Power Plant Bromide Discharges and Downstream Drinking Water

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Power plant bromide discharges and downstream drinking water systems in Pennsylvania Kelly D Good, and Jeanne M. Vanbriesen Environ. Sci. Technol., Just Accepted Manuscript • DOI: 10.1021/acs.est.7b03003 • Publication Date (Web): 25 Sep 2017 Downloaded from http://pubs.acs.org on September 29, 2017

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Environmental Science & Technology

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Power plant bromide discharges and downstream drinking

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water systems in Pennsylvania

6 Kelly D. Gooda, Jeanne M. VanBriesenb*

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a

Graduate Research Assistant, Department of Civil and Environmental Engineering, Carnegie

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Mellon University, 5000 Forbes Ave., Pittsburgh, PA 15213, USA. Email: [email protected]

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b

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Systems (Water-QUEST), Department of Civil and Environmental Engineering and Department

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of Engineering and Public Policy, Carnegie Mellon University, 5000 Forbes Avenue, Pittsburgh,

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PA 15213, USA. Email: [email protected]

Duquesne Light Company Professor, Director of Water Quality in Urban Environmental

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ACS Paragon Plus Environment


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ABSTRACT

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Coal-fired power plants equipped with wet flue gas desulfurization (FGD) systems have been

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implicated in increasing bromide levels and subsequent increases in disinfection by-products at

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downstream drinking water plants. Bromide was not included as a regulated constituent in the

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recent steam electric effluent limitations guidelines and standards (ELGs) since the U.S. EPA

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analysis suggested few drinking water facilities would be affected by bromide discharges from

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power plants. The present analysis uses a watershed approach to identify Pennsylvania drinking

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water intakes downstream of wet FGD discharges and to assess the potential for bromide

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discharge effects. Twenty-two (22) public drinking water systems serving 2.5 million people

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were identified as being downstream of at least one wet FGD discharge. During mean August

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conditions (generally low-flow, minimal dilution) in receiving rivers, the median predicted

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bromide concentrations contributed by wet FGD at Pennsylvania intake locations ranged from

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5.2 to 62 µg/L for the Base scenario (including only natural bromide in coal) and 16 to 190 µg/L

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for the Bromide Addition scenario (natural plus added bromide for mercury control); ranges

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depend on bromide loads and receiving stream dilution capacity.

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KEYWORDS: source water, disinfection by-products, bromide, mercury control, coalfired power plants

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TOC/ABSTRACT ART:

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INTRODUCTION

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Bromide in surface waters is of concern due to its interaction with applied disinfectants in

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drinking water treatment systems. Elevated bromide concentrations increase the rate and extent

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of formation of disinfection by-products (DBPs)1–4 and shift speciation towards brominated

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DBPs, which are more toxic.5–7 Thus, drinking water sources containing bromide may lead to

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formation of DBPs in treated drinking water that present higher health risks to consumers.8,9

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In surface water sources, background bromide levels may be affected by nonpoint runoff sources

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such as road salt or brine10–12 or by soil releases.13,14 Historically, elevated bromide in drinking

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water sources was associated with coastal groundwater and estuary sources, which are subject to

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saltwater intrusion.15–19 Recently, rising bromide concentrations have also been associated with

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anthropogenic point sources (e.g., flame retardants for plastics or textiles,20 municipal waste

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incineration21), as well as water resource changes associated with altered climate, including sea

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level rise increasing bromide in estuaries and near shore groundwater16,22,23 and drought affecting

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dilution capacity of surface waters that receive bromide loads.24,25

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Of particular note, point source discharges associated with energy extraction and utilization

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activities have been implicated in increased surface water concentrations of bromide in the

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United States (U.S.) since oil and gas (O&G) wastewater,26,27 coal mine discharges,28–30 coal

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combustion residue (CCR) effluent,31 and coal-fired power plant wet flue gas desulfurization

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(FGD) wastewater32–35 are elevated in bromide. The rapid expansion of unconventional gas

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drilling and subsequent increase in produced water discharges in Pennsylvania (PA) led to

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elevated bromide levels that were well-documented,26,33,36–38 prompting the PA Department of

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Environmental Protection (PADEP) in 2011 to request that drillers voluntarily stop using surface

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discharging plants for unconventional produced water disposal.39

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These recent bromide management challenges from O&G wastewater highlight the importance

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of understanding bromide sources and options for managing discharges; however, due to limited

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surface water monitoring of bromide, few studies have evaluated anthropogenic bromide source

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contributions at the regional scale.21 Several recent studies have looked specifically at the

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Allegheny River Basin in Pennsylvania,26,33,40 where O&G produced water and wastewater

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associated with coal-fired power plant discharges have been implicated in elevated bromide

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concentrations at downstream drinking water plants.

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Bromine is naturally present in coal in trace amounts,41,42 and bromide addition to coal has been

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proposed to enable compliance with the Mercury and Air Toxics Standards (MATS).43–46 During

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coal combustion, bromine is primarily converted to volatile hydrogen bromide (HBr) and

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subsequently to bromine gas (Br2) upon cooling, with minimal transfer to residue streams such as

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fly ash and bottom ash (typically >90% remains in the vapor or gas phase).47–51 Halogen species

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such as bromine, which would otherwise be released into the atmosphere out of the stack,50 are

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reduced to soluble ionic forms and are commonly observed in flue gas desulfurization (FGD)

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wastewater.52,53 Additional details on bromide at power plants are provided in SI Section A.

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Discharges of bromide have historically been unregulated34,54 since bromide is not expected to

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harm humans or ecosystems at concentrations typically observed in surface waters.13,55 However,

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due to its effect on drinking water DBPs, the U.S. Environmental Protection Agency (EPA) has

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recently increased its attention to bromide by including it in the Safe Drinking Water Act

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(SDWA) fourth Unregulated Contaminant Monitoring Rule (UCMR 4)56 and by discussing the

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potential for FGD discharges to affect drinking water quality in the Steam Electric Power

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Effluent Limitations Guidelines and Standards (ELGs) final rule57 and supporting

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documentation.58 As part of its analysis for the ELGs, the EPA evaluated the proximity of steam

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electric power plant discharges to public drinking water resources, including intakes, wells, and

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sole-source aquifers using an 8 km (5 mi) geographic buffer,58 and concluded that “only a

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fraction of steam electric power plants have downstream drinking water intakes.”59

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The ELGs focused predominately on controlling discharges of toxic metals and nitrogen and did

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not set numeric limits for bromide.57 Instead, the EPA included recommendations for permitting

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authorities to consider regulation of bromide discharges on a permit-by-permit basis, depending

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on how the discharges affect downstream drinking water plants.57 The ELGs also recommended

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that permitting authorities require monitoring and reporting of bromide, which is currently not

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required and which would enable improved quantification of wet FGD bromide contributions.

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Our recent work, focused on the Allegheny River Basin in PA, demonstrated that multiple power

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plants operating wet FGD currently contribute approximately one third of the total bromide

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concentration at a drinking water treatment plant located a significant distance downstream

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(12.8-142 km).40 This suggests that the use of a geographic buffer for evaluating the effects of

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wet FGD discharges on surface water sources is not appropriate and that power plant

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contributions are relevant even in the context of other sources (oil and gas produced water

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accounted for approximately half of the total concentration predicted). The present work uses a

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watershed approach to identify drinking water intakes that have wet FGD discharges upstream

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(regardless of the distance). Then bromide load and concentration contributions from wet FGD at

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each intake are evaluated. The analysis includes consideration of the population served by public

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drinking water that is potentially affected by wet FGD discharges. It further demonstrates how

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concentration-based goals for bromide at drinking water intakes could be used to evaluate the

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effect of bromide discharges from power plants on drinking water treatment plants.

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METHODS

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Bromide is nonreactive under typical environmental conditions, and thus the magnitude of the

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discharge and the dilution capacity of the surface water at the intake – not geographic proximity

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– govern the concentration at the intake. The purpose of this work was to identify any intakes

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potentially affected by at least one wet FGD discharge and to estimate the bromide concentration

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contribution from upstream wet FGD discharge(s) at each intake location.

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The analysis used a watershed approach to identify Pennsylvania drinking water intakes (for

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systems primarily using rivers and serving greater than 10,000 people) that were downstream of

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a wet FGD discharge, regardless of whether the discharge was located in Pennsylvania. The

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analysis was limited to large systems as defined by SDWA,60 following Rice and Westerhoff

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(2015),61 and captures 60% of the total PA population and 70% of the PA population served by

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community water systems.

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To do this, the following data were mapped in ArcGIS: watersheds intersecting PA, rivers

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within the watersheds, wet FGD discharge locations, and PA drinking water intakes. Then,

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drinking water intakes downstream of wet FGD discharges were identified by visual inspection 7 of 31



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(Figure 1), and loads and concentrations were modeled following the methods described in Good

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and VanBriesen (2016).40 A schematic summarizing the watershed analysis and modeling

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approach used here is provided in Figure S1.

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Data sources

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The watershed-level analysis required the following geospatial data: watersheds intersecting PA,

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rivers within the watersheds, coal electricity generating units (EGUs) associated with wet FGD,

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and PA river segments providing source water to community water systems serving greater than

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10,000 people. For estimation of bromide loading, coal-fired power plant EGU data (i.e., coal

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consumption) and characteristics (i.e., the presence of wet FGD) were required. Streamflow data

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enabled estimation of wet FGD concentration contributions from the modeled bromide loads. In

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order to compare the identified drinking water utilities with those described in the proximity

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analysis results discussed in the ELGs, data were requested and received from EPA. This

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included the power plants identified as having at least one drinking water system within 5 miles

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of a discharge that would be regulated under the ELGs.62 These data sources and detailed

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methods are described in SI Section B.

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Modeling bromide load and concentration contributions from wet FGD at intakes

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Once the downstream intakes were identified, bromide loads from each upstream wet FGD plant

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were modeled for August and on an average annual basis for two scenarios: Base (natural Br in

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coal) and Br Addition (natural plus Br added for mercury control) following the method from

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Good and VanBriesen (2016).40 August was selected because it is a low-flow period in

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Pennsylvania40,63,64 and because it is a summer month when elevated temperatures typically

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require increased disinfectant dosing,65,66 leading to higher DBP concentrations during third

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quarter compliance sampling.9,67,68 A summary of load model input and data are provided in SI

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Section C; the method was described in detail previously.40

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This method does not use concentration-based discharge data from the NPDES permitted

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locations as power plants have not typically been required to monitor bromide in their effluent.

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Rather, these load estimates are based on wet FGD-associated coal consumption, a range of

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bromide content in coal, a range of percent capture of bromide in wet FGD wastewater, and a

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range of bromide addition dosage; uncertainty is incorporate using Monte Carlo simulations.

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Then, in-stream wet FGD bromide concentration contributions at each intake site were calculated

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using the estimated loads under mean August and mean annual flows (estimated from the

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National Hydrography Dataset [NHD],69 as described in SI Section B).

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To provide context for these wet FGD contributions, total in-stream bromide loads were

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calculated using monthly 2015-2016 bromide concentration data from the PADEP Water Quality

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Network (WQN)70 and corresponding streamflow data for each sample date from the U.S.

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Geological Survey (USGS).71 The WQN sites were selected based on proximity to the modeled

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intakes. These calculated in-stream total loads were compared to the wet FGD loads at the

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nearest intake site. Additional details are provided in SI Section D.

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RESULTS AND DISCUSSION

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Identification of potentially affected PA drinking water systems

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The present analysis identified 21 river locations (numbered sites in Figure 1) for 23 intakes

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providing source water for 22 drinking water systems in Pennsylvania that are downstream of at

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least one wet FGD discharge from 9 power plants in Pennsylvania and West Virginia (see Table

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S2 for more details). These 22 drinking water systems serve 2.5 million people, or 20% of the

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PA population. Figure S2 shows the service areas for all public water systems in Pennsylvania,

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and the service areas for the drinking water systems identified in this analysis are highlighted to

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show the geographic extent of potentially affected populations.

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Figure 1. Map of Pennsylvania drinking water intakes (for public water systems utilizing

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primarily surface water and serving more than 10,000 people) and coal-fired power plants

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operating wet FGD. 10 of 31


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EPA ELG national proximity analysis

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The EPA drinking water proximity analysis evaluated 222 discharge locations from 195 steam

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electric power plants in the U.S.58 From this analysis (described in more detail in SI Section B),

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the EPA identified 113 drinking water intakes or reservoirs as being potentially affected by

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discharges from 67 coal-fired power plants.62 These 113 intakes or reservoirs were associated

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with 92 public drinking water systems, and 14 (15%) of the 92 systems were located in

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Pennsylvania. The map in Figure S3 uses color gradation to show the distribution of these 92

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buffer-identified drinking water systems in each state, where darker shading indicates a higher

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number of systems. Coal EGUs with wet scrubbers are also shown on this map for reference.

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Four of the 14 EPA-identified drinking water plants in Pennsylvania are within 5 miles of power

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plants that do not use wet FGD (stars inside the circles with dashed outlines in Figure S3). These

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plants would discharge bromide only if they added it as a biocide in the cooling towers and are

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outside the scope of the present analysis. The remaining 10 Pennsylvania drinking water systems

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identified by EPA were within EPA’s geographic buffer around a wet FGD power plant

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discharge and were compared to the present watershed analysis. The population served by these

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drinking water systems was not discussed in the ELGs or its supporting documentation; however,

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using the latest available SDWIS data (2016 Quarter 4),72 the population served by these 10

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drinking water systems was determined to be 150,000. Additional details on the EPA ELG

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proximity analysis and comparison to the current watershed analysis are provided in SI Section

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B.

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Wet FGD bromide loads

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Wet FGD bromide loading depends on coal consumption, which can vary by month. Results are

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shown at the watershed level in Figure 2 (and Table S10), with additional tables and figures

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provided in SI Section D. Wet FGD bromide loads are higher in the Allegheny and Monongahela

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Basins in western PA (August Base median of 610 kg/day and 590 kg/day, respectively)

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compared with the Susquehanna Basin in eastern PA (August Base median of 310 kg/day). This

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is because there are more power plants in the western basins and because they had higher coal

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consumption in the modeled period (2015-2016). The Allegheny and Monongahela Rivers meet

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in Pittsburgh, PA to form the Ohio River, which therefore receives wet FGD bromide loads from

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those river basins (August Base median of 1200 kg/day). These loads could affect additional

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drinking water plants on the Ohio River outside of Pennsylvania (not considered in this analysis).

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Dilution of the Allegheny and Monongahela bromide loads as well as additional bromide loads

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from coal-fired power plants in the Ohio Basin would affect bromide concentrations at Ohio

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River drinking water plants.

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Figure 2. Boxplot of watershed-level August and average annual total predicted bromide

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loads from wet FGD discharges for Base and Br Addition Scenarios. Boxes extend from the

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first to third quartile with a line at the median; whiskers extend 1.5 times the interquartile

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range. Summary statistics and power plants contributing to each watershed are provided

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in Table S10.

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Using 2015-2016 observed bromide and flow data for the rivers, the wet FGD discharges were

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estimated to contribute 31% (Allegheny), 30% (Monongahela), 38% (Ohio), and 14%

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(Susquehanna) of total in-stream bromide under Base conditions (see SI Section D for more

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details). Wet FGD bromide loads estimated for the power plants in the present analysis are lower

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than if estimated using the approach provided by McTigue et al. (2013),34 which utilized power

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plant capacity, and thus, represented a theoretical maximum bromide load, rather than an

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anticipated load. The present work considers reported coal consumption, variable bromide

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addition rates, and observed bromide capture rates for FGD. A power plant-by-power plant

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comparison of the two methods is provided in Table S12.

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Wet FGD bromide concentration contributions at drinking water intakes

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The effect of bromide loads on in-stream concentrations depends on the magnitude of the load

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and the dilution capacity of the receiving stream at the downstream location of interest (i.e., for

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this analysis intake sites labeled 1 through 21 in Figure 1). The contributed concentrations from

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wet FGD discharges presented here cannot be directly compared with observed bromide

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concentrations as in-stream concentrations include multiple sources. However, for context,

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information collection rule (ICR) bromide concentrations at large Pennsylvania surface water

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intakes (in 1996-1997) ranged from below detection (

Power Plant Bromide Discharges and Downstream Drinking Water

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