Design for Degradation

Chemical products should be designed so that at the end of their function they break down
into innocuous degradation products and do not persist in the environment.

Contributed by Rich Williams, Founder and President at Environmental Science & Green Chemistry
Consulting, LLC

Green chemistry practitioners aspire to optimize the commercial function of a chemical while
minimizing its hazard and risk. Hazard, the capability to cause harm, is an inherent characteristic
arising, like function, from a chemicals stereochemistry (the content and arrangement of atoms).
Green chemistry principles 3, 4, 5, and 12 guide designers to reduce the hazards of chemicals.
Principle 10, however, guides the design of products that degrade after their commercial function in
order to reduce risk or the probability of harm occurring. Risk is a function of both a molecules
inherent hazard AND exposure contact between a chemical and a species. Degradation can eliminate
significant exposure, thereby minimizing risk regardless of the hazard of the chemical involved.

Exposure to persistent chemicals can be significant as a result of global dispersion enabled by

properties such as volatility or sorption to particles and partitioning into organisms based on properties
such as fat solubility. Regulators have established criteria (half-lives in water, soil, air) that define
persistence within frameworks used to identify chemicals as PBT (Persistent, Bioaccumulative, Toxic).

A green chemistry objective is to design out molecular features responsible for hazardous
characteristics and risk. Trade-offs, or alternative approaches, must be evaluated when the molecular
features to be designed in for commercial function overlap with those to be designed out to reduce
hazard and risk.

Biodegradation, hydrolysis, and photolysis can be designed into chemical products. In the same way
that mechanistic toxicology knowledge is essential to identify and design out molecular features that
are the basis for hazards, an understanding of the mechanisms of degradation and persistence are
required to design in chemical features that promote degradation and eliminate features that promote
persistence. Many persistent compounds are extensively chlorinated. Halogens such as chlorine are
electron withdrawing, thereby inhibiting the enzyme systems of microbes because aerobic microbial
degradation favors electron rich structures.

Prediction methods that can guide the design of molecular architecture expected to degrade include
rules of thumb linking structural features to degradability or persistence, databases of existing
knowledge, models that evaluate biodegradability or PBT attributes, and experimental testing. All of
these tools can be adapted to individual chemical sectors and specific objectives.

Understanding the anticipated release and transport pathways for a chemical informs the selection of
an effective design strategy. Degradation must occur within the relevant environmental
compartment(s) and at a meaningful rate. Domestic wastewater typically passes through a vigorous
bioreactor within wastewater treatment plants (WWTP). The consumer product industry has designed
molecules for removal within these bioreactors. In the early 1960s, industry transitioned from nonbiodegradable branched surfactants, which caused extensive foaming and other health problems in
surface waters receiving WWTP effluent, to biodegradable linear alkyl benzene sulfonate based
detergents an approach to innovative design that continues today.

Tools currently exist to enable the implementation of principle 10, but advances in mechanistic
understandings linking molecular features to hazards and degradability will enable more
comprehensive application of green chemistry to control hazard and risk. Effective communication
across disciplines is also essential to provide designers with knowledge they can factor into the
complexities of product design. Because of regulatory and business constraints, many product design
decisions must be made relatively early. Predictive decision-making tools must provide confidence
about hazard and risk in a way that is aligned with the timing and magnitude of development
decisions, and most importantly, while there is still flexibility to alter a molecular design or product
formulation.

I recently had the opportunity to present a lecture on biodegradation to a master watershed class at
the University of Arizonas Yavapai extension office. According to theMaster Watershed website,
[t]he Master Watershed Steward Program educates and trains citizens across the state of Arizona to
serve as volunteers in the protection, restoration, monitoring, and conservation of their water and
watersheds. I was excited to present to this audience because they clearly have the passion and
motivation to take action in their communities, and they are easily the most interactive and engaging
group to which I have ever presented. I began my lecture with three questions:

What is biodegradation?

What are some examples of biodegradation?

Is biodegradation a good thing?

The class provided a strong definition of biodegradation and successfully listed many examples,
including wastewater treatment plants, composting, reduction of plant detritus in the environment,
and landfilling. Most intriguing was their response to whether biodegradation is good or bad; the
overwhelming response was that biodegradation was good. Since the demographics of this group
included young and old, from a variety of careers and backgrounds, it is probably fair to say that their
response is representative of the publics perceptions. In reality, biodegradation is a complex process
reliant upon a wide range of variables and given a certain set of circumstances biodegradation
can certainly be a negative and potentially damaging process. We can briefly examine two examples
where biodegradation did not give the positive results that people associate with the process.
Example 1
When people think of massive chemical spills in the ocean, they often think of massively damaging
petroleum spills. There are, however, other chemical spills that pose a risk too. Take the molasses
spill from an underwater pipeline in September 2013 at the Honolulu Harbor in Hawaii. An estimated
233,000 gallons of molassesassumed an innocuous material, because we enjoy ingesting it
regularly as a societywas released into the harbor, where it sank and suffocated thousands of
animals living on the ocean floor. Animals were initially suffocated by either the formation of a barrier
between the animal and oxygen containing water or by clogging the gills. As the molasses spread, it
began to dissolve into the bulk ocean water, where microbial organisms proliferated as they
degraded the sugar rich solution. The increase in microbe populations led to the depletion of
dissolved oxygen in the water (a process called eutrophication), which led to further suffocations.
While not as obviously toxic as petroleum, the conditions offered by the molasses spill resulted in
rapid biodegradation of the contaminant, and a high mortality rate of animals in and around the spill.

Example 2
A second example of negative impacts is when a compound is not fully mineralized (broken down to
carbon dioxide and water) during biodegradation, and secondary products, which can be more toxic
than the parent compound, are produced. For instance, when the common ground water
contaminants perchloroethylene (PCE), a common dry cleaning chemical, and trichloroethylene
(TCE), a common degreaser, are degraded in anaerobic conditions, they are transformed to the
more toxic daughter products cis-1,2-dichloroethene and vinyl chloride, where the former is a
suspected carcinogen and the latter is a known carcinogen (1-3). This transformation due to
biodegradation is of major concern for human and environmental health, especially when
considering groundwater supplies.
Given the above examples, it is not my intention to argue against biodegradation as a consideration
of contaminant design and/or control. On the contrary, I am a staunch advocate of using
biodegradation as a mechanism to manage contaminants in industrial processes and the
environment alike. I introduced these examples because it is important to impart the complex nature
and potential impacts of biodegradation.
Design for Degradation, the tenth principle of green chemistry, is a laudable and important guide for
chemists and researchers as they conceive and design green processes and chemicals. It is,
however, a principle that must be thoroughly thought-out and tested before it can be used to label a
process green, especially when the method of degradation is biodegradation. Ask yourself
questions such as:

Do reagents and the product chemical degrade completely into simple

compounds (carbon dioxide, water, methane, ammonia, etc.) or are secondary
compounds generated which have similar or higher toxicity?

Is the product accessible in systems, or does the product partition into areas not
accessible for degradation? That is, is the compound available for degradation?

Is the compound only degradable in a very narrow set of conditions or by a

limited number of organisms?

Furthermore, the twelve principles of green chemistry do not carry equal weight at all times. The
degradation principle is an example of one which may vary. Consider the surfactant industry; by the
very nature of their use, surfactants are widely and copiously introduced to soil and water systems.
In this case, the degradation principle should be heavily weighted when assessing whether a

compound is green or not. Contrastingly, when a material is produced in a research lab in volumes of
only milligrams or grams, the degradation principle carries less weight.
The weight assigned to the degradation principle should be determined by the scale of production
and distribution. In essence, chemicals produced in mass and widely distributed are at higher risk of
large-scale spills and have a difficult to control fate; these chemicals should be degradable to be
considered green. Chemicals produced for narrow applications and in small masses are less likely
to enter environmental systems and are easier to control; they may still be considered green
chemicals if not degradable, given they abide by the other principles. This being said, degradability is
always desirable and encouraged for all compounds.