Transcript Occurrence and Fate of EDCs In Biosolids and Biosolids

Protecting Our Water Environment
Metropolitan Water
Water Reclamation
Reclamation District
Metropolitan
District of
of Greater
Greater Chicago
Chicago
Occurrence And Fate Of EDCs In
Biosolids And Biosolids–Amended
Soils – An Overview
Dr. Lakhwinder Hundal
Sr. Environmental Soil Scientist
EM&R Department
Metropolitan Water Reclamation District of Greater Chicago
Endocrine Disrupting Compounds

What are they?
– Compounds that alter the functions of Endocrine System
and consequently cause adverse health effects in intact
organism, its progeny or populations.

How may it happen?
OH
HO
HO
Recent Concerns!
 Concerns raised regarding the presence of
“emerging organic contaminants” or “endocrine
disrupting compounds” in biosolids.
 Majority of these so called endocrine disrupting
compounds (EDCs) are basically “everyday
domestic use chemicals”.
 These compounds enter the environment mainly
via regular or everyday domestic use and routine
activities.
Universe of EDCs
EPA plans to screen ~87,000 chemicals for EDC effect
 75,500 industrial chemicals
 3,100 agriculture related chemicals
 8,000 cosmetics, food additives, and supplements

Examples of Common EDCs
 Steroids – estrogens (17-estradiol, 17αethynilestradiol), testosterone
 Surfactants – nonylphenol and its ethoxylates
 Pesticides – DDT, atrazine, methoxychlor, dieldrin, etc.
 Dioxins, PAHs, PCBs, PBDEs, PFCs, etc.
 Bisphenol A, phthalates, musks, etc.
EDCs, Where Do They Come From?
• Pharmaceuticals
• Personal care products
• Consumer products
• Food
• Waste incineration
• Industrial chemicals
• Farming, livestock, &
forestry
• Household sewage
Common Sources!
Phthalates
PFCs, Musks
TCC, TCS
Dioxins
Steroids
Flavonoids
PBDEs
Pesticides
Not So Common!
Surfactants, 4-NP
Bisphenol A
Pharmaceutical Production and Use
Worldwide Sales
Market Share
US $ (Billion)
800
17%
700
9%
600
43%
31%
500
400
Year
Source: Statistics 2008, VFA
VFA is the trade organization of research-based pharmaceutical companies in Germany
USA
Europe
Japan
Other
Power of Advertising
• Direct-to-consumer advertising (DTCA)
• Only legal in US and New Zealand
• $2.20 earnings for every $1 spent on DTCA
Annual Spending
(millions of US $)
32,000
24,000
Direct-toconsumer
16,000
Profesional
Promotion
8,000
0
Year
Source: Donohue et al., 2007. The New England Journal of Medicine
“The red are for the
illness, the blues are for
the side effects of the red
and the greens are for the
side effects of the blue.”
Why Now?

Recent advances in analytical chemistry have enabled study of
chemicals that were previously undetected in the environment.

The advent of LC-MS, especially LC-tandem MS has
revolutionized the environmental analysis with ppt (ng/L) level
detection of polar compounds in water samples.
Trillions
(ppt)
>Billions
(ppb)
>Millions
(ppm)

Recent studies are largely focused on survey or monitoring
(chemical occurrence/exposure effects) with majority of data
on occurrence and effects based on aquatic systems.

These publications are attracting growing attention from
regulatory agencies, environmental advocates, news media and
the public.
Land Application of Biosolids
Not to scale
2010 State-Of-The-Science Review –
(Funded by WERF)
• BFRs – PBDEs, TBBPA, etc.
• Plasticizers – Bisphenol A (BPA)
• PPCPs – Antibiotics (tetracyclines, ciprofloxacin, etc.)
– Antimicrobials (TCS and TCC)
– Musks and fragrances (AHTN and galaxolide)
• Steroids – Hormones (17α-ethynilestradiol, 17β-estradiol, etc.)
• PFCs – PFOA and PFOS
Pesticides – DDT (1874 – 1972)







One of the most effective
pesticides
Saved lives
Increased food production
Ubiquitous in the environment
House dust = 0.3-9.6 µg/g
Trace concentrations in biosolids,
<0.01 µg/g
Not an issue in land applied biosolids
PAHs (BaP) and PCBs
PCBs banned in 1977

PCBs used as coolants and insulating fluids; were used in
plastics, carbonless copy paper, wood floor finishes, etc.

PAHs produced by incomplete
burning of C-containing materials

Ubiquitous in the environment

Concentrations in biosolids –
Coal burning power plant
BaP = 1.5-4.0 µg/g; PCBs = 0.6-1.6 µg/g
House dust, PCBs = 0.2-70 µg/g BaP = 0.4-18 µg/g

Degradation is slow in soil (half-life of PAHs =
~24-570 days; PCBs = 940 days) – not expected to be
mobile in biosolids-amended soil.
Dioxins

2,3,7,7-tetrachlorodibenzo-p-dioxin (TCDD) – the
most toxic compound ever known

Ubiquitous in the environment

Trace levels in biosolids – declining trend

After 5 years of study, Screening
Ecological Risk Analysis, and
outside peer review, EPA concluded
that “dioxins in land applied biosolids
do not pose a significant risk to human
or environmental health”.

Dioxins disrupt birth ratio:
More girls than boys !
Long-term biosolids land application data collected
from the Fulton County supported EPA’s decision.
(Hundal et al., 2008, JEQ)
Flame Retardants – PBDEs

Found in polyurethane foam, furniture,
electronics, toys, etc.

Ubiquitous in the environment
House dust, 0.3-36 µg/g (ppm)

Common sources of PBDEs
Concentrations in biosolids,
0.1-2 µg/g – below levels of
concern for human health

LogKOW = 6.53-6.71

Degradation is slow in soil (half-life ~10
years) – not expected to be mobile in
biosolids-amended soil
Levels of total PBDEs
in soil profile after
33 years of
continuous biosolids
application
PBDEs Conc., µg/g
Fate of PBDEs in Biosolids-Amended Soil
0.8
24-48"
12-24"
0.6
6-12"
0-6"
0.4
0.2
0.0
0
554
1109
2218
Cumulative Biosolids Loading, Mg/ha
Bisphenol A (BPA)

Polycarbonates, epoxy resins,
polystyrene cups, baby bottles,
yogurt containers, etc.

Ubiquitous in the environment

Estrogenic effect known since 1936

Levels in biosolids – 0.03-36 µg/g;
House dust – 0.2-17 µg/g
(Rudel et al., 2003, ES&T 37:4583-4553)

Degrades relatively easily in soil
(half-life ranges from 1-10 days) –
not mobile in biosolids-amended soil.
Plastic bottles and hot
liquids – A bad combo
Surfactants – Nonylphenol (NP)

Alkylphenol ethoxylates used in detergents, spermicidal
lubricant; as emulsifiers in pesticides, paints; etc.

Degradation product 4-NP has estrogenic effect

Estrogenic effect of NP is known since 1938

Estrogenicity of NP is 106 times lower than 17-estradiol, a
natural female hormone

NP is 10 times less potent than genistein, an isofalavonoid
found in soybeans – 3 mg/kg

EU banned production and use

NP partitions into biosolids during the wastewater
treatment process
WWTP May Generate 4-NP
 Mass
balance for 4-NP in a WWTP
4-NP input
4-NP output
61%
from influent
6%
39%
produced in
WWTP
WWTP May Generate 4-NP
H H
NPnEOs
R
O C C OH
H H n (4-20)
H H
R
O C C O CH2 COOH R
H H
H H
n (0, 1)
NP1EC, NP2EC
R
H H
O C C OH
n (1, 2)
NP1EO, NP2EO
OH
4-Nonylphenol (4-NP)
Surfactants – 4-NP

Concentration in biosolids, 600-800 µg/g;
House dust = 0.02-85 µg/g
Degrades rapidly in soil, half-life = 3-30 days

Not stable or mobile in biosolids-amended soil
Levels of 4-NP in
soil profile after 33
years of continuous
biosolids application
4-NP Conc., µg/g

12.0
24-48"
10.0
12-24"
6-12"
0-6"
8.0
6.0
4.0
2.0
0.0
0
554
1109
2218
Cumulative Biosolids Loading, Mg/ha
Phthalates – DEHP, DBP, …

Plasticizer - plastics (PVC, etc.),
cosmetics, medical products (bags,
tubing, etc.)

Ubiquitous in the environment

Levels in biosolids – 0.1-200 µg/g
House dust, DEHP = 16-7700 µg/g
DBP = 3.9-1310 µg/g

Degrades relatively easily in soil (halflife ranges from 20-25 days) – not
expected to be stable and mobile in
biosolids-amended soil
What’s Up Down There!
Phthalates alter boys’ genitals!
Reduce anogenital distance (AGD)
AGD = Distance between penile
and anal openings
Antimicrobials – TCC, TCS

Used in toothpastes, mouthwash, hand
soaps, creams, detergents, etc.

Introduced TCC in 1957, TCS in 1964

No benefits from use to consumer

Preferably partition into biosolids,
LogKow = 4.8

Detected in biosolids
TCC = 20-50 µg/g; TCS = 5-30 µg/g

Half-life in soil, TCS = ~18-30 days,
TCC = 108-540 days – TCS is not
expected to be mobile in biosolidsamended soil but TCC may persist longer.
TCC 5% by weight
TCC and TCS Concentration in Soil after
33 Years of Biosolids Application
TCS
TCC
1800
1200
900
600
300
0
0
554
24-48"
6-12"
0-6"
80
TCS Conc., µg/kg
1500
TCC Conc., µg/kg
100
24-48"
6-12"
0-6"
1109
2218
Cumulative Biosolids Loading, Mg/ha
60
40
20
0
0
554
1109
2218
Cumulative Biosolids Loading, Mg/ha
Steroids

Natural – testosterone, 17-estradiol


Degrade rapidly during activated sludge
process
Synthetic – 17-ethinylestradiol




Degrades slowly during activated sludge
process and partitions into biosolids
Traces could be found in biosolids
Degrades rapidly in agricultural soil
(half-life ranges from 1-10 days)
Mobility is not a serious concern
Musks – AHTN, HHCB, …

Synthetic musks and fragrances are used in
formulations of body-care products, soaps,
detergents, and cleaners

Ubiquitous in the environment

Levels in biosolids – AHTN = ND-51 µg/g
HHCB = ND-86 µg/g
Levels in house dust – AHTN = 0.1-16 µg/g
HHCB = 1.9-81 µg/g

HHCB degrades in soil quite rapidly but AHTN
degrades slowly but it is not expected to be highly
mobile in biosolids-amended soils
PFCs – PFOA, PFOS, …

Used in nonstick cookware, stain resistant sofa,
carpets, food packaging (candy wrappers, pizza
boxes, etc.), personal care and cleaning
products, electrical goods, etc.

Ubiquitous in the environment

Levels in biosolids – PFOA = ND-4,780 ng/g
PFOS = ND-5,383 ng/g
Levels in house dust – PFOA = 10.2-1,960 ng/g
PFOS = 8.9-12,100 ng/g

PFOA and PFOS do not seem to degrade in soil,
degradation of other PFCs produce PFOA and
PFOS – mobile in biosolids-amended soils
What can you do!
Act, don’t react
 Reduce indiscriminate use of
chemicals
– Prevent release of toxic pollutants in
the environment
– Prevention is easier and lot cheaper
Reality
 EDCs (esp. estrogens) were, are, and will
always be with us
– phytoestrogens and naturally released
estrogens by females (human and animals)
– Most of the anthropogenic contaminants that
exhibit estrogenic effect are ~10-106 times less
potent than the natural estrogen, 17-estradiol
Peeking At The Future
New Generation Drugs
Antisense
Drug
Cholesterol lowering drug – Mipomersen
 Designed to target mRNA that controls disease causing
protein
 Based on single stranded oligonucleotides resembling
DNA & RNA

Incretin
Mimetics
Type 2 diabetes drug – Exenatide
 Mimics incretin hormone GL-1 produced by endocrine
cells

Questions
[email protected]
(708) 588-4201
What Does It Mean?
Something Public Can Relate To