A practical book for professionals who rely on water quality data for decision making, this book is based on three decades experience of three highly published water and watershed resource professionals. It focuses on the analysis of air pollution sensitive waters and the consequent effects associated with soil and water acidification, nutrient-N enrichment, or the effects of atmospherically deposited toxic substances. It also covers lake zooplankton and/or stream macroinvertebrate biomonitors. Explanations of the reasons behind various recommendations provide readers with the tools needed to alter recommended protocols to match particular study needs and budget.

List of Figures xiii

List of Tables xvii

Preface xxi

Acknowledgments xxiii

About the Authors xxv

Acronyms and Abbreviations xxvii

Glossary xxxi

1 Purpose and Study Design 1

1.1 Background 1

      1.1.1 Resources Sensitive to Atmospheric Deposition 4

      1.1.1.1 Sensitive Chemical Indicators of Water Quality 7

      1.1.1.2 Potential Confounding Factors 10

      1.1.2 Study Purpose and Objectives 10

1.2 Study Design 16

      1.2.1 Lake or Stream Characterization 16

      1.2.2 Synoptic Survey 19

      1.2.3 Characterization of Stream Chemistry during Hydrologic Events 20

      1.2.4 Long-Term Monitoring 21

      1.2.5 Other Uses of Resulting Data 21

      References 23

2 Water Chemistry Field Sampling 25

2.1 Background 25

2.2 Where, What, and When to Sample 26

      2.2.1 Where to Sample 27

      2.2.1.1 Selection of Sampling Locations 27

      2.2.1.2 Selection of Specific Sampling Sites 32

      2.2.1.3 Establishing and Locating Sampling Sites 35

      2.2.2 What to Measure 36

      2.2.2.1 Acidification Studies 36

      2.2.2.2 Eutrophication Studies 40

      2.2.2.3 Bioaccumulation and Toxicity Studies 43

      2.2.3 When to Sample 44

      2.2.3.1 Lake or Stream Characterization 46

      2.2.3.2 Synoptic Survey 46

      2.2.3.3 Characterization of Episodic Chemistry during Hydrologic Events 48

      2.2.3.4 Long-Term Monitoring 48

2.3 Field Methods 49

      2.3.1 Pretrip Preparations 50

      2.3.1.1 Permits and Access 50

      2.3.1.2 Laboratory and Sample Bottle Arrangements 53

      2.3.1.3 Acquisition of Equipment, Supplies, and Data Forms 55

      2.3.1.4 Plan for Staffing 56

      2.3.2 Sample Collection 57

      2.3.2.1 Collection of Stream Water 58

      2.3.2.2 Collection of Lake Water 63

      2.3.3 On-Site Measurements 66

      2.3.3.1 Evaluation of Site Characteristics 66

      2.3.3.2 Stream Stage and Discharge and Lake Level 66

      2.3.3.3 Ancillary Data (Chemical and Physical Information That Is Not Necessary But May Be Useful) 69

      2.3.3.4 On-Site Processing of Samples 72

      2.3.4 Postcollection Sample Processing, Documentation, and Cleanup 73

      2.3.4.1 Sample Documentation 73

      2.3.4.2 Postsampling Equipment Cleanup 73

      2.3.5 Sequence of Field Activities 75

      2.3.6 Safety in Field Activities 75

      2.3.6.1 Key Safety Considerations 75

      2.3.6.2 Job Hazard Analysis 76

      References 77

3 Laboratory Analyses 81

3.1 Introduction 81

3.2 Laboratory Preparation Prior to Sample Analysis 82

      3.2.1 Bottle Cleaning 82

      3.2.1.1 Cleaning Bottles Used for Sample Collection in the Field 85

      3.2.1.2 Cleaning Bottles Used for General Laboratory Use, Unacidified Aliquots 85

      3.2.1.3 Cleaning Bottles Used for General Laboratory Use, Acidified Aliquots 85

      3.2.2 Sample Processing, Preservation, and Storage 86

3.3 Chemical Analysis 90

4 Quality Assurance/Quality Control 93

4.1 Introduction 93

4.2 Attributes of Data Quality 95

      4.2.1 Method Detection and Reporting Limits 95

      4.2.1.1 Method Detection Limit 95

      4.2.1.2 Reporting Limit 98

      4.2.2 Precision and Accuracy 101

      4.2.3 Completeness 102

      4.2.4 Comparability 103

      4.2.5 Representativeness 103

      4.2.6 Recommended Laboratory Data Quality Objectives 104

4.3 QA/QC Sample Types 105

      4.3.1 Filter Blanks, Analytical Blanks, and Field Blanks 109

      4.3.2 Replicate Environmental Samples 109

      4.3.3 Spiked Project Samples 110

      4.3.4 External Quality Assurance Samples 111

4.4 Field QA 113

      4.4.1 Sample Containers 113

      4.4.2 Field Measurements 113

4.5 Reporting QA Data 115

4.6 Laboratory Audits and Certification 117

4.7 Data Entry 118

4.8 Summary 119

References 120

5 Data Analysis 121

5.1 Background and Objectives 121

5.2 Evaluation of Data Quality 122

      5.2.1 Charge Balance 126

      5.2.2 Calculated versus Measured Conductivity 132

      5.2.3 Calculated versus Measured ANC 133

      5.2.3.1 Carbonate Alkalinity versus Titrated ANC 133

      5.2.3.2 Calculated versus Titrated ANC 134

      5.2.4 Other Validation Procedures 136

      5.2.5 Final Data Quality Determination 137

5.3 Apply Procedures to Prepare Raw Data for Graphical and Statistical Analysis 137

      5.3.1 Censored Data 137

      5.3.2 Outliers and Missing Values 138

      5.3.3 Multiple Observations 141

      5.3.4 Treatment of Zeros and Negative Values 142

      5.3.5 Treatment of Seasonality 142

5.4 Conduct Exploratory Analyses 144

      5.4.1 Analysis of Water Quality Status 144

      5.4.2 Graphing and Qualitative Analysis 144

      5.4.3 Recommended Data Analyses 146

      5.4.3.1 Creating Data Subsets 147

      5.4.3.2 Determine Whether One Lake or Stream, or a Group of Lakes or Streams, Is N Limited for Algal Growth 148

      5.4.3.3 Quantify Episodic Excursions from Base Flow Conditions in Surface Water Chemistry during Hydrologic Events 149

      5.4.3.4 Determine the Distribution of Lake or Stream Water Chemistry across a Particular Study Area 152

      5.4.3.5 Quantify Long-Term Changes in Lake or Stream Chemistry over Time 155

      5.4.3.6 Determine to What Extent Air Pollution Is Currently Affecting the Water Resources in a Study Area 158

      5.4.3.7 Evaluate Whether the Current Condition of Acidor Nutrient-Sensitive Waters Warrants Mitigation 163

5.5 Conduct, If Needed, Statistical Analyses 163

      5.5.1 Statistical Tests for Difference 163

      5.5.2 Trend Detection 165

      5.5.3 Statistical Power 169

5.6 Summary and Conclusions 170

References 171

6 Field Sampling for Aquatic Biota 175

6.1 Background 175

      6.1.1 Lake Zooplankton 175

      6.1.2 Stream Macroinvertebrates 176

6.2 Aquatic Invertebrate Study Design 177

6.3 Site Selection 179

      6.3.1 Laying Out the Support Reach for Stream Macroinvertebrate Sampling 180

      6.3.2 Lake Selection for Zooplankton Sampling 182

6.4 Pretrip Preparation 184

      6.4.1 Equipment and Supplies 184

      6.4.2 Equipment-Cleaning Protocols 186

6.5 Collection Procedures 186

      6.5.1 Stream Benthic Macroinvertebrates 186

      6.5.2 Lake Zooplankton 193

6.6 Sample Processing, Preservation, and Handling 195

      6.6.1 Stream Benthic Macroinvertebrates 195

      6.6.2 Lake Zooplankton 197

6.7 Documentation and Tracking 199

6.8 Laboratory Analysis of Biological Samples 199

6.9 Quality Assurance 199

6.10 Interpretation 201

      6.10.1 Streams 208

      6.10.2 Lakes 210

      References 212

7 Transition Plan 215

7.1 Background 215

7.2 Transition Steps 215

7.3 Decision of Whether to Change Protocols 219

Appendix A: Protocols, Guidance Documents, and Methods Manuals Reviewed 221

Appendix B: Basic Standard Operating Procedures for Stream Field-Sampling Activities 223

Contents 223

B.1 Introduction 223

B.2 Pretrip Activities 223

      B.2.1 Background 223

      B.2.2 Daily Itineraries 224

      B.2.3 Instrument Checks and Calibration 226

B.3 Site Documentation 226

      B.3.1 Background 226

      B.3.2 Objective 227

      B.3.3 Material Needed for Use in Field for Site Documentation 227

      B.3.4 Sequence of Site Documentation Activities 228

B.4 Stream Sampling 230

      B.4.1 Background 230

      B.4.2 Documentation of Data and Sample Collection 231

      B.4.3 Sequence of Activities for Data Collection 232

      B.4.4 Sample Collection 233

      B.4.4.1 Sample Collection Procedure 235

      B.4.4.2 Sample Handling 236

      B.4.4.3 Postsampling Actions 237

      B.4.5 Field Measurements 237

      B.4.6 Post-trip Activities 239

      B.4.6.1 Equipment Cleanup and Check 240

      B.4.6.2 Shipment of Samples and Forms 240

      B.4.6.3 Processing Site Documentation Data and Information 240

B.5 Stream Discharge 241

      B.5.1 Background 241

      B.5.2 Velocity-Area Procedure 242

      B.5.3 Timed-Filling Procedure 242

      B.5.4 Equipment and Supplies 245

B.6 Acknowledgments 246

References 246

Appendix C: Basic Standard Operating Procedures for Lake Field-Sampling Activities 249

Contents 249

C.1 Introduction 249

C.2 Pretrip Activities 249

      C.2.1 Background 249

      C.2.2 Daily Itineraries 250

      C.2.3 Instrument Checks and Calibration 250

      C.2.4 Supply Inventories 251

      C.2.5 Sample Container Preparation 251

C.3 Site Documentation 251

      C.3.1 Background 251

      C.3.2 Objective 253

      C.3.3 Material Needed for Use in the Field for Site Documentation 253

      C.3.4 Sequence of Site Documentation Activities 254

      C.3.5 Lake Verification at the Launch Site 256

      C.3.6 Index Site Location 257

C.4 Lake Sampling 258

      C.4.1 Background 258

      C.4.2 Documentation of Data and Sample Collection 259

      C.4.3 Sequence of Activities for Data Collection 260

      C.4.4 Sample Collection 260

      C.4.4.1 Deep-Water Index Sample 260

      C.4.4.2 Lake Outlet Sample 262

      C.4.4.3 Shoreline Sample 263

      C.4.5 Field Measurements 265

C.5 General Lake Assessment 266

      C.5.1 Background 266

      C.5.2 General Lake Assessment Procedures 267

      C.5.2.1 General Lake Hydrologic Information 267

      C.5.2.2 Shoreline Characteristics 268

      C.5.2.3 Qualitative Macrophyte Survey 268

C.6 Post-trip Activities 269

      C.6.1 Data Forms and Sample Inspection 269

      C.6.2 Launch Site Cleanup 269

      C.6.3 Processing Site Documentation Data and Information 269

C.7 Acknowledgments 270

References 270

Appendix D: Data Entry Forms and Labels for Field-Sampling Activities 271

Stream-Sampling-Site Documentation Form 272

Stream-Sampling-Site Documentation Form Instructions 274

Stream-Water-Sampling Record Form 276

Stream-Water-Sampling Record Form Instructions 279

Lake-Sampling-Site Documentation Form 281

Lake-Sampling-Site Documentation Form Instructions 284

Lake-Water-Sampling Record Form 287

Lake-Water-Sampling Record Form Instructions 289

Chain-of-Custody Form 291

Chain-of-Custody Form Instructions 292

Labels for Water, Zooplankton, and Stream Benthic Macroinvertebrate Samples 294

Water Sample 294

Zooplankton Sample 294

Stream Benthic Macroinvertebrate Sample 294

Label Instructions 295

Zooplankton Sample 296

Stream Benthic Macroinvertebrate Sample 296

Stream Benthic Macroinvertebrate Sampling Data Form 298

Stream Benthic Macroinvertebrate Sampling Data Form Instructions 299

Zooplankton-Sampling Data Form 300

Lake-Zooplankton-Sampling Data Form Instructions 301

Index 303

Dr. Timothy Sullivan holds a BA in history from Stonehill College, Easton, Massachusetts (1972); an MA in biology from Western State College, Gunnison, Colorado (1977); and a PhD in biological sciences from Oregon State University, Corvallis (1983) through an interdisciplinary program that included areas of focus in ecology, zoology, and environmental chemistry. He did his postdoctoral research at the Center for Industrial Research in Oslo, Norway, on surface and groundwater acidification, episodic hydrologic processes, and aluminum biogeochemistry. His expertise includes the effects of air pollution on aquatic and terrestrial resources, watershed analysis, critical loads, ecosystem services, nutrient cycling, aquatic acidbase chemistry, episodic processes controlling surface water chemistry, and environmental assessment. He has been president of E&S Environmental Chemistry, Inc., since 1988 and E&S Environmental Restoration, Inc., since 1996. He has served as project manager or lead author for a wide variety of projects that have synthesized for diverse audiences complex air and water pollution effects science. He was project manager of the effort to draft a scientific summary and Integrated Scientific Assessment (ISA) of the effects of nitrogen and sulfur oxides on terrestrial, transitional, and aquatic ecosystems for the US Environmental Protection Agency (EPA) in support of its review of the National Ambient Air Quality Standards (NAAQS). He was author of the National Acid Precipitation Assessment Program (NAPAP) State of Science and Technology Report on past changes in surface water acid-base chemistry throughout the United States from acidic deposition. He served as project manager for preparation of air quality reviews for national parks throughout California and coauthored similar reviews for the Pacific Northwest and the Rocky Mountain and Great Plains regions. He has summarized air pollution effects at all 272 Inventory and Monitoring national parks in the United States and has managed dozens of air and water pollution modeling and assessment studies throughout the United States for the National Park Service, US Forest Service, and EPA. He has published a book on the aquatic effects of acidic deposition and more than 125 peer-reviewed journal articles, book chapters, and technical reports describing the results of his research. PA\Dr. Alan Herlihy is a senior research professor at Oregon State University in the Department of Fisheries and Wildlife. His current research projects focus on developing survey design methodology, assessment approaches, and ecological indicators for assessing surface water ecological condition at large regional scales. He was a primary technical contributor to the 1990 National Acid Precipitation Assessment Program’s Integrated Assessment report to Congress, the EPA/Environmental Monitoring and Assessment Program (EMAP) Mid-Atlantic Highlands Stream Assessment, and the Western Streams and Rivers Assessment. He was the primary author of the chapters in the EMAP stream and river field manual on water chemistry sampling, qualitative site assessment, and sample reach layout. Currently, he is involved with the data analysis and assessment of the National Aquatic Resource Surveys conducted by the EPA Office of Water. PA\James Webb holds a BS in environmental science from Davis and Elkins College, Elkins, West Virginia (1983) and an MS in environmental science from the University of Virginia, Charlottesville (1988). He is presently a senior scientist in the Department of Environmental Sciences at the University of Virginia, where he served for 25 years as projects coordinator for the Shenandoah Watershed Study and the Virginia Trout Stream Sensitivity Study (http://swas.evsc.virginia.edu). He has authored and coauthored numerous reports and journal articles concerning watershed response to atmospheric acidic deposition in the forested mountains of the central Appalachian Mountains region. He has participated in the design and management of water quality studies and surveys, monitoring programs, and assessments related to national park, national forest, and other conservation lands in the region. He served as an academic community representative on the Technical Oversight Committee and as coauthor of the Aquatic Effects Technical Report for the multiagency Southern Appalachian Mountains Initiative. He has contributed to multiple National Park Service assessments, including participation as coprincipal investigator for the Shenandoah National Park: Fish in Sensitive Habitats project and the Assessment of Air Quality and Air Pollutant Impacts in the Shenandoah National Park. He was a coauthor of the Trout Unlimited report, Current and Projected Status of Coldwater Fish Communities in the Southeastern US in the Context of Continued Acid Deposition. He has contributed to EPA reports on status and changes in the acid-base chemistry of surface waters in the United States related to implementation of the Clean Air Act. His previous involvement in protocol and standard operating procedure development for environmental monitoring has included work for the National Park Service and the US Department of Agriculture Forest Service.

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