Nanoparticles to Remove Coral Bleaching Oxybenzone

Sunblocks contain a number of different compounds including oxybenzone which acts as a UV filter. The skeletal structural formula of oxybenzone is shown below:

Oxybenzone is soluble in water.
Before you go snorkeling in the Great Barrier Reef to be amazed by the beautiful corals, fascinating fish and other exciting wonders, you smother yourself in sunblock. When you step into the water, the oxybenzone starts to dissolve. Unfortunately, oxybenzone contributes to coral bleaching, the killing off of the tiny, colourful zooxanthellae marine algae that live inside corals. The result is that the coral loses its colour and appears white, as if it has been bleached.

Researchers have found a way to soak up the oxybenzone from the seawater using magnetite nanoparticles.

Magnetite, Fe₃O₄ , is a mineral made up of iron(II) and iron(III) oxides and is one of the main iron ores, that is, magnetite is mined in order to produce iron. Magnetite is ferromagnetic, that is, it is attracted to a magnet. It is the most magnetic naturally occurring mineral on Earth. If you could get the oxybenzone in the seawater to attach to magnetite nanoparticles then you could pull the oxybenzone out of the water using a magnet.

First, the researchers coated the magnetite nanoparticles with sodium oleate. The skeletal structural formula of sodium oleate is shown below:

Next, they oxidised the oleate coating to increase the number of hydroxyl (OH) functional groups:

Since oxybenzone can interact with other molecules via hydrogen bonds, magnetite nanoparticles  covered in a coating rich with hydroxyl functional groups increases the interactions between oxybenzone and the nanoparticles. Once the oxybenzone has hydrogen bonded to the nanoparticle coating, a magnet can be used to extract the particles from water.

Does it work?
One brave researcher applied sunblock, stepped into the ocean, waited 10 minutes, then collected a sample of the surrounding seawater. Back at the lab, chromatography was used to determine the concentration of oxybenzone in the water, 1.3 ppm. This is a disturbing result since it is known that the concentration needed to bleach coral is measured in parts per billion.
Next, the researchers prepared seawater samples. Some had no magnetite nanoparticles added, others had the nanoparticles added. Then they added 30 ppm oxybenzone to  all the samples. The concentration of oxybenzone in the samples with no nanoparticles did not change in an hour. In the samples that contained the nanoparticles, 95% of the  oxybenzone  was removed within the hour.

Reference
American Chemical Society. "Sopping up sunblock from oceans to save coral reefs." ScienceDaily. ScienceDaily, 21 August 2017.

Further Reading
Solutions Concepts
Water as a Solvent
Transition Metals (magnetism)
Fatty Acids
Carboxylic Acids
Nanoparticles and Nanotechnology
Parts per Million (ppm)
Chromatography
Experimental Design
Variables
2-Dimensional Structural Formula
Skeletal Structural Formula
Molecular Formula

Suggested Study Questions

1. For a molecule of oxybenzone:
• draw the 2-dimensional structural formula
• give the molecular formula
2. On the 2-dimensional structural formula of oxybenzone identify and name each functional group present.
3. Use diagrams to explain why oxybenzone is soluble in water.
4. Draw the 2-dimensional structural formula for oleic acid.
5. On your structural formula of oleic acid, identify and name the functional group(s).
6. Suggest a method by which you could change oleic acid into sodium oleate in the laboratory.
7. Suggest a method by which you could oxidise sodium oleate in the laboratory.
8. Explain the term "nanoparticle".
9. Why do you think the researchers chose nanoparticles of magnetite rather than bulk magnetite for this research?
10. Consider the description of the experiment used to determine the effectiveness of the magnetite nanoparticles in removing oxybenzone from seawater:
• What was the hypothesis being tested?
• What was the aim of the experiment?
• What variables need to be considered in this experiment?
• What is the independent variable in the experiment?
• What is the dependent variable in the experiment?
• Which variables are constant variables in the experiment?
• Why did the experimenters add nanoparticles to some samples but not to others?
• Write out a suitable method for this experiment.

Coral Killing Sunscreens

More than a year ago, a study involving marine scientists from Virginia, Florida, Israel, the US National Aquarium and the US National Oceanic and Atmospheric Administration, identified a common chemical component of sunscreens capable of damaging coral reefs.
This chemical is commonly known as oxybenzone and its structure is shown below:

This molecule has the systematic IUPAC name of (2-hydroxy-4-methoxyphenyl)(phenyl)methanone
Notice how every carbon atom (except that of the terminal methyl group, the carbon atom of the methoxy group) is involved in a double bond?
This kind of arrangement leads to some interesting properties. One of these properties is that molecules like this one are good at absorbing UV light. So, oxybenzone is added to products such as plastics, sunscreens, hairsprays, nail varnish and cosmetics like lipstick and mascara, as a UV filter.
Sunscreen lotion can contain between 1 and 10% oxybenzone.
Unfortunately, oxybenzone enters the water when people wearing sunscreens or other cosmetics decide to go for a swim. Researchers estimate that between 6,000 and 14,000 tonnes of sunscreen lotion are emitted into the waters of coral reefs each year.
The same property that makes it ideal as a sunscreen makes it a catastrophe for our coral reefs! Blocking UV light to baby corals causes growth deformities, and worse, the coral becomes encased in its own skeleton and dies.
In 2016, a study of Hawaii's sea waters found the oxybenzone concentration ranged from 0.8 to 19.2 µg/L. A previous study found that oxybenzone concentrations as low as 0.062 µg/L could harm the coral.
Hawaii's government asked swimmers, surfers and divers to avoid using sunscreens that contain oxybenzone as a measure towards protecting their reef.

Reference:
Hawaii targets sunscreens with oxybenzone 

Suggested Study Questions:

1. Draw a molecule of oxybenzone, and, locate and name each functional group. 
2. Give the molecular formula for oxybenzone.
3. Calculate the molar mass of oxybenzone.
4. Draw the 2-dimensional structural formula for oxybenzone.
5. Oxybenzone readily dissolves in ethanol. Explain how oxybenzone can dissolve in ethanol.
6. Oxybenzone does not dissolve in water. Explain why oxybenzone dissolves in ethanol but not in water.
7. Given the data in the article, calculate the mass of oxybenzone that could be emitted into coral reef waters each year.
8. Convert the following concentrations of oxybenzone to concentrations in parts per million
   • 0.062 µg/L
   • 0.8 µg/L
   • 19.2 µg/L
9. Convert the following concentrations of oxybenzone to concentrations in moles per litre (molarity)
   • 0.062 µg/L
   • 0.8 µg/L
   • 19.2 µg/L
10. Assume a 375 g tube of sunscreen lotion contains 10% by mass oxybenzone. Use the data in the article to calculate an "average" number of tubes of sunscreen that washed into the ocean each year. Justify your answer.