Cork industry wastewater characterization assessment of the biodegradability, reuse and of the relationship between BOD, COD and tannins with TOC

Cork processing involves a boiling step to make the cork softer, which consumes a high volume of water and generates a wastewater with a high organic content, rich in tannins. An assessment of the final wastewater characteristics and of the boiling water composition along the boiling process was performed. The parameters studied were pH, color, total organic carbon (TOC), chemical and biochemical oxygen demands (COD, BOD5, BOD20), total suspended solids (TSS), total phenols and tannins (TP, TT). It was observed that the water solutes extraction power is significantly reduced for higher quantities of cork processed. Valid relationships between parameters were established not only envisaging wastewater characterization but also to provide an important tool for wastewater monitoring and for process control/optimization. Boiling water biodegradability presented decreasing values with the increase of cork processed and for the final wastewater its value is always lower than 0.5, indicating that these wastewaters are very difficult to treat by biological processes. The biodegradability was associated with the increase of tannin content that can rise up to 0.7 g/L. These compounds can be used by other industries when concentrated and the clarified wastewater can be reused, which is a potential asset in this wastewater treatment.

Analysis of constructed wetland performance for irrigation reuse

Most of the wastewater treatment systems in small rural communities of the Cova da Beira region (Portugal) consist of constructed wetlands (CW) with horizontal subsurface flow (HSSF). It is believed that those systems allow the compliance of discharge standards as well as the production of final effluents with suitability for reuse. Results obtained in a nine-month campaign in an HSSF bed pointed out that COD and TSS removal were lower than expected. A discrete sampling also showed that removal of TC, FC and HE was not enough to fulfill international irrigation goals. However, the bed had a very good response to variation of incoming nitrogen loads presenting high removal of nitrogen forms. A good correlation between mass load and mass removal rate was observed for BOD5, COD, TN, NH4-N, TP and TSS, which shows a satisfactory response of the bed to the variable incoming loads. The entrance of excessive loads of organic matter and solids contributed for the decrease of the effective volume for pollutant uptake and therefore, may have negatively influenced the treatment capability. Primary treatment should be improved in order to decrease the variation of incoming organic and solid loads and to improve the removal of COD, solids and pathogenic. The final effluent presented good physical-chemical quality to be reused for irrigation, which is the most likely application in the area.

Cork processing wastewater treatment/valorisation by nanofiltration

Nanofiltration process for the treatment/valorisation of cork processing wastewaters was studied. A DS-5 DK 20/40 (GE Water Technologies) nanofiltration membrane/module was used, having 2.09 m(2) of surface area. Hydraulic permeability was determined with pure water and the result was 5.2 L.h(-1).m(-2).bar(-1). The membrane presents a rejection of 51% and 99% for NaCl and MgSO4 salts, respectively. Two different types of regimes were used in the wastewaters filtration process, total recycling mode and concentration mode. The first filtration regime showed that the most favourable working transmembrane pressure was 7 bar working at 25 degrees C. For the concentration mode experiments it was observed a 30% decline of the permeate fluxes when a volumetric concentration factor of 5 was reached. The permeate COD, BOD5, colour and TOC rejection values remained well above the 90% value, which allows, therefore, the concentration of organic matter (namely the tannin fraction) in the concentrate stream that can be further used by other industries. The permeate characterization showed that it cannot be directly discharged to the environment as it does not fulfil the values of the Portuguese discharge legislation. However, the permeate stream can be recycled to the process (boiling tanks) as it presents no colour and low TOC (< 60 ppm) or if wastewater discharge is envisaged we have observed that the permeate biodegradability is higher than 0.5, which renders conventional wastewater treatments feasible.

Ruthenium(II) Arene Complexes Bearing Tris(pyrazolyl)methanesulfonate Capping Ligands.Electrochemistry, Spectroscopic, and X-ray Structural Characterization

Novel [Ru(L)(Tpms)]Cl and [Ru(L)(Tpms(Ph))]Cl complexes (L = p-cymene, benzene, or hexamethylbenzene, Tpms = tris(pyrazolyl)-methanesulfonate, Tpms(Ph) = tris(3-phenylpyrazoly)methanesulfonate) have been prepared by reaction of [Ru(L)(mu-Cl)(2)](2) with Li[Tpms] and Li[Tpms(Ph)], respectively. [Ru(p-cymene)(Tpms)]BF4 has been synthesized through a metathetic reaction of [Ru(p-cymene)(Tpms)]Cl with AgBF4. [RuCl(cod)(Tpms)] (cod = 1,5-cyclooctadiene) and [RuCl(cod)(Tpms(Ph))] are also reported, being obtained by reaction of [RuCl2(cod)(MeCN)(2)] with Li[Tpms] and Li[Tpms(Ph)], respectively. The structures of the complexes and the coordination modes of the ligands have been established by IR, NMR, and single-crystal X-ray diffraction (for [RuL(Tpms)]X (L = p-cymene or HMB, X = Cl; L = p-cymene, X = BF4)) studies. Electrochemical studies showed that each complex undergoes a single-electron R-II -> R-III oxidation at a potential measured by cyclic voltammetry, allowing to compare the electron-donor characters of the tris(pyrazolyl)methanesulfonate and arene ligands, and to estimate, for the first time, the values of the Lever E-L ligand parameter for Tmps(Ph), HMB, and cod.

Cork industry wastewater partition by ultra/nanofiltration: A biodegradation and valorisation study

Wastewater from cork processing industry present high levels of organic and phenolic compounds, such as tannins, with a low biodegradability and a significant toxicity. These compounds are not readily removed by conventional municipal wastewater treatment, which is largely based on primary sedimentation followed by biological treatment. The purpose of this work is to study the biodegradability of different cork wastewater fractions, obtained through membrane separation, in order to assess its potential for biological treatment and having in view its valorisation through tannins recovery, which could be applied in other industries. Various ultrafiltration and nanofiltration membranes where used, with molecular weight cut-offs (MWCO) ranging from 0.125 to 91 kDa. The wastewater and the different permeated fractions were analyzed in terms of Total Organic Carbon (TOC), Chemical Oxygen Demand (COD), Biochemical Oxygen Demand (BOD), Total Phenols (TP), Tannins, Color, pH and Conductivity. Results for the wastewater shown that it is characterized by a high organic content (670.5-1056.8 mg TOC/L, 2285-2604 mg COD/L, 1000-1225 mg BOD/L), a relatively low biodegradability (0.35-0.38 for BODs/COD and 0.44-0.47 for BOD20/COD) and a high content of phenols (360-410 mg tannic acid/L) and tannins (250-270 mg tannic acid/L). The results for the wastewater fractions shown a general decrease on the pollutant content of permeates, and an increase of its biodegradability, with the decrease of the membrane MWCO applied. Particularly, the permeated fraction from the membrane MWCO of 3.8 kDa, presented a favourable index of biodegradability (0.8) and a minimized phenols toxicity that enables it to undergo a biological treatment and so, to be treated in a municipal wastewater treatment plant. Also, within the perspective of valorisation, the rejected fraction obtained through this membrane MWCO may have a significant potential for tannins recovery. Permeated fractions from membranes with MWCO lower than 3.8 kDa, presented a particularly significant decline of organic matter and phenols, enabling this permeates to be reused in the cork processing and so, representing an interesting perspective of zero discharge for the cork industry, with evident environmental and economic advantages. (C) 2010 Elsevier Ltd. All rights reserved.

Sistemas de arrefecimento de instalações frigoríficas utilizando três agentes frigoríficos

Trabalho Final de Mestrado para obtenção do grau de Mestre em Engenharia Mecânica