Bromide in the Allegheny River System

Tao Wen, Pennsylvania State University-Main Campus
Author Profile

Introduction

Before April 2011, it was acceptable to discharge Marcellus brines into rivers. Therefore, brines were discharged to some PA rivers through publicly operated treatment works (POTW) and industrial waste plants (IWP). However, many larger rivers in PA are used for drinking water after treatment with chlorinated compounds. Brines from shale gas wells contain dissolved bromide at concentrations up to 2,000,000 ppb and bromide can react with the chlorinated disinfectants and with other natural compounds in the river to make brominated disinfection byproducts (BDB) which can be carcinogenic.
In 2010, the Pittsburgh Water and Sewer Authority observed an increase in concentration of bromide-containing species in their water from the Allegheny River after they treated it for drinking . We will explore the bromide in the Allegheny River and where it comes from (Figure 1) using data published in the Shale Network public database of water quality. We use HydroClient to find these data: HydroClient was built by the Consortium of Universities for the Advancement of Hydrologic Science, Inc. (CUAHSI), a non-profit funded by the National Science Foundation, as a tool to find water quality data from entities like Shale Network, along with bigger groups such as the US Geological Survey and NASA.

Conceptual Outcomes

Students will be asked to think critically, analyze data, and synthesize information
Student will learn how disposed brine impacts surface water quality in Pennsylvania

Practical Outcomes

Students will learn how to use HydroClient

Time Required

45 minutes

Computing/Data Inputs

Bromide Data from the Shale Network discovered using HydroClient

Computing/Data Outputs

None

Hardware/Software Required

Internet Browser

Instructions

The first thing we will do is get a file from HydroShare and upload it into HydroClient. This will allow us to see some of the sites in the Allegheny River system where waste is discharged, to track down bromide sources in the river.

Getting a File from HydroShare

· Open up Internet Explorer. To do this, type in "Internet Explorer" into the bar at the bottom left of the screen and click on it. It should open up after clicking.

· Type HydroShare.org into the browser and click on it – it should open up.

· Click Discover (located at the top of the page -- you don't have to sign in).

· Type Industrial Plants PA in the search box and click on the title Industrial Plants PA. You should see a page that contains an Abstract, Subject, and information on how to cite the data.

· Scroll down the page to the Content section.

· Click on the little file icon and click Download All Content as Zipped Bagit Archive.

· Wait a moment. An orange message should appear at the bottom of your screen asking if you want to open or save the folder. Click "Open". A zip file folder should appear (depending on your browser). Click to "Open" the folder (do NOT click save), click on "Data", click on "Contents". You should then see the file "industrial plants".

· Right click on the "industrial_plants" file and select "Copy". Now, minimize all the windows until you can see your desktop: click on your desktop screen and paste the file on your desktop.

Opening HydroClient

· Find the browser again and open up HydroClient by typing and clicking http://data.cuahsi.org/.

· Once it is open, click Layer Control.

· In the popup, Click Add GeoJSON.

· Click on Browse, and click on Desktop (right-side panel of the pop-up window) and navigate to the file you saved in the previous step by going to your Desktop. If you do not see the file, use the Search Desktop search box in the top right of the pop up and type "industrial_plants", click on the drop-down option, and click Open. The markers should appear on the map as shown at right.

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The red balloons identify possible waste sources into the Allegheny River system.The zoom buttons, located in the top left corner under the search box, allow you to adjust the map extent. The "+" sign allows you to zoom in and the "-" allows you to zoom out of the map. (Alternately, you can use the roller on the mouse to scroll in or out.) Increase the magnification and navigate to Pennsylvania and the Allegheny system. You can click on each red marker and a pop up will appear with information: IWP -- Industrial Waste Plant, PP -- Power Plant, SP -- Steel plant, and POTW -- Publicly Operated Treatment Works.

We will now navigate around the Allegheny River system and try to find bromide concentrations upriver and downriver from the different possible pollution sources. Use the instructions below to get concentrations. We suggest you use the schematic Allegheny River in Figure 1 (below) to help navigate, and write down the bromide concentrations for the sites you explore.If at any point you refresh your browser, you will need to add the layer of industrial waste plants back on to HydroClient.

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Figure 1. SCHEMATIC ALLEGHENY RIVER SYSTEM MAP showing how the river flows north to south (vertical blue line), with many smaller tributaries (horizontal and diagonal blue lines). Also shown with big blue dots are some of the publicly operated treatment works (POTW), power plants (PP), and industrial waste plants (IWP). Some POTWs were allowed to treat and discharge Marcellus brines into the river before April 2011. IWPs and PPs also can discharge water + waste into the river. Steel plants (SPs) also use and discharge water with some contamination into the river and acid mine drainage (AMD) inputs also impact the river. (Neither SPs nor AMD are shown.) No known waste treatment plants are located above POTW-A. The map is not to scale: Freeport lies many river miles above the Pittsburgh Water and Sewer Authority intake: along this reach of the river that is not shown, one SP, two PPs and 1 POTW are located. Sampling spots on the river are shown as black dots: data and locations were taken from States et al. (2013). The following plants were known to process and discharge Marcellus waste waters before the May 2011 ban: POTW-A, -B, -C. The following sites also treated such wastes before the ban and are thought to still treat such wastes from conventional oil and gas wells: IWP-A, -B, -C.


Site 1: Intake Waters at Pittsburgh Water Treatment Plant at the PWSA

The first stop will be the intake site for water from the Allegheny River for the Pittsburgh Water and Sewer Authority (at the bottom of Figure 1). As you move through the sites, we suggest that you write down on Figure 1 the maximum and minimum bromide concentrations for each site. For example, the value in the Clarion river at the Route 58 Bridge is already on Figure 1.

The Pittsburgh Water Treatment Plant for the Pittsburgh Water and Sewer Authority provides water and sewer service to more than 300,000 consumers throughout Pittsburgh. [1]

Procedure:

· Use the Enter a location search box at the top left of the screen to zoom to a geographic area. Start typing "Pittsburgh Water Treatment Plant, Freeport Road, Pittsburgh, PA, United States" ...and the dropdown list will popup. Use cursor to click the option on the dropdown list.

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The map will zoom to the plant: the area of the map is shown at the bottom center with a green "thumbs up" notifying you the area is small enough to search for data. In this case, however, it will be helpful if the search encompasses a larger map area.

· Click on the zoom in (+ sign) or zoom out (negative sign) until you can view Sycamore Island and you have a green thumbs up. Sycamore is an island in the middle of the Allegheny River and is circled at right. Your map should look similar to the screenshot at right but each monitor may look slightly different.

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Now you will define your search criteria in the right-side tool bar to find all the bromide data from January, 1900 to today in the area that your map is currently showing.

· Begin by clicking on the blue Select Date Range button and typing in "1/1/1900" to "5/18/2017" in the From and To boxes... then click Save.

· Click Select Keyword(s),to search only for Bromide.

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o There are a lot of species in the database so you must find bromide. You'll see the Common and Full List: click Full Listand use the Filter to type "bromide" into the window as shown at right.

o Click on the little plus sign next to Chemical as circled at right. Next, click on the plus sign next to Inorganic.

o Continue to click on the little plus sign under Inorganic>Major>Major, non-metals>Bromide. Make sure to click on the square next to Bromide so that a green check mark appears to show it is selected. To move forward, click Save.

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· Next, use the Select Data Service(s)button. All the sources of data are shown, including Shale Network, EPA, and US Geological Survey. Use the Search box as shown at right to type "Shale Network." Shale Network is a team of scientists based in Pennsylvania, led by Penn State, that has been publishing water quality data online in the area of shale gas development. Click on the row to highlight the Shale Network data service as shown below. (Don't click on Shale Network tab).

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· Click Close.

· Click Search Map to begin the search. After a few seconds one or more blue markers will pop up on the map as shown at right. If you hover over a blue marker, it has a number that indicates how many data series are available in the database for that location. If you zoom in, the blue markers show more precise locations, while if you zoom out the locations will be more generalized.

· To view only the data series that are located upstream of the Pittsburgh Water Treatment Plant on this map, click on the blue data marker circled at right and you will get a table describing the data at that location.

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· Highlight the row of data by clicking anywhere on row as shown below.

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· Now that you have highlighted the row, we will preview a plot of the data with the Data Series Viewer. To View the data: click Select Action, Save selection to workspace,and click on theWorkspace button in the top right corner of the table. In the Workspace, highlight the data by clicking on the row, click Select Tool,select Data Series Viewer,and click Launch Tool. The Data Series Viewer will open in a new window and will allow you to preview a plot of bromide concentration in the river (left axis) versus time (bottom axis). These data were reported by States et al. (2013).

Questions:

· Look at the data in the graph or the table for the Allegheny River water intake to the PWSA. Estimate the highest and lowest values. The bromide concentrations are given in the DataValues column (column E) or you can read from the graph. (Write answer here or on Figure 1).

· Notice that the bromide concentrations are high in the summer when it doesn't rain much and low in the fall and spring when concentrations are diluted by lots of rain.

We are now going to estimate bromide concentrations for other sites on the Allegheny River moving from north to south to fill out these concentrations on Figure 1. You can either follow all the instructions below, or you can navigate around the river on your own, looking for bromide concentrations, using all the steps just discussed, to fill out on Figure 1 and then go to "Questions to Think About".

Site 2: The Most Northern Spot: Warren County, Allegheny River

We will now go to the most northern sampling spot on the river (top of Figure 1). Close the Data Series Viewer by finding the tiny x and clicking on it (don't click the x for the entire browser!). In the Workspace, click the blue button labelled Search in the upper right to return to the map. DO NOT CLICK REFRESH. If you click refresh by accident, you probably will want to add the layer of industrial plants back on.

Procedure:

· We will go to Warren, PA well above all the industrial inputs to the river (see Figure 1). Enter a location: type " Paws Along the River Human Society, Warren PA, United States"(This is just a landmark, we are not investigating the Humane Society.)

· Keep search criteria the same as Site 1 (Date Range:01/01/1900 to 5/18/2017, Keyword: Bromide, Data Service: Shale Network.) Click Search Map. Click on the blue data marker located in the stream to view the search results with the Site Name: Warren. Put your data in the Workspace and then look at it in the Data Series Viewer. Note that you will want to click on the PWSA data row to un-highlight it if it is still in your workspace. Otherwise, both datasets will be plotted in Data Viewer.

Question

· Write down the range of values at Warren here and on Figure 1. How do the bromide concentrations at Warren compare to concentrations at the PWSA? What might this tell us?

Site 3: Moving South: Tionesta County, Allegheny River

We will now move to Tionesta (see Figure 1). Follow the previous directions on how to search for and preview data in the Data Series Viewer. Keep all search parameters, including the Date Range, Keyword, and Data Service the same.

· Location:Station Rd, Tionesta, PA, United States

Question

· What are the concentrations of bromide at Tionesta and how do they compare to Warren? What does this tell us about natural bromide concentrations in the Allegheny River? Note that most natural stream samples in PA without human impacts are 10 ppb or lower but most analytical labs have a detection limit of 20 to 60 ppb bromide. The EPA recommendation for bromide is 60 ppb.

Site 4: Kennerdell, Venago County, Allegheny River

Location: Kennerdell, PA, United States

· Click Search Mapand then Show Search Results.

Click on the blue data marker shown at right and preview in the Data Series Viewer.

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Write the range of values here and on Figure 1.

Site 5: Franklin, Venago County, Allegheny River

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Location: Franklin, PA, United States

· Click Search Mapand then Show Search Results.

· Click on the blue data marker shown at right and preview in the Data Series Viewer.

Questions:

· What do you think explains the bromide concentrations between Warren and Kennerdell?

Site 6: Crooked Creek near Stitt Hill Bridge, Armstrong County

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Now we will proceed downstream to Crooked Creek before it flows into the Allegheny River.

· Location: Lumac Inc, Pennsylvania 66, Ford City, PA, United States

· Click on the blue data marker circled at right and preview in the Data Series Viewer.

Questions:

· Look at the range of values at the Stitt Hill bridge on Crooked Creek and write values here and on Figure 1. What might explain the values you found in Crooked Creek? Note that IWP-B treated and released Marcellus brines before 2011: before dilution these waters can have bromide concentrations up to 2,000,000 ppb bromide.

Site 7: Kiski River Bridge, Leechburg

Now let's look downstream where the Kiskiminetas ("Kiski") River enters the Allegheny (see Figure 1).

· Location: Kiski Camp Drive, Leechburg, PA, United States

· Zoom out until map is similar to the one at right.Search Map.

· The most northern blue dot is Schenley (LDB) and the most southern is Kiski Railroad Bridge. Click Show Search Results to view both sites.

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· Highlight both rows of data and navigate to the Data Series Viewer for each site and add concentrations to Figure 1.

Questions:

· Look at the HydroClient map or at Figure 1 and investigate the surrounding area on the Kiski River. What might explain the values you found at Kiski Railroad Bridge?

· If you are interested, you might look at Figure 1 and use HydroClient to determine whether the bromide concentrations in the Kiski river above and below the POTW between Apollo and Leechburg bridges are different. This POTW accepted brines from Marcellus shale gas wells and discharged them to the river before 2011. Can you see an increase in bromide below the POTW? What about above and below the IWP on the same river? What does this mean about the source of bromide? If you have time, you might look above and below POTW-B on the Conemaugh river by comparing bromide concentrations at the Route 56 Bridge (Rte 56, Johnstown) and at the Johnstown railroad bridge (Daisytown, Pennsylvania). This POTW (municipal sewage treatment plant) received Marcellus wastewaters before April 2011. (Note that the POTW does not show up on the map as a red balloon.) Bromide is also used in coal to suppress mercury emissions. Do you see any evidence for high bromide downstream from PP-A or PP-B?

· You can also explore the IWP on Blacklick Creek, which flows into the Conemaugh river, which flows into the Kiski, which flows into the Allegheny River (see Figure 1).

Questions to Think About

· After investigating the sites and placing values on Figure 1: where does the bromide come from at the PWSA and how does it compare to background values (and what does background mean)?

· Which river do you think is responsible for most of the bromide? This cannot be determined simply by concentration because the concentration could be high but the flow rate (i.e. discharge) of the river could be low. Here is the relative discharge of the rivers: Kiski river (1505 to 7539 m3/minute) > Clarion River (668 to 3724 m3/minute) >> Crooked Creek. The "bromide load" of a river is the concentration multiplied by the discharge. Which river do you think might have the largest load (i.e. concentration multiplied by discharge) and be most responsible for the bromide at PWSA? What is upstream on that river?

· One conclusion from this study is that discharge of bromide-containing brine to the Allegheny is not a good idea. But what else should we be thinking about?




[1] Annual Drinking Water Quality Report 2015, http://apps.pittsburghpa.gov/pwsa/2015CCR.pdf

Additional Activities and Variants

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