Evaluation of the reaction artifacts in an annular denuder-based sampler resulting from the heterogeneous ozonolysis of naphthalene

The heterogeneous ozonolysis of naphthalene adsorbed on XAD-4 resin was studied using an annular denuder technique. The experiments involved depositing a known quantity of naphthalene on the XAD-4 resin and then measuring the quantity of the solid naphthalene that reacted away under a constant flow of gaseous ozone (0.064 to 4.9 ppm) for a defined amount of time. All experiments were performed at room temperature (26 to 30 °C) and atmospheric pressure. The kinetic rate coefficient for the ozonolysis reaction of naphthalene adsorbed on XAD-4 resin is reported to be (10.1?±?0.4)?×?10^?19 cm³ molecule^?1 s^?1 (error is 2σ, precision only). This value is five times greater than the currently recommended literature value for the homogeneous gas phase reaction of naphthalene with ozone. The obtained rate coefficient is used to evaluate reaction artifacts from field concentration measurements of naphthalene, acenaphthene, and phenanthrene. The observed uncertainties associated with field concentration measurements of naphthalene, acenaphthene, and phenanthrene are reported to be much higher than the uncertainties associated with the artifact reactions. Consequently, ozone reaction artifact appears to be negligible compared to the observed field measurement uncertainty results.     

An executive review of sludge pretreatment by sonication

Ultrasonication (US), which creates hydro-mechanical shear forces in cavitation, is an advanced technology in sludge pretreatment. However, there are many factors affecting the efficacy of cavitation and ultrasonication disintegration of sludge as a consequence. The objective of this work is to present an extensive review of evaluation approaches of sludge US pretreatment efficiency. Besides, optimization methodologies of related parameters, the differences of optimum values and the similarities of affecting trends on cavitation and sludge pretreatment efficiency were specifically pointed out, including ambient conditions, ultrasonic properties, and sludge characteristics. The research is a prerequisite for optimization of sludge US pretreatment efficiency in lab-scale and practical application. There is not-yet a comprehensive method to evaluate the efficiency of sludge US pretreatment, but some main parameters commonly used for this purpose are degree of sludge disintegration, proteins, particle size reduction, etc. Regarding US parameters, power input P_US, intensity I_US, and frequency F_S seem to have significant effects. However, the magnitude of the effect of P_US and probe size in terms of I_US has not been clearly detailed. Investigating very low F_S seems interesting but has not yet been taken into consideration. In addition, static pressure effect has been marginally studied only and investigation on the effect of pH prior to US process has been restricted. Their effects therefore should be varied separately and simultaneously with other related parameters, i.e. process conditions, ultrasonic properties, and sludge characteristics, to optimize sludge US pretreatment process.     

Co-composting of paper mill sludge and hardwood sawdust under two types of in-vessel processes

Recycling of organic residues by composting is becoming an acceptable practice in our society. Co-composting dewatered paper mill sludge (PMS) and hardwood sawdust, two readily available materials in Canada, was investigated using uncontrolled and controlled in-vessel processes. The composted materials were characterized for total C and N, water-soluble, acid-hydrolyzable, and non-hydrolyzable N, extractable lipids, and by Fourier Transform Infrared (FT-IR) spectrophotometry. In the controlled scale process, the loss of organic matter was approximately 65% higher than in the uncontrolled process. After undergoing initial fluctuations in N fractions during the first two days of composting, by the end of the process, concentrations of water-soluble N decreased while those of acid-hydrolyzable and nonhydrolyzable N increased in the controlled process, whereas in the uncontrolled process, water-soluble N increased, but N in the other two fractions decreased continuously, indicating that the biochemical transformations of organic matter were not completed. Data on extractable lipids and FT-IR spectra suggest that the compost produced from the controlled process was bio-stable after 14 days, while the uncontrolled process was not stabilized after 18 days. In addition, FT-IR data suggest the biological activity during composting centered mainly on the degradation of aliphatic structures while aromatic structures were preserved. The co-composting of the PMS and hardwood sawdust can be successfully achieved if aeration, moisture, and bio available C/N ratios are optimized to reduce losses of N.     

Reactivity, interactions and transport of trace elements, organic carbon and particulate material in a mountain range river system (Adour River, France)

The background levels, variability, partitioning and transport of eleven trace elements-Ag, Al, As, Cd, Co, Cr, Cu, Mn, Pb, Zn and U-were investigated in a mountain range river system (Adour River, France). This particular river system displayed a turbulent hydrodynamic regime, characterized by flash-transient discharge conditions leading to fast shifts in suspended particulate matter (SPM) concentrations as high as two orders of magnitude (12 to 600 mg l(-1)). The distribution of SPM was accurately predicted with a "hysteresis" transport model, indicating that about 75% of the annual solids load was exported within 20 to 40 days. Dissolved and particulate concentrations of most trace elements were low compared to their concentrations in other reference river systems expect for Pb and Cr, associated with historical anthropogenic activities. Although dissolved and particulate metal concentrations were steady for most elements during low and average discharge conditions, significant changes were observed with increasing river discharge. The changes in trace element concentrations in the two compartments was found to induce a partitioning anomaly referred to as the particulate concentration effect. This anomaly was significant for Cr, Mn, Pb, Zn, Cu and organic carbon (p < 0.03). The processes driving this anomaly were possibly linked to the modification and/or increase of colloidal organic and inorganic vectors, suggested by the significant increase of DOC (p < 0.001) and dissolved Al concentrations (p < 0.05) during flood conditions. A complementary process linked to the influence of coarse particles of low complexation capacity and transported mainly during high discharge may also effect trace element concentrations. Annual metal fluxes transported by this river system were estimated using the hysteresis SPM model with consideration of these fate processes. Metals in the Adour River system are primarily exported into the Bay of Biscay (Atlantic Ocean).     

Spatial variance in multimedia mass balance models: comparison of LOTOS-EUROS and SimpleBox for PCB-153

The aim of this study was to determine whether nested generic box models can be used to predict spatial variance. An inter-comparison study was performed for the nested box model SimpleBox, and the spatially resolved model LOTOS-EUROS, using PCB-153 emissions in Europe as an example. We compared the two models concerning (1) average environmental concentrations, (2) spatial concentration variances, (3) spatial concentration patterns (maps), and (4) agreement with measured concentrations for the air and soil compartments. In SimpleBox, the spatial concentration variances and patterns were calculated subsequently for each separate grid cell surrounded by a regional and a continental shell with homogeneous, averaged circumstances. Average European PCB-153 concentrations calculated by LOTOS-EUROS and SimpleBox for the period 1981-2000 agree well for the air and soil compartments. Moreover, the predicted concentrations of both models are in line with the measured PCB-153 concentrations in Europe during that period. For PCB-153, the prediction of spatial concentration variances with the nested multimedia fate model SimpleBox performs adequately in most cases, except for the lower concentration boundary in the air compartment. It is concluded that SimpleBox can be used to predict the spatial maximum and average concentrations of PCB-153 in the air and soil compartments. The proposed method has to be tested systematically for different types of compounds, emission scenarios, environmental compartments and spatial scales in order to allow conclusions about the general applicability of the method.     

Biocatalytic dechlorination of hexachlorocyclohexane by immobilized bio-Pd in a pilot scale fluidized bed reactor

Lindane (??-hexachlorocyclohexane, ??-HCH) is a recalcitrant and toxic organochlorine insecticide. Due to its non-selective production process and widespread use, HCH isomers and their degradation products have been detected frequently in soils and groundwater. An innovative technology using microbial produced Pd(0) nanoparticles, i.e. bio-Pd, was developed to treat groundwater containing a mixture of HCHs and chlorobenzenes. In a first step, the groundwater was de-ironized and most of the chlorobenzenes were removed in a biological trickling filter. The ??g?L^?1 levels of HCHs and chlorobenzenes were removed in a second step by the bio-Pd-based technology. Therefore, a 200-L pilot scale reactor was developed with 100?mg?L^?1 bio-Pd encapsulated in alginate beads. Hydrogen gas was bubbled at the bottom of the reactor and served to charge the bio-Pd catalyst. The reactor influent contained 5.2???g?L^?1 HCHs and 51.1???g?L^?1 chlorobenzenes. During a test period of 10?days, 29% of the HCH isomers and 63% of the chlorobenzenes were removed applying a nominal hydraulic residence time of 4?h. These removal percentages could be increased to 75 and 68% by doubling the nominal hydraulic residence time to 8?h. This study demonstrated that biologically produced nanoparticles of Pd can be applied for the large-scale remediation of groundwater contaminated with HCHs.     

Lithium availability in the EU27 for battery-driven vehicles: The impact of recycling and substitution on the confrontation between supply and demand until2050

The adverse impacts of climate change are widely recognized as well as the importance of the mitigation of carbon dioxide (CO₂). Battery driven vehicles are expected to have a bright future, since GHG emissions can be reduced. Lithium-ion (Li-ion) batteries appear to be the most promising, due to their high energy density. Recently, the discussion concerning adequate lithium carbonate (Li₂CO₃) resources is resolved. The current challenge is the needed increase in flow rate of Li₂CO₃ into society to foresee in forecasted demand. This research determines ten factors which influence the availability of Li-ion batteries for the EU27 in the coming decades. They are used in a system dynamics analysis. The results of this research show that undersupply can be expected in the EU27 until 2045 somewhere between 0.5 Mt and 2.8 Mt. Substitution of Li₂CO₃ in other end-use markets and recycling can relieve the strain on Li₂CO₃ supply to some extent. In 2050, 20% of the vehicle fleet in the EU27 can be battery electric vehicles (BEVs). The lack of resources in the EU27 and the geographical distribution of lithium in politically sensitive areas suggest that the shares of lithium available for the EU27 will be less than assumed in this research. The increase in flow rate shows to be the bottle-neck for a transition to (partly) battery driven vehicles in the EU27, at least when Li-ion batteries are used. Focusing on large-scale application of BEVs with Li-ion batteries in order to substantially mitigate CO₂ emissions in transport is a futile campaign.     

Campomelic acampomelic dysplasia presenting with increased nuchal translucency in the first trimester

This is the first report of a fetus affected with campomelic acampomelic dysplasia presenting with increased nuchal translucency. Ultrasonography at 13 weeks of amenorrhea showed a nuchal translucency 5.6 mm thick. The karyotype performed on amniotic fluid cells was normal (46,XY). Ultrasonography at 22 weeks revealed a normal femoral length and female genitalia. A second amniocentesis was performed to confirm the karyotype and for dosage of steroid hormones. Testosterone dosage was low, corresponding to a female fetus. Ultrasonography at 32 weeks showed growth retardation of the long bones (<3rd centile) that were not curved. A severe malformation syndrome was suspected and the pregnancy was terminated at 33 weeks. The fetus displayed macrocephaly, facial dysmorphism and female external genitalia. X ray showed straight and thickened long bones, hypoplastic scapulae and moderate platyspondyly. In view of the association of sex reversal, hypoplasia of the scapulae, and the presence of straight long bones, campomelic acampomelic dysplasia was suspected and confirmed by the finding of a SOX9 mutation. This case shows the importance of a careful echographic survey in a fetus with a nuchal translucency > 4 mm, especially if there is discordance between phenotypic and genotypic sex, since growth retardation may occur later during the pregnancy. Copyright © 2004 John Wiley & Sons, Ltd.