A set of constitutive relationships accounting for residual NAPL in the unsaturated zone

Although laboratory experiments show that non-aqueous phase liquid (NAPL) is retained in the unsaturated zone, no existing multiphase flow model has been developed to account for residual NAPL after NAPL drainage in the unsaturated zone. We developed a static constitutive set of saturation-capillary pressure relationships for water, NAPL and air that accounts for both this residual NAPL and entrapped NAPL. The set of constitutive relationships is formulated similarly to the set of scaled relationships that is frequently applied in continuum models. The new set consists of three fluid-phase systems: a three-phase system and a two-phase system, that both comply with the original constitutive model, and a newly introduced residual NAPL system. The new system can be added relatively easily to the original two- and three-phase systems. Entrapment is included in the model. The constitutive relationships of the non-drainable residual NAPL system are based on qualitative fluid behavior derived from a pore scale model. The pore scale model reveals that the amount of residual NAPL depends on the spreading coefficient and the water saturation. Furthermore, residual NAPL is history-dependent. At the continuum scale, a critical NAPL pressure head defines the transition from free, mobile NAPL to residual NAPL. Although the Pc-S relationships for water and total liquid are not independent in case of residual NAPL, two two-phase Pc-S relations can represent a three-phase residual system of Pc-S relations. A newly introduced parameter, referred to as the residual oil pressure head, reflects the mutual dependency of water and oil. Example calculations show consistent behavior of the constitutive model. Entrapment and retention in the unsaturated zone cooperate to retain NAPL. Moreover, the results of our constitutive model are in agreement with experimental observations.     

A modelling assessment of the atmospheric fate of volatile methyl siloxanes and their reaction products

Volatile methyl siloxanes break down in the atmosphere by reacting with OH radicals to form OH-substituted silanols. As the silanols become increasingly OH substituted they are increasingly likely to be removed from the atmosphere by wet and dry deposition. A simple equilibrium partitioning model was constructed to explore the relative rates of removal by different mechanisms (reaction vs. deposition) for siloxanes and their resultant silanols. A mass balance is calculated for the parent siloxane molecule and for each silanol, characterised by the number of OH substitutions. The model includes the effect of incomplete equilibrium between the vapour, adsorbed and dissolved phases of silanols in the atmosphere using a non-equilibrium factor (epsilon) expressing relative departure from equilibrium. Model results show: (1) maximum vapour-phase concentrations for non-substituted siloxanes and single-OH-substituted silanols; (2) maximum dissolved-phase and adsorbed-phase concentrations for two-OH-substituted silanols; (3) >99% of the original material will be removed in wet deposition and <1% in dry deposition as silanols. For increasing OH-substitutions, the decreasing concentration of precursor molecules (as a consequence of combined removal processes) means that concentrations are negligible, in all phases, beyond three or four substitutions. Predictions were relatively insensitive to assumed departures from phase equilibrium. Predictions of silanol hydrolysis in liquid water droplets suggest that the mix of diol chain lengths in precipitation may not be in thermodynamic equilibrium and will depend on atmospheric residence time and pH.     

Temporal variation of trace metal geochemistry in floodplain lake sediment subject to dynamic hydrological conditions

Climate change and land use may significantly influence metal cycling in dynamic river systems. We studied temporal variation of sediment characteristics in a floodplain lake, including concentrations of dissolved organic carbon, acid volatile sulfide and trace metals. The sampling period included a severe winter inundation and a dramatic water level drop during summer. Temporal changes were interpreted using multivariate analysis and chemical equilibrium calculations. Metal concentrations in sediment increased with depth, indicating a gradual improvement of sediment quality. In contrast, dissolved metal concentrations were highest in top layers due to mobilization from oxyhydroxides and precipitation with sulfides in deeper layers. Inundation had a mobilizing effect as it stimulated resuspension and oxygenation of sediment top layers. Water table lowering combined with organic matter decomposition led to immobilization due to sulfide formation. The chemistry of the sediments was consistent with model calculations, especially for macro-elements. The results illustrate the importance of seasonality for metal risk assessment.     

Dioxins: WHO's tolerable daily intake (TDI) revisited

In December 1990, the World Health Organization (WHO) established a tolerable daily intake (TDI) of 10 pg/kg b.w. (body weight) for TCDD, based on liver toxicity, reproductive effects and immunotoxicity in experimental animals, and making use of kinetic data in humans and experimental animals. Since then new epidemiological and toxicological data have emerged, in particular with respect to neurodevelopmental and endocrine effects of dioxin. Therefore, the European Centre for Environment and Health of the World Health Organization (WHO-ECEH) and the International Programme on Chemical Safety (IPCS) jointly organized a consultation on the "Assessment of the health risk of dioxins: re-evaluation of the TDI", May 1998, Geneva, Switzerland. The participants discussed the health risks for infants, cancer and non-cancer endpoints in humans and animals, mechanistic aspects, kinetic behaviour, modelling, exposure, and the applicability of the toxic equivalency (TEQ) concept. For the health risk assessment of dioxin-like compounds, the WHO Consultation focused on the most sensitive effects that are considered adverse (hormonal, reproductive and developmental effects) seen at low doses in animal studies (rats and monkeys). Human daily intakes corresponding with body burdens similar to those associated with adverse effects in animals could be estimated to be in the range of 14-37 pg/kg b.w./day. To arrive at a TDI expressed as TEQ, a composite uncertainty factor of 10 was recommended. By applying this uncertainty factor a TDI range of 1-4 pg TEQs/kg body weight was established. An extensive executive summary of the results of this WHO Consultation with all the underlying background documents will be published in Food Additives and Contaminants (in press).     

Degradation of ethinyl estradiol by nitrifying activated sludge

Degradation of ethinyl estradiol (EE2) by nitrifying activated sludge was studied with micro-organisms grown in a reactor with feedback of sludge fed with only a mineral salts medium containing ammonium as the sole energy source. Ammonium was oxidised by this sludge at a rate of 50 mg NH4+ g(-1) DW h(-1). This activated sludge was also capable of degrading EE2 at a maximum rate of 1 microg g(-1) DW h(-1). Using sludge with an insignificant nitrifying capacity of 1 mg NH4+ g(-1) DW h(-1), no degradation of EE2 was detected. Oxidation of EE2 by nitrifying sludge resulted in the formation of hydrophilic compounds, which were not further identified. Most probably degradation by nitrifying sludge results in a loss of estrogenic activity, as hydroxylated derivatives of EE2 are known to have a substantially lower pharmacological activity than EE2.     

Aerosol light-scattering in The Netherlands

The relation between the (midday) aerosol light-scattering and the concentrations of nitrate and sulfate has been assessed at a site near the coast of the North Sea in The Netherlands. Midday was selected for the measurements because this is the time at which the aerosol is most effective in the scattering of solar radiation. Automated thermodenuders were used for the hourly measurement of the concentration of nitrate and sulfate with a lower detection limit of 0.1 μ m⁻³. The site is operational since October 1993. The first-year average dry aerosol light-scattering (measured with an integrating nephelometer at a wavelength of 525 nm) was 0.71 × 10⁻⁴ m^1&#x0304;. In arctic marine air the aerosol light-scattering was a factor of 10 lower than the average value, in polluted continental air it was up to a factor of 10 higher. The ratio of the total aerosol light-scattering to the concentration of sulfate was 20 m² g⁻¹. The contribution of nitrate to the aerosol light-scattering was higher than that of sulfate in the winter and of about equal magnitude in the summer period. In November and December of 1993, the humidity dependence of the aerosol light-scattering was investigated. Two types of (continental) aerosol were found with respect to the humidity behavior. One type showed a significant increase in light-scattering at the deliquescence points of ammonium nitrate and ammonium sulfate, with that of ammonium nitrate the most pronounced. The second type of continental aerosol did not show deliquescence, but followed the typical humidity dependence of aerosol in a supersaturated droplet state. In this latter aerosol type, nitrate dominated over sulfate. It was concluded from the study that the aerosol light-scattering in The Netherlands, in particular its humidity dependence, is governed by (ammonium) nitrate.     

Flood-risk management strategies for an uncertain future: living with Rhine River floods in The Netherlands?

Social pressure on alluvial plains and deltas is large, both from an economic point of view and from a nature conservation point of view. Gradually, flood risks increase with economic development, because the expected damage increases, and with higher dikes, because the flooding depth increases. Global change, changing social desires, but also changing views, require a revision of flood-risk management strategies for the long term. These should be based on resilience as opposed to the resistence strategy of heightening dikes. Resilience strategies for flood-risk management imply that the river is allowed to temporarily flood large areas, whereas the flood damage is minimized by adapting land use. Such strategies are thus based on risk management and 'living with floods' instead of on hazard control. For The Netherlands, one of the most densely populated deltas in the world, alternative resilience strategies have been elaborated and assessed for their hydraulic functioning and 'sustainability criteria'.     

A practical method for quantification of phosphorus- and glycogen-accumulating organism populations in activated sludge systems.

Enhanced biological phosphorus removal (EBPR) from wastewater relies on the enrichment of activated sludge with phosphorus-accumulating organisms (PAOs). The presence and proliferation of glycogen-accumulating organisms (GAOs), which compete for substrate with PAOs, may be detrimental for EBPR systems, leading to deterioration and, in extreme cases, failure of the process. Therefore, from both process evaluation and modeling perspectives, the estimation of PAO and GAO populations in activated sludge systems is a relevant issue. A simple method for the quantification of PAO and GAO population fractions in activated sludge systems is presented in this paper. To develop such a method, the activity observed in anaerobic batch tests executed with different PAO/GAO ratios, by mixing highly enriched PAO and GAO cultures, was studied. Strong correlations between PAO/GAO population ratios and biomass activity were observed (R2 > 0.97). This served as a basis for the proposal of a simple and practical method to quantify the PAO and GAO populations in activated sludge systems, based on commonly measured and reliable analytical parameters (i.e., mixed liquor suspended solids, acetate, and orthophosphate) without requiring molecular techniques. This method relies on the estimation of the total active biomass population under anaerobic conditions (PAO plus GAO populations), by measuring the maximum acetate uptake rate in the presence of excess acetate. Later, the PAO and GAO populations present in the activated sludge system can be estimated, by taking into account the PAO/GAO ratio calculated on the basis of the anaerobic phosphorus release-to-acetate consumed ratio. The proposed method was evaluated using activated sludge from municipal wastewater treatment plants. The results from the quantification performed following the proposed method were compared with direct population estimations carried out with fluorescence in situ hybridization analysis (determining Candidatus Accumulibacter Phosphatis as PAO and Candidatus Competibacter Phosphatis as GAO). The method showed to be potentially suitable to estimate the PAO and GAO populations regarding the total PAO-GAO biomass. It could be used, not only to evaluate the performance of EBPR systems, but also in the calibration of potential activated sludge mathematical models, regarding the PAO-GAO coexistence.     

The use of XAD-resins for the detection of mutagenic activity in water: I. Studies with surface water

A study of the effects of different XAD-resins, bed volume, flow rate, pH and type of eluent on the extraction of organic mutagens from surface water is presented. XAD-4/8 is as effective as XAD-2 in concentrating organic mutagens from surface water and dimethylsulfoxide (DMSO) is as efficient as acetone in eluting the adsorbed organic mutagens. The latter allows direct testing up to 0.5 ml of DMSO concentrate in the Ames test. Variation of the pH of the water after passing the XAD-4/8, followed by readsorption, shows that the majority of the mutagenic activity due to dissolved organics is adsorbed at neutral pH. Only a minor fraction is readsorbed at pH 3. Further a XAD-4/8 concentrate and a similar concentrate prepared by freeze drying gives similar mutagenic activity. This indicates that many of the organic mutagens are recovered in the XAD-4/8 concentrate.It is concluded that adsorption on XAD-4/8, followed by direct testing of the DMSO eluates in the Ames test, presents a rapid and relatively simple way to detect low concentrations of organic mutagens in surface water. The general suitability of the method is shown for different types of surface water.