Self-ignition of tetrafluoroethylene induced by rapid valve opening in small diameter pipes

This work investigates the ignition of tetrafluoroethylene induced by the adiabatic compression that can arise by activating a high speed valve separating two portions of a pipeline with a high pressure difference. In the tests performed the high pressure zone contained tetrafluoroethylene at pressures between 15 and 30 bar. For the low pressure zone, experiments with nitrogen, air and tetrafluoroethylene were carried out. The pressure range in the low pressure zone was comprised between 0.05 and 1 bar. The pipe diameters analyzed were 15 and 20 mm. For the analyzed geometries, special conditions were required in order to reach reproducible ignitions, namely air at temperatures of at least 105 °C had to be present in the compression pipe. Furthermore, a minimum length of the compression pipe had to be used. The current work describes the experimental setup employed for the tests and discusses the achieved results. Numerical simulations were performed in order to clarify unexpected findings.     

Evident but context-dependent mortality of fish passing hydroelectric turbines

Globally, policies aiming for conservation of species, free-flowing rivers, and promotion of hydroelectricity as renewable energy and as a means to decarbonize energy systems generate trade-offs between protecting freshwater fauna and development of hydropower. Hydroelectric turbines put fish at risk of severe injury during passage. Therefore, comprehensive, reliable analyses of turbine-induced fish mortality are pivotal to support an informed debate on the sustainability of hydropower (i.e., how much a society is willing to pay in terms of costs incurred on rivers and their biota). We compiled and examined a comprehensive, global data set of turbine fish-mortality assessments involving >275,000 individual fish of 75 species to estimate mortality across turbine types and fish species. Average fish mortality from hydroelectric turbines was 22.3% (95% CI 17.5–26.7%) when accounting for common uncertainties related to empirical estimates (e.g., handling- or catch-related effects). Mortality estimates were highly variable among and within different turbine types, study methods, and taxa. Technical configurations of hydroelectric turbines that successfully reduce fish mortality and fish-protective hydropower operation as a global standard could balance the need for renewable energy with protection of fish biodiversity.     

Elucidation of the behavior of tannery wastewater under advanced oxidation conditions

Diverse advanced oxidation process (AOP) techniques applying UV, TiO2/UV, O3 and O3/UV were used to degrade pollutants contained in tannery wastewater. The total mineralization of these pollutants is desirable, but it is quite energy consuming and sometimes impossible. Therefore the objective was to achieve an enhancement of biodegradability, preferentially with a decrease in toxicity in parallel. This work demonstrates that the dominant pollutants were chemically degraded by oxidation, while changes in carbon content were only marginal. These results were obtained monitoring the total organic carbon content (TOC), chemical and biochemical oxygen demand (COD and BOD), and substance-specific pollutant content by application of gas chromatography/mass spectrometry (GC-MS) and liquid chromatography/mass spectrometry (LC-MS). Daphnia magna toxicity testing performed in parallel proved a decrease in toxicity after AOP treatment of the tannery wastewater.     

The impact of chronic pain patients' psychotropic drug knowledge and warning labels on the decision whether to drive a car or not

OBJECTIVE: The attitudes of patients towards driving a car while taking medication with psychotropic side effects is unclear. A growing number of patients use these psychotropic medicines on a daily basis, and this may interfere with their ability to drive a car. METHODS: By means of a survey, we examined attitudes towards driving while using psychotropic medicinal drugs and the effect of warning labels on the decision whether to drive a car or not in patients with chronic pain. RESULTS: Fifty-eight of 100 patients possessing a driver's license used psychotropic medication. Despite warning labels affixed on the packages that these drugs might impair driving ability, the majority (71%) of these patients continued driving a car. A point of concern is that 40% of these patients reported not to be more cautious in traffic after taking psychotropic drugs. CONCLUSION: The results of this survey indicate that drug warning labels applied by Dutch pharmacies do not significantly change attitudes towards driving a car in patients taking medicinal drugs with psychotropic side effects. Future road-safety campaigns should pay more attention to the impairing effects of psychotropic drugs on driving.     

Estrogenic and dioxin-like compounds in sediment from Zierikzee harbour identified with CALUX assay-directed fractionation combined with one and two dimensional gas chromatography analyses

The identity of compounds responsible for estrogenic and dioxin-like activities in sediment from the harbour of the small town Zierikzee in Zeeland, The Netherlands, was investigated using a bioassay directed fractionation approach with the in vitro estrogen and dioxin responsive reporter gene assays ER- and DR-CALUX. For identification of compounds exhibiting activity in the bioassays, either one or two-dimensional GC in combination with quadrupole (MSD), ion trap (ITD) or time-of-flight mass spectrometric detection (ToF-MS) was used, depending on the biological and chemical characteristics and the complexity of the fractions. The natural estrogenic hormone 17-β-estradiol and its metabolite estrone were identified with GC–ITD as the main contributors to the estrogenic activity. After successive rounds of fractionation, the dioxin-like activity could be explained by the presence of various polycyclic aromatic hydrocarbons identified with GC–MSD and two-dimensional comprehensive GC × GC–ToF-MS. Some estrogenic activity of a relatively non-polar nature remained unidentified.     

Determination of trichloroacetic acid in environmental studies using carbon 14 and chlorine 36

Radioisotopes carbon 14 and chlorine 36 were used to elucidate the environmental role of trichloroacetic acid (TCA) formerly taken to be a herbicide and a secondary air pollutant with phytotoxic effects. However, use of ¹⁴C-labeling posed again known analytical problems, especially in TCA extraction from the sample matrix. Therefore—after evaluation of available methods—a new procedure using decarboxylation of [1,2-¹⁴C]TCA combined with extraction of the resultant ¹⁴C-chloroform with a non-polar solvent and its subsequent radiometric measurement was developed. The method solves previous difficulties and permits an easy determination of amounts between 0.4 and 20 kBq (10–500 ng g⁻¹) of carrier-less [1,2-¹⁴C]TCA in samples from environmental investigations. The procedure is, however, not suitable for direct [³⁶Cl]TCA determination in chlorination studies with ³⁶Cl. Because TCA might be microbially degraded in soil during extraction and sample storage and its extraction from soil or needles is never complete, the decarboxylation method—i.e. 2 h TCA decomposition to chloroform and CO₂ in aqueous solution or suspension in closed vial at 90 °C and pH 4.6 with subsequent CHCl₃ extraction—is recommended here, estimated V < 7%. Moreover, the influence of pH and temperature on the decarboxylation of TCA in aqueous solution was studied in a broad range and its environmental relevance is shown in the case of TCA decarboxylation in spruce needles which takes place also at ambient temperatures and might amount more than 10–20% after a growing season. A study of TCA distribution in spruce needles after below-ground uptake shows the highest uptake rate into current needles which have, however, a lower TCA content than older needle-year classes, TCA biodegradation in forest soil leads predominatingly to CO₂.     

Competitive sorption and diffusion of chromate and sulphate in a flow system with goethite in gel beads

Column experiments and model simulations were employed to evaluate the processes involved in multicomponent solute transport in a system with heterogeneous flow. Column experiments were performed with goethite embedded in polyacrylamide gel beads. The gel forms an immobile water region that can be accessed by diffusion. A two-region transport model with diffusion into spheres was combined with a surface complexation model to predict reactive transport in the goethite-gel bead system. Chromate and sulphate breakthrough curves were measured in a set of transport experiments, along with corresponding changes in the pH of the effluent. Sorption and transport of sulphate and chromate in separate columns were predicted from independently measured sorption parameters. The model overestimated the pH changes in the effluent, possibly because of proton buffering by the polyacrylamide gel. The effect of competitive sorption on transport was examined in experiments with both anions present. The model predicted the effect of competition very well in a system initially equilibrated with sulphate, followed by infiltration with chromate. However, when sulphate was infiltrated after equilibration with chromate, chromate desorption and sulphate adsorption were clearly overestimated by the transport model. The exchange between the more strongly bound chromate and the sulphate added subsequently may be too slow to cause a substantial chromate peak in the effluent. This suggests that the local equilibrium assumption was not applicable in this case.     

Functional and community-level soil microbial responses to zinc addition may depend on test system biocomplexity

The effect of zinc on soil nitrification and composition of the microbial community in soil was investigated using a full factorial experiment with five zinc concentrations and four levels of biological complexity (microbes only, microbes and earthworms (Eisenia fetida), microbes and Italian ryegrass (Lolium multiflorum var. Macho), and microbes, ryegrass and earthworms). After 6 weeks of exposure, the activity of soil nitrifying bacteria was measured and the microbial community structure was characterized by phospholipid fatty acid (PLFA) analysis. Soil nitrification and several PLFA markers were significantly influenced by either zinc addition and/or the presence of earthworms or ryegrass, and one of the most pronounced changes was the increase of fungi and decrease of bacteria with increasing concentrations of zinc. Of particular interest, however, was the potential interaction between the presence of plants and/or earthworms and the effect of zinc, which the factorial study design allowed us to explore. Such an effect was observed in two cases: Earthworms reduced the positive effect of zinc on the fungal biomass (ANOVA, p=0.03), and the effect of earthworms on the soil nitrification activity depended on zinc concentration (ANOVA, p<0.05). The effect of earthworm presence was not very large, but it does show that multispecies tests might give information about metal toxicity or bioavailability that cannot be predicted from single-species tests.     

Operator-splitting errors in coupled reactive transport codes for transient variably saturated flow and contaminant transport in layered soil profiles

One possible way of integrating subsurface flow and transport processes with (bio)geochemical reactions is to couple by means of an operator-splitting approach two completely separate codes, one for variably-saturated flow and solute transport and one for equilibrium and kinetic biogeochemical reactions. This paper evaluates the accuracy of the operator-splitting approach for multicomponent systems for typical soil environmental problems involving transient atmospheric boundary conditions (precipitation, evapotranspiration) and layered soil profiles. The recently developed HP1 code was used to solve the coupled transport and chemical equations. For steady-state flow conditions, the accuracy was found to be mainly a function of the adopted spatial discretization and to a lesser extent of the temporal discretization. For transient flow situations, the accuracy depended in a complex manner on grid discretization, time stepping and the main flow conditions (infiltration versus evaporation). Whereas a finer grid size reduced the numerical errors during steady-state flow or the main infiltration periods, the errors sometimes slightly increased (generally less than 50%) when a finer grid size was used during periods with a high evapotranspiration demand (leading to high pressure head gradients near the soil surface). This indicates that operator-splitting errors are most significant during periods with high evaporative boundary conditions. The operator-splitting errors could be decreased by constraining the time step using the performance index (the product of the grid Peclet and Courant numbers) during infiltration, or the maximum time step during evapotranspiration. Several test problems were used to provide guidance for optimal spatial and temporal discretization.     

Water quality dynamics and hydrology in nitrate loaded riparian zones in the Netherlands

Riparian zones are known to function as buffers, reducing non-point source pollution from agricultural land to streams. In the Netherlands, riparian zones are subject to high nitrogen inputs. We combined hydrological, chemical and soil profile data with groundwater modelling to evaluate whether chronically N loaded riparian zones were still mitigating diffuse nitrate fluxes. Hydraulic parameters and water quality were monitored over 2 years in 50 piezometres in a forested and grassland riparian zone. Average nitrate loadings were high in the forested zone with 87 g NO(3)(-)-N m(-2) y(-1) and significantly lower in the grassland zone with 15 g NO(3)(-)-N m(-2) y(-1). Groundwater from a second aquifer diluted the nitrate loaded agricultural runoff. Biological N removal however occurred in both riparian zones, the grassland zone removed about 63% of the incoming nitrate load, whereas in the forested zone clear symptoms of saturation were visible and only 38% of the nitrate load was removed.