QUALITY OF WET DEPOSITION IN THE 

GRAND CALUMET RIVER WATERSHED, 

NORTHWESTERN INDIANA, 

JUNE 30, 1992-AUGUST31, 1993

By Timothy C. Willoughby

Prepared in cooperation with the

INDIANA DEPARTMENT OF ENVIRONMENTAL MANAGEMENT

U.S. GEOLOGICAL SURVEY 

Water-Resources Investigations Report 95-4172

Indianapolis, Indiana 

1995
U.S. DEPARTMENT OF THE INTERIOR 

BRUCE BABBITT, Secretary

U.S. GEOLOGICAL SURVEY 

Gordon P. Eaton, Director

For additional information, write to: 

District Chief 

U.S. Geological Survey 

Water Resources Division 

5957 Lakeside Boulevard 

Indianapolis, IN 46278-1996

Copies of this report can be purchased from:

U.S. Geological Survey

Earth Science Information Center

Open-File Reports Section

Box25286, MS 517

Denver Federal Center

Denver, CO 80225
CONTENTS

Abstract.................................................................................... 1

Introduction................................................................................. 2

Purpose and Scope ........................................................................ 2

Site Location............................................................................. 3

Acknowledgments ........................................................................ 3

Methodology ................................................................................ 3

Sampling Site Selection .................................................................... 3

Constituent Selection and Analytical Techniques ................................................. 3

Collector Modifications .................................................................... 6

Equipment Cleaning....................................................................... 8

Sample Collection and Processing............................................................ 9

Water-Sample Analysis .................................................................... 10

Quality of Wet Deposition...................................................................... 11

Quality Assurance............................................................................ 25

Laboratory Quality Assurance ............................................................... 28

Field Quality Assurance.................................................................... 28

Summary ................................................................................... 33

References Cited ............................................................................. 35

Supplemental Data............................................................................ 37

FIGURES

1. Map showing location of wet-deposition sampling site at the Gary (Indiana) Regional Airport ... 4

2. Diagram showing modified AeroChem Metric 301 wet/dry collector........................ 7

3-4. Truncated boxplots showing:

3. Weekly wet-deposition amounts for the Gary (Indiana) Regional Airport ................. 13

4. Constituent concentrations for major ions measured in wet-deposition samples collected

at the Gary (Indiana) Regional Airport ........................................... 15

5. Map showing location of wet-deposition site at the Gary (Indiana) Regional Airport and 

two National Atmospheric Deposition Program sampling sites at the Indiana Dunes 

National Lakeshore and Huntington Reservoir ......................................... 16

6-7. Truncated boxplots showing:

6. Major ion concentrations measured in samples collected at the Gary (Indiana) Regional 

Airport and two National Atmospheric Deposition Program sites located at the Indiana 

Dunes National Lakeshore and Huntington Reservoir ................................ 17

7. Constituent concentrations for trace metals measured in wet-deposition samples collected

at the Gary (Indiana) Regional Airport ............................................ 19

£-9. Plots showing:

8. Estimated weekly major ion loadings determined from wet-deposition samples collected

at the Gary (Indiana) Regional Airport ............................................ 20

9. Estimated weekly trace-metal loadings determined from wet-deposition samples collected

at the Gary (Indiana) Regional Airport ............................................ 22

Contents Hi
CONTENTS

FIGURES Continued

10. Map showing location of drainage area for the Grand Calumet River upstream from Kennedy 

Avenue, Indiana Department of Environmental Management surface-water stations, and the 

wet-deposition sampling site at the Gary (Indiana) Regional Airport........................ 26

11. Median constituent concentrations computed for the deionized-water funnel rinses and the 

acidified deionized-water funnel rinses compared to the median constituent concentrations 

computed for the wet-deposition samples and the method reporting limit .................... 31

TABLES

1. Constituent, method of analysis, and the method reporting limits for the 29 constituents

analyzed from samples collected at the Gary (Indiana) Regional Airport..................... 12

2. Water-quality characteristic measured; number of samples measured for that characteristic; 

number of samples measured greater than the method reporting limit; and the 25th, 50th, and 

75th percentile rankings for wet-deposition samples collected at the Gary (Indiana) 

Regional Airport................................................................. 14

3. Range for the estimated annual loadings determined from wet-deposition samples collected

at the Gary (Indiana) Regional Airport for 1 year beginning June 30,1992 ................... 27

4. Constituent measured; 25th, 50th, and 75th percentile rankings; and F-pseudosigmas for

laboratory standard reference water sample (P17)....................................... 29

5. Comparison among median concentrations for the standard reference water sample (Tl 17) 

funnel rinse processed at the Gary (Indiana) Regional Airport, median concentrations for the 

laboratory standard reference water sample (T117), and reported concentrations and 

F-pseudosigmas for standard reference water sample (T117) .............................. 32

6. Reported concentrations for wet-deposition samples collected at the Gary (Indiana) Regional

Airport ........................................................................ 38

7. Reported concentrations for laboratory quality-control samples processed at the U.S. Geological Survey office laboratory in Indianapolis, Ind. .................................... 44

8. Reported concentrations for field quality-control samples processed at the Gary (Indiana)

Regional Airport................................................................. 50

Iv Quality of Wet Deposition In the Grand Calumet River Watershed, Northwestern Indiana
CONVERSION FACTORS AND ABBREVIATED WATER-QUALITY UNITS

Multiply By To Obtain

centimeter (cm)

gram(g)

hectare (ha)

kilogram (kg)

kilometer (km)

liter (L)

meter (m)

microgram (U£)

milligram (mg)

milliliter (mL)

millimeter (mm)

0.394

0.0353

2.471

2.205

0.6214

1.057

3.281

3.530 X 10'8

3.530 X 10'5

0.03381

0.0394

inch

ounce

acre

pound

mile

quart

feet

ounce

ounce

ounce, fluid

inch

Temperature is given in degrees Celsius (°C) which can be converted to degrees Fahrenheit (°F) as follows:

°F=1.8x°C + 32

Sea level: In this report, "sea level" refers to the National Geodetic Vertical Datum of 1929 (NGVD of 1929) a 

geodetic datum derived from a general adjustment of the first-order level nets of the United States and Canada, 

formerly called Sea Level Datum of 1929.

Abbreviated water-quality units used in this report: Chemical concentrations and temperature are given in metric 

units. Chemical concentration is given in milligrams per liter (mg/L) and micrograms per liter (f4.g/L). Milligrams 

per liter is a unit expressing the concentration of chemical constituents in solution as weight (milligrams) of solute 

per unit volume (liter) of water. One thousand micrograms per liter is equivalent to one milligram per liter. Loadings 

are reported in kilograms per hectare (kg/ha) and grams per hectare (g/ha).

Specific conductance of water is expressed in microSiemens per centimeter at 25 degrees Celsius (|j.S/cm). This unit 

is equivalent to micromhos per centimeter at 25 degrees Celsius (jimho/cm), formerly used by the U.S. Geological 

Survey.

Volume of samples is given in liters (L).

Contents v
QUALITY OF WET DEPOSITION IN THE 

GRAND CALUMET RIVER WATERSHED, 

NORTHWESTERN INDIANA, 

JUNE 30, 1992-AUGUST31, 1993

By Timothy C. Willoughby

Abstract

Northwestern Indiana is one of the 

most heavily industrialized and largest steelproducing areas in the United States. High 

temperature processes, such as fossil-fuel 

combustion and steel production, release 

contaminants to the atmosphere that may 

result in wet deposition being a major contributor to major ion and trace-metal loadings in 

northwestern Indiana and Lake Michigan. A 

wet-deposition collection site was established 

at the Gary (Indiana) Regional Airport in June 

1992 to monitor the chemical quality of wet 

deposition.

Weekly samples were collected at this 

site from June 30, 1992, through August 31, 

1993, and were analyzed for pH, specific 

conductance, and selected major ions and trace 

metals. Forty-eight samples collected during 

the study were of sufficient volumes for at least 

some of the determinations to be performed. 

Median constituent concentrations were 

determined for samples collected during warm 

weather (April 1 through October 31) and 

during cold weather (November 1 through 

March 31). These median concentrations 

then were substituted for missing values from 

samples collected during the same periods with 

insufficient volumes for analysis of all the constituents of interest. Constituent concentrations 

were converted to weekly loadings. Two values 

were calculated to provide a range for the 

weekly loading for samples with measured 

concentrations of constituents less than the 

method reporting limit. The minimum weekly 

loading was computed by substituting zero 

for the constituent concentration, and the 

maximum weekly loading was computed by 

substituting the method reporting limit for the 

concentration. If, for a constituent, all of the 

sample concentrations measured were greater 

than the method reporting limit, a single annual 

loading value was computed. Ranges for the 

annual loadings for samples collected at the 

Gary (Indiana) Regional Airport, calculated by 

summing the minimum and maximum weekly 

loadings, were determined for sulfate (26.0 to 

26.4 kilograms per hectare), copper (9.9 to 

11 grams per hectare), and lead (10 to 11 grams 

per hectare). A single annual loading value 

was computed for manganese (69 grams per 

hectare) and zinc (24 grams per hectare). These 

annual loadings could be used to assist in 

estimating the contribution of wet deposition 

to the total annual constituent loadings in the 

Grand Calumet River in northwestern Indiana.

Abstract 1
INTRODUCTION

The Great Lakes compose the largest area 

(244,000 km2) of fresh water on Earth (Herdendorf, 

1982). This important natural resource for the 

United States and Canada is managed under the 

1972 Great Lakes Water Quality Agreement This 

agreement describes the need for surveillance, 

monitoring, and research activities to protect and, 

if necessary, to reclaim the chemical and physical 

quality of the Great Lakes Basin (Klappenbach, 

1991). The chemical composition of wet deposition 

is affected by the chemistry of atmospheric aerosols 

and airborne particles (Schroder and others, 1989). 

Contaminants are deposited to the surface as components of wet deposition and dry deposition. Wet 

deposition is rain, snow, sleet, dew, and hail; dry 

deposition is dust. In the early 1970's, Shiomi 

and Kuntz (1973) recognized the importance of 

wet and dry deposition to the chemical quality 

of the Great Lakes.

The two major processes that introduce 

contaminants to wet deposition are rainout and 

washout. Rainout is the process that occurs in 

clouds, such as condensation, nucleation, or gas 

dissolution. Washout is the process that scavenges 

the airborne participates between the cloud base 

and the ground. During a wet-deposition event, 

both of these processes probably occur continuously because most storms produce convective 

air-current components that add large masses of 

near-surface air to overlying clouds (Schroder and 

Hedley, 1986).

For the past 20 years, much of the emphasis 

regarding the effects wet deposition has on the 

environment has been in the research and monitoring of the major ions found in wet deposition 

and how these constituents affect acid rain. One 

of the largest monitoring efforts currently is being 

conducted by the National Atmospheric Deposition 

Program (NADP). The NADP has monitored the 

major ion constituents of wet deposition since 

1978. These data are collected at over 200 sites to 

monitor the spatial and temporal trends in the 

chemical composition of acidic wet deposition 

(Galloway and others, 1978). The NADP, 

however, does not analyze samples for trace metals.

In recent years, an increasing emphasis on the 

effects of the trace-metal components in wet 

deposition has emerged.

Wet and dry deposition may be a major 

component to nonpoint-source pollution. Northwestern Indiana is the State's highest priority area 

for nonpoint-source pollution control (Indiana 

Nonpoint Source Task Force, 1989). Some of the 

recommendations made by the Indiana Nonpoint 

Source Task Force are to evaluate and quantify 

water-quality impacts of airborne pollutants in 

inland waters and Lake Michigan, cooperate in 

Great Lakes air-monitoring programs, initiate a 

statewide monitoring program for airborne toxic 

and acid pollutants, improve integration of State 

air- and water-pollution control programs, and 

develop and implement enhanced air-pollution 

control strategies. To evaluate some of these 

recommendations, the U.S. Geological Survey 

(USGS) established a wet-deposition collection 

site at the Gary (Indiana) Regional Airport (hereafter referred to as the Gary airport) in June 1992 

to monitor the chemical quality of wet deposition. 

This project was done in cooperation with the 

Indiana Department of Environmental Management (IDEM).

Purpose and Scope

This report describes the chemistry for pH, 

specific conductance, and selected major ions 

and trace metals found in wet-deposition samples 

collected at the Gary airport from June 30,1992, 

to August 31,1993. In addition, this report:

(1) displays truncated boxplots (Helsel 

and Hirsch, 1992) showing the distribution of constituent concentrations;

(2) presents estimated weekly and annual 

loadings for the measured constituents 

and describes how these loadings 

could be used to assist in calculating 

the nonpoint-source contribution of 

wet-deposition loadings to the total 

constituent loadings in the Grand 

Calumet River;

2 Quality of Wet Deposition in the Grand Calumet River Watershed, Northwestern Indiana
(3) compares the results of major ion 

concentrations found in wet deposition 

with results from two NADP sites 

(Indiana Dunes National Lakeshore 

and Huntington Reservoir) located in 

northern Indiana. This comparison is 

intended to evaluate if the chemistry 

of wet-deposition samples collected at 

the Gary airport is localized or if 

the chemistry of these samples is 

consistent with sites outside the 

industrialized Gary area; and

(4) describes the results for 52 qualityassurance samples and their effect 

on interpretation of the constituent 

concentrations measured in wetdeposition samples collected during 

this study.

Site Location

The wet-deposition sampling site was located 

at the Gary airport, a small airport that services 

mainly privately owned aircraft. Gary is in northwestern Indiana (fig. 1) and is one of the most 

industrialized areas in the United States. Major 

industries located near the sampling site include 

steel manufacturing, petroleum refining, smelting 

operations, and coal-fired electric-generating plants.

The wet-deposition sampling site is located 

at an altitude of 178 m above sea level, approximately 400 m north of Interstate 90, 3.5 km south 

of Lake Michigan, and 18 km west of the Lake and 

Porter County boundary. The sampling equipment, 

an AeroChem Metric 301 1 wet/dry collector and a 

Belfort weighing rain gage, was located 30.5 m 

north of the traffic control tower at the Gary airport. 

Air traffic at the airport did not pass over the 

sampling equipment. Access to the equipment 

was by an improved single-lane road within the 

secured grounds of the airport.

1 Any use of trade, product, or firm names in this publication 

is for descriptive purposes only, and does not imply endorsement 

of products by the U.S. Government.

Acknowledgments

The author acknowledges the efforts of 

Gary Depositar of the IDEM for his help in locating 

an acceptable sampling site. The staff at the Gary 

airport provided access to the sampling site and 

assisted with shipping samples to the USGS office 

in Indianapolis, Ind. The author also thanks the 

project assistant, Robert E. Sheffer, for his efforts 

in servicing the sampling equipment.

METHODOLOGY

This section describes the selection of the 

sampling site, constituents selected and the analytical methods used to measure their concentrations 

in the samples, and the modifications made to the 

AeroChem Metric 301 wet/dry collector that were 

necessary for the collection of trace metals in wet 

deposition. No modifications were necessary for 

the collection and analysis of the major ions. This 

section also describes the methods used for cleaning 

the equipment and for processing and analyzing 

the samples.

Sampling Site Selection

The sampling site was chosen in cooperation 

with the IDEM. The decision to locate the sampling 

site at the Gary airport was based on the need to 

minimize the possibility of local point sources that 

could directly affect wet-deposition chemistry. 

The airport site also provided a secure location for 

the sampling equipment, an electrical power source, 

an open flat field with no obstructions projecting 

onto the collector or rain gage with an angle greater 

than 45 degrees from horizontal as recommended 

for the NADP. The sampling equipment was 

installed in accordance with NADP protocols 

(Bigelow, 1984).

Constituent Selection and 

Analytical Techniques

Calcium, magnesium, sodium, potassium, 

sulfate, chloride, and nitrate are constituents 

measured in samples collected by the NADP

Site Location 3
87°27'30" 87°22'30" 87°17'30"

41°40

41°37'30'

41°35

Base from U.S. Geological Survey digital data, 1:24,000 digital line graphs

Albers Equal-Area Conic Projection

Standard Parallels 29°30' and 45°30', central meridian -86°

3 1 2

i 1 1

3

1

4

1

5 MILES

1

1 1 1 1 1 1

012345 KILOMETERS

Study Area

EXPLANATION 

Gary city boundary

Sampling site

Figure 1. Location of wet-deposition sampling site at the Gary (Indiana) Regional Airport.

4 Quality of Wet Deposition in the Grand Calumet River Watershed, Northwestern Indiana
for acid-rain studies. These constituents were 

analyzed in the Gary airport wet-deposition 

samples to evaluate their differences with the 

concentrations measured at the NADP sites located 

at the Indiana Dunes National Lakeshore and 

Huntington Reservoir. The Indiana Dunes National 

Lakeshore site is located approximately 26 km east 

of the Gary airport, and the Huntington Reservoir 

site is located approximately 180 km southeast of 

the Gary airport. The only major constituent 

analyzed by the NADP that was not analyzed 

during this study was ammonia. All analytical 

techniques utilized for this study were standard 

USGS methods for determination of inorganic 

substances in water. All of the following methods 

are described in Fishman and Friedman, 1989. 

Calcium (method 1-1152-85, p. 137-139), 

magnesium (method 1-1454-85, p. 275-276), 

sodium (method 1-3736-85, p. 427-428), and 

potassium (method 1-1630-85, p. 393-394) were 

analyzed by flame atomic absorption spectrometry. 

Major anions (sulfate, chloride, fluoride, bromide, 

and nitrate) were analyzed by ion chromatography 

(method 1-2058-85, p. 527-530).

The trace metals measured for this study 

(because they are by-products of industrial 

processes located in the Gary, Ind., area and 

because of their toxic potentials) included arsenic, 

cadmium, copper, lead, manganese, mercury, and 

zinc. Although copper, manganese, and zinc are 

necessary for proper cellular development, these 

metals may bioaccumulate, especially in aquatic 

organisms, and therefore may present a health risk 

(Amdur and others, 1993). Arsenic, cadmium, lead, 

and mercury are not essential metals, and exposure 

at very low concentrations may present a risk.

Following are brief descriptions of possible 

sources for arsenic, cadmium, copper, lead, manganese, mercury, and zinc in northwestern Indiana and 

the analytical techniques used to analyze for these 

trace metals.

Arsenic is released to the atmosphere by 

fossil-fuel combustion, smelting, and the spraying 

of arsenical herbicide sprays. Arsenic is bioconcentrated by organisms but is not biomagnified in the 

food chain (Eisler, 1988). Arsenic was analyzed by 

atomic absorption spectrometry, hydride formation 

(method 1-2062-85, p. 77-81).

Cadmium is released to the environment 

by fossil-fuel combustion, smelting, electroplating 

or galvanizing, and the production of nickelcadmium batteries (Amdur and others, 1993). 

Cadmium was analyzed by graphite furnace atomic 

absorption spectrometry (method 1-1137-85, 

p. 129-132).

Copper is one of the more widely used trace 

metals and is released to the atmosphere by fossilfuel combustion, smelting, and steel manufacturing. 

Copper was analyzed by graphite furnace atomic 

absorption spectrometry (method 1-1272-85, 

p. 197-200).

Lead is released to the atmosphere by fossilfuel combustion, combustion of lead-containing 

automobile exhaust or industrial emissions, and 

the manufacturing of lead batteries. Lead is in the 

atmosphere as either particulates of lead dioxide or 

in the form of vapors, particularly alkyl lead. Lead 

was analyzed by graphite furnace atomic absorption 

spectrometry (method 1-1401-85, p. 249-252).

Manganese and its compounds are released 

to the environment in the manufacturing of steel 

alloys, dry-cell batteries, electrical coils, and 

ceramics. Other sources for manganese include 

fertilizers, oxidizing agents, and animal food 

additives. Manganese was analyzed by graphite 

furnace atomic absorption spectrometry (method 

1-1455-85, p.277-280).

Mercury appears in nature in three forms: 

elemental mercury and inorganic and organic 

compounds. The major source of mercury in the 

atmosphere is from the natural degassing of the 

Earth's crust, including land areas, rivers, and 

oceans. Elemental mercury in the atmosphere 

represents the major pathway of global mercury

Constituent Selection and Analytical Techniques 5
transport. Other sources of mercury include 

fossil-fuel combustion, mining, smelting, and 

emission from paper pulp industries. Regardless 

of the source, organic and inorganic forms of 

mercury may undergo environmental transformations. Elemental mercury may be oxidized 

to inorganic divalent mercury, such as what occurs 

in an aquatic environment. When conditions are 

appropriate for reducing reactions, divalent 

inorganic mercury may be reduced to elemental 

mercury. Divalent mercury also may undergo 

methylation to dimethyl mercury which can diffuse 

into the atmosphere and be redeposited to the 

biosphere as methyl mercury in wet deposition. 

Methyl mercury is the most toxic form of mercury 

and is known to bioaccumulate in aquatic biota 

(Amdur and others, 1993). Mercury was analyzed 

by flameless atomic absorption spectrometry, cold 

vapor (method 1-2462-85, p. 289-291).

Zinc is released to the atmosphere by fossilfuel combustion, steel manufacturing, smelting, 

and galvanizing processes. Zinc was analyzed by 

graphite furnace atomic absorption spectrometry 

(method 1-1901-85, p. 509-511).

In addition to the seven trace metals 

mentioned above, samples collected at the Gary 

airport also were submitted for analysis by inductively coupled argon plasma atomic emission 

spectrometry (ICAP). The ICAP method provides 

concentrations for a large number of trace metals 

during a single analytical run (method 1-1472-85, 

p. 517-522). The ICAP method was used in this 

study to determine if any other trace metals could 

be included in future studies. The ICAP method 

included measurement of iron and silica. Iron and 

silica, because of the steel industry and the silicabased soils in northwestern Indiana, may be two 

of the more abundant constituents measured in the 

wet deposition at the Gary airport.

Collector Modifications

For the collection of trace metals, it was 

necessary to modify the standard AeroChem 

Metric 301 wet/dry collector. Teflon was used

whenever possible for components of the collector 

that came in contact with wet deposition. Teflon is 

the preferred material for trace-metal collection 

and storage, especially for mercury and zinc (Fogg 

and Fitzgerald, 1979). Glass is also an acceptable 

material for the collection and storage of samples 

containing mercury. Glass bottles were used to 

ship the sample aliquot used for the analysis of 

mercury to the laboratory. Polyethylene or Teflon 

are excellent materials for the collection and 

storage of major ions in wet deposition.

The AeroChem Metric 301 wet/dry collector 

was modified to decrease the possible sources of 

trace-metal contamination to the sample (fig. 2). 

The bottom of the collector was enclosed with 

aluminum sheeting to house the collection bottle 

and thermometer. Holes were drilled through the 

sides of this enclosure and covered with a polyethylene screen to allow for cooling in summer, the 

screen helped prevent contaminants from blowing 

into the enclosure. The lid and lid arms of the 

collector were coated with Teflon to minimize 

contamination from wet deposition splashing off 

the lid and/or lid arms into the collection funnel 

(Dossett and Bowersox, 1991). The bottom of a 

13-L polyethylene bucket was removed and a hole 

was cut through the collector frame to allow the 

collection funnel to pass through the collector 

frame into the bottom enclosure. A 31-cm diameter 

high-density polyethylene funnel was installed so 

that the funnel rested on the top of the 13-L polyethylene bucket. The bucket housing was adjusted so 

that the polyethylene-covered foam pad, attached 

to the bottom of the collector lid, fit tightly against 

the top of the funnel. This polyethylene foam pad 

assisted in preventing contaminants from blowing 

into the funnel when the sampler lid was closed. 

A fitting was attached to a silicon stopper in the 

bottom of the funnel to allow a 1.3-cm Teflon tube 

to connect to the funnel. The Teflon tube then 

passed through a 1.3-cm hole in the cap of a 5-L 

Teflon collection bottle. Two 100-watt light bulbs 

were installed as close as possible to the hole cut 

in the collector frame. These two light bulbs were

6 Quality of Wet Deposition in the Grand Calumet River Watershed, Northwestern Indiana
31-centimeter 

polyethylene funnel

Bucket housin

Collector frame 

Light bulb

1.3-centimete 

Teflon tubing

5-Liter Teflon 

collection bottle

Thermometer

Sensor 

Bucket housing

13-liter polyethylene 

bucket

Motor box

Bottom enclosure

Figure 2. Modified AeroChem Metric 301 wet/dry collector.

Collector Modifications 7
connected to a thermostat and were used to heat 

the area around the collection funnel to avoid 

snow and ice buildup in the funnel. Light bulbs 

were used instead of an electric heater to prevent 

possible contamination from the heating of 

copper wires. The thermostat was set to activate 

at about 5°C.

The collector was activated by a sensor 

consisting of a metal plate separated by approximately 1 mm from a metal grating. When wet 

deposition came in contact with the sensor, the wet 

deposition was trapped between the metal plate and 

the metal grating, completing an electrical circuit 

and opening the lid of the collector. When the lid of 

the collector was open, the metal plate on the sensor 

heated to approximately 50°C to melt snow and to 

evaporate the trapped wet deposition, breaking the 

electrical circuit and closing the collector lid after 

the wet-deposition event had ended.

Equipment Cleaning

All of the equipment cleaning was done in 

the laboratory located at the USGS office in 

Indianapolis, Ind. The 5-L Teflon collection bottles 

were cleaned with deionized water (DIW); the 

bottles were rinsed three times, filled, and then 

leached for 24 hours. All DIW used for this study 

met the National Institute for Standards and 

Technology type 1 standard (greater than 

16.7 megOhm). The bottles then were rinsed three 

more times with DIW and filled with a 10-percent 

nitric-acid and DIW solution and leached for an 

additional 24 hours. All of the nitric acid used for 

cleaning and sample preservation was Ultrex-grade 

nitric acid. The bottles then were rinsed three more 

times with DIW, filled, and leached for 24 hours. 

The bottles were rinsed a third time with three 

aliquots of DIW, and the excess water was shaken 

from the bottle and the bottles were stored in a 

sealed prerinsed polyethylene bag.

The funnels were rinsed three times with large 

amounts of DIW. Any debris attached to the sides 

of the funnel was removed with a plastic brush. 

The funnels were rinsed again with DIW, followed 

by a 1-L rinse with a 10-percent nitric-acid and 

DIW solution. The funnels then were rinsed a final 

time with DIW and stored in a sealed prerinsed 

polyethylene bag.

The Teflon tubing was rinsed three times 

with large amounts of DIW, followed by three 

100-mL rinses with a 10-percent nitric-acid and 

DIW solution. The Teflon tubing then was rinsed 

a final time with DIW and stored in a sealed, prerinsed polyethylene bag.

The 250-mL Teflon and glass bottles used 

to ship the samples to the laboratory were cleaned 

in the same manner as described previously for 

the 5-L collection bottles. The aliquot of the 

sample used for the determination of major anion 

concentrations was shipped to the laboratory in 

high-density polyethylene bottles. Because nitrate 

was one of the major ions measured during this 

study, no acid-rinsing techniques were used on the 

polyethylene bottles. New 250-mL polyethylene 

bottles were rinsed three times with DIW, filled, 

and leached for 24 hours. The polyethylene bottles 

then were rinsed an additional three times with 

DIW. The 250-mL Teflon, glass, and polyethylene 

bottles were stored at the USGS office laboratory 

in Indianapolis, Ind.

The filters were cleaned immediately before 

use; the filters were rinsed with 50 mL of a 10- 

percent nitric-acid solution followed by three 

50-mL rinses with DIW. The filters then were 

rinsed with 20 mL of the sample before the sample 

was filtered into the 250-mL bottles.

The collector was cleaned weekly when the 

samples were removed. The lid, lid arms, polyethylene lid pad, and the top of the collector frame 

were wiped clean with a lint-free paper towel and 

DIW to remove dust and debris that collected 

during the previous sampling week. The cleaning 

of the sampler was performed after the sample had

8 Quality of Wet Deposition in the Grand Calumet River Watershed, Northwestern Indiana
been removed from the collector and before a clean 

funnel was installed for the next week of sampling 

to minimize any possible contamination resulting 

from the paper towel.

Sample Collection and Processing

Wet-deposition samples were removed 

from the collector every Tuesday. The Tuesday 

to Tuesday sampling period was consistent with 

the sampling period used by the NADP (Bigelow 

and Dossett, 1988).

A clean 5-L Teflon collection bottle, funnel, 

Teflon tube, approximately 1 L of deionized water 

(used for cleaning the collector), and any other 

equipment needed at the sampling site were packed 

in a cooler and sealed with packing tape. The cooler 

was shipped to the airport by an overnight mailing 

service. Field personnel would obtain the sealed 

cooler from airport employees every Tuesday. 

Approximately every other week an additional 

clean collection bottle, funnel, Teflon tube, and a 

quality-control sample also were shipped to the 

airport. Processing of the quality-control samples 

is discussed in the Field Quality Assurance section 

of this report.

Field personnel took every possible precaution to minimize contamination when removing 

the sample and installing clean equipment in 

the collector. These precautions included field 

personnel always wearing polyethylene gloves 

when working around the collector, always standing 

downwind from the collector to prevent contaminants from the body and/or clothing of field 

personnel being transported into the funnel or 

collection bottle; and ensuring that the collector was 

not activated until the collection bottle containing 

the sample was removed. Field personnel indicated 

on the collection bottle the date and time the sample 

was removed.

The following procedures were used in 

securing the sampling equipment:

(1) the collector lid was opened, the 

funnel and tubing were removed, 

and the collector was wiped clean;

(2) a clean funnel and tubing were 

installed, and the collector lid 

was closed;

(3) once the collector had closed, a tared, 

clean, collection bottle was installed. 

Field personnel indicated on the bottle 

the date and time the collection bottle 

was installed;

(4) the rain-gage chart was removed from 

the Belfort rain gage, and the wet 

deposition collected in the rain gage 

was discarded. Field personnel 

indicated on the rain-gage chart the 

date and time the chart was removed;

(5) a new rain-gage chart was installed 

after field personnel indicated on the 

chart the date and time the chart was 

installed; and

(6) the rain gage was zeroed.

Field personnel also completed a field 

form indicating the date and time the sample was 

removed and the clean equipment was installed; 

the tare weight of every bottle; current weather 

conditions, and the maximum and minimum 

temperature measured inside the collector housing 

for the previous week were recorded.

The bottle containing the previous week's 

sample, funnel, tubing, rain-gage chart, and field 

form were sealed in a cooler with tape. The cooler 

was delivered to airport personnel, and an overnight 

mailing service was contacted. The cooler was 

shipped to the USGS office in Indianapolis, Ind.

After the cooler was received by personnel of 

the USGS office in Indianapolis, Ind., the following 

steps were used to process the sample before it was 

shipped to the USGS National Water Quality Laboratory (NWQL) in Arvada, Colo., for analyses:

(1) sample volume was determined; the 

sample in the collection bottle was 

weighed, and the tare weight of the 

bottle was subtracted from the weight 

of the bottle plus the sample;

Sample Collection and Processing 9
(2) 15 mL of the sample were removed 

and the pH was determined (this pH 

value will be referred to as the "field

PH");

(3) approximately 250 mL of the sample 

were filtered with a 47-mm 0.45- 

micrometer polycarbonate filter into 

a 250-mL high-density polyethylene 

bottle for laboratory determination 

of specific conductance and major 

anions;

(4) an additional 250-mL aliquot 

was filtered into a 250-mL glass 

bottle and preserved with 10 mL of a 

1-percent potassium dichromate and 

nitric-acid solution for laboratory 

determination of mercury;

(5) the 5-L collection bottle then was reweighed, and the volume of the 

sample remaining was computed. 

The remaining sample was acidified 

with nitric acid to 2 percent by 

volume;

(6) the sample was shaken vigorously; 

15 mL of the acidified sample were 

removed and the pH was measured. 

If the measured pH were greater than 

2.0, additional nitric acid was added 

and this step was repeated;

(7) the sample was allowed to stand for 

a minimum of 24 hours at 4°C; and

(8) a 250-mL aliquot of the acidified 

sample was filtered with a 47-mm, 

0.45-micrometer polycarbonate filter 

into a 250-mL Teflon bottle for 

laboratory analysis of trace metals 

and major cations.

All sample handling performed at the USGS office 

in Indianapolis, Ind., was done on a laboratory 

bench top covered with Teflon. The bench top 

was covered with an adhesive-backed Teflon 

sheet to help minimize contamination during the 

preservation and filtering processes. The samples 

then were packed in ice and the cooler was sealed 

with tape and sent to the NWQL in Arvada, Colo., 

by overnight delivery service.

The NWQL required a minimum of 600 mL 

of sample for the analysis of major cations and 

anions, mercury, and the selected trace metals. 

Small-volume samples (less than 600 mL) were 

not diluted to prevent the decreasing of some of 

the trace-metal concentrations below the method 

reporting limits. Therefore, a priority was established for analysis of small-volume samples. 

Weekly samples, with measured volumes smaller 

than 200 mL, were analyzed only for field pH. 

Samples with volumes between 200 and 400 mL 

were analyzed for field pH and trace metals 

(excluding mercury). Samples with volumes 

between 400 and 600 mL were analyzed for field 

pH, trace metals (excluding mercury), and major 

cations and anions. Samples with measured 

volumes greater than 600 mL were analyzed for 

field pH, specific conductance, trace metals, major 

cations and anions, and mercury. These priorities 

for analyses were adjusted occasionally to best 

utilize the volume collected.

Water-Sample Analysis

All samples were submitted to the Low 

Ionic Strength Section of the NWQL for analysis. 

Analytical techniques were chosen to provide the 

lowest reporting limits. Major cation (calcium, 

magnesium, sodium, and potassium) concentrations were determined by flame atomic absorption 

spectrometry (FAAS). FAAS provided the lowest 

reporting limit for major cations measured by the 

NWQL. If an insufficient sample volume were 

available for major cation concentrations to be 

determined by FAAS, and if sufficient volume 

were available for analysis by ICAP, the constituent 

concentrations reported by ICAP (except for 

potassium) are presented. Potassium concentrations 

were not reported by the NWQL when constituent 

concentrations for major cations were determined 

by ICAP. Major anions (sulfate, chloride, fluoride, 

bromide, nitrate, and phosphate) concentrations 

were determined by ion chromatography (1C). 

Arsenic was analyzed by atomic absorption spectrometry, hydride formation (HF). Silica, barium, 

beryllium, cadmium, chromium, cobalt, iron,

10 Quality of Wet Deposition in the Grand Calumet River Watershed, Northwestern Indiana
lithium, molybdenum, nickel, silver, strontium, 

and vanadium were analyzed by ICAP. Cadmium, 

copper, lead, manganese, and zinc were analyzed 

by graphite furnace atomic absorption 

spectrometry (GFAAS); mercury was determined 

by atomic absorption spectrometry, cold vapor 

(CV). The method of analysis and method 

reporting limit for each of the constituents 

measured are listed in table 1.

QUALITY OF WET DEPOSITION

Fifty-eight weekly samples were collected 

during the 62-week sampling period (June 30, 

1992-August 31, 1993). During 4 weeks, no wet 

deposition was collected in the collection bottle. 

Only 48 of the 58 samples were included in the 

analysis of data because of problems related to 

sample collection: 6 samples were lost as a result 

of the collector malfunctioning, 1 sample was lost 

in the mail, and 3 samples were lost because of 

gross contamination (bird droppings). During 3 

of the other sampling weeks, the sample volume 

exceeded the volume of the collection bottle (5 L). 

Samples that overflowed the collection bottle were 

included in the analysis of the results.

Weekly wet-deposition amounts were 

measured from the continuous monitoring raingage charts and compared to the wet-deposition 

amounts computed from the measured volume of 

sample collected. Catch efficiencies were computed by dividing the wet-deposition amounts 

computed from the collected sample volume by 

the wet-deposition amounts measured from the 

rain-gage charts. Thirty-nine samples were used 

to compute the catch efficiencies; samples that 

overflowed the collection bottle were not used 

in the calculation. A median catch efficiency of 

100.2 percent was computed. Because the catch 

efficiencies were close to 100 percent and because 

the Belfort rain gage was installed almost 1 month 

after the installation of the collector, wet-deposition 

amounts computed from the sample volume collected were used in determining loadings. Sample 

volumes computed from the wet-deposition 

amounts measured from the rain-gage charts were 

used in determining loadings for the three samples 

that overflowed the collection bottle. Figure 3 

shows a truncated boxplot (Helsel and Hirsch, 

1992) of the wet-deposition amounts.

Because the sample volumes varied during 

the study period, not all of the water-quality 

characteristics could be measured in small-volume 

samples. Of the 48 weekly samples collected,

25 samples were analyzed for all parameters 

(table 2); 5 samples were analyzed for all parameters (excluding mercury); 4 samples were analyzed 

for trace metals (excluding mercury), major cations 

(excluding potassium), and field pH; 3 samples 

were analyzed for trace metals (excluding mercury) 

and major cations (excluding potassium); 3 samples were analyzed for trace metals (including 

mercury), major cations (excluding potassium), and 

field pH; and 8 samples were analyzed for only 

field pH (table 6, at back of report).

No results were reported greater than the 

method reporting limit for wet-deposition samples 

for arsenic, cobalt, mercury, molybdenum, 

nickel, and vanadium. Table 2 lists the characteristic measured; the number of times samples were 

measured for that characteristic; the number of 

times a value was measured greater than the 

method reporting limit; and the 25th, 50th, and 

75th percentile rankings.

Truncated boxplots of the measured concentrations determined for major ions collected at 

the Gary airport for all of the constituents that had 

more than 50 percent of the results reported as 

greater than the method reporting limit are shown 

in figure 4. These results were compared to the 

weekly medians determined at the NADP sites 

located at the Indiana Dunes National Lakeshore 

and Huntington Reservoir. The Indiana Dunes 

National Lakeshore site is located approximately

26 km east of the Gary airport, and the Huntington 

Reservoir site is located approximately 180 km 

southeast of the Gary airport (fig. 5). Truncated 

boxplots comparing major ion concentrations 

measured from samples collected at the Gary 

airport with concentrations measured in samples 

collected at the Indiana Dunes National Lakeshore 

and Huntington Reservoir sites are shown in 

figure 6.

Calcium, magnesium, potassium, sulfate, 

chloride, and nitrate concentrations measured in 

samples collected at the Gary airport were similar 

to concentrations measured in samples collected at

Quality of Wet Deposition 11
Table 1 . Constituent, method of analysis, and the method reporting limits for the 29 constituents analyzed from 

samples collected at the Gary (Indiana) Regional Airport

[FAAS, flame atomic absorption spectrometry; ICAP, inductively coupled argon plasma atomic emission spectrometry; mg/L, milligrams 

per liter, 1C, ion chromatography; HF, atomic absorption spectrometry, hydride formation; ug/L, micrograms per liter, GFA AS, graphite 

furnace atomic absorption spectrometry; CV, atomic absorption spectrometry, cold vapor]

Constituent

Calcium

Magnesium

Sodium

Potassium

Sulfate

Chloride

Fluoride

Bromide

Silica

Nitrate

Phosphate

Arsenic

Barium

Beryllium

Cadmium

Chromium

Cobalt

Copper

Iron

Lead

Lithium

Manganese

Mercury

Molybdenum

Nickel

Silver

Strontium

Vanadium

Zinc

Method of 

analysis

FAAS/ICAP

FAAS/ICAP

FAAS/ICAP

FAAS

1C

1C

1C

1C

ICAP

1C

1C

HF

ICAP

ICAP

GFAAS

ICAP

ICAP

GFAAS

ICAP

GFAAS

ICAP

GFAAS

CV

ICAP

ICAP

ICAP

ICAP

ICAP

GFAAS

Method reporting 

limit

0.01/0.02

.01/.01

.01/.2

.01

.01

.01

.01

.01

.01

.04

.03

1

2

.5

.1

5

3

.5

3

.5

4

.2

.1

10

10

1

.5

6

.5

Method reporting 

units

mg/L

mg/L

mg/L

mg/L

mg/L

mg/L

mg/L

mg/L

mg/L

mg/L

mg/L

M-g/L

M-g/L

M-g/L

M-g/L

M-g/L

M-g/L

M-g/L1

M-g/L"

M-g/LM-g/LM-g/L"

M-g/L"

M-g/L"

M-g/LM-g/L"

M-g/L"

M-g/LM-g/L"

12 Quality of Wet Deposition in the Grand Calumet River Watershed, Northwestern Indiana
[METERS

H

O

0.3

6.0

5.5

5.0

4.5

4.0

3.5 

3.0

2.0

1.5 

1.0

0.5 

0

-

-

-

-

-

-

-

-

-

-

-

-

-i

-

r-

-

§

HHH

C/3 VJ

£ 

S

H

EXPLANATION

90th percentile

75th percentile 

Median 

25th percentile 

10th percentile

Figure 3. Weekly wet-deposition amounts for the Gary (Indiana) Regional Airport.

Quality of Wet Deposition 13
Table 2. Water-quality characteristic measured; number of samples measured for that characteristic; number of samples 

measured greater than the method reporting limit; and the 25th, 50th, and 75th percentile rankings for wet-deposition 

samples collected at the Gary (Indiana) Regional Airport

[uS/on, microSiemens per centimeter at 25 degrees Celsius; NA, not applicable; mg/L, milligrams per liter, <, less than the method reporting limit; 

Ug/L, micrograms per liter]

Water-quality 

characteristic

Specific conductance

Field pH

Calcium

Magnesium

Sodium

Potassium

Sulfate

Chloride

Fluoride

Bromide

Silica

Nitrate

Phosphate

Arsenic

Barium

Beryllium

Cadmium

Chromium

Cobalt

Copper

Iron

Lead

Lithium

Manganese

Molybdenum

Mercury

Nickel

Silver

Strontium

Vanadium

Zinc

Number of 

samples 

measured

30

45

40

40

40

28

30

30

30

30

40

30

30

40

40

40

40

40

40

40

40

40

40

40

40

28

40

40

40

40

40

Number of 

samples 

measured 

greater than 

the method 

reporting limit

30

NA

40

40

18

28

30

30

29

5

39

30

2

0

32

1

15

3

0

35

40

36

1

40

0

0

0

6

29

0

37

Percentile ranking

25th

18.8

4.23

.26

.05

<.2

.02

2.1

.13

.03

<.01

.073

1.44

<.03

<1

2

<.5

<.l

<5

<3

.8

13

.8

<4

4.2

<10

<.l

<10

<1

<.5

<6

1.3

50th

21.8

4.48

.74

.10

<.2

.03

2.9

.24

.04

<.01

.18

1.73

<.03

<1

3

<.5

<.l

<5

<3

1.5

24

1.3

<4

7.3

<10

<.l

<10

<1

1.0

<6

2.9

75th

31.0

4.79

1.50

.24

.2

.06

4.3

.39

.06

<.01

.33

3.10

<.03

<1

4

<.5

.1

<5

<3

2.7

56

2.7

<4

18.0

<10

<.l

<10

<1

3.0

<6

4.5

Method 

reporting 

units

liS/cm

units

mg/L

mg/L

mg/L

mg/L

mg/L

mg/L

mg/L

mg/L

mg/L

mg/L

mg/L

M£/L

U-g/L

U-g/L

M£/L

(J-g/L

M-g/L

U-g/L

M£/L

M-g/L

(J-g/L

\Lg/L

M-g/L

M-g/L

\lg/L

\Lg/L

ug/L

Hg/L

\Lg/L

14 Quality of Wet Deposition in the Grand Calumet River Watershed, Northwestern Indiana
IU

1

tc uj

fc 0.1

tf 

u

Ou

5 0.01 

1

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EXPLANATION

90th percentile

 75th percentile

 Median

10th percentile

1

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1

urH1

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1

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Q 3 H 

Q ^ 1

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Figure 4. Constituent concentrations for major ions measured in wet-deposition samples collected at the 

Gary (Indiana) Regional Airport.

Quality of Wet Deposition 15
N,Lake Michigan

1 Wet Deposition Sfte

LAKE !

r PORTER

'Indiana Dunes National Lakeshore

r HUNTINGTOI^. , ., . .,..,., 

\ 0 Hiintington fteservoir

KILOMETERS

Base from U.S. Geological Survey, 1:100.000, 1983

Albers Equal-Area Conic projection

Standard parallels 29°30' and 45°30', central meridian -86°

Figure 5. Location of wet-deposition site at the Gary (Indiana) Regional Airport and two National 

Atmospheric Deposition Program sampling sites at the Indiana Dunes National Lakeshore 

and Huntington Reservoir.

MILES

16 Quality of Wet Deposition in the Grand Calumet River Watershed, Northwestern Indiana
1U

1

C£ a 0.1

5 

a

Cu 0.01

COi

O ^^1 0001 V/«V/vli.

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2

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CALCIUM 1 T M M H U

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MAGNESIUM | [

POTASSIUM

i i i i i i i i i i i

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rj _ |~j JL I-U |

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SULFATE ' :

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^^hn ^^^

1 1

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EXPLANATION

90th percentile

 25th percentile

10th percentile

0.01 

Htftoi Htftoi Htftoi

z o z o z 5

aBgq §QS ^Ba <<ffl ^^S3 ^<ffl ( 1 2 ^ , i 2 ^ >-i -1 Z ??

<<^ ^S^ ^s5 §56 §05 §55 

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Figure 6. Major ion concentrations measured in samples collected at the Gary (Indiana) Regional Airport 

and two National Atmospheric Deposition Program sites located at the Indiana Dunes National Lakeshore 

and Huntington Reservoir.

Quality of Wet Deposition 17
the Indiana Dunes National Lakeshore. Sulfate 

and nitrate concentrations measured in samples 

collected at the Gary airport also were similar to 

concentrations measured in samples collected at 

Huntingdon Reservoir. Calcium, magnesium, 

potassium, and chloride concentrations measured 

in samples collected at the Gary airport were 

generally larger than concentrations measured in 

samples collected at Huntingdon Reservoir, The 

similarity between the concentration distributions 

observed for samples collected at the Gary airport 

and for samples collected at the Indiana Dunes 

National Lakeshore is an indication that the 

sources affecting the chemistry of wet-deposition 

samples collected at the Gary airport may be the 

same sources affecting wet-deposition chemistry 

at the Indiana Dunes. It is possible that industrial 

processes in the Gary area are releasing contaminants to the atmosphere that are being transported, 

downwind, to the Indiana Dunes National Lakeshore site. Smaller concentrations measured in 

samples collected at the Huntington Reservoir 

site may indicate that contaminants being released 

to the atmosphere in the Gary area are not affecting 

the Huntington Reservoir site to the same extent as 

the Indiana Dunes National Lakeshore. Truncated 

boxplots of the measured concentrations for trace 

metals collected at the Gary airport for all of the 

constituents with more than 50 percent of the 

results reported greater than the method reporting 

limit are shown in figure 7. None of the median 

concentrations determined for major ions or 

trace metals at the Gary airport exceeded the 

U.S. Environmental Protection Agency guidelines 

for Maximum Contaminant Levels for drinking 

water (U.S. Environmental Protection Agency, 

1992).

Median constituent concentrations were 

determined for samples collected during warm 

weather (April 1 through October 31) and during 

cold weather (November 1 through March 31). 

These median concentrations were substituted for 

missing values from samples collected during the 

same periods that had insufficient volumes for 

analysis of all the constituents listed in table 1.

The calculated weekly and annual loadings are, 

therefore, referred to as "estimated" values. If a 

measured constituent concentration were less 

than the method reporting limit, a range for that 

constituent's weekly loading was computed. 

To compute this range, zero was substituted for 

the constituent concentration (estimated minimum 

loading) and the method reporting limit was 

substituted for the constituent concentration 

(estimated maximum loading). A single value for 

the estimated weekly loading was calculated when 

the measured constituent concentration was greater 

than the method reporting limit. Estimated weekly 

major ion and trace-metal loadings are presented 

in figures 8 and 9. Bars indicate that the measured 

sample was less than the method reporting limit 

and, therefore, a range for the weekly loading is 

presented.

An insufficient number of samples was 

collected at the Gary airport to perform a statistical 

seasonal trend analysis. A statistical trend analysis 

may be possible after a second year of sampling. 

Constituent concentrations appeared to be larger 

during times of the year when wet deposition was 

in the form of rain and not snow. The larger concentrations observed in rain are probably due to rain 

scavenging contaminants from the atmosphere 

more efficiently than snow.

The IDEM collects surface-water samples at 

six sites on the Grand Calumet River. Monthly 

samples collected from these sites could be used 

to assist in estimating the contribution that wet 

deposition has on the overall annual loadings from 

the Grand Calumet River. The USGS attempted to 

make this calculation by:

(1) estimating the drainage for the area 

of interest;

(2) calculating the discharge of the Grand 

Calumet River at the point farthest 

downstream in the drainage area;

18 Quality of Wet Deposition in the Grand Calumet River Watershed, Northwestern Indiana
IUU

10

B!

UJ

H

CC

UJ

CU

S 0.1 1 

r

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^^ ^5 

QM ^^

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Cd ^

y

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LU

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1

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i

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0

S EXPLANATION

" «H/V\ 1CX) 

2

0

H

cd 10

H

2 

UJ 

U

2

O 1

U

: i :

-

^ 

; T

-

0.1 

UJ

CO

LU

z

S

z

JL

\

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-

5 O

ID

F

O

P£

CO

"2. »

90th percentile

75th percentile

Median

25th percentile

10th percentile

N

Figure 7. Constituent concentrations for trace metals measured in wet-deposition samples collected at the 

Gary (Indiana) Regional Airport.

Quality of Wet Deposition 19
0.8

0.6

0.4 

W 

DC

(J 0.2

W

£

DC

CO

0

3

2 0.15

z

g 0.10

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5

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2

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CALCIUM

-

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i "i- V ."i i i - -.1 i ' j i.. i

JJASONDJFMAMJ 

1992 1993

I i I i I i II II

; SODIUM

-

m

; . ;

-

,1lJ.lll.r,'- -,.,-, -r-.l,h

JJASONDJFMAMJ

1992 1993

I i i i i i i i I i i i 

SULFATE

-

-

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i i. . " ' i ' .i J..-' ."'i ..j . j i " i

JJASONDJFMAMJ

0.20

0.15

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I I I I I I I I I I I i 

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1 "l- 1' M 1 .1 1.". ."-I ..i J " 1 .. 1

JJASONDJFMAMJ 

1992 1993

I I I I i I I I I I I I . 

; POTASSIUM

: .

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I I « I 1 1 .1 1. . ll m.± * 4 I.I

JJASONDJFMAMJ

1992 1993

i I i i i i i I i i i I 

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' illlil.l.lllil .1 ill .1.1*1 . li __i . j .1 1. ii 1 :

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1992 1993 1992 1993

Figure 8. Estimated weekly major ion loadings determined from wet-deposition samples collected 

at the Gary (Indiana) Regional Airport. Bars indicate a possible range for the weekly loading and were 

computed when a measured constituent concentration was less than the method reporting limit. 

The minimun value for a range is zero; the maximum value was computed by substituting the method 

reporting limit for the constituent concentration.

20 Quality of Wet Deposition in the Grand Calumet River Watershed, Northwestern Indiana
0.4

0.3

UJ

0.1

0*

UJ

a. o

0.20

0.15

g 0,0

n i i i i i i i i i i r

CHLORIDE

J .J A S O N D 

1992

J F M A M J 

1993

o

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J JASOND 

1992

J F M A M J 

1993

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1992 1993

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NITRATE

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1992

JFMAMJ 

1993

Figure 8. Estimated weekly major ion loadings determined from wet-deposition samples collected at the 

Gary (Indiana) Regional Airport-Continued.

Quality of Wet Deposition 21
u.o

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Figure 9. Estimated weekly trace-metal loadings determined from wet-deposition samples collected 

at the Gary (Indiana) Regional Airport. Bars indicate a possible range for the weekly loading and were 

computed when a measured constituent concentration was less than the method reporting limit. 

The minimun value for a range is zero; the maximum value was computed by substituting the method 

reporting limit for the constituent concentration.

22 Quality of Wet Deposition in the Grand Calumet River Watershed, Northwestern Indiana
ESTIMATED WEEKLY LOADINGS, IN GRAMS PER HEC

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(3) using the discharge and the constituent 

concentrations from samples collected 

at the IDEM surface-water site located 

near the point where the discharge 

was determined to calculate the overall annual constituent loadings;

(4) using the drainage area and the 

concentrations measured for wetdeposition samples collected at 

the Gary airport to calculate the 

loadings to the Grand Calumet River 

from wet deposition; and

(5) computing the percent of the overall 

annual loading that is contributed by 

wet deposition.

A drainage area of 63.5 hectares for the 

Grand Calumet River upstream from Kennedy 

Avenue was calculated. This drainage area was 

calculated from USGS 1:24,000 scale maps 

(U.S. Geological Survey, 1991 a, b). The drainage 

area, the six IDEM surface-water sites, and the wetdeposition collection site are shown in figure 10. 

It was beyond the scope of this project to determine 

the fate of wet deposition runoff in this drainage 

area that was redirected from the basin by sewers.

Discharge was measured at two sites on the 

Grand Calumet River, however, a stage-discharge 

relation could not be determined because of backwater affecting the discharge measurements 

(J.A. Stewart, U.S. Geological Survey, oral 

commun.). To alleviate the backwater problem, 

four ultrasonic velocity meters (UVM's) that 

measure the velocity of the Grand Calumet River 

at least once every hour were installed from 1992 

through 1994. From the velocities measured by 

the UVM's, it would be possible to determine the 

stage-discharge relation; determining the stagedischarge relation would make it possible to 

estimate the overall loadings in the Grand 

Calumet River.

The range for the estimated annual constituent 

loadings (table 3) was calculated from the sum 

of the weekly loadings. Weekly loadings from 42 

samples collected for 1 year beginning in June 30, 

1992, at the Gary airport were used to calculate 

the range for the estimated annual loadings. The 

minimum annual loading was calculated by 

summing the minimum weekly loadings, and 

the maximum annual loading was calculated by 

summing the maximum weekly loadings. If a 

single value were calculated for a weekly loading, 

that value was included in the calculations of the 

minimum and maximum annual loading. If all of 

the 42 values for a constituent were greater than 

the method reporting limit, a single value was 

calculated and is reported as the maximum and 

minimum estimated annual loading.

By determining the product of the drainage 

area (63.5 hectares) and the estimated minimum 

and maximum annual loadings, a range for the 

contribution wet deposition has on the overall loadings in the Grand Calumet River can be determined. 

It will not be possible to determine the contribution 

wet deposition has on the overall loadings in the 

Grand Calumet River until a stage-discharge 

relation is available.

QUALITY ASSURANCE

Because of the low analyte concentrations 

observed in wet deposition, 52 samples submitted 

to the NWQL during the study period were for 

quality control. Two types of quality-control 

samples were submitted. Laboratory qualitycontrol samples (table 7, at back of report) were 

submitted to evaluate the quality of the DIW used 

in preparing quality-control-check solutions and in 

cleaning the equipment, and to evaluate laboratory 

accuracy and precision. Field quality-control 

samples (table 8, at back of report) were used to 

evaluate possible contamination resulting from

Quality Assurance 25
87°2730" 87°22'30" 87° 1730"

41°40' ^

41°37'30"

41°35' 

Base from U.S. Geological Survey digital data, 1:24,000 digital line graphs

Albers Equal-Area Conic Projection

Standard Parallels 29°30' and 45°30', central meridian -86°

MILES

I I I ] I I

012345 KILOMETERS

EXPLANATION

Drainage area

Gary city boundary

U.S. Geological Survey wet-deposition sampling site

Indiana Department of Environmental 

Management surface-water station

Study Area

Figure 10. Location of drainage area for the Grand Calumet River upstream from Kennedy Avenue, 

Indiana Department of Environmental Management surface-water stations, and the wet-deposition 

sampling site at the Gary (Indiana) Regional Airport.

26 Quality of Wet Deposition in the Grand Calumet River Watershed, Northwestern Indiana
Table 3. Range for the estimated annual loadings determined from wet-deposition samples collected at the Gary 

(Indiana) Regional Airport for 1 year beginning June 30, 1992

[kg/ha, kilograms per hectare; g/ha, grams per hectare]

Constituent

Calcium

Magnesium

Sodium

Potassium

Sulfate

Bromide

Chloride

Fluoride

Silica

Nitrate

Phosphate

Arsenic

Barium

Beryllium

Cadmium

Chromium

Cobalt

Copper

Iron

Lead

Lithium

Manganese

Mercury

Molybdenum

Nickel

Silver

Strontium

Vanadium

Zinc

Estimated 

minimum 

annual loading

4.9

.85

.36

.24

26

.09

1.9

.34

1.1

14

.01

0

18

.14

.42

27

0

9.9

310

10

0

69

0

0

.70

.88

9.1

0

24

Estimated 

maximum 

annual loading

4.9

.85

1.2

.25

26.4

.14

1.9

.34

1.1

14

.21

6.6

21

3.4

.86

57

20

11

310

11

26

69

.66

6.6

6.5

6.8

10

39

24

Reporting 

units

kg/ha

kg/ha

kg/ha

kg/ha

kg/ha

kg/ha

kg/ha

kg/ha

kg/ha

kg/ha

kg/ha

g/ha

g/ha

g/ha

g/ha

g/ha

g/ha

g/ha

g/ha

g/ha

g/ha

g/ha

g/ha

g/ha

g/ha

g/ha

g/ha

g/ha

g/ha

Quality Assurance 27
cleaning, transporting, and installing the clean 

equipment in the collector, possible contamination 

from the funnel, tubing, and collection bottle 

installed in the collector at the sampling site for 

1 week; and possible decreases in trace-metal 

concentrations resulting from trace metals 

absorbing onto the surfaces of the funnels, 

bottles, tubing, or filters. All sample processing 

procedures remained the same for field qualitycontrol samples, and all parameters and analytical 

techniques remained the same for the laboratory 

and field quality-control samples as those used 

for the wet-deposition samples.

Laboratory Quality Assurance

Nine DIW blanks were submitted periodically 

during the length of the study to determine if there 

were any sources of contamination resulting from 

the water used to prepare solutions and clean the 

equipment. None of the constituents measured, 

except fluoride (0.01 mg/L), had median concentrations greater than the method reporting limit. The 

median concentration for fluoride in the DIW 

blanks was equal to the method reporting limit 

and is equivalent to 25 percent the median concentration determined in the wet-deposition samples 

(table 6, at back of report). The results for the DIW 

laboratory blanks indicate that no significant source 

of contamination was present in the DIW used for 

DIW funnel rinses, preparing acidified DIW funnel 

rinses, and cleaning the equipment.

Two U.S. Geological Survey standard 

reference water samples (SRWS) with reported 

concentrations also were submitted to the laboratory for analysis. These samples were used to 

evaluate laboratory accuracy and precision, and 

to evaluate the SRWS's used as field qualitycontrol samples.

To determine laboratory precision, 10 precipitation SRWS's (P17) prepared by the USGS 

SRWS Project were rebottled in the USGS office 

laboratory in Indianapolis, Ind., and submitted to 

the NWQL for analysis. Concentrations measured 

less than the method reporting limit were set

equal to the method reporting limit. The 25th, 

50th, 75th percentile rankings and the calculated 

F-pseudosigmas (Hoaglin and others, 1983) for 

SRWS (P17) are listed in table 4. F-pseudosigma 

(eq. 1) is analogous to a standard deviation.

F-pseudosigma =

P15-P25 

1.349

where

P75 is the 75th percentile; and 

P25 is the 25th percentile.

F-pseudosigmas are presented in this report 

because they are resistant to outliers. Laboratory 

precision for this report is defined as plus or 

minus the F-pseudosigmas computed for the 

SRWS (P17). Laboratory precision was within 

10 percent of the median concentration determined 

for the wet-deposition samples collected at the 

Gary airport (table 6, at back of report) for all 

constituents except chloride (45 percent), fluoride 

(50 percent), silica (22 percent), and copper 

(40 percent).

Field Quality Assurance

DIW funnel rinses and acidified DIW funnel 

rinses were processed during the length of the study 

to evaluate the possible contamination resulting 

from cleaning the equipment, shipping the clean 

equipment to the Gary airport, installing the equipment in the collector, and processing the sample 

prior to sending it to the NWQL. DIW funnel rinses 

and acidified DIW funnel rinses were processed 

immediately after installation of clean equipment 

in the collector. The rinses were completed by 

passing 750 mL of the solution through the funnel, 

with as much of the inside of the funnel surface as 

possible exposed to the solution; the solution was 

collected in the collection bottle. The collection 

bottle was immediately removed and processed 

in the same manner as the wet-deposition samples. 

Median concentrations greater than the method

28 Quality of Wet Deposition in the Grand Calumet River Watershed, Northwestern Indiana
Table 4. Constituent measured; 25th, 50th, and 75th percentile rankings; and F-pseudosigmas for laboratory 

standard reference water sample (P17)

[mg/L, milligrams per liter, <, less than method reporting limit; NA, not applicable; ug/L, micrograms per liter]

Percentile Ranking

Constituent

Calcium

Magnesium

Sodium

Potassium

Sulfate

Chloride

Fluoride

Bromide

Silica

Nitrate

Phosphate

Arsenic

Barium

Beryllium

Cadmium

Chromium

Cobalt

Copper

Iron

Lead

Lithium

Manganese

Molybdenum

Nickel

Silver

Strontium

Vanadium

Zinc

25th 50th

0.31 0.32

.04 .04

.3 .3

.06 .06

.5 .5

.39 .45

<.01 <.01

<.01 <.01

.06 .09

1.19 1.20

<.03 <.03

<1 <1

<2 <2

<.5 <.5

<.l .1

<5 <5

<3 <3

.9 1.2

<3 3

<.5 <.5

<4 <4

9.2 9.4

<10 <10

<10 <10

<1 1

2 2

<6 <6

9.8 10

75th

0.32

.04

.4

.06

.6

.57

.04

<.01

.11

1.25

<.03

<1

2

<.5

.1

<5

<3

1.7

4

<.5

<4

9.9

<10

<10

2

2

<6

10

F-pseudosigma

0.01

0

.1

0

.1

.13

.02

0

.04

.04

NA

NA

0

NA

0

NA

NA

.6

0.7

NA

NA

.5

NA

NA

1

0

NA

.1

Reporting 

units

mg/L

mg/L

mg/L

mg/L

mg/L

mg/L

mg/L

mg/L

mg/L

mg/L

mg/L

Ug/L

Ug/L

Ug/L

Ug/L

Ug/L

Ug/L

Ug/L

Ug/L

Ug/L

Ug/L

ug/L

Ug/L

Ug/L

UgA->

Ug/L

Ug/L

Ug/L

Quality Assurance 29
reporting limit were determined from aliquots of 

the DIW funnel rinses for sulfate (0.01 mg/L), 

fluoride (0.02 mg/L), silica (0.04 mg/L), nitrate 

(0.13 mg/L), and manganese (0.3 M-g/L). All of 

these median concentrations (except for fluoride 

and silica) were below 10 percent of the median 

concentrations determined for the wet-deposition 

samples (fig. 11). The median concentrations 

determined for the DIW funnel rinses were 

50 percent of the median concentration determined in the wet-deposition samples for fluoride; 

however, the median concentration determined for 

fluoride in the wet-deposition samples (0.04 mg/L) 

was low (4 times the method reporting limit). The 

median concentration determined for the DIW 

funnel rinses was 22 percent of the median 

concentration determined in the wet-deposition 

samples for silica.

The results determined from the DIW funnel 

rinses indicate that contamination resulting from 

cleaning the equipment, shipping the clean equipment to the Gary airport, installing the equipment 

in the collector, and processing the samples did 

not result in significant contamination when 

compared to the concentrations measured in the 

wet-deposition samples. The median concentration 

of 0.13 mg/L determined for nitrate (fig. 10) in the 

DIW funnel rinses was probably a result of crossover contamination from the large quantity of nitric 

acid used during this study to clean the equipment 

and preserve the samples.

Because the median pH reported for wetdeposition samples collected at the NADP Indiana 

Dunes National Lakeshore site was approximately 

4.5, acidified DIW funnel rinses also were processed. The acidified DIW funnel rinses were 

prepared by diluting Ultrex nitric acid to a target 

pH of 4.5 with DIW.

Seven 750-mL acidified DIW funnel rinses 

were processed during the length of the study and 

median concentrations were computed; nitrate was 

excluded because nitric acid was used in the preparation of the acidified DIW funnel rinses. Median

concentrations greater than the method reporting 

limit were determined for silica (0.04 mg/L), 

copper (0.6 ug/L), manganese (0.6 U£/L), and zinc 

(1 H-g/L). The median concentration measured for 

the acidified DIW funnel rinses was 40 percent 

for copper and 22 percent for silica and zinc of 

the median weekly concentration computed for 

the wet-deposition samples (fig. 10). The median 

concentration measured for the acidified DIW 

funnel rinses for manganese was less than 

10 percent the median weekly concentration 

measured for the wet-deposition samples.

To examine if the constituent concentrations 

were altered by the funnel, Teflon tubing, Teflon 

collection bottle, or sample filtering, SRWS's 

(Tl 17) were processed in the same manner as the 

DIW and acidified DIW funnel rinses. Not all of 

the constituents were present in sufficient concentrations for all of the constituents of interest to be 

compared; however, some constituent comparisons 

were possible. Five samples of the same matrix 

(SRWS Tl 17) were rebottled in the USGS office 

laboratory in Indianapolis, Ind., and submitted to 

the NWQL for analysis. These samples will be 

referred to as "SRWS (Tl 17) funnel rinses." Five 

SRWS's (Tl 17) were processed as funnel rinses. 

The constituent, median concentrations computed 

for the SRWS (Til 7) funnel rinses, median 

concentrations computed for the laboratory 

SRWS's (Til7), the reported concentrations and 

F-pseudosigmas for SRWS (Til7) (Keith Long, 

U.S. Geological Survey, written commun.) are 

listed in table 5.

All of the median concentrations determined 

for the SRWS (Tl 17) funnel rinses (except for the 

median concentrations determined for zinc) were 

within the reported median concentrations plus 

or minus the reported F-pseudosigmas. All of the 

median concentrations determined for the laboratory SRWS's (Tl 17) (except for the median 

concentrations determined for cobalt, strontium, 

and zinc) were within the reported median concentrations plus or minus the F-pseudosigmas.

30 Quality of Wet Deposition In the Grand Calumet River Watershed, Northwestern Indiana
CC 3.0 UJ

5 2.5 

0.

DC 

UJ 

CL

c/)

cc

QD

O 

DC 

U

z

o

u

O

u

2.0

03

J

5

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Ofi

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UJ 

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z

8

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9 5 g

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CO

LUQ 

cc 

o CO

EXPLANATION 

H Method Reporting Limit

D

Deionized-Water Funnel 

Rinse

O Acidified DeionizedWater Funnel Rinses

Q Wet-Deposition Samples 

Collected at the Gary 

(Indiana) Regional Airport

< Less than the Method 

Reporting Limit

N

Figure 11 . Median constituent concentrations computed for the deionized-water funnel rinses 

and the acidified deionized-water funnel rinses compared to the median constituent concentrations 

computed for the wet-deposition samples and the method reporting limit.

Quality Assurance 31
Table 5. Comparison among median concentrations for the standard reference water sample (T117) funnel rinse 

processed at the Gary (Indiana) Regional Airport, median concentrations for the laboratory standard reference water 

sample (T117), and reported concentrations and F-pseudosigmas for standard reference water sample (T117)

[SRWS; U.S. Geological Survey standard reference water sample; mg/L, milligrams per liter, flg/L, micrograms per liter, <, reported less than the 

method reporting limit]

Constituent

Calcium

Magnesium

Sodium

Silica

Arsenic

Barium

Beryllium

Cadmium

Chromium

Cobalt

Copper

Iron

Lead

Lithium

Manganese

Molybdenum

Nickel

Silver

Strontium

Vanadium

Zinc

Median 

concentration for 

SRWS (T117) 

funnel rinses

22.0

10.0

20.0

12.0

7.0

97

4.9

2.6

10

4

6.5

480

5.5

21

21

10

<10

<1

270

<6

59

Median 

concentration 

for laboratory 

SRWS (T117)

22.0

10.0

19.0

12.0

8.0

97

4.9

2.5

9

<3

5.6

480

5.1

22

20

<10

<10

<1

280

<6

190

SRWS 

(T117) reported 

concentration

20.9

10.1

20.0

11.85

6.9

98

4.8

2.2

10

4.3

6.0

474

5.0

20

22

12

10

1.4

265

4.7

176

SRWS 

(T117) reported 

F-pseudosigma

1.2

.4

1.3

.64

1.4

6

.4

.4

2

.7

1.8

18

1.3

3

3

2

2

6.4

11

1.8

9

Reporting 

unit

mg/L

mg/L

mg/L

mg/L

Hg/L

M-g/L

M-g/L

M-g/L

M-g/L

M-g/L

M-g/L

M-g/L

M-g/L

M-g/L

M-g/L

M-g/L

M-g/L

M-g/L

M-g/L

M-g/L

M-g/L

32 Quality of Wet Deposition in the Grand Calumet River Watershed, Northwestern Indiana
The median strontium concentration 

measured for the SRWS (Tl 17) funnel rinses and 

the laboratory SRWS's (Tl 17) were within 10 percent of the reported concentration. The median 

cobalt concentration determined for the laboratory 

SRWS's (Tl 17) was less than the method reporting 

limit of 3 ug/L, which is at least 30 percent lower 

than the reported concentratioa None of the wetdeposition samples collected at the Gary airport 

had measured concentration greater than the 

method reporting limit for cobalt, indicating no 

significant cobalt contamination from the funnel, 

Teflon tubing, Teflon collection bottle, or filtering 

of the wet-deposition samples. The measured 

zinc concentrations determined for the five SRWS 

(Tl 17) funnel rinses ranged from 5.3 ug/L to 

490 ug/L when analyzed by GAFFS (table 8). In 

addition, the median concentration determined 

for the laboratory SRWS's (Tl 17) was 8 percent 

larger than the reported concentration. This scatter 

in the zinc results was not observed in the wetdeposition samples (less than 0.5 to 42 ug/L) or 

in any of the DIW or acidified DIW funnel rinses 

and is probably not an indication that there was a 

contamination problem with the wet-deposition 

samples. In addition, zinc also was analyzed by 

ICAP; however, zinc concentrations determined 

by ICAP are not presented because the method 

reporting limit was greater than most of the concentrations observed in the wet-deposition samples. 

On review of the ICAP results for zinc, the median 

concentration reported was 190 ug/L, which is 

equivalent to the median concentration determined 

for the laboratory SRWS's (Tl 17) (table 4). The 

median concentration determined for the laboratory 

SRWS's (Tl 17) for zinc was also within 10 percent 

of the reported concentration.

To evaluate possible contamination resulting 

from the equipment remaining on the sampler for 

1 week, four system blanks were processed on 

weeks when no wet deposition was collected in the 

collection bottle. System blanks were processed in 

the same manner as funnel rinses, except they were 

done at the end of the sampling week before installation of clean equipment in the collector. Median

concentrations were computed for the system 

blanks (table 8). Of the constituents measured, 

calcium (0.045 mg/L), magnesium (0.005 mg/L), 

potassium (0.03 mg/L), sulfate (0.035 mg/L), 

chloride (0.025 mg/L), fluoride (0.07 mg/L), 

silica (0.04 mg/L), manganese (0.9 ug/L), and 

zinc (0.65 ug/L) had median concentrations 

greater than the method reporting limit. These 

concentrations were equal to or greater than the 

median concentrations determined for the DIW 

funnel rinses and acidified DIW funnel rinses, 

indicating that contamination of the wet-deposition 

samples increased during the period the funnel, 

Teflon tubing, and Teflon collection bottle 

remained in the collector.

SUMMARY

Modifications were made to an AeroChem 

Metric 301 wet/dry collector for the collection and 

analysis of wet-deposition samples to evaluate the 

effects wet deposition may have on the chemical 

quality of the Grand Calumet River watershed 

and Lake Michigan. Wet-deposition samples 

were collected at the Gary (Indiana) Regional 

Airport from June 30,1992, through August 31, 

1993, and analyzed for pH, specific conductance, 

and selected major ions and trace metals. Fortyeight samples were collected over the 62-week 

study with sufficient volumes for some or all of the 

parameters to be measured. None of the samples 

collected at the Gary airport had measured concentrations greater than the method reporting limit for 

arsenic, cobalt, mercury, molybdenum, nickel, and 

vanadium. Sample concentrations measured at the 

Gary airport for calcium, magnesium, potassium, 

sulfate, and chloride, were similar to concentrations 

measured at the NADP site located at the Indiana 

Dunes National Lakeshore but larger than concentrations measured at the NADP site located at 

Huntington Reservoir. The Indiana Dunes National 

Lakeshore site is located approximately 26 km east 

and the Hunnington Reservoir is located approximately 180 km southeast of the Gary airport.

Summary 33
Similar concentrations were measured for major 

ions at the Indiana Dunes National Lakeshore, 

compared to samples collected at the Gary airport. 

This may indicate that the sources affecting 

samples collected at the Gary airport are the 

same sources affecting samples collected at the 

Indiana Dunes National Lakeshore.

A drainage area was estimated, not taking 

into account redirection of storm runoff, for a part 

of the Grand Calumet River. Ranges for weekly 

and annual loadings were calculated from the 

measured concentrations for samples collected at 

the Gary airport to estimate the contribution wet 

deposition has on the overall loadings in the Grand 

Calumet River. The calculation of the streamflow 

loadings was not possible for this study because 

a stage-discharge relation was not available for 

the Grand Calumet River. The USGS has installed 

UVM's to measure the velocity of the Grand 

Calumet River and determine a stage-discharge 

relation. This calculation may be possible following 

an additional year of sampling.

An insufficient number of samples was 

collected at the Gary airport to perform a seasonal 

trend analysis; however, sample concentrations 

from weeks when rain was the predominant form 

of wet deposition were larger than for weeks 

when snow was predominant. Concentrations

measured in samples collected from rain events 

were probably larger than concentrations measured 

in samples from snow events because of better 

scavenging of the atmosphere by rain.

In addition to the wet-deposition samples 

collected at the Gary airport, 52 quality-assurance 

samples were submitted for analysis to determine 

if the cleaning, transporting, installing, or filtering 

of the samples contributed contamination to 

the samples. Quality-control samples also were 

submitted to examine the accuracy of analytical 

procedures used by the NWQL for this study. 

Some problems associated with contamination in 

the field and possibly with the analyses for zinc 

were observed; however, these problems did not 

appear to affect substantially the wet-deposition 

samples.

Northwestern Indiana is the State's highest 

priority area for nonpoint-source pollution control. 

The impact of airborne pollutants in this industrialized area may have a major effect on the chemical 

quality on inland waters and Lake Michigan. More 

wet-deposition data are needed to evaluate the 

transport of airborne pollutants and to determine 

the contribution that wet deposition has on the 

overall loadings in the Grand Calumet River.

34 Quality of Wet Deposition in the Grand Calumet River Watershed, Northwestern Indiana
REFERENCES CITED

Amdur, M.O.; Doull, John; and Klaassen, C.D., eds., 

1993, Casarett and Doull's toxicology, the basic 

science of poisons (4th ed.): New York, McGrawHill, p. 623-680.

Bigelow, D.S., 1984, Instruction manual NADP/NTN 

site selection and installation: National Atmospheric 

Deposition Program, National Resources Ecology 

Laboratory, Colorado State University, Fort Collins, 

Colo., 23 p.

Bigelow, D.S., and Dossett, S.R., 1988, instruction 

manual NADP/NTN site operation: National 

Atmospheric Deposition Program, National 

Resources Ecology Laboratory, Colorado State 

University, Fort Collins, Colo., 40 p.

Dossett, S J*., and Bowersox, V.C., 1991, The potential 

for sample contamination due to raindrop splash 

off of the NADP wet/dry precipitation collector, in 

NADP Technical Committee Meeting, Proceedings: 

Philadelphia, Pa., October 7-10,1991, National 

Atmospheric Deposition Program, p. 6.

Eisler, Ronald, 1988, Arsenic hazards to fish, wildlife, 

and invertebrates a synoptic review: U.S. Fish and 

Wildlife Service Biological Report 85(1.12), 92 p.

Fishman, M J., and Friedman, L.C., eds., 1989, Methods 

for determination of inorganic substances in water 

and fluvial sediments (3d ed.): U.S. Geological 

Survey Techniques of Water-Resources Investigations, book 5, chap. Al, 545 p.

Fogg, T.R., and Fitzgerald, W.F., 1979, Mercury in 

southern New England coastal rain: Journal of 

Geophysical Research, v. 84, no. cl 1, p. 6987-6989.

Galloway, J.N.; Cowling, E.B.; Gorham, Eville; and 

McFee, W.W., 1978, A national program for assessing the problem of atmospheric deposition (acid 

rain) National Atmospheric Deposition Program 

report to the U.S. Council on Environmental 

Quality: Washington, D.C., 94 p.

Herdendorf, C.E., 1982, Large lakes of the world: Journal of Great Lakes Research, v. 8, no. 3, p. 379-412.

Helsel, D.R., and Hirsch, R.M., 1992, Statistical method 

in water resources, studies in environmental science 

49: Elsevier Science Publishing Co. Inc., New York, 

p. 26.

Hoaglin, D.C.; Mosteller, F.; and Tukey, J.W., 1983, 

Understanding robust and exploratory data analysis, 

John Wiley & Sons, Inc., New York, NY, p. 40.

Indiana Nonpoint Source Task Force, 1989, Indiana 

Nonpoint Source Water Pollution Management 

Program, p. 68,98.

Klappenbach, E.W., 1991, Analysis and deposition of 

trace metals around the Great Lakes, in The deposition and fate of trace metals in our environment, 

Philadelphia, October 1991, Proceedings: USDA 

Forest Service, North Central Forest Experimental 

Station, p. 37-43.

Schroder, LJ., and Hedley, A.G., 1986, Variation in 

precipitation quality during a 40-hour snowstorm in 

an urban environment Denver, Colo., International 

Journal of Environmental Studies, 28 p.

Schroder, LJ.; WiUoughby, T.C.; See, R.B.; and 

Malo, B.A., 1989, The chemical composition of 

precipitation, dew and frost, and fog in Denver, 

Colo., in Atmospheric Deposition, Proceedings 

of the Baltimore Symposium: Baltimore, Md., 

May 1989, p. 83.

Shiomi, M.T., and Kuntz, K.W., 1973, Great Lakes 

precipitation chemistry, Part 1, Lake Ontario Basin, 

in Proceedings: 16th International Conference 

on Great Lakes Research, p. 581-602.

U.S. Environmental Protection Agency, 1992, Drinking 

water regulations and health advisories: Washington, D.C., U.S. Environmental Protection Agency, 

13 p.

U.S. Geological Survey, 199la, Gary Quadrangle, scale 

1:24,000.

___1991b, Highland Quadrangle, scale 1:24,000.

References Cited 35
SUPPLEMENTAL DATA
Table 6. Reported concentrations for wet-deposition samples collected at the Gary (Indiana) Regional Airport

Quality ofWetD

*

g

A

O

5'

3-

9

o

5

a.

0?

c

3

£

2

J

09

a

3

I

z

o

1»

a

5

3

a5*

09

[FAAS, sample analyzed by flame atomic absorption spectrometry; 1C, sample analyzed by ion chromatography; ICAP, sample analyzed by inductively coupled arg

HF, sample analyzed by atomic absorption spectrometry hydride formation; GFAAS, sample analyzed by graphite furnace atomic absorption spectrometry; CV, sam

spectrometry, cold vapor, |iS/cm, microSiemens per centimeter at 25 degrees Celsius; mg/L, milligrams per liter, Hg/L, micrograms per liter, , not analyzed; <, co

reporting limit; O.F., sample overflowed the 5-liter collection bottle]

Date

on

06/30/92

07/07/92

07/14/92

07/21/92

07/28/92

08/04/92

08/11/92

08/18/92

08/25/92

09/01/92

09/08/92

09/15/92

09/22/92

10/06/92

10/13/92

10/20/92

10/27/92

Time 

on

(24-

hour

time)

1015

0944

1053

1040

1115

1115

1115

1130

1105

1220

1200

1230

1150

1145

1145

1140

1245

Date

off

07/07/92

07/14/92

07/21/92

07/28/92

08/04/92

08/11/92

08/18/92

08/25/92

09/02/92

09/08/92

09/15/92

09/22/92

09/29/92

10/13/92

10/20/92

10/27/92

11/03/92

Time

off

0928

1039

1000

1105

1315

1055

1120

1050

1215

1130

1205

1145

1105

1115

1120

1120

1130

Volume

(liters)

0.967

.971

1.063

.778

2.090

.085

1.117

.130

1.890

1.103

O.F.

.785

1.515

.444

1.065

.001

2.415

Specific

conductance

(jiS/cm)

23.0

19.0

21.0

32.0

15.0

-

14.0

~

25.5

18.0

19.0

22.0

20.0

28.0

33.0

-

21.0

Field 

pH

(standard

units)

6.99

5.11

4.23

4.23

4.54

-

4.48

4.67

4.55

4.46

4.44

4.42

5.34

5.70

3.52

4.64

Calcium

(FAAS)

(mg/L)

4.00

1.20

1.20

.36

.37

1.80*

.97

2.60*

1.50

.19

.16

.06

.28

1.70

3.10

~

.53

Magnesium

(FAAS)

(mg/L)

1.40

.24

.23

.09

.08

.36*

.22

.69*

.07

.04

.02

.01

.06

.35

.27

-

.09

Sodium

(FAAS)

(mg/L)

0.20

.50

<.20

<.20

<.20

.30*

<.20

<.20*

<.20

<.20

<.20

<.20

<.20

<.20

<.20

-

.03

Potassium

(FAAS)

(mg/L)

0.09

.08

.05

.02

.03

-

.09

.04

.02

.01

<.01

.06

.22

.14

-

.02

Sulfate

(1C)

(mg/L)

5.4

3.9

4.1

3.8

2.1

~

2.7

~

24.0

2.1

2.1

2.2

2.4

4.2

5.8

-

3.6

(
Table 6. Reported concentrations for wet-deposition samples collected at the Gary (Indiana) Regional Airport Continued

3)

 8

O

i

g>

o

1

o'

3

6"

I

*"§

w

o"

1 o

8

CO<o

Date 

on

11/03/92

11/10/92

11/24/92

12/01/92

12/08/92

12/15/92

12/22/92

01/05/93

01/12/93

01/19/93

02/09/93

02/16/93

02/23/93

03/09/93

03/16/93

03/23/93

03/30/93

04/06/93

04/13/93

04/27/93

05/04/93

Time 

on 

(24- 

hour 

time)

1136

1245

1200

1250

1150

1205

1215

1140

1215

1235

1115

1145

1210

1045

1100

1110

1045

0955

0930

1010

0955

Date 

off

11/10/92

11/17/92

12/01/92

12/08/92

12/15/92

12/22/92

12/29/92

01/12/93

01/19/93

01/26/93

02/16/93

02/23/93

03/02/93

03/16/93

03/23/93

03/30/93

04/06/93

04/13/93

04/20/93

05/04/93

05/11/93

Time 

off

1215

1200

1215

1150

1205

1215

1145

1215

1136

1210

1145

1100

1130

1040

1015

1030

0935

0915

0940

0940

1010

Volume 

(liters)

1.910

1.967

.287

.018

.668

.999

.959

.039

.784

1.195

.061

.002

.012

.164

2.425

.001

2.485

.375

4.776

1.086

.359

Specific 

conductance

(US/cm)

16.0

17.0

-

--

13.0

13.0

23.0

-

25.0

43.0

-

-

--

--

30.7

_.

39.6

-

23.5

47.0

Fieid 

pH 

(standard 

units)

4.74

4.96

5.45

4.25

4.71

4.71

4.50

3.88

4.29

5.50

3.84

3.61

3.55

--

4.71

3.55

4.27

4.04

4.00

4.25

4.45

Calcium 

(FAAS) 

(mg/L)

0.82

.60

1.80*

-

.28

.18

.13

--

.25

.08

~

-

1.70*

1.30

_.

.87

.65*

.33

.99

.17*

Magnesium 

(FAAS) 

(mg/L)

0.13

.07

.37*

--

.06

.04

.02

--

.04

.02

--

.16*

.22

_.

.06

.15*

.11

.15

.03*

Sodium 

(FAAS) 

(mg/L)

0.04

.04

<.20*

-

.34

.16

.15

-

.18

.10

-

.50*

.30

_

<.20

.20*

<.20

.07

.20*

Potassium 

(FAAS) 

(mg/L)

0.03

.02

-

--

.02

.02

.05

--

.03

<.01

-

--

--

.03

_

.02

.03

.07

Sulfate 

(1C) 

(mg/L)

2.5

2.9

--

--

1.2

1.5

1.9

--

2.8

1.4

--

--

--

4.9

_

4.6

2.7

5.8

Ch

ri

(1

(mg

0.

.

.

.

.

.
g Table 6. Reported concentrations for wet-deposition samples collected at the Gary (Indiana) Regional Airport Continued

8

=-.

!

& Date 

o on

£ 05/11/93 o'

\ 05/18/93

» 06/08/93 

O

5 06/15/93

a.

» 06/29/93

c 

I 07/20/93

3D

| 08/03/93

| 08/10/93

<D

1- 08/17/93

s.

z 08/23/93 

o

Time

on 

(24- 

hour Date 

time) off

1200 05/18/93

1030 05/25/93

1300 06/15/93

0900 06/22/93

0945 07/06/93

0915 07/27/93

1105 08/10/93

1300 08/17/93

1000 08/24/93

0915 08/30/93

Time Volume 

off (liters)

1005 .065

1140 .743

0825 1.446

1130 O.F.

1630 1.534

1230 1.830

1234 2.234

0930 .260

0900 1.154

1030 O.F.

Specific 

conductance

(US/cm)

..

--

--

--

162.0

21.5

19.9

--

19.6

37.9

Field

pH 

(stan- Calcium 

dard (FAAS) 

units) (mg/L)

4.54

6.76 3.40*

4.71 .43*

4.48 .41*

7.39 1.50

4.48 .25

4.84 .87

4.05 1.30*

5.78 1.50

4.20 .25

Magnesium 

(FAAS) 

(mg/L)

.51*

.09*

.05*

.33

.05

.23

.24*

.40

.04

Sodium 

(FAAS) 

(mg/L)

<.20*

<.20*

<.20*

.40

.30

<.20

<.20*

<.20

<.20

Potassium 

(FAAS) 

(mg/L)

--

--

-

3.30

.03

.04

--

.04

.02

Sulfate

(1C) 

(mg/L)

_

--

-

-

6.7

1.4

2.6

--

3.8

3.9

C

r

(m

f "'Constituent was analyzed by induaively coupled argon plasma atomic emission spectrometry.

w

5

3

a. £'
Table 6. Reported concentrations for wet-deposition samples collected at the Gary (Indiana) Regional Airport Continued

Date Date 

on off

06/30/92 07/07/92

07/07/92 07/14/92

07/14/92 07/21/92

07/21/92 07/28/92

07/28/92 08/04/92

08/04/92 08/11/92

08/11/92 08/18/92

08/18/92 08/25/92

08/25/92 09/02/92

09/01/92 09/08/92

09/08/92 09/15/92

09/15/92 09/22/92

09/22/92 09/29/92

10/06/92 10/13/92

10/13/92 10/20/92

10/20/92 10/27/92

10/27/92 11/03/92

11/03/92 11/10/92

11/10/92 11/17/92

11/24/92 12/01/92

12/01/92 12/08/92

Nitrate 

(1C) 

(mg/L)

2.61

3.32

2.35

2.43

1.51

-

1.73

-

1.33

1.46

1.33

1.24

1.51

4.43

5.32

--

1.73

1..64

1.20

--

_.

Phosphate 

(1C) 

(mg/L)

<0.03

<.03

<.03

--

<.03

--

<.03

--

<.03

<.03

<.03

<.03

<.03

.09

<.03

--

<.03

<.03

<.03

--

__

Arsenic Barium 

(HF) (ICAP) 

(Mg/L) (jig/L)

<1 15

<1 4

<1 4

<1 2

<1 <2

<1 6

<1 3

<1 7

<1 7

<1 <2

<1 2

<1 <2

<1 <2

<1 5

<1 12

--

<1 <2

<1 7

<1 2

<1 3

Beryllium Cadmium 

(ICAP) (GFAAS) 

(jig/L) (ng/L)

<0.5 0.3

<.5 <.l

<.5 <.l

<.5 <.l

<.5 <.l

<.5 .4

<.5 <.l

<.5 .2

<.5 <.l

<.5 .2

<.5 <.l

<.5 <.l

<.5 <.l

<.5 .2

1.0 .1

--

<.5 <.l

<.5 .1

<.5 .1

<.5 4.0

Chromium 

(ICAP)

<5

<5

<5

<5

<5

<5

<5

<5

<5

<5

<5

<5

<5

21

<5

--

<5

<5

<5

<1

Cobalt 

(ICAP)

(WI/L)

<3

<3

<3

<3

<3

<3

<3

<3

<3

<3

<3

<3

<3

<3

<3

--

<3

<3

<3

<1

_.

Copper 

(GFAAS)

11.0

2.1

1.2

1.1

2.0

7.1

1.2

3.8

.7

1.0

<.5

<.5

.7

7.3

4.1

--

.7

2.1

2.7

5.0

__

Iron 

(ICAP)

(ng/L)

420

93

72

31

14

63

61

180

30

10

15

6

8

45

57

--

61

26

19

49

__

Lead 

(GFAAS)

(ng/L)

8.7

.6

.8

1.5

<.5

1.0

.8

10.0

2.3

1.3

1.2

.7

1.8

4.2

5.8

--

1.5

2.7

1.8

4.0

._

Lithium 

(ICAP)

(ng/L)

<4

<4

<4

<4

<4

<4

<4

<4

<4

<4

<4

<4

<4

<4

<4

--

<4

<4

<4

<4

Manganese Mercury 

(GFAAS) (CV) 

(mg/L) (ng/L)

64.0 <0.1

19.0 <.l

18.0 <.l

4.9 <.l

6.1 <.l

19.0

17.0 <.l

30.0

5.3 <.l

5.0 <.l

2.3 <.l

.9 <.l

3.2 <.l

18.0

23.0 <.l

-

14.0 <.l

7.3 <.l

20.0 <.l

59.0

__

M

d

(
Table 6. Reported concentrations for wet-deposition samples collected at the Gary (Indiana) Regional Airport Continued

Date 

on

12/08/92

12/15/92

12/22/92

01/05/93

01/12/93

01/19/93

02/09/93

02/16/93

02/23/93

03/09/93

03/16/93

03/23/93

03/30/93

04/06/93

04/13/93

04/27/93

05/04/93

05/11/93

05/18/93

06/08/93

06/15/93

Date 

off

12/15/92

12/22/92

12/29/92

01/12/93

01/19/93

01/26/93

02/16/93

02/23/93

03/02/93

03/16/93

03/23/93

03/30/93

04/06/93

04/13/93

04/20/93

05/04/93

05/11/93

05/18/93

05/25/93

06/15/93

06/22/93

Nitrate 

(1C) 

(mg/L)

1.37

1.64

1.20

--

1.24

5.76

--

--

--

--

3.10

--

3.10

--

1.68

4.03

--

--

--

--

__

Phosphate Arsenic Barium 

(1C) (HF) (ICAP) 

(mg/L) (jig/L) (fig/L)

<0.03 <1 <2

<.03 <1 2

<.03 <1 3

--

<.03 <1 2

<.03 <1 2

--

-

..

<1 5

<.03 <1 3

..

<.03 <1 3

<1 3

<.03 <1 3

<.03 <1 3

<1 3

--

<1 6

<1 2

<1 <2

Beryl- Chromiium Cadmium ium 

(ICAP) (GFAAS) (ICAP) 

(jig/L) (ftg/L) (fig/L)

<0.5 0.1 <5

<.5 .1 <5

<.5 <.l 190

--

<.5 <.l <5

<.5 <.l <5

--

--

--

<.5 <.l <5

<.5 <.l 5

--

<.5 <.l <5

<.5 .3 <5

<.5 <.l <5

<.5 <.l <5

<.5 <.l <5

-

<.5 .1 <5

<.5 <.l <5

<.5 .1 <5

Cobalt 

(ICAP)

<3

<3

<3

-

<3

<3

--

-

-

<3

<3

-

<3

<3

<3

<3

<3

-

<3

<3

<3

Copper 

(GFAAS)

2.6

1.6

2.1

--

2.7

.9

--

-

-

2.7

2.3

--

1.3

2.9

1.3

2.3

2.4

-

.8

.6

<.5

Iron 

(ICAP)

20

11

51

--

27

14

--

--

--

21

320

--

22

92

10

42

13

--

6

10

9

Lead 

(GFAAS) 

(H9/L)

1.8

.8

.6

--

1.0

<.5

--

-

--

2.7

3.4

--

1.2

3.9

<.5

1.8

1.1

-

1.1

.8

.9

Lithium 

(ICAP) 

(H9/L)

<4

<4

<4

--

<4

<4

--

--

--

<4

<4

--

<4

<4

<4

<4

<4

--

<4

<4

<4

Manga- 

nese Mercury 

(GFAAS) (CV) 

(mg/L) (jig/L) 

7.3 <0.1 

2.2 <.l 

2.5 <.l 

--

4.7 <.l 

1.1 - 

-

-

--

14.0 - 

38.0 - 

--

5.6 - 

17.0 - 

4.0 - 

15.0 - 

3.7 - 

-

16.0 <.l 

6.2 <.l 

4.4 <.l 
Table 6. Reported concentrations for wet-deposition samples collected at the Gary (Indiana) Regional Airport Continued

Beryl- Chrom- Manga- M

Nitrate Phosphate Arsenic Barium Hum Cadmium ium Cobalt Copper iron Lead Lithium nese Mercury d

Date Date (1C) (1C) (HF) (ICAP) (ICAP) (GFAAS) (ICAP) (ICAP) (GFAAS) (ICAP) (GFAAS) (ICAP) (GFAAS) (CV) (

on off (mg/L) (mg/L) (jig/L) (fig/L) (fig/L) (fig/L) (fig/L) (fig/L) (jig/L) (jig/L) ((ig/L) (jig/L) (mg/L) (fig/L) (

06/29/93 07/06/93 1.73 3.41 <1 3 <0.5 0.4 <5 <3 1.6 18 <0.5 4 2.0 <0.1 <

07/20/93 07/27/93 2.97 <.03 <1 2 <.5 <.l <5 <3 <.5 33 1.0 <4 4.5 <.l <

08/03/93 08/10/93 4.08 <.03 <1 4 <.5 <.l <5 <3 1.0 19 2.5 <4 9.9 <.l <

08/10/93 08/17/93 - - <1 4 <.5 .2 <5 <3 1.3 42 2.8 <4 20.0 - <

08/17/93 08/24/93 2.08 <.03 <1 4 <.5 .1 <5 <3 .84 1.1 <4 17.0 <.l <

08/23/93 08/30/93 1.68 <.03 <1 <2 <.5 <.l <5 <3 <.5 13 1.5 <4 4.1 <.l <

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Reported Concentrations for Laboratory Quality-Control Samples 45
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Table 7. Reported concentrations for laboratory quality-control samples processed at the U.S. Geological Survey office laboratory in 

Date

09/04/92

09/04/92

09/04/92

09/04/92

09/04/92

09/04/92

09/04/92

09/04/92

09/04/92

08/25/93

08/25/93

08/25/93

08/25/93

08/25/93

08/30/93

08/30/93

08/30/93

08/30/93

08/30/93

Sample type

Blank

Blank

Blank

Blank

SRWS (P17)

SRWS (P17)

SRWS (P17)

SRWS (P17)

SRWS (P17)

Blank

Blank

Blank

Blank

Blank

SRWS (Till)

SRWS (Till)

SRWS (P17)

SRWS (P17)

SRWS (P17)

Arsenic Barium 

(HF) (ICAP) 

(W/L) (Mfl/L)

<1 <2

<1 <2

<1 <2

<1 <2

<1 <2

<1 <2

<1 <2

<1 <2

<1 <2

<1 <2

<1 <2

<1 <2

<1 <2

<1 <2

8 94

8 94

<1 2

<1 <2

<1 2

Beryllium Cadmium Chromium 

(ICAP) (GFAAS) (ICAP)

<0.5 <0.1 <5

<.5 <.l <5

<.5 <.l <5

<.5 <.l <5

<.5 .1 <5

<.5 .1 <5

<.5 .1 <5

<.5 <.l <5

<.5 <.l <5

<.5 <.l <5

<.5 <.l <5

<.5 <.l <5

<.5 <.l <5

<.5 <.l <5

4.5 2.5 9

4.5 2.5 9

<.5 .1 <5

<.5 .1 <5

<.5 .1 <5

Cobalt 

(ICAP) 

(Mfl/L)

<3

<3

<3

<3

<3

<3

<3

<3

<3

<3

<3

<3

<3

<3

<3

4

<3

<3

<3

Copper 

(GFAAS) 

(WJ/L)

<0.5

<.5

<.5

<.5

1.7

1.7

1.1

2.3

.9

<.5

<.5

1.2

<.5

<.5

5.6

4.9

1.2

.7

1.8

Iron 

(ICAP)

<3

<3

<3

<3

3

4

<3

<3

<3

<3

<3

<3

<3

<3

460

460

4

<3

6

Lead 

(GFAAS) 

(Mfl/L) 

<0.5 

<.5 

<.5 

<.5 

<.5 

<.5 

<.5 

<.5 

<.5 

<.5 

<.5 

<.5 

<.5 

<.5 

5.0 

5.1 

.7 

<.5 

<.5 
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Reported Concentrations for Laboratory Quality-Control Samples 47
Table 7. Reported concentrations for laboratory quality-control samples processed at the U.S. Geological Survey office laboratory in 

Quality ofWel

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Date

09/04/92

09/04/92

09/04/92

09/04/92

09/04/92

09/04/92

09/04/92

09/04/92

09/04/92

08/25/93

08/25/93

08/25/93

08/25/93

08/25/93

08/30/93

08/30/93

08/30/93

08/30/93

08/30/93

08/30/93

Nickel 

(ICAP) 

Sample type (M£/L)

Blank <10

Blank <10

Blank <10

Blank <10

SRWS (P17) <10

SRWS (P17) <10

SRWS (P17) <10

SRWS (P17) <10

SRWS (P17) <10

Blank <10

Blank <10

Blank <10

Blank <10

Blank <10

SRWS (T117) <10

SRWS (T117) <10

SRWS (P17) <10

SRWS (P17) <10

SRWS (P17) <10

SRWS(T117) <10

Silver Strontium 

(ICAP) (ICAP) 

(Ufl/L) (u.g/L)

2 <0.5

1 <.5

<1 <.5

<1 <.5

<1 2.0

1 2.0

<1 2.0

<1 2.0

3 2.0

<1 <.5

<1 <.5

<1 <.5

<1 <.5

<1 <.5

<1 270

<1 260

1 2.0

<1 2.0

2 2.0

<1 280

Vanadium 

(ICAP)

<6

<6

<6

<6

<6

<6

<6

<6

<6

<6

<6

<6

<6

<6

<6

<6

<6

<6

<6

<6

Zinc 

(GFAAS)

<0.5

<.5

<.5

<.5

9.6

10.0

11.0

8.8

10.0

<.5

<.5

<.5

<.5

<.5

180

190

10.0

9.9

10.0

190
0)

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Reported Concentrations for Laboratory Quality-Control Samples 49
g Table 8. Reported concentrations for field quality-control samples processed at the Gary (Indiana) Regional Airport

Oc

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[FAAS, sample analyzed by flame atomic absorptoon spectrometry; 1C, sample iinalyzed by ion chromatography; ICAP, sample analyzed by inductively coupled arg

HF, sample analyzed by atomic absorption spectrometry hydride formation; GFAAS, sample analyzed by graphite furnace atomic absorption spectrometry; CV, sam

spectrometry, cold vapor, US/cm, microSiemens per centimeter at 25 degrees Celsius; mg/L, milligrams per liter; DIW, deionized water; Ug/L, micrograms per liter

method reporting limit; SRWS

Date

06/30/92

07/21/92

08/11/92

08/25/92

09/15/92

09/29/92

10/06/92

10/20/92

11/17/92

12/01/92

01/05/93

01/19/93

01/26/93

02/02/93

02/02/93

02/23/93

03/09/93

Time

1005

1035

1105

1105

1212

1120

1126

1131

1206

1250

1201

1206

1010

1021

1045

1110

1031

, U.S. Geological Survey standard reference water sample;

Sample type

Funnel Rinse

Funnel Rinse

Funnel Rinse

Funnel Rinse

Funnel Rinse

System Blank

Funnel Rinse

Funnel Rinse

Funnel Rinse

Funnel Rinse

Funnel Rinse

Funnel Rinse

System Blank

Funnel Rinse

System Blank

Funnel Rinse

Funnel Rinse

Specific

conducSample tance

matrix ((iS/cm)

DIW 4.0

DIW 3.0

SRWS (P17) 33.0

Acid 17.3

DIW 2.0

DIW 2.0

SRWS (Tl 17)

Acid 19.0

Acid 10.0

DIW 3.0

SRWS (Tl 17)

DIW 2.0

DIW

DIW 2.2

DIW

SRWS (Tl 17)

Acid 18.5

pH

(standard

units)

5.10

5.50

4.10

4.87

6.30

7.90

--

4.30

4.40

5.10

--

5.30

6.21

5.39

--

4.41

 , not analyzed]

Calcium

(FAAS)

(mg/L)

0.06

<.02

.34

.02

<.02

.03

21.00*

<.02

<.02

.08

21.00*

.04

.06*

.03

<.02*

22.00*

.07

Magnesium

(FAAS)

(mg/L)

0.02

<.01

.05

<.01

<.01

<.01

9.90*

<.01

<.01

.02

10.00*

<.01

.02*

<.01

<.01*

10.00*

.02

PotasSodlum slum

(FAAS) (FAAS)

(mg/L) (mg/L)

<0.20 <0.01

<.20 <.01

.30 .41

<.20 <.01

<.20 <.01

<.20 .05

20.00*

<.20 .06

<.20 <.0l

<.01 <.01

20.00*

<.01 <.01

<.20*

<.20 <.01

<.20*

21.00*

<.20 <.01

Sulfate

(1C)

(mg/L)

<0.01

.01

.73

<.01

.02

.03

--

<.01

<.01

.03

--

<.01

.02

--

--

.02

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Reported Concentrations for Field Quality-Control Samples 51
Table 8. Reported concentrations for field quality-control samples processed at the Gary (Indiana) Regional Airport Continued

Quality ofWe

T3 1

O

2L

3

5"

3

9

O^

0)

a

ff

c

3 

2

3)

1

0)

5

w

f

Q.

z

o

1

13

5"

a5*

0)

Date

06/30/92

07/21/92

08/11/92

08/25/92

09/15/92

09/29/92

10/06/92

10/20/92

11/17/92

12/01/92

01/05/93

01/19/93

01/26/93

02/02/93

02/02/93

02/23/93

03/09/93

03/23/93

04/06/93

04/20/93

Sample type

Funnel Rinse

Funnel Rinse

Funnel Rinse

Funnel Rinse

Funnel Rinse

System Blank

Funnel Rinse

Funnel Rinse

Funnel Rinse

Funnel Rinse

Funnel Rinse

Funnel Rinse

System Blank

Funnel Rinse

System Blank

Funnel Rinse

Funnel Rinse

Funnel Rinse

Funnel Rinse

Funnel Rinse

Sample 

matrix

DIW

DIW

SRWS (P17)

Acid

DIW

DIW

SRWS (Tl 17)

Acid

Acid

DIW

SRWS (T117)

DIW

DIW

DIW

DIW

SRWS (T117)

Acid

Acid

SRWS (T117)

DIW

Nitrate 

(1C) 

(mg/L)

0.40

.13

<.04

3.10

.04

<.04

--

3.23

1.15

.22

<.04

-

<.04

--

3.15

2.48

-

.13

Phosphate Arsenic 

(1C) (HF) 

(mg/L) (M4/L)

<1

<1

<1

<.03 <1

<.03 <1

<.03 <1

7

<.03 <1

<.03 <1

<.03 <1

8

<.03 <1

<1

<.03 <1

<1

7

<.03 <1

<.03 <1

7

<.03 <1

Barium 

(ICAP) 

(Mfl/U

<2

<2

2

<2

<2

<2

96

<2

<2

<2

97

<2

<2

<2

<2

98

<2

<2

100

<2

Beryllium Cadmium Chromium 

(ICAP) (GFAAS) (ICAP) 

(ug/L) (Hg/L) (ug/L)

<0.5 <0.1 <5

<.5 <.l <5

<.5 <.l 530

<.5 <.l <5

<.5 <.l <5

<.5 <.l <5

5.6 2.5 9

<.5 <.l <5

<.5 <.l <5

<.5 <.l <5

4.8 2.0 11

<.5 <.l <5

<.5 <.l <5

<.5 <.l <5

<.5 <.l <5

4.8 2.6 10

<.5 <.l <5

<.5 <.l <5

4.9 2.7 12

<.5 <.l <5

Cobalt 

(ICAP)

(Mfl/L)

<3

<3

<3

<3

<3

<3

4

<3

<3

<3

4

<3

<3

<3

<3

3

<3

<3

4

<3
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Reported Concentrations for Field Quality-Control Samples 53
£ Table 8. Reported concentrations for field quality-control samples processed at the Gary (Indiana) Regional Airport Continu

ality ofWet Deposit

o

3

5"

the Grand

O

a

2

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h&

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Date

06/30/92 

07/21/92

08/11/92

08/25/92 

09/15/92

09/29/92

10/06/92

10/20/92

11/17/92 

12/01/92

01/05/93

01/19/93

01/26/93

02/02/93

02/02/93

02/23/93

03/09/93

03/23/93

04/06/93

04/20/93

Sample type

Funnel Rinse 

Funnel Rinse

Funnel Rinse

Funnel Rinse 

Funnel Rinse

System Blank

Funnel Rinse

Funnel Rinse

Funnel Rinse 

Funnel Rinse

Funnel Rinse

Funnel Rinse

System Blank

Funnel Rinse

System Blank

Funnel Rinse

Funnel Rinse

Funnel Rinse

Funnel Rinse

Funnel Rinse

Sample 

matrix

DIW 

DIW

SRWS (PI 7)

Acid 

DIW

DIW

SRWS (Til 7)

Acid

Acid 

DIW

SRWS (T117)

DIW

DIW

DIW

DIW

SRWS (T117)

Acid

Acid

SRWS (T117)

DIW

Manganese Mercury Molybdenum Nickel 

(GFAAS) (CV) (ICP) (ICAP) 

(lig/L) (H9/L) (H9/L) (H9/L)

<.2 .1 <10 <10

9.1 .2 <10 <10

<.2 <.l <10 <10

.2 <.l <10 <10

200 .7 10 10

.3 <.l <10 <10

1.1 <.l <10 <10

210 1.0 10 10

.3 <.l <10 <10

1.7 <.l <10 <10

<.2 - <10 <10

.9 <.l <10 <10

230 .3 <10 <10

2.7 -- <10 <10

<.2 - <10 <10

250 .3 20 <10

.3 -- <10 <10

Silver Strontium Vanadium 

(ICAP) (ICAP) (ICAP) 

((ig/L) (|ig/L) (|ig/L)

<1 <0.5 <6 

<1 <.5 <6

<1 2.0 <6

<1 <.5 <6 

<1 <.5 <6

<1 <.5 <6

<1 270 <6

<1 <.5 <6

<1 <.5 <6 

<1 <.5 <6

<1 270 <6

<1 <.5 <6

2 <.5 <6

<1 <.5 <6

1 <.5 <6

<1 270 <6

<1 <.5 <6

<1 <.5 <6

<1 280 <6

<1 <.5 <6
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Reported Concentrations for Field Quality-Control Samples 55