Chemicals of Emerging Concern

in our Water.How concerned

should we be?

Dr. Joseph Colosi

DeSales University
jcc0@desales.edu
 Outline

1. Progress in water treatment since World War II.

2. Most chemicals are not monitored or regulated.
3. What are Chemicals of Emerging Concern (CEC)?
4. The sources of chemicals in our waters.
5. The fate of chemicals in wastewater treatment plants.
6. Chemicals found in sewage sludge, streams, public
water sources, finished drinking water, and wildlife and
people.
7. Focus on perfluorinated chemicals.
8. Wildlife effects have been documented, effects on
humans are suspected.
We live in the Delaware River Watershed.
The Delaware River is much less polluted today than
30 years ago

Low for
trout

Not well
tolerated
by most
fish
Sewage treatment is Primarily designed to prevent
oxygen sag and pathogens in receiving waters.

O2 sag
Regular monitoring of wastewater treatment
plant effluent required by regulation.
Total suspended solids
BOD
NH3
pH
Fecal coliforms
Residual Chlorine
For Chesapeake Bay watershed:
limits on total N and total P and coming to a WWTP
near you http://www2.epa.gov/nutrient-policy-data/action-towards-limiting-total-nitrogen-total-phosphorus-and-total-inorganic

Beginning January 2011 to PA industrial dischargers:

limits on total dissolved solids (because of fracking)
No monitoring of: CEC- Detergents, EDC’s,
Antibiotics, Drugs, ETC., ETC., ETC.
 CEC Chemicals of Emerging Concern- include:

Pharmaceuticals and Personal Antibiotics, analgesics, blood pressure drugs,

Care Products (PPCPs) psychotropic drugs, skin care products.
Alkylphenols Octylphenols and nonylphenols (antioxidants,
lubricating oil additives, laundry and dish
detergents, emulsifiers)
Flame retardants Organophosphorus compounds (TCP, TPP),
polybrominated diphenyl ethers (PBDEs)
PFCs (perfluorinated chemicals):
Stain repellents Perfluorooctane sulfonate (PFOS) and others
PFCs: Nonstick chemicals Perfluorooctanoic acid (PFOA) and others
Plasticizers Bisphenol A, phthalates, and others
Pesticides Insecticides (DDT family), herbicides, (atrazine)
fungicides (vinclozolin), and others
Endocrine Disrupting Natural estrogens, birth control estrogens,
Compounds (EDCs) nonylphenols, plasticizers, pesticides, and
others.
 Number of publications including "Chemicals of
Emerging Concern” obtained by Google Scholar
20000 10/26/2015

18000

16000
Number of publications per year

14000

12000

10000

8000

6000

4000

2000

0
1980 1985 1990 1995 2000 2005 2010 2014
Publication year
We use a lot of drugs
 http://www.imshealth.com/deployedfiles/imshealth/Global/Content/Corporate/Press%20Room/2012_U.S/Top_Therapeutic_Classes_Dispensed_Prescriptions_2012.pdf

millions

Over 4 billion scripts in 2012

One Ibuprofen pill = 0.3g. 4 billion times 0.3g = 1200 metric tons
 OTC Sales by Category 2010-2013
OTC Category 2010 2011 2012 2013
(in millions) (in millions) (in millions) (in millions)
Acne Remedies $605 $615 $625 $617
Analgesics, External $468 $499 $517 $556
Analgesics, Internal (includes $3,994 $4,027 $3,904 $3,999
other pain products)
Antidiarrheals $248 $213 $217 $225
Anti-Smoking Products $795 $828 $858 $855
Cough/Cold and Related $6,311 $6,572 $6,828 $7,224
Eye Care $767 $803 $850 $895
First Aid $2,733 $2,799 $2,895 $2,972
Foot Care $1,028 $1,030 $1,061 $1,094
Heartburn (includes anti-gas) $2,377 $2,328 $2,300 $2,283
Laxatives $1,285 $1,346 $1,373 $1,347
Lip Remedies $727 $748 $822 $916
Oral Antiseptics and Rinses $1,303 $1,359 $1,396 $1,432
Sunscreens and Blocks $873 $954 $1,009 $985
Toothpaste $2,606 $2,722 $2,746 $2,790
All Others $4,619 $4,657 $4,749 $4,914
Total $30,739 $31,500 $32,150 $33,104
Source: The Nielsen Company - total U.S. all outlets (food, drug, mass, select club and dollar store retailers, convenience, and militar
stores). Sales are in millions of U.S. dollars. A few categories include a combination of OTC medicines as well as health-related
products which are not classified as medicines by the Food and Drug Administration. http://www.chpa.org/OTCsCategory.aspx
US consumption of soaps and detergents 2006
Marketresearch.com
$19,347,000,000
• More than 85,000 chemicals in commerce in US.
• About 2,500 “high production volume” (HPV) chemicals,
(over one million pounds/year)
• Nearly 45 percent of HPV chemicals lack adequate
toxicological studies.
• About 2,000/year new commercial chemicals in US
• Seven new chemicals a day in US.

https://www.dtsc.ca.gov/AssessingRisk/EmergingContamin
a nts.cfm
Where much of the chemicals
end up, one way or the
other
The chemicals flow here, some are destroyed,
others persist.

Bethlehem Sewage Treatment Plant

 The chemicals enter the environment at wastewater
plant outfalls into streams, rivers, lakes, and the ocean
 Fate of chemicals in wastewater

Applied
to farm
fields or
landfill, or Remainder
burned to river
Loss to
sediments
Loss
to the
air
Loss to
microbial
degradation
So, let’s not flush chemicals down the toilet.

Municipal treatment plants are designed to

treat poop not 1001 different chemicals.
But….A large proportion of many of the
drugs that we take into our bodies is
excreted in our feces and urine.
And… what should you do with leftover
prescription and over-the-counter drugs (not
to mention drugs left over from the party)?

The old advice was to flush them down the

toilet.

The new advice?

Narcotic medicines currently http://www.fda.gov/Drugs/ResourcesForY

recommended for disposal Flushinhttp://www.pharmacy.ca.gov/publications/dont_flush_meds.pdf

ou/Consumers/BuyingUsingMedicineSafel
y/EnsuringSafeUseofMedicine/SafeDispo
salofMedicines/ucm186187.htm

by Medicine Active Ingredient

g
Actiq, oral transmucosal
Fentanyl Citrate
lozenge
Avinza, capsules
Morphine Sulfate
(extended release)
Daytrana, transdermal
Methylphenidate
patch system
Demerol, tablets * Meperidine Hydrochloride
Demerol, oral solution * Meperidine Hydrochloride
Diastat/Diastat AcuDial,
Diazepam
rectal gel
Hydromorphone
Dilaudid, tablets *
Hydrochloride How to dispose
Hydromorphone
Dilaudid, oral liquid *
Hydrochloride of other drugs
Dolophine
Methadone Hydrochloride
in the garbage
Hydrochloride, tablets *
Duragesic, patch
Fentanyl
(extended release) *
Embeda, capsules Morphine Sulfate;
(extended release) Naltrexone Hydrochloride
http://www.fda.gov/downloads/Drugs/ResourcesForYou/Consu
Fentora, tablets (buccal) Fentanyl Citrate mers/BuyingUsingMedicineSafely/UnderstandingOver-the-
CounterMedicines/ucm107163.pdf
 Leachate from all
Proper three Northampton
disposal of County landfills
drugs to treated at municipal
garbage wastewater
treatment plants
Wateer leaches
throug h
garbage

Liner captures leachate

 Fate of chemicals in wastewater

Applied
to farm
fields or
landfill, or Remainder
burned to river
Loss to
sediments
Loss
to the
air
Loss to
microbial
degradation

Allentown
 What actually gets out into the
environment?

.
A function of:
• Source (amount consumed and % excreted), for example.
• Fate in WWTPs (affinity for water or solids, usable by
bacteria.
• Rate of degradation in the environment.
 1 part
per
thousand
 USGS Water-quality
survey, 1999-2000 Cholesterol derivative

Insect repellant
First nationwide survey to
detect 95 pharmaceuticals,
Flame retardant
antibacterial

hormones, and other surfactant

surfactant

organics in 139 urban and Fungicide

surfactant
plasticizer
agricultural streams in 30
states. Two chemicals
found in 80% of the
samples, and 82 chemicals
occurred in at least one
sample.

Keep in mind - You can

only find what you seek.

Survey study 2002

http://pubs.acs.org/hotartcl/est/es011055j_rev.html
 Closer to Home

Delaware River Basin Study of PPCPs

Opiate analgesic

for type 2 diabetes

Fungicide and parasitici

Anti-inflammatory meta

Antibacterial in soaps

Antidepressant

Antihypertensive metab

Analgesic

Antibiotic

Antibiotic

Anti-
inflamma
tory

Cholesterol reducer

Antibiotic

Antibiotic

Anti-seizure
It is not just our rivers and lakes
 Survey of 19 US Drinking Water Utilities for 51
compounds 2006-07
11 most commonly detected compounds
(in minute concentrations)
Atenolol beta blocker for heart disease
Atrazine herbicide
Carbamazepine bipolar drug
Estrone natural estrogen
Gemfibrozil anti-cholesterol drug
Meprobamate tranquilizer
Naproxen anti-inflammatory
Phenytoin anticonvulsant
Sulfamethoxazole antibiotic
TCEP Flame retardant
Trimethoprin antibiotic
Benotti, M. J., Trenholm, R. A., Vanderford, B. J., Holady, J. C., Stanford, B. D., & Snyder, S. A. (2008). Pharmaceuticals and
endocrine disrupting compounds in US drinking water. Environmental Science & Technology, 43(3), 597-603.
 40% of Americans rely on groundwater.

Evaporation

Water well

Septic drain field

chemicals

Water table

Not all recycling is

2014
 Effects of PPCPs on selected wildlife
Species PPCP Effect Authors
Freshwater Triclosan & Upstream and downstream cultures Fair et al.
algae Cirprofloxicin responded differently 2009
Marine Serotonin Increase in phototaxis and geotaxis after 2 Guler and
amphipod weeks of 0.1µg/l Ford. 2010
Marine Fluoxetine Increase in phototaxis and geotaxis after 1 Guler and
amphipod week of 0.01µg/l and 0.1µg/l respectively Ford. 2010
Baltic sea Diclofenac Bioconcentration>100 X after 8 day Ericson et
blue exposure to 1µg/l. Lowering of scope al. 2010
mussels for growth after 2 week exposure to
100µg/l.
Baltic sea Ibuprofen Lowering of byssus tread strength after 3 Ericson et
blue weeks of 10,000µg/l. Lowering of scope for al. 2010
mussels growth after 2 week exposure to 1000µg/l.
Baltic sea Propanodol Bioconcentration>100 X after 8 day Ericson et
blue exposure to 1µg/l. Lowering of scope for al. 2010
mussels growth after 2 week exposure to 1000µg/l.
Baltic sea Diclofenac Bioconcentration>100 X after 8 day Ericson et
blue exposure to 1µg/l al. 2010
mussels
Kaplan, S. 2013. Review: Pharmacological Pollution in water. Critical Reviews in
 Effects of PPCPs on selected wildlife
Species PPCP Effect Authors
New triclosan More unshelled embryos after 4 week Giudice
Zealand exposure to 1.6µg/l. More total embryos &Young.
mudsnail after 4 week exposure to 0.2µg/l. 2010
Rainbow diclofenac Bioaccumulation in fish bile to 320-950 X after Kallio et
trout 10 day exposure to 1.9µg/l. al.
2010
Several Fluoxetine, Found in all fish downstream from WWTP but Brooks
fish sertraline, not above et al.
species norfluoxertine, 2005

desmethylser-
traline
Zebrafish Diazepam Differential expression of circadian rhythm Oggler et
genes in all life stages after exposure to al. 2010
environmentally relevant concentrations.
Sand gobi 17α-ethinyl Non correlation between male size and Saaristo
estradiol courtship behavior and more time parenting et al.
by males after 10-31 day exposure to 41ng/L. 2010
Fathead 17α-ethinyl Population collapse after exposure to 5ng/l in Kidd et
minnow estradiol experimental lake study al. 2007
Bottlenose Triclosan Found in blood in 7 of 26 wild dolphins in Fair et al.
 Perfluorinated hydrocarbons (PFCs)
• Released in manufacture of nonstick cookware (some released
in use)

• Water and stain resistant carpet, upholstery, and clothin g.

• Grease proof food packaging such as French fry boxes,

microwave popcorn bags.

• Waxes, polishes, paints, adhesives.

• Firefighting foams

• Water soluble and highly persistent in the environment.

 PFC family

Houde, M., JW Martin,

RJ Letcher, KR Solomon,
and DCG Muir. 2006
Biological monitoring of
polyfluoroaklyl
substances: A Review.
Envronmental Science
and Technology 40:
3463-3473.
 DRBC

South North

Perfluoroundecanoic acid (PFUdA) in water and fish tissue in the lower

Delaware River.
 Perfluorooctane sulfonate (PFOS) stain repellent and
nonstick cookware in wildlife

Species Geography Year Sample PFOS (ppb)

Bald eagle Midwestern USA 1990–93 plasma 2,200
Brandt's cormorant California, USA 1997 liver 970
Guillemot Baltic Sea 1997 egg 614
Carrion crow Tokyo Bay, Japan 2000 liver 464
Red-throated loon North Carolina, USA 1998 liver 861
Polar bear Sanikiluaq, Nunavut 2002 liver 3,100
Harbor seal Dutch Wadden Sea, Denmark 2002 muscle 2,725
Bottlenose dolphin Charleston, South Carolina, 2003 plasma 1,315
Common dolphin Mediterranean Sea, Italy 1998 liver 940
Mink Michigan, USA 2000–01 liver 59,500

Houde, M., JW Martin, RJ Letcher, KR Solomon, and DCG Muir. 2006 Biological
monitoring of polyfluoroaklyl substances: A Review. Environmental Science and
Technology 40: 3463-3473. https://en.wikipedia.org/wiki/Perfluorooctanesulfonic_acid
 Houde, M., JW Martin, RJ Letcher, KR Solomon, and DCG Muir. 2006 Biological
monitoring of polyfluoroaklyl substances: A Review. Environmental Science and
Technology 40: 3463-3473.

• PFOS in pregnant women associated with preeclampsia.

• PFOS associated with altered thyroid hormone and higher cholesterol in adults..
PFOS in US children aged 12–15 associated with attention deficit hyperactivity
disorder (ADHD).
• Infants get it from breast milk. https://en.wikipedia.org/wiki/Perfluorooctanesulfonic_acid
 Cancer incidence and mortality of US
National residents, ages 0 to 20
Cancer 20

18
US childhood cancer incidence rate
Institute y = 0.1079x - 199.27
Number per 100,000 per year
http://seer.cancer.gov/csr/1975_20
16 R² = 0.7448
12/browse_csr.php?sectionSEL=28

&pageSEL=sect_28_table.03.html
14

12

10

6
US childhood cancer mortality rate
4

2
y = -0.0698x + 142.43
0 R² = 0.918

1970 1980 1990 2000 2010 2020

 Summary
1. Since the clean water act of 1972 and the work of the Delaware
River Basin Commission (1961), American waters are much
less polluted with organic matter and have higher dissolved
oxygen levels.
2. Wastewater treatment plants are designed to protect receiving
waters from oxygen depletion and pathogens, not PPCPs
hormones, flame retardants, detergents, or plasticizers.
3. We use a very large and growing set of chemicals, many of which
pass through WWTPs.
4. Most chemicals are not monitored or regulated.
5. A long and growing list of chemicals have been found in rivers,
lakes, groundwater, finished drinking water in the US and around
the world and in wildlife and people.
6. Regulations and treatment are not keeping up with the ever
increasing use of chemicals.
7. Wildlife effects have been documented, effects on humans are
suspected.