Prediction of Klason lignin and lignin thermal degradation products by Py-GC/MS in a collection of Lolium and Festuca grasses

A rapid method for the analysis of biomass feedstocks was established to identify the quality of the pyrolysis products likely to impact on bio-oil production. A total of 15 Lolium and Festuca grasses known to exhibit a range of Klason lignin contents were analysed by pyroprobe-GC/MS (Py-GC/MS) to determine the composition of the thermal degradation products of lignin. The identification of key marker compounds which are the derivatives of the three major lignin subunits (G, H, and S) allowed pyroprobe-GC/MS to be statistically correlated to the Klason lignin content of the biomass using the partial least-square method to produce a calibration model. Data from this multivariate modelling procedure was then applied to identify likely "key marker" ions representative of the lignin subunits from the mass spectral data. The combined total abundance of the identified key markers for the lignin subunits exhibited a linear relationship with the Klason lignin content. In addition the effect of alkali metal concentration on optimum pyrolysis characteristics was also examined. Washing of the grass samples removed approximately 70% of the metals and changed the characteristics of the thermal degradation process and products. Overall the data indicate that both the organic and inorganic specification of the biofuel impacts on the pyrolysis process and that pyroprobe-GC/MS is a suitable analytical technique to asses lignin composition. © 2007 Elsevier B.V. All rights reserved.

Intermediate pyrolysis and product identification by TGA and Py-GC/MS of green microalgae and their extracted protein and lipid components

The thermo-chemical conversion of green microalgae Chlamydomonas reinhardtii wild type (CCAP 11/32C), its cell wall deficient mutant C. reinhardtii CW15 (CCAP 11/32CW15) and Chlorella vulgaris (CCAP 211/11B) as well as their proteins and lipids was studied under conditions of intermediate pyrolysis. The microalgae were characterised for ultimate and gross chemical composition, lipid composition and extracted products were analysed by Thermogravimetric analysis (TG/DTG) and Pyrolysis-gaschromatography/mass-spectrometry (Py-GC/MS). Proteins accounted for almost 50% and lipids 16-22 % of dry weight of cells with little difference in the lipid compositions between the C. reinhardtii wild type and the cell wall mutant. During TGA analysis, each biomass exhibited three stages of decomposition, namely dehydration, devolatilization and decomposition of carbonaceous solids. Py-GC/MS analysis revealed significant protein derived compounds from all algae including toluene, phenol, 4-methylphenol, 1H-indole, 1H-indole-3methyl. Lipid pyrolysis products derived from C. reinhardtii wild type and C. reinhardtii CW15 were almost identical and reflected the close similarity of the fatty acid profiles of both strains. Major products identified were phytol and phytol derivatives formed from the terpenoid chain of chlorophyll, benzoic acid alkyl ester derivative, benzenedicarboxylic acid alkyl ester derivative and squalene. In addition, octadecanoic acid octyl ester, hexadecanoic acid methyl ester and hydrocarbons including heptadecane, 1-nonadecene and heneicosane were detected from C. vulgaris pyrolysed lipids. These results contrast sharply with the types of pyrolytic products obtained from terrestrial lignocellulosic feedstocks and reveal that intermediate pyrolysis of algal biomass generates a range of useful products with wide ranging applications including bio fuels.

SPME-GC technika alkalmazása élelmiszer-technológiai kutatásokban

Az illékony komponensek vizsgálata számos tudományterületen fontos feladat. Ez különösen igaz az élelmiszertudomány esetében, ahol sok esetben ezeknek a vegyületeknek nemcsak mint kémiai markerekként van jelentősége, hanem részt vesznek az illat, mint érzékszervi tulajdonság kialakításában is. Az illékony vegyületek gázkromatográfiás vizsgálata hosszú múltra tekint vissza, ugyanakkor a rutinszerűen használható, oldószermentes, bonyolult mintaelőkészítést nem igénylő gázkromatográfiás technika csak az utóbbi néhány évtizedben vált elérhetővé. Az SPME (szilárd fázisú mikroextrakció) technikát az 1980-a évek végén mutatták be, mára azonban a gázkromatográfiás gyakorlatban alkalmazott, alternatív mintaelőkészítési móddá vált. A technika kellően érzékeny, jó reprodukálhatóságot biztosító, költséghatékony és egy lépésben valósítja meg az extrakciót, a koncentrálást és mintainjektálást. Az SPME technika sikeres alkalmazására mind több példa mutatkozik. Közleményünkben a Budapesti Corvinus Egyetem Élelmiszertudományi Kar Hűtő- és Állatitermék Technológiai Tanszékén végzett olyan kutatások eredményeiből mutatunk be néhány példát, ahol az élelmiszer-előállítási, -feldolgozási technológiák fejlesztésében az élelmiszerek illékony komponensei vizsgálatának nagy jelentősége van.

2011-12 Worlds Ahead Strategic Plan Implementation (GC)

2011-12 Worlds Ahead Strategic Plan Implementation Meeting held at Graham Center, Modesto Maidique Campus. Speakers included President Mark B. Rosenberg, Provost and Executive Vice President for Academic Affairs Douglas Wartzok,

Stable isotopes and Mg/Ca ratios on foraminifera and Ba/Ca ratios of sediment core SK168/GC-1

The past variability of the South Asian Monsoon is mostly known from records of wind strength over the Arabian Sea while high-resolution paleorecords from regions of strong monsoon precipitation are still lacking. Here, we present records of past monsoon variability obtained from sediment core SK 168/GC-1, which was collected at the Alcock Seamount complex in the Andaman Sea. We utilize the ecological habitats of different planktic foraminiferal species to reconstruct freshwater-induced stratification based on paired Mg/Ca and d18O analyses and to estimate seawater d18O (d18Osw). The difference between surface and thermocline temperatures (delta T) and d18Osw (delta d18Osw) is used to investigate changes in upper ocean stratification. Additionally, Ba/Ca in G. sacculifer tests is used as a direct proxy for riverine runoff and sea surface salinity (SSS) changes related to monsoon precipitation on land. Our delta d18Osw time series reveals that upper ocean salinity stratification did not change significantly throughout the last glacial suggesting little influence of NH insolation changes. The strongest increase in temperature gradients between the mixed layer and the thermocline is recorded for the mid-Holocene and indicate the presence of a significantly shallower thermocline. In line with previous work, the d18Osw and Ba/Ca records demonstrate that monsoon climate during the LGM was characterized by a significantly weaker southwest monsoon circulation and strongly reduced runoff. Based on our data the South Asian Summer Monsoon (SAM) over the Irrawaddyy strengthened gradually after the LGM beginning at ~18 ka. This is some 3 kyrs before an increase of the Ba/Ca record from the Arabian Sea and indicates that South Asian Monsoon climate dynamics are more complex than the simple N-S displacement of the ITCZ as generally described for other regions. Minimum d18Osw values recorded during the mid-Holocene are in phase with Ba/Ca marking a stronger monsoon precipitation, which is consistent with model simulations.

(Table 1) Radiocarbon dates of core JM05-085-GC, South-Barents Sea

The Late Weichselian-Early Holocene variability of the North Atlantic Current has been studied with focus on the zonal component of this meridional transport during the transition from glacial to interglacial conditions. The investigated sediment core is from 409 m water depth in the SW Barents Sea. Eight Accelerator mass spectrometry (AMS) 14C dates show that the core covers the last 20,000 cal yr B.P. with a centennial scale resolution during Late Weichselian-Early Holocene. Planktic foraminiferal assemblages were analyzed using the >100 ?m size fraction and foraminiferal planktic and benthic d13C and d18O isotopes were measured. Furthermore, a range of physical and chemical analyses has been carried out on the bulk sediment samples. Four time periods have been identified which represent the varying oceanographic conditions in Ingøydjupet, a glacial trough located off the north coast of Norway in the SW Barents Sea. 1) The late glacial (before ca 15,000 cal yr B.P.) influenced by the nearby ice sheets with high amounts of sea ice- or iceberg-transported detritus. 2) The late Oldest Dryas stadial and the Bølling-Allerød interstadial (ca 15,000-12,700 cal yr B.P.) with cold surface water conditions influenced by the collapse of the nearby ice sheets, high amounts of sea ice- or iceberg-transported detritus and melt water and weak subsurface inflow of Atlantic Water. 3) The Younger Dryas cold stadial (12,700-11,650 cal yr B.P.) with low primary productivity and extensive sea ice cover and 4) The Preboreal and Early Holocene (11,650-6800 cal yr B.P. cal yr B.P.) with strong influx of Atlantic Water into the area, near absence of ice rafted debris and generally ameliorated conditions in both surface and bottom water masses as seen from a high flux of foraminifera and increased marine primary production.

(Table 1) Chemical composition of palygorskite and host sediments from Core VITYAZ4599-GC

Palygorskite streak veinlets were studied in the lower part of a sediment core collected at Station VITYAZ4599 in the central (Mid-Indian) basin of the Indian Ocean. It is suggested that this palygorskite is of hydrothermal origin and was formed in pre-Pliocene time.

Gas hydrates of nonpressurized (GC) and pressurized (DAPC) sediment cores from the Hakon Mosby Mud Volcano, SW Barents Sea

The occurrence of gas hydrates at submarine mud volcanoes (MVs) located within the gas hydrate stability zone (GHSZ) is controlled by upward fluid and heat flux associated with MV activity. Determining the spatial distribution of gas hydrates at MVs is crucial to evaluate their sensitivity to known episodic changes in volcanic activity. We determined the hydrocarbon inventory and spatial distribution of hydrates at an individual MV structure. The Håkon Mosby Mud Volcano (HMMV), located at 1,250 m water depth on the Barents Sea slope, was investigated by combined pressure core sampling, heat flow measurements, and pore water chemical analysis. Quantitative pressure core degassing revealed gas-sediment ratios between 3.1 and 25.7, corresponding to hydrate concentrations of up to 21.3% of the pore volume. Hydrocarbon compositions and physicochemical conditions imply that gas hydrates incipiently crystallize as structure I hydrate, with a dissociation temperature of around 13.8°C at this water depth. Based on numerous in situ measurements of the geothermal gradient in the seabed, pore water sulfate profiles and microbathymetric data, we show that the thickness of the GHSZ increases from less than 1 m at the warm center to around 47 m in the outer parts of the HMMV. We estimate the total mass of hydrate-bound methane stored at the HMMV to be about 102.5 kt, of which 2.8 kt are located within the morphological Unit I around the center and thus are likely to be dissociated in the course of a large eruption.

Sediment age, abundance of planktonic foraminifera shells, degree of their dissolution, percentage of benthic foraminifera in total foram fauna, Core GC-11, Sea of Okhotsk

Taxonomic composition and distribution of planktonic foraminifera are studied in section of Core GC-11 penetrated through Upper Quaternary sediments of the Bowers Ridge western slope, south Bering Sea. It is shown that structure of foraminiferal assemblage and productivity varied substantially during the last 32000 calendar years in response to changes in surface water temperatures and water mass circulation in the North Pacific including the Bering Sea. Productivity was maximal during the deglaciation epoch, being notably lower in Holocene and minimal at glaciation time.