Long-Term Coastal Ecosystem Program at Cape Cod National Seashore 

Monitoring Ground-Water Quality in 

Coastal Ecosystems 

Open-File Report 2007–1149 

Prepared in cooperation with the 

NATIONAL PARK SERVICE 
U.S. Department of the Interior 

U.S. Geological Survey 

Monitoring Ground-Water Quality in 

Coastal Ecosystems 

By John A. Colman and John P. Masterson 

Open-File Report 2007–1149 

Prepared in cooperation with the 

NATIONAL PARK SERVICE 

As part of a series of monitoring protocols for the 

LONG-TERM COASTAL ECOSYSTEM MONITORING PROGRAM 

AT CAPE COD NATIONAL SEASHORE 

USGS Patuxent Wildlife Research Center 

Coastal Research Field Station 

University of Rhode Island 

Narragansett, Rhode Island 

ii
U.S. Department of the Interior 

DIRK KEMPTHORNE, Secretary 

U.S. Geological Survey 

Mark D. Myers, Director 

U.S. Geological Survey, Reston, Virginia: 2007 

For product and ordering information: 

World Wide Web: http://www.usgs.gov/pubprod 

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its natural and living resources, natural hazards, and the environment: 

World Wide Web: http://www.usgs.gov 

Telephone: 1-888-ASK-USGS 

Suggested citation: 

Colman, J.A., and Masterson, J.P., 2007, Monitoring ground-water quality in coastal ecosystems: 

U.S. Geological Survey Open-File Report 2007–1149, 94 p. 

Any use of trade, product, or firm names is for descriptive purposes only and does not imply 

endorsement by the U.S. Government. 

Although this report is in the public domain, permission must be secured from the individual 

copyright owners to reproduce any copyrighted material contained within this report. 

iii
PREFACE 

Overview of Long-Term Monitoring Program 

The Cape Cod National Seashore serves as a National Park Service prototype monitoring park for the Atlantic and 

Gulf Coast biogeographic region. The U.S. Geological Survey, in cooperation with the National Park Service, is 

charged with designing and testing monitoring protocols for implementation at Cape Cod National Seashore. It is 

expected that many of the protocols will have direct application at other coastal park units, as well as U.S. Fish and 

Wildlife Service coastal refuges within the biogeographic region. 

The Long-Term Coastal Ecosystem Monitoring Program at Cape Cod National Seashore will rely upon numerous 

protocols that are relevant to the major ecosystem types (Estuaries and Salt Marshes, Barrier Islands/Spits/Dunes, 

Ponds and Freshwater Wetlands, Coastal Uplands). The ground-water-quality protocol is associated with all of these 

ecosystem types. The overall monitoring program is designed so that all of the protocols are interrelated. Roman 

and Barrett (1999) present a conceptual description of the entire monitoring program. 

Protocol Organization 

To maintain consistency among the various monitoring protocols, each protocol is organized as follows: 

PART ONE of the protocol details the objectives of the monitoring protocol and provides justification for the 

recommended sampling program. The relevant literature and data collected during the protocol-development phase 

of the project are used to illustrate a particular sampling design, sampling method, or data-analysis technique. For 

example, PART ONE describes the objectives of a ground-water-quality monitoring program, the types of solute 

constituents addressed, and justification as to why certain monitoring wells and measurement schedules were 

selected. 

PART TWO is a step-by-step description of the field, data-analysis, and data-management aspects of the protocol. 

For example, PART TWO states the recommended frequency and step-by-step procedures for collecting water 

samples for analysis of nitrogen chemical species at a monitoring well. 

iv
EXECUTIVE SUMMARY 

Long-term monitoring of ground-water quality by means of a standard data-collection protocol is essential for the 

effective management of terrestrial, aquatic, and estuarine ecosystems in the coastal park environment. This study 

develops a consistent protocol for monitoring changes in water-quality constituents in ground water, including plant 

nutrients, toxic compounds, and physical and chemical field parameters (alkalinity, conductance, pH, and 

temperature) by using methods and techniques established by the U.S. Geological Survey for use in the Long-Term 

Coastal Monitoring Program at Cape Cod National Seashore. The protocol establishes a ground-water-quality 

sampling network in the five ground-water-flow cells in the National Seashore area, and provides justification for 

the sampling method, water-quality constituents, and spatial and temporal sampling frequencies selected. Data 

collected during the first year of network observations are included in this report, as are maps indicating groundwater-flow direction and contributing areas to surface-water features. Long-term water-quality monitoring at the 

Seashore will aid in interpretation of the findings of other monitoring programs, especially those monitoring 

productivity of lakes and estuaries. Developing and initiating long-term ground-water-quality monitoring programs 

will provide a better understanding of the effects of natural and human-induced change at both the local and global 

scales on coastal water resources in park units. 

v
TABLE OF CONTENTS 

PREFACE..............................................................................................................................................................................iv

Overview of Long-Term Monitoring Program...........................................................................................................iv

Protocol Organization ...................................................................................................................................................iv

EXECUTIVE SUMMARY .....................................................................................................................................................v

ACKNOWLEDGMENTS ......................................................................................................................................................x

PART ONE Protocol Background and Justification .....................................................................................................1

INTRODUCTION ..................................................................................................................................................................1

MONITORING QUESTIONS: Specific Ground-Water-Quality Trends and Issues to Address ............................4

Climate Change ...............................................................................................................................................................4

Sea-Level Rise and Erosion ......................................................................................................................................4

Temperature Change .................................................................................................................................................5

Baseline and Trends...................................................................................................................................................5

Urbanization.....................................................................................................................................................................5

Eutrophication .............................................................................................................................................................5

Phosphorus Sources and Transport....................................................................................................................8

Nitrogen Sources and Transport .........................................................................................................................9

Limiting Nutrients....................................................................................................................................................9

Computing Nutrient Loads...................................................................................................................................10

Baseline and Trends.............................................................................................................................................10

Ground-Water Transport of Toxins, Mutagens and Endocrine Disruptors....................................................10

Types of Contaminants.........................................................................................................................................10

Background, Baseline, and Trends ...................................................................................................................14

Ground-Water Transport of Materials Deposited From the Atmosphere— 

Major Ions, Nitrogen, Acidity, and Mercury ........................................................................................................14

Types of Contaminants.........................................................................................................................................15

Baseline and Trends.............................................................................................................................................16

Munitions and Discharge from Firearms..................................................................................................................16

Types of Contaminants ............................................................................................................................................16

Background, Baseline, and Trends .......................................................................................................................16

DESIGN OF A GROUND-WATER-MONITORING NETWORK.....................................................................................17

Type of Water Resource and Use of the Information ............................................................................................17

Types of Measurements..............................................................................................................................................17

Monitoring-Site Selection...........................................................................................................................................17

Site-Selection Approaches.....................................................................................................................................17

Monitoring Networks ...............................................................................................................................................24

Atmospheric Deposition and Background .......................................................................................................24

Septic-System and Other Nonpoint Sources Associated with Development ...........................................24

Septic Systems at CACO Facilities.....................................................................................................................25

Landfills and Other Hazardous Waste Sites.....................................................................................................25

Firing Ranges .........................................................................................................................................................26

Sampling Frequency and Duration of Program.......................................................................................................26

Quality Assurance ........................................................................................................................................................27

Data Reduction and Database ...................................................................................................................................29

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PART TWO Specific Protocols.......................................................................................................................................30

OVERVIEW OF DATA-COLLECTION PROCEDURES ....................................................................................................30

GROUND-WATER-QUALITY WELL NETWORK............................................................................................................40

Nonpoint Sources.........................................................................................................................................................40

Atmospheric Deposition and Background ...........................................................................................................40

Septic Systems and Other Nonpoint Sources Associated with Development..............................................45

Point Sources ................................................................................................................................................................48

Septic Systems as Point Sources ..........................................................................................................................48

Gull Pond.................................................................................................................................................................48

Salt Pond.................................................................................................................................................................50

Landfills and Other Hazardous-Waste Sites........................................................................................................52

Eastham Landfill ....................................................................................................................................................52

Truro Landfill ..........................................................................................................................................................53

Other Landfills........................................................................................................................................................54

Firing Ranges .........................................................................................................................................................54

WELL INSTALLATION ......................................................................................................................................................55

Monitoring-Well Installation.......................................................................................................................................55

Multilevel-Sampler (MLS) Installation ......................................................................................................................55

Internal-Tube Construction.....................................................................................................................................56

Drilling and Installation............................................................................................................................................58

External-Tube Construction ....................................................................................................................................60

Installations For Monitoring Trace Contaminants ..................................................................................................61

Trace Inorganic Contaminants...............................................................................................................................61

Trace Organic Contaminants..................................................................................................................................61

GROUND-WATER-QUALITY SAMPLING ......................................................................................................................62

Equipment.......................................................................................................................................................................62

Pumps..........................................................................................................................................................................62

Tubing, Gloves, and Filters ......................................................................................................................................63

Temperature, Dissolved Oxygen, pH, and Electrical-Conductance Meters ..................................................63

Field-Meter Calibration and Measurement .............................................................................................................66

Logbook and Field Forms.........................................................................................................................................66

Temperature ..............................................................................................................................................................66

Calibration ..............................................................................................................................................................66

Measurement.........................................................................................................................................................66

Electrical Conductance ...........................................................................................................................................67

Calibration ..............................................................................................................................................................67

Measurement.........................................................................................................................................................67

pH.................................................................................................................................................................................67

Calibration ..............................................................................................................................................................68

Measurement.........................................................................................................................................................70

Dissolved Oxygen......................................................................................................................................................70

Calibration ..............................................................................................................................................................70

Measurement.........................................................................................................................................................72

Alkalinity and Acid-Neutralizing Capacity............................................................................................................72

Determination of Alkalinity ..................................................................................................................................72

vii
Measurement.........................................................................................................................................................73

Well Purging and Field Measurements of Water Quality......................................................................................75

Collection of Water Samples......................................................................................................................................76

Preventing Sample Contamination and Cross Contamination..........................................................................76

Labeling Sample Bottles..........................................................................................................................................77

Filling Sample Bottles...............................................................................................................................................77

Prevention of Degassing and Maintenance of Anaerobic Conditions............................................................78

Sample Preservation....................................................................................................................................................78

QUALITY-ASSURANCE PROCEDURES..........................................................................................................................81

DATA MANAGEMENT .....................................................................................................................................................82

Data Computations .......................................................................................................................................................82

Maintenance of Project Files and Records .............................................................................................................82

Primary-Record Files................................................................................................................................................82

Field Notebook...........................................................................................................................................................83

Meter-Calibration Logbook .....................................................................................................................................83

Database ........................................................................................................................................................................83

Archiving Procedures ..................................................................................................................................................83

REFERENCES CITED .........................................................................................................................................................84

LIST OF FIGURES 

1. Map showing Cape Cod National Seashore, Massachusetts, with ground-water contours indicating 

the five ground-water-flow lenses beneath or adjacent to the Seashore lands ............................................2

2. Photograph showing algae, mostly Cladophora and Ulva, festooning Salt Pond salt marsh grass, 

June 12, 2001, in a northward view toward the Cape Cod National Seashore Visitor Center......................6

3. Map showing land use on lower Cape Cod, Massachusetts, 1999 data layer ................................................7

4. Map showing landfills and selected Massachusetts General Law, Chapter 21E sites near Cape Cod 

National Seashore ....................................................................................................................................................13

5. Map showing ground-water-flow vectors for the Pilgrim flow lens, Cape Cod, Massachusetts..............19

6. Map showing ground-water-flow vectors for the Pamet flow lens, Cape Cod, Massachusetts...............20

7. Map showing ground-water-flow vectors for the Chequesset flow lens, Cape Cod, Massachusetts.....21

8. Map showing ground-water-flow vectors for the Nauset flow lens, Cape Cod, Massachusetts .............22

9. Map showing ground-water-contributing areas for embayments of the Cape Cod National 

Seashore, Massachusetts ......................................................................................................................................23

10. Map showing ground-water-quality well network for atmospheric deposition and background 

investigation, Cape Cod, Massachusetts .............................................................................................................41

11. Graphs showing concentration profiles for the background multilevel sampler along Prince Valley 

Road, Truro, Massachusetts...................................................................................................................................43

12. Map showing simulated recharge locations for Prince Valley Road multilevel sampler, Cape Cod, 

Massachusetts..........................................................................................................................................................44

13. Map showing ground-water-quality well network for nutrient loading to coastal embayments ..............46

14. Graphs showing water-quality profiles from multilevel samplers near Nauset Marsh Estuary, 

Cape Cod, Massachusetts ......................................................................................................................................47

15. Graphs showing nitrogen profiles from 2001 to 2005 from the MLS near Nauset Marsh Estuary, 

Cape Cod, Massachusetts ......................................................................................................................................48

viii
16. Map showing well network for the point-source leachfield for the bathhouse at Gull Pond, 

Cape Cod National Seashore, Massachusetts....................................................................................................49

17. Map showing well network for the septic-system leachfield at the Cape Cod National Seashore 

Visitor Center, Massachusetts ...............................................................................................................................51

18. Aerial photograph of Eastham landfill, Molls Pond, and Minister Pond, Cape Cod Massachusetts ........52

19. Diagram of multilevel sampler used to plan required lengths of PVC pipe and to guide drilling 

of ports for tubing......................................................................................................................................................57

20. Photograph showing multilevel sampler before installation at Prince Valley Road ....................................58

21. Photograph showing installation of multilevel sampler in hollow-stem auger at Prince Valley Road, 

Truro, Massachusetts ..............................................................................................................................................59

22. Photograph showing finished flush-mount multilevel sampler well................................................................60

23. Photograph showing filling the Hydrolab multimeter calibration chamber to just below the level of 

the dissolved oxygen membrane ...........................................................................................................................64

24. Photograph showing flow-through cell for field measurements of water quality ........................................65

25. Photograph showing filling the Ross pH probe with KCl filling solution.........................................................69

26. Photograph showing pH meter for alkalinity measurements ...........................................................................73

27. Photograph showing addition of acid during titration .......................................................................................74

28. Photograph showing geopump set up for pumping multilevel sampler ports ...............................................76

29. Photograph showing preservation of samples by using concentrated acid from a Teflon dropping 

bottle............................................................................................................................................................................79

30. Photograph showing potential contamination problems are associated with samples that are 

opened in a laboratory, for example, during preservation by acid addition ..................................................80

LIST OF TABLES 

1. Selected solid-waste-disposal sites (landfills) and Massachusetts General Law Chapter 21E 

sites, as of July 2005, in Massachusetts Department of Environment Protection Region 4, near 

Cape Cod National Seashore, Massachusetts....................................................................................................11 

2. Methods and detection limits for chemical constituents included in the ground-water-quality 

monitoring protocol, Cape Cod National Seashore, Massachusetts..............................................................28 

3. Description of wells by network.............................................................................................................................31 

4. Water-quality properties, constituents, and sampling-frequency interval in years, by network, 

Cape Cod National Seashore, Massachusetts....................................................................................................38 

5. Sample-bottle types, preservation, shipping, and holding requirements for monitoring groundwater, Cape Cod National Seashore, Massachusetts.......................................................................................39 

6. Assignment of colors to multilevel-sampler ports for monitoring at Cape Cod National Seashore, 

Massachusetts..........................................................................................................................................................56 

7. Solubility of oxygen in water as a function of temperature and pressure .....................................................71 

ix
LIST OF APPENDIXES 

Appendix 1. Example of a field-meter-calibration form............................................................................................88 

Appendix 2. Example of an alkalinity-calculation field form....................................................................................89 

Appendix 3. Example of a well-purge log....................................................................................................................90 

Appendix 4. Example of a conventional-well field form ...........................................................................................91 

Appendix 5. Example of a multilevel-sampler field form ..........................................................................................92 

Appendix 6. Example of an analytical-services request form.................................................................................93 

Appendix 7. Example of a laboratory-analysis results form ....................................................................................94 

ACKNOWLEDGMENTS 

The U.S. Geological Survey’s Water Resources Discipline and the National Park Service supported development of 

this protocol with funds administered by the USGS Patuxent Wildlife Research Center at the University of Rhode 

Island. The authors thank Carrie Phillips of the National Park Service for her advice in site selection and for 

arranging access at the Cape Cod National Seashore. 

CONVERSION FACTORS, CONCENTRATION UNITS, AND HORIZONTAL AND 

VERTICAL DATUMS 

Multiply By To obtain 

Length 

centimeter (cm) 0.3937 inch (in.) 

millimeter (mm) 0.03937 inch (in.) 

meter (m) 3.281 foot (ft) 

kilometer (km) 0.6215 mile (mi) 

micrometer (μm) 0.0000394 inch (in.) 

Area 

square meter (m2) 0.0002471 acre 

hectare (ha) 2.471 acre 

Temperature in degrees Celsius (°C) may be converted to degrees Fahrenheit (°F) as follows: 

 °F=(1.8×°C)+32

Temperature in degrees Fahrenheit (°F) may be converted to degrees Celsius (°C) as follows: 

 °C=(°F-32)/1.8

CONCENTRATION UNITS 

Specific conductance is given in microsiemens per centimeter at 25 degrees Celsius (μS/cm at 25°C). 

Concentrations of chemical constituents in water are given in milligrams per liter (mg/L), micrograms per liter (μg/L), 

nanograms per liter (ng/L), or parts per million (ppm). 

HORIZONTAL AND VERTICAL DATUMS 

Horizontal coordinate information is referenced to the North American Datum of 1983 (NAD 83). 

Vertical coordinate information is referenced to the National Geodetic Vertical Datum of 1929 (NGVD 29). Altitude, as 

used in this report, refers to distance above or below the NGVD 29. 

x
Monitoring Ground-Water Quality in 

Coastal Ecosystems 

By John A. Colman and John P. Masterson 

PART ONE 

Protocol Background and Justification 

INTRODUCTION 

The Cape Cod National Seashore (CACO) extends along more than 70 km of Atlantic Ocean open-beach 

coastline and includes three large saltwater bays—Wellfleet Harbor, Nauset Marsh, and Pleasant Bay 

(fig. 1). CACO encompasses about 18,000 ha of uplands, lakes, wetlands, and tidal lands (Godfrey and 

others, 1999) including most habitats typical of the sandy coast in National seashores and parks extending 

southward from Massachusetts to Florida. In 1995, CACO was selected by the National Park Service 

(NPS) as a prototype park typifying the Atlantic and Gulf Coast biogeographic region for long-term 

coastal ecosystem monitoring. The U.S. Geological Survey (USGS) is currently (2007) assisting the NPS 

in the development of protocols for a Long-Term Coastal Ecosystem Monitoring Program at the CACO in 

Massachusetts. The overall purpose of the monitoring program is to characterize both natural and humaninduced change in the biological resources of the CACO, over a time scale of decades, in the context of a 

changing global ecosystem. 

1 
Figure 1. Cape Cod National Seashore, Massachusetts, with ground-water contours indicating 

the five ground-water-flow lenses beneath or adjacent to the Seashore lands. 

2 
This protocol, for long-term ground-water-quality monitoring, developed in cooperation with the NPS for 

CACO, will help define baseline conditions and trends in ground-water quality. The ground-water 

hydrologic system of the lower Cape Cod consists of five distinct ground-water lenses, or flow cells, 

which receive recharge through precipitation. These lenses are separated by tidal bays, freshwater 

streams, marshes, and glacial outwash valleys, which receive discharge from the ground-water system 

(fig. 1). The protocol for monitoring ground water addresses the strategy and methodology for 

characterizing chemical constituents and properties of the ground water as it moves from recharge sources 

to discharge sinks, and builds on the earlier hydrologic-monitoring protocol (McCobb and Weiskel, 2003) 

and the findings of current field and modeling studies that the USGS is conducting at CACO (Masterson, 

2004). The ground-water-quality monitoring protocol excludes consideration of seawater intrusion, which 

is covered in the hydrologic-monitoring protocol (McCobb and Weiskel, 2003). 

The conceptual framework for developing the long-term monitoring protocols relates (1) agents of 

change; (2) ecosystem stresses, which occur when the agents of change operate outside the range of 

natural variability; and (3) ecosystem responses, which are “detectable changes or trends in any 

measurable value of the coastal ecosystem’s structure” (Roman and Barrett, 1999). Altered ground-water 

quality is classified mainly as an ecosystem stress resulting from agents of change such as sea-level rise, 

erosion, climate change, and probably most importantly, from urbanization. Urban sources of 

contamination of ground water in the CACO include the visitor and personnel facilities, which, like many 

private and commercial facilities on Cape Cod, dispose of wastewater to the ground. Ground-water 

movement from private inholdings in the CACO and upgradient town development also can transport 

contaminated water to CACO land. Five town landfills on the lower Cape may affect or are on CACO 

lands. The CACO aquifer also is affected by airborne constituents such as acid precipitation and 

atmospheric deposition of mercury, sulfate, and nitrate. 

The ground-water ecosystem stresses cause ecosystem change in surface waters receiving ground water. 

These surface-water bodies include kettle lakes, which are in close hydraulic connection with the Cape 

Cod aquifer; wetlands or seasonally flooded vernal ponds; and coastal wetlands, embayments, and tidalcreek systems. The water and nutrient budgets of many of these sensitive resources are dominated by 

ground water. (The ecosystem of the aquifer, in which bacteria are the most investigated life form 

(Chapelle, 1993), is considered in the protocol only in relation to biogeochemical alteration of solutetransport processes.) 

Drinking water is an important water-management issue for the CACO. Certain constituents in ground 

water degrade drinking-water quality as well as coastal ecosystem health. Nitrate from wastewater 

disposal, for example, is a toxin in drinking water, as well as a nutrient that contributes to eutrophication 

in marine waters. The CACO has water-supply requirements for its own infrastructure and may also, at 

some time in the future, be requested to allow development of water supplies on CACO land for use in 

adjacent towns. Thus, this protocol is concerned with effects on existing or potential drinking-water 

supplies as well as on ecosystems. 

In a program of assessing long-term coastal ecosystem change, adherence to the procedures and qualityassurance methods for ground water as outlined in this protocol is particularly important. Because ground 

water moves slowly and transported solutes are buffered by chemical interaction with the large surface 

area of aquifer solids, changes in the concentrations of some ground-water constituents are slow and 

difficult to detect. The methodological integrity of the data set will determine whether changes detected 

over time can be attributed conclusively to changes in the environment, rather than to the effects of 

methodological differences that have inadvertently become incorporated into the data. 

3 
MONITORING QUESTIONS: Specific Ground-Water-Quality 

Trends and Issues to Address 

Long-term ground-water-quality monitoring is essential for evaluating the ecosystem stresses resulting 

from agents of change such as coastal erosion, sea-level rise, climate change, and urbanization; and 

for evaluating the effects of such stresses on the aquatic and estuarine ecosystems of the CACO. 

Characteristics of the agents of change determine the temporal and spatial monitoring requirements 

necessary to quantify the effects of these agents on ground-water quality. 

Baseline water-quality conditions must be assessed to provide a basis for measuring any changes in those 

conditions. Baseline conditions may reflect the effects of anthropogenic influences that occurred before 

the time of the assessment. Evaluation of changes that may have occurred prior to the baseline assessment 

requires comparison with background conditions, which do not include anthropogenic influences. For 

example, determination of whether metal contamination has occurred in the ground water at a firing range 

could be approached by comparing the concentrations of the metals in ground water at the firing range 

with concentration of the metal in ground water at a background location, where sources of metal 

contamination are not present locally and are not present in locations upgradient in the ground-water 

flow field. 

Climate Change 

Climate change has multiple effects on ground-water quality. Sea-level rise changes the way ground 

water flows in the aquifer, and temperature fluctuations affect rates of reaction. 

Sea-Level Rise and Erosion 

Sea level has been rising at the Boston Harbor tidal gage at the rate of about 2.65 mm/yr (±0.1 mm/yr) 

or about 0.265 m/100 years (Masterson, 2004). This rate, which has been confirmed in nearshore 

wells on Cape Cod (Masterson, 2004), is estimated to double, on average, over the next 100 years 

(Intergovernmental Panel on Climate Change, 2001). Likely effects of sea-level rise include alteration of 

ground-water-flow paths through the erosion of the eastern shore of Cape Cod (fig. 1) and increased 

ground-water discharge to stream runoff because of a rising water table (Masterson, 2004). Although the 

rate of change of these effects is increasing, the cumulative difference over the past 1,000 years of sealevel rise has already accounted for substantial erosion of the seaward side of the lower Cape. Coastal 

erosion has decreased the lateral extent of the lower Cape and likely shifted the locations of the 

freshwater lenses. 

A shift in recharge location can shift ground-water-flow paths and thus alter aquifer geochemistry. 

Because of the slow geochemical weathering of the aquifer sediments of Cape Cod, water quality in a 

given location in the aquifer is determined largely by natural and anthropogenic chemical conditions at 

the recharge area, and to a lesser extent, by ground-water-flow paths that extend from the recharge area 

to deep locations in the aquifer. For example, leaching of organic carbon from wetlands can cause 

alterations in the solid phase of aquifers, for example, reductive dissolution of iron hydroxides. Along 

flow paths downgradient from wetlands, aquifer sediments can be stripped of iron, which could alter their 

ability to sorb phosphate. If flow paths change over time, geochemical conditions in the aquifer would 

logically change as well in accordance with conditions present at the new recharge area. 

The tops of the flow-cell mounds on the lower Cape are generally halfway between the coastlines; 

however, erosion of the beach escarpment on the eastern shore would, over a long time, shift the top of 

the flow cells westward. Evidence for westward movement of the seaward side of the lower Cape is given 

by the changing relative position of a historic shipwreck. The Sparrow Hawk, which was wrecked on the 

4 
inner shore of Nauset Beach in Pleasant Bay in 1626, was discovered 237 years later on the outer shore 

because the beach had moved west about 300 m (Wood, 2002). Escarpment erosion at the rate of 1 m per 

year accounts for the loss of a coastal strip of land 1 km wide during the last 1,000 years, when sea level 

has been sufficiently high to cause erosion of the land surface (Leatherman and Zaremba, 1986). 

Temperature Change 

Ground-water temperature generally reflects the average air temperature of the region; therefore groundwater temperature would be expected to change if global warming changes the air temperature. The 

temperature-change effects on ground-water geochemistry have not been investigated widely, although 

temperature change has been hypothesized to influence some geochemical reactions, for example, the 

precipitation of travertine (Dramis and others, 1999). Temperature change can shift chemical equilibrium 

(changes are reaction-specific) and rates of both biological and chemical reactions (roughly a doubling in 

rate for every 10°C increase in temperature). 

Baseline and Trends 

Monitoring sea-level rise and erosion is covered by the hydrologic protocol written by McCobb and 

Weiskel (2003). Data about baseline conditions and trends in the temperature of aquifer water could be 

used to determine how climate warming might alter ground-water chemistry. Temperature could be 

monitored by recording ground-water temperature with a thermistor in a deep borehole. These data could 

be used for correlation with average air-temperature trends and for interpreting changes in chemical data. 

Urbanization 

Urbanization (and suburban development) is one of the biggest environmental stresses on the Cape. The 

effects of urbanization on ground water can include eutrophication of discharge areas (from ground-water 

transport of nutrients), which can happen in both freshwater and saltwater bodies; altered chemical 

constituents in precipitation, which can change ground-water chemistry; and introduction of toxic 

elements and compounds to ground water from point sources such as municipal landfills. 

Eutrophication 

Eutrophication of both freshwater and coastal saltwater is a big concern in developing areas, because 

increased waste generation, lawn-fertilizer use, and runoff from impervious surfaces increases the loads 

of plant nutrients (primarily phosphorus and nitrogen) delivered to surface water. In a recent survey of 

water quality in Massachusetts lakes and ponds, more than 75 percent of the surveyed water acreage did 

not support its designated use (U.S. Environmental Protection Agency, 1998). The reason for unsupported 

use was usually excessive plant growth. Introduction of nonnative species plays a role, but overall, 

growth of both native and nonnative plants can continue only to the extent that plant nutrients, such as 

phosphorus, are available. Disposal of wastewater can result in significant eutrophication of receiving 

freshwater because of the phosphorus contained in the effluents (Moore and others, 2003). Eutrophication 

of coastal waters is a global problem, caused by intense development of coastal areas. A recent analysis of 

population distribution has concluded that nearly 75 percent of the United States population resides 

within 80 km of coastal waters (National Research Council, 2000). Eutrophication as a consequence of 

the activities of an increasing population is of particular concern on Cape Cod, where data from the 

U.S. Census Bureau indicate that the population has increased by more than 130 percent during the past 

30 years. Coastal embayments are adversely affected by increased delivery of nutrients, which cause 

nuisance blooms of algae (fig. 2), loss of eelgrass habitat, and depletion of oxygen from deep water 

(Hauxwell and others, 2001; Hauxwell and others, 2003). The development of lower Cape Cod in areas 

outside of the CACO borders is clearly shown in a land-use map (fig. 3). 

5 
Figure 2. Algae, mostly Cladophora and Ulva, festooning Salt 

Pond salt marsh grass, June 12, 2001, in a northward view toward 

the Cape Cod National Seashore Visitor Center. Photo by Barbara 

Dougan, National Park Service. 

6 
Figure 3. Land use on lower Cape Cod, Massachusetts, 1999 data layer (MassGIS, 2001). 

7 
Phosphorus Sources and Transport 

The principal sources of nutrients in ground water are fertilizer, atmospheric deposition, septic systems, 

(Valiela and Bowen, 2002), and landfills (Christensen and others, 1994). These sources contain 

substantial amounts of phosphorus, but investigation of phosphorus transport in sandy, noncalcareous, 

aerobic aquifer sediments indicates that phosphorus does not move readily because of sorption to 

sediment surfaces and precipitation of iron- and aluminum-phosphate minerals (Robertson, 2003; 

Colman, 2005); large phosphorus loads, such as originate from disposal of wastewater at municipal 

treatment plants, may, however, overcome attenuation in the subsurface (Parkhurst and others, 2003). 

High concentrations of phosphorus would be expected in landfill leachate, but phosphorus concentrations 

measured in plumes downgradient of landfills have not been high (Stollenwerk and Colman, 2002). 

Phosphate is unlikely to be transported in landfill plumes because of the potential for precipitation with 

calcium, iron, and aluminum. 

Because phosphorus movement is attenuated in aerobic aquifers, surface-water bodies that receive 

ground-water discharge may not be appreciably affected by phosphorus that enters the aquifers from 

contamination sources upgradient of the surface-water bodies. Transport of phosphorus under natural 

anaerobic conditions, such as those that may be present downgradient from a wetland, has been less well 

investigated, although phosphorus sorption and precipitation processes should also apply there. A current 

area of research pertains to whether a long-term natural phosphorus release associated with a long period 

of reductive dissolution of iron hydroxide on the sediments could fill all of the sorption sites in the 

aquifer solids, so that any additional phosphorus loads from a contamination source would progress 

downgradient undiminished. 

Surface water also may be affected by ground-water transport of phosphorus associated with altered 

aquifer geochemistry such as changes in pH resulting from acidic atmospheric deposition. If the increase 

in pH were transmitted to the aquifer by infiltrating precipitation, phosphorus would have been released 

from sorption sites on the aquifer sediments. Even a small shift in the background load of phosphorus in 

ground water could affect the ecosystem of the relatively oligotrophic CACO lakes. Long-term lakemonitoring records indicate that some of the kettle-hole lakes of the CACO are becoming more eutrophic 

(Portnoy and others, 2001). Although aesthetic degradation of the lakes is not yet manifest (nuisance 

growths of algae are not present), the causes of eutrophication should be identified so that the future 

conditions of the lakes can be anticipated and management decisions can be informed. Algal growth in 

these now (2006) relatively oligotrophic lakes may be limited by phosphorus; if so, their progression 

toward a more eutrophic state implies that annual loads of phosphorus are increasing. 

Possible sources of increasing phosphorus include swimmers and atmospheric deposition, but the possible 

source of greatest importance in the development of this protocol is the aquifer. Changes in phosphorus 

load to CACO lakes from on-site sewage disposal (septic systems) is a possibility, even though no 

additional disposal installations have been allowed since the establishment of CACO in 1961. Although 

phosphorus is greatly attenuated during transport through noncalcareous sediments such as those on the 

Cape (Colman, 2005; Weiskel and Howes, 1992), upgradient phosphorus plumes would, in theory, 

continue to move forward from source to discharge into surface water as long as disposal of wastewater 

continues at the source. Thus, phosphorus could be discharging to lakes from phosphorus plumes 

advancing from on-site disposal sources constructed before 1961. 

Duck Pond, which has only one private cottage inholding, and that on the downgradient shore, has a 

20-year Secchi-disc record of decreasing depth (Portnoy and others, 2001); this record indicates an 

increase in planktonic algae. (Secchi-disc depth, the depth at which a white disc can no longer be seen 

from the surface, is a measure of water clarity.) Increased phosphorus loading from the aquifer could be 

the cause of increasing planktonic algae, but this area has no septic-system sources of phosphorus. 

Another ground-water-based mechanism for kettle-lake eutrophication that might account for increased 

phosphorus loading is large amounts of phosphorus on sediment surfaces of the aquifer in equilibrium 

8 
with the low concentrations of dissolved phosphorus. Small changes in aquifer geochemistry, such as a 

small change in pH, could shift the equilibrium, change the concentrations of dissolved phosphorus, and 

thus change the phosphorus load to a lake. 

Precipitation monitoring at the National Atmospheric Deposition site operated by the National Seashore 

in Truro, Massachusetts, indicates that the pH of precipitation has increased from 4.4 to 4.6 during the 

period 1989–2001, in concert with decreases in sulfate in precipitation during the same period. Monitoring 

of phosphorus and pH in background locations of the CACO aquifer (away from the influence of any 

development) would indicate whether this potential source of increased phosphorus load is important. 

Nitrogen Sources and Transport 

Ground-water sources of nitrogen have been investigated on Cape Cod, especially at Waquoit Bay in the 

town of Falmouth (Valiela and others, 1997; Valiela and Bowen, 2002), and in Nauset Marsh in the towns 

of Eastham and Orleans (Portnoy and others, 1998). Similar to Pleasant Bay and Nauset Marsh in the 

National Seashore, Waquoit Bay receives little surface-water input and has become increasingly eutrophic 

as a result of recent development in its ground-water contributing area. Septic-system, fertilizer, and 

atmospheric deposition accounted for 48, 15, and 30 percent, respectively, of the estimated total groundwater nitrogen loading to Waquoit Bay (23,100 kg/yr) (Valiela and Bowen, 2002). High concentrations of 

nitrogen also have been measured in ground water discharging to the subembayments of Nauset Marsh 

(Portnoy and others, 1998). 

Landfills are an additional nitrogen source for CACO embayments, but are not present in the contributing 

area of Waquoit Bay. The National Seashore has six town landfills either inside the park boundary or near 

enough to affect the ecosystem of CACO lands (Cape Cod National Seashore, 2000). Nitrogen loading 

from even one landfill could be large enough to cause eutrophication of a coastal embayment. Nitrogen in 

landfill leachate derives from decomposition of the organic wastes in disposed fill materials (Christensen 

and others, 1994). 

In small sources like septic systems, nitrogen is converted to nitrate in the unsaturated zone before 

reaching the water table, and is transported in the ground water as nitrate (Colman and Friesz, 2001). 

In large discharges of nitrogen, such as that from the sewage-disposal site at the Massachusetts Military 

Reservation on the lower Cape (LeBlanc, 1984), the Tritown septage-treatment facility in Orleans 

(DeSimone and Howes, 1998), and from landfills (Christensen and others, 1994), some or all of the 

nitrogen gets transported in the reduced form, as ammonia. Reducing conditions develop in the aquifer 

because not all of the organic carbon discharged from the larger sources is oxidized in the unsaturated 

zone (DeSimone and Howes, 1998; Parkhurst and others, 2003). Whereas nitrate travels at approximately 

the same velocity as ground water (about 0.3 m per day), ammonia is transported at about one half that 

velocity. At the pH values typically found in ground water, ammonia occurs primarily in the cation form 

(ammonium ion) and is slowed by cation exchange with the solids. 

Nitrogen from fertilizer likely is transported in the aquifer in the nitrate form. Little organic carbon 

would be expected to leach from the soil zone through the unsaturated zone beneath lawns or agricultural 

fields. Conditions in the aquifer in these areas would likely be aerobic so that the nitrate form of nitrogen 

would persist.

Limiting Nutrients 

Phosphorus is commonly the limiting nutrient for plant growth in freshwater, and thus its supply to 

surface water can control eutrophication (Scheffer, 1998). In noncalcareous rock areas such as Cape Cod, 

most phosphorus that enters lakes is sequestered in iron compounds in the bed sediments (Colman and 

Friesz, 2001). The CACO kettle lakes may be phosphorus-limited even in the presence of ground-water 

contamination, because although nitrogen from inputs would be transported with the ground water, 

phosphorus would not. 

9 
In calcareous rock areas and in marine systems, sulfur is more abundant (than in non-calcareous areas) 

and combines with iron as FeS, so that phosphorus brought to the sediment-water interface by settling 

algae can be released (remineralized) and used in primary production (Rozan and others, 2002). With 

recycling of phosphorus, marine and calcareous systems are less likely to be phosphorus limited and 

more likely to become nitrogen limited. In addition, atmospheric nitrogen may be fixed more slowly in 

marine water than in freshwater (Paulsen and others, 1991), thereby contributing to nitrogen limitation 

in marine water. 

Computing Nutrient Loads 

Because the ecosystem at risk is in surface water rather than ground water, loads of chemical constituents 

that may discharge from ground water into surface water are important to determine, in addition to the 

concentrations of these constituents in the aquifer. Distances along flow lines from the top of the Nauset 

flow cell in Eastham to locations on the CACO coast range from 2.8 km to the east to 4.5 km to the south 

(near Salt Pond), with the longest travel times in excess of 100 years. Along most of the CACO coast, the 

nitrogen load associated with the last 20 years of development will not yet have arrived. The monitoring 

of ground-water nitrogen concentrations at the coast and at upgradient boundaries of the CACO would 

allow determination of nitrogen concentrations in ground water moving toward the coast. The monitoring 

data also could be used to calibrate and verify reactive solute-transport models of nitrogen flux to the 

coast. Fluxes from models that simulate real-time loads would be useful for determining the effect of 

nutrient loading on aquatic ecosystems and for anticipating future loads. 

Baseline and Trends 

Baseline concentrations of nutrients could be determined by monitoring their concentrations in ground 

water; such information could be used in evaluating the role of ground water in eutrophication. In 

addition, increased transport of nutrients to the marine margin may be predicted and tracked through use 

of reactive-solute-transport models that incorporate sources and reactions kinetics. Monitoring in strategic 

places would provide data to calibrate the models. If nutrient remediation measures are taken, continued 

collection of monitoring data will be needed to determine if management actions are having their 

intended effect. 

Ground-Water Transport of Toxins, Mutagens and Endocrine Disruptors 

Many potentially toxic or ecosystem-affecting constituents, in addition to nutrients, may be present in 

ground water on or near CACO. Through on-site disposal of wastewater, spills or leaks from tanks, or 

leaching of land-surface applications, these constituents can be introduced to the aquifer. In addition 

to contaminating ground water, these materials may be transported through the subsurface to surfacewater ecosystems. 

Types of Contaminants 

More than 100 toxic contaminants may be present in ground water on the lower Cape; these include 

volatile organic compounds (VOCs), including solvents and gasoline hydrocarbons, as well as pesticides, 

trace elements, and organic compounds used for cosmetic and medicinal purposes. Potential sources of 

VOCs and pesticides include commercial and residential septic tanks, landfills, leaking underground or 

above-ground storage tanks, spills, runoff from lawns and other places where pesticides are applied, and 

atmospheric deposition (Fetter, 1999). Trace elements occur naturally in ground water although their 

distribution may be related to variations in subsurface geology and geochemistry. Organic compounds 

used for cosmetic and medicinal purposes enter ground water through the disposal of wastewater 

(nationally—Kolpin and others, 2002; Cape Cod—Zimmerman, 2005).

10 
The Massachusetts Department of Environmental Protection maintains a list of reported releases of oil 

and hazardous materials from point sources. There are about 30 known hazardous-materials-release sites 

and 5 landfills upgradient of CACO land or coastal interests or on CACO property (table 1, fig. 4). 

Nonpoint sources, by contrast, are ubiquitous, including atmospheric deposition and domestic wastewater 

disposal through septic systems. 

Table 1. Selected solid-waste-disposal sites (landfills) and Massachusetts General Law 

Chapter 21E sites, as of July 2005, in Massachusetts Department of Environment 

Protection Region 4, near Cape Cod National Seashore, Massachusetts. 

Release 

tracking 

number 

Name Address Town Status

4-0013321

4-0011126 

4-0013651

4-0000537

4-0014194 

4-0000897 

4-0013753 

4-0013690 

4-0010729 

4-0000847

4-0000895 

4-0013524

4-0015960

4-0010357 

4-0013463 

4-0011959

4-0000707

4-0000921

4-0016246 

4-0001222

4-0013084 

4-0011656 

 CAPE COD OIL 

BULK FAC 

NO LOCATION AID 

 DUARTES 

BRADFORD ST 

MALL 

 RODS SERVICE 

STATION INC 

BREWSTER ST 

S HIGHLAND RD 

LANDFILL 

NO LOCATION AID 

JACKS GAS 

OFF RTE 6 

 MOBIL STATION 

01-N3T 

WELLFLEET 

TEXACO STATION 

 ROCKWELL 

HOUSE 

 UNITED 

METHODIST 

CHURCH 

LOT ORV II 

NO LOCATION AID 

 NATL SEASHORE 

RANGER STATION 

 NEIGHBORHOOD 

SERVICE CTR 

 EASTHAM 

SUNOCO STATION 

CAPE COD CITGO 

 CHRIS BULLOCK 

TOYOTA 

NO LOCATION AID 

NO LOCATION AID 

30 WINTHROP ST 

150 COMMERCIAL ST 

132 BRADFORD ST 

CONWELL ST PO BOX 625 

HARRY KEMP WAY 

HIGHLAND RD 

7 PROFESSIONAL 

HEIGHTS RD 

100 RTE 6 

6 HIGHLAND RD 

2665 U.S. ROUTE 6 

ROUTE 6 RURAL ROUTE 2 

95 OCEAN VIEW DR 

241 MAIN ST 

135 OAK RIDGE RD 

200 SUMMIT AVE 

1050 NAUSET RD 

RTE 6 

4565 STATE HWY 

4565 STATE HWY 

6 WEST RD 

100 TONSET RD 

21 SALTY RIDGE RD 

PROVINCETOWN 

PROVINCETOWN 

PROVINCETOWN 

PROVINCETOWN 

PROVINCETOWN 

TRURO 

TRURO 

TRURO 

TRURO 

WELLFLEET 

WELLFLEET 

WELLFLEET 

WELLFLEET 

EASTHAM 

EASTHAM 

EASTHAM 

EASTHAM 

EASTHAM 

EASTHAM 

ORLEANS 

ORLEANS 

ORLEANS 

TIER 2 

DEF TIER 

1B 

TIER 2 

TIER 2 

TIER 2 

TIER 2 

DEF TIER

1B 

TIER 1C 

DEF TIER 

1B 

TIER 1B 

TIER 1B 

TIER 2 

DEF TIER 

1B 

DEF TIER 

1B 

DEF TIER 

1B 

TIER 2 

TIER 1A 

TIER 1C 

DEF TIER 

1B 

TIER 2 

TIER 2 

DEF TIER 

1B 

11 
Table 1. Locations of solid-waste-disposal sites (landfills) and Massachusetts General 

Law Chapter 21E sites, as of July 2005, in Massachusetts Department of Environment 

Protection Region 4, near Cape Cod National Seashore, Massachusetts.—Continued 

Release 

tracking 

number 

Name Address Town Status

4-0012613 

4-0012092 

4-0011728

4-0013026 

4-0013191 

4-0000518 

4-0001200

4-0006015

4-0000406

4-0000923

4-0014517

NO LOCATION AID 

RTE 28 & GREY 

NECK RD 

 CANTO 

RESIDENCE 

NO LOCATION AID 

NO LOCATION AID 

RESIDENCE 

 HARWICHPORT 

TEXACO STATION 

 PROPERTY 

 ACME LAUNDRY 

CO 

 CLARKS AUTO 

SERVICE 

 OYSTER RIVER 

BOATYARD 

26 GIDDIAH HILL RD 

219 MAIN ST 

21 PLEASANT PARK RD 

11 CRANBERRY LN 

120 FOREST ST 

622 DEPOT ST 

570 MAIN ST 

321 OAK ST EXTENSION 

497 ORLEANS RD 

2345 MAIN ST 

END OF BARN HILL LN 

EXT 

ORLEANS 

HARWICH 

HARWICH 

HARWICH 

HARWICH 

HARWICH 

HARWICH 

HARWICH 

CHATHAM 

CHATHAM 

CHATHAM 

DEF TIER 

1B 

DEF TIER 

1B 

TIER 2 

DEF TIER 

1B 

TIER 2 

TIER 1B 

TIER 2 

TIER 2 

TIER 2 

TIER 2 

TIER 2 

12 
13 

Figure 4. Landfills and selected Massachusetts General Law, Chapter 21E, sites (table 1) near 

Cape Cod National Seashore. 
Toxic contaminants differ considerably in their transport characteristics in the subsurface and in 

their attenuation through interaction with aquifer sediments, or for organic compounds, through 

biodegradation. Solubility and density characteristics cause some toxic organic contaminants to float on 

top of the water table, and others to sink through the saturated zone. The variability in concentrations of 

trace elements in water may be controlled by subsurface pH or redox conditions; dissolved oxygen 

concentrations also may affect the transport of organic compounds by favoring or inhibiting specific 

biodegradation reactions. 

Landfill-leachate plumes are potential concentrated sources of multiple toxins such as VOCs and 

semivolatile organic compounds, such as polychlorinated biphenyls (PCBs). Landfills as sources of toxins 

are of particular concern to the CACO, because five landfills on the lower Cape are upgradient of CACO 

water resources (fig. 4). Uncertainty regarding the presence and probable concentrations of toxic 

constituents flowing from landfills stems from lack of knowledge regarding the deposited waste as well as 

the potential for attenuation of toxic constituents. All of the landfills on the lower Cape are closed or in 

the process of being closed and are monitored onsite and near the sites in accordance with State 

requirements. Contaminants detected in these investigations may be transported downgradient and are 

candidates for additional monitoring. However, the only way to assess downgradient contaminants in 

landfill plumes is to locate the plume and determine analytically what materials are present in it. Plumes 

of landfill leachate tend to sink because of density effects but still move downgradient in the direction of 

ambient ground-water flow. For the CACO, discharge of landfill-leachate plumes to surface water is the 

principal concern, as none of the landfills are within the ground-water contributing areas of public or 

CACO drinking-water supplies. 

Background, Baseline, and Trends 

Determining both background and baseline concentrations of toxic compounds is necessary for 

monitoring ground-water quality in the CACO. For trace metals, which occur naturally at low 

concentrations in aquifer materials, and even for synthetic organic constituents that could be transported 

through the atmosphere, detectable concentrations of compounds are possible in background locations. 

One task of investigators of toxic materials in plumes from point sources or in suspected affected areas is 

to determine whether measured concentrations are significantly different from those in background areas. 

Determination of baseline conditions is part of the investigation of trends. Baseline conditions are 

determined by monitoring of wells installed wherever a trend analysis is to be conducted. Initial sampling 

provides the data that constitute the baseline. Subsequent sampling could be periodic or a one-time event 

to determine trends or change. 

Ground-Water Transport of Materials Deposited From the Atmosphere— 

Major Ions, Nitrogen, Acidity, and Mercury 

Although atmospheric deposition is the topic of another protocol in the series for Long-Term Coastal 

Ecosystem Monitoring, discussion of atmospheric deposition is included here because it is an important 

source of some constituents in ground water. Atmospheric-deposition monitoring programs, such as the 

National Atmospheric Deposition Program/National Trends Network (NADP/NTN) (National 

Atmospheric Deposition Program, 2005), monitor only wet deposition, which does not account for the 

other substantial deposition component, dry atmospheric deposition. Monitoring of ground water, which 

is affected by wet and dry atmospheric deposition, however, can be used to determine total atmospheric 

deposition of some constituents. 

14 
Types of Contaminants 

Constituents of atmospheric deposition become part of ground water after infiltration through the soil and 

unsaturated zones and are subject to the effects of evapotranspiration and chemical alteration during 

passage. Whereas the ground water will always include the constituents from atmospheric deposition, 

ground-water composition may not be dominated by them. The effects of atmospheric deposition on 

ground-water chemistry may be overcome for those constituents that are released or removed in soils or 

aquifer solids in large amounts. 

Nitrogen loading to the landscape and directly to surface water from atmospheric deposition contributes 

to the eutrophication of coastal water, which is discussed under the first topic in this section. Sources of 

nitrates in atmospheric deposition (NOx

 compounds) include anthropogenic sources such as combustion 

of gasoline in automobiles. In the northeastern United States, atmospheric deposition has been identified 

as a dominant source of nitrogen to estuaries and their associated watersheds (Jaworski and others, 1997). 

For the Waquoit Bay system investigated on the Cape, however, nitrogen from atmospheric deposition 

constituted only 30 percent of the total nitrogen loading (Valiela and Bowen, 2002). The atmosphere 

contributes nitrogen to embayments on the Cape, but is not likely to be a dominant source, and the 

nitrogen loading rate from the atmosphere during the past 20 years appears to have remained fairly 

constant. Nitrate concentrations in precipitation in the U.S. may have leveled off during the 1980s. 

Statistically significant downward trends in wet deposition of nitrate were found at 3 of 33 NADP stations 

(Baier and Cohn, 1993); visual inspection of the NADP/NTN nitrate data collected during 1981–2002 

from the lower Cape (station MA01), which were not included in the Baier and Cohn analysis, indicated 

no trend. Deposition of ammonia also is affected by anthropogenic activity, but the source is mostly in 

agricultural areas in the Midwest (NADP/NTN); visual inspection of the NADP/NTN MA01 ammonia 

deposition data collected during 1981–2002 indicated no trend. 

Nitrogen loading from atmospheric sources to embayments through the aquifer may be better quantified 

by measurements of nitrogen in background locations in the aquifer rather than by estimates based on 

wetfall, the data available from the NADP/NTN network. Processes such as dryfall and plant uptake 

cause the amount of nitrogen from atmospheric deposition delivered to the aquifer to differ from the 

amount deposited by wetfall. Nitrogen load from atmospheric deposition can be determined as the 

product of recharge and nitrogen concentration in the aquifer at the water table in a background location. 

Another plant nutrient, phosphorus, is also present in atmospheric deposition. Phosphorus from 

atmospheric deposition may be important to ground-water chemistry, but little is known about total 

deposition rates of phosphorus or about the leaching of deposited phosphorus from the soil zone to 

ground water. There are measurable concentrations of phosphorus in ground water at background 

locations, but unlike nitrogen, which is not present in crystalline rock, the source of phosphorus could be 

either dissolution (weathering) of aquifer solids or leaching from the surface. 

Acid rain also needs to be considered in ground-water-quality monitoring. Changes in the acidity of 

deposition can alter the surface chemistry of the aquifer solids, resulting in the leaching of calcium and 

other base cations from soil and aquifer solids. Changes in the pH of water-solid systems can also change 

the sorption of oxyanions such as phosphate. Changes in ground-water pH are likely to be small because 

of buffering in the soil and aquifer and because pH changes in precipitation are not large. Because even 

small changes in aquifer pH could substantially affect phosphorus movement, however, careful 

monitoring of ground-water pH should be a part of the ground-water-monitoring protocol. 

In surface-water systems dominated by ground water (kettle-hole lakes), ground-water transport of 

atmospherically deposited trace materials may be important. For instance, part of the mercury load to 

kettle lakes in amounts that cause high levels of mercury in fish may originate from atmospheric 

deposition (Krabbenhoft and Babiarz, 1992; Krabbenhoft and others, 1998). 

15 
Baseline and Trends 

Ground-water-monitoring baseline and trends for atmospherically deposited materials may be especially 

useful. Monitoring for trends can be done by repeated samplings at a fixed point in the aquifer 

(monitoring well) or, for some constituents, by sampling at one time at multiple levels within the aquifer 

(multilevel sampler). Changes in concentrations of conservative constituents with depth can be interpreted 

as changes in the atmospheric-deposition rate over time, because older water on longer flow paths is 

collected in progressively deeper samples in the aquifer (Robertson and others, 1989). 

Munitions and Discharge from Firearms 

Firing ranges and hunting areas can be sources of contamination by trace elements, which are associated 

with bullets, casings, and unconsumed explosives (Peddicord and LaKind, 2000). Organic contaminants 

have been detected in ground water beneath firing ranges (Ogden Environmental and Energy Services, 

1999). Distinguishing between background concentrations of inorganic constituents in ground water and 

concentrations resulting from munitions at firing ranges is a topic of current investigation at the 

Massachusetts Military Reservation on upper Cape Cod. 

Types of Contaminants 

An investigation of trace metals in the streambed sediments of the 67 tributaries of Lake Champlain in 

Vermont, New York, and Quebec (Colman and Clark, 1994) identified highest concentrations for some 

elements at three sites that were apparently affected by munitions—two in a National Wildlife Area 

where duck hunting was common, and one at a State Police firing range, where guns on one side of a 

stream were aimed at targets on the other side. Concentrations of several inorganic constituents—

antimony, cadmium, lead, and tin—were higher at these sites than at the 95 other sites in the Lake 

Champlain Basin. The concentrations of several additional constituents—arsenic, iron, manganese, 

molybdenum, and zinc—were second highest at these sites, and the concentration of chromium was fifth 

highest. Because the elements were measured in sediment samples, their effects on water quality are not 

known. Firing ranges and hunting areas should be considered, however, in establishing a network for 

determination of background concentrations for these constituents. 

Residues of explosives have been measured in the ground water beneath the impact area at Camp 

Edwards in the Massachusetts Military Reservation (AMEC, 2001). Compounds detected that are of 

concern because of environmental risk are perchlorate, 2A-DNT, 4A-DNT, and RDX. 

Background, Baseline, and Trends 

Many of the contaminants that might be expected from a firing range are metals and could be present at 

low concentrations in ground water even under natural conditions. Background measurements for a firing 

range could be made by using a well network for assessing the effects of atmospheric deposition, 

described previously under Ground-Water Transport of Materials Deposited From the Atmosphere—

Major Ions, Nitrogen, Acidity, and Mercury. The background data could be compared to that in samples 

from wells in the firing range or hydraulically downgradient from the range. 

Baseline data for ground-water quality beneath a firing range could be obtained by a well network in the 

range or downgradient from the range. Monitored over time, the network would indicate any trends in 

contaminant concentrations. 

16 
DESIGN OF A GROUND-WATER-MONITORING NETWORK 

Criteria considered for establishing a water-quality-sampling network have been reviewed by past 

investigators (Roman and Barrett, 1999; DeSimone and others, 2001). Monitoring objectives must be 

established. Monitoring objectives, discussed in detail previously, are to (1) establish baseline and 

background conditions and (2) determine changes in ground-water quality resulting from agents of 

change in a way that would be useful in determining ecosystem response. In addition, monitoring 

approaches to achieve the objectives must be determined. According to DeSimone and others (2001), five 

criteria need to be considered in developing these approaches: (1) type of water resource, (2) use of the 

collected information, (3) type of measurement, (4) monitoring-site selection (targeted or probability 

based), and (5) sampling frequency and duration of the program. 

In addition, for this protocol for long-term monitoring, sufficient documentation about quality assurance, 

data storage, and methods of sample collection, preservation, and chemical analysis must be kept so that 

any changes in water quality caused by changes in methodology can be distinguished from those caused 

by changes in the environment. 

Type of Water Resource and Use of the Information 

This protocol is concerned with monitoring the quality of ground water at the CACO. The intended use of 

the monitoring data is the evaluation of ecosystem stresses and the interpretation of ecosystem changes 

observed in surface water. The community of organisms in ground water is not considered except in 

relation to how microorganisms might alter ground-water quality. 

Types of Measurements 

The types of measurements required in this monitoring protocol are dictated by current and future 

environmental agents of change and resulting stresses. The measurements are of chemical characteristics 

and physical properties of ground water, which are affected by environmental agents of change and which 

may stress ecosystems after discharge to surface water. These measurements are discussed under the 

subtopics Types of Contaminants for each environmental agent of change. For example, under the section 

Munitions and Discharge from Firearms, the inorganic contaminant list includes antimony, arsenic, 

cadmium, chromium, iron, lead, manganese, molybdenum, perchlorate, tin, and zinc. The organic 

contaminant list includes 2A-DNT, 4A-DNT, and RDX. Ancillary monitoring data are required as well 

for interpretation of the stresses resulting from changed ground-water quality. Ancillary data include 

information on ground water, hydrology, and flow covered in the Hydrologic Protocol (McCobb and 

Weiskel, 2003); chemical constituents such as major ions, iron, manganese, and dissolved organic carbon; 

and physical and chemical properties, such as pH, alkalinity, temperature, ionic strength, redox state, 

and specific conductance. Ancillary data requirements are described in the Part Two step-by-step 

sampling approach. 

Monitoring-Site Selection 

The issues for site selection include the general question of random sampling versus targeted sampling. 

After determination of the appropriate type of sampling, a sampling design must be adjusted for the 

particular contaminant source that is being investigated. 

Site-Selection Approaches 

There are several possible approaches for site selection for ground-water monitoring. The approaches 

recommended in this protocol are those best suited to the monitoring objective of establishing baseline 

ground-water quality conditions and determining changes associated with the identified agents of 

change—sea level rise, urbanization, and firearms discharge. 

17 
An important criterion for the recommended site-selection approach is that it is appropriate for long-term 

monitoring, because the changes associated with the identified agents of change occur over decades. The 

need for long-term monitoring, along with logistic and resource considerations, indicate that fixed-station 

monitoring of a limited number of sites selected by using a targeted approach is appropriate. In fixedstation site selection, specific sites are chosen for monitoring on the basis of prior knowledge about 

important factors affecting ground-water quality, such as the locations of contaminant sources and 

ground-water flow direction. 

Wells installed for fixed-station monitoring have known construction and are available for repeated 

sampling. The alternative—short-term surveys either of private wells or randomly placed wells—could be 

difficult to arrange (for private wells outside the CACO), costly to install (random coverage requiring 

many wells), and difficult to use in assessing trends. The area of CACO is large, so monitoring would 

likely proceed by quantifying data for each type of source rather than for every source. 

Choosing monitoring sites to best represent the water-quality conditions of interest depends on knowledge 

of (1) ground-water-flow paths, which determine whether a given site is in the flow path from a 

contamination source (agent of change) and (2) what environmental resource the resulting stress might 

affect. Ground-water flow is also a consideration in the placement of monitoring wells intended to detect 

the effects of atmospheric deposition and background conditions, that is, monitoring in areas protected 

from development or upgradient from human activities. This is also true of wells for monitoring the 

effects of nonpoint sources such as agricultural practices. 

Subsurface flow, especially in unconsolidated materials common in sandy coastal areas, is predictable by 

numerical ground-water modeling. For the CACO, results from simulations of ground-water models show 

the contours of the ground-water table and vectors of flow at the water table (figs. 5–8). The vectors could 

be used to determine the best placement of monitoring wells between contamination sources and surfacewater bodies receiving ground-water discharge. Ground-water-flow vectors also could be used to define 

ground-water contributing areas for surface-water features such as lakes and embayments (fig. 9). The 

contributing areas must be determined to identify source areas for ground water that eventually discharges 

to a surface-water body. 

18 
19 

Figure 5. Ground-water-flow vectors for the Pilgrim flow lens, Cape Cod, Massachusetts. 

Modified from Masterson (2004). 
Figure 6. Ground-water-flow vectors for the Pamet flow lens, Cape Cod, Massachusetts. 

Modified from Masterson (2004). 

20 
Figure 7. Ground-water-flow vectors for the Chequesset flow lens, Cape Cod, Massachusetts. 

Modified from Masterson (2004). 

21 
22 

Figure 8. Ground-water-flow vectors for the Nauset flow lens, Cape Cod, Massachusetts. 

Modified from Masterson (2004). 
Figure 9. Ground-water-contributing areas for embayments of the Cape Cod National Seashore, 

Massachusetts. Modified from Masterson (2004). 

23 
Monitoring Networks 

Separate monitoring networks are needed to define conditions associated with atmospheric deposition and 

background conditions, and to assess the effects of nonpoint and point sources of contamination. 

Atmospheric Deposition and Background 

Background and atmospheric deposition effects cannot be distinguished from the effects of point sources 

of contamination on the basis of data from wells downgradient of such sources. Their combined effects 

can be separated from point-source effects, however, by choosing monitoring sites without upgradient 

point sources. The main requirement for investigation of atmospheric deposition and background in 

ground water is that no point or nonpoint source (other than atmospheric deposition) be present 

upgradient on the flow paths to the monitoring wells. 

In the northern Chequesset flow cell, long flow paths that are entirely within the present-day protected 

CACO lands are minimally affected by point sources of contamination (figs. 1, 3, 4, and 7). Modelsimulated traveltimes along flow paths in this cell range up to 150 years in the top 50 m of aquifer sand 

sediments. The chemical reactivity of many constituents with the sands during this time frame is 

negligible. Therefore, chemical analysis of the ground water along a flow path would result in a timeseries record of atmospheric deposition. The early parts of these records would indicate atmospheric 

deposition before many anthropogenic influences were in effect. 

Septic-System and Other Nonpoint Sources Associated with Development 

Septic systems are used in large areas of residential and commercial development outside of the CACO 

boundary, and in isolated inholdings and CACO facilities inside the boundary. Practical considerations 

indicate that the hundreds of private septic systems outside the boundary that may affect CACO lands 

cannot be monitored individually. The nutrient plumes of many individual disposal sites become 

indistinguishable in the water of the downgradient aquifer and thus can be treated as nonpoint sources. 

Monitoring of several leachfields within CACO that are close enough to CACO surface water for 

possible individual effects could be done with separate networks and is addressed in the next section 

of this protocol. 

A monitoring network to characterize the effects of septic tanks outside the CACO must take into account 

the direction of ground-water flow. The tops of three of the five ground-water flow cells that influence 

CACO lands are within the park boundaries (fig. 1). The CACO aquifer and CACO coast are generally 

protected from ground-water contamination originating in the three cells because the direction of 

subsurface flow of water is from the CACO lands to the developed areas rather than the reverse. Thus, 

monitoring ground-water quality is low priority in those areas. The tops of the Nauset and Monomoy flow 

cells, however, are outside the CACO boundary. The ground-water flow from these cells affects the 

principal embayments of CACO, Nauset Bay and Pleasant Bay, so that monitoring water quality in the 

flow from these is a priority for the ground-water-quality monitoring protocol. In addition, ground water 

from the Nauset, Chequesset, and Pilgrim lenses flows to Wellfleet Harbor and Provincetown Harbor 

on the west side of the Cape. The CACO lands of Long Point in Provincetown and Great Island in 

Wellfleet border these harbors. Thus the quality of ground water flowing from these developed areas is 

also a concern. 

Likely tools and locations for intercepting the nutrient loads from the developed portion of the Cape 

include multilevel samplers (MLS) installed near the receiving water. These samplers are operated by 

peristaltic pump, and thus the water must be within suction depth of the water table, a maximum of about 

7.5 m (25 ft). The depth to water near locations of ground-water discharge to surface-water bodies 

generally is shallow enough for efficient use of MLS. Also, ground-water flow begins to converge as flow 

lines get close to discharge at the surface; as a result, an MLS depth of 45 m (150 ft), which is the 

approximate maximum depth of installation possible by hollow-stem auger, may be able to intercept most 

of the flow paths along which nutrients would be transported to the overlying surface-water body. 

24 
Monitoring water quality at locations near discharge points cannot provide data to characterize conditions 

that exist upgradient, however. Thus, water-quality monitoring adjacent to surface water should be in 

conjunction with the use of a 3-D reactive solute-transport model. In areas for which such a model is 

available, ground-water-quality monitoring data are used for model calibration and verification. 

After verification, the model could be used to compute the ground-water loads of nonpoint-source 

contamination to a surface-water body, likely conditions upgradient, and simulations of loads that will 

discharge to the surface water in the future. 

Septic Systems at CACO Facilities 

Leachfields associated with facilities within the CACO contribute more directly to CACO ground-water 

quality than those outside of the boundary. Investigation of individual plumes is warranted because of 

their proximity to CACO surface-water bodies and because, in some cases, their remediation is under the 

control of the CACO. Results of investigations of individual septic systems elsewhere that were 

monitored for downgradient water quality have been published (Robertson, 2003; Colman and Friesz, 

2001), and instrumentation of a few such systems on CACO lands to characterize the plumes could 

indicate similarities between the CACO plumes and the published examples. 

The plume from the leachfield for the CACO Visitor Center is being investigated by using the USGS 

automatic well-sampling system (Granato and Smith, 2005). In 2002, the leachfield that had been 

servicing the Visitor Center was decommissioned and replaced with a new system that was capable of 

removing nitrogen from the wastewater. The investigation has measured the effect of the old system on 

ground-water quality and the decrease in nutrient concentrations during the decommission period. The 

investigation is also intended to collect data on the effect of the new system on ground-water quality. 

Wells upgradient from the leachfield provide data needed for a background determination, and a “fence” 

of wells downgradient intercepts the plume from the leachfield. 

A second leachfield that has been investigated is that serving a bathhouse facility at Gull Pond in the town 

of Wellfleet. Again, wells have been installed upgradient and in a fence downgradient to determine the 

effect of the leachfield on the ground water. Both the investigation and the wells are described in detail in 

Part Two of this report on the GROUND-WATER-QUALITY WELL NETWORK. 

Landfills and Other Hazardous Waste Sites 

Determination of the full extent of a landfill plume is very costly, partly because a large number of toxic 

constituents may be involved in addition to nutrients that cause eutrophication. However, the potential 

effect of the leachate discharging to a coastal embayment makes landfill-plume monitoring essential. 

Leachate from several of the landfills—in Provincetown, Truro, and Wellfleet—likely is already 

discharging to adjacent coastal water. The nitrogen loads associated with these expected current 

discharges could be investigated to determine effects that may be observed eventually in other coastal 

areas where the nitrogen loading apparently is still upgradient (for example, at the Eastham landfill). 

At several of the landfills, only the near-landfill part of the plume is well defined. But defining a plume at 

a distance from the source may be difficult because the plume may be narrow and of unknown depth 

below the surface. Before monitoring wells are drilled, the likely location of the plume should be defined 

by means of flow-vector diagrams, particle tracking, or other output from existing ground-water-flow and 

solute-transport models, and surface and downhole electromagnetic-induction surveys. Ionic constituents 

of landfill leachate greatly increase the conductance of leachate-contaminated ground water over that of 

ambient water. Periodic electromagnetic logging of deep wells (45 m) installed in the expected path of a 

landfill plume can indicate the depth and progress of the plume. Also the “footprint” of leachate discharge 

can be determined by using pushpoint sampling on the shore of the receiving water (McCobb and others, 

2003). After the flow path of the plume is defined, wells may be drilled (1) near the source, to enable 

sampling for analyses of a broad spectrum of contaminants, which would include some that move slowly 

in ground water; and (2) downgradient, to enable sampling for analysis of nitrogen, which may move 

more rapidly. This approach would characterize those compounds that are or may become concerns for a 

25 
given landfill (near-landfill sampling) as well as characterize the transport of nitrogen, which will almost 

certainly be present and moving downgradient (downgradient sampling). More constituents may be 

included in the analyses of downgradient samples as those constituents are detected (at the near-landfill 

wells) and determined to be a potential stress to the environment. The data from these investigations 

would be used to determine whether more elaborate investigations were necessary, to maintain databases 

on toxic constituents, and to evaluate the transport of nitrogen, an ecologically important constituent in 

landfill leachate. The downgradient concentrations and time trends could be used to calibrate the solutetransport model of nitrogen loading. 

Under Massachusetts General Law, Chapter 21E, the Massachusetts Department of Environmental 

Protection (MDEP) maintains a database of sites where oil or hazardous materials have been discharged 

into the environment (fig. 4). These sites, such as leaking underground storage tanks at gas stations, are 

generally monitored by MDEP. Additional monitoring of such sites within CACO would depend on 

review of the MDEP monitoring measures already in place, which is beyond the scope of this protocol. 

Firing Ranges 

The ground-water contamination that may occur on firing ranges can be assessed by the collection and 

analysis of water samples from wells installed within, downgradient, and upgradient of the ranges. 

Special precautions must be observed for drilling within ranges where unexploded ordnance may be 

present. At some military firing ranges, drill rigs have been operated remotely to prevent injury in case 

ordnance is encountered and detonated. 

Wells constructed of polyvinyl chloride (PVC) are appropriate for monitoring of explosives and trace 

metals. Careful sampling and analytical methods are necessary for detection of trace metals. These may 

be present at low, parts-per-billion concentrations in affected wells and below-detection concentrations in 

wells that are not affected, even when very sensitive analytical methods are used. Because contaminants 

from munitions may move very slowly through the soil to the water table and in the aquifer, long-term 

monitoring at wells is usually warranted. 

Sampling Frequency and Duration of Program 

The frequency of sampling required in a ground-water-quality monitoring program is dictated by the 

expected rate of change in the concentrations of chemical constituents in and the physiochemical 

properties of the water being measured. Ground water moves slowly, perhaps only a few centimeters to a 

few decimeters per day, so that day-to-day fluctuations in concentrations of constituents and in properties 

at a point (or well) commonly are too small to be detected. For monitoring concentrations of major ions 

and nutrients, and values of physical properties of ground water, twice yearly sampling should be 

sufficient, and by varying the season selected for sampling, conditions during all four seasons could be 

documented over a 2-year cycle. A second group of constituents, trace inorganic and organic compounds, 

could be adequately monitored by collecting samples once every 2 years from wells in background areas 

(those areas unaffected by human activities), but more frequent sampling should be considered if the 

types and conditions of any upgradient sources of these compounds are changing. 

Consideration of several factors suggests that monitoring of ground-water quality should be a long-term 

activity. Not only does the structure of the program described herein mandate long-term monitoring, but 

the scales over which ground-water quality is likely to fluctuate also are long. Because of the slow rate of 

ground-water movement, any changes in factors that affect the quality of the water in recharge areas can 

take a long time to be reflected in surface-water bodies that are discharge areas for the ground water. 

Where ground-water-flow paths are relatively short, such as those within local ground-water cells near the 

coasts of Cape Cod, the water may move from recharge to discharge areas within a few years to a few 

decades. Flow paths between the tops of the five principal flow cells that constitute the ground-water 

system of lower Cape Cod and the coastlines of the Cape, however, are much longer, and represent 

traveltimes of perhaps 100 to 200 years. Even longer flow paths that extend through the deep lacustrine 

26 
clay beneath some of the flow cells may exist, but the effects of these impermeable deposits on the quality 

of ground water discharging to the surface-water ecosystems is unknown. 

The duration of a ground-water-quality monitoring program also is affected by the time scale of changes 

in the source area for the chemical constituents of interest. Water quality can be affected by land-use 

activities associated with ongoing development, but also by long-term changes in climate and sea-level 

rise. In summary, planning for 100 years of monitoring ground-water quality in an area should not be 

considered unreasonable. 

Quality Assurance 

Quality-assurance (QA) procedures help the investigator determine whether data collected are accurate 

and precise. Especially when measurements of trace constituents are involved, the potential for 

contamination of samples is a common problem. Quality-assurance procedures, a required part of any 

ground-water-quality investigation, are especially important for long-term monitoring projects. Data from 

these projects should be examined for time trends and changes. It is important to determine whether a 

measured change is a result of changes in methods or reflects real environmental changes. Qualityassurance data are needed to determine the answer. 

Chain of custody, a component of quality-assurance procedures required in U.S. Environmental 

Protection Agency (USEPA) investigations, legally ensures that samples were not tampered with before 

analysis. This is not required for investigations with primarily scientific rather than legal objectives. 

Quality-assurance procedures should be described for each water-quality investigation in a qualityassurance plan, which also is required in USEPA investigations. A quality-assurance plan contains (1) 

data-quality objectives, which describe the required precision and accuracy for the data to be collected so 

that scientific inferences from the data will be reliable, (2) verification procedures that ensure that the data 

collected are meeting the required levels of precision, and (3) a laboratory quality-assurance plan that 

applies to analytical laboratory procedures. 

In ground-water-quality monitoring, the analytical methods selected should have detection limits low 

enough for quantification of data that are environmentally significant. Appropriate levels by constituent 

are given in table 2. 

27 
Table 2. Methods and detection limits for chemical constituents included in the groundwater-quality monitoring protocol, Cape Cod National Seashore, Massachusetts. 

[Methods listed are suggestions rather than required specifications. Methods in parentheses are currently used 

at the North Atlantic Coastal Laboratory of the Cape Cod National Seashore. mg/L, milligrams per liter; μg/L, 

micrograms per liter; ng/L, nanograms per liter] 

Water-quality parameter 

or property Analytical method Desired reporting level to meet data-quality objectives 

Field measurements: 

pH, conductance, 

temperature, 

dissolved oxygen 

Field alkalinity 

Dissolved organic carbon 

Dissolved nitrate 

Dissolved ammonia 

Total nitrogen 

Dissolved phosphorus 

Total phosphorus 

Dissolved iron and 

manganese 

Dissolved major ions— 

Ca, Mg, Na, K, Cal, SO4

Trace inorganic contaminants 

Volatile organic compounds 

Trace organic contaminants 

Endocrine disruptors 

Mercury 

See discussion Part 2 

See discussion Part 2 

UV-promoted persulfate oxidation 

and infrared spectrometry 

Spectrophotometry 

(Lachat QuikChem Method 

31-107-04-1-A) 

Spectrophotometry 

(Lachat QuikChem Method 

10-107-06-1-C) 

Persulfate digestion and 

spectrophotometry 

Spectrophotometry 

(Lachat QuikChem Method 

31-115-01-1-G) 

Persulfate digestion and 

spectrophotometry 

Atomic absorption spectroscopy 

Atomic absorption spectroscopy 

Inductively coupled plasma-mass 

spectrometry 

Purge and trap gas chromatography 

mass spectrometry 

Gas chromatography mass 

spectrometry 

High pressure liquid chromatography 

Oxidation, purge and trap, and 

cold vapor atomic fluorescence 

spectrometry 

See discussion Part 2 

See discussion Part 2 

0.1 mg/L 

1 μg/L 

1 μg/L 

1 μg/L 

1 μg/L 

1 μg/L 

10 μg/L 

0.1 mg/L 

0.1 μg/L 

0.1 μg/L 

1 μg/L 

1 μg/L 

0.1 ng/L 

28 
Several kinds of quality-assurance samples and standards are available to verify that data-quality 

objectives are being met. These include blank samples, equipment blanks, duplicate samples, spike 

samples, and standard reference materials. The quality-assurance samples address potential data problems 

of systemic contamination, random contamination, sample-matrix problems and analyte loss. Systemic 

contamination can be determined by analyses of sample blanks, which indicate whether sampling 

materials, such as sample bottles, pumps, pump tubing, and preservation acids, contain analyte or are 

leaching analyte into the sample. Blank water is pumped through the system, collected in a sample bottle, 

and preserved and analyzed in the usual way to indicate whether any of these sources is a problem. 

Random contamination, such as might occur from airborne contaminants falling into a sample, can be 

checked by using sample duplicates. A small particle of metal oxide dissolved in a sample with acid 

preservation may cause a large change in sample trace-metal concentrations. Sample replicates can help 

in these cases to identify random contamination. Analyses of two ground-water samples obtained 

sequentially at the same location should result in the same concentration; otherwise, contamination from a 

random source is suspected. 

Sample spikes are used to determine whether the sample matrix can alter the sensitivity of the analytical 

method used to quantify analyte concentration. Duplicate samples are taken and a known amount of 

analyte is added (spiked) to one sample. Recovery of the spike is computed by comparison of analytical 

results from the spiked and unspiked samples. Spikes are useful, for example, during PCB sampling and 

extraction to determine whether all of the PCBs in a sample have been extracted. The requirement for two 

samples can be avoided by spiking analyte with a different isotope, such as C-13 labeled PCBS. 

Standard reference materials are samples that have a known concentration and are prepared in 

laboratories. Standard reference materials are used to evaluate the accuracy of the measurement procedure 

in the analytical laboratory and are generally are not used in field quality-assurance procedures. 

Data Reduction and Database 

Equally important as collecting data correctly is the processing and storage of data after collection. 

Trends analysis and baseline comparisons for long-term monitoring can be accomplished only if all data 

collected over the years can be retrieved with appropriate ancillary information sufficient to determine 

how the data were collected and what the accuracy and precision of the data were. 

As a result of its experience in assessing data-documentation requirements and storage, the USGS has 

confronted the problems of changes in methods, database platform, and software. The ideal system 

consists of dual record keeping—on paper and in computer files. The computer files are necessary for 

ease of data retrieval and analyses by the individual investigator and for public use through the internet. 

The paper files are necessary because long-term storage by paper is more reliable and because the 

database updates lag program changes, so that not all of the data collected can be stored electronically. 

The record-keeping system must be clearly defined, used systematically, and offer a means of 

checking data entry. 

29 
PART TWO 

Specific Protocols 

OVERVIEW OF DATA-COLLECTION PROCEDURES 

 bottle labels, referring to the section 

Labeling Sample Bottles. 

ng 

This part of the protocol includes descriptions of existing well networks and step-by-step instructions 

for the installation of additional wells and for water-quality sampling. After an initial reading, these 

descriptions may be skipped by many protocol users. That is because the ground-water-sampling 

personnel will collect data after the sampling network has been established and the monitoring wells 

drilled. The steps for data-collection preparation and sampling follow: 

1. Identify the wells to sample. Use table 3 to determine which network and how many wells or 

multilevel sampler (MLS) ports are to be sampled. 

2. Determine the number of samples required for analysis of each water-quality property and 

constituent. Use table 4 to determine properties and constituents for each sampled well, and add

the required QA samples as described in the QA section. 

3. Prepare samples bottles. Use table 5 to calculate the required number of each type of sample 

bottle and the types of preservation acids needed. Print out

4. Prepare field forms. Collect the field forms required for MLS and wells to be sampled, referri

to the section Logbook and Field Forms. 

5. Sample wells. Follow the steps in the sampling protocol under GROUND-WATER QUALITY 

SAMPLING. 

30 
Table 3. Description of wells by network. 

[NA, not available, referring to multilevel-sampler installations that are proposed; --, not included in sample count; 

NR, not registered in the USGS database; BLS, below land surface; MLS, multilevel sampler; m, meters] 

Sample 

count Local name Station name USGS number Latitude Longitude 

Port 

altitude 

or (depth 

BLS), 

in m 

ATMOSPHERIC DEPOSITION NETWORK 

1 

2 

NA 

-- 

3

4

5

6

7

8

10

11

12

13

14

15

16

17

18

Near NADP site 

Lombard Hollow 

Rd 

Proposed MLS 

Prince Valley Rd 

water-table well 

 Prince Valley 

Road MLS 

 Prince Valley 

Road MLS 

 Prince Valley 

Road MLS 

 Prince Valley 

Road MLS 

 Prince Valley 

Road MLS 

 Prince Valley 

Road MLS 

 Prince Valley 

Road MLS 

 Prince Valley 

Road MLS 

 Prince Valley 

Road MLS 

 Prince Valley 

Road MLS 

 Prince Valley 

Road MLS 

 Prince Valley 

Road MLS 

 Prince Valley 

Road MLS 

 Prince Valley 

Road MLS 

 Prince Valley 

Road MLS 

MA-TSW-256 

MA-TSW-257 

NA 

MA-TSW 266 

MA-TSW 265-01PT 

MA-TSW 265-

02GNT 

MA-TSW 265-03RT 

MA-TSW 265-

04BUT 

MA-TSW 265-

05BKT 

MA-TSW 265-06WT 

MA-TSW 265-07O 

MA-TSW 265-08GY 

MA-TSW 265-09Y 

MA-TSW 265-10P 

MA-TSW 265-11GN 

MA-TSW 265-12R 

MA-TSW 265-13BU 

MA-TSW 265-14BK 

MA-TSW 265-15W 

415821069591601 

415808070024301 

NA 

415808070034516 

415808070034501 

415808070034502 

415808070034503 

415808070034504 

415808070034505 

415808070034506 

415808070034507 

415808070034508 

415808070034509 

415808070034510 

415808070034511 

415808070034512 

415808070034513 

415808070034514 

415808070034515 

41 58 

41 58 

41 57 

41 58 

41 58 

41 58 

41 58 

41 58 

41 58 

41 58 

41 58 

41 58 

41 58 

41 58 

41 58 

41 58 

41 58 

41 58 

41 58 

22 

08 

54.8 

08.6 

08.6 

08.6 

08.6 

08.6 

08.6 

08.6 

08.6 

08.6 

08.6 

08.6 

08.6 

08.6 

08.6 

08.6 

08.6 

69 57 

70 02 

79 03 

70 03 

70 03 

70 03 

70 03 

70 03 

70 03 

70 03 

70 03 

70 03 

70 03 

70 03 

70 03 

70 03 

70 03 

70 03 

70 03 

16 

43 

53.2 

45.9 

45.9 

45.9 

45.9 

45.9 

45.9 

45.9 

45.9 

45.9 

45.9 

45.9 

45.9 

45.9 

45.9 

45.9 

45.9 

(58.71–

60.71) 

(32.55–

34.55) 

NA 

(5.64–

6.25) 

0.67 

-3.60 

-6.65 

-9.71 

-12.77 

-15.83 

-18.89 

-21.94 

-25.00 

-28.06 

-31.10 

-34.16 

-37.22 

-40.27 

-43.31 

NONPOINT-SOURCE NETWORK 

--

1 

2

3 

4 

 Kennedy 

water table 

Kennedy MLS 

 Kennedy MLS 

Kennedy MLS 

Kennedy MLS 

MA-EGW 57 

MA-EGW 54-01PT 

MA-EGW 54-

02GNT 

MA-EGW 54-03RT 

MA-EGW 54-04BUT 

415019069574816 

415019069574801 

415019069574802 

415019069574803 

415019069574804 

41 50 19.1 

41 50 19.1 

41 50 19.1 

41 50 19.1 

41 50 19.1 

69 57 48.5 

69 57 48.5 

69 57 48.5 

69 57 48.5 

69 57 48.5 

(13.02–

13.62) 

4.83 

3.92 

3.01 

1.92 

31 
Table 3. Description of wells by network.—Continued

[NA, not available, referring to multilevel-sampler installations that are proposed; --, not included in sample count; 

NR, not registered in the USGS database; BLS, below land surface; MLS, multilevel sampler; m, meters] 

Sample 

count Local name Station name USGS number Latitude Longitude 

Port 

altitude 

or (depth 

BLS), 

in m 

NONPOINT-SOURCE NETWORK--Continued 

5 

6 

7 

8 

9 

10 

11 

12 

13 

14 

15 

-- 

16 

17 

18 

19 

20 

21 

22 

23 

24 

25 

26 

27 

28 

29 

30 

Kennedy MLS 

Kennedy MLS 

Kennedy MLS 

Kennedy MLS 

Kennedy MLS 

Kennedy MLS 

Kennedy MLS 

Kennedy MLS 

Kennedy MLS 

Kennedy MLS 

Kennedy MLS 

Grist Mill 

water-table 

Grist Mill MLS 

Grist Mill MLS 

Grist Mill MLS 

Grist Mill MLS 

Grist Mill MLS 

Grist Mill MLS 

Grist Mill MLS 

Grist Mill MLS 

Grist Mill MLS 

Grist Mill MLS 

Grist Mill MLS 

Grist Mill MLS 

Grist Mill MLS 

Grist Mill MLS 

Grist Mill MLS 

MA-EGW 54-05BKT 

MA-EGW 54-06WT 

MA-EGW 54-07O 

MA-EGW 54-08GY 

MA-EGW 54-09Y 

MA-EGW 54-10P 

MA-EGW 54-11GN 

MA-EGW 54-12R 

MA-EGW 54-13BU 

MA-EGW 54-14BK 

MA-EGW 54-15W 

MA-EGW 56 

MA-EGW 55-01PT 

MA-EGW 55-

02GNT 

MA-EGW 55-03RT 

MA-EGW 55-04BUT 

MA-EGW 55-05BKT 

MA-EGW 55-06WT 

MA-EGW 55-07O 

MA-EGW 55-08GY 

MA-EGW 55-09Y 

MA-EGW 55-10P 

MA-EGW 55-11GN 

MA-EGW 55-12R 

MA-EGW 55-13BU 

MA-EGW 55-14BK 

MA-EGW 55-15W 

415019069574805 

415019069574806 

415019069574807 

415019069574808 

415019069574809 

415019069574810 

415019069574811 

415019069574812 

415019069574813 

415019069574814 

415019069574815 

414941069581416 

414941069581401 

414941069581402 

414941069581403 

414941069581404 

414941069581405 

414941069581406 

414941069581407 

414941069581408 

414941069581409 

414941069581410 

414941069581411 

414941069581412 

414941069581413 

414941069581414 

414941069581415 

41 50 19.1 

41 50 19.1 

41 50 19.1 

41 50 19.1 

41 50 19.1 

41 50 19.1 

41 50 19.1 

41 50 19.1 

41 50 19.1 

41 50 19.1 

41 50 19.1 

41 49 41.5 

41 49 41.5 

41 49 41.5 

41 49 41.5 

41 49 41.5 

41 49 41.5 

41 49 41.5 

41 49 41.5 

41 49 41.5 

41 49 41.5 

41 49 41.5 

41 49 41.5 

41 49 41.5 

41 49 41.5 

41 49 41.5 

41 49 41.5 

69 57 48.5 

69 57 48.5 

69 57 48.5 

69 57 48.5 

69 57 48.5 

69 57 48.5 

69 57 48.5 

69 57 48.5 

69 57 48.5 

69 57 48.5 

69 57 48.5 

69 58 14.0 

69 58 14.0 

69 58 14.0 

69 58 14.0 

69 58 14.0 

69 58 14.0 

69 58 14.0 

69 58 14.0 

69 58 14.0 

69 58 14.0 

69 58 14.0 

69 58 14.0 

69 58 14.0 

69 58 14.0 

69 58 14.0 

69 58 14.0 

1.16 

0.25 

-0.67 

-1.59 

-2.51 

-3.42 

-5.87 

-8.93 

-12.61 

-16.28 

-19.94 

(5.57–

6.18) 

1.88 

0.97 

0.05 

-1.02 

-1.79 

-2.70 

-3.61 

-4.54 

-5.45 

-6.36 

-9.12 

-12.79 

-16.48 

-20.14 

-23.81 

32 
Table 3. Description of wells by network.—Continued

[NA, not available, referring to multilevel-sampler installations that are proposed; --, not included in sample count; 

NR, not registered in the USGS database; BLS, below land surface; MLS, multilevel sampler; m, meters] 

Sample 

count Local name Station name USGS number Latitude Longitude 

Port 

altitude or 

(depth 

BLS), 

in m 

NONPOINT-SOURCE NETWORK--Continued 

31 

32 

33 

34 

35 

36 

37 

38 

39 

40 

41 

42 

43 

44 

45 

Minister Pond 

MLS 

Minister Pond 

MLS 

Minister Pond 

MLS 

Minister Pond 

MLS 

Minister Pond 

MLS 

Minister Pond 

MLS 

Minister Pond 

MLS 

Minister Pond 

MLS 

Minister Pond 

MLS 

Minister Pond 

MLS 

Minister Pond 

MLS 

Minister Pond 

MLS 

Minister Pond 

MLS 

Minister Pond 

MLS 

Minister Pond 

MLS 

MA-EGW 58-01PT 

MA-EGW 58-

02GNT 

MA-EGW 58-03RT 

MA-EGW 58-04BUT 

MA-EGW 58-05BKT 

MA-EGW 58-06WT 

MA-EGW 58-07O 

MA-EGW 58-08GY 

MA-EGW 58-09Y 

MA-EGW 58-10P 

MA-EGW 58-11GN 

MA-EGW 58-12R 

MA-EGW 58-13BU 

MA-EGW 58-14BK 

MA-EGW 58-15W 

415024069583001 

415024069583002 

415024069583003 

415024069583004 

415024069583005 

415024069583006 

415024069583007 

415024069583008 

415024069583009 

415024069583010 

415024069583011 

415024069583012 

415024069583013 

415024069583014 

415024069583015 

41 50 24 

41 50 24 

41 50 24 

41 50 24 

41 50 24 

41 50 24 

41 50 24 

41 50 24 

41 50 24 

41 50 24 

41 50 24 

41 50 24 

41 50 24 

41 50 24 

41 50 24 

69 58 30 

69 58 30 

69 58 30 

69 58 30 

69 58 30 

69 58 30 

69 58 30 

69 58 30 

69 58 30 

69 58 30 

69 58 30 

69 58 30 

69 58 30 

69 58 30 

69 58 30 

(2.97) 

(6.00) 

(9.08) 

(12.13) 

(15.18) 

(18.23) 

(21.28) 

(24.32) 

(27.37) 

(30.42) 

(33.47) 

(36.52) 

(39.56) 

(42.61) 

(45.66) 

POINT-SOURCE NETWORK—GULL POND

-- 

-- 

1 

2 

3 

4 

5 

6 

7 

 

Bee well water 

table 

Hill well water 

table 

Gull Pond MLS-

#1 

Gull Pond MLS-

#1 

Gull Pond MLS-

#1 

Gull Pond MLS-

#1 

Gull Pond MLS-

#1 

Gull Pond MLS-

#1 

Gull Pond MLS-

#1 

MA-WNW 131 

MA-WNW 132 

MA-WNW 125-

01BKT 

MA-WNW 125-

02WT 

MA-WNW 125-03O 

MA-WNW 125-

04GY 

MA-WNW 125-05Y 

MA-WNW 125-06P 

MA-WNW 125-

07GN 

415719070004631 

415718070004701 

415718070004601 

415718070004602 

415718070004603 

415718070004604 

415718070004605 

415718070004606 

415718070004607 

41 57 18.8 

41 57 17.7 

41 57 18.5 

41 57 18.5 

41 57 18.5 

41 57 18.5 

41 57 18.5 

41 57 18.5 

41 57 18.5 

70 00 46.5 

70 00 46.9 

70 00 46.5 

70 00 46.5 

70 00 46.5 

70 00 46.5 

70 00 46.5 

70 00 46.5 

70 00 46.5 

(7.79–

8.43) 

(6.49–

7.09) 

(4.05) 

(4.36) 

(4.66) 

(4.97) 

(5.27) 

(5.88) 

(6.49) 

33 
Table 3. Description of wells by network.—Continued

[NA, not available, referring to multilevel-sampler installations that are proposed; --, not included in sample count; 

NR, not registered in the USGS database; BLS, below land surface; MLS, multilevel sampler; m, meters] 

Sample 

count Local name Station name USGS number Latitude Longitude 

Port 

altitude or 

(depth 

BLS), 

in m 

POINT-SOURCE NETWORK—GULL POND--Continued

8 

9 

10 

11 

12 

13 

14 

15 

16 

17 

18 

19 

20 

21 

22 

23 

24 

25 

26 

27 

28 

29 

30 

31 

Gull Pond MLS-

#1 

Gull Pond MLS-

#1 

Gull Pond MLS-

#1 

Gull Pond MLS-

#1 

Gull Pond MLS-

#2 

Gull Pond MLS-

#2 

Gull Pond MLS-

#2 

Gull Pond MLS-

#2 

Gull Pond MLS-

#2 

Gull Pond MLS-

#2 

Gull Pond MLS-

#2 

Gull Pond MLS-

#2 

Gull Pond MLS-

#2 

Gull Pond MLS-

#2 

Gull Pond MLS-

#2 

Gull Pond MLS-

#3 

Gull Pond MLS-

#3 

Gull Pond MLS-

#3 

Gull Pond MLS-

#3 

Gull Pond MLS-

#3 

Gull Pond MLS-

#3 

Gull Pond MLS-

#3 

Gull Pond MLS-

#3 

Gull Pond MLS-

#3 

MA-WNW 125-08R 

MA-WNW 125-

09BU 

MA-WNW 125-

10BK 

MA-WNW 125-11W 

MA-WNW 126-

12BKT 

MA-WNW 126-

13WT 

MA-WNW 126-14O 

MA-WNW 126-

15GY 

MA-WNW 126-16Y 

MA-WNW 126-17P 

MA-WNW 126-

18GN 

MA-WNW 126-19R 

MA-WNW 126-

20BU 

MA-WNW 126-

21BK 

MA-WNW 126-22W 

MA-WNW 127-

01BKT 

MA-WNW 127-

02WT 

MA-WNW 127-03O 

MA-WNW 127-

04GY 

MA-WNW 127-05Y 

MA-WNW 127-06P 

MA-WNW 127-

07GN 

MA-WNW 127-08R 

MA-WNW 127-

09BU 

415718070004608 

415718070004609 

415718070004610 

415718070004611 

415718070004610

415718070004611 

415718070004612 

415718070004613 

415718070004614 

415718070004615 

415718070004616 

415718070004617 

415718070004618 

415718070004619 

415718070004620 

415718070004801 

415718070004802 

415718070004803 

415718070004804 

415718070004805 

415718070004806 

415718070004807 

415718070004808 

415718070004809 

 

41 57 18.5 

41 57 18.5 

41 57 18.5 

41 57 18.5 

41 57 18.3 

41 57 18.3 

41 57 18.3 

41 57 18.3 

41 57 18.3 

41 57 18.3 

41 57 18.3 

41 57 18.3 

41 57 18.3 

41 57 18.3 

41 57 18.3 

41 57 18.9 

41 57 18.9 

41 57 18.9 

41 57 18.9 

41 57 18.9 

41 57 18.9 

41 57 18.9 

41 57 18.9 

41 57 18.9 

70 00 46.5 

70 00 46.5 

70 00 46.5 

70 00 46.5 

70 00 47.7

70 00 47.7 

70 00 47.7 

70 00 47.7 

70 00 47.7 

70 00 47.7 

70 00 47.7 

70 00 47.7 

70 00 47.7 

70 00 47.7 

70 00 47.7 

70 00 45.9 

70 00 45.9 

70 00 45.9 

70 00 45.9 

70 00 45.9 

70 00 45.9 

70 00 45.9 

70 00 45.9 

70 00 45.9 

(7.10) 

(7.71) 

(8.32) 

(8.93) 

(4.13)

(4.44) 

(4.74) 

(5.05) 

(5.35) 

(5.96) 

(6.57) 

(7.18) 

(7.79) 

(8.40) 

(9.01) 

(4.05) 

(4.36) 

(4.66) 

(4.97) 

(5.27) 

(5.88) 

(6.49) 

(7.10) 

(7.71) 

34 
Table 3. Description of wells by network.—Continued

[NA, not available, referring to multilevel-sampler installations that are proposed; --, not included in sample count; 

NR, not registered in the USGS database; BLS, below land surface; MLS, multilevel sampler; m, meters] 

Sample 

count Local name Station name USGS number Latitude Longitude 

Port 

altitude or 

(depth 

BLS), 

in m 

POINT-SOURCE NETWORK—GULL POND--Continued

32 

33 

34 

35 

36 

37 

38 

39 

40 

41 

42 

43 

44 

45 

46 

47 

48 

49 

50 

51 

52 

53 

54 

55 

Gull Pond MLS-

#3 

Gull Pond MLS-

#3 

Gull Pond MLS-

#4 

Gull Pond MLS-

#4 

Gull Pond MLS-

#4 

Gull Pond MLS-

#4 

Gull Pond MLS-

#4 

Gull Pond MLS-

#4 

Gull Pond MLS-

#4 

Gull Pond MLS-

#4 

Gull Pond MLS-

#4 

Gull Pond MLS-

#4 

Gull Pond MLS-

#4 

Gull Pond MLS-

#5 

Gull Pond MLS-

#5 

Gull Pond MLS-

#5 

Gull Pond MLS-

#5 

Gull Pond MLS-

#5 

Gull Pond MLS-

#5 

Gull Pond MLS-

#5 

Gull Pond MLS-

#5 

Gull Pond MLS-

#5 

Gull Pond MLS-

#5 

Gull Pond MLS-

#5 

MA-WNW 127-

10BK 

MA-WNW 127-11W 

MA-WNW 128-

01BKT 

MA-WNW 128-

02WT 

MA-WNW 128-03O 

MA-WNW 128-

04GY 

MA-WNW 128-05Y 

MA-WNW 128-06P 

MA-WNW 128-

07GN 

MA-WNW 128-08R 

MA-WNW 128-

09BU 

MA-WNW 128-

10BK 

MA-WNW 128-11W 

MA-WNW 129-

12BKT 

MA-WNW 129-

13WT 

MA-WNW 129-14O 

MA-WNW 129-

15GY 

MA-WNW 129-16Y 

MA-WNW 129-17P 

MA-WNW 129-

18GN 

MA-WNW 129-19R 

MA-WNW 129-

20BU 

MA-WNW 129-

21BK 

MA-WNW 129-22W 

415718070004810 

415718070004811 

415719070004601 

415719070004602 

415719070004603 

415719070004604 

415719070004605 

415719070004606 

415719070004607 

415719070004608 

415719070004609 

415719070004610 

415719070004611 

415719070004612

415719070004613 

415719070004614 

415719070004615 

415719070004616 

415719070004617 

415719070004618 

415719070004619 

415719070004620 

415719070004621 

415719070004622 

35 

41 57 18.9 

41 57 18.9 

41 57 18.8 

41 57 18.8 

41 57 18.8 

41 57 18.8 

41 57 18.8 

41 57 18.8 

41 57 18.8 

41 57 18.8 

41 57 18.8 

41 57 18.8 

41 57 18.8 

41 57 18.5 

41 57 18.5 

41 57 18.5 

41 57 18.5 

41 57 18.5 

41 57 18.5 

41 57 18.5 

41 57 18.5 

41 57 18.5 

41 57 18.5 

41 57 18.5 

70 00 45.9 

70 00 45.9 

70 00 45.8 

70 00 45.8 

70 00 45.8 

70 00 45.8 

70 00 45.8 

70 00 45.8 

70 00 45.8 

70 00 45.8 

70 00 45.8 

70 00 45.8 

70 00 45.8 

70 00 45.5

70 00 45.5 

70 00 45.5 

70 00 45.5 

70 00 45.5 

70 00 45.5 

70 00 45.5 

70 00 45.5 

70 00 45.5 

70 00 45.5 

70 00 45.5 

(8.32) 

(8.93) 

(3.90) 

(4.21) 

(4.51) 

(4.82) 

(5.12) 

(5.73) 

(6.34) 

(6.95) 

(7.56) 

(8.17) 

(8.78) 

(4.05)

(4.36) 

(4.66) 

(4.97) 

(5.27) 

(5.88) 

(6.49) 

(7.10) 

(7.71) 

(8.32) 

(8.93) 
Table 3. Description of wells by network.—Continued

[NA, not available, referring to multilevel-sampler installations that are proposed; --, not included in sample count; 

NR, not registered in the USGS database; BLS, below land surface; MLS, multilevel sampler; m, meters] 

Sample 

count Local name Station name USGS number Latitude Longitude 

Port 

altitude or 

(depth 

BLS), 

in m 

POINT-SOURCE NETWORK—GULL POND--Continued

56 

57 

58 

59 

60 

61 

62 

63 

64 

65 

66 

Gull Pond MLS-

#6 

Gull Pond MLS-

#6 

Gull Pond MLS-

#6 

Gull Pond MLS-

#6 

Gull Pond MLS-

#6 

Gull Pond MLS-

#6 

Gull Pond MLS-

#6 

Gull Pond MLS-

#6 

Gull Pond MLS-

#6 

Gull Pond MLS-

#6 

Gull Pond MLS-

#6 

MA-WNW 130-

01BKT 

MA-WNW 130-

02WT 

MA-WNW 130-03O 

MA-WNW 130-

04GY 

MA-WNW 130-05Y 

MA-WNW 130-06P 

MA-WNW 130-

07GN 

MA-WNW 130-08R 

MA-WNW 130-

09BU 

MA-WNW 130-

10BK 

MA-WNW 130-11W 

415718070004501 

415718070004502 

415718070004503 

415718070004504 

415718070004505 

415718070004506 

415718070004507 

415718070004508 

415718070004509 

415718070004510 

415718070004511 

41 57 18.4 

41 57 18.4 

41 57 18.4 

41 57 18.4 

41 57 18.4 

41 57 18.4 

41 57 18.4 

41 57 18.4 

41 57 18.4 

41 57 18.4 

41 57 18.4 

70 00 45.6 

70 00 45.6 

70 00 45.6 

70 00 45.6 

70 00 45.6 

70 00 45.6 

70 00 45.6 

70 00 45.6 

70 00 45.6 

70 00 45.6 

70 00 45.6 

(3.99) 

(4.30) 

(4.60) 

(4.91) 

(5.21) 

(5.82) 

(6.43) 

(7.04) 

(7.65) 

(8.26) 

(8.87) 

POINT-SOURCE NETWORK—VISITORS CENTER SEPTIC-SYSTEM LEACHFIELD 

1 

2 

3 

4 

5 

6 

7 

8 

9 

10 

A1 

A1a 

A2 

A3 

A4 

A5 

A6 

B2 

B4 

B5 

MA-EGW-62 

MA-EGW-63 

MA-EGW-64 

MA-EGW-65 

MA-EGW-66 

MA-EGW-67 

MA-EGW-68 

MA-EGW-69 

MA-EGW-70 

MA-EGW-71 

415012069582201 

415012069582202 

415012069582203 

415012069582204 

415012069582205 

415012069582206 

415012069582207 

415012069582101 

415012069582102 

415012069582103 

 

 

41 50 

41 50 

41 50 

41 50 

41 50 

41 50 

41 50 

41 50 

41 50 

41 50 

12.0 

12.0 

12.0 

12.0 

12.0 

12.0 

12.0 

12.2 

12.2 

12.2 

69 58 

69 58 

69 58 

69 58 

69 58 

69 58 

69 58 

69 58 

69 58 

69 58 

22.2 

22.2 

22.2 

22.2 

22.2 

22.2 

22.2 

21.8 

21.8 

21.8 

(5.94–7.47) 

(5.94–7.47) 

(7.47–8.99) 

(8.99–

10.52) 

(10.52–

12.04) 

(12.04–

13.56) 

(13.56–

15.09) 

(7.42–8.99) 

(10.52–

12.04) 

(12.04–

13.56) 

 

36 
Table 3. Description of wells by network.—Continued

[NA, not available, referring to multilevel-sampler installations that are proposed; --, not included in sample count; 

NR, not registered in the USGS database; BLS, below land surface; MLS, multilevel sampler; m, meters] 

Sample 

count Local name Station name USGS number Latitude Longitude 

Port 

altitude or 

(depth 

BLS), 

in m 

POINT-SOURCE NETWORK—VISITORS CENTER SEPTIC-SYSTEM LEACHFIELD--Continued 

11 

12 

13 

14 

15 

16 

17 

C3 

C4 

Y4 

Z2 

Z4 

Z5 

ROBO-BG1 

NR 

NR 

NR 

MA-EGW-72 

MA-EGW-73 

MA-EGW-74 

MA-EGW-61 

NR 

NR 

NR 

415011069582201 

415011069582202 

415011069582203 

415016069582503 

41 50 

41 50 

41 50 

41 50 

41 50 

41 50 

41 50 

12.3 

12.3 

11.8 

11.9 

11.9 

11.9 

16.1 

69 58 

69 58 

69 58 

69 58 

69 58 

69 58 

69 58 

21.2 

21.2 

23.1 

22.7 

22.7 

22.7 

26.0 

(10.52–

12.04) 

(12.04–

13.56) 

(10.52–

12.04) 

(7.47–

8.99) 

(10.46–

11.98) 

(12.04–

13.56) 

(8.42–

11.16) 

JOINT VISITOR CENTER LEACHFIELD AND EASTHAM LANDFILL 

18 

-- 

Upgradient PVC 

well 

Upgradient 

geophysical 

logging well 

MA-EGW-60 

MA-EGW-59 

415016069582502 

415016069582501 

41 50 

41 50 

16.2 

16.2 

69 58 

69 58 

25.9 

25.7 

(34.7–

39.7) 

(43.59–

45.11) 

37 
Table 4. Water-quality properties, constituents, and sampling-frequency interval in years, 

by network, Cape Cod National Seashore, Massachusetts. 

[NS, no sampling]

 -------------------------WELL NETWORK------------------------------ 

Point Back- Point source: Point Water-quality ground/ Nonpoint- Point Point 

source: Under- source: parameter atmos- source source: source: Visitors ground Firing or property pheric nutrients Gull Pond Landfill Center storage range deposition tanks 

Frequency per year 0.5 0.5 0.5 0.5 0.5 1 1 

Field measurements: 0.5 0.5 0.5 0.5 0.5 1 1 

pH, conductance, 

temperature, 

dissolved oxygen 

Field alkalinity 0.5 0.5 0.5 0.5 0.5 NS NS 

Dissolved organic 2 2 2 2 2 NS NS 

carbon 

Dissolved nitrate 0.5 0.5 0.5 0.5 0.5 NS 1 

Dissolved ammonia 0.5 0.5 0.5 0.5 0.5 NS NS 

Dissolved total 0.5 0.5 0.5 0.5 0.5 NS NS 

nitrogen 

Dissolved 0.5 0.5 0.5 0.5 0.5 NS NS 

phosphorus 

Dissolved total 0.5 0.5 0.5 0.5 0.5 NS NS 

phosphorus 

Dissolved iron and 0.5 0.5 0.5 0.5 0.5 NS 1 

manganese 

Dissolved major 2 NS NS NS 0.5 NS NS 

ions— 

Ca, Mg, Na, K, SO4

 

Trace inorganic 2 2 2 2 0.5 1 1 

contaminants 

Mercury1 2 2 NS NS 2 NS 2 

VOCs NS NS NS NS 0.5 1 NS 

Trace organic 2 2 NS NS 0.5 1 1 

contaminants 

Endocrine 2 2 2 2 2 NS NS 

disruptors, 

pharmaceuticals, 

and antibacterial 

compounds2

 

1

 Requires installation of wells with Teflon casing. 

2

 Requires installation of wells with Teflon or stainless-steel casing. 

38 
Table 5. Sample-bottle types, preservation, shipping, and holding requirements for monitoring 

ground water, Cape Cod National Seashore, Massachusetts. 

[FC, filtered brown polyethylene bottle; DOC, baked amber glass bottle; FA, 250-mL acid rinsed polyethylene 

bottle; d, days; mL, milliliter] 

Water-quality constituents Bottle type Preservation Shipping 

requirements 

Holding 

requirements 

Dissolved organic carbon 

Dissolved nitrate 

Dissolved ammonia 

Dissolved phosphorus 

Dissolved total nitrogen 

Dissolved total phosphorus 

Dissolved iron and manganese 

Dissolved major ions— 

Ca, Mg, Na, K, Cl, SO4

 

Trace inorganic contaminants 

Trace organic contaminants 

125 mL DOC 

125 mL FC 

125 mL FC 

125 mL FC 

125 mL FC 

125 mL FC 

125 mL FA 

125 mL FA 

125 mL FA 

Baked glass 

H2SO4

 to pH < 2 

HCl to pH < 1.5 

HCl to pH < 1.5 

HCl to pH < 1.5 

Freezing 

Freezing 

HNO3

 to pH < 1.5 

HNO3

 to pH < 1.5 

HNO3

 to pH < 1.5 

Variable 

On ice 20 hours 

On ice 20 hours 

On ice 20 hours 

On ice 20 hours 

On ice 20 hours 

On ice 20 hours 

No chilling or 

time requirements 

No chilling or 

time requirements 

No chilling or 

time requirements 

Variable 

15 d refrigerated 

30 d refrigerated 

30 d refrigerated 

30 d refrigerated 

30 d frozen 

30 d frozen 

6 months 

6 months 

6 months 

Variable 

39 
GROUND-WATER-QUALITY WELL NETWORK 

The design of the ground-water-quality network was covered in Part One. The design descriptions 

included types of networks and water-quality constituents and properties to be included in each 

network, which is summarized here in Part Two in tables 3 and 4, respectively. Part Two also includes 

descriptions of the wells that have been installed and their uses for each network. A part of the intended 

ground-water-quality network for the Cape Cod National Seashore (CACO) is not yet installed. The 

network description below includes suggestions for expanding the networks and procedures for 

monitoring-well installation. 

Nonpoint Sources 

The nonpoint sources are atmospheric deposition, which contributes everywhere to background, and the 

cumulative effects of waste disposal by septic systems. Separate networks are described to monitor these 

two types of sources. 

Atmospheric Deposition and Background 

The atmospheric deposition and background network is located in the Chequesset flow cell (fig. 10, 

table 3) in Truro. This flow cell was chosen for monitoring because it is within protected CACO lands, 

so that recharge for all the flow paths intercepted by a downgradient MLS could be assumed to be 

uncontaminated, and because of proximity to the NADP atmospheric-deposition collector at Truro. The 

network consists of the MLS at Prince Valley Road, several water-table wells, and a proposed second 

MLS near the Prince Valley site (fig. 10) as discussed below. 

40 
Figure 10. Ground-water-quality well network for atmospheric deposition and background 

investigation, Cape Cod, Massachusetts. MLS, multilevel sampler. 

41 
The network has been monitored since 2000. Analyses of ground water from the Prince Valley Road 

MLS show consistent zones of high and low dissolved oxygen (fig. 11). The variation in oxygen likely is 

caused by a variation in the amounts of organic-carbon leakage from the soil layer (Pabich and others, 

2001) at the points of recharge (fig. 12). The concentration of dissolved oxygen, in turn, affects the 

concentrations of other constituents such as iron and nitrate. Simulation of traveltimes by the regional 

flow model (Masterson, 2004) indicates that the age of the water increases with depth, ranging from 

several years at the most shallow port to 150 years at the deepest port. Variability in the concentrations of 

solutes measured in samples obtained from the MLS ports reflect, in part, variability in concentrations 

recharged over time. For example, the sulfate record may be interpreted in this way if oxic conditions are 

assumed to apply to the travel path (Robertson and others, 1989). To obtain a more complete record of the 

ground-water chemistry under completely oxic conditions, a second background MLS could be installed 

(fig. 10). The proposed site, downgradient from areas of recharge through a thick unsaturated zone, would 

likely yield data that reflects the effect of atmospheric deposition and background recharge for a 

completely aerobic flow path. 

42 
Figure 11. Concentration profiles for the background multilevel sampler along 

Prince Valley Road, Truro, Massachusetts. 

43 
Figure 12. Simulated recharge locations (red dots) for Prince Valley Road multilevel sampler, 

Cape Cod, Massachusetts. 

44 
The design for the atmospheric deposition and background network, described in Part One and 

summarized in table 4, includes sampling for trace metals and trace-organic compounds in addition to the 

water-quality constituents and properties just discussed (table 4). Sampling for most metals could be done 

with the existing well network; sampling for trace organic compounds would require installation of 

additional monitoring wells constructed of stainless steel or Teflon. Sampling for mercury would require 

monitoring wells constructed of Teflon. 

The network wells were sampled twice per year during 2001–2003. The frequency of measurement 

specified in the design is twice per year and is varied among seasons so that all four seasons are sampled 

in a 2-year period (table 4). 

Septic Systems and Other Nonpoint Sources Associated with Development 

Three MLS have been installed in the ground-water monitoring network for nonpoint sources associated 

with development (fig. 13, table 3). These include the Kennedy Barn MLS, which is sited to intercept 

ground-water plumes to Nauset Bay from septic systems associated with housing that was recently 

constructed (1991–1999) east of the landfill; the Grist Mill MLS, which is sited to intercept plumes in 

ground water from development along Route 6; and the Minister Pond MLS, which is sited to intercept 

water exiting Minister Pond and a possible underflow plume from the Eastham landfill. 

The MLS that are already installed may intercept ground-water plumes from the principal types of 

nonpoint sources that affect CACO lands or coastal water that borders CACO land. Determination of 

water-quality baseline conditions and trends can be conducted at these sites. These MLS sites do not, 

however, intercept flow affected by the area of most intense land use that contribute to CACO coastal 

embayments waters, which are the urban centers of Provincetown, Wellfleet, Orleans, and Chatham, and 

there are not a sufficient number of MLS installed to characterize spatial variability of water quality from 

nonpoint sources in the CACO. Additional installations of MLS would be required to characterize plumes 

from the urban sites and to characterize spatial variability of ground-water quality in the CACO. 

45 
Figure 13. Ground-water-quality well network for nutrient loading to coastal embayments. The 

Minister Pond multilevel sampler and the geophysical logging well may be affected by the plume 

from the Eastham landfill, Cape Cod, Massachusetts. 

46 
47 

Ground-water quality has been monitored at two of the nonpoint source MLS during 2000–2003. Waterquality measurements indicate that ammonia and phosphorus concentrations were low in all of the 

samples obtained (fig. 14). Concentrations of nitrate in samples from the Kennedy Barn MLS have been 

increasing, and nitrate concentrations in samples from the Grist Mill MLS have been variable (fig. 15). 

Trends are not yet known for the Minister Pond MLS, which was installed in 2003 and has been sampled 

only once. Frequency for sampling of the MLS in the network design is twice per year for measurements 

of most water-quality constituents and properties (table 4). 

Figure 14. Water-quality profiles from multilevel samplers near Nauset Marsh Estuary, Cape 

Cod, Massachusetts. 
Figure 15. Nitrogen profiles from 2001 to 2005 from the MLS near Nauset Marsh Estuary, Cape 

Cod, Massachusetts. 

Point Sources 

Well networks have been installed at the CACO to monitor the ground-water plumes from individual 

point sources to characterize types of point sources. The types of point sources considered in this protocol 

are septic systems and landfills. 

Septic Systems as Point Sources 

Monitoring wells have been installed around the leachfields of two septic systems on CACO lands. 

The plume from one septic system, at the bathhouse at Gull Pond landing, discharges to a freshwater site, 

Gull Pond. The plume from the other septic system, at the CACO Visitor Center, discharges to a saltwater 

site, Salt Pond. Both installations include wells with PVC casing or plastic tubing, which can be used 

to collect samples for analysis of nitrogen, phosphorus, major elements, iron, and manganese. The 

installation at the CACO Visitor Center includes stainless-steel wells, which can be used to collect 

samples for analysis of emerging contaminants such as endocrine disruptors and pharmaceuticals that 

may be present in disposed sewage. 

Gull Pond 

MLS and water-table wells have been installed in the leachfield of the septic system at the Gull Pond 

bathhouse. Five MLS were installed downgradient from the leachfield to intercept the ground-water 

plume as it moves from the disposal site towards Gull Pond; one MLS was installed upgradient from the 

leachfield site to determine background conditions (fig. 16). The direction of ground-water flow around 

the leachfield was determined by triangulation (McCobb and Weiskel, 2003) by using measurements of 

water level of the lake and in the water-table wells (fig. 16). Phosphorus and nitrogen are constituents of 

principal concern in septic system leachate at Gull Pond because aquatic plant growth in the lake may be 

controlled by the supply of one or both of these elements. In the data resulting from the MLS sampling 

during 2001 to 2003, concentrations of phosphorus have been very low, even in zones where high specific 

48 
49 

conductance and concentrations of nitrate indicate that septic-system leachate is passing through. 

Apparently the transport of phosphorus is attenuated compared to that of nitrogen during the movement of 

ground water from the leachfield to the positions of the MLS. 

Figure 16. Well network for the point-source leachfield for the bathhouse at Gull Pond, Cape 

Cod National Seashore, Massachusetts. 
Although the twice-yearly sampling is listed in the design (table 4) for the Gull Pond MLS, more frequent 

sampling, four times per year, may be appropriate until a consistent pattern emerges. The bathhouse is 

used only in the summer months, and the associated seasonal discharge of wastewater to the leachfield 

may result in fluctuations in water-quality data measured in the MLS. 

Salt Pond 

Seventeen drive-point stainless-steel wells, a PVC water-table well, and a geophysical logging well have 

been installed around the leachfield that receives wastewater from the Visitor Center (Granato, 2002) 

(fig. 17, table 3). The stainless-steel wells have an inside diameter of 1.6 cm (5/8 inch)—too small for 

submersible pumps to be used—so they are sampled by suction applied to tubing that is inserted from the 

surface. The PVC water-table well and the logging well are upgradient from the leachfield, and the 

stainless-steel wells are aligned in a well “fence” across the estimated path of the leachfield plume. 

Geophysical logs have been completed for the logging well in each fall during 2003 to 2005. The logs 

were analyzed to determine whether a landfill plume from the Eastham landfill was present. Interpretation 

of results from the downgradient wells would be more complex if two plumes, from a landfill and the 

Visitor Center, were present in the same location. There is no indication from the three logs that landfill 

leachate is intercepted by the well. 

High concentrations of nitrogen were measured in samples from downgradient wells in 2003. 2003 was 

the year that discharge to the leachfield was discontinued because of temporary closing of the Visitor 

Center for reconstruction. Concentrations measured in samples from downgradient wells in 2004 were 

substantially lower than they had been in 2003. When leachfield construction is complete, discharge will 

resume with a system designed to remove more nitrogen. Nitrogen is the principal nutrient of concern 

because of the proximity of Salt Pond, where nitrogen may control aquatic plant growth. Phosphorus 

should also be monitored, because nitrogen input to Salt Pond may have increased so much that the 

limiting nutrient has changed to phosphorus. 

The stainless-steel well installations would be appropriate for sampling trace organic contaminants 

(emerging contaminants) as well as nitrogen and phosphorus. The network should be sampled four times 

per year until a consistent pattern emerges, at which time the 0.5-year interval (table 4) should be used. 

50 
Figure 17. Well network for the septic-system leachfield at the Cape Cod National Seashore 

Visitor Center, Massachusetts. Information about the wells A, B, C, Y, and Z is given in table 3. 

51 
52 

Landfills and Other Hazardous-Waste Sites 

Of the five municipal landfills on or near CACO lands, two are discussed in this protocol in the context of 

designing networks of water-quality monitoring wells. These are the Eastham landfill, from which ground 

water likely discharges to Minister Pond (freshwater) and to Salt Pond (saltwater) (fig. 4, 13, and 18) and 

the Truro landfill, which has produced a leachate plume moving toward freshwater. No CACO project has 

yet (2007) been established to include monitoring of the landfill plumes. Several wells installed during 

the investigations of plumes from nonpoint sources and the Visitor Center are downgradient from the 

Eastham landfill and may be useful for investigation of the landfill plume. 

Eastham Landfill 

The direction of the ground-water flow in the area of the Eastham landfill (fig. 13) may be inferred from 

computer simulations of ground-water flow in the area (fig. 8). The local ground-water flow would likely 

cause a plume from the Eastham landfill to discharge into Minister Pond. The expected heavy nitrogen 

loading of Minister Pond, however, may saturate removal processes, so that some nitrogen may exit 

Minister Pond and move downgradient to Salt Pond. Plume water from the Eastham landfill that is not 

intercepted by Minister Pond would also enter Salt Pond. 

Figure 18. Aerial photograph of Eastham landfill (above white wing), Molls Pond (bottom left), 

and Minister Pond (left above Molls Pond), Cape Cod Massachusetts. Photograph by Barbara 

Dougan, National Park Service. 
One geophysical logging well (MA-EGW-59) between the landfill and Salt Pond has been installed in 

the inferred landfill plume path (figs. 13 and 17, and table 3). Gamma radiation and electromagnetic 

inductance can be logged in the well. Assuming that the well has been correctly placed and the plume is 

shallower than the 45-m well depth, annual logging of the well would record changes in the conductance 

of the saturated zone and thus would show the advance of the landfill plume. 

MLS EGW58 (fig. 13) would also likely intercept plume water from the landfill. Shallow ports of the 

MLS may receive water that has exited from the lake to the aquifer. Deep ports may receive water that 

includes landfill leachate transported under the lake; however, no systematic sampling of this MLS has 

been initiated to date. Additional wells may have to be installed to monitor nitrogen concentrations in 

ground water entering Salt Pond once evidence of the plume has been detected in upgradient wells. 

Downgradient portions of the landfill plume would not be expected to change quickly, so that sampling of 

this MLS once or twice per year for nutrients should be adequate. Trace metals and organic contaminants 

possibly present in landfill leachate would be monitored once every 2 years in locations where groundwater analyses have confirmed the presence of the plume. The MLS (MA-EGW58) was installed near 

Minister Pond in 2003 to a depth of 30 m. 

Truro Landfill 

Access to this landfill may be easier than access to landfills on the lower Cape because of its location 

within the CACO boundary. The simple hydrogeology of the area (no intervening lakes between landfill 

and discharge area) and short distance from the landfill source to the discharge area (the Pamet River) 

should enable an accurate delineation of the boundaries of the landfill plume, the chemical characteristics 

of the plume, and the discharge areas. Surface geophysical conductance measurements could be used to 

mark the center of the plume, and downhole geophysical logging of wells installed along the center line 

of the plume could indicate the depth of the plume. Installation of wells with well screens at the depth of 

maximum of aquifer conductance, as determined from the well logs, could make possible the collection of 

samples of concentrated leachate. 

Data from monitoring wells used in previous studies (Cape Cod Commission, 1989) facilitate plume 

mapping and characterization. Data from analyses of water samples collected from wells installed 

between the landfill and the Pamet River indicate that the landfill plume is moving toward the river. 

Ground-water-flow simulations also indicate that flow would be toward the river (fig. 7). The long period 

of plume formation relative to the likely short traveltime between the landfill and to the hypothesized 

discharge area in the river means that the plume may already discharge there. If so, a distinct discharge 

footprint of the plume could be mapped in the Pamet River using pushpoint samplers to extract ground 

water from the river sediments. 

Similar to the approach used for the Eastham landfill, monitoring at the Truro landfill should be planned 

on the basis of the results from ground-water modeling investigations and water-quality measurements. 

Nitrogen loads can be estimated from nitrogen concentrations measured in water samples taken under the 

landfill and the output from solute-transport models. Following the method used at the Massachusetts 

Military Reservation for the mapping of a nutrient plume entering surface water (McCobb and others, 

2003), a fence of MLSs could be installed on the shore of the Pamet River to intercept the existing plume. 

On the basis of the plume boundary delineated from analysis of water samples collected from the MLS 

fence, the footprint of discharge into the river could be determined by installing temporary or permanent 

drive points in the river sediments. The loading of nitrogen into the Pamet River could be determined by 

multiplying the cross-sectional concentration field determined at MLS fence by the velocities determined 

by the ground-water-flow model. 

53 
The monitoring approaches outlined above would characterize nutrients and trace contaminants in the 

landfill plume, but currently (2007) only the Cape Cod Commission study wells have been installed. A 

full investigation of either the Eastham or the Truro landfill plumes would likely require additional 

funding. 

Other Landfills 

Because landfills are potential major sources of nitrogen and trace contaminants, their effects on CACO 

land may be large. Landfill investigations require large amounts of funding, however, for the installation 

and monitoring of additional sites. Until additional funding becomes available, the data collected in 

previous and ongoing investigations (Provincetown Landfill, Urish and others, 1993; Truro, Cape Cod 

Commission, 1989) should be maintained as part of the CACO long-term-monitoring database. 

Firing Ranges 

No specific monitoring network for firing ranges is included in this protocol. If monitoring at or near 

firing ranges become a priority, however, information presented in the section Munitions and Discharge 

from Firearms in Part One of in this protocol could be used to design a network. 

54 
WELL INSTALLATION

This section can be used as a guide for installing new wells to expand the monitoring network. It can 

also help inform well users about the characteristics, uses, and limitations of wells that are already in 

the network. 

Monitoring-Well Installation 

Well installation has been covered in the companion protocol on hydrologic monitoring (McCobb and 

Weiskel, 2003). The installation of monitoring wells for water-quality monitoring is the same process as 

the installation of wells for determination of ground-water levels. Many wells are used to provide both 

water-level and water-quality information. Well materials and diameter requirements may be more 

restrictive for water-quality sampling, however (non-contaminating materials and a 5.08-cm (2-in.) well 

diameter for pump insertion), than for water-level measurements. 

Multilevel-Sampler (MLS) Installation 

The construction of an MLS according to the sample design and tubing-color conventions described by 

Rudolph and others (1996) facilitates their use by sampling personnel. Planning and careful construction 

of parts are key to the successful installation of an MLS. The samplers consist of joined 3.048-m (10-ft) 

lengths of PVC pipe with color-coded 0.635-cm (1/4-in.) tubing that extends from the ground surface to 

the sampling depth. 

Two forms of the MLS have been used at CACO: the conventional form, with sampling tubes on the 

inside of a 3.18-cm (1 1⁄4-in.) PVC pipe (internal-tube MLS), from which the tubes emerge for sampling 

the water in the aquifer; and a new form, installed at the Gull Pond bathhouse leachfield, with the tubes 

on the outside of a 1.91-cm (3⁄4-in.) PVC pipe (external-tube MLS). The internal-tube MLS is installed 

with a drill rig and hollow-stem auger. The external-tube MLS is installed inside a schedule-40 plastic 

well casing (subsequently removed) by portable drilling equipment. The PVC pipe in the external-tube 

MLS can be used to obtain a water level in the aquifer because the sampling tubes are on the outside. No 

water-level measurements are possible with the internal-tube MLS because there is no extra space inside 

the MLS for a water-level recorder. 

Typically 15 or fewer ports have been used in the conventional internal-tube MLS. The practical limit for 

the number of ports for the internal-tube MLS is determined by the number of sampling tubes that will fit 

inside the diameter of the PVC pipe. The number of ports in the external-tube MLS is limited by the 

number of sampling tubes that will fit between the outside of the PVC pipe and the inside of the schedule40 casing. 

Sampling tubes are color-coded according to depth; the same color code (table 6) has been used for the 

nearly 100 MLS that have been installed by the USGS on Cape Cod. Only 8 colors are available for the 

15 ports. The duplicate colors have a distinguishing tape mark and are designated WT, BKT, for white 

tape, black tape, and so on. The colors listed in table 6 are assigned from the bottom up, so that the color 

corresponding to the greatest depth is always white, the next is black, and so on. When fewer than 15 

ports are used, the upper rather than lower colors are not used. 

55 
Table 6. Assignment of colors to multilevelsampler ports for monitoring at Cape Cod National 

Seashore, Massachusetts. Because colors are 

assigned from the bottom up, samplers with fewer 

than 15 ports lack one or more of the taped colors. 

Port color Color abbreviation 

Purple tape 

Green tape 

Red tape 

Blue tape 

Black tape 

White tape 

Orange 

Gray 

Yellow 

Purple 

Green 

Red

Blue 

Black

White 

PT 

GNT 

RT 

BUT 

BKT 

WT 

O 

GY 

Y 

P 

GN 

 R 

BU 

 BK 

W 

Internal-Tube Construction 

First, diagrams are drawn indicating all sampler dimensions and locations of the sampling ports (fig. 19). 

Second, the materials are assembled (fig. 20). Lengths of PVC pipe are measured (and discrepancies from 

3.048-m (10-ft) lengths noted), numbered from deepest to shallowest, and the following items marked on 

the pipes: (1) locations of all sampling ports, (2) tubing color at each port, and (3) the points 0.3048 m 

(1ft) from the ends of the pipes for use in determining the length of the pipe joint at MSL installation. 

Third, 0.63 cm (1⁄4-in.) holes are drilled in the PCV pipes at the locations of sampling ports with the drill 

pulled down so that tubing will fit through the hole without crimping. Before tubing is attached, couplings 

should be attached with PVC solvent cement only on the upper end of each pipe. The tubing of the correct 

color is threaded through each port and the ends are attached with nylon-mesh covering (stocking) to the 

PVC pipe using stainless-steel wire. The tubing is cut to lengths long enough to reach the surface and 

made ready for stringing by being stretched out on the ground from the PVC pipes to the tubing ends. 

56 
Figure 19. Diagram of multilevel sampler used to plan required lengths of PVC pipe and to 

guide drilling of ports for tubing.

57 
Figure 20. Multilevel sampler before installation at Prince Valley Road. Each pipe 

segment is nominally 10 feet long. Internal tubing emerges through the PVC segments 

at their midsections. 

Stringing the MLS—threading the tubes through the inside of the pipes—is accomplished sequentially, 

beginning with the second deepest pipe, with its tubing attached at ports, by threading through the tubes 

from the deeper pipe. When the stringing is finished for all the pipes, the pipe segments can be folded 

against each other so that the bundled MLS assembly is only about 3 m long, the length of one pipe 

segment (fig. 20). 

Drilling and Installation 

The internal-tube MLS is installed with a hollow-stem drill rig. After augering down to the desired depth, 

the auger toe plate is knocked out and the depth is checked. Once the correct depth has been reached 

inside the auger, the pipes can be lowered, their joints cemented, and the distances between joints 

recorded (fig. 21). (Each glue joint may have a different vertical dimension, which would affect the final 

port depths.) After the complete MLS is inside the drill hole, the sampling tube ends are taped up so that 

they will not be damaged by removing the auger. While the PVC pipe is initially held down, the auger is 

spun out. Sand can be shoveled down the hole and the well finished either with a flush mount or stickup 

(fig. 22). 

58 
Figure 21. Installation of multilevel sampler in hollow-stem auger at 

Prince Valley Road, Truro, Massachusetts. The distance between marked 

sections of two pipes is being measured to determine length of the joint. 

59 
Figure 22. Finished flush-mount multilevel sampler well. Repeat colors are marked with yellow 

tape. 

External-Tube Construction 

External-tube MLS construction is similar to that for internal tubes, except that drilling holes for the ports 

is not necessary because the tubes are on the outside of the PVC pipe, and stringing is not required. The 

tubes may be taped on a PVC pipe in the position required for the sampling port and higher on the pipe, 

but the remainder of the tube is gathered with the other tube remainders and bundled in a coil for 

transportation to the drill site. 

At the drill site, schedule-40 pipe is installed in the ground as for a monitoring well (McCobb and 

Weiskel, 2003). At Gull Pond, 9.1-m (30-ft) MLSs were installed with a portable non-hollow auger. The 

hole was augered to a depth of 9.1 m and the auger spun in place to clean out the hole. Then the auger 

was removed and the hole collapsed below the water table at a depth of about 3 m, but the sediments were 

loose enough to allow the schedule-40 casing to be pushed to the correct installation depth. The casing 

was filled with water to help force it down. The MLS was installed inside the casing and used to push out 

an end cap on the casing. Finally, the casing was removed and the sediment allowed to collapse around 

the MLS. 

60 
Installations For Monitoring Trace Contaminants 

Wells that will be used for monitoring trace contaminants in samples of ground water must be constructed 

of materials that will not contribute to the concentrations of the trace contaminants in the well water. In 

general, appropriate materials for well construction differ according to whether inorganic or organic 

contaminants are being sampled. 

Trace Inorganic Contaminants 

Most trace inorganic contaminants that are measured in water-quality-monitoring programs are trace 

metals, for example, copper, lead, or zinc. Prevention of contamination of well water with trace metals 

from the well casing requires monitoring wells to be constructed of plastic or Teflon. Because metal 

compounds are components of some plastic dyes, well materials that are made of colored plastic must be 

tested for potential contamination of well water before they are used. Teflon, which generally does not 

contaminate well water, may be a necessary material to use for well construction if samples from the 

wells are to be analyzed for low-concentration constituents such as mercury or cadmium. 

Trace Organic Contaminants 

Plastics generally should be avoided as well construction materials if water samples are intended for the 

analysis of trace organic contaminants, because plasticizers in these materials may leach into the well 

water. Plasticizers such as phthalate esters can interfere with the analysis of other trace materials, and may 

themselves be of interest as water contaminants. Stainless steel or Teflon is appropriate for the casings of 

wells that will be for monitoring trace organic contaminants in well water. 

61 
GROUND-WATER-QUALITY SAMPLING 

A detailed description of water-quality sampling of ground water is available in the National Field 

Manual (NFM) for the Collection of Water Quality Data, which is available through the internet 

(http://pubs.water.usgs.gov/twri9A). References to the appropriate chapter of the NFM will be included in 

the sections below as: U.S. Geological Survey, variously dated, chapter number. The NFM descriptions 

can be consulted for more detailed accounts of ground-water-quality sampling and for procedures for 

constituents that are not included here. 

The ground-water-quality sampling methods described here apply to the monitoring networks discussed 

above and to the constituents and water properties listed in table 4. The methods generally are compatible 

with the methods described in the NFM; some procedures (for example, the clean sampling technique) are 

derived from additional references. 

Equipment 

Specialized equipment for pumping the wells, making measurements of water-quality properties in the 

field, and processing water samples that will be analyzed subsequently in a laboratory is required to 

prevent contamination of samples during the sampling procedure. Any equipment touching a water 

sample, or in some cases, being close to a sample, could change constituent concentrations from those 

that are present in the ground water. Exhaust from gas motors, airborne copper from electric motors, or 

metal oxides from corroding equipment could contaminate a sample through transport of fumes or small 

particles in the air. 

Pumps 

Pumps (U.S. Geological Survey, variously dated, chapter 2.1.2.A) are used to transport water from the 

subsurface to the land surface either by suction lift (such as by peristaltic pumps on the land surface) or 

by positive pressure (such as by inertial submersible and centrifugal pumps placed below the water table). 

Sampling of the MLS used in the CACO network requires peristaltic pumps because of the small 

diameter (1⁄4 in.) of the sampling tubes. Samples may be collected from the conventional wells either by 

submersible pumps, or by peristaltic pumps if the water table is within suction depth of the land surface. 

The depth to the water table, the possible exposure of samples to air, and degassing are important 

considerations for choosing a pump. Peristaltic pumps are convenient because they are light, can be run 

with power from a small battery, and are less likely than other types of pumps to contaminate the sample 

because the water contacts only the inside of the pump tubing. Peristaltic pumps with a robust reversing 

switch and variable-speed motor, like the GeoPump, are useful for developing the sampling ports of an 

MLS because they keep the sampling lines clear of clay and silt. Limitations of peristaltic pumps include 

low pumping rates (1 to 2 L/min); the maximum height of suction, about 9 m, and an operational lift as 

little as 6 m (20 ft); degassing from the water sample; and exposure of the sample water to air. Because of 

decreased pressure on the water when suction is applied, gases that were dissolved in the ground water 

may come out of solution (degas). Dissolved gases can also increase in a water sample. Atmospheric 

gases (oxygen) can diffuse through the tubing during the pumping process, especially in the pump head, 

where rollers deform the tubing. Diffusion of oxygen into the water sample can be minimized by selecting 

low-permeability tubing for the pump head. 

Submersible downhole pumps are useful for sampling conventional monitoring wells. As compared to 

perastaltic pumps, submersible pumps have higher pumping rates, can lift water higher, can make use of 

noncontaminating, nonpermeable pump tubing, and do not create a vacuum in the lift portions of the tube. 

Downhole pumps can also be equipped with packers. Packers close off the well bore above the pump. 

They can be used to obtain water samples from deep wells without the need to flush full casing volumes 

to obtain a representative sample. They also prevent oxygen from contacting the sample, which otherwise 

mixes in from the well-water surface. Packer pumps can be used to obtain samples for measurement of 

62 
accurate concentrations of redox-sensitive ground-water constituents (Colman and Friesz, 2001). An 

inexpensive nonpacker model (such as the Purge Pump) will lift water to a height of 18 m (60 ft). 

Grundfos and Keck pumps can pump at variable rates and to a greater height above the water table. 

Tubing, Gloves, and Filters 

The tubing selected (U.S. Geological Survey, variously dated, chapter 2.2.4) for use with peristaltic 

pumps should keep water samples from being contaminated by constituents that may leach from the 

tubing and keep constituents in the water from sorbing to the tubing. The tubing used for pumping an 

MLS is short, so that the effect of the tubing on the constituents usually sampled will be minimal. For 

the monitoring of trace contaminant work, however, the noncontaminating properties of the tubing, 

even tubing used in an MLS, must be verified through analysis of equipment blanks. Pump tubing for 

submersible pumps are typically 30 m long. Usually submersible pump tubing is permanently attached 

to the pump and reused from well to well. Thus, the tubing would need to reach to the bottom of the 

deepest well that is sampled with a given pump. Teflon tubing generally is used in these situations so that 

the pump can be used for all types of network-well sampling without concern about contamination from 

the tubing. 

Disposable gloves (U.S. Geological Survey, variously dated, chapter 2.0.2) should be worn during 

sampling and changed when contaminated. Although disposable gloves are appropriate for sampling, 

care should be taken that sample water does not touch the gloves. 

Capsule, rather than membrane, filters (U.S. Geological Survey, variously dated, chapter 2.2.3) generally 

are most useful for ground-water sampling. The filter pore size should be 0.45 μm. Capsule filters, such as 

AquaPrep 600 Capsules, can be inserted into the sample tubing and will prevent the well water sample 

from exposure to air. Samples filtered before exposure to air will not be subject to changes in redoxsensitive species, such as oxidation and precipitation of iron. AquaPrep 600 capsules were used in the 

network sampling through 2003. Smaller, less expensive filters are available, such as the Millipore 

Milex–HV, hydrophylic PVDF filters. These plug more easily than the bigger filters, but often work for 

ground water, which may be clear of particulate material. 

Temperature, Dissolved Oxygen, pH, and Electrical-Conductance Meters 

Meters used to make field water-quality measurements can be equipped either with multiple probes or 

individual probes. Meters and probes for all of the measurements of water quality that are completed in 

the field—temperature, dissolved oxygen (DO), pH, and electrical conductance—are reviewed in the 

NFM (U.S. Geological Survey, variously dated, chapter 6.3.1). A multiple probe meter (fig. 23) with 

flow-through cell (fig. 24) (U.S. Geological Survey, variously dated, chapter 6.0.3B) produces data that 

are accurate enough for most purposes, although the most accurate electrical conductance and pH values 

can be obtained with separate meters, such as the Orion 115A conductance meter and a separate pH meter 

with a Ross Electrode pH probe. Meters such as the Orion 115A measure temperature and conductance 

and can be run in a mode to display conductance results corrected to 25°C. The Ross pH electrode 

responds quickly and accurately in water of low conductance, such as the ground water on Cape Cod. 

63 
64 

Figure 23. Filling the Hydrolab multimeter calibration chamber to just below the 

level of the dissolved oxygen membrane. After the cap is screwed on, and 100 percent 

humidity has developed in the chamber, calibration can proceed. 
65 

Figure 24. Flow-through cell for field measurements of water quality. 
Field-Meter Calibration and Measurement 

Whether or not a multiple probe meter is used, field meters must be calibrated before use. In small field 

areas such as the CACO, where overnight field trips are not necessary, calibrations can be completed at 

the laboratory, and with the exception of temperature, at the beginning of each day of sampling. 

Temperature probes should be calibrated twice per year. 

Logbook and Field Forms 

Calibration data for field equipment should be stored in two places: with the primary water-quality 

records in the project office (on calibration field forms, appendix 1) and in a logbook kept with the field 

meter. Logbooks for field meters should identify the meter by manufacturer, model description, and serial 

or property number and contain records of calibration and any adjustments or repairs made to the meter. 

When more than one field site is sampled on the same day, the calibration field form should be duplicated 

so that a copy can be attached to the data sheets that are filed for each site. 

Temperature 

Usually, thermistors rather than liquid-in-glass thermometers are used to measure temperature, and must 

be calibrated in each instrument that includes the thermistors—the multiple probe instrument, the 

conductance meter, and the pH meter. Detailed temperature-calibration instructions are in U.S. Geological 

Survey, variously dated, chapter 6.1.2. 

Calibration 

1. The frequency of calibration is once every 6 months. 

2. Calibration should be against a National Institute of Standards and Technology traceable 

thermometer in a beaker of stirred water that is insulated against heating from the stirring plate by 

a Styrofoam pad. 

3. The calibration checks should include the range of temperatures anticipated in the field, such as 

from ice water to room temperature. 

4. For routine ground-water work, temperature sensors should be accurate to within 0.1°C. 

Measurement 

1. For the true temperature of the water in an aquifer, measure the temperature of water downhole in 

a well, as described by Lapham (1989), or 

2. Measure the temperature of well water in a flow-through cell at the surface to give a result close 

to the temperature of the water in the aquifer. The accuracy of the measurement depends on 

whether flow through the pump tubing alters the water temperature before the water reaches the 

temperature probe. 

3. Record the temperature of the water at the surface in association with measurements of 

conductance, dissolved oxygen, and pH. 

4. Record temperature to the nearest 0.1°C. 

66 
Electrical Conductance 

Electrical conductance (U.S. Geological Survey, variously dated, chapter 6.2.1) is a measure of the 

capacity of water to conduct an electrical current. Electrical conductance is a function of the types and 

concentrations of dissolved ions in water. Specific conductance, which is the conductance measure 

usually reported, is electrical conductance adjusted to 25°C. The purpose of the calibration procedure is to 

verify that the cell constant and temperature correction are set correctly. Procedures for calibrating 

conductance meters vary (U.S. Geological Survey, variously dated, chapter 6.3.2). Meters may or may not 

be adjustable and may or may not have built-in temperature compensation. Calibration procedures are: 

Calibration 

1. The frequency of calibration is once during each day of use. 

2. Use two KCl calibration standards that bracket the range of conductance expected. 

3. Rinse the conductance probe and container with three rinse aliquots of standard before filling the 

container a fourth time for a reading. 

4. Immerse the probe and dislodge any bubbles that may be adhered to the conductance probe. 

Record the temperature, conductance, and cell constant for each standard, adjusted to 25°C, both before 

and after any meter adjustments in microsiemens per centimeter at 25 degrees Celsius (μS/cm at 25°C). 

Measurement 

1. Rinse the probe and measuring container with sample water three times to ensure that no solution 

remains from the last sample. 

2. Immerse the probe in the sample and dislodge any bubbles that be adhered to the probe. 

3. Record sample temperature and specific conductance (conductance corrected to 25°C) on the 

field forms. 

4. The probe should be cleaned for storage soon after use by rinsing in distilled water and wiping 

dry with a lab paper tissue. 

pH 

Details of pH measurement and calibrations are in the U.S. Geological Survey, variously dated, chapter 

6.4. Standardization of pH electrodes requires two pH buffer standards—one of pH 7 and another which, 

with the pH-7 buffer, brackets the expected pH range. For Cape Cod ground water, appropriate standards 

are pH 7 and pH 4. 

67 
Calibration 

1. The frequency of calibration is once during each day of use. 

2. Determine if pH filling solution is needed. For the Ross pH electrode, filling solution should be 

supplied through the hole in the side of the electrode to a level higher than that in the sample 

when the probe is immersed in the sample (fig. 25). Filling solution should be flowing out 

through the liquid junction in the bottom of the probe driven by the difference in height between 

the levels of fluid inside the probe and outside the probe in the sample. (The flow is too small to 

be visible.) Also the filling hole must be left open during measurement to facilitate the flow of 

solution; if air cannot move in to replace the solution, it will stop flowing. When the probe is not 

in use, the filling hole can be closed to keep solution from running out if the probe is stored 

horizontally. 

3. The reference electrode (fig. 23) of the Hydrolab needs to be supplied with KCl filling solution 

every 2 weeks. 

4. Start the calibration with the buffer of pH 7. Rinse the pH and temperature electrodes in three 

aliquots of buffer before filling the beaker for the calibration and recording the pH and 

temperature. 

5. Using the zero adjust, calibrate the meter to the actual pH of the buffer at that temperature. 

(A complication is that the standard buffers change pH slightly as a function of temperature.) 

6. Rinse the beaker and electrodes with distilled water and blot them dry with a lab tissue. 

7. Rinse the electrodes and beaker with three aliquots of the second buffer. Record the initial pH, 

and then adjust the slope control to read the actual pH of the buffer at the measured temperature. 

8. Record the calibration slope of the relation between pH and the potential difference between 

electrodes. 

68 
69 

Figure 25. Filling the Ross pH probe with KCl filling solution. The level of the filling solution 

should be above the level of the surface of the sample during measurement. 
Measurement 

pH can be measured by multiple probe in a flow-through cell or in a separate sample drawn just for pH 

measurement. Because the dissolved carbon dioxide concentration in the water can affect pH, 

measurement by use of a flow-through cell might be preferable if degassing of carbon dioxide from a 

sample is likely; the flow-through cell minimizes the time during which carbon dioxide could leave the 

sample. Measurement of low conductance ground water like that on Cape Cod is more accurate by Ross 

electrode, however, which responds more quickly than other pH probes in low conductance water. 

1. Rinse the electrodes and beaker with three aliquots of the sample solution. 

2. Immerse the electrodes in the sample and record the pH to hundredths of a unit. 

3. Record the temperature of the sample when measuring pH, but do not correct pH to a standard 

temperature. 

Dissolved Oxygen 

The concentration of dissolved oxygen (DO) can be measured by an electrode method, the Winklertitration method, or by spectrophotometric methods. The electrode method is accurate to 0.1 mg/L oxygen 

at concentrations above 1.0 mg/L, if the temperature of the electrode during calibration has been at or 

near the temperature of the sample water. The Winkler titration method is more cumbersome but more 

accurate than the electrode, especially at low DO concentrations at which precise electrode-method 

results are not possible. The Winkler and spectrophotometric methods are described in the NFM 

(U.S. Geological Survey, variously dated, chapter 6.2). 

Calibration

A DO probe can be calibrated in water-vapor-saturated air, which has a constant proportion of oxygen 

(U.S. Geological Survey, variously dated, chapter 6.2). A calibration chamber with 100-percent humidity 

is used. 

1. Check for bubbles beneath the DO electrode membrane (fig. 23), which indicate damage or loss 

of electrolyte filling solution. Change the membrane immediately if damaged and otherwise once 

per month. Record membrane changes in the record book. 

2. Turn the multiple probe meter so that the DO membrane faces up (fig. 23). Pour water into the 

calibration chamber to a water level that approaches but does not cover the membrane. 

3. Cap the chamber and wait 5 minutes for the humidity to build up to 100 percent in the chamber. 

4. Read and record on the calibration field form and in the instrument logbook the atmospheric 

pressure from a barometer and the temperature of the probe in the calibration chamber. 

5. Look up and record the value of the DO concentration at saturation for the measured pressure and 

temperature (table 7). 

6. After the 5-minute wait, record the reading of the DO sensor in the chamber. Finally, adjust the 

meter to the value for 100-percent DO saturation determined in the table. The DO meter should 

not drift more than 1 mg/L per day; a drift larger than this indicates that the meter or probe needs 

to be serviced or replaced. 

7. Store the DO probe with water in the chamber so that the membrane does not dry out. 

70 
Table 7. Solubility of oxygen in water as a function of temperature and pressure. 

[mmHg, millimeters of mercury; oC, degrees Celsius]

Tem- Atmospheric pressure, in mmHg perature 790 785 780 775 770 765 760 755 750 745 740 735 730 725 in oC 720 

 

0 15.2 15.1 15.0 14.9 14.8 14.7 14.6 14.5 14.4 14.3 14.2 14.1 14.0 13.9 13.8 

1 14.7 14.7 14.6 14.5 14.4 14.3 14.2 14.1 14.0 13.9 13.8 13.7 13.6 13.5 13.4 

2 14.3 14.3 14.2 14.1 14.0 13.9 13.8 13.7 13.6 13.5 13.4 13.3 13.3 13.2 13.1 

3 14.0 13.9 13.8 13.7 13.6 13.5 13.4 13.3 13.3 13.2 13.1 13.0 12.9 12.8 12.7 

4 13.6 13.5 13.4 13.3 13.3 13.2 13.1 13.0 12.9 12.8 12.7 12.6 12.6 12.5 12.4 

 

5 13.3 13.2 13.1 13 12.9 12.8 12.7 12.7 12.6 12.5 12.4 12.3 12.2 12.2 12.1 

6 12.9 12.8 12.8 12.7 12.6 12.5 12.4 12.3 12.3 12.2 12.1 12.0 11.9 11.8 11.8 

7 12.6 12.5 12.4 12.4 12.3 12.2 12.1 12.0 12.0 11.9 11.8 11.7 11.6 11.6 11.5 

8 12.3 12.2 12.1 12.1 12.0 11.9 11.8 11.7 11.7 11.6 11.5 11.4 11.3 11.3 11.2 

9 12.0 11.9 11.8 11.8 11.7 11.6 11.5 11.5 11.4 11.3 11.2 11.2 11.1 11.0 10.9 

 

10 11.7 11.6 11.6 11.5 11.4 11.3 11.3 11.2 11.1 11.0 11.0 10.9 10.8 10.7 10.7 

11 11.4 11.4 11.3 11.2 11.2 11.1 11.0 10.9 10.9 10.8 10.7 10.6 10.6 10.5 10.4 

12 11.2 11.1 11.0 11.0 10.9 10.8 10.8 10.7 10.6 10.5 10.5 10.4 10.3 10.3 10.2 

13 10.9 10.9 10.8 10.7 10.7 10.6 10.5 10.4 10.4 10.3 10.2 10.2 10.1 10.0 10.0 

14 10.7 10.6 10.6 10.5 10.4 10.4 10.3 10.2 10.1 10.1 10.0 9.9 9.9 9.8 9.7 

 

15 10.5 10.4 10.3 10.3 10.2 10.1 10.1 10.0 9.9 9.9 9.8 9.7 9.7 9.6 9.5 

16 10.2 10.2 10.1 10.0 10.0 9.9 9.8 9.8 9.7 9.6 9.6 9.5 9.5 9.4 9.3 

17 10.0 10.0 9.9 9.8 9.8 9.7 9.6 9.6 9.5 9.4 9.4 9.3 9.3 9.2 9.1 

18 9.8 9.8 9.7 9.6 9.6 9.5 9.4 9.4 9.3 9.3 9.2 9.1 9.1 9.0 8.9 

19 9.6 9.6 9.5 9.4 9.4 9.3 9.3 9.2 9.1 9.1 9.0 8.9 8.9 8.8 8.8 

 

20 9.4 9.4 9.3 9.3 9.2 9.1 9.1 9.0 8.9 8.9 8.8 8.8 8.7 8.6 8.6 

21 9.2 9.2 9.1 9.1 9.0 8.9 8.9 8.8 8.8 8.7 8.6 8.6 8.5 8.5 8.4 

22 9.1 9.0 9.0 8.9 8.8 8.8 8.7 8.7 8.6 8.5 8.5 8.4 8.4 8.3 8.2 

23 8.9 8.8 8.8 8.7 8.7 8.6 8.6 8.5 8.4 8.4 8.3 8.3 8.2 8.1 8.1 

24 8.7 8.7 8.6 8.6 8.5 8.4 8.4 8.3 8.3 8.2 8.2 8.1 8.0 8.0 7.9 

 

25 8.6 8.5 8.5 8.4 8.3 8.3 8.2 8.2 8.1 8.1 8.0 8.0 7.9 7.8 7.8 

26 8.4 8.4 8.3 8.3 8.2 8.1 8.1 8.0 8.0 7.9 7.9 7.8 7.8 7.7 7.6 

27 8.3 8.2 8.2 8.1 8.0 8.0 7.9 7.9 7.8 7.8 7.7 7.7 7.6 7.6 7.5 

28 8.1 8.1 8.0 8.0 7.9 7.9 7.8 7.7 7.7 7.6 7.6 7.5 7.5 7.4 7.4 

29 8.0 7.9 7.9 7.8 7.8 7.7 7.7 7.6 7.6 7.5 7.5 7.4 7.3 7.3 7.2 

 

30 7.8 7.8 7.7 7.7 7.6 7.6 7.5 7.5 7.4 7.4 7.3 7.3 7.2 7.2 7.1 

71 
Measurement 

1. Turn on the stirring device in the multiple probe meter. 

2. Immerse the DO probe in the water sample. 

3. Record the DO concentration, temperature, and percent saturation. 

Alkalinity and Acid-Neutralizing Capacity 

Alkalinity and acid-neutralizing capacity (ANC) are measures of the ability of a sample to neutralize 

strong acid (U.S. Geological Survey, variously dated, chapter 6.6). These quantities are determined by 

acid titration of a sample to either the inflection point of the titration curve or fixed pH value designated 

as the endpoint of the titration. The difference between the procedures for measuring alkalinity and ANC 

is that the alkalinity sample is filtered, whereas the ANC sample is not filtered. Particulate concentrations, 

which cause the difference between alkalinity and ANC, are difficult to measure in ground water because 

pumping of well water stirs up particulates in the well resulting in particulate concentrations that are not 

necessarily the same as particulate concentrations of ground water in the aquifer. Therefore alkalinity 

measurements of filtered samples, rather than ANC measurements, are recommended for most groundwater investigations. 

Determination of Alkalinity 

Alkalinity in most natural waters is attributable to the presence of bicarbonate and carbonate ions, in 

proportions determined by the pH of the sample. The fact that the pH of most ground water is less than 

8.3, the pH of equal concentrations of carbonate and bicarbonate ions, indicates that most ground water 

contains more bicarbonate ions than carbonate ions. Alkalinity may also include contributions from 

borates, phosphates, silicates, or other bases, including hydroxide, which would combine with acid during 

the titration. 

Alkalinity determination should be completed as soon as possible after sample collection. Although not as 

strongly affected by air contact as a dissolved oxygen measurement would be, alkalinity should be 

measured in the field to minimize the period of exposure to air before titration. Exposure to air can affect 

alkalinity through degassing or chemical precipitation. Gain or loss of CO2

 does not affect the total 

alkalinity of a sample, although it does affect proportions of bicarbonate to carbonate. Introduction of 

oxygen may cause oxidation of reduced iron, which releases acid and would change the alkalinity. 

Immediate titration is most important for anaerobic samples that have dissolved iron concentrations 

greater than 1 ppm. If a sample must be stored, it must be kept in a stoppered glass biological oxygen 

demand (BOD) bottle in the cold (4°C) and in the dark, but for not longer than 24 hours before titration. 

The USGS commonly obtains alkalinity titration acid, of 0.16 or 1.6 normality, from the Hach company. 

Most CACO samples can be titrated successfully by adding 0.16 normal acid to a 100-mL sample. Some 

ground-water samples that contain appreciable concentrations of organic carbon (such as downgradient 

from wetlands or landfills) will have much larger alkalinities. For these samples, higher concentrations of 

acid (1.6 normal) and smaller sample volumes (50 mL) can be used. The object is to use enough titrant so 

that its volume can be accurately measured. 

72 
73 

Measurement 

1. Filter the alkalinity samples with the 0.45-μm flow-through disposable filter capsule. Collect a 

sample for alkalinity by directing the outflow from the capsule filter to the bottom of the sample 

container. Allow three volumes of overflow to flush away sample water that has contacted air. 

2. Set up a beaker, magnetic stirring plate, titrant dispenser, and the calibrated pH meter for a 

titration (figs. 26 and 27). 

3. Use three rinses of the beaker and probes that will touch the sample to remove any acid from the 

previous sample. Because titrations end at pH 3.0, a small amount carried over from the previous 

sample will decrease the initial pH of the next sample. 

4. After the rinses, the beaker and electrodes should be dried with a lab tissue. 

5. Measure out the sample (usually 50 mL) with a cleaned plastic 100-mL graduated cylinder. Pour 

the sample into a beaker with magnetic stirring bar. 

6. Insert the pH electrodes into the sample, wait for equilibration, and record the pH of the unstirred 

sample. 

7. Start the magnetic stirring at a slow but constant rate. Use a Hach titrator to deliver the acid to the 

titration sample (fig. 27). Use a constant time interval between additions of acid, and, after every 

addition, write down the pH and volume of acid added. Continue the titration to pH 3.0. 

8. Analyze the titration curve to determine the titration endpoint and alkalinity. Alkalinity 

determined by fixed endpoint, inflection point, and Gran plot methods can all be determined 

quickly by computer program (U.S. Geological Survey, 2003). Alternatively, alkalinity can be 

determined by using the formula on the alkalinity field forms (appendix 2). 

Figure 26. pH meter for alkalinity measurements. 
Figure 27. Addition of acid during titration. 

74 
Well Purging and Field Measurements of Water Quality 

Water in the well casing must be removed and replaced, prior to sample collection, with water drawn in 

through the well screen from the aquifer. The well is pumped, or purged, to exchange the water. Purging 

is necessary so that the composition of the water sample collected is as close to the composition of the 

aquifer as is possible. For a conventional well, three well-casing volumes must be purged before 

sampling. The well-casing volume equals the well cross section times the distance from the water table to 

the bottom of the well. For wells with a packer pump, only three times the volume of the casing below the 

packer needs to be purged. Purging can stir up more sediment into the water from the bottom of the well 

than would be representative of the water in the aquifer. Low-flow purging and sampling has been 

proposed to overcome this problem (Sevee and others, 2000). Low-flow sampling, however, takes a long 

time and may still not produce completely representative samples; for instance, oxygen may be entrained 

from the water-column surface. This protocol recommends conventional purging, sampling, and inline 

filtration of samples to remove particulates. 

Casing volume in the sampling tubes of an MLS is small, about 560 mL for 45 m of tubing. Also, because 

water mixing in an MLS is less than in a conventional well casing, purging 1 L before collection of water 

samples is sufficient for any MLS sampling port. 

Measurements of temperature, electrical conductance, pH, and alkalinity must be completed during or 

close to the time of sampling. Except for alkalinity, which is determined by titration, these measurements 

can be used to monitor the process of well purging. The effectiveness of purging can be checked by 

determining whether measurements of each quantity have reached a constant value. A constant value 

would indicate that the original water in the well casing had been completely replaced with water from 

the aquifer. 

The usual device for monitoring water quality during purging is the multiple probe meter with a flowthrough cell (fig. 24). Operation of the multiple probe meter probe with a flow-through cell involves the 

following steps: 

1. After the probes have been calibrated, turn on the pump (fig. 28); all or part of the pumped water 

will be routed through the flow-through cell. Although flow is continuous through the cell, the 

oxygen-probe stirrer must be turned on for accurate oxygen measurements. 

2. Periodically record water-quality measurement from the multiple probe meter on a well purge log 

data sheet (appendix 3). 

3. When the measurements have stabilized, record the final readings and the time of sampling on the 

field form (conventional well appendix 4 or MLS, appendix 5). The station number, date, and 

time constitute a unique sample designation, which is used to identify the final values of each 

water-quality measurement completed in the field as well as for the samples collected for any 

additional analyses in the laboratory. 

4. After the well is purged, collect water for determination of alkalinity by disconnecting the flowthrough cell and inserting a capsule filter on the pump tubing. 

75 
Figure 28. Geopump set up for pumping multilevel sampler ports. 

Collection of Water Samples 

After calibration of instruments, purging of the well, and determination of field water-quality properties, 

water samples intended for analysis in a laboratory are collected. Determination of which bottle materials, 

handling procedures, and preservation methods are appropriate depends on constituent and concentration 

range of interest (table 5). 

Preventing Sample Contamination and Cross Contamination 

Keeping sample equipment and bottles clean is an important part of any ground-water-quality monitoring 

program. For ultra-low-level constituents like mercury, whose range in concentrations is at the low 

nanogram-per-liter level, extraordinary measures must be taken during sampling to prevent sample 

contamination. Even for constituents such as nitrogen and phosphorus with concentrations in the low 

microgram-per-liter levels, care must be taken to keep sampling equipment and bottles clean. For 

analyses of dissolved phosphorus, small amounts of dust (phosphate is in many cleaners, detergents, and 

in pH buffer) can alter sample concentrations. 

76 
Measures that help prevent contamination during sampling include: 

1. Keeping sample bottles in new plastic bags before and after sampling; 

2. During sampling, not allowing bottles to touch surfaces that might be contaminated; 

3. Keeping bottles on a clean surface and using a clean bottle-holder rack (carry it around in a 

plastic bag) to keep bottles upright, even under windy conditions; 

4. Wearing plastic gloves during bottle handling and changing them after touching contaminated 

surfaces. For example, gloves protect samples from lotions applied to skin to prevent sunburn, 

which have been found to contaminate samples with zinc; and 

5. Preventing contamination of samples during sample preservation. Preservatives contain high 

concentrations of chemicals. Care must be taken that fumes from preservative acids, HNO3

 or 

HCl, for example, do not contact samples intended for analysis of the acid anion constituent, 

NO3

-

 or Cl-. 

In collecting water samples for analyses of constituents present at very low concentrations (nanograms 

per liter), the protocol designated “clean hands-dirty hands” is used (U.S. Geological Survey, variously 

dated, chapter 4.0.1). The collection of samples for mercury analysis, for example, involves two people, 

one designated “clean hands” and the other “dirty hands,” and specially cleaned bottles that are double 

bagged (usually plastic Ziploc bags are used). Contamination is prevented by allowing only clean hands 

to manipulate the inner bag and bottle contained therein. The steps are: 

1. The gloved dirty-hands person opens the outer bag and presents the inner bag with sample bottle 

to the gloved clean-hands person. 

2. The inner bag is extracted and opened by clean hands only. 

3. The clean-hands person removes the bottle from the inner bag and fills it with sample water. 

4. After the sample is in the bottle, the clean-hands person puts the bottle back in the inner bag and 

stuffs it into the outer bag, which is held open by the dirty-hands person. 

5. Finally, the dirty-hands person puts the doubled bagged bottle away in a plastic bag that carries 

all the samples. 

Labeling Sample Bottles 

Labeling sample bottles includes the following steps: 

1. Create labels for all sample bottles with lines or spaces for station, date, time, and intended 

analyses. 

2. Print the labels on waterproof paper with adhesive back (for example, Avery labels). Microsoft 

Word/tools/letters and mailings/mail merge wizard/ can be used to set up the template and merge 

the data to create the labels. 

3. Apply the labels to the bottles before filling the bottles. This will ensure that no bottle is 

mislabeled and that the labels stick to the bottles. 

Filling Sample Bottles 

1. Generally, bottles are rinsed three times by shaking at least 30 mL of sample water in the bottle 

with the cap on and discarding the water before the final filling with sample. 

2. For filtered samples, a capsule filter with 0.45-μm pore size is attached to the pump line to filter 

samples inline before collection into bottles. 

3. For whole-water samples, the filter is removed and samples pumped directly to bottles. 

77 
Prevention of Degassing and Maintenance of Anaerobic Conditions 

Degassing and contamination of ground-water samples by oxygen are potential problems in ground-water 

sampling. Water in deep wells is under multiple atmospheres of pressure (one atmosphere is about 10 m 

of water), and, as a result of bacterial decomposition of organic matter, may contain large amounts of 

dissolved gases (such as CO2

 and CH4). Concentrations of gases in excess of equilibrium with one 

atmosphere of pressure will degas when brought to the surface. Loss of carbon dioxide would cause pH to 

decrease and the proportions of the components of alkalinity (carbonate and bicarbonate) to change, but 

would not affect the total alkalinity. Most ground-water samples, however, contain only bicarbonate 

alkalinity so that altered proportions of bicarbonate and carbonate alkalinity are not a concern. Degassing 

can be minimized by using submersible pumps to obtain samples rather than suction pumps. 

Ground water is typically either low in oxygen concentration (below atmospheric equilibrium) or, 

occasionally completely anaerobic. When anaerobic samples contact air, concentrations of oxygen and 

reduced species (for example, NH3

, As (III), Fe (II), and Mn (II)) can change dramatically. When iron 

oxidizes, it precipitates as iron hydroxide and can substantially change dissolved concentrations of other 

species, such as arsenic and phosphate, that coprecipitate with it. Commonly the sample is filtered inline, 

and then the sample is acidified to keep iron and other constituents in solution. 

Sample Preservation 

Samples often need to be preserved with chemicals (acids are used in this protocol) or kept cold so that 

water-quality constituents do not change before analysis (table 5). Because sample bottles are to be rinsed 

with sample water, preservation acids must be added in the field after the sample is collected. Acid can be 

conveniently applied in the field by counting drops from a Teflon dropping bottle (fig. 29). Teflon does 

not degrade, even in contact with strong acids. The number of drops required to bring the sample to a 

given preservation pH can be determined by titration of the sample with the acid. The possibility of 

sample contamination is high during preservation because most preservatives are concentrated chemicals 

(fig. 30). Samples should be acidified outside in the field or in a fume hood in the laboratory to prevent 

personnel from breathing in acid fumes and to prevent sample contamination. Storing preserved samples 

in separate plastic bags for each preservative added is also good practice. 

78 
Figure 29. Preservation of samples by using concentrated acid from a Teflon dropping bottle. 

79 
80 

Figure 30. Potential contamination problems are associated with samples that are opened in a 

laboratory, for example, during preservation by acid addition. 
QUALITY-ASSURANCE PROCEDURES 

Quality of data can be verified by use of QA sample blanks, analyte-spike solutions, and sample 

duplicates. So that QA data can reflect the effects of those processes and problems that occur in field 

work, most QA samples in a sampling program are generated in the field. Sampling equipment and 

bottles must be cleaned and protected during transportation in a standard way so that a minimal number of 

QA samples will be sufficient to describe and document sampling error. Because the ground-waterquality monitoring program at the CACO is designed to continue for a long period, a small fraction of the 

total number of samples—for example between 5 and 10 percent—is required to be duplicates and blanks. 

The QA samples can be pooled from several sampling rounds to calculate QA statistics. Thus, one 

duplicate sample for each constituent at one port of a 15-port MLS is appropriate, or one blank sample for 

each MLS. A greater percentage of duplicates and blanks is needed to define QA for the conventional 

monitoring wells (20 percent) because fewer samples will be generated during each round of sampling at 

a monitoring well. 

Field spikes of analyte into samples are appropriate QA procedures for investigations of metals, VOCs, or 

trace organics. Recovery investigations of spikes are recommended to determine if the particular water 

matrix is affecting results or if analyte is being lost on equipment, such as bottles and filters in contact 

with the sample. 

81 
DATA MANAGEMENT 

Data management is as important as data collection for the success of a long-term monitoring program. 

Management includes both computations and storage of the data. 

Data Computations 

Two types of data analysis can be defined: the analysis of QA data, and analysis of data from the field. 

For QA data analysis, variance should be computed on duplicate samples from each constituent analyzed 

and compared to the variance computed from laboratory splits. This computation is described for mercury 

data by Colman and Breault (2000). The variances reflect variability of the data caused by random error 

associated with sampling and analysis. If the variance associated with field duplicates is not greater than 

that of laboratory splits, then the random contamination of samples during sampling (such as from dust or 

oxide coatings on sampling equipment) is not a problem. Blank samples and equipment blank samples 

should be compared to determine the extent of any systemic contamination associated with the leaching 

of constituents into samples from sampling equipment or from preservation chemicals. Finally, spike 

recoveries should be computed to determine if the sample matrix is causing an incomplete response from 

known additions of spiked analyte. 

Water-quality data from the ground-water protocol should be analyzed first for time trends. Statistical 

methods for analysis of time trends in water-quality data are covered by Helsel and Hirsch (1992) and for 

data including “less than” values by Helsel (2005). Other more complex analyses beyond the scope of this 

protocol may also be warranted. In particular, solute-transport modeling based on calibration data 

collected through the ground-water-quality protocol might be needed to simulate nutrient loading to 

estuaries. 

Maintenance of Project Files and Records 

In a long-term monitoring program, records must be clearly understood so that data can be used and 

interpreted years after collection. In addition to computer databases, paper records are still used by the 

USGS and archived to store data. 

Primary-Record Files 

Today, record keeping is more commonly done by computer rather than paper files. The convenience and 

reliability of paper files used in the field, however, mean that paper records of field notes and fieldinstrument calibrations are still in common use. Recently, more of these “original” records are actually 

generated by computer, such as analytical results from a laboratory-information management system. For 

each well sampled, the field forms with results of measurements completed in the field, instrument 

calibrations, analytical request forms, and paper results from the lab should be kept in primary-record 

files sorted according to station ID number. For MLS, however, all data from one MLS is kept in one file, 

even though each port of every MLS has a different station ID number. 

Water-quality measurements made in the field and the purging data for each monitoring well sampled are 

recorded on a field-data form. Example forms are in appendixes 3 and 4. Field forms for MLS are similar, 

except that data from all levels of sampling ports can be recorded on one sheet (appendix 5). For each 

field alkalinity measurement, an alkalinity-titration sheet (appendix 2) should be completed and filed in 

the sample primary record. 

The analytical-services request form, also included in the primary record file, records the analyses 

requested of the laboratory and the bottle types and preservatives used in the samples that were sent to the 

laboratory (appendix 6). Finally a paper copy of the analytical results that are returned from the laboratory 

should be kept in the primary record file (appendix 7). 

82 
Field Notebook 

Use a bound notebook with numbered pages. The first 3 pages should be reserved for a table of contents 

to be compiled as the notebook is filled. Photocopies of new sections of the book should be made 

periodically and kept in the office as a backup in case the field notebook is lost. Record general notes 

about the sites, dates, times, and samples collected. The notebook serves as a chronological record of 

what was sampled. The same information is in the primary record files, but is not a chronological record 

of the field work. 

Meter-Calibration Logbook 

Equipment calibration information for the field meters is recorded in bound notebooks kept with the 

meters. These records are used to keep track of the accuracy of the instruments and to prove that the fieldmeasured properties are accurate. The calibration data for each meter for each day should be photocopied 

from the meter book and kept as part of the primary record file for sampling of a well or MLS. 

Database 

Electronic data storage is an important component of long-term monitoring programs. Databases should 

contain sufficient ancillary and QA data that results can be fully interpreted when retrieved. The database 

must be maintained and moved without error from one computer platform to the next and possibly from 

one software data-management system to the next, because platforms and systems become obsolete and 

are periodically replaced. The USGS database for water quality, QWDATA, meets these requirements. 

The use of this database for CACO data is now under review. 

Archiving Procedures 

Typically data records are kept in file cabinets in the office of the project chief. Records need to be kept 

up to date and available for reference during project report writing and for project reviews. 

When the volume of files for long-term projects becomes very large, the files may need to be put in a 

permanent storage facility. Archiving space is available in Federal storage facilities and is an appropriate 

location for primary records and other project materials when space in the office becomes inadequate. 

83 
REFERENCES CITED 

AMEC, 2001, Final IAGWSP technical team memorandum 01-6 central impact area 

groundwater report, for the Camp Edwards impact area groundwater quality study, 

Massachusetts Military Reservation Cape Cod, Massachusetts: AMEC Earth and 

Environmental Inc., Westford, Mass. 

Baier, W.G., and Cohn, T.A., 1993, Trend analysis of sulfate, nitrate and pH data collected at 

National Atmospheric Deposition Program/National Trends Network stations between 1980 

and 1991: U.S. Geological Survey Open-File Report 93–56, 13 p. 

Cape Cod Commission, 1989, Hydrogeologic assessment of the Truro landfill: Water Resources 

Office of the Cape Cod Planning and Economic Development Commission, November 1989. 

Cape Cod National Seashore, 2000, Water-resources management plan for Cape Cod National 

Seashore, accessed January 23, 2003, at 

http://www.nps.gov/caco/management/water_resources_plan/index.html

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88 

Appendix 1. Example of a field-meter-calibration form. 
89 

Appendix 2. Example of an alkalinity-calculation field form. 
90 

Appendix 3. Example of a well-purge log. 
91 

Appendix 4. Example of a conventional-well field form. 
92 

Appendix 5. Example of a multilevel-sampler field form. 
93 

Appendix 6. Example of an analytical-services request form. 
94 

Appendix 7. Example of a laboratory-analysis results form. 
Prepared by Publications Service Centers 1 and 2

For more information concerning the research in this report, contact:

Wayne H. Sonntag, Director

U.S. Geological Survey

MA/RI Water Science Center

10 Bearfoot Rd.

Northborough, MA 01532

or visit our Web site at:

http://ma.water.usgs.gov
Colman—Monitoring Ground-Water Quality in Coastal Ecosystems—Open-File Report 2007–1149

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