CAICE SeaSCAPE 2019

A Deep Dive

A view of the Pacific Ocean from La Jolla, California

What do you see when you look out over the Pacific Ocean?  One time, I saw a colorful sunset with promise of a green flash. Another time, I saw a pod of dolphins jumping along the coastline. Now, I see the opportunity to dive deep into chemistry and the vast complexity of the atmosphere and ocean.  

Microscopic marine algae, called phytoplankton, turn carbon dioxide from the atmosphere into different chemicals. Some of these chemicals store energy, while others may be incorporated into cell walls.  An individual phytoplankton lives only a few days, and ultimately returns these chemicals back into the ocean. Some of these newly formed chemicals accumulate on the ocean surface, similar to oil rising to the surface of a puddle. The chemicals at the ocean surface can be transferred back into the atmosphere as sea spray particles when waves crash. Once in the atmosphere, these particles interact with sunlight, act as seeds for clouds and ice, and undergo chemical reactions that can alter these properties.

Glorianne Dorcé and Elias Hasenecz, graduate students at the University of Iowa, preparing equipment to collect sea spray aerosol particles that have undergone chemical aging.

In the Sea Spray Chemistry And Particle Evolution Experiment (called SeaSCAPE for short), dozens of talented, dedicated, and inspiring scientists are working tirelessly to study sea spray particle chemistry, transformations, and impacts on the environment. Sea spray particles are collected onto carefully cleaned filters and then shipped to the University of Iowa where we analyze the naturally occurring and man-made chemicals. Other particles first undergo chemical reactions, similar to those that occur in the atmosphere in the presence of sunlight and oxidants, and are then collected. In this case, we examine how reactions alter the chemistry of sea spray particles. 

Our journey only begins this summer and will be followed by years of chemical measurements, discussions, and research collaborations.

Written by: Betsy Stone, Associate Professor, University of Iowa


Any opinions, findings, and conclusions or recommendations expressed in this material are those of the author(s) and do not necessarily reflect the views of the National Science Foundation (NSF).

CAICE SeaSCAPE 2019

Let’s get it started!

SeaSCAPE (Sea Spray Chemistry And Particle Evolution) 2019 is ramping up this week! As you look around the Hydraulics Laboratory “H-Lab” at UC San Diego’s Scripps Institution of Oceanography, you will find NSF CAICE researchers working hard to set up and calibrate their instruments for summer long experiments. You can feel the excitement!  The collaborative team of researchers will soon fill the glorious 33-meter-long wave channel with seawater (see video of waves with the test waters, courtesy of CAICE researcher Prof. Betsy Stone at University of Iowa), and sampling will start next week and last all summer. Bulk seawater, sea surface microlayer (SSML), and sea spray aerosol (SSA) will be collected and measured around the clock, as the crashing waters within the wave tank experiences blooms of biological activity similar to that found in open oceans and seas.

Video of the wave channel in action, courtesy of CAICE researcher Prof. Betsy Stone at the University of Iowa.

For our group, this is a key chance to test how these biological blooms impact the physical chemical phase of SSA. We will take the samples back to our laboratory at the University of Minnesota to use custom build microfluidic (lab-on-a-chip) platforms with on-chip temperature control, to study water uptake and ice nucleation of these sea spray waters and aerosols. In collaboration with the Prather group at UC San Diego, we recently published work on multistep phase transitions that can occur in samples of SSML samples spiked with an organic acid common in the aerosol.  In the time-lapsed 11 second video, you will that as the relative humidity drops, the samples evolve through steps of crystallization, liquid-liquid phase separation, a second crystallization, and a second liquid-liquid phase separation. Each of these phase states impacts how the aerosol particle interacts with the environment, reflects and absorbs solar radiation, forms clouds, and nucleates ice crystals in the atmosphere.

Multistep phase transitions of SSML sample spiked with an organic acid, from Nandy et al. ACS Earth and Space Chemistry (2019). 
DOI: 10.1021/acsearthspacechem.9b00121

We are so excited to collaborate this summer with the many outstanding CAICE groups participating in SeaSCAPE 2019, to collectively tackle the big unanswered questions of SSA properties and dynamics, and their impacts on our climate.

Written by: Associate Professor Cari Dutcher, Mechanical Engineering, University of Minnesota


Any opinions, findings, and conclusions or recommendations expressed in this material are those of the author(s) and do not necessarily reflect the views of the National Science Foundation (NSF).
CAICE Summer 2018

Where the circle of life meets the colors of the wind

Like many people, I grew up watching Disney animated movies. But now as a Ph.D. student who studies connections between ocean and atmospheric chemistry, these childhood ideas are much more real than I ever expected.

We’ve all heard the story: lions eat the antelope. And when they die, their bodies become the grass and the antelope eat the grass. What most people don’t realize is that this same process can be seen in the ocean with a microscope.

Mitch Figure
Concentrated colored (yellow) organic matter, including humic substances, extracted during a phytoplankton bloom

Tiny algae in the ocean grow in number, and when they die, their bodies are broken down by bacteria in the ocean to provide nutrients for other organisms. During this microscopic circle of life, a class of molecules is made called “humic substances”, and these are the molecules I study.

Humic substances are special because they are colored, in other words they can absorb light. They can be also launched from the ocean into the air via sea spray (what I call here the “colors of the wind”).

And when they absorb light in the air, they can start reactions that transform the chemistry of the atmosphere. This exchange from the ocean to the air doesn’t always happen, so my work tries to uncover when and how these molecules get into the air during these ocean life-and-death processes.

The part that I love the most about this research is that you quickly learn that everything is connected. Ocean chemistry is linked to atmospheric chemistry, what happens on the microscopic scale can affect the global scale, and the ocean’s circle of life can give rise to the colors of the wind.

Mitch Photo
Mitch Santander sitting next to a spectrofluorometer, a tool used to measure the relative abundance of humic substances.

 

 

 

 

 

— Mitch Santander, CAICE Graduate Student

 

 

 

Any opinions, findings, and conclusions or recommendations expressed in this material are those of the author(s) and do not necessarily reflect the views of the National Science Foundation (NSF).
CAICE Summer 2018

Particles for Days

Aerosols influence the climate and the environment directly by interacting with incoming and outgoing radiation and indirectly by acting as cloud seeds.  Because of their influence on climate, it is important to measure aerosols, but what are the different ways that our group analyzes them?

ATOFMS
The Aerosol Time of Flight Mass Spectrometer

The pinnacle instrument of the Prather research group is the aerosol time-of-flight mass spectrometer, known as the ATOFMS.  The ATOFMS measures the aerodynamic diameter and the positive and negative chemical spectra for a single aerosol particle in real time. This instrument allows us to look at the chemical signature of the sea spray aerosols released from a breaking wave. With this instrument we can distinguish between different aerosol particle types including sodium rich aerosols, organic rich aerosols, or biological aerosols.  To distinguish between these particle types, we analyze the chemical spectrum from a particle and look for distinct chemical peaks.

However, we have another instrument used to distinguish between biological and non-biological single particles.  This instrument is known as the wideband integrated bioaerosol sensor (WIBS) and determines if a particle is biological based off fluorescence of known biological compounds.  Specifically, the WIBS uses ultra-violet light to excite an aerosol particle and, if it is biological,

The Wideband Integrated Bioaerosol Sensor

the WIBS will then collect the fluorescent signal.  Fluorescence in biological particles occurs because they often contain the amino acid tryptophan and/or the biological co-factor NADH, both of which contain conjugated bond systems and allows for the absorption and transfer of the excitation light source. In addition to the fluorescence signature of a single particle, the WIBS provides information on the particles’ diameter and the asphericity of the particle.

This summer, both of these instruments will be used in tandem to analyze sea spray aerosols released from breaking waves to better understand the role of sea spray on cloud formation and climate.

Brock_Mitts

 

 

-Brock Mitts, Graduate Student

 

Any opinions, findings, and conclusions or recommendations expressed in this material are those of the author(s) and do not necessarily reflect the views of the National Science Foundation (NSF).
CAICE Summer 2018

Is the Ocean Healthy? Let’s Sniff it to Find Out!

This summer I have been fortunate to be a part of the CAICE summer experiment at the Scripps Institution of Oceanography. My mentor, Jon Sauer, and I have been using a Chemical Ionization Mass Spectrometer (CIMS) to analyze the carbon-containing gases, also known as volatile organic compounds (VOCs), produced from the ocean.

CIMS summer expt 2018
The CIMS instrument next to the wave channel

In conjunction with the Aerosol Time of Flight Mass Spectrometer (ATOFMS), which measures the chemical composition of individual aerosol particles, and aerosol particle sizing equipment we can effectively measure the chemical nature of gases and particles produced from seawater in our experiment. The CIMS plays a crucial role in analyzing the health and stability of the phytoplankton bloom in the ocean water within our sampling tanks. To do this, we use the CIMS to sample gases produced in the headspace above the ocean water in our tanks. Looking for specific species reassures us that successive phytoplankton communities are similar to one another and remain healthy.

Along with a lot of amazing knowledge, one of the most important and useful things I will take away from this experience is the importance of communication. This large of an experiment requires constant communication between everyone involved and the people in this group set an amazing example for how to communicate effectively. From group meetings to day to day problem solving, constant sharing of ideas and findings never go unheard.

Summer Expt 2018
Dr. Kim Prather talking to Ben Rico and Jon Sauer about their experiment

The environment promotes curiosity and collaboration and the people I’ve been so lucky enough to work with are always willing to help. I owe a great deal of thanks to my mentor Jon who not only went out of his way to make me feel a part of the group but who made the long days of work enjoyable. Whether we were acquiring data from the CIMS or he was telling me about all the fish he caught from his last fishing trip, Jon managed to make every day of my summer experiment a memorable one.

 

I am looking forward to the rest of my time being a part of this summer experiment and cannot wait to see the results of all the hard working people that are a part of it.

— Ben Rico, Undergraduate Researcher

— Jon Sauer, Graduate Student Researcher

Any opinions, findings, and conclusions or recommendations expressed in this material are those of the author(s) and do not necessarily reflect the views of the National Science Foundation (NSF).
CAICE IMPACTS 2014

DNA in the Clouds

As a third year graduate student in a biochemistry lab, I don’t often get experiences like this. A giant wave-generating tank is novel to me and quite a bit different than the pipet-land I usually live in. Walking into the transformed hydraulics lab always leaves an impression on me. The facility has come alive. It is crammed full with buzzing whirring equipment, and buzzing, whirring people. Scientists and students from all over the country all pointed at a common goal. Every time I walk in there, I step back and really understand what I am a part of. I’m proud. This experience hasn’t always been easy, but it has been rewarding. Certainly, the unwavering dedication of everyone down at the waveflume day to day is truly inspiring.

JMM blog pic[5]
Author Jennifer Michaud in the lab extracting DNA

I am not the only biochemist/biologist involved in IMPACT, but definitely my work stands apart from what others are doing. The name of my game is DNA. My efforts are to collect cells from the waveflume and extract their DNA, which will then be used to identify all the species present.   I would like to characterize not only what microbes are there, but also how they change across a bloom and relate to a natural ocean phytoplankton bloom. More specifically, I am interested to learn which species transfer from bulk to the sea surface to aerosols (airborne particles) and how this changes in conjunction with the growth of phytoplankton and correspondingly bacteria. My highest hope is that certain phenomenon, like ice nuclei, particle types, and interesting organic molecules, might be able to be connected to the predominance of a species or group at the time of their occurrence.

To do this I collect water samples. Harvesting cells is done by vacuum filtration under sterile conditions serially with different sized filters to fractionate the samples into phytoplankton, bacteria, and viruses and vesicles. The major hurdle to my sampling is having enough. Cells are not overly abundant in the marine environment and many liters of water are generally required for DNA analysis. Here we are trying to optimize our methods so that that we get as much DNA from minimal sample amounts so that other analyses are not disrupted. Additionally, sampling cells from aerosols poses its separate challenges. We are using a SpinCon PAS 450-10A Wet Cyclone Portable Air Samplers (Sceptor Industries, Kansas City, MO) to concentrate cells in the aerosols. This instrument has previously been used to sample air above a NY city high-rise and other sites for microbes. The instrument pumps aerosols into a glass chamber containing buffer creating a vortex in which cells are trapped which then are collected by our standard methods. DNA is isolated using an optimized phenol chloroform extraction. Then our precious samples will be sent away for sequencing to identify species.

Yesterday was big sample collection day for me. Lots of filtration. Today, I am extracting DNA from the aerosol samples. I hope they have lots!

Jennifer Michaud, Graduate Student, Burkart Group, Department of Chemistry and Biochemistry, UC San Diego

CAICE IMPACTS 2014

Approaching the Finish Line…

Although it was a ton of hard work, I have enjoyed being part of the CAICE (Center for Aerosol Impacts on Climate and the Environment) IMPACTS (Investigation into Marine Particle Chemistry and Transfer Science) 2014 intensive. Professors and students from all over the country are gathered here to better understand the link between ocean biology and the composition and physical properties of particles emitted from sea spray.

10457561_692410517491553_292097329586178028_n[2]I am a 3rd year graduate student in Chris Cappa’s group at UC Davis. I came to UC San Diego to investigate how much these particles grow as a result of humidification using a cavity ring-down spectrometer (CRD). The larger these particles grow, the more light they scatter. By scattering solar radiation, these particles cool the planet and are therefore important for understanding the Earth’s climate. Particles emitted from sea spray take up a lot of water because they are mostly composed of salt. However, the biology of the ocean impacts what these particles are made of and, by making the particle less “salty,” can decrease the how much water they take up.

The "beach" area of the wave flume in the Hydraulic Lab at SIO
The “beach” area of the wave flume in the Hydraulic Lab at SIO

My goal is to quantify how changes in particle composition due to biological processes in seawater influence how much these particles grow due to humidification.
During this unique, once-in-a-lifetime experiment, everyone I have worked with has been incredibly positive and fun to be around. At the end of IMPACTS, I will leave with both exciting data and many new friends.

 

Sara Forestieri, Graduate Student, Cappa Group, Department of Civil and Environmental Engineering at UC Davis

CAICE IMPACTS 2014

Collaboration and teamwork are a key to great discoveries

Dozens of instruments from many universities, this is what it takes to do real science! Nowadays, great discoveries are not possible within one laboratory working in isolation. Collaborations of research teams that have various techniques, approaches, and backgrounds from multiple scientific disciplines are necessary for innovations and advances. This summer professors, graduate and undergraduate students from all over the country came to Scripps Institution of Oceanography at University of California, San Diego to participate in 2014 NSF Center for Aerosol Impacts on Climate and the Environment (CAICE) IMPACTS (Investigation into Marine PArticle Chemistry and Transfer Science) campaign.

image001
The author, Olga, and her group mate Jon preparing for particle collection on MOUDI

I came from the University of Iowa where I just started my fifth year of graduate school in Dr. Vicki Grassian research group. My area of interest is phase, composition and hygroscopicity of individual sea spray aerosol particles. We collect particles generated during wave breaking and then take them back to Iowa for detailed micro-structural analysis with a variety of microscopic and spectroscopic techniques. Atomic force microscopy is a tool to image the surface of particles at the nanoscale and it is exceptionally noteworthy that it can reveal 3D shape of particles. Scanning electron microscopy and transmission electron microscopy can image particles down to 1 nm resolution and when used with energy-dispersive X-ray spectroscopy can reveal spatial elemental composition of particles. Raman microspectroscopy gives information about vibrations of functional groups thus revealing chemical composition of particles as small as several hundred nanometers. Elemental and molecular composition derived from these techniques can be combined with on-line measurements such as aerosol time-of-flight mass spectrometry to get the most complete information about particles’ composition. All microscopy techniques can be performed in chambers where relative humidity is be controlled and size of particles is monitored using microscope. Therefore, we can detect how particles grow in humid environment. Raman microspectrometer can detect the water in particles spectroscopically and thus can be additionally used to monitor water content of particles as relative humidity changes. It is very important to know how particles interact with water as it determines how particles will interact with light, form clouds and react with trace gases in the atmosphere (which can be fairly humid). Finally, as we learn about the dependence of particles’ properties on their detailed chemical composition we can understand and more importantly predict their properties in the environment better!

As I have already mentioned collaboration is a key for breakthrough research discoveries. Collaboration and teamwork! This picture illustrates teamwork in action where Jon and Olga (author) are putting together stages to collect sea spray aerosol particles. This is a great campaign that unites many research groups and I look forward to analyzing our particles and working with other participating groups to shade more light on marine atmosphere.

Olga Laskina, Research Assistant, Grassian Research Group, Department of Chemistry at University of Iowa

CAICE Intensive 2011

Just the beginning in our quest to understand complex chemistry impacts on climate……

As I sit here on Thanksgiving morning thinking of all I am thankful for, I think of many things but the CAICE intensive, just completed a little more than one week ago, keeps springing to mind.  We ran a few days longer than we expected, but on November 15, we officially stopped sampling with all instruments.

Due to the dedication of the team of scientists involved in this project, we took full advantage of the suite of measurements to run experiments 24/7 for the final 10 days.  In the final 5 days, thanks to input (and samples) from our biology colleagues, we ran a complete mesocosm experiment, studying how a mixture of bacteria, viruses, and other ocean critters affect the chemistry of the seawater and in turn, these changes affect the chemistry of sea spray.  Our experiments went from “simple” filtered seawater to single “critter” additions covering a range of properties to the full complexity of a real mesocosm bloom. We did all that we set out to do and more with many exciting surprises along the way.  I will say that the one thing that sticks out in my mind is how much easier it is to see instantaneous changes and make sense of the chemical complexity when you know for a fact you are looking at one source, in this case, sea spray.  This study has already helped our group explain critical observations we have seen countless times in field studies but never been able to explain.  It reinforces exactly why we moved the real world to the lab to perform complex chemistry experiments.  I think

Chemical complexity...the soup of bacteria, viruses, protozoa, organics, salts...formed some very interesting aerosols...

we will be able to clearly show how this represents a new approach for  “integrating reductionist and complexity approaches to solve complicated problems”, one of the grand NSF challenges we set out to address.

Everyone is recovering now, but feeling extremely rewarded by all we have accomplished as a collective group.  The fruits of all of our labor will become evident in the coming weeks and months, as we merge all we have found into one set of stories.  I want to personally thank everyone who has been involved in this study, Hlab staff, grad, undergrad, postdocs, faculty, and advisors, for your dedication to this CAICE project.

It has been a wonderful experience, one of the best of my 20 year career, working with everyone involved and I look forward to digging more deeply into the results together.  Today, I am thankful for all we were able to accomplish together–but I can’t help feeling that this is just the beginning of a long and productive scientific journey….

Here’s to hoping everyone has a wonderful Thanksgiving…

Kimberly A. Prather, Director of CAICE (http://caice.ucsd.edu)