1. DUQUESNE
UNIVERSITY
BAYER SCHOOL OF NATURAL AND ENVIRONMENTAL SCIENCES
Water quality monitoring in the lower Allegheny River and its tributaries 
Beth Dakin, Brady Porter, and John Stolz, Center for Environmental Research and Education, Duquesne University, Pittsburgh, PA
Abstract:
Since January 2013, we have monitored multiple parameters of water quality at 14 sites in the lower Allegheny River drainage (from Pittsburgh upstream to Parker, PA, just downstream of the Clarion River). This sampling is a part of the 3 Rivers QUEST (Quality Useful Environmental Study Teams), a comprehensive water quality monitoring and reporting program, which gathers data on the Monongahela, Allegheny, and upper Ohio River systems. Sampling took place biweekly from January 2013 to July 2015, and has continued on a monthly basis to the present. Some of the parameters measured have established levels for drinking water standards, while other chemical parameters or ratios between parameters can serve as indicators for specific types of pollution, such as abandoned mine drainage (AMD), road salt runoff, and produced water from hydraulic fracturing for natural gas extraction.
Since we now have accumulated four full years of biweekly/monthly data for these sites, we have begun to analyze both trends over time within sites as well as comparing concentrations and ratios of various parameters between sites within the lower Allegheny River drainage. Blacklick Creek, a tributary of the Conemaugh River, is known to have been impacted by both AMD and Marcellus Shale treated water and shows distinctly different pH, Ca:Mg vs. Ca:Sr, and Cl vs. Br:Cl when compared to other sites in the region. Other anomalous values are seen at Pine Creek (Allegheny Co., sampled in Etna, PA) and Deer Creek (Allegheny Co., sampled in Harmar, PA).
Methods: Sampling
Field:
YSI multimeter measures air and water temperature, specific conductance, and pH
Additional field information reported:
sample date & time
weather (sunny/cloudy/rainy/snowy)
24hr precipitation (trace/light/moderate/heavy)
water level (low/normal/high)
visual turbidity (clear/cloudy/tea-colored/muddy/murky/milky)
Lab (PACE Analytical):
TDS (SM2540C-97)
Dissolved metals (EPA 6010B, atomic emission spectrometry)
Includes aluminum, calcium, iron, magnesium, manganese, sodium, and strontium
Alkalinity (SM2320B-97)
Inorganic ions (EPA 300.0, ion chromatography)
Includes bromide, chloride, and sulfate
All field and lab data, along with flow data from nearby USGS gages, are entered into the 3RQ database (see 3riversquest.org).
Ca/Mg:Ca/Sr
Marcellus produced water (MSC) has a signature high in strontium compared to calcium
AMD and most freshwater systems in this region have a signature with low strontium compared to calcium
Results:
We now have four consecutive years of biweekly/monthly sampling for fourteen sites in the lower Allegheny River system. Below are a some of the results and analyses to come out of our portion of the 3RQ project.
What is 3 Rivers QUEST?
3 Riverst QUEST (3RQ) is a collaborative water quality monitoring and reporting program led by the West Virginia Water Research Institute at WVU. Since 2013, 3RQ research partners at WVWRI, Wheeling Jesuit University, Duquesne University, and the Iron Furnace Chapter of Trout Unlimited/Redhorse Environmental have been sampling the Ohio, Monongahela, and Allegheny Rivers (Fig. 1), including both field data and detailed lab analysis of grab samples. In addition, volunteer organizations are involved in 3RQ and have added valuable information on conductivity, pH, and water temperature in smaller watersheds. Data entered into the 3RQ database is displayed on the interactive data map (3riversquest.org).
National secondary drinking water standard exceedences
Although secondary maximum contaminant levels (SMCLs) are not enforceable standards, exceeding these values can cause aesthetic, cosmetic, or technical effects on drinking water. The Allegheny River supplies drinking water for over a million people in the Pittsburgh area, so high levels of these chemicals in the local waterways can impact the effort and cost associated with producing acceptable drinking water.
Comparing parameter levels between sites
Figure 1: Geographic range of overall 3RQ project
Parameter Al Cl Fe Mn
low pH
high pH
SO4
TDS
SMCL (mg/L) *
250
0.3
0.05
<6.5
>8.5
500
Allegheny - Kittanning
1/51
3/51
39/51
1/50
1/74
Allegheny - Parker
4/74
32/74
2/74
Allegheny - Tarentum
31/51
Allegheny L&D 2
2/77
3/76
42/77
Allegheny L&D 5
1/77
53/77
Allegheny L&D 7
20/26
Blacklick - Josephine
18/76
5/76
56/76
76/76
9/76
16/76
Buffalo Creek
1/26
13/26
Conemaugh - Seward
19/76
6/77
4/77
Conemaugh - Tunnelton
70/76
1/76
7/77
Crooked Creek - Ford City
2/51
44/51
Crooked Creek - Idaho
1/25
25/25
3/25
Deer Creek
47/51
38/51
Kiski - Leechburg
4/51
Kiski - Vandergrift
Loyalhanna - Kingston
3/77
31/77
2/76
Mahoning Creek
25/26
Mahoning Creek - Templeton
22/47
Pine Creek
9/26
10/26
2/26
18/26
Redbank Creek
24/26
Redbank Creek at SR1003
35/50
* Analysis here uses SMCL of 0.2mg/L for aluminum
highlighting:
>10%
>50%
>75%
Allegheny-
Kittanning
Parker
Tarentum
Allegheny L&D 2
Allegheny L&D 5
Allegheny L&D 7
Blacklick-Josephine
Buffalo Creek
Conemaugh-Seward
Conemaugh-Tunnelton
Crooked Cr- Ford City
Crooked Cr- Idaho
Deer Creek
Kiski-Leechburg
Kiski-Vandergrift
Loyalhanna-Kingston
Mahoning Creek
Mahoning-Templeton
Pine Creek
Redbank Cr.
Redbank Cr. at SR21003
Allegheny-
Kittanning
Parker
Tarentum
Allegheny L&D 2
Allegheny L&D 5
Allegheny L&D 7
Blacklick-Josephine
Buffalo Creek
Conemaugh-Seward
Conemaugh-Tunnelton
Crooked Cr- Ford City
Crooked Cr- Idaho
Deer Creek
Kiski-Leechburg
Kiski-Vandergrift
Loyalhanna-Kingston
Mahoning Creek
Mahoning-Templeton
Pine Creek
Redbank Cr.
Redbank Cr. at SR21003
Allegheny-
Kittanning
Parker
Tarentum
Allegheny L&D 2
Allegheny L&D 5
Allegheny L&D 7
Blacklick-Josephine
Buffalo Creek
Conemaugh-Seward
Conemaugh-Tunnelton
Crooked Cr- Ford City
Crooked Cr- Idaho
Deer Creek
Kiski-Leechburg
Kiski-Vandergrift
Loyalhanna-Kingston
Mahoning Creek
Mahoning-Templeton
Pine Creek
Redbank Cr.
Redbank Cr. at SR21003
Allegheny-
Kittanning
Parker
Tarentum
Allegheny L&D 2
Allegheny L&D 5
Allegheny L&D 7
Blacklick-Josephine
Buffalo Creek
Conemaugh-Seward
Conemaugh-Tunnelton
Crooked Cr- Ford City
Crooked Cr- Idaho
Deer Creek
Kiski-Leechburg
Kiski-Vandergrift
Loyalhanna-Kingston
Mahoning Creek
Mahoning-Templeton
Pine Creek
Redbank Cr.
Redbank Cr. at SR21003
Bromide
Bromide is of interest for two main reasons:
It is found in very low levels in freshwater systems, but much higher concentrations in marine systems.
Deep formation brines (such as the Marcellus Shale) are in high in bromide
Bromide is important in drinking water because it can be incorporated with disinfectant byproducts to form carcinogenic Trihalomethanes (TTHMs). While bromide in water is not regulated, the EPA has set a MCL (maximum contaminant level) of 0.08mg/L for TTHMs under the NPDWR (National Primary Drinking Water Regulation).
There is a wide range in bromide concentration throughout the lower Allegheny River system. Blacklick Creek frequently has high levels, while Loyalhanna Creek rarely exceeds the 0.02mg/L detection level. There does not appear to be a trend in bromide concentration or load over time.
Methods: Site Selection
Fourteen sampling sites were selected in January 2013 (see yellow and green pins in Figure 2 and Table 1) in order to represent the lower Allegheny watershed and accessibility to USGS flow gages. In January 2014, several sites were moved downstream in order to cover the full watershed of several tributaries, as well as a few other changes (see blue and green pins, Fig. 2; Table 1).
Discussion:
The lower Allegheny River watershed shows great variety in water quality and is threatened by multiple pollution sources.
Blacklick Creek is the most impacted of our study sites. Elevated levels of Br, Cl, SO4, Sr, and low pH indicate that it continues to be affected by AMD and Marcellus Shale activities.
There is a pattern of increasing Sr and Mg (relative to Ca concentration) from sites upstream to downstream along the mainstem of the Allegheny River. In the major tributaries along this stretch of river, Sr also increases, but Mg decreases from upstream to downstream. These patterns may be related to the underlying geology of the region
Elevated levels of several parameters, especially manganese, may have an impact on local water treatment plants that use water from the lower Allegheny River for drinking water in the future
Table 1: Locations and frequency of sampling
Location
Biweekly Sampling Jan Jan. 2104
Biweekly Sampling Jan June 2015
Monthly Sampling July 2015-present
Pine Creek X
Allegheny L&D 2
Deer Creek
Allegheny - Tarentum
Buffalo Creek
Kiski - Leechburg
Kiski - Vandergrift
Loyalhanna - Kingston
Conemaugh - Tunnelton
Blacklick Creek - Josephine
Conemaugh - Seward
Allegheny L&D 5
Crooked Creek - Idaho
Crooked Creek - Ford City
Allegheny - Kittanning
Allegheny L&D 7
Mahoning Creek - MC Dam
Mahoning Cr. - Templeton
Redbank Creek - St. Charles
Redbank Creek at SR 1003
Allegheny - Parker
References:
Katz B., E.S., Kauffman L. , Using Cl/Br ratios and other indicators to assess potential impacts on groundwater quality from septic systems: A review and examples from principal aquifers in the United States. Journal of Hydrology, : p
Isotope ratios can be useful in discriminating between multiple potential sources of pollution because the sources often have distinct ratios and because while concentrations change with total discharge, ratios remain similar. In this set of four graphs, the ratio of chloride to bromide is graphed by chloride. For comparison, dilution curves for halite and seawater (Katz, 2011) are included.
Figure 2: Sample sites in the lower Allegheny River system sampled by Duquesne University for 3RQ. Yellow pinned locations were sampled in 2013, green locations 2013-present, and blue sites 2014-present.
Acknowledgements
Funding: Colcom Foundation
Sampling Assistance: Maria Nagle, Lauren Drumm, Emily Mashuda, Lisa Barreiro, Emily Valentine, Oliver Dugas, Maria Wheeler-Dubas, Rob Dubas
3RQ Partners: Melissa O’Neal, Ben Stout, Bruce Dickson