FINAL REPORT

A Survey of the Water Quality of Streams in the Primary Region of

Mountaintop / Valley Fill Coal Mining

October 1999 to January 2001

April 8, 2002

Mountaintop Mining / Valley Fill

Programmatic Environmental Impact Assessment

Prepared by:

Gary Bryant

Scott McPhilliamy

USEPA Region III

Wheeling, WV

and

Hope Childers

Signal Corporation

Wheeling, WV

Acknowledgments

This report would not have been possible without the excellent support and cooperation of many
people. Three key persons deserve special recognition for their role guiding, supporting and
resolving problems. Those persons are:

Project Officer

William Hoffman

Quality Assurance Officer

Joseph Slayton

Contract Oversight - Jeffery Alper

The sampling of the streams was conducted by staff of the West Virginia Department of
Environmental Protection, Office of Mining & Reclamation. Special thanks is due to those
persons who are listed below:

John Ailes (Office Chief)

David Vande Linde

Joe Parker, Deputy Chief (oversee mine inspectors who collect samples)

Bill Simmons, Logan Office, (oversees mine inspectors who collect samples)

Dan Bays, Inspector (sites MT01, 02, 03, 13, 14, 15, 18, 23, 24)

Ray Horricks, Inspector (sites MT39, 40 42, 45, 48, 32, 25B, 34B)

Darryl O’Brien, Inspector (sites MT49, 51, 52, 57B, 60, 55)

Joe Lockery, Inspector (sites MT78, 79, 81)

Tom Woods, Inspector (sites MT62, 64, 69, 75)

Bill Little, Inspector (sites MT86, 87, 91, 95)

Pat Lewis, Inspector (sites MT98, 103, 104)

Report Outline

1. Summary

1.1. Background

1.2. Evaluation of Results

2. Study Objectives

3. The Project Plan

3.1. Monitoring Sites Description

3.2. Monitoring Frequency

3.3. Monitoring Parameters and Sampling Methods

3.3.a Stream Water Quality Criteria

3.3.b Mining Permit Monitoring

3.3.c Laboratory Parameters

3.3.d Field Parameters

3.4. Stream Sample Collection and Shipping

3.5. Methods and Detection Limits for Water Quality Criteria Parameters

4. Data Quality Requirements and Assessments

4.1. Field Work

4.1.a Field Work Completeness Assessment

4.1.b Field Work Sampling Errors Assessment

4.1.c Field Duplicates

4.1.d Blanks

4.1.e Field Work Completeness Evaluation

4.2. Laboratory Work

4.2.a Data Submission

4.2.b Data Qualifiers or Flags

4.2.c Laboratory Data Completeness Evaluation

4.3. Corrective Actions

4.4. Database of the Results

5. Evaluation and Discussion of Results

5.1. Parameters Likely To Be Impacted By MTM/VF Mining

5.1.a Filled Sites vs Unmined Sites

5.2. Sulfate Data

5.2.a Sulfate Concentration in Stream Samples

5.2.b QA Samples for Sulfate

5.2.c Sulfate Yield

5.3. Calcium Data

5.4. Magnesium Data

5.5. Total Hardness Data

5.5.a Hardness Concentration in Stream Samples

5.5 b QA Samples for Hardness

5.5.c Hardness Yield

5.6. Total Dissolved Solids Data

5.6.a Dissolved Solids Concentration in Stream Samples

5.6 b QA Samples for Dissolved Solids

5.6.c Dissolved Solids Yield

5.7. Manganese, Total and Dissolved Data

5.8. Specific Conductance Data

5.9. Selenium Data

5.10. Alkalinity Data

5.10.a Alkalinity Concentration in Stream Samples

5.10.b QA Samples for Alkalinity

5.10.c Alkalinity Yield

5.11. Potassium Data

5.11.a Potassium Concentration in Stream Samples

5.11.b QA Samples for Potassium

5.11.c Potassium Yield

5.12. Sodium Data

5.12.a Sodium Concentration in Stream Samples

5.12.b QA Samples for Sodium

5.12.c Sodium Yield

5.13. Chloride Data

5.14. Acidity Data

5.15. Nitrate and Nitrite Data

5.15.a Nitrate-Nitrite Concentration in Stream Samples

5.16. Parameters Present in Low Concentrations

5.16.a Total Phosphorous

5.16.b Total Copper, Lead, and Nickel

5.17. Other Parameters Detected in Measurable Concentrations

5.17.a Total Barium

5.17.b Total Zinc

5.17.c Total Organic Carbon and Dissolved Organic Carbon

5.17.c Total Suspended Solids

6. Comparison with Applicable Stream Water Quality Criteria

6.1. Total Aluminum

6.1.a Aluminum Concentration in Stream Samples

6.1.b Aluminum Yield

6.1.c Dissolved Aluminum

6.2. Total Beryllium

6.3. Chloride

6.4. Dissolved Oxygen

6.5. Total Iron

6.5.a Iron Concentration in Stream Samples

6.5.b Iron Yield

6.5.c Dissolved Iron

6.6. Total Mercury

6.7. pH

6.8. Total Selenium

iii

6.8.a Selenium Concentration in Stream Samples

6.8.b Selenium Yield

6.8.c Distribution of Sites Violating the Stream Criterion - Lab 2 Only

6.9. Total Silver
6.10. Temperature

7. Other Evaluations

7.1. Parameters With Concentrations Below Detection Limits

7.1.a Hot Acidity
7.1.b Total Arsenic, Antimony, Cadmium, Chromium, Cobalt, Vanadium, and

Thallium

7.2. Flow Rate Data

8. References Cited

Attachments

1 - West Virginia Water Quality Criteria Discussion
2 - Field Sheet Forms
3 - Information on Parameters Monitored
4 - Electronic Spreadsheet of Results of the Study

List of Tables

Table 1 - Monitoring Site Attributes

Table 2 - Water Quality Criteria and Method Detection Limits

Table 3 - Contamination Detected in Blanks

Table 4 - Field Work Data Summary

Table 5 - Percent Completeness for Analytical Results by Laboratory

Table 6 - Median Values at All Filled vs All Unmined Sites - Lab 2 Only

Table SO

-1. Number of Samples Exceeding the Secondary Maximum Contaminant Level of

250 mg/l for Sulfate

Table SO

-2. RPD for Field Duplicates for Sulfate

Table DO-1. Samples Not Meeting Aquatic Life Minimum Criterion of 5.0 mg/L for Dissolved

Oxygen

Table pH -. Samples Not Meeting pH Criteria - 6.0 to 9.0

List of Figures

Figure 1 Map of Stream Sampling Site Locations

Figure 2 Organization of Database

Figure SO

-1 Sulfate Concentration for All Sites vs Date

Figure SO

-2 Comparison of Duplicate Samples - Sulfate Concentrations

Figure SO

-3 Sulfate Yield for All Sites vs Date

Figure Ca-1 Comparison of Duplicate Samples - Calcium

Figure Mg-1 Comparison of Duplicate Samples - Magnesium

Figure H-1 Hardness Concentration for All Sites vs Date

Figure H-2 Hardness Yield for All Sites vs Date

Figure DS-1 Total Dissolved Solids Concentrations for All Sites vs Date

Figure DS-2 Comparison of Duplicate Samples - Total Dissolved Solids

Figure DS-3 Total Dissolved Solids Yield for All Sites vs Date

Figure Mn-1 Concentration of Total Manganese for All Sites vs Date - Lab 2 Only

Figure Mn-2 Comparison of Duplicates - Total Manganese

Figure Mn-3 Comparison of Duplicates - Dissolved Manganese - Lab 2 Only

Figure Cond-1 Field Conductivity of All Sites vs Date

Figure Cond-2 Field Conductivity vs. Instantaneous Flow/Watershed Area

Figure Alk-1 Alkalinity Concentration for All Sites vs Date

Figure Alk-2 Concentration of Duplicate Samples for Alkalinity

Figure Alk-3 Alkalinity Yield for All Sites vs Date

Figure K-1 Potassium Concentration for All Sites vs Date

Figure K-2 Comparison of Duplicate Samples - Potassium

Figure K-3 Potassium Yield for All Sites vs Date

Figure Na-1 Sodium Concentration at All Sites vs Date

Figure Na-2 Sodium Concentration of Duplicate Samples

Figure Na-3 Sodium Yield for All Sites vs Date

Figure Ba-1 Concentration of Barium for All Sites vs Date - Lab 2 Only

Figure Ba-2 Comparison of Duplicate Samples - Barium - Lab 2 Only

Figure Zn-1 Concentration of Zinc for All Sites vs Date - Lab 2 Only

Figure Zn-2 Comparison of Duplicate Samples - Zinc - Lab 2 Only

Figure TOC-1 Comparison of Duplicate Samples - Total Organic Carbon - Lab 2 Only

Figure DOC-1 Comparison of Duplicate Samples - Dissolved Organic Carbon - Lab 2 Only

Figure Al-1 Total Aluminum Concentration for All Sites vs Date - Lab 2 Only

Figure Al-2 Comparison of Duplicate Samples - Total Aluminum - Lab 2 Only

Figure Al-3 Aluminum Yield for All Sites vs Date - Lab 2 Only

Figure Fe-1 Total Iron Concentrations for All Sites vs Date - Lab 2 Only

Figure Fe-2 Comparison of Duplicate Samples - Total Iron - Lab 2 Only

Figure Fe-3 Iron Yield for All Sites vs Date - Lab 2 Only

Figure Se-1 Selenium Concentrations at All Sites vs Date - Lab 2 Only

Figure Se-2 Comparison of Duplicate Samples for Total Selenium - Lab 2 Only

Figure Se-3 Selenium Yield for All Sites vs Date - Lab 2 Only

Figure Se-4 Mean Selenium Concentrations for USEPA Stream Sampling Stations within the

Region of Major Mountaintop Removal Mining Activity in West Virginia

Figure Se-5 Mean Selenium Concentration for USEPA Stream Sampling Stations within the

Upper Mud River Watershed, West Virginia

Figure Se-6 Mean Selenium Concentration for USEPA Stream Sampling Stations within the

Island Creek Watershed, West Virginia

Figure Se-7 Mean Selenium Concentration for USEPA Stream Sampling Stations within the

Spruce Fork Watershed, West Virginia

Figure Se-8 Mean Selenium Concentration for USEPA Stream Sampling Stations within the

Clear Fork Watershed, West Virginia

Figure Se-9 Mean Selenium Concentration for USEPA Stream Sampling Stations within the

Twentymile Creek Watershed, West Virginia

Figure Flow-1. Normalized Flow Rate vs Date
Figure Flow-2. Field Conductivity vs Log (Instantaneous Flow / Watershed Area)

vii

1. SUMMARY

1.1 Background

The Project Plan was designed to characterize and compare impacts to stream chemistry from
mountaintop mines and associated valley fills (MTM/VF).  This study used the same 37 stream
monitoring sites used in the aquatic biology study of this same region. Most sites were visited,
sampled, and had flow rate measured 13 times between October 1999 and February 2001 by
field crews who are Mine Inspectors for the state of West Virginia. Four field parameters and 37
laboratory parameters were selected to be monitored at each site.  Ten of those parameters had
stream water quality criteria limits which were used to set measurement detection limits.  One set
of duplicate samples and two blank samples were to be collected each day by each field crew to
enable assessment of sampling errors and sampling precision.  The field work exceeded the goal
of 90% completeness for site visits, steam sampling, flow measurements, and duplicate samples,
but only 83 % of the number of blank samples were collected.

The contract for chemistry analyses was changed to a second laboratory in July 2000.  EPA
Region III chemists provided a QA/QC review of the laboratory data.  Only 83 % of the values
reported by the first laboratory passed the QA/QC review.  The second laboratory had 98% of
their data pass the QA/QC review.  Corrective actions were implemented during the study to
resolve problems in the field and laboratory.  The data from this study is stored in a relational
database which is part of this report.

1.2 Evaluation of Results

The results were evaluated and are presented under three lines of reasoning: 1) parameters
altered by MTM/VF mining; 2) parameters violating stream water quality standards; 3)
parameters not detected in any sample.  Parameters likely to be impacted by MTM/VF mining
were identified and used as an outline for evaluating the entire database from all categories of
sites.  Variations in data quality were assessed using the results of the duplicate samples and
blank samples.  Additional characterization of the categories of sites is provided by calculation
of “Yield”rates, an idea taken from a USGS publication.

The data indicate that MTM/VF mining activities increase concentrations of the several
parameters in streams. Sites in the category Filled had increased concentrations of the following
parameters: sulfate, total calcium, total magnesium, hardness, total dissolved solids, total
manganese, dissolved manganese, specific conductance, total selenium, alkalinity, total
potassium, acidity, and nitrate/nitrite. There were increased levels of sodium at sites in the
category Filled/Residences which may be caused by road salt and/or sodium hydroxide treatment
of mine discharges.

The data were inconclusive for several other parameters which were detected in only a few

samples or at very low concentrations.  Those parameters: total phosphorous, total copper, total
lead, total nickel, total barium, total zinc, total organic carbon, dissolved organic carbon, and
total suspended solids. Other parameters were detected but there was no clear indication of
stream impacts resulting from MTM/VF mining operations.  Those parameters are: chloride,
total aluminum, dissolved aluminum, total iron, dissolved iron, temperature, dissolved oxygen,
and pH.  Data from the second laboratory indicated that only three samples for total aluminum
exceeded the stream criterion and all were collected August 9, 2000at sites with fills upstream.
Dissolved aluminum was detected in only five samples and all were near the detection limit of
100 ug/L.  There were no samples for total iron exceeding the stream criterion but several
samples in the category Filled approached the limit in the fall of 2000.  Dissolved iron was
detected at a few sites in the category Filled at levels slightly higher than other sites.  MTM/VF
mining operations can increase iron concentrations in streams but there is no clear evidence that
this occurred during the study.  Temperature, pH, conductivity, and dissolved oxygen were
measured in the field.  The only field parameter clearly impacted by MTM/VF mining was
conductivity which was noticeably increased at sites in the category Filled.

Parameters which were not detected in any sample analyzed at the second laboratory were: total
arsenic, total antimony, total cadmium, total chromium, total cobalt, total vanadium, total
thallium, total beryllium, total mercury, and total silver. Hot acidity was analyzed for a few
samples and none was detected.

Only the data from the second half of the study was used to evaluate compliance with stream
limits due to problems with contamination in blanks, excessive holding times and less precision
which occurred during the first part of this study. The latter data indicate that MTM/VF mining
is associated with violations of the stream water quality criteria for total selenium.  Selenium
violations were detected in each of the five study watersheds and all were at sites in the category
Filled, downstream of MTM/VF operations.  No other site categories had violations of the
selenium limit.  There were no violations of the limits for total beryllium, chloride, total
mercury, total silver, temperature.  The data do not support a conclusion regarding stream water
quality violations for aluminum, dissolved oxygen, iron and pH which can be impacted by
MTM/VF mining activities.

While outside the scope of this report, there would be value in having experts evaluate the flow
rate data from this study to identify impacts attributable to mining. Base flows of streams with
valley fills are reported to be 6 to 7 times greater than the base flows of unmined areas. During
base flow conditions, the more highly mineralized water from fills becomes a larger portion of
stream flow, altering the stream water chemistry.

2. STUDY OBJECTIVES

The final Project Plan for this study listed two objectives:

Characterize and compare conditions in three categories of streams:

1) streams that are not mined;
2) streams in mined areas with valley fills; and
3) streams in mined areas without valley fills.

Characterize conditions and describe any cumulative impacts that can be detected in
streams downstream of multiple fills.

This study was designed to supplement other studies of  stream water quality impacts resulting
from  mountaintop mining and valley fill (MTM/VF) coal mining operations.  This study
compliments the aquatic biology study for this same region by gathering chemistry data on the
same stream sites used by USEPA Biologists in their evaluation of MTM/VF impacts to aquatic
organisms. The aquatic biology study report by Green, Passmore, and Childers is titled A Survey
of the Condition of Streams in the Primary Region of Mountaintop Mining/Valley Fill Coal
Mining.  A separate report is being prepared to evaluate the relationships between the chemical
data and biological data.

3. THE PROJECT PLAN

A Project Plan was drafted for this study in the summer of 1999 under the direction of the
Environmental Impact Statement Steering Committee. The plan was posted on EPA Region III’s
web site. The plan was revised several times as the study progressed in response to comments
and problems encountered during the study.

3.1 Monitoring Sites Description

The thirty seven (37) stream monitoring sites are exactly the same sites used by the USEPA
Biologists in their study of MTM/VF.  They provide a synoptic survey of stream conditions in
five watersheds across  the primary MTM/VF region in West Virginia.  These watersheds are
Twentymile Creek, Clear Fork, Island Creek, upper Mud River and Spruce Fork.  The locations
of the sites are shown in Figure 1. They are spread across the region of mountaintop mining in
West Virginia.  The sites were selected with the experienced assistance of WVDEP Mine
Inspectors familiar with mining activities in the region and with the cooperation of coal
companies in the area.

FIGURE 1. Map of Stream Sampling Site Locations

The distribution of sites within the three categories identified in the study objectives are:

1) streams that are not mined - Unmined -

9 sites

2) streams in mined areas with valley fills -

21 sites

(Filled 15sites + Filled/Residences 6 sites)

3) streams in mined areas without valley fills -

6 sites

(Mined 4 sites + Mined/Residences 2 sites)

Flow diversion

ditch at a valley fill -

1 site

TOTAL

37 sites

The site numbers and descriptions are listed in Table 1.  The station numbers are not sequential
since the 37 biological sampling sites were chosen from 127 possible sampling sites.  The sizes
of the drainage areas upstream of the sites vary from 125 acres to 27,742 acres.  Only three of the
37 sites have watersheds larger than 3,200 acres.

TABLE 1

Monitoring Site Attributes

Site

Identification

EIS Class

Watershed

Area

(acres)

No. of

Fills

Comment/

Permit Date

No. of

Visits

No. of

Samples

No. of

Flowrates

MT-01

Mined/Residence

upper Mud River

1,897

Past Logging

MT-02

Unmined

upper Mud River

511

Past Logging

MT-03

Unmined

upper Mud River

717

Past Logging

MT-13

Unmined

upper Mud River

335

Past Logging

MT-14

Filled

upper Mud River

1,527

‘85,’ 88, ‘89

MT-15

Filled

upper Mud River

1,114

‘88,’89,’91,’92’95 13 13 12

MT-18

Filled

upper Mud River

479

‘92, ‘’95

MT-23

Filled/Residence

upper Mud River 10,618 26 ‘85,’88,’89,’91’92,’95

,’96

MT-24

Ditch

upper Mud River

N/A

‘88, ‘91

MT-25B

Filled

Spruce Fork

997

‘86

MT-32

Filled

Spruce Fork

2,878

‘86,‘88,‘89,‘91

MT-34B

Filled

Spruce Fork

1,677

‘85, ‘86

MT-39

Unmined

Spruce Fork

669

MT-40

Filled/Residence

Spruce Fork

11,955

7 VF + 3 refuse

MT-42

Unmined

Spruce Fork

447

MT-45

Mined

Spruce Fork

1,111

‘87 strip @ head

MT-48

Filled/Residence

Spruce Fork

27,742

4 communities

MT-50

Unmined

Island Creek

563

MT-51

Unmined

Island Creek

1,172

gas well

MT-52

Filled

Island Creek

316

underground entry &

fill / ‘84

MT-55

Filled/Residence

Island Creek

3,167

‘86,’88,’‘89, ‘93, ‘94,

‘98

MT-57B

Filled

Island Creek

125

‘88

MT-60

Filled

Island Creek

790

‘88, ‘93

MT-62

Filled/Residence

Clear Fork

3,193

‘89,’91,’92

MT-64

Filled

Clear Fork

758

‘92, ‘93

MT-69

Mined/Residence

Clear Fork

708

pre- ‘65

MT-75

Filled/Residence

Clear Fork

876

‘89, ‘92

MT-78

Mined

Clear Fork

524

pre- ‘65

MT-79

Mined

Clear Fork

448

MT-81

Mined

Clear Fork

1258

NaOH / pre ‘65

MT-86

Filled

Twentymile Creek

2,201

NaOH/ ‘90,’93

MT-87

Filled

Twentymile Creek

752

NaOH/’90,’93

MT-91

Unmined

Twentymile Creek

1,302

haul road

MT-95

Unmined

Twentymile Creek

968

logging?

MT-98

Filled

Twentymile Creek

1,208

‘77,’82,’90

MT-103

Filled

Twentymile Creek

1,027

‘77,’82,’90

MT-104

Filled

Twentymile Creek

2,455

‘77,’82,’90

Totals

37 sites

494

479

466

3.2 Monitoring Frequency

Stream samples were collected during the period of October 1999 thru February 2001.  The sites
were to be sampled monthly but the scheduling of when samples were taken was determined by
availability of the field crews.  The stream sampling effort was stopped in May 2000 due to
problems with timely delivery of chemistry laboratory data.  A contract was completed with a
different laboratory and monthly sampling resumed in August 2000 and continued through
February 2001. Most sites were visited 13 times for sampling.  One field crew took an
additional set of samples from the seven sites in Twentymile Creek in November 1999 and
another crew took an additional set of sample from the seven sites in Clear Fork in June of 2000.
A few times, some of the sites had no flow to sample.  The field crew found stream flow on only
two occasions at site MT-78.  There were 479 stream samples collected in this survey, not
counting the duplicates and other QA samples. Flow measurements were also made during
sampling but there were several occasions when flows were not measured.  This was especially
true during winter months when the stream was frozen over.  There were 467 flow measurements
for this study.  Table 1 lists this information for each sample site.

3.3 Monitoring Parameters and Sampling Methods

The parameters to be monitored were discussed by numerous groups and experts. The list of
parameters finally selected was shaped by constraints of holding times, detection limits,
difficulty in sampling and other factors. The discussion on what parameters to monitor began
with a review the stream water quality parameters for the streams in the study area.

3.3.a Stream Water Quality Criteria

There are limits set on the concentrations of chemicals allowed in streams across the nation.
Each State has established these stream water quality criteria for the surface waters of their State.
West Virginia has three categories of stream water quality criteria set to protect specific water
uses.  Those categories of water uses are: 1) Aquatic Life, 2) Human Health, and 3) All Other
Uses.  The Aquatic Life Criteria are the limits most applicable to this study because those are
designed to protect aquatic life in the stream. There can be separate limits for warm water and
cold water (trout) streams.  Sometimes there are also separate limits for acute and chronic
exposure.  Acute exposures would be those experienced during a short time period such as a
spill.  Chronic limits are usually lower than Acute limits since the organisms are exposed for a

longer time period.  Water quality criteria also vary with sample methods.  Some criteria specify
“Not to exceed” which is a grab sample of the stream.  These criteria are applicable to the
sampling methods used in this study.  There are also some criteria set for a “one-hour average”
which are not strictly applicable to the single grab sample results of this study, but they are still
valuable in evaluating if there are concerns about the concentrations of chemicals identified in
this study.  The West Virginia Water Quality Criteria limits are discussed in Attachment 1.

3.3.b Mining Permit Monitoring

Coal companies seeking permits must monitor streams above and below their proposed mining
sites as part of the process for getting a mining permit.  It was agreed that the list of parameters
being monitored for permits would be expanded to include the parameters being monitored in
this study.  Discussions with coal companies were held to invite their comments on the list of
parameters.  This list of “interim protocol” parameters was adopted for coal companies seeking
permits in West Virginia.  They were asked to monitor for the list of “interim protocol”
parameters as part of their pre-mining data gathering effort.  The data gathered by the coal
companies and their consultants could also be used to in evaluating the impacts of mining but
that data has not been included in this report. A separate report is being prepared using coal
company data for this EIS effort.

3.3.c Laboratory Parameters

After much discussion and evaluation, the 37 chemical parameters listed below were selected for
laboratory analyses. The samples were to be collected and preserved and analyzed following
procedures consistent with 40 CFR Part 136.

Water Quality (10)

Acidity

Nitrate + Nitrite

Total Organic Carbon

Alkalinity

Sulfate

Dissolved Organic Carbon

Chloride

Total Suspended Solids

Hardness

Total Dissolved Solids

Total Metals (27)

Aluminum

Cobalt

Nickel

Dissolved Aluminum

Copper

Potassium

Antimony

Iron

Phosphorous

Arsenic

Dissolved Iron

Selenium

Barium

Lead

Silver

Beryllium

Magnesium

Sodium

Cadmium

Manganese

Thallium

Calcium

Dissolved Manganese

Vanadium

Chromium

Mercury

Zinc

Hot acidity was also analyzed for a brief period by the second laboratory by mistake.

3.3.d Field Parameters

Field crews were WVDEP Mine Inspectors. They were briefed in the standard monitoring
procedures at the start of this study. The briefing included instructions in measuring Dissolved
Oxygen, Specific Conductivity, Temperature, and pH

in situ

using calibrated electrometric field

meters.  The field chemistry measurements taken at each sampling site were consistent with 40
CFR Part 136.  The field crew recorded measurements and other sample site information on field
sheets which were  sent to the lab with the samples.  They also measured flow rate at the time of
sampling using methods suitable for effluent discharge monitoring under the NPDES program.
EPA office staff used a computer program to calculate stream flows from the field stream gaging
data. A copy of the blank field sheets used in this study is included as ATTACHMENT 2.

3.4 Stream Sample Collection and Shipping

The laboratory provided sample containers, chemical preservatives, lab-pure water, labels, and
shipping containers. They were shipped to the WVDEP field offices.  The sampling procedures
used were consistent with the 40 CFR Part 136 and samples were collected as grab samples in
mid-stream.  The samples were preserved and stored on ice in the shipping containers until they
were ready to ship to the lab following chain-of-custody procedures.  A separate field sheet for
each sample, as shown in Attachment 2, was to be placed in the shipping containers.

3.5 Methods and Detection Limits for Water Quality Criteria Parameters

Ten of the parameters monitored during this study have an applicable stream water quality
criteria.  These criteria were used to select methods of analysis and detection limits for the
laboratory analyses. The concern was that values reported by the laboratory as exceeding the
stream criteria would be measured precisely enough to confidently say that stream criteria were
exceeded.  Therefore the detection limit or lowest measurable concentration reported by the
laboratory was arbitrarily designated to be no greater than one third of the lowest applicable
water quality criterion. The detection limit for this study was set after discussions with chemists
as to what detection limits are achievable following excellent laboratory practices.  The method
selected and the detection limit for each parameter with a criterion are included in Table 2.

TABLE 2

Water Quality Criteria and Method Detection Limits

Water Quality

Parameter

Criterion

Method

Detection Limit

Total Aluminum

750 ug/L

EPA 200.7

100 ug/L

Total Beryllium

130 ug/L

EPA 200.7

1 ug/L

Chloride

230 mg/L

EPA 300.0

5.0 mg/L

Dissolved Oxygen* 5.0 mg/L

Field Meter 0.1 mg/L

Total Iron

1.5 mg/L

EPA 200.7

0.10 mg/L

Total Mercury

2.4 ug/L

EPA 245.1

0.2 ug/L

pH*

6.0 to 9.0

Field Meter 0.1 pH unit

Total Selenium

5 ug/L

EPA 200.8

3 ug/L**

Total Silver

1 to 43 ug/L

EPA 200.7

10 ug/L

Temperature*

or 87

Field Meter +/- 2

* Field meter required to measure these parameters.
** The estimated instrument detection limit for selenium in water using Method 200.8
(Inductively Coupled Plasma - Mass Spectrometry) is around 5 ug/L according to the 1983 EPA
Methods Manual.

4. DATA QUALITY REQUIREMENTS AND ASSESSMENTS

4.1 Field Work

The field work was conducted by personnel from the West Virginia Division of Environmental
Protection, Office of Mining & Reclamation and reviewed by the EPA staff.

4.1.a Field Work Completeness Assessment

The project plan requires a monthly visit to each site, a sample from each site when there is flow,
and a flow measurement. The field data are recorded on field sheets for each sample. The field
crews sent copies of their field sheets to the EPA as well as to the contract labs with the samples.
The EPA monitored the progress of the field work by reviewing and evaluating these field
sheets. Some crews also reported problems and progress through telephone conversations with
the EPA.

The data and notes from the field sheets was transferred to the electronic database by the EPA
staff.  All flow rates were calculated from the field readings by laboratory personnel or EPA staff
using the same computer program. The electronic records were then completely checked for data
entry errors.  These records were then used to cross check the records and data received from the
laboratories and the QA/QC review.  The calibration records for field meters were not included
in the electronic database of data for this study, but the comments from the field sheets are
included.

4.1.b Field Work Sampling Errors Assessment

The Project Plan specified three types of QA samples be collected by each crew each day of
sampling.

Field Duplicate Samples

were collected as two identical sets of stream samples from

a stream monitoring site. The second set was labeled as a Duplicate Sample. The concentrations
of each parameter in these pairs of Duplicate Samples should be nearly identical.

Blank

Samples

were collected in a set of sample containers using lab-pure water from the laboratory

and preserving them just like the stream samples, including filtering. These samples were called
Blanks and the concentration of all parameters in each sample should be at or near the detection
limit. The third type of QA sample used in this survey was a

Trip Blank Sample

. This was a set

of sample containers filled with lab-pure water in the laboratory and sent to the field crews with
the other sample containers and preservatives.  This Trip Blank was opened in the field at the
sample site and preserved as the stream samples, except there was no water filtered in the field in
the Trip Blank.  Any measurable concentrations parameters in these blank samples would
indicate concerns with sample handling or contaminated sampling equipment.  QA samples were
tested in the laboratory for the same parameters as the stream samples.  Although the QA
samples were collected to evaluate problems with sample collection and handling in the field,
they can also be used to detect errors in measurement which occur in the laboratory.

4.1.c Field Duplicates

Field Duplicate data can be used to calculate an estimate the precision of sampling methods. This
estimate of precision includes error associated with field collections at the site, error in sample
handling, and error associated with laboratory activities as well as true variation in the water
being sampled.  Since it is not possible to separate the variation caused by sampling error or
sample handling error from the variation caused by measurement error, the differences between
sets of duplicate samples can only give an estimation of precision in sampling.  The estimate of
precision in this study is based on laboratory results of Field Duplicate samples.  Field Duplicate
samples were to be collected at 10% of the sites on each sampling occasion (one Field Duplicate
per sampling crew per day).  Only the first of the two sets of sample results was used in
calculating and evaluating the monitoring trends and statistics for a site.

Precision estimates were calculated from the data for Field Duplicate samples using

Relative

Percent Difference (RPD)

. RPD is calculated using the following equation:

RPD = ((C

- C

)x100)÷ ((C

)/2)

where: C

= the larger of the two values and

= the smaller of the two values.

Often the smaller of the two values was below the minimum concentration the laboratory could
detect (called the Detection Limit or DL). In calculating statistics on the concentration at a site,
every time a reported value was below the DL, a value of one half the DL was assigned as the

smaller value (C

), rather than zero. The RPD varies with each parameter and for each set of

duplicates.  There are tables of RPD results for selected parameters in this report under the
section Evaluation and Discussion of Results.  As the concentrations in the duplicate samples
approach the detection limit, the RPD values are not as meaningful an estimate of precision.
There is a trend in the data from this study for the RPD to improve (get much lower) with later
samples.  This may be due to improvements in sample collection and handling in the field and
laboratory or due to differences between the laboratories.

There is also a trend in the results from this study for the concentrations to be lower in the
second half of the study.  This may be due to lingering effects of the drought conditions
experienced just before the beginning of the sampling in 1999. It could also result from
improvements in sample collection and handling in the field and laboratory as the study
progressed.  It could also be due to differences between the two laboratories.  There were
detectable concentrations of arsenic, cadmium, lead, manganese, silver and thallium in results
from the first laboratory but the second laboratory found no detectable concentrations of these
metals in any samples.  The first laboratory also reported generally higher concentrations of
antimony and nickel than the second laboratory.

Another way to evaluate precision is to

plot concentration of duplicate samples

. The X-axis is

the concentration of the first sample and the Y-axis is the concentration of second sample A
point is plotted for each set of duplicate samples. If the values for all sets of duplicate samples
are equal, they will make a straight line from the detection limit to the maximum value detected.
This approach can be used on duplicate samples of stream samples as well as the duplicate sets
of blank samples.

It is recognized that even the best laboratories can not “hit a bulls eye” every time with analytical
tests so the study plan allows for a general “precision limit” of plus or minus 25%.  The
precision limits can also be plotted on the graph of duplicate sample results to illustrate when
values of duplicate samples are “out of control” or beyond the precision limit.  Graphs of
duplicate sample results have been plotted for various parameters using a unique symbol for each
laboratory.  Errors in sample collection or handling in the field may cause duplicate samples to
be “out of control,” but the problem may also be in the laboratory.  The plots of duplicate sample
results also indicate the precision of the sampling at the second laboratory was much better than
the first.  This may be due to improvements with experience in collecting and handling samples
in the field or it may be related to the laboratory.  The end result is that there is more confidence
in the precision of sample data from the later portion of the study.  There were twice as many
duplicate samples analyzed at the second laboratory and the sites were more varied with fewer
Unmined sites.  As a result the range of concentrations in duplicates is generally wider than at
the first laboratory.

4.1.d Blanks

Field crews were to collect two blanks each day they sampled.  Not all field crews were equally
diligent in collecting and identifying Blank Samples.  Problems were identified with each crew
not always having the supply of lab pure water and adequate sample containers when they
needed them.  There were also other communication problems. There were intermittent problems
with unacceptable concentrations of contaminants in the blank samples.  Some problems were
thought to have been caused by field errors such as putting the acid preservatives in the wrong
bottle, but this was not confirmed.  There was also an intermittent problem with inadequate
supplies of lab pure water for blanks and at least one crew noted they purchased distilled water
on two occasions to use in the blanks.  The quality of the blank water was sometimes questioned
by chemists running the samples.  The data for all Field Blank samples has been evaluated as a
group to identify variability among the parameters.  The number of Field Blank samples with
detectable concentrations of contamination for each laboratory are listed by parameter in Table
3.

Within the group of blank samples there were 28 pairs of duplicate blanks.  These were
duplicates for all parameters except those which were filtered in the field. The graph plots of
these “duplicate blanks” for selected parameters are included in this report under the section
Evaluation and Discussion of Results.  The precision and amount of contamination revealed in
these graphs indicates that the contamination of blanks decreased in data from the second
laboratory.  This could be due to improvements in sample handling in the field or in the
laboratory. The end result is that there is less contamination of blank samples during the later
portion of the study, and there are several parameters which have unreliable results from the first
laboratory.  The parameters with unreliable results from the first half of this study included
acidity, alkalinity, antimony, arsenic, lead, phosphorous, potassium, selenium, thallium, and
most critically both suspended and dissolved solids.

The Project Plan calls for sample results from a site to be “flagged” when the concentration of a
parameter in the blank (field or laboratory blank) exceeds 1/10th of the value reported in the
stream sample. The electronic spreadsheet of the data included as ATTACHMENT 3 has a
column identifying all “flagged” data. The code letter “B” identifies results with problems with
the excessive contamination in the blank samples.

TABLE 3

Contamination Detected in Blanks

PARAMETER

LAB 1

Number From 30

Samples Greater Than

Detection Limit

LAB 2

Number From 50

Samples Greater Than

Detection Limit

ACIDITY

ACIDITY HOT

ALKALINITY

ALUMINUM, DISSOLVED

ALUMINUM, TOTAL

ANTIMONY, TOTAL

ARSENIC, TOTAL

BARIUM, TOTAL

BERYLLIUM, TOTAL

CADMIUM, TOTAL

CALCIUM, TOTAL

CHLORIDE

CHROMIUM, TOTAL

COBALT, TOTAL

COPPER, TOTAL

DISSOLVED, ORGANIC CARBON

IRON, DISSOLVED

IRON, TOTAL

LEAD, TOTAL

MAGNESIUM, TOTAL

MANGANESE, DISSOLVED

MANGANESE, TOTAL

MERCURY, TOTAL

NICKEL, TOTAL

NITRATE

NITRITE

NITRATE+NITRITE

PHOSPHORUS, TOTAL

POTASSIUM, TOTAL

SELENIUM, TOTAL

SILVER, TOTAL

SODIUM, TOTAL

SULFATE

THALLIUM, TOTAL

TOTAL DISSOLVED SOLIDS

TOTAL ORGANIC CARBON

TOTAL SUSPENDED SOLIDS

VANADIUM, TOTAL

ZINC, TOTAL

* The number of Blank samples for these parameters is less than for other parameters.

4.1.e Field Work Completeness Evaluation

Completeness is a quality assurance/quality control term and is defined as the measure of the
amount of valid data obtained from a measurement system compared to the amount that was
expected to be obtained under normal conditions.  Completeness was measured by calculating
what percentage of  samples were collected and analyzed with valid results.  The goal for this
project was 90% completeness.  Completeness is calculated according to the following equation.

C = 100 x (V/N)

where: C = percent completeness

V = number of measurements judged valid
N = total number of measurements.

The percent completeness was calculated for the field work and is presented in Table 4.

TABLE 4

Field Work Data Summary

Factor Being Measured

Numbers (V and N)

Percent Completeness

Attempted Visits to Sites

495 of 495

100

Actual Visits to Sites

494 of 495 Attempts

99.8

Number of Times Sites Dry @ Visit

N/A

Number of Samples at Sites

479* of 494 Visits

97.0

Number of Flow Measurements

466 of 479 Samples

97.3

Number of Duplicate Sample Sets

44 of 479 Samples

9.18% / 10% Goal = 91.8%

Number of Blank Samples

80 of 479 Samples

16.7% / 20% Goal = 83.5%

*Excluding the Duplicate and Blank samples

The field work was especially complete in this study. There was only one occasion during this
entire survey when a field crew could not reach a site.  A tree had fallen and blocked the road to
site MT-57B on September 28, 2000.  The percent completeness is 494 visits out of 495 attempts
or 99.8 %.  This was excellent and greatly exceeded the goal of 90% completeness.

Samples were collected at all sites on every visit unless the streams were dry.  Site MT-78 was
dry12 times in this study.  In the entire study, there were only 15 site visits which found no
stream flow.  There were 479 stream samples collected in this survey, not counting duplicates
and other QA samples.  The percent completeness is 479 samples out of 494 visits or 97.0 %.
This was excellent.

Flow rate was to be measured on each sampling occasion.  The crews were generally able to
measure flows with each round of sampling.  However, when they made the sample runs in
January of 2001 they found 12 stream sites were covered with ice and stream flows were not
measured.  The total number of missed flow measurements in this study was only 13.  The
percent completeness is 466 flows out of 479 samples or 97.3 %.  This was also an excellent
effort from the field crews.

The goal for field duplicate samples listed in the project plan was to have duplicate analyses
performed on 10% of the sites on each sampling occasion.  Field crews did not collect any
duplicate samples until March 2000 due to several problems with supplying an adequate number
of sample containers as well as confusion.  From March 2000 on, the crews sampled duplicates
as in the work plan.  There were 44 duplicates for 479 samples so overall the study performed
duplicate analyses on 9.18 % of the sites sampled.

The work plan did not list a numeric goal for the collection of blank samples but the ideal
number of blanks should have been 20% of the number of samples.  Field crews did not all
collect blank samples the same way nor on each sampling day for several reasons.  There was an
intermittent problem with inadequate supplies of extra sample bottles and lab pure water.  There
were also communication problems which continued until the end of the study.  Some crews
collected two sets of blank samples each sampling day calling one set the Field Blank and the
other set the Trip Blank. There were 28 pairs of blank samples (56 samples) collected during this
study.  There were 23 solitary blank samples collected and one day when three blank samples
were collected by one crew.  There were a total of 80 blank samples collected during the study
for 479 samples for a percentage ratio of 16.7%.  This falls short of the goal.  Although the
number of blank samples was high, they were not collected as planned and the differences
between crews did not get resolved during the study.

4.2 Laboratory Work

The chemistry analyses of the samples were performed by contractor laboratories. The first lab
appeared to be unable to keep up with the work load. Samples were not analyzed within
allowable holding times and there were unacceptable delays in submitting laboratory reports and
records. In July 2000, a second contract laboratory took over the chemistry analytical work and
continued to the end of the study.

EPA Region III’s Office of Analytical Services and Quality Assurance (OASQA) developed the
plans for doing the QA/QC review of the laboratory data. The data validation process was
consistent with those listed in the “

Innovative Approaches for Validation of Organic and

Inorganic Data-SOPs

”, June 1995, Section IM-1, entitled:

“Validation of Target Analyte List

Metals and Cyanide Data, Manual Approach IM-1

.” The review process was designed using

experience from the QA/QC procedures  that EPA uses in overseeing the Contract Laboratory
Program (CLP).  The plan was modified when the contract was developed for the second
laboratory to focus on a thorough review of 10% of the data.  All data from sites MT-03, MT-15,
MT-24, and MT32 for the following ten analytes were recalculated by EPA chemists: Sulfate,

(NO

+NO

)-N, TOC, DOC, Total Iron, Total Aluminum, Total Manganese, Dissolved Iron,

Dissolved Aluminum, Dissolved Manganese. They continued to review the reports to confirm
that good laboratory practices were being followed with regard to lab methods, detection limits,
spiked samples, etc.

Both laboratories evaluated accuracy by preparing and analyzing duplicate spiked samples. The
matrix spiked and matrix spiked duplicate (MS/MSD) results were included in the QA/QC
review. The parameters which had MS/MSD evaluations were sulfate, chloride, nitrate-nitrite,
total phosphorous, total metals, dissolved metals, total organic carbon, and dissolved organic
carbon.

4.2.a Data Submission

The data reports from the laboratory were sent to the EPA QA/QC staff.  The following
additional items were included in each laboratory report: Name and location of laboratory;
signature of the Laboratory Director (approval signature); project name; report date; stations;
date and time of sampling; laboratory sample ID;  listing of all problematic quality control items
(for that set of samples) and supporting documentation of the necessary corrective action/s;
analytical methods used for each parameter; date of analysis for each analyte; units; analytical
results;  results for laboratory and field blanks (field blanks are identified by samplers to the lab);
sequential page number with total number of pages indicated; fully defined header information
with tables of QC results; QC acceptance limits for each QC result; results of preservations
checks; MDLs for each analyte and referenced procedure; the QC results summary in each data
package is to be limited to that associated with the samples in a months data package; the date
and time or position in the analysis sequence of the analysis of QC sample (included in each QC
sample result summary for each month); quantitation limits and a reference to method for
establishing the QL (e.g. >3*MDL); and all calibration, analysis run logs, and sample “raw data”
(instrument readings) for the key sites and parameters monitored, to allow the reconstruction of
the analytical results, as part of data validation for this project

Additional supporting analytical

data was requested if problems were encountered in performing the data validation. The report
included the analytical results for the sample set, any QA/QC problems encountered during the
analyses; changes in the QAPP; and data quality assessment in terms of precision, accuracy,
representativeness, completeness, and comparability.

EPA chemists developed checklists and codes for different QA/QC issues or concerns they might
find.  They used these checklists in their review of the laboratory reports for compliance with
QA/QC requirements.  They made notes on the laboratory reports using the codes and guidelines
they had developed.  Those are described in this report in the section

Data Qualifiers or Flags

Once the QA/QC review of the reports was completed, the original laboratory records were
placed in storage. Copies of the lab reports with the handwritten codes were sent to the Project
Officer and report writers.

The laboratories provided an electronic record of the chemistry results for most of the samples.
The transfer of these data into the electronic database for this study is described in this report in

the section

Database of Results

4.2.b Data Qualifiers or Flags

EPA Region III Chemists performed the quality review of the analytical data evaluating

methods, holding times, preservatives, minimum detection limits (MDL), back calculation of
results from lab bench sheets, and compliance with good laboratory practices. Based on this
review they assigned “Qualifiers” or “flags” to the data. In general the qualifiers were either
Estimates or Rejects.

Estimate codes were assigned in the following categories:

No filter blank for DOC or Dissolved Metals, or the blank results exceed 1/10 the sample results.
Calibration not performed or documented, or the results vary from the standard concentration by more than
20%.

Minimum Detection Limit exceeds QAPP specifications.

Holding Times not documented or beyond specification in 40 CFR Part 136.

Method not specified or not complying with 40 CFR Part 136.

Proper preservative not used or not documented.

Matrix spikes outside of specifications for recovery limits (either lab limits or +/- 25%) or RPD of duplicate
spikes beyond precision limits (either lab limits or < 20% RPD). 10 % of samples for selected parameters
were to include a matrix spike.

Other (e.g. N.D. = no raw data to support result for critical stations and parameters).

Reject codes were assigned for the following categories:

R(H)

Holding time two days or more beyond the required holding time.

R(B)

Sample value did not exceed the level in the laboratory blank or field blank.

R(?)

Reject for other specified reason.

These flagging codes were hand written on the lab reports during the QA/QC review by the
Chemists.  EPA staff reviewed the coded lab reports and identified all the data flagged as
Rejected.  Some additional data was rejected after further evaluation by the report writers after
reviewing field and lab notes.  These “flags” were entered in the electronic spreadsheet for this
study and cross checked for data entry errors.

No rejected data has been included in any

statistical evaluations of stream quality for this study.

Significant amounts of data from the first lab were rejected in the QA/QC review.  Roughly 60
% of the values were rejected for Total Suspended Solids, Total Dissolved Solids, Total
Phosphorous, and Total Mercury. Overall about 20% of the entire data set from the first
laboratory rejected.  The data quality from the second laboratory was much better.  The second
laboratory had fewer problems with excessive holding times and very little contamination of
blanks.  The same codes for data qualifiers or flags were used by the EPA Chemists reviewing
the data.  Again codes were manually written on a lab report form and EPA staff reviewed the
coded lab reports and identified all the data flagged as Rejected. They entered these “flags” in
the electronic spreadsheet for this study and cross checked this entire data entry effort.

rejected data has been included in any statistical evaluations of stream water quality for

this study.

4.2.c Laboratory Data Completeness Evaluation

Completeness of the entire data set varies with each parameter and with each laboratory.
Completeness is calculated according to the following equation:

C = ((N - R) ÷ N) x (100)
where: C = percent completeness

N = total number of values
R = number of values flagged as Rejected

The percent completeness of each parameter is included in Table 5.  The percent completeness
for the entire dataset is 89.7 %, just missing the goal of 90%.  The first laboratory achieved 82.77
% while the second laboratory achieved 97.88 %.  The most common cause of rejection was
when the first laboratory failed to perform the analyses within the holding times specified in the
Method.  This was especially true for sulfate, chloride, total suspended solids, total dissolved
solids, mercury, nitrate, and nitrite.  Even though the second laboratory achieved 100 %
completeness for sulfate, chloride, total suspended solids, total dissolved solids, and total
phosphorous, the overall percent completeness for those parameters fell short of the goal of 90%.
The second laboratory analyzed for (NO

+NO

)-N instead of nitrate and nitrite so the percent

completeness values for those each of those parameters is from only one laboratory. The data in
Table 5 indicate that several other parameters were analyzed at only one laboratory. Several
parameters were reported at the second laboratory only due to automated procedures which
include groups of parameters, beyond what was tested at the first laboratory.

The changes to levels of organic nutrients in the stream was a concern which initiated the
monitoring for total organic carbon (TOC) and dissolved organic carbon (DOC). The values
found in this study were consistently near the limits of measurability and there appeared to be
something leach from the filter which interfered in the analysis causing the dissolved
concentration to be higher than the total concentration. For this reason many of the values for
TOC and DOC were rejected, resulting in the very low percent completeness for those two
parameters.

Several values for total and dissolved metals were also rejected in the QA review

when the dissolved value exceeded the total value. This resulted in the lower percent
completeness values for aluminum, iron and manganese.

TABLE 5

Percent Completeness for Analytical Results by Laboratory

ANALYTE

UNITS

LAB 1

- #

LES

LAB 1

LES

NOT

REJECTED

LAB 1 -

COMP

LETE

LAB 2 -

LES

LAB 2 -

LES

NOT

REJECTED

LAB 2 -

COMP

LETE

ACIDITY

mg/l

266

208

78.20

191

100.00

ALKALINITY

mg/l

266

265

99.62

213

100.00

ALUMINUM, DISSOLVED

ug/l

266

234

87.97

213

100.00

ALUMINUM, TOTAL

ug/l

266

221

83.08

213

212

99.53

ANTIMONY, TOTAL

ug/l

266

251

94.36

213

100.00

ARSENIC, TOTAL

ug/l

266

264

99.25

213

100.00

BARIUM, TOTAL

ug/l

213

100.00

BERYLLIUM, TOTAL

ug/l

266

257

96.62

213

100.00

CADMIUM, TOTAL

ug/l

266

100.00

213

100.00

CALCIUM, TOTAL

ug/l

266

264

99.25

213

100.00

CHLORIDE

mg/l

266

161

60.53

213

100.00

CHROMIUM, TOTAL

ug/l

266

245

92.11

213

100.00

COBALT TOTAL

ug/l

213

100.00

COPPER, TOTAL

ug/l

266

255

95.86

213

211

99.06

DISSOLVED, ORGANIC CARBON

mg/l

266

208

78.20

213

170

79.81

HARDNESS, TOTAL

mg/l

212

100.00

IRON, DISSOLVED

ug/l

266

222

83.46

213

208

97.65

IRON, TOTAL

ug/l

266

208

78.20

213

205

96.24

LEAD, TOTAL

ug/l

266

255

95.86

213

100.00

MAGNESIUM, TOTAL

ug/l

266

100.00

213

100.00

MANGANESE, DISSOLVED

ug/l

266

228

85.71

213

210

98.59

MANGANESE, TOTAL

ug/l

266

218

81.95

213

210

98.59

MERCURY, TOTAL

mg/l

266

129

48.50

213

174

81.69

NICKEL, TOTAL

ug/l

266

239

89.85

213

100.00

NITRATE+NITRITE (N)

mg/l

212

199

93.87

NITRATE

mg/l

266

144

54.14

NITRITE

mg/l

266

175

65.79

PHOSPHORUS, TOTAL

mg/l

266

106

39.85

213

100.00

POTASSIUM, TOTAL

mg/l

266

264

99.25

213

100.00

SELENIUM, TOTAL

ug/l

266

259

97.37

213

210

98.59

SILVER, TOTAL

ug/l

266

100.00

213

100.00

SODIUM, TOTAL

mg/l

266

265

99.62

213

100.00

SULFATE

mg/l

266

171

64.29

213

100.00

THALLIUM, TOTAL

ug/l

266

250

93.98

213

100.00

TOTAL DISSOLVED SOLIDS

mg/l

266

116

43.61

213

100.00

TOTAL ORGANIC CARBON

mg/l

266

206

77.44

213

180

84.51

TOTAL SUSPENDED SOLIDS

mg/l

266

115

43.23

213

100.00

VANADIUM, TOTAL

ug/l

213

100.00

ZINC, TOTAL

ug/l

266

244

91.73

213

199

93.43

TOTALS FOR EACH LAB

9310

7706

82.77

7857

7690

97.88044

OVERALL % COMPLETENESS

89.70

4.3 Corrective Actions

There was a problem early in the study with the field crews not collecting the proper number of
Field Duplicate samples.  None were collected during the first four rounds of samples.  The
problem was resolved through increased communication and coordination with the laboratory
and field crews.  From March through the end of the study, the crews usually collected one
duplicate sample every day they were sampling.  Field Duplicates made up more than 10% of the
samples being collected after March of 2000.

There was also a problem early in the study with the field crews not collecting Blank Samples
each day which were to be processed and analyzed just like the stream samples.  There was
continuing confusion regarding collection and preservation of Blank Samples.  Some field crews
collected two sets of Blank Samples each day calling one set a Trip Blank and the other set a
Field Blank. There was also an intermittent problem with some crews not having adequate
supplies of sample containers and lab pure water for the blanks.  There was a meeting to improve
coordination with the field crews and the laboratory prior to the start of work with the second
laboratory, but the Blanks continued to be called different names by different crews.

There were problems with the quality of laboratory data and supporting information during this
study forcing a change of laboratories performing the analyses.  Timely submission of the
laboratory data for QA review by EPA staff was a problem throughout the study.  Corrective
actions taken included requiring submission of corrections to laboratory reports and submission
of additional records.  The improvement in percentage completeness between the two
laboratories indicates success of the corrective actions.

4.4 Database of the Results

The evaluation of the large amount of data collected during this study has been facilitated by
compiling it in an electronic database.  Much of the results of analyses from both laboratories
were provided to EPA in an electronic format.  These data were merged into a single database.
This process included standardizing field names, chemical parameter names, and units of
measurement.  The mountaintop mining chemistry database was established using the Microsoft
Access97® relational database.  It is included in this report as APPENDIX 3.  The database is
compatible with most other database software.  It can be linked to other applications such as
ArcView®,  ArcInfo®,  or USEPA’s STORET.  Figure 2 illustrates how the database is
organized.  The chemistry database contains a collection of four tables that are linked by one or
more fields in order to facilitate data analysis.  Information regarding each sampling site is listed
in the table

01-Stations

. Information about each sample is in the table

02-ChemSamps

Laboratory results for each sample are stored in the table

03-ChemValues.

Information about the

chemical parameters is in the table

04-ChemParameters

This vast amount of information was

separated into four tables to reduce repetition within the database.

At least one field in each of the tables is the primary key for the table which functions as a

unique identifier for the information stored in that table. Primary keys are used to link the tables
to one another using one-to-many relationships. For example, the field

StationID

is the primary

key for table

01 - Stations

and is used to link to table

02 - ChemSamps

StationID

is not

duplicated in table

01 - Stations

, but it is duplicated in table

02-ChemSamps

because stations

were sampled multiple times in this study.

Figure 2.

Organization of Database

Not all the chemical analyses were provided in electronic form from the laboratories. Four

months of lab chemistry data and field chemical parameters for all of the samples were only
available in paper form. This data was entered into the database by EPA staff using a set of data
entry forms they created to simplify and standardize the data entry process. Staff at the Wheeling
office completed an independent check of 100% of the data entry performed at Wheeling and
also checked the remainder of the values in the database against the paper copies of laboratory
reports and field sheets. Additional checks on the quality of the data and data entry were made

using queries of the database.  A request to retrieve or manipulate data from the database is
called a query.  Queries can filter and summarize data from one or more of the database tables by
setting specific criteria and then displaying the results in tabular form.  For example, queries can
select specific data such as finding all of the samples where a particular value is greater than a
specified water quality criteria.  They can also perform functions such as calculating hardness
from total calcium and total magnesium values.  Range checks were performed using queries
for each parameter.  They provided an extra indication of the accuracy of the data entry since
outliers were again verified using the original lab reports.  The range checks were useful because
they indicated a group of samples where the values for dissolved aluminum, iron and manganese
were reported by the laboratory using incorrect units.  This problem was then resolved with a
letter from the laboratory correcting the errors. An examination of the range of the data also
highlighted the importance of considering the values reported for blank samples and highlighted
temporal and/or laboratory differences for several chemical parameters.

As a result of QA/QC verification and validation procedures, additional information was added
to the original database preserving the original data, but allowing for a record of QA/QC
evaluations. The

03-ChemValues

table contains a

QA_QC

field for recording data “flags”. A

“R”

was placed in the QA field for chemistry values that were rejected in the QA/QC data

review. Likewise a “

B”

was added to the QA field when the laboratory results for blanks was

greater than or equal to 10% of the sample results. A

“RWHL

” was entered in the

QA_QC

field

where the report writers identified problems with the data such as when the value for dissolved
organic carbon was greater than the value for total organic carbon or when a note from the
chemist indicated acid appeared to have been added to the wrong sample container. Some other
values were rejected based on the field sheet notes of problems encountered at the time of
sampling. For example, the field sheet for one sample noted they only acidified bottles 2 & 6.
These field sampling problems were flagged

“RWHL”

and the appropriate values were rejected

from the data evaluation.

5. EVALUATION AND DISCUSSION OF RESULTS

Several methods of evaluating the data were undertaken in seeking to characterize and compare
conditions in streams below mountaintop removal / valley fill mining operations.  This
evaluation was made more complicated by several factors including variations in the quality of
the data.  The precision of sampling results varied with each parameter as well as with laboratory
over the duration of the study.  The results of the duplicate samples and blank samples are used
to assess the precision of sample results and better evaluate the true impact.  This evaluation was
facilitated by storing the data in an electronic database which is described first in this evaluation
and discussion.

The initial evaluation seeks to identify

parameters likely to be impacted by MTM/VF mining.

The average water quality at all Filled sites is compared to the water quality at all Unmined sites
sampled during this study.  The parameters most altered are then examined for all categories of
sites for the entire data set to evaluate mining impacts on each parameter.  Variations in data
quality are evaluated using the duplicate sample results.  Additional insight is provided through
calculation of a value called “Yield,”an idea taken from a USGS publication (Sams & Beer 2000,
page 10).  Yield rates are calculated by dividing loading values by the drainage area.

The second approach in this evaluation is to identify the samples and sites which

exceeded West

Virginia’s stream water quality criteria

. Sites which have multiple violations are described

and characterized.

Finally, the eight parameters which had

little or no detectable concentrations

in any samples

are listed and briefly discussed.

5.1 Parameters Likely To Be Impacted By MTM/VF Mining

5.1.a Filled Sites vs Unmined Sites

The median concentration from all Filled sites was compared to the median concentration from
all Unmined sites to identify which parameters were most likely to be impacted by MTM/VF
mining.  The ratio of Mined to Unmined was used to prioritize the discussion and evaluation of
the data from all categories of  sites.  Only data from the second laboratory was used in this
comparison since there were data quality differences between the two laboratories.  Table 6 lists
the median values for all Filled site data and all Unmined site data as well as the ratios for each
parameter.  There are 16 parameters with a ratio greater than 1.0 and each will be discussed
individually beginning with sulfate.  The 25 remaining parameters will also be discussed but
they may be discussed in groups of parameters or in later sections of this report.

Table 6. Median Values at All Filled vs All Unmined Sites - Lab 2 Only

Parameter

Median Unmined*

Median Filled*

Ratio Filled/Unmined

Det. Limit @ Lab 2*

Sulfate

12.55

523.5

41.7

Calcium

4.875

104

21.3

0.1

Magnesium

4.095

86.7

21.2

0.5

Hardness

29.05

617

21.2

3.31

Solids, Dissolved

50.5

847

16.8

Manganese, Total

0.005

0.04395

8.8

0.01

Conductivity, Field (uS/cm)

66.4

585

8.8

N/A

Selenium

0.0015

0.01168

7.8

0.003

Alkalinity

149.5

7.5

Potassium

1.58

8.07

5.1

0.75

Sodium

1.43

4.46

3.1

0.5

Manganese, Dissolved

0.005

0.01035

2.1

0.01

Chloride

2.5

4.5

1.8

Acidity

2.5

4.25

1.7

Nitrate/Nitrite (N)

0.81

0.95

1.2

0.1

pH, Field (std)

6.78

7.77

1.1

N/A

Acidity, Hot

2.5

1.0

Aluminum, Dissolved

0.050

1.0

0.1

Antimony

0.0025

1.0

0.005

Arsenic

0.001

1.0

0.002

Beryllium

0.0005

1.0

0.001

Cadmium

0.0005

1.0

0.001

Chromium

0.0025

1.0

0.005

Cobalt

0.0025

1.0

0.005

Copper

0.0025

1.0

0.005

Lead

0.001

1.0

0.002

Mercury

0.0001

1.0

0.0002

Nickel

0.010

1.0

0.02

Organic Carbon, Total

1.35

1.4

1.0

Phosphorous

0.05

1.0

0.1

Silver

0.005

1.0

0.01

Thallium

0.001

1.0

0.002

Vanadium

0.005

1.0

0.01

Barium

0.02885

0.02465

0.9

0.02

Dissolved Oxygen, Field

13.6

11.045

0.8

N/A

Organic Carbon, Dissolved

2.45

1.95

0.8

Solids, Suspended

5.75

4.25

0.7

Iron, Total

0.417

0.1935

0.5

0.1

Iron, Dissolved

0.220

0.096

0.4

0.1

Zinc

0.006

0.0025

0.4

0.005

Aluminum, Total

0.147

0.050

0.3

0.1

* Concentrations are in mg/L unless noted.

5.2 Sulfate Data

Although there is no stream criterion for sulfate in West Virginia to protect aquatic life, several
groups have looked at the impacts of sulfate on other water uses. The adverse effects of high
concentrations of aluminum in water supplies were noted in EPA’s “Blue Book 1972." Their
recommendation was:

On the basis of taste and laxative effects and because the defined treatment process does
not remove sulfates, it is recommended that sulfate in public water sources not exceed
250 mg/l where sources with lower sulfate concentrations are or can be made available.
(Rolich et al 1972, page 89)

This recommendation was set to protect human health at water supplies using surface waters as a
source. Additional research should be conducted to investigate the effects of sulfates on aquatic
life. Regarding the impact on aquatic life, the California State Water Resources Control Board
publication

Water Quality Criteria

1963 edition states:

In U.S. waters that support good game fish, 5 percent of the waters contain less than 11
mg/l of sulfates, 50 percent less than 32 mg/l, and 95 percent less than 90 mg/l.
Experience indicates that water containing less than 0.5 mg/l sulfate will not support
growth of algae. (McKee et al 1963, page 276)

MTM/VF permit writers in West Virginia recognize sulfates as a significant indicator of mining
activity. Their Cumulative Hydrologic Impact Assessment (CHIA) report for the Twentymile
Creek watershed states:

The data indicate that the sulfate concentrations are increased with mining.  Sulfates are
endemic to mining areas and are indicators of mining in a watershed.  A rule of thumb
can be observed from the water quality data researched for this CHIA.  This rule is (A)
below 20 mg/l there is no mining in the watershed (B) between 20 and 30 mg/l there has
been very little or no impact from mining in a watershed (C) from 30 to 100 mg/l there
has been some impact from mining (D) above 100 mg/l there has been certain impact
from mining. (West Virginia Department of Environmental Protection, CHIA for
Twentymile Creek, pages not numbered)

5.2.a Sulfate Concentration in Stream Samples

The concentration of sulfate at each site varied with time during this study. The values for each
sample from all sites have been plotted against time in Figure SO

-1. Each category of site has

been plotted with a different symbol so the variation of concentrations classes of sites can be
evaluated. The detection limit was 10 mg/L at the first laboratory and 5 mg/L at the second
laboratory.

The sulfate concentrations at the Unmined sites fit the rule of thumb for unmined watersheds set
by the CHIA report writers and were well below the recommended drinking water criterion of
250 mg/l. The median concentration for all Unmined sites was only 14.25 mg/L. The US
Geological Survey report Water Quality in the Allegheny and Monongahela River Basins,
Circular 1202", published in 2000 indicates the regional background concentration of sulfate in
unmined watersheds in the northern portion of the Appalachian coal field averages about 21 mg/l
(Anderson et al 2000, page 20), which is similar to the concentrations at Unmined sites in this
study.

Many samples from the categories Filled and Mined had sulfate values exceeding the
recommended drinking water standard of 250 mg/L. Especially noteworthy are the values for
the samples from site MT-24, a yellow diamond symbol in Figure SO

-1. The concentrations

ranged from 800 to 2,300 mg/L and are consistently higher than the concentration at all other
types of sites. This site is not a stream but a flow diversion ditch at an MTM/VF mine.
Obviously the site is a source of sulfate to the stream below. The sites in the category Filled
comprise the majority of the higher concentrations.

Figure SO4-1. Sulfate Concentrations for All Sites vs. Date

2500

2250

2000

1750

1500

g/L)

Sulfate (m

1250

1000

Filled
Mined
Unmined
Filled/Residential
Mined/Residential
Sediment Control Structure

750

500

* 250

10/1/99

12/1/99

2/1/00

4/1/00

6/1/00

8/1/00

10/1/00

12/1/00

2/1/01

USEPA secondary maximum contaminant level

Date

Table SO

-1 lists a summary of the 172 samples which exceed the Secondary Maximum

Contaminant Level of 250 mg/L for Sulfate.  Roughly 45 % of the samples which passed the
QA/QC review exceeded the sulfate criterion but none came from sites in the category Unmined.
There are 110 samples from the category Filled, and another 37 samples from the category
Filled/Residences.  There are 4 samples at Mined sites and another 10 from the category
Mined/Residences.  There were 11 samples from the diversion ditch exceeding the criterion.
The sites where the sulfate concentration was high were scattered across the study area in areas
where coal mining has occurred.

Table SO

-1. Number of Samples Exceeding the Secondary Maximum Contaminant Level

of 250 mg/L for Sulfate

Station ID

EIS Class

No. Samples > 250 mg/L

MT-14

Filled

10 of 11

MT-15

Filled

10 of 10

MT-18

Filled

11 of 11

MT-25B

Filled

7 of 10

MT-32

Filled

4 of 10

MT/34B

Filled

10 of 10

MT-52

Filled

3 of 8

MT-57B

Filled

6 of 7

MT-64

Filled

11 of 11

MT-87

Filled

3 of 13

MT-98

Filled

13 of 13

MT-103

Filled

12 of 13

MT-104

Filled

10 of 13

MT-23

Filled/Residences

10 of 11

MT-48

Filled/residences

3 of 10

MT-55

Filled/Residences

2 of 8

MT-62

Filled/Residences

11 of 11

MT-75

Filled/Residences

11 of 11

MT-79

Mined

4 of 11

MT-69

Mined/Residences

10 of 11

MT-24

MTM/VF Diversion Ditch

11 of 11

5.2.b QA Samples for Sulfate

Evaluation of the results of duplicate samples indicate the values for sulfate are generally
precise. The QA/QC review of the data checked for accuracy. The sulfate data remaining are
suitable for evaluating the impacts to stream chemistry resulting from MTM/VF mining. The
Relative Percent Difference (RPD) values for the 44 sets of field duplicate samples are listed in
Table SO

-2.

Table SO

-2. RPD for Field Duplicates for Sulfate

Station ID

Sample Date

Laboratory

RPD

MT104

3/8/00

LAB 1

194

MT62

3/8/00

LAB 1

MT86

3/8/00

LAB 1

MT02

4/19/00

LAB 1

MT02

5/10/00

LAB 1

MT75

6/13/00

LAB 1

MT25B

8/8/00

LAB 2

MT104

8/9/00

LAB 2

MT52

8/9/00

LAB 2

MT62

8/9/00

LAB 2

MT24

8/30/00

LAB 2

MT98

9/5/00

LAB 2

MT75

9/6/00

LAB 2

MT24

9/19/00

LAB 2

MT48

9/27/00

LAB 2

MT51

9/28/00

LAB 2

MT79

10/3/00

LAB 2

MT95

10/11/00

LAB 2

MT57B

10/24/00

LAB 2

MT25B

10/25/00

LAB 2

MT15

10/31/00

LAB 2

MT87

11/16/00

LAB 2

MT24

11/28/00

LAB 2

MT81

11/28/00

LAB 2

MT40

11/30/00

LAB 2

MT50

11/30/00

LAB 2

MT79

12/11/00

LAB 2

MT91

12/19/00

LAB 2

MT55

1/3/01

LAB 2

MT34B

1/4/01

LAB 2

MT01

1/10/01

LAB 2

MT64

1/16/01

LAB 2

MT86

1/17/01

LAB 2

MT02

2/6/01

LAB 2

MT32

2/9/01

LAB 2

MT55

2/14/01

LAB 2

The highest RPD for the duplicates was 11 and many values were 1. This indicates the data for
sulfate was generally precise throughout the study. The results of duplicate samples are also
presented in Figure SO

-2, Comparison of Duplicate Samples - Sulfate Concentration. In this

graph, duplicate sets of sample results are plotted with one value being plotted on the x-axis and
the other plotted on the y-axis.  If a set of duplicate samples had exactly the same concentration
value, the point would fall on a line from zero/zero to 3000/3000.  A general limit on precision
of plus or minus 25% was used in this study.  This precision limit is also shown on the Figure to
illustrate if a set of duplicate samples are out of normal precision limits or “out of control.”  In
addition, the values from the two laboratories are plotted with different symbols to determine if
there is a difference in precision between the data from the two parts of the study.  There were
nine sets of duplicate samples rejected in the QA/QC review of laboratory results, and all were
during the early part of the study at laboratory 1. No duplicates were rejected in data from the
second laboratory.

Figure SO -2. Comparison of Duplicate Samples - Sulfate Concentrations

3000

2700

2400

2100

1800

1500

1200

900

600

300

+/- 25% Precision Limits

LAB 1

( n = 6 duplicate pairs)

LAB 2

( n = 30 duplicate pairs)

g/L)
(m

ATE

- SUL
E 2

DUPLICAT

300

600

900 1200 1500 1800 2100 2400 2700 3000

DUPLICATE 1 - SULFATE (mg/L)

The agreement in results for each set of duplicates is evident. Duplicate samples run at the
second laboratory had a wider range of concentrations but were still quite precise.

The concentration of sulfates in the 80 blank samples should have been below the detection
limit. There was only one sample with a detectable concentration of sulfate and it was at the first
laboratory. Of the 80 blank samples, there were 28 pairs of duplicate blank samples and all were
below the detection limit in the laboratory indicating no detectable contamination occurred from
sample handling in the field or the laboratory. The quality of the data for sulfate is good.

5.2.c Sulfate Yield

Sulfate has long been considered a good indicator of the presence of coal mine drainage in
streams in Appalachia.  The relationship between coal mining and sulfate in streams is the focus
of the US Geological Survey Water-Resources Investigations Report 99-4208 (Sams & Beer,
2000).  The report notes that sulfate is an excellent indicator of mine drainage because the sulfate
ion is very soluble and chemically stable at the pH levels normally encountered in streams, and
the treatment of mine drainage to remove metals and neutralize acidity has little or no effect on
sulfate concentration.  The authors calculated the annual discharge of sulfate at selected stream
monitoring points and divided that loading by the drainage area above the monitoring point to
determine “Sulfate Yield” in tons per year per square mile.  They used these Sulfate Yield rates
to rank stream degradation attributable to mining.  A similar approach has been used in this
report to evaluate the impacts of mining on the streams.

Sulfate Yield was calculated for each sampling event at each site. The first step was to calculate
the instantaneous sulfate load for each sample event by multiplying the sulfate concentration
(mg/L) times the instantaneous flow rate (cubic feet per second) times the conversion factor
(5.39) to get a load in pounds per day.  The Sulfate Yield was then determined by dividing the
instantaneous sulfate load by the drainage area above that site.  The Sulfate Yield in this report is
measured in pounds of sulfate per day per acre.  These Sulfate Yield values vary at each site with
each sampling event.  They also vary with the categories of sites being evaluated in this study -
Unmined, Mined, Filled, Filled with Residences, and Mined with Residences.  No Sulfate Yield
values were calculated for site MT- 24 since there is no accurate data on the area now draining to
the site.  Mountaintop mining has changed the original drainage patterns and there is no accurate
map of the new watershed boundary.  The variations in Sulfate Yield can be plotted against time
to compare categories of sites.  Figure SO

-3 is a graph of Sulfate Yield rates for all sites vs date.

The production of sulfate per acre at sites in the “Filled” category is much higher than at
“Unmined” sites.  The highest yields are consistently from “Filled” sites and range from 0 to
over 14 pounds per acre per day.  Sulfate Yield rates at Unmined sites are consistently less than
one pound per acre per day.  There are two samples collected in December 1999 at Unmined
sites with yield rates greater than 2 pounds per day per acre.  Those samples are from sites MT-
50 and MT-51.  The field sheet includes the note “Heavy precipitation in the last 24 hours,”
which would explain the higher yield rate values for these Unmined sites.

acre /

lfate/day

unds of Su
Po

Filled
Mined
Unmined
Filled/Residential
Mined/Residential

Figure SO

-3. Sulfate Yield for All Sites vs. Date

10/1/99

12/1/99

2/1/00

4/1/00

6/1/00

8/1/00

10/1/00

12/1/00

2/1/01

Date

The Sulfate Yield rates described in the US Geological Survey Water-Resources Investigations
Report 99-4208 (Sams & Beer, 2000) were measured in tons per year per square mile.  The Yield
rate for two unmined watersheds in this USGS study was calculated to be 24 tons in one
watershed and 25 tons per year per square mile in another. (Sams et al 2000, page 9)  This is
equivalent to about 0.2  pounds per day per acre.  Mined watersheds produced up to 580 tons per
year per square mile (about 5 pounds per day per acre).  These sulfate yield rates are for drainage
areas that are many miles away from the region of mountaintop mining and have different
geology.  The Allegheny and Monongahela River watersheds are dominated by high sulfur coals
while low sulfur coals dominate the geology of the region of mountaintop mining.  Even so, the
values for Sulfate Yield in the northern high sulfur region are similar to those in the study area.
Unmined watersheds produce less than a pound of sulfate per day per acre and heavily mined
watersheds can produce 5 pounds per day per acre or more.  Sulfate is an excellent indicator of
coal mining activity throughout the northern Appalachian coal field.  MTM/VF mining
operations increase the concentration of sulfate in streams draining the mining sites.

5.3 Calcium Data

Calcium is a significant part of hardness, but like magnesium, it does not have water quality
limits. According to the California State Water Resources Control Board’s

Water Quality

Criteria

, calcium salts and calcium ions are among the most commonly encountered substances

in water. They result from the leaching of soil and other natural sources. Calcium is an essential
element for plants and animals. Concerning the impacts to fish and other aquatic life, the report
notes:

Calcium in water reduces the toxicity of many chemical compounds to fish and other
aquatic fauna. ..... According to a reference cited by Hart et al., of the U.S. water
supporting a good mix of fish fauna, ordinarily about 5 percent have less than 15 mg/l of
calcium; 50 percent have less than 28 mg/l; and 95 percent have less than 52 mg/l.

Figure Ca-1. Comparison of Duplicate Samples - Calcium

600000

500000

+/- 25% Precision Limits

LAB 1

( n = 14 duplicate pairs)

LAB 2

( n = 30 duplicate pairs)

/L)

IUM (UG

400000

300000

2 - C
TE

A
LIC

200000

DUP

100000

200000

300000

400000

500000

DUPLICATE 1 - CALCIUM (UG/L)

The results of duplicate samples for calcium are shown in Figure Ca-1. The detection limit was
100 ug/L. The precision was good for both laboratories, and again there were higher values from
the second laboratory.  There were 13 blank samples of the 80 collected which had detectable
concentrations of calcium.  All were collected in the first half of this study and analyzed at the
first laboratory.  Further discussion of the calcium concentrations from this study will focus on
the significant contribution of calcium to hardness.

5.4 Magnesium Data

According to the California State Water Resources Control Board’s

Water Quality Criteria

magnesium constitutes about 2.1 % of the crust of the earth being widely distributed in ores and
minerals.  The salts of magnesium are very soluble.  Magnesium is an essential element for
plants and animals.  Magnesium is considered relatively non-toxic to humans and not a health
hazard because, before toxic concentrations are reached in water, the taste becomes quite
unpleasant.  Concerning the impacts to fish and other aquatic life, the report notes:

Hart et al. cite a report that among U.S. waters supporting a good fish fauna, ordinarily 5
percent have less than 3.5 mg/L of magnesium; 50 percent have less than 7 mg/L; and 95
percent have less than 14 mg/L.

The results of duplicate samples are plotted in Figure Mg-1. The detection limit was 100 ug/L.
None of the laboratory values for magnesium in this study were rejected in the data quality

revi
ews.

Figure Mg-1. Comparison of Duplicate Samples - Magnesium

500000

400000

G/L)

2 - MAGNESIUM (U

300000

DUPLICATE

200000

100000

+/- 25% Precision Limits

LAB 1

( n = 14 duplicate pairs)

LAB 2

( n = 30 duplicate pairs)

DL = 100 ug/L

100000

200000

300000

400000

500000

DUPLICATE 1 - MAGNESIUM (UG/L)

The results of duplicate samples are very precise across a wide range of concentrations.  The
values at the second laboratory were higher than those at the first.  Ten percent of the eighty
blank samples had detectable concentrations of magnesium.  All of these contaminated blank
samples were collected in the first half of the study.  The detection limit for magnesium is 100
ug/L which is 3% of the median value detected at Unmined sites so the increase is well above the
minimum detectable values.  Further discussion of the magnesium concentrations from this study
will focus on the significant contribution of magnesium to hardness.

5.5 Total Hardness Data

According to the California State Water Resources Control Board’s

Water Quality Criteria

, the

term “Hardness” refers to the soap-neutralizing power of water.  Any substance that will form an
insoluble curd with soap causes hardness.  Hardness is attributable principally to calcium and
magnesium ions but other metals can increase hardness.  Indeed the standard method (Method
2340 B) for calculating hardness is determined using only the concentrations of calcium and
magnesium.  The equation is:

Hardness in mg/L = 2.497 (Calcium in mg/L) + 4.118 (Magnesium in mg/L)

The hardness values were calculated for each sample and used in this evaluation of hardness
concentration. Acceptable levels of hardness in drinking waters vary with consumer preference
and “good drinking water” can have a maximum hardness from 140 mg/l to 270 mg/l.
Regarding the impact of hardness on aquatic life, this reference states, “Soft water solutions
increase the sensitivity of fish to toxic metals; in hard waters toxic metals may be less
dangerous.”

Several stream water quality criteria for toxic metals have been established with a limit that
varies with the hardness in the stream.  The harder the water the more of the toxic metal can be
present without causing toxicity. West Virginia has set water quality limits on toxic metals to
protect aquatic life in streams in this study area.  These limits are calculated from equations
which use the hardness concentration to calculate the maximum allowable concentration of the
metal.  Limits have been set for the following dissolved metals: cadmium, copper, lead, nickel,
silver, and zinc. Hardness is an acceptable contaminant for most water uses in low
concentrations.

5.5.a Hardness Concentration in Stream Samples

The concentration of hardness at each site varied with time during this study.  The values for
each sample from all sites have been calculated and plotted against time in Figure H-1.  Each
category of site has been plotted with a different symbol so the variations between categories can
be evaluated.  Unmined sites consistently have the lowest concentration of hardness while the
Sediment Control Structure (MT-24) has the highest concentrations.  All types of sites which
have mining activity upstream also have elevated concentrations of hardness, with the Filled
category sites generally being higher.

3500

Filled
Mined
Unmined
Filled/Residential
Mined/Residential
Sediment Control Structure

Figure H-1. Hardness Concentration for All Sites vs. Date

3000

by Calculation (mg/L)

2500

2000

Hardness

1500

1000

500

10/1/99

12/1/99

2/1/00

4/1/00

6/1/00

8/1/00

10/1/00

12/1/00

2/1/01

Date

5.5.b QA Samples for Hardness

Hardness values were calculated from the concentration of calcium and magnesium. The QA
samples for those parameters have been presented so there is no need for additional discussion.

5.5.c Hardness Yield

The Yield of hardness in pounds per day per acre for each sample is presented in Figure H-2.
The Yield for Unmined sites is generally less than one pound per day per acre while the Yield
for Filled sites is generally above two pounds per day per acre with some values nearly 25
pounds per day per acre.  Higher Yields are also evident at Filled/Residential and
Mined/Residential sites.  There appear to be higher Yield values in the second half of the study.
There are also two samples collected in December 1999 at two Unmined sites with yield rates
above 2 pounds per day per acre.  A note on the field sheet states “Heavy rainfall for the
previous 24 hours,” which would account for these higher yield rates. The data from both
laboratories indicate Filled sites have elevated values for Hardness Yield.

Figure H-2. Hardness Yield for All Sites vs. Date

/acre

Calculation/day

bys

f Hardn

s o
und

Filled
Mined
Unmined
Filled/Residential
Mined/Residential

10/1/99

12/1/99

2/1/00

4/1/00

6/1/00

8/1/00

10/1/00

12/1/00

2/1/01

Date

5.6 Total Dissolved Solids Data

In natural waters the dissolved solids are various minerals in their ionic form including
carbonates, bicarbonates, chlorides, sulfates, phosphates, and nitrates of various metals.  Since
dissolved solids are often a diverse mix of various salts, the effect on use of the water can be
equally diverse.  For drinking water, the U.S. Public Health Service in 1962 recommended that
the total dissolved solids should not exceed 500 mg/l if more suitable supplies are or can be
made available.  Regarding protection of fish and aquatic life, the California State Water
Resources Control Board’s

Water Quality Criteria

states:

It has been reported that among inland waters in the United States supporting a good
mixed fish fauna, about 5 percent have a dissolved solids concentration under 72 mg/L;
about 50 percent under 169 mg/L; and about 95 percent under 400 mg/L.

5.6.a Dissolved Solids Concentration in Stream Samples

Figure DS-1 presents all the data that passed the QA review for concentration of dissolved solids
for all sites. The detection limit was 5 mg/L. A separate symbol represents each category of site
to allow trends to be more easily observed.

Figure DS-1. Total Dissolved Solids Concentration for All Sites vs. Date - Lab 2 Only

4000

3500

L) 3000

ds (mg/

ed Sol

i 2500

Dissolv

2000

Total

1500

1000

500

Filled
Mined
Unmined
Filled/Residential
Mined/Residential

Sediment Control Structure

DL = 5 mg/L

8/1/00

9/1/00

10/1/00

11/1/00

12/1/00

1/1/01

2/1/01

3/1/01

Date

The QA review of data rejected 57 % of the values for dissolved solids at the first laboratory
while 100 % of the values at the second laboratory passed the review.  The values for all
dissolved solids samples from the first laboratory were near zero while the values at the second
laboratory range up to over 3,700 mg/L.  There should have been high concentrations of
dissolved solids during the first half of the study since sulfate and hardness were high.  The data
from the first lab was therefore not used in this evaluation.

5.6.b QA Samples for Dissolved Solids

A major reason for rejection of data at the first laboratory was excessive holding time before
analysis.  As for the blank samples, 27 of the 30 blanks at the first laboratory had detectable
levels of dissolved solids.  Only one of the 50 blanks tested at the second laboratory had
measurable levels of dissolved solids.  All 30 duplicate samples run at the second laboratory
passed the QA/QC review.  The results of duplicate samples are shown in Figure DS-2.

Figure DS-2. Comparison of Duplicate Samples-Total Dissolved Solids-Lab 2 Only

1400

1200

DUPLICATE

- TOTAL DISSOLVED SOLIDS

(MG/L)

+/- 25% Precision Limits

LAB 2

( n = 30 duplicate pairs)

DL = 5 mg/L

1000

800

600

400

200

400

600

800

1000

1200

1400

DUPLICATE 1 - TOTAL DISSOLVED SOLIDS (MG/L)

The duplicate samples results at the second laboratory are quite precise over a broad range of
concentrations. The detection limit for dissolved solids was 5 mg/L which means the median
value of 46 mg/L at Unmined sites is well above the limits of measurability. The dissolved solids
values from the second laboratory have acceptable precision and can be used to evaluate the
impacts of MTM/VF on stream water quality.

5.6.c Dissolved Solids Yield

Figure DS-3. Total Dissolved Solids Yield for All Sites vs. Date - Lab 2 Only

Total Dissolved Solids (m

g/L) 25

Filled
Mined
Unmined
Filled/Residential
Mined/Residential

8/1/00

9/1/00

10/1/00

11/1/00

12/1/00

1/1/01

2/1/01

3/1/01

Date

Figure DS-3 plots the Yield of dissolved solids for all sites. Yield rates for the second half of the
study indicate Filled sites have elevated values of dissolved solids, up to 30 pounds per day per
acre. Yield rates at Unmined sites are less than 2 pounds per day per acre.

5.7 Manganese, Total and Dissolved Data

There are discharge limits on total manganese for active mines set forth in the Code of Federal
Regulations, Title 40, Part 434.  The limits are 4.0 mg/L (4000 ug/L) maximum for any one day
and 2.0 mg/L (2000 ug/L) maximum for thirty consecutive days.  Although none of the
monitoring points in this study is a discharge monitoring point for a permit, the limits serve as a
reference when evaluating the concentrations in the streams.  Manganese laden overburden is a
concern for MTM/VF operations requiring special handling during the mining.  The goal is to
minimize leaching of manganese from the site in quantities that exceed the permit limit.  There
are reclaimed MTM/VF mines that continue to require chemical treatment of the discharges in
order to comply with permit effluent limits (WVDEP CHIA for Twentymile Creek).

Data from the first lab lacked precision and was not included in this evaluation. Total manganese
was detected in 70 % of the 210 samples analyzed at the second laboratory.  The detection limit
was 10 ug/L.  It was found in all categories of sites and in all five watersheds studied. The
maximum concentration of total manganese identified was 518 ug/L (site MT-23, category
Filled/Residences, date - 11/28/00).  This is about 12 % of the daily maximum effluent limit for
coal mines.  The maximum value detected at any Unmined site was 145 ug/L (MT-13, date -
08/30/00).  Manganese concentration data is presented in Figure Mn-1. The higher values are
generally at sites in the category “Filled”, but the values are not consistent for specific sites.

Figure Mn-1. Concentration of Total Manganese for All Sites vs. Date - Lab 2 Only

700

600

Filled
Mined
Unmined
Filled/Residential
Mined/Residential

Sediment Control Structure

DL = 10 ug/L

Total Manganese (ug/L)

500

400

300

200

100

8/1/00

9/1/00

10/1/00

11/1/00

12/1/00

1/1/01

2/1/01

Date

An example is range of concentrations for the Sediment Control Structure (MT-24) which go
from less than 100 ug/L to more than 400 ug/L.  The highest values were at site MT-23, which is
the Mud River near the town of Mud.  The manganese values at sites throughout the Mud River
watershed are the higher values in this figure.  Site MT-13, the mouth of Spring Branch in the
Mud River watershed, is an Unmined site which had manganese values of 145 ug/L on 8/30/00
and 137 ug/L on 9/19/00.  These higher values were associated with low flows (13 gpm and 0.5
gpm respectively) as the concentration at this site dropped below the detection limit when the
flow rose to 150 gpm in February.

Figure Mn-2 plots the concentration of duplicate samples. The precision is only fair at the second
lab. The values range up to about 25 times the detection limit.

Figure Mn-2. Comparison of Duplicates - Total Manganese - Lab 2 Only

300

280

260

240

220

200

180

160

140

120

100

+/- 25% Precision Limits

LAB 2 (DL = 10 ug/L)

( n = 29 duplicate pairs)

)

SE (UG

ANGANE

TAL M

2 - T

PLICATE
DU

0 20 40 60 80 100 120 140 160 180 200 220 240 260 280 300

DUPLICATE 1 - TOTAL MANGANESE (UG/L)

Dissolved manganese was also measured in this study. Results of duplicate samples for dissolved
manganese are plotted in Figure Mn-3. Precision is better than that for total manganese, but the
range of concentration is smaller, being only about 8 times the detection limit.

Figure Mn-3. Comparison of Duplicates - Dissolved Manganese - Lab 2 Only

300

280

260

L) /

240

(UG

220

NES

200

NGA

180

VED

160

140

ATE 2 - DIS

120

100

PLIC

+/- 25% Precision Limits

LAB 2

( n = 29 duplicate pairs)

(DL = 10 ug/L)

0 20 40 60 80 100 120 140 160 180 200 220 240 260 280 300

DUPLICATE 1 - DISSOLVED MANGANESE (UG/L)

The data for manganese indicate it occurs across the study area. MTM/VF mining can increase
the concentration of manganese in streams and require long term chemical treatment of
discharges. Careful analysis and special handling of mine overburden is required to minimize the
concentration of manganese in permitted wastewater discharges from MTM/VF mines.

Yield rates for manganese are presented in Figure Mn-4 for the second laboratory only. Yield
rates are all less than 0.003 pounds per acre per day and the higher values are from most
categories of sites. This indicates that higher manganese values in streams are not closely related
to mining activities and that mines are complying with permit limits on manganese.

/acre

/day

of Total Manganes

Pounds

0.005

Filled
Mined
Unmined
Filled/Residential
Mined/Residential

Figure Mn-4. Total Manganese Yield vs. Date - Lab 2 Only

0.004

0.003

0.002

0.001

0.000

8/1/00

9/1/00

10/1/00

11/1/00

12/1/00

1/1/01

2/1/01

Date

5.8 Specific Conductance Data

Specific conductance or conductivity is a quick method of measuring the ion concentration of
water. The 18

Edition of

Standard Methods for the Examination of Water and Wastewater

states:

Conductivity is the measure of the ability of an aqueous solution to carry an electric
current.  This ability depends on the presence of ions: on their total concentration,
mobility, and valence: and on the temperature of measurement.  Solutions of most
inorganic compounds are relatively good conductors.  Conversely, molecules of organic
compounds that do not dissociate in aqueous solution conduct a current very poorly, if at
all.

The unit of measure is micromhos per centimeter or in the International System of Units,
millisiemens per meter. Specific conductance is measured in the field using a calibrated meter.
The median conductance value of samples from site MT-24 was 2,856 while the median
conductance of all samples at Unmined sites was 62.6 micromho/cm, indicating higher

concentrations of ions came from the area upstream of MT-24 site.

Although there is no stream criterion for conductivity in West Virginia, it is commonly measured
as part of streams surveys. Regarding the impact of conductivity on fish and aquatic life, the
California State Water Resources Control Board’s

Water Quality Criteria

states:

.... Hart et al. have reported that among United States waters supporting a good fish fauna
about 5 % have a specific conductivity under 50x10

-6

mhos [50 micromhos/cm]

at 25

about 50 percent under 270x 10

-6

mhos

[ 270 micromhos/cm]

; and about 95 percent under

1100x10

-6

mhos

[1100 micromhos/cm]

The conductivity of the streams during the sampling event has been included in Figure Cond-1.

A different symbol has been used for each category of site so evaluation of trends is more evident.

Conductivity at Filled sites can be 100 times greater than that at Unmined sites. The highest

values are consistently at the Sediment Control Structure (MT-24) which is on a reclaimed

MTM/VF mine.

It is no surprise that MTM/VF operations increase the conductance of streams draining the
disturbed areas.  Figure Cond-2 plots the conductivity vs the normalized flow rate (the flow rate
measured at the time of sampling divided by the drainage area for that site)for two categories of
sites - Filled and Unmined.  Unmined sites have a consistently low conductivity no matter what
the flow.  Filled sites have a broad range of conductivity much higher than Unmined sites
indicating that MTM/VF mining increases specific conductance in streams.  In larger drainage
area sites it is common to have lower flows associated with higher conductivity.  This is discussed
at the end of this report under the topic Flow Rate Data.

Figure Cond-1. Field Conductivity of All Sites vs. Date

4000

)

ld Conductivity (Umhos/c

3000

2000

Fie

1000

Filled
Mined
Unmined
Filled/Residential
Mined/Residential

Sediment Control Structure

10/1/99

12/1/99

2/1/00

4/1/00

6/1/00

8/1/00

10/1/00

12/1/00

2/1/01

Date

5.9 Selenium Data

The selenium data indicate numerous violations of the West Virginia stream water quality
criterion related to MTM/VF mining. Further discussion of selenium results is located in the

Figure Cond-2. Field Conductivity vs. Instantaneous Flow / Watershed Area

3000

2500

)

hos/c

onductivity (Um

Field C

Filled
Unmined

2000

1500

1000

500

0.0001

0.001

0.01

0.1

100

log (Instantaneous Flow (GPM) / Watershed Area (Acres))

section of this report describing compliance with stream water quality criteria.

5.10 Alkalinity Data

According to the 18

Edition of Standard Methods, alkalinity of a water is its acid-neutralizing

capacity and is primarily a function of carbonate, bicarbonate, and hydroxide content. Alkalinity
is not a specific substance but rather combination of substances. Regarding the impact of
alkalinity on aquatic life, the California State Water Resources Control Board’s

Water Quality

Criteria

states:

It is generally recognized that the best waters for support of diversified aquatic life are
those with pH values between 7 and 8, having a total alkalinity of 100 to 120 mg/L or
more. This alkalinity serves as a buffer to help prevent any sudden change in pH value,
which might cause death to fish or other aquatic life.

5.10.a Alkalinity Concentration in Stream Samples

The concentration of alkalinity in samples from all sites vs date are plotted in Figure Alk-1.

The detection limit was 4 mg/L. Values for many Filled sites are several times higher than the

Unmined sites. Twelve of the thirteen highest values are from site MT-34B and those

concentrations are even higher than the values at the Sediment Control Structure which is on a

reclaimed MTM/VF mine. The increase in alkalinity at a MTM/VF mine site is sometimes

augmented by liming of areas being reclaimed to improve vegetation growth or by addition of

alkaline materials during the mining process to line ditches to neutralize acidic materials. There

are also some chemical treatment facilities upstream of some sites. These facilities usually add

excess alkalinity as they neutralize acid mine drainage or remove manganese to comply with

Figure Alk-1. Alkalinity Concentration for All Sites vs. Date

700

600

500

400

300

200

100

Filled
Mined
Unmined
Filled/Residential
Mined/Residential
Sediment Control Structure

DL = 5 ug/L

g/l)

y (mt

Alkalini

10/1/99

12/1/99

2/1/00

4/1/00

6/1/00

8/1/00

10/1/00

12/1/00

2/1/01

Date

permit limits on discharges. These factors also influence other parameters like specific
conductance, dissolved solids, and hardness.

5.10.b QA Samples for Alkalinity

Figure Alk-2 presents a plot of the concentration of duplicate samples. Data from both
laboratories is precise over a range from the detection limit of 5 ug/L to a maximum of 600 mg/L

Figure Alk-2. Concentration of Duplicate Sam ples for Alkalinity

800

700

+/- 25% Precision L im its

LA B 1

( n = 14 duplicate pairs)

LA B 2

( n = 30 duplicate pairs)

DL = 5 mg/L

L ALKALINITY (M

600

500

400

E 2 - T

300

ICAT

200

DUPL

100

200

300

400

500

600

700

800

DUPLICATE 1 - TOTAL ALKALIN ITY (M G /L)

5.10.c
Alkalinit
y Yield

Figure
Alk-3
plots the
Yield of
alkalinity

day/acre

Alkalinity

ds o

Poun

Filled
Mined
Unmined
Filled/Residential
Mined/Residential

Figure Alk-3. Alkalinity Yield for All Sites vs. Date

10/1/99

12/1/99

2/1/00

4/1/00

6/1/00

8/1/00

10/1/00

12/1/00

2/1/01

Date

for all samples.  Yield rates for Unmined sites are less than 1 pound per day per acre while Yield
rates at Filled sites range to 5 pounds per day per acre.  There appears to be a slight decrease in
alkalinity yield during fall and winter months.  The highest yield was at MT-34B in August 2000.
Other high yield values are from various sites scattered across the study area.

5.11 Potassium Data

The California State Water Resources Control Board’s

Water Quality Criteria

reports that

potassium is a common element constituting 2.4 percent of the earth’s crust.  Potassium salts are
extremely soluble and can usually only be removed from water through evaporation.  Potassium
is an essential nutritional element for humans but acts as a cathartic in concentrations greater than
2000 mg/L.  Regarding impacts to fish and other aquatic life, the report states:

The toxicity of potassium to fish is reduced by calcium, and, to a lesser degree, by sodium.
Potassium is more toxic to fish and shellfish than calcium, magnesium, or sodium. ...
Several investigators found, independently, that potassium could be toxic to fish in soft or
distilled waters at concentrations of 50-200 mg/L .....

Potassium is a component of many fertilizers which are sometimes applied to mined areas to
stimulate vegetation growth. This practice could be augmenting the increase of potassium in
streams below mine sites being reclaimed.

5.11.a Potassium Concentration in Stream Samples

Figure K-1 shows the concentration of potassium in samples from all sites vs date. The detection
limit was 0.1 mg/L for Laboratory 1 and 0.75 mg/L for Laboratory 2. The potassium data from
both laboratories passed the QA review with only two samples being rejected and those were at
Laboratory 1.

The higher concentrations are consistently at sites in the Filled category indicating that MTM/VF

Figure K-1. Concentration of Potassium for All Sites vs. Date

Filled
Mined
Unmined
Filled/Residential
Mined/Residential

Sediment Control Structure

Lab 1 DL = 0.1 mg/L
Lab 2 DL = 0.75 mg/L

/L) g

ssium (a
Pot

10/1/99

12/1/99

2/1/00

4/1/00

6/1/00

8/1/00

10/1/00

12/1/00

2/1/01

Date

mining operations increase the concentration of potassium in streams. There are 40 values above
10 mg/L and 29 of those are in the Mud River, 10 in the Spruce Fork, and one in the Clear Fork
watersheds. All sites in the Unmined category have low concentrations of potassium.

5.11.b QA Samples for Potassium

Figure K-2 plots the concentration of potassium in all duplicate samples collected during this
study. The plot indicates the data are more precise at the second laboratory over the range of
concentrations from the detection limit to about 30 mg/L.

Figure K-2. Comparison of Duplicate Samples - Potassium

(UG/L

)

- POTASSIUM
E

CAT

DUPL

+/- 25% Precision Limits

LAB 1 - DL = 0.1 mg/L

( n = 14 duplicate pairs)

LAB 2 - DL = 0.75 mg/L

( n = 30 duplicate pairs)

DUPLICATE 1 -POTASSIUM (UG/L)

5.11.c Potassium Yield

Figure K-3 plots the Yield of potassium for samples from all sites vs date.  The data would
indicate that potassium Yield rates are generally below 1 pound per day per acre, but the higher
values are usually from sites in the Filled category.  The three higher yield values for samples
collected in December 1999 are all in the same watershed.  They are sites MT-50, 51, and 52.  The
yield rates are believed to elevated on this occasion due to recent rains.  The note on the field sheet
states “Heavy precipitation in the last 24 hours.” None of the higher concentrations for the
December 1999 samples were from these three sites so the increase in flow rates  resulted in higher
yield  rates.

5.12 Sodium Data

Figure K-3. Potassium Yield for All Sites vs. Date

1.0

0.9

0.8

day/acre

m/ui

s
taso

P
of s

dn
Pou

Filled
Mined
Unmined
Filled/Residential
Mined/Residential

0.7

0.6

0.5

0.4

0.3

0.2

0.1

0.0

10/1/99

12/1/99

2/1/00

4/1/00

6/1/00

8/1/00

10/1/00

12/1/00

2/1/01

Date

The California State Water Resources Control Board’s

Water Quality Criteria

states:

This very active metal does not occur free in nature, but sodium compounds constitute 2.83
percent of the crust of the earth. Owing to the fact that most sodium salts are extremely
soluble in water, any sodium that is leached from soil or discharged by industrial wastes
will remain in solution.

Regarding the impact on fish and aquatic life, the report states:

Of the United States waters supporting good fish fauna, ordinarily the concentration of
sodium plus potassium is less than 6 mg/L in about 5 percent; less than 10 mg/L in about
50 percent; and less than 85 mg/L in about 95 percent.

5.12.a Sodium Concentration in Stream Samples

Sodium concentrations for all sites are plotted in Figure Na-1.  The detection limit was 1 mg/L
The highest values are for sites in the category Filled/Residences and occurred in the Spruce Fork
watershed at sites MT-40 and MT-48.  MT-40 is downstream of 7 MTM/VF mine permits and 3
refuse piles while MT-48 is below four communities.  Possible sources of sodium would be mine
drainage treatment facilities using sodium hydroxide and winter time salting of highways.

5.12 c QA Samples for Sodium

The results of duplicate samples are plotted in Figure Na-2. The detection limit was 1 mg/L. The

Figure Na-1. Sodium Concentration at All Sites vs. Date

250

225

200

175

150

Filled
Mined
Unmined
Filled/Res (Other Stressors)
Mined/Res (Other Stressors)
Sediment Control Structure

mg/L)

125

iumd
(So

100

10/1/99

12/1/99

2/1/00

4/1/00

6/1/00

8/1/00

10/1/00

12/1/00

2/1/01

Date

data are very precise with multiple values below about 60 mg/L. The one value at slightly over
200 mg/L also is very precise. Both laboratories have good precision for this parameter.

Figure Na-2. Sodium Concentration of Duplicate Samples

250

200

150

100

+/- 25% Precision Limits

LAB 1

( n = 14 duplicate pairs)

LAB 2

( n = 30 duplicate pairs)

DL = 1 mg/L

UM (UG

SODI
2 -
TE
CA

DUP

100

150

200

250

DUPLICATE 1 -SODIUM (UG/L)

5.12.c
Sodium
Yield

Yield rates
for sodium
are plotted
in Figure
Na-3. Mos
values are
less than
0.25

pounds per day per acre. The higher values at the Filled/Residence sties were noted in Figure Na-1
also and are possible related to use of road salt or the use of sodium hydroxide in chemical
treatment facilities at mine discharges.  There are higher values on two sample occasions -
December 1999 and September 2000.  The three values near 0.75 pounds per day per acre in
December 1999 were at MT-50, 51, and 52.  The field sheet not for those samples noted “Heavy
precipitation in the last 24 hours.”  The higher yield rates for the Filled/ Residential sites is for
MT-40 and MT-48, which correspond to the higher concentrations listed earlier in Figure Na-1
showing concentrations vs date. The highest yield of 1.5 pounds per day per acre is at site MT-60.
The flow rate for that sample was the highest recorded for that site during this study while the

1.50

1.25

cre

/ay

1.00

/da

Sodiu

0.75

ds of

Poun

0.50

1.75

Filled
Mined
Unmined
Filled/Residential
Mined/Residential

Figure Na-3. Sodium Yield for All Sites vs. Date

0.25

0.00

10/1/99

12/1/99

2/1/00

4/1/00

6/1/00

8/1/00

10/1/00

12/1/00

2/1/01

Date

concentration was 21.1 mg/L, below the average for that site (30.5 mg/L). There were no
comments on the field sheet indicating anything unusual.

5.13 Chloride Data

Chloride is one of the parameters limited by WVDEP water quality criteria and is discussed later
in the report under that topic.

5.14 Acidity Data

Acidity, like alkalinity is not a specific chemical but instead is a measure of the effects of a
combination of substances and conditions in the water.  Waters can have both acidity and
alkalinity values at the same time.  Acidity may be present from  natural causes and from human
activity.  Acid waters are sometimes formed as a result of mining activity, especially in sulfur
bearing formations.  Regulations have sought to address concerns with excess acidity resulting

from mining activities through the permitting processes. There are elaborate regulations which
focus on determining and minimizing the potential for forming acid waters. There are also effluent
limits on the pH (discussed later in this report) of discharges.

Acidity was detected in 20 % of the 399 samples that passed the QA/QC review.  The second
laboratory found acidity in 31 samples above the detection limit of 2 mg/L.  Twenty of these
detected values came from sites in the Filled category.  The site with the highest concentrations of
acidity was MT-34B, a site in the Filled category with an active mine upstream.  Five of the 31
values came from this site and they ranged from 29 mg/L to 40 mg/L.  However, there were no
violations of the stream limits on pH at this site.  The only violations of the stream criteria for pH
detected were at Unmined sites.

Acidity in streams can be increased by MTM/VF mining but mine permitting activities address
this potential problem.

5.15 Nitrate and Nitrite Data

The

Water Quality Criteria, 1972

“Blue Book” discusses Nitrate-Nitrite in water supplies and

notes that chlorination converts the nitrite to nitrate. They make the following recommendation
concerning nitrate in water:

On the basis of adverse physiological effects on infants and because the defined treatment
process has no effect on the removal of nitrate, it is recommended that the nitrate-nitrogen
concentration in public water supply sources not exceed 10 mg/L. On the basis of its high
toxicity and more pronounced effect than nitrate, it is recommended that the nitrite-
nitrogen concentration in public water supply sources not exceed 1 mg/L.

The California State Water Resources Control Board’s

Water Quality Criteria

also discusses

nitrate and nitrite and notes that nitrites are often formed in streams by the natural degradation of
ammonia and organic nitrogen.  Since they are usually quickly oxidized to nitrates, they are
seldom present in surface waters in significant concentrations.  The presence of nitrates and nitrites
usually indicates an organic loading source such as sewage or fertilizer.  Regarding the impact on
fish and other aquatic life, the report states:

High nitrate concentrations in effluents and water stimulate the growth of plankton and
aquatic weeds. By increasing plankton growth and the development of fish food
organisms, nitrates indirectly foster increased fish production. Hart et al. report references
to the effect that United States waters supporting a good fish life ordinarily 5 percent have
less than 0.2 mg/L of nitrates; 50 percent have less than 0.9 mg/L; and 95 percent have less
than 4.2 mg/L.

5.15.a Nitrate-Nitrite Concentration in Stream Samples

The laboratory data for nitrate and nitrite is somewhat confusing and of mixed quality, partly due
to changes in what parameters were being measured.  The first laboratory began this survey
analyzing for nitrates and nitrites separately but it was soon evident that the 48 hour holding time
was difficult to meet.  The parameter was switched to nitrate - nitrite (nitrogen) which has a 28 day
holding time for the contract with the second laboratory.  The data from the first laboratory was
often rejected for holding time violations and only 54 % of the nitrate samples and 66% of the
nitrite samples passed the QA review.  The second laboratory began testing for nitrate and nitrite
separately but soon switched to nitrate plus  nitrite as nitrogen.  The first samples at the second
laboratory were manually converted to nitrate plus nitrite as nitrogen values and entered into the
database.  Overall 94 % of the data from the second laboratory for nitrate plus nitrite as nitrogen
passed the QA/QC review.  The detection limit was 0.1 mg/L.  The highest value detected at the
second laboratory was 23.4 mg/L at site MT-18, a site in the Filled category, on 01/10/00.  Some
high values might be caused by careless handling of the nitrogen compound explosives used at
surface mines or when nitrogen containing fertilizers are spread on surface mines to encourage
growth of vegetative cover during reclamation, but it is not known if this might be part of the
cause for this elevated value.  Many samples had no detectable concentrations and they were in all
categories of sites.  The Unmined site with the most detectable concentrations and the highest
values (second lab data only) was MT-95 in the Twentymile Creek watershed.  Nitrate plus nitrite
as nitrogen values ranged from 0.73 mg/L to 1.1 mg/L in each of the six samples from the site.

MTM/VF mining operations can increase the concentration of nitrate plus nitrite as nitrogen in
streams.

5.16 Parameters Present in Low Concentrations

5.16.a Total Phosphorous

Phosphorous was detected in only one of 213 samples at the second laboratory. The concentration
was 0.12 mg/L. No samples were rejected in the QA/QC review. Since the detection limit was
0.10 mg/L, this would indicate that stream concentrations of phosphorous are not being
measurably impacted by MTM/VF mining.

5.16.b Total Copper, Lead and Nickel

Copper, lead, and nickel were usually below the detection limit for all samples tested at the second
laboratory but several samples had detectable concentrations as listed below.  The only obvious
pattern observed in the data is that many of the detections were in the Mud River watershed (MT-
01 through MT-24).  Site MT-24, a site on a reclaimed MTM/VF mine, had three measurable
values of copper, all near the detection limit, no nickel values, and six of the eight detections for
nickel.  There is no clear indication that MTM/VF mining caused any changes in these metal
concentrations in streams.

Site ID

Category Date

Copper

Lead

Nickel

(DL = 5 ug/L)

(DL = 2 ug/L)

(DL= 20 ug/L)

MT-01

Min/Res

01/10/01

10.3

MT-13

Unmined

11/28/00

14.8

3.76

MT-14

Filled

08/30/00

7.64

2.14

MT-18

Filled

08/30/00

7.41

MT-23

Fill/Res

08/30/00
11/28/00

20.4

5.6

2.1

ND
ND

MT-24

Sediment

Control

Structure

08/30/00
09/19/00
10/31/00
11/28/00
01/10/01
02/06/01

8.15

6.56
5.83

ND
ND

ND
ND
ND
ND
ND
ND

35.5
36.8
71.8
63.4

115

80.4

MT-39

Unmined

11/29/00

5.23

7.4

MT-50

Unmined

08/09/00

4.48

MT-57B

Filled

08/09/00

16.2

MT-62

Fill/Res

09/06/00

37.6

MT-64

Filled

09/06/00

39.5

MT-69

Min/Res

11/28/00

6.72

MT-79

Mined

11/28/00
01/16/01

8.01
5.23

ND
ND

MT-81

Mined

11/28/00

13.8

5.17 Other Parameters Detected in Measurable Concentrations

5.17.a Total Barium

Barium was detected in 96 % of the 213 samples analyzed at the second laboratory.  The detection
limit was 20 ug/L.  Concentrations are plotted in Figure Ba-1.  They range to 250 ug/L but most
values are below 75 ug/L.  There were higher values on 9/27/00 and 11/28/00.  The three samples
in September were from MT-39 (138 ug/L), MT-40 (145 ug/L) and MT-42 (214 ug/L), all in the
Spruce Fork watershed.  Each concentration was two to three times the average for each site and
flows were higher than average as well.  A note on the field sheets for that day stated, “ Recent
heavy rains have changed the stream bottom ...”  Sites MT-39 and 42 are both Unmined.  The
data would indicate there was a temporary release of barium in these two tributary watersheds and
in fact the decreasing concentration of barium at downstream site MT-48 (47.8 ug/L) would also
fit that theory.  Barium muds are used in drilling for oil and gas.  The highest concentration at any
site was detected 11/28/00 at site MT-01 (214 ug/L) in the headwaters of the Mud River.  The next
site downstream on the Mud, MT-23 also had a higher than normal concentration of barium area.
(107ug/L).  This appears to be another instance of a temporary release of barium in a headwater
area.

Figure Ba-1. Concentration of Barium for All Sites vs. Date - Lab 2 Only

250

Filled
Mined
Unmined
Filled/Residential
Mined/Residential

Sediment Control Structure

200

Barium (ug/L)

150

100

8/1/00

9/1/00

10/1/00

11/1/00

12/1/00

1/1/01

2/1/01

3/1/01

Date

The only field note the crew made for that set of samples was for site MT-23 where they

stated,”Beaverdam constructed downstream affecting depth and velocity flow measurements.”
The mix of categories of sites across the range of concentrations and over the study period have no
obvious patterns. Some Unmined sites have an elevated barium concentration while the sediment
control structure and some Filled sites consistently have low concentrations of barium.

Duplicate sample results are presented in Figure Ba-2. The data indicate excellent precision to
roughly 100 ug/L (five times the detection limit).

There is no clear indication that MTM/VF mining changes the concentration of barium in streams.

Figure Ba-2. Comparison of Duplicate Samples - Barium - Lab 2 Only

100

)

UG/L

BARIUM (

CATE

DUPL

100

DUPLICATE 1 - BARIUM (UG/L)

+/- 25% Precision Limits

LAB 2

( n = 30 duplicate pairs)

(DL = 20 ug/L)

5.17.b Total Zinc

Zinc was detected in 51 % of the 199 samples that passed the QA/QC review and were analyzed in
the second laboratory. The detection limit was 10 ug/L. The values are presented in Figure Zn-1.

Most values are below 20 ug/L where there was less precision in laboratory results. Zinc
concentrations were elevated at MT-24, the Sediment Control Structure indicating that MTM/VF
mining could cause elevated levels of zinc in streams, however there are also high values for zinc
at four different Unmined sites (MT-50 on 8/9/00, MT-95 on 9/5/00, MT-13 on 11/28/00 and MT-
39 on 11/29/00).

Duplicate sample results are presented in Figure Zn-2. The data indicate there were precision
problems below a concentration of roughly 25 ug/L. Duplicate sample values range to roughly 45
ug/L which is 4.5 times the detection limit. Since most of the values from sites were below 25

ug/L where there was less precision, there is no clear indication that MTM/VF mining changes the
concentration of zinc in streams.

Figure Zn-1. Concentration of Zinc for All Sites vs. Date - Lab 2 Only

120

100

Zinc (ug/L)

Filled
Mined
Unmined
Filled/Residential
Mined/Residential

Sediment Control Structure

DL = 5 ug/L

8/1/00

9/1/00

10/1/00

11/1/00

12/1/00

1/1/01

2/1/01

3/1/01

Date

Figure Zn-2. Comparison of Duplicate Samples - Zinc - Lab 2 Only

+/- 25% Precision Limits

LAB 2

( n = 28 duplicate pairs)

(DL = 5 ug/L)

/L)

(

2 -
TE
CA

DUPLICATE 1 -ZINC (UG/L)

5.17.c Total Organic Carbon & Dissolved Organic Carbon

TOC and DOC results were generally very low near the detection limit of 1 mg/L.  There was a
confounding factor with the DOC test in that something appeared to be leaching from the filter used
to remove the suspended matter in the field. The field crews used 45micron cellulose acetate
membrane disposable sterile syringe filters. Whatever this interfering material was, it would create
an organic value of up to 2 mg/L in some samples resulting in QA/QC flags on data.  Of the 213
samples collected, 180 TOC values passed the QA/QC review and 170 DOC samples passed.  TOC
was detected in 77 % of the samples and DOC was detected in 86 % of the samples passing QA/QC
review.

Figure TOC-1 plots the results of duplicate samples for TOC at the second laboratory.  It illustrates
the lack of precision in concentrations below about 2.5 mg/L.  The range of duplicate sample values
went to 3 mg/L.  The maximum concentration of TOC recorded at the second laboratory was 4.4
mg/L.  Only 14 (10%) of the 138 values detected were above 2.5 mg/L.  Four of the 14 were at
Unmined sites.

Figure TOC-1. Comparison of Duplicate Samples - Total Organic Carbon - Lab 2 Only

G/L)

ON (M

ANIC C

L ORG

ATE 2 - TOTA

PLIC

DUPLICATE 1 - TOTAL ORGANIC CARBON (MG/L)

+/- 25% Precision Limits

LAB 2

( n = 23 duplicate pairs)

(DL = 1 mg/L)

Figure DOC-1. Comparison of Duplicates - Dissolved Organic Carbon - Lab 2 Only

+/- 25% Precision Limits

LAB 2

( n = 22 duplicate pairs)

(DL = 1 mg/L)

L) /

(MG

RBON
CA

ANI

D O

SSO

DUPLICATE 2 -

DUPLICATE 1 - DISSOLVED ORGANIC CARBON (MG/L)

Figure DOC-1 plots the results of duplicate samples for DOC at the second laboratory. It also
illustrates the lack of precision in concentrations for the range of values which went to about 4
mg/L. There is no clear indication that MTM/VF mining changes the concentration of TOC or
DOC in streams.

5.17.d Total Suspended Solids

Coal mines have specially designed and constructed ditches and sedimentation ponds to reduce
erosion and minimize the amount of suspended solids carried from a mine site in surface runoff.
Large surface mine operations have elaborate systems required as part of their mining permits.
Mine operators regularly monitor and maintain these facilities to capture sediment being washed
from their mine site.

There were 213 samples for total suspended solids (TSS) analyzed at the second laboratory and
none were rejected in the QA/QC review.  A total of 69 of those samples (32 %)  had
concentrations at or above the detection limit of 5 mg/L.  The values were low and this could be
due to several factors including: dry fall weather; staff who chose not to sample on rainy days;
because the sediment ponds below mined areas were working well; or other unknown causes.
Whatever the cause, only 28 samples had a concentration above 10 mg/L.  These values were from
all categories of sites and are listed below. The data indicate that the concentration of TSS in the
streams in the study area was usually below 5 mg/L during the study period.

Site Identification

Category

Concentration (mg/L)

MT-02

Unmined

MT-13

Unmined

MT-24

Sediment Control Ditch

21, 15, 14, 11

MT-34B

Filled

MT-42

Unmined

65, 12

MT-45

Mined

MT-48

Filled/Residences

MT-52

Filled

MT-55

Filled/Residences

MT-57B

Filled

MT-60

Filled

60, 25, 14

MT-62

Filled/Residences

20, 16

MT-64

Mined/Residences

32, 13, 12

MT-69

Mined/Residences

MT-75

Filled/Residences

19, 15

MT-79

Mined

MT-86

Filled

MT-91

Unmined

Document Outline