Bridging the gaps between atmospheric physics, chemistry and marine biology

6 11 2011

The author, Darius Ceburnis (NUI Galway, at left), and Meilu He (Clarkson) discuss results in real-time.

Organic matter enrichment in sea spray particles was discovered few decades ago, but general wisdom did not recognise it largely due to poor instrumentation to study it. Oceans occupy nearly 70% of the Earth’s surface giving marine atmosphere its special status. Anything happening at ocean-atmosphere boundary has enormous global implications due to its sheer volume. Earth’s climate is dependant on marine atmosphere as is human welfare on marine life.

For a long time marine atmosphere particles were believed to consist only of sea salt and sulphate, both inorganic compounds easy to detect and quantify. Organic compounds in the atmosphere are as variable as the life on Earth making them particularly difficult to study. In a similar way that many bacteria, plant and animal species still remain unknown to science, organic matter in the air is no different.

A monoculture of Duneliella tertiolecta (green algae) is added to the wave tank on Nov 5th to imitate oceanic bloom conditions. This photo was taken before the algae was given time to mix in the tank, and so is highly concentrated.

Significant progress has been made in the last decade identifying organic compounds in the marine atmosphere mainly due to the progress of sophisticated analytical techniques making it possible to peek into individual particles in real time and to quantify the organic material in them. We know that organic particles are present in the air over the oceans and are seeding the marine clouds; we can sometimes generate organic particles in the laboratory, but so much more in unknown about their specific chemical composition, biological origin and ways they are produced and transformed. Quite clearly we have to bridge many gaps between biology, chemistry and physics of the ocean and the atmosphere to understand a coupled system.

MOUDIs and Berner Impactors are collecting samples for offline analysis using a variety of spectroscopic and microscopic techniques.

A unique CAICE facility is a perfect laboratory to study physical and biological processes together by joining forces of different scientific groups. The two groups I am representing are from Ireland (National University of Ireland Galway) and Italy (Institute of Atmospheric Sciences and Climate of the Italian National Research Council) who joined their forces a decade ago and I had a privilege to be part of. The two setups – an online High Resolution Time-of-Flight Aerosol Mass Spectrometer capable of quantifying particles smaller than 1 micrometer in real time and an off-line system consisting of low pressure impactors designed to quantify inorganic particle compounds, water soluble  and water insoluble organic matter as well as Proton Nuclear Magnetic Resonance method for resolution of organic matter species – will give the best quantitative measurement of organic compounds released by different algae species or present naturally in sea water. I am excited as everyone else here to use a wonderful facility and benefit from scientific discussions.

Today we started our first experiment by adding living algae into the huge wave channel which is the closest thing to the real ocean we can have. An exiting week is ahead to find out what those tiny plants of the ocean will reveal in the lab.

Darius Ceburnis, Centre for Climate and Air Pollution Studies, National University of Ireland, Galway





Shedding light on properties of ocean-wave generated particles

6 11 2011

Professor Suresh Dhaniyala and Meilu He (Clarkson University) work on deploying their instrument to measure fast size distributions of sea spray particles generated in our ocean-atmosphere chamber.

An ancient Eastern parable describes the difficulty of identifying an elephant in a dark room if you are only able to feel one part of the animal and are unaware of what others in the room are “feeling”.  This parable has parallels in the study of atmospheric aerosol – analysis of small particles suspended in the atmosphere will reveal different stories when examined with different instruments, and scientists working in isolation cannot fully comprehend this system.  The study of atmospheric aerosol often requires scientists from different backgrounds working closely with each other using a wide variety of tools.   The current measurement campaign at the wave channel facility of UCSD provides for such collaboration.

Aerosol particles play a critical role in global climate because of their ability to reflect or absorb sunlight.  On one hand, the particle-light interaction is significantly enhanced when particles grow to become cloud droplets by taking up water vapor, while on the other hand the further growth of clouds droplets to form precipitation can remove aerosol from the atmosphere and significantly decrease aerosol interaction with sunlight.  Characterizing the properties of particles originating from different sources, particularly with respect to their ability to form clouds and precipitate, can help us stitch together a comprehensive picture of the role aerosol particles on global climate.

A replica of a breaking open ocean wave produced in the ocean-atmosphere chamber at the SIO Hydraulics Lab.

In this study, we concentrate on the contribution of one major natural global source of particles – ocean waves.  Particles produced from ocean waves, especially in the presence of biological material, may be especially active as cloud condensation nuclei and ice nuclei.  The wave channel facility at UCSD/SIO produces realistic and repeatable wave conditions that enable measurements at a range of time scales and with a wide variety of physical and chemical probes.  Our contribution to the experiment is in the form of two instruments that provide high time resolution sizing of particles smaller than 1 mm.   Particle size plays a critical role in determining the lifetime of particles, attractiveness to uptake of water vapor and other gas-phase species, and extent of interaction with light. Our measurements of size distributions, combined with data from other probes, will help establish the properties of particles from an important global source of aerosol and we are very excited to see what the data will tell us.

Suresh Dhaniyala, Department of Mechanical and Aeronautical Engineering, Clarkson University





From Molecular to Global Scales

4 11 2011

Let’s try this for starters: This is such an amazing project!!! It is environmental molecular science at its best, it bridges the length scale of a molecular bond, which is ridiculously short, with the ocean and the atmosphere, which are ridiculously big, and it brings the real world into a chemist’s lab! You couldn’t have done this kind of stuff ten years ago, and it is beautiful to see it all unfold right in front of our eyes.

Our first spectra of organic molecules on sea spray produced by the breaking waves in the Scripps wave tank (top) and the spectra of organic molecules on the top surface of the Baltic sea (bottom) seem to point us into the right direction.

We are physical chemists from Northwestern University in Evanston, which is the first suburb just north of Chicago. It’s not nearly as nice in San Diego as it is in Chicago during the month of November, but then again … what? No, of course we enjoy it a lot! Franz Geiger is blogging – he is the Irving M. Klotz professor of physical chemistry at NU. What’s physical chemistry? well, it’s physics – and chemistry – combined! There’s even a journal named after it – go check it out at http://pubs.acs.org/journal/jpcafh. Carly Ebben is a third-year PhD student in the Geiger group  who is also a National Science Foundation Graduate Student Fellow. She  participated in a really cool large-scale study in Southern Finland just last year, and together with samples collected during an equally impressive study in the central Amazon, Carly is now managing the sample acquisition, data collection and analysis, and paper writing for three important field studies, which is the focus of her PhD thesis.

Seaweed on the beach near Scripps pier - can we find the signatures of life on sea spray particles?

Here at the tank, we are studying the chemical composition of sea spray particle surfaces – not the bulk, which contains many, many molecules – but the surface, which houses much fewer molecules. Try it out on a sheet of paper – sketch a cube and fill it with small circles, then count how many are at the surface vs. the interior. In fact, there are so few molecules on the surface of a particle compared to the particle interior that one needs some pretty nifty tools to detect them – that’s what we bring to the CAICE. A second motivation for our studies is that there is a high likelihood that our methods can distinguish surface molecules on sea spray particles prepared in the tank when bugs are absent and when bugs are present – like a signature of life, if you will. This is how it works: We all know that living things contain DNA and proteins, and that the walls of cells are made of phospholipids and sugars. These compounds have a particular handedness, which allows for key molecular processes to occur in the biological machinery that we call ‘life’. A core concept in these biochemical processes is that of molecular recognition – and the handedness we just mentioned plays a key role in it: Imagine the handshake between two people – it typically involves the right hand of one person shaking another person’s right hand – the same happens in molecular recognition. If you were to shake somebody’s right hand by extending your left hand, it’ll be really awkward to say the least – the same is true for proteins and DNA, for which handedness is a key requisite for proper function. But for us, handedness is also an intrinsic marker for the presence of biological material on the particles that are produced at the wave tank, and that is what we are here to study these two weeks. This is a tough problem, because we look for the footprints of life without having to destroy the particles. To do so, we combine particle sampling at the tank with ultrafast laser spectroscopy at Northwestern University – this approach has already allowed us to establish that the particles from the wave tank have organic species on them, and we didn’t have to destroy the particles to learn that.

Andy Ault (Iowa) and Carly Ebben (Northwestern) enjoy working on the samplers.

How do we do it? We began work at the tank one week ago by installing sampling systems that allow us to collect sea spray particles for a certain amount of time and in certain size ranges on Teflon filters – and yes, even though it’s common sense that ‘nothing sticks to Teflon (hence the famous pan)’, the samplers we use can do the job because of some pretty cool particle collection physics. Nevertheless, there are very few particles on the filters, and not many tools can be used to detect them. Our lasers can do it, though, because they are quite special: we can adjust their energies – i.e. colors – to match those of the molecules we are looking for, and  the pulses our laser produce are just one tenth of one millionth of a millionth of a second short, which means we don’t burn up our samples like Han Solo’s blaster did when he sat across Greedo, Jabba’s repo man. We detect the signals with a supersensitive camera chip that’s cooled to the surface temperature of the dark side of the moon – because it’s so cold, unlike the camera in your cell phone, ours picks up really little noise, so it’s perfect for the job (but also much more expensive). Still, the samples we are studying only produce a few photons each minute, and so we need to work carefully.

Assembling the Northwestern University Particle Sampler (NUPS).

So, what do we learn? We learn that while water is of course important in ocean spray, the surfaces of the sea spray particles contain organic molecules, and it is those molecules that interact with the external world and that are important for the climate system. The graphic on the left shows the spectral signature of those organic molecules on particles collected during the crashing of breaking waves inside the wave channel, and how that is in qualitative agreement with what professor Gernot Friedrichs, a colleague of Franz’ in Kiel, Germany, published recently when he applied a similar laser method to the sea surface microlayer he collected on the other side of the planet – the Baltic Sea in Northeastern Europe! Now, here at the wave tank in Southern California we looked at the organic molecules on the surfaces of the sea spray particles, and the Baltic sample was collected by skimming the ocean surface using a boat miles offshore, but doesn’t the good agreement between the data suggest that the organic molecules on the ocean surface are similar to the organic molecules we see on the sea spray? And wouldn’t that suggest that when phytoplankton is present in the ocean, the biomolecules associated with the bugs could be associated with the sea spray particles? And doesn’t that imply that there may be a possibility for a biosphere-atmosphere feedback cycle that would be awesome to understand if we want to understand the complexity of the climate system? That’s where our part of the CAICE project is going, and that is what we’ll be looking for when the wave tank is filled with critters tomorrow!

Franz Geiger, Irving M. Klotz Professor of Chemistry & Associate Chair, Department of Chemistry, Northwestern University





When the Ocean Breathes

4 11 2011

Ever enjoyed walking along the shoreline and listening to the roar of breaking surf? Underwater, the sound of breaking waves is the sound of air breaking into bubbles, each one of which rings with its own tone, large low and small high. Their chorus forms a hissing roar, and provides an audible clue to their number and size. This turns out to be important, because large bubbles in open ocean whitecaps are ephemeral and difficult to measure. We want to count all the bubbles in the sea, and we plan to do it by studying the noise they make. We have tried other methods. I have personally spent miserable hours on the deck of the Research Platform Flip during storms with my finger on a big red button, waiting to trigger an underwater camera just as a wave breaks overhead. That’s one of many good reasons to make breaking waves in a flume – we know when and where the waves are going to break.

Bubbles in a whitecap taken during a storm off the Martha's Vineyard Coastal Observatory

So why the great interest in bubbles anyway? When the wind blows and waves break, they play an important role in exchange processes between the atmosphere and ocean. They enhance the transfer of gases across the air-sea interface, they change ocean color, they make underwater noise, they scavenge and transport organic surfactants and, when they rise to the surface, they create surfactant-enriched aerosols. The production of marine aerosols is, of course, the connection with CAICE. The Hydraulics Laboratory glass channel is the closest thing we have to an ocean in the laboratory. With the flume, we can create our own whitecaps and study the aerosols they produce. Then we can compare aerosols produced by breaking waves with other (more portable and convenient) production methods like frits and plunging water sheets.

And when we’re done with the flume? There will more laboratory work to do, but the great challenge will be to go back to sea, in ships and planes, to apply what we’ve learned in our laboratory ocean to the real thing.

Grant Deane, Research Oceanographer and Director of the Hydraulics Laboratory, SIO/UC San Diego





So there are particles in the air…

3 11 2011

Particles are a ubiquitous feature of the atmosphere. These particles impact climate in two main ways: they scatter and absorb sunlight and they influence the properties of clouds. By scattering sunlight back to space, particles act to cool the planet.

Prof. Cappa and student Sarah Forestieri working on their Cavity Ring-down and Photoacoustic Spectrometer system at the Hydraulics Lab.

How much sunlight an individual particle scatters depends on both the size and the composition of the particle. The bigger the particle, the more sunlight it can scatter (just like if you held a bowling ball, a baseball and a ping-pong ball in front of a flashlight, the bowling ball would take out a bigger chunk of the light). However, the number of “big” and “small” particles in the atmosphere is not equal; there are usually many more small particles than big particles and thus particles of all sizes can influence climate. (Sort of like if you had 10 baseballs but only 1 bowling ball in front of your flashlight.)

Another important aspect of particles that influences how much light they will scatter is how much the particles “like” water. This is termed their hygroscopicity, and particles with a bigger hygroscopicity like water more than particles with a low hygroscopicity. Particles formed from sea-spray are generally some of the most hygroscopic found in the atmosphere. Because of this, sea-spray particles take up lots of water and can grow to twice their dry size. Now, because the particle is bigger, it will scatter more light and cool the planet to a greater extent.

One important question is how do the plants and other organisms growing at the ocean surface affect the composition of sea-spray particles. They likely make the particles less hygroscopic, but what is unknown is by how much? During the CAICE intensive, we will be working to measure how the addition of different ocean-dwelling organisms, such as  phytoplankton, to sea water influence the light scattering and water uptake by the sea-spray particles. Through this work, we will learn how human activities that modify the frequency of things like algal blooms influence climate by changing the properties of sea-spray particles.

Of course, we shouldn’t forget that particles can also absorb sunlight, but that’s a story for another day!

Chris Cappa, Department of Civil and Environmental Engineering, UC Davis





A Theoretical Perspective

3 11 2011

While our colleagues are busy with the intensive campaign measurements at the wave flume at SIO, we spread the excitement for our CAICE research at the University of Utah. Before a quite interested audience of undergraduate, graduate, postdocs, and faculty, we described our recent efforts in modeling water and ice based on “first principles” approaches with specific focus on the link between structural, thermodynamic and dynamical properties, spectroscopic signatures and reactivity. Our computer-based simulations provide new molecular-level insights into the dynamics of the hydrogen bond network in liquid water, which can be directly related to measurements of ultrafast infrared spectra. Going down in temperature, our simulations also show the importance of the quasi-liquid layer on top of ice surfaces below the melting point for understanding heterogeneous reactions that take place on ice particles in the atmosphere. A nice way of complementing the intensive studies that are going on at the Hydraulics Lab with cutting edge theoretical and computational tools.

Snapshots from molecular dynamics simulations. Left: Calculated nonlinear infrared spectra in liquid water related to the dynamics of the underlying hydrogen bond network. Right: Excess protons resulting from acid dissociation on ice Ih and amorphous ice below the ice melting temperature. The presence of a thin quasi-liquid layer directly affects proton mobility and the reactivity of the two surfaces.

Stay tuned for new developments!

Francesco Paesani, Department of Chemistry and Biochemistry, UC San Diego

paesanigroup.ucsd.edu





A Great First Day

1 11 2011

The author himself working on gathering chemical composition data from the breaking waves.

After several weeks and countless hours of preparation, the CAICE intensive study finally started.  Clocks synchronized, sampling lines in place, instruments ready and we went for it.  All day we were breaking wave packets every minute while measuring single particle chemical composition, size distributions, ice nucleation, particle hygroscopic properties, filter sampling and the list goes on and on.  This is my second intensive study since joining Prof. Prather’s lab and it was exciting to start.  It was even more exciting when collaborators show their enthusiasm and knowledge about the ongoing measurements.  This study will provide the first step towards understanding sea spray and marine aerosol properties and how this relates to the chemistry of the atmosphere.  Can’t wait to start spiking the seawater with “gooey” monocultures and observe the effects on the marine aerosols properties during the next two weeks.  We have started and it was a great first day. Now we are on day two going at it again…

Luis Cuadra-Rodriguez, Postdoctoral Researcher, Prather Research Group; University of California, San Diego








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