Sr. Environmental Soil Scientist
EM&R Department
Metropolitan Water Reclamation District of Greater Chicago

 What are they?
–
Compounds that alter the function s of Endocrine System and consequently cause adverse health effects in intact organism, its progeny or populations.

How may it happen?
OH
HO

 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.


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, 17 αethynilestradiol), testosterone

Surfactants – nonylphenol and its ethoxylates

Pesticides – DDT, atrazine, methoxychlor, dieldrin, etc.

Dioxins, PAHs, PCBs, PBDEs, PFCs, etc.

Bisphenol A, phthalates, musks, etc.

• Pharmaceuticals
• Personal care products
• Consumer products
• Food
• Waste incineration
• Industrial chemicals
• Farming, livestock, & forestry
• Household sewage
Not So Common!
Phthalates
PFCs, Musks
TCC, TCS
Common Sources!
PBDEs
Dioxins
Flavonoids
Steroids
Pesticides
Bisphenol A
Surfactants, 4-NP

800
700
600
500
400
Worldwide Sales
Year
Market Share
9%
17%
31%
43%
Source: Statistics 2008, VFA
VFA is the trade organization of research-based pharmaceutical companies in Germany
USA
Europe
Japan
Other

•
Direct-to-consumer advertising (DTCA)
•
Only legal in US and New Zealand
•
$2.20 earnings for every $1 spent on DTCA
32,000
24,000
16,000
Direct-toconsumer
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.”


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 >Billions >Millions
(ppt) (ppb) (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.

Not to scale

•
BFRs –
PBDEs, TBBPA, etc.
•
Plasticizers –
Bisphenol A (BPA)
•
PPCPs –
Antibiotics
(tetracyclines, ciprofloxacin, etc.)
–
Antimicrobial s
(TCS and TCC)
–
Musks and fragrances
(AHTN and galaxolide)
•
Steroids –
Hormones
(17 α-ethynilestradiol, 17β-estradiol, etc.)
•
PFCs –
PFOA and PFOS








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


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.


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)



Found in polyurethane foam, furniture, electronics, toys, etc.
Ubiquitous in the environment
Common sources of PBDEs
House dust , 0.3-36 µg/g (ppm)



Concentrations in biosolids,
0.1-2 µg/g – below levels of concern for human health
Log
KOW
= 6.53-6.71
Degradation is slow in soil (half-life ~10 years) – not expected to be mobile in biosolids-amended soil

0.8
Levels of total PBDEs in soil profile after
33 years of continuous biosolids application
0.6
0.4
0.2
24-48"
12-24"
6-12"
0-6"
0.0
0 554 1109 2218
Cumulative Biosolids Loading, Mg/ha


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

 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 10 6 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


4-NP input 4-NP output
61% from influent
39% produced in
WWTP
6%

NPnEOs
R O
H H
C C OH
H H n (4-20)
H H
R O C C O CH
2
COOH
H H n (0, 1)
NP1EC, NP2EC
R
H
O C
H
C OH
H H n (1, 2)
NP1EO, NP2EO
R OH 4-Nonylphenol (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
12.0
10.0
8.0
6.0
4.0
24-48"
12-24"
6-12"
0-6"
2.0
0.0
0 554 1109 2218
Cumulative Biosolids Loading, Mg/ha


Plasticizer - plastics (PVC, etc.), cosmetics, medical products (bags, tubing, etc.)
What’s Up Down There!

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 Phthalates alter boys’ genitals!
Reduce anogenital distance (AGD)

Degrades relatively easily in soil (halflife ranges from 20-25 days) – not expected to be stable and mobile in biosolids-amended soil AGD = Distance between penile and anal openings


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,
Log
Kow
= 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
1800
1500
1200
900
600
300
24-48"
6-12"
0-6"
0
0 554 1109 2218
Cumulative Biosolids Loading, Mg/ha
TCS
100
80
60
24-48"
6-12"
0-6"
40
20
0
0 554 1109 2218
Cumulative Biosolids Loading, Mg/ha


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


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




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

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 ~10-10 6 times less potent than the natural estrogen, 17  -estradiol

 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

hundall@mwrd.org
(708) 588-4201