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.     

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.     

Effect of Long Retention Time in the Settler on Phosphorus Removal from Communal Wastewater (4 pp)

- Goals. The objective of the paper is to illustrate the solution of a chronic problem occurring in a wastewater treatment facility with a capacity of 12,000 inhabitant equivalent. A drastic phosphorus concentration increase (two or three times higher than the Hungarian limit of 1 mg/l) was observed in the wastewater treatment facility for a long time (12–24 h) with changing time periods indicating malfunctioning in the operation of the facility. Methods Computer-aided simulation technique was used to develop a solution for the treatment of the problem using a software developed by the Department of Environmental and Chemical Engineering, University of Veszprém, Hungary. Results and Discussion The simulation studies show that if the nightly inflow is less than 200 m3/h at least for two hours, the system doesn't then receive enough fresh nutrients which can cause a deficiency in the nutrient uptake of the PAOs in the anaerobic zones. This can result in the fact that the PAOs accumulate less phosphorus into the aerobic zones. Conclusion Long retention time (10 h) is the reason for the problem, namely – under special conditions – the phosphorus in the sludge of the settling tank of the wastewater treatment plant. The problem was caused by phosphorus dissolution from the sludge of the settling tank during the undesirably long retention time.     

Analysis of conservative tracer measurement results inside a planted horizontal subsurface flow constructed wetland filled with coarse gravel using Frechet distribution

Environmental Science and Pollution Research - We worked out a method in Maple environment to help understand the difficult transport processes in horizontal subsurface flow constructed wetlands...     

Application of divided convective-dispersive transport model to simulate variability of conservative transport processes inside a planted horizontal subsurface flow constructed wetland

Environmental Science and Pollution Research - This paper offers a novel application of our model worked out in Maple environment to help understand the very complex transport processes in...     

Sensitivity of Indices of Biotic Integrity to Simulated Fish Assemblage Changes

Multimetric indices of biotic integrity (IBIs) are commonly used to assess condition of stream fish assemblages, but their ability to monitor trends within streams over time is largely unknown. We assessed the trend detection ability of two IBI formulations (one with traditional scoring and metrics, and one with nontraditional scoring and region-specific metrics) and of similarity and diversity indices using simulations that progressively altered the fish assemblages of 39 streams in the United States mid-Atlantic Highlands region. We also assessed responses to simulated 50% variability in fish abundances, as a measure of background noise. Fish assemblage indices responded little to changes that affected all species proportionally despite substantial changes in total fish number. Assemblage indices responded better to scenarios that differentially affected fish species, either according to life history traits or by increasing dominance of already common species, but even these changes took some time to detect relative to background variability levels. Ordinations of stream fish assemblage data suggested that differences among sites were maintained even after substantial alterations of fish composition within sites. IBIs are designed to detect broad assemblage differences among sites while downplaying abundance changes and variability increases that were the first indications of within-site changes, and they appear more suited to detecting large departures from natural fish assemblages than for monitoring gradual changes such as those our simulations produced. Inferences about causes of assemblage changes should be made with caution because of correlations among species traits and interdependence among IBI component metrics. Site trend assessments should be made based on all available data rather than just by summary indices.