Human Pharmaceuticals, Human Pharmaceuticals, Hormones, and Personal Care Hormones, and Personal Care

Products in Products in Water Reuse ProcessesWater Reuse Processes

Joel A. PedersenJoel A. Pedersen11, Mary Soliman, Mary Soliman22, Heesu Park, Heesu Park33,, Angelica Castaneda-JimenezAngelica Castaneda-Jimenez33 and Mel Suffet and Mel Suffet33

1 1 Environmental Chemistry and Technology Program and Soil Environmental Chemistry and Technology Program and Soil Science Department, University of Wisconsin - MadisonScience Department, University of Wisconsin - Madison

2 2 California Department of Health ServicesCalifornia Department of Health Services3 3 Environmental Science and Engineering Program, UCLAEnvironmental Science and Engineering Program, UCLA

Flow Chart of Water Reuse Flow Chart of Water Reuse PlantsPlants

Influent

Flocculation Disinfection Title 22water

Lime Barrier water

MF

RO

Sampling points

.

California Water Recycling California Water Recycling CriteriaCriteria

-Title 22 Water --Title 22 Water - Application to food crops Application to food crops

- minimum of secondary treatment + disinfection- minimum of secondary treatment + disinfection

Irrigation water in contact w/ edible portion Irrigation water in contact w/ edible portion secondary + chemical coagulation + filtration secondary + chemical coagulation + filtration disinfection (“disinfected tertiary recycled disinfection (“disinfected tertiary recycled water”)water”)

Effluent discharged to streams to be pumped out Effluent discharged to streams to be pumped out downstream for irrigation purposes downstream for irrigation purposes secondary treatmentsecondary treatment============================================================

============== Recharge groundwater to prevent saltwater Recharge groundwater to prevent saltwater

intrusionintrusion - Lime/RO or MF/RO treatment - Lime/RO or MF/RO treatment

Wastewater Contains ChemicalsWastewater Contains Chemicals1. Inorganic chemicals and NOM found

naturally in drinking water.2. Inorganics & organics from industrial,

commercial and other human activities - Target and Non-Target Compounds

3. Chemicals added or byproducts of water and wastewater treatment

==============================================================

• Measure Target Compounds -HOWEVER -There is a health risk from unidentified chemical(s) at ng to pg/L levels - Non-Target Compounds

ObjectivesObjectives Confirm and quantifyConfirm and quantify (19) (19) target

compounds - - PhACs, PCPs, human and PhACs, PCPs, human and synthetic hormones, antioxidants, plasticizerssynthetic hormones, antioxidants, plasticizers

Tentative identification of (Tentative identification of (35) 35) non-target compounds - MS library search - - MS library search -

Evaluate the effects of different water reuse Evaluate the effects of different water reuse treatment processes on their removal treatment processes on their removal

- Conventional treatment process - Conventional treatment process (Title 22 (Title 22 water)water) - Lime/RO (Barrier water) - Lime/RO (Barrier water)

- MF/RO (Barrier water)- MF/RO (Barrier water)Compare reclaimed water to raw drinking water sourcesCompare reclaimed water to raw drinking water sources

Broad Spectrum Analytical Broad Spectrum Analytical SchemeScheme

Sample

Metals, Boron TOC, UVCompliance Analysis

Acidification (pH3)Na2SO4, Ascorbic Acid, and Surrogate added

Continuous Liquid-Liquid Extraction

CondensationGC/MS Analysis

• Identification• Quantification

Target and Non- Target Analysis

Experimental SettingExperimental Setting((10 L influent/40 L effluent) - Baker et al. 10 L influent/40 L effluent) - Baker et al.

19871987

Water Sample

Solvent 10 L/hr1 L/hr

Mixture Inlet

Water Outlet

CLLE

Heater

Condenser

1919 Targeted Analytes Targeted Analytes (Recovery = 84%, SD = 21%)(Recovery = 84%, SD = 21%)

Human Pharmaceuticals Hormones

caffeine 17-estradiol

carbamazepine Estrone, Esterol

carisoprodol ethinyl estradiol

clofibric acid progesterone

diazepam stanolone

fenofibrate testosterone

gemfibrozil Other compounds

ibuprofen BHT (Antioxidant)

p-toluenesulfonamide

Note: Bold- not seen

BHA (Antioxidant)N-butyl benzene- sulfonamide(plasticizer)

Targeted AnalysisTargeted Analysis (PTGC - 12 m HP-1, 20 min run time)(PTGC - 12 m HP-1, 20 min run time)

Carbamazepine – 142-650 ng/LCarbamazepine – 142-650 ng/L AntiepilepticAntiepileptic, <3% excreted in urine as parent or , <3% excreted in urine as parent or

epoxideepoxide Inhibits high-frequency neuronal firing by Inhibits high-frequency neuronal firing by

reducing Nareducing Na++ currents currents(Drewes et al., 2001; Metcalfe et al., 2001)(Drewes et al., 2001; Metcalfe et al., 2001)

Pharmaceuticals & Pharmaceuticals & HormonesHormones

NONH2

Ethinylestradiol - 43-50 ng/LEthinylestradiol - 43-50 ng/L Synthetic oral contraceptiveSynthetic oral contraceptive (Ternes et al., 1999; Huang and Sedlak, 2001)(Ternes et al., 1999; Huang and Sedlak, 2001)

Progesterone - 5*-50 ng/LProgesterone - 5*-50 ng/L (Li et al., 2002)(Li et al., 2002)

** < MDL < MDL

HOOHHHH

OOHHH

Non-Target Analysis Non-Target Analysis Compound Class 35 - Compounds

Identified

Industrial chemicals & solvents

9

Pesticides (methyl parathion, metolachlor)

2

Human pharmaceuticals (Naproxen)

1

Personal care product ingredients

3

Plasticizer compounds (Phthalates)

6

Antimicrobials (chloroxylenol, chloropene)

PAHs (napthalene and phenanthrene)

Fire retardant (tris(2-chloroethyl) phosphate)

Steroid related hormones (cholestanol, cholesterol, cholest-4-en-3-one, stigmasterol)

7214

Kováts Index

1600 1800 2000 2200 2400 2600 2800 3000 3200 3400

Relative Response

0.0

0.1

0.2

0.3

0.4

myclobutanil

AHTN

BBP

TBEP

benzophenone

p-TSA

TCEP

N-BBSA

TCPP

HHCB

DBP

TDCPP

DIOP

globulol

1-iodo-2-methylnonane

sesquiterpenoid

Non-target Analysis Non-target Analysis (PTGC - 30 m DB-5MS, 75 min run time)(PTGC - 30 m DB-5MS, 75 min run time)

Personal Care Product Personal Care Product IngredientsIngredients

Diethyltoluamide (DEET)Diethyltoluamide (DEET) Insect repellentInsect repellent(Snyder et al., 2002)(Snyder et al., 2002)

BenzophenoneBenzophenone Fragrance fixativeFragrance fixative(Paxéus, 1996)(Paxéus, 1996)

Polycyclic musks Polycyclic musks AHTN (Tonalide) and HHCB (Galaxolide)AHTN (Tonalide) and HHCB (Galaxolide) Synthetic fragrancesSynthetic fragrances(Simonich et al., 2000)(Simonich et al., 2000)

NO

O

OO

WATER RECYCLING PLANT

Flow Chart of Water Reuse Flow Chart of Water Reuse PlantsPlants

Influent

Flocculation Disinfection Title 22water

Lime Barrier water

MF

RO

Sampling points

.

Secondary EffluentSecondary Effluent

Compound Class Plant 1

Plant 2 Plant 3 *Raw DW SPW,CRW,GW

•Of 19 Target 13 Chemicals (> 95% are ng/L) No Estriol

16 14 4

or Diazepan is observed

•Of 35 Non-target 16 ChemicalsTOTAL 29------------------------------------- * Much lower conc. levels BHA, BHT, NBBSA and

18 20 9

34 34 13

than secondary effluent -Caffeine are highest level

Plant 1-32oEff

Plant 1T-22

Plant 2 T-22**

Plant 3 T-22

Compound ng/L %R %R %RBHA 128-1050 68 88 87

ibuprofen 50-469 79 76 0

carbamazepine 142-650 48 99 100

clofibric acid* 10-550 100 0 53

Ethinyl estradiol 20-50 0 100 20

stanolone nd-162 100 100 na

estrone 50-220 100 81 100

gemfibrozil nd-480 100 100 nap-Toluene* sulfamide

350-520 65 67 71

----------------------All Compounds

---------5 >100 ng/L

-----------13 to 8 T

15 to 15 NT2 new ones

-----------16 to 9 T

18 to 10NT

-----------14 to 7 T18 to 9NT

% Removal by Title 22 Waste Treatment

24-hour composite - Plant 1 and 3 - four 6-hr; *** Plant 2 - 24 - 1-hr

1000 1100 1200 1300 1400 1500 1600 1700 1800 1900 2000 2100 2200 2300 2400 2500 2600 2700 2800 2900 30000

250

500

750

1000

Kovats Index

1000 1100 1200 1300 1400 1500 1600 1700 1800 1900 2000 2100 2200 2300 2400 2500 2600 2700 2800 2900 3000

0

100

200

300

1

2

1

3

3

45

6

6

7

8

9

9

10

11

12

12

13

14

15 16

17

Lime/RO

MF/RO

ng/L

ng/L61 peaks20,400 ng/L

21 peaks670 ng/L

TRACE ORGANICS IN RECLAIMED WATER

I.S.

I.S.

I.S. I.S.

I.S. I.S.

I.S.

I.S.

Remaining after Tertiary Remaining after Tertiary

TreatmentsTreatments Compound Plant 2Class T-22 L-RO

Plant 3 T-22 L-RO MF-RO

•Of 19 Target 10 5* Conc. (ng/L) <350 <70*

8 4* 3* <520 <62* <50*

•Of 35 Non- 10 1* targetTOTAL 20 6Hourly samples for 24 hrs.------------------------------------- *Much lower levels than BHA, BHT, NBBSA -- Note- GW recharge of 50%

9 2* 2*

17 6 5 6 Hour composite for 24 hrs.

secondary effluent -and Caffeine were observedL-RO and MF-RO waters

ConclusionsConclusions1.1. STP>Title 22> L-RO> MF-RO ( No. and STP>Title 22> L-RO> MF-RO ( No. and

Conc.)Conc.)

2.2. 5 Comp’ds > 100 ng/L - 5 Comp’ds > 100 ng/L - BHA and BHT, NBBSA,

Caffeine and Clofibric acid after Title 22 Treatment.

3. Best treatment alternative was MF/RO.

35% of Target and 15% of non-target compounds are

present at > DL for RO and MF/RO treatment.

4. Antioxidants BHA and BHT, plasticizers as NBBSA and Caffeine are observed after MF/RO. Remember BHA and BHT have been shown to leach from polyethylene pipe.

5. Sampling an actual treatment system for correct evaluation of a variable hourly, daily and seasonal influent and effluent and remains a problem.

Water Quality Assessment Water Quality Assessment for for Indirect Potable Reuse Indirect Potable Reuse

of Waterof Water In water reuse, the source is not “pollution In water reuse, the source is not “pollution free”. Monitoring for a few “target” free”. Monitoring for a few “target” compounds is meaningless.compounds is meaningless.

Many other compounds are observed by Many other compounds are observed by GC or LC/MS and are ignored. “Non -GC or LC/MS and are ignored. “Non -target”compounds are significant.target”compounds are significant.

Idea - Broad Spectrum Analysis and Idea - Broad Spectrum Analysis and lowering the detection limit of trace lowering the detection limit of trace organic compounds by large volume of organic compounds by large volume of water samples to ng/L to pg/L? level.water samples to ng/L to pg/L? level.

Broad Spectrum Broad Spectrum Analysis Analysis

of Organic Chemicalsof Organic Chemicals Screening strategy that uses GC or LC Screening strategy that uses GC or LC

profiles to analyze for temporal and spatial profiles to analyze for temporal and spatial changes of both target and non-target changes of both target and non-target compoundscompounds

Tentative identification of non-target Tentative identification of non-target compounds -- MS library searchcompounds -- MS library search

Confirmation of target compounds and Confirmation of target compounds and subsequent quantitationsubsequent quantitation

New Strategies for Evaluation of Water Quality for Water Reclamation

1.1. Present Strategy - MCLs Present Strategy - MCLs 2.2. Future Strategies -Future Strategies -

A. “A. “Treatment ReliabilityTreatment Reliability” Standards” Standards a. Treatment Redundancya. Treatment Redundancyb. Mandate Unit Operationsb. Mandate Unit Operationsc. Access Treatment Reliabilityc. Access Treatment Reliability

\\

B. “B. “Broad Spectrum Chemical AnalysesBroad Spectrum Chemical Analyses”” a. a. Analyze target and “non-target”Analyze target and “non-target” compounds present compounds present above a defined a defined

concentration level. Toxicologist- concentration level. Toxicologist- Help.Help.

C. “C. “Develop NEW Health and Safety TestsDevelop NEW Health and Safety Tests”” a. a. Specify Priority Hazards. e.g. EDCsSpecify Priority Hazards. e.g. EDCsb. Study Mixtures and Matrices for above.b. Study Mixtures and Matrices for above.

AcknowledgementsAcknowledgements

California DHS (Larry Barrett, DVM)California DHS (Larry Barrett, DVM) Samples from Orange County Water Samples from Orange County Water

District, West Basin Water District, and District, West Basin Water District, and Los Angeles Sanitation District.Los Angeles Sanitation District.