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Removal of Soluble Phosphorus from Surface Water using Iron (Fe-Fe) and Aluminum (Al-Al) Electrodes Tanner Ryan Devlin, Alessandro di Biase, Victor Wei, Maria Elektorowicz, and Jan Oleszkiewicz Environ. Sci. Technol., Just Accepted Manuscript • DOI: 10.1021/acs.est.7b02353 • Publication Date (Web): 09 Nov 2017 Downloaded from http://pubs.acs.org on November 10, 2017

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GRAPHICAL ABSTRACT 224x123mm (150 x 150 DPI)

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Removal of Soluble Phosphorus from Surface Water using Iron (Fe-Fe) and

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Aluminum (Al-Al) Electrodes

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T.R. Devlin1, *, A. di Biase1, V. Wei1, M. Elektorowicz2, J.A. Oleszkiewicz1

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1

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R3T 5V6, Canada

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2

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Maisonneuve Blvd. W., Montreal, QB H3G 1M8, Canada

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* Corresponding author. E-mail address: [email protected]

Civil Engineering, University of Manitoba, 15 Gillson St. Room E1-368A, Winnipeg, MB

Building, Civil, & Environmental Engineering, Université Concordia, 1455 De

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Abstract

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Soluble phosphorus removal using iron and aluminum electrodes was studied on water

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samples from the Red River, a hyper-eutrophic stream in Winnipeg, Canada. Four trials

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were conducted: I) mixed batch with 150-900 mA applied for 1 min to 1 L; II) stagnant

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batch with 600-900 mA applied for 1 min to 1 L; and III, IV) continuously stirred-tank

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reactor with 6.25-10 min hydraulic retention times and constant 900 mA. Maximum

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soluble phosphorus removals of 70-80% were observed in mixed batch and there was

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no significant difference between aluminum and iron electrodes (i.e., P-value 0.0526 to

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0.9487). Aluminum electrodes performed significantly worse than iron electrodes under

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higher hydraulic loads, with iron removing >70% soluble phosphorus and aluminum

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70% of

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soluble phosphorus at an HRT of 10 min, would be the preferred choice of material

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when applied under natural, flowing conditions. In comparison, aluminum electrodes

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failed to achieve >40% removal at HRTs of 6.25-10 min.

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In general, flowing conditions with turbulence would be preferred over stagnant

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conditions, which had a significant negative impact on soluble phosphorus residual in

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batch. For this reason, ponds and lakes are not ideal locations to apply electrodes,

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while streams and rivers would provide more appropriate mixing conditions. In addition,

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higher phosphorus loads provided greater efficiency per ampere applied. A 350%

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increase in soluble phosphorus load (from 0.28 to 0.97 mg-P min–1) resulted in a 300%

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increase in specific removal rate (from 0.21 to 0.64 mg-P C–1) for iron electrodes when

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900 mA was applied (Fig. 5). Therefore, tributary streams with higher phosphorus load

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and concentration should be targeted to improve efficiency.

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Fig. 5. Specific sequestration rate as a function of soluble phosphorus load for iron

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electrodes at 900 mA applied current intensity.

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Scale-up and application to other watersheds would require bench-scale testing

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to determine site specific design parameters. For instance, water characteristics such

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as conductivity would likely influence process design and performance (Fig. 6). Bench-

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scale testing would help assess site specific SARs and SRRs for desired levels of

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phosphorus removal. Furthermore, electrode configuration and operational procedures 26 ACS Paragon Plus Environment

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must be developed to maximize process efficiency. It would be interesting to examine

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the ratio of power consumption to phosphorus removal as it related to operational

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changes such as electrode spacing, submerged electrode surface area, and electrode

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shape and number. The configuration must also be designed such that electrode

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material could be readily replaced, since the sacrificial anode will be constantly losing

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mass as it is solubilized to remove phosphorus.

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Fig. 6. Current density as a function of applied voltage for iron and aluminum

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electrodes, grouped into two sets of conductivity, shown with extrapolated trendlines for

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water conductivity (K).

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Typically, smaller electrode spacing would result in lower power requirements

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and therefore lower operational costs for electricity. However, smaller electrode

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spacings would also restrict the flow of water between the cathode and anode which 27 ACS Paragon Plus Environment

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could have both positive and negative impacts. On one hand, smaller cross-sectional

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areas between the electrodes would increase flow-though velocities and may therefore

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mitigate surface fouling of the electrodes. If significant fouling was observed, however,

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smaller electrode spacings may have a negative impact since the flow of water through

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the cross-sectional area may be completely restricted.

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address physicochemical fouling of the electrodes would be to operate with intermittent

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DC or transformed AC. The alternating role of anode-cathode in both cases would allow

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for scouring of accumulated material on the electrodes through hydrogen gas

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production (3). Biological fouling could be addressed by operating at current intensities

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that inhibit the growth of microorganisms within the microenvironment of the anode and

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cathode. 30

A foreseeable measure to

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The simplest mechanism of phosphorus removal by the electrochemical device

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would be by sedimentation and burial as precipitated/entrapped matter within iron or

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aluminum hydroxides. Larger, natural basins such as lakes that have sufficient retention

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time for settling of the chemical complexes would act as phosphorus sinks if the

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electrochemical device was applied in more turbulent locations such as rivers and

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streams. However, natural basins with highly active anaerobic sediment may not be

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suitable for the burial method of phosphorus compounds or may require additional

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treatment to increase oxidation reduction potential.10,11 There is potential to modify the

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electrochemical device to extract precipitated/entrapped phosphorus, although this

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method would need to be studied in more detail to determine capture rates and

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operational efficiency. Instead of operating the electrochemical device to remove

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accumulated physicochemical foulant and release it into the environment, the process

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may be optimized to collect the accumulated material and completely remove it from

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suspension. Thereby, the precipitated/entrapped phosphorus in the physicochemical

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foulant would be removed from the watershed. Further considerations for the

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development of this method include the mechanism of removal from the electrode,

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mechanism of material transfer to a drying/processing area, and ultimately end use of

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the “recovered” material. In the worst case the material would be landfilled, while in the

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best case it could be used as slow-release phosphorus fertilizer.

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A more detailed discussion on the electrical and material costs for operation

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based on experimental parameters determined from this study is provided in Supporting

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information S.1. In general, consumable costs, reported per million litres treated, to

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remove 70% soluble phosphorus from Red River water with soluble phosphorus of 0.35

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g m-3 would include 5 USD to 17.5 USD electricity costs and material costs of 5.3 USD

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to 12.2 USD for iron and 39.2 USD for aluminum. Further discussion is provided in

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Supporting information S.2 to S.4 on the impact of the electrochemical process on pH,

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conductivity, and sediment properties.

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Acknowledgements

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The authors are grateful to graduate students Damian Kruk, Mario Poveda, and

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Kamil Wisniewski, who assisted with collecting water samples from the Red River. The

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authors acknowledge the Natural Sciences and Engineering Research Council of

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Canada for the Undergraduate Student Research Award (USRA) and Canada Graduate

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Scholarship-Master’s (CGS-M) to the senior author.

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