INDEX

I. Oxybenzone Structure / Characteristics

a. Properties

b. Prevalence

c. How it works

II. Effects Overview

a. Endocrine Disruptor

b. Affects Everything and everyone

c. Ubiquitous toxicant

i. Absorbed in skin

ii. Found in 97% of Americans

d. Photo-Allergen

e. Photo-toxicant (especially UV)

III. The Flow of Oxybenzone

a. Manufactured for mainly sunscreen products

b. Consumption / Human Application

c. A) factory runoff B) Your runoff in ocean or shower

d. WWTP

e. Back into water system

f. Fish

g. Humans

h. THE CLOSED LOOP

i. BIOACCUMULATION

j. BIOMAGNIFICATION

IV. Oxybenzone Effects by Category

a. Universal

b. Humans

c. Mammals (ex dolphin)

d. Marine vertebrates (ex fish)

e. Marine invertebrates (ex sea urchin)

f. Coral

g. Algae

V. Oxybenzone Toxicity Levels

a. Observed Concentrations

VI. Toxic By-Products

a. BP-1

b. Reaction with Chlorine

VIII. Relative to PABA

IV. Safe Alternatives

a. Non-nano Zinc oxide & Titanium dioxide

b. The relative efficacy vs toxicity of oxybenzone

V. Conclusions

Oxybenzone Overview

Ubiquitous environmental contaminant
Insoluble in water
Photostable
Bioaccumulative
Rapidly absorbed via oral and dermal routes
Found in 97% of Americans
Phototoxic
ENDOCRINE DISRUPTOR - mimics the hormone estrogen
Uses: primarily sunscreen; volumes up to 10%

Oxybenzone is a notorious endocrine disruptor, voraciously spreading toxicity throughout waterways of the world.

THE PROBLEM:

OXYBENZONE IS BECOMING MORE HEAVILY USED, AND MORE HEAVILY TOXIC TO ENVIRONMENT AND US.

Oxybenzone is in nearly every waterway and in nearly everyone and it’s toxic to nearly everything it touches.

For over a decade, oxybenzone has been proven to be toxic to humans, corals, and other marine life, yet companies continue to put it in more than 3,500 skincare products worldwide. [i]

SUNSCREEN USE IS INCREASING, LEVELS OF OXYBENZONE ALONG WITH IT. WE NEED TO STOP THIS TOXICITY FROM DISRUPTING EVERYTHING

Oxybenzone, also known as benzophenone-3 (BP-3), is an aromatic hydrocarbon most commonly used as a chemical UV absorber in sunscreens (has been available since the 1980’s).

Zhao H, Wei D, Li M, Du Y (2013) Substituent contribution to the genotoxicity of benzophenone-type UV filters. Ecotoxicol Environ Saf 95:241–246

Oxybenzone Overview

Peak absorption:

Short-wave UVB (290-320 nm) &

Short-wave UVA (320-340 nm)

Levels of use permitted in sunscreens:

Up to 6% in US

Up to 10% in EU and elsewhere

Up to 0.5% in personal care products

Molecular weight: 228.26 Daltons (<500 Daltons is the general contact allergen weight) [i]

INSOLUBLE IN WATER + VERY PHOTO STABLE

= BAD COMBINATION

1990: Added to the High Production Volume Challenge Program for manufacturing in or importing to the US chemicals more than 1 million pounds per year

Insoluble in Water

Very Photostable

[i] Bos JD, Meinardi MMHM. The 500 Dalton rule for the skin penetration

of chemical compounds and drugs. Exp Dermatol. 2000;9:165-169.

ENDOCRINE DISRUPTOR

Endocrine disruptor definition:

It’s also widely incorporated into: (Based on an allergy handout given by a doctor if one has allergies to oxybenzone (16-25% of the population does)[i]

[i] Oxybenzone Contact Allergan Sheet

USES

Widely Incorporated Into:

· Makeups

· Sunscreens

· Lip balms

· Hair products

· Plastics

· Textiles

· Added to some perfumes for its rose-like scent

Other Names / Trade Names:

· Benzophenone-3 (BP-3)

· 2-hydroxy-4-methoxy-benzophenone

· 2-benzoyl-5-methoxyphenol

· Eusolex 4360

· Escalol 567

· Cyasorb UV9

Where Might It Be Found?

· Sunscreen

· Moisturizer, cream, lotion

· Bath or body oil

· Shampoo, conditioner

· Hair gel, mousse, hair spray

· After-shave

· Make-up foundation, concealer

· Lipstick, lip gloss

· Nail polish

· Perfume, cologne

Some Industrial Uses of Oxybenzone:

· Color preserver in paints and varnishes

· Color retainer in fluorescent lacquers

· Protection against fading in textiles and plastics

· Color preserver in dental composite fillings

· Product for drug, dye, pesticide manufacture

· “Oxybenzone is a photo-toxicant; adverse effects are exacerbated in the light. Whether in darkness or light, oxybenzone transformed planulae from a motile state to a deformed, sessile condition.” 4

· Oxybenzone is both bioaccumulated and biomagnified [i] [ii]

[i] Haereticus

Oxybenzone Unsuitable For Children 2006

Kim S, Choi K. Occurrences, toxicities, and ecological risks of ben- zophenone-3, a common component of organic sunscreen products: a mini-review. Environ Int. 2014;70:143-157 )

[ii] Gago-Ferrero et al (2012) An overview of UV-absorbing compounds (organic UV filters) in aquatic biota. Anal Bioanal Chem 404:2597-2610.

Universal Toxicity

· Universal toxicant – found everywhere – cannot be broken down by wastewater treatment or by living organisms (including us) – bioaccumulated and biomagnified.

· Developmental deformities

· Endocrine disruption

· Feminization

· Deformities in embryonic development of fish, sea urchins, coral, shrimp.

· Increase in reproductive diseases in marine invertebrate species (sea urchins), vertebrate species (fish like wrasses, eels, parrotfish), and mammals (like Hawaiian monk seal).

Toxic To:

· Humans

· Corals

· Fish

· Larvae

· Bird Eggs

· Marine Mammals

Oxybenzone threatens coral and the 25% of marine species that depend on coral.

Furthermore, it infects and bleaches them at temperatures lower than 87.9 F – the temperature it is considered “warming”

And threatens their ability to recover after climate change

Entering the Environment

UV filters have been found in water sources worldwide, with oxybenzone noted as the most frequently detected and in the largest concentrations. [i]

2 major sources of oxybenzone:

human recreational activities and
wastewater treatment plant (WWTP) effluents.

· *Oxybenzone cannot be broken down! Waste Water Treatment Plants (WWTPs) cannot remove oxybenzone!

· Point and non-point sewage and treated wastewater effluent discharges are the largest source of contamination.

o Sewage contamination – unable to remove oxybenzone via wastewater treatment.

o Discharged to ground and surface waters from cesspools, leaking septic systems, and municipal wastewater collection and treatment systems.

· Through wastewater effluent

o Produced by swimmers and municipal, residential, and boat/ship wastewater discharges 4

· Directly from swimmers wearing sunscreen (Gonzalez - around 4% of oxybenzone is absorbed percutaneously (under the skin), and the remaining 96% washes off into our waterways. (ex – shower – still goes to ocean)

[i] Cuderman P, Heath E. Dermination of UV filters and antimicrobial agents in environmental water samples. Anal Bioanal Chem. 2007,387(4):1343-1350.

In 1990, Oxybenzone added to the Environmental Protection Agency High Production Volume Challenge Program, which identifies ingredient manufactured or imported into the United States in amounts greater than one million pounds per year [i]

[i] DiNardo JC, Downs CA. Dermatological and environmental toxicological impact of the sunscreen ingredient oxybenzone/benzophenone-3. Journal of Cosmetic Dermatology. 2018; 17:15-19.

The Flow Of Oxybenzone

Production —> Human Use —> Sewage / Wastewater Treatment —> Back into Ocean —> Into Fish —> Back into our mouths via dinner

Found In

EVERYWHERE

· Ubiquitous phototoxicant – doesn’t break down – remains and travels up food chain.

· Swimming pools, hot tubs (very high concentrations)

o ALERT: OXYBENZONE REACTS WITH CHLORINE to produce far more toxic byproducts

· Water, soil, sediments, sludge, biota

· Streams

· Rivers

· Lakes

· Ocean

· Marine environments from the Arctic Circle (Barrow, Alaska) to the beaches and reefs along the equator.

· Drinking water (municipal treated and desalinated)

· *Near universal presence in humans (96.8%)

o Has the highest percutaneous absorption of all UV filters

o CDC Fourth National Report on Human Exposure – 96.8% people had it present in their urine.

· Urine

· Breast milk

· Beaches

· Waterways

· Marine mammals

· Bird eggs

· Fish, Fish Lipid, Fish Liver

· Coral

o Estimated 8,000 to 16,000 TONS of sunscreens enter coral reefs each year [i]

The Closed Loop

Humans —> Waterways —> Fish —> Humans

Absorbed by the skin —> excreted by urine (4%) —> enters the plumbing —> enters the water supply

What is not absorbed by the skin: washed off either in natural water sources or in shower —> all enter the water supply

Manufacturing and waste run-off produced from factories also places UV filters in the water supply.

Sewage is the biggest source of sunscreen UV filters anywhere. (Downs)

WASTEWATER TREATMENT PLANTS (WWTPS)

WWTPs are critical in the water recycling process. Water utilized by humans passes through these facilities for treatment before reentering rivers and streams.

Higher population density usually = higher levels of oxybenzone

WWTPs worldwide have been tested for UV filters in the influent (incoming water sources) and effluent (water that has been treated).

Waste Water Treatment Plants cannot filter oxybenzone, so it comes back to us via the fish we eat in the food chain.

THE ACCUMULATION OF OXYBENZONE

[Touches us (human runoff), becomes toxic to us, —>

gets into everything else (waterways, etc), —>

becomes toxic to everything else

*CLOSED LOOP

Travels up the food chain back to us

14,000 TONS of sunscreen enters the waters around our reefs every year

MORE OXYBENZONE IS FOUND…

Concentrations increase with heavier population densities and heavy tourist sites.

BIOACCUMULATION

BIOMAGNIFICATION

EFFECTS

OXYBENZONE IS A PHOTOALLERGEN [i]

*Exacerbated in heat and doesn’t break down.

In-vitro, oxybenzone has anti-androgenic and pro- and anti-estrogenic effects (Kim)

[Androgen: male sex hormone. // Estrogen: female sex hormone]

Oxybenzone Ecotoxicology

Oxybenzone and many of its metabolites are documented mutagens, especially when exposed to sunlight 26,27,28,29,30.

They can cause genotoxicity either from induction of photooxidative stress or adduction to DNA directly through bio-activation by cytochrome P450 enzymes 31,32,33.

Oxybenzone and other benzophenones can induce procarcinogenic activities by inducing cell proliferation in cancer cells lines that are receptive to estrogenic compounds 34,35,36.

[i] European Commission Health & Consumer Protection Directorate General. Opinion on benzophenone-3. COLIPA N° S38. 19 December 2006. Opinion adopted by the SCCP during the 10th plenary of 19 December 2006

Recent studies have also documented that oxybenzone increases metastasis potential (cellular proliferation and migration) via a nonestrogenic mechanism 37,38.

Oxybenzone is a photo-toxicant, especially in the presence of ultraviolet light.

This means that the greater the light intensity, especially in the UV and near-UV spectrum, new forms of toxicity manifest, and usually in a dose-dependent manner of both oxybenzone and light.

Oxybenzone is a photo-toxicant – adverse effects are exacerbated in light

(Kim, Choi) BP-3 is transformed into 3 major metabolites:

1. Benzophenone-1 (BP-1)

a. Longer half-life than BP-3 and exhibits greater estrogenic potency

2. Benzophenone-8 (BP-8)

3. 2,3,4-trihydroxybenzophenone (THB)

ENDOCRINE DISRUPTION

OXYBENZONE IS A NOTORIOUS ENDOCRINE DISRUPTOR

What is endocrine disruption?

Based on a receptor binding assay, BP-3 has shown strong anti-androgenic and weak estrogenic activities as well as anti-estrogenic activity. (Kim, Choi 2014) ^ ;;;

Predicted no effect concentration (PNEC) for BP-3 was derived at 1.32 ug/L.

- The levels observed in ambient water are generally lower than PNEC, but

- In wastewater influents, hazard quotients (HQs) greater than 1 were noted.

Oxybenzone and Humans – A Clearer Picture

REACTIVITY

- Reactions in 16-25% of patients

OXYBENZONE AND OUR ENVIRONMENT

OXYBENZONE AND CHLORINE

Key point: you’re not looking for the levels needed for fully bleaching coral – even threatening them is enough.

WE HAVE BETTER ALTERNATIVES.

Major effects on coral

90% of snorkeling/diving sites occur on 10% of the world’s reefs.

(4 major effects according to [i]

· Increased susceptibility to bleaching

· DNA damage

· Abnormal skeleton growth (via endocrine disruption)

· Gross deformities of baby coral

This means 10% of global reefs and 40% of coastal reefs are at risk of bleaching.

Increased rates of bleaching are completely correlated with increased rates of oxybenzone. —> CAUSATION.

Even at the lowest concentrations (10 parts per billion)

· Viruses released

· In light: oxybenzone caused injury directly to zooxanthellae

· In dark: coral digests zooxanthellae

Results to Coral (based on Archives of Environmental Contamination and Toxicology (4))

· Planulae exhibited an increasing rate of coral bleaching in response to increasing concentrations of oxybenzone.

· Oxybenzone is a genotoxicant to corals, exhibiting a positive relationship between DNA-AP lesions and increasing oxybenzone concentrations.

· Oxybenzone is a skeletal endocrine disruptor; it induced ossification of the planula, encasing the entire planula in its own skeleton.

[i] https://oceanservice.noaa.gov/news/nov15/sunscreen-corals.html

[Olympic swimming pool holds

2.5 million liters of water]

* Trunk Bay

· Minimum of 2,000 swimmers per day (up to 5,000, but we’ll be conservative)

· Assuming 36 grams of sunscreen every 2 hours (or calculating for twice as many people with 1 application) for a 4 hour visit = 72 grams per person per visit

· This means 72 grams x 2,000 people = 144 kilograms of sunscreen into Trunk Bay on an average day

· Assuming an average 8% oxybenzone concentration in sunscreens, that means 144 kg * 0.08 = 8.6 kg oxybenzone into Trunk Bay on an average day

· = 260 kg oxybenzone per month (570 pounds per month)

· = 3,139 kilograms of oxybenzone per year or 6,920 pounds per year.

· For 3 sample sites, levels of oxybenzone found were:

o 1,395 pp billion

o 580 pp billion

o 98 pp billion (farther from beach)

WHAT TO USE INSTEAD

THERE ARE FAR BETTER ALTERNATIVES

Oxybenzone: Attenuation in NM: 290-370

Peak absorption: 290-300 and 325-340

UVB: Test on 10 human subjects

UVA: Analytic (in vitro) à must have critical wavelengths > 370 nm (represents 90% of total area under the curve in UV region)

Only 5 Ingredients Qualify:

1. Zinc oxide

2. Titanium Dioxide

3. Avobenzone

4. Oxybenzone (tied for last)

5. Octocrylene

Average annual adults treated for skin cancer

2002-2006: 3.4 million people Annual cost $3.6 billion

2007-2011: 4.9 million people Annual cost $8.1 billion (126.2% increase)

THE SUNSCREEN ARGUMENT

PABA

- Reactivity rates vs paba

Key Note: Compared to PABA which was BANNED so quickly (much less harmful than oxybenzone)

THERE IS NO REASON TO CONTINUE TO USE OXYBENZONE.

YOU ARE JUST NEGLIGENT AT THAT POINT

REFERENCES

[1] NOAA – Sunscreen, Corals https://oceanservice.noaa.gov/news/nov15/sunscreen-corals.html

Zhao H, Wei D, Li M, Du Y (2013) Substituent contribution to the genotoxicity of benzophenone-type UV filters. Ecotoxicol Environ Saf 95:241–246

[1] Bos JD, Meinardi MMHM. The 500 Dalton rule for the skin penetration

of chemical compounds and drugs. Exp Dermatol. 2000;9:165-169.

[1] Oxybenzone Contact Allergan Sheet

[1] Haereticus

Oxybenzone Unsuitable For Children 2006

Kim S, Choi K. Occurrences, toxicities, and ecological risks of ben- zophenone-3, a common component of organic sunscreen products: a mini-review. Environ Int. 2014;70:143-157 )

[1] Gago-Ferrero et al (2012) An overview of UV-absorbing compounds (organic UV filters) in aquatic biota. Anal Bioanal Chem 404:2597-2610.

[1] Cuderman P, Heath E. Dermination of UV filters and antimicrobial agents in environmental water samples. Anal Bioanal Chem. 2007,387(4):1343-1350.

[1] DiNardo JC, Downs CA. Dermatological and environmental toxicological impact of the sunscreen ingredient oxybenzone/benzophenone-3. Journal of Cosmetic Derrmatology. 2018; 17:15-19.

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[1] https://oceanservice.noaa.gov/news/nov15/sunscreen-corals.html

[1] Hawaii Bill SB 2571

[1] HEAERETICUS

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