pollution – Lightsources.org

Efficient production technique for a novel ‘green’ fertiliser

2022/05/112022/05/11

Advanced milling technique produces slow-release soil nutrient crystals

A purely mechanical method can produce a novel, more sustainable fertiliser in a less polluting way. That is the result of a method optimised at DESY’s light source PETRA III. An international team used PETRA III to optimise the production method that is an adaptation of an ancient technique: by milling two common ingredients, urea and gypsum, the scientists produce a new solid compound that slowly releases two chemical elements critical to soil fertilisation, nitrogen, and calcium. The milling method is rapid, efficient, and clean—as is the fertiliser product, which has the potential to reduce the nitrogen pollution that fouls water systems and contributes to climate change. The scientists also found that their process is scalable; therefore, it could be potentially implemented industrially. The results by scientists from DESY; the Ruđer Bošković Institute (IRB) in Zagreb, Croatia; and Lehigh University in the USA have been published in the journal Green Chemistry. The new fertiliser still needs to be tested in the field.

For several years, scientists from DESY and IRB, have been collaborating to explore the fundamentals of mechanical methods for initiating chemical reactions. This method of processing, called mechanochemistry, uses various mechanical inputs, such as compressing, vibrating, or, in this case, milling, to achieve the chemical transformation. “Mechanochemistry is quite an old technique,” says Martin Etter, beamline scientist at the P02.1 beamline at PETRA III. “For thousands of years, we’ve been milling things, for example, grain for bread. It’s only now that we’re starting to look at these mechanochemical processes more intensively using X-rays and seeing how we can use those processes to initiate chemical reactions.”

Etter’s beamline is one of the few in the world where mechanochemistry can be routinely performed and analysed using X-rays from a synchrotron. Etter has spent years developing the beamline and working with users to fine-tune methods for analysing and optimising mechanochemical reactions. The result has been a globally renowned experiment setup that has been used in studying many types of reactions important to materials science, industrial catalysis, and green chemistry.

Read more on the DESY website

Image: The co-crystals of the novel fertiliser (symbolised here with gypsum) release their nutrients much more slowly

Credit: DESY, Gesine Born

Metal pollutants cause metabolic alterations in algae

2021/08/252021/08/26

Contamination by metals like cadmium or mercury is considered a serious threat to the environment and human health. Several human activities such as mining, metallurgy industry, and extensive use of mineral fertilizers are the main sources of ongoing metal pollution in numerous ecosystems. This environmental risk is potentiated by bioaccumulation and trophic chain biomagnification phenomena, which are associated with the long persistence of toxic metals in the polluted ecosystems. Aquatic and soil ecosystems affected by runoffs loaded with toxic metals are particularly vulnerable, where primary producers photosynthetic organisms (phytoplankton and soil microalgae) represent the first stage of pollution build-up. Knowledge about mechanisms of toxicity in these organisms is essential for appropriate assessment of environmental risks.

Researchers from the Plant Physiology Laboratory of the Department of Biology, also affiliated with the Research Centre for Biodiversity and Global Change, at the Autonomous University of Madrid (UAM), have discovered the major changes of biomolecules caused by cadmium and mercury in the model green microalga Chlamydomonas reinhardtii.

The use of synchrotron technology at MIRAS beamline was a valuable tool and has made it possible to analyze in detail variations in the biomolecular pattern caused by heavy metals at levels of resolution rarely described before. “Among the cellular components that readily changed upon metal treatments, we detected alterations in the lipid composition by synchrotron light infrared spectroscopy at ALBA, which corresponded to accumulation of neutral lipids and increased fatty unsaturation” specifies Ángel Barón, scientist at UAM.

Read more on the ALBA website

Image: Electron transmission microscopy of Chlamydomonas reinhardtii cells to show alterations caused by cadmium and mercury. The pyrenoid (p) looks aberrant, with proliferation of lipid vesicles (green arrowhead) and starch grains (s). Metals also triggered the appearance of autophagy vesicles (red arrowhead). Right: image of Chlamydomonas reinhardtii

Credit: image of Chlamydomonas reinhardtii Wikimedia Commons.

Looking for photochemistry inside particles

2021/03/182021/03/25

At the Swiss Light Source (SLS), a new photochemical reaction cell was developed for the X-ray microscope at the PolLux beamline. This allowed the researchers to mimic sunlight mediated chemical reactions in airborne particles we normally inhale. Utilizing the new reaction cell, the X-ray microscope was used to image the interior of particles for the chemistry that produced a high concentration of persistent carbon centered radicals (CCR) and reactive oxygen species (ROS), which are harmful compounds when inhaled and can cause damage in the respiratory tract. Two main factors were 1) a very high particle viscosity that effectively locks the CCRs in a glass-like state and 2) oxygen deficiency, or anoxia, to prevent smaller ROS to be formed with a shorter lifetime that easily diffuse out of the particle before inhalation. When relative humidity in air is <60%, particles can become highly viscous or even glass-like, which drastically reduces the mobility of all molecules. Although sunlight induced radical formation is likely to be unhindered, high viscosity would instead inhibit molecular diffusion and block oxygen from accessing the particle interior. This leads to preservation of large amounts of radicals. Amazingly, this may apply to all organic light absorbing atmospheric compounds making radical abundance and persistence an unforeseen issue until now.

Particles composed of citric acid and iron were investigated as a model for iron containing organic particles. About 1 in 20 airborne particles contain iron in urban areas at a significant concentration as identified by previous studies. The oxidation state of iron was mapped across individual particles using X-ray spectromicroscopy to reveal where photochemical reactions, oxidation and molecular diffusion took place inside. Oxidation and formation of ROS took place rapidly, but surprisingly, only near the particle surfaces, i.e. an oxidized reaction front extending only hundreds of nanometers was directly observed. This was entirely due to the rapid depletion of oxygen in the particle due to slow molecular transport and fast reaction cycling. In addition to X-ray microscopy, the researchers used an electrodynamic balance (collaboration with ETHZ) and a coated wall flow tube reactor to study these radical forming particles and constrain the overall reactive cycle and the production and release of radicals to air.

Read more on the PSI website

Image: A chemical scheme and X-ray image showing particles oxidized only near their surface. Light in iron-organic particles start a cycle of oxidizing reactions (purple text) forming carbon centered radicals (yellow text) and reactive oxygen species (red text). We directly imaged oxidation happening only near the particle surfaces indicated by the brighter colour in micrometer and submicrometer viscous particles in the right image.

Credit: PSI

Cooking pollution more resilient than previously thought

2020/12/102020/12/17

Following research undertaken at Diamond, particulate emissions from cooking have been discovered to stay in the atmosphere for longer than initially thought, causing a prolonged contribution to poor air quality and human health.

A new study, led by researchers at the University of Birmingham, demonstrated how cooking emissions can survive in the atmosphere over several days, rather than being broken up and dispersed.

The team collaborated with Diamond, the University of Bath and the Central Laser Facility to show how these fatty acid molecules react with molecules found naturally in the earth’s atmosphere. During the reaction process, a coating is formed around the outside of the particle that protects the fatty acid inside from gases such as ozone which would otherwise break up the particles.

This research was made possible by using Diamond’s powerful X-ray beamline (I22). For the first time researchers we able to recreate the reaction process in a way that enables it to be studied in laboratory conditions.

Read more on the Diamond website

New materials for the reduction of vehicle pollution

2019/04/262019/05/02

Research develops nanostructured material with high oxygen storage and release capacity for the improvement of catalytic converters

Complete combustion of both fossil and biofuels generates carbon dioxide ( $C O_{2}$ ) and water as final products. However, incomplete combustion of these substances can occur in automobile engines, generating important pollutants such as carbon monoxide ( $C O$ ), hydrocarbons, and nitrogen oxides (such as $N O$ and $N O_{2}$ ).
To reduce the emission of these toxic substances, an equipment called a catalytic converter is used in the exhaust of vehicles. Materials called catalysts promote and accelerate chemical reactions without being consumed during the process. They retain on their surface the reactant molecules, weakening the bonds between the atoms and causing the pollutants to be converted into less harmful gases.
The action of the catalytic converter happens in three stages. The first stage converts the nitrogen oxides into nitrogen ( $N_{2}$ ) and oxygen ( $O_{2}$ ) gases. The second stage breaks down bonds of unburnt hydrocarbons and carbon monoxide, turning them into $C O_{2}$ . Finally, the third stage has an oxygen sensor to regulate the intake of air and fuel to the engine, so that the amount of oxygen is always close to the most efficient for the different reactions.

“Molecular scissors” for plastic waste

2019/04/122019/04/12

A research team from the University of Greifswald and Helmholtz-Zentrum-Berlin (HZB) has solved the molecular structure of the important enzyme MHETase at BESSY II.

MHETase was discovered in bacteria and together with a second enzyme – PETase – is able to break down the widely used plastic PET into its basic building blocks. This 3D structure already allowed the researchers to produce a MHETase variant with optimized activity in order to use it, together with PETase, for a sustainable recycling of PET. The results have been published in the research journal Nature Communications.

Plastics are excellent materials: extremely versatile and almost eternally durable. But this is also exactly the problem, because after only about 100 years of producing plastics, plastic particles are now found everywhere – in groundwater, in the oceans, in the air, and in the food chain. Around 50 million tonnes of the industrially important polymer PET are produced every year. Just a tiny fraction of plastics is currently recycled at all by expensive and energy-consuming processes which yield either downgraded products or depend in turn on adding ‘fresh’ crude oil.

Image: At the MX-Beamlines at BESSY II, Gottfried Palm, Gert Weber and Manfred Weiss could solve the 3D structure of MHETase.
Credit: F. K./HZB

Urea susbstitutes noble metal catalysts

2019/02/222019/02/25

… for the photodegradation of organic polluants.

A new laser-based technique developed by the Institute of Materials Science (ICMAB-CSIC) uses urea, a common substance in the chemical industry and a low-cost alternative to noble metal co-catalyst, to enable a more efficient, one-step production of hybrid graphene-based organic-inorganic composite layers for environmental remediation, photodegradation of antibiotic contaminants from wastewater. The composition and chemical bonds of the urea-enriched thin layers were studied in detail using synchrotron light at the ALBA Synchrotron.
Human activity is increasing the amount of pollutants in water and air, as well as in all sorts of materials at home and work place. The existence of antibiotic contamination is undeniably one of the most threatening challenges to date, at a time when antibiotic-resistant bacteria has already been flagged as the next world-wide pandemic crisis.
Semiconductor photocatalysts have long been investigated for environmental remediation because they can degrade or mineralize a wide range of organic contaminants as well as pathogens. Research focuses on addressing some drawbacks that prevent their use on a large scale. On the one hand, many photocatalysts are activated only by UV radiation which represents solely a small fraction of the total available solar emission. On the other hand, the recombination of the photogenerated electron-hole pairs that enable the decomposition of the pollutant is usually faster than the oxidation reactions that cause the degradation of organic molecules. As a consequence, noble metal co-catalysts acting as electron scavengers, such as gold or platinum, are needed in the process.

>Read more on the ALBA website

Image: Researchers Ángel Pérez del Pino and Enikö György from the ICMAB-CSIC together with Ibraheem Yousef, scientists responsible of MIRAS beamline at ALBA.

Mine tailings dumped into the sea analysed with synchrotron light

2019/02/142019/02/14

The case of Portmán Bay, at the Spanish Mediterranean coast, is one of the most extreme cases in Europe causing great impact on the marine ecosystem by disposal of mine tailings.

For more than 40 years, 60 million tonnes of mine waste were dumped directly into the sea, resulting from the open pit mining that took place in Sierra Minera in Cartagena. As a consequence, the Bay was literally filled with metal-rich artificial soil. Since 2014, a research group from the University of Barcelona (UB) has been studying Portmán Bay. Now, they have analysed samples of these sediments at ALBA because with synchrotron light they can obtain unprecedented information about the heavy metals contamination, such as arsenic.

Very few people know about Portmán Bay, where took place one of the most extreme cases of coastal ecological impact by mine activity in Europe. Figures speak for itself: the mining company Peñarroya dumped more than 60 million tonnes of mine waste into the sea through a 2km-long pipeline located at the west part of the bay. Over the years, the bay became totally filled with a mountain of artificial sediment. The shoreline moved 600m seaward and the trace of the pollution reached 12km out to sea.

>Read more on the ALBA website

Image: Miquel Canals putting sample supports, which were specifically designed and printed with 3D technology at ALBA, at the CLAESS beamline to be analysed with synchrotron light; with Carlo Marini, beamline scientist and Andrea Baza, PhD student from UB.

Scientist discover that charcoal traps ammonia pollution

2019/02/112019/03/19

Discovery could have implications for agricultural management and climate change mitigation

Cornell University scientists Rachel Hestrin and Johannes Lehmann, along with collaborators from Canada and Australia, have shown that charcoal can mop up large quantities of nitrogen from the air pollutant ammonia, resulting in a potential slow-release fertilizer with more nitrogen than most animal manures or other natural soil amendments. The results were published Friday in Nature Communications.

Ammonia is a common component of agricultural fertilizers and provides a bioavailable form of the essential nutrient nitrogen to plants. However, ammonia is also a highly reactive gas that can combine with other air pollutants to create particles that travel deep into the lungs, leading to a host of respiratory issues. It also indirectly contributes to climate change when excess fertilizer inputs to soil are converted into nitrous oxide, a potent greenhouse gas.

In Canada, ammonia emissions have increased by 22 per cent since 1990, and 90 per cent are produced by agriculture, particularly from manures, slurries and fertilizer applications. Mitigating this pollutant—without limiting fertilizers and food growth for our growing world population—is key to a sustainable future.

Image: Rachel Hestrin (right) on the beamlines at Canadian Light Source with fellow Cornell researcher Angela Possinger.