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

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 IMPACTS 2014

CAICE IMPACTS a UCSD Undergrad

After finishing my second year of undergrad at UCSD, I am thrilled to already be a part of the CAICE IMPACTS experiments. My interests revolve around understanding the surface chemistry of seawater and its impact on the selective transfer of species from the bulk seawater to the surface seawater and ultimately to the sea spray aerosols during the phytoplankton bloom in the wave-flume.

A Tensiometer measuring the surface tension of surface seawater via a Platinum plate
A Tensiometer measuring the surface tension of surface seawater via a Platinum plate

To get a sense of the changes occurring in the surface of the seawater, I have been measuring the surface tension in the sea-surface microlayer (upper most millimeter of the surface) and the bulk seawater (the water beneath the surface) using a tensiometer shown in the image on the right. Surface tension can be thought of as the force that causes a liquid’s surface to pull closely together for minimal surface area, and the tensiometer uses a platinum plate to measure the force the liquid exerts on it. I am looking for changes in the surface tension day-by-day in the wave-flume as the phytoplankton bloom progresses to see how this surface property changes and how it impacts the chemical properties of the surface water and sea spray aerosols.

image003
A preliminary infrared spectrum of dehydrated bulk seawater

To determine the changing chemical and biological composition of bulk seawater, sea-surface microlayer, and sea spray aerosols, I am using infrared (IR) spectroscopy, which essentially uses light in the infrared region to cause molecules to vibrate. These vibrations can be seen as peaks in the IR spectrum shown on the right, and each peak corresponds to a certain chemical group. It should be interesting to see if changes in functional groups are apparent to better understand the transfer of molecules from the surface of the ocean to sea spray aerosols.

While learning all of the chemistry behind CAICE is exciting, the true nature of its impact on my undergrad experience comes from the diversity and perseverance of everyone I have met. From biologists to oceanographers, I am so grateful to be around this atmosphere of scientists coming together to work on the impact sea spray aerosols have on our climate and environment. I have met numerous PIs, postdocs, and grad students, and they have all given me insight into what I want to do in the future. I want to continue to explore and help determine the true impact the changing environment has on our lives and how we can all make the effort to improve our understanding of the world’s scientific complexity.

Joshua L. Cox, Undergraduate Researcher, Prather Group, Dept. of Chemistry and Biochemistry, UCSD

CAICE IMPACTS 2014

How science gets done

A lack of sleep, lots of laughs, and a room full of loud pumps: how science gets done!

What a whirlwind the past few weeks have been! It’s hard to believe that we are already about halfway through IMPACTS (Investigation into Marine Particle Chemistry and Transfer Science), the Center for Aerosol Impacts on Climate and the Environment (CAICE) summer 2014 intensive campaign. The hydraulics lab at Scripps Institution of Oceanography has been overtaken by students, postdocs, and instrumentation (and TONS of noisy pumps!) in hopes of measuring changes in various chemical and physical properties of sea spray aerosol over the course of a phytoplankton bloom and understanding how these changes may influence the climate and environment.

I am a grad student, just starting my 3rd year at UC San Diego in Timothy Bertram’s research group. Most of the researchers here are interested in measuring sea spray aerosols; however, particles are not the only interesting component generated and released from the ocean surface.

IMG_0077
The author, Nicole Campbell, poses with the CITOFMS, which measures trace marine gases

The ocean also emits various gas-phase species; the specific trace gases that are produced can change as a function of the biological conditions present at the sea surface. Once introduced to the atmosphere, gas-phase molecules can undergo interesting chemistry; some gases can even serve as precursors for new aerosol particle formation! I am operating a piece of instrumentation to measure these trace marine gases, a chemical ionization time of flight mass spectrometer (the CITOFMS), which allows for real-time, simultaneous detection of gas-phase molecules in a specific mass range of interest.

This is my first field study, and it has definitely been an eye-opening experience, filled with the full spectrum of emotions. I have learned SO much during the past few weeks, not only about science, but also about teamwork and collaboration. This experiment has been a huge undertaking for everybody involved and has definitely tested the patience of many, but I can honestly say that I couldn’t have asked for a better group of people to spend a month of 15+ hour workdays with. The creativity, dedication, positivity (most of the time…don’t get me wrong, there have been some challenging moments for sure!), and excitement of the grad students, postdocs, professors, facility staff, and visitors is incredible and has made this such a fun and exciting environment to work in. I can’t wait to see what we learn and the story that unfolds in the coming months!

Nicole R. Campbell, graduate student, Bertram Group at UC San Diego, Department of Chemistry and Biochemistry

CAICE IMPACTS 2014

CAICE IMPACTS 2014

I have the privilege of writing the very first blog for our major 2014 NSF Center for Aerosol Impacts on Climate and the Environment (CAICE) summer intensive named IMPACTS (Investigation into Marine PArticle Chemistry and Transfer Science). Things have been incredibly busy with many people working long days (phytoplankton don’t sleep!). We are now at the mid-point in the study. We have about 40 students, ranging from high school through graduate school, and postdoctoral fellows working on this project. They came from many places with their unique instrumentation to work with us at UCSD/SIO including U. of Iowa, U. of Wisconsin, Colorado State University, UC Davis, UC Berkeley, Colby College, and Rwanda via Cal Baptist College. It is an exciting but very challenging experiment where we are setting out to produce the world’s largest indoor phytoplankton bloom in 3000 gallons of seawater in a 33 m wave flume equipped with real breaking waves. Phytoplankton are tiny microscopic plants (just think of the ocean as an underwater forest) that fix carbon from the atmosphere and produce almost 50% of the oxygen we breathe.  Chlorophyll is an indicator of the quantity of phytoplankton that is present. When a bloom occurs, scientists can watch chlorophyll change from space using satellite imagery.

image001
Red tide phytoplankton bloom off the Scripps Pier at UC San Diego

The image on the left shows what a phytoplankton bloom (called a red tide) looks like off the Scripps Institution of Oceanography pier. When these blooms occur, they can cover large regions of the ocean and dramatically change ocean chemistry. The ultimate goal of our study is to investigate the transfer of chemical and biological species from seawater into sea spray aerosols and measure how this chemistry evolves over the course of a phytoplankton bloom. Over the past 2 years, we have found we can reproducibly induce phytoplankton blooms in much smaller tanks. It turns out it is much more challenging in a wave flume! This is due to the fact that the tank is filled with a myriad of species (bacteria, phytoplankton, viruses) all competing for nutrients (i.e. food) we initially put in the tank. Another major challenge is the large “grazers” that are like little Pacmen that go around and consume the phytoplankton before they can grow into a bloom. Once we get a bloom and sea spray is emitted, we measure the ability of the particles to undergo chemical reactions, induce ice cloud formation, form cloud droplets, as well as interact with sunlight. The grand challenge involves understanding how the chemical complexity of the seawater changes and how this impacts climate and reactivity properties of the sea spray. The premise for CAICE is to perform the next generation of lab studies where we learn about the real world by bringing its true complexity into the lab where we can control many of the parameters at a level that cannot be done in the field. I believe this has to be one of the most challenging experiments ever done in a laboratory setting due to how difficult it is to rely on the complexity of biological processes to naturally evolve under lab conditions (less light, changing temperatures, etc.)….the good news is I think we have finally done it!

IMPACTS-2014: graph showing growth of phytoplankton over time as indicated by chlorophyll-a concentrations in CAICE ocean-atmosphere wave flume in July 2014. This represents the world's largest indoor ocean phytoplankton bloom in natural seawater equipped with breaking waves
IMPACTS-2014: graph showing growth of phytoplankton over time as indicated by chlorophyll-a concentrations in CAICE ocean-atmosphere wave flume in July 2014. This represents the world’s largest indoor ocean phytoplankton bloom in natural seawater equipped with breaking waves

After waiting nervously for almost 2 weeks of “background” measurements, the bloom started taking off on July 10 and it has been growing since then. We know this by monitoring chlorophyll levels which have been increasing over time. We are all very excited that we are finally getting to measure what we set out to measure. That is not always the case in complex “field studies” and certainly not the case just because this one is in the lab. Now chemists are positioned to directly measure the chemical composition and physical properties of complex sea spray aerosol in ways that have never been done before. This was made possible by a devoted team that has been brought together through CAICE. Finally on a personal note, I will say that the last month has been one of the most challenging ones I have faced as a professor; yet, it has been the most rewarding research experience I have ever been involved in. I have so enjoyed the day-to-day interactions with this team of young scientists and getting the opportunity to work in the trenches with them to help make a difficult experiment take off. Their drive and positive can-do attitudes make it clear to me that the next generation of scientists is well equipped to tackle the complex environmental problems that we will be facing. In subsequent blogs, you will get to hear from other CAICE scientists about their experiences and measurements and how they are trying to address the questions above. I hope you enjoy following the CAICE IMPACTS-2014 blog over the next couple of weeks.

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