SERVICES & FACILITIES ANNUAL REPORT - FY April 2007 to March 2008
SERVICE
Life Sciences Mass Spectrometry Facility
(LSMSF)
FUNDING
Block
AGREEMENT
EK: R8/H10/09
L: R8/H10/20
B: -R8/12/15
ESTABLISHED as S&F
East Kilbride
Lancaster
Bristol
TERM
5 years
1994
1984
1992
TYPE OF SERVICE PROVIDED:
Facility: Under the auspices of the LSMSF, NERC maintains three facility nodes for provision of organic and light stable isotope
mass spectrometry to the UK life sciences community, namely the East Kilbride node located at SUERC, the Lancaster node
located within CEH-Lancaster and the Bristol node housed within the School of Chemistry at the University of Bristol. By adopting
this more integrated approach accessibility to said Facility nodes has been increased as has been the organisation between
Facilities. Whilst this move has not resulted in the physical amalgamation of the three Facilities, the ‘one-stop-shop’ exists as a
single point of contact for users, with increased efficiency and synergistic operation thus making better use of the resources
currently used in the maintenance of the mass spectrometry services offered. All three Facilities are contracted by NERC to provide
‘free-at-point-of-delivery’ support according to their respective service level agreements (SLAs) or contracts and the NERC
LSMSF steering committee oversees their operation. Each of the three nodes offers a different portfolio of analytical techniques for
which UK based researchers may apply to use through NERC Services and Facilities (S&F) by standard peer review procedure.
East Kilbride has strong associations with migration, agro-ecology and conservation studies whilst the primary remit of Lancaster
is terrestrial and fresh-water studies (including those deriving from NERC programmes). Bristol fields a wide range of projects to
which a compound specific approach is essential, e.g. palaeoclimatic reconstruction (alkenone UK37), organic matter sourcing
(biomarkers), faunal population and dietary studies (isotopic PLFA and FFA profiling) and palaeodietary reconstruction.
Analytical portfolio of the LSMSF:


Isotopically enriched water (D218O to energy expenditure studies)
Natural abundance e.g. 13C/12C, 15N/14N, 18O/16O and 34S/32S analyses of bulk animal organic matter to study food webs &
element cycling
Enriched & natural abundance analyses of organic and inorganic matter to study carbon and nitrogen fluxes within soil
ecosystems e.g. 13C/12C, 15N/14N, 18O/16O
Enriched & natural abundance analyses of gases: e.g. 13C/12C, 15N/14N 18O/16O of CO2, CH4, N2O & N2
Natural & near natural abundance compound specific 13C/12C, 15N/14N, D/H analyses of biochemical extracts
Organic mass spectrometric analyses of complex mixtures of compounds e.g. volatiles, functionalised molecules etc




NB. Nodes are designated as follows: L = Lancaster, EK= East Kilbride, B = Bristol
ANNUAL TARGETS AND PROGRESS TOWARDS THEM
Lancaster node to: upgrade its trace gas IRMS technology through automation of the pre-concentrator, to improve throughput of
CO2 samples (Upgrade complete. Awaiting factory testing of new auto sampler)
EK Node to: develop dual hydrogen-oxygen analysis in organic materials to the point that it is a routine analysis.
Bristol node to: Install new LC/MS (done, developing methods), recruit new staff (done), deliver sample preparation service (done)
SCORES AT LAST REVIEW (each out of 5)
Need
Uniqueness
5
4.5
CAPACITY of HOST ENTITY
FUNDED by S&F
Lancaster
East Kilbride
Bristol
58%
100%
30%
Quality of Service
5
Date of Last Review: March 2008
Quality of Science & Training
5
Staff & Status
Dr AW Stott (SSO), Miss H. Grant (SO), Mr AP Rowland (0.3FTE)
Dr. J Newton (RA2) & Dr. R. McGill (RA1A)
Dr. ID Bull (URF Grade K; 100% University of Bristol funded), Mrs.
A Kuhl (Technician Grade H), Mr JM Williams (Technician Grade H)
FINANCIAL DETAILS: CURRENT FY
Total resource
Unit Cost £k
allocation £k
½ day unit
Analysis
Training/Labwork
EK 159.08
EK
0.49
0
0
L
97.70
L
0.46
0
0
B
123.84
B
0.64
0
0
FINANCIAL COMMITMENT (by year until end of current agreement)
20082009
EK
218.91
L
167.24
B
20092010
127.67
STEERING COMMITTEE
LSMSF
EK
256.81
L
192.96
B
202.13
20102011
Independent
Members
5
EK
262.75
L
200.18
B
211.18
20112012
EK
270.50
L
208.19
B
220.65
Meetings per annum
2
20122013
Average
4.88
Next
Review
(Jan)
2013
Capital
Expend £k
77.85
18.30
132.50
Income
£k
0
0
0
EK
277.66
L
215.99
B
230.57
20132014
Other S&F Overseen
0
Contract
Ends
(31 Mar)
2014
Full cash
cost £k
209.72
113.73
147.26
EK
284.81
L
224.62
B
240.98
APPLICATIONS: DISTRIBUTION OF GRADES (Current FY — 2007/08)
R*/Pilot
5
4
3
2
1

NERC Grant projects
0
2
0
0
0
0
1
Other academic
0
5
0
1
0
0
4
Students
0
3
2
0
0
0
2
Pilot
0
0
0
0
0
0
0
0
10
2
1
0
0
7
TOTAL
APPLICATIONS: DISTRIBUTION OF GRADES (per annum average previous 3 years —2004/2005, 2005/2006 & 2006/2007)
R*/Pilot
5
4
3
2
1

NERC Grant projects
0.33
4.66
0.33
0
0
0
1
Other academic
1.33
3.66
1
0.33
0
0
1.33
Students
1.33
5.66
5
0
0
0
3
Pilot
0
0
0
0
0
0
0
3
14
6.33
0.33
0
0
5.33
TOTAL
PROJECTS COMPLETED (Current FY — 2007/08)
5
NERC Grant projects
0
Other Academic
2
Students
0
Pilot
0
4
3
7
4
0
3
0
1
7
0
2
0
0
0
0
USER PROFILE (current FY — 2007/08) (need Bristol data)
Infrastructure
Grand
Student
NERC
Total
Supplement to NERC Grant *
C/S
Total NERC
51
2
25
10
5
USER PROFILE (per annum average previous 3 years — 2004/2005, 2005/2006 &
2006/2007)
Grand
Total
67
Infrastructure
Student
Supplement to NERC Grant *
Total NERC
7
38.66
21.66
Other
19
1
0
0
0
0

0
0
0
0
Reject
0
1
0
0
1
Reject
0
0.66
0.33
0
1
R*/Pilot
0
0
1
0
*Combined non-Directed and Directed
PAYG
Student
NERC
NERC
Other
Grant* Total NERC
C/S
0
0
0
0
0
*Combined non-Directed and Directed
NERC
R/C
Other
6.66
14.66
NERC
Grant*
0
USER PROFILE (current FY — 2007/08) Needs Bristols data
Academic
Centre/Survey
NERC Fellows
PhD
21
5
0
25
USER PROFILE (per annum average previous 3 years —2004/2005, 2005/2006 & 2006/2007)
Academic
NERC R/C
NERC Fellows
PhD
15.66
5.66
0.33
31.66
PAYG
Student
Total NERC
0
0
NERC
C/S
0
Other
0
Commercial
0
Commercial
0.33
OUTPUT & PERFORMANCE MEASURES (current FY — 2007/08)
Publications (by science area & type)
SBA
ES
MS
AS
TFS
EO
Polar
Grand Total
Refereed
Non-Ref/ Conf Proc
PhD Theses
3
2
22
0
32
0
0
59
25
20
9
Distribution of Projects (by science areas)
SBA
ES
MS
AS
TFS
EO
Polar
1
0.5
5
0.5
6
0
1
OUTPUT & PERFORMANCE MEASURES (per annum average previous 3 years —2004/2005, 2005/2006 & 2006/2007)
Publications (by science area & type)
SBA
ES
MS
AS
TFS
EO
Polar
Grand Total
Refereed
Non-Ref/ Conf Proc
PhD Theses
4.33
7.0
11.33
0
36
0
0
58.66
39.66
13.66
5.33
Distribution of Projects (by science areas)
SBA
ES
MS
AS
TFS
EO
Polar
1
1.5
8
0.5
9
0
1
Distribution of Projects (by old NERC strategic priority)
Earth’s life support systems
Climate Change
Sustainable Economies
Underpinning Science
Specific Research
9.5
3.5
1.5
0
6.5
Distribution of Projects (by new NERC strategic priority)
Sustainable use of
Environment,
Earth System
Climate Systems
Biodiversity
Natural Resources
Natural Hazards
Pollution &
Technologies
Science
Human Health
3.5
9.5
8
0
0
0
Yes
OVERVIEW & ACTIVITIES IN FINANCIAL YEAR (2007/08):
Node overview
EK: As predicted, dual 13C and 15N analysis comprises the majority of requests to the node, with 2H (and 18O) coming a close
second. Some time was put aside to make improvements to the latter technique, and some developmental work was carried out in
anticipation of the arrival of enriched 13C samples from the deep ocean floor, as part of a proposal which involves all three nodes.
There was a marked increase in the number of applications submitted to the node for SC approval last year (13 applications including
joint nodal applications), and a similar number this year, with no obvious dip in quality. Because of the investment in instrumentation,
and improvements in sample throughput by node staff, we are able to accommodate more or larger projects. Peer reviewed
publications continue to rise, with ten for 2007, with seven either in press or under review. Node staff participated in the British
Ecological Society Annual Meeting in Glasgow and SIMSUG in Newcastle.
Lancaster: 2007/2008 saw very intense and long periods of demand from LSMSFSC approved research specifically regarding trace
gas analyses. The failure of the trace gas IRMS early in the year, (June 2007) created a large backlog of external and internal samples
and emergency counteractive measures had to be quickly taken. Funds were requested and granted from NERC and CEH to upgrade
the stricken instrument whilst maintaining throughput of samples as best we could by coupling the trace gas pre-concentrator to
another IRMS. The upgrade of the IRMS has now taken place and we are awaiting delivery of the Gilson 271 auto sampler which will
free up staff resources and improve throughput of gas samples. The EA-IRMS 13C and 15N methods were externally audited as part of
UKAS ISO 17025 and have been found fit for purpose and operating to the highest standards. The number of external enquires
received this year was 10, resulting in 9 applications (including joint nodal applications) to the LSMSFSC. Publications from node
supported research amounted to fifteen this year, with 3 co-authorships. Five PhD students were trained in stable isotope
methodologies, specifically trace gas CO2 and CH4 and seven alpha 4 projects were completed this FY.
Bristol: This has been a challenging year for the node that has seen a significant change in staffing and the way in which the node
operates. September saw the departure of Dr Robert Berstan who had decided to move to a new career. This had been pre-empted and,
having obtained the agreement of NERC S&F, two new technical posts were created to the replace the postdoctoral research associate
post. These were filled by Mrs Alison Kuhl and Mr James Williams who started in their new positions in November and December,
respectively. This increase in staffing levels enables the Bristol node to provide a complete wet chemical extraction/separation service
to compliment the instrument analysis service already in place; the new contracted commitment to NERC will be 30%. The current
increase in number of users from a non-chemical background makes this addition to the node’s portfolio of services particularly
timely. Following a successful capital bid to NERC S&F, the node tendered for a new bench top LC-MS instrument. The successful
bidder was ThermoFisher Scientific and the new instrument, a Quantum Access, was installed in October. All staff have recently
attended a training course at the European ThermoFisher Scientific training centre and methods are currently being developed for, and
migrated to, the new instrument. The node received 9 applications (including joint nodal applications) for analytical support over the
07-08 period. Peer reviewed publications arising from node users and staff for the same period amounted to 7 and the node, as part of
an ongoing reorganisation, shall be exploring more effective ways of capturing OPM data. Dr Bull attended and chaired a session at
SIMSUG in Newcastle.
Generic LSMSF training protocol
Students have had little if any previous experience of ‘wet chemical’ preparative methodologies, high precision quantitative stable
isotope analyses or mass spectrometry and this was their first introduction to vacuum-line cryogenic chemistry and/or isotope-ratio
mass spectrometry or related mass spectrometric techniques. The often intensive training they receive within the LSMSF therefore
develops skills different and complementary to those required in the field or later in their career development. The combination of
laboratory analysis and data interpretation skills is considered an attractive attribute of our 'alumni' and fulfills NERC’s
responsibilities to students and fellows as part of their skill development portfolio.
LSMSF capital
EK: A total of £143,738 was requested for a Delta V Plus mass spectrometer. The Costech ECS 4010 which was originally interfaced
with the Europa is now attached to the new Delta V Plus. This instrument will be used in the main for the development and analysis
of 2H and 18O in organic samples by continuous flow. Much work is still needed to improve sensitivity and throughput. In addition,
a second Delta V Plus was bought, which is to be shared with the ICSF. NERC SF & T contribution to the LSMSF-EK was £77.845
The EK node will use this to streamline doubly-labelled water measurements.
Lancaster: No capital was formally requested for FY 2007/2008, however, emergency funds to upgrade the terminally failed
electronics on the trace gas IRMS were granted by NERC Scientific Facilities & Technology in July 2007 to the sum of £18.3K.
Bristol: A total of £132,500 was requested for a Quantum Access high pressure liquid chromatography-triplequadrupole mass
spectrometer. This instrument will be used primarily for the quantification of glycerol dialkyl glycerol tetraethers (GDGTs), to
determine TEX86 and BIT indices, proxies used for palaeoenvironmental reconstruction and organic matter sourcing. Furthermore it
shall also be used for the analysis of intact phospholipids, another analytical service that is likely to see increasing demand in the
future.
SCIENCE HIGHLIGHTS:
EK: Increasingly, the EK node of the LSMSF has become involved in the development of techniques to improve knowledge of
animal migration, particularly those which are difficult to study because of their longevity (e.g. whales), or because of their size (e.g.
small passerine birds). Over the last year, we have been working with Dr. Jane Hill and her PhD student, Carolyn Jewell at the
University of York, to develop an accurate methodology to simultaneously measure hydrogen and oxygen isotope ratios in
butterfly/moth wings. Groundtruthing of Lepidoptera of known geographic origin has already been successful; recent data from
migrating silver Y moths which migrate to the UK after wintering in the Mediterranean is under interpretation, and Ms Jewell has
been invited to present her data at the Isoscapes meeting in Santa Barbara in April. This comprises crucial evidence for the
investigation of increased UK over wintering of Lepidoptera in relation to climate change. Another student, Gill Andrew is
responsible for the majority of conference proceedings publications attributed to the LSMSF-EK on the previous page; one of these
received the SEPA prize for best oral presentation for the Scottish Marine Group Postgraduate Meeting Edinburgh: “Seaweed or
biofilm? Combining stable isotope and gut contents approaches to examine the diet of the common limpet Patella vulgata”.
Lancaster: An alpha 5 graded, NERC funded PhD project from the University of Cambridge, studying the first ever large scale ‘insitu’ attempt to quantify soil priming in a tropical forest under a series of controlled experimental conditions using a stable isotopic
approach is producing some novel data sets. Elevated atmospheric CO2 results in increased inputs of carbon to soils from roots and
litter fall, which can lead to an increase in soil carbon decomposition, a ‘priming effect’. There remains little understanding of
priming effect dynamics and how they may be controlled by specific soil microbial groups. Using natural abundance isotopes, the
researchers examined changes in microbial groups as identified by PLFAs following C3 soil priming effects caused by C4 sugar cane
sucrose and Zea mays leaves. For all treatments an earlier pulse of priming effect CO 2 and a later pulse of substrate derived CO2,
showing that priming effects can be induced rapidly following changes in substrate supply. Sucrose treatments caused significant
priming effects, causing a 68% increase in soil carbon decomposition over 32 days. The study provides evidence that specific
microbial groups can induce rapid changes in soil C storage following an increase in belowground C-supply (Stott, co-authored
manuscript currently in press Soil Biol & Biochem 2008).
Bristol: The node continues to operate a dual mode of operation supporting the characterisation (qualitative and quantitative) of
samples and the development/refinement of new methodologies to facilitate such measurements. One development that exemplifies
the former is a study to assess the high resolution alkenone sea surface temperature variability on the North Icelandic Shelf and its
implications for Nordic Seas paleoclimatic development during the Holocene. In this study the palaeoceanography of the northern
Icelandic Shelf for the Holocene period was reconstructed from alkenone indices measured in core JR51-GC35 (determined by the
Bristol node). This contains a continuous record of Holocene sedimentation spanning 0-10.2 cal. kyr BP with a resolution of similar to
20 yr/cm. The users identified a general Holocene cooling trend that has superimposed millennial-scale oscillations of > 2 degrees C
with a timing that is in close agreement with the timing of glacier advances in northern Iceland. For the later half of the Holocene, the
alkenone-sea surface temperature (SST) record from JR51-GC35 correlates with proxy data for the strength of NADW formation
recorded in cores south of Iceland. This is interpreted as evidence of a close connection existing between north Icelandic sea surface
temperatures and the North Atlantic meridonal overturning circulation. The timing of the millennial-scale SST variability in the core
off North Iceland is found to be out of phase, or anti-phased, with the SST variability of a record in the eastern Nordic Seas
(MD952011). This suggests that the evolution of Holocene climate in the Nordic Seas was more complex than previously proposed;
and it is likely to be caused by differential responses of the Irminger and Norwegian Currents and modulated by changes in
atmospheric circulation analogous to the North Atlantic Oscillation. The Holocene 17, 19-24, 2007. Another output published in
Analytical Chemistry gives a good example of the development work conducted by the Facility. N-acetyl methyl (NACME)
esterification, was developed to improve the accuracy and precision of amino acid 13C value determination using gas
chromatography-combustion-isotope ratio mass spectrometry (GC/C/IRMS). Standard mixtures of 15 protein amino acids were
converted to NACME and N-acetyl-isopropyl (NAIP) esters; the latter established derivative was employed for comparison purposes.
Both procedures yielded baseline-resolved peaks for all 15 amino acids when GC columns coated with polar stationary phases were
employed. The isotopic robustness of both derivatization procedures was observed over a concentration range of 52-500 g of amino
acid. NACME esters displayed low errors (±0.6‰ for phenylalanine to ±1.1‰ for serine) due to the higher sample-to-derivative
carbon ratio of this derivative. Finally, the integrity of the new NACME procedure was confirmed through analysis of diet and bone
collagen amino acids of rats reared on C3 or C4 diets, which indicated the high degree of both accuracy and precision of the 13C
values obtained for individual amino acids. This new procedure will have wide ranging applications. Analytical Chemistry 79, 90829090, 2007.
FUTURE DEVELOPMENTS/STRATEGIC FORWARD LOOK
EK: we predict that dual 2H and 18O analysis of organic samples will become an important technique in our portfolio, with two
applications already in the May 2008 round, and two more expected applications in advanced stages of planning. To decrease the time
spent on changeover from one type of analysis to another, and to avoid cross-contamination from enriched samples, we now have a
designated C-N continuous flow workhorse instrument, and one which will be used for dual H-O and enriched 13C samples. We have
had a couple of informal enquiries regarding 34S analysis of organics: we flirted with sulphur isotopes a couple of years ago, but it
requires development to improve reliability of the measurement, and we intend to defer such development until H-O is routine, and
when we have sufficient interest to warrant allocation of instrument time. Given the recent large rise in the number of applications,
particularly involving requests for analyses currently either with our current portfolio or requiring significant development time, we
will be seeking to increase staffing levels in the near future.
Lancaster: The terminal failure of our trace gas IRMS in July 2007 warranted an emergency upgrade of its source electronics, run
through a Windows based Ion Vantage software as opposed to the previously outdated DOS based TG.1.67 software. The upgrade
includes the latest Gilson 271 auto-sampler purchased to counteract the increasing nodal demand for trace gas CO2, CH4 and N2O
analyses which have risen in volume by 30% since the last SRG 2003. Validation of the new system is planned for late Spring 2008.
Other research involves the development of a tried and tested ‘in house’ method of gas sample storage prior to CO2 analysis to cease the
ongoing debate in the scientific field as to length of storage time in order to retain isotopic integrity of gas samples. We are currently
seeing a continuing trend in the volume of trace gas analyses entering the Lancaster node, predominantly CO2 but ever increasing
amounts of N2O and CH4. Our existing GVI trace gas pre concentrator is in need of replacement in 2008-09 and a capital bid has been be
recently granted from NERC S & F for its essential replacement. We have had several enquiries about the possibility of performing bulk
18
O measurements on leaf material and waters for water use efficiency studies. The node manager considers that there is enough interest
in this from the outside user base to warrant the introduction and development of this technique at Lancaster in the near future.
Documented evidence of potential users is currently being compiled for use as a business case for future capital bids.
Bristol: We are currently in a tender process for the acquisition of two new isotope ratio mass spectrometers using funds secured through
an early capital bid to NERC S&F. The major part of the analytical support provided for successful applicants to NERC LSMSF
(Bristol) requires compound specific stable isotope analysis. As predicted in previous reports to NERC LSMSFSC the analytical
demand for this service has increased with the demand for the 13C analysis of phospholipids fatty acids (PLFAs) being one of the
most commonly requested analytical services. Moreover, as the experiments requiring this service become increasingly complex so
the amount of analytical time requested in applications to the Facility has seen an increase. Purchase of a Delta V Plus isotope ratio
mass spectrometer for routine compound specific D analysis will enable the node to: (i) double its working capacity for provision of
compound specific 13C analyses and (ii) with the same purchase make compound specific D analyses a routine analytical service
(due to the high automated nature of the latest available instrumentation). Currently the node has one GC/C/IRMS (Finnigan MAT
Delta S) permanently configured for the provision of 13C analyses. The addition of the above instrument would enable compound
specific D analyses to be shifted to the new analyser thereby freeing another analyser (ThermoQuest DeltaplusXL). This would
obviously have huge advantages for the provision of compound specific 13C analyses by the node.
Beyond providing a routine analytical service for successful applicants to NERC LSMSF the Bristol node also has a remit to develop
new cutting edge analytical methodologies and thereby enable yet further advances to be made as they are adopted by UK life
scientists. Whilst many compounds found in the natural environment are amenable to analysis by GC and therefore GC/C/IRMS the
greater percentage are at best intractable or more often impossible to analyse by GC/C/IRMS. Such compounds are simply too large
or too polar and may only be isolated and characterised using HPLC. For many years this posed a problem since interfacing an HPLC
to an IRMS has an inherent problem in the need to remove the mobile phase which is a solvent (cf. helium for GC/C/IRMS). A
solution remained elusive until very recently when ThermoFisher Scientific developed the ISOLINK interface. With this one
development the stable isotopic (13C) analysis of compounds (amino acids, carbohydrates, peptides, proteins, complex polar lipids,
purine/pyrimidine bases, nucleosides and nucleotides) that were either difficult or impossible to analyse is now possible. Furthermore,
the interface is also an ideal method for enabling the 13C of dissolved organic carbon (DOC), a carbon pool that is currently
receiving a large amount of study. The Organic Geochemistry Unit recently purchased an ISOLINK interface and it has been installed
within the Bristol node since early 2007. The interface currently shares an IRMS with another heavily used inlet and consequently it
has proved difficult to develop and fully exploit this powerful new analytical technique. Purchase of a dedicated IRMS and
autosampler will greatly expedite the development of methods that would then be integrated with the already extensive analytical
portfolio of the Bristol node. The ability to provide LC/IRMS as an analytical service would be, as far as we can ascertain, unique
within the UK and help ensure that NERC is supporting science with services that are at the very cutting edge. In addition, the
purchase of this second Delta V Plus analyser would help minimise downtime and costs through replication of spare parts and inlet
swapping in the event of any failure of either analyser.
In addition to the purchase and installation of new instrumentation the 08-09 period will see an intense amount of activity centred on
training as the new technical staff are given the appropriate guidance and instruction to operate and maintain the wide range of
instruments housed by the node. Furthermore, they shall be taught all of the wet chemical preparative methods commonly required by
users as well as all of the administrative duties associated with the Facility. Significant time over the ensuing period shall be spent
augmenting and developing the HPLC capabilities (both organic and stable isotope MS) of the Facility as this is perceived to be a growth
area for the future.
Non-Mandatory Facility-specific OPMs: utilisation, allocation of capacity etc