Tag Archives: nitrates

Algae outbreaks (dead zones) in wetlands and waterways

It’s been over seven years since I first started writing about Duke University’s  Center for the Environmental Implications of Nanotechnology and mesocosms (miniature ecosystems) and the impact that nanoparticles may have on plants and water (see August 11, 2011 posting). Since then, their focus has shifted from silver nanoparticles and their impact on plants, fish, bacteria, etc. to a more general examination of metallic nanoparticles and water. A June 25, 2018 news item on ScienceDaily announces some of their latest work,

The last 10 years have seen a surge in the use of tiny substances called nanomaterials in agrochemicals like pesticides and fungicides. The idea is to provide more disease protection and better yields for crops, while decreasing the amount of toxins sprayed on agricultural fields.

But when combined with nutrient runoff from fertilized cropland and manure-filled pastures, these “nanopesticides” could also mean more toxic algae outbreaks for nearby streams, lakes and wetlands, a new study finds.

A June 25, 2018 Duke University news release (also on EurekAlert) by Robin A. Smith, which originated the news item, provides more detail,

Too small to see with all but the most powerful microscopes, engineered nanomaterials are substances manufactured to be less than 100 nanometers in diameter, many times smaller than a hair’s breadth.

Their nano-scale gives them different chemical and physical properties from their bulk counterparts, including more surface area for reactions and interactions.

Those interactions could intensify harmful algal blooms in wetlands, according to experiments led by Marie Simonin, a postdoctoral associate with biology professor Emily Bernhardt at Duke University.

Carbon nanotubes and teeny tiny particles of silver, titanium dioxide and other metals are already added to hundreds of commercial products to make everything from faster, lighter electronics, self-cleaning fabrics, and smarter food packaging that can monitor food for spoilage. They are also used on farms for slow- or controlled-release plant fertilizers and pesticides and more targeted delivery, and because they are effective at lower doses than conventional products.

These and other applications have generated tremendous interest and investment in nanomaterials. However the potential risks to human health or the environment aren’t fully understood, Simonin said.

Most of the 260,000 to 309,000 metric tons of nanomaterials produced worldwide each year are eventually disposed in landfills, according to a previous study. But of the remainder, up to 80,400 metric tons per year are released into soils, and up to 29,200 metric tons end up in natural bodies of water.

“And these emerging contaminants don’t end up in water bodies alone,” Simonin said. “They probably co-occur with nutrient runoff. There are likely multiple stressors interacting.”

Algae outbreaks already plague polluted waters worldwide, said Steven Anderson, a research analyst in the Bernhardt Lab at Duke and one of the authors of the research.

Nitrogen and phosphorous pollution makes its way into wetlands and waterways in the form of agricultural runoff and untreated wastewater. The excessive nutrients cause algae to grow out of control, creating a thick mat of green scum or slime on the surface of the water that blocks sunlight from reaching other plants.

These nutrient-fueled “blooms” eventually reduce oxygen levels to the point where fish and other organisms can’t survive, creating dead zones in the water. Some algal blooms also release toxins that can make pets and people who swallow them sick.

To find out how the combined effects of nutrient runoff and nanoparticle contamination would affect this process, called eutrophication, the researchers set up 18 separate 250-liter tanks with sandy sloped bottoms to mimic small wetlands.

Each open-air tank was filled with water, soil and a variety of wetland plants and animals such as waterweed and mosquitofish.

Over the course of the nine-month experiment, some tanks got a weekly dose of algae-promoting nitrates and phosphates like those found in fertilizers, some tanks got nanoparticles — either copper or gold — and some tanks got both.

Along the way the researchers monitored water chemistry, plant and algae growth and metabolism, and nanoparticle accumulation in plant tissues.

“The results were surprising,” Simonin said. The nanoparticles had tiny effects individually, but when added together with nutrients, even low concentrations of gold and copper nanoparticles used in fungicides and other products turned the once-clear water a murky pea soup color, its surface covered with bright green smelly mats of floating algae.

Over the course of the experiment, big algal blooms were more than three times more frequent and more persistent in tanks where nanoparticles and nutrients were added together than where nutrients were added alone. The algae overgrowths also reduced dissolved oxygen in the water.

It’s not clear yet how nanoparticle exposure shifts the delicate balance between plants and algae as they compete for nutrients and other resources. But the results suggest that nanoparticles and other “metal-based synthetic chemicals may be playing an under-appreciated role in the global trends of increasing eutrophication,” the researchers said.

Here’s a link to and a citation for the paper,

Engineered nanoparticles interact with nutrients to intensify eutrophication in a wetland ecosystem experiment by Marie Simonin, Benjamin P. Colman, Steven M. Anderson, Ryan S. King, Matthew T. Ruis, Astrid Avellan, Christina M. Bergemann, Brittany G. Perrotta, Nicholas K. Geitner, Mengchi Ho, Belen de la Barrera, Jason M. Unrine, Gregory V. Lowry, Curtis J. Richardson, Mark R. Wiesner, Emily S. Bernhardt. Ecological Applications, 2018; DOI: 10.1002/eap.1742 First published: 25 June 2018

This paper is behind a paywall.

Cleaning up water polluted by agricultural fertilizers

Researchers at Rice University (Texas, US) have announced a new catalyst for cleaning nitrites from water polluted by agricultural fertilizers (from the Rice University November 25, 2013 news release ,[also on EurekAlert]),

Chemical engineers at Rice University have found a new catalyst that can rapidly break down nitrites, a common and harmful contaminant in drinking water that often results from overuse of agricultural fertilizers.

Nitrites and their more abundant cousins, nitrates, are inorganic compounds that are often found in both groundwater and surface water. The compounds are a health hazard, and the Environmental Protection Agency places strict limits on the amount of nitrates and nitrites in drinking water. While it’s possible to remove nitrates and nitrites from water with filters and resins, the process can be prohibitively expensive.

There is a map illustrating the problem,

CAPTION: Many areas of the United States are at risk of contamination of drinking water by nitrates and nitrites due to overuse of agricultural fertilizers. CREDIT: USGS

CAPTION: Many areas of the United States are at risk of contamination of drinking water by nitrates and nitrites due to overuse of agricultural fertilizers.
CREDIT: USGS Courtesy: Rice University

Here’s more about these new catalysts designed to ‘scrub’ water clean (from the news release; Note: Links have been removed),

.. Michael Wong, professor of chemical and biomolecular engineering at Rice and the lead researcher on the new study [says] “Our group has studied engineered gold and palladium nanocatalysts for several years. We’ve tested these against chlorinated solvents for almost a decade and in looking for other potential uses for these we stumbled onto some studies about palladium catalysts being used to treat nitrates and nitrites; so we decided to do a comparison.”

Catalysts are the matchmakers of the molecular world: They cause other compounds to react with one another, often by bringing them into close proximity, but the catalysts are not consumed by the reaction.

In a new paper in the journal Nanoscale, Wong’s team showed that engineered nanoparticles of gold and palladium were several times more efficient at breaking down nitrites than any previously studied catalysts. The particles, which were invented at Wong’s Catalysis and Nanomaterials Laboratory, consist of a solid gold core that’s partially covered with palladium.

Over the past decade, Wong’s team has found these gold-palladium composites have faster reaction times for breaking down chlorinated pollutants than do any other known catalysts. He said the same proved true for nitrites, for reasons that are still unknown.

“There’s no chlorine in these compounds, so the chemistry is completely different,” Wong said. “It’s not yet clear how the gold and palladium work together to boost the reaction time in nitrites and why reaction efficiency spiked when the nanoparticles had about 80 percent palladium coverage. We have several hypotheses we are testing out now. ”

He said that gold-palladium nanocatalysts with the optimal formulation were about 15 times more efficient at breaking down nitrites than were pure palladium nanocatalysts, and about 7 1/2 times more efficient than catalysts made of palladium and aluminum oxide.

I gather this team will be doing more work before promoting the use of gold-palladium nanocatalysts (from the news release),

Wong said he can envision using the gold-palladium catalysts in a small filtration unit that could be attached to a water tap, but only if the team finds a similarly efficient catalyst for breaking down nitrates, which are even more abundant pollutants than nitrites.

“Nitrites form wherever you have nitrates, which are really the root of the problem,” Wong said. “We’re actively studying a number of candidates for degrading nitrates now, and we have some positive leads.”

Here’s a link to and a citation for the paper,

Supporting palladium metal on gold nanoparticles improves its catalysis for nitrite reduction by Huifeng Qian, Zhun Zhao, Juan C. Velazquez, Lori A. Pretzer, Kimberly N. Hecka and Michael S. Wong. Nanoscale, 2014, Advance Article DOI: 10.1039/C3NR04540D First published online 30 Oct 2013

This paper is behind a paywall.