volume Routing
Acid added mL
/ N
/ /No
/
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Metals Cleaning Procedures for
Teflon Bottles and Rigid HOPE
Stephen J. Vermette and Clyde W. Sweet
Illinois State Water Survey
Office of Air Quality
Champaign, IL 61820
December 1993
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Metals Cleaning Procedures for
Teflon Bottles and Rigid HOPE
1.0 Teflon Bottles & Rigid HOPE
1.1 Rinse the bottle and cap three times with DI water by filling the bottle approximately Vs full.
capping, and shaking vigorously. Discard water is poured into cap as part of the cleaning
procedure.
1.2 Fill the bottle with 10% reagent nitric acid, screw on the cap and let soak for 24 hours. The boulc
should be shaken once at the beginning and once at the end of the 24-hour period.
1.3 Discard the acid solution and rinse three times with DI water, follow same procedure as in Step 1
above.
1.4 Fill the bottle with DI water, screw on cap and let soak for 24 hours. The bottle should be shaken
once at the beginning and once at the end of the 24-hour period.
1.5 Discard the DI water and rinse three times with DI water, follow the same procedure as in Step 1
above.
1.6 Shake out excess water, cap snugly, and store for use.
2.0 Teflon Bucket Assembly Cleaning Procedures
2.1 Upon receipt at the ISWS laboratory, the bucket assembly is removed from the polyethylene bag,
and the removable components separated from the bucket. These components, the teflon fitting,
o-ring, and tubing assembly are placed in a 10% HNO3 bath.
2.2 The inside of the bucket is wiped with a wet sponge (and DI water) and the inverted bucket is
cleaned in a FORMA-FURY laboratory glassware washer using DI water and the same washing
sequence and procedures as used for the NADP/NTN collection buckets. A rubbermaid mesh
screening is placed under the buckets to prevent abrasion of the teflon coating on the bucket, and
prevent contact with the stainless steel interior.
2.3 The bucket and components are washed twice in the Forma-Fury unit. During the first wash, the
tube assemblies are set up in the hole atop the inverted bucket, and the partially assembled teflon
and o-ring fittings are placed in the washer also. During the second wash, the teflon and o-ring
fittings are assembled with the bucket, and the tubing assembly pk'ced next to the buckets
vertically.
2.4 Upon removal from the glassware washer, the bucket assembly is shaken to remove excess water.
The interior of the assembly is rinsed with 1 (Kf reagent grade nitnc acid from a squeeze bottle,
and then copiously rinsed with DI \\ater
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2.5 The bucket assembly is then placed in a closed polyethylene bag and placed in a well padded
16"xl6"xl6" box for shipment.
2.6 The tubing assembly is placed in a separate 1 gallon resealable single use teflon bag.
3.0 Assembly Package
3.1 A 16"xl6"xl6" heavy duty cardboard box is assembled and taped with several layers of high
quality packaging tape.
3.2 Sufficient packaging to prevent damage is placed in the bottom of the box.
3.3 The following materials are then placed in the box.
Teflon bucket assembly
Tared 2.0 L teflon sample collection bottle
Cleaned tubing assembly in 1 gallon resealable bag
Dry side bag
Data sheet, including shipping date, tare weight, and site ID already completed
Weekly memo - including specific instructions for the week
On occasion, field blank and or system blank bottles and materials are included along with specific
instructions.
3.4 The boxes are then filled with packaging materials, sealed, and mailed to the site operators.
4.0 Sample Handling Procedures
4.1 Samples are received at the ISWS from one to seven days after being removed by the operator,
with a typical sample arriving three days after sampling. Samples are generally treated on the day
of arrival at the ISWS.
4.2 Upon arrival at the ISWS, the sample bottle is taken and reweighed. This and the tare weight are
used to calculate the weight and volume of the sample.
4.3 A 0.2r; HNO. solution is added to each sample based on volume. The sample is then shaken and
allowed to equilibrate a minimum of 24 hours, and if possible over a weekend.
4.4 After equilibration, the samples are decanted into previously cleaned 60 mL, 125 mL, 250 mL, or
500 mL sample bottles, based on volume of the sample. The sample bottles are rinsed twice with
the sample solution before the entire sample is placed in the bottle. The rinsing procedure is
waved in sample of less than 60 mL of solution, as use of the sample would leave too little for
analytical analvsis.
4.5 Samples aie labeled and stored at the !S\VS. and taken to the HWRIC for anaKsis once per month.
Sample-- ,it the HWRIC are stored ai 4 (' both before and alter anaKsis
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Standard Operating Procedure for
Sampling of Vapor Phase Mercury
Gerald J. Keeler and Matthew S. Landis
University of Michigan
Air Quality Laboratory
109 South Observatory Street
Ann Arbor, Ml 48109-2029
June 1,1994
Version 2.0
-------
Standard Operating Procedure for
Sampling of Vapor Phase Mercury
1.0 Introduction to Principals of Vapor Phase Mercury Sampling and
Analysis
Mercury in the atmosphere exists predominantly in the gas phase in the form of elemental mercury
(Schroeder, 1982). Other species of mercury found in the gas phase include methyl and
dimethylmercury, and mercuric chloride, mercuric hydroxide and free divalent mercury. Vapor
phase mercury is quantitatively removed from an air stream by amalgamation onto gold. While the
amalgamation process is believed to remove most vapor phase mercury species with >99%
efficiency, the analytical procedure employed determines whether or not 'total mercury' or
predominantly elemental mercury is quantified. At the University of Michigan Air Quality
Laboratory (UMAQL) vapor phase mercury is collected onto gold-coated borosilicate glass bead
traps by drawing air at a low flow rate through a baked glass fiber pre-filter followed by the gold-
coated borosilicate glass bead trap. The air is prefiltered to eliminate particles from the gas phase
collection traps. After sampling, vapor phase mercury is quantified by cold vapor atomic
florescence spectrometry (CVAFS).
In the past, methods for collection of vapor phase mercury have dictated long sampling duration,
often from 24 hours up to a week. The collection method employed for the Lake Michigan
Loading Study and described in this protocol uses gold-coated borosilicate glass bead traps, which
UMAQL has determined to be >99% efficient at collection of vapor phase mercury (at a flow rate
<1 1pm). Dual-amalgamation and subsequent analysis by cold-vapor atomic florescence, allows
detection of mercury at picogram levels. After thermal desorption, gold-coated bead traps are re-
used since they do not exhibit memory effects. Due to the collection efficiency of gold-coated
beads and the ability to detect picogram amounts of mercury, sampling strategies using gold-
coated bead traps can employ much shorter duration samples than have previously been possible.
Short sampling duration provides the resolution necessary to use receptor models in determining
sources and source contributions of measured vapor phase mercury.
Preparation and collection of accurate and reliable data on mercury concentrations in
environmental samples requires that ultra clean procedures are used. All sampling supplies with
which a sample will come into contact must be acid cleaned in a Class 100 Clean Room. At the
sampling site, precautions taken to avoid contamination of the sample include storing samples at
an outdoor staging area and special operator handling. These and other techniques employed to
minimize contamination of the samples are described in detail in this protocol.
2.0 Sample Preparation
2.1 Acid Cleaning Procedure
All Teflon filter packs. Teflon jars. Teflon tubing, gold trap fittings and end plugs (referred to
below as 'supplies') are cleaned using an I I-dav procedure described h\ Rossmunn and Barres
(1991).
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Supplies to be acid cleaned are first rinsed in reagent grade acetone under a fume hood, then
washed in hot tap water and diluted Alconox. Supplies are rinsed five times in cold tap water then
rinsed three times in DI water. The supplies are then heated in 3M hydrochloric acid (EM Science
TracepurHCl in Milli-Q water (18.2 MQ/cm)) for six hours at 80°C. One liter of 3M HC1 is
prepared by adding 750 mL of Milli-Q water to 250 mL of concentrated EM Science Tracepur
HC1. The 3M HC1 can be used several times and is stored for reuse in a polyethylene carboy
dedicated for this purpose. The supplies are placed into clean polyethylene tubs which are then
filled with the 3M HC1, making sure that all of the surfaces are submersed in the HCI. The tubs
are covered and placed in a water bath which is heated to 80°C in a fume hood. The water in the
bath is maintained at the level of the acid inside the tubs. After the water in the bath reaches
80°C, the supplies in the tubs are allowed to soak for six hours.
After the six hours, 80°C soak, the tubs are removed from the water bath and allowed to cool in
the fume hood. When cool, the 3M HCI is poured back into its polyethylene carboy. The supplies
are rinsed in the tubs three times with Milli-Q water. The supplies are then soaked in a 0.56M
nitric acid solution (Baker Instra-Analyzed HNO, in Milli-Q water) for 72 hours at room
temperature in the same polyethylene tubs in which they were heated with HCI. The nitric acid
solution is made by adding 35 mL Baker Instra-Analyzed HNO, to 965 mL of Milli-Q water.
Nitric acid is reused for up to six months and is stored in a carboy dedicated for HNO,. At the end
of the three-day soak, the supplies being cleaned are rinsed three times with Milli-Q water and
transferred into a Class 100 Clean Room.
Inside the clean room, the supplies are again rinsed three times with Milli-Q water. The tubs
containing the supplies are filled with 0.56M Baker Instra-Analyzed HNO3 that is kept in the clean
room and is dedicated for this final step only. The supplies are then allowed to soak in this acid
for seven days. This acid is prepared by adding 35 mL of the Instra-Analyzed HNO3 to 965 mL of
Milli-Q water. At the end of the seven day acid soak inside the clean room, the supplies are rinsed
five times with Milli-Q water and allowed to air dry on a clean surface. When the supplies are dry,
they are triple bagged in new polyethylene bags and removed from the clean room, ready for use in
sampling.
2.2 Preparation of Gold-Coated Bead Traps and Pre-Filters
Gold-coated borosilicate glass bead traps are constructed at The University of Michigan Air
Quality Laboratory and tested prior to use in the field. The gold-coated beads used in the traps are
made by generating a gold plasma under vacuum conditions that uniformly deposits onto the
surface of the heads, The thickness of the coating generated using this process is about 300 A.
The gold-coated beads are contained in a quartz tube which is 10 cm long with an inner diameter
of 5 mm and an outer diameter of 7 mm. Teflon heat-shrink tubing is attached to both ends of the
tube into which Teflon endplugs are placed when the trap is in storage or connectors when the trap
is being used to collect a sample. Each trap contains approximately 0.7 g of gold-coated
borosilicate glass beads which are held in place using quartz wool and two sets of three radial
indentations in the quartz tube. The gold-coated beads, quartz tubes and quartz wool are baked at
600°C for one hour prior to making the trap. In addition. Teflon endplugs and heat shrink tubing
are acid cleaned as previously described.. After each trap is made, it is given a unique number
identifier in order to chart the history and performance of the trap. Ne\\ traps are firsi conditioned
by drawing approximately 0.4 in1 of air through the trap then healing the trap to 500 C for five
minutes. Inert gas is purged through the traps at 300 cc/mm during heating procedure to remove
moisture and other volatile constituents. The conditioning procedure is performed twice prior to
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Volume 1, Chapter 1 SOP for Sampling of Vapor Phase Mercury
testing the trap. The trap is then tested by injecting a known amount of elemental mercury vapor
and comparing the result to an analytical standard. The trap must exhibit duplicate measurements
that are within 5% of the standard and the replicate measurements must also be within 5% of each
other. Following this test, the trap is then blanked (described below) and stored for seven days.
After seven days, the trap is analyzed for a storage blank (sample analysis is described in the
Standard Operating Procedure for Analysis of Vapor Phase Mercury). The storage blank must be
less than 15 pg for the trap to be accepted for use in field sampling. Gold traps arc stored with
endplugs in place, triple bagged in polyethylene before and after sampling.
Just before going into the field to collect vapor phase mercury samples, gold-coated bead traps are
blanked again. Blanking a trap removes all mercury from the gold-coated bead surface and will
also remove water vapor and other unwanted constituents. Traps are blanked by placing them in
the analytical train and heating them to 500aC for two minutes, identical to a normal sample
analysis.
Vapor phase mercury samples collected onto gold-coated borosilicate glass bead traps must be
prefiltered to exclude particles. Glass fiber filters (Gelman Sciences) are pre-treated to remove all
mercury prior to use in sampling. Glass fiber filters, 47 mm in diameter, are placed in a clean
crucible with a lid. The crucible is placed in a muffle furnace which is heated to 500°C and the
filters are allowed to bake at this temperature for one hour. While hot, filters are removed from the
crucible with acid-cleaned Teflon-coated forceps and placed in an acid-cleaned Teflon jar which is
closed and sealed with Teflon tape. The Teflon jar is triple bagged and stored at -40°C until use.
Filters are stored no more than three months prior to use and frequent blanks are taken to ensure
the filters remain clean.
3.0 Vapor Phase Mercury Sample Collection
During sample collection the filter packs and gold bead traps are housed in a sampling box that is
mounted on a pole or tower at least 3 meters above ground level. The sampling boxes were
custom-made at UMAQL from fiberglass enclosures (Stahlin Enclosures) using quick connect
couplings to connect the vacuum lines from the pump to the sampling devices. Sample intakes are
at least 30 cm apart and are not positioned near any potential contaminant sources.
A flow rate of approximately 300 cc/min. is typically used to sample with gold-coated bead traps,
however, in highly contaminated areas flow rates less than 300 cc/min. may be desirable. Sample
duration and flow rate depend on the study design. The sampling flow rate is maintained with a
mass flow controlling device in order to maintain constant flow throughout the sampling period.
During the Lake Michigan Loading Study all samples collected will consist of two traps in series.
The front trap (A) is used to remove mercury from the air stream and the second trap (B) is used as
a back up to characterize any breakthrough from the front trap. The flow rate through the inlet of
the front trap must be confirmed before setting up each sample using 'test' traps instead of the
sample traps, since any flow measuring device in front of the inlet could potentially contaminate
the sample. Air is not drawn into a gold trap without a pre-filter attached since this will result in
particle buildup inside the trap. All pumps used for sampling are allowed to warm up for at least
30 minutes prior to use.
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SOP for Sampling of Vapor Phase Mercury Volume 1, Chapter I
3.1 Setting Up Gold-Coated Bead Samples
During all phases of sample set-up and removal, the operator stands downwind of the sample in
order not to contaminate the sample by shedding particles from clothing, etc. In addition, particle-
free gloves are worn when handling gold bead traps and prefilters. An acid-cleaned filter holder is
loaded with a fired glass fiber filter for each new gold bead trap sample to be collected. The filter
pack is placed in one of the inner holes in the mercury sampling box (Appendix B). An acid
cleaned piece of 0.64 cm Teflon tubing is placed in the ferrule fitting on the outlet of the filter
pack and is tightened down with a ferrule nut. The 'test' traps are removed from their plastic tubes,
the endplugs are removed from the trap and placed in the plastic tube which is then capped and
returned to a clean plastic bag. The Teflon sleeve of the front test trap is placed snugly over the
0.64 cm Teflon tube on the outlet of the filter pack. A piece of 0.64 cm Teflon tubing is placed in
the back end of the front trap and a second trap is attached to this piece of Teflon tubing. Another
piece of Teflon tubing is secured to the vacuum line and attached to the back end of the second
trap (Appendix C). A calibrated rotameter is attached to the inlet of the prefilter pack by a 9 cm
long piece of black latex tubing. The flow rate is allowed to stabilize and is then read from the
rotameter. After recording the flow rate, the test traps and the rotameter are removed and sample
traps are installed in their place in the same manner as described. A trap heating assembly is
placed over the front sampling trap. The heating assembly consists of a 12.5 cm length of 0.9 cm
ID stainless steel tube wrapped with 1.27 cm silicon heating tape and covered with insulated vinyl
tape. A variable transformer is set (-3-4 V) to maintain a constant temperature of 93°C to prevent
condensation of water vapor in the sampling traps. The sample number, date, time, flow rate,
meteorological information and any other pertinent information are recorded on a log sheet
(Appendix D).
3.2 Taking Down Gold Bead Trap Samples
Particle-free gloves are worn during this procedure. The gold-coated bead traps are removed from
the sampling stream and the endplugs are replaced. The juncture of the Teflon plugs/gold trap is
wrapped with Teflon tape. The trap is placed in its plastic shield which is capped, and the sample
number is placed on the plastic tube. As soon as the trap is removed from the sampling stream, the
time is recorded. The tube containing the sample is then sealed in polyethylene bags and is
immediately shipped to the UMAQL for analysis. Test trips are placed in line after the filter and
the flow rate is read using a calibrated rotameter. All other pertinent information is recorded on
the sample log sheet. After the flow rate has been checked, the pump is turned off. The prefilter is
discarded.
3.3 Taking Blanks
A minimum of 25% field blanks and 10% shipping/storage blanks are taken to ensure samples are
being collected in a contaminant-free manner. Field blanks involve setting up a gold bead trap in
the same manner as a sample. The filter pack and attached gold trap are placed in the sampling
box for u\o minutes without the vacuum line attached. After the t\\o minutes, the sample is taken
off. labeled and stored as described for samples. Shipping/storage blanks are traps that have been
blanked. Teflon taped and triple bagged The traps are then sent to the sampling site along with
sampL naps hut are ne\er reimned Irmn the triple hag nor is the IVtl>n tape remoxed. The traps
arc '.hen vent hack with sample traps u> the I MAQL for anal\si-
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Volume 1, Chapter 1 SOP for Sampling of Vapor Phase Mercury
3.4 Trouble-Shooting
If flow through the gold trap or filter pack sample is low:
3.4.1 Check to make sure that all the connections are sealed tightly (make sure the ferrule nut
fittings are tightened down, tubing connectors are tightly inside tubing from gold trap and
on filter pack tubing, 'flow check' filter pack is screwed together tightly, tubing from the
pump to the sampler is intact and connected securely.)
3.4.2 Make sure that the exhaust of the rotameter is not impeded in any way when using the
rotameter to check flow.
3.4.3 Check the black latex tubing in the sampling box for cracks or tears due to weathering.
3.4.4 Make sure the mass flow controller is on and reading the normal output for the sample.
If all systems seem to be working properly and the flow remains low or erratic, operators
are instructed to notify Matthew Landis at UMAQL (313) 763-7714 or at home
(313) 663-9615 immediately.
4.0 Performance Criteria, Quality Assurance and Quality Control
4.1 Field operators are carefully instructed in the techniques of contaminant-free vapor phase mercury
collection. All of the operators are currently operating sampling equipment for either the National
Dry Deposition Network, the National Atmospheric Deposition Program, the Integrated
Atmospheric Deposition Network or the Great Lakes Acid Deposition Network.
4.2 Every six months UMAQL personnel will inspect the sampling sites to audit the sampling
equipment and make all necessary repairs or adjustments.
4.3 Co-located samples are collected from one sampling site during the study to quantify method
precision. Reported concentrations are based on the mean of the two co-located samples.
4.4 Precision and accuracy levels will be set and maintained for each type of analysis. A relative
precision for total mercury of less than 10% is maintained for samples with values at least three
standard deviations greater than the detection limit. Analysis of standards and controls is within
5% of the stated value.
4.5 A minimum of 25% of all samples analyzed are field blanks or analytical blanks to ensure that
samples are collected in a contaminant-free manner.
4.6 Every three months maintenance on the CVAFS analyzer is conducted, including replacement of
the UV lamp, the Teflon tubing, and the detection cell.
4.7 Gold traps are checked prior to every sample with 0.8 ng of mercury in order to ensure that their
use during the previous sample collection has not diminished trap performance.
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SOP for Sampling of Vapor Phase Mercury Volume 1, Chapter 1
5.0 References
5.1 Bloom, N.S. and Fitzgerald, W.F (1988) Determination of Volatile Mercury Species at the
Picogram Level by Low-Temperature Gas Chromatography with Cold-Vapor Atomic Fluorescence
Detection. Anal. Chem. Ac/a. 208, 151.
5.2 Dumurey. R.. Temmerman, E., Dams, R. and Hoste, J. (1985) The Accuracy of the Vapour-
Injection Calibration of Mercury by Amalgamation/Cold-Vapour Atomic Absorption
Spectrometry. Anal. Chem.. Acta. 170,337-340.
5.3 Dumarey, R., Dams, R., and Hoste, J. (1985) Comparison of the collection and desorption
efficienc\ of activated charcoal, silver, and gold for the determination of vapor-phase atmospheric
mercury. Anal. Chem. 57, 2638-2643.
5.4 Fitzgerald, W.F., and Gill, G.A. (1979) Sub-Nanogram Determination of Mercury by Two-Stage
Gold Amalgamation and Gas Phase Detection Applied to Atmospheric Analysis. Anal. Chem. 15,
1714.
5.5 Lindberg, S.E. (1981) Author's Reply 'Mercury partitioning in a power plant plume and its
influence on atmospheric removal mechanisms.' Atmos. Environ. 15, 631-635.
5.6 Rossmann, R. and Barres, J. (1991) Trace element concentrations in near-surface waters of the
Great Lakes and methods of collection, storage, and analysis J. Great Lakes Res. 14,: 188.
5.7 Schroeder, W.H. (1982) Sampling and analysis of mercury and its compounds in the atmosphere.
Environ. Sci.. Technol. 16, 394-400.
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Volume 1, Chapter 1 SOP for Sampling of Vapor Phase Mercury
Appendix A. Facilities, Equipment and Reagents
Following is a list of the required facilities, equipment, supplies and reagents for sample preparation,
sample collection and sample analysis that are outlined in this document. The make and model of the
following items are those used at The University of Michigan Air Quality Laboratory. Many of these items
are available from a variety of sources.
1. Preparation of Field Supplies
Class 100 Clean Room, Work Stations
Clean Room Gloves
Particle-free Wipes
Clean Room Cap, Gown and Boots
Milli-Q Water (18.2MQ/cm)
Exhaust Hood
Acetone
Alconox
Polyethylene Tubs
EM Science Tracepur and Suprapur Hydrochloric Acid
Polytherm Water Bath (Science/Electronics)
Baker Instra-Analyzed or EM Science Suprapur Nitric Acid
New Polyethylene Bags
20 L Polyethylene Carboys
2. Sample Collection
Mass Flow Controlled Vacuum Pump (URG, Model 3000-02M)
Calibrated 300 cc/min. Rotameter (Matheson)
HOPE Tubing with quick connects
Black Latex Tubing
Mercury Sampling Box (UMAQL, See Appendix B)
Acid-Cleaned 47 mm Teflon Filter Holders (Savillex, PFA Labware)
47 mm Preheated Glass Fiber Filters (Gelman Sciences A/E)
Acid-Cleaned Teflon Jars (Savillex, PFA Labware)
Teflon-Coated Forceps
'Blanked' Gold-Bead Traps (UMAQL)
Teflon Endplugs
Trap Heater & Variable Transformer
Acid-Cleaned Teflon Tubing
Particle-Free Gloves
Teflon Tape
Sample Labels
Field Operator Log Book
Shipping Boxes
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SOP for Sampling of Vapor Phase Mercury Volume 1, Chapter 1
Appendix A. Facilities, Equipment and Reagents (Cont'd)
3. Sample Analysis
Cold Vapor Atomic Florescence Detector (Brooks Rand, LTD.)
Line Tamer/Conditioner (Shape Magnetronics Model PCLT 150)
Integrator (Hewlett-Packard Model 3390A)
Helium, Ultra High Purity Grade (99.999%)
Mass Flow Controller (Tylan)
Nichrome Coils (UMAQL)
Electric Leads
Variable Transformers (Staco Energy Products Co. Type 3PN1010)
Cooling Fans
Gold-Coated Glass Bead Traps (UMAQL)
Gas Tight Syringe (Hamilton series 1800)
Injection Port (UMAQL)
Constant Temperature Circulating Water Bath (Fisher Model 901)
Instrument Grade Metallic Mercury (Triple Distilled)
Mercury Flask (UMAQL)
Certified Immersion Thermometer (Kessler Instruments, Inc. 15041 A)
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Appendix B. Diagram of Mercury Sampling Box
TRAMSFoRMER BOX
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Appendix C. Diagram of Assembled Gold-Coated Bead Traps
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LAKE MICHIGAN LOADING STUDY
IIT-CHICAGO
Vapor Phase Mercury
o
en
Sample
No.
Au Trap #A/B
Date
On/Off
Time
On/Off
Flow On
(LPM)
Flow Off
(LPM)
Wind
Speed
Wind
Direction
Sky
Conditions
Notes
Init.
I
(b
9
0)
o
2?
(D
3
D.
x'
a
CO
O
TJ
SP
3_
5"
a
(n
PUMP SYSTEM USED:_
ROTAMETEk #:
CALIBRATION CURVE=
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SOP for Sampling of Vapor Phase Mercury Volume 1, Chapter?
Appendix D. (Cont'd)
LAKE MICHIGAN LOADING STUDY SAMPLE TRACKING FORM
ITT--CHICAGO
Vapor Phase Mercury Samples: Gold-Coated Bead Trap
Sample Number*:
Gold Trap Number:_
Operator:
Date On: Date Off:
Time On: Time Off:
Rotameter Reading On: Rotameter Reading Off:.
*If Blank Sample Note Type and How It Was Handled (Shipping Blank. Field Blank, etc.
Notes: (ambient conditions, anything out of the ordinary, using freshly cleaned filter packs, etc.)
For Use at Univ. Of Michigan Air Quality Lab
Date Sample Received:
Date Sample Analyzed:
Analvzer #:
Notes: (Appearance of Sample, Are Endpluj
Rec'd By:
Rec'd B\:
>s Teflon-taped, etc.)
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Standard Operating Procedure for
Sampling of Mercury in Precipitation
Gerald J. Keeler and Matthew S. Landis
University of Michigan
Air Quality Laboratory
109 South Observatory Street
Ann Arbor, Ml 48109-2029
June 1,1994
Version 2.0
-------
Standard Operating Procedure for
Sampling of Mercury in Precipitation
1.0 Introduction/Overview
The objective of the Lake Michigan Loading Study is to assess the contribution of atmospheric
deposition to the concentration of mercury and other toxic trace species found in Lake Michigan.
The atmosphere has been implicated as one of the dominant sources of mercury and trace elements
to bodies of water and it is clear from investigations in remote reg'ons of the globe that long range
transport of mercury and other toxics from source regions is occurring. By quantifying the wet
deposition and ambient concentrations of mercury it will be possible to determine the relative
importance of precipitation and dry deposition in accounting for the atmospheric loading of
mercury to Lake Michigan. In addition, investigating other ambient trace species will aid in the
identification of significant mercury sources.
2.0 Preparation for Precipitation Sampling
Acid Cleaning Procedure
All field sampling and analytical supplies which will come into contact with the samples are
cleaned according to the following procedure.
Supplies to be acid cleaned are first rinsed in reagent grade acetone under a fume hood, then
washed in hot tap water and diluted Alconox. Supplies are rinsed five times in cold tap water then
rinsed three times in DI water. The supplies are then heated in 3M hydrochloric acid (EM Science
Tracepur HC1 in Milli-Q water (18.2 MQ/cm)) for six hours at 80°C. One liter of 3M HC1 is
prepared by adding 750 mL of Milli-Q water to 250 mL of concentrated EM Science Tracepur
HC1. The 3M HC1 can be used several times and is stored for reuse in a polyethylene carboy
dedicated for this purpose. The supplies are placed into clean polyethylene tubs which are then
filled with the 3M HC1, making sure that all of the surfaces are submersed in the HC1. The tubs
are covered and placed in a water bath which is heated to 80°C in a fume hood. The water in the
bath is maintained at the level of the acid inside the tubs. After the water in the bath reaches
80°C, the supplies in the tubs are allowed to soak for six hours.
After the six hour, 80°C soak, the tubs are removed from the water bath and allowed to cool in the
fume hood. When cool, the 3M HC1 is poured back into its polyethylene carboy. The supplies are
rinsed in the tubs three times with Milli-Q water. The supplies are then soaked in a 0.56M nitric
acid solution (Baker Instra-Analyzed HNO, in Milli-Q water) for 72 hours at room temperature in
the same polyethylene tubs in which they were heated with HC1. The nitric acid solution is made
by adding 35 mL Baker Instra-Analyzed HNO3 to 965 mL of Milli-Q water. Nitnc acid is reused
for up to six months and is stored in a carboy dedicated for HNO3. At the end of the three day
soak, the supplies being cleaned are rinsed three times with Milli-Q water and transferred into a
Class 100 Clean Room.
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Standard Operating Procedure for
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Inside the clean room, the supplies are again rinsed three times with Milli-Q water. The tubs
containing the supplies are filled with 0.56M Baker Instra-Analyzed HNO3 that is kept in the clean
room and is dedicated for this final step only. The supplies are then allowed to soak in this acid
for seven days. This acid is prepared by adding 35 mL of the Instra-Analyzed HNO, to 965 mL of
Milli-Q water. At the end of the seven day acid soak inside the clean room, the supplies are rinsed
five times with Milli-Q water and allowed to air dry on a clean surface. When the supplies are dry,
they are triple bagged in new polyethylene bags and removed from the clean room, ready for use in
sampling.
The Teflon precipitation sampling bottles are not allowed to dry. After the seven day HNO, soak,
the Teflon bottles are rinsed three times with Milli-Q water and are filled with 0.05M
Hyd.ochloric acid (EM Science Suprapur HCl in Milli-Q water) and allowed to soak in the clean
room until needed. When needed, the Teflon bottles are emptied, rinsed with Mi!li-Q water five
times and 20 mL of HCl preservative is added. The bottles are then weighed, sealed with Teflon
tape and triple bagged in new polyethylene bags.
3.0 Preparation and Set-up of the MIC-B Precipitation Collector
3.1 Summary
The automatic precipitation collector works by detecting precipitation on a sensor grid. During
precipitation the sensor grid energizes a relay which switches on the motor-relay and, in turn, the
motor. The motor acts through a chain sprocket drive system to move the cover from the funnel to
the wet cover support. The motor is stopped by micro switches which trip as soon as the cover is
properly seated on the cover support. When precipitation stops, the sensor grids dry out and the
cover returns to seal the collector. This wet only collection prevents dry deposition from
contaminating the collection funnel.
A heater is laminated to the underside of the sensor board to accelerate evaporation at the end of
precipitation. The temperature of the heater is controlled so that the grid dries at the same rate
independent of ambient temperature. To prevent excessive back and forth movement of the lid
during extremely light precipitation, a time delay for return of the cover is incorporated into the
control circuit.
During sample collection the screen to the right of the funnel reduces rain/snow splash-off into the
precipitation collector. The sensor array is mounted two feet awa\ from the collection funnel for
the same reason.
The University of Michigan Air Quality Laboratory (UMAQL) has developed a new modified
MIC-B collector that enables the installation of up to four discrete precipitation sampling systems.
This configuration allows for two mercury sampling trains and two trace element & nutrient
sampling trains. A mercury sampling train consists of a Borosilicate glass collection funnel with
an effective collection area of 181 cm2, a Teflon adapter, a glass vapor lock and a I L Teflon
sample bottle A trace element sampling train consists of a polypropylene funnel with an effective
collection area of 167 cnr, a polypropylene adapter and a I L polypropylene sample bottle
(Figure I i This ne\v sampling configuration allots for the discrete collection and preservation of
lour independent precipitation samples using one MIC-B sampling instrument.
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Standard Operating Procedure for
Sampling of Mercury in Precipitation
I
s
2
.is*
till
Figure I. Modified MIC-B1 Sampling Trains for the Collection of Hg(a) and Trace Elements (b)
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Standard Operating Procedure for
Sampling of Mercury in Precipitation . Volume 1, Chapter_?
3.2 Sampler Set-up
The MIC-B collector is placed on a 1 meter tall wooden platform in a location free from
obstruction in every direction. The collector cannot be located within 2 meters of other pieces of
equipment or splash off may result and contaminate the sample. The sensor grid must also free of
any obstruction.
3.3 Sampler Start-up
Connect the instrument to a grounded receptacle. Switch on the main power toggle located on the
front of the instrument (only when the hood is in the closed position over the collection funnel
insert). Touch one of the sensor grids with a wetted finger. The cover will lift up from the
collection funnel insert and over to the rest bar. The motor will then turn off (be sure that you can
hear the motor turn off, so that in the event it does not turn off, corrective measures can be taken).
Wait one to two minutes and the hood will move back to cover the funnels and the motor will turn
off. If the motor does not turn off after seating on the collection funnel insert then refer to the
trouble-shooting guide (Section 4.3).
Note: The sampler hood must always be over the collection funnel insert when turning on the
instrument's main power!
A space heater and heat tape funnel nests are placed inside the precipitation collector during cold
months to melt snow and slush that lands in the funnel and to prevent freezing of the collected
sample. The space heater is plugged into the outlet provided inside the sampler cabinet and is
maintained on the setting required to keep the cabinet at approximately 10°C.
3.4 Installing the Collection Funnels
The acid-cleaned collection funnels are shipped with the adapters and vapor lock system pre-
assembled and packaged in protective polyethylene wrapping. To keep the collector hood open
during installation of the funnels into the MIC-B insert, place a wet towel or cloth onto the sensor
grid. Open the sampler cabinet, and put on a pair of particle free gloves. Carefully remove the
polyethylene wrapping and place each funnel system into the corresponding hole on the funnel
support base (Figure 2). Be sure funnels are properly seated into the support base to insure a tight
seal. Once all the sampling trains have been installed, cover any unused funnel support bases with
the sealing caps provided to prevent water intrusion into the interior of the sampling instrument.
Remove the wet towel and allow the collector hood to close.
In order to minimize evaporative loss of mercury from the sample t ottle in the collector, a vapor
lock system and hydrochloric acid preservative have been incorporated into the new collection
system. Each Teflon sample bottle is shipped from UMAQL containing 20 mL of 0.08M HC1
preservative. Extreme care is exercised when handling these bottles to avoid spilling the acid and
causing personal injury. In the unlikely event that acid does come into contact with exposed skin,
the area is immediately flushed with water. Wearing gloves and safety glasses, remove one Teflon
sample collection bottle from the three polyethylene bags, unscrew the cap and place it in the inner
bag from which you removed the bottle. Reseal the bags to keep the cap clean. Thread the 1 L
bottle into the Teflon funnel adapter to complete the mercury sampling train setup. The sample
bottles must he snug, houever. care must be taken to avoid OUT nduelling. Teflon threads on the
sample bottles and the adapters are easily stripped.
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Standard Operating Procedure for
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fiml
Acryl ic Collfclion
Funl liwrt
OoinHolt
Figure 2. The University of Michigan Custom Acrylic Insert d'M-B)
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Standard Operating Procedure for
Sampling of Mercury in Precipitation Volume 1, Chapter^
The other trace elements collected are not volatile, therefore, the sampling train does not utilize a
vapor lock or acid for preservation in the field. Wearing particle free gloves, remove one
polypropylene sample collection bottle from the three polyethylene bags, unscrew the cap and
place it in the inner bag from which you removed the bottle. Reseal the bags to keep the cap clean.
Thread the I L polypropylene sample collection bottle into the polypropylene funnel adapter to
complete the metals sampling train setup.
Note: The funnels and sample bottles have been acid-cleaned in a laborious 11-day procedure and
packaged to ensure no particle contamination. Extreme care is exercised when handling the
funnels and open sample bottles to prevent anything from falling in or contacting them during
installation.
4.0 Sample Collection Procedure
4.1 Daily Site Visit
The operator must arrive at the sampler every morning at 8:00 a.m. tocal time to perform the
following tasks:
1) Check the polypropylene sample bottle for any collected precipitation.
2) Check the Belfort rain gauge for any precipitation and record amount for each event.
3) Fill in information in the daily Sampler/Site Log Book.
4) Check the sampler to make sure, if appropriate, that the heater is working, the funnels are
free of obvious contamination and the sampler is operating (by tripping the sensor grid).
If it is raining or snowing when the operator visits the site in the morning, the sample is not
collected until the next morning, unless it appears that the sample bottle is going to overfill. If it is
still raining the following morning, the site operator collects the sample as usual and replaces the
sampling trains. The duration of the rain event is recorded by the operator on the sample log sheet.
If it appears that the sample bottle is going to overfill then the operator removes the sample bottle
while it is raining/snowing and collects the sample according to the procedure below. If the
operator is unclear about what should be done, they are instructed to call Matthew Landis at
UMAQL to determine if the sample should be collected.
4.2 Sample Collection
Supplies necessary to collect a sample: (quantities may vary depending on configuration)
1) One triple-bagged acid-cleaned Teflon bottle
2) One triple-bagged acid-cleaned polypropylene bottle
3) Two log books: samples and meteorological data
4) Panicle-Free Gloves
5) Teflon Tape
6) Sample Label Stickers
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Standard Operating Procedure for
Volume 1, Chapter 1 Sampling of Mercury in Precipitation
Open the sampler cabinet, put on a pair of particle-free gloves. If there is evidence that
precipitation has overflowed the sample bottle, put the two gallon white plastic bucket underneath
the funnel before unscrewing the sample bottle from the funnel adapter. Unscrew the bottle from
the funnel adapter, screw the cap on tightly and seal it to the bottle using the Teflon tape provided.
Place the appropriate sample number label on the vinyl tape that is on the bottle (This tape will
have the bottle weight and a batch number to identify the bottle, avoid placing the sample label
over these numbers). Seal the sample bottle into three successive polyethylene bags.
Fill out a tracking form (Appendix B) to send with each sample, funnel rinse and control. Please
note if the sample overflowed. Fill out the Sample Log and Collector Log sheets. Use the note
column for important and/or unusual observations/notes (e.g., pesticide spraying nearby, road
construction near site, leaves found in collector funnel, etc.). Do not fill in 'Sample Volume' this
is for lab use.
The samples are shipped to UMAQL in Ann Arbor the day they are collected. If the operator is
unable to do so, the samples are refrigerated until they can be shipped the next day. Do not allow
the samples to freeze.
Precipitation samples will be collected on an event basis during the intensive months of May
through October and on a weekly basis for the remainder of the sampling period. During event
precipitation sampling, collection funnels and funnel adapters will be replaced after ever)'
precipitation event or after a period of seven successive calendar days without a precipitation
event, whichever occurs first. The old funnels and the funnel adapters are removed and replaced
with freshly cleaned ones from UMAQL. The old funnels and funnel adapters are shipped back to
UMAQL as soon as possible so they can be cleaned. Site operators log the date and time the
funnels are replaced on the sample log (an entire line in the log is used).
4.3 Funnel Blank Collection
In order to confirm that the collection funnel assemblies are free of mercury and other
contaminants, 'funnel blank' samples are collected. Particle-free gloves are worn by the operator
for this procedure. Clean sample bottles with no HCI preservative are attached to each sampling
train and are used to collect the funnel rinses. To keep the collector hood open during this
procedure, a wet towel is placed on the sensor grid. An acid-cleaned I L Teflon sample bottle and
an acid-cleaned I L polypropylene sample bottle are filled with Milli-Q water and Control
identification sticker labels are affixed. The operators are instructed to positions themselves down
wind of the sample before the bottles arc opened, to prevent particles from their clothing from
being sh;d into the sample. Each funnel is rinsed with approximately 0.5 L of the water making
sure all the surfaces of the funnel are covered, the sample bottles are capped and sealed using the
Teflon tape provided. The Teflon and polypropylene bottles are removed from the funnel
adapters, the caps are threaded on, the bottles are sealed with Teflon tape and the Rinse
identification sticker labels are attached. Care is taken to prevent the mouth of the sample bottles
from contacting anything during this procedure. The Rinse and Control solutions are re-bagged
and packed into a shipping box. The tracking forms are completed for the Rinses and Controls
separately.
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Standard Operating Procedure for
Sampling of Mercury in Precipitation Volume 1, Chapter 1
4.4 Shipping a Sample
It is very important that samples reach UMAQL as soon as possible after being collected. To ship
a sample, wrap the triple bagged sample bottle in a layer of bubble-wrap and place it in a shipping
container provided. Any extra space in the container is packed with additional bubble-wrap so the
bottles will not move inside.
Sample tracking forms for each sample are completed and sent with the samples to UMAQL.
4.5 Maintenance of MIC-B Precipitation Collector
4.5.1 Routine Maintenance
The precipitation collector sensor array is cleaned every month with a damp cloth and mild
detergent (1 % Alconox), both of which are provided. The detergent film is rinsed off the
sensor array with a second, clean, damp cloth.
An operational check on sampler performance is conducted daily. This is done by placing
a wetted finger on one of the sensor grids and waiting to make sure the cover seats in the
open rest position properly and that one and a one-half to two and a one-half minutes after
the hood returns to cover the funnels the hood is seated properly and the motor turns off.
If the cover does not seat properly on either side or if the hood drops over excessively
when open, refer to the trouble-shooting guide for the appropriate remedy.
4.5.2 Trouble-Shooting
If a collector fails to operate properly or the operator has to replace a fuse or make
adjustments, they are instructed to notify Matthew Landis at UMAQL as soon as possible.
Some of the parts that can fail will need to be replaced by UMAQL personnel. These
cases are noted below.
1. Collector Fails to Operate:
a. No Power to Instrument
Check to make sure the instrument is plugged in and the power source is
on (no tripped fuses/breakers etc.).
b. Blown Fuse
Replace the blown fuse with appropriate fuse.
c. Faulty Sensor Board or Faulty Power Control Board
The sensor board \\'\\\ have to be replaced h\ UMAQL personnel or sent
to the operator tor replacement. It' \ou ha\e exhausted the t\\o options
above call Malthas l.andis or Jerr\ Keelcr as soon as possible so
replacement parts can be shipped.
1-116
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Volume 1. Chapter 1
Standard Operating Procedure lor
Sampling of Mercury in Precipitation
2.
Motor Will Not Switch Off
3.
4.
a. Limit switch adjusting screw and/or cam out of adjustment
Readjust the limit switch cam and/or actuating screw.
This is done by:
i) Switching off main power and unplugging the sampler (be sure to
do this with the cover seated on the funnel).
ii) While holding the nut still, loosen the set screw on the
appropriate micro-switch cam and readjust it until the switch is
depressed. Tighten the set screw, and repeat the procedure on the
right side. When both sides have been adjusted, test the collector
by placing a slightly wetted finger on one of the sensor grids.
Wait to see if the motor stops when the hood is seated on the
hood support and after the hood returns to its resting position
over the funnel.
b. Limit switch may be broken - if this is the case the switch needs to be
replaced.
Cover Drops Once It Moves Over Dead Center
a. The set-screw on the motor sprocket may be loose. Locate the set-screw
and tighten it.
b. The chain may be loose and is tightened.
Cover Does Not Return To Collection Funnel Insert
a. Clean the sensor array with a damp cloth and mild detergent - making
sure to wipe the detergent off the sensor array.
b. Heater on sensors may not be operating. If this is the case the heater
element may be burned out in which case the sensor board needs to be
replaced or there ma\ be a faulty component on the pouer control board
and the power control board needs to be replaced.
5.0 Clean Room Procedures
5.1 Entering the Clean Room
Shoes are taken off outside the clean room b> all UMAQL personnel. Personnel then enter the
outer vestibule (changing room). Once inside, the hood is put on followed by the clean room suit
and clean room hoots. The boots are snapped to the suit at the back of the leg (to hold up the
boots) and are buckled in the front. Personnel (hen step over a di\ idmg bench \\hcrc the\ put on
clean room cloves and snap the clean room suit at the v^nst. Nou tuli\ clothed ihc\ enter the
clean room making sure to securely close the door behind.
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Standard Operating Procedure for
Sampling of Mercury in Precipitation Volume 1, Chapter 1
5.2 Taking Supplies into the Clean Room
All supplies to be taken into the clean room are double bagged in polyethylene. The supplies to be
taken into the clean room are placed in the outer dressing room. Upon entering the clean room, the
outer bag is removed and left in the entry room. All supplies that enter the clean room that have
not been bagged are rinsed with MQ-water and wiped off with particle-fee wipes.
1-118
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Standard Operating Procedure for
Volume 1, Chapter 1 Sampling of Mercury in Precipitation
Appendix A. Facilities, Equipment and Reagents
Following is a list of the required facilities, equipment, supplies and reagents for sample preparation and
sample collection that are outlined in this document. The make and model of the following items are those
used at The University of Michigan Air Quality Laboratory. Many of these items are available from a
variety of sources.
1. Preparation of Field Supplies
-Class 100 Clean Room, Work Stations
-Clean Room Gloves
-Particle-free Wipes
-Clean Room Cap, Gown and Boots
-Milli-Q Water (i 8.2MQ/cm)
-Exhaust Hood
-Acetone
-Alconox
-Polyethylene Tubs
-EM Science Tracepur and Suprapur Hydrochloric Acid
-Polythenn Water Bath (Science/Electronics)
-Baker Instra-Analyzed or EM Science Suprapur Nitric Acid
-New Polyethylene Bags
-20 L Polyethylene Carboys
2. Sample Collection
-MIC-B Wet-Only Precipitation Collector (MIC)
-UMAQL Modified Acrylic Insert
-Digital Indoor/Outdoor Recording Thermometer
-BSG Collection Funnels
-Polypropylene Collection Funnels
-Teflon & Polypropylene Precipitation Adapters
-Glass P-trap Vapor Lock
-1 L Teflcn & Polypropylene Sample Bottles
-Funnel Heat Tape Nests & Variable Transformer
-Ceramic Space Heater
-2 Gallon HOPE Bucket
-Particle-Free Gloves
-Teflon Tape
-Sample Labels
-Permanent Label Markers
-Field Operator Log Book
-Shipping Crates
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Volume 1, Chapter 1
Standard Operating Procedure for
Sampling of Mercury in Precipitation
Appendix B.
LAKE MICHIGAN LOADING STUDY
PRECIPITATION SAMPLE TRACKING FORM
I.I.T.-CHICAGO
Sample Number:
OPERATOR:
Date of Precipitation:
Date Sample Collected:
Time Sample Collected:
Date Shipped:
Comments:
FOR USE AT THE UNIV. of MICH. AIR QUALITY LAB:
Date Received at UMAQL:
.Rec'dBy:
Volume of Sample Received.
Sample Analyzed in the Following Fractions:
Type of
Analysis
Volume of
Precip (mL)
Vol. Of HCI,
HN03, or
BrCI (mL)
Lot/Batch of
BrCI, HCI or
HNO3
Date Filtered,
Acidified,
Oxidized
Date
Analyzed
Analyzed
By
pH/i.c.
ICP-MS (0.2%)
Filtered
Reactive Hg
Total Hg
Bottle Type (circle one): BSG Polypropylene Teflon
Bottle Batch: ^ Init. Wt. (g)
COMMENTS:
1-121
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(/> cn
g sr
3 3
LAKE MICHIGAN LOADING STUDY
IIT-CHICAGO
Vapor Phase Mercury
DMK
TIME
Outdoor
Min Temp
(in b.sl 24 hrsl
Cabinet
Min 'I'emp
(in l.isi 24 hrs)
Outdoor
Max Temp
(in last 24 hrs)
Cabinet
Max Temp
(in last 24 hrs)
PRLCIP.
TYPE
Notes
Initials
8
«• 3
(D
3
Q.
x"
UJ
o
13
i-h
CL
(0
-------
Standard Operating Procedure for
Sampling of Particulate Phase Mercury
Gerald J. Keeler and Matthew S. Landis
University of Michigan
Air Quality Laboratory
109 South Observatory Street
Ann Arbor, Ml 48109-2029
June 1,1994
Version 2.0
-------
Standard Operating Procedure for
Sampling of Participate Phase Mercury
1.0 Introduction/Overview
The objective of the Lake Michigan Loading Study is to assess the contribution of atmospheric
deposition to the concentration of mercury and other toxic trace species found in Lake Michigan.
The atmosphere has been implicated as one of the dominant sources of mercury and trace elements
to bodies of water and it is clear from investigations in remote regions of the globe that long range
transport of mercury and other toxics from source regions is occuiring. By quantifying the wet
deposition and ambient concentrations of mercury it will be possible to determine the relative
importance of precipitation and dry deposition in accounting for the atmospheric loading of
mercury to Lake Michigan. In addition, investigating other ambient trace species will aid in the
identification of significant mercury sources.
Particle-phase mercury, Hg(p), generally represents a small but significant fraction of total
atmospheric mercury. Recent advances in analytical chemistry have made quantification of the
extremely low levels of Hg(p) possible, however, tremendous care must be exercised in all phases
of sample handling and analysis. This protocol describes analysis of 'acid-extractable' total
mercury from atmospheric paniculate samples.
2.0 Preparation for Particulate Mercury Sampling
2.1 Acid Cleaning Procedure
All field sampling and analytical supplies which will come into contact with the samples are
cleaned according to the following procedure.
Supplies to be acid cleaned are first rinsed in reagent grade acetone under a fume hood, then
washed in hot tap water and diluted Alconox. Supplies are rinsed five times in cold tap water then
rinsed three times in DI water. The supplies are then heated in 3M hydrochloric acid (EM Science
Tracepur HC1 in Milli-Q water (18.2 MQ/cm)) for six hours at 80 C. One liter of 3M HC1 is
prepared by adding 750 mL of Milli-Q water to 250 mL of concentrated EM Science Tracepur
HCI. The 3M HC1 can be used several times and is stored for reuse in a polyethylene carboy
dedicated for this purpose. The supplies are placed into clean polyethylene tubs which are then
filled with the 3M HC1, making sure that all of the surfaces are submersed in the HC1. The tubs
are covered and placed in a water bath which is heated to 80°C in a fume hood. The water in the
bath is maintained at the level of the acid inside the tubs. After the water in the bath reaches
80°C, the supplies in the tubs are allowed to soak for six hours.
After the six hours, 803C soak, the tubs are removed from the water hath and allowed to cool in
the fume hood. When cool, the 3M HCI is poured back into its polyethylene carboy. The supplies
are rinsed in the tubs three times with Milli-Q water. The supplie^ arc ihen soaked in a 0.56M
nitric acid solution (Baker InMra-Analy/ed HNO, in Milli-Q \\atcp tm " . hours at room
temperature in the same polyethylene tubs m which they were heated with HCI. The nitric acid
solution is made by adding 35 mL Baker Instra-Analyzed HNO; to l)(o mL of Milli-Q water.
1-125
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SOP for Sampling of Particulate Phase Mercury Volume 1, Chapter^
Nitric acid is reused for up to 6 months and is stored in a carboy dedicated for HNO3. At the end
of the three-day soak, the supplies being cleaned are rinsed three times with Milli-Q water and
transferred into a Class 100 Clean Room.
Inside the clean room, the supplies are again rinsed three times with Milli-Q water. The tubs
containing the supplies are filled with 0.56M Baker Instra-Analyzed HNO3 that is kept in the clean
room and is dedicated for this final step only. The supplies are then allowed to soak in this acid
for seven days. This acid is prepared by adding 35 mL of the Instra-Analyzed HNO3 to 965 mL of
Milli-Q water. At the end of the seven day acid soak inside the clean room, the supplies are rinsed
five times with Milli-Q water and allowed to air dry on a clean surface. When the supplies are dry,
they are triple bagged in new polyethylene bags and removed from the clean room, ready for use in
sampling.
2.2 Preparation of Glass Fiber Filters
Glass fiber filters (Gelman Sciences) are pre-treated to remove all mercury prior to use in
sampling. Glass fiber filters, 47 mm in diameter, are placed in a clean crucible with a lid. The
crucible is placed in a muffle furnace which is heated to 500°C and the filters are allowed to bake
at this temperature for one hour. While hot, filters are removed from the crucible with acid-
cleaned Teflon-coated forceps and placed in an acid-cleaned Teflon jar which is closed and sealed
with Teflon tape. The Teflon jar is sealed in three successive polyethylene bags and stored at
40°C until use. Filters are stored no more than three months prior to use and frequent blanks are
taken to ensure the filters remain clean.
3.0 Particulate Phase Mercury Sample Collection
During sample collection the filter packs are housed in a sampling box that is mounted on a pole or
tower at least 3 meters above ground level. The sampling boxes are custom-made at UMAQL
from fiberglass enclosures (Stahlin Enclosures) using quick connect couplings to connect the
vacuum lines from the pump to the sampling devices. Sample intakes are at least 30 cm apart and
are not close to any potential contaminant sources.
Since paniculate mercury occurs at ultra-trace levels in the atmosphere and since mercury has a
high vapor pressure, the selection of sampling flow rate and sampling duration has been carefully
considered. It is typically necessary to sample at flow rates of 10-30 !pm for a minimum of 12-
24 hours to collect enough paniculate mercury for analysis.
The volume of air sampled is measured using a calibrated dry test meter (DTM). In addition, the
flow rate is confirmed at the sample inlet before each sample using a calibrated rotameter. The
pumps used (URG-3000-02M) are specially designed for trace level mercury sampling. They
feature high efficiency oil less, brush less pumps. All pumps used for sampling are turned on at
least 15 minutes prior to use.
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Volume 1, Chapter 1 SOP for Sampling of Particulate Phase Mercury
3.1 Setting Up Glass Fiber Filter Samples
All sample preparation including filter pack assembly is done outdoors. In extreme weather
conditions, operators may elect to complete some tasks in a clean indoor area, making sure
sampling supplies (filter packs, forceps etc.) do not contact any surfaces other than in the clean
bags in which they were received. Particle free gloves are worn during all sampling activities.
When outdoors, site operators position themselves downwind of the sample at all times.
Before sampling commences, it is necessary to confirm the flow rate through the sampling train
using a calibrated 30 Ipm rotameter. To prevent potential contamination of the sample by the
rotameter a 'flow check' filter pack is utilized. The 'flow check' filter pack is equipped with quick
connects on either side for attachment of the vacuum line and the rotameter. The glass fiber filter
in the 'flow check' filter pack is changed on a regular basis because is will rip or tear over time.
The 'flow check' filter pack is placed into the mercury sampling box (Appendix B) such that the
orange clampdown nut is on the inside of the mercury sampling box. The male quick-connect on
the designated black latex vacuum line for the particulate mercurv sample is secured into the
female quick-connect on the back of the 'flow check' filter pack. An audible click is heard when
the quick-connects are properly sealed.
The calibrated 30 Ipm rotameter is equipped with an air diffusion muffler at the inlet and a 22 cm
length of black latex tubing with a male quick connect at the outlet. The male quick connect on
the rotameter tubing is connected to the female quick connect on the inlet of the test flow filter
pack. The system is allowed to stabilize before taking the reading from the rotameter. The scale
on the rotameter is read from the midpoint of the silver ball. The calibration curve and 30 Ipm set
point are indicated on the side of the rotameter. If the flow is below 30 Ipm the operators are
referred to the trouble shooting section (3.4) to look for possible remedies. If all systems appear
normal, the operator adjusts the pump flow as necessary to achieve 30 Ipm before starting the
sample. The rotameter and 'flow check' filter pack are then removed and stored it in the plastic
box provided.
Note: Once set, the flow on the URG-3000-02M is relatively stable. If frequent adjustments are
necessary to achieve the desired flow operators are instructed to contact Matthew Landis at
UMAQL immediately.
An 'open face' Teflon filter pack is utilized by UMAQL for particulate phase mercury collection.
The filter pack is an assemblage of three main components-a threaded 47 mm opaque Teflon
cylinder, a circular opaque Teflon filter support base with a 0.64 cm tube ferule nut, and an orange
Teflon clamp down nut. After confirming the flow rate to be 30 Ipm an acvd-cleaned Teflon 'open-
face' filter pack is removed from the field site box and unbagged. The filter pack is disassembled
by unscrewing the orange clampdown nut and removing the 47 mm Teflon cylinder. The Teflon
jar holding the pre-baked glass fiber filters is carefully opened. One 47 mm baked glass fiber filter
is placed on the grid of the filter holder with the 'rough' side up using acid-cleaned Teflon-coated
forceps. While holding the filter support base vertically to prevent the filter from falling out, the
filter pack is reassembled by attaching the 47 mm Teflon tube and threading it firmly into the
orange clampdown nut. The Teflon jar holding the remaining pre-baked glass fiber filters is
quickly closed. Operators attempt to have the jar open for as little tune as possible.
1-127
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SOP for Sampling of Particulate Phase Mercury Volume 1, Chapter^
The sample filter pack is then inserted into the mercury sampling box hole designated for the
paniculate mercury sample. The quick-connect from the vacuum line to the outlet of the filter
pack is secured. The DTM reading is immediately recorded along with the time, sample number,
date, unusual meteorological conditions and any problems encountered on the sample log and
tracking form.
3.2. Taking Down Glass Fiber Filter Samples
After putting on a new pair of particle free gloves, the black latex vacuum line is disconnected
from the sample filter pack by uncoupling the quick connectors. The DTM reading is immediately
recorded, along with the time, date, unusual meteorological conditions and any problems
encountered, on the sample log and tracking form. The sample filter pack is removed from the
mercury sampling box. While holding the filter pack vertically with the open tube facing up, the
Teflon inlet cylinder is unscrewed from the orange clampdown nut. The Teflon cylinder is
removed and the filter support base is lightly pushed up until the glass fiber filter is just below the
top of the orange clampdown nut. The filter is then removed from the filter support base with
acid-cleaned Teflon-coated forceps, making sure to only touch the exterior edge of the filter. The
filter is carefully inserted into the base of the petri dish. The petri dish cover is replaced and
sealed with a length of 1.27 cm Teflon tape around the joint between the lid and the base of the
petri dish. The sample identification label is then attached to the cover of the petri dish. The
sample filter pack is reassembled and sealed in a clean polyethylene bag and stored in the plastic
container provided. The petri dish is triple bagged and shipped to UMAQL the day they it is
collected. If the operator is unable to ship the sample, the sample is placed in a freezer until it can
be shipped the next day.
3.3. Taking Blanks
A minimum of 25% field blanks and 107c storage blanks are taken to ensure samples are being
collected in a contaminant-free manner. Field blanks involve loading a glass fiber filter into the
open-face filter pack as described in Section 3.1 for a sample. The filter pack is placed in the
mercury sampling box for two minutes without the vacuum line attached. After two minutes, the
sample is taken down and labeled in the same manner as described in Section 3.2 for samples.
Storage blanks are collected by transferring a new, unexpose.1 filter from the Teflon jar into an
acid-clean petri dish. The petri dish is sealed with Teflon tape and labeled appropriately. Blanks
are shipped to UMAQL along with the samples taken on the same date.
3 4 Trouble Shooting
If flow through the 'flow check' filter pack is low:
• Check to make sure that all the connections are sealed (make sure the 'flow check1 filter
pack ferule nut fitting is tight, tubing quick connectors are all properly fastened, filter pack
is screwed together tightly, tubing from the pump to the sampler is intact and connected
securely).
Make Mire that the exhaust of the rotaineter is not impeded in any way when usine the
nUameter to check Ihm
1-128
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Volume 1, Chapter 1 SOP for Sampling of Paniculate Phase Mercury
• Check the vacuum gauge on the URG-3000-02M. If a high vacuum is indicated, quickly
turn off the pump and look for a kink in the tubing or an obstruction in the exhaust tubes.
• Check the black latex tubing in the sampling box for cracks or tears due to weathering.
If all systems seem to be working properly and the flow remains low or erratic the operators are
instructed to notify Matthew Landis at UMAQL (313) 763-7714 or at home (313) 663-9615
immediately.
4.0 Clean Room Procedures
4.1 Entering the Clean Room
Shoes are taken off outside the clean room by all UMAQL personnel. Personnel then enter the
outer vestibule (changing room). Once inside, the hood is put on followed by the clean room suit
and clean room boots. The boots are snapped to the suit at the back of the leg (to hold up the
boots) and are buckled in the front. Personnel then step over a dividing bench where they put on
clean room gloves and snap the clean room suit at the wrist. Now fully clothed they enter the
clean room making sure to securely close the door behind.
4.2 Taking Supplies into the Clean Room
All supplies to be taken into the clean room are double bagged in polyethylene. The supplies to be
taken into the clean room are placed in the outer dressing room. Upon entering the clean room, the
outer bag is removed and left in the entry room. All supplies that enter the clean room that have
not been bagged are rinsed with MQ-water and wiped off with particle-fee wipes.
5.0 Performance Criteria, Quality Assurance and Quality Control
5.1 Field operators are carefully instructed in the techniques of contaminant-free particulate phase
mercury sample collection. All of the operators are currently operating sampling equipment for
either the National Dry Deposition Network, the National Atmospheric Deposition Program, the
Integrated Atmospheric Deposition Network or the Great Lakes Acid Deposition Network.
5.2 Every six months UMAQL personnel inspect each of the sampling sites to audit the performance
ot the equipment and to make all necessary repairs or adjustments
5.3 Co-located samples are collected from one sampling site during the study to quantify method
precision. Reported concentrations for co-located samples are based on the mean of the two
samples.
5.4 Precision and accuracy levels will be set and maintained for each t\pe of analysis. A relative
precision for total mercury of less than \5V( is maintained for samples with values at least three
standard deviations greater than the detection limit. Analysis of standards and controls is within
I0r/r of the stated value
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SOP for Sampling of Paniculate Phase Mercury Volume 1, Chapter 1
A minimum of 25% of all samples are analyzed in duplicate. Reported concentrations are based
on the mean of the replicates. Analytical precision averages better than 6%.
5.5 Every three months maintenance on the CVAFS analyzer is conducted, including replacement of
the UV lamp, the Teflon tubing, and the detection cell.
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Volume 1, Chapter 1 SOP for Sampling of Paniculate Phase Mercury
Appendix A. Facilities, Equipment and Reagents
Following is a list of the required facilities, equipment, supplies and reagents for sample preparation and
sample collection that are outlined in this document. The make and model of the following items are those
used at The University of Michigan Air Quality Laboratory. Many of these items are available from a
variety of sources.
I. Preparation of Field Supplies
Class 100 Clean Room, Work Stations
Clean Room Gloves
Particle-free Wipes
Clean Room Cap, Gown and Boots
Milli-Q Water (18.2MQ/cm)
Exhaust Hood
Acetone
Alconox
Polyethylene Tubs
EM Science Tracepur and Suprapur Hydrochloric Acid
Polytherm Water Bath (Science/Electronics)
Baker Instra-Analyzed or EM Science Suprapur Nitric Acid
New Polyethylene Bags
20 L Polyethylene Carboys
2. Sample Collection
Vacuum Pump (URG, Model 3000-02M)
Calibrated Dry Test Meter (DTM)
Calibrated 30 1pm Rotameter (Matheson)
HOPE Tubing with quick connects
Black Latex Tubing
Mercury Sampling Box (UMAQL, See Appendix B)
Acid-Cleaned 47mm Teflon Filter Holders (Savillex, PFA Labware)
47mm Preheated Glass Fiber Filters (Gelman Sciences A/E)
Acid-Cleaned Teflon Jars (Savillex, PFA Labware)
Teflon-Coated Forceps
Particle-Free Gloves
Teflon Tape
- Sample Labels
Field Operator Log Book
Sample Tracking Forms
Shipping Boxes
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Volume 1, Chapter 1
SOP for Sampling of Particulate Phase Mercury
Appendix B.
BOX
1-133
-------
LAKE MICHIGAN LOADING STUDY
IIT-CHICAGO
Open-Face Filter Pack: Particulate Mercury Filter (Glass Fiber)
I
CJ
tn
Sample No.
Date On
Time On
Flow On
(LPM)
DTMOn
Date Off
Time Off
DTM Off
Notes
Init.
-a
~o
(D
D
Q.
X*
O
PUMP SYSTEM USED:
DTM#:
ROTAMETER #:
CALIBRATION CURVE=
Co
O
CO
o>
IQ
O
I
O'
5r
f?
5
SI
I
3
-------
SOP for Sampling of Particulate Phase Mercury Volume 1, Chapter/
Appendix C. (Cont'd)
LAKE MICHIGAN LOADING STUDY SAMPLE TRACKING FORM
FIT-CHICAGO
Particulate Mercury Samples: Glass Fiber Filter
Sample Number*:
Gold Trap Number:_
Operator:
Date On: Date Off:
Time On: Time Off:
Rotameter Reading On: Rotameter Reading Off:_
"If Blank Sample Note Type and How It Was Handled (Shipping Blank, Field Blank, etc.
Notes: (ambient conditions, anything out of the ordinary, using freshly cleaned filter packs, etc.)
For Use at Univ. Of Michigan Air Quality Lab
Date Sample Received:
Date Sample Analyzed:
Analyzer #:
Notes: (Appearance of Sample, Are Endplug
Rec'd By:
Rec'dBy:
s Teflon-taped, etc.)
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Standard Operating Procedure for
Dry Deposition Sampling:
Dry Deposition of Atmospheric Particles
Regendra D. Paode and Thomas M. Holsen
Department of Chemical and Environmental Engineering
Illinois Institute of Technology
Air Quality Laboratory
10 W 33rd Street
Chicago, IL 60616
February 10,1996
Revision 2
-------
Standard Operating Procedure for
Dry Deposition Sampling:
Dry Deposition of Atmospheric Particles
1.0 Introduction - Principles of Dry Deposition Sampling
Pollution can exist in soil, in the waters of lakes, rivers and streams and in water below the ground.
Pollution can also exist in the air, whether it is in the air close to the ground or in the air of the
upper atmosphere. Probably every place it has been sought, some form of pollution has been
found. "Pollution" is the everyday word used to describe material found anywhere in the
environment that would not be there if it were not for mankind's activities. The technical term
used to describe pollution is "anthropogenic", which means "man-made"
When the term "atmospheric dry deposition" is used, "atmospheric" refers to the place where
pollution may reside and, unfortunately, the place from which pollution may be transferred. In
fact, pollution may be transferred among several or all the components of land, water and air.
"Dry deposition" refers to one pathway-there are several-through which pollution can be
transferred from the component of air to a component of land or water.
This dry deposition pathway is not reserved for man alone. It is part of a natural global process of
cycling that has always been there, only now anthropogenic matter—pollution—is being carried
alongside natural matter. Dry deposition is defined as the deposition to land or water of particulate
matter. If particles are attached to snow or suspended in rain droplets, then the term "wet
deposition" is used to describe the process.
So dry deposition is one of several types of atmospheric deposition that occur. But whereas wet
deposition is associated with a particular event-rainfall or snowfall-dry deposition can be thought
of as occurring year round, even when another kind of deposition is also taking place
It would be difficult or impossible to collect dry deposition during a rainfall event, so the dry
deposition sample surface is covered whenever it rains or snows. Doing this manually would
require a constant vigil, especially on a cloudy day or overnight. So instead a sampler (the
EAGLEII) is used that senses wet conditions and automatically covers the sampling surface until
the sensor dries off.
The sampling surface itself is a I x 3 inch greased Mylar strip which has been previously mounted
onto a clean PVC plate.. This plate then holds the strips horizontal!) so that dry deposition can
collect on the strips' greased surfaces. The grease is there to prevent particle bounce which can
occur if only a hard surface is used. This collection technique is not unlike the collection of dust
by an automobile windshield which is commonly seen even when there has been no precipitation.
The grease used (L-Apiezon) is non-volatile, so the difference between before and after sampling
weights of the strips is a measure of the amount of deposited material.
The plates on which the greased strips are mounted have a sharp leading edge and are kept
pointing into the wind. The sharp leading edge is to provide a laminar or non-turbulent flow of
air mor the strips (turbulence increases dr\ deposition). The less turbulence a natural surface
creates, the less the deposition B\ UMiig a surface which provides a laminar (Km of air. the
material collected on the strips will he a lowest approximation of the deposition at that sampling
location.
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The plates are kept pointing into the wind by the large tail on the back of the Eaglell. There are
two reasons for this. One is to avoid reentrainment of material collected on the sampler which
could redeposit on the strips. The other reason is to avoid turbulence created by the structure of
the Eaglell, which would increase deposition.
Sampling times vary, depending on the ultimate use of the strips. Short-term samples are generally
exposed from eight to 72 hours. Short-term samples are usually taken only in urban areas, because
of the large amount of dry deposition there. Long-term samples are generally exposed for one to
four weeks. These longer sampling times are needed in some non-urban and rural areas, where
there may be much lower amounts of dry deposition. The Eaglell was designed with long-term
sampling in mind.
2.0 Sample Collection: Atmospheric Particulate Dry Deposition
2.1 Preparation for Particle Dry Deposition Sampling
A list of equipment and supplies for field investigations is given in Appendix A. All Mylar strips,
strip covers, strip sample box, SP Brand Five-Slide Mailer, dry deposition plates, plate holders and
Rubbermaid plate containers are cleaned in double distilled methanol and deionized water in a
seven-day procedure before use in sample collection. Apiezon grease-coated strips equilibrate for
24 hours in the strip sample box before weighing. After weighing the four strips are mounted onto
each dry deposition plate with strip cover and Teflon-coated clips. Dry deposition plates are stored
in the Rubbermaid sample container before and after sampling. Field blanks are also prepared for
each sampling period; four preweighed grease-coated Mylar strips are mounted onto the dry
deposition plate and kept in the Rubbermaid sample container during the sampling period.
During sample plate set-up and removal, the operator must be very careful not to touch the greased
strip surface. This is very important to maintain sample integrity. During sample collection the
dry deposition plates are taken out from the Rubbermaid sample container and placed on each side
of an automatic dry deposition sampler (Eaglell-see Figures 1 and 2) about 2 meters above ground
level.
2.2 Particulate Dry Deposition Sampling
During the course of this study atmospheric particles will be collected onto greased Mylar strips
each vvith exposure area 10.3 cnr fur a total of 41.2 cnr on each dr\ deposition plate. Two dry
deposition plates are needed in one sampling period.
2.2.1 Taking Off Dry Deposition Plate Samples
2.2.1.1 Record total sampling time and open sampling time in minutes on the Eagle's log
sheets (see Appendix A). These times can be determined by switching the middle
switch up and down on the right side of the control box. The times will be
displayed on the red display panel. The open time will be preceded by the letters
"OPE" and the total tune \\ill he preceded b> "TOIL, You may have to shade
the control box to read the display on a sunn\ da\ Record the rest of the
information required in the log sheet.
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SOP for Dry Deposition Sampling:
Dry Deposition of Atmospheric Particles
•ieion
Figure 1. Drawing of Eagle II
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Volume 1, Chapter 1
10cm
o
K — a
If
1.8cm
MX
21.6 cm
1.6 cm
4
0 65 cm
Figure 2. Top View of a Dry Deposition Plate
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2.2.1.2 Put on particle-free gloves. Take down the dry deposition plates from both sides
of the Eagle by unscrewing the nuts on the bolts. Be careful not to touch the
surface of greased strips.
2.2.1.3 Place these two dry deposition plates back into the Rubbermaid sample container
along side the field blank. Slide the plates sideways into slots with the sharp edge
pointed into the thin slot. Take the Rubbermaid sample box out from the field
blank storage box and take it (or send it) back to the Illinois Institute of
Technology Air Quality Lab (IITAQL).
2.2.1.4 The rain sensor has to be cleaned at each sample change. Use a
Polyester/Cellulose Blend Wiper wetted with deionized water to gently wipe-off
the surface of the rain sensor.
2.2.2 Setting up Dry Deposition Plate Samples
2.2.2.1 Turn on the control box (see Figure 3) on the automatic dry deposition sampler by
switching up the third switch on right side of the control box (turn it off by
switching down).
2.2.2.2 Examine the timer in the control unit by switching the middle switch up and down
(see Figure 3) to ensure the correct counting of total sampling time and open
sampling time (exact exposure time) of the dry deposition plates. One can ensure
th& correct running of the timer by comparing the minutes shown on the display
with a watch (normal counting test is around two to three minutes).
2.2.2.3 Perform a wet test by putting a little bit of water on the Eagle sensor (see
Figure 1) to make sure the Eagle covers on both sides close when the sensor is wet
and reopen when it is dry.
2.2.2.4 Put on particle-free gloves. Take dry deposition plates out from Rubbermaid plate
container (which are been prestored into the sample holder in the Rubbermaid
sample container) and place one plate on each side of the automatic dry deposition
sampler using two '/»inch bolts and nuts.
2.2.2.5' Reset the timer by pressing the red button (press and hold the button for five
seconds), which is the first button on the right side of the control box.
2.2.2.6 Place the Rubbermaid sample container (which contains the field blank) into the
field blank storage box.
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OPE
3650
or
TOIL
4120
reset red button
open/total time toggle switch
( position varies on each unit"
.P power on
power off
rain sensor connector
left
cover
connector
power right
connector cover
connector
FIGURE 2
CONTROL BOX
Figure 3. Dry Deposition Sampler Control Box
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2.2.3 Taking Blanks
Field blanks will be taken during each sampling period of this study. To take a field
blank, four preweighed grease-coated Mylar strips will be mounted onto the dry deposition
plate and put it in the Rubbermaid sample container along with the sample plates. Unlike
the sample plates, the field blank will stay in the Rubbermaid sample container during the
entire sampling period. All Field blanks have to be labeled appropriately. Field blanks
are given the designation BK after the sample number, such that the field blank is
labeled:-OlBK. For example the field blank taken with Sample 9 from IIT site will
be labeled IIT-8BK.
3.0 Sample Transport
Samples should be transported to the Illinois Institute of Technology Air Quality Lab (IITAQL)
immediately after sampling. Samples should be stored in sealed Rubbermaid sample containers
during transport. In case the samples cannot be taken to IITAQL immediately after sampling, store
the samples at room temperature away from any possible contaminate sources until shipment.
Send the sample log sheet along with each of the samples collected. When a sample log sheet is
completed, make a photocopy of the sheet, and keep the photocopy in the three-ring binder
provided.
Ship samples to:
Dr. Thomas M. Holsen
Associate Professor
10 West 33rd Street
Department of Chemical and Environmental Engineering
Illinois Institute of Technology
Chicago, IL 60616-3793
4.0 Troubleshooting
When troubleshooting the Eaglell, follow secure the sample first" principle. Ideally, no work should
be done with samples in place.
When the Eaglell is turned off then on again, both covers should cover then uncover the sample
area.
4.1 Cover is Loose
The cover can become loose under normal operating conditions after a few months' time. (This
problem is being addressed in the next Eagle design, the Eaglefll.) Two set screws hold the cover
in place. These set screws require an alien ke\ in order to be loosened. One set screw is located
on the top and one on the side of the cover pivot shaft. (See Figure 4)
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cover
pivot shaft-
gear box
motor
Figure 4. Top and Side View of Plate Cover
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4.1.1 Top Set Screw
Rarely needs adjustment and should only be touched if care is taken to ensure that all parts
of the cover and the brass shaft on which it is mounted have proper clearance to rotate.
4.1.2 Side Set Screw
This set screw is trouble-prone. Through wear and tear, the set screw wears down the flat
part of the cover pivot shaft, and the cover develops greater-than-normal play Normal
play is l/2 inch of play back and forth (1 inch total) at the end of the cover farthest away
from the cover pivot shaft..
4.1.3 Cover Inspection
1) Make sure there is no sample in place.
2) Turn the Eaglell off (the on/off switch down).
3) Turn it on long enough to move the covers about halfway, then turn off again.
4) Gently move the covers back and forth to check play. If play is less than 1 inch,
turn the Eaglell on and take no further action. If play is greater than 1 inch, then
call for assistance since the cover may need to be removed and the Hat on the
cover pivot shaft filed.
4.1.4 Cover Adjustment
t
The sides of the covers should be about 1A inch above the sampling surfaces. If a cover is
too low, it may touch and ruin a sample. If too high, the cover will not protect the sample.
Covers should be horizontal, which can be gauged by the eye.
To adjust a cover:
1) Call for assistance.
2) If the cover is not horizontal, loosen the top set screw and gently tilt the cover
until level. Then tighten the set screw.
3) If the cover has been determined to be too high or too low, loosen the side set
screw and move the cover into a position where the bottom of the cover sides are
about '/4 inch above a dumim plate. This will require the covers ho mmed above
the sampling area, which is accomplished with the on/off switch. Turn it off
(down). Turn it on (up). When the covers move into the desired position, turn the
switch off again. The cover-to-sampling-plate clearance can now be seen.
4) Before resuming normal operation, turn the switch off then on again to make sure
the cover rotates freely, is not loose and does not contact the dummy plate.
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4.2 Cover Will Not Move
Call for assistance.
4.2.1 Only One Cover Moves
Check the two wires that connect to the motor. If both connections are good, then either a
motor is bad or a connector has become corroded. Replace the motor. 1) Remove the two
machine screws that hold the motor to the underside of the pivot shaft gear box.
2) Disconnect the two wires. 3) Install the new motor and reconnect the two wires,
disregarding the polarity, since the motor functions either way.
4.2.2 Neither Cover Moves
Perhaps the Eaglell has lost power. See the instructions under "No power."
4.3 No Power
4.3.1 If the display is not lit when the on/off switch is on (up), it is likely that there is no power.
Two related conditions will cause this. Either one or both of the fuses in the power box
are blown, or a power connector is shorting. When a power connector shorts, it will blow
a fuse in the power box.
4.3.2 Check power box. Disconnect the power connector from the power box.
Warning: The connectors used on the Eaglell are kept in place by a lock ring which only
makes a one-quarter turn; care should be taken not to over rwist the lock ring, as this will
damage the connector. Use a multi-meter set on "DC Volts " to measure the DC Volts
output of the power box. If output is 17 VDC, then proceed to check the power
connectors. If there is no output, then remove the four machine screws holding down the
cover of 'the power box and remove the cover.
Warning: Unplug the power box before opening it. Use the multi-meter ''el on "Ohms"
to see which fuse is bad. With the multi-meter on "Ohms", put the red and hlack leads
together and zero the needle on the meter. This ma\ not he necessary on some models,
for e \ample models with digital readouts. \'ow put one lead on each end of the fuse to he
checked. If the fuse is good, the readout will indicate 0 ohms. If bad, the readout will
show infinity. This may be done safely with the fuse in place. After replacing any faulty
fuse with one of the same Amp rating (on fuse), replace cover, plug it back in. then check
again to see if output is 17 VDC. The power box should work at this point. Before
connecting the power connector from the Eaglell, both power connectors should be
checked for signs of corrosion.
4.3.3 Check power connectors. Disconnect the one power connector from the power box and
the other from the control box.
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Warning: The connectors used on the Eaglell are kept in place by a lock ring which onlv
makes a one-quarter turn; care should be taken not to over twist the lock ring, as this will
damage the connector. Use a multi-meter set on "Ohms" to determine if there is
continuity from one to the other connector. This is done just like checking a fuse (see
preceding paragraph). Zero the multi-meter. Put one lead on one electrode of the
connector that goes to the power box. Put the other lead on an electrode of the connector
that goes to the control box. If the meter shows infinity, then try touching the lead to the
other electrode of the control box connector. If the meter again shows infinity', then there
is no continuity bet\veen the t\vo connectors and a connector is bad and needs to he
replaced. If there is continuity (meter reads 0 ohms), then check across the two electrodes
of each connector. If there is continuity, then a connector is bad and needs to be
replaced, and the bad connector is probably causing the fuses in the power box to fail.
Over listing the connectors can cause the same problems experienced from a corroded
connector.
4.4 Power Cord Wrapping Around Support Pole
The slip ring bearing has a shaft which protrudes into the support pole. The bearing is designed so
that while the top rotates, the bottom is stationary. The shaft on the bottom of the bearing has to
be secured. If it is not, the bottom and top will rotate together. The power cord which goes to the
power box is attached to the bottom of the bearing and will therefore be dragged around and
around the support pole. An undue strain would be placed on the power box connector. To avoid
this condition, a hole is drilled through the support pole and bearing shaft. A machine screw and
nut is placed through this hole.
Note: The hole was not drilled through the exact center of the shaft and pole. If the screw is
removed and the shaft turned 180°, the screw will probably not fit back in. This also means that a
pole and shaft come as a matched pair, since they were drilled at the same time. Shafts and poles
are not interchangeable. If a problem arises where the screw will not fit in, a wire or nail can be
used to temporarily solve this problem until a nut and bolt can be used.
4.5 No Timer/No Display
If the display is lit, but the timer does not function, or if there is no display but power comes to the
control box, call for assistance. The microprocessor in the control box may need to he replaced.
4.6 Eaglell is Loose
Each Eaglell has a hold down peculiar to the site, but each must be monitored for excess looseness
which may cause damage in a high wind to itself, other instruments or may pose a ha/ard to
people. Call for assistance.
4.7 Samples Covered. No Rain
This can occur in very humid conditions, such as when the weather is in a transition period, or
when the rain sensor connector has shorted The connector shorting duo to corrosion \\ill make
the covers co\ei the samples. The sensor itself operates on the principle that uhen lam hits its
surface, a short occurs that makes the covers cover the sample. The sensor connector needs to be
replaced. Call tor assistance.
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5.0 Quality Assurance and Quality Control
Field blanks will be collected to ensure samples are being collected and extracted in a
contaminant-free manner. Split samples will also be collected and analyzed. See the Standard
Operating Procedures for Preparation, Handling and Extraction of Dry Deposition Plates for
details.
If you have any questions, at any time, please do not hesitate to call Jeff Lu or John Kelly at the
Illinois Institute of Technology (312) 567-3553. If you cannot reach someone at the lab phone
during business hours, call Prof. Tom Holsen at (312) 567-3559 and leave a message on his
machine. We will get back to you as soon as possible.
6.0 Contact List
For questions or problems send a message or call:
Jeff Lu
IIT Air Quality Lab.
(312) 567-3553 (lab)
(312) 791-9649 (home, leave message)
or
Dr. Thomas M. Holsen
Associate Professor
10 West 33rd Street
Department of Chemical and Environmental Engineering
Illinois Institute of Technology
Chicago, IL 60616-3793
Tel (312) 567-3559( leave message)
Fax(312)567-3548
E-Mail ENVEHOLSEN@MINNA.IIT.EDU
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Dry Deposition of Atmospheric Particles
Appendix A. Sample Log Sheet
EAGLE SAMPLE LOG SHEET
SAMPLE NUMBER
SAMPLE LOCATION
DATE
WEATHER CONDITIONS
(CIRCLE ONE)
COVER STATUS
(CIRCLE ONE)
SUNNY
OPEN
RAINY
CLOSED
CLOUDY
OPEN TIME, MIN
TOTAL TIME, MIN
RESET TIMER?*
YES
NO
WET TEST RESULTS
(CIRCLE ONE)
COVER THEN
UNCOVER
NO RESPONSE
OTHER
(EXPLAIN
BELOW)
* RESET TIMER ONLY WHEN STARTING A NEW SAMPLE
COMMENTS
How to fill out 'he Eagle's log sheet:
Example 1. In this example it is a sunny September 13, 1994, so the site operator enters 09/13/94 into the
date, and circles sunny in the weather conditions row. Since it is a sunny day the plate covers should be
open and operator should circle open in the cover status row. The open time and the total time should then
be recorded. These times can be determined by switching the middle switch up and down on the right side
of the control box. The times will be displayed on the red display panel. The open time will be preceded
by the letters "OPE" and the total time will be preceded by "TOTL" You may have to shade the control
box to read the display on a sunn\ day. A wet test should then he performed by putting a little hit of \vater
on the Eaale senior i-.ee hsuire I i to make Mire the Kiglc oners on both sides close when the sensor is wet
and reopen when it is dry Any comments can be entered at the bottom of the log sheet.
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Appendix B. Parts List
One power box (gray; input 120 VAC, output 17 VDC; one 10 amp fuse, one 5 amp fuse)
One control box (white; includes a display, sensor connector, two motor/position-sensor
connectors, power connector, on/off switch, total-time/open-time switch, red reset switch, 2 blue
relays for the two motors, black microprocessor).
One base
One support pipe
One support pipe screw (prevents rotation of slip ring bearing shaft)
Four set screws
Two cover motors
Two cover motor gear boxes
Two covers (left and right)
Tail
One sensor (for rain and snow)
One sensor holder (mounted on tail)
One slip ring bearing (allows free rotation of upper section, while maintaining a continuous
connection to power supply)
Two power connectors (one to power box, one to control box; two-pin connectors)
Two motor/position-sensor connectors (on control box; six-pin connectors)
One sensor connector (on control box)
Four position sensors (two for each cover; not to be confused with rain sensor)
Two sampling plates (dry deposition plates)
One sample blank
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Appendix C. Terminology
Sampling area: Where plates get mounted
Cover mount shaft: Horizontal brass shaft from cover
Cover pivot shaft: Vertical steel shaft on which cover pivots to the closed and open positions
Closed cover: The cover is over the sampling area, sampling has been discontinued during a rain or snow
event; the timer continues to count total time, but stops counting open time until the cover is again in the
open position.
Open cover: The cover is not over the sampling area, the Eaglell is in sampling mode; the timer counts
open time as well as total time
Dry deposition: Deposition to land or water of paniculate matter, both man-made and natural
Anthropogenic: Man-made material found in the environment
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Volume 1
Chapter 2: Water
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Standard Operating Procedure for
Sample Collection of Atrazine
and Atrazine Metabolites
Steven Eisenreich, Shawn Schottler, and Neal Mines
Department of Environmental Sciences
Rutgers University
P.O. Box 231
New Brunswick, NJ 08903
1994
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Standard Operating Procedure for
Sample Collection of Atrazine and Atrazine Metabolites
1.0 Procedures
1.1 Water will be collected using the method outlined in LMMB 013, Field Sampling Using the
Rosette Sampler. The rosette will be deployed and retrieved in accordance with standard ship
operating procedures.
Sampling locations and depths are outlined in Section 2 with a map provided in Figure 1.
1.2 Sampling Open Water Stations
If the water column is stratified, sampling depths will be the mid-epilimnion and mid-
hypolimnion. If the water column is not stratified samples will be collected two feet below the
surface and at the mid-water column. The following stations are to be sampled as open water
stations: mb63, mb72, mb57, gb24, gb!7, 45, 52, 43, mb38, 31, 36, mb26, mb25, mb24, mb21,
mb20, mb!9m, 340, mb!3, mb9, 17, 1, 5, 3.
In addition, duplicate samples should be collected at Station 1 and Station 72m.
1.3 Sampling Master stations
Stations 18 and 41
If the water column is stratified, samples should be collected at the following depths: 2 ft below
the surface, 5 ft below the surface, mid-epilimnion, thermocline, mid-hypolimnion, and 5 ft off the
bottom. Duplicate samples should be taken at the 2 ft below the surface and 5 ft off the bottom
depths.
If the water column is not stratified samples should be taken 2 ft below the surface, mid-water
column, 5 ft off the bottom. Duplicates should be collected at all of these depths.
Stations 23. 27. 47
If the water column is stratified, samples should be collected at the following depths: 2 ft below
the surface, mid-epilimnion, mid-hypolimnion, and 5 ft off the bottom. In addition, duplicate
samples should be collected from all depths at Station 23. These samples will be labeled with "BE
Dup.", and are samples to be used in a comparison study.
If the water column is not stratified, samples should be collected 2 ft below the surface, mid-water
column and 5 ft off the bottom. Duplicate samples should be collected from all these depths.
1.4 Sample Collection
1.4.1 Objective: Water will be transferred from individual rosette canisters to amber 1 L bottles
and placed in cold storage until processed by scientists from the University of Minnesota.
\.4.1 Once the rosette has been curelulK positioned to Us proper location on the deck of the ship
examine the canisters to confirm that all canisters slated tor sampling have properly fired.
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1.4.3 All operations executed on the deck of the ship require personal flotation devices to be
worn.
1.4.4 Remove amber I L bottle from storage area and visually inspect for cracks or severely
chipped cap threads.
1.4.5 Confirm with marine tech. or other rosette operator which sampling depths correspond to
which rosette canisters.
1.4.6 With the sampling depth of each canister noted, vent lower valve on canister allowing
water to drain out. Allow several hundred milliliters to drain out before sampling.
1.4.7 Remove cap and aluminum foil from amber one-liter bottle. Rinse bottle and cap three
times from the canister discharge stream. Be sure to nnse bottle and cap with the same
water that is to be sampled. Use about 200 mL for each rinse, and thoroughly wet all
interior surfaces of bottle.
1.4.8 While filling bottle be careful not to place aluminum foil on any dirtv surface or to allow
aluminum foil to wash or blow away. While the amber bottle is urcapped the cap should
be placed upside down (concave surface up) on clean surface and aluminum foil placed
inside of cap.
1.4.9 Once bottle has been thoroughly rinsed carefully fill bottle with water. Fill bottle to within
I or 2 cm of the very top of the bottle.
1.4.10 While filling bottle be careful not to touch discharge stream before it enters the bottle, and
be sure not to let any foreign debris enter the bottle. Avoid all possible contaminants
including smoking.
1.4.11 For each depth a 2 L sample is required, therefore, two one liter bottles should be filled for
each depth. Each sample must come from the same rosette canister even if two canisters
are fired at the same depth.
1.4.12 Label bottle and cap. A label is provided on each bottle. The label has locations marked
for the following information: Lake, Station, Date, Depth, and code number. The code
number is simply the sequential number of the sample, i.e. the first sample collected is 1,
the second 2, etc. Numbering will continue in progressi\e order throughout the mass
balance study, do not start renumbering at each location or in each lake, i.e. the last
sample collected will nave a code number of about 550.
1.4.1 3 Since there are two bottles per sample depth, label one sample "a" and one "b", e.g., a
code number might be la and 1 b or 450a and 450b.
1.4.14 The code number should be written on the cap of each bottle as well as the label. The
code number is the only information necessary on the cap. A labeling surface is provided
on each cap.
1415 When labeling has lxvn completed move to next cani-ur
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1.4.16 Once water from all required depths has been transferred to amber bottles, carefully move
bottles to cold storage. Cold storage will be the walk-in cooler provided on board the ship.
Storage crates are provided but care should be taken to ensure that crates are secure while
ship is moving.
1.4.17 The walk-in cooler should be maintained at approximately 4°C. The cooler should not be
any colder than this since it is possible that the samples would freeze and break the bottles.
If the cooler goes above 10°C for any period over an hour a note should be made of this in
the sample log book.
1.4.18 Once samples are secure in cold storage, information about the samples collected and the
sampling site should be entered into the sample log book provided by the University of
Minnesota. All information on bottle labels should be entered into the log book as well as
a sketch of a temperature depth profile, a note on weather conditions, and who collected
the samples.
1.4.19 The temperature depth profile should list the surface temperature of the water the
hypolimnion temperature, and the location of any stratification. An accurate temperature
depth profile is available from the EBT printout. An example of a sample log sheet is
included.
2.0 Sample Locations
Remember:
Rinse three times
Fill two bottles per one sample
Label bottle and cap
2.1 Open Water Stations:
2.1.1 If Stratified
*Mid Epi
*Mid Hypo (If possible sample hypo at depth that corresponds to mean particle mass as
measured by transmissometery)
2.1.2 If Not Stratified
*2 ft below surface
*Mid water column
Collect duplicates of two open water stations. One station in Northern LM and one in
Southern LM. Put "DUP" on label.
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SOP for Sample Collection ofAtrazine
and Atrazine Metabolites Volume 1, Chapter 2
2.2 Master Stations:
2.2.1 If Stratified
Stations 18 and 41
*2 ft below surface plus duplicate
*5 ft below surface
*Mid Epi
*Thermo
*Mid Hypo
*5 ft off bottom plus duplicate
Stations 23.27, 47
*2 ft below surface
*Mid Epi
*Mid Hypo
*5 ft off bottom
*Plus duplicates of all depths at Station 23 and put "BE DUP" on label
2.2.2 If Not Stratified
All Master Stations (18. 23. 27. 41. 47)
*2 ft below surface
*Mid water column
*5 ft off bottom
*Duplicates of all depths at Stations 18, 23, 41 (put BE on Station 23 label)
Mark Station 18 and Station 41 Duplicates with "DUP", Station 23 with "8E DUP" in
addition to regular sample label.
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Volume 1, Chapter 2
SOP for Sample Collection of Atrazine
and Atrazine Metabolites
Lake Michigan Stations
Master Stations
gb24m
'".« o
Figure 1
Lake Michigan Stations
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SOP for Sample Collection of Atrazine
and Atrazine Metabolites
Volume 1, Chapter 2
Herbicide Sample Log
Date: ff\
Lake: (_
Station:
Collector: £
— /
Station: ~/ 7
Collector:
/
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HOC Sampling Media
Preparation and Handling;
XAD-2 Resin and GF/F Filters
Eric Crecelius and Lisa Lefkovitz
Pacific Northwest National Laboratory
Battelle Marine Sciences Laboratory
1529 West Sequim Bay Road
Sequim, WA 98382
Standard Operating Procedure MSL-M-090-00
November 1994
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HOC Sampling Media Preparation and Handling;
XAD-2 Resin and GF/F Filters
1.0 Scope and Application
This method is applicable to the preparation of sampling media used in the collection of
hydrophobic organic compounds (HOCs) from water.
The dissolved HOC phase is collected on XAD-2 resin, a macroreticular resin bead that selectively
scavenges HOC from other media such as water and/or air. The manufacturing process of this
material results in very dirty product and a very rigorous clean-up procedure is needed to remove
these potential interferences. Also, care needs to be taken when handling the resin to avoid
damage of the beads which could lead to reintroduction of the original contaminants possibly
bound into the beads.
Glass fiber filters are used to filter out the "paniculate" fraction of the water. Since HOCs are
preferentially bound to particulates in these media, this material needs to be isolated to determine
the particulate-bound fraction of HOCs present. Again, special cleaning and handling procedures
are required to obtain filters clean enough for trace level HOC analyses.
2.0 Definitions
HOC Hydrophobic organic contaminants
GF/F Glass fiber filter
XAD-2 Manufacturers name for a class of polymeric resin beads used to isolate HOCs from
water.
LRB Laboratory Record Book
3.0 Responsible Staff
Laboratory Supervisor. A Technical Specialist or Scientist having expertise in the principles
involved with this procedure and in the use of laboratory operations in general. Responsible for
ensuring that analysts are trained in the use of the instrument and that maintenance logs are being
completed.
Analyst. A Technician, Technical Specialist, or Scientist assigned to utilize the instrument for
actual sample analysis using this procedure. Responsible for 1) understanding the proper use of
tools and solvents; 2) recording information regarding maintenance of the instrument in the
appropriate logbooks; 3) reporting any significant problems with the instrument to the Laboratory
Supervisor, and 4) tabulating and reporting sample data to the Laboratory Supervisor.
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HOC Sampling Media Preparation and Handling;
XAD-2 Resin and GF/F Filters Volume 1, Chapter2
4.0 Procedure
4.1 XAD-2 Resin
XAD-2 resin can be obtained from a number of different vendors but is manufactured solely by
Rohm and Haas. The size of the resin beads is 20-60 mesh. A rigorous clean-up procedure must
be applied prior to use of the resin for collection of HOCs.
4.1.1 Apparatus and Reagents
Methylene Chloride, Acetone, Hexane, Methanol; HPLC grade or better
Glass wool/soxhlet extracted in hexane/acetone (50:50)
Amberlite XAD-2 Resin, 20-60 mesh. Rohm and Haas manufacturer
4.1.2 Resin Clean-up Method
The XAD-2 resin is cleaned in the lab by a series of solvent extractions in a large soxhlet
apparatus (or in multiple set-ups). The resin is extracted sequentially for 24 hours each
in methanol, acetone, hexane and methylene chloride. This is followed by sequential 4-
hour extractions in hexane, acetone and methanol which cycles the resin back to a polar
solvent. The methanol is then displaced from the resin by numerous rinses with organic-
free water. The resin can be stored at this point in clean jars immersed in the water in a
dark place for up to three months. The final four-hour hexane extract may be used for a
laboratory XAD-2 blank. The last methanol rinse may be used as the starter methanol on
the next XAD-2 batch.
4.1.3 QC of Resin/Is it Clean?
A portion of the resin from each clean-up batch must be tested to ensure a thorough
clean-up has been performed. As noted above, the final four-hour hexane extract may be
used for a laboratory XAD-2 blank. Alternatively, a representative amount of
pre-cleaned resin from a given clean-up batch may be extracted using the extraction
scheme to be used for the project of interest and the extract analyzed as a resin blank.
The cleanliness of the resin will be evaluated on a project specific basis.
4.1.4 XAD-2 Resin Column Preparation
XAD-2 resin must be packed into a column for use as a sampling media for dissolved
phase HOCs. The resin columns may be glass, stainless steel or tetlon and can vary in
size. This procedure is specific to glass columns with dimensions of 300 mm x 50 mm,
fitted with nylon end plugs sealed with viton O-rings.
XAD-2 resin columns are prepared by first attaching one teflon adaptor with a swagelock
fitting and a 3 inch length of latex tubing to one end of the glass column, and pushing a
large plug of cleaned glass wool into the bottom. The column is filled about '/z full with
organic free water and clean resin is poured into the column in a slurry to a final packed
length of -19.5 cm (-400 cc). The resin is packed by pumping excess water out from the
bottom using a water aspirator peristaltic pump but alwa\s maintaining enough water in
the colimn to cover the resin. The column should not contain air bubbles or channels.
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HOC Sampling Media Preparation and Handling;
Volume 1, Chapter 2 XAD-2 Resin and GF/F Filters
Glass wool is added at the top to take up the space between the XAD-2 and the column
threads. A solid nylon end cap with O-ring is placed on the top and then, after inverting
the column and unscrewing the adaptor, the other end is capped in the same fashion.
4.1.5 Column Handling and Storage
Upon receipt of a cleaned batch of resin, the batch is named for the date of receipt and
recorded in the project LRB. A copy of the chromatogram of the resulting XAD-2 resin
blank that is determined for that batch is also included in the LRB. All columns are
assigned individual numbers based on the resin batch number which is written in
permanent marker on a piece of tape wrapped around the outside of the column.
Columns are stored in a clean, cool place in the dark and can be stored up to 6 months
prior to use. After sampling, columns should be stored at 4CC in the dark. There is no
holding time for sampled resin columns prior to extraction.
4.2 Glass Fiber Filter
4.2.1 Apparatus and Reagents
Muffle Furnace
Al foil, heavy duty, extra wide
Whatman 293 mm GF/F 0.7um nominal pore size glass fiber filters
4.2.2 Filter Clean-up Method
Filters are wrapped in a single layer of heavy duty aluminum foil which is sealed around
the filter to create a "bag." The filter and aluminum foil are then ashed for four hours at
450°C(±20°C).
4.2.3 QC of Filter/Is it Clean9
One filter (or more, since more than a single filter may be used for a given sample)
should be extracted using the extraction scheme to be used for the project of interest and
the extract analyzed as a filter blank. The cleanliness of the filter will be evaluated on a
project specific basis.
4.2.4 Filter Storage and Handling
Cleaned filters are stored inside of their foil bags in a clean, cool place prior to sampling.
Multiple filter/ foil units can be stored in sealed polyethylene bags for storage and/or
shipping. The bags containing cleaned filters from the same lot are labeled as the
preparation date of filters, the initials of the technician who prepped them, the number of
filters in the bag and the page number of the LRB where the preparation information is
recorded.
After filters are used tor sampling, they are to be folded in quarters (pie shaped) and
placed in sealed ashed toil bags and stored frozen in plastic hags. There is no holding
time for storage of sampled filters prior to extraction.
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HOC Sampling Media Preparation and Handling;
XAD-2 Resin and GF/F Filters Volume 1, Chapter 2
4.3 Interferences
Take appropriate precautions to prevent contamination of any equipment associated with this
analysis.
5.0 Data Analysis and Calculations
Not applicable.
6.0 Quality Control
6.1 Solvent Blanks. Use only HPLC grade or higher purity solvents for clean-up. Only a single lot
number of each solvent should be used. A solvent blank test will be performed upon the start of a
new lot number by concentrating a representative volume of solvent to 1 mL and analyzing on the
appropriate analytical instrument. Cleanliness of the solvent will be determined on a project
specific basis.
6.2 Resin Blank per batch. Resin used for a given project should be isolated to a single
manufacturer's lot number since the original level of contamination of the resin can vary
significantly with lot. Resin blanks will be analyzed per clean-up batch as specified in
Section 4.1.3. Cleanliness of the resin will be determined for each new lot number on a project
specific basis.
6.3 One Filter blank per batch. Filters used for a given project should be isolated to a single
manufacturers lot number. Filter blanks will be analyzed per clean-up batch as specified in
Section 4.2.3. Cleanliness of the filters will be determined on a project specific basis.
6.4 All results will be recorded in an LRB which is reviewed periodically by the laboratory supervisor
and monthly by the project manager.
7.0 Safety
All analysts following this procedure should be aware of routine laboratory safety concerns,
including the following:
7.1 Protective clothing and eyeglasses should be worn when appropriate.
7.2 Proper care must be exercised when processing samples because volatile and flammable solvents
are involved.
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HOC Sampling Media Preparation and Handling;
Volume 1, Chapter 2 XAD-2 Resin and GF/F Filters
8.0 Training Requirements
All staff preparing sampling media described above must first read this SOP and then demonstrate
proficiency in the process prior to performing the work under the supervision of the laboratory
manager.
9.0 References
MSL-A-006. Marine Sciences Laboratory Training.
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Standard Operating Procedure for
Site Selection and Sampling
for Mercury in Lakewater
Robert P. Mason and Kristin A. Sullivan
Chesapeake Biological Laboratory
University of Maryland
P.O. Box 38
Solomons, MD 20688
June 26,1996
-------
Standard Operating Procedure for Site Selection and Sampling
for Mercury in Lakewater
The mercury samples will be collected at all the master stations, as designated within the LMMB/MB plan
(Figure 1). Samples will be collected from mid-depth at each station if the water column is unstratified, or
from two or three depths during stratification. If a nephloid layer exists at the lake bottom, this will also be
sampled. Water will be collected using Teflon-lined Go-Flo bottles that have been rigorously cleaned. All
stages of field apparatus cleaning and preparation will be performed within a clean lab following strict
trace metal protocols (Patterson and Settle, 1976), as adapted for mercury analysis by Gill and Fitzgerald
(1985). This paper, which forms the basis of current sampling procedures and sample collection, is
attached as Appendix 1.
Cleaning consists of an initial soaking in detergent, a MilliQ water rinsing and a further soak in dilute
(0.05% HC1). A detailed outline of the cleaning and bottle preparation techniques is contained in
Appendix 1. The Go-Flo bottles will be filled with laboratory grade MilliQ water and allowed to sit for six
hours (i.e. significantly longer than the expected residence time of the sample in the bottle in the field)
before sampling to assess contamination due to leaching of mercury from the Go-Flo bottle walls. Bottles
showing any contamination will be recleaned. Initially, two Go-Flo bottles supplied by EPA will be used
until additional Go-Flo bottles can be purchased, cleaned and checked. At least three bottles are desirable
for periods when three depths are to be sampled per station. Additional bottles are also required as
backups in case of loss or contamination.
After cleaning, and between deployment, Go-Flo bottles are stored in two or more polyethylene bags
within a tight plastic or wooden container. Prior to storage, bottles will be rinsed with dilute acid and then
MilliQ water. If contamination is noted or suspected, bottles will be returned to the UMCBL for cleaning.
If the bottles are not to be used within 30 to 60 days, bottles will be shipped back to the UMCBL for
rechecking of blanks and for cleaning and maintenance.
Details of sample collection procedures are also contained in Appendix 1. Sample collection will only be
performed by personnel trained by UMCBL or another recognized laboratory in the methods of the
so-called "clean techniques." Improper use of the Go-Flo bottles can result in permanent contamination.
Handling procedures are detailed in Appendix 1. The PI, or a designated substitute, will be on site during
each deployment and will be in charge of the planning and co-ordination of on-site activities. The PI will
determine when to collect the mercury samples, after consultation with the ship's officers and other Pi's on
board. The PI will monitor the sample collection and determine whether the samples have been collected
"without obvious contamination." If the PI feels that the sample has been compromised, a redeployment
with one of the other Go-Flo bottles will be the designated contingency.
Go-Flo bottles will be deployed from non-contaminating Kevlar line. Bottle messengers will be
Teflon-coated and the line weight will be non-metallic and Teflon-coated, if possible. Due to the nature of
the activity i.e. the attachment of the bottles requires the personnel to reach out over the guard rail, the
personnel should be attached to a safety line. Also, personnel should wear a hard hat and steel cap boots to
prevent injury. Go-Flo bottles will be removed from the polyethylene bags as close to deployment as
feasible and will be returned to the pnl\eth\lene bags as soon as possible after retrieval. Bottles will he
transported around the ship within hags and water will only be decanted within the clean room on board
ship.
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SOP for Site Selection and Sampling for Mercury in Lakewater
Volume 1, Chapter 2
Figure 1. Map of Lake Michigan Mass Budget/Mass Balance Study
Lake Michigan Mass Budget/
Mass Balance Study
D Polygons represent Biota Sites
Scale: 1 in = 41. 09 ml
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Volume 1, Chapter 2 SOP for Site Selection and Sampling for Mercury in Lakewater
Inside the clean room, water will be decanted, as soon as possible, from the Go-Flo bottles into
acid-cleaned Teflon bottles. Two liters of sample will be collected for total mercury analysis (and for
methyl mercury analysis even though methyl mercury measurement is not part of the LMMB). Laboratory
replicates will consist of subsamples of water taken from the same Go-Flo bottle or from the same Teflon
sample bottle. Field replicates will consist of duplicate deployments at the same sampling location. To
ascertain the field blank, MilliQ water of known concentration will be added to an empty Go-Flo and
allowed to sit for a period comparable to the deployment time before being decanted from the bottle. This
blank will represent, as near as possible, the blank associated will all sources of contamination from field
collection to analysis. All samples will be collected in acid-cleaned Teflon bottles. Trace metal grade
acids will be used in all cleaning and storage stages. Potential for contamination will be minimized by
prepackaging sample bottles in double polyethylene bags. Bottles, and acidification acid will be analyzed
for contamination before use.
Paniculate samples will be collected onto quartz fiber filters, of nominally 0.8 /jm pore size. Filters will be
cleaned of mercury by heating in a muffle furnace for 12 hours at 600°C. After cooling in situ, filters will
be removed and stored in a bagged acid-washed Teflon vial. Filters will be placed, under clean room
conditions, within an in-line Teflon filter holder. Water will be pumped through the filter using a
peristaltic pump. Tubing will be acid-cleaned Teflon, except for the small amount of tubing within the
pump apparatus, which will be acid-cleaned silicone tubing. One or more liters of water will be pumped
through the filter, the exact volume being recorded. The filter will be removed and placed in a clean
Teflon vial placed in a polyethylene bag. Filters will be frozen as soon as possible after collection.
Additional paniculate collections will be stored for duplicates (and for methyl mercury analysis).
Appropriate QA/QC procedures will be adopted during field samples. The QC requirements are detailed
in the previous section and details of QA related issues are in Appendix I.
Samples will be stored frozen on board and will be shipped overnight to the University of Maryland by
Federal express in particle-free plastic boxes soon after arrival in port. A maximum interval of two months
is expected between sample collection and completion of analysis. However, samples have been
successfully stored for six months by other investigators without loss (Hurley, pers. comm.). Thus, if a
holding time of six months is exceeded and no evidence to support a longer interval is provided, the
sample data will be qualified as estimated. Field labels are attached to the Go-Flo bottles are soon as
possible after retrieval. This label will have an ID number that will be used as the primary control number
for chain of custody. This ID number will be attached to the outer bag of the Teflon bottle etc. See chain
of custody section below. The only calibration required is for the winch as the depth is determined from
the "line out" record of the winch operator. The calibration of the winch is monitored by the ship
personnel.
Teflon equipment will be cleaned in concentrated HNO, (ACS Reagent grade) for a week and rinsed with
deionized water. Bottles will then be filled with lOT acid and will be kept for a week. After further
MilliQ rinsing, bottles will be filled with l% HCl and this dilute acid will remain in the bottles until
samples are collected. Samples will be dispensed in the clean room into 2 L Teflon bottles as described
above.
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Volume 1, Chapter 2 SOP for Site Selection and Sampling for Mercury in Lakewater
Appendix 1.
Field Sampling Protocols (from QAPjP)
1.0 Preparation of Sampling Bottles and Subsequent Collection of
Mercury in Open Waters
This SOP is intended to provide a step by step procedure for the preparation of samplers and
sample bottles necessary for the collection of contamination-free water samples from depth in open
water environments, and for the collection methods to be employed in the sample collection.
l.l Overview
Samples collected for mercury analysis form part of the LMMB study and the data will be used to
constrain a mass balance for mercury in Lake Michigan. The samplers used in the collection of
samples are specially designed Teflon-lined Go-Flo bottles, manufactured by General Oceanics.
The bottles are able to be remotely triggered using a Teflon-coated metal "messenger" and thus can
be used to collect samples at any pre-determined depth in the water column. The bottles are
deployed attached to a non-metallic Kevlar line to ensure that the sampling apparatus does not lead
to sample contamination. Procedures are designed to ensure that the Go-Flo bottles do not leach
mercury into the sample water during deployment, recovery and before decanting of samples into
specially prepared Teflon bottles. All bottles are kept in plastic bags when not in the clean room
or in use to minimize contamination. Personnel handling the Go-Flo bottles need to wear plastic
gloves and to avoid contact with the ball valves and internal parts of the Go-Flo bottles. All
precaution is required if uncompromised samples are to be obtained. The Go-Flo bottles should
never be placed directly on the deck or any hard surface otherwise foreign particles might be
lodged in the plastic ball valves leading to subsequent contamination.
1.2 Go-Flo Bottle Preparation
Newly purchased Go-Flo bottles are first checked for obvious defects and the closing and opening
mechanisms checked. The bottles are then rinsed and scrubbed, using a soft brush, with soapy
water to remove any loose particles from inside or outside the bottle. The mechanism of the ball
valves is removed and the bottle O-ring removed and washed. The components are then rinsed
with deionized water. The bottle is then re-assembled. The bottles are then soaked in a weak
0.05% HC1 solution for a week - this is done by placing the bottle in a plastic garbage pail that has
been lined with a clean polyethylene bag. The ball valves are rotated periodically to ensure that all
parts of the ball valve that could contact the sample water after the bottles are closed is cleaned.
The bottle is then rinsed with MilliQ water and filled with water and allowed to stand for six hours
with the balls in the closed position, A sample of the MilliQ water is taken for later comparison
with the water concentration in the bottle after 6 hours of leaching. After six hours the water in the
Go-Flo bottle is sampled and analyzed, along \\ith the initial sample. Any significant increase in
concentration o\5c/c) will suggest that the botilc is still contaminated and leaching mercury. If so,
the bottle \vill be recleaned using the procedure above.
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SOP for Site Selection and Sampling for Mercury in Lakewater Volume 1, Chapter^
1.3 Teflon Bottle Preparation and Handling
All sample bottles used for sample collection are constructed of Teflon as this has been found to
be the material that results in the least contamination of samples, after the bottles have been
rigorously cleaned. New Teflon bottles are washed with soapy water, and then with acetone to
remove any organic residues. The bottles are then leached with concentrated HNO, (ACS Reagent
grade) for a week. After being rinsed with deionized water, bottles are then be filled with 10%
acid and will be kept for a week. After further MilliQ rinsing, bottles will be filled with 1% HC1
and this dilute acid will remain in the bottles until samples are collected. Bottles are hermetically
sealed (i.e. the caps are wrenched tight using a wrench whose metal parts have been covered with
several layers of plastic) at this point and stored and transported within two poly ziplock bags. The
bottles are packed into a large poly bag and are typically transported in plastic coolers. On board,
the coolers will be opened in the ante room of the clean room. When the bottles are removed from
the coolers, the outer bag is removed and the bottle is taken into the clean room. Samples will be
dispensed in the clean room from the Go-Flo bottles into the Teflon bottles as described below.
Just prior to sample decanting, the Teflon bottles will be unbagged, emptied of their acid solution
and rinsed with MilliQ water. Strict clean techniques will be used in the collection and decanting
of samples, i.e. gloves are worn at all times and are changed whenever the personnel switch from
handling "clean" and "dirty" things e.g. outer poly bags are considered dirty, inner bags clean; all
things within the clean room are considered clean, otherwise they should not be inside.
1.4 Sample Collection
The samples are collected using a "hydrowire" deployment system, with Kevlar as the wire. The
non-metallic weight, which is stored in a plastic bag in-between sampling events, is first attached
to the end of the wire. The weight is lifted overboard by the winch operator and lowered until it is
in the water. At least 10 m of wire should be extended prior to Go-flo bottle attachment. Prior to
sampling, Go-Flo bottles should be moved to the ante room of the clean room, or a suitably clean
environment closer to the deployment site, and placed in a container for easy access. The bottles
are still bagged at this stage. The Go-Flo bottles are "pre-cocked" in the clean room. Details of
the cocking methods are contained in the manual that is supplied with the Go-flo bottles. Briefly,
the ball valve is rotated so that the string parts of the Go-Flo can be attached to the plunger
mechanism. Throughout the whole cocking procedure, the Go-Flo should be either placed on a
plastic covering on the floor or be hand-held. The pressure release valve is pulled out and the
plastic balls on the string positioned around the valve. The "bungie cord" attached to the ball
valve is then rotated back so that both the string and the cord are under tension. The cocking
should be checked to ensure that it has been correctly cocked. Pushing the pressure release valve
should cause the balls valves to move to the open position. Pressing the plunger should then
release the string and result in the closure of the bottle. Recock the bottle after this check in a
similar manner. The cocked bottle is then placed in poly bags and removed to the ante room and
placed in the bottle container. The bottles are individually unbagged when required, and are
carried by gloved personnel to the deployment site. The bottle is attached to the line by the person
carrying the bottle with additional help, if required. The bottle is then lowered down into the
water and slowly lowered to about 20 m. As the pressure release valve opens the Go-Flo
underwater, a parcel of air is released to the surface. The bubbles are typically easily seen, and this
is indicative that the bottle is open. If. on the rare occasion that bubbles are not seen, there is a
concern that the bottle has not opened - this again is not the typical scenario - the bottle can be
raised sKm K so that personnel looking o\ er the side of the ship can look and see if the bottle is
open. This, ot course, is only feasible in clear water as it is undesirable, from a contamination
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Volume 1, Chapter 2 SOP for Site Selection and Sampling for Mercury in Lakewater
standpoint, to bring the bottle to the surface. If the water is unclear or rough, it is better to just
assume the bottle is open and accept the associated risk i.e. a redeployment. The weight of the
retrieved bottle will be indicative of it being empty of filled with water. The bottle is lowered to
the correct depth and then the messenger is attached to the line and released. The messenger will
trigger the bottle and it can then be retrieved to the surface. Adequate time, based on the time
required for the messenger to reach the bottle must be allowed before retrieval. When the bottle is
retrieved to deck level, the person who attached the bottle will disengage it and carry it, without
putting it down or touching the ship's parts to the box and replaced it in the plastic bags. The
Go-Flo bottle is then taken into the cleanroom as soon as possible. The Go-Flo bottles can be
deployed singularly or a string of bottles can be deployed at the same time, depending on the
circumstance.
1.5 Sample Decanting and Labeling
The Go-Flo bottle is taken into the clean room and placed on the bench, on a plastic bag, in the
upright position. Personnel should put on clean gloves at this point. The air release valve is
opened and the sample is decanted into the rinsed and ready Teflon bottles. About 20 mL of water
is decanted into the Teflon bottle, and the bottle rinsed. The sample is then decanted. As the
samples will be frozen, the bottles should only be filled to the beginning of the neck to allow for
the expansion of the water on freezing. If insufficient airspace is left, samples can leak or. if the
bottle is very tightly sealed, the bottle can split. After filling, the bottle cap is immediately
replaced and any additional samples taken. After all samples are taken, the caps of the Teflon
bottles are wrenched tight using a plastic coated wrench. The bottles are then double-bagged, and
taken to the freezer for storage. The information on station #, depth, collection date, Go-Flo #, and
ID # will be entered into the data sheet.
Date
ID#
Station #
Depth (m)
Go-Flo #
Bottle #
Vol. (L)
As # H,0 Analy.
Hg-T Analy.
SHIPPED BY: Box # RECEIVED BY: Date:
Notes: I) The ID # will consist of the date, station, and depth.
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Field Sampling Using
the Rosette Sampler
Glenn J. Warren
U.S. Environmental Protection Agency
Great Lakes National Program Office
77 West Jackson Boulevard
Chicago, IL 60604
May 1996
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Field Sampling Using the Rosette Sampler
1.0 Rosette Sampler
The Rosette sampler is the primary sampling instrument for the collection of all Nutrient
parameters, phytoplankton, chlorophyll a, phaeophytin a, and dissolved oxygen from the
Biological Category, and temperature, total suspended solids, turbidity, specific
conductance, and pH from the Physical Category.
A 12-bottle Rosette sampler system (Sea-Bird Electronics 32 Carousel Water Sampler)
will be used to collect water samples. This equipment allows an operator to remotely
actuate a sequence of up to 12 water sampling bottles. This system consists of a CTD
(conductivity, temperature and depth sensor - Sea-Bird Electronics Model 9 Underwater
Unit) attached at the bottom of the Rosette, an A-frame, 1000 feet of multi-conductor
cable, a variable speed winch and Sea-Bird Electronics Model 11 Deck Unit with attached
computer. The CTD measures water depth and temperature, which is graphically (CRT)
displayed onboard the research vessel. The bottles can be closed in any predetermined
order, remotely from the deck of the vessel while the array is submerged at the various
sampling depths. The Rosette sampler is equipped with 8 L Niskin bottles.
The depth at which samples will be collected is detected by a pressure transducer on the
CTD. To assure that the display parameters are set to include the entire water column, the
Rosette winch operator obtains a depth sounding from the bridge and writes this on the
Rosette form, then adjusts the computer program parameters controlling the depth range to
be displayed (See "Instructions for use of the Sea-Bird 9/11+..."). The Rosette sampler
will then be lowered to the bottom at between .5 and 1 meter/second, raised at least 5
meters after contacting the bottom. The operator will wait three minutes to allow the
sampler to drift away from the disturbed area before the B-2 (2 meters up from the
bottom) sample is taken. The Rosette sampler will be lowered to B-2 and the sample
taken.
Additional time intervals of three minutes are allowed to elapse prior to taking the
thermocline sample and the lower epilimnion sample. These intervals provide time for
water equilibration within the Niskins.
The knees of the EBT temperature depth trace will be determined by trisecting the angle
between the epilimnion and mesolimnion temperature traces (upper knee) and the angle
between the mesolimnion and hypolimnion temperature traces (lower knee). The upper
knee is the upper '/a angle intercept, the lower knee is the lower Va angle intercept. The
lower epilimnion sample is one meter above the upper knee. The upper hypolimnion
sample is one meter below the lower knee.
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Field Sampling Using
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2.0 Sequence of Sampling Events
The following is a brief summary of the sampling events. Some events may be done
simultaneously and event order will be subject to conditions.
2.1 Visual and Physical Station Observations
Air temperature, wind speed, aesthetics, wind direction, depth, and wave height.
2.2 Rosette Sampling
Run Rosette/CTD down to define the temperature profile and determine the thermocline
location during stratified situations. Examine the CTD profile. Select sampling depths
according to depth selection. Trigger sample bottle at correct depths, while verifying the
temperature profile Split Rosette Niskin samples into the required sample
bottles/preservatives. A composite 20 m sample is taken for phytoplankton, chlorophyll a,
pheophytin, and, when appropriate, primary productivity, by compositing Niskin samples
at 1, 5, 10 and 20 meters.
3.0 Sample Integrity
Concentrations of chemicals in lake water are very dilute. A small amount of sample
contamination can have a large effect on the results. Avoiding contamination is, therefore,
a major quality control goal. Each Niskin sampling bottle shall be emptied into the sample
bottles as soon as possible. All chemistry sample bottles shall be rinsed once with sample
before filling. New 1 g polyethylene containers (PEC) will be used to hold the sample for
the on board analyses and preparations.
One gallon polyethylene containers filled directly from Niskin sampling bottles are used
for nutrients, pH, specific conductance, alkalinity and turbidity analyses. Samples for
analysis of dissolved nutrients are taken from the 1 g containeis and filtered into new
125 mL sample bottles.
Samples for chlorophyll a analysis are collected directly from Niskin sampling bottles into
300 mL brown polyethylene sampling bottles. Water to be used for primary productivity
analysis taken directly from Niskin sampling bottles into 960 mL polyethylene bottles.
These samples are composited into brown, 4 L polyethylene bottles.
To reduce contamination from atmospheric dust, empty bottles will be capped during
preparation for sampling. Care should also be taken in the storage of bottles to reduce
exposure to "dirty" environmental conditions. During sampling, each bottle is rinsed with
sample water, emptied, and filled with sample water. The cap is replaced after addition of
the preservative, or immediately on samples that require no preservative. Transfer of the
samples from one container to another or manipulations of the sample are avoided as
much as possible since each such action can result in contamination.
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Field Sampling Using
Volume 1, Chapter 2 the Rosette Sampler
To reduce contamination and to control the volume of the preservatives, automatic pipettes
or dispensers are used to dispense all preservatives. Prevention of inadvertent use of the
wrong preservative is accomplished by the use of the same color tag on the sample bottle
and preservative dispenser. Dissolved oxygen samples are "set up" immediately. This
involves filling the bottle to overflowing, allowing overflowing to continue five seconds
before adding, in series, the first two reagents, allowing the floe to settle, mixing and
allowing floe to settle again. D.O. samples are then completed in the main laboratory.
4.0 Nutrient Sample Filtration
A number of samples must be filtered, after sample splitting. The following are brief
summaries. Dissolved nutrient samples will be prepared by vacuum filtration (<7 psi) of
an aliquot from the PEC for onboard analyses within an hour of sample collection. A
47 mm diameter 0.45 urn membrane filter (Sartorius) held in a polycarbonate filter holder
(Gelman magnetic) with a polypropylene filter flask prewashed with 100 to 200 mL of
demineralized water or sample water will be used. New 125 mL polyethylene sample
bottles with linerless closures will be rinsed once with filtered sample prior to filling.
5.0 Instructions for Use of Sea Bird 9/11 + and Rosette for
Collection of Water Samples and Cast Information
The SeaBird 9/11 + is built to provide real time information on a number of water quality
parameters as it moves through the water. The software used to run the instrument and
collect data (Seasave) has been configured for generalized sampling conditions.
Depending on the depth and expected values of the parameters, the configuration will
likely require modifications.
The Dolch computer in the Rosette control room is loaded with the software to run the
SeaBird 9/11+. After turning on the computer, go to the C:\SEA911 subdirectory. Enter
the Seasave program by typing Seasave. The first screen that you see will give you
choices on whether to Acquire Real Time Data or to Display Archived Data. Highlight
the "Acquire..." option and press . The next screen will require verification that
the data will be written to disk, as well as the entry of a file name for the data to be
acquired. After these are entered, highlight the "XY parameters to be plotted" and make
sure that the ranges for depth, temp, etc. are appropriate for the station. After making any
necessary changes, you exit from this screen by pressing . At this point (or before)
turn on the SeaBird deck unit. Press to begin acquiring data. Next you will see a
header information screen. At a minimum, enter the station number. You may enter the
position (latitude & longitude) information and any notes that you have about the station.
After exiting this screen (by following the instructions on the screen), the program will
delay slightly to initialize the rosette, and a graph will be displayed with function key
menus on the top and bottom of the graph.
Remove the FAR sensor cover, remove the butler bottle from the pH probe, and remme
the Tygon tubing (GENTLY!) from the temperature probe. Deploy the SeaBird Rosette
Keep the Rosette |iist under the surface ot the water tor one minute, then turn on the pump
by entering Wait another minute and then begin the cast. If the altimeter is
working, stop the Rosette 1-2 meters off the bottom. If it is not working, let the Rosette
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Field Sampling Using
the Rosette Sampler Volume 1, Chapter 2
touch bottom, then raise it to 5 meters off the bottom. Determine the sample depths and
mark them on a data sheet. If the deepest sample will be below 5 meters off the bottom,
wait two minutes before taking the sample. Otherwise begin sampling as the Rosette is
raised. Bottles are fired by entering . A number will appear in the upper
right hand of the screen when the bottle has fired. Continue taking samples until the
Rosette reaches the surface. Take the surface sample, if required, then turn off the pump
by entering . Exit the Seasave program by entering , and turn
off the deck unit. Bring the Rosette onto the deck. Cover the PAR sensor, return the
buffer bottle to the pH probe, return the Tygon tubing to the end of the temperature probe,
and fill this with deionized water.
Exit completely from the Seasave program, until you see the C:\SEA9l I prompt. Place a
formatted disk in the A: drive of the Dolch. Enter "castproc filename", where filename is
the file with the freshly gathered data. The data will be processed and copied to the A:
disk. Take this disk into the wet lab and place it in the A: drive of the Compaq LTE Lite.
From the Windows screen select the SeaBird icon, then the Seaplot icon. Once in Seaplot,
make sure the file of interest is the one to be used by the program. Modify the parameter
ranges to coincide with those of the station, and run Seaplot. This will graph the data for
display.
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Volume 1, Chapter 2
Field Sampling Using
the Rosette Sampler
Appendix A. Sample Log
U.S. EPA The R/V LAKE GUARDIAN 19
STATION DATA SHEET - SEABIRD 9/11+ AND ROSETTE
DATE
GMT
LAKE
STATION
QA DEPTH: FIELD DUP(D).
SONAR (BRIDGE) DEPTH _
WEATHER
LATITUDE
LAB SPLIT(C)_
AIR TEMP
SEA STATE
LONGITUDE
SURFACE WATER TEMP.
PERSONNEL: ROSETTE
SECCHIDEPTH
NET
OTHER
Sample
Number
Bottle
Number
Depth Code
Use (S,D,I)
Depth
Profile Code
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Standard Operating Procedure for the
Sampling of Particulate-Phase and
Dissolved-Phase Organic Carbon in
Great Lakes Waters
Grace Analytical Lab
536 South Clark Street
10th Floor
Chicago, IL 60605
August 2, 1994
-------
Standard Operating Procedure for the
Sampling of Particulate-Phase and Dissolved-Phase
Organic Carbon in Great Lakes Waters
1.0 Scope and Application
This Standard Operating Procedure describes the sampling of Great Lakes Waters for particulate-
phase organic carbon (POC) and dissolved-phase organic carbon (DOC). Samples of lake water
are collected and passed through a 0.7 uM pore-size glass fiber filter. POC is operationally defined
as the mass of organic carbon retained on the filter per unit volume of water, and DOC is the
material that passes through the filter.
2.0 Safety and Waste Handling
All applicable safety and waste handling rules are to be followed. These include the proper
labeling and disposal of chemical wastes. Over-board discharges of chemical wastes are forbidden.
Refer to the GLNPO Safety, Health, and Environmental Compliance Manual for specific rules.
3.0 Summary of Procedure
Great Lakes water samples are collected at pre-determined sampling stations and depths via either
a submersible pump or Rosette sampler. The water is then filtered under vacuum through ashed
47 mm diameter glass fiber filters in an all-glass filtration apparatus. The samples are acidified
during the filtration to remove inorganic carbonates. The POC is retained on the filter and frozen
at -10 °C until analysis. The filtrate is collected and promptly analyzed for DOC in a ship-board
laboratory.
4.0 Description of Apparatus
Water samples (typically I-4 liter.; for open-lake locations) are collected from an over-board pump
or Rosette sampler. Ashed glass fiber filters are supported in a commercially-available, all-glass,
350 mL vacuum filtration apparatus. Two filtration apparatuses are attached, side-by-side, to ring
stands. Samples are filtered simultaneously in duplicate. Tygon tubing (3/8" ID) is used to connect
the filtration flasks to an oil-less vacuum pump. The equipment needed are listed in Table I.
5.0 Preparation of Filters and Reagents
5.1 Preparation of Filters
5.1.1 I-iltcr preparation should take place as close to the start of the survey as possible.
5.1.1 Filters are to be handled only with stainless steel forceps. Filters that arc mishandled after
the ashing procedure (5.1.4i should be discarded.
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SOP for the Sampling of Particulate-Phase and
Dissolved-Phase Organic Carbon in Great Lakes Waters Volume 1, Chapter^
5.1.3 47 mm diameter GF/F filters (0.7 uM pore-size) are placed individually in aluminum toil
envelopes, dull side of foil facing inward, with three sides folded closed. The fourth side is
left open to allow gases to escape from the envelope during ashing.
5.1.4 The filters are stacked in a muffle furnace and ashed for four hours at 450 "C.
5.1.5 Upon removal from the muffle furnace, the envelopes are sealed on the fourth side.
5.1.6 Fifty envelopes containing individual filters are placed into a Ziplock bag and the bag is
labeled with the date and initials of the analyst who prepared the filters.
5.2 Preparation of Reagents
A solution of 0.2N HCL is prepared by transferring 17 mL of concentrated HCL (16.1N) to a
1000 mL volumetric flask and diluting to the mark with organic-free, distilled, deionized water
(from now on referred to as organic-free water). Transfer the solution to a 1 L Teflon squeeze
bottle.
6.0 Filtration Procedure
6.1 Using stainless steel forceps, place one 47 mm GF/F filter onto the fitted glass support of the
sampling apparatus. Place the glass funnel on top of the filter and secure with the clamp. Label the
Great Lake name, station number, sampling depth, and date onto the aluminum foil envelope.
6.2 Collect the lake water sub-samples from the submersible pump hose or Rosette sampler. Allow the
overboard pump line to flush for 15-30 minutes. Collect the lake water into a 4 liter Cubitainer or
four, 1 L Teflon bottles. Rinse the container(s) twice with approximately 1 liter of lake water
before collecting the sample. If the lake water is to be collected from the Rosette, rinse the
container(s) with only 200-300 mL of lake water to ensure there is enough remaining to establish a
significant paniculate load on the filter (see section 6.7).
6.3 Measure the volume of lake water to be filtered in a graduated cylinder, or mark four, 1 L Teflon
bottles at the 1 liter level. Prior to filling, rinse the bottles, or cylinder, twice with approximately
100 mL of lake water.
6.4 Connect the \acuum pump to the filtration flask. Pour a measured volume of lake water into the
glass filtration funnel. Turn on the vacuum pump. Maintain the vacuum between 5-10 inches of
Hg during filtration.
6.5 After approximately 300 mL of lake water has been filtered, turn off the vacuum pump Rinse the
200 mL DOC glass sample bottle several tunes with filtrate and collect approximate!} 150 mL of
the filtrate. Label the Great Lake name, station number, sampling depth and date onto the DOC
bottle. Collect the filtrate before step 6.6.
NOTF. Step f> 6 must be done before all the Like water is filtered to ensure that the distribution of
the particles mi the filter is not disturbed
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SOP for the Sampling of Paniculate-Phase and
Volume 1, Chapter 2 Dissolved-Phase Organic Carbon in Great Lakes Waters
6.6 Turn on the vacuum pump, and continue pouring lake water into the funnel until sufficient
material has been collected (see section 6.7). Just before the last portion of the lake water has been
filtered, squirt approximately 5 mL of 0.2N HCL solution into the funnel.
6.7 The volume of lake water required to produce a reliable POC measurement (i.e., an amount of
material that is within the analytical instrument's linear range) will vary with lake station location,
depth, and time of year. For open-lake, oligotrophic conditions, typically 2-4 liters will provide
enough material. For near-shore locations, or meso-eutrophic and eutrophic conditions, lake water
volumes in the range of 200-500 mL are typical. A filter that becomes visibly loaded with particles
and a flow of water through the filter that drops significantly are evidence that sufficient
paniculate material has been collected.
6.8 After the lake water has been filtered, rinse the sides of the funnel with approximately 20 mL of
organic-free water and filter this rinse. Turn off the vacuum pump.
6.9 Remove the funnel. Using stainless steel forceps, fold the filter in half and place back it into the
labeled aluminum foil envelope. Place groups of foil envelopes in a labeled Ziplock bag and store
at -10 "C. Record the Great Lake name, station number, sampling depth, volume filtered, analyst,
date, and time of day on the POC/DOC Sampling Log Sheet.
6.10 Empty the remaining filtrate from the filtration flask.
6.11 Rinse the filtration funnel, fitted glass support, filtration flask, and the container(s) with organic-
free water.
6.12 Re-assemble the filtration apparatus.
6.13 Place aluminum foil covers over the filtration funnels.
7.0 Quality Control
7.1 A duplicate sample will be filtered in parallel at least once during the sampling of each Great
Lake.
7.2 A POC/DOC matrix blank will be collected, in duplicate, at the beginning of each survey of the
Great Lakes, and at least once during the sampling of each Great Lake. A TSS matrix blank is
collected by filtering 1 liter of organic-free water. A DOC matrix blank consists of the filtrate from
a POC matrix blank. The matrix blanks are processed identically to Great Lakes water samples.
7.3 A POC field blank will be collected, in duplicate, at the beginning of each survey of the Great
Lakes, and at least once during the sampling of each Great Lake. A POC field blank is prepared by
taking a filter out of the foil envelope, placing it onto the fitted glass support of a clean filtration
apparatus, wetting the filter with organic-free water and assembling the filtration apparatus The
apparatus is disassembled, and the filter is removed and processed in the same manner as a sample.
There is no field blank for DOC.
7.4 Two trip blanks for POC will be processed alter the sur\e\ has ended. This is done b\ placing two
filters in their unopened foil envelopes into the /iplock hag and processing these filters like
samples There is no DOC trip blank.
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SOP for the Sampling of Particulate-Phase and
Dissolved-Phase Organic Carbon in Great Lakes Waters Volume 1, Chapter 2
7.5 DOC samples are analyzed promptly, in a ship-board laboratory, during the course of a survey.
7.6 Because POC/DOC are parameters which are ancillary to the determination of hydrophobic
organic contaminants (HOCs), the POC/DOC samples during an organics survey are taken
simultaneous to the HOC samples. Therefore when a HOC matrix blank, field blank or duplicate
sample is collected, a POC/DOC matrix blank, field blank or duplicate sample will also be
collected.
Table 1: List of Filtration Equipment
Quantity Equipment Source or Equivalent
2 Oil-less Vacuum Pump Schuco 5711-130
6 Teflon wash bottle Cole-Parmer N-06052-60
2 350 ml, all-glass Filtration apparatus Nucleopore
2 Stainless Steel Forceps
2 Support/ring stand for filtration apparatus
Miscellaneous (some quantities depend on number of samples)
- 47 mm GF/F filters (0.7 uM pore-size) Whatman 1825-47
Cubitainers
Tygon tubing (3/8"ID)
- 200 ml glass bottles for DOC
- permanent markers
Ziplock freezer bags
Aluminum foil
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Standard Operating Procedure for
Chlorophyll-a Sampling Method:
Field Procedure
Grace Analytical Lab
536 South Clark Street
10th Floor
Chicago, IL 60605
-------
Standard Operating Procedure for
Chlorophyll-a Sampling Method:
Field Procedure
1.0 Scope and Application
This method is used to filter chlorophyll-^ samples from the Great Lakes and Tributary streams.
2.0 Summary of Method
A representative lake water sample is collected from Niskin bottles from various depths and
filtered by vacuum filtration in dim light. The filter is then placed in a screw cap culture tube in
the dark. The tube is stored in the dark at sub-freezing temperatures and shipped to the laboratory
for extraction and analysis.
3.0 Apparatus
Plastic filter funnel, Gelman
Vacuum system (3-4 psi)
GF/F filters, Whatman (47 mm)
16 X 100 mm screw cap culture tubes
Pasteur short disposable pipets
Rubber bulb
Plastic wash bottle, 500 mL
Plastic wash bottle, 500 mL, for MgCO,
Filter forceps
Opaque sample bottles, 500 mL (Nalgene or equivalent)
4.0 Reagents
Saturated Magnesium Carbonate Solution Add 10 grams magnesium carbonate to 1000 mL of
deionized water. The solution is settled for a minimum of 48 hours. Decant the clear solution into
a new container for subsequent use. Only the clear "powder free'' solution is used during
subsequent steps.
5.0 Sample Handling and Preservation
The entire procedure should be carried out as much as is possible in subdued light (green) to
prevent photodecomposition. The frozen samples should also be protected from light during
storage for the same reason. During the filtration process, the samples are treated with MgCO,
solution (section 4.1) to eliminate acid induced transformation of chlorophyll to it's degradation
product, pheophytin. Samples are stored by station in aluminum foil and transported to a land-
based laboratory in a cooler \\ith dry ice. Analysis should he performed as soon as possible
following sampling.
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SOP for Chlorophyll-a
Sampling Method: Field Procedure Volume 1, Chapter 2
6.0 Field Procedure
6.1 Samples are provided in 500 mL opaque Nalgene bottles, labeled with the sample depth, eg,
Surface, representing a surface sample, MI, representing the mid depth sample, or B-2,
representing a bottom minus 2 meter sample.
6.2 Place filters, using forceps, textured side up. Assemble the filtration apparatus just prior to
filtration.
6.3 Due to differing trophic levels among the Great Lakes, the volume of water filtered varies. For
Lake Erie, 150 mLs of sample will be filtered. For Lakes Ontario, Huron, Michigan, and Superior,
250 mLs of sample will be filtered. After inverting the sample bottle several times to create a
uniform mixture, carefully measure out the appropriate amount of sample using a graduated
cylinder and pour contents into filtration funnel.
6.4 Turn on vacuum pressure on, not exceeding 3 psi.
Check Frequenth During Filtration to Insure Pressure Does Not Go Above 3 PSI!!!
6.5 When approximately 10-50 mL of sample remains on the filter, add 10 drops of the MgCO,
(section 4.1) solution using a disposable pipet. Thoroughly rinse the filter apparatus and graduated
cylinder, using a squirt bottle, with deionized water. Turn off vacuum pressure as soon as the
liquid disappears to prevent the breakage of cells.
6.6 Using the forceps, fold and remove the filter and carefully place it into the bottom portion of the
prelabeled culture tube (see section 10) and close tightly. Lay all tubes flat and completely wrap in
aluminum foil. Clearly label the Lake, station and date on masking tape and attach to above
mentioned aluminum foil package. Immediately freeze. All the above procedures should be
completed in subdued light.
7.0 Quality Control
The following controls are to be collected:
Control Frequency
Lab Dupl. Once/batch
Field Dupl. Once/batch
Field Blk. Once/batch
Field blanks (Field Blk) consist of water obtained from reverse osmosis and are filtered in the
same method as described in the Procedure section. A laboratory duplicate (Lab Dupl.) results
when a water sample, from the same sampling bottle, is filtered twice. A field duplicate (Field
Dupl.). although sampled from the same depth, is contained in a separate bottle, marked "Fid
Dup"
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SOP for Chlorophyll-a
Volume 1, Chapter 2 Sampling Method: Field Procedure
8.0 Waste Disposal
Follow all laboratory waste disposal guidelines regarding the disposal of MgCO3 solutions.
9.0 Shipping
Once a lake has been completely sampled for chlorophyll or a batch of 35 samples has been
completed, wrap all samples into one complete batch and clearly label with survey, lake and date.
Pack tightly in a medium sized cooler and fill all spaces with enough dry ice to last 24 hours. Dry
ice is considered a hazardous chemical by most shipping companies and has to be accompanied by
authorizing paperwork. Once receipt at CRL, the samples should be immediately placed in the
freezer.
10.0 Labeling
Sample identification information is provided on printed labels both prior to and during the survey.
The labels are affixed to the side of the 16x100mm chlorophyll tube. The sample identification
number is covered with clear tape in case the tube becomes wet.
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Standard Operating Procedure for
Primary Productivity Using 14C:
Field Procedure
Grace Analytical Lab
536 South Clark Street
10th Floor
Chicago, IL 60605
April 13,1994
-------
Standard Operating Procedure for
Primary Productivity Using 14C: Field Procedure
1.0 Scope and Application
This method is used to determine primary productivity and primary productivity parameters from
Great Lakes waters.
2.0 Summary of Method
Samples of water, for which the productivity parameters are to be determined, are inoculated with
a known quantity of bicarbonate substrate which is labeled with the radiotracer UC. Samples are
incubated at various light intensities for two to four hours, after which the algal cells are separated
from the water by filtration. Because the measured radioactivity of each filter will be proportional
to the quantity of carbon fixed by the algae into organic material, the radioactivity of the filter
containing the algal cells is determined by liquid scintillation counting. Calculation of the
productivity parameter also require information about the total inorganic carbon available in the
incubation vessel, the length of time of incubation, the chlorophyll content of the incubated sample
and specific activity of the radiotracer.
3.0 Safety and Waste Handling
3.1 Safety
3.1.1 I4C is classified as a low-level beta emitter. Wearing personnel protective laboratory gear
(rubber apron, protective gloves and glasses) at all times when using with I4C and in the
primary productivity lab, can effectively prevent any exposure.
3.1.2 All spills of radioactive or suspected radioactive materials must be immediately reported
to the person in charge of radiation safety and decontaminated immediately.
3.1.3 All radioactive samples and standards should be properly labeled with the isotope and
activity indicated and properly stored in designated locations.
3.1.4 Use only labeled radioactive items, e.g. glassware, forceps, filtration apparatus. If
returned to general use, all equipment must be properly decontaminated.
3.1.5 Use spill trays lined with absorbent paper for all analyses involving 14C.
3.1.6 Since UC is an inhalation hazard, all innoculations need to he performed under a
functional hood.
3.1.7 Under the Atomic Energy Act of 1954, a license is required designating the radioactive
source, its use as applicable to the laboratories and conditions by which the licensed
material should be used The current license (#12-10243-01 ) expires on December 31.
2000.
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SOP for Primary Productivity
Using 14C: Field Procedure Volume 1, Chapter 2
3.2 Waste Handling
3.2.1 Liquid wastes cannot be poured down the drain in any circumstances. All radioactive
liquid waste is contained within 5 gallon cubitainers, and when full, are wrapped up in
heavy radioactive waste bags. The following information is clearly marked on the outside
using radioactive waste placards: type of radioactive waste, approximate activity
(millicuries) and waste volume.
3.2.2 To estimate activity for a complete label, keep accurate records as to the volume contained
within each cubie. Multiply the number of milliliters by 0.0167 (assuming the BOD
bottles contain 300 mL and the specific activity of 1 mL of I4C is 5|_iCi: 5^Ci/300 =
0.0167uCi/mL) to obtain an estimation of the activity in microcuries.
3.2.3 From each waste cubie take a 1.0 mL sample and put into a liquid scintillation vial. Add
20 mL of Ecoscint. Add 1 mL of phenylethylamine. Clearly label cap to match that of the
cubie sampled. Put this vial with sample vials to be analyzed for actual activity at CRL.
3.2.4 The disposal of solid wastes and contaminated articles should be into designated
containers and, under no circumstances, into ordinary trash receptacles.
4.0 Apparatus
Two Darkened carboys
Two large insulated coolers
Pipettor (MLA equivalent), 1.0 mL with disposable tip
Pipettor (MLA equivalent), 0.5 mL with disposable tip
Pipettor (MLA equivalent), 0.3 mL with disposable tip
100 mL graduated cylinder
Two incubators capable of achieving temperatures from 0-20°C
Cool white fluorescent lights, six per incubator (General Electric F24T12CWHO 800)
Filtration units, for 47um, 0.45 diameter filters
Forceps
300 mL BOD bottles
Vacuum system with pressure regulator and waste container system
Brinkman Repippetor with 20 mL capacity
Shallow tray, smooth, non-absorbent surface
Irradiance meter with a remote sensor
Thermometer
Geiger Counter
5.0 Supplies
Liquid scintillation vials, 20 mL capacity
Membrane filters. 47 mm diameter. 0.45 urn pore size Sartorius cellulose acetate
Liquid scintillation cocktail. Hcoscmt brand
HCL 0.5 X
Radiotracer-labeled substrate as N'aH"CO.: working stock solution of
Phenvlethvlamine, CO^-tree
1-208
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SOP for Primary Productivity
Volume 1, Chapter 2 Using "C; Field Procedure
Absorbent bench paper, plastic backed
Decontaminant surfactant, Radiacwash or equivalent
Kimwipes
Paper towels
Pipette tips, Eppendorf large, medium
Masking tape
Waterproof marker
6.0 Sample Collection and Preparation
6.1 Using a Geiger counter, make an initial check of the laboratory to ensure no residual
contamination is present from other assays.
6.2 Using a waterproof marker, numerically label the caps of the scintillation vials.
6.3 Obtain water samples from desired depths using a non-metallic water sampler such as Niskin water
bottles. Record the water temperature of the sample using a thermometer.
6.3.1 When lake water temperatures are isothermal, the water sample is a composite or
integrated sample, resulting in one set of incubated bottles.
6.3.2 When thermal stratification of lake water occurs in summer, samples are collected from
both the hypolimnion and epilimnion. Representative hypolimnion samples are obtained
from the M-3 depth. The epilimnion samples are designated from the integrated
subsamples. The temperatures used for incubation (to 0.1 °C) should be the temperature
determined from the M-3 and integrated samples.
6.4 Transfer the water sample from the collection bottle to a 4 L plastic, darkened bottle, marked
"sample", taking care to avoid agitation or bubbles that could disrupt cells. A wash bottle labeled
"wash" is also filled with any water left over in the rosette.
6.5 Immediately place the darkened bottle into a light-tight, insulated container to maintain constant
temperature during transport to the on-board ship laboratory. During the summer, add freezer
packs or ice to maintain the hypolimnion temperature.
6.6 Record the following information into field notebook; station number, depth, pH, alkalinity,
temperature, date, sampling time and analyst identification.
7.0 Instrument Set-Up Procedure
7.1 Before introducing samples to the incubator, adjust the temperature control to that of the water
from which the samples were taken. Confirm temperature setting with thermometer to the nearest
o.rc.
7.2 Before introducing samples for the first time into the incubator, determine the appropriate
locations for two sets of incubation bottles at each of at least five light le\els. Each shelf should
allow approximately half the light through as the one above it, e.g 300. I 50. 75. 37. and
I 7 uE VI :sec ' Perform this procedure with all other bottles in place and filled with water. Mark
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SOP for Primary Productivity
Using "C: Field Procedure Volume 1, Chapter 2
on the shelf using tape where the bottles should be placed during subsequent incubation. Use grey
screening material (e.g., window screen material commonly found in hardware stores) between
shelves or bottles if needed to adjust irradiance to those suggested above.
8.0 Analytical Procedures
8.1 Field Operations
8.1.1 Sample collection and initial preparation, see Section 6.0.
8.1.2 In the laboratory, record in the logbook the following data: bottle number, station, depth.
date, sampling time.
**All of the Following Procedures Should Be Performed in Green Light**
8.1.3 If possible, each darkened carboy (both rinse and sample water) should be filled to the top
with lake water, about 4 L.
8.1.4 In the summer begin with the hypolimnion sample (see Section 6.3.2) first to avoid excess
sample warming. Gently mix the water by inversion or rolling. Rinse each incubation
bottle with sample lake water and empty into sink.
8.1.5 Place all incubation bottles onto absorbent paper-lined tray and carefully fill each of the
12 incubation bottles with sample water keeping agitation and bubbling to a minimum.
Make sure to minimize the air space by filling the bottles up to the top with sample water.
Cap each bottle using glass stopper and tilt bottle to remove excess water.
8.1.6 Remove 1.0 mL of NaH'4CO3 stock solution using a pipettor. Remove the sample bottle
stopper and gently inject the stock solution into the bottom half of the bottle. Immediately
replace stopper and put a plastic cap over the top of the stopper to eliminate leakage. Only
put a plastic cap over those sample bottles which ha\e been inoculated!
8.1.7 Using a new pipette tip for each inoculation, repeat Step 8.1.6 until all 12 bottles hav
been inoculated. Discard the remaining 1 mL of stock solution into the liquid waste cubie
and dispose of the empty vial in the solid waste receptacle.
8.1.8 Place each sample bottle on tape-marked areas (see Section 7.2) in the incubator. Use a
spherical irradiance sensor, and measure the light intensity at each bottle location with all
other bottles in place. Record readings into logbook.
8.1.9 Incubate the samples for two hours, recording the incubation starting time into the
logbook. If conditions dictate, the incubation period can persist for up to four hours.
However, to maintain consistency, attempt to keep the incubation period as close to two
hours as possible
8.1.10 Remove the top two bottles receiving the highest light intensity (top shelf, nearest the
lights). Record the Time when the samples were removed and incubator temperature into
the losbook.
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SOP for Primary Productivity
Volume 1, Chapter 2 Using "C; Field Procedure
8.1.11 After gently mixing the sample by inversion, remove the cap, measure 100 mL in a
graduated cylinder and filter through 47 mm Sartorius 45 urn pore cellulose acetate filter
under 8 PSI (equal to 2.3 inches in mercury) vacuum. Sample volume to be filtered may
be adjusted to conditions, i.e. reduce volume if high density of algae causes clogging of
the filter.
8.1.12 Rinse the filter funnel thoroughly with distilled water.
8.1.13 Remove the filter from the funnel base by grasping the edge with forceps and rolling it
into a loose cylinder, algae side inward. Set into a clean liquid scintillation vial and
loosely cap.
8.1.14 Repeat Steps 8.1.10 through 8.1.13 until a sample from each incubation bottle has been
filtered.
8.1.15 From one of the incubation bottles exposed to one of the three highest irradiances, filter a
second duplicate sample. Record the bottle number of the sample and the duplicate onto
the logbook.
8.1.16 Filter 100 mL deionized water through a filter and place it into a clean liquid scintillation
vial to serve as a blank.
8.1.17 Into each liquid scintillation vial that contains a filter, inject 0.3 mL of 0.5 N HCL into the
bottom. Loosely cap, and let sit for at least one hour.
8.1.18 After one hour, add 20 mL of liquid scintillation cocktail, Ecoscint brand or equivalent,
into each vial that has received the acid treatment.
8.1.19 Cap each vial and gently shake it until all of the filter has been covered with cocktail and
has sunk to the bottom of the vial.
8.1.20 Into two clean liquid scintillation vials, add 20 mL liquid scintillation cocktail plus I mL
phenoethylamine (a CO, absorber).
8.1.21 Choose, at random, two incubation vessels and transfer 1.0 mL of each into a
corresponding vial containing the cocktail and phenolethylamine (Section 8.1.20). These
subsamples will be used to confirm the actual specific activity of the isotope in the
incubation vessels. Record the bottle numbers into the logbook.
8.1.22 Make sure each vial cap is rightly secured and properly labeled. Store the vials for
transport to CRL for scintillation counting.
8.2 Clean-up Procedures
8.2.1 Dispose of remaining sample in the sample bottles m the liquid waste cubic.
8.2.2 Soak incubation bottles m decontaminant surfactant tor at least one hour. Rinse at least
three times \\ith tap water, until nh\oliitcl\ no sm/s i;-i>uitn. Using deionized water, rinse
all bottles a final tune and allow to air drv.
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SOP for Primary Productivity
Using "*C: Field Procedure Volume 1, Chapter 2
8.2.3 As needed, or once per day, wipe working areas with decontaminant wash. Wipe dry with
paper towels.
8.2.4 Change absorbent bench paper if it becomes contaminated or ineffective because spills.
8.2.5 Dispose of potentially radioactive solid waste in specified receptacle.
8.2.6 At the end of the survey, after the lab has been completely cleaned, use filters moistened
with distilled water to wipe 4 inch smears of all working surfaces. Put into a clean
scintillation vial with 20 mL of Ecoscint and I mL of phenethylamine. Label cap with
smear number and record location information into the logbook.
8.2.7 All solid and liquid waste is required to be labeled with estimated activity, volume and
radioactive source. Prepare for transport to CRL by putting parafilm around the lid and
covering liquid waste containers in radioactive waste bags. Tape solid waste boxes
completely shut. The waste activity must be clearly seen from the outside of transport
material and be accompanied by a Bill of Lading and a IJC .waste form (see Appendix I).
9.0 Quality Control
Although a blank, duplicate and two total activity samples are completed for each depth, there is
no on board analysis capabilities for reanalysis.
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Waslc is jirtt|xrly packugcJ mlJ IjbclcJ for lrjnii|Mil1:
Received il CRL in good onulilnm unJ pUccJ in Huz wisle room
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M}tlK
-------
USGS Field Operation Plan:
Tributary Monitoring
USGS/Steve Eisenreich
Department of Environmental Sciences
Rutgers University
P.O. Box 231
New Brunswick, NJ 08903
December 1993
Version 2.0
-------
USGS Field Operation Plan:
Tributary Monitoring
Samples for organic analyses will consist of a composite sample obtained using USGS quarter-point
sampling procedures. The stream will be visually divided into three equal flow areas using field data
obtained during discharge calibration measurements. At the center of each flow area, water samples will
be obtained at 0.2 and 0.8 times the depth. Water samples from each of the six sampling locations will be
composited. Water for PCB, PAH, pesticide, and Atrazine analyses will be pumped by a submersible
pump through a tee in the pump line. A peristaltic pump will draw water from the tee and pump water
through the 293 mm, stainless steel, pentaplate filter holder. Two to five glass fiber filters will be used
depending on the concentration of suspended material in the water column. The backpressure from the
filter head shall not exceed 5 psi. Residual water will be evacuated from the filter head using the
peristaltic pump. Filters from the pentaplate filter holders will be folded in quarters and wrapped in clean,
acetone rinsed aluminum foil. The filtrate will be collected in clean, acetone-rinsed, 20 liter glass carboys.
The filtrate will be processed through a large, 250 gram, XAD-2 resin column, at a flow rate between 500
and 1000 mL per minute. Water for DOC, POC, and conventional constituents will be obtained from an
overflow line attached to the tee from the submersible pump tubing and composited from each of the six
sampling locations into a polyethylene chum splitter. The churn splitter provides for efficient subsampling
of the composite sample to provide the necessary samples required by the Wisconsin State Lab of Hygiene.
Preprinted, site-specific, laboratory request forms will have the date, time, and sequential sample number
recorded for each sample. Filters, resin columns, and sample bottles will have an adhesive label attached
which will identify the site, sample number, date and time of sampling. Processed samples will be kept in
a chilled ice chest until refrigerated at the USGS. Samples and laboratory request forms will be delivered
to the WSLH, chilled, in plastic coolers, by either the USGS or Federal Express. The WSLH will log the
receipt of the samples into its Laboratory Information Management System (LIMS) database and sign the
chain of custody on the laboratory request form.
The constituent list for which a contract laboratory will perform analyses is as follows:
Constituent Field Requirement
Total Phosphorus
Total Kjeldhal Nitrogen
Total Ammonia Nitrogen
Nitrate Nitrogen
Dissolved Reactive Phosphorus
Dissolved Chloride
Dissolved Silica
250 mL nutrient bottle preserved with sulfuric
acid to pH <2.0
60 mL, filtered/.45 urn membrane, chilled
60 mL, filtered/.45 urn membrane, chilled
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USGS Field Operation Plan: Tributary Monitoring
Volume 1, Chapter 2
Constituent Field Requirement (con't)
Total Alkalinity
Total Suspended Solids
Volatile Suspended Solids
Conductivity
pH
710 mL, no preservative chilled
Dissolved!!!!!
Dissolved Calcium
Dissolved Sodium
Dissolved Potassium
Hardness as CaCO,
125 mL filtered/0.45 u membrane filter in
(250 mL) nutrient bottle (unacidified) (write "ff'
on bottle cap)
Chlorophyll-a
200 to 1000 mL, filtered using 5.0 |jm glass fiber
filter retained in glass vial and chilled
Dissolved Organic Carbon
Total Organic Carbon
25 to 50 mL filtered until filter clogs.
Use syringe.
A variety of field parameters will be measured during the actual sample collection. A Hydrolab
multiparameter meter will be used to measure temperature, conductivity, dissolved oxygen, and pH.
A light extinction measurement will be made using standard Secchi disc equipment and techniques.
Velocity and direction of flow will be recorded at each of the subsampling locations.
Field Operation
The procedure to be followed while obtaining water samples and field parameters will be as follows:
1. At each of the proposed sampling locations a cross section of the stream will be measured. The
data will be used to subdivide the cross section into three approximately equal flow cells. The
centroid of each of these cells will be identified on the field map.
2. The field crews will use visual reference points to position themselves on station during each
sampling trip.
3. At each of the cell centroids water samples and Hydrolab parameters will be obtained at 0.2 and
0.8 times the total depth. Samples are to be taken during periods of downstream flow with the
additional limitation that downstream flow must be established for a least l/i hour prior to sample
initiation. Data from the AVM gaging stations or field determinations of velocity will be used to
determine the proper sampling periods.
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Volume 1, Chapter 2 USGS Field Operation Plan: Tributary Monitoring
4. Water samples from each of the six centroid sampling locations will be composited in order to
reduce analytical costs. Therefore the field crew will obtain 1/6 of the total required volume for
organic and inorganic analyses at each of the subsampling locations. The flow rate through the
293 mm organics filter will be monitored to maintain an effective subsampling of the cross section.
The 293 mm filters will be retained for paniculate PCB analyses. The filtered sample will be
stored in a 20 L glass carboys and transported to shore for soluble PCB extraction. Water samples
for inorganic analyses will be taken from a tee in tubing between the peristaltic pump and the
293 mm filter holder. A 47 mm stainless steel filter holder will be used for dissolved inorganic
constituent sample collection. The filtrate will be processed through a large, 250 g, XAD-2 resin
column, at a flow rate between 500 and 1000 mL per minute.
5. Secchi disk observations will be taken at the cell centroid locations for each cross section.
6. Velocity and flow direction will be recorded at each of the subsampling locations.
7. Preprinted adhesive labels shall be affixed to each sample container which will be delivered to the
analytical laboratory. Sample log forms will be completed and included with the sample
containers. An itemized list will be included with each shipment of samples to the labs. A copy of
the memo should be noted with the date received and returned to the USGS to preserve a chain of
custody for the samples. Samples delivered to contract laboratories which will be hand carried
must have drop-off date and time recorded in the Sample Log.
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Trace Metal and Mercury Sampling Methods
for Lake Michigan Tributaries
Martin Shafer
Water Chemistry Program
University of Wisconsin-Madison
April 1994
Revision 2
-------
Trace Metal and Mercury Sampling Methods for
Lake Michigan Tributaries
1.0 Bottle Labeling and Supply Sorting
Prior to boat deployment, all sample bottles must be selected, labeled, and sorted into a cooler for
easy access during sampling. Consult the master sampling plan, and/or specific instructions for a
given sampling trip to determine what samples should be obtained. Remove the requisite number
of Teflon Sampling Bottles from each of the Trace Metal and Mercury Bottle storage containers.
With a black Sharpie label the outer bag with the site code, date, and type of sample (unfiltered,
filtered, replicate, blank, spike, etc.). Record this same information on the Field Data Sheet, which
is to be consulted during the sampling process to prevent mixup of sample bottles and bags. A
sample bottle label can be affixed to the outer bag after sampling is completed. Remove a
1000 mL poly bottle from the storage bag and using a black Sharpie label it as a SPM/DOC Trace
Metal Composite, and with site code.
The following sampling supplies should also be placed into the cooler for transport:
1. Calyx Filters
2. Pump Head Tubing
3. Trace Metal Acidification Kit
4. Mercury Acidification Supplies (Acid and Vials)
5. Bagged Wrench
The 1 gallon tubing rinse container must be filled % full with 2% HNO, from the 20 L carboy and
then placed into the egg crate for use on the boat.
2.0 Boat Deployment and Anchoring
The Boston Whaler must always be transported with cover intact. Periodically wash cover in a
manual car wash to prevent build-up of contaminants.
The inside surfaces of the Boston Whaler should have been rinsed after completion of previous
sampling (see clean-up), if not, rinse them now before loading and launching.
Position equipment containers into the Boston Whaler in a manner which will minimize
reorganization out on the river. Review equipment checklist to verify that all necessary supplies
have been loaded. Prior to launching, all required (consult sample bottle manifest) sample bottles
should be organized and labeled (see above).
Anchor Boston Whaler at sampling site (above centroid of river) using two anchors, bow and
stern. The bow anchor line is threaded through metal eye and tied-off on port cleat. Transport
anchors, especially bow anchor, in plastic bags. Upon completion of sampling, thoroughly wash
anchors with river water before bringing on-board, and place directK into plastic bags to avoid
muddvmg up the boat.
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3.0 Set-Up
Steps 3.1-3.3 may be performed without clean suits.
3.1 Equipment Organization
Position tubs, and other sampling equipment in appropriate locations in boat.
3.2 Boom Installation
Hook fiberglass cleat adaptor into place on bow cleat. Remove plastic protective bags (place in
bag container) from bow sampling boom and put boom in place by resting in fiberglass cleat
adaptor, hooking straight end under bungie cord, and securing boom in fiberglass cleat by tieing
with an arm-length glove.
3.3 Sampling Platform Pump Installation
Wrap a large PE bag over the starboard gunnels of the boat. Hook the plexiglass sampling
platform over the gunnels on top of the plastic bag. Insert the canopy frame into the sampling
platform. Place a plastic bag over the canopy frame, and secure with split tubing clamps. Attach
power cord to Geo-pump, wrap pump with an arm-length glove, and set into sampling platform.
Run power cord to stern of boat and attach to pump battery.
4.0 Sampling
Clean Suits and Gloves Must Be Worn For All The Following Steps.
4.1 Lowering Tubing Line
Open plastic cartons containing sampling line and kevlar support rope. Tie kevlar rope to loop of
Teflon string attached to sampling-line weight. (The end of the rope is two feet above sampling
intake). Slowly and carefully begin removing lower end of sampling line (i.e. Teflon weight end)
from plastic bag (use extreme caution to avoid kinking and contamination), insert weight through
receptacle on end of boom and lower into river to first depth (0.2 x River Depth). Secure kevlar
support rope onto starboard plastic cleat. Keep remainder of sampling line tubing in plastic bag
until pump head tubing is attached.
Note: Rope is marked in one foot increments - beginning six inches from the end. Use the six
inches to tie off to Teflon string. The distance from sampling ports to top of Teflon string is two
feet. A double line is marked every five feet, and a triple line is marked every 10 feet.
To drop the sampling line to the knver depth, the kevlar rope is un-cleated, and both rope and
Teflon sampling line slowly let out to (0.8 x River Depth). It is usually necessary to uncouple
Sampling Line from pump-head tubing before lowering line. Clean-hands uncouples and re-
couples sampling line from pump-head tubing.
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4.2 Geo-Pump Loading and Sample Line Connection
Load pump-head tubing into Geo-Pump using clean protocol. (Gloved dirty hands opens pump
head clamp lever and holds outer bag of pump-head tubing, while gloved clean hands removes
inner bag and loop of tubing. Clean hands inserts closed tubing loop into pump head and dirty
hands closes clamp lever making sure that tubing is properly positioned. Dirty hands makes sure
that Teflon Tubing Adaptor Fitting (TTAF) and plexiglass clamp ring (PCR) are ready. At this
point dirty hands re-gloves, and retrieves open end of sampling line from storage bag, while clean
hands opens pump head tubing loop. Dirty hands gives clean hands sampling line who inserts it
into pump head tubing. Dirty hands collects TTAF bag and opens outer bag, while clean hands
opens inner bag and removes TTAF and tightly inserts it into the long end of the pump head
tubing. The TTAF bags should be kept in the sample transport cooler during sampling (inner bag
is always kept inside dirty outer bag. Dirty hands, with new gloves, collects PCR from storage
bag, removes PCR, and holds it while clean hands inserts TTAF into PCR. Dirty hands then
inserts assembly into groove in sampling platform. The PCR bag should also be kept in the cooler
during sampling to minimize contamination and prevent it from being blown away.
4.3 Sample Collection
Place the appropriate sample bottles into the plastic sample organizing container using the
following protocol. The outer bags should have been previously labeled with site and sample type
information. The outer bags are removed using clean techniques and sample bottles with inner bag
are placed in the organizing container. Dirty hands (with new gloves) retrieves appropriate double
bagged Teflon sample bottle and opens outer bag. Clean hands (with new gloves) pulls inner-bag
out of outer bag and places single-bagged bottles in the organizing container. Outer bags are
stowed in the sample transport cooler, out of the wind.
The typical sampling sequence will be:
[ I ] 250 mL Unfiltered sample for Trace Metals
[2] 500 mL Unfiltered sample for Mercury
[3] 125 mL Unfiltered sample for Methyl Mercury (see Note)
[4] 1000 mL Unfiltered sample for SPM and DOC
[5] 250 mL Filtered sample for Trace Metals
[6] 500 mL Filtered sample for Mercury
[7] 125 mL Filtered sample for Methyl Mercury (see Note)
Filling each bottle 1/2 full.
Note: For Methyl Mercury; Sheboygan, Manistique, Pere Marquette, and Grand rivers only.
This sequence will be repeated at the lower depth (except that filtered samples will be collected
first) to fill the remaining '/z of bottle and then samples are acidified, and double-bagged.
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Trace Metal and Mercury Sampling
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4.3.1 Upper Depth
4.3.1.1 Unfiltered Sample Collection
Dirty hands starts Geo-pump and adjusts to moderately high speed to flush lines
(Verify that water flow is correct, through platform hole, and not splashing sides).
Sampling lines are flushed for a minimum of five minutes before unfiltered
samples are collected.
Sample Bottle Handling: Clean hands (with new gloves) pulls appropriate bottle
out of inner-bag leaving inner-bag in organizing container.
Trace Metal Sample Collection: Teflon bottles are supplied empty and dry.
Clean hands reaches under water stream and partially (Va) fills bottle. The bottle
is loosely capped and gently shaken to rinse. This process is repeated for a total
of three bottle rinses. On the fourth collection the bottle is filled '/2 full. Do Not
Touch Bottle Mouth To TTAF Or Any Other Surface. Clean hands then returns
sample bottle to inner-bag in organizing container. The bags do not have to be
sealed at this point. Dirty hands removes and replaces organizing container lid
during sampling.
Mercury Sample Collection: Teflon bottles are supplied filled with dilute HC1.
Clean hands dumps acid into waste container. Do Not Touch Bottle Mouth To
Waste Container Or Anv Other Surface. Clean hands reaches under water stream
and partially (Ve) fills bottle. The bottle is loosely capped and gently shaken to
rinse. This process is repeated for a total of four bottle rinses. On the fifth
collection the bottle is filled '/2 full. Clean hands then returns sample bottle to
inner-bag in organizing container. The bags do not have to be sealed at this point.
SPM - Carbon Sample Collection: One-Liter polyethylene bottles are supplied
empty and dry. Clean hands reaches under water stream and partially fills bottle.
The bottle is loosely capped and gently shaken to rinse. This process is repeated
for a total of three bottle rinses. On the fourth collection the bottle is filled '/2 full.
Clean hands re-gloves after handling the poly bottle.
4.3.1.2 Filtered Sample Collection
After all unfiltered samples are obtained from the upper depth, dirty hands
reduces pump speed and then shuts off pump. Dirty hands re-gloves, retrieves a
bagged Calex filter, and opens outer bag. Clean hands opens inner bag, removes
filter capsule, opens vents, and drains off storage MQ into river (The filter bags
may be discarded - the filter capsule is a disposable, single-site use, item). Dirty
hands removes PCL/TTAF assembly from sampling platform, and clean hands
uncouples TTAF and screws filter capsule onto TTAF. Clean hands inserts filter
capsule into support on sampling platform. Dirty hands starts Geo-pump and
adjusts to moderate speed to flush capsule (Verify that \\ater flow is correct,
through platform hole, and not splashing sides). The filter capsule is flushed for
five minutes or appro\ ^ 1. before filtered samples are collected. At this point
Filtered Trace Metal samples and Filtered Mercury samples are collected in an
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Volume 1, Chapter 2 Methods for Lake Michigan Tributaries
identical manner to Unfiltered samples as described above. To minimize the
potential for filter clogging, dirty hands shuts off pump after each rinse or sample
has been obtained. Upon completion of Filtered sample collection from the upper
depth, clean hands un-couples Teflon sampling line from pump-head tubing and
dirty hands lowers tubing to 0.8 depth. When at depth, the sample tubing line is
then reattached to the pump-head tubing using the clean technique.
4.3.2 Lower Depth
The collection process is identical to that described above for Upper Depth, except that
obviously Vi full bottles are not rinsed and filtered samples are collected first. The
protocol for flushing and equilibration of sampling line and filter is similar to Upper
Depth, except that here one is flushing the line and filter as a unit. Flushing as a unit for
five minutes should not present a problem except under conditions of very high
suspended solids levels. If during Upper Depth sampling or early stages of Lower Depth
flushing, significant reduction of sample flow rate through the filter is noted, do the
following to minimize filter clogging. Uncouple filter capsule from the TTAF and flush
the sample tubing line for the full five minutes. While tubing is flushing, drain the river
water from the capsule filter. After tubing is flushed, connect to drained filter and flush
filter for 90 seconds. Clean techniques must be followed. Bottles are filled to near
capacity, leaving space for preservation acid. After each sample bottle is filled, and before
re-bagging, preservation acid is added to the sample.
4.4 Acidification
4.4.1 Trace Metal Sample Acidification (250 mL Sample Bottles)
Acid (50% Ultrex HNO3) is supplied pre-measured in small Teflon Vials, one for each
sample. Acid transfer to the sample must be quantitative. Dirty hands (with new gloves)
retrieves the bag containing acid vials and opens it. Clean hands reaches in and removes a
vial. Dirty hands wrenches open the vial while clean hands holds it. Clean hands then
removes vial cap and pours acid into sample bottle which should be available and loosely
capped on work surface. Used acid vials are re-capped and placed into a designated
Zip-bag, to be returned to Water Chemistry Lab along with metal samples. Note the acid
batch number on the field data sheet. The acidified sample is ready to be double-bagged
using clean-hands protocol after the cap is wrenched tight. Clean hands holds bottle
tightly while dirty-hands takes a double-bagged channel-lock pliers to cap. Clean-hands
twists bottle to secure cap. Place new bags on the wrench before use at each site, and
during a sampling period if the bags appear worn.
4.4.1 Mercury Sample Acidification (500 mL Sample Bottles)
Acid (50% HCI) is supplied in a 250 mL double-bagged Teflon bottle. Also supplied is a
Teflon measuring vial into which acid is poured to measure out 10 mL aliquots. Before
starting the acidification process, verify that the samples to be acidified are organized on
the clean work surface, and that their bottle caps are loose. Dirts-hands retrieves acid
bottle and opens outer bag. Clean hands opens inner bag and remmes Teflon acid bottle,
setting it on plastic covered work surface. Dirty-hands retrieves Teflon measuring vial and
opens outer bag. Clean hands opens inner bag and removes xial. Temporarily place acid
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Methods for Lake Michigan Tributaries Volume 1, Chapter 2
and vial bags (inner bag inside outer bag) in the sample organization box. Clean hands
pours acid into the vial up to the etched line and then quickly pours contained volume into
the sample bottle. Do not let acid measuring vial touch lip of sample bottle. Clean-
hands - dirty-hands procedures are then used to wrench shut and double-bag sample
bottles, and to double bag acid bottle and measuring vial.
Do not acidify 125 mL methyl Hg bottles.
Verify that Everything Has Been Recorded and that Bags are Labeled.
5.0 Clean-up
5.1 Tubing-Line and Weight
Upon completion of lower depth sampling, the sampling line and support line are retrieved by
slowly pulling on the Kevlar line (Dirty-hands person) while the clean-hands person coils the
tubing into the storage bag. The sample line tubing should be un-coupled from the pump-tubing
before retrieval so that the river water drains out. Untie the support line and seal in storage box.
The weight and tubing must be flushed with dilute acid to prevent cross-contamination and to
prevent contaminant build-up. A dilute acid solution is supplied in a 1 gallon PE bottle. Before
inserting the tubing weight into the acid bottle, wipe the top outer surfaces of the weight with a
clean-room wiper. Insert the tubing weight into the acid bottle, connect the free end of the
sampling line to the pump-head tubing, and flush at moderate-high pump speed. Pump until all of
the acid solution has flushed through the tubing, and then continue pumping until a majority of the
tubing has been pumped dry (you may have to lift the tubing weight out of the acid jar to ensure
that the tubing pumps dry). Remove the weight from the acid bottle, place in a new plastic bag,
and wipe the top outer surfaces with a new clean room wiper. Recoil the tubing, tie with an arm
length glove, and place in plastic bag. Store in dedicated storage container. Tubing will be
periodically resupplied from the Water Chemistry Lab.
5.2 Sampling Platform
Calex filter is discarded.
Rinse PCL and TTAF with MQ, double-bag using clean techniques, and place in tubing storage
container. (The TTAF fittings should be periodically returned to Madison along with samples for
more rigorous cleaning).
Canopv bag is discarded.
Platform is rinsed with MQ and wiped with clean-room wipers.
Canopy frame and platform are bagged and placed in rubbermaid container.
5.3 Boom
Bagged in two large PE bags.
Fiberglass cleat adaptor is bagged and stored in supplies container.
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Volume 1, Chapter 2 Methods for Lake Michigan Tributaries
5.4 Anchors and Anchor Line
Any sediment on anchors or line is washed off in the river before bringing into the boat. When
anchor is clean, remove from water and place directly into a plastic bag.
5.5 Boat Rinsing
The inside surfaces of the boat must be rinsed with water after sampling is completed. If simple
flushing with water is not sufficient to remove grime, then use the supplied brush to loosen dirt.
6.0 Additional Trace Metal (Non-Hg) QC Procedures
6.1 Trip Bottle Blank
With every batch of bottles a field bottle blank is created. The bottle blank is a 250 mL Teflon
bottle, prepared identically to the sample bottles, except that before double-bagging it is filled with
MQ water in the lab. This bottle travels to the field along with the sample bottles (In the field
keep this bottle in the QC sample container). The bottle blank is to be acidified in the field with
the same pre-measured acid vials as supplied for the samples. Soon after receipt of a batch of
samples bottles, include the associated bottle blank with the set of sample bottles that are taken out
in the boat. Handle the bottle/sample using clean techniques, and acidify in an identical manner as
described for actual samples. Send bottle blank immediately back to Madison along with samples
from that site.
6.2 Analyte Spiking
At a frequency of approximately 10% (see master sampling schedule), duplicate un-filtered and
filtered river water samples, as well as a MQ water blank will be spiked with an acidified solution
of the analytes of concern. The MQ water blank for spike addition (Blank Spike) and spiking
solutions are kept in the QC sample container. The large 6 mL vials are used for the un-filtered
river water, and the small 3 mL vials are used for the filtered river water and MQ blank. These
vials contain sufficient acid to properly stabilize the sample - Do Not Acidify Again with Normal
Acid Vials. The spike addition must be quantitative. The procedure is to simply collect sequential
duplicate un-filtered and filtered samples in the standard 250 mL Teflon bottles using clean
protocols (i.e. fill an additional 250 mL bottle for the un-filtered spike and an additional 250 mL
Teflon bottle for the filtered spike at the same time you are collecting normal filtered and
un-filtered samples. Composite 0.2 and 0.8 us usual). It is important for the duplicate samples to
be as similar as possible These samples along with the Blank Spike MQ bottle are then acidified
in the boat using clean techniques with the spiked acid solution in place of the normal acid. Send
the three spiked samples back to Madison along with other samples from that site.
7.0 Field Blanking Procedure
Field blanking is performed to estimate the level of metal contamination from the sample tubing
line, filter cartridge, and general handling of the sampling apparatus. In addition these blanks are
used as hold diagnostic tools, and to izciicrato method detection limits.
1-229
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Trace Metal and Mercury Sampling
Methods for Lake Michigan Tributaries Volume 1, Chapter 2
The field blank kit consists of the following gear:
1 5000 mL Teflon bottle filled with Milli-Q water.
1 3000 mL Teflon bottle filled with Milli-Q water.
3 250 mL Teflon bottles for trace metal samples.
3 500 mL Teflon bottles for mercury samples.
Short length (3 ft) of Teflon Tubing.
Zip-lock bags for 5 L bottle caps.
Plastic bags.
Blank collection will follow the sequence:
Source Water.
Filter Blank.
Tubing Blank.
Please perform the blanking procedure before beginning normal sampling.
Trace Metal Clean Procedures Must be Followed.
[1] Label three sets (250 mL trace metal, 500 mL mercury) of bottles as follows:
Source Water Filter Blank Tubing Blank
Record bottle numbers and type on field data sheets.
[2] Set up filtration platform as usual. Install a new section of pump head tubing in peri-
pump. Attach TTAF and lock in PCL. Uncouple tubing weight from sample line.
[31 Remove Teflon cap/insert from 5 L bottle, place caps in zip-lock bag. Insert short length
of Teflon tubing into bottle and connect other end to pump head tubing in peri-pump.
Place a plastic bag over 5 L bottle to isolate during blanking procedure.
[4] Flush approx. 500 mL of blank water through pump head tubing. Collect Source Water
samples as per protocol, with appropriate number of rinses. Conserve water! Shut off
peri-pump when not collecting samples or flushing.
[5] Remove Teflon tubing from 5 L bottle and place into 3 L bottle (Rinse MQ). Connect a
filter cartridge to TTAF and lock into holder. Flush approx. 1500 mL of Rinse MQ
through filter cartridge. Place tubing back into 5 L blank water bottle and collect Filter
Blank samples as per protocol.
[6] Remove filter cartridge (save for later use). Uncouple short Teflon line - rebag. Insert one
end of sampling line into 3 L bottle, connect other end to peri-pump. Flush approx.
1 500 mL of Rinse MQ through line. Place sample tubing line into 5 L blank water bottle
and collect Tubing Blank samples as per protocol.
[7] Acidif) samples as per protocol.
1-230
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Trace Metal and Mercury Sampling
Volume 1, Chapter 2 Methods for Lake Michigan Tributaries
[8] Cap 3 L and 5 L bottle. Place samples bottles, 3 and 5 L bottles, short Teflon tubing in
Blank Kit Cooler and return to Water Chemistry in Madison.
[9] Re-couple tubing weight to sample line (Fasten Securely).
8.0 Equipment List
[I] Plastic bow boom packaged in two large PE bags.
[2] Fiberglass boom cleat adaptor.
[3] Rubbermaid carton for plastic bags.
[4] Rubbermaid carton containing plexiglass sampling platform and canopy.
[5] Geo-pump and power cord.
[6] Deep-discharge battery in plexiglass case for running peri-pump.
[7] Rubbermaid container with kevlar support line (50 feet - marked in increments of
one foot).
[8] Rubbermaid container with Teflon san.pling line, Teflon sampling weight.
[9] Plastic container with insert to secure and organize sample bottles.
[10] Sampling Supplies.
a. Teflon sample bottles
b. Pump-head tubing (Double-bagged)
c. Teflon fitting for end of sampling line (TTAF)
d. Plexiglass clamp ring (PCR)
e. Calex Filter capsules
f. Acidification supplies
g. Double-bagged channel-locks
h. Arm-length gloves
i. Wrist-length gloves
[I I] Dilute acid solution in 1 gallon container.
Electric Motor
Motor Battery
Oars
Two Plastic Coated Anchors with poly- line
1-231
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Trace Metal and Mercury Sampling
Methods for Lake Michigan Tributaries
Volume 1, Chapter 2
Trace Metal Field Quality Assurance Plan Summary - 1994 and 1995
Sample Type
Field
Replicates
Analyte Spike
Sample Matrix
Analyte Spike
Blank Matrix
Field
Bottle Blank
Filter Blank
Tubing Blank
Lab
Bottle Blank
QAPjP
Frequency
1 5-20%
10%
5%
5%
2.5%
2.5%
5%
1994 Accomp.
25 (13.7%) U
21 (11.5%)F
18(9.8%)U
18 (9.8%) F
21 (4.7%)
23(5.1%)
5(1.1%)
5(1.1%)
28(6.2%)
1995
Goal
15%U
15%F
10%U
10%F
2.5%
5%
2%
2%
5%
1995 #
Samples
40 U
40 F
27 U
27 F
15
30
12
12
30
Comments
one every other
bottle batch (20)
one every bottle
batch (20)
four per team
four per team
one every bottle
batch (20)
Replicate and spike percentages given as a percent of site visits (183 in 1994).
Blank percentages are expressed as a percent of non-blank samples (449 in 1994).
1995 QA samples based on 271 site visits (Jan- Nov) and 596 non-blank samples.
Trace Metal Field Quality Assurance Plan Summary - 1995
Site
Manistique
Menommee
Fox
Sheboygan
Milwaukee
Grand Cal.
St. Joseph
Kalamazoo
Grand
Muskeeon
P Marquette
V
Replicates
Spring
Runoff
1
1
1
1
1
1
1
1
1
1
1
1 1
Summer
Event
0
2
i
T
1
0
1
i
i
0
0
13
Baseflow
1
1
1
2
t
1
2
i
i
1
1
15
£
2
4
4
5
5
->
4
5
S
T
->
40
Spikes
Spring
Runoff
1
1
1
1
1
1
1
1
1
1
1
1 1
Summer
Event
0
0
1
0
1
0
1
1
1
0
0
5
Baseflow
1
1
1
1
1
1
1
1
1
1
1
11
I
->
->
3
i
-i
/i
->
3
3
3
-)
->
-17
Large
Me-Hg
Bottle
Site Count
1-232
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Volume 1, Chapter 2
Trace Metal and Mercury Sampling
Methods for Lake Michigan Tributaries
I. Replicates and Spikes are obtained from both Unfiltered and Filtered Samples. Hg
samples are not spiked in the field.
2. Field Bottle Blanks are sent with each batch of 20 bottles and should be acidified as soon
as possible and returned to lab.
3. Field Spike Blanks are sent with every other batch of 20 bottles and should be spiked
when performing a sample spike.
4. The Blanking Kit (Filter and Tubing Blanks) will be rotated between field teams, and
must be performed as soon as possible in order that each team can obtain four method
blanks over the study year.
5. One 250 mL Teflon MeHg bottle must be substituted for one of the unfiltered or filtered
125 mL MeHg bottles every 5'h site visit. Site visits can be recorded in MeHg site count
column.
Trace Metal Sample Treatment Summary
Sample Type
Routine Field Sample
-Unfiltered
-Filtered
Field Bottle Blank
-milli-Q
Field Sample Spike
-Unfiltered
-Filtered
Field Blank Spike
-milli-Q
Blank Kit
-Feed Water
-Filter Blank
-Line Blank
Bottle Size
250 mL
250 mL
250 mL
250 mL
250 mL
250 mL
250 mL
250 mL
250 mL
Treatment
contents (3 mL) of one acidification vial
contents (3 mL) of one acidification vial
contents (3 mL) of one acidification vial
contents (3 mL) of one large spiking vial
contents (2 mL) of one small spiking vial
contents (2 mL) of one smalt spiking vial
contents (3 mL) of one acidification vial
contents (3 mL) of one acidification vial
contents (3 mL) of one acidification vial
Field Acidification vials are packaged in zip-lock bags labeled Field Acidification Solution,
Lot #FS95##. All vials are the large 6 mL capacity.
1-233
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Trace Metal and Mercury Sampling
Methods for Lake Michigan Tributaries
Volume 1, Chapter 2
Field Spiking vials are packaged in zip-lock bags labeled as follows:
a. Unfiltered (or Total) Sample Spiking Solution, Lot #SPU95##. All vials are the
large 6 mL capacity.
b. Filtered Sample Spiking Solution, Lot #SPF95##. All vials are the small 3 mL
capacity. Both the Unfiltered and Filtered Spiking Solutions contain sufficient
acid to stabilize the samples. Do not use an acidification vial in addition to
spiking solution. Please do not interchange spiking solutions - they are designed
for a specific matrix.
Field Bottle Blanks should be acidified in the boat in a manner identical to routine field samples,
and returned to the lab within two to three weeks of receipt.
Field Blank Spikes should be spiked at the same time as sample spikes. If you have scheduled a
sample spike and a blank spike bottle exists - spike it. Return to lab as soon as possible.
Blank Accounting
Field Sampling QA Final Project (1994-1995) Accounting
Source
QC Sample Type
Number of
Samples
Percent of Non-Blank
Samples (891)
Teflon Sample Bottle
(prep, and sample storage)
Sample Bottle Handling in
Field and Acidification
Acidification Acid
Filter
Filter/Pump-Head Tubing
and Filtering in Field
Pump-Head Tubing
Field Sample Tubing
Lab Bottle Blanks
Field Bottle Blanks
Acid Batch Qualifier
Dedicated Lab Study
Field Filter Blanks
Dedicated Lab Study
Field Tubing Blanks
56
54
14
13
— -
13
63
6.1
Each Acid Batch
—
1.5
—
1.5
Recovery
Field Analyte Spike (Blank Matrix)
Field Analyte Spike (Filtered Sample Matrix)
Field Analyte Spike (Unfiltered Sample Matrix)
Field Surrogate Spike (four rare metals in Sample)
Precision
Field Replicates (Filtered Sample Matrix)
Field Replicates (Unfiltered Sample Matrix I
Acciirucv
Interlab Studies (Prepared Samples)
Int.crLih Studies (Ambient Sampk-si
Number of
Samples
41
42
42
1081
46
50
3 studies
2 studies
Percent of Site
Visits (356)
4.6
11.8
11.8
100
12.9
14.0
1-234
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Volume 1, Chapter 2
Trace Metal and Mercury Sampling
Methods for Lake Michigan Tributaries
ICP-MS Batch Analysis QA Outline
15-18 Samples per Batch
Sample Type
Frequency
ICP-MS Qualification
-Blank Levels
-Stability
-Sensitivity
-Resolution
-Interference Check
Blanks Levels During Run
Calibration Blank
Check Blanks
Memory Check
Recovery
Lab Analyte Spike, Blank Matrix
Lab Analyte Spike, Sample Matrix
Internal Standards, 3-metals
Precision
Replicate Sample Acquisitions
Lab Sample Replicates (within batch)
Lab Sample Replicates (different batch)
Accuracy
Standard Reference Material (SLRS-3)
Laboratory Control Sample (Trib Matrix)
Before each sample batch
Before each sample batch
Before each sample batch
Before each sample batch
Once per week
One per batch
Four per batch
One per batch
One per batch
Two per batch
All samples
Four per sample
Two per batch
20%
Three per batch
One per batch
1-235
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Volume 1
Chapter 3: Sediment
-------
Standard Operating Procedure for
Collection of Sediment Samples
David N. Edgington
Great Lakes Water Institute
University of Wisconsin
Milwaukee, Wl
and
John A. Robbins
Great Lakes Environmental Research Laboratory
NOAA
Ann Arbor, Ml
1991
-------
Standard Operating Procedure for
Collection of Sediment Samples
1.0 Scope and Application
The application of this sampling procedure is for the collection of sediment cores, using a box
corer, for the analysis of radionuclides to provide estimates of the sedimentation rate and mixing
depth for the GLNPO Lake Michigan Mass Balance Study.
2.0 Summary of Procedure
Before any box cores are taken, test grabs, using a ponar, will be taken to determine the suitability
of the sediment for coring. If coring is possible, then the box corer will be deployed. Once the
box coring is completed and box core is back onboard the ship, then four 10 cm (ID) plastic tubes
will be inserted by hand into the Master box core, thereby creating 4 subcores (A-D). Each of the
subcores will be sectioned and these subsamples stored for future analysis.
3.0 List of Equipment
Item Quantity
Modified box corer (Soutar corer) 1
Box corer extraction rigging 1
Set of critical spare parts for box corer and extraction rigging 1
Hydraulic extruding stand for 4" diameter subcores 1
Set of core sectioning gear 1
125 mL Polyethylene bottles/ pre-labeled and tared as needed
Ponar grab sampler 2
Winch for Ponar deployment 1
10 cm/4" diameter subcore butyrate tubes 12
vacuum-extractor caps 2
Portable vacuum pumps with tygon tubing 2
4.0 Sampling Procedure
4.1 Test grabs, using a Ponar grab sampler, will be taken to determine the suitability of the sediment
for coring. If three grabs return without a sample, then the site will be vacated. If the Ponar grabs
are obtained but coring is not feasible, then surface samples from the grabs will be obtained. If
coring is possible then box coring will be undertaken as long as there appears to be a limited nsk
of damage to the box core.
4.2 Once the box core has been retrieved and is back on the ship's deck, then the core is examined for
acceptability. This examination is done by using the viewing window on the front side of the box
core. If the core is unacceptable, then the contents of the box core will be released and the box
corer redeployed.
1-241
-------
SOP for Collection of Sediment Samples Volume 1, Chapters
4.3 Acceptable box cores are sub-cored by carefully inserting a 10 cm diameter butyrate tube into the
core. Distortion of the sediment during the tube insertion is minimized by the application of a
partial vacuum to the tube top. By continuous manual adjustment of the vacuum as the core is
inserted, the interface within the tube remains in alignment with the interface of the surrounding
sediment in the box core.
4.4 Sediments within the tube are hydraulically extruded and sectioned onboard the ship. Extrusion is
done by the application of water pressure from the ship's hose line to a rubber stopper inserted into
the base of the core tube. Fine control of water flow allows slow movement of the core upward
into a separate short section of tube (the collar) placed in-line with the core tube top. The collar is
scribed in cm intervals so as to define the amount of core section to be displaced laterally into an
aluminum receiving tray.
4.5 Sub-core taken for the analysis of radionuclides will be sectioned with plastic utensils.
4.6 Sub-core samples are stored in conformity with EPA QA/OC requirements.
4.7 A back-up core is taken in case of unexpected problems in analyzing the first core or if an interest
in analysis of additional material develops.
4.8 Core lengths are expected not to exceed 50 cm in length and should more than cover the entire
post-settlement history of deposition.
4.9 A detailed record of the sediment characteristics, as a function of depth, as well as a notation of
any unusual properties (i.e. large wood chips) will be entered in the sampling log. An example of
the sampling log form is shown in Figure 1.
5.0 Sample Custody
After the sectioning of each core, the Co-Pi's will verify that all the samples are accounted for and
that they are transferred to proper storage. After sampling has been completed and the samples
transported to the lab, the CO-PI's will again verify that all samples have properly transferred and
stored. The location of all samples is noted in the sample log.
6.0 Sample Labeling and Logs
Prior to each sampling jvent a complete set of sample bottle labels will be prepared. The number
and type of these labels will depend on the length of the sediment core recovered and the estimated
sedimentation rate. An example of a typical label is seen in Figure 2.
1-242
-------
Volume 1, Chapter 3
SOP for Collection of Sediment Samples
Lake Michigan Mass Balance and EMAP Study Sediment Sampling Log
Station No Core No
Date Time
Latitude Longitude
Section
0- 1
1 -2
2-3
3-4
4-5
5-6
6-7
7-8
8-9
9- 10
10- 11
Description
Section
29 - 30
31 32
32 33
33-34
34-35
35-36
36-37
37 38
38-39
39-40
40-41
Description
28-29
59 - 60
Sectioned by_
Samples Checked by_
Samples Stored at
Recorded by_
Received & Checked by_
Date
Figure 1. Sediment Sampling Log
1-243
-------
SOP for Collection of Sediment Samples
Volume 1, Chapter^
Lake Michigan Mass Balance Study
1994 1995
Sediment Station LM94-099
Core#l
Section 25 26 CM
Date Collected
1994
Time
Initials
Bottle tare g Initials
4- sed g Initials
Figure 2. Sample Bottle Label
1-244
-------
Trap Sample Splitting (wet):
Use of Sediment Traps for the Measurement
of Particle and Associated
Contaminant Fluxes
Brian J. Eadie
NOAA/Great Lakes Environmental Research Lab
2205 Commonwealth Boulevard
Ann Arbor, Ml 48105-1593
November 1995
-------
Trap Sample Splitting (wet):
Use of Sediment Traps for the Measurement of
Particle and Associated Contaminant Fluxes
Flux is equal to the mass collected divided by the length of collection and the trap cross section. In order
to calculate fluxes from the trapped material a reliable measurement of the total weight is required. In
previous studies we had always split sediment trap samples after they were freeze dried and weighed. Pat
VanHoof, who will be analyzing these samples for PCBs and other trace organic contaminants, wants to
extract all of her samples while they are still wet. In splitting the sample while wet, it is necessary to be
able to estimate the total weight of the sample from some fraction of that material.
Thus it was necessary to buy or develop a wet sample splitting procedure. A wet splitter for trap samples,
designed at Woods Hole, is commercially available for $6-7000 and it splits samples into four or eight
subsamples. This was both too expensive and fractionated the samples too much; we would need to
recombine to get our two fractions requiring considerable container cleaning, etc. as excess overhead.
After further literature and catalog searches we purchased an all stainless steel dry sediment sample micro-
splitter (Model SP-241x; Gilson Co. Inc., PO Box 677, Worthington, OH, 43085-0677). This device has
a reservoir of approximately 80 mL into which the sample is poured. A bottom vent is then opened and the
sample pours into 30 evenly spaced (1 mm) slots. The even numbered slots empty into a stainless steel
tray on the left and the odd numbered slots empty on the right. We then tested this device for our wet
sample splitting requirements and came up with satisfactory results, described below.
Sample Matrices: We examined four samples. The objective was to determine the precision of splitting
and the ratio of the two samples. The four samples were:
1. Distilled water (DDW)
2. Distilled water (55 mL) + chloroform (6 mL); our standard trap poison solution
3. Ground Lake Michigan sediment in # 2
4. A sediment trap sample from Lake Michigan near LMMB station 6; 5m above bottom
from a 100m deep station.
Five replicates of each matrix were made. The samples were poured into ths splitter and the left and right
trays weighed for matrices 1 and 2. For matrices 3 and 4, the left and right trays were emptied into
preweighed beakers which were dried at 90°C then weighed. The data are presented in Table 1.
1-247
-------
Trap Sample Splitting (wet):
Use of Sediment Traps for the Measurement of
Particle and Associated Contaminant Fluxes
Table
DDW
DDW
DDW
DDW
DDW
DDW(55):CHC13(6)
DDW(55):CHC13(6)
DDW(55):CHCI3(6)
DDW(55):CHC13(6)
DDW(55):CHC13(6)
Gmd Sed in DDW(55):CHC13(6); DRY
Grnd Sed in DDW(55):CHC13(6); DRY
Grnd Sed in DDW(55):CHC13(6); DRY
Grnd Sed in DDW(55):CHC!3(6); DRY
Grnd Sed in DDW(55):CHCI3(6); DRY
Trap from 5m AB @ 100 m sta.; DRY
Trap from 5m AB @ 100 m sta.; DRY
Trap from 5m AB @ 100 m sta.; DRY
Trap from 5m AB @ 100 m sta.; DRY
Trap from 5m AB @ 100 m sta.; DRY
1. Sample Splitting Data
Total Dry
Wt(g)
0.5639
1.387
2.9349
3.9479
5.1343
0.4434
0.7476
1.2745
1.3124
2.2998
Wt (left)
(g)
33.4473
32.5575
32.9653
32.2945
31.7108
31.6683
30.2318
31.2056
30.8368
31.0031
0.2779
0.6952
1.5035
1 .9049
2.5843
0.2224
0.367
0.6423
0.648
1.1689
Wt (Right)
(g)
31.4184
30.962
30.9628
29.296
29.3542
33.0099
31.3103
31.5524
31.6704
33.3368
0.286
0.6918
1.4314
2.043
2.55
0.221
0.3806
0.6322
0.6644
1 . 1 309
Fract left
0.516
0.513
0.516
0.524
0.519
0.490
0.491
0.497
0.493
0.482
0.493
0.501
0.512
0.483
0.503
0.502
0.491
0.504
0.494
0.508
Fract Rt
0.484
0.487
0.484
0.476
0.481
0.510
0.509
0.503
0.507
0.518
0.507
0.499
0.488
0.517
0.497
0.498
0.509
0.496
0.506
0.492
Excellent replication was obtained in the tests (Table 2). Matrices 3 and 4, with sediment or trap materials.
were split into two equal portions without bias. In other studies we have determined that replicate traps
placed side b> side have a coefficient of variation (100*sd/mean) of a little less than 109K The splitting
errors appear substantially smaller and will not degrade our interpretation of the data.
1-248
-------
Trap Sample Splitting (wet):
Use of Sediment Traps for the Measurement of
Volume 1, Chapter 3 Particle and Associated Contaminant Fluxes
Table 2. Accuracy and precision of sample splitting (n=5; all mixtures)
Mixture
DDW
DDW + CHCI3
Ground sediment
Ground sediment Org C
Trap
Left Side Fraction
0.51 8 ±0.004
0.491 ±0.005
0.501 ±0.001
6.68 ±0.01
0.500 ± 0.006
Right Side Fraction
0.483 ±0.004
0.509 + 0.005
0.499 ±0.001
6.62 ±0.02
0.500 ±0.006
P (paired t)
0.92
0.56
0.93
Our standard splitting procedure will be:
1. Allow the 60 mL trap bottles to settle for approximately 24 hours in refrigeration.
2. Pour off approximately 25 mL of the overlying water into a pre-cleaned beaker.
3. Pour the remaining trap sample through a 700 um screen into the splitter reservoir.
4. Split by opening the bottom valve.
5. Rinse with the water from #2.
6. Further rinse (if needed) with pre-extracted DDW.
7. Pour left tray back into trap sample bottle for freeze drying.
8. Pour right side into pre-cleaned glass jar for PCB, etc.
9. Transfer >700 um materials to precleaned, preweighed scintillation vial.
10. Rinse screen and splitter under faucet, then with pre-extracted DDW.
1-249
-------
Volume 1
Chapter 4: Plankton
-------
Standard Operating Procedure for
Sampling Lake Michigan Lower Pelagic
Foodchain for PCBs, Nonachlor, and Mercury
Deborah L. Swackhamer and Annette G. Trowbridge
Division of Environmental and Occupational Health
School of Public Health
Box 807 Mayo Building
University of Minnesota
Minneapolis, MN 55455
and
Edward A. Nater
Department of Soil, Water, and Climate
439 Borlaug Hall
University of Minnesota
St. Paul, MN 55108
August 31,1994
Revision 1
-------
Standard Operating Procedure for Sampling Lake Michigan Lower
Pelagic Foodchain for PCBs, Nonachlor and Mercury
1.0 Zooplankton Sampling (>102 //m net, >500 ^m net)
1.1 Equipment and Materials
• Zooplankton net, 1 m diameter, 4 m long, 102 /^m mesh Nitex netting
Zooplankton net, 1 m diameter, 4 m long, 500 um mesh Nitex netting
• PVC sample cups, 1000 mL volume, with 102 or 500 ,um mesh
• Winch
• 5 Ib weight
• Lake water hose
• 4 L glass bottle
• 1 L glass bottle
• Poly pro funnel, 20 cm diameter
• 102 fj.m Nitex netting, 18" x 18", supported by poly pro large mesh strainer
• Stainless steel kitchen strainer stainless spatula
• Rectangular baking pan
• Glass Qorpak 9 or 16 oz wide mouth jars
• Spray bottle for filtered lake water
500 mL PFA tenon jar
• PFA teflon spatula
• Nalgene polycarbonate disposable analytical filter unit, 0.45 /j.m, 100 mL
60 mL PFA teflon jar
30 mL PFA teflon vial
• 10 mL autopipetter and disposable poly pro tips
• Shurco vacuum pump
• Nylon forceps
1.2 Preparation of materials and equipment
1.2.1 Net: wash by hosing down with lake water between stations and between casts.
1.2.2 Collection materials: rinse dewatering netting and strainer between uses with nanopure
water.
1.2.3 Organics (PCBs and nonachlor): Qorpak jars are ashed at 450°C for minimum of 4 hours
before use.
1.2.4 Mercury
1.2.4.1 All teflonware is acid-washed in concentrated nitric acid and rinsed with nanopure
water and either dried under dust-free conditions or stored filled with 1 "c
HC1. It is stored in acid-washed polypro bags, double bagged.
1-255
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SOP for Sampling Lake Michigan Lower Pelagic Foodchain
for PCBs, Nonachlor, and Mercury Volume 1, Chapter 4
1.2.4.2. All polypro and nylon is washed in 1.0 M nitric acid and rinsed in nano-pure
water, and dried under dust free conditions.
1.2.4.3. Filtration units are used as received from vendor (come sealed).
1.3 Collection Procedure
1.3.1 Sample locations: pre-selected by GLNPO and LMMBS. Sites include three Biota Zones
(Stations 110, 140, 180, 240, 280, 310, 340, and 380), two Master Stations (Stations 18
and 47), and Station 5 off of Chicago for organics and mercury. The order of sample
collection is 47, 180, 140, 110,280,240, 18, 380,340, 310,5. All other Master Stations
(8) are sampled for mercury analyses only, when possible.
1.3.2 Depth of tow: Vertical tows from near the bottom to surface (depth depends on water
depth, time of day, and sea conditions) are done under standard net tow procedures from
port side A-frame winch with the assistance of ship's crew. Net is attached to winch and
safety line is attached to one of net cables. Cup safety line is attached to net rim.
1.3.3 Number of tows: is dependent on mass collected per tow. Several grams of wet weight of
material are required for organics and mercury analyses; a few hundreds of mg of material
are needed for mercury analyses only. Approximately 4-6 tows are typically needed for
organics, 1-2 tows are needed for mercury only.
1.3.4 Isolating sample
1.3.4.1 Net is brought to just above the surface and lake water hose is used to wash down
sides of net from outside so that material adhering to inside of net collects in
bottom cup.
1.3.4.2 The cup is removed from the net and poured into the glass bottle (4 L bottle for
102 /^m net, 1 L bottle for 500 ^m net) via the funnel. Cup is rinsed and rinsate
added to bottle. If another tow is required, the procedure is repeated.
1.3.5 Dewatering 102 /^m sample: Contents of 4 L bottle are poured into netting held by
strainer. Dewatered maternal is removed by spatula to appropriate container for either
organics or mercury (see below).
1.3.6 Dewatering 500 jj.m sample: Contents of 1 L bottle are poured through stainless stell
strainer, or into rectangular pan. Using forceps, sample is segregated into species-specific
groups as much as possible. For instance, mysis are picked out with tweezers and
removed to sample jar. Remainder of sample is removed to jar with spatula.
1.3.7 Apportionment of sample for organics and mercury analyses: Approximately 5% of the
sample is reserved for mercury analysis. Only a minor fraction is required due to the
difference in detection limits between PCBs and mercur\ The aliquot for mercury is
either taken directly from the bottle to the 500 mL PFA tetlon jar by pouring prior to
dewatenng (if sample is highly concentrated), or after deuatermg (if sample is not highK
concentrated) The remainder of the sample is transferred b\ spatula to the Qorpak jar for
oraanics analvsis.
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1.3.8 Sample Processing and Handling
1.3.8.1 Mercury: Sample is isolated for analysis by filtration.
1.3.8.1.1 A mass determination is necessary to know the amount of sample
being analyzed. This is accomplished by homogenizing sample
by swirling container. A 10, 20, or 30 mL subsample is removed
by pipet to a 30 mL PFA teflon vial and frozen for later
dehydration and mass determination by standard gravimetric
procedures.
1.3.8.1.2 Prior to sample filtration the filter is leached with 10 mL of \7c
HC1. A known volume (10-100 mL) of sample suspension is
filtered through the disposable analytical filtration unit. The filter
is removed, placed in 60 mL PFA teflon jar, labeled according to
labeling procedure (see Sampling QAPjP), double bagged, and
frozen for transport and storage. If dewatered sample is used, it is
resuspended in nanopure water and handled as above.
1.3.8.2 Organics: Dewatered sample is frozen in bulk.
Material in Qorpak jar is labeled according to labeling procedure (see Sampling
QAPjP) and frozen for transport and storage. All appropriate tracking information
is recorded in field notebooks. This includes the label i.d., the number of tows,
the depth of the tow, and any species identification that has been made from
microscopic analysis.
2.0 Phytoplankton Sampling (102 > P > 10 /^m)
2.1 Equipment and Materials
• Phytovibe with 10 /j.m Nitex netting and 700 mL PVC cup
• Lake water hose
• Two submersible pumping systems attached to nylon- I I hose
• 102 /j.m Nitex net cover
500 mL PFA tenon jar
• PFA teflon spatula
• Nalgene polycarbonate disposable analytical filter unit, 0.8 /jm, 100 mL
60 mL PFA teflon jar
30 mL PFA teflon vial
• 10 mL autopipetter and disposable poly pro tips
• Shurco vacuum pump
• Nylon forceps
• 1 L glass jar with graduated markings
• 10 mL glass graduated pipets
• Pipet bulb
• 47 mm glass Millipore filtration apparatus (2)
• 47 mm plastic magnetic Nalgene filtration apparatus i 2 i
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• Stainless forceps
• 47 mm polycarbonate Nuclepore filters, pre-weighed
• 47 mm GF/F glass fiber filters, ashed
Plastic petri dishes
• Aluminum foil, ashed
• 125 mm ceramic Buchner funnel
• 125 mm GF/F glass fiber filters, ashed
2.2. Preparation of Materials and Equipment
2.2.1 Phytovibe: is washed down with lake water between uses. If necessary, remove the 102
,um net cover from the end of the hoses and clean thoroughly with lake water, and replace.
Cups are rinsed thoroughly with lake water. If flow through net during collection is
restricted, net is removed between stations from phytovibe support and washed in the
washing machine.
2.2.2 Organics
2.2.2.1 All glassware is wrapped in foil and ashed. All ashed materials are combusted at
450°C for a minimum of 4 hours.
2.2.2.2 Nuclepore filters are preweighed on a Satorius analytical balance in the
laboratory, and individually stored in petri dishes for transport to and from the
field.
2.2.2.3 The 47 mm GF/F glass fiber filters are wrapped in foil in packages of 9 and ashed.
The 125 GF/F filters are individually wrapped in foil and ashed.
2.2.3 Mercury
2.2.3.1 All teflonware is acid-washed in concentrated nitric acid and rinsed with nano-
pure water and either dried under dust-free conditions or stored filled with 1 c/c
HC1. It is stored in acid-washed polypro bags, and double bagged.
2.2.3.2 All prolypro and nylon is washed in 1.0 M nitric acid and rinsed in nano-pure
water, and dried under dust free conditions.
2.2.3.3 Filtration units are used as received from vendor (come sealed).
2.3 Collection Procedure
2.3.1 Sample Locations: pre-selected by GLNPO and LMMBS. Sites include three Biota Zones
(Stations 110, 140, 180. 240. 280, 310, 340, and 380). two Master Stations (Stations 18
and 47), and Station 5 off of Chicago for organics and mercury. The order of sample
collection is 47. 180. 140. 110,280,240, 1 8, 380. 340. 3 10. 5. All other Master Stations
(8) are sampled for mercur\ when possible.
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2.3.2 Depth the collection (pumping) depth is chosen based on an interpretation of the
temperature, fluorescence, and BA profiles from the SeaBird. The objective is to choose a
depth that maximizes the occurrence (and hence collection) of Phytoplankton that are
being grazed. This generally will be mid-epilimnion, or at the subthermocline chlorophyll
maximum in stratified conditions.
2.3.3 Phytovibe operation
2.3.3.1 Once the ship is at anchor following the SeaBird and Rosette operations and with
clearance from the Chief Scientist, pumps are placed at the sampling depth.
2.3.3.2 The outflow end is covered with a bag of 102 ^m Nitex netting to remove large
particles and secured with a hose clamp. The lines are flushed for a minimum of
15 minutes.
2.3.3.3 After flushing, the outflows are directed into the phytovibe, the vibrating motors
turned on, and the pumps are allowed to pump for the duration of the time on
station, or until sufficient mass (several grams of wet weight material for organics
and mercury; several hundred mg material for mercury) is collected. Pumping
rate is approximately 20-30 L/min. The netting at the end of the hose must be
checked frequently to check for plugging. It is cleaned and/or replaced as
necessary. The phytopvibes should be covered with a tarp if it is raining or if
insects appear to be fouling the sample. Eight to ten hours of pumping time may
be necessary. At several points during the pumping lake water should be used to
rinse the sides of the net down by spraying the outside of the net.
2.3.4 Sample isolation: lake water is used to wash the material adhering to the net surface down
into the cup by rinsing the outside of the net. When all the water has drained to below the
top of the cup, the cup is removed to the extraction lab.
2.3.5 Apportionment of sample for organics and mercury analyses:
Approximately 5-10% of the sample is reserved for mercury analysis. Only a minor
fraction is required due to the difference in detection limits between PCBs and mercury.
The aliquot for mercury is taken directly from the cup to the 500 mL PFA teflon jar by
pouring. This split is not quantitative, as the mass of sample analyzed for organics and
mercury is determined separately for the different analyses. The remainder of the sample
is transferred to the 1 L glass bottle for organics analysis.
2.3.6 Sample Processing and Handling
2.3.6. 1 Mercury: Sample is isolated for analysis by filtration.
2.3.6. 1.1 A mass determination is necessary to know the amount of sample
being analyzed. This is accomplished by homogenizing sample
bv swirling the container. A 10. 20. 30 mL subsample is
removed by pipet to a 30 mL PFA teflon vial and frozen for later
dehydration and mass determination by standard gravimetric
procedures.
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2.3.6.1.2 Prior to sample filtration the filter is leached with IO mL of 1 %
HC1. A known volume (10- 100 mL) of sample suspension is
filtered through the disposable analytical filtration unit. The filter
is removed, placed in 60 mL PFA teflon jar, labeled according to
labeling procedure, double bagged, and frozen for transport and
storage.
2.3.6.2 Organics: The sample is diluted to a known volume, subsampled for mass and
carbon determinations, and collected on a filter for analysis.
2.3.6.2.1 Subsampling: This is accomplished by diluting the sample in the
1 L bottle to a known volume with filtered lake water.
2.3.6.2.1.1 Dry mass: A known volume (1 - 2 mL) is
removed in duplicate by pipet for filtering
through a pre-weighed 1.0 ^m 47 mm Nuclepore
filter for dry mass determination by standard
gravimetric procedures. The filter reservoir is
rinsed with a small amount of nanopure water,
and the filter folded in quarters and placed back
in the petri dish for transport and storage. All
volumes and pertinent information is recorded in
the Mass field notebook and master file. This
includes: filter i.d. number, tare weight in mg
(previously recorded in notebook in lab), sample
label i.d., volume of sample filtered.
2.3.6.2.1.2 Organic Carbon: A known volume (1 2 mL) is
removed in duplicate by pipet for filtering
through an ashed 47 mm. GF/F filter for
particulate organic carbon (POC) determination.
The filter reservoir is rinsed with a small amount
of nanopure water. The filter is folded in half,
wrapped in ashed foil, labeled, and the wrapped
filters placed in labeled ziplock bags which are
frozen for transport and storage. All pertinent
information is recorded in the POC field
notebook and master file. This includes: sample
label i.d., and volume filtered.
2.3.6.2.2 Processing: The remainder of the sample is filtered through a 125
mm GF/F glass fiber filter in a Buchner funnel to isolate the
Phytoplankton from suspension. The filter :is placed in the
Buchner funnel, wetted with nanopure water, and vacuum
applied. The bottle contents are then carefully poured in. The
bottle is rinsed twice with filtered lake water and the rinsate
passed through the filter. The filter is folded in quarters, wrapped
in ashed foil, labeled (see Sampling QAPjP) placed in labeled
/iplock bag, and frozen for transport and storage. If any residual
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sample is on the inner rim of the Buchner funnel, the rim is wiped
with a wetted kimwipe, and the kimwipe added to the foil
package within the ziplock, This is analyzed along with the filter.
Pertinent information to be recorded includes: sample label i.d.,
approximately time the phytovibe was turned on and off, depth of
the water that was sampled, volume the organic sample was
diluted to, volumes of subsamples removed for mass and carbon
determinations.
3.0 Detrital Fraction Sampling (Organic Analytes Only)
3. 1 Materials and Equipment
• 293 mm stainless filtration apparatus
• 280 mm stainless stacked filtration apparatus
• Peristaltic pumps .
• '/2M od polyethylene tubing
• 293 mm GF/F glass fiber filters, ashed
• 280 mm 102 /^m nitex netting
• 280 mm 10 /^m nitex netting
• Teflon wash bottle with nanopure water
• Teflon wash bottle with methanol
• Large kimwipes
• Large stainless steel forceps (2)
• Ziplock bags
3.2 Preparation of Materials and Equipment
3.2. 1 The filtration apparati are wiped clean with a kimwipe wetted with methanol, and rinsed
with nanopure water between samples.
3.2.2 Nitex netting is rinsed with nanopure water.
3.3 Collection Procedure
An ashed 293 mm GF/F glass fiber filter is placed on the filter holder with forceps and
wetted with nanopure water. The top of the filter head is replaced and secured.
3.3.2 The 10 ^m nitex net is placed on a stainless steel screen support on the bottom-most layer
of the stacked filter system, the next stage is added, and the 100 ^m net is placed on the
stainless steel screen support. The top of the system is then added and secured. The
system is slowly filled with nanopure water from the bottom (reverse direction from
sample collection) so that undue pressure from the incoming sample does not rupture or
break the seal of the 10 ^m net. The system is charged by attaching the outflow hose from
the bottom of the filtration system to the outflow of the nanopure water.
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3.3.3 The polyethylene tubing is replaced at the beginning of the sampling cruise (prior to
Station 47), after the first Biota Zone (after Station 110), and after the end of the third
Biota Zone (Station 310). This is to prevent contamination from a more contaminated site
to a less contaminated site by desorption of the target analytes from the tubing.
3.3.4 The submersible pump is placed at the appropriate sample collection depth (see 2.0
Phytoplankton Sampling, above) and the lines are flushed (up to the peristaltic pump) for
approximately 30 minutes. The pump and plumbing from the pump to the extraction lab
are provided by the ship. The plumbing within the extraction lab is provided by the
University of Minnesota.
3.3.5 The water flow is as follows: water is drawn by submersible pump through nylon- 11 line
to the deck of the ship and flows to the outer door of the extraction lab. A T in the line
allows for some of the water to be drawn into the lab, with the remainder returned to the
lake. Water is drawn by peristaltic pump through polyethylene tubing from the T,
delivered to the top of the stacked filtration apparatus, and the outflow from the apparatus
is drawn by a second head of the same peristaltic pump and delivered to the top of the 293
mm filter head. The outflow is collected in teflon lined stainless steel kettles for dissolved
contaminant extraction, or discharged overboard. Water must be pumped to and from the
stacked filtration apparatus to minimize pressure on the 10 /um nitex layer.
3.3.6 The pumps are turned on, and the time recorded in the field notebook. The pump setting
should be approximately 4. Air is removed from the system by holding the outflow closed
with a finger and opening the pressure release valve at the top of the 293 mm filter head
until water comes out. The flow rate of the water through the glass fiber filter is
determined at the beginning, and every hour until filtering ends, unless a filter is changed
in which case the flow rate is determined a minimum of at the beginning of the filtering
and at the end just prior to changing the filter. Flow rate is determined by collecting
exactly 1 L of water in a polypropylene graduated cylinder and noting the time on a
stopwatch. The flow rate should be 4-5 L/min. When time permits duplicate flow rate
measurements should be taken at any given time point. The setting should not require
adjustments during a cruise. If changes are made, flow rate must be determined at the
time of change and the time the setting was changed must be recorded to determine the
volume of water processed with sufficient accuracy.
3.3.7 When pressure on the 293 filter head exceeds 5-6 psi, the glass fiber filter should be
changed. This is to prevent significant lysis of cells in the detrital fraction. To change a
filter, the peristaltic pump is stopped and the time recorded. The outflow from the stacked
filtration apparatus is disconnected from the peristaltic pump and directed to waste, and
the pumps turned on to remove water from the 293 mm filter head (i.e. air is being
pumped through the 293 mm filter head). The peristaltic pump is turned off, and the filter
head is dissassembled, the filter is folded in quarters using the large forceps, and wrapped
in ashed foil. It is labeled, placed in a ziplock bag, and frozen for transport and storage.
All filters for one sample are stored together in one ziplock bag. The order of the filter is
indicated on the individual lilter label. All filters will be analwed together as one sample.
The filter head is wiped clean \\ith a kimwipe wetted \\ith nunopure water, and a new-
filter installed as described above. The outflow from the stacked filtration apparatus is
reconnected to the peristaltic pump, and the pumps restarted. The time of restart is noted,
and flow rate determined.
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SOP for Sampling Lake Michigan Lower Pelagic Foodchain
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3.3.8 When sufficient mass of the detrital fraction has been collected (approximately 1000 L of
water, or 4 x 293 mm filters) the peristaltic pump is turned off and the time noted. The
293 mm filter is removed as described above. The stacked filtration apparatus is
dissassembled, and the netting removed, washed thoroughly in nanopure water, and
examined for rips or -holes before being replaced for the next sample. Total water volume
for this sample is calculated as:
volume = [(rale, L/min) * (min)l - (volume of subsamnples removed for filtering, L)
3.3.9 Subsampling
3.3.9.1 Dry Mass: A known volume (150-250 mL) is removed through the valve in the
water stream on the 293 mm filter head just prior to the 293 mm filter. Water is
filtered through a pre-weighed 0.4 /^m 47 mm Nuclepore filter for dry mass
determination by standard gravimetric procedures. The filter reservoir is rinsed
with a small amount of nanopure water, and the filter folded in quarters and
placed back in the petri dish for transport and storage. All mass determinations
are done in duplicate. All volumes and pertinent information is recorded in the
Mass field notebook and master file. This includes: filter i.d. number, tare weight
in mg (previously recorded in notebook in lab), sample label i.d., and volume of
sample filtered, and volume removed for filtering.
3.3.9.2 Organic Carbon: A known volume (1.5 2 L) is removed by dispensing from the
valve in the water stream on the 293 nim filter head just prior to the 293 mm
filter. Water is filtered through a 47 mm GF/F filter for particulate organic carbon
(POC) determination. The filter reservoir is rinsed with a small amount of
nanopure water. The filter is folded in half, wrapped in ashed foil, labeled, and
the wrapped filters placed in labeled ziplock bags which are frozen for transport
and storage. All POC filiations are done in duplicate. All pertinent information
is recorded in the POC field notebook and master file. This includes: sample label
i.d., volume filtered, and volume removed for filtering.
4.0 Transport and Storage
4.1 Sample Packing: All frozen samples are removed from the ship's freezers and immediately packed
in coolers with frozen blue ice just prior to transport. XAD-2 columns are stored in refrigerators at
4 C. They are also packed in coolers and kept cold with blue ice during transport. Coolers are
taped shut to prevent inadvertent opening during transport.
4.2 Sample transport: Samples are transported in coolers by University of Minnesota personnel.
Samples will remain either directly in the custody of the personnel performing transport, or in the
possession of commercial air carriers if the personnel travel by air.
4.3 Sample Logging: All samples are logged out of ship's storage at the time they are packed into
coolers, and again at arrival at the Pis' laboratories at the University of Minnesota as they are
placed into storage. Sample logs \\\\\ note sample number, date of each sample transfer, initials of
personnel responsible for custody during each stage of transport, and final storage location of each
sample in the Pis' laboratories. Examples of tracking forms are shown in hgures 1 and 2.
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SOP for Sampling Lake Michigan Lower Pelagic Foodchain
for PCBs, Nonachlor, and Mercury Volume 1, Chapter 4
4.4 Sample Custody: The sample log indicates the personnel responsible for sample custody during
transport. Samples will remain in the custody of ship's personnel while in storage onboard ship,
the University of Minnesota personnel during transport, and their respective PI once checked into
the Pi's laboratory.
4.5 Sample Storage in the Laboratory: Labeled samples will be stored in freezers or refrigerators
located in the Pi's laboratories. All labs are locked except when in use.
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SOP for Sampling Lake Michigan Lower Pelagic Foodchain
Volume 1, Chapter 4 for PCBs, Nonachlor, and Mercury
CRUISE:
date/initials date date date date date date
Sample i.d. from ship tolIMN extracted cleaned GC-ECD NCI baselines final quant.
1
2
3
4
5
6
7
8
9
10
1 1
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
Sample id:
Date collected:
Time collected:
Initials of individual collecting sample:
Time of storage:
Date of removal from storage:
Initials of transport personnel:
Date of arrival at laboratory:
Location of storage:
Date of processing
Digestion:
Denydration:
Date of analysis
Hg measurement:
Weighing:
Standard curve identifier:
Figure 2. Example tracking form for Hg
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SOP for Sampling Lake Michigan Lower Pelagic Foodchain
for PCBs, Nonachlor, and Mercury Volume 1, Chapter 4
5.0 Dissolved Fraction Sampling (Organic Analytes Only)
5.1 Materials and Equipment
• 75 L teflon lined stainless steel kettles with stainless steel lids (2)
• Small peristaltic pump
• Teflon and tygon tubing, 3/8 " id
• Glass columns, 3x30 cm, packed with cleaned XAD-2 resin
Wash bottle with methanol
• Wash bottle with nanopure water
• Kimwipes
• Strap wrench
• 100 mL polycarbonate bottle
5.2 Preparation of Material and Equipment
5.2.1 XAD-2 resin: The resin is pre-cleaned in the laboratory by sequential Sohxlet extraction,
and packed in individual extraction columns for transport to and from the field. It is
cleaned in large batch quantities by extracting for 24 hours with methanol, followed by 24
hours with acetone, followed by 24 hours with hexane, followed by 24 hours with
dichloromethane. It is then extracted with the same solvents in reverse order for 4 hours
each, and then washed thoroughly with nanopure water. It is stored in amber bottles under
water until the columns are packed.
5.2.2 Resin Columns: The glass columns are ashed at 450°C for a minimum of 4 hours. A
teflon end cap with outflow hole is placed on one end, and a plug of ashed glass wool is
added. The outflow is blocked, and resin in nanopure water is poured into the top of the
column through a funnel. The water is allowed to drain from the outflow as necessary to
allow the resin to settle and to reduce the volume of water in the column, while never
allowing the level of the water to fall below the resin. The columns are filled to
approximately 2/3 their capacity (approximately 150 mL resin and water), a glass wool
plug added to secure the resin in place, and the columns are topped with nanopure 'vater
and end caps secured on either end. The columns are wrapped in foil, wrapped in
bubblewrap, and stored in a cooler for transport and storage.
5.2.2 Stainless steel kettles: The kettles are wiped thoroughly with kimwipes and methanol,
followed by a thorough rinse with nanopure water. The lids are taped on to prevent
contamination before use.
5.2.3 The polycarbonate bottles are for dissolved organic carbon samples. They are washed
with soap and water, rinsed with tap water followed by nanopure water, soaked in 2%
nitric acid for 24 hours, rinsed with nanopure water, soaked for 4 hours with nanopure
water, and filled with nanopure water until use.
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5.3 Sample Collection
5.3.1 The outflow from the 293 mm filter is directed to the kettles. The foil is removed from two
XAD columns. The endcap of the outflow end of each of the XAD columns is replaced
with an endcap with a quick-connect fitting to teflon tubing which flows to the small
peristaltic pump. The column and tubing are wiped a kimwipe wetted with methanol,
followed by a wipe using nanopure water. The inflow endcap is replaced with an endcap
with a hole, any air is relieved with nanopure water, and using a finger to hold this closed
the column is immersed in the water and the finger released. The peristaltic pump is
started at the same time, and the time noted. A setting of about 3 should produce the
desired flow rate of 300 mL/min. The outflow of the peristaltic pump is directed
overboard.
5.3.2 Flow rates are determined at the beginning, at 30 minutes, at 60 minutes, and then hourly
until the extraction is complete. Flow rate is determined by filling a 250 mL graduated
cylinder and noting the time with a stopwatch. The outflows from each column are both
monitored. Time of measurement, and flow rate, are recorded in the XAD field notebook.
Total volume in L is a volume-weighted sum of minutes pumped times the flow rate for
that time period in L/minute. A minimum of 200 L is extracted; 300 L is desirable. Thus
several volumes of the kettles are processed. Particulate filtering must occur long enough
to allow for the generation of a sufficient volume of water to complete the dissolved phase
extraction.
5.3.3 When sufficient volumes of water have been passed through the resin, the peristaltic pump
is turned off and the time recorded. The resin column endcaps are replaced with the
storage endcaps, the sample is labeled, the foil and bubblepack are replaced, and the
columns are placed in the refrigerator until transit back to the laboratory.
5.3.4 Subsamples: Samples for the measurement of dissolved organic carbon are collected from
the XAD inflow. A 100 mL polycarbonate bottle is rinsed with the sample water, filled
approximately halfway, labeled, and frozen for transport and storage.
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Sampling Procedure for Collection of
Benthic Invertebrates for
Contaminant Analysis
Glenn J. Warren
U.S. Environmental Protection Agency
Great Lakes National Program Office
77 West Jackson Boulevard
Chicago, IL 60604
May 1996
-------
Sampling Procedure for
Collection of Benthic Invertebrates for Contaminant Analysis
1.0 Benthic Sled Tow
The benthic sled is used to collect benthic invertebrates for contaminant analysis. The sled is
fabricated of mild steel and consists of a rectangular frame, to which a net is attached, welded to
two runners which slide along the bottom as the sled is towed. A small float is attached to the top
of the frame to maintain upright orientation as the sled is deployed. The net has a rectangular
opening of dimensions? and a mesh size?
The net should be clean from previous deployment and sample removal. If it is not, clean it using
lakewater supplied by a submersible pump.
Float
2.0 Deployment and Collection
The sled is deployed from the stem of the ship from a cable running through a pulley (sheave) on
the main A-frame and to the main stern winch. The sled is first attached to the cable on the fantail,
with the A-frame in its forwardmost position. The center section of stern guardrail is removed for
deployment. After the net is ready, the winch operator lifts the sled from the deck as the A-frame
is extended over the water. The pilot is apprised of the progress in deployment over two-way
radio. The pilot maintains a steady course with a speed of 2 - 3 knots. This is accomplished by
clutching the propellers in and out. The winch operator lowers the sled into the water, preferably
during a period of glide, rather than with the propellers engaged, and continues paying out wire.
If a tension meter is used, if is often possible to determine when the sled reaches the bottom by an
increase in load displayed on the meter's readout. The winch operator continues to pay out cable to
a length of between two and three times the depth of the water column. The tow is most often
timed from the contact of the sled with the bottom. Tows may be of variable length, but are
generally between 10 and 20 minutes long. At completion of the tow, the winch operator retrieves
the sled. When the sled is visible at the surface, retrieval is slowed. As the sled is pulled from the
water, the A-frame is brought back over the deck. The sled is lowered to the deck.
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Sampling Procedure for Collection
of Benthic Invertebrates for Contaminant Analysis Volume 1, Chapter 4
The benthos collected during the tow will be at the cod end of the net. These are removed with
clean utensils (e.g., spatulas, clean spoons, etc.) with the aid of water from squirt bottles or hoses
supplied with lakewater. They are placed into a clean pan for later processing. After transfer of
the contents of the net to the pan, it is taken to the laboratory where the organisms of interest are
picked from the collection using clean forceps. Other techniques may be used to separate taxa
within the collection, including stirring, dilution with clean water, etc.
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Standard Operating Procedure for
Phytoplankton Sample
Collection and Preservation
Grace Analytical Lab
536 South Clark Street
10th Floor
Chicago, IL 60605
April 13, 1994
-------
Standard Operating Procedure for
Phytoplankton Sample Collection
and Preservation
1.0 Scope and Application
This Standard Operating Procedure describes the sampling and preservation of phytoplankton
samples taken for the GLNPO open water Great Lakes surveys.
2.0 Summary of Method
Phytoplankton samples are created from a composite of water samples taken at discrete depths
(surface, 5M, 10M, and 20M) with the rosette. Aliquots from each depth are combined, and
approximately I L of the composite sample is preserved with Lugol's Solution for analysis at the
CRL.
3.0 Safety and Waste Handling
Preservation of the phytoplankton samples with Lugol's solution must take place in a hood, and
gloves and safety glasses should be worn.
4.0 Equipment and Supplies
960 mL plastic sample bottle
1 gallon cubitainer
Repipetter with 10 mL delivery capability
Distilled or super Q H2O
Glacial Acetic Acid
I,
KI
Hotplate
1L Flask
Opaque 1L container
Magnetic Stirring Bar
Glass funnel
5.0 Reagents
5.1 Lugol's Solution: Prepare at least one week prior to surve\
5.1.1 Using a Mettler balance or equivalent, measure 100 g Kl and 50 g of I2. Cover the I:
reagent with tinfoil as it is light sensitive and will evaporate.
5.1.1 Combine MOO mL Super Q H:0 and dr\ chemicals m a large flask. This should he
performed in a fume hood.
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SOP for Phytoplankton Sample
Collection and Preservation Volume 1, Chapter 4
5.1.3 Add a magnetic stir bar and place on hotplate equipped with stirring action.
5.1.4 Warm slightly while stirring to facilitate dissolution of the dry chemicals. Do Not Boil!
5.1.5 In about an hour, once the solution is completely dissolved, pour into an opaque container
using a glass funnel. Add 100 mL Glacial Acetic Acid to container and cap tightly. Invert
several times to mix solution.
5.1.6 Label container with date, contents, and pH (usually around 2.4).
6.0 Sample Collection and Preservation
Note: Steps 6.1 -6.4 are generally done by the ship contractor or EPA personnel. GLAS contract
personnel will conduct this task when requested.
6.1 Remove 1 L of water from each of the Niskin bottles on the rosette from 20M, 10M, 5M and IM,
and add them to a 1 gallon cubitainer. This is the composite sample.
6.2 Mix the sample by gently turning the cubitainer over several times.
6.3 Pour approximately 1 L of the sample into the plastic sample bottle which has been labeled with
station, sample number and survey.
6.4 In the Biology lab add Lugol's solution (5.1) to make the concentration 1 %. If the sample nearly
fills the entire sample container, add 10 mL of Lugol's solution to the sample. If less sample has
been added to the container, adjust the volume of Lugol's solution that is added to achieve a 17c
preservative concentration.
6.5 Samples must be stored in the dark and under refrigeration. Store the sample in the area
designated by the sample coordinator.
1-276
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Standard Operating Procedure for
Zooplankton Sample Collection
and Preservation
Grace Analytical Lab
536 South Clark Street
10th Floor
Chicago, IL 60605
April 13,1994
-------
Standard Operating Procedure for Zooplankton
Sample Collection and Preservation
1.0 Scope and Application
This standard operating procedure describes the sampling operations and the preservation methods
for open lake zooplankton samples taken for the GLNPO Great Lakes surveys.
2.0 Summary of Method
Samples are taken using a plankton tow net that is maneuvered using a winch on the starboard side
of the rear work area of the R. V Lake Guardian. The tow net, with a screened sample bucket
attached to the end, is lowered to the desired depth, and raised at a constant, slow speed to collect
the sample. Once the net is lifted out of the water, it is rinsed from the outside to free organisms
from the side of the net, and to concentrate them into the sample bucket. The sample is transferred
to a sample container, the organisms are narcotized and preserved. The samples are brought back
to the CRL for analysis.
3.0 Safety and Waste Handling
Formaldehyde is a known carcinogen. During the preservation of samples, the formalin should be
dispensed under a hood, using gloves and safety glasses.
4.0 Equipment and Supplies
Plankton tow net 64 /um pore size (#25).
Tow net sample bucket with a 61 /^m pore size metal screen.
Flowmeter
Weights 10-201bs.
Safety line for sample bucket
Lines for attaching weights
Garden hose with attached water source
Spray bottle
Soda water (Club soda)
Formalin (37% formaldehyde)
500 mL plastic sample bottles
Repipettor with 10 mL delivery capability
Graduated cylinder 50 - 100 mL capacity
Waterproof notebook
CDT
5.0 Sample Depth
Sample tows are generally taken from a depth of 20 meters from the water surface (integrated
sample). In waters which are shallower than 20 meters, (Western basin of L. Erie) samples (B-l
sample) are collected from I meter above the bottom to the surface In cases such as this, only a
B-l sample will be taken. At Master stations, duplicate tows arc taken
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SOP for Zooplankton
Sample Collection and Preservation Volume 1, Chapterjt
Note: During each survey season, when calm weather permits, the flowmeter should be calibrated
by repeatedly lowering it to 20 meters in very calm seas, and recording the reading. This is
performed using just the flowmeter with the accompanying support ring (no net). This should be
repeated 20 times. The mean value of these 20 readings divided by the depth will be used to
calculate filtering efficiency for sample tows.
Note: If a CDT instrument is being used on the tow line, real depth will be used for sampling
instead of line length. In this case, the distance from the depth meter on the CDT to the rim of the
plankton net (about 1 meter) must be measured and that distance will taken into account when
reading the CDT depth. Subtract this distance from the sample depth, and have the winch operator
stop the winch when the CDT indicates the corrected depth.
6.0 Sampling Procedure
6.1 Once on station, obtain the bottom depth from the rosette information provided in the wet lab.
6.2 Convert the bottom depth into meters by means of a conversion table, or 3.281 ft - 1 M.
6.3 Screw on the sample bucket so that it becomes snug. Do not over tighten. Attach the net to the
winch line. Attach the safety line from the winch cable to the net ring.
6.4 Open the hatch on the flowmeter and reset all the dials to zero.
6.5 Inform the winch operator the depth of the sample to be taken.
6.6 Have the winch operator lower the net to the desired depth. The zero point for the depth on the
winch is when the top of the net is at the water surface. Make sure that the tow line is as vertical
as possible. If the angle exceeds 30°, repeat the tow using the CTD, and if needed, contact the
bridge to have the ship re-positioned.
Note: If weather conditions continually produce drifting net tows, inform the EPA Chief Scientist.
6.7 The net should be raised at a constant speed until the rim is above the water. Refer to the factory
calibration for each flowmeter as each one has an optimal speed at which it functions most
efficiently. Currently, the winch speed used for flowmeter #3478 is on setting "8" and corresponds
to approximately 0.60 m/s. It is very important to complete each zooplankton tow using this
setting. When the flowmeter or winch is eventually replaced, a new speed will have to be
determined.
6.8 Do not interrupt the tow by stopping and starting the which while the net is being raised to the
surface. If this occurs, repeat the tow.
6.9 Rinse the net down gently with the garden hose from the outside to wash all of the organisms off
of the side of the net. Detach the sample bucket. Rinse the screening and the sides of the bucket
with the spray bottle or very gently with the garden hose to collect all of the sample into the 500
ml. sample container which has been appropriately labeled. Double check the labels on the bottles
to make sure that the caps and bottle labels match, and that the sample is ^oing into the appropriate
bottle-.
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SOP for Zooplankton
Volume 1, Chapter 4 Sample Collection and Preservation
6.10 Record the date, station, flowmeter reading, depth of tow, and angle of tow into the waterproof
notebook while on deck.
6.11 In the biology lab, pour 20 mL of soda water into the sample to narcotize the organisms. Let sit
for 30 minutes. Adjust the volume of the sample, using distilled water, to accommodate 20 mL of
formalin solution. Once the formalin has been added, the container should be nearly full. If the
container is too full to add the correct amount of formalin, allow the sample to sit for at least 1
hour after addition of the soda water. Using a pipette covered with netting, draw off enough
solution in the top portion of the sample to accommodate the formalin. Store the sample in the
area designated by the sample coordinator.
6.12 Transfer the recorded information taken during the sampling process from the field notebook to
the Zooplankton Field Collection Sheet in the biology lab on the ship immediately after the sample
is put into the cooler. The following information should be entered on each sheet: Lake, Survey,
Date, Flowmeter #. The following information should be entered for each sample taken: Station,
Sample type (INT, B-l), Angle, Meter start, Meter reading end, Station depth.
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Volume 1
Chapters: Fish
-------
Fish Processing Method
Standard Operating Procedure SOP No. HC 523A.SOP
Robert J. Hesselberg
U.S. Geological Survey
Great Lakes Science Center
1451 Green Rd.
Ann Arbor, Ml 48105-2899
May 13,1996
Version 1.0
-------
Fish Processing Method
The following aging, compositing, and grinding method was used for fish collected for the Lake Michigan
Mass Balance Study.
Fish were collected for the Lake Michigan Mass Balance study during the spring, summer, and fall of
1994, and spring and fall of 1995 from Sturgeon Bay, Port Washington, and Saugatuck on Lake Michigan.
Information on the species, and number of fish caught is shown in Table 1. Coho shown in Table 1 were
collected along varying locations each season (depending on migration) in 1994 and in 1995 collection
occurred only during the spring and fall.
Table 1. Species, Seasons, and Number of Fish Collected for the
Lake Michigan Mass Balance Study.
Biota Sampled
lake trout 2-4 yr
lake trout 5-7 yr
lake trout 8-10yr
coho hatchery
coho 1 + jacks
coho 2 + adults
chubs 0 - 2 yr
chubs 4+ yr
alewife 60-120 mm
alewife »120 mm
smelt »100 mm
sculpin slimy
sculpin deepwater
Spring 94
25
25
25
25
25
25
25
25
25
25
25
25
Summer 94
25
25
25
25
25
25
25
25
25
25
25
Fall 94
25
25
25
25
25
25
25
25
25
25
25
25
Spring 95
25
25
25
25
25
25
25
25
25
25
25
25
Fall 95
25
25
25
25
25
25
25
25
25
25
25
25
Note: Lake trout were composited by age rather than length.
The same number of fish (except coho) shown in the table were repeated at Saugatuck. Port Washington,
and Sturgeon Bay. The number of coho sampled was according to the table and taken across various sites
each season depending on their migration location (see QA plan for Holey & Hlloit. USFWS, Greenbay,
WI).
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Fish Processing Method Volume 1, Chapters
1.0 Fish Processing Method
The following sample preparation procedure was originally developed for the International Joint
Commission (I.J.C.) Surveillance Program. The sites, species, sizes and seasons collected and
composites were modified for the Mass Balance Study.
2.0 Collection
Whole fish were collected from Lake Michigan (intact, with all body fluids and no incisions,
except lake trout, which had stomachs removed), wrapped in aluminum foil, placed in 4 mil thick
polyethylene bags after collection, tagged, and frozen as soon as possible on board the vessel. The
information on the tag included species, size, date, location of collection and labeled for the Lake
Michigan Mass Balance Study. Fish were transported to NBS/GLSC in coolers and stored frozen
at about-20°C.
3.0 Aging
Prior to homogenization lake trout were first aged. To age the fish, the head of each whole fish
was checked for the presence of a coded wire tag (CWT) and clipped fins to age the fish. If a
CWT was detected, (CWTs are only a few mm long) with a special metal detector the first two or
three cm of the fish snout was cut off and checked again with the detector to see if it contained the
CWT. If not the next few cm of the snout was cut off and checked with the detector. The cut off
section of the snout containing the CWT was cut in half and the half containing the CWT was cut
in half again. This procedure was repeated until the tag was found or the remaining piece was less
than a gram. At this point the tissue containing the CWT was placed in 10 mL solution of 15-30%
NaOH for digestion. After a few hours the CWT was removed from the solution of NaOH using a
small suitable teflon coated magnet and placed under a microscope. Using 5 or 10 magnification
on the scope, the series of marks on the CWT were recorded. The sequence of these markings was
decoded using an instruction sheet which made it possible to determine the date the fish was
hatched along with other information. This date was subtracted from the date collected to
determine age.
Scales were also taken from each lake trout and the fin clips were recorded. Lake trout that
contained no CWT were aged by a combination of reading annual rings on the scales and fin clips.
Because of the uncertainty of aging lake trout over seven years old from the scale, these age results
were compared to fish in stocking records that would have the same combinations of fin clips and
resulting age was base on the stocking data. If the age determined from the scale and fin clips did
not match the age by the scale method we would substitute the aged lake trout in question with one
of the extra lake trout collected. In cases where there were no extra fish (rare) and the age by
scales and fin clips in Lake Michigan stocking records were more than two years apart the fin clips
records from other Great Lakes were checked for a better match. It has been determined from
tagging records that a few lake trout migrate to Lake Michigan from other Great Lakes.
4.0 Homogenization
Fish were removed from the freezer at the GLSC and allowed to thaw slowly over an 8 to 12 hour
period in their scaled bags igeneralls mcrmght). Prior to homogem/ation. glass jurs (4 o/.j that
were used to store subsamples were prepared by first washing in a dishwasher, then rinsed (in
sequence) with in HNO3. Millipore-hkered water, and acetone.
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Volume 1, Chapter 5 Fish Processing Method
The contents of the polyethylene bag (fish and fluids) were weighed and recorded in the grinding
log. For each species, location, and season sampled (Table I) about 75 fish (covering three sizes
or age for lake trout) were composited into about 15 samples and then ground. For a given year,
site, and season lakes trout were sorted into composite samples. Depending on the number of fish
in an age group available, each composite contained 2-5 fish (five when available) of the same age.
Other species of the fish were sorted into five fish composite samples according to year, location,
species, and size range. Each composite is put into an aluminum pan which had been cleaned with
detergent and water and rinsed with deionized water. The fish were measured (millimeters) on a
measuring board that was washed with detergent/water, and rinsed with distilled water. Each fish
was weighed to the nearest gram and length measured to the nearest mm. The measuring board,
balance, and scalpel were cleaned between each group. Homogenization equipment was washed
with detergent/water, rinsed with millipore water, and then with acetone (alcohol for plastic
pieces) before each sample was ground. Each composite sample was homogenized (except lake
trout which were homogenized individually) and a fixed weight was sub-sampled from each lake
trout for the composite and then the resulting sample was re-homogenized. Large fish such as
adult lake trout and coho were homogenized using a high speed 40 qt. Hobart vertical cutter Mixer
(VCM). Medium size fish were homogenized with a 12 qt. Stephan Machinery vertical cutter
(UM 12) and small fish with a high speed two quart Robot Coupe (RSI241). When the large and
medium size vertical cutters were used for homogenization about 1000 g of subsamples was taken
and re-homogenized using the Robot Coupe cutter which obtained a finer consistency. From the
final homogenized tissue about 80 g was added to each of three (depending on the amount of
homogenized tissue) 4 oz jars, the lids (lined with acetone rinse aluminum foil) were screwed on,
and then each jar was labeled with the identification number and the grams of tissue. The jars
were boxed and then placed into the freezer (approx. -20° C) until analyzed.
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Quality Assurance Project Plan for
Lake Trout and Forage
Fish Sampling for Diet Analysis
and/or Contaminant Analysis
Edward H. Brown, Jr. and Gary W. Eck
U.S. Geological Survey
Great Lakes Science Center
1451 Green Road
Ann Arbor, Ml 48105-2899
May 1994
Version 1.0
-------
Quality Assurance Project Plan for
Lake Trout and Forage Fish Sampling
for Diet Analysis and/or Contaminant Analysis
1.0 Project Description
1.1 Introduction
The Great Lakes National Program Office (GLNPO) of the U.S. EPA has initiated a Mass Balance
Study for selected toxic contaminants in Lake Michigan. The Mass balance effort will be part of a
"Lake Michigan Enhanced Monitoring Program" which includes tributary and atmospheric load
monitoring, source inventories, and fate and effects evaluations. In general, the primary goal of
this enhanced monitoring program is to develop a sound, scientific base of information to guide
future toxic load reduction efforts at the Federal, State and local levels.
A modeling team will construct a mass budget and mass balance model for a limited group of
contaminants which are present in Lake Michigan at concentrations which pose a risk to aquatic
and terrestrial organisms (including humans) within the ecosystem. Components to the mass
balance model will be designed to predict contaminant concentrations in the water column and
target fish species over a two-year period, relative to loadings. Predictions of contaminant levels
in three species of fish will be calculated as final output of the model. The target fish species
include:
Lake trout (Salvelinus namaycush)
Coho salmon (Oncoryhynchus kisutch)
Bloater chub (Coregonus hoyi)
The calibration of the food web model(s) for these target species requires data on contaminant
concentrations and fluxes (diet) not only in these species, but also in the supporting trophic levels.
The contaminant burden of each prey species varies based on feeding patterns at lower trophic
levels. The concentration of contaminants in lake trout and bloater chubs will depend on what
prey items they choose to consume. The diet information for lake trout sampled by this project
will enable the modelers to quantify the movement of contaminants from their source, through the
food web, and ultimately the body burden in lake trout.
The basic design and data requirements for the fish samples have been outlined in Tables 5 and 6
and in Appendix 4 of Lake Michigan Mass Budget/Mass Balance (LMMB) work plan of
October 14, 1993. This project addresses a subset of the work objectives for lake trout and bloater
chubs, two of the target species described in the LMMB work plan, and for the five principal
forage species also described in that work plan, including bloater chub, alewife, smelt, slimy
sculpin, and deepwater sculpin, which are consumed by lake trout and coho salmon.
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QAPP for Lake Trout and Forage Fish Sampling
for Diet Analysis and/or Contaminant Analysis Volume 1, Chapters
The specific objectives are to:
I. Collect representative samples of lake trout, bloater chubs, alewives, smelt, slimy sculpins,
and deepwater sculpins for contaminant analysis.
2. Describe the diet of lake trout in Lake Michigan from May through October 1994.
3. Review past published and unpublished information on the diet of lake trout in Lake
Michigan and report on the comparability of the data collected in 1994 to past data.
1.2 Experimental Design
Because of spatial and temporal variations in feeding habits and/or distributions of lake trout,
bloater chub, and the other four forage species we will collect them in spring, summer, and fall
from each of three Biota Sampling Sites identified in the LMMB work plan of October 1994; these
include (1) the northwestern region near Sturgeon Bay, WI, (2) the southeastern region near
Saugatuck, MI, and (3) the central Midlake Reef region east of Port Washington, WI (Fig. 1). The
bloater chub was identified as both a target species and a forage species for trout and salmon in the
LMMB work plan of October 1994. The sampling regimes in Table 1.0 will be followed at each
of the three Biota Sites in spring (May to early June), summer (July to early August), and fall
(October to early November):
The staff on this project will have the advantage of making all of its targeted fish collections for
contaminants and diet analyses from the R/V Cisco which is assigned to the NBS' Lake Michigan
Project in the Section of Resource Assessment and Fish Community Dynamics at the GLSC and is
stationed at the Saugatuck Vessel Base. The most difficult part will be obtaining all of the
specified age and size groups of lake trout and forage fish at all locations and in all seasons,
because of vagaries partly associated with changes in weather, stocking densities and locations of
the trout reared in Federal Hatcheries, and natural variations and trends in abundance of forage
fish. Sampling on the Sheyboygan or Midlake Reef, more than 30 miles offshore of the nearest
port (Port Washington), poses the most difficult physical problem because a round trip takes
six hours or longer and there is no protection from sudden storms.
1.2.1 Contaminant Sampling
Because of the cost of the analytical chemistry, the total number of lake trout listed in the
LMMB Work Plan for contaminant analysis has been reduced from 450 to 225 per season:
i.e., 75 per Biota Site (Table 1.0) times three sites. These samples will be packaged as
required for contaminant analysis, frozen, and delivered to the GLSC Laboratory of NBS
in Ann Arbor.
1.2.2 Diet Sampling
The LMMB Work Plan did not have a sample size objective for describing the diet of lake
trout. However, based on recent diet variations observed in coho salmon. Holey and
Elliott (1994) estimated that at least 100 salmon per season per region would be necessary
to provide a reasonable analysis of the variation. Although past work has shown that
higher percentages of lake trout than salmon are found with food in their stomachs. 75
lake trout in addition to those collected for contaminant analysis will be collected per
Biota Site per season (Table 1.0) Published information on the diet of Lake Michigan lake
trout will also be reviewed to complement and aid in interpretation of that which will be
collected in the present study in 1994
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Volume 1, Chapter 5
QAPP for Lake Trout and Forage Fish Sampling
for Diet Analysis and/or Contaminant Analysis
Both critical and noncritical parameter measurements for the evaluation of contaminants
and diet of lake trout and contaminants of bloater chub are summarized in Table 1.1.
Table 1.0. Sample size objectives for the collection of lake trout, bloater chub, and
four other forage species in Lake Michigan by season, age or
size group, and pending analysis.
Biotic group
Lake trout
Bloater chub
Alewife
Smelt
Slimy sculpin
Deepwater
sculpin
Total fish
Age or
size
2-4 yr
5-7 yr
8-10 yr
0-2 yr
4+ yr
60- 120 mm
>120 mm
>100mm
Number collected for
Contaminants
and diet
25
25
25
75
Contaminants
only
25
25
25
25
25
25
25
175
Diet only
25
25
25
75
Total
samples
50
50
50
25
25
25
25
25
25
25
325
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QAPP for Lake Trout and Forage Fish Sampling
for Diet Analysis and/or Contaminant Analysis
Volume 1, Chapters
Table 1.1. Summary of critical and non-critical parameter measurements for the
evaluation of contaminants and diet of lake trout, and contaminants of bloater chub.
Parameter
-ocation
(critical)
Sample Date
(critical)
Lake Trout
enath
(critical)
Lake Trout
weight
(critical)
Lake Trout age
(critical)
Diet Species of
Lake Trout
(critical)
Diet Item length
(critical)
Diet Item
weight
(critical)
Bloater age
(critical)
Sample Depth
(non-critical)
Time of Sample
(non-critical)
Water Temp.
when sampled
(non-critical)
Sampling
Instrument
GPS, Loran,
Port Location
none
measuring
board ruler
spring or
electronic-
balance
knife and
envelope
NA
NA
NA
NA
echo sounder
clock
electronic BT
Sampling
Method
SOP-1
NA
NA
SOP-1
SOP-1 and
Bowen
1983
SOP-1
NA
NA
SOP-1
operating
instructions
NA
NA
Analytical
Instrument
NA
NA
NA
NA
bi-noc scale
projector
NA
ruler
spring or
electronic
Balance
scale
projector
microscope
NA
NA
NA
Analytic
al
Method
NA
NA
NA
NA
SOP-2, 3
SOP-2
SOP-2
SOP-2
SOP-2
NA
NA
MA
Reporting
Units
biota sites
mo / day / yr
XX / XX / XX
mm
Kg
years
otal number
mm
;rams
years
meters
HH:MM
degrees C
LOD
southeast.
central and
northwest
day
1 mm
0.1 Kg
year
Species - fish
& common
nvertebrates
Order for
ess common
nvertebrates
mm
0.1 gram
year
0. 1 meters
minutes
degree C
1-296
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QAPP for Lake Trout and Forage Fish Sampling
Volume 1, Chapter 5 for Diet Analysis and/or Contaminant Analysis
2.0 Project Organization and Responsibilities
Paul Bertram John Gannon Lou Blume
EPA Project Officer NBS EPA QA Manager
Biota Co-Chair Biota Co-Chair
Edward Brown
NBS
Project Manager
Gary Eck
NBS
Field Manager
Ralph Stedman George Boyce
Randall Owens Tim Desorcie
NBS NBS
Alternate Field Field Sampling
Managers Analysis
2.1 GLNPO Project Officer and Biota Co-Chair
The GLNPO Project Officer is the Agency official who initiates the grant, evaluates the proposal,
and is the technical representative for EPA. The Project officer is responsible for:
Budgeting
Program planning, scheduling, and prioritization
Developing project objectives and data quality objectives
Ensuring that project meet GLNPO missions
Technical guidance
Program and data reviews including audits
Data quality
Final deliverables
2.2 GLNPO QA Manager
The GLNPO QA Manager (QAM) is responsible for ensuring that each project funded by HPA
satisfies the Agency's requirements for QA programs. The QAM is responsible for:
Offering guidance on QA techniques
Evaluating QA Project Plans (QAPjPs) and approving QAPjPs for the Agency
Assisting in the coordination of audits
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QAPP for Lake Trout and Forage Fish Sampling
for Diet Analysis and/or Contaminant Analysis Volume 1, Chapters
2.3 NBS Biota Co-Chair
The Biota Co-Chair from NBS works in partnership with the GLNPO QA Project Leader to
implement the Biota portion of the Lake Michigan Mass Balance Project. Duties are:
Program planning, scheduling, and prioritization
Developing project objectives and data quality objectives
Ensuring that project meets GLNPO missions
2.4 NBS Project Manager
The Project Manager is the NBS official who initiated the proposal to perform the lake trout and
forage fish sampling portions of the LMMB project and is responsible for:
Developing the sampling plan for lake trout and forage fish collections
Administration of the lake trout and forage fish segment of the Biota objectives
Overall supervision of field work
Ensures QA objectives are met
Technical supervision
Final deliverables
Data quality assessment
2.5 NBS Field Manager
The Field Manager is the NBS position that will provide daily supervision of the field collection
activities and achievement of the QA objectives. This position is responsible for:
Collecting field data
Directly supervise the field crew activities
Reviews progress toward QA objectives
Develops and implements sampling and analytical procedures
Prepares reports and deliverables
Trains field crews on sampling and analytical procedures
Data quality assessments and audits for lab and field segments
2.6 Field Sampling and Analysis Personnel
These positions are responsible for the majority of the field sampling and lab identification. They
will receive training and guidance from the Project and Field Managers, who will also audit their
work to ensure QA objectives are met.
At a minimum, Field Sampling and Analytical Personnel have or, if future hires, will have
Bachelors Degrees in biological science, natural resources, or related fields, or appropriate relevant
experience. Project and Field Managers who will provide job-specific training all hold Masters
Degrees in natural resources or fishery science and have I 5 years or more of experience in fishery
research, ecolosv, and management on the Great Lakes.
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QAPP for Lake Trout and Forage Fish Sampling
Volume 1, Chapter 5 for Diet Analysis and/or Contaminant Analysis
3.0 Quality Assurance Objectives
As outlined in the Lake Michigan Mass Budget/Mass balance Work Plan, the proposed model
output should be within a factor of two of the observed concentrations in the water column and
target fish. It is also estimated that the required level of model accuracy can be achieved if
loadings and contaminant mass in significant environmental compartment are determined to within
±20 to 30% of the actual value.
3.1 Objectives
I) Within each season and regional biota site, collect as representative samples of lake trou'
and forage fish as possible so as to minimize the spatial and temporal population
uncertainty (Sp) to the extent possible (given the sample size that can be collected with the
financial, logistic, and biological constraints of this project).
2) To collect, package, and transport each sample, and to record, summarize, and report each
physical measurement with a level of recision, accuracy, deductibility, and completeness
that will ensure the Measurement.
Uncertainty (Sm) will be nominal compared to Sp and therefore not affect the interpretation of the
results.
The level of population uncertainty can not be determined prior. That the contaminant levels in
the lake trout and forage fish collected will be within ±20 to 30% of the actual population values is
a function of sample size and the collection procedures. The sample size for contaminants has
been established by the LMMB Work Plan and subsequent modifications. The designed collection
procedures described here attempt to make the most of the sample size target.
Variability in the diet of Lake Michigan lake trout can be great, especially when examined from a
lakewide perspective encompassing large scale spatial and temporal gradients. The desired sample
size for determining diet is to a large degree constrained by the difficulty of collecting these fish.
Presently lake trout abundance and therefor catch is very low off Saugatuck, a biota site, and some
other areas in the southern basin because of changes in interagency stocking protocols (Lake
Michigan Lake Trout Technical Committee 1985). Alewife abundance is also low throughout the
Lake and they are no longer the dominant forage species that they were in the 1960s and early
1970s (Eck and Wells 1987).
3.2 Measurement Quality Objectives
Measurement quality objectives are designed to control various phases of the measurement process
and to ensure that total measurement uncertainty is within ranges prescribed by the DQOs. The
MQOs can be defined in terms of data quality attributes; precision, accuracy, completeness,
delectability, representativeness, and comparability. The first four can be defined in quantitative
terms, while the latter two are qualitative.
Precision. A measure of mutual agreement among multiple measurements of the same property,
usualK under prescribed similar conditions. Precision will be evaluated through auditing of data
collection activities to determine whether actisilies are performed in a consistent manner, and by
established protocol.
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Accumc\. The degree of agreement between a measurement (or an average of measurements of
the same thing), and the amount actually present.
Completeness. For this QAPJP, completeness is the measure of the number of valid samples
obtained compared to the amount that is needed to meet the DQOS. The completeness goal is
90%.
Detectability. The determination of the low-range critical value of a characteristic that a method-
specific procedure can reliably discern or is necessary to meet program objectives.
Representativeness. Expresses the degree to which data accurately and precisely represent
characteristic of a population, parameter variations at a sampling point, a proceed condition, or an
environmental condition.
Comparability. Expresses the confidence with which one data set can be compared to another.
3.3 Field MQOs
The following information describes the procedures used to control and assess measurement
uncertainty occurring during the field sampling. Field parameters in this section will include
location, lake trout length, lake trout weight, and lake trout age and forage fish lengths, weights
and ages. Since these measurements are straightforward, the measurement quality evaluations will
be simple remeasurements.
The majority of the uncertainties occurring in the field can be alleviated by the development of
detailed standard operating procedures (SOPs), an adequate training program at appropriate
frequency, and a field audit program. SOPs have been developed and training has occurred. Field
audits will be implemented during the course of the program implementation.
3.4 Precision
Another term for precision is repeatability. Repeatability in the field is very important to
precision, as well as data comparability. Repeatability is controlled by the development of detailed
SOPs and adequate training in those SOPS. Field precision will be checked by remeasuring 5% of
the samples. Remeasurements must be within the acceptance criteria as stated in Table 3.0. Field
precision can also be evaluated through the implementation of field technical systems audits.
These audits will be used to evaluate the adherence to the SOPS. Audits are discussed in
Section 8.0.
3.5 Accuracy
As stated earlier, accuracy is based on the differences between an estimate derived from data and
the true value of the parameter being estimated. For the field measurements, with the exception of
location, the true value is dependent on the calibration of the instrument (ruler or scale).
Following calibration procedures and precision requirements will provide an indication of
accuracy. Following SOPs as written should reduce contamination as much as possible. Accuracy
is aNo based on training. Therefore, during audits the trainer will remeasure 5r/f of the samples to
determine accuracy. If accuracy requirements are not met, the trainer will review the methods with
the sampler until agreement is reached
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3.6 Detectability
Detectability in this study is a function of how accurate and repeatable the measuring instruments
can be maintained. Rulers or tape measurements, unless broken, will be considered accurate.
Therefore, delectability of lake trout length is a function of following the SOPS. Similarly, scales,
if calibrated properly, should reflect an accurate weight unless various conditions (wind or rain)
create a situation where an accurate weight (within detectable limits) cannot be met. The SOPs
will discuss ways to measure samples within the delectability requirements.
3.7 Completeness
Completeness for the field is defined as the successful collection of all viable samples in the
appropriate time frame. A viable sample would be defined as any single sample whose integrity
has not been effected during the collection process and would therefore not be flagged with a field
qualifier. In some cases the sampler has no control on the integrity (e.g., samples remaining in the
sun too long) while in other cases the sampler might effect the integrity (e.g., contaminating a
sample through improper handling).
In any case, the DQOs are based on the evaluation of a statistically relevant number of samples
which are affected by all errors occurring in the field and laboratory. Therefore, the overall goal is
a completeness of 90%. The completeness objective for the measurement phase is 100%. As with
the other data quality attributes, completeness can be controlled through the adherence to the SOPs
in order to minimize contamination and sampling errors.
3.8 Representativeness
Representativeness, with respect to the overall program objectives, is a function of the statistical
sampling design and how well this design estimates the measurement parameters to this project.
Variation in lake trout diet is expected seasonally but also from year-to-year, depending on the
abundance of prey and environmental factors that might affect feeding behavior. Since the
sampling period for this project is only one year, the review of past lake trout diet data will assist
in determining how representative the 1994 diet of lake trout is to the yearly variation that can be
expected.
3.9 Comparability
Comparability will be maintained by the adherence to the SOPs. Adherence to these SOPs by all
samplers will allow for comparability of data among sites and throughout the project. Evaluation
of comparability occurs through the implementation of the training program and the field technical
systems audits.
Measurement quality objectives for the parameters that will be used to evaluate lake trout diet in
this project are summarized in Table 3.0.
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Table 3.0. Measurement quality objectives for parameters for the evaluation of lake
trout diet.
.ocation
'arameters
Sample Type
,ake Trout Length
Precision
Accuracy
Completeness
^measurement
ndependent
remeasurement
,ake Trout Weight
Precision
Accuracy
Completeness
^measurement
ndependent
remeasurement
,ake Trout Age
Precision
Accuracy
Completeness
Diet Species of
Lake Trout
Precision
Accuracy
Completeness
^oded-wire tag
Re-age, inspection
[ndependent
Re-age, inspection
Re-identify,
inspection
Re-identify,
inspection
Frequency
5%
5%
NA
I cm of original measurement - recalibrate
instrument and remeasure sample to compare
to closest.
1 cm of original measurement - review
protocols and remeasure another sample.
90%
5 %
NA
100%
5 %
5 %
NA
5 r/c
N!A
Acceptance; Other Corrective Action
The accuracy required is to regions of the
lake.
0.1 Kg of original measurement - recalibrate
instrument and remeasure sample to compare
to closest.
0.1 Kg of original measurement - review
Drotocols and remeasure another sample.
100 % for lake trout collected for
contaminant analysis. 0 % for lake trout
collected only for diet analysis.
Confirmation with scale aging.
Direct match with original.
Direct match with original.
95 7c identification, precision will be
maintained through training and periodic
audits to verity accuracy of identification of
prey items.
95 % identification, to determine accuracy,
samples will be re-identified and compared tc
reference samples.
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Table 3.0. Measurement quality objectives for parameters for the evaluation of lake
trout diet. (Cont'd)
Parameters
Diet Item Length
Precision
Accuracy
Completeness
Diet Item Weight
Precision
Accuracy
Sample Type
Remeasurement
Independent
remeasurement
Remeasurement
Independent
remeasurement
Frequency
5 %
5%
NA
5%
5 %
Acceptance; Other Corrective Action
2 mm of original measurement - recalibrate
instrument, remeasure sample and compare
to closest.
2 mm of original measurement - review
protocols and remeasure another sample.
90 %
0. 1 g of original measurement - recalibrate
instrument, remeasure sample and compare
to closest.
0.1 g of original measurement - review
protocols and remeasure another sample.
4.0 Site Selection and Sampling Procedures
Lake trout and five forage species, bloater chub, alewife, smelt, slimy sculpin, and deepwater
sculpin, will be sampled from the NBS's R/V Cisco in spring, summer, and fall at each of the three
Biota Sites identified in the Lake Michigan Mass Budget/Mass Balance Work Plan. The precise
locations will depend on the differential seasonal distributions of the six species at each site.
4.1 Sampling Procedures and Sample Custody
Each entire fishing operation or cruise in each season will be permanently documented in
considerable detail in the Captain's Log and in the Section of Resource Assessment and Fish
Community Dynamics' Research Vessel Catch Information System (RVCAT). An overview of
this system is given in Appendix 4.
Fishing operation data (e.g., location, gear, total catch and effort by species) and biological data
and measurements on individual fish are now entered directly into a laptop computer aboard the
vessel. This has eliminated the need for much of the hand recording on a detailed set of field data
forms that was done in the past. Each lake trout or other predator species, for example, is uniquely
identified by an individual I. D. Number, while the catch from which it came is identified by a
unique Serial Number. The data entry screens used aboard the vessel are shown in Appendix 5.
Samples of individual fish and composite samples of several or more fish will be labeled with tags
bearing the information shown in Appendix 6. Any temporary or permanent change in the custody
of these samples will be recorded on the Chain of Custody Record shown as Appendix 7. Any
detected changes in the quality of these samples which might compromise their intended use(s)
will he indicated by an appropriate FLAG (See list in Section 10) in the Chain of Custody Record,
and corrective action to prevent it happening again will be taken by the Field Manager and
reported to the Project Manager who uill take additional reinforcing action if warranted. In either
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case, emphasis will be placed in identifying the cause and whether it resulted from an inherent
system or procedural problem or from negligence. Training to correct the situation will be
provided by the Managers if appropriate. A separate set of Custody records will be filed with each
of the Projects or Sections at the GLSC of NBS in Ann Arbor that played a significant role in
collection and or temporary or final custody of the given samples.
4.2 Contaminant Sampling
All of the lake trout and forage species (identified above) to be used in contaminant analysis will
be collected from the NBS's R/V Cisco, using gradedmesh gill nets to obtain the trout and a
standard 12 meter bottom trawl to obtain the forage fish. The field sample preparation procedures
are described in SOP 1. An NBS biologist will be on board during all of the fishing operations to
insure proper handling of the samples. Immediately after they are processed, packaged, and
labeled (Appendix 6), all samples of lake trout and forage fish will be frozen in a chest freezer
aboard the vessel. If freezer capacity is exhausted, the fish will be held on ice for up to about
eight hours so that they can be frozen and stored temporarily at a shore facility or transported
frozen in coolers to either the Saugatuck Vessel Base of NBS for temporary storage in chest
freezers or directly to the GLSC in Ann Arbor, Michigan for storage in a walkin freezer. All
samples will be transported in an NBS vehicle. Custody forms will be used for transfer of samples
between authorized individuals, showing the dates(s) when frozen and subsequently delivered, and
the receiving location/facility. The number of samples and the range of 1 .D. numbers, if
individual fish, will also be recorded on the Chain of Custody form. A set of Custody records will
be filed with the Lake Michigan Project at the GLSC of NBS in Ann Arbor; a duplicate set of
records will be filed as backup in another appropriate location at the GLSC.
4.3 Diet Analysis
Stomachs for lake trout diet analysis will be removed with their contents intact from the fish being
processed and packaged above in accordance with SOP 1 (Appendix 1). The stomachs will be
frozen individually, labeled (Appendix 6), stored, transported, and transferred as described under
contaminant sampling of the whole fish above. Diet analysis will take place in the laboratory at
GLSC in Ann Arbor after field work is completed.
All members of the Lake Michigan Project at GLSC including the Project Manager for this segment of
NBS's LMMB Projects, Edward Brown, the Field Manager, Gary Eck, alternate Field Managers, Ralph
Stedman and Randall Owens, and Biological Technicians, Tim Desorcie and George Boyce, will
participate in part or all of the field sampling in various capacities. These and other qualified staff
whose services may become available later \\ill collect and label all field samples.
5.0 Analytical Procedures and Calibration
Analytical procedures will generally follow those outlined in Bowen 1983, Elliott 1994, Miller and
Holey 1992. and others. Details of the various analytical procedures that will be used in the field
and laboratory are contained in SOPs 1 and 1 in (Appendices 1 and 2). Measurements of length
and \\eighl are the basic analytical procedures to be conducted for this project. Lengths of lake
trout and (heir diet items will be measured to the nearest mm with a measuring hoard or ruler.
Weight uill be measured to the nearest 0.1 Kg for lake trout and 0.1 gram (g) for their diet items.
Tables ot calibration equipment, technique, and frequency are also given in SOPs I and 2 for the
respective field and laboratory operations. Lake trout will be aged by reading coded-wire tags (see
SOP-3 Appendix 3).
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6.0 Data Reduction, Validation, and Reporting
The main responsibility for data reduction, validation, and reporting will be shared by Edward
Brown and Gary Eck with assistance from other qualified staff. Following is a description of the
step by step procedure used to reduce the raw diet data into summary statistics, verify those
statistics, and report them as products that describe the diet of lake trout in the manner required for
this project.
6.1 Overview and Summary of Method
The raw data as entered and described in SOP 2 (Appendix 2) will be reduced so that the average
diet of all lake trout within a given stratum (age-region season) can be reported. Diet will be
reported for both lake trout that are sampled for contaminants, and for those that are sampled for
diet alone (Table 1.0). The primary descriptive statistic calculated and reported will be the percent
that each prey type contributes to the average wet weight of all prey found in the stomachs. The
range and frequency distribution of individual weight values and percent weight values from
which the average values are calculated will indicate the variance associated with these data. The
range and distribution of site specific and biological variables will characterize the lake trout
sample within each major stratum. Length distributions of prey fish in the diet will describe the
characteristics of each species found in the stomachs of lake trout.
Data collected and results reported during other diet studies of Lake Michigan lake trout will be
reviewed to provide a reference framework with which to help evaluate the representativeness of
the diet information collected during this project.
It is assumed that the sampling design will provide samples of lake trout that are representative,
especially in regard to diet, of all trout available to the sampling gear in each of the three age
strata, at each of the three sampling sites, and in each of the three seasons. The samples combined
across age strata would not be representative of all fish available to the gear in those strata
combined, however, unless the samples in each stratum were first weighted by the relative
abundance at the sampling sites offish in those age intervals.
6.2 Reduction Procedures
The following procedures will be discussed:
- testing between samples
- combining or averaging samples, etc.
Using the database developed in SOP 2 (Appendix 2), calculate the percent that each prey type
contributes to the average wet weight of all prey found in the stomach as follows.
Within each stratum (age, region, season), group lake trout and their associated data by general
location (port) and date-specific groups.
For each of the location-date specific groups, calculate the average weight (O.lg) per stomach, and
percent (0. lcr) of the total weight, for each prey category. Also calculate the percent (l<7r) of the
stomachs found empty or \oid of prey. Omit data flagged as outliers from these and subsequent
calculations.
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Use Wilcoxon-Mann Whitney two sample tests and Chi-square tests of independence to determine
if and where significant differences in the diet exist between the location-date groups.
If significant differences between groups exist, compute a grand average of all location-date
specific average weight values. Then calculate the percent that these average prey weights are of
the total grand average weight of all prey combined.
If no significant differences between groups exist, combine data for all lake trout sampled within
that strata, recalculate average weights, and then calculate the percent that these average prey
weights are of the total average weight of all prey combined.
For each stratum, calculate the range and the frequency distribution of individual weight values
and percent weight values for each prey species. If necessary, adjust the weight value intervals to
reflect fresh weights using conversion formula determined in SOP 2.4.3.
For each stratum, calculate the range and the frequency distribution of prey lengths for each prey
fish species. If necessary, adjust the lengths to reflect fresh lengths using conversion formula
determined in SOP 2.4.3.
For each stratum, calculate the range and frequency distribution of site specific and biological
variables (lake trout length, weight, sex, time, water depth, capture depth, temperature, where
captured etc.).
Maintain updated/backed up independent copies of the reduced data (hard drive, disk, and hard
copy printout) in the same manner as is done for the raw database (SOP 2.4.4) for the duration of
the project.
6.3 Validation Procedures
Verification of the raw database is described in SOP 2.4.4. Validation of reductions/calculations is
divided into two procedures: validation of correctness, and validation of representativeness.
6.4 Validation of Correctness
Reductions/calculations result from manipulations of the database by a personal computer using a
set sequence of commands and formula (a program). This ensures that all reductions/calculations
are consistent and not subject to random error. Verify that the values resulting from the
reduction/calculation procedures are correct by reproducing by hand the process earned out by the
computer for a randomly selected portion of the d:\tabase.
6.5 Validation of Representativeness
To determine if the results of the reductions/calculations of this data set are representative of the
diet of lake trout in Lake Michigan for this year and for other years in recent history, data collected
and results reported during other diet studies of Lake Michigan lake trout will be summarized and
compared to the results produced from this database.
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6.6 Reporting Procedures
The average size and variability of lake trout and the size, variability, and contribution of the diet
taxa to the total diet within age-season-region strata will be reported (Table 6.1), based on
reduction of the raw data as detailed above. The raw data itself will be permanently archived in
RVCAT computer files at the NBS GLSC. Copies of all files are held separately at the NOAA
Great Lakes Environmental Research Laboratory for backup protection against fire, vandalism,
and computer failure.
Table 6.1. Reported statistics associated with each biotic element.
Biotic
element
Lake trout
Lake trout diet
Stcata
age, season,
region
age, season,
region, diet
taxon
Measurement
length, weight
number, wet
weight, length
Statistic
mean, standard error,
range, sample size
mean, frequency of
occurrence, percent by
weight of all prey,
standard error, range,
sample size
This information together with QA findings will be reported to the GLNPO, PO, QAM, and Biota
Group.
7.0 Internal Quality Control Checks
Quality assurance for this project will be achieved primarily through specific training both prior to
sampling and during the sampling season. Several persons on the GLSC staff are experienced in
diet sampling (Eck and Wells 1983, Gary Eck, and Edward Brown, Cruise Reports of the R/V
Cisco on file at GLSC of NBS, Ann Arbor), and will provide training on procedures before the
sampling begins and while it is in progress. Less experienced field staff will work with
experienced staff until such time that the quality of their work justifies them working
independently. The quality of field staff work will be checked by the Field Manager or Project
Manager sampling at least once or twice during each sampling cruise throughout the duration of
the project. Additional checks will be made whenever needed.
Measurements of length and weight required for this project are straight forward, and their
variation will be a function of the ruler or weight scale used rather than the person taking the
measurements. Measuring boards or rulers will be examined prior to field work to ensure that the
error between them is less than ±2 mm. As indicated in Table 1.1, tiie readabihtv of the weight
scales used is 0.1 g for small fish and diet items measured in g, and 50 grams for most lake trout
which are much larger and therefore measured in Kg.
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In the field, the Project and Field Manager will make independent measurements and Field
Sampling Analysts will make remeasurements as detailed in SOP I (Appendix I) for at least 5% of
the samples from each season/region stratum. Similarly, in the lab, the Field Manager will make
independent measurements and Field Sampling Analysts will make remeasurements as detailed in
SOP 2 (Appendix 2) for at least 5% of the samples from each season/region stratum. The resulting
data will be recorded on separate Field and Lab Data Sheets, as described in SOPs I and 2, and
identified as QC Audits. Using these data and data from original measurements, precision.
accuracy, and completeness will be calculated for all parameters identified in Table 3.0.
During the diet analysis of lake trout stomach contents in the lab, examples of each species of prey
fish and taxonomic group of invertebrate consumed by the trout will be preserved in glass jars with
5% formalin for reference in identification. Examples should cover the range in stages of
digestion of the different sizes of prey observed. These specimens will aid in documenting the
methods of identification and quantification used in the stomach contents analysis. Each sample
will be labeled as to its source (Sample I. D. No.), taxonomic identification, and measurement
values (i.e. length and weight, etc.).
In addition, identification criteria will be developed during training when no good ones exist.
8.0 Performance and Systems Audits
Specific audits will not be conducted as part of this sampling project. Procedures required for the
project are straight forward and uncomplicated. The duration of the project is also short enough
that at least one or two checks per field trip and per month in the laboratory on performance of the
field and lab staff will serve as audit checks for the project. The number of staff involved in this
project will be small, therefore, the ability to control the quality of the project will not require
elaborate auditing procedures. Quality control audits at each stage of the field sampling and
analysis will be conducted by the Project Manager, the Field Manager, or the EPA QA Manager.
The auditing will focus mainly on the precision, accuracy, and completeness of the parameter
measurements identified in Table 3.0 as well as on the proper handling and processing of the
contaminant and diet samples. The auditing will involve remeasurement and independent
measurement procedures listed in Table 3.0 and discussed as to frequency in Section 8.0, and
observation of the sampling/processing operation and the condition of the samples. Audit reports
will be kept on file at the GLSC of NBS and available for review at any time. Moreover, EPA
may audit at any time.
Inadequacies in sampling procedures or the quality of the data collected will immediately be
addressed immediately by the Project Manager or Field Manager when discovered. All previous
and current data collected by the person when the inadequacies were first discovered will be
reviewed for accuracy. Additional training and supervision will then be provided until the quality
of work is adequate. In addition, an audit form for this project will be developed.
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9.0 Calculation of Data Quality Indicators
This QA Plan has defined the DQOs and MQOs (Section 3.0). This section describes the
statistical assessment procedures that are applied to the data and the general assessment of the data
quality accomplishments.
9.1 Precision
The precision will be evaluated by performing duplicate analyses. Various types of duplicate
samples are described in Section 3.0. Precision will be assessed by relative percent difference
(RPD).
Relative Percent Difference (RPD)
RPD
(X, +XJ/2
Relative standard deviation (RSO) may be used when aggregating data.
Relative Standard Division (RSD)
RSD = (s/v)*100
Where: s = standard deviation
y~ = mean of replicate analyses
Standard deviation is defined as follows:
(v, -y)2
5^
Where: v, = measured value of the i the replicate
v~ = mean of replicate analyses
n = number of replicates
9.2 Accuracy
Accuracy will be based upon expert remeasurements of a percentage of samples.
Accuracy will be evaluated by determining whether the measurements are within the acceptance
limits. Deviations beyond the acceptance criteria could be justification for retraining technicians.
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Bias can be estimated from the theoretical "true" value of the expert measurement. "System" bias
for the study may be calculated from individual samples and is defined:
a. E(v*,)
Bias =
Where: Ylk = the average observed value for the i the audit sample and k observations.
R, — is the theoretical reference value
n = the number of reference samples used in the assessment
9.3 Completeness
Completeness for most measurements should be 90%. Completeness is defined:
V
Completeness = — .r 100
n
Where: V = number of samples judged valid
n = total number of measurements necessary to achieve project objectives
The 90% goal means that the objectives of the survey can be met, even if 10% of the samples are
deemed to be invalid. An invalid sample is defined by a number of combination of flags
associated with the sample. This value will be reported on an annual basis.
9.4 Representativeness
Based upon the objectives, the three seasonal collections (spring, summer, fall) represent different
lake trout diet conditions. In order to determine whether a change is statistically significant, the
samples must be representative of the population, and the samples must be collected and analyzed
in a consistent manner.
Representativeness will be evaluated through variance estimates of routine sample in comparison
to previous years estimates if the latter are available. These estimates would be performed at
within-site and between-site levels, as appropriate. Analysis of variance (ANOVA) will be used to
determine whether variances are significantly different.
9.5 Comparability
Comparability is very similar to representativeness in that comparability is ensured through the use
of similar sampling and analytical techniques. Comparability will be assessed through the
evaluation of precision and accuracy measurements and technical systems audits.
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10.0 Corrective Action
The possible corrective actions that can be anticipated in advance have been covered and discussed
in Table 3.0 and in Sections 7.0 and 8.0. If any nonroutine corrective action is required it will be
initiated and implemented by the Project Manager, Edward Brown, or by the Field Manager (Gary
Eck, Ralph Stedman, or Randall Owens) as appropriate. Such action will be documented in audit
reports, through data flags listed in Table 10.0 or yet to be developed, in revisions of the QA Plan
if methods must be changed, and in the final report.
Table 10.0. List of data flags.
LAC
FAC
ISP
CON
UNK
EER
OTL
Laboratory accident
Field accident
Improper sample preservation
Consensus
Unknown sex
Entry error
Data point outlier
There was an accident in the laboratory that either
destroyed the sample or rendered it not suitable for
analysis.
There was an accident in the field that either
destroyed the sample or rendered it not suitable for
analysis.
Due to improper preservation of the sample, it was
rendered not suitable for analysis.
Consensus to report a range of ages.
In the case of species, indicates undetermined sex.
The recorded value is known to be incorrect but the
correct value cannot be determined to enter a
cortecton.
When a series of data are plotted and anaylzed, this
point is obviously not within the normal distribution
of data, and eliminated from further analysis.
11.0 Quality Control Reports to Management
A progress report outlining the achievement of the Quality Assurance Objectives will be provided
to the Program Manager, the QA Manager, and the Project Co-coordinators at the end of the
project. The Project Manager will be notified immediately, however, if substantive changes are
made to the QAPJP The Quality Control Report will include a summary of the results of audits
that were conducted, data quality assessment, and the corrective actions that were taken. In short,
the degree to which the targeted precision, accuracy, and completeness goals were met will be
indicated in the Final Report.
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12.0 References
12.1 Bowen , S.H. 1983. Quantitative description of the diet, p. 325-336. In Nielson, L. A. and
Johnson. D. L. (eds.) Fisheries Techniques. American Fisheries Society, Bethesda, MD. 468 pp.
12.2 Eck, Gary W. and Wells, L. 1983. Biology, population structure, and estimated forage
requirements of Lake Trout in Lake Michigan. Technical Papers of the U- S. Fish & Wildlife
Service, No. Ill, 18 pp.
12.3 Eck. Gary W. and Wells, L. 1987. Recent changes in Lake Michigan's fish community and their
probable causes, with emphasis on the role of the alewife (Alosa pseudoharengus\.
Can. J. Fish. Aquat. Sci. 44 (Suppl. 2): 53-60.
12.4 Elliott, Robert F. 1993. Feeding habits of chinook salmon in eastern Lake Michigan. M.S.
Thesis, Michigan State University, Lansing, MI, 108 pp.
12.5 Holey. Mark E. and Elliott, Robert F 1994. Quality assurance project plan for coho sampling for
contaminant and diet analysis in Lake Michigan. Biota Work Group, Lake Michigan Mass
Budget/Mass Balance Project, 21 pp. Mimiog.
12.6 Lake Michigan Lake Trout Technical Committee. 1985. A draft lakewide management plan for
lake trout rehabilitation in Lake Michigan. Minutes of Lake Michigan Committee, Great Lakes
Fishery Commission, 1985 Annual Meeting, Ann Arbor, Michigan, March 1985.
12.7 Miller, Michael A. and Holey, Mark E. 1992. Diets of lake trout inhabiting nearshore and
offshore Lake Michigan environments. J. Great Lakes Res. 18(1.): 51-60.
12.8 Nielson. L.A. and Johnson, D.L. eds. 1983. Fisheries Techniques. American Fisheries Society,
Bethesda, MD. 468 pp.
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Appendix 1.
SOP-1:
Sampling Lake Trout and Forage Fish for
Contaminant Analysis
and for Diet Analysis of the Trout
1.0 SAMPLING LAKE TROUT AND FORAGE FISH FOR
CONTAMINANT ANALYSIS AND FOR DIET ANALYSIS OF THE
TROUT
This SOP provides the step by step procedure for collecting, measuring, preserving, and
transporting Lake Trout and forage fish and stomach contents removed from lake trout for the
Enhanced Monitoring Program Lake Michigan Mass Balance Study.
1.1 Overview
Lake trout and forage fish samples will be collected at the three Biota Sites identified in the Lake
Michigan Mass Balance Work Plan of October 14, 1993. These samples will be used to measure
contaminant concentrations in the fish tissue of PCBs, Mercury, and trans-nonachlor and to
examine the diet of the trout by evaluating their stomach contents. The following critical and
noncritical information associated with the samples will be recorded:
Critical Noncritical
1. Location 1. Gear
2. Date of sample 2. Sampling depth
3. Sample length 3. Time sampled
4. Sample weight 4. Water temperature
5. Fin clip (Or absence of clip)
The lake trout and forage fish samples to be collected for contaminant analysis are of primary
importance and therefore must be prepared and preserved as soon after collection as possible for
transport to the laboratory for analysis. During the field processing, stomachs will be removed
from the lake trout and preserved for diet analysis in the laboratory.
1.1.1 Summary of Method
Lake trout will be sampled with graded-mesh gill and forage fish with trawls fished from
the NBS's R/V Cisco on the bottom at each of the three Biota Sites in spring, summer, and
fall. The numbers of fish specified in the LMMB Work Plan together with the extracted
stomachs of the trout will be transported frozen to the GLSC laboratory of NBS in Ann
Arbor. Michigan for contaminants and diet analyses. Individual lake trout will be aged at
GLSC from coded wire tags inserted in their snouts and indicated by adipose I'm clip or
from other tin clips or scales. Bloater chubs, one of the three target species, uill be aged
from scales.
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1.2 Safety
In any field operation, emphasis must be placed on safety. Samplers must be aware of the
potential safety hazards to which they are subjected. Follow all safety protocols and
equipment guidelines, and be prepared for emergency situations. The sampler is primarily
responsible for his/her safety from potential hazards.
1.3 Equipment check and calibration
The following is a list of all needed equipment and consumables.
1.3.1 Equipment
Serviceable Equipment
Fishing vessel equipped with
-Locational instruments (GPS, Loran, Radar)
-Sampling gear (gill nets, bottom and midwater trawls)
-Electronic BT
Ice chests and bagged ice
Measuring board (mm markings required)
Plastic buckets (3- and 5-gallon)
Spring scale (1-10 Kg; Kg markings required)
Beam balance scale (0.1 to ? g; g markings required)
Calibrating weight
Dissecting pan (contaminant fish sampling only)
Dissecting knives
Thermometer (contaminant fish sampling only)
Lap-top computer
Consumable Equipment
Dissecting gloves (contaminant fish sampling only)
Aluminum foil (contaminant fish sampling only)
Plastic fish storage bags (contaminant fish sampling only)
Whirl-pac bags
Sample labels (contaminant fish sampling only)
Marking tools (pencils & permanent markers)
Fish scale envelopes
Cleaning sponge and brush
Rubber gloves for
-preserving fish
-handling fish
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1.3.2 Calibration and Standardization
Equipment necessary for calibration and the required frequency can be
found in Table 1.
Table 1. Equipment necessary for calibration and the required frequency.
Instrument
Thermometer
Locational device
Measuring Board
Scale
Calibration technique
Ice bath and boiling water
Calibration to a standard of
known Lat and Long
Check against second device
Check against standard S class
weights; 1,5, 10,25 kgs
Frequency
I/year
per trip
I/year
daily
Acceptance criteria
+/- 2 degrees C
H/-0.25 Km
+/- 2mm
+/-0.1 kg
1.4 Procedures
1.4.1 Collection of Contaminant Samples
Contaminant samples will be collected onboard the NBS's R/V Cisco, using gill nets for
lake trout and trawls for forage fish. Because age of fish will only be roughly
approximated in the field based on length, the Field Manager should oversample as
necessary to help insure that the specified sample sizes are met for both contaminants and
diet analyses (Table 1.0).
1.4.1.1 Daily location, weather, and fishing operation data are routinely recorded
by the Vessel Captain in the Ship's Log. Detailed information on location, gear,
fishing effort, catch (total number and weight by species), length frequencies of
selected species, predator-prey data including size and stomach contents of
selected species such as lake trout, etc, were formerly recorded on a detailed set of
field forms, but are now entered directly into a lap-top computer for later
transferral to the GLSC's RVCAT data base. (See RVCAT overview in Appendix
4 and Data Entry Screens in Appendix 5 of the QAPP). Surface to bottom water
temperature profiles are taken with an electronic BT when each gear is set and are
later downloaded in table format.
1.4.1.2 For each lake trout collected and each composite sample of each forate species.
record the following site and sample indentification data on two I.D. Labels, and
on a whirl-pac bag (see Appendix 6 of the QAPP Planfor data required on label).
Note: The recorded data will include: Sampling objective (contaminant, diet.
audit). Date, Lake, Location (including Biota Site & Port), Serial No., Species,
Sample I.D. No., Age/Size Group, Field Qualifier Flag, Collector's Name, and
Preservative.
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1.4.1.3 For all lake trout sampled determine and record the following in the field or in the
laboratory of GLSC if indicated otherwise.
-Maximum Total Length (mouth closed and caudal fin dorso-ventrally
compressed) to nearest mm using the measuring board.
-Total Weight (to the nearest 0.1 Kg. using the spring balance) offish taken for
diet only; fish for both contaminant and diet analyses will be weighed in the
GLSC laboratory.
-Fin clips will be recorded in the field for diet samples only; fish for both
contaminants and diet will have clips recorded in the laboratory.
1 A. 1.4 For each lake trout referred to in Section 1.3 that is 600 mm and longer remove at
least five scales (from just above the lateral line and below the posterior insertion
of the dorsal fin) with a clean knife when fin clips are recorded and place the
scales in a scale envelope. Label the envelope.
1.4.1.5 Line the examination tray with aluminum foil and place a lake trout in the tray.
Make a 3-5 inch incision with a clean knife in the belly of the fish. Pull out and
remove the stomach (anterior esophagus to pyloric sphincter) and all its contents.
The spleen and any other organs or excess flesh that may be attached to the
stomach should be placed back inside the fish. If the stomach appears empty,
open it to verify that it is completely void. Indicate so in the predator-prey file in
the Lap-Top Computer. Void stomachs need not be kept. Pack the whirl-pac bag
with the stomach and its contents and preserve them in the chest freezer.
1.4.1.6 Wrap each lake trout completely with the foil lining the examination tray and
attach one I.D. label to the foil, while being careful to retain all body fluids within
the foil. Place wrapped fish in a 4 mil polyethylene (Arcan Manufacturing,
Plainwell, MI), seal the bag and attach the other I.D. label.
1.4.1.7 Place the bagged fish in Vessel's chest freezer for preservation, or in a cooler and
pack with ice until it can be transferred to another freezer.
1.4.1.8 Thoroughly clean and rinse all equipment that comes in contact with sampled fish
between sampling individual fish.
1.4.1.9 Keep all samples in your possession in their preserved state (frozen or on ice) until
they have been delivered to the GLSC laboratory of NBS in Ann Arbor where
subsequent analysis will be conducted. Transport only in NBS approved vehicles.
Initiate a Chain of Custody form showing date of delivery and state of
preservation, etc. (See a copy of the form in Appendix 7 of the QAPP) Flags if
appropriate should be included in the Remarks or Comments columns of the
Custody form.
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1.4.1.10 Wrap Forage Fish including the Bloater Chub, which is categorized as both a
target and forage species in the LMMB PLAN, in the aggregate in aluminum foil.
Make no incisions in these fish. Then place them in the polyethylene bags in the
aggregate by species and age/size groups specified in the PLAN. Label each bag
inside and out with the information shown in Appendix 6 of the QAPP, except for
Sample No. which is applicable only for individual predator species (e.g. lake
trout), and preserve them in the chest freezer or a cooler with ice. Keep these
samples in possession in accordance with instructions for lake trout in 1.4.1.9
above.
1.4.1.11 Within the constraints of the demarcation of forage fish for diet sampling into the
age and size groups specified in the LMMB Plan of October 14, 1993, special
care must be taken to assure that these fish are representative by size (and hence
age) of all fish caught of the various categories being sampled.
1.4.1.12 When the trawl catch is small, the entire catch is retained and sorted by species on
the sorting table in the bow of the R/V Cisco. When the catch is large, however,
it is first randomly subsampled in the stern of the boat after running it into plastic
fish boxes that hold about 50 Ibs. each. The randomization is accomplished by
running the fish box or boxes back over a 5 gallon bucket or buckets while fish
are slowly "pouring" from the box. The subsample in the buckets is sorted into
species in the lab, and each species is counted and weighed. The numbers and
weight of the individual species in the total trawl catch are estimated from the
total weight of the trawl catch and the proportions (weights and numbers) of the
individual species in the subsample.
1.4.1.13 A sample of the catch offish in each diet group will then be obtained by first
mixing and spreading all fish in a given group on the sorting table. All fish on a
section of the table will then be retained for the diet sample. This procedure is
intended to avoid the inevitable bias that occurs when the sorter picks fish
individually from the catch.
1.4.1.14 Because the age of bloater chubs will not be known in the field, a length cut-off
based on sampling in recent years will be used to obtain an approximate
separation by age into the specified age categories for chubs of 0-2 years and 4 +
years of age.
1.4.1.15 As for lake trout as described in 1.4.1.9 above, keep all field samples of forage
fish for contaminant analysis in your possession in their preserved state (frozen or
on ice) until they have been delivered to the GLSC laboratory of NBS in Ann
Arbor where the analysis will be conducted. Transport only in NBS approved
vehicles. Initiate a Chain of Custody form showing date of delivery and state of
preservation, etc. (See copy of the form in Appendix 7 of the QAPP). Flags if
appropriate should be included in the Remarks or Comments columns of the
Custody Form.
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Appendix 2.
SOP-2:
Lab Analysis of Lake Trout Stomachs
and Data Entry
2.0 LAB ANALYSIS OF LAKE TROUT STOMACHS AND DATA ENTRY
This SOP is intended to provide a step by step procedure for examining and quantifying the
contents of the stomachs sampled, and then entering all data on the computer as part of
determining the diet of lake trout for the Enhance Monitoring Program Lake Michigan Mass
Balance Study.
2.1 Overview
2.1.1 Summary of method
2.2 Safety
In any laboratory operation, emphasis must be placed on safety. Personnel must
be aware of the potential safety hazards to which they are subjected. Follow all
safety protocols and equipment guidelines, and be prepared fcr emergency
situations. Each person is primarily responsible for his/her safety from potential
hazards.
2.3 Equipment Check and Calibration Check
Check to insure that all equipment and supplies are available in required amounts.
The following is a list of all needed equipment and consumables.
2.3.1 Equipment
Serviceable Equipment
Fume hood
Rinse water supply and rinsing bath
Rinse tray
Dissecting tray and tools (scalpel, forceps, scissors)
Dissecting microscope
Electronic balance and calibration weights
Plastic ruler (mm divisions)
Glass specimen jars
Scale press
Scale projector/reader
Computer & printer (with hard drive, disk dn\e. and necessary
software!
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Consumable Equipment/Supplies
Formalin (57c)
Rubber gloves
Impression acetate
Paper toweling
Plastic bags (2-5)
Reporting sheets and marking devices
2.3.2 Calibration and Standardization
Equipment necessary for calibration and the required frequency can be found in Table 2.1.
Table 2.1 Equipment necessary for calibration and required frequency
Instrument
Plastic ruler
Electronic balance
Computer
Calibration technique
Check against second
device
Use calibration weight
(300 g) and slope
adjust
Virus scan
Frequency
Start-End/ season
Daily
Every boot-up
Accepted criteria
+/- I mm
+/-0.lg
No viruses
2.4 Procedures
The following procedures will be discussed:
Sample preparation
Identification and quantification of prey items
-Numeration and estimation (for invertebrates)
-Length measurement and
-Weight measurement and estimation
Archiving representative samples
Mounting and aging scales
Data recording
Verifying data
Determining conversion data and developing formula
2.4.1 Analysis of Stomach Contents
Proceed with the following steps in a well ventilated (fume hood operating if necessary)
area intended for such work. Wear rubber gloves when handling preserved prey items.
Have equipment set up. calibrated, and ready for use. and start with and maintain a clean
work area.
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2.4.1.1 Identify each prey fish to species, assign it a percent digested state, and measure
(nearest mm) and weigh (nearest O.I g) it. Record data as indicated on the lab
data sheet. Measure length to the level of precision allowed by the amount of fish
remaining. Order of priority is: I) maximum total length, 2) standard length, 3)
vertebral column length, 4) length of a multiple of 5 vertebrae (preferably near the
caudal region). For those fish or parts of fish that cannot be positively identified,
record as unidentified remains.
2.4.1.2 Identify and group invertebrates into appropriate taxa and weigh (nearest 0.1 g)
each taxon as a group. Either count all individuals in a group or estimate the total
number based on weight (at least 0.5 g or 25 individuals) of a known number
representative of the group. Record data as indicated on a lab data sheet.
2.4.1.3 Repackage stomach contents in their whirl-pac bag and freeze. To facilitate
sample retrieval and verification under quality control, store groups (10-25) of the
whirl-pool bags containing the individual samples from similar locations and dates
together in clear plastic bags in freezer storage.
2.4.1.4 Make several photo copies of each completed Lab Data Sheet and file at separate
designated locations.
2.4.2 Aging Lake Trout and Bloater Chubs from Scales
The methods for preparing scales for aging fish and for verifying age are adequately
described in Fisheries Techniques (Nielson and Johnson 1983) and in the published
literature. The following highlight the procedure.
2.4.2.1 Make an impression of at least 5 lake trout scales from each scale envelope on an
acetate slide and return the scales and slide to the envelope after checking the
slide for clarity and detail.
2.4.2.2 Age each fish by counting annuli observed on a clear impression of one of the
scales viewed on a scale projector. Record the age in years using the convention
that a fish is age O in the year hatched and becomes one on January 1 st of each
subsequent year of life.
2.4.2.3 Follow the same procedure for bloater chubs. However, if detail needed for aging
is incomplete, the scales may be placed between glass slides, cleared with water.
and read direct with the scale projector.
2.4.2.4 At least 5fr of the fish should be reaged by the original person making the
determination and by a second person. Assign and record final age on the
envelope based on consensus reached by both of these individuals or by the
majority if a third independent reader is necessary. A length at age frequency
distribution based on known-age lake trout as determined from coded-wire tags
may be used to locate possible outliers for reaging. but allowance must be made
for previously observed differences in growth rate between Biota Sites (e.g.
growth has been slower on the Midlake Reef)
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2.4.3 Standard Measurements for Developing Conversion Equations
To allow reconstruction of total prey length and weight from partial length measures, and
to allow the conversion of total length and weight of preserved prey to length and weight
of fresh prey (or vice-versa), the following procedures will be followed.
2.4.3.1 For up to 50 intact individuals representing all sizes of each prey fish species (5
per 1/10 of size range encountered from preserved stomachs), measure total length
and weight, and then dissect the fish and measure (nearest mm) the standard
length, the vertebral column length, and the length of 5 vertebrae from the
posterior and anterior regions of the vertebral column; also count the total number
of vertebrae. Record these measures on a separate lab data sheet and identify as
Standard Measures.
2.4.3.2 When in the field, the Project Field Manager will conduct independent
measurements of enough stomach contents (steps 2.4.1.2 and 2.4.1.2 of SOP 2) so
that at least 50 prey fish representing all sizes and digested states be identified and
measured prior to preservation for later lab analysis'. These data will be recorded
on a lab data sheet identified as Standard Measurements.
2.4.3.3 Enter all data from Standard Measurements Data Sheets into prescribed fields of
the appropriate data base.
2.4.3.4 Develop the following conversion equations with associated errors for each prey
species:
Vertebrae length to vertebral column length and total length
Vertebral column length to standard length and total length
Standard length to total length
Total length to wet weight
Preserved total length to fresh total length
Preserved wet weight to fresh wet weight
2.4.3.5 Compare to similar equations developed from other studies to determine validity.
2.4.4 Data Entry and Verification
2.4.4.1 Maintain three independent copies of the data (on hard drive, on disk, and hard
copy printout) in different locations and update/backup each on a daily basis when
altered.
2.4.4.2 Record all data generated in the laboratory on lake trout diet and age on special
Lab Data Sheets that will be designed for that purpose. Record complementary
observations and qualitative data in a Lab Log Book. On a daily basis if practical,
enter these data from the data sheets into the RVCAT data base from which it can
be accessed and analyzed with the aid of personal computers.
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2.4.4.3 Using equations determined in 2.4.3:
-Calculate missing total length measures from partial length measures and add to
the database.
-If entered data are from both fresh and preserved prey, transform one and add to
the database so that a consistent measure is entered for all.
2.4.4.4 Identify and correct inaccuracies in data recording and entry, and identify outliers
as follows:
1) Plot data variables, identify peripheral values, and cross-reference with
original data records. Example plots include:
-Predator length vs weight -Prey length vs date
-predator length vs date -prey length vs weight
(by length type)
2) Query all data fields for values above and below expected values and
cross-reference with original data records.
3) Visually compare and verify each computer record with field and lab records
on original data sheets.
4) Resolve with the data collector any possible errors in recording.
5) Flag as an outlier any data that after completing the above, still appears to be
outside the range of expected values.
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Appendix 3.
SOP-3, Coded Wire Tags (CWT)
STANDARD OPERATING PROCEDURE (Modified from Lake Ontario SOP)
Lake Michigan
Purpose:
Use of a coded wire tag (CWT) injected into the snout for marking hatchery-reared lake trout stocked into
Lake Michigan began in earnest in 1985. Lake trout marked with CWTs have also been stocked into
Lakes Erie, Huron, and Ontario. Chinook salmon have been marked with CWTs and stocked into Lakes
Michigan and Ontario. Evaluation of the returns from fish injected with CWTs provides information about
growth, movement, and mortality of populations of hatchery-reared fish released to the lakes.
Marking Convention:
The Great Lakes Fishery Commission has reserved the adipose fin clip, as a single clip, for lake trout that
receive a CWT. For fish that do not receive a CWT the adipose fin may be clipped in combination with
another fin. Sometimes hatchery personnel fail to clip the adipose fin or clip some other fin of fish that are
injected with a CWT. In addition, a dorsal, pectoral, or pelvic fin may be injured, malformed, or
congenitally missing. Thus, a few fish with no clip or a mark other than an adipose clip may have a CWT
in their snout. An electronic wand used to detect and signal the presence of metal in the snouts of fish may
be used either in the field or in the laboratory to help verify the presence of CWTs in individual fish.
Field Procedure:
Record total length (mm), weight (g), fin clips, sex, maturity, sea lamprey wounds and scars, and stomach
contents using the computer or standard field data entry form.
If there is a possibility that a fish has been marked with a CWT, cut off the snout behind the eye sockets,
and place the snout in a compartmented polypropylene box. Each box should have a unique number
engraved on the lid and front, and each compartment should be permanently numbered. Record the box
and compartment numbers on the field data form in the space provided.
If the snout is too large for the compartment, or if no compartmented box is available, place the snout in a
jar or plastic bag (one snout per container). Record the sample, serial number and fish number on a
waterproof label and place the label in the bag or jar and securely close the top.
Freeze the collection of snouts. In the special circumstance that a fish identified as containing a CWT is
also a fish required for contaminant analysis, the fish is left intact and handled according to the
contaminant analysis protocol in force. The CWT is extracted later at the laboratory under joint
responsibility of Lake Michigan and Contaminant Monitoring personnel.
Laboratory Procedure:
Prepare a solution of sodium hydroxide (effective concentration of 15%). Warning - Sodium hydroxide is
caustic and should he handled with extreme care. When preparing the solution, laboratory gloves, lab coat
and e\e protection should be worn. Sodium hydroxide solution is to be slow l\ added and stirred into the
water. NOT the reverse; that is, water is NOT to be added to the solution. Remember that a highly
exothermic reaction results from adding sodium hvdroxide to uuter so be caietul about the integrity of the
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containers used to carry the solution. Refer to the Material Safety Data Sheet (MSDS) in the Laboratory
Safety Manual. Cover each snout with the sodium hydroxide solution and let stand until the flesh is
liquified (usually overnight). Remove the CWT from the solution with a magnetic stirring rod. Rinse the
stirring bar/CWT in vinegar and then in water and transfer the CWT to a magnetic pencil.
Using a tag-reading jig and a binocular microscope, decipher the code. A procedure provided by the tag
manufacturer for deciphering the CWT code is attached.
Record the six-digit code in the space provided on the field data form. Affix the CWT to the field data
form adjacent to the code using a double strip of clear adhesive tape.
A second reading by an independent observer without reference to the code recorded on first reading is
required. If the two readings do not agree, another reading by each of the observers should resolve the
disagreement.
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BINARY CODED MICRO-TAG
B
D
MASTER WORD
1 2 4 8 16 32
II I I I I
DATA ROW 2
DATA ROW 1
0
DATA ROW 3
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BINARY CODED TAG FORMAT
Data is carried on binary coded wire tags in six binary-digit words, or numbers. Consider the number
1066. It might similarly be called a four decimal-digit word, and can be written in columns as follows:
1000s 100s 10s Is
1066
Said another way, it means the sum of 1 thousand, no hundreds, six tens, and six ones.
Binary-digit words, or numbers, can be written in columns in the same way:
32s 16s 8s 4s 2s Is
1 10101
The binary number 110101 thus means the sum of 1 thirty two, 1 sixteen. O eights, 1 four, 0 twos, and 1
one, or 1 10101 binary = 53 decimal.
The binary coded wire tag material is marked with four six-digit binary words written lengthwise on the
wire, 90° apart around its circumference. Three of these words carry the data, and following them is a
seventh digit in each row which is used as an error check as explained below. The fourth word is known
as the master word and is always the same. Its purpose is to mark the beginning of the data words and to
identify the direction in which they are to be read.
The information is carried by notches on the wire spaced .0048" apart. Notches are read as binary 1; no
notch is read as binary 0. At the standard length .042", this means that there are at least 8 visible mark
positions on a tag. The logic in the coding system is such that tags as short as .030" guarantee
unambiguous data recovery. (A similar, but not identical, scheme is used to mark "half-length" or .020"
tags. Reading instructions for half-length tags are available request.)
The data format on a coded wire tag is keyed to the seven-bit word which we call the master word. This
word, always the same, is unusual in that it contains an extra, in-between, mark, i.e., the word looks like
00111M.
The half-interval mark between the first and second normal marks is instantly apparent. Every tag bears
this word, although it may start and end in different places, e.g., 11M001, as a result of the random nature
of the cutting process.
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To read a coded wire tag, find the master word and orient the tag horizontally so that the master word reads
in the correct direction, 00111M. Then the remaining data are to be read according to the following
conventions:
1. The column labels for the data words are derived from the master word:
00111111 MASTER
Ck 32 16 8 4 2 1 COLUMN IDENTIFICATION
2. With the master word on top of the wire and running in the proper direction, rotate the tag on its axis
so that the master word moves up. As the three data words come into view, they are, in order:
1. DATA WORD 1
2. AGENCY CODE
3. DATA WORD 2
If one were to imagine the surface of the tag unrolled as if it were a sheet or paper, it would look like this:
Check 32s 16s 8s 4s 2s Is COLUMN IDENTIFICATION
0 0111111 MASTER WORD
1 10110 1 DATA 1 = DECIMAL 45
1 00111 1 AGENCY = DECIMAL 15
0 11001 0 DATA 2 = DECIMAL 50
The convention adopted for the seventh column, the check bit, is that the sum of the notches in each of the
three data rows must always be odd. This provides a check against coding errors in the data. For-example,
if the required number was
101101 (six bit word),
there are four binary ones, or notches; the sum is, therefore, even; and the check bit must also be a one.
The data would appear on the tag wire as
1101101.
If the data were to be
010110,
the checked data would appear on the tag wire as
0010110
since the data word already has an odd number of bits, and the check bit must be zero.
The information on each of the four sides of the tag wire is repeated continuously every seven spaces.
Since tags are cut off every 8.5 spaces, actual tags may be cut at any point in the word. An example of a
tag cut between the 4s and the 8s columns follows:
4s 2s Is Ck 32s 16s 8s COLUMN IDENTIFICATION
1 111001 1 MASTER
101110 1 DATA 1 = DECIMAL 45
111100 1 AGENCY = DECIMAL 15
010011 0 DATA 2 = DECIMAL 50
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APPENDIX 4.
Research Vessel Catch Information System (RVCAT)
Introduction
RVCAT - System Overview
This is an overview of the information system used by the Resource Assessment Section of the National
Fisheries Center - Great Lakes. The system will be referred to simply as RVCAT (Research Vessel Catch
Information System). It is a living and growing system pulling raw data from the Great Lakes and
producing information of use to the Lakes Community. The purpose of RVCAT is to provide clear,
consistent and easy access to research vessel data for vessel biologists.
Research vessel data was first collected on Lake Superior in 1953 and each year since the vessel base was
established in 1957. Data was collected from Lake Michigan in 1954, 1955 and annually since 1960.
Collections were made in 1-956, 1969 and regularly beginning in 1972 on Lake Huron. The Lake Erie
Vessel base was established in 1959 with collections made as well in 1957 and 1958. The Lake Ontario
station was begun in 1977 with vessel operations beginning in 1978.
The intended computer hardware platform for RVCAT is any system which supports Statistical Analysis
System (SAS Institute, Gary, NC) and ORACLE (ORACLE Corp., Belmont, CA) software. Currently,
RVCAT is implemented an a Data General MV series mini-computer and IBM-PC compatible
micro-computers. One goal of RVCAT is to be transportable to diverse computing environments, so that it
is not limited by hardware or software which becomes out of date, or of differing capacities.
ORACLE is used for all basic data management and reporting functions, and SAS is used for statistical
analysis. Other software may be used as well for specialized needs.
RVCAT is implemented and maintained jointly by Vessel Biologists of Resource Assessment and
Biometrics and Computer Services staff. The system has been partitioned into 12 compartments. A list of
Responsible People and their suggested assignments is included elsewhere in this manual.
RVCAT Background
The RVCAT system began in 1972 as a collection of miscellaneous batch programs written for the IBM
1130. As the need arose for specific reports, new programs were added. Several users took part in
designing these reports and the new data record formats needed to enter data into the system. Data were
originally stored on punched cards.
In 1976, the laboratory gained access to the University of Michigan MTS computing system, as a remote
batch station.
Programs and data files were gradually transferred to that system and backed on magnetic tapes. Edit
programs were written to provide greater control o\cr data accuracy.
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Over the years, it became necessary to change record formats, and programs had to be modified in various
ways to accommodate changing needs. In 1978, the entire data base was rewritten in the new format.
Then, in 1984, it was decided that the programs should be rewritten to be interactive, giving users various
options in the way data was to be organized and tabulated. At the same time, data retrieval programs were
written to allow users to retrieve subsets of data from the original master files, and routines were developed
to permit users to run the various programs associated with the data. This system was called RVCAT I.
In the spring of 1985, Viking Forms Management software was purchased for ffiM-XTs to replace
key-to-card data entry with key-to-disk data entry.
In the fall of 1985, a Data General MV4000 mini-computer was purchased to replace the 1130 system, and
it became necessary to transfer programs and data to a new operating system. Data files were converted
from the tape format used by MTS to a form acceptable by the Data General, and transferred to the new
system. At the same time, various report format changes were decided upon, and the need for more
flexibility in running the programs was recognized. To meet these needs, the system called RVCAT II was
developed, and became operational in September, 1986.
In January, 1988, a committee was formed to completely review and revise RVCAT. A relational database
management system (ORACLE) was identified which would permit the development of a system which
would be compatible between the field stations and the Center. It was projected that ORACLE could
provide DBMS needs and Statistical Analysis System (SAS) could provide statistical support. Automated
data entry on the research vessels was proposed including digital measuring devices.
In the fall of 1988, ORACLE was purchased as part of a GCMS purchase and installed on the
mini-computer, The process of designing database tables was completed in the spring of 1989. At that
point, the process of loading existing data into the database was begun.
In the fall of 1989, 80386 micro-computers and ORACLE were purchased for the field stations. The field
stations were then nearly identical in computing capability with the Center.
By March, 1990, data tables were designed, loading of card image data into the tables was progressing, and
a prototype data selection and reporting system was demonstrated.
In June 1990, proposals were circulated specifying how a more comprehensive approach to implementing
the RVCAT system might be handled. In July, manuals and starter systems were circulated to the field
stations. The starter system included table definitions, a data entry form, a data selection system, and trawl
length frequency report linked to the selection system.
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Data. Tables (Hierarchical)
TR CATCH TR FISH TR LF GN CATCH GN U? GM FISH
Lookup Tables (alphabetical - no schema)
Data Selection Tables (hierarchical)
CRUISE
_SET
FISHING DEPTH SET
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Table Definitions
This document defines the Research Vessel Catch Information System tables. It is divided into these
sections:
Naming Conventions
Abbreviations
Table Schemas
Data Table Definitions
Lookup Table Definitions
Selection Table Definitions
Report Table Definitions
Naming Conventions
Table names are in capital letters and column names are in lower case. Next to each table name is the table
pneumonic used in report specifications. There are four groups of tables: Data, Lookup, Selection, and
Report. Tables are listed in hierarchical or alphabetical order. Listed below each table name are: the
column number (used for report definitions), column name, the data type and size, and the primary key -
not null designator. The primary key (pk) is a column or group of non-superfluous columns that insure the
uniqueness of rows within a table. Columns designated primary key are assumed not null unless otherwise
specified.
1. Table names are unique.
2. Column names are unique within a table.
3. Names are descriptive and meaningful.
4. Names will be displayed on terminals and hardcopy.
5. Users will be familiar with and will use names to communicate with the system.
6. Names are brief, using whole names where possible.
7. Names are consistent between tables.
Abbreviations
aero acronym
ave average
bt bathy thermograph slide number
cu chub management unit
cwt coded wire tag
dc diameter at capture
gn gillnet
id identification number (system assigned key)
If length frequency
Iw length weight
n number or frequency
nn not null
op operation
pk primary key
sci scientific
sd statistical district
sta station
temp temperature
tr trawl
wtu \vhitetish management unit
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Table Descriptions
This document describes the system of tables as defined in the document "Table Definitions" The model
captures the spirit of the method described in "Relational Database Design" The model minimizes
redundancy (it is impossible to eliminate redundancy), update anomalies are eliminated, and it has a high
degree of maintenance-resistance (the model will stand the test of time, will be widely accepted, and will
require few alterations other than additions). Non-loss data reduction has been achieved. Goals of the
design process are simplicity, use-ability, and efficiency.
A data model is a collection of constructs, operators and integrity rules which together support a dynamic
representation of real-world objects and events, The only construct in a relational model is the table.
Operators are add, change, delete, select, project, join, group, and so forth. Integrity rules include no null,
primary key and no duplicate; and serve to maintain order and consistency in the database.
The scope of this document is construct and integrity. Beyond the scope of this document are operators
which are used by data entry and report tools for input and output, and values that can be calculated from
table values.
Many of the tables composing this model are lookup tables, They have one numeric column containing the
code, and one or two columns containing the description(s). These tables are largely static in the content.
They are used for system integrity and to provide labels when output is generated.
The remaining tables are those which will contain the actual Research Vessel data. They will continue to
grow in content as data are collected and entered. Each table models a particular kind of data, and is related
to the other tables in a clear and consistent fashion. These tables are related to each other hierarchically,
that is, there is one master table, and a number of dependent tables, The master table is called OP
(operation). Most of the subordinant table names begin with either GN (gillnet), or TR (trawl). Another
subordinate table is BT which contains temperature profile data.
All data stored in the tables is represented the same as in the ASCII (card image) data sets with the
following exceptions:
Port is stored as the combination of lake code and port code. For example, Saugatuck (24) in
Lake Michigan (2) is stored as 224. This convention will keep port codes unique throughout the
system.
Likewise grid is stored as the combination of lake code and grid number. For example, grid 721
in Lake Ontario (6) is stored as 60721. This convention will keep grid codes unique throughout
the system.
Depths are stored in meters rather than fathoms or feet. Precision is to the nearest decimeter. This
is a consistent simple way of storing depth that will accomodate the needs of all five lakes.
Although meters is the only accepted unit in the scientific literature, depth measurements can be
displayed in any unit desired through a simple conversion factor.
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The following is a description of each data base table starting with OP and working down the hierarchy.
OP
Table OP (operation) contains a log of Research Vessel operations. Each row represents a deployment of a
sampling device by a research vessel. The primary key is composed of year, vessel, serial, and
sample_type. Column op_id represents the primary key, is system (arbitrarily) assigned, and is a key to
each operation throughout the system. Information includes time, location, conditions, and target
organism(s). Examples of distinct operations are: trawl tow, gillnet set, gillnet lift, remote operated vehicle
(ROV) transect, hydroacoustic transect, and plankton tow. A separate op row is created even when two
operations are done simultaneously (Note: This does not necessarily imply more than one Vessel
Operations Form.).
GN_OP
Table GNJDP (gillnet operation) contains information about each whole gillnet deployed by a research
vessel. There will be one row in GN_OP for each gillnet set row in OP. The primary key is column op_id.
TR_OP
Table TR_OP (trawl operation) contains information about each trawl tow. There will be one row in
TR_OP for each trawl-set row in OP. The primary key column is op_id.
GN_EFFORT
Table GN_EFFORT (gillnet effort) contains information about each panel of a whole gillnet. Each panel is
represented as a row in GN_EFFORT. The primary key is composed of columns op_id, mesh-size, and
net_material. Column gn_effort_id is system assigned, is representative of the primary key, and is used to
relate rows in GN_CATCH, GN_LF, and GN_FISH to a panel of net. GN_EFFORT is in a many to one
(M: 1) relationship with OP Notice that a particular gillnet-set row in OP will key directly to one row in
GN_OP and many rows in GN_EFFORT. Information includes fishing depth, mesh size, length, and
material composition of the panel.
GN_CATCH and TRJTATCH
These tables represent the gross catch of each unit of gillnet or trawl effort. They are identical in structure
except for the system assigned key. GN_CATCH is subordinate to GN_EFFORT linked through
gn_effort_id and TR_CATCH is subordinate to TR_OP linked through op_id. The primary key for
GN_CATCH is composed of the columns gn_effort_id, species, and life_stage. The primary key for
TR_CATCH is op_id. species, and life_stage. Information includes fish species, life stage, and total
number and weight.
GN_LF and TR_LF
These tables will contain length frequency data and are keyed through gn_effort_id and op_id to related
units of effort. Each nm models a number of a species of fish at a particular length. The primar\ kc> tor
GN_LF is gn_cffort_id. species, and length. The primary ke\ for TR_LF is op_id, species, and length.
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GN_FISH and TR_FISH
Individual fish are modeled in these tables. Rows are keyed through gn_effort_id or op_id to related units
of effort. Information includes fish species, length, weight, sex, maturity, age, diameter at capture of age
structure, fin clip, cwt number, scar and wound information. These tables are a combination of the
historical Length Weight, Scale, and Predator Prey data. There is no primary key for these tables!
TR_fish_id and gn_fish_id are system assigned and key to subordinate information which includes annulus
and prey data.
GN_PREY and TR_PREY
These tables are identical in structure to GNJLF and TR_LF except that rows are subordinate to a predator
in GN_FlSH or TR_FISH rather than a unit of effort. Rows are keyed to individual predators through
gn_fish_id and tr_fish_id. The primary key is composed of columns gn_fish_id, species, and length for
GN_FISH, and tr_fish_id, species, and length for TR_FISH.
GN_ANNULUS and TR_ANNULUS
The annulus tables model individual annulus measurements. Rows are keyed to individual fish through
gn_fish_id and tr_fish_id. Each row includes the annulus number, age_struct, and size. The primary key is
composed of gn_fish_id, age_struct, and annulus for GN_ANNULUS and tr_fish_id, age_struct, and
annulus for TR_ANNULUS.
BT
Each row in BT represents a temperature at a depth for a particular operation and bt cast. The primary key
is composed of op_id, bt, and depth. As many depths as desired may be stored for each profile.
LffE_SIZE
Each row in LIFE_SIZE represents a range of cut off lengths for the life_stage of a species of fish for a
lake and year. It documents this information within the database, and is used to segregate length frequency
data during report generation. The primary key is composed of year, lake, species and life_stage.
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SOL> describe op
Null?
Type
OP_ID
YEAR
VESSEL
SERIAL
SAMPLE TYPE
TARG£T~
LACE
PORT
CRUISE
OP DATE
TIME
GRID
BEG X
BEG~Y
ENO'X
ENO~Y
LATITUDE
LONGITUDE
AVE DEPTH
8EGJ>«J>TK
BEG^BT
END'BT
TEMP METHOD
SURF'TEMP
SECCHI
WEATHER
VINO SPEED
SE« CONDITION
BOTTOM
VESSEL DIRECTION
U1HD DIRECTION
BEG LORAN
ENO~LORAN
COMPLETE
REMARK
BEG ST_1D
END~BT_10
SOL» describe op_t«rget
Name
OP ID
TARGET
SOL> describe bt
H«CM
OP ID
BT~
DEPTH
TEMP
SOL> describe ebt
Name
BT ID
DEPTH
TEMP
LIGHT
SQL> describe gn op
N«ne
OP ID
SET TIME
L1FT_TIKE
NIGHTS OUT
TYPE SET
NOT NULL NUMBEB(6)
NOT NULL VuMBGKA)
HOT NULL NUMBER<2)
NOT NULL UUHBEKO
HOT NULL NUK8ER<2)
NUttERO)
HOT NULL NUHBE<(2>
NOT NULL NLMDCR(6)
NOT NULL NUMBER<2)
NOT NULL DATE
HOT HULL NUMfiERCO
HUH8ERCS)
HUMB£R(7.2}
NUMBER<7,2>
HUMe£R(7.2>
HUHBER(7.2)
NUHBCR(A)
NUMBER(S)
NUMBER
NUH8£R
NUMBER<3)
NUMBER(3>
NUMBER<1)
KUMBER<3,1)
NUMBCR<4,1)
NUHaER
NUN8ERC1}
NUMBERd)
NUHBERC7,1)
NUM8ER(7. 1)
UUN6ERC1)
CHAR(SO)
NUMBERC6)
NUMSERC6)
Null? Type
NOT NULL NUM8ER<6)
NOT NULL NLMBERC3)
Null? Type
NOT NULL HUMBERT)
HOT NULL NUMeER<2>
NOT NULL MUMBER(5,1)
NOT NULL NUH8ER(3,1)
Hull? Type
NOT NULL HUMBER(6>
NOT NULL NUMBER(«,1)
NOT HULL X
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HSHIIIC_TEMP JET
GRID *"
FlStUHG_TEW_LlFT
»XS£t<3,l>
uumacs)
HUHBEKI,!)
HuU?
GH EFFORT ID
Of>~IO
MESH SIZE
NET MATERIAL
BE6~OEPTH
END DEPTH
HETJ.EHGTH
SOL> describe gn_catch
Uaoe
NOT HULL UUMBER(6)
HOT HULL MUMER<&)
HOT HULL NLNSEK2)
HOT HULL HUMBEHO)
HOT HULL HUHBEXt)
HuU?
Type
CH EFFORT_JD
SPECIES
11 FE_STACE
M
WEIGHT
LFJI
SOL> describe sn_U
HOT HULL NUH8EI)(6)
HOT HULL HUH8EJK3)
HUKBED(I)
UOT HULL UJH8ERC6)
Hull?
Typ.
GN EFFORT 10
SPECIES
LENGTH
N
LIFE_STAGE
SOL> describe s"_fish
UOT NULL *M&CR(6)
HOT NULL HUHBE8O)
HOT HULL MUMS£R<4>
HOT NULL UUHgE«O
HUHBERd)
Hull?
Type
GH_FIS«_IO
G« EFFORT ID
SAMPLE
SPECIES
LENGTH
WEIGHT
SEX
MATURITY
AGE
AGE_STIUCT
DC
FIU CLIP
TAG'
CUT
STOMACH
M
A2
A3
B2
S3
SCAR
UOUHO
SQL> describe gn_vnjtui
HOT NULL HUHBER(6)
HOT NULL UUnBERCA)
HUNBER(i)
HOT HULL HUN8EJi(3)
HOT HULL NUNBERC4)
HUKBERCS)
HUMBER(l)
HUMBER(1>
HUMBEK(2>
NUHBER(2)
HUNBERO
HUM8ER<2>
UUHBER(l)
uumucA)
HUHBERC1)
HUH8ER<1>
UUNBERd)
HUHSERC1>
NUMBER(I)
HUM8ER<1)
HUMBERC1)
WJNBEIid)
HUMBERO)
NUMBER(l)
HUHBERd)
Hull?
CU_FISH ID
ACE STRUCT
AHHULUS
DIAKETEP
SQL> describe 9O_prey
HOT HULL HUHBER(6)
HOT HULL HUHeER(2>
HOT NULL HUHSER<2)
NOT HULL HUHBEIt(t>
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Type
GN_FISN_IO
SPECIES"
LENGTH
M
SOL> describe gn_icaucH
CU_FISH ID
SPECIES"
H
AVE LENGTH
WEIGHT
VOLUME
SOL> describe tr op
Hwe
OP_IO
SST Tit*
TOW'TIHE
SPEED
SPEED UHIT
TYPE SET
FISIUMG T6KP
FISHINGJJEPTH
MESH SIZE
T«_D£Sl describe tr utch
OP 10
LIFE_STAC£
SPECIES
u
WEIGHT
LFJJ
SQL> describe bucket
OP_IO
WEIGHT
SOL> dexcrib* tr
HOT HULL MUM«£JU6>
HOT HULL UUMBERO)
Null?
Type
HOT HULL NUM6ERC6>
HOT NULL NUKBERO)
NUHJEKC2)
NUNBEKO
Hull? Type
NOT HULL NUHBER<6)
NOT HULL UUMSER(],1]
HOT NULL UUHBER(S,1>
NOT HULL NUH8ERO)
NOT HULL NUMIEK1)
HOT HULL HUMBEIK2)
HOT MILL MUH6ER(2J
NUH8ER<5)
Hull?
Type
HOT NULL HUHBER(6)
HLMEKI)
HOT HULL NUM8ERC3)
HOT HULL MUM8£R<6)
Hull? Type
HOT NULL HUHeEB(6)
HOT HULL NUMER<7)
OP ID
LIFE STAGE
SPECIES
NX H
LF_»
SUB.WEIGHT
HOT NULL NUNBER<6)
HUMBER(I)
HOT HULL NUMBEXCO
MJmERCI)
HUMBEI)(6)
de«crib* tr_U
OP 10
SPECIES
LEHGTH
H
LIFE_ST«CE
SQL> describe tr_l
OP_IO
LIFE STAGE
Null?
Typt
NOT UJLL HUHBCR(6)
HOT MULL NUKBERC3)
HOT HULL UUKB£R(4)
HOT HULL HUM8EIK4)
NUIUE(I(1)
Type
HOT NULL MJMSERC6)
NUMBERU)
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SPECIES
LENGTH
SOL> describe tr fish
Hull? Type
TR FISH ID
OP'lD
SAKPLE
SPECIES
LENGTH
UEICHT
SEX
HATUBITY
AGE
AGE STRUCT
DC
FIN CLIP
TAG"
CUT
STOMACH
A1
A2
A3
81
82
83
SCAR
UOUNO
LF
SQL> describe tr a/tnulus
MOT HULL IUttER(6>
NOT HULL UUHKKi)
NOT HULL MJHSEIO)
HOT HULL NUHKK<
NLMEIKS)
ULM££<1)
ULMOEIK1)
NUHfiEXZ)
HUHSEX4)
NUMEK2)
MJNIEltd)
HUHKR(l)
HLHBEKd)
NUHBEXU
NUHBCRd)
HUMSERCU
NUHBEHCU
HUK8ERC1)
WJHBEXI)
WJKBESd)
HUHBERd)
MuU?
IB FISM_10
AO£_ST«UCT
AHMLU.US
DIAM£TE(
SQL> da«crib« tr^prev
NOT NULL KUK8W6)
NOT HULL NUM8EX2)
HOT HULL NUM8£8(2>
HOT HULL NUNMRCM
Type
TR FISH ID
SPECIES
LEHGTH
HOT NULL MUMBEIXi)
NOT HULL «UKS£a(i>
S0l> spool Off
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SQL*
SQL> vclect * ffon *gc_stnjct order by «g*_struct;
1 Sell*
2 otolich
3 Opereulun
4 CUT
5 Fin Clip
& Spine
7 Fin Kay
8 Vertebra
8 records selected.
S0l> ealact • fre» batten enter by bottce;
BOTTCM BOTTOM MAKE
1 Badrocn
2 I
3
4 Fine gravel
S Sand
6 Silt
7 Cl«y
8 Hart
9 Hud
10 Organic dabrii
11 Hud t Gravel
12 Gravel t Clay
13 Sand 1 Clay
U Sand I Sitt
IS Sand t Gravel
16 Sand I Hud
17 Silt I Clay
U Mud <, Silt
19 Hud 1 Clay
20 ottwr (raoarks)
99 «/I>
21 records celectad.
SQU> salact • froa. diraction order by direction;
aiKECTlON D1REC
a v
1 HE
2 E
3 SE
4 S
5 SU
6 U
7 HU
8 N
9 U/II
10 rvcords salactad.
SOL> Hlact * fro* fin_clip ordar by fin_clip;
Fi«_aip FI«_CUP_». Fi«_a.ip_u*ic
a NC no clip
1 AD Adipaaa
2 ADLV AdipoM-ltft vcntrnl
3 MWV IdlpMa-rioht vantral
4 ADLV8V Adlpoce-left ventral-right ventral
S ADLP Adicou-left pectoral
6 MXiP Adipo&e-right pectoral
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7 ADLM
a LPRM
9 RPRM
10 LV
11 RV
12 BV LVHV
IS LP
14 Sf
15 BP LP*P
16 LPIV
17 RVLP LPHV
18 RPLV
19 D
20 OLV
21 DRV
22 08V OKVLV
23 DIP
24 OOP
2S u«
26 «M
27 LN
2fi RPHV
29 A08C
30 OU>
31 LPLM
99 Mo Code
Adipose-left •u select • froa food order by food;
FOOD FOODJUME
0 MT
1 Ponr
2 Mysil
3 Clam
A UFR
S Leech
6 Incacti
7 Fish Eggs
a snaifc
9 Vegetable
10 Cacttis
11 UlR
12 tiopodc
13 Hidge Larvae
H Hicrodrilac
15 Crayfish
16 HegacVllas
17 Bythotracnca
18 Spheridc
19 Zooplankton
106 «leuife
1QQ 9iz.tard shad
109 Smelt
127 burbot
129 Thretspine Sticklaba
130 Uineipine Sticklebac
131 Irout Perch
200 Coregontds
204 Bloater
216 chub
301 Chinook
307 Lake Trout
706 Johnny Darter
801 yellow perch
900 Sculpins
902 SI lay Sculpin
904 0«epuater Sculpin
1001 Acrcparus harp
1002 Mona
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1003 Bosalna lonsir
1004 Calanaid camp
1005 Ceriodaph«ia
1006 Coptpad race I i
1007 Oiydorxa ifiuer
1008 Cyclopoid ccpep
1009 Dlacyctapt thaa
1010 cyclop* varlc
1011 Acanthocyclaps v
1012 Oaphnia
1013 DaphnU galtata
1014 Oaphnia puLex
10
1020 turp»ccic«\d*
FOOD rOOO_HAME
1021 Hacrocyclcps
1022 Mtsacyclop «daA
10Z5 Ophryo«u»
1025 Polypt»«»J»
1026 Sopholeberis
1027 siaacephatui
1028 skUcodiaprous
1029 Tpopocyct prmc
1030 Acarirva
1031 Argulm
1032 Bnrazoan siatbl
1033 Ceratiiai (Prot)
1034 Ceracopooonid
1035 Chaoborus p^^ct
1036 Chiron, larvae
1037 CoUaabala
1036 Ergasilus
1039 Hydra
1040 MCMtoda
1041 oligodiaera
1042 Oscracoda
1043 Oiaporefa affin
1044 Tardigrade
1Q4J KalUcoctia
1046 »U ochar xxifan
1047 Hayf ly
1048 cyclopoid adult
1049 AlcneUa
10SO Tarr. lns«CT
10S1 olptara (larv. )
1052 Ectoc/clops
1053 Trichoptara
1054 CxJonata nyaph
1055 Chiron, pupae
1056 Cortxldae
10S7 Paracyclopa
1058 Holopadiui
10S9 Turtaatlaria
1060 Ceptodiap. siciUs
1061 Lianocalanus
1062 Ilyocryptus
1063 Asplanclvni
1064 Macrothrix
106S Chirxxi. e^g£
1066 Sida
1067 leptodiap. uli
1068 Leptodiap. ain
1069 Hysift r«Licca
1070 Bvttotrcphet cc
1071 Ceracopog. pupa
1-344
-------
QAPP for Lake Trout and Forage Fish Sampling
Volume 1, Chapter 5 for Diet Analysis and/or Contaminant Analysis
1072 Dapteiia r«tfocu
1073 EurytwBara af f i
1074 Eubouina caret
1075 leptodora kindc
1076 Daphnla -i-i'-tiii
1077 Oaptmia parvula
FOOD FOODJUNE
1076 uaphnia pulicaria
1079 Daphnla schodleri
1080 Latona setitera
1081 leptodiaptoaauc
1082 Cyclopoloa
1043 eucyclopa
10M OlaptoiildM
10B5 Adult ulanald
1044 S«nee.ll«
1087 Lcptad[»«c. «lcUo.d
12A records lelectad.
SO1.> Mlect • froi l»k« oroer by Uk«;
LAKE l»t£_«*hE
1 Superior
2 Hichigjn
J Huron
4 St. CUir
5 erfe
6 Ontario
7 Oalw
8 St. Cliir River
9 Oecroic River
10 St. H»ryi «i«r
11 Anchor (ujy
99 Oth«f
12 record! utectcd.
SOL> Mtect * froa (Ut_»CMe order by tife_it»g«;
LIF£_STACE t!FE_ST»CE_>UIC
0 Young of Y«ar
2 Beyond neond year (Mc-jroup II «nd older)
3 Subiwple
4 Subucple
s sitiimit»
6 life Stag* Hot Mcardad
7 Adult
8 Leci than 7 inches
9 Greater than 7 inches
10 records selected.
SOL> select * froB Hturity order by MturUy;
HATUR1TY HATUKITY HANc
0 Unknown
1 loasture
2 nutuoe
3 Gravid
4 Ripe
5 Partly spent
6 Spent
7 Abnormal
8 Unrecorded
1-345
-------
QAPP for Lake Trout and Forage Fish Sampling
for Diet Analysis and/or Contaminant Analysis
Volume 1, Chapters
records selected.
*t> select * fro* •uh_clu order by •esh_siz«;
000
I 0 1/8
2 0 2/8
3 0 5/8
4 0 4/8
5 0 5/0
6 0 6/8
7 0 7/S
0
>/«
2/8
3/8
4/8
5/8
6/a
7/8
20 2 0
2) 2 1/8
22 2 2/8
23 2 3/8
24 2 4/8
25 2 5/5
26 2 6/8
27 2 7/8
30 3 0
31 3 1/8
32 3 2/8
33 3 3/8
34 3 4/8
35 3 5/8
36 3 6/8
37 3 7/8
40 4 0
41 4 1/8
42 4 2/8
43 4 3/8
44 4 4/8
45 4 5/8
46 4 6/8
47 4 7/8
50 5 0
51 5 1/8
52 5 2/8
53 5 3/8
54 5 4/8
55 5 5/8
56 5 6/8
57 5 7/8
60 6 0
61 6 1/8
62 6 2/8
63 6 3/8
64 6 4/8
65 6 5/8
66 6 6/8
67 6 7/8
70 7 0
71 7 1/8
72 7 2/8
73 7 3/8
74 7 4/8
75 7 5/8
76 7 6/8
1-346
-------
QAPP for Lake Trout and Forage Fish Sampling
Volume 1, Chapter 5 for Diet Analysis and/or Contaminant Analysis
77 7 7/8
o4 records selected.
£Ql> select * from net eaueriel order by n«t_nat«ri«l;
NET MATERIAL VET MATERIAL HA
1 Nylon
2 Cotton
3 Linen
4 NonofUaocnt
SOL> select • fro» port order by port;
PCBT PORTJUME
102 Sault St*. Marie Mich.
104 UMtefish Bay
106 Grand Uarais
108 H^icing
110 Shelter Bay
11Z Marquette
1U Stvrard Rock
116 Big Bay
118 Huron 8»y
120 I'AAte
122 Portaoe Entry
124 Grand Traverx Bay
126 8 Bay
128 Copper Hr..s««l« Mr.
130 upper Entry
132 fonage Lake
134 Qntonagon
136 Black River
138 Chequaaeson Bay
HO ApostU Ulandx
142 Cornucopia-Port uins
1
-------
QAPP for Lake Trout and Forage Fish Sampling
for Diet Analysis and/or Contaminant Analysis
Volume 1, Chapters
214 Ludinoton
216 Pcntuatar
POUT POBTIUME
218 Uhit« Lake
220 Kuakegon
222 Grand Haven
223 Port Sheldon
224 Saugatuek-Molland
226 South Hawan. Palisade*
228 Benron Mr.-St. Joe. Cook
229 Uew Buffalo
230 Michigan City
231 Gary, Indiana
232 Chicago
234 Uaia-agan
235 Highland Park
216 «acine-K«no«h«
238 Nftuaukee
240 Port Washington
241 Mi luaukec Beef
242 Sheboygan
244 ManftOHOc-Tuo liwn
246 Kmaunw-AlgoM
248 Sturg«on «ay
249 Baily'i Nartaor
250 Uadtington Uland
2S2 Fdrport
2S4 HM>UtiQo«
2S6 uubinuay, Epoufatte
2S7 North Shore
258 simoni leef
259 Uhita Sho.lt
270 uaxhington lilts
272 Gills Sock
274 Sturgeon Bay
276 Suaarico
278 Oconto
280 Marfnette. Henininee
282 Cedar Rivw
284 Escanaba
286 Little Say Oe Hoc
288 Big Bay Oa Hoc
290 Fail-port
302 Kacklnac-St. lgnac«
303 Six-ftthoa Sank
304 OMboygan
30S Haanand Bay
306 Rogarc City
307 prasque Itte, Rockport
308 AlpervThunder Say
309 Yankee R»<
310 H«rri«vill«, Occoo>
311 Au Sable Point
312 Taun City
314 Bay City
316 Bay Port
318 Port Austin
320 Harbor Beach
322 Port Sanilac
324 Lexington. Port Huron
PORT PORT_*AM£
325 St. Clair River
326 coder I ch
328 Kincardine
330 Southaopton
332 Pike Bay
334 Toberoory
336 South Baywuth
1-348
-------
QAPP for Lake Trout and Forage Fish Sampling
Volume 1, Chapter 5 for Diet Analysis and/or Contaminant Analysis
338 South Bay
340 Burnt Island
342 Detour
344 Cedwille
346 Kefuoe
ISO Tobennry
3S2 L
-------
QAPP for Lake Trout and Forage Fish Sampling
for Diet Analysis and/or Contaminant Analysis
Volume 1, Chapters
614 Mexico Bay
615 southwick
616 Callo-Stoney 1»land*
618 Henderson Bay
620 Black River Bay
622 Chauiont Bay
623 Cape Vincent
624 St. Lawrence River
626 Aflhent
628 worth Channel
630 Adolphus Reach
632 Bay of Oulnte
634 Prince Edward Bay
635 Prince Edward Point
636 Wellington
638 Lakeport
640 Port Hope-Cobourj
642 Oshaua-Pt. Uhitney
644 Toronto
645 Port Credit
646 Hamilton
648 Jordan Harbor
650 Nteaara-on-tha-Lake
844 Marine City
9980 unknown source
9981 non*Gr«at Lakes saaples
9982 round robin saeples
9984 reference material saaple
9990 laboratory saaples
9994 Great Lafc* saaple no pore
9996 natrix maple unspiked
9997 matrix caeple spiked
9996 check samples
223 record* selected.
SQL> select • fro* saaple_type order by
SAMPLE_TTPE SAMPLE_rrPE_NAME
1 Trawl
2 Gillnet Set
3 Cillnet Lift
4 Gillnet Set and Lift
5 Hydroacoustics
6 ROV
7 Zooplankton
8 Bongo Net Fry Tow
9 Ponar Dredge
10 Uater OieaUtry
11 Trap Net
12 Teaperatur* Only
13 Light Trap Set
14 Light Trap Lift
U records selected.
SQL> select * from sea_condition order by sea_condition;
SEA COKDiriON SEA COUOIT
0 0 ft.
1 < 1 ft.
2 1 - 2 ft.
3 2 - 4 ft.
44 6 ft.
5 6 - 8 ft.
6 6> ft.
9 M/D
& records selected.
1-350
-------
Volume 1, Chapter 5
QAPP for Lake Trout and Forage Fish Sampling
for Diet Analysis and/or Contaminant Analysis
SOL> select * from sex order by sex;
SEX SEXJtAME
0 unknown
1 Nate
2 Fea»le
3 Heriuphrodite
SOL> aelact • frofl top order by top;
SOP SOP_NAHE
0 Standard Operating Procedures
SOL> Mlect • froa speciea order by species;
SPECIES COMMON NAME
SCI NAME
0 No fish caught
1 Cheatnut laaprey
2 Northern brook laaprey
3 Silver lamprey
4 American brook iMprey
5 Sea lacprey
101 Lake sturgeon
102 Paddlefish
103 Spotted gar
104 Longnose gar
105 Bowfin
106 Alewife
107 American shad
108 Gizzard shad
109 Rainbow M»lT
110 Mooneye
111 Central aixjninnow
112 Grass pickerel
113 northern pike
IK Muskel lunge
115 uhite catfish
116 Black bullhead
117 Yellow bullhead
118 Brown bullhead
119 Channel catfish
120 Stonecat
121 Tadpole oadtoa
122 Brindled sadtoii
123 Flathead catfish
124 Anti-lean eel
12S Banded killifish
126 Mosquitofish
127 Burbot
124 Brook stickleback
129 Threecpine stickleback
130 Ninespine stickleback
131 Trout-perch
132 white parch
133 Uhite bass
134 Freshwater dna
135 Shortnose sturgeon
136 Pallid sturgeon
137 Shovelnose sturgeon
138 Gar
139 Alligator gar
HO Shortnose gar
142 Ohio chad
143 Skipjack herring
146 Gotdeye
ISO Blue catfish
1S1 Bullheads
160 Muskellunge x Northern Pike ifybrld
170 Brook silverside
Icfathyoayzon cactaneu£
Ichthyo..yz0n l*ots*or
Ichthyoavyxon unicuspis
laopctra Laauttei
Ptfftrcayun Bavinus
Acip*rtt«r fulvescens
Potyodon spAtfeula
Lepisoctcm ocuiacus
LcplCOCtCUB CAMUS
Aaiai calva
Ale** pMudoharengus
Alo*« capidicfiati
OCTO.U.U c*pedi»nu»
OMMTU.* B.ordu
Hiodon torgtcuc
Ua.br* li«>
Esox atwricanus vcmiculatus
Csox luciuc
Esox Bvuxjuinangy
Ictalurus catus
Ictaluruc taclas
Ictalurus natali*
lcc»luruc nebulosus
Ictalurus punctaitufi
Noturuc flavus
Hoturue gyrinus
Noturus Minurus
Pytodictus oLivsris
AnguiUa rottrat*
finduluc diaphanus
G*mbusta affmic
Lota lota
€ucatia inconstans
Ga«c*ro9tcus «cul*acus
Pungitius fxr>gitius
P*rcopc{« caiscaemycus
Moron* aawricAfuis
Horona chrysops
Aplodlnotus grunniens
Actpens«r brevirottrui
Scaph i rhynchus
Scaph I rhynchus plfttorynchus
Laptsosteus spatula
lepifiosteus platostonjs
Olosa ohiensis
Alosa chryaochloris
Hiodon alosoides
tctalurus furcatua
Labioesthes siccului
1-351
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QAPP for Lake Trout and Forage Fish Sampling
for Diet Analysis and/or Contaminant Analysis
Volume 1, Chapters
190 Wiite perch/Unit* has* (hybrid)
200 White*iahe*
201 Long jaw Cisco (rare)
202 Cisco (lake herring)
SPtCIES OOMMOM_IUME
Coregonus-(Leucichthys) «lp«n««
Coresonus (LeucichthysJ artedi
SCI MANE
203 Like uhitefish
204 Bloater
206 Outfitter citco (extinct)
206 Klyi
207 Slsckf in Cisco (rare or extinct)
2O6 Shortnose ctaco
209 L. Superior Shortnose
210 shortjeu Cisco (rare)
211 Pygay Uiiteflsh
212 Round iciiteftsh
213 unidentified chubs
214 Chubs (large)
215 Chute (saell)
216 Chute
217 Unidentified coregonid
300 Trouts and graylings
301 Chinook saleun
302 cutthroat trout
303 Rainbou trout (Sce«lhe*d)
304 Atlantic utcon
3O5 Broun trout
3O6 Brook trout
307 Lake trout
308 SI scoutt (fat Trout}
309 Artie grayling
310 Coho saloon
311 Kolum*
312 tknper lake trout
313 HaUbTMd lake trout
31& splake (brook trout x lake trout)
315 Released lake trout (cwnerciall «oui
316 Pink saloon
317 Dative lake trout
400 Suckers
401 Goldfish
402 Carp
403 Ouillback
404 Longnose sucker
40S White sucker
406 Lake cnubauckar
407 Northern hogsucker
408 Bignouth buffalo
409 Spotted sucker
410 Silver redhorse
411 Black redhorse
412 Golden redhorse
413 northern redhorse
414 Greater redhorse
41S Unidentified redhorse
U6 Goldfish x carp hybrid
417 River redhorse
418 shorthesd Redhorse
423 River carpsucker
424 Highfin carpsucker
425 Plains carpsucker
429 Blue tucker
435 Smalltuuth UrHnlo
Coregonus clup*afor>fs
Coregerus (Lcucichthys) hoyi
Coregonus (Leuclchtky(> Johanna*
Coregenus (Leucichthys) kiyi
Coregonus (Louclchthys) nigripinnls
Coregonus (Leucichthys) reishardi
Coregonus (Leucichthys) rvfghardi dyaundi
Coregonus (Leucichthys) lenithicus
Proaoplust coulteri
Proxopiusi cylindraceun
Oncorhynchus tshawytscha
salvo clarki
SalK> galrdneri
Saleo salar
Salno trutta
Salvelfnus fontinalis
Salvelinus na«aycush
Salvelinus nanaycush siscouet
Thyvallus arcticus
Oncorhynchus kfsutch
oncorh>vicnus narka
Oncorhynchus gortxscha
Carassius auratus
Cyprinus carpio
Carpiodu cyprinus
CatostoBufi catostoous
Catostoious conaersoni
Erisyzon suc*tta
Hypenteliua nlgricans
Ictlobus cyprinallus
Minytreoa aelanops
Hoxostoaa anisurun
Moxostom duquesnei
Hoxostos* erythrurum
MoxostooKi •acrolepidotun
Hoxostosa valencie
Hoxostona carirvatun
Mojcosiooa breviceps
Oarpiodes carpio
Carpiooes velifer
Carpiodes forbesi
Cycleptus elongatus
Ictiobus bubalus
SPECIES COHMON_UAKE
436 Block buffalo
500 Minnows
SOI Silver chub
502 Golden shiner
503 Pugnose shiner
SCI_HAH£
Ictiobus niger
Hytoopsis ctoreriana
Noceaigonus crysoleucas
Notropis onog«r*us
1-352
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Volume 1, Chapter 5
QAPP for Lake Trout and Forage Fish Sampling
for Diet Analysis and/or Contaminant Analysis
504 Eserald shiner
505 riaaam shiner
506 BlackcJiin shiner
507 Blacknos* shiner
508 Sport*iI shiner
509 Spotfln shiner
510 Sand shiner
511 Ni.ic shlnar
512 Pugnou Minnow
513 Bluntncoc ainnau
514 Fathead siinnau
515 Longnose dice
516 Unidentified call
517 StonaroUer
518 Creek; chub
519 Lake, chub
520 Sturgeon chub
521 Fallfish
522 Silver dimou
523 Cut lips ninnou
524 Bridle shiner
525 Striped shiner
526 HomeyhMd chub
527 Redf In «hln.r
528 Silver shiner
600 Suifish and bsss
601 Rockbscc
602 U^nuuth
603 Green sunf ich
604 PmpMnseed
605 BliMsUl
606 Longcsr sunfish
607 SiHltKuth bus
60A Urgesnuth btss
609 White creppie
610 elsck crappi*
611 Crappln
612 Orange spatted salfish
700 Darters
701 Eastern sand darter
702 Greenside darur
703 (oua darter
704 Fanufl darter
705 Least darter
706 Johnny darter
707 Logperch
708 Channel darter
709 Blackslde darter
710 River darter
711 Unidentified darters
fiOO Yellov perch and pikeperch
801 TelloM perch
SPECIES CXMttN NAME
Notrapls atfcerinoidAS
Notrapis conutuc
Notrapis hexarodon
Natrapis neteralcpis
Notrapis hudsonius
Hatrapis spilapterus
Hotrapis straaiineui
Hotropls volucellus
PiaKphales notatus
Pieephales promelas
flhinichthys cataract ae
CavpostoikB anoealtal
Sesutllus atrouculaua
Hybepsls pluotn*
Kybopsis gelid*
Sestotitus corporalis
Hybognathus nuchal is
Exoglascue mil lingua
Motropis bifrenatic
-Motropis ubratilix cyanaccplulus
AatHoplltas rupestrfi
Chaenobryttus gulosus
Lepooiis cyaneltus
Lepoais fiibbosus
Lepcais •acrochtrus
Lepooiia awgalotis
Hicropterus dolotaieul
Hicropteria salaaldes
Poaaxis annularis
P«c*is nigrooaculatut
Posnxis spp.
Lepaais nuailis
Aomocrvpta pellucida
Etheostoau blennoides
Etheostoam exile
Etheostoaa flabellara
Eth«ostoaa ancropcrca
Etheostoaa nigruo
Percina caprodes
Percins copelandi
Perctna aHculata
Percina shunardi
Perca flavescens
SCI NAME
802 Sauger
803 Ualleve
804 Blue pike (ran or extinct)
805 Ruffe
9OO Sculpin
901 Mottled sculpin
902 Sliny scuLpin
903 Spocnhead cculpin
904 Oeepwater sculpin
950 z«bra_au&sal
999 Miscetlaneous or unidentified species
^&Z records selected.
SOL> select * fro« speed_unit order by speed_unit;
SP££0 UNIT SPE
Stitostedion canadense
Stizostadion vitreuo vitreu*
Stizostedion vitreu* glaucua
Gyanocephalus cernuus
Cottus bairdi
Cottus cognatus
Cottus ricei
Hyoxouphalus thoapsoni
drefssena_polyaorpha
1-353
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QAPP for Lake Trout and Forage Fish Sampling
for Diet Analysis and/or Contaminant Analysis
Volume 1, Chapters
1 HPH
2 RPM
SOL> select • fro* (touch order by
STOMACH STOMACH UA
Not Taken
0 Eopcy
1 LF
2 VolUM
SuL» ealect • select * from teap_«thod order by ta«p_aethod;
TEMP KETHOD TEMP METHOD
0 Other
1 Bucket
2 Injection
3 Rev. Thena.
4 Theraograph
5 Bt
6 Elctrnc-YSI
9 Unkwwn
8 records Mlacted.
SOL> select • fro» tr design order by tr_d«»lgo;
1-354
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OAPP for Lake Trout and Forage Fish Sampling
Volume 1, Chapter 5 for Diet Analysis and/or Contaminant Analysis
TRJIESICU TR_OCSIGItJIAM£
1 K-3a; 52' balloon 7' wing
4 39- Trawl
16 K-1; 52' (Cod end: 1/2 tn
21 47' Midwater
Z2 54' Headrope alduter
21 70' Wing trawl
24 £0' Hlghrise bottca trawl
25 39' Roller Trawl
26 18* aotcoi trawl
27 3 *etar naturalist Crawl
28 4' Bea« trtwl
29 8' Tucker crawl
30 20' MR Trawl (Steelhcad)
II 89' NR Hidwater
32 20' HR Hidwater old
13 25' He Hidwater rcu
34 16' Roclchoppar
35 26' SB Bottom
36 20'HR Ions CSteelhead)
19 records lelected.
SOU Mlect • frai type_s«t ord«r by type_s*t;
TrPE_SET nP€_SEI_iUME
1 Bottca acro» contour
2 Bottoa along contour
3 Oblique
4 Surface
S
SOL> salcct • from vessel order by vessel;
VESSEL VESSELJUWE
1 Siscouat
2 Cisco
3 Husky II
4 Kaho
S Buffalo
6 Hiodon
7 Judy
8 Mooneye
9 Daphnia
10 HadtoH and little Boston whaler select • fro*, weather order by weather;
WEATHER UEATMERJIAME
0 Clear (no clouds at any level)
1 Partly cloudy (scattered or broken)
2 Continuous layer(s) of cloud(s)
3 Sandstooa, duststone or blowing snow
1-355
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QAPP for Lake Trout and Forage Fish Sampling
for Diet Analysis and/or Contaminant Analysis Volume 1, Chapter 5
4 Fog, thick o\at. or KftU
5 OHule
6 R»Cn
7 Snou. sleet, hail
a Star*
9 U/D
10 records selected.
SQL> spaol off
1-356
-------
Volume 1, Chapter 5
QAPP for Lake Trout and Forage Fish Sampling
for Diet Analysis and/or Contaminant Analysis
Appendix 5.
Research Vessel Data Entry Screens Used Under RVCAT
OP_DATE
SET TIME
LIFT TINE MIGHTS OUT _ TYPE SET FISKIMC TEMP SET
"~~~ "" FISHING TEMP LIFT
GN_EFFORT
MESH NET ~ MET BEG END
SIZE HATERIM. LENGTH DEPTH DEPTH
GM_CATCH
LIFE
STAGE SPECIES M WEIGHT
| GN LF
I SPEC LS LENGTH N
.I
Forn; gillnet Block: fliTOP P«se: 1SELECT: Char Mode: Replace
1-357
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QAPP for Lake Trout and Forage Fish Sampling
for Diet Analysis and/or Contaminant Analysis
Volume 1, Chapter 5
OP DATE
VESSEL
SERIAL
TR_Of>
T8 DESIGN __
MESH SIZE
SET'TIME 3
TOU TIME _
SPEED _
SPEED UNIT
TYPE_S£T I
FISHING DEPTH
FISHING TEJXP ~
"GRID
TR_CATCH
BUCKET
TR_LF
TR FISH
LIFE TR CATCH
STAGE SPECIES ~ N
LF N UEIOHT
TR_LF
SfCCIES LS LENGTH N
r fUJCKffTii
Form: trail
Block: tr_op
P«a»: 1 SELECT:
Char Mod*: ftcplac*
1-358
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Volume 1, Chapter 5
QAPP for Lake Trout and Forage Fish Sampling
for Diet Analysis and/or Contaminant Analysis
OP_DATE _
TR_FISH SP
SAMPLE
WEIGHT
LENGTH _
FIN CLIP
SCAR/WOUND
A1 B1
A2 ~ 82 ~
A3 ~ S3 "
A4 ~ 84 ~
SEX~ 3
MATURITY
STOMACH
CUT
AGE
DC
TAG
sp strc _ lf_
FOPII: tr_ffsh
VESSEL SERIAL FISHIUG_DEPTH POET
STgC LF PORT IN
- __ _
C
A
L
E
D
T R_AKIIULUS •
JUINULUS DIAMETER
I i
S
T
R
1
8 1
u I
TR PREY
SPECIES LENGTH N
T 1
I 1
0
II i
* I
Block: tr_control Psa«: 1 SELECT: Char Hade: Replace
1-359
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QAPP for Lake Trout and Forage Fish Sampling
for Diet Analysis and/or Contaminant Analysis
Volume 1, Chapters
OP DATE
VESSEL _ SERIAL
MESH_SIZE _ METJUTEHIAL _
CM FISH
SAMPLE ~
SPECIES ___
WEIGHT ._____.
LENGTH
FIN CLIP
SCA8/UOJKD
GUJUUIULUS- f
AUUULUS DIAMETER
CM PREY
SPECIES LENGTH
SPECIES
LENGTH
Form:
Block: an.control Page: 1 SELECT: Our Mode: RcpUc*
1-360
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QAPP for Lake Trout and Forage Fish Sampling
Volume 1, Chapter 5 for Diet Analysis and/or Contaminant Analysis
TRAUL INDIVIDUAL LEUCTHS
OP_OATE _____ VESSEL SEJUAL _
LIFE_STME _ SPECIES __
LENGTH COMMIT COUNT
Fora: trjf Block: control P«ge: 1 SELECT: Char Mode: Keplace
1-361
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QAPP for Lake Trout and Forage Fish Sampling
Volume 1, Chapter 5 for Diet Analysis and/or Contaminant Analysis
Appendix 6.
Label Information Recorded on Fish Sample Tags
Sample Label
NATIONAL BIOLOGICAL SURVEY
Great Lakes Science Center
1451 Green Road
Ann Arbor, MI 48105-2899
Sample Description and Objective_
Date
Lake
Location
Serial No.
Species
Sample No._
1-363
-------
Chain of Custody Record
Projecl. No.
Project Name:
Samplers: (Signature)
Sin. No. Data Time
Rollnqulahod By (Signature)
Station Description
Dale
Time
Sample
Type
Numbar and
Type o(
Containers
Remarks
Recleved By: (Signature)
(Print)
Commenls
Rosourca Assessmanl; Lalo Michigan Project 1994.
o
3-
0)
O >
C 73
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Quality Assurance Project Plan for Coho
Sampling for Contaminant and Diet Analysis
Biota Work Group
Mark E. Holey and Robert F. Elliott
U.S. Fish & Wildlife Service
Fishery Resources Office
1015 Challenger Court
Green Bay, Wl 54311
April 1994
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Quality Assurance Project Plan for Coho Sampling
for Contaminant and Diet Analysis
1.0 Introduction and Project Description
l.l Overview
The Great Lakes National Program Office (GLNPO) of the US EPA has initiated a Mass Balance
Study for selected toxic contaminants in Lake Michigan. The mass balance effort will be part of a
"Lake Michigan Enhanced Monitoring Program" which includes tributary and atmospheric load
monitoring, source inventories, and fate and effects evaluations. In general, the primary goal of
this enhanced monitoring program is to develop a sound, scientific base of information to guide
future toxic load reduction efforts at the Federal, State and local levels.
A modeling team will construct a mass budget/mass balance model for a limited group of
contaminants which are present in Lake Michigan at concentrations which pose a risk to aquatic
and terrestrial organisms (including humans) within the ecosystem. Components to the mass
balance model will be designed to predict contaminant concentrations in the water column and
target fish species over a two year period, relative to loadings. Predictions of contaminant levels in
three species of fish will be calculated as final output of the model. The target fish species
include:
Lake trout (Salvelinus namuycush)
Coho salmon (Oncorhynchits kisutch)
Bloater chub (Coregomts hoyi]
The calibration of the food web model(s) for these target species requires data on contaminant
concentrations and fluxes (diet) not only in these species, but also in the supporting trophic levels.
The contaminant burden of each prey species varies based on feeding patterns at lower trophic
levels. The concentration of contaminants in coho salmon will depend on what prey items they
choose to consume. The diet information for coho salmon sampled by this project will enable the
modelers to quantify the movement of contaminants from their source, through the food web, and
ultimately the body burden in coho salmon.
The basic design and data requirements for the fish samples have been outlined in Tables 5 and 6
and in Appendix 4 of the Lake Michigan Mass Budget/Mass Balance (LMMB) work plan of
October 14, 1993. This project addresses a subset of the work objectives for coho salmon, one of
the target species described in the LMMB work plan.
The specific objectives are to:
1) Describe the diet of coho salmon in Lake Michigan from April-October 1994.
2) Collect representative samples of coho salmon from spring, summer, and fall in 1994 for the
purpose of conducting contaminant analysis.
3) Review past published and unpublished information on the diet of coho salmon in Lake
Michigan and report on the comparability of the data collected in 1994 to past data.
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Quality Assurance Project Plan for Coho
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1.2 Experimental Design
Spatial and temporal variations in coho salmon feeding habits and movement will require fish to
be collected in spring, summer, and fall and from both the east and west shore of Lake Michigan.
Based on coho migration patterns, spring samples will be collected primarily from the southern
region of the lake, summer samples from the central region, and fall samples from the north central
region of the lake near the egg collection facilities (Table 1.0). The 1993 year class (age 1.1) of
coho will be sampled during the entire sampling period (Table 1.0). The 1994 year class will be
sampled while in the hatchery (age 1.0) and once in the fall (Table 1.0). The hatchery sample will
quantify the amount of contaminants the coho acquired, if any, from the hatchery before they enter
the lake and began feeding on natural foods.
Table 1.0. Sample Size Objectives for the Collection of Coho Salmon in Lake Michigan by
Season and Location
Season Location Age Contaminants Diet Total
Spring
(April to mid-June)
Hatcheries 1.0 25 0 25
East Shore 1.1 25 15 100
(Indiana to Benton Harbor, MI)
West Shore 1.1 25 75 100
(Illinois waters)
Summer
(mid-June to mid-August)
East Shore 1.1 25 75 100
(Benton Harbor to Ludington, MI)
West Shore 1.1 25 75 100
(Kenosha to Sheboygan, WI)
Fall
(mid-August to October)
East Shore 1.0 25 75 100
(Ludington to Frankfort, MI) 1.1 25 75 100
West Shore 1.0 25 75 100
(Sheboygan to Kewaunee, WI) 1.1 2_5_ 7_5_ 1QQ
Total 225 600 K25
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Volume 1, Chapter 5 Sampling for Contaminant and Diet Analysis
The most difficult part of this project will be the collection of the necessary samples of coho
salmon. Netting techniques to capture salmon in the open water of the Great Lakes is difficult,
expensive, and not widely practiced. For salmon, angling is the most appropriate method for
addressing the specific needs of this project. Coho salmon collected for contaminant analysis will
be obtained by contracting sport charter anglers from the areas sampled (Table 1.0). As necessary
and available, samples from assessment netting or creel surveys by state or other research agencies
will be used. Standard biological and site specific information (length, weight, age, sex, location,
and season) will be recorded for all coho collected.
1.3 Contaminant Sampling
The total number of coho required for contaminant analysis outlined in the LMMB work plan was
been modified from 450 to 225 (Table 1.0). Samples will be packaged as required for contaminant
analysis, frozen, and delivered to the NBS Great Lakes Research Center. To make these
collections as representative as possible, samples will be taken throughout each season to the
extent possible. Salmon for contaminant analysis will be collected primarily by contracted charter
fishermen.
1.4 Diet Sampling
The LMMB work plan did not have a sample size objective for describing the diet. Based on
recent diet work describing variation typically observed in the diets of salmon from Lake Michigan
(Elliott 1993), we estimate the sample size goal should be at least 100 fish per season per region
(Table 1.0). To account for as much of the spatial and temporal variation as possible, sampling
effort will be distributed throughout each season in the regions of the lake where the fish are
commonly found. To achieve the 100 fish per season per region goal, 75 fish (per season per
region) in addition to the salmon collected for contaminant analysis will have to be collected. Diet
samples will be collected from contracting charter fishermen and from sampling sport angler
catches at boat ramps (see section 4.0 for description of methods).
Historical data describing coho diet will be analyzed and summarized to complement the
information collected from those coho sampled in 1994 and 1995. This will serve to put the 1994-
95 diet information in perspective and minimize the dangers of having to assume that the diet of a
relatively small number offish collected in 1994-95 is representative of typical years.
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Volume 1, Chapters
Table 1.1 Summary of Critical and Non-Critical Parameter Measurements for the
Evaluation of Coho Salmon Diet.
*arameter
.ocation
(critical)
Sample Date
(critical)
Coho length
(critical)
Coho weight
(critical)
Coho age
(critical)
Diet Species
(critical)
Diet item
Length
(critical)
Diet item
Weight
(critical)
Sample Depth
(non-critical)
Time of
Sample
(non-critical)
Water
Temperature
when sampled
(non-critical)
Sampling
Instrument
GPS, Loran,
Port
Location
None
measuring
board ruler
spring or
electronic
balance
Knife and
envelope
NA
NA
NA
echo
sounder
clock
thermometer
Sampling
Method
SOP-1
NA
NA
SOP-1
SOP-1 and
Bowen
1983
SOP-1
NA
NA
operating
instructions
NA
NA
Analytical
Instrument
NA
NA
NA
NA
scale
projector
NA
ruler
ruler or
electronic
balance
NA
NA
NA
Analytical
Method
NA
NA
NA
NA
SOP-2
SOP-2
SOP-2
SOP-2
NA
NA
NA
Reporting
Units
Lake
Regions
mo/day/yr
xx/xx/xx
mm
Kg
years
total
number
mm
grams
meters
HH:MM
degrees C
LOD
Basin-
East, West-
North,
Central,
Southern
day
1 mm
0-1 Kg
1 year
Species-fish
& Common
nvertebrates
Order for less
common
nvertebrates
mm
0.1 gram
0.1 meters
minutes
1°C
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Volume ^, Chapter 5
Quality Assurance Project Plan for Coho
Sampling for Contaminant and Diet Analysis
2.0 Project Organization and Responsibilities
John Gannon
NBS
Biota Co-Chair
Paul Bertram
EPA Project Officer
Biota Co-Chair
Lou Blume
EPA QA Manager
Mark Holey
USFWS
Project Manager
Robert Elliott
USFWS
Field Manager
Stewart Cogswell
USFWS
Field Sampling
Analysis
Positions
Two Temporary
USFWS
Field Sampling
Analysis
— Project communication
= QA communication
2.1 GLNPO Project Officer and Biota Co-Chair
The GLNPO Project Officer is the Agency official who initiates the grant, evaluates the proposal,
is the technical representative for EPA, and is also co-chair of the Biota workgroup for the Lake
Michigan Mass Balance Program. The Project Officer is responsible for:
Budgeting
Program planning, scheduling, and prioritization
Developing project objectives and data quality objectives
Ensuring that project meet GLNPO missions
Technical guidance
Program and data reviews including audits
Data quality
Final deliverables
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2.2 GLNPO QA Manager
The GLNPO QA Manager (QAM) is responsible for ensuring that each project funded by EPA
satisfies the Agency's requirements for QA programs. The QAM is responsible for:
Offering guidance on QA techniques
Evaluating QA Project Plans (QAPjPs) and approving QAPjPs for the Agency
Assisting in the coordination of audits
2.3 NBS Biota Co-Chair
The Biota Co-Chair from NBS works in partnership with the GLNPO QA Project Leader tu
implement the Biota portion of the Lake Michigan Mass Balance Project. Duties are:
Program planning, scheduling, and prioritization
Developing project objectives and data quality objectives
Ensuring that project meets GLNPO missions
2.4 USFWS Project Manager
The Project Manager is the USFWS official who initiated the proposal to perform the coho
sampling portion of the LMMB project and is responsible for:
Developing the sampling plan for coho collection
Administration of the coho segment of the Biota objectives
Overall supervision of field work
Ensures QA objectives are met
Technical supervision
Final deliverables
Data Quality Assessment
2.5 USFWS Field Manager
The Field Manager is the USFWS position that will provide daily supervision of the field
collection activities and achievement of the QA objectives. This position is responsible for:
Collecting field data
' Directly supervise the field crew activities
Reviews progress toward QA objectives
Develops and implements sampling and analytical procedures
Prepares reports and deliverables
Trains field crews on sampling and analytical procedures
Technical systems audits for field and laboratory activities
Data quality assessments for lab and field segments
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Quality Assurance Project Plan for Coho
Sampling for Contaminant and Diet Analysis
2.6 Field Sampling and Analysis Personnel
These positions are responsible for the majority of the field sampling and lab ID. They will
receiving training and guidance from the Project and Field Managers, who will also audit their
work to ensure QA objectives are met. These positions will be temporary positions hired at a GS-5
fishery biologist level. Minimum requirements for a GS-5 are six college credits of fishery related
courses and 12 credits of related natural resources or animal science related courses or appropriate
experience.
3.0 Quality Assurance Objectives
As outlined in the Lake Michigan Mass Budget/Mass Balance Work Plan, the proposed model
output should be within a factor of two of the observed concentrations in the water column and
target fish. It is also estimated that the required level of model accuracy can be achieved if
loadings and contaminant mass in significant environmental compartments are determined to
within +/- 20 to 30 percent of the actual value.
Objectives:
1) Within each season/region strata, collect as representative a sample of coho salmon as
possible so as to minimize the spatial and temporal population uncertainty (Sp:) to the extent
possible (given the sample size that can be collected with the financial, logistic, and
biological constraints of this project).
2) To collect, package, and transport each sample, and to record, summarize, and report each
physical measurement with a level of precision, accuracy, detectability, and completeness that
will ensure that Measurement Uncertainty (Sm2) will be nominal compared to Sp2 and
therefor not affect the interpretation of the results.
The level of population uncertainty can not be determined priori. That the contaminant levels in
the coho collected will be within +/- 20 to 30 percent of the actual population values is a function
of sample size and the collection procedures. The sample size for contaminants has been
established by the LMMB Work Plan and subsequent modifications. The designed collection
procedures described here attempt to make the most of the sample size target.
Variability in the diet of Lake Michigan salmon can be great, especially when examined from a
lakewide perspective encompassing large scale spatial and temporal gradients. The desired sample
size for determining diet is to a large degree constrained by the difficulty of collection of these
fish. Presently coho abundance in Lake Michigan and therefor catch is very low.
3.1 Measurement Quality Objectives
Measurement quality objectives (MQOs) are designed to control various phases of the
measurement process and to ensure that total measurement uncertainty is within ranges prescribed
by the DQOs. The MQOs can be defined in terms of data quality attributes; precision, accuracy,
completeness, detectability. representativeness, and comparability The first four can be defined in
a quantitative terms, while the later tuo are qualitative. MQOs are listed in table 3.0.
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Precision: A measure of mutual agreement among multiple measurements of the same property,
usually under prescribed similar conditions. Precision will be evaluated through auditing of data
collection activities to determine whether activities are performed in a consistent manner, and by
established protocol.
Accuracy: The degree of agreement between a measurement (or an average of measurements of
the same thing), and the amount actually present.
Completeness: For this QAPjP, completeness is the measure of the number of valid samples
obtained compared to the amount that is needed to meet the DQOs. The completeness goal is
90%.
Detectability: The determimtion of the low-range critical value of a characteristic that a method-
specific procedure can reliably discern or is necessary to meet program objectives.
Representativeness: Express the degree to which data accurately and precisely represent
characteristics of a population, parameter variations at a sampling point, a process condition, or an
environmental condition.
Cnmparahility: Express the confidence with which one data set can be compared to another.
3.2 Field MQOs
The following information describes the procedures used to control and assess measurement
uncertainty occurring during the field sampling. Field parameters in this section will include
location, coho length, coho weight, and coho age. Since these measurements are straightforward,
the measurement quality evaluations will be simple remeasurements.
The majority of the uncertainties occurring in the field can be alleviated by the development
detailed standard operating procedures (SOPs), an adequate training program at appropriate
frequency, and a field audit program. SOPs have been developed (appendices A and B) and
training has occurred. Field audits will be implemented during the course of the program
implementation.
3.3 Precision
Another term for precision is repeatability. Repeatability in the field is very important to
precision, as well as data comparability. Repeatability is controlled by the development of detailed
SOPs and adequate training in those SOPs. Field precision will be checked by remeasuring 5% of
the samples. Remeasurements must be within the acceptance criteria as stated in Table 3.1. Field
precision can also be evaluated through the implementation of field technical systems audits.
These audits will be used to evaluate the adherence to the SOPs. Audits are discussed in section 8.
3.4 Accuracy
As stated earlier, accuracy is based on the difference between an estimate, derived from data, and
the true \alue of the parameter benii! estimated. For the field measurements, with the exception of
location, the true \alue is dependent on the calibration of the monument (ruler or scale).
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Following calibration procedures and precision requirements will provide an indication of
accuracy. Following SOPs as written should reduce contamination as much as possible. Accuracy
is also based on training. Therefore, during audits the trainer will remeasure 5% of the samples to
determine accuracy. If accuracy requirements are not met, the trainer will review the methods with
the sampler until agreement is reached.
3.5 Detectability
Detectability in this study is a function of how accurate and repeatable the measuring instruments
can be maintained. Rulers or tape measurements, unless broken, will be considered accurate.
Therefore, detectability of coho length is a function of following the SOPs. Similarly, scales, if
calibrated properly, should reflect an accurate weight unless various conditions (wind or rain)
create a situation where an accurate weight (within detectable limits) cannot be met. The SOPs
will discuss ways to measure samples within the detectability requirements.
3.6 Completeness
Completeness for the field is defined as the successful collection of all viable samples in the
appropriate time frame. A viable sample would be defined as any single sample whose integrity
has not been effected during the collection process and would therefor not be flagged with a field
qualifier. In some cases, the sampler has no control on the integrity (e.g., samples remaining in the
sun too long) while in other cases the sampler might effect the integrity (e.g., contaminating a
sample through improper handling).
In any case, the DQOs are based on the evaluation of a statistically relevant number of samples
which are effected by all errors occurring in the field and laboratory. Therefore, the overall goal is
a completeness of 90%. The completeness objective for the measurement phase is 100%. As with
the other data quality attributes, completeness can be controlled through the adherence to the SOPs
in order to minimize contamination and sampling errors.
3.7 Representativeness
Representativeness, with respect to the overall program objectives is a function of the statistical
sampling design and how well this design estimates the measurement parameters to this project.
Variation in coho diet is expected seasonally but also from year-to-year, depending on the
abundance of prey and environmental factors that might affect feeding behavior. Since the
sampling period for this project is only one year, the review of past coho diet data will assist in
determining how representative the 1994 diet of coho salmon is to the yearly variation that can be
expected.
3.8 Comparability
Comparability will be maintained by the adherence of the SOPs. Adherence of these SOPs by all
samplers will allow for comparability of data among sites and throughout the project. Evaluation
of comparability occurs through the implementation of the training program and the field technical
svstems audit.
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Table 3.0. Measurement Quality Objectives for Parameters for the Evaluation of Coho
Salmon Diet
Parameters
Location
Coho Length
Precision
Accuracy
Completeness
Coho Weight
Precision
Accuracy
Completeness
Coho Age
Precision
Accuracy
Completeness
Diet Species
Precision
Accuracy
Completeness
Sample Type
Remeasurement
Independent
remeasurement
Remeasurement
Independent
remeasurement
Length
Frequency
Re-age,
inspection
Independent
Re-age,
inspection
Re-identify,
inspection
Re-identify,
inspection
Frequency
5%
5%
NA
5%
5%
NA
100%
5%
5%
NA
5%
5%
NA
Acceptance; Other Corrective Action
The accuracy required is to regions of the lake.
1 cm of original measurement - recalibrate
instrument and remeasure sample to compare to
closest.
1 cm of original measurement - review protocols
and remeasure another sample
90%
3.1 Kg of the original measurement - recalibrate
instrument and remeasure sample to compare to
closest.
3.1 Kg of original measurement - review
jrotocols and remeasure another sample
100% for salmon collected for contaminant
analysis
0% for salmon collected only for diet analysis
Confirmation with scale aging
Direct match with original
Direct match with original
95% identification, precision will be maintained
through training and periodic audits to verify
accuracy of identification of prey items
95% identification, to determine accuracy,
samples will be re-identified and compared to
reference samples.
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Volume 1, Chapters
Quality Assurance Project Plan for Coho
Sampling for Contaminant and Diet Analysis
Table 3.0. Measurement Quality Objectives for Parameters for the Evaluation of Coho
Salmon Diet
Parameters
Diet Item
Length
Precision
Accuracy
Completeness
Diet Item
Weight
Precision
Accuracy
Completeness
Sample Type
Remeasurement
Independent
remeasurement
Remeasurement
Independent
Remeasurement
Frequency
5%
57c
NA
5<7c
5%
NA
Acceptance; Other Corrective Action
+/- 2 mm of original measurement - recalibrate
instrument, remeasure sample and compare to
closest
+/- 2 mm of original measurement - review
protocols and remeasure another sample
90%
0.1 g of the original measurement - recalibrate
instrument and remeasure sample to compare to
closest
0.1 g of the original measurement - review
protocols and remeasure another sample
90%
4.0 Site Selection and Sampling Procedures
A site-specific sampling plan for coho salmon is not available prior to the sample period since it
depends on the migration patterns of the salmon and how that pattern is affected by environmental
factors. In each of the three seasonal periods (spring, summer, and fall), we will sample coho
where ever they happen to be in their migration pattern. The exact location of our sampling will
also be determined by the location the anglers who caught the fish chose to fish on any given day.
Table 1.0 outlines the anticipated sampling regions by season.
4.1 Sampling Procedures and Sample Custody
Detailed sampling procedures can be found in Appendix A. Method summaries are presented in
this section.
4.2 Contaminant Sampling
We plan on collecting all the coho salmon used in contaminant analysis from contracted sport
charter anglers or on board USFWS vessels. The field sample preparation procedures will follow
the SOP guidelines. A Service biologist will be onboard during all the fishing to insure proper
handling of the samples. After capture, the stomach of a coho salmon will be removed in such a
way that all body fluids will be captured in the aluminum foil that the fish will be frozen in for
analysis. After the fish has been put in the storage bag and labeled, it will be kept on ice until it
can be frozen within 24 hours alter capture. The samples will be transported frozen in a cooler to
the Given Bay Fishery Resources Office \\here they \\ill logged and placed in a chest freezer until
delivery to the Great Lakes Center in Ann Arbor. MI. All samples \\ill he dehxered by Service
vehicle. Hach transfer to a new location uill be recorded on the sample collection sheets
(Appendix C) and each sample will he labeled individually and recorded on a summary data sheet.
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4.3 Diet Analysis
Diet samples may be collected from contracted sport charter anglers, sport anglers, or from
assessment activities of the USFWS. Each fish sampled only for diet will have the stomach
removed as soon after it was caught as possible. The stomach will be placed in individually
numbered whirl-pac bags, preserved with 10-15% formalin, recorded on a summary data sheet,
and stored in a sealable five gallon plastic bucket. Diet samples will be transported to the GBFRO
for analysis. Chain-of custody procedures for transported samples will be the same as those
mentioned above.
The GBFRO is a small developing office and all staff will be involved in the sampling in some
way. Those individuals include, Mark Holey, Robert Elliott, Stewart Cogswell, Pat Bouchard, and
Bruce Peffers. These biologists will collect all field samples and prepare the field labeling of the
samples. Each sample will be clearly identified with date, location, species, length, weight, and
sampling gear (see attached table example).
5.0 Analytical Procedures and Calibration
Analytical procedures will follow those outlined in Bowen 1083, Elliott 1994, and Miller and
Holey 1992. Standard Operating Procedures for the laboratory activities are included in the SOP
for Lab Analysis of Coho Salmon Stomachs and Data Entry.
6.0 Data Reduction, Validation, and Reporting
The responsibility for data reduction, validation, and reporting will be shared between Mark Holey
and Robert Elliott. This section is intended to describe the step by step procedure used to reduce
the raw diet data into summary statistics, verify those statistics, and report them as products that
describe the diet of coho salmon in the manner required for this project.
6.1 Overview and Summary of Method
The raw data as entered and described in SOP-2 will be reduced so that the average diet of all coho
within a given strata (age-region-season) can be reported. Diet will be reported for both coho that
were sampled for contaminants, and for all coho sampled during this project. The primary
descriptive statistic calculated and reported will be the percent that each prey type contributes to
the average wet weight of all prey found in the stomach. The range and frequency distribution
individual weight values and percent weight values from which the average values.are calculated
will indicate the variance associated with these data. The range and distribution of site specific
and biological variables will characterize the coho sample within each major strata. Length
distributions of prey fish in the diet will describe the characteristics of each species found in the
stomachs of coho.
Data collected and results reported during other diet studies of Lake Michigan coho will be
summarized to provide a framework with which to ascertain how valid and representative the diet
information collected during this project is.
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It is assumed that the sampling design will provide a sample of coho having characteristics
(including diet) that are representative of all coho available for capture by anglers, and that
collected samples will be representative of the entire strata. Therefore, although variables such as
date, general location, depth, time, temperature, sex, exact location, and gear etc. will vary within a
strata, determining their effect on diet will not be necessary for this project.
6.2 Reduction Procedures
Methods of data analysis will generally follow those outlined in the Lake Michigan Technical
Committee's document entitled "Conducting Diet Studies Of Lake Michigan Piscivores, A
Protocol" (Elliott et. al 1996).
In brief, using the database developed in SOP-2, calculate the percent that each prey type
contributes to the average wet weight of all prey found in the stomachs of coho salmon as follows.
Within each strata (age, region, season), group coho and their associated data by general location
(port) and date specific groups. This will generally result in groups of data that will describe the
diet on a weekly basis in each region of the lake.
For each of the location-date specific groups, calculate the average weight (0.1 g) per stomach, and
percent (0.1 %) of the total weight, for each prey category. Also calculate the percent (I %) of the
stomachs found empty or void of prey. Omit data flagged as outliers from these and subsequent
calculations.
Compute a grand average of all location-date specific average weight values. Then calculate the
percent that these average prey weights are of the total grand average weight of all prey combined.
For each strata, calculate the range and the frequency distribution of individual weight values and
percent weight values for each prey species. If necessary, adjust the weight value intervals to
reflect fresh weights using conversion formula determined in SOP 2.4.3.
For each strata, calculate the range and the frequency distribution of prey lengths for each prey fish
species. If necessary, adjust the lengths to reflect fresh lengths using conversion formula
determined in SOP 2.4.3.
For each strata, calculate the range and frequency distribution of site specific and biological
variables (coho length, weight, sex; time, water depth, capture depth, temperature, where captured
etc).
Maintain updatedftacked up independent copies of the reduced data (hard drive, disk, and hard
copy printout) in the same manner as is done for the raw database (SOP 2.4.4) for the duration of
the project.
6.3 Validation Procedures
Verification of the raw database is described in SOP 2.4.4. Validation of reductions/calculations is
di\ided into t\\o procedures: validation ol"••orrcctness, and validation of representativeness.
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6.4 Validation of Correctness
Reductions/Calculations result from manipulations of the database by a personal computer using a
set sequence of commands and formula (a program). This ensures that all reductions/calculations
are consistent and not subject to random error. Verify that the values resulting from the
reduction/calculation procedures are correct by reproducing by hand the process carried out by the
computer for a randomly selected portion of the database.
6.5 Validation of Representativeness
To determine if the results of the reductions/calculations of this data set are representative of the
diet of coho in Lake Michigan for this year and for other years in recent history, data collected and
results reported during other diet studies of Lake Michigan coho will be summarized and
compared to the results produced from this database.
6.6 Reporting Procedures
For each strata, report graphically and/or in table form the following:
The percent that each prey type contributes to the average wet weight of all prey found in
the stomach.
The range and frequency distribution individual weight values and percent weight values
from which the average values are calculated.
The range and distribution of site specific and biological variables.
Length distributions of prey fish in the diet will describe the characteristics of each species
found in the stomachs of coho.
Summarize the results of data collected and results reported during other diet studies of Lake
Michigan coho and contrast and compared to the results produced from this database.
Raw data in paper and electronic medium, and copies of the reports generated from the data will
be stored at the GBFRO for a minimum period of five years.
7.0 Internal Quality Control Checks
Quality assurance for this project will be achieved primarily through specific training both prior to
sampling and during the sampling season. Several persons on the GBFRO staff are experienced in
diet sampling (Miller and Holey 1993, Elliott 1994), and will provide training sessions on
procedures in the SOPs and parameter measurement requirements in Table 1.1 before the sampling
begins and while in progress. Field staff will work in pairs with experienced staff until such a time
that the quality of their work justify them working independently. The quality of field staff work
will be checked periodically throughout the project duration, roughly once or twice per month.
The field staff hired will be required to ha\e completed six credits of fisher) related college course
work and I _? credits of related natural resources or animal science courses, or ha\e appropriate
eqimalent work experience.
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Measurements of length and weight required for this project are straight forward, and their
variation will be a function of the ruler or weight scale used than the person taking the
measurement. The rulers or measuring boards will be examined prior to the field season to ensure
the error between them is less than +/- 2 mm. The weight scales used for this project will be
standardized against standard weights at the beginning of the project and compared to each other
throughout the sampling period. The readability of the scales used is 0.1 g for small fish and prey
types measured in g, and 50 grams for large fish measured in Kg.
8.0 Performance and Systems Audits
Specific Audits will not be conducted as part of this sampling project. Procedures required for this
project are straight forward and not complicated. The duration of the project is also short enough
that the periodic checks on performance of the field and lab staff will serve as audit checks for this
project. The amount of staff involved in this project will be few, therefor, the ability to control the
quality of the project will not require elaborate auditing procedures. Quality control audits at each
stage of the field sampling and analysis will be conducted by the Project Manager, the Field
Manager, or the EPA QA Manager. Audit reports will be kept on file at the GBFRO and available
for review at any time.
Inadequacies in sampling procedures or the quality of the data collected will be addressed
immediately by the Project Manager or Field Manager when discovered. All previous and current
data collected by the person when the inadequacies will be review for accuracy. Additional
training and supervision will be provided until the quality of work is appropriate.
9.0 Calculation of Data Quality Indicators
This QA Plan has defined the DQOs and MQOs (Section 3). This section describes the statistical
assessment procedures that are applied to the data and the general assessment of the data quality
accomplishments.
9.1 Precision
The precision will be evaluated by performing duplicate analyses. Various types of duplicate
samples are described in Section 3. Precision will be assessed by relative percent difference
(RPD)
9.2 Relative Percent Difference (RPD)
(X.-X,)*100
RPD=-
(X, -XJ/2
Relative standard deviation (RSD) may be used when aggregating data.
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9.3 Relative Standard Deviation (RSD)
/?SD=(.v/y)xlOO
Where: s = standard deviation
y = mean of replicate analyses
Standard deviation is defined as follows:
\n = \ <"-')
Where: \, = measured value of the I the replicate
v = mean of replicate analyses
n = number of replicates
9.4 Accuracy
Accuracy will be based upon expert remeasurements of a percentage of samples.
Accuracy will be evaluated by determining whether the measurements are within the acceptance
limits. Deviations beyond the acceptance criteria could be justification for retraining technicians.
Bias can be estimated from the theoretical "true" value of the expert measurement. "System" bias
for the study may be calculated from individual samples and is defined:
Where: Ylk = the average obsen'ed value for the \th audit sample and k observations.
/?, = is the theoretical reference value
n = the number of reference samples used in the assessment
9.5 Completeness
Completeness for most measurements should be 909r. Completeness is defined:
Completeness =— x 1 00
n
Where. \' = number of samples judged valid
n = total number oj measurements necessary to achieve project objectives
The MO' i p'.il means that the objectives ut the Mir\e\ can be met. e\en it' lO'r of the samples are
deemed to he imalid. An invalid sample is defined by a number or combination of flaes
associated uiih the sample. This value v\ill he reported on a annual basis.
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9.6 Representativeness
Based upon the objectives, the three seasonal collections (spring, summer, fall) represent different
coho diet conditions. In order to determine whether a change is statistically significant, the
samples must be representative of the population, and the samples must be collected and analyzed
in a consistent manner.
Representativeness will be evaluated through variance estimates of routine sample in comparison
to previous years estimates. These estimates can be performed at within-site and between-site
levels. Analysis of variance (ANOVA) will be used to determine whether variances are
significantly different.
9.7
r
omparability
Comparability is very similar to representativeness in that comparability is ensured through the use
of similar sampling and analytical techniques. Comparability will be assessed through the
evaluation of precision and accuracy measurements and technical systems audits.
10.0 Corrective Action
Corrective actions are discussed in Table I. I, the internal quality control section (7.0). SOPs, and
in the performance and systems audit section (8.0). The Project Manager and the Field Manager
will initiate corrective actions. Corrective actions will be documented in audit reports, through
data flags, and revisions to the QA plan if methods are changed.
Table 10.0 List of Data flags
LAC
FAC
ISP
AVG
UNK
HER
OTL
laboratory accident
field accident
improper sample
preservation
average value
unknown sex
entry error
data point outlier
There was an accident in the laboratory that either destroyed
the sample or rendered it not suitable for analysis.
There was an accident in the field that either destroyed the
sample or rendered it not suitable for analysis.
Due to improper preservation of the sample, it was rendered
not suitable for analysis.
Average value-used to report a range of values.
In the case of species, indicates undetermined sex.
The recorded value is known to be incorrect but the correct
value cannot be determined to enter a correction.
When a series of data are plotted and analyzed, this point is
obviously not within the normal distribution of the data, and
eliminated from further analysis.
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11.0 Quality Control Reports to Management
A progress report outlining the achievement of the Quality Assurance Objectives will be provided
to the Program Manager at the end of the project. The Project Manager will be notified
immediately, however, if substantive changes are made to the QAPjP. The Quality control report
will include a summary of the results of audits that were conducted, data quality assessment, and
the corrective actions that were taken. Quality control reports will be provided to the Project
Officer and QA Manager at EPA-GLNPO and the Biota Work Group.
12.0 References
12.1 Auer. N. A. 1982. Identification of larval fishes of the Great Lakes basin with emphasis on the
Lake Michigan drainage. 744 pp. Spec. Publ. 82-3, Great Lakes Fishery Commission, Ann Arbor,
MI.
12.2 Bowen, S. H. 1983. Quantitative description of the diet, p. 325-336. In Nielson, L A. and
Johnson, D. L. (eds.) Fisheries Techniques. American Fisheries Society, Bethesda, MD. 468 pp.
12.3 Becker, G. C. 1983. Fishes of Wisconsin. 1052 pp. University of Wisconsin Press, Madison, WI.
12.4 Elliott, R. F 1993. Feeding habits of chinook salmon in eastern Lake Michigan. M.S. Thesis,
Michigan State University, Lansing, MI, 108 pp.
12.5 Elliott, R. F and eight other authors. 1986. Conducting diet studies of Lake Michigan piscivores,
a protocol. U.S. Fish and Wildlife Service, Green Bay fisheries Resources Office,
Report No. 96-2.
12.6 Miller, M. A. and M. E. Holey. 1992. Diets of lake trout inhabiting nearshore and offshore Lake
Michigan environments. J. Great Lakes Res. 18( 1 ):51 -60.
12.7 Nielson, L. A. and Johnson D. L. eds. 1983. Fisheries Techniques. American Fisheries Society,
Bethesda, MD. 468 pp.
12.8 Scott, W. B. and E. J. Grossman. 1973. Freshwater fishes of Canada. Bulletin 184. Fish. Res.
Board Can. 966 p.
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Appendix A.
Standard Operating Procedure
for Sampling Coho Salmon
This SOP is intended to provide a step by step procedure for collecting measuring, preserving and
transporting Coho salmon and stomach contents from coho salmon for the Enhanced Monitoring
Program Lake Michigan Mass Balance.
1.0 Overview
Coho salmon samples will be collected at various region within Lake Michigan in order to
measure contaminant concentrations in the fish tissue of PCBs, Mercury, and trans-nonachlor and
to examine the diet of the salmon by evaluating the stomach contents. Specific details of the study
are documented in the Lake Michigan Mass Balance work plan and in the QA project plan.
Critical and non-critical associated information, as follows, will be recorded:
Critical Non-critical
Location Fin clip
Date of sample Sex
Sample length Stomach fullness
Sample weight Sample depth
Age Water temperature
Physical characteristics
Capture Time
Sample Time
Preservation Time
Two techniques will be used to collect samples: contaminant sampling and diet sampling. Of
primary importance is the collection offish samples for contaminant analysis which must be
collected, prepared, and preserved as soon as possible for transport to the laboratory for analysis.
These samples will be collected by USFWS personnel while on a chartered fishing vessel.
Therefore, there is a good chance that both critical and non-critical measurements will be taken.
Locational accuracy will also be much improved. Diet sampling will involve the collection of
samples after they arrive from various fishing vessels and sport fisherman. Due to various types of
locational equipment (some fisherman may not have sophisticated equipment), locational accuracy
may be low and non-critical measurements may not be collected. However, critical measurements
will occur when fish are collected and the same techniques will be used as those aboard the fishing
vessel.
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1.1 Summary of Method
Samplers will visit the ports (weekly/daily) in the regions mentioned in the Sampling QAPjP to
check for catches. Boats will be chartered as frequently as necessary in order to collect the
minimum number of samples (25) for contaminant analysis is each region within the specified time
frame. The following sampling activities will take place and are discussed in detail in the order
listed.
1) Collection of sample
2) Size measurement
3) Scale collection
4) Stomach removal/preservation
5) Data reporting
6) Sample labeling
7) Sample preservation and storage
8) Waste disposal and clean-up
9) Sample shipment
1.2 Safety
In any field operation, emphasis must be place on safety. Samplers must be aware of the potential
safety hazards to which they are subjected. Follow all safety protocols and equipment guidelines,
and be prepared for emergency situations. The sampler is responsible for his/her safety from
potential hazards.
1.3 Equipment check and calibration
Check to make sure all equipment and supplies are available in required amounts. The following
is a list of all needed equipment and consumables.
1.3.1 Serviceable Equipment
Fishing vessel equipped with navigational instruments and appropriate sampling gear
to catch coho salmon.
Ice chests, including appropriate amount of ice or freeze packs
5-gallon plastic bucket (diet sampling only)
Measuring board (mm markings required)
Spring or electronic scale (1-10 Kg, 0.1 Kg markings required)
Calibrating weight
Dissecting pan
Dissecting knives
Thermometer
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1.3.2 Consumable Equipment
Dissecting gloves for preserving and handling fish
Aluminum foil
Fish storage bag
Whirl-pac bags
Formalin (10-15% and full strength for mixing)
Sample labels
Reporting sheet
Marking equipment
Scale envelopes
Cleaning sponge and brush
1.3.3 Calibration and Standardization
Equipment necessary for calibration and the required frequency can be found in table
Table 1. Equipment Calibration and Required Frequency
Instrument
Thermometer
Locational
Device
Measuring
Board
Scale
Calibration Technique
Ice bath and boiling water
Calibration to a standard of
known Lat and Long
Check against second device
Check against a standard S class
weights 1,5, 10, 25 kgs.
Frequency
1 /year
per trip
1 /year
daily
Acceptance
Criteria
+/- 2 degrees
+/- .25 Km
+/- 2 mm
+/- . 1 kg
2.0 Procedures
2.1 Collection Of Contaminant Samples
Contaminant samples will be collected on-board a chartered or USFWS owned vessel using
angling equipment.
2.1.1 Throughout each season, contract charter operators to fish for coho salmon in areas where
coho are currently or are most likely to be caught. Verify that chartered vessels will have
on-board adequate instrumentation and gear to catch fish and establish the location, time,
and depth of capture. Samples of age 1.0 coho before they are stocked into the lake will
be sampled at the state fish hatcheries where they are reared.
2.1.2 For each cnho salmon captured, record all site and sample identification data specified on
the Field Data Sheet, on two I.D. Labels, and on a whirl-pac bag (see attached examples).
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Note: Data recorded will include: Objective (contaminant, diet, audit) Gear, Lake,
Region, Nearest Port, Lat/Long or Statistical Grid, Species, Date, I.D. number, Lake
Depth/Capture Depth, Water Temperature, Time Of Capture/Time Of Sampling, Field
Qualifier Flag, Collectors Name.
Immediately after capture:
2.1.3 Determine and record:
Maximum Total Length (mouth closed and caudal fin dorso-ventrally compressed to
nearest mm) using the measuring board.
Total Weight (0.1 kg) using the spring or electronic balance. For the hatchery sample.
weigh fish with an electronic balance to the nearest O.I g.
2.1.4 Remove at least five scales (from just above the lateral line and below the posterior
insertion of the dorsal fin) with a clean knife and place in the scale envelope. Record on
the label the fish length, weight if taken, date, location sampled, and sample number.
2.1.5 Line the examination tray or measuring board with foil and place the coho on the board or
in the tray. Make a 3-5 inch incision with a clean knife in the belly of the fish. Determine
and record the sex and physical characteristics. Pull out and remove the stomach (anterior
esophagus to pyloric sphincter) and all its contents. The spleen and any other organs that
may be attached to the stomach should be removed and left inside the fish. Make a small
slit in the stomach to allow preservative to enter, and place in the whirl-pac bag. If the
stomach appears empty, open the stomach completely to verify that it is completely void.
Indicate so on the field data sheet. Void stomachs do not need to be kept. Pack the whirl-
pac bag with stomach contents on ice until you return to port where they can be safely
preserved (see 2.1.9).
2.1.6 Maintaining all body fluids within the foil, wrap the coho completely with the foil lining
the measuring board and attach one I.D. label to the foil. Place wrapped fish in a 4 mil
polyethylene bag, seal the bag and attach the other I.D. label.
2.1.7 Place the bagged fish in a cooler and pack with ice until it can be transferred to a freezer
and frozen. Verify that the samples were frozen within 24 hour? by recording the date and
time when the fish was captured, sampled, and placed in the freezer.
2.1.8 Clean/rinse all equipment thoroughly that comes in contact with sampled fish between
sampling each fish.
2.1.9 After returning to port, preserve the stomach contents in the whirl-pac bag with at least 2X
their volume of 10% formalin. Seal the bag and place in the scalable 5 gallon bucket.
When handling formalin, wear rubber gloves, keep away from fish, food, and other
people, stay in a well ventilated area, and thoroughly rinse with water any object or
surface that comes in contact with the formalin.
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2.1.10 Keep all samples in your possession and in their preserved state (on ice, frozen, in
formalin etc.) until they have been delivered to the laboratory where the subsequent
analysis will occur. For foil-wrapped coho, this is the NBS-Great Lakes Center in Ann
Arbor. For preserved stomachs and all Field Data Sheets, this is the FWS Green Bay
FRO. Transport only in FWS approved vehicles. With each transfer between locations,
record the date and sample ID number to verify sample integrity.
2.1.11 Contaminant samples will be composited by the GBFRO. Samples for contaminant
analysis will be taken throughout each season sampled. The five fish composites will be
prepared after each season has been sampled. Each season is roughly eight weeks long
(56 days). Composites will be combine as similar as fish as possible based on size,
location of capture, and when possible, sex in consultation with the LMMB modelers.
2.2 Collection of Diet Samples
In addition to diet samples (stomachs) collected from coho sampled for contaminant analysis, diet
samples will be collected at port from various fishing vessels.
2.2.1 As soon as anglers/operators return to shore, obtain permission to examine and sample
their catch. Permanent cleaning stations located near boat launches and marinas provide
ideal locations for this sampling. To ensure that as representative a sample as possible is
collected, sample from as many boats as possible over all hours of the day, and sample all
coho creeled by anglers aboard an individual boat.
2.2.2 For all fish sampled, record all site and sample identification data specified on the Field
Data Sheet, and on a whirl-pac bag (see attached examples).
Note: Data recorded will include: Objective (contaminant, diet, audit) Gear, Lake, Region,
Nearest Port, Lat/Long or Statistical Grid, Species, Date, l.D. number, Lake Depth/Capture Depth,
Water Temperature, Time Of Capture/Time Of Sampling, Field Qualifier Flag, Collectors Name,
As soon as possible after capture:
2.2.3 Determine and record:
Maximum Total Length (mouth closed and caudal fin dorso-ventrally compressed to
nearest mm) using the measuring board. Flex fish several times if rigor mortis has set in
so that fish lays flat on the board.
Total Weight (0.1 kg) using the spring or electronic balance (when time permits).
2.2.4 Remove at least five scales (from just above the lateral line and below the posterior
insertion of the dorsal fin) with a clean knife and place in the scale envelope.
2.2.5 Make a 3-5 inch incision in the belly of the fish. Determine and record the sex and the
clinical condition of the fish. Pull out and remove the stomach (anterior esophagus to
pylonc sphincter) and all its contents. Return the fish to the angler/operator. Make a
small slit in the stomach to allow presenatne to enter, and place in the whirl-pac bag It
the stomach appears empty, open the stomach completely to verify that it is completely
void. Indicate so on the field data sheet Void stomachs do not need to be kept.
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Temporarily place the whirl-pac bag with stomach contents on ice until they can be safely
preserved (see 2.2.7). Stomachs from hatchery sampled fish will not be taken.
Note: Step 2.2.5 may be done after the fish has been filiated if the angler/operator prefers
to clean the fish before the stomach is removed.
2.2.6 Preserve the contents in the whirl-pac bag with at least 2X their volume of 10% formalin.
Seal the bag and place in the scalable 5 gallon bucket. When handling formalin, wear
rubber gloves, keep away from fish, food, and other people, stay in a well ventilated area,
and thoroughly rinse water any object or surface that comes in contact with the formalin.
If extra personnel are available, preservation can be done as soon as the stomach contents
are removed. If not, wait until all fish have been worked up, packed, and stored.
2.2.7 Keep all samples and data sheets in your possession until they have been delivered to the
FWS Green Bay FRO. Transport only in FWS approved vehicles. Upon renim to the
GBFRO, make photocopies of the original Field Data Sheets to be kept on file at a
location other than where the original data sheets are filed. With each transfer between
locations, record the date and sample ID number to verify sample integrity.
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Appendix B.
Standard Operating Procedure for
Lab Analysis of Coho Salmon Stomachs and Data Entry
This SOP is intended to provide a step by step procedure for examining and quantifying the
contents of the stomachs sampled, and then entering all data on the computer as part of
determining the diet of coho salmon for the Enhanced Monitoring Program Lake Michigan Mass
Balance Study.
1.0 Overview
Contents of stomachs collected from Lake Michigan coho salmon will be identified, enumerated,
and weighed. Data will be recorded on data sheets and entered into a computer data base.
Summary of Method
Stomachs will be rinsed to free excess formalin and allow for safe handling of the sample. Fish
found in the stomachs will be identified to species, assigned a percent digested state, measured and
weighed. Invertebrates will be identified into the appropriate taxon and weighed as a group. The
age of the fish will be determined by a length frequency analysis and a subsample will be verified
through scale aging. Reconstruction of the prey length will also be used to determine
reconstructed weight. The data will be entered into database (FoxPro) and spreadsheet (Lotus)
software, verified, and summary reports created.
2.0 Safety
In any lab operation, emphasis must be place on safety. Samplers must be aware of the potential
safety hazards to which they are subjected. Follow all safety protocols and equipment guidelines,
and be prepared for emergency situations. The sampler is responsible for his/her safety from
potential hazards.
3.0 Equipment Check and Calibration
Check to make sure all equipment and supplies are available in required amounts. The following
is a list of all needed equipment and consumables.
3.1 Equipment
Serviceable Equipment
Fume Hood
Rinse Water SuppK and rinsing bath
Rinse Tra\
Dissecting Tra\ and Tools (scalpel, forceps, scissors)
Dissecting Microscope
Electronic Balance and calibration \\eiahts
Plastic Ruler (mm divisions)
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Glass Specimen Jars
Scale Press
Scale Projector/Reader
Computer & Printer (with hard drive, disk drive, and necessary software)
Consumable Equipment/Supplies
Weighing trays
Formalin (5%)
Rubber Gloves
Impression Acetate
Paper Toweling
Plastic Bags (2-5 gal)
Reporting Sheets and Marking devices
3.2 Calibration and Standardization
Equipment necessary for calibration and the required frequency can be foi'nd in Table I.
Table 1. Equipment Necessary for Calibration and Required Frequency.
Instrument
Plastic Ruler
Electronic Balance
Computer
Calibration Technique
Check against second
device
Use calibration weight
methods as prescribed by
scale manufacturer
Virus scan
Frequency
Start-end/season
Daily
Every boot-up
Accepted Criteria
±1 mm
±0.1 g
No viruses
4.0 Procedures
The following procedures will be discussed:
Sample preparation
Identification and quantification of prey items
Numeration and estimation (for invertebrates)
Length measurement and
Weight measurement and estimation
Archiving representative samples
Mounting and ageing scales
Data Recording
Data Entry
Verifying Data
Determining conversion data and developing formula
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4.1 Analysis of Stomach Contents
Proceed with the following steps in a well ventilated (fume hood operating if necessary) area
intended for work of this nature. Wear rubber gloves when handling preserved prey items, have
equipment set up, calibrated and ready for use, and start with and maintain a clean work area.
4.1.1 Open whirl-pac bag, pour contents into rinsing container with 365 micron mesh screen,
flush with rinse water until contents are free of excess formalin, remove from rinse
container and allow to drip free of excess water.
4.1.2 For each prey fish, identify to species, assign an estimated percent digested state, measure
(nearest mm) and weigh (nearest 0.1 g for large items and 0.02 g for small prey items).
For identification of fish, Becker (1983), Scott and Grossman (1973), Auer (1982), and
Elliott et al. (1996) will be used as reference material. In addition, during the training
period we will develop our own reference specimens for identification purposes. Record
data as indicated on the lab data sheet (see attached). Measure length to level of precision
allowed depending on how much of the fish is remaining. Order of priority is:
1) maximum total length, 2) standard length, 3) vertebral column length, and 4) length of
as many vertebrae as possible. For those fish or parts of fish that can not be positively
identified, record as unidentified.
4.1.3 For invertebrates, group into appropriate taxon and weigh (nearest 0.02 g). Either count
directly or estimate indirectly the total number based on weight (at least 0.5 g or
25 individuals) of a known number representative of the group. Determine an average
length and digested state for each taxon group. Record data as indicated on the lab data
sheet.
4.1.4 If the identification of a prey item is uncertain, the item will be examined by a second
identifier and compared to the reference collection of diet items prepared for training. It
an agreement on the identification can not be reached, the prey item shall be recorded as
unidentifiable.
4.1.5 Throughout the stomach analysis, set aside and preserve in glass jars with 5% formalin,
examples of each species of prey fish and taxonomic group of invertebrate. Examples
should represent the range of both digested conditions and sizes of prey observed and be
able to document the methods of identification and quantification used in this analysis.
Label saved samples as to their source (sample I.D. number), their identification.
4.1.6 Package contents back into whirl-pac bag and preserve. To facilitate easy retrieval of
samples for quality control verification, package samples from similar locations and dates
together (groups of 10-25) into clear plastic bags. Maintain the reference collection for
identification until the final project report is accepted by EPA.
4.1.7 Make photocopies of each completed Lab Data Sheet and file at designated separate
locations.
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4.2 Aging Coho Scales
The method aging fish by length frequencies or scales, and verifying age is adequately described in
fisheries Techniques (Nielson and Johnson 1983). The following highlights the procedure to use.
4.2.1 Prepare a length frequency histogram by 10 mm increments of all the coho samples for
each season sampled. Only two year classes of coho will be in the lake at any one time,
therefore separation of age by length should be obvious. Based on the length of each
sample, assign an age based on the age/length frequency histogram developed. To verify
the ages determined from the length frequency analysis, especially if ages overlap in
length, scales will be aged.
4.2.2 Remove scales from the envelope and clean them in a solution of 5% Clorox in water with
brush or wooden stick.
4.2.3 Place cleaned scales on the glass plate of a microfiche reader, add a few drops of water,
and cover with a glass slide. Examine all scales to determine which scale exhibits the
most representative growth pattern of the available scales. Age that scale by counting
annuli observed. Record the age using the European method (stream years lake years) on
the scale envelope along with the readers initials.
4.2.4 To verify, re-age those fish that would have different ages assigned using the two
methods. Also, re-age enough additional fish that have sizes nearest the size division
indicated by the length frequency analysis so that at least 5% of all fish are re-aged.
Re-aging is to be done by both the individual who originally aged the fish and a second
individual who has not yet aged that fish, both using the same methods as in Section 4.2.2.
Assign and record final age on the envelope based on consensus reached by both
individuals or by the majority if a third independent reader is necessary.
4.3 Standard Measurements for Developing Conversion Equations
To allow reconstruction of total prey length and weight from partial length measures, and to allow
the conversion of total length and weight of preserved prey to length and weight of fresh prey (or
visa-versa), the following procedures will be followed.
4.3.1 For up to 50 intact individuals representing all sizes of each prey fish species (5 per 1/10
of size range encountered from preserved stomachs), measure total length and weight.
dissect the fish and measure (nearest mm) the standard length, the vertebral column
length, the length of as many vertebrae as possible, and count the total number of
vertebrae. Record these measures on a lab data sheet identified as Standard Measures.
4.3.2 When in the field, the Project Field Manager will conduct independent measurements of
enough stomach contents (Section 4.1) so that representing all sizes and digested states
will be identified and measured prior to preservation for later lab analysis. Data will be
recorded on a lab data sheet identified as Standard Measures.
4.3.3 Enter all data from Standard Measurements Data Sheets into database in prescribed fields.
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4.3.4 Develop the following conversion equations with associated errors for each prey species:
Vertebrae length to vertebral column length and total length
Vertebral column length to standard length and total length
Standard length to total length
Total length to wet weight
Preserved total length to fresh total length
Preserved wet weight to fresh wet weight
4.3.5 Compare to similar equations developed from other studies to determine validity.
4.4 Data Entry and Verification
4.4.1 Maintain three independent copies of the data (on hard drive, on disk, and hard copy
printout) in different locations and update/backup each on a daily basis when altered.
4.4.2 Enter all data from Field and Lab Data Sheets into database in prescribed fields.
4.4.3 Using equations determined in 4.3, calculate missing total length measures from partial
length measures and add to the database.
4.4.4 Identify and correct inaccuracies in data recording and entry, and identify outliers as
follows:
Plot data variables, identify peripheral values, and cross-reference with original
data records. Example plots include:
Predator length vs. weight Predator length vs. date (by age)
Prey length vs. date Prey length vs. weight (by length type)
Query all data fields for values above and below expected values and cross-
reference with original data records.
Visually compare and verify each computer record with field and lab records on
original data sheets.
Resolve with the data collector any possible errors :n recording.
Identify data points as an outlier, that after completing the above, still appears to
be outside the range of expected values.
1-397
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I \KI. MICHIGAN MASS BUDGET/MASS BALANCE PROJECT
C oliu Salmon Containmanl Sample
SI-.ASON REGION AGE
LENGTH (mm)
WEIGHT (kg)
SEX (M,F)
SI' SU I:A
W E - S C N
0 1 2
i VI \K MONIII- DAY I FISH 0 COLLFXTOK I D.
IK'Liiun mlumialii.il contact USFWS (iieeii Bay Eishciy Kesiiurces Oll'ice
Maik Hok-v - IVoiecl l.eailei ph -114-411-1X01
CO
CO
00
I \K1- MICHIGAN MASS BUDGET/MASS BALANCE PROJECT
Culm Salmon Ci.ntammant Sample
RECKON AGE
LENGTH (mm)
WEIGHT (kg)
SP SU 1;A
W E, - S C N
0 1 2
I) \ 11.
i>l\k MONIH-DAY) FISH H COLLECTOR I D.
SEX(M,F)
iitiMNi.iliiin contact: USFWS (lieen Bay Fishery Resouices Ollice
Mark Hulev - I'rojecl i.eadei ph 4I4-411-.1K01
I \KI. MICHIGAN MASS BUDGET/MASS BALANCE PROJECT
Coho Salmon ('ontanunant Sample
SEASON REGION AGE
LENGTH (mm)
WEIGHT (kg)
SP SU I;A
W E - S C N
0 1 2
I VI \K MONIH-DAY) FISH « COLLECTOR I I)
SEX (M,F)
M.nk HuU", - 1'iou'U I eailei ph 414-411
LAKE MICHIGAN MASS BUDGET/MASS BALANCE PROJECT
Coho Salmon Contaminant Sample
SEASON REGION AGE
LENGTH(mm)
WEIGHT (kg)
SP SU FA
WE - S C N
0 1 2
DATE:
( YEAR - MONTH - DAY ) FISH # COLLECTOR I.D
SEX(M,F)
For sample collection information contact USFWS Green Bay Fishery Resources Ollice
Mark Hnley - Project Leader pli: 414-411-1X01
LAKE MICHIGAN MASS BUDGET/MASS BALANCE PROJECT
Coho Salmon Contaminant Sample
SEASON REGION
AGE
SP SU FA
WE - S C N
0 1 2
LENGTH (mm)
DATE. WEIGHT (kg)
( YEAR - MONTH - DAY ) FISH # COLLECTOR I D
SEX (M,F)
For sample collection information contact USFWS Cireen Bay Fishery Resources Office
Mark Holey - Project Leader ph' 414-411-1X01
cn o
a F
3 SL
O
o
B>
LAKE MICHIGAN MASS BUDGET/MASS BALANCE PROJECT
Coho Salmon Contaminant Sample
SEASON REGION
SP SU FA
WE - S C N
AGE
0 1
2
LENGTH (mm)
DATE. WEIGHT (kg)
YEAH - MONTH - DAY I FISH # COLLECTOR I D
SEX(M,F)
En, sample culleciii.ii ii,r.,imatiun contact USFWS Green Bay Fishery Resources Ollice
Mark Holey - Projeci Leader ph 414-411-1X0.1
!
5
-------
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Quality Assurance Plan for Coho
Volume 1, Chapter 5 Samolina for Contaminant and Diet Analvsis
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Quality Assurance Plan for Coho
Sampling for Contaminant and Diet Analysis Volume 1, Chapter 5
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. i' ' - - f W : s c i • r i s i r i
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CHAIN OF CUSTODY RECORD
7-87
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Signature
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Sample Description
Lab ID
Number
I hi-i'l'V i. i City that I received, properly handled, and disposed of these samples as
nol ed I.,-!.... :
[•:<•! i iuj'. i :iln d by (Signature)
Date /Time
Received by: (Signature)
No . ot
Containers
Comment s
Disposition of Unused Portion of Sample
CO
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-------
Quality Assurance Plan for Coho
Sampling for Contaminant and Diet Analysis Volume 1, Chapter 5
Audit Finding
Audit Title: Audit #: Finding #:_
Finding:
Discussion:
1-402
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Quality Assurance Plan for Coho
Volume 1, Chapter 5 Sampling for Contaminant and Diet Analysis
Audit Title:
Audit Finding
Response Form
Audit #: Finding #:
Finding:
Cause of the problem:
Actions taken or planned for correction:
Responsibilities and timetable for the above actions:
Prepared by: Date:
Reviewed bv:
Remarks:
Date:
1-403
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