Formation of organic acids from the gas-phase ozonolysis of terpinolene

Gas-phase ozonolysis of terpinolene was studied in static chamber experiments using gas chromatography coupled to mass spectrometric and flame ionisation detection to separate and detect products. Two isomers of C-7-diacids and three isomers of C-7-aldehydic acids were identified in the condensed phase after derivatisation. Possible mechanisms of formation of these acids were investigated using different OH radical scavengers and relative humidities, and were compared to those reported earlier for the ozonolysis of beta-pinene. In addition, branching ratios for some of the individual reaction steps, e. g. the branching ratio between the two hydroperoxide channels of the C-7-CI, were deduced from the quantitative product yield data. Branching ratios for POZ decomposition and the stabilisation/decomposition of the C-7-CI were also obtained from measurements of the C-7 primary carbonyl product.

A stereocontrolled total synthesis of methyl (+/-)-O-methylpodocarpate

A stereocontrolled total synthesis of methyl (+/-)-O-methyl podocarpate (4) has been successfully accomplished using the trans-fused diester 21 as a key intermediate. Intramolecular Michael reaction of the enone-diester 18 afforded the cis-fused keto-diester 19 in high yield which was stereoselectively converted into 21 via the enone 20. (C) 2003 Elsevier Science Ltd. All rights reserved.

Soil phosphorus dynamics and phytoavailability from sewage sludge at different stages in a treatment stream

The effect of different stages of sewage sludge treatment on phosphorus (P) dynamics in amended soils was determined using samples of undigested liquid (UL), anaerobically digested liquid (AD) and dewatered anaerobically digested (DC) sludge. Sludges were taken from three points in the same treatment stream and applied to a sandy loam soil in field-based mesocosms at 4, 8 and 16t ha−1 dry solids. Mesocosms were sown with perennial ryegrass (Lolium perenne cv. Melle), and the sward was harvested after 35 and 70 days to determine yield and foliar P concentration. Soils were also sampled during this period to measure P transformations and the activities of acid phosphomonoesterase and phosphodiesterase. Data show that the AD amended soils had the greatest plant-available and foliar P content up to the second harvest, but the UL amended soils had the greatest enzyme activity. Characterisation of control and 16t ha−1 soils and sludge using solution 31P nuclear magnetic resonance (NMR) spectroscopy after NaOH–EDTA extraction revealed that P was predominantly in the inorganic pool in all three sludge samples, with the highest proportion (of the total extracted P) as inorganic P in the anaerobically digested liquid sludge. After sludge incorporation, P was immobilised to organic species. The majority of organic P was in monoester-P forms, while the remainder of organic P (diester P and phosphonate P) was more susceptible to transformations through time and showed variation with sludge type. These results show that application of sewage sludge at rates as low as 4t ha−1 can have a significant nutritional benefit to ryegrass over an initial 35-day growth and subsequent 35-day re-growth periods. Differences in P transformation, and hence nutritional benefit, between sludge types were evident throughout the experiment. Thus, differences in sludge treatment process alter the edaphic mineralisation characteristics of biosolids derived from the same source material.