Simple and surprisingly effective one-step extraction-cleanup by Soxflo for DDT and its metabolites from environmental samples

A pilot study found that DDT breakdown at the GC inlet was extensive in extracts from some-but not all-samples with high organic carbon contents. However, DDT losses could be prevented with a one-step extraction-cleanup in the Soxflo instrument with dichloromethane and charcoal. This dry-column procedure took 1 h at room temperature. It was tested on spiked soil and peat samples and validated with certified soil and sediment reference materials. Spike recoveries from freshly spiked samples ranged from 79 to 111% at 20-4000 mug/kg concentrations. Recoveries from the real-world CRMs were 99.7-100.2% of DDT, 89.7-90.4% of DDD and 89.6-107.9% of DDE. It was concluded that charcoal cleanups should be used routinely during surveys for environmental DDX pollution in order to mitigate against unpredictable matrix-enhanced breakdown in the GC. (C) 2004 Elsevier B.V. All rights reserved.

Soil carbon and litter development along a reconstructed biodiverse forest chronosequence of South-Western Australia

Soil organic matter (SOM) increases with time as landscape is restored. Studying SOM development along restored forest chronosequences would be useful in clarifying some of the uncertainties in quantifying C turnover rates with respect to forest clearance and ensuing restoration. The development of soil organic matter in the mineral soils was studied at four depths in a 16-year-old restored jarrah forest chronosequence. The size-separated SOM fractionation along with δ13C isotopic shift was utilised to resolve the soil C temporal and spatial changes with developing vegetation. The restored forest chronosequence revealed several important insights into how soil C is developing with age. Litter accumulation outpaced the native forest levels in 12 years after restoration. The surface soils, in general, showed increase in total C with age, but this trend was not clearly observed at lower depths. C accumulation was observed with increasing restoration age in all three SOM size-fractions in the surface 0–2 cm depth. These biodiverse forests show a trend towards accumulating C in recalcitrant stable forms, but only in the surface 0–2 cm mineral soil. A significant reverse trend was observed for the moderately labile SOM fraction for lower depths with increasing restoration age. Correlating the soil δ13C with total C concentration revealed the re-establishment of the isotopically depleted labile to enriched refractory C continuum with soil depth for the older restored sites. This implied that from a pedogenic perspective, the restored soils are developing towards the original native soil carbon profile.

Pyrohydrolysis-IRMS determination of silicate chlorine stable isotope compositions. Application to oceanic crust and meteorite samples

This contribution describes the optimization of chlorine extraction from silicate samples by pyrohydrolysis prior to the precise determination of Cl stable-isotope compositions (637 Cl) by gas source, dual inlet Isotope Ratio Mass Spectrometry (IRMS) on CH(3)Clg. The complete method was checked on three international reference materials for Cl-content and two laboratory glass standards. Whole procedure blanks are lower than 0. 5 mu mol, corresponding to less than 10 wt.% of most of the sample chloride analysed. In the absence of international chlorine isotope rock, we report here Cl extracted compared to accepted Cl contents and reproducibilities on Cl and delta Cl-37 measurements for the standard rocks. After extraction, the Cl contents of the three international references compared within error with the accepted values (mean yield = 94 +/-10%) with reproducibilities better than 12% (10). The laboratory glass standards - andesite SO100DS92 and phonolite S9(2) - were used specifically to test the effect of chloride amount on the measurements. They gave Cl extraction yields of 100 +/-6% (1 sigma-; n = 15) and 105 +/- 8% (1 sigma-; n = 7), respectively, with delta Cl-37 values of -0.51 0.14%o and -0.39 0.17%o (1g). In summary, for silicate samples with Cl contents between 39 and 9042 ppm, the Pyrohydrolysis/HPLC method leads to overall CI extraction yields of 100 8%, reproducibilities on Cl contents of 7% and on delta Cl-37 measurements of 0.12%o (all 1 sigma). The method was further applied to ten silicate rocks of various mineralogy and chemistry (meteorite, fresh MORB glasses, altered basalts and setpentinized peridotites) chosen for their large range of Cl contents (70-2156 ppm) and their geological significance. delta Cl-37 values range between -2.33 and -0.50%o. These strictly negative values contrast with the large range and mainly positive values previously reported for comparable silicate samples and shown here to be affected by analytical problems. Thus we propose a preliminary, revised terrestrial CI cycle, mainly dominated by negative and zero delta Cl-37 values. (C) 2007 Elsevier B.V. All rights reserved.

Carbon (13C) and nitrogen (15 N) translocation in a maize-striga hermonthica association

The translocation of C and N in a maize-Striga hermonthica association was investigated at three rates of nitrogen application in a glasshouse experiment. The objectives were to measure the transfer of C and N from maize to S. hermonthica and to determine whether the amount of N in the growing medium affected the proportions of C and N transferred. Young plants of maize were labelled in a (CO2)-C-13 atmosphere and leaf tips were immersed in ((NH4)-N-15)(2)SO4 Solution. The Striga x N interaction was not significant for any of the responses measured. Total dry matter for infected maize was significantly smaller than for uninfected maize from 43 to 99 days after planting, but N application increased total dry matter at all sampling times. Infected maize plants partitioned 39-45 % of their total dry matter to the roots compared with 28-31 % for Uninfected maize. Dry matter of S. hermonthica was not affected by the rate of N applied. S. hermonthica derived 100 % of its carbon from maize before emergence, decreasing to 22-59 % thereafter; the corresponding values for nitrogen were up to 59 % pre-emergence and Lip to 100 % after emergence. The relative proportions of nitrogen depleted from the host (up to 10 %) were greater than those of carbon (maximum 1.2 %) at all times of sampling after emergence of the parasite. The results show that the parasite was more dependent on the host for nitrogen than for carbon.

Local orientational disorder in peptide fibrils probed by a combination of residue-specific 13C-18O labelling, polarised infrared spectroscopy and molecular combing

A novel combination of site-specific isotope labelling, polarised infrared spectroscopy and molecular combing reveal local orientational ordering in the fibril-forming peptide YTIAALLSPYSGGRADS. Use of 13C-18O labelled alanine residues demonstrates that the Nterminal end of the peptide is incorporated into the cross-beta structure, while the C-terminal end shows orientational disorder

Movement of newly assimilated 13C carbon in the grass Lolium perenne and its incorporation into rhizosphere microbial DNA

One of the key processes that drives rhizosphere microbial activity is the exudation of soluble organic carbon (C) by plant roots. We describe an experiment designed to determine the impact of defoliation on the partitioning and movement of C in grass (Lolium perenne L.), soil and grass-sterile sand microcosms, using a (13)CO(2) pulse-labelling method. The pulse-derived (13)C in the shoots declined over time, but that of the roots remained stable throughout the experiment. There were peaks in the atom% (13)C of rhizosphere CO(2) in the first few hours after labelling probably due to root respiration, and again at around 100 h. The second peak was only seen in the soil microcosms and not in those with sterilised sand as the growth medium, indicating possible microbial activity. Incorporation of the (13)C label into the microbial biomass increased at 100 h when incorporation into replicating cells, as indicated by the amounts of the label in the microbial DNA, started to increase. These results indicate that the rhizosphere environment is conducive to bacterial growth and replication. The results also show that defoliation had no impact on the pattern of movement of (13)C from plant roots into the microbial population in the rhizosphere.

1H-13C HSQC NMR spectroscopy for estimating procyanidin/prodelphinidin and cis/trans-flavan-3-ol ratios of condensed tannin samples: correlation with thiolysis

Studies with a diverse array of 22 purified condensed tannin (CT) samples from nine plant species demonstrated that procyanidin/prodelphinidin (PC/PD) and cis/trans-flavan-3-ol ratios can be appraised by 1H-13C HSQC NMR spectroscopy. The method was developed from samples containing 44 to ~100% CT, PC/PD ratios ranging from 0/100 to 99/1, and cis/trans ratios from 58/42 to 95/5 as determined by thiolysis with benzyl mercaptan. Integration of cross-peak contours of H/C-6' signals from PC and of H/C-2',6' signals from PD yielded nuclei adjusted estimates that were highly correlated with PC/PD ratios obtained by thiolysis (R2 = 0.99). Cis/trans-flavan-3-ol ratios, obtained by integration of the respective H/C-4 cross-peak contours, were also related to determinations made by thiolysis (R2 = 0.89). Overall, 1H-13C HSQC NMR spectroscopy appears to be a viable alternative to thiolysis for estimating PC/PD and cis/trans ratios of CT, if precautions are taken to avoid integration of cross-peak contours of contaminants.

Terrestrial biosphere changes over the last 120 kyr and their impact on ocean δ 13C

A new global synthesis and biomization of long (>40 kyr) pollen-data records is presented, and used with simulations from the HadCM3 and FAMOUS climate models to analyse the dynamics of the global terrestrial biosphere and carbon storage over the last glacial–interglacial cycle. Global modelled (BIOME4) biome distributions over time generally agree well with those inferred from pollen data. The two climate models show good agreement in global net primary productivity (NPP). NPP is strongly influenced by atmospheric carbon dioxide (CO2) concentrations through CO2 fertilization. The combined effects of modelled changes in vegetation and (via a simple model) soil carbon result in a global terrestrial carbon storage at the Last Glacial Maximum that is 210–470 Pg C less than in pre-industrial time. Without the contribution from exposed glacial continental shelves the reduction would be larger, 330–960 Pg C. Other intervals of low terrestrial carbon storage include stadial intervals at 108 and 85 ka BP, and between 60 and 65 ka BP during Marine Isotope Stage 4. Terrestrial carbon storage, determined by the balance of global NPP and decomposition, influences the stable carbon isotope composition (δ13C) of seawater because terrestrial organic carbon is depleted in 13C. Using a simple carbon-isotope mass balance equation we find agreement in trends between modelled ocean δ13C based on modelled land carbon storage, and palaeo-archives of ocean δ13C, confirming that terrestrial carbon storage variations may be important drivers of ocean δ13C changes.

Use of TD-GC-TOF-MS to assess volatile composition during post harvest storage in seven accessions of rocket salad (Eruca sativa)

An important step in breeding for nutritionally enhanced varieties is determining the effects of the post-harvest supply chain on phytochemicals and the changes in VOCs produced over time. TD- GC-TOF-MS was used and a technique for the extraction of VOCs from the headspace using portable tubes is described. Forty-two compounds were detected; 39 were identified by comparison to NIST libraries. Thirty-five compounds had not been previously reported in Eruca sativa. Seven accessions were assessed for changes in headspace VOCs over 7 days. Relative amounts of VOCs across 3 time points were significantly different - isothiocyanate-containing molecules being abundant on 'Day 0'. Each accession showed differences in proportions/types of volatiles produced on each day. PCA revealed a separation of VOC profiles according to the day of sampling. Changes in VOC profiles over time could provide a tool for assessment of shelf-life.