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

Perspective of IMPACTS from a middle school student

I am a 12 year old boy who is going into 7th grade at the San Diego Jewish Academy. I have two siblings named Rebecca and Jacob and a mother and father. Also, I have a pet dog named Rocky. I like playing basketball and watching shows like Sports Center, football, and basketball games.

This summer, I have been lucky enough to join the Scripps Institution of Oceanography for a volunteer chemistry week, July 21 – 25, 2014. During the start of the week, I worked with the wave machine. In the wave machine, we create waves, conduct experiments and detect particles. Some experiments included detecting particles while others needed very high technology. The main reason for having the wave machine is to have a simulation of sea spray. Sea spray is a big factor in world climate as it controls how many clouds form. I learned this week that the prediction on the amount that comes out of the ocean ranges from one to 1 trillion.  CAICE scientists are trying to learn how chemistry controls the amount of sea spray that makes its way into the atmosphere.

Most of the week, I was in the Marine Ecosystem Sensing, Observation and Modeling (MESOM) lab. There are two freezers in the lab – one is set at -80* C and the other is setAaron at -20* C. There is ice in the freezers and also samples or dyes used for detecting bacteria. One of the days, I took a ride on the truck that collects ocean water from the dock. Once the ocean water sample is collected, it is then brought back to the Hydraulics Lab (H Lab). We use the water in the wave machine, for outside tanks, and for other scientific purposes. The water we collect is filtered to the point where only viruses and bacteria remain in the water.

One important chemistry concept I learned about is the difference between a particle and a molecule. A molecule is just a mixture of atoms whereas a particle is more like a big mixture of molecules. For example, a molecule would be CO2 or H2O but a particle would contain billions of molecules mixed together. One thing that I learned a lot about are aerosols (many particles) which are a big question because of people predicting how many there are and because we don’t understand the climate effects from a single aerosol. An aerosol, also a particle and created by “ocean foam”, gets released into the air and carries bacteria and viruses up to six miles high into our atmosphere!!

Phytoplankton is a small plant that floats around in the ocean and is in the bottom of the food chain. It gets concentrated in a special layer of the ocean called the “sea surface microlayer.” Phytoplankton is important to our earth because it feeds the entire ocean and produces much of the oxygen we breathe.

The work conducted in the MESOM and H Labs is important because it will help us better understand our climate and the world. I really enjoyed volunteering in Dr. Prather’s lab and working with all of the graduate students. I learned a lot during my week and hope to come back next summer.

Aaron Bronstein

San Diego Jewish Academy

CAICE IMPACTS 2014

Head in the Clouds

As an incoming graduate student working on my first independent project, I had no idea what to expect from the CAICE IMPACTS chemistry intensive. I quickly found out that this was going to be one of the most challenging but also most rewarding experiences I’ve had so far.

I am an incoming student in Dr. Tim Bertram’s group and am studying cloud condensation nuclei (CCN) activity. One of the least well understood aspects of climate modeling is the indirect effect of aerosols on cloud formation and lifetime. CCN are a subset of aerosol particles which are capable of having water vapor condense onto them. An increase in CCN concentrations means more cloud droplets being formed in the atmosphere as well as longer cloud lifetimes. These clouds can then reflect sunlight causing cooling of the atmosphere.image001

Salt particles are especially great at serving as CCN because of their ability to uptake water (just think how well salt dissolves a pot of water). Organic type particles are more hydrophobic (not attracted to water) meaning they are poor CCN species. When one thinks of the composition of seawater they almost always think about salt, however during a phytoplankton bloom and death a substantial amount of organic matter is released. What I hope to study is how the CCN activity of sea-spray aerosols changes with the course of the bloom and its release of organics.

As we approach the last few days of the intensive I am very thankful for the opportunity to contribute to this research and to work with so many great scientists in our CCI (Chemical Center of Innovation). I look forward to building on this research and this experience for a long time to come.

 

Gordon Novak, Graduate Student, Bertram Group at UC San Diego, Department of Chemistry and Biochemistry

CAICE IMPACTS 2014

The study of ocean – atmosphere interactions

When waves crash and underwater bubbles burst at the surface, tiny particles are ejected from the ocean into the atmosphere. As the water evaporates away, a particle is left behind that we call sea spray aerosol. Our research through the Center for Aerosol Impacts on Climate and the Environment (CAICE) is focused on understanding the physical, chemical, and biological processes that affect the composition sea spray aerosol. Knowledge of this composition is critical to understanding the effect of sea spray in the atmosphere, such as how it reacts and how it affects cloud formation.

image001
Marine Aerosol Reference Tanks (MART) provide a unique opportunity to capture sea spray aerosol in the laboratory

During the IMPACTS field experiment at Scripps Institute of Oceanography in La Jolla, California, we are collecting samples of ocean water, sea surface microlayer, sea foam, and sea spray aerosol from the wave flume and Marine Aerosol Reference Tanks (MART). We transport these samples back to our laboratories at the University of Iowa, where we measure individual organic molecules and inorganic ions. We use liquid chromatography (LC for short) that allows us to separate compounds of interest from the complex environmental sample. Conductivity, electrochemistry, and mass spectrometry provide sensitive methods of detection that allow us to quantify trace amounts of compounds. By determining the distribution of chemicals across the phases of the ocean and atmosphere relative to one another, we can characterize the selective processes that lead to organic molecule enrichment in sea spray aerosol. Collaborating in the IMPACTS field study means that we can combine our knowledge of chemistry with evolving ocean biology and the physical properties of the sea spray aerosol.

image003
CAICE researchers (clockwise) Hosiana Abewe, Olga Laskina, Jon Trueblood, Thilina Jayarathne, and Grace de Dieu Irumva testing a laboratory experiment on the measurement of surface reflectivity (a.k.a. albedo)

In addition to conducting research, CAICE provides an opportunity to engage with students and the community in learning about climate science. I had the pleasure of teaching at the California State Summer School for Mathematics and Science (COSMOS) while at UCSD earlier this month. I worked with undergraduate and graduate students to design and adapt curricula about global change and climate for high school students. Together, we explored how the earth’s surface affects our energy balance with the sun, how some gases cause greenhouse warming, and how different molecules interact with solar energy.

I am thrilled to be part of a dynamic research center that combines cutting-edge research, innovation, and education about climate science. Through this summer’s IMPACTS experiment, we have new capabilities to understand complex environmental processes through intricately-designed laboratory experiments.

Elizabeth Stone, Assistant Professor, Department of Chemistry, University of Iowa

CAICE IMPACTS 2014

Sea water; is it only Salt?

I am a third year graduate student from Prof. Betsy Stone research group, University of Iowa. It was a tremendous opportunity for me to participate in IMPACTS (Investigation into Marine Particle Chemistry and Transfer Science) summer 2014 intensive campaign at the Center for Aerosol Impacts on Climate and the Environment (CAICE). These days SIO (Scripps Institution of Oceanography), UCSD is filled with budding atmospheric scientists who are exploring the largest indoor phytoplankton bloom in the world. It is awesome to see everybody is working hard towards the same goal day and night. I am so proud of myself for being a member in this team who are “IMPACTed” by the sea spray aerosols. Originally, I am from Sri Lanka, the island of paradise in Indian Ocean. Being an individual from a small island which is just 270 miles long and 140 miles wide with 800 miles of beaches I was never amazed by seeing the ocean. After I joined the CAICE project I got an opportunity to investigate the importance of ocean to atmospheric science and climate change which changed my perspective about the ocean.

Wimage001e think the ocean is full of salty water and the best place for a day out. However, ocean water is not only salt; it contain thousands of organic compounds. These organic compounds are results of phytoplankton and bacterial activities. Breaking waves on the ocean surface generate splash water droplets and air bubbles that scavenge sea salt and organic matter from the sea surface to the atmosphere. These small particles are called sea spray aerosols (SSA) which has important effects in cloud formation and earth’s radiative balance. However, all the organic compounds that can be seen in sea water is not transferred to sea spray aerosol. Some of these compounds get enriched in upper most layer of the ocean (sea surface micro layer) and selectively transferred in to the atmosphere. This selectively transfer mechanism is poorly studied and yet to be fully understood. Therefore, during this study I am collecting sea water, sea surface micro layer and sea spray aerosols and analyze them for organic molecules such as carbohydrates, carboxylic acids, proteins and lipopolysaccharides to understand the selective transfer mechanism of these organic compounds in the ocean to the atmosphere.

Thilina Jayarathne, Research Assistant, Stone Research Group, Department of Chemistry at University of Iowa.

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