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.

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.

Recurrent rotavirus diarrhoea outbreaks in a stud farm, in Italy.

A total of 47 stool samples were collected at the same stud farm from young foals with rotavirus diarrhoea and from their stud mares. Illness involved foals during three consecutive winter seasons. Infection in the farm appeared firstly in January-February 2008. After vanishing in the warm seasons, cases reappeared in March 2009 and 2010. Determination of the rotavirus G- and P-types was carried out using nested RT-PCR in samples collected in 2009 and 2010. A total of 19 of 47 samples resulted positive for rotavirus. The G type was determined in 19/47 samples, whereas the P genotype was determined in 17/47 samples. All equine strains presented a G14 VP7 in combination with a P[12] VP4, suggesting persistence of the same viral strain in the stud farm, during at least two consecutive winter periods. Sequence analysis of the genes encoding the outer capsid rotavirus proteins VP7 and VP4 revealed that the virus had a close relationship between strains recently isolated in the rest of Europe.