Author Archives: jennifer liu

Efficient Removal of Heavy Metal Ions from Water by Nanoporous Thin Films

The term heavy metal refers to any metallic chemical element that is toxic or poisonous at low concentrations. The most common heavy metals include mercury (Hg), arsenic (As), chromium (Cr), cadmium (Cd) and lead (Pb).

Heavy metals are natural components of Earth’s crust. They are non-degradable. They enter our bodies via food, drinking water and air. At very low concentrations, some heavy metals, such as copper and zinc, are essential to maintain the metabolism of the human body. However, at higher concentrations they can cause poisoning and put our lives at risk. For example, high levels of lead (II) cations can hinder brain development in children who drink from contaminated sources and cause organ damage to people of all ages. Similarly, water supplies contaminated with cadmium (II) cations cause the weakening of bones and damage our kidneys and livers.

Heavy metals are dangerous because they tend to bioaccumulate. In other words, their concentrations increase in our bodies over time. They are stored faster than they are broken down or excreted.

Heavy metals can enter a water supply by industrial and consumer waste, or from acidic rain breaking down soils and releasing heavy metals into streams, groundwater and other water sources.

In order to remove the heavy metals from our water supplies, Weidman and co-workers functionalized nanoporous thin films of poly(acrylic acid) (PAA) with glutathione and cysteamine. Glutathione and cysteamine are peptides that exist in many organisms to counter the accumulation of heavy metal ions. For example, glutathione, which is found in many plants and animals, can bind to the metal ions and remove the ions from transport pathways within the organism.

Coupling glutathione to PI−PS−PAA films can remove over 93% of heavy metal ions for drinkable water. (Source: Weidman et al., 2017)

Unlike the conventional packed bed processes, which require long residence times for effective removal of heavy metals; the nanoporous films have a lot of built-in functional groups, which allow the coupling of glutathione and cysteamine to the groups. The ready attachment of glutathione and cysteamine to the films enable efficient removal of toxic heavy metals from water supplies.

The thin films were tested with cadmium (Cd2+) and lead (Pb2+) ions. Results showed that the films could remove over 93% of the heavy metal ions. Furthermore, in mixed ion solutions, the capacity and removal rates of the films did not reduce. After repeatedly regenerating the films, the films showed no loss in capacity.

The percent of metal removed in the solution containing cysteamine-functionalized films (left) and in the solution containing glutathione-functionalized films (right). (Source: Weidman et al., 2017)

In conclusion, these thin films provide a sustainable platform for the efficient purification of lead- and cadmium- contaminated water sources to safe levels.

-Jennifer Liu-

A New Wastewater Treatment Strategy by a Porous β-cyclodextrin Polymer

Micropollutants are residue from substances, used everyday in modern society, including pharmaceuticals and personal care products (PPCPs), hormones, pesticides and industrial chemicals. According to University of Georgia Office of Research, 90% of consumed prescription drugs ultimately end up in our waste water. Micropollutants are hazardous, persistent, and not bio-degradable. They cannot be removed with conventional waste water treatment technologies. The continued release of micropollutants with wastewater effluent can cause long-term hazards such as rise of antibiotic-resistant organisms and reproductive and developmental abnormalities on sensitive species.

Wastewater treatment plant (Photo source: IWA)

Activated carbons are the most common materials used to remove organic pollutants from water. However, they have several deficiencies, including slow pollutant uptake (of the order of hours), poor removal of relatively hydrophilic micropollutants and poor regeneration performance. Since activated carbons bind to most substances through London dispersion forces, they adsorb larger molecules and non-polar molecules preferentially.

Scientists from Cornell University had synthesized porous β-cyclodextrin-containing polymers (P-CDPs) to remove the micropollutants from water. β-cyclodextrin (β-CD) is an inexpensive, sustainably produced cyclic macromolecule of glucose. It was crosslinked with rigid aromatic groups, providing a high-surface-area polymer of β-CD containing pores of 1.8–3.5 nm diameter. The resulting polymer can rapidly remove a variety of organic micropollutants with adsorption rate constants 15 to 200 times greater than those of activated carbons. In addition, the polymer can be easily and repeatedly regenerated by rinsing the polymer with methanol at room temperature while with no loss in performance. Finally, it can rapidly remove a complex mixture of organic micropollutants, including aromatic model compounds, pesticide, plastic components and pharmaceuticals, at environmentally relevant concentrations. The porous cyclodextrin-based polymers offer a rapid, flow-through water treatment.

P-CDPs were derived from nucleophilic aromatic substitution of hydroxyl (-OH) groups of β-CD by tetrafluoroterephthalonitrile (1) (Fig. a). The side groups of the P-CDPs, including fluoride (-F), cyano (-CN) and hydroxyl (-OH) groups, can bind to pollutants of different sizes and hydrophobicities through London dispersion forces and ionic, covalent and hydrogen bonds.

Figure a | Left, synthesis of the high-surface-area porous P-CDP from β-CD and 1. Right, schematic of the P-CDP structure. (Alsbaiee et al., 2016)

β-CD and 1 were polymerized in a suspension of potassium carbonate (K2CO3) in tetrahydrofuran (THF) at 80 °C to provide a pale-yellow precipitate, which proved to be the P-CDPs. P-CDPs obtained from 1:β-CD ratio of 3:1 exhibited the highest surface areas. A cost analysis of P-CDP indicates raw materials costs of US dollar (USD) 3.70 per kg.

Existing biological wastewater treatment plants are not specifically designed to remove micropollutants, and conventional activated carbons have poor removal performance and slow pollutant uptake. Therefore, the P-CDP, which can remove a wide range of micropollutants, presents a possible solution for wastewater treatment.

-Jennifer Liu-

Biodegradable Plastic: The New Potential Waste Management Solution

Production of plastic has increased from 0.5 million tonnes in 1950 to 260 million tonnes in 2007. It is versatile, lightweight, flexible, moisture resistant and relatively inexpensive. Their attractive qualities lead us, around the world, to an over-consumption of plastic products. However, conventional plastics, which make up 60-80 percent of marine litter from the poles to the equator, are durable and very slow to degrade. They are harmful to marine animals as they release toxic additives including flame retardants, antimicrobials and plasticizers into the marine environment during degradation. Use of a biodegradable polymer that degrades more quickly than conventional plastics may present a solution to the problem.

Mouth of the Los Angeles River, Long Beach, California. (Photo source: ©© Bill McDonald, Algalita Foundation / Heal The Bay)

During April 2008 – March 2009, researchers from Marine Biology and Ecology Research Centre of University of Plymouth investigated breakdown of four types of plastics in the marine environment, including two different oxo-biodegradable formulations trademarked as TDPATM, a biodegradable bag manufactured using GM-free corn starch, vegetable oils and compostable polyesters, and a standard polyethylene bag produced from 33% recycled materials.

The scientists fastened 20 wooden sample holders to a beam attached to a floating pontoon at Queens Anne Battery Marina, Coxside Plymouth, Devon and examined degradation at 4, 8, 16, 24, and 40 weeks. After 24 weeks of exposure, the compostable polyester samples lost 100% of their surface area. However, the other materials lost only approximately 2% of their surface area over 40 weeks exposure. Fouling by marine organisms reduced the sunlight reaching the surfaces of the standard polyethylene, TDPATM 1 and 2 samples, which resulted in much slower degradation.

Plastics in the Ocean Affecting Marine Life

Plastic bags are especially harmful to marine animals since many animals confuse the plastic litter in the ocean with food. Ingestion of plastic debris may present a threat as chemicals including phthalates, polychlorinated biphenyls and organochlorine pesticides on plastic fragments may present a toxicological hazard.

One in three leatherback sea turtles has plastic in its stomach, based on a study of over 370 autopsies. (Photo: Laura Beans)

“A large number of marine species is known to be harmed and/or killed by plastic debris… One possibility to mitigate the problem is the development and use of biodegradable and photodegradable plastics.” (Derraik, 2002)

Biodegradable polymers offer potential waste management solutions. However, there are still limitations and ethical issues about their application.

-Jennifer Liu-