Leaf surface wax is a source of plant methane formation under UV radiation and in the presence of oxygen.

The terrestrial vegetation is a source of UV radiation-induced aerobic methane (CH4 ) release to the atmosphere. Hitherto pectin, a plant structural component, has been considered as the most likely precursor for this CH4 release. However, most of the leaf pectin is situated below the surface wax layer, and UV transmittance of the cuticle differs among plant species. In some species, the cuticle effectively absorbs and/or reflects UV radiation. Thus, pectin may not necessarily contribute substantially to the UV radiation-induced CH4 emission measured at surface level in all species. Here, we investigated the potential of the leaf surface wax itself as a source of UV radiation-induced leaf aerobic CH4 formation. Isolated leaf surface wax emitted CH4 at substantial rates in response to UV radiation. This discovery has implications for how the phenomenon should be scaled to global levels. In relation to this, we demonstrated that the UV radiation-induced CH4 emission is independent of leaf area index above unity. Further, we observed that the presence of O2 in the atmosphere was necessary for achieving the highest rates of CH4 emission. Methane formation from leaf surface wax is supposedly a two-step process initiated by a photolytic rearrangement reaction of the major component followed by an α-cleavage of the generated ketone.

Influence of plant growth on degradation of linear alkylbenzene sulfonate in sludge-amended soil.

Widespread application of sewage sludge to agricultural soils in Denmark has led to concern about the possible accumulation and effects of linear alkylbenzene sulfonate (LAS) in the soil ecosystem. Therefore, we have studied the uptake and degradation of LAS in greenhouse pot experiments. Sewage sludge was incorporated into a sandy soil to give a range from very low to very high applications (0.4 to 90 Mg dry wt. ha(-1)). In addition, LAS was added as water solutions. The soil was transferred to pots and sown with barley (Hordeum vulgare L. cv. Apex), rape (Brassica napus L. cv. Hyola 401), or carrot (Daucus carota L.). Also, plant-free controls were established. For all additions there was no plant uptake above the detection limit at 0.5 mg LAS kg(-1) d.w, but plant growth stimulated the degradation. With a growth period of 30 d, LAS concentrations in soil from pots with rape had dropped from 27 to 1.4 mg kg(-1) dry wt., but in plant-free pots the concentration decreased only to 2.4 mg kg(-1) dry wt. When LAS was added as a spike, the final concentration in soil from planted pots was 0.7 mg kg(-1) dry wt., but in pots without plants the final concentration was much higher (2.5 mg kg(-1) dry wt.). During degradation, the relative fraction of homologues C10, C11, and C12 decreased, while C13 increased.

Investigation of the initial reactions of the Calcote mechanism for soot formation.

The first three reactions of the Calcote mechanism for soot formation, that is, C3H 3 (+) +C2H2→C5H 5 (+) , C5H 5 (+) →C5H 3 (+) H2, and C5H 3 (+) +C2H2→C7H 5 (+) , have been studied based on chemi-ions withdrawn directly from a premixed methane-oxygen flame by supersonic molecular beam sampling. The first reaction is reversible and involves the formation of a specific encounter complex sensitive to pressure and ion kinetic energy. The second reaction appears to require large amounts of internal energy in the C5H 5 (+) ion to proceed. The third reaction is reversible; however, in contrast to the initiating reaction, the C5H 3 (+) ion formed from the [C7H 5 (+) ]* complex exhibits a much lower reactivity. The conclusions are based on ion-molecule reactions as well as collision activation mass spectrometry of isolated chemi-ions. In addition, the product distributions as functions of pressure and ion kinetic energy were studied.

Catabolism of indole-3-acetic acid and 4- and 5-chloroindole-3-acetic acid in Bradyrhizobium japonicum.

Some strains of Bradyrhizobium japonicum have the ability to catabolize indole-3-acetic acid. Indoleacetic acid (IAA), 4-chloro-IAA (4-Cl-IAA), and 5-Cl-IAA were metabolized to different extents by strains 61A24 and 110. Metabolites were isolated and analyzed by high-performance liquid chromatography and conventional mass spectrometry (MS) methods, including MS-mass spectroscopy, UV spectroscopy, and high-performance liquid chromatography-MS. The identified products indicate a novel metabolic pathway in which IAA is metabolized via dioxindole-3-acetic acid, dioxindole, isatin, and 2-aminophenyl glyoxylic acid (isatinic acid) to anthranilic acid, which is further metabolized. Degradation of 4-Cl-IAA apparently stops at the 4-Cl-dioxindole step in contrast to 5-Cl-IAA which is metabolized to 5-Cl-anthranilic acid.

Contact allergy to 2-hydroxy-5-tert-butyl benzylalcohol and 2,6-bis(hydroxymethyl)-4-tert-butylphenol, components of a phenolic resin used in marking pens.

2-hydroxy-5-tert-butyl benzylalcohol and 2,6-bis(hydroxymethyl)-4-tert-butylphenol were identified as contact allergens in a phenolic resin used as a tackifier in the ink of a marking pen, which, after being used directly on the skin, caused an acute contact dermatitis on the hand of a 13-year-old boy. The patient also reacted to 4-tert-butylphenol-formaldehyde resin (BPF resin) 1% pet. included in the European standard series.

Carvone: an overlooked contact allergen cross-reacting with sesquiterpene lactones?

The terpene l-carvone is one of the main constituents of spearmint oil. The sensitizing potential of l-carvone has been considered low, but it has occasionally caused contact allergy in users of spearmint toothpaste and chewing gum. l-Carvone is also an oxidation product of d-limonene that occurs in solvents used increasingly in industry. We included l-carvone 5% pet. in the standard patch test series. In the 1st year, 541 patients were tested and 15 (2.77%) had positive, and 12 doubtful positive (?+) reactions to l-carvone. The strongest reactions were observed in 9 patients with concomitant Compositae sensitivity. The key clinical features and other contact allergies of the patients are presented. When re-testing with l-carvone in the same or lower concentrations, only 2 out of 8 patients had positive reactions. Possible reasons for this discrepancy are discussed in terms of cross-reactions, concomitant sensitization, excited skin syndrome, irritancy and facilitated immunological response.

Release of thiurams and carbamates from rubber gloves.

A method for quantitative determination of thiuram and carbamate derivatives released from rubber gloves into synthetic sweat is presented. The analysis was based upon determination of ester derivatives using gas-chromatography/mass spectrometry and isotope-dilution. The detection limit was 0.1 mg thiuram/carbamate in 200 ml synthetic sweat (0.5 ppm). The release of thiurams and carbamates from 5 household and 5 surgical types of gloves into synthetic sweat was determined. Each of the natural rubber gloves released varying amounts of thiurams (0-4.3 mg) as well as carbamates (0-8.1 mg). 22 thiuram-sensitized patients were patch tested with pieces of the gloves. Gloves releasing considerable amounts of thiurams and/or carbamates seemed to cause more positive patch test reactions in these patients than gloves releasing smaller amounts. Surgical gloves made from natural rubber caused a substantial larger number of positive patch test reactions than household gloves made from natural rubber. The amounts released per cm2 of the gloves were of the same order of magnitude as the content per cm2 patch test of thiuram mix, diluted 1:10. The accessibility of a quantitative, chemical analysis for thiurams and carbamates released from rubber gloves makes it reasonable to ask for declarations of rubber gloves. Proposals for threshold values for release of thiurams and carbamates from rubber gloves may be given in the future.

Mass spectrometry of underivatized 15-hydroxyeicosatetraenoic acid and 15-hydroxyeicosapentaenoic acid.

A direct mass spectrometric method for 15-hydroxy metabolites of arachidonic acid and of eicosapentaenoic acid is described. 15-Hydroxyeicosanoids have the capacity to inhibit the formation of leukotrienes, potent mediators of inflammation formed by the 5-lipoxygenase pathway of arachidonic acid metabolism and may therefore have anti-inflammatory properties. 15-Hydroxyeicosatetraenoic acid (15-HETE) and 15-hydroxyeicosapentaenoic acid (15-HEPE) were synthesized using soybean lipoxygenase and arachidonic acid and eicosapentaenoic acid as substrates. These hydroxy fatty acids were then purified by reversed-phase high-performance liquid chromatography. This modified procedure provides rapid synthesis of multimilligram quantities of 15-hydroxyeicosanoids for in vitro and in vivo studies. Electron impact mass spectra of 15-HETE and 15-HEPE could be obtained directly without derivatizations.

Triphenyl phosphate allergy from spectacle frames.

A case of triphenyl phosphate allergy from spectacle frames is reported. Patch tests with analytical grade triphenyl phosphate, tri-m-cresyl phosphate, and tri-p-cresyl phosphate in the concentrations 5%, 0.5% and 0.05% pet. showed positive reactions to 0.05% triphenyl phosphate and 0.5% tri-m-cresyl phosphate, but no reaction to tri-p-cresyl phosphate. Gas chromatography of the tricresyl phosphate 5% pet. patch test material supplied from Trolab showed that it contained a mixture of a wide range of triaryl phosphates, including 0.08% triphenyl phosphate which is above the threshold for detecting triphenyl phosphate allergy in our patient.

Contact sensitivity and bioavailability of chlorocresol.

Chlorocresol sensitization from 5 topical preparations was determined in guinea pigs using the cumulative contact enhancement test. Chlorocresol 5% in olive oil/acetone (4/1), and 5% in aqueous suspension stabilized with carbomer 941 were more sensitizing (55% and 60% of the animals positive, respectively) than chlorocresol 5% in propylene glycol with or without carbomer 941 (20% positive). The sensitization from a saturated aqueous chlorocresol solution (about 0.38% w/v) was comparable to that of a 5% propylene glycol solution containing 13 times more chlorocresol. The fraction of the applied dose (from each preparation) that remained in the bandage material and the patch test skin site was determined by combined gas chromatography-mass spectrometry using an isotopic dilution technique. From 0.2% to 1.6% of the applied doses remained at the patch test skin sites as free chlorocresol. 75% of the chlorocresol in aqueous suspension permeated the skin in contrast to 34% and 35% of the chlorocresol in olive oil/acetone (4/1) and propylene glycol, respectively. In spite of the same amount of chlorocresol absorption from the 2 latter preparations, they showed a significant difference in sensitizing capacity. No simple relationship between the sensitization rates and the calculated bioavailability was observed with the preparations tested.

Identification of ononitol and O-methyl-scyllo-inositol in pea root nodules.

Ononitol (4-O-methyl-myo-inositol) and O-methyl-scyllo-inositol were identified in pea (Pisum sativum L.) root nodules formed by twoRhizobium leguminosarum strains. Ononitol was the major soluble carbohydrate in nodules formed by strain 1045 while O-methyl-scyllo-inositol and two unidentified components were dominant in the carbohydrate pattern of the nodules formed by strain 1 a. The cyclitols were also present in the denodulated roots, but to a much smaller extent; in the above-ground plant parts only traces were found. The identification of ononitol and O-methyl-scyllo-inositol was established by gas chromatography and gas chromatography-mass spectrometry utilizing trimethylsilyl- and acetyl-derivatives.

A controlled clinical trial of iohexol and diatrizoate in aortofemoral angiography.

Iohexol is a recently synthesized non-ionic low-osmolar contrast medium. It has been compared to the conventional ionic hyperosmolar contrast medium diatrizoate (Urografin 60%) in a randomized double-blind crossover study of aortofemoral angiographies of 50 consecutive patients. The intraarterial blood pressures, the pulse rate and ECG were recorded continuously and the reactions of pain and warmth were evaluated. Iohexol caused significantly less haemodynamic changes than Urografin and also the pain reactions were significantly reduced. The quality of the angiograms was equal.

N-Nitrosodiethanolamine revisited.

N-nitrosodiethanolamine is believed to be a weakly carcinogenic chemical, and as it occurs widely--in consumer products for example--it may constitute a significant hazard to humans. However, the chemical evidence concerning the identity, purity and properties of N-nitrosodiethanolamine is incomplete, and this casts some doubt on the basis of the current interest in this substance. In the present paper a purification procedure of synthetic N-nitrosodiethanolamine based on high-performance liquid chromatography is given. Other fractionation procedures such as gas liquid chromatography, ambient pressure column chromatography and distillation are shown to be inadequate. The purity and identity of purified N-nitrosodiethanolamine is established by means of electron impact and field ionization mass spectrometry, including metastable defocusing and collision induced decomposition techniques. Furthermore, 1H and 13C nuclear magnetic resonance and, to a lesser extent, infrared and ultraviolet spectroscopy are used. Deuterium labelled analogues of N-nitrosodiethanolamine and the parent diethanolamine are employed in rationalizing the results obtained.

Determination of mass spectrometric sensitivity of different metalloporphyrin esters relative to porphyrin ester.

Quantitative determination of metalloporphyrin contamination in preparations of biologically important porphyrins was achieved mass spectrometrically by application of the integrated ion current technique. For this purpose, the relative molecular ion sensitivities of the contaminating metal complexes were determined from the ratios of the integrated molecular ion currents of a series of calibration samples containing a porphyrin ester and one of its metal complexes in known molar ratio. Complexes formed with divalent ions of Cu, Zn, Fe, Co and Ni of copro- as well as uro-porphyrin permethylester were all found to have the same molecular ion sensitivities as their metal-free porphyrin ester. The relative metalloporphyrin ester content in a sample of porphyrin ester was thus obtained directly as the integrated ion current ratios of the normalized molecular ions. The preparation of calibration samples, including complex formation and the mass spectrometric methodology, is described and discussed.