Carbonaceous material export from Siberian permafrost tracked across the Arctic Shelf using Raman spectroscopy

In this paper, published in The Cryosphere, we used Raman spectroscopy to trace carbonaceous material from the shoreline to the furthest reaches of the East Siberian Arctic Shelf.

Raman spectroscopy uses laser light to determine the molecular structure of a wide range of materials. During my PhD, I showed that Raman could be used to probe individual particles of organic carbon to show whether they were disordered, like coal, or crystalline sheets of graphite. This collection of carbon particles, known as carbonaceous materials, are particularly hardwearing and resistant to breaking down during erosion and transport. During my post-doctoral research, I then used a range of organic geochemistry techniques to investigate the transition from terrestrial to marine carbon across the East Siberian Arctic Shelf, showing that coastal erosion and river erosion were both supplying organic matter to the ocean.

Map of the samples used in this study. Red lines are areas of intense coastal erosion
Map of the samples used in this study. Red lines are areas of intense coastal erosion

This study uses the Raman technique on those same Arctic Shelf sediments to look at the sources and distribution of carbonaceous material on the shelf. The samples used in our paper were collected from close to the mouths of some major rivers, from areas experiencing rapid coastal erosion, and from hundreds of kilometres offshore.

Groups of spectra found in the shelf samples
Groups of spectra found in the shelf samples

The hardest work, collecting over 1400 Raman spectra, was carried out by two undergraduate students, Melissa Maher and Jerome Blewett, who are co-authors on the paper. The collected spectra were then analysed using an automated peak fitting script, and grouped according to the shape of the fitted peaks. This provides an unbiased method for determining whether a carbon particle is highly graphitised, mildly graphitised, disordered, or somewhere in between. For each of the sites on the shelf we collected spectra from up to 30 particles, and looked at how many fitted into each group. Statistics were then used to spot patterns across the shelf.

Distribution of "Disordered" and "Intermediate" carbon
Distribution of “Disordered” and “Intermediate” carbon

Our first finding is that the relative proportion of “disordered” and “intermediate” carbon particles varies, and that there are patches with more of one or the other group. At the coastline these patches align with two of the major rivers (Kolyma and Indigirka) and areas of rapid coastal erosion. Surprisingly, the patches can then be traced all the way across the shelf. We would have expected the currents in the ocean to have mixed the particles together further offshore, and in the biomarker studies we’ve done before we did not spot this kind of pattern. This means that Raman is a great way to trace the different sediment and carbon sources on the shelf.

"Highly Graphitised" carbon is found in high proportions far offshore
“Highly Graphitised” carbon is found in high proportions far offshore

Our second finding is that the amount of “highly graphitised” carbon particles is highest in the furthest offshore samples. These very crystalline flakes of graphite are behaving differently to all the other carbon particle groups. It’s not clear exactly why this is, but one option is that everything else is breaking down and degrading before getting that far offshore. Or, the graphite particles could be so light that they sink very slowly, floating out to the shelf edge much easier than the other types.

This problem has implications for the global carbon cycle. These carbon particles have been released from permafrost on land and transported for hundreds of kilometres offshore, a trip that has taken thousands of years. If all of the carbonaceous material can survive the journey, it means that this fraction of the organic matter is not at risk of being degraded and released to the atmosphere as greenhouse gases. Burying it in the ocean provides protection from degradation for thousands or millions of years. Future studies should look at just how well the carbon particles can survive erosion and burial.

In summary, carbonaceous material is resilient to degradation and can be used to trace sediment sources across the Arctic shelf.

The Cryosphere, 12, 3293-3309, 2018
https://doi.org/10.5194/tc-12-3293-2018

Macromolecular organic matter across the East Siberian Arctic Shelf

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

Map of radiocarbon ages across the ESAS
Map of radiocarbon ages across the ESAS

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
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
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.

Distributions of bacterial and archaeal membrane lipids in surface sediments reflect differences in input and loss of terrestrial organic carbon along a cross-shelf Arctic transect

This paper was published in Organic Geochemistry, and is available open-access through the journal website and the MMU e-space repository. In the paper we take a detailed look at lipid biomarkers along a transect from the Kolyma River to the Arctic Ocean.

The data used in this paper is a subset of the data from across the East Siberian Artic Shelf (ESAS) published shortly afterwards in Biogeosciences. In this paper we took a closer look at the offshore trends seen in material delivered to the ocean by the Kolyma River, the easternmost of the Great Russian Arctic Rivers. The Kolyma River catchment is entirely underlain by continuous permafrost, which makes this are an extreme endmember in terms of permafrost systems. The main sources of organic matter from the Kolyma region are river erosion, mostly from top few metres of soil, the active layer that freezes and thaws each year, and coastal erosion from the “yedoma” cliffs along the shoreline.

Sample locations for the Kolyma River - ESAS transect
Sample locations for the Kolyma River – ESAS transect

These samples had previously been analysed for bulk properties (total organic carbon content, carbon isotope ratios) and some basic biomarker measurements, but we added complex lipid analyses to the story. We measured both GDGT and BHP lipids, these are found in microbes and can be analysed using LCMS. Amongst the many applications of these lipids, they can be used to trace the amount of soil found in offshore sediments. Each group of molecules has an index associated with it: GDGTs are used in the BIT index and BHPs are used in the R’soil index. Values of 0 would have no soil input and 100% marine carbon, while values towards 1 would be dominated by soil.

Offshore trends in the BIT and R'soil indices
Offshore trends in the BIT and R’soil indices

Usually these indices show the same offshore trends, which would be expected since they are both supposed to be tracing the same number – the proportion of carbon coming from soil. However, as the figure above illustrates, the two indicies have very different patterns from the river mouth (0 km) across the shelf (500 km). The BIT index drops quickly offshore, making a curved offshore profile, but the R’soil index forms a straight line offshore. Therefore two different techniques, supposedly measuring the same thing, don’t show the same results.

We think that this is due to the source of lipids used to make each index. Branched GDGTs (from soils) are common in sediments close to the river mouth, but their concentration drops quickly offshore. Marine GDGT concentrations increase across the shelf and this combination causes the BIT index to decrease rapidly. Branched GDGT concentrations in soils and lakes on land are high, but they are very rare in the coastal permafrost cliffs. Therefore any coastal erosion is not really affecting the BIT index.

On the other hand, soil marker BHP molecules are found in river sediment and coastal permafrost, and so there are two terrestrial sources. The concentration of soil marker BHPs drops much slower offshore than for the GDGTs. Also different, the concentration of the marine BHP marker doesn’t increase offshore. This combination means that the R’soil index drops much slower than the BIT index.

In the end, what this paper mainly shows is that when using biomarkers as proxy measurements for something else one single result is probably not enough. Proxy measurements are valuable tools, but they depend on measuring one thing to discover another. Combining multiple proxies together adds value and reliability to a study, either by confirming a hypothesis or bringing new insights.

GDGT distributions on the East Siberian Arctic Shelf

Our paper, “GDGT distributions on the East Siberian Arctic Shelf: implications for organic carbon export, burial and degradation” has now been published. You can download the paper, and the underlying data, from the Biogeosciences website here.

As I mentioned before, this paper has been submitted, reviewed and published completely open-access. This means that the original paper, the reviews and our response are all archived online forever. All of this is available freely to anyone, without the need to pay for access. You are free to copy, distribute and make use of the data and graphs as long as the original paper is cited (also known as a CC-BY copyright license)

Boxplots showing how GDGT biomarkers vary offshore
Boxplots showing how GDGT biomarkers vary offshore

In the paper we show the first map of GDGT biomarkers from the East Siberian Arctic Shelf. This region is extremely remote yet very important within the global carbon cycle. Our work shows that this is an area of complex interaction between rivers, coastal erosion and open ocean productivity. The GDGT biomarkers are very useful here as a tracer of carbon being washed away by the rivers and being produced in the oceans, and this allowed me to make a model of the Arctic Ocean in this region to better understand how all of the different processes interact.

Our model of biomarker export across the Arctic Shelf
Our model of biomarker export across the Arctic Shelf

As an author, the publishing process for Biogeosciences was interestingly different. There was a reasonable amount of time between submitting the paper and final publication, but that was mostly due to the interactive public discussion stage which most journals do not have. During this time the paper was available and citable, which means that although it was relatively slow progress towards final publication the story was out there very quickly. I’m keen to go for this style of publishing again in the future.

GDGT distributions on the East Siberian Arctic Shelf: Discussion paper

My last post talked about Open Access publishing, and the various philosophies for spreading (and/or making money from) academic knowledge. Now there is a chance to play an active part in the publishing process. My latest paper has been submitted to a journal called “Biogeosciences” which is administered by the European Geosciences Union (EGU). Their journals are published using a super open process, where more than just the final paper is released free-of-charge to the world. Whereas in regular Open Access publishing anyone is free to read the final reviewed work, in EGU journals the initial version is also made available. Two reviewers are selected from the community, and their reviews are shown on the website as well. Everyone else is free to read and comment on the paper, raising questions that the authors have to respond to. It is hoped that this system is a) transparent b) open to more (constructive) criticism than the standard two-review system and c) faster, since the paper is available for people to read at an earlier stage of the process.

A figure from the paper showing land-sourced GDGT molecules
A figure from the paper showing land-sourced GDGT molecules

Our paper discusses the distribution of GDGT biomarkers on the East Siberian Arctic Shelf. We measured these biomarkers to determine whether the organic matter deposited on the shelf came from land or ocean sources. When we had made these measurements, a model was created to try and explain the observations and work out the budget for carbon being delivered to the shelf from large Arctic rivers.

If you want to read and comment on the paper it is available on the Biogeosciences website

Manchester Museum – Siberia Exhibition

Starting this Saturday 4th October, and lasting until 1st March, the Manchester Museum will be holding a special exhibition on Siberia. This will contain a collection of special items from British and Russian museums, including a mummified baby mammoth and a brown bear, along with displays on the culture and natural history of the region, taking visitors beyond the stereotypical view of Siberia as an icy wasteland. Along with colleagues in Manchester, Newcastle and London, I have made a display board and video about Siberian climate change, which will be showing throughout the exhibition. More to follow once the exhibition opens…

Official Museum Poster

What Is: GRAR?

Russia is big, really big, and to go with that, it has some very big rivers. The majority of the Russian river outflow is into the Arctic Ocean, especially in the central and eastern parts of the country, and this is generally concentrated into a series of very large rivers. The largest of these are known as the Great Russian Arctic Rivers (GRARs). From west to east, these are the Ob, Yenisety, Lena, Indigirka and Kolyma, of which the Ob and Lena are largest, and Indigirka the smallest (small enough to not count in some people’s list of GRARs).

Catchment areas of the Great Russian Arctic Rivers
Catchment areas of the Great Russian Arctic Rivers

The Ob river is the world’s fifth-longest and has the sixth-largest drainage basin, yet has only the 19th highest annual discharge, being overtaken by the smaller Yenisey and Lena rivers to the east of it. All of these river basins contain some permafrosted land, which can reduce discharge during the winter months and have a very large flood-period in late spring / early summer when the meltwater arrives (the “freshet”).

Permafrost within catchments of the GRARs
Permafrost within catchments of the GRARs

As the amount and continuity of permafrost increases from west to east, so the proportion of each permafrost type increases within the river basin. The Ob and Yenisey are largely free of continuous permafrost, allowing water to flow through the ground to the bedrock and into the river, whilst the Indigirka and Kolyma are practically 100% continuous permafrost, and thus any water discharging will have run along the top of the ground before entering the river itself. This can have consequences for the type of material, especially carbon, carried by the rivers.

Proportion of each type of permafrost within river basins
Proportion of each type of permafrost within river basins

This east-west contrast is worth exploring in more detail in a later post, since it shows how Siberia may behave very differently if the permafrost were to thaw. As a final reminder of just how large the rivers are, even the smallest, Indigirka, manages to cover more area than the British Isles! As usual the full-resolution PDFs of the figures from this article can be downloaded here: River catchments no permafrost, Catchments and permafrost, Permafrost chart, Catchments and UK.

Comparing the catchment areas to the British Isles
Comparing the catchment areas to the British Isles

 

Just how much permafrost is there?

The extent and type of Russian permafrost
The extent and type of Russian permafrost

Permafrost covers 24% of the Earth’s northern hemisphere land surface, but how much is that? Well 24% corresponds to 23,000,000 km2. That is a pretty big number, and doesn’t even count the subsea permafrost that covers lots of the Arctic Shelf (see the map above) so here are a few comparisons and measurements in less standard units.

Great Britain compared to the Russian permafrost area.
Great Britain compared to the Russian permafrost area.

Firstly, let’s compare the permafrost area to some other countries and continents. Here is Britain in comparison, at 243,000 km2 it is almost inconsequential. Only one tenth of the northern hemisphere permafrost. Going up the scale Australia, with an area of 7,700,000 km2, is one third of the northern hemisphere permafrost, and roughly the same size as the 7,400,000 km2 that continuous and discontinuous permafrost represent in Siberia alone.

The land area of Australia compared to the Siberian permafrost
The land area of Australia compared to the Siberian permafrost

The maps above use data from the National Snow and Ice Data Centre

PDF versions are also available. Map1, Map2, Map3.

The World according to Siberia

When displaying data near the poles, the choice of map projection is very important. Displaying a 3D object in a 2D screen is always problematic, and involves compromises in either accuracy, practicality or legibility. The standard Mercator projection, as used in the majority of maps seen on a day-to-day basis, stretches the polar regions to infinity. Greenland looks enormous on this map, yet it is actually just smaller than the Democratic Republic of the Congo, and only one quarter of the area of Brazil. To get around this problem, other map projections are available.

Siberan-centred map
LAEA projection centred on Siberia – click to enlarge

The projection I have chosen to use for maps of the Siberian permafrost is the Lambert Azimuthal Equal Area map. This projection adjusts shapes and distances in order to preserve the true area of each country. If you look at the full-size version of the map above (click it, or download here) then the view of the Arctic region is relatively consistent with the true layout as viewed from above, but there is an increasing amount of distortion as the distance from Siberia increases.

Look out for this projection in future posts!