Optimization of biochar quality and yield from tropical timber industry wastes.

The conversion of timber industry waste to biochar was investigated, based on residues from local tropical hardwoods in Cameroon. Closed and flow reactors, loaded with few grams of the sample and fluxed with different inert gases, were used with the aim of converting these wood residues to a safe and efficient solid fuel that can be exploited by the local community for cooking purposes. The pyrolysis temperature had the highest impact on the process up to approximately 700 °C as biochar yields decreased from 87 to 23.5% while increasing the temperature. A significant concentration of carbon required temperatures greater than 500 °C for the biochar to become a good solid fuel, approaching the heating value of coal. The role of heating rate appeared marginal even in a broad range: 0.1 to 70 °C/min. The dwell time (in the range 0.5 to 5 h) at maximum temperature revealed to be of little influence on the charring which occurred mostly during the first few minutes of the isothermal phase. Thus, actual production time can be <1 h/batch (up to 500 °C at 10 °C/min). Stepwise heating revealed a sequence of devolatilization reactions following their activation energies. Use of CO2 as inert gas increased the char yield. The inert gas flow rate had two contrasting effects on the biochar yield, in relation to volatile components residence time and the biomass temperature. The reactivity of biochar in combustion suggests a trade-off between heating content and reactivity. Charring in a closed, pressurized reactor produced biochar of low value as fuel, with tars absorbed in the porous solid residue.

Effective energy exploitation from horse manure combustion.

We investigated the exploitation of horse manure for energy recovery by combustion. First, the impact of the waste origin and management (storage conditions) was evaluated in terms of elemental analysis, moisture content, heating value, and ash melting temperature. Besides some carbon loss over the time, horse manure origin and management policy do not impact its profitable exploitation by combustion. More relevant, the ignition tests disproved the current industrial opinion that combustion of manure alone is difficult, without the addition of auxiliary fuel, like wood shavings. It has been demonstrated through ignition tests that the major limitation in manure combustion is just the high moisture content (approx. 60% w.b.). The study focused on overcoming the detrimental effect of the large moisture content, and specifically its removal efficiency. The latter requires the understanding of manure permeability which is determined by the bedding material and the stable management. Here we provide indications of the impact of the manure composition and its sample size on the efficiency of moisture removal, whose energy impact must be minimized for an effective energy recovery. The energy balance confirms that the total removal of 62% w.b. moisture reduces by 23% the potential energy content of the manure; this drying penalty on energy is largely offset by the dramatic improvement in reactivity of the residual solid fuel.

Combustion of a Pb(II)-loaded olive tree pruning used as biosorbent.

The olive tree pruning is a specific agroindustrial waste that can be successfully used as adsorbent, to remove Pb(II) from contaminated wastewater. Its final incineration has been studied in a thermobalance and in a laboratory flow reactor. The study aims at evaluating the fate of Pb during combustion, at two different scales of investigation. The flow reactor can treat samples approximately 10(2) larger than the conventional TGA. A detailed characterization of the raw and Pb(II)-loaded waste, before and after combustion is presented, including analysis of gas and solids products. The Pb(II)-loaded olive tree pruning has been prepared by a previous biosorption step in a lead solution, reaching a concentration of lead of 2.3 wt%. Several characterizations of the ashes and the mass balances proved that after the combustion, all the lead presents in the waste remained in ashes. Combustion in a flow reactor produced results consistent with those obtained in the thermobalance. It is thus confirmed that the combustion of Pb(II)-loaded olive tree pruning is a viable option to use it after the biosorption process. The Pb contained in the solid remained in the ashes, preventing possible environmental hazards.

Self-heating of dried industrial tannery wastewater sludge induced by pyrophoric iron sulfides formation.

Similarly to many powders of solids, dried sludge originated from tannery wastewater may result in a self-heating process, under given circumstances. In most cases, it causes a moderate heating (reaching 70-90°C), but larger, off-design residence times in the drier, in a suboxic atmosphere, extremely reactive solids can be produced. Tannery waste contains several chemicals that mostly end up in the wastewater treatment sludge. Unexpected and uncontrolled self heating could lead to a combustion and even to environmental problems. Elaborating on previous studies, with the addition of several analytical determinations, before and after the self-heating, we attempted to formulate a mechanism for the onset of heating. We demonstrated that the system Fe/S/O has been involved in the process. We proved that the formation of small quantities of pyrophoric iron sulfides is the key. They are converted to sulfated by reaction with water and oxygen with exothermic processes. The pyrite/pyrrhotite production depends on the sludge drying process. The oxidation of sulfides to oxides and sulfates through exothermic steps, reasonably catalyzed by metals in the sludge, occurs preferentially in a moist environment. The mechanism has been proved by reproducing in the laboratory prolonged heating under anoxic/suboxic atmosphere.

Improved compaction of dried tannery wastewater sludge.

We quantitatively studied the advantages of improving the compaction of a powder waste by several techniques, including its pelletization. The goal is increasing the mass storage capacity in a given storage volume, and reducing the permeability of air and moisture, that may trigger exothermic spontaneous reactions in organic waste, particularly as powders. The study is based on dried sludges from a wastewater treatment, mainly from tanneries, but the indications are valid and useful for any waste in the form of powder, suitable to pelletization. Measurements of bulk density have been carried out at the industrial and laboratory scale, using different packing procedures, amenable to industrial processes. Waste as powder, pellets and their mixtures have been considered. The bulk density of waste as powder increases from 0.64 t/m(3) (simply poured) to 0.74 t/m(3) (tapped) and finally to 0.82 t/m(3) by a suitable, yet simple, packing procedure that we called dispersion filling, with a net gain of 28% in the compaction by simply modifying the collection procedure. Pelletization increases compaction by definition, but the packing of pellets is relatively coarse. Some increase in bulk density of pellets can be achieved by tapping; vibration and dispersion filling are not efficient with pellets. Mixtures of powder and pellets is the optimal packing policy. The best compaction result was achieved by controlled vibration of a 30/70 wt% mixture of powders and pellets, leading to a final bulk density of 1t/m(3), i.e. an improvement of compaction by more than 54% with respect to simply poured powders, but also larger than 35% compared to just pellets. That means increasing the mass storage capacity by a factor of 1.56. Interestingly, vibration can be the most or the least effective procedure to improve compaction of mixtures, depending on characteristics of vibration. The optimal packing (30/70 wt% powders/pellets) proved to effectively mitigate the onset of smouldering, leading to self-heating, according to standard tests, whereas the pure pelletization totally removes the self-heating hazard.

On the understanding and control of the spontaneous heating of dried tannery wastewater sludge.

We studied the spontaneous heating of dried sludge produced by treating wastewater mainly originating from tanneries. Heating up to burning has been observed in the presence of air and moisture, starting at ambient temperature. To understand and prevent the process we combined chemical and morphological analyses (ESEM) with thermal activity monitoring in insulated vessels. Selective additions of chemicals, either to amplify or depress the reactivity, have been used to investigate and identify both the chemical mechanism causing the sludge self-heating, and a prevention or a mitigation strategy. FeS additions accelerate the onset of reactivity, while S sustains it over time. On the contrary, Ca(OH)2, Na2CO3, NaHCO3, FeCl2, EDTA, NaClO can limit, up to completely preventing, the exothermic activity. All the experimental evidences show that the reactions supporting the dried sludge self-heating involve the Fe/S/O system. The total suppression of the reactivity requires amounts of additives that are industrially incompatible with waste reduction and economics. The best prevention requires reduction or removal of S and Fe from the dried solid matrix.

Self-heating of dried industrial wastewater sludge: lab-scale investigation of supporting conditions.

We studied the reactivity of dried sludge produced by treatment of wastewater, mainly from tanneries. The solids transformations have been first characterized with thermal analysis (TGA and DSC) proving that exothermic transformation takes place at fairly low temperature, before the total organic combustion that occurs in air above 400°C. The onset of low temperature reactions depends on the heating rate and it can be below 100°C at very small heating rate. Then, we reproducibly determined the conditions to trigger dried sludge self-heating at the laboratory scale, on samples in the 0.2-0.3 kg size. Thermal insulation, some aeration and addition of water are key factors. Mastering the self-heating at this scale allows more detailed investigations as well as manipulation of conditions, to understand its nature, course and remediation. Here we report proves and discussions on the role of air, water, particle size, porosity and biological activity, as well as proving that also dried sludge from similar sources lead to self-heating. Tests demonstrate that air and water are simultaneously required for significant self-heating to occur. They act in diverging directions, both triggering the onset of the reactions and damping the temperature rise, by supporting heat loss. The higher the O2 concentration, the higher the solids heating rate. More added water prolongs the exothermic phase. Further additions of water can reactivate the material. Water emphasizes the exothermic processes, but it is not sufficient to start it in an air-free atmosphere. The initial solid moisture concentration (between 8% and 15%) affects the onset of self-heating as intuitive. The sludge particles size strongly determines the strength and extent of the heat release, indicating that surface reactions are taking place. In pelletized particles, limitations to water and air permeability mitigates the reaction course.

Self-heating of dried wastewater sludge.

We experimentally studied the occurrence of spontaneous self-heating of sludge after drying, to understand its nature, course and remediation. The sludge originates from primary and biological treatment of both municipal and industrial wastewater, the latter largely dominant (approx. 90% total organic carbon, mainly from local tanneries). Dried sludge is collected into big-bags (approx. 1.5m(3)) and landfilled in a dedicated site. After several years of regular operation of the landfill, without any management or environmental issue, indications of local warming emerged, together with smoke and smelling emissions, and local subsidence. During a two year monitoring activity, temperatures locally as high as 80°C have been detected, 6-10 m deep. Experiments were carried out on large quantities of dried sludge (≈ 1t), monitoring the temperature of the samples over long periods of time (months), aiming to reproduce the spontaneous self-heating, under different conditions, to spot enhancing and damping factors. Results demonstrate that air is a key factor to trigger and modulate the self-heating. Water, in addition to air, supports and emphasizes the heating. Unusual drying operation was found to affect dramatically the self-heating activity, up to spontaneous combustion, while ordinary drying conditions yield a sludge with a moderate self-heating inclination. Temperature values as well as heating time scales suggest that the exothermic process nature is mainly chemical and physical, while microbiological activity might be a co-factor.

Entropy generation across Earth's collisionless bow shock.

Earth's bow shock is a collisionless shock wave but entropy has never been directly measured across it. The plasma experiments on Cluster and Double Star measure 3D plasma distributions upstream and downstream of the bow shock allowing calculation of Boltzmann's entropy function H and his famous H theorem, dH/dt≤0. The collisionless Boltzmann (Vlasov) equation predicts that the total entropy does not change if the distribution function across the shock becomes nonthermal, but it allows changes in the entropy density. Here, we present the first direct measurements of entropy density changes across Earth's bow shock and show that the results generally support the model of the Vlasov analysis. These observations are a starting point for a more sophisticated analysis that includes 3D computer modeling of collisionless shocks with input from observed particles, waves, and turbulences.

Development and characterization of a new thief sampling device for cohesive powders.

New sampling probes and methods for investigating cohesive powders are conceived, designed and characterized. Probes are made of two metallic shells (a slide and a cover) which need to be inserted sequentially into the bed of powder in order to extract representative samples. The thin profile of the shells, combined with a particular insertion procedure, is intended to minimize stresses on the powder; thereby reducing both the invasiveness and the dragging of material through the bed. Probes of similar design with different shape and size have been tested on stratified beds of cohesive powders of different colors. Sampling performances are quantitatively compared among different probes (for size and shape) and also with literature data. The comparison has indicated that the new sampling devices effectively improved sampling efficiency, reliability and possibilities. The simple construction and use suggest they can be viable and effective alternatives to traditional probes for cohesive mixtures.

Three dimensional anisotropic κ spectra of turbulence at subproton scales in the solar wind.

We show the first three dimensional (3D) dispersion relations and k spectra of magnetic turbulence in the solar wind at subproton scales. We used the Cluster data with short separations and applied the k-filtering technique to the frequency range where the transition to subproton scales occurs. We show that the cascade is carried by highly oblique kinetic Alfvén waves with ω(plas) ≤ 0.1ω(ci) down to k(⊥) ρ(i)∼2. Each k spectrum in the direction perpendicular to B0 shows two scaling ranges separated by a breakpoint (in the interval [0.4,1]k(⊥)ρ(i): a Kolmogorov scaling k(⊥)⁻¹â±7 followed by a steeper scaling ∼k(⊥)⁻4ⁱ5. We conjecture that the turbulence undergoes a transition range, where part of the energy is dissipated into proton heating via Landau damping and the remaining energy cascades down to electron scales where electron Landau damping may predominate.

Solitary electromagnetic pulses detected with super-Alfvénic flows in Earth's geomagnetic tail.

Solitary nonlinear (deltaB/B>>1) electromagnetic pulses have been detected in Earth's geomagnetic tail accompanying plasmas flowing at super-Alfvénic speeds. The pulses in the current sheet had durations of approximately 5 s, were left-hand circularly polarized, and had phase speeds of approximately the Alfvén speed in the plasma frame. These pulses were associated with a field-aligned current J(parallel) and observed in low density (approximately 0.3 cm(-3)), high temperature (T(e) approximately T(i) approximately 3x10(7) K), and beta approximately 10 plasma that included electron and ion beams streaming along B. The wave activity was enhanced from below the ion cyclotron frequency to electron cyclotron and upper hybrid frequencies. The detailed properties suggest the pulses are nonlinearly steepened ion cyclotron or Alfvén waves.

Characterization of platelet adhesion under flow using microscopic image sequence analysis.

A method for quantitative analysis of platelet deposition under flow is discussed here. The model system is based upon perfusion of blood platelets over an adhesive substrate immobilized on a glass coverslip acting as the lower surface of a rectangular flow chamber. The perfusion apparatus is mounted onto an inverted microscope equipped with epifluorescent illumination and intensified CCD video camera. Characterization is based on information obtained from a specific image analysis method applied to continuous sequences of microscopical images. Platelet recognition across the sequence of images is based on a time-dependent, bidimensional, gaussian-like pdf. Once a platelet is located,the variation of its position and shape as a function of time (i.e., the platelet history) can be determined. Analyzing the history we can establish if the platelet is moving on the surface, the frequency of this movement and the distance traveled before its resumes the velocity of a non-interacting cell. Therefore, we can determine how long the adhesion would last which is correlated to the resistance of the platelet-substrate bond. This algorithm enables the dynamic quantification of trajectories, as well as residence times, arrest and release frequencies for a high numbers of platelets at the same time. Statistically significant conclusions on platelet-surface interactions can then be obtained. An image analysis tool of this kind can dramatically help the investigation and characterization of the thrombogenic properties of artificial surfaces such as those used in artificial organs and biomedical devices.

Cassini measurements of cold plasma in the ionosphere of Titan.

The Cassini Radio and Plasma Wave Science (RPWS) Langmuir probe (LP) sensor observed the cold plasma environment around Titan during the first two flybys. The data show that conditions in Saturn's magnetosphere affect the structure and dynamics deep in the ionosphere of Titan. The maximum measured ionospheric electron number density reached 3800 per cubic centimeter near closest approach, and a complex chemistry was indicated. The electron temperature profiles are consistent with electron heat conduction from the hotter Titan wake. The ionospheric escape flux was estimated to be 10(25) ions per second.

Radio and plasma wave observations at Saturn from Cassini's approach and first orbit.

We report data from the Cassini radio and plasma wave instrument during the approach and first orbit at Saturn. During the approach, radio emissions from Saturn showed that the radio rotation period is now 10 hours 45 minutes 45 +/- 36 seconds, about 6 minutes longer than measured by Voyager in 1980 to 1981. In addition, many intense impulsive radio signals were detected from Saturn lightning during the approach and first orbit. Some of these have been linked to storm systems observed by the Cassini imaging instrument. Within the magnetosphere, whistler-mode auroral hiss emissions were observed near the rings, suggesting that a strong electrodynamic interaction is occurring in or near the rings.

Ulysses radio and plasma wave observations at high southern heliographic latitudes.

Ulysses spacecraft radio and plasma wave observations indicate that some variations in the intensity and occurrence rate of electric and magnetic wave events are functions of heliographic latitude, distance from the sun, and phase of the solar cycle. At high heliographic latitudes, solartype Ill radio emissions did not descend to the local plasma frequency, in contrast to the emission frequencies of some bursts observed in the ecliptic. Short-duration bursts of electrostatic and electromagnetic waves were often found in association with depressions in magnetic field amplitude, known as magnetic holes. Extensive wave activity observed in magnetic clouds may exist because of unusually large electron-ion temperature ratios. The lower number of intense in situ wave events at high latitudes was likely due to the decreased variability of the high- latitude solar wind.

Modifications in tissue histamine levels in mast cell-deficient mice (W/Wv) and in their littermates (Wv/+, W/+ and +/+) grafted with a methylcholanthrene-induced fibrosarcoma: correlation with tumour rejection.

There is evidence that mast cells and their degranulation products are involved in resistance against tumours. Previously, we have shown that tumour incidence and growth were inversely correlated with basal histamine levels, i.e. mast cell numbers, in tissues of W/Wv (mast cell-deficient), Wv/+ (partially mast cell-depleted), and +/+ (mast cell-sufficient) mice, and that histamine levels were increased in numerous tissues of tumour-bearing animals, including C57BL/6 and C3H mice, Sprague-Dawley and Commentry rats. The aim of this work was to analyse the incidence and growth of a grafted tumour (fibrosarcoma MC-B6-1) in W/+ mice, as compared with W/Wv, Wv/+ and +/+ mice, and to study the modifications in tissue histamine levels in W/+, W/Wv, Wv/+ and +/+ tumour-grafted mice, in order to determine whether or not these modifications were correlated with resistance to tumours. We report confirmation that tumour incidence and growth are inversely correlated with basal tissue histamine levels in W/Wv, Wv/+, and +/+ fibrosarcoma-bearing mice. However, in W/+ mice (normal tissue histamine levels), tumour incidence was the same as in Wv/+ mice. Histamine levels in tissues of W/Wv, Wv/+, W/+ and +/+ tumour bearing mice were not significantly different from those in controls. They were higher in some tissues of Wv/+ mice rejecting the tumour than in Wv/+ mice not rejecting the tumour. However, in W/+ and +/+ mice, histamine levels were not significantly different, and even tended to be lower in most tissues of mice rejecting the tumour than in mice accepting the tumour. Overall, these results suggest that resistance to tumours cannot be ascribed solely to mast cells, and that other mechanisms may also be involved. Thus, further experiments are needed to clarify the exact role of mast cells and mast cell-derived mediators and cytokines in the defence against tumours.

Ulysses radio and plasma wave observations in the jupiter environment.

The Unified Radio and Plasma Wave (URAP) experiment has produced new observations of the Jupiter environment, owing to the unique capabilities of the instrument and the traversal of high Jovian latitudes. Broad-band continuum radio emission from Jupiter and in situ plasma waves have proved valuable in delineating the magnetospheric boundaries. Simultaneous measurements of electric and magnetic wave fields have yielded new evidence of whistler-mode radiation within the magnetosphere. Observations of aurorallike hiss provided evidence of a Jovian cusp. The source direction and polarization capabilities of URAP have demonstrated that the outer region of the lo plasma torus supported at least five separate radio sources that reoccurred during successive rotations with a measurable corotation lag. Thermal noise measurements of the lo torus densities yielded values in the densest portion that are similar to models suggested on the basis of Voyager observations of 13 years ago. The URAP measurements also suggest complex beaming and polarization characteristics of Jovian radio components. In addition, a new class of kilometer-wavelength striated Jovian bursts has been observed.

Modifications in tissue histamine levels in mice treated with chronic epicutaneous application of phorbol-12-myristate-13-acetate.

Chronic epicutaneous application of phorbol-12-myristate-13-acetate (PMA) on the right flank of C 57 BL/6 mice induces an inflammatory reaction and a selective increase in skin histamine level at the site of treatment. Tissue histamine levels were not increased at other sites such as contralateral skin, stomach rumen and skeletal muscle, and were decreased in stomach fundus and dorsal skin. These results are in agreement with the hypothesis that mast cells play a significant role in cutaneous inflammation induced by PMA.