Pharmaceuticals and Personal Care Products in U.S. Water ......Oct 21, 2008 · Products in U.S....
Transcript of Pharmaceuticals and Personal Care Products in U.S. Water ......Oct 21, 2008 · Products in U.S....
Pharmaceuticals and Personal CareProducts in U.S. Water Resources
Rolf Halden, PhD, PESpecialty Area Coordinator for Water Resources and Environmental Engineering
Department of Civil, Environmental and Sustainable Engineering, Arizona State University
Presented at: Interstate Technology & Regulatory Council (ITRC) Fall MeetingOctober 21, 2008, Phoenix, AZ
Outline
PPCPs
Sources
Status Quo
Tox Data
Summary
• 1 Acronym, 2 distinct issues
PPCPs
Image: Beyond Pesticides
http://www.diamond.ac.uk/
U.S. Animal ProductionBroilers 8,788,281,000Turkeys 254,455,000Hogs 103,584,000Cattle 32,734,000Sheep 2,844,000Calves 847,000
Total 9,182,745,000
USDA
http://photogallery.nrcs.usda.gov/Detail.asp
http://photogallery.nrcs.usda.gov/Detail.asp
Industrial Farm Animal Production (IFAP)New business model brings new challenges
• 70-80% of antibiotic usage• 55% of soil and sediment erosion• 37% of U.S. pesticide usage• 30% of N and P loading to drinking water resources
http://photogallery.nrcs.usda.gov/Detail.asphttp://photogallery.nrcs.usda.gov/Detail.asp
USGS Stream Monitoring Network
Source: USGS 2002
(1999-2000)
Target Chemicals (95 total)22 Antibiotics
14 Prescription drugs
5 Nonprescription drugs
15 Hormones and sterols
39 Household and industrial compounds
Source: USGS 2002
22 Veterinary and Human Antibiotics
• 4 Tetracyclines (Doxycycline)
• 4 Fluoroquinolones (Ciprofloxacin)
• 3 Macrolides (Erythromycin-H2O*)
• 7 Sulfonamides (Sulfamethazine)
• Others (Lincomycin, Trimethoprim Carbadox, Virginiamycin)
*metabolite
Source: USGS 2002
• Pharmaceuticals detected in ~80% of streams
• 75 of 95 pharmaceuticals detected
• Concentrations generally low
~5% hits > 1µg/L
~25% of sampling sites > 6 µg/L total compounds
75% > 1 compound => Mixtures
35% > 10 compounds
Few standards/guidelines exceeded, as few exist
USGS Results, 2002
Source: USGS 2002
Looking back:Pharmaceuticals in freshwater: NOT
a new problem! CH3H3C
COOHOCl
1976 Detected in WWTP effluent
1991 Detected in drinking water, Berlin, FRG
1995 River Elbe, FRG (27-157 ng/L)
1998 Detected in various Swiss lakes (1-9 ng/L)
1998 Detected in the North Sea, FRG (1-2 ng/L)
Buser et al. 1998, ES&T 32:188-192
Clofibric Acid
• phenoxyalkanoic acid
• 2-[4-chlorophenoxy]-2-methylpropionic acid
• blood lipid regulator (ethyl ester; clofibrate)
• 1-2 g/day therapeutic dosage
• structural isomer: herbicide mecoprop, MCPP
CH3H3C
COOHOCl
CH3H
COOHOCl
CH3
MCPP
• New, more sensitive analytical tools (e.g., MS-MS)
• Drugs typically are polar compounds
- native (underivatized) drugs & metabolites areinvisible to GC-MS
• LC-MS ==> polar, thermo-labile compounds
Why is the problem identifiednow?
HN
O
HN
ClCl
Cl
Triclocarban (TCC)
1957
1964
Cl
OH
O
Cl
Cl
Triclosan (TCS)
Triclocarban (TCC)
HN
O
HN
ClCl
Cl
Triclosan (TCS)
Cl
OH
O
Cl
Cl
4.94.8Log KOW (at 25ºC, pH 7)
TriclocarbanTriclosanProperty
Persistent Biocides as Surrogates for Multiple Issues• Personal care products
• Pharmaceuticals
• Pesticides
• Endocrine disruptors
• Persistent halogenated aromatic compounds
• Promoter of antimicrobial resistance
• Modulator of microbial communities
• Pollutant of aquatic & terrestrial environment
• Others
Heidler and Halden 2008 (In Revision)
Update of info from ES&T 39(6):1420-6 (2005)
PPCPs in the Environment: An Emerging Issue
Environmental and Human Health Concerns
Triclosan
Cross-resistance to Antibiotics
Endocrine Disruption
Bioaccumulation
PersistentEnvironmentalContaminant
Acts as Carcinogen,Mutagen orTeratogen
Impurities
O
O
Cl
ClCl
Cl
Degradates(including chloroform)
O
O
ClCl
TCS - A Case Study of Non-Green Chemistry (In Preparation)
Triclocarban
Cross-resistance to Antibiotics
?
Endocrine Disruption
Acts as Carcinogen,Mutagen orTeratogen
(Indirectly through metabolites) ?
Bioaccumulation?
PersistentEnvironmentalContaminant
Impurities
?
H2N Cl
Degradates
NH2
Cl
Cl
H2N Cl
Environmental and Human Health Concerns
TCC - A Case Study of Non-Green Chemistry (In Preparation)
Triclocarban: Case Study of an Emerging Contaminant
[M-H]-m/z 313315317
m/z 313315317
100
0
HPLC
Rel
ativ
e In
tens
ity (%
)So
lven
t (%
) 100
0
25
75
Time (min)
[M+60-H]-
(CH3COOH Adduct)
100
0 302010
m/z 373375377
15 2550
O
O-
HN
O
HN
ClCl
Cl
HN
O
HN
ClCl
Cl
Introduction of an LC-ESI-MS Method in 2004
ES&T 38(18):4849-4855 (2004)
Triclocarban in Maryland Streams
ES&T 38(18):4849-4855 (2004)
Co-Occurrence of Triclocarban and Triclosan
Triclosan [ng/L]
100 101 102 103 104 105 106
Tric
locarb
an
[ng/L
]
100
101
102
103
104
105
106
TCC
[ng/
L]
TCS [ng/L]
R2 = 0.9882
MeasureTCS
CalculateTCC
ES&T 39(6):1420-6 (2005)
• Activated sludge WWTP
• 600 ML/D (180 MGD)
• Population served: 1.3 M
Wastewater Treatment Plants are PrincipalSources of Antimicrobials in the U.S.
Environment
ES&T 40:3634-9 (2006)
Influent MechanicalScreens
PrimaryClarifiers
Activated SludgeTreatment
Secondary Clarifiers
SandFilters
Effluent
PrimarySludge
Chlorine
AnaerobicDigesters
SludgeThickeners
Air
Dewatered sludge
SecondarySludge
Sampling Locations
ES&T 40:3634-9 (2006)
Schematic Overview of Local Activated Sludge WastewaterTreatment Plant (WWTP)
Accumulation of TCC in Digested Sludge During Wastewater Treatment
0.1
1
10
100
1000
10000
100000
Influent Effluent Digested Sludge
ppb
Acc
umul
atio
n
Rem
oval
ES&T 40:3634-9 (2006)
Fate of Triclocarban During Activated Sludge Treatment
Mass in effluentMass in sludgeMass transformed/lost
21 ± 30%795 g/d
3 ± 1%127 g/d
76 ± 30%2815 g/d
ES&T 40:3634-9 (2006)
HN
O
HN
Cl Cl
Cl
Triclocarban (TCC)
2 ± 1%55 g/d
48 ± 19%1540 g/d
50 ± 19%1640 g/d
Mass in effluentMass in sludgeMass transformed/lost
Chemosphere 66(2):362-9 (2007)
Fate of Triclosan in Activated Sludge WWTP
O
Cl
Cl
Cl
OH
Triclosan (TCS)
Meta-analysis of Published Mass Balances
• 13 Peer-reviewed mass balance papers
• 19 Organic wastewater contaminants
• Approach: regression analysis
ES&T 42(17):6324-6332 (2008)
InfluentFinal
effluent
Primary
effluent
Activated
sludge
3
97
3
62
TSS removal in
primary clarifiers
= 36%
35 59
(log Koc= 6)
TSS removal in
final clarifiers
= 90%
100
0
19
8381
017
(log Koc= 2)
0
100
0
74
26
13
0
78
(log Koc= 4)
9
74
17
4
87
0
65
3
3
A
B
C
The Role of Partitioning & Sorption
ES&T 42(17):6324-6332 (2008)
Meta-Analysis ofMass Balances
Sludge
Effluent
Lost
ES&T 42(17):6324-6332 (2008)
Biosolids: An Emerging Research Area
Halden, unpublished
The ASU National Biosolids Repository
What Happens to Compounds That PassThrough the Plant?
ES&T 40:3634-9 (2006)
Environmental Persistence: Predicted & Measured
Estimated using quantitative structure activity relationship (QSAR) analysis
1
60120
540
0.75
0.1
1
10
100
1000
10000
Air Water Soil Sediment
Estim
ated
Hal
f-life
(day
s)
TriclosanTriclocarban
ES&T 39(6):1420-6 (2005)
Some PPCPs Persist in the Environment
TCS and/or TCC...
• are consistently found at ppm levels in biosolids from around the world(Bester 2003; Morales, Canosa et al. 2005; Heidler, Sapkota et al. 2006; Kinney, Furlong et al. 2006; Chuand Metcalfe 2007; Ying and Kookana 2007; Heidler and Halden 2008a,b).
• persist in anaerobic soils (Ying, Yu et al. 2007).
• persist and bioaccumulate in algae and earthworms (Coogan, Edziyie et al. 2007;Kinney, Furlong et al. 2008).
• persist in sediments for decades (Miller et al. 2008; in revision)
ES&T 2008, 42:4570-76Environmental Persistence: Empirical Evidence
ES&T 2008, 42:4570-76
Occurrence of Antimicrobialsin Estuarine Sediments
ES&T 2008, 42:4570-76
Young et al. 2008. ES&T 42(9):3335-3340Chalew and Halden 2008 (In Press)
Antimicrobials in Surface WaterCan Serve as Indicators ofMicrobial Contamination
log CFU/100 mL
• Microbes tolerate low levels of antimicrobials in surface waters
• TCS/TCC in surface waters can indicate presence of pathogens
• In contrast, more susceptible receptors (algae, crustacea) may
experience lifetime exposure to toxic TCS/TCC levels
Nationwide Data of PPCPs in Biosolids
• 110 Wastewater treatment facilities
• 30+ U.S. States
• 70+ PPCPs examined
McClellan and Halden (In internal review)
Present study73 PPCPs total
38 PPCPs
Kolpin et al.(2002) Total of 95 organic wastewater compounds
By taking care of2 chemicals, wecould take care of66% of the PPCPproblem
McClellan and Halden 2008 (In internal review)
TCC+TCS
Breakup of 73 PPCPs by Total Mass in Biosolids
Endocrine Disruption: A Risk Driver
UC Davis news release
Triclosan: Endocrine Disruption in Human Cells
Antimicrobials: Endocrine Disruption in Frogs
Cell assay: concentrations of as low as 30 ng/Lalter thyroid hormone receptor mRNA expression
http://www.vettorpisani.net/
Antimicrobials: Adverse Effects in Mussels
http://www.ealing.gov.uk/
Antimicrobials: Endocrine Disruption in Rats
Triclosan in U.S. Breast MilkTriclosan detectable in 97%of U.S. breast milk samplesanalyzed
Summary of Nationwide Data• TCC &TCS occur nationwide* in:
– raw sewage (1.86 – 26.8 µg/L for TCS; 0.4 – 50 µg/L for TCC)– sewage treatment plant effluent (0.027 – 2.7 µg/L for TCS; 0.1 – 6 µg/L for TCC)– surface waters (<2.3 µg/L for TCS; typically <0.25 µg/L; up to 6.75 µg/L of TCC in sewage
impacted streams)– biosolids (90 – 32,900 µg/kg for TCS; 3,050 – 51,000 µg/kg for TCC)– sediments (up to 53,000 µg/kg for TCS; up to 24,000 µg/kg for TCC)
• TCC & TCS are persistent, particularly under anaerobic conditions– can persist for decades in aquatic sediments
• PPCPs in the environment: dilution is not the solution
– ppb WWTP Influent => ppt WWTP Effluent => ppm Biosolids, Sediments, Earthworms, House Dust
* Chalew and Halden 2008 (In Press)
• PPCPs is an issue that won’t go away by itself; action is needed
• Endocrine disrupting properties are drivers of human health risks
• Emergence of drug-resistant pathogens is another major concern
• Environmental effects of PPCP mixtures are mostly unexplored
Summary & Conclusions
• Agriculture– discontinue use of antibiotics for growth promotion
– end the use of human drugs in animals (food animal production and veterinary medicine)
• Education (protect source water and increase acceptance that water is always “reused”)– the toilet is not a garbage bin
• promote drug take-back & disposal programs
• “wastewater” is a misnomer; used water is raw drinking water (“fortified drinking water”; “post-consumer drinking water”...)
– the sink is not a garbage bin or compost pile• remove persistent biocides and other unnecessary organohalogens from consumer products
• limit use of electrical garbage disposals for disposal of food waste
– avoid future problems• keep problematic compounds like organohalogens out of the water cycle
• Industry (organohalogens are persistent pollutants that should be replaced where possible– where feasible, phase-out/remove/replace organic compounds carrying -F; -Cl, -Br, -I substituents
• Policy (eliminating the root cause will saves $$ and has biggest impact most quickly)– consider a universal tax on halogen-carbon bonds* as an incentive for sustainable chemistry
– discontinue the unnecessary use of persistent biocides• >60% of the PPCP mass in biosolids are persistent biocides
• TCS/TCC have no proven benefits (compared to “regular” soaps) but pose numerous potential risks
• TCS/TCC alone represent several hundred thousand lbs/year of organohalogens that enter agriculture through sludge disposed on land
Opportunities/Possible Actions
*Graham & Halden, 2009 (Under Consideration at Chemical Reviews)
Acknowledgements
Contributors
• Kristin McClellan, MS
• Randhir Deo, PhD
• Daniel Paull, B.S.
• Jochen Heidler, PhD
• Amir Sapkota, PhD
• Todd Miller, PhD
• Thayer Young, MS
• Amelia DeLaquil, BS
• Talia Chalew, MS
• Steven Chillrud, PhD
• Richard Bopp, PhD
• Jerry Ritchie, PhD
Funding/Support
• US EPA
• NIEHS
• CDC
• JHU-CLF
• Gifts
Technical Assistance
• US EPA
• City of Baltimore
• John Martin, PhD and Nick Frankos
• WEF Collaborators
• Groundwater Foundation