Influence of dissolved humic substances on the mass transfer of organic compounds across the air-water interface

The effect of dissolved humic substances (DHS) on the rate of water-gas exchange of two volatile organic compounds was studied under various conditions of agitation intensity, solution pH and ionic strength. Mass-transfer coefficients were determined from the rate of depletion of model compounds from an apparatus containing a stirred aqueous solution with continuous purging of the headspace above the solution (dynamic system). Under these conditions, the overall transfer rate is controlled by the mass-transfer resistance on the water side of the water-gas interface. The experimental results show that the presence of DHS hinders the transport of the organic molecules from the water into the gas phase under all investigated conditions. Mass-transfer coefficients were significantly reduced even by low, environmentally relevant concentrations of DHS. The retardation effect increased with increasing DHS concentration. The magnitude of the retardation effect on water-gas exchange was compared for Suwannee River fulvic and humic acids, a commercially available leonardite humic acid and two synthetic surfactants. The observed results are in accordance with the concept of hydrodynamic effects. Surface pressure forces due to surface film formation change the hydrodynamic characteristics of water motion at the water-air interface and thus impede surface renewal.     

Partitioning of polar and non-polar neutral organic chemicals into human and cow milk

The aim of this work was to develop a predictive model for milk/water partition coefficients of neutral organic compounds. Batch experiments were performed for 119 diverse organic chemicals in human milk and raw and processed cow milk at 37°C. No differences (<0.3 log units) in the partition coefficients of these types of milk were observed. The polyparameter linear free energy relationship model fit the calibration data well (SD=0.22 log units). An experimental validation data set including hormones and hormone active compounds was predicted satisfactorily by the model. An alternative modelling approach based on log K(ow) revealed a poorer performance. The model presented here provides a significant improvement in predicting enrichment of potentially hazardous chemicals in milk. In combination with physiologically based pharmacokinetic modelling this improvement in the estimation of milk/water partitioning coefficients may allow a better risk assessment for a wide range of neutral organic chemicals.     

Monoterpene emissions and carbonyl compound air concentrations during the blooming period of rape (Brassica napus)

An increasing percentage of agricultural land in Germany is used for oil seed plants. Hence, rape has become an important agricultural plant (in Saxony 1998: 12% of the farmland) in the recent years. During flowering of rape along with intensive radiation and high temperatures, a higher production and emission of biogenic VOC was observed. The emissions of terpenes were determined and more importantly, high concentrations of organic carbonyl compounds were observed during this field experiment. All measurements of interest have been carried out during two selected days with optimal weather conditions. It is found that the origin or the mechanism of formation of different group of compounds had strong influence on the day to day variation of their concentrations. The emission flux of terpenes from flowering rape plants was determined to be 16–32 μg h⁻¹ m⁻² (30–60 ng h⁻¹ per g dry plant––540–1080 ng h⁻¹ per plant), in total. Limonene, -thujene and sabinene were the most important compounds (about 60% of total terpenes). For limonene and sabinene reference emission rates (M_S) and temperature coefficients were determined: β_limonene=0.108 K⁻¹ and M_S=14.57 μg h⁻¹ m⁻²; β_sabinene=0.095 K⁻¹ and M_S=5.39 μg h⁻¹ m⁻².

The detected carbonyl compound concentrations were unexpectedly high (maximum formaldehyde concentration was 18.1 ppbv and 3.4 ppbv for butyraldehyde) for an open field. Possible reasons for these concentrations are the combination of primary emission from the plants induced by high temperature and high ozone stress, the secondary formation from biogenically and advected anthropogenically emitted VOC at high radiation intensities and furthered by the low wind speeds at this time.     

Monoterpene emissions and carbonyl compound air concentrations during the blooming period of rape (Brassica napus)

An increasing percentage of agricultural land in Germany is used for oil seed plants. Hence, rape has become an important agricultural plant (in Saxony 1998: 12% of the farmland) in the recent years. During flowering of rape along with intensive radiation and high temperatures, a higher production and emission of biogenic VOC was observed. The emissions of terpenes were determined and more importantly, high concentrations of organic carbonyl compounds were observed during this field experiment. All measurements of interest have been carried out during two selected days with optimal weather conditions. It is found that the origin or the mechanism of formation of different group of compounds had strong influence on the day to day variation of their concentrations. The emission flux of terpenes from flowering rape plants was determined to be 16–32 μg h⁻¹ m⁻² (30–60 ng h⁻¹ per g dry plant––540–1080 ng h⁻¹ per plant), in total. Limonene, α-thujene and sabinene were the most important compounds (about 60% of total terpenes). For limonene and sabinene reference emission rates (M_S) and temperature coefficients were determined: β_limonene=0.108 K⁻¹ and M_S=14.57 μg h⁻¹ m⁻²; β_sabinene=0.095 K⁻¹ and M_S=5.39 μg h⁻¹ m⁻².The detected carbonyl compound concentrations were unexpectedly high (maximum formaldehyde concentration was 18.1 ppbv and 3.4 ppbv for butyraldehyde) for an open field. Possible reasons for these concentrations are the combination of primary emission from the plants induced by high temperature and high ozone stress, the secondary formation from biogenically and advected anthropogenically emitted VOC at high radiation intensities and furthered by the low wind speeds at this time.     

Complex performance of novel CoNiMnB electrodeposits in alkaline borohydride solutions

The complex performance of newly synthesized CoNiMnB electrodeposits in base-stabilized sodium borohydride solutions was examined. The rate of hydrogen generation due to borohydride hydrolysis was determined at different temperatures. Activation energy of approximately 33 kJ/mol was estimated, which is lower than the values reported for other catalysts. At electrochemical conditions, there is a competition between borohydride hydrolysis and electrooxidation reactions. The electrooxidation of borohydride takes place with low overpotentials at relatively high current densities. The long-term discharge at galvanostatic conditions as well as possibilities for partial storage of generated hydrogen indicates potentials for application of studied electrodeposits as anode material in direct borohydride fuel cells (DBFC).     

Catalytic activity of NiW electrodeposits

NiW systems are known as one of the best catalysts for various desulfurization processes. In this study, we examined catalytic properties of NiW electrodeposits, produced from two different electrolytes, towards sulfide ion oxidation in alkaline solution. Despite the big difference in morphology and structure of both materials, they exhibit almost the same catalytic activity for the examined reaction. A possible explanation of this experimental fact is that the overall reaction is controlled by the transport of oxygen through the catalyst samples.     

Feather-like development of Triassic diapsid skin appendages

Of the recent sauropsid skin appendage types, only feathers develop from a cylindrical epidermal invagination, the follicle, and show hierarchical branching. Fossilized integuments of Mesozoic diapsids have been interpreted as follicular and potential feather homologues, an idea particularly controversially discussed for the elongate dorsal skin projections of the small diapsid Longisquama insignis from the Triassic of Kyrgyzstan. Based on new finds and their comparison with the type material, we show that Longisquama's appendages consist of a single-branched internal frame enclosed by a flexible outer membrane. Not supporting a categorization either as feathers or as scales, our analysis demonstrates that the Longisquama appendages formed in a two-stage, feather-like developmental process, representing an unusual early example for the evolutionary plasticity of sauropsid integument.     

Stabilization of potassium permanganate particles with manganese dioxide

A new potassium permanganate reagent with slow-release properties was designed and tested for possible application in in situ chemical oxidation. For this purpose, MnO₂-coated KMnO₄ particles (MCP) were prepared by partial reduction of solid KMnO₄ using the acid-catalyzed reaction with n-propanol or the comproportionation of Mn(VII) and Mn(II) in n-propanol as reaction medium. Column tests showed that, for MCP with a residual KMnO₄ fraction of 70 wt%, the duration of permanganate release under flow-through conditions was prolonged by a factor of 10 compared to untreated KMnO₄. While KMnO₄ is too soluble to be used in reactive barriers, MCP could be introduced into the aquifer by filling of trenches or boreholes; this would allow a prolonged passive dosing of permanganate into the flowing groundwater. In addition, experiments were conducted in order to determine the oxidation capability of native KMnO₄ particles and MCP in CH₂Cl₂, a representative non-polar non-aqueous phase liquid (NAPL). It may be possible to utilize the significantly higher reactivity of MCP under these conditions for the design of slow-release permanganate particles for NAPL source treatment.