Shirley E. Clark, Ph.D., P.E., D. WRE Penn State Harrisburg. Robert Pitt, Ph.D., P.E., BCEE, D. WRE University of Alabama

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1 Shirley E. Clark, Ph.D., P.E., D. WRE Penn State Harrisburg Robert Pitt, Ph.D., P.E., BCEE, D. WRE University of Alabama

2 Site Stormwater Characteristics and Permit Limits Analytes on Permit 90 th percentile Permit Limit Exp. Exceedence (% > historical conc. limit if untreated) Oil and grease (mg/l) Chloride (mg/l) Sulfate (mg/l) <<0.01 Ammonia (mg/l as N) NA 10.1 SMALL NO 2 +NO 3 (mg/l as N) Total Zinc (µg/l) Total Copper (µg/l) Total Mercury (µg/l) Total Lead (µg/l) Total Thallium (µg/l) ND 2 UNK TCDD (µg/l) 5x x Perchlorate (µg/l)

3 Pollutants Used to Guide Media Selection Potential for Exceedence in 40% of Storms Dioxin (TCDD) Total Lead Potential for Exceedence in 15% of Storms Total Mercury Potential for Exceedence in 10% of Storms Total Copper Total Zinc NO2+NO3 Potential for Exceedence in 5% of Storms Oil and Grease

4 Influent Water Chemistry: Our Historical Classifications Solids Wide range of sizes from colloidal to sands/gravels Pollutants (fraction of total load) that are associated with, or attached, to solids Metals, Phosphorus, Organics, Bacteria Pollutants that are dissolved or unbound to solids Remainder of total load metals, phosphorus, organics, bacteria Nitrates, Nitrites, Ammonia, Chloride, etc.

5 Pollutant Size Associations Percent Pollutant Reductions after Removing all Particulates Greater than Size Shown 20 m 5 m 1 m 0.45 m Suspended Solids Turbidity Total-P Nitrate Cadmium Copper Lead Zinc Reference: Morquecho 2005

6 Anticipated Physical Filtration Performance (assume sediment forebay) Need (bio)chemically active media to remove some pollutants

7 Can permit limits be reached? Tailor media to improve pollutant removal and reduce permit violations. Dissolved Zinc Source: International BMP Database

8 Types of Media Sand relatively inert (without modification) Common modifications are iron oxide and manganese oxide coatings. Ion exchangers/zeolites molecular sieves Exchanges out ions with stronger attractive forces and correct size Activated carbon Hydrogen bonding and van der Waals forces through dipole interactions Organic Non Activated Media (soil, peat, compost, biosolids) Function of base material Organic fraction contains plant nutrients (N,P, S); increases soil water holding and cation exchange capacities; and enhances soil aggregation and structure. Most chemically active: colloidal clays & organic matter. Soil ph affects nutrient transformations and solubility (nutrients & metals).

9 Treating Cations and Anions (NH 4+, NO 3, PO 4 3, Cl, Metals) Nitrogen removal: Ammonia (NH3) uncharged Ammonium (NH4 + ) positively charged (+1) Ammonia pka = 9.3; at runoff ph, ammonia typically charged ion if an ion and not complexed with metals. Charged positive ion removed by ion exchange resin, although not bound as tightly as ions with higher valence charge (+2 or greater). Ammonia/ammonium: small molecule and can be removed by ionexchange resins acting as molecular sieves Nitrate (NO3 ) negatively charged ( 1) Need media with higher anion exchange capacity or uptake with vegetation Because of small valence charge, not strongly held and can leach out from organic media

10 Treating Cations and Anions (NH 4+, NO 3, PO 4 3, Na +, K +, Cl, Metals) Phosphorus Removal: If in root zone, plant uptake possible Higher valence charge than nitrogen anion; more likely to be attracted to cations on surface of media Reacts and forms stable compounds with iron and aluminum oxides. Can form precipitates with some metals. (measure using Ksp). Chloride Removal: Similar problems for removal as nitrate, but limited uptake by plants. For non salt tolerant plants, can cause plant stress.

11 General Rule of Thumb: For nutrients, if soil is Low, it is more likely to remove nutrients from runoff. If soil is High, leaching more likely.

12 Treating Cations and Anions (NH 4+, NO 3, PO 4 3, Na +, K +, Cl, Metals) +1 Valence Cations: Sodium and potassium difficult to remove because comparatively weakly charged. Easily leached from soils if stronger cation enters soil. If limited competition by +2 cations, ion exchange resins/zeolites could provide treatment. Sodium at high concentrations (relative to calcium and magnesium) destabilizes clay sized particles (measured by SAR, the sodium adsorption ratio), reducing infiltration rate. Metals: Challenge because of complexation with other components in runoff. Removal based on valence state and size of molecule.

13 METALS TREATABILITY Particulate forms Filterable forms Inorganic distribution No DOM assumed (0rganic complexation greatly changes distribution) What form are those compounds that pass through a 0.45 µm filter? p = Zinc % Ionic % Bound Zinc Copper Cadmium Lead 12 88

14 Treatability of Organics (example: Pesticides, PAHs) High Log Kow compounds (preferentially partition to organic phase) typically better removed by organic based media(gac, peat moss, compost). High solubility (Log S) compounds have variable removal by media; likely tied to whether they are negatively or positively charged in solution. Limited removal in ionexchange resins such as zeolite because of molecular size. These molecules are removed in organic based media because of variety of removal sites. Plus media that support microbial growth (organic content) encourage degradation.

15 Dioxin Control Observations Kow = Ks = ranges from 0.1 mg/l for monochloro isomers to 10 9 mg/l for octochloro isomers. 2.8 X 10-8 µg/l permit limit These samples less than the detection limit

16 Log Kow = 2.1; pka = ; Log S ~ 2 Some organic media removal, plus weak ionic potential Clark and Pitt (1999). Stormwater Runoff Treatment: Evaluation of Filtration Media. EPA 600/R 00/010. U.S. Environmental Protection Agency. 405 pages.

17 Kow = Ks = 2 x 10 5

18 High vs. Low Influent Concentrations Best removals seen in deeper columns. Percent removals improved by high influent concentrations. (however, unable to meet permit limits of 0.13 µg/l). Mixed media results showed removal potentially possible at low concentrations but cannot confirm since all samples below detection limit. Mercury removal problematic at high flows (low contact time) and high influent concentrations for all media

19 Analytes on Permit NO2+NO3 Total Zinc and Total Copper Total Lead TCDD Total Mercury Oil and grease Treatment Technology Options Ion exchange or plant uptake (potential denitrification? Other problems with denitrification) Chemically active filtration (organic media sorption/ion exchange) after pre settling Physical filtration of larger particulate associated lead after pre settling. Chemically active filtration (organic media sorption and potential ion exchange) Chemically active filtration with strong organic sorption (GAC) after pre settling. Other organics potential elevated parent material contamination. Chemically active filtration with sorption for MeHg & ion exchange for inorganic mercury and complexes. Chemically active filtration with strong organic sorption component (GAC) after capture of freefloating material if concentrations are high and visible. Peat and compost also possible.

20 Selecting the Media Mixture from a Set of Potential Components: Dissolved Copper Example Model prediction: 25% +2 valence, 10% +1 valence, 65% 0 valence charge. Sand with modification: prefers ion exchange (+2 charge) Zeolite (SMZ) ion exchange resin (+2 charge) GAC and peat moss have multiple types of exchange/adsorption sites good for all valence charges; GAC performing better for filtered copper but EXPENSIVE

21 Selecting the Media Mixture from a Set of Potential Components: Dissolved Copper Example Modified sand and zeolite mixture best removal 50%, but generally poor removal. GAC and peat moss were better than sand and zeolite; GAC performing better for filtered copper, but may not support plant life Adding small amount of peat moss as organic matter for plant life support only slightly reduced performance.

22 Other Design Considerations Clogging Kinetics of pollutant removal Media Capacity Nutrient Releases from Organic Component of Media due to Changes in Porewater Chemistry Nutrient and Water Uptake by Biomass Maintenance Intervals

23 Conclusions and Questions Conclusion: Media can be tailored to address specific pollutant problems. Conclusion: Removal function of both water and media chemistry Knowledge rich and data poor on water quality chemistry and speciation. Media specs beginning to address fundamental media characteristics. Limited understanding of bacterial effect on pollutant removal. Question: How to improve media specs to reduce variability in treated water concentrations? Question: Improve/develop models for predicting media effectiveness and lifespan for filtered metals removal? Question: And many more.