Occurrence of dioxins in cow's milk in the vicinity of municipal waste incinerators and a metal reclamation plant in the Netherlands

Over 200 samples of cow's milk have been analysed for dioxins in a survey on the occurrence of dioxins in milk from the vicinity of municipal waste incinerators (MSWs) and other potential dioxin sources in The Netherlands. Levels in milk were found to vary considerably with time, depending on emission rates, the direction and distance to the source and the feeding and housing of cows. Highest levels of up to 13.5 pg TEQ/g of milk fat were found in the Lickebaert area and Zaandam near two incinerators with highest emission rates. The background level ranged between 0.7 and 2.5 pg TEQ/g of milk fat. Levels in winter were comparable to those found in summer and, in some areas, even higher, when cows were fed with hay and silage harvested on the same farm. After the closure of the MSW in Zaandam, cow's milk from neighbouring farms showed a significant decrease in dioxin levels to below the critical limit of 6 pg TEQ/g of milk fat. Dioxin levels in the vicinity of a metal reclamation plant were comparable to those in milk from the vicinity of a MSW with moderate emissions. Differences were observed in the ratio PCDF/PCDD, which was higher in milk near the metal reclamation plant. Principal component analysis has been applied on a large data set of patterns of the 2,3,7,8-chlorine substituted PCDDs and PCDFs in cow's milk. This technique has proved to be useful for distinguishing and identification of sources on the basis of the isomer pattern in milk.     

System performance assessment of final repository for radioactive wastes using first-order reliability method

When a final option for radioactive waste is determined, it is necessary to demonstrate compliance of disposal system chosen with relevant regulations. Considering the large number of physical and chemical factors involved, the complexity of their interrelationships, and long time periods, a system approach is required. A stochastic analysis is also needed to ensure that these regulatory criteria can be met with confidence. Among a variety of models developed to treat the effect of uncertainty on system performance, the first-order reliability method is suggested as an attractive tool to stochastic problems incorporating any amount of probabilistic information. Based on the first-order approximation, the method can give a probability of failure against a preselected target value, and information concerning the sensitivity of the outcome to variations in the input random variables and their statistical moments. In this paper, for reliable prediction of the performance of repository for radioactive wastes, first-order reliability method is applied in treating the parameter uncertainties of predictive models. First, a thickness of canister corrosion and breach time of canister is calculated using a uniform corrosion model, combined with the diffusional transport modeling of radionuclides in the backfill material. Second, a fractional release rate for each radionuclide is derived from the evaluation of the performance of a waste package which consists of canister and backfill material. Third, a cumulative release rate at the accessible environment is obtained by geosphere transport modeling with the source term given as a fractional release rate. The proposed first-order reliability method can be applicable to a full range of problems occurring in radioactive waste management and beyond.     

Chemical defence in ladybird beetles (Coccinellidae). I. Distribution of coccinelline and individual variation in defence in 7-spot ladybirds (Coccinella septempunctata)

Summary 7-spot ladybirds secrete alkaloid (coccinelline)-rich fluid (reflex blood) from leg joints as a defence mechanism against predators. A technique is described that enables the collection and accurate quantification of reflex blood produced, and the amount of coccinelline therein. Coccinelline was found distributed throughout the body, although concentrated in the reflex blood. Reflex blood was collected from a large set of beetles at several time points. Significant variation was found among beetles in the amount of reflex blood produced (for males and for females corrected for body weight) and the coccinelline concentration of the reflex blood. The results are discussed in relation to automimicry and the maintenance of variation through energy trade-offs. The relationships between tendency to aggregate, ability to reflex bleed and the possession of aposematic coloration are also considered.     

Determination of butyltins in harbour sediment and water by aqueous phase ethylation GC-ICP-MS and hydride generation GC-AAS

Sediment and water samples have been collected between 1992 and 1995 for evaluating butyltin contamination in two marinas from the coastal area in The Netherlands, two years after the ban of TBT. Sediments extracts were analysed by capillary gas chromatography-inductively coupled plasma-mass spectrometry. Sediment concentrations for TBT showed no trend of decrease between 1992 and 1995 and were extremely high in the marina secluded from tidal action; 17.5 +/- 8.0 microg g(-1) and much lower for the marina with tidal action; 0.117 +/- 0.073 microg g(-1). High ratios between TBT and DBT in the sediments indicate that degradation mechanisms in the sediments are of minor importance. Dissolved butyltin compounds were analysed in water by means of gas chromatography-atomic absorption spectrometry. Water concentrations of TBT showed no clear trend of decrease between 1992 and 1995 and were high in the marina secluded from tidal action; 139 +/- 166 ng litre(-1) but much lower for the marina with tidal action; 48 +/- 98 ng litre(-1). An active degradation mechanism during summer periods was indicated by low (<1) TBT/DBT ratios in the water phase of the marina secluded from tidal action.     

Base-cation deposition in Europe—part II. Acid neutralization capacity and contribution to forest nutrition

An assessment was made of the capacity of base cations to neutralize acid deposition and of the contribution of base cation deposition to forest nutrition in Europe. In large parts of southern Europe more than 50% of the potential acid deposition was found counteracted by deposition of non-sea salt Mg²⁺ + Ca²⁺ + K⁺. In central and northwestern Europe, base cation deposition usually amounted to less than 25% of the acid input. Smallest base cation deposition relative to potential acid deposition was found in southern Scandinavia, Denmark, northern Germany and The Netherlands. A similar spatial pattern was found for the neutralization of acid anions in precipitation. Whereas in Scandinavia weathering is the dominant supplier of base cation to forest soils, in eastern and southern Europe, forests mainly rely on atmospheric deposition for the supply of base cations. Using error propagation, the random and systematic error in acid neutralization capacity for an average grid cell of 10 × 20 km was estimated to equal 45–55% and 50–55%, respectively.     

Ozone disintegration of excess biomass and application to nitrogen removal.

A pilot-scale facility integrated with an ozonation unit was built to investigate the feasibility of using ozone-disintegration byproducts of wasted biomass as a carbon source for denitrification. Ozonation of biomass resulted in mass reduction by mineralization as well as by ozone-disintegrated biosolids recycling. Approximately 50% of wasted solids were recovered as available organic matter (ozonolysate), which included nonsettleable microparticles and soluble fractions. Microparticles were observed in abundance at relatively low levels of ozone doses, while soluble fractions became dominant at higher levels of ozone doses in ozone-disintegrated organics. Batch denitrification experiments showed that the ozonolysate could be used as a carbon source with a maximum denitrification rate of 3.66 mg nitrogen (N)/g volatile suspended solids (VSS) x h. Ozonolysate was also proven to enhance total nitrogen removal efficiency in the pilot-scale treatment facility. An optimal chemical oxygen demand (COD)-to-nitrogen ratio for complete denitrification was estimated as 5.13 g COD/g N. The nitrogen-removal performance of the modified intermittently decanted extended aeration process dependent on an external carbon supply could be described as a function of solids retention time.     

Effect of cold-temperature shock on nitrification.

Nitrification is known as the most temperature-sensitive step among the biological processes in wastewater treatment. The purpose of this study was to investigate the effect of temperature on nitrification, in the case of a sharp decrease of temperature, and to compare this effect with that of a gradual temperature decrease. It was found that a sudden temperature decrease affected nitrification much more than predicted. The immediate decrease of temperature by 10 degrees C led to a 20% larger decrease of specific nitrification rate than predicted by the temperature correction factor of 1.072. The change of nitrification rate resulting from a gradual temperature decrease was modeled correctly with the current default temperature correction factor of 1.072. It was concluded that the correction factor actually can be applied to a gradual temperature-change situation; however, in the case of a sudden temperature decrease, measures need to be taken to avoid nitrifier washout.     

Long-term operation of a biofilter for simultaneous removal of H2S and NH3

Simultaneous removal of NH3 and H2S was investigated using two types of biofilters--one packed with wood chips and the other with granular activated carbon (GAC). Experimental tests and measurements included analyses of removal efficiency (RE), metabolic products, and results of long-term operation (around 240 days). The REs for NH3 and H2S were 92 and 99.9%, respectively, before deactivation. After deactivation, the RE for NH3 and H2S were decreased to 30-50% and 75%, respectively. The activity of nitrifying bacteria was inhibited by high concentrations of H2S (over 200 ppm) but recovered gradually after H2S addition was ceased. However, the Thiobacillus thioparus as sulfur oxidizing bacteria did not show inhibition at the NH3 concentration under 150-ppm conditions. The deactivation of the biofilter was caused by metabolic products [elemental sulfur and (NH4)2SO4] accumulating on the packing materials during the extended operation. The removal capacities for NH3 and H2S were 6.0-8.0 and 45-75 mg N, S/L/hr, respectively.     

Hydrodehalogenation of chlorobenzene on activated carbon and activated carbon supported catalysts

Chlorinated aromatic compounds in (waste) gases can be removed and/or dehalogenated by passing over a bed of activated carbon (AC) in a hydrogen containing atmosphere. Dehalogenation of the model compound chlorobenzene (PhCl) to HCl is complete at 490 degrees C--rather than the approximately 900 degrees C needed for the mere gas-phase reaction--but part of the benzene moieties is retained on the AC, resulting in its rather rapid deactivation, apparently due to a large decrease in surface area. Therefore, <1 mmol PhCl per gram of 'catalyst' could be processed. At 600 degrees C chlorobenzene yields 100% of both HCl and benzene, but still the AC lost most of its activity in time. Performances are compared of three different commercial ACs. As a HCl-washed AC is just as active, metals are not involved. This acid-washed AC was used as a support for 10 wt% Ni or Fe catalysts. While Fe did not show appreciable activity, results with Ni are promising. The yields of HCl and benzene from PhCl are approximately 100% already at T<400 degrees C, and T(50%) congruent with 260 degrees C, over 200 degrees C lower than with AC alone. There is no appreciable decrease of activity after having injected >20 mmol PhCl per gram of catalyst at partial conversion.     

Advanced treatment of oil recovery wastewater from polymer flooding by UV/H2O2/O3 and fine filtration

In order to purify oil recovery wastewater from polymer flooding （ORWPF） in tertiary oil recovery in oil fields, advanced treatment of UV/H2O2/O3 and fine filtration were investigated. The experimental results showed that polyacrylamide and oil remaining in ORWPF after the conventional treatment process could be effectively removed by UV/H2O2/O3 process. Fine filtration gave a high performance in eliminating suspended solids. The treated ORWPF can meet the quality requirement of the wastewater-bearing polymer injection in oilfield and be safely re-injected into oil reservoirs for oil recovery.