Researchers at
the University of Michigan published a paper in the journal Nature Chemistry
that shows how they were able to develop an iron complex that can break down
leftover groundwater nitrate from fertilizer, which is typically very stable in
the environment. Nitrates are notoriously difficult to chemically reduce and
remove from the environment. They are also responsible for harmful algal
blooms, promoting cyanobacteria growth, inducing eutrophication, and death of
marine life. The new method can reduce nitrate into components that can be
recycled for fertilizer.
According to Phys.org, lead author
and chemist Nathaniel Szymczak noted:
"Now we tend to overfertilize crops, and a huge
majority of the fertilizer we apply actually leaches away with runoff into
streams, groundwater, lakes and oceans," Szymczak said. "Human
impacts have basically caused an imbalance, and it's impossible for biological
systems to compensate for as much nitrate as we're dumping into them."
They first studied nitrogen
transport and chemical interactions in the environment. They found that
hydrogen bonds were the key to binding nitrates as well as to enhancing the
chemical reduction of them.
“They found that nitrate transporter proteins—proteins
that help plants use nitrates—bind to nitrates using hydrogen bonds. These
hydrogen bonds are found in a halo of surrounding molecules called the
"secondary sphere."
"When we look at this problem of how we actually
tackle nitrate reduction, we look to the enzymes, we look to biology, and what
we've found is nature has provided cues about how to bind and reduce
nitrate," he said. "We found that just by having well-positioned
hydrogen bonds, you can actually change the bonding structure in nitrate and
force a subsequent reduction step."
They began with an iron complex surrounded by a secondary sphere of hydrogen bonds. They were then able to turn hydrogen bonds on, essentially targeting the binding sites on nitrates, in order to prime, or ready them for the next chemical reaction in the reduction process.
The researchers note that there
are two types of reduction sequences for nitrates: stoichiometric reduction and
catalytic reduction.
“Nature’s solution to achieve binding/activation of
nitrate is to use networks of hydrogen-bonding (H-bonding) interactions, amino
acid residues that are critical to the function of nitrate transport proteins
and nitrate reductases.”
The researchers compared the use
of heat and light to power the chemical reaction and got two different chemical
results.
“When the researchers used heat to drive the chemical
reaction, the iron complex was able to grab oxygen atoms from nitrate, reducing
it to nitric oxide. When the researchers used light, the iron complex was able
to remove oxygen atoms from nitrate altogether, converting it to ammonia.”
The ammonia can be reused as
fertilizer, and the nitric oxide has medical and industrial uses. The
experiments should be considered to be an early step in the development of
chemical remediation of nitrates in water, which is needed where fertilizer use
is heavy. It should be combined with more efficient, better targeting, timing,
and overall optimization of fertilizer applications. Devices would need to be
built that could facilitate and control the reduction step. The method could
one day be used at facilities like wastewater treatment plants.
"The timeframe for development of solutions to big
picture problems has a large time horizon, and they require fundamental studies
to develop principles and invent new ways to do molecular transformations that
are societally important," Szymczak said. "We are giving people a
roadmap of how to achieve the difficult reduction step that we hope could be
translated to engineered systems that might be used down the road."
References:
Iron
complex breaks down stubborn pollutant using light-powered reaction. University
of Michigan. edited by Sadie Harley, reviewed by Robert Egan. Phys.org.
September 22, 2026. Iron complex breaks down stubborn
pollutant using light-powered reaction
Secondary-sphere
hydrogen bonding promotes catalytic nitrate reduction at iron. Writhabrata
Sarkar, Andrew R. LaDuca, Riley W. Kazukiewicz & Nathaniel K. Szymczak. Nature
Chemistry (2026). Secondary-sphere hydrogen bonding
promotes catalytic nitrate reduction at iron | Nature Chemistry



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