PharmaceuticalsPharmaceuticalsA Mixed Bag: analyzing for PPCPs, waste A Mixed Bag: analyzing for PPCPs, waste

water treatment, and one ugly pharmacy water treatment, and one ugly pharmacy

Laurie TenaceLaurie Tenace

Florida DEPFlorida DEP

NAHMMA 2005NAHMMA 2005

Thanks to my good buddy Jazz for helping mefigure out my topicsfor this presentation

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Today’s topicsToday’s topics

• Analyzing for EPOCs or PhACs or Analyzing for EPOCs or PhACs or Micro constituents – different groups Micro constituents – different groups have different acronyms & focuses have different acronyms & focuses

• What happens at the waste water What happens at the waste water treatment plant?treatment plant?

• The legacy of a family-owned The legacy of a family-owned pharmacypharmacy

How much? How much? “Typical occurrence is <100ng/L (<0.1μg/L)”“Typical occurrence is <100ng/L (<0.1μg/L)”

• 1 part/million = .001g/L or 1 part/million = .001g/L or 1mg/L or 1 mg/kg or 4 drops of 1mg/L or 1 mg/kg or 4 drops of ink in a 55 gallon drumink in a 55 gallon drum

• 1ppb = .000001g/L or 1μg/kg or 1ppb = .000001g/L or 1μg/kg or 1μg/L or 1 pinch of salt in 10 1μg/L or 1 pinch of salt in 10 tons of potato chipstons of potato chips

• <100ng/L (<0.1μg/L) = <100ng/L (<0.1μg/L) = concentration many PhACs (or concentration many PhACs (or whatever you want to call whatever you want to call them!) occur =<0.0000001g/L them!) occur =<0.0000001g/L or <1 pinch of salt in 100 tons of or <1 pinch of salt in 100 tons of potato chipspotato chips

Methods DevelopmentMethods Developmentanalytical determination in environmental samples

is difficult and involves multiple tasks

• Sample collection - possible Sample collection - possible contaminationcontamination

• Separation & ExtractionSeparation & Extraction• ConcentrationConcentration• Detection & QuantificationDetection & Quantification• Many methods for doing all these things Many methods for doing all these things

– methods development is time – methods development is time consuming & expensive – usually for one consuming & expensive – usually for one compound at a timecompound at a time

Analytical MethodsAnalytical Methods

• GC/MS – Gas Chromatography/ Mass GC/MS – Gas Chromatography/ Mass SpectrometrySpectrometry

• HPLC/MS – High Performance Liquid HPLC/MS – High Performance Liquid Chromatography/ Mass Spec.Chromatography/ Mass Spec.

• LC/MS – Liquid Chromatography/Mass Spec.LC/MS – Liquid Chromatography/Mass Spec.• Combinations of these things in sequenceCombinations of these things in sequence• Different compounds require different Different compounds require different

analytical methodsanalytical methods• QA/QC – Quality Assurance/Quality Control QA/QC – Quality Assurance/Quality Control

is very difficultis very difficult

Obstacles to AnalysisObstacles to Analysis

• Test for each compound separatelyTest for each compound separately

• Very low detection levels may Very low detection levels may require putting analytical equipment require putting analytical equipment in sequencein sequence

• Few labs are capableFew labs are capable

• Cost prohibitiveCost prohibitive

PretreatmentPretreatment

• Removal, reduction, or alteration of Removal, reduction, or alteration of pollutants in industrial wastewater pollutants in industrial wastewater priorprior to discharge or introduction into to discharge or introduction into a domestic wastewater treatment a domestic wastewater treatment facilityfacility

Standard PretreatmentStandard Pretreatment

• Primary – filtration for particulatesPrimary – filtration for particulates

• Secondary – oxidation introducing Secondary – oxidation introducing bacteria bacteria (can also be aerobic)(can also be aerobic)

• Tertiary - chlorinationTertiary - chlorination

Advanced Treatment Advanced Treatment TechnologiesTechnologies• Coagulation/FlocculationCoagulation/Flocculation

– >50% removal of PAHs– <40% removal of organic chemicals

• pesticides, steroids, inorganics, industrial chemicals

• SofteningSoftening– 70-90% removal of pesticides– <20-40% removal of industrial chemicals and steroids

• Chlorine Chlorine – 70-90% removal of pesticides and other organics – <20% removal of inorganics, industrial chemicals

• UltravioletUltraviolet– >90% removal of pesticides, industrial chemicals, and

steroids– <20% removal of inorganics

New Technology New Technology

• Activated Carbon – good at removing 17a-Activated Carbon – good at removing 17a-ethynylestradiol (EE2) but expensiveethynylestradiol (EE2) but expensive

• MnOMnO2 2 – Manganese oxide – also good for EE2, – Manganese oxide – also good for EE2, increases degradation rate for othersincreases degradation rate for others

• Membrane Filtration - semi-permeable polymeric Membrane Filtration - semi-permeable polymeric membrane - $$$$membrane - $$$$

• Membrane Bioreactors – adds bio-substrate – Membrane Bioreactors – adds bio-substrate – pesticides, herbicides, EDCs - $$$$, lots of pesticides, herbicides, EDCs - $$$$, lots of maintenancemaintenance

• Fenton process, Advanced Electrochemical Fenton process, Advanced Electrochemical Oxidation Process, Phytoremediation – now you’re Oxidation Process, Phytoremediation – now you’re getting really esotericgetting really esoteric

AFTER PretreatmentAFTER Pretreatment

• Aerated, Partial Mix LagoonsAerated, Partial Mix Lagoons• Anaerobic LagoonsAnaerobic Lagoons• Ammonia StrippingAmmonia Stripping• Ballasted FlocculationBallasted Flocculation• Chemical PrecipitationChemical Precipitation• DechlorinationDechlorination• Granular Activated Carbon AbsorptionGranular Activated Carbon Absorption• Oxidation DitchesOxidation Ditches• Trickling Filter Nitrification Trickling Filter Nitrification • Trickling FiltersTrickling Filters• Etc!Etc!

The best way to treat them?The best way to treat them?

KEEP THEM OUT OF THE WATER IN THE KEEP THEM OUT OF THE WATER IN THE FIRST PLACE!FIRST PLACE!

Anhydrous

morphine

methadoneMore anhydrous

morphine

hydrocodone

Laurie TenaceLaurie Tenace

Florida DEPFlorida DEP

Laurie.Tenace@dep.state.fl.us

850-245-8759850-245-8759