open access – Defrosting the Freezer

Rapid carbon accumulation at a saltmarshrestored by managed realignment exceeded carbon emitted in direct site construction

In the last few years, I have expanded my research into the burial of carbon in saltmarsh environments, especially around the UK. This is the first paper I have published on the topic. The paper is available Open Access via the journal website.

A composite map/aerial image of the Steart Marshes saltmarsh site

Saltmarshes, which is an coastal wetland which is flooded and drained by saltwater brought in on the high tide, are natural features acrosst the UK and around the world. In the UK, many saltmarshes were drained to form farmland, with a sea defence built between the drained marsh and the river or estuary. Rising sea levels threaten the reclaimed marshes, and the nearby fields, towns and villages, with flooding. Often it is decided that retreating from the drained land is the best way to protect other, more valuable, assets nearby. Through a process called “managed realignment”, the sea defences are breached and the tide returns to the saltmarsh.

Realigned saltmarshes are often lower than the local high tide level, and are rapidly filled with sediment and saltmarsh plants when the water returns. This creates a habitat that can attract wetland birds and, since the sediment has organic carbon associated with it, also generates and opportunity to bury carbon in the marsh.

This paper investigates two things: how much organic carbon was buried on a realigned saltmarsh in the first years after it was created, and how does this carbon burial compare to the emissions generated by the construction of the site.

Samples were collected from Steart Marshes, a site in Somerset, UK, that was flooded in 2014. The samples were analysed for their total carbon and organic carbon content using analytical facilities here at Manchester Met. The carbon concentrations were scaled up to the entire site using sedimentation data calculated from laser scans of the marsh collected at different time points.

There has been a very rapid build-up of sediment at Steart Marshes since the sea defences were breached

We found that the organic carbon burial rate (19 tonnes per hectare per year) was very high compared to other saltmarsh sites, mostly because the sediment built up very rapidly (75 mm per year) after the sea defences were breached. The organic carbon buried on site is much greater than the carbon emissions generated by the diggers and bulldozers used to make the new marsh, and so it seems that there has been a net climate benefit by creating the marsh.

However, the next piece of the puzzle is to fully understand the types of organic carbon being buried on the site. Not all carbon has the same climate benefit associated with it, and so further work is required to properly calculate the climate change mitigation potential of restoring saltmarshes.

Characterization of diverse bacteriohopanepolyols in a permanently stratified, hyper-euxinic lake

This paper is available Open Access via the journal website.

Water filters, extracts and column chromatography for the samples from Mahoney Lake

This publication, led by Molly O’Beirne from the University of Pittsburgh is a really exciting look at BHP biomarkers and microbes in an unusual Canadian lake. My role was to measure and identify the BHPs present in the lake, including finding a ‘new’ BHP that had not been described before.

Mahoney Lake, British Columbia, is a small lake with a really high concentration of sulfur, and a low concentration of oxygen. This classifies it as ‘euxinic‘, and Mahoney Lake is 100 times more sulfidic than the Black Sea. Not only that, but the lake switches from oxic to euxinic within the top 7-8 metres, meaning that sunlight can penetrate into the euxinic layer. This study looked at the changing bacterial communities and BHP biomarkers present in the different layers of the lake.

Water filter samples were collected at a series of depths in the lake, from the oxic layer, through the changeover to euxinia (the ‘chemocline’), down to the sediment at the bottom. At the chemocline, a large community of purple sulfur bacteria were collected which made the filters turn a bright pink-purple colour (see the picture above), which makes a nice change from the usual brown-grey water filters usually collected from lakes and rivers.

Chromatogram and mass spectrum showing the novel BHP with m/z 710

Back in the lab in Pittsburgh, these filters were extracted using solvents and the BHP molecules were separated out from everything else, transferred into small vials, and posted across the Atlantic. After a few days in customs, they made it to Manchester Metropoltian to be analysed on the LC-MS. When looking through the data, there were several common BHPs present, but also a large amount of a previously unknown BHP molecule. It was seen on the chromatogram at a similar time to the ubiquitous ‘aminotriol’ BHP, but careful analysis of the mass spectrum showed that the molecule and its fragments were four mass units ligher than aminotriol, with m/z (mass to charge ratio) 710 rather than 714. We think that this molecule has the same structure as aminotriol, but has two carbon-carbon double bonds in the structure.

Since this molecule was only found in the lower parts of the lake, we think it could be directly linked to euxinic environments. In future work, I will look for this molecule in other euxinic and oxic lake samples to test whether it is a reliable biomarker for euxnia. If it is, BHP 710 can be used to identify euxinia in ancient lakes throughout the geological record.

To find out which bacteria might be making these molecules, Trinity Hamilton from the University of Minnesota sequenced the bacterial genomes present in the lake filters. Genes that produce BHPs were found in samples from the lower parts of the lake, and the BHP producing bacteria are probably Deltaproteobacteria, Chloroflexi, Planctomycetia, and Verrucomicrobia.

At the bottom of the lake, the BHPs present change again. Bacteriohopanetetrol (BHT) is the most common, and methylated BHTs are only found in the lake sediments. This makes us think that bacteria living in the oxygen-free sediments at the bottom of the lake are the source of the methylated BHTs, rather than bacteria living in the oxygenated upper layer of the lake.

Overall, this has been a really fun and interesting study to be part of, and provides loads of new research questions as well as answers. Other researchers looking to analyse BHPs in their samples are welcome to get in touch to discuss collaborations.

The quantification of di-octyl terephthalate and calcium carbonate in polyvinyl chloride using Fourier transform-infrared and Raman spectroscopy

This article is available Open Access via the journal.

Typical results when measuring PVC using Raman spectroscopy

A slight detour from my usual environmental chemistry work, this paper was led by PhD student Kate Irvin and looks at characterising PVC samples in an industrial setting, finding ways to optimise the product development process.

When developing a new polymer product, it is important to regularly test its properties and confirm its ingredients. Typical tests take hundreds of hours and can delay the development cycle, adding costs to the process. In this paper we demonstrate some rapid, non-destructive techniques for quantifying the amount of plasticiser (dioctyl terephthalate) and filler (calcium carbonate) within a PVC sample.

Fourier transform-infrared spectroscopy and Raman spectroscopy were used, since they are quick, easy-to-use and non-destructive methods of identifying samples. The time savings alone of using these methods compared to using traditional hardness, softness and tensile tests could reduce product development costs by 50%.

Methanotroph-derived bacteriohopanepolyol signatures in sediments covering Miocene brown coal deposits

This paper is available Open Acess via the journal website.

When I joined Manchester Metropolitan University in 2016, I was awarded a small grant to set up an analysis facility measuring a group of molecular biomarkers, bacteriohopanepolyols (BHPs), that are found in environments throughout the world. This paper is the first to be published on BHPs measured at Manchester Met.

Cores of polish lignite used in this study

In this paper, led by Anna Pytlak, samples from two Polish lignite deposits were analysed via LC-MS to see which BHPs were present in the samples, and whether these could be linked to methane-generating bacterial living in the rocks now, or millions of years ago.

My role, along with PhD student Saule Akhmetkaliyeva, was to extract the BHP biomarkers from the sediment samples and analyse them on the time-of-flight mass spectrometer at Manchester Met. The molecules found in the mass spectrometer were compared against known BHP results, and identified as being from various types of bacteria. This included both Type I and Type II methanotrophs (bacteria that consume methane), including some living methanotrophs.

BHP concentrations were higher in the lignite than the surrounding mineral soil, suggesting some form of active bacterial commuity supported by the lignite deposits that cannot be sustained in regular soil. Living methanotrophs means that there’s a chance some of the methane released over time by the lignite is eaten by the bacteria and not released to the atmosphere.

If you would like to measure BHPs in your own samples, please get in touch to discuss collaborations!

Signatures of the post-hydration heating of highly aqueously altered CM carbonaceous chondrites and implications for interpreting asteroid sample returns

Backscatter electron microscope images of a meteorite

This paper is available as an Open Access article via the journal.

This research paper continues the work of Paula Lindgren, who I worked with earlier when looking at a suite of meteorites. In this paper, a single carbonaceous chondrite meteorite was heated in the laboratory to simulate the heating that took place during the life of a meteorite. A sample was studied using a series of different techniques, including scanning electron microscopy, Raman spectroscopy, infra-red spectroscopy, oxygen isotopic analysis and X-ray diffraction. It was then heated to 400 °C and 800 °C and studied again. We found that the minerals, isotopes and organic matter all changed with heating. Sometimes 400 °C was enough to make a change, sometimes no change was observed until 800 °C.

Changing Raman spectropscopy measurements from unheated (blue), 400 °C (yellow) and 800 °C (red) samples of the same meteorite

These changes can be used to work out the thermal history of meteorites collected on Earth, and even for asteroids sampled in space!

Macromolecular organic matter across the East Siberian Arctic Shelf

Update: The paper is now published and can be downloaded from the journal webpage.

The study continues our work on the East Siberian Arctic Shelf, and contains two new datasets. The first is a radiocarbon study, measuring the age of organic matter on the shelf using carbon dating (see map above). By measuring the age, we can determine whether the carbon has come from the ocean (very young), the topsoil (quite young) or the coastal permafrost (thousands of years old). We combined our results with those already measured on the shelf to form the most complete radiocarbon map for this area. The high-resolution map shows that areas close to the shore and away from the major rivers are home to very old carbon, almost certainly sourced by erosion of old permafrost cliffs. Elsewhere on the shelf, the carbon is younger but not as young as modern topsoils or ocean carbon. Therefore the coastal erosion carbon is having an influence right across the shelf.

A pyrolysis probe can heat samples to 900 C in milliseconds

Our second technique is pyrolysis GCMS, where samples are smashed into small pieces using high temperatures and the small pieces are then analysed using GCMS. This technique generates a large amount of small pieces, too many to analyse each one individually, and so we decided to concentrate our efforts on a few target molecules. These included Phenols, which are probably sourced from lignin, a major component of land plants, and Pyridines, which are nitrogen-containing compounds probably sourced from proteins. We think that a lot of the Pyridines in the Arctic Ocean will come from organisms living in the ocean itself, and therefore the Pyridines are a potential tracer for marine organic matter. By comparing the concentrations of Phenols and Pyridines, we can estimate the amount of terrestrial and marine organic carbon in a sample.

Phenol-Pyridine ratio on the Arctic Shelf

In the map above, red areas are dominated by Phenols and are therefore rich in terrestrial carbon, blue areas are dominated by Pyridines and are therefore rich in marine carbon. This pattern matches very well with our previous work in the region, showing that there is a transition from terrestrial to marine conditions across the Arctic Shelf, and that the transition zone lasts for hundreds of kilometres offshore. This means that there is a lot of terrestrial carbon being deposited, and hopefully buried, on the shelf, rather than all of the eroded carbon being degraded and released as CO₂.

The Cryosphere, 10, 2485-2500, 2016
https://doi.org/10.5194/tc-10-2485-2016

Source, transport and fate of soil organic matter inferred from microbial biomarker lipids

06/09/2016 UPDATE: The paper has been accepted and is now published. The final version is available from the journal.

Our international team of East Siberian researchers currently has a paper in open review at Biogeosciences. The discussion paper, and its interactive comments, can be downloaded from the journal website.

The paper studies a group of compounds called “bacteriohopanepolyols” (BHPs for short), which are found in the cell membranes of a range of microbes and are therefore one of the most common organic compounds around. They are found in modern and ancient sediments from all over the world. This study has concentrated on two groups of these. Group 1 is the soil marker compounds. These are only found in soils, and so have been used as tracers for soil material in rivers, lakes and offshore. Here is how they are spread across the East Siberian Artic Shelf:

BHPfig2a (Custom) — Soil marker compounds across the Arctic Shelf

Note how the soil marker concentrations are highest (orange colours) near to the rivers and coastlines. By measuring the concentration next to the river mouths, and in the sediments being washed away by coastal erosion, we show that it is not just rivers that are delivering the soil markers to the Arctic Ocean.

There is no single compound that is a true tracer for carbon produced in the ocean itself, but the compound bacteriohopanetetrol (BHT) is most abundant in marine settings despite being found in soils as well. Therefore if your sample is rich in BHT, and poor in soil markers, it is likely dominated by carbon from the ocean. Here’s a map of BHT across the East Siberian Arctic Shelf:

BHPfig2b (Custom) — BHT, a marine marker, is present across the Arctic Shelf

The BHT results show a fairly constant amount across the ocean floor. If we compare the soil marker concentrations to the BHT concentrations, we can see which areas are rich in soil carbon (more soil markers than BHT) and which are rich in marine carbon (more BHT than soil markers). This comparison is called the R’soil index, and is shown below:

R'soil index on the Arctic Shelf — R’soil index on the Arctic Shelf

The R’soil index shows that all along the East Siberian Arctic coastline, offshore sediments are dominated by carbon from the land. As you go further offshore, especially in eastern parts nearer to the Pacific Ocean, marine carbon is more important. This result shows a similar pattern to that seen using stable carbon isotopes, but is different to the pattern shown by the BIT index. Therefore these two indices, both based on microbial biomarkers, are tracing different parts of the carbon cycle.

Preservation of terrestrial organic carbon in marine sediments offshore Taiwan

This paper was published in the open access journal Earth Surface Dynamics, and is available through the journal website and the MMU e-space repository.

The paper is a combined effort from a large team of researchers interested in the way that organic carbon is exported from small tropical islands. These islands are very biologically productive, the forest grows quickly in the warm, wet climate. They are also responsible for delivering large amounts of sediment to the ocean. Rocks are weakened by earthquakes and then eroded by the frequent tropical storms that hit the islands. This washes sediment and carbon out to sea via two mechanisms. High sediment concentrations lead to ‘hyperpycnal’ plumes of material flowing along the ocean floor, lower sediment concentrations cause ‘hypopycnal’ flows that stay at the ocean surface. Both systems can spread sediments and carbon a long way offshore.

Marine sediment cores look very similar to the sediment coming out of the rivers

It had long been thought that hyperpycnal delivery of sediment, which usually only occurs in the most extreme weather conditions when floods deliver vast amounts of sediment to the ocean in a short period of time, were efficient methods of organic carbon preservation. Our data confirmed this hypothesis, showing that little terrestrial organic carbon was lost during transport, and little marine carbon added to the mixture.

However, the dataset also investigated how efficient hypopycnal delivery can be. Sediment and carbon are delivered throughout the year, in smaller floods and less extreme storms, and it had been suspected that this mechanism exposed the carbon to oxidising conditions where it could be degraded and released as CO₂. We showed that in Taiwan, where hypopycnal conditions exist but are still receiving and accumulating a large amount of sediment, the burial efficiency of carbon in hypopycnal conditions is still very high. Marine carbon is mixed into the sediments, but at least 70% of the terrestrial carbon survives.

This means that small tropical islands are even better at exporting and burying carbon than was previously thought, and therefore better at sequestering atmospheric CO₂. We estimated that more than 8 Teragrams (million tonnes) of carbon could be buried each year throughout Oceania.

Decadal carbon discharge by a mountain stream is dominated by coarse organic matter

This paper, with Jens Turowski and Bob Hilton, was recently published as an open-access article in Geology and is available from the journal website and via the MMU e-space repository. In it we show that erosion and transport of large woody material (coarse particulate organic carbon; CPOC) is very important in terms of the overall carbon cycle, but is concentrated in very extreme events.

The research is based in the Erlenbach, a small river in the Alps that has been studied by Swiss researchers for several years. They have built a very sophisticated stream sampling station, which can capture everything that flows down past a gauging station. There is a large retention pond that catches the logs/pebbles/sediments and a shopping-trolley sized wire basket that can be moved into the middle of the stream to catch a particular time point (for example the middle of a large storm). The photo below was taken during winter when the river was frozen over, but you can see the v-shaped river channel, the three wire baskets ready to move into position to catch material, and the snow in the foreground covering the retention pond.

The sampling system in the Erlenbach River during winter

This sampling system led to Jens observing that there was a lot of CPOC coming down the river and piling up in the retention pond. A quick calculation suggested that this was a significant portion of the total carbon coming out of the river catchment, but the scientific consensus was that actually more carbon came through as fine particles than CPOC. An experiment was designed to test this.

Across a wide range of river flow speeds, the amount and size of woody debris flowing down the river was measured, both waterlogged and dry material. This allowed a rating curve to be defined – that is for a given river flow speed, how much organic carbon would be expected to flow down the river? The rating curve was very biased towards the high-flow end for CPOC, much more so than for fine carbon (FPOC) or dissolved carbon (DOC). At low flow rates, very little CPOC is moved, but at high flow rates a very large amount is mobilised.

Rating curve of organic carbon types vs. river discharge

During the 31 years of data collection there were four particularly large storms. Integrating over the rating curve shows two things. Firstly, if the large storms are ignored then the Erlenbach is already a major source of CPOC, about 35% of the total carbon, with CPOC being roughly equal to the FPOC estimate. Thus it is much more important than might previously have been imagined. If the extreme events are included, the CPOC becomes ~80% of the total organic carbon transported by the river.

A majority of the CPOC transported by the river was waterlogged, having sat on the river bank or behind a log jam while waiting for a large storm to wash it downstream. Waterlogging increases the density of the wood and makes it more likely to sink when it reaches a lake or the sea. My contribution to the paper was to provide evidence of this process. My PhD work in the Italian Apennines found CPOC, from millimetre scale up to large tree trunks, that had been preserved in ocean sediments for millions of years. Again, a lot of this CPOC is too large to measure using standard techniques, and suggests that rivers can deliver organic carbon from mountains to the ocean far more efficiently than previously thought.

Elephant Moraine 96029, a very mildly aqueously altered and heated CM carbonaceous chondrite

This paper is a result of collaboration with researchers at the University of Glasgow who I met while interviewing for a position. I didn’t get the job, but I did get talking to Paula Lindgren and we discovered a common interest in using Raman Spectroscopy to study organic carbon. This publication is the first result of that, and is available as an open-access article.

A little bit of meteorite, under an electron microscope

The paper is a comprehensive study of a meteorite collected from Antarctica. Antarctica is a great place to find meteorites because they sit on top of the ice and are easy to spot – sometimes the flow of ice even concentrates them into particular areas to makes things even easier. This meteorite is classified as a “CM carbonaceous chondrite” and has experienced very little change since it was part of the protoplanetary disc billions of years ago. Therefore we can use it like a time capsule to look at what the early solar system was like.

However, some meteorites are better time capsules than others. As they float around the solar system, they can build up ice, which can then be melted by radioactivity and the water released can alter the crystallography of the meteorite. Our paper uses a wide range of techniques to characterise the meteorite and show that it is one of the least altered carbonaceous chondrites ever found.

The techniques used included electron microscopy (both scanning and transmission techniques; SEM and TEM), X-ray analysis, X-ray diffraction, thermogravimetric analysis (TGA), oxygen isotope measurements and Raman Spectroscopy. My contribution was to use my automatic Raman processing technique to determine how crystallised the carbon in this meteorite was in comparison to carbon in other meteorites.