Nature: Isotopic constraint on the twentieth-century increase in tropospheric ozone


Rice University researchers and collaborators used ice cores, like the one shown here from Antarctica, in combination with atmospheric chemistry models to establish an upper limit for the increase in ozone levels in the lower atmosphere since 1850. (Photo by Jeff Fitlow/Rice University)

Isotopic constraint on the twentieth-century increase in tropospheric ozone

Laurence Y. Yeung, Lee. T. Murray, Patricia Martinerie, Emmanuel Witrant, Huanting Hu, Asmita Banerjee, Anaïs Orsi & Jérôme Chappellaz

Nature 570 (2019) 224-227


Tropospheric ozone (O3) is a key component of air pollution and an important anthropogenic greenhouse gas. During the twentieth century, the proliferation of the internal combustion engine, rapid industrialization and land-use change led to a global-scale increase in O3 concentrations; however, the magnitude of this increase is uncertain. Atmospheric chemistry models typically predict an increase in the tropospheric O3 burden of between 25 and 50 per cent since 1900, whereas direct measurements made in the late nineteenth century indicate that surface O3 mixing ratios increased by up to 300 per cent over that time period. However, the accuracy and diagnostic power of these measurements remains controversial. Here we use a record of the clumped-isotope composition of molecular oxygen (18O18O in O2) trapped in polar firn and ice from 1590 to 2016 ad, as well as atmospheric chemistry model simulations, to constrain changes in tropospheric O3 concentrations. We find that during the second half of the twentieth century, the proportion of 18O18O in O2 decreased by 0.03 ± 0.02 parts per thousand (95 per cent confidence interval) below its 1590–1958 ad mean, which implies that tropospheric O3 increased by less than 40 per cent during that time. These results corroborate model predictions of global-scale increases in surface pollution and vegetative stress caused by increasing anthropogenic emissions of O3 precursors. We also estimate that the radiative forcing of tropospheric O3 since 1850 ad is probably less than +0.4 watts per square metre, consistent with results from recent climate modelling studies.

DOI: 10.1038/s41586-019-1277-1



Chem Geo: Decarbonation in the Ca-Mg-Fe carbonate system at mid-crustal pressure as a function of temperature and assimilation with arc magmas – Implications for long-term climate

Chem Geo: Decarbonation in the Ca-Mg-Fe carbonate system at mid-crustal pressure as a function of temperature and assimilation with arc magmas – Implications for long-term climate

Decarbonation in the Ca-Mg-Fe carbonate system at mid-crustal pressure as a function of temperature and assimilation with arc magmas — Implications for long-term climate 

By: Laura Carter, Rajdeep Dasgupta

Carbon is commonly locked in the crust in two carbonate minerals: 1) calcite; and 2) dolomite. Pure, dry calcite is thermally stable to high temperatures, but can be assimilated by melts ascending from the mantle to the surface. Dolomite can decarbonate at high temperatures in addition to being consumed by subarc magmas. In this study, experiments containing carbonate with compositions between dolomite and calcite (with minor iron) give evidence for decarbonation at temperatures as low as 800 °C at 0.5 GPa, at nominally dry conditions, with increasing carbon dioxide release corresponding to increasing Mg/Ca ratios. Allowing these carbonates to interact with typical arc dacite and basaltic magmas at ~15 km depth and temperatures of 1000 and 1150 °C, respectively, depresses the liquidi, produces periclase and olivine with Mg-rich carbonate, expands the stability field of clinopyroxene, and releases CO2. Calculations indicate assimilation- and thermal breakdown-induced release of CO2 both increase with increasing Mg/Ca ratio of carbonate sediments. Extrapolating to conditions of natural systems with magmatic recharge suggests assimilation produces ≤1010–1012 g/y CO2, expelling as much as ~105 g CO2/m3 of carbonate, similar to that which can occur by thermal breakdown of carbonate at 600–800 °C, or potentially less depending on the heat, size and timescale of the aureole formation. Though more dolomitic systems assimilate more and thus release more crustal carbon to the atmosphere than more limestone-rich carbonate, our results indicate both assimilation and thermal breakdown processes can each contribute a significant and important flux of greenhouse gas to the atmosphere. Likely happening concurrently, these extra sources from the crustal carbon reservoir could affect climate, which may be particularly relevant during Earth’s Eocene-Cretaceous warm period.

Full text at:

AJS: Volatile-bearing partial melts beneath oceans and continents – Where, how much, and of what compositions?

Volatile-bearing partial melts beneath oceans and continents – Where, how much, and of what compositions?

Abstract: Besides depth and temperature, CO2 and H2O, are the two most important variables in stabilizing partial melts in the Earth’s mantle. However, despite decades of experimental studies on the roles of these two volatile species in affecting mantle melting, ambiguity remains in terms of the stability, composition, and proportion of volatile-bearing partial melts at depths. Furthermore, the difference in the influence of H2O versus CO2 in production of mantle melts is often inadequately discussed. Here I first discuss how as a function of depth and concentration of volatiles, the peridotite + H2O versus peridotite + CO2 near-solidus melting conditions differ – discussing specifically the concepts of saturation of volatile-bearing phases and how the mode of storage of ‘water’ and carbon affects the near solidus melting relations. This analysis shows that for the Earth’s mantle beneath oceans and continents, deep, volatile-induced melting is influenced mostly by carbon, with water-bearing carbonated silicate melt being the key agent. A quantitative framework that uses the existing experimental data, allows calculation of the loci, extent of melting, and major element compositions of volatile-bearing partial melts beneath oceans and continents. How the domains of volatile-bearing melt stability are affected when possible oxygen fugacity variation at depths in the mantle is taken into account is also discussed. I show that trace amount hydrous carbonated silicate melt is likely stabilized at two or more distinct depths in the continental lithospheric mantle, at depths ranges similar to where mid-lithospheric discontinuity (MLD) and lithosphere-asthenosphere boundary (LAB) have been estimated from seismology. Whereas beneath oceans, hydrous carbonated silicate melt likely remain continuously stable from the base of the thermal boundary layer to at least 200 km or deeper depending on the prevailing oxygen fugacity at depths. Hotter mantles, such as those beneath oceans, prevent sampling strongly silica-undersaturated, carbonated melts such as kimberlites as shallower basaltic melt generation dominates. Thick thermal boundary layers, such as those in cratonic regions, on the other hand allow production of kimberlitic to carbonatitic melt only. Therefore, the increasing frequency of occurrence of kimberlites starting at the Proterozoic may be causally linked to cooling and growth of sub-continental mantles through time.


Dasgupta, R. (2018). Volatile bearing partial melts beneath oceans and continents – where, how much, and of what compositions? American Journal of Science 318 (1), 141-165. doi:10.2475/01.2018.06

“Data report: reanalysis of interstitial water barium, iron, and sulfur concentrations at Sites U1426 and U1427”, by Clint Miller and Gerald Dickens, in Volume 346 of the Proceedings of the Integrated Ocean Drilling Program.


Within the south of the marginal sea between Japan and Korea, interstitial water (IW) profiles exhibit a prominent sulfate–methane transition (SMT) in the upper few meters of sediment. As the SMT has become a focus of attention, IW samples were collected at high spatial resolution within shallow sediment at Sites U1426 and U1427 and examined on board the R/V JOIDES Resolution, under the auspices of the Integrated Ocean Drilling Program, for a wide range of dissolved species. However, irregularities were noted for the sulfate (SO42–), Ba, and Fe concentration profiles, each of importance to understanding the SMT. Splits of 134 IW samples, prepared with HNO3 during the expedition, were therefore reanalyzed at Rice University for S, Ba, and Fe, with S as a proxy for SO42–. Results of 134 samples included 29 duplicates with low percent difference (0.01%–34.69%, 0.01%–14.90%, and 0.03%–35.19%) and 6 spiked blanks with low percent error relative to stock solution concentration (1.59%, 2.41%, and 4.11%). The shore-based S and Ba profiles have trends similar to those determined on ship but with obvious offsets. The remeasured Fe profiles are comparable to those measured on ship, albeit with more data points. Although the IW samples were measured between 95 and 113 days after the expedition, the new results have high data reproducibility, render smooth profiles, and give more expected chemistry across the SMTs. For these three elements, we suggest the new results should replace the shipboard data.

1 Miller, C., and Dickens, G., 2017. Data report: reanalysis of interstitial water barium, iron, and sulfur concentrations at Sites U1426 and U1427. In Tada, R., Murray, R.W., Alvarez Zarikian, C.A., and the Expedition 346 Scientists, Proceedings of the Integrated Ocean Drilling Program, 346: College Station, TX (Integrated Ocean Drilling Program).

2 Department of Earth Sciences, Rice University, Houston, TX, 77005, USA. Correspondence author:

Initial receipt: 21 April 2017
Acceptance: 3 August 2017
Publication: 3 October 2017
MS 346-203

Laurence Yeung wins 2016 F. W. Clarke award from the Geochemical Society

Yeung headshotClarke medal

Laurence Yeung, assistant professor of Earth Science, will be awarded the F. W. Clarke medal from the Geochemical Society at this year’s V. M. Goldschmidt meeting in Yokohama, Japan. The award is named after Frank Wigglesworth Clarke, who determined the composition of the Earth’s crust and is considered by many to be the father of Geochemistry. From the Geochemical society’s announcement:

The Clarke Award recognizes an early-career scientist for a single outstanding contribution to geochemistry or cosmochemistry published either as a single paper or a series of papers on a single topic. Prof. Yeung is recognized for developing, both experimentally and theoretically, a new clumped isotopologue system with applications to natural systems.

With Dr. Yeung’s award, the Department of Earth Science now has three F. W. Clarke medalists: Profs. Cin-Ty Lee (2009), Rajdeep Dasgupta (2011), and Laurence Yeung (2016). We are tied (with Caltech) for the most Clarke medalists in any department in the world. Here’s to many more!

Link to story on Rice News

An Experimental Study of Trace Element Fluxes from Subducted Oceanic Crust

New publication in Journal of Petrology from Laura Carter’s Master’s research at the University of Bristol with Susanne Skora, Jon Blundy, Tim Elliott, and Cees-Jan De Hoog at the University of Edinburgh. Carter et al. 2015

We have determined experimentally the hydrous phase relations and trace element partitioning behaviour of ocean floor basalt protoliths at pressures and temperatures (3 GPa, 750–1000C) relevant to melting in subduction zones. To avoid potential complexities associated with trace element doping of starting materials we have used natural, pristine mid-ocean ridge basalt (MORB from Kolbeinsey Ridge) and altered oceanic crust (AOC from Deep Sea Drilling Project leg 46, 20N Atlantic).  Approximately 15 wt % water was added to starting materials to simulate fluid fluxing from dehydrating serpentinite underlying the oceanic crust. The vapour-saturated solidus is sensitive to basalt K2O content, decreasing from 825 +/- 25C in MORB (0.04 wt % K2O) to 750C in AOC (0.25 wt % K2O). Textural evidence indicates that near-solidus fluids are sub-critical in nature. The residual solid assemblage in both MORB and AOC experiments is dominated by garnet and clinopyroxene, with accessory kyanite, epidote, Fe–Ti oxide and rutile (plus quartz–coesite, phengite and apatite below the solidus). Trace element analyses of quenched silica-rich melts show a strong temperature dependence of key trace elements. In contrast to the trace elementdoped starting materials of previous studies, we do not observe residual allanite. Instead, abundant residual epidote provides the host for thorium and light rare earth elements (LREE), preventing LREE from being released (RLREE <3ppm at 750–900C). Elevated Ba/Th ratios, characteristic of many arc basalts, are found to be generated within a narrow temperature field above the breakdown temperature of phengite, but below exhaustion of epidote. Melts with Ba/Th >1500 and La/SmPUM (where PUM indicates primitive upper mantle) 1, most closely matching the geochemical signal of arc lavas worldwide, were generated from AOC at 800–850C.


ESCI 322 – Going Across Southern California

Mafic enclaves in the Bernasconi Hills Pluton in southern California. Emily Pain for scale.

Mafic enclaves in the Bernasconi Hills Pluton in southern California. Emily Paine for scale.

Students in 322 go on a geology trip across southern California led by their professor Cin-Ty Lee and graduate student Hehe Jiang.  This is a mid-term field trip that the department has used to give a students a chance to apply some of their classroom knowledge to the field.  When it comes to looking at rocks and minerals, there is nothing better than going to the field where one has context.  It makes learning about rocks much more meaningful and more memorable. 

So this year, the class did a transect across southern California.  We arrived Friday afternoon in Ontario, California.  Our first stop was in the northern Peninsular Ranges Batholith, part of a continental volcanic arc that extended from Mexico all the way up through Canada during the Cretaceous.  This volcanic arc would form the backbone for much of our trip, so-to-speak.  We visited the Bernasconi Hills pluton, where we examined outcrops showing extensive mafic-felsic mingling in the form of mafic xenolith swarms and highly attenuated schlieren.  We then made our way across the San Jacinto Valley, a late Miocene-Pliocene graben formed by extension in the vicinity of the San Jacinto Fault, a splay of the San Andreas Fault. Around us, rising above the valley floor were large knobs of Cretaceous granitoids.  We made our way down to Green Acres, where we had a chance to examine olivine-gabbros, examples of cumulates in a shallow mafic magma chamber. 

We found ourselves the next morning in San Diego.  After a quick breakfast at McDonald’s, we headed out to Point Loma to examine the Point Loma and Cabrillo formations.  We picked the perfect place to look at these outcrops because we were right along the ocean, with waves crashing, sea gulls squawking, pelicans diving and the cool breeze blowing against us.  These are late Cretaceous sediments. We examined them under our hand lens and discovered that they consisted of quartz, feldspars, and lots of fresh biotite and hornblende. Normally, biotite and hornblende don’t last long in the weathering regime, so their presence suggests a very juvenile sediment.  These sediments, it turns out, were being shed off the Cretaceous volcanic arc, most likely while the arc was still active, given its age.  Yesterday, we were looking at the eroded plutons and today, we are seeing their eroded tops in an ancient basin!

Cretaceous fore-arc sediments at Point Loma, California.

Cretaceous fore-arc sediments at Point Loma, California.

It was hard to pry ourselves from the ocean, but we had to because we a schedule to stay on.  Our goal was to head east.  On the way, we stopped by some Eocene forearc sediments exposed in a roadcut. These sediments were completely devoid of biotite and hornblende and were formed by the erosion of deeply weathered surfaces of the batholith, well after magmatism and mountain building had ended.  A few of the students found some shell fossils in the sediments, indicating a shallow marine origin.  After our brief foray into the Eocene, our drive along I-8 took us back into the Cretaceous plutons.  We turned north to Cuyama Valley, where we looked at more olivine-gabbro cumulates along the shore of Lake Cuyama. But our excitement quickly turned to a large area of exposed migmatites.  Here, the metasediments had been metamorphosed, deformed, and recrystallized to such a degree that they looked like a gneiss and in some cases looked like a highly foliated granite, but the tell-tale signs of migmatization were the abundant quartz- and feldspar-rich veins and dikes that appear to have formed during ductile deformation.  This was the birth place of some of the granites that contributed to the Cretaceous batholith.  There were a lot of mortar holes on the outcrop, left behind by Native Americans. How nice it must have been to grind food on migmatites!



Our next stop on Saturday was high up in the San Jacinto Mountains, just above Palm Springs. We stopped specifically at the top of Deep Canyon, where if one looked south, we could see a large dip slope composed of late Cretaceous mylontinized granites and tonalites.  We crawled all over the mylonites in search of two things: pseudotachylites and titanites.  Pseudotachylites are melts of the rock generated by intense frictional heating during an earthquake.  These melts were everywhere, some in foliation and many crosscutting.  The titanites, aka sphene, were large pistachio-green porphyroblasts formed during ductile deformation.   All of these deformational features are associated in intra-arc thrusting and exhumation during the late Cretaceous and early Paleogene.  Our day was soon coming to an end.  We descended into the Coachella Valley, but not before stopping at a vista point to look at the San Andreas Fault and the Salton Sea.  We ended our day in Palm Desert with a big Italian dinner!

We started Sunday morning with some unfortunate news. One of our students had his camera bag, tootbrush, and some clothes stolen out of his room, which had been inadvertently left slightly ajar in the chaos of organizing 18 students.  We spent several hours searching for the bag, looking at security videos, and calling the police, but deep down, we knew that we weren’t going to see his bag again. The good thing, if there was a good thing, was that he still had his wallet and identification.  So we moved on, but being a few hours behind, we decided to skip some of the stops.  We ended up driving down the west side of the Salton Sea, stopping briefly at North Shores to touch the sea and to talk about the opening of the Gulf of California.  The sea keeps receding each year as water supplies to agriculture have been steadily declining, so each year, we seem to have to walk further out across the barnacle beach to reach the water. 

After we got our fix of dead fish, we drove another hour south and found ourselves at the mud volcanoes.  The high water table and high heat flow here is what causes these mud volcanoes to form. Geothermal power plants have taken advantage of this combination.  The mud volcanoes gave us an analog for many of the different volcanoes and lava flows we talked about in class: spatter cones, pahoehoe, aa, etc.  It was great to see some of these mud volcano eruptions in action!  Our next stop was Obsidian Butte, a Pleistocene rhyolitic lava flowwhich generated a large obsidian dome.  We marveled at all the beautiful flow banding and we discussed why obsidian flows tend to be big blobs rather than long, thin lava flows. Viscosity!

Talking about mud volcanoes in the Salton Sea. Emily Paine, Detao He, Cin-Ty Lee, Josh Crozier.

Talking about mud volcanoes in the Salton Sea. Emily Paine, Detao He, Cin-Ty Lee, Josh Crozier.

The rest of the day was spent getting from the Salton Sea into the Mojave Desert.  We stopped briefly at Salt Creek, where we crossed over the railroad tracks to look at the San Andreas Fault up close and personal.  Unfortunately, while we were on the other side, the longest train in the world came up and decided to park itself there.  We decided it was too dangerous for us to climb through the train back to our cars as there was no telling when the train might start up again.  The only way was to go around or, in this case, we knew there was a bridge we could go under, but the bridge was quite a ways to the north. Should we wait or walk? We had no idea how long the train was going to stay, so we decided to do the long hike.  By the time we got back to our cars, delayed by an additional hour, the train still had not moved, so it was a good decision. 

Re-energizing with a good dose of fluids, we drove up out of the Salton trough, crossing the San Andreas Fault to the north and passing through Pliocene deltaic sediments, variably deformed and tilted.  We stopped here to look at a wonderful assortment of textbook sedimentary structures (sorting, cross-bedding, soles, soft-sediment deformation), and then further up the canyon, we found the contact between these sediments and the basement, only here the basement was a new rock for the trip – Pelona greenschists associated with subducted sediments or basaltic crust during the Cretaceous.  We ended our long Sunday trip in Joshua Tree National Park, with the students climbing up and down the giant quartz monzonite boulders.

On top of a boulder in Joshua Tree National Park. L to R: Detaho He, Michale Farner, Evan Neustater, Kate Nicholson, Elizabeth Finlay.

On top of a boulder in Joshua Tree National Park. L to R: Detaho He, Michale Farner, Evan Neustater, Kate Nicholson, Elizabeth Finlay.

students examining pebble lag deposits in the Mecca Hills. Yunong Xu, Beineng Zhang, Stephanie Zou, Farah Ashraf.

students examining pebble lag deposits in the Mecca Hills. Yunong Xu, Beineng Zhang, Stephanie Zou, Farah Ashraf.

Monday would be our last day out in the field.  Our first stop would be Amboy Crater in the Mojave Desert on the North American plate. This was our opportunity to discuss why basaltic lava flows can flow much further than rhyolitic flows. Close inspection of the lava flows revealed tiny euhedral crystals of olivine and lots of vesicles! Off in the distance, we could see a pristine cinder cone.  This must have been quite the sight when it was erupting.  After our Amboy Crater stop, our goals were to look for xenoliths at Dish Hill and then trilobites in the Marble Mountains, but due to all the rains and flash floods that had happened earlier in the season, the highways were all closed.  We had no choice but to change our plans on the fly.  Our professor, Cin-Ty, decided then to try a place he had never been to before.  Off in the distance, one could see limestones jutting up against some granitic basement, so we parked our cars and walked across the alluvial plain.  We had no idea what to expect, so we were told to fan out and just explore.  With 18 pairs of eyes, we were bound to see something, and soon, students were coming up with little fragments of Vesuvianite, a clear indicator mineral for skarns!  But where was the actual skarn?  So we fanned out again, falling the trail of bread crumbs and looking around for the contact.  And there it was, all the vesuvianite was forming right up against the contact!

Vesuvianite with Elizabeth Finlay and Sarah Gerenday

Vesuvianite with Elizabeth Finlay and Sarah Gerenday

With our pockets filled with new minerals, we continued north, deep into the Mojave.  We stopped briefly at the Kelso Sand Dunes and then had lunch at the Kelso train depot, a nice green spot in the middle of the desert.  We then headed to the Cima Volcanic field, where there are numerous cones, all erupted in the Late Miocene to present.  We stopped at well-known but difficult to find lava tubes, and then we drove a little further up a rough road to look for xenoliths. Normally, we don’t do this latter part because the road is so rough, but since our plans at Dish Hill were diverted, we thought it would be a nice way to end the trip.  Unfortunately, the road became far too rough to continue further, so we hiked the last stretch.  And xenoliths we did find!  Peridotites everywhere!

Hunting xenoliths in Cima. L to R: Cin-Ty Lee (hideen), Evan Neustater, Kate Nicholson, Yunong Xu, Farah Ashraf.

Hunting xenoliths in Cima. L to R: Cin-Ty Lee (hideen), Evan Neustater, Kate Nicholson, Yunong Xu, Farah Ashraf.

Our luck, however, would not hold out.  As we turned our cars around and headed back down the slope, one of our cars hit a rock hard, twisting its axle. Definitely not good because it made it hard to drive.  What to do now?  The sun had set, the students were tired and hungry, and we had early flights out the next morning, but all the way back in Ontario, a three hour drive with a good car.  We convened at the Mad Greek in Baker and it was decided that the everyone would pile into the other working cars and just go back to Ontario so they could get a good night’s sleep.  Our professor and a couple of visiting grad students would drive the disabled vehicle back, slowly.   It took the five hours and a tire blow out in the last 20 miles, but they arrived home safely.