Arlindo C. Gomes

Determination of fast ozone oxidation rate for textile dyes by using a continuous quench-flow system

To study the fast kinetic decolourisation of textile dyes by ozone a continuous quench-flow system was used. This system has not been used before for these purposes. Reaction times in the range of 7-3000 ms were explored. The reaction was quenched with potassium iodide, which proved to be very effective, and the indigo method was used to follow the ozone concentration. Dyes from the most representative chemical classes currently used in the textile industry, i.e. azo and anthraquinone, were selected. Using the initial slope method, the effect of dye and ozone concentrations was researched and the kinetic equations thus established. Using tert-butyl alcohol, as radical scavenger, and pH close to 2.5, the second-order rate constant of the reactant dyes at 280 K varies in the range of 1.20x10(4)-7.09x10(5)M(-1)s(-1); the Acid Orange 7 exhibiting thus its lowest value, the Acid Blue 45 its highest value and the Acid Green 25 and 27 and Direct Yellow 4 intermediate values (approximately 1.6x10(5)M(-1)s(-1)). Without radical scavenger and the pH close to 4, the reaction rate increases one order of magnitude, but, on the reverse, the efficiency of ozone to decolourisation decreases.

Biodegradability enhancement and detoxification of cork processing wastewater molecular size fractions by ozone

Cork boiling wastewater pollutants were fractionated by sequential use of four ultrafiltration membranes and five fractions were obtained: four retentates (>100, 50-100, 20-50 and 10-20 kDa) and one permeate (<10 kDa); which were used to study the correlation of molecular size with biodegradability and toxicity before and after ozonation. The results show that molecular size is correlated with organic load and restrains biodegradability. The fraction with >100 kDa corresponds to 56% of the organic load and the one with <10 kDa only 8%. The biodegradability of fractions increased 182% with fractions molecular size reduction from >100 to <10 kDa and the chemical oxygen demand (COD) was from 3436 to 386 mg L(-1). For biodegradability enhancement the best outcome of ozonation was obtained with compounds having molecular size >20 kDa and range from 5% up to 175% for applied ozone doses to COD ratios between 0.15 and 0.38.

The rejection of anionic dyes and salt from water solutions using a polypropylene microfilter

Previous work reported by this laboratory showed that inorganic membranes such as stainless steel and ceramic microfilters were capable of rejecting anionic dyes and sodium nitrate from water solutions. It was of interest to see if this were possible with organic membranes such as propylene microfilters. Experimental data are presented showing that a polypropylene microfilter will reject both salt and Direct Red 2 from aqueous solutions when the conductivity of the solution is below 500/~Siemens. The use of microfiltration to remove color is an important phenomenon considering that microfiltration comprises the largest fraction of the total membrane production in the world and is now used commercially for tertiary biological wastewater treatment. The effect ofpH and salt concentration on the filtration rate and color rejection is also presented. Kegwords: Organic membranes; Microfiltration; Tertiary treatment; Dye filtration

Electrochemical treatment of cork boiling wastewater with a boron-doped diamond anode

Anodic oxidation at a boron-doped diamond anode of cork boiling wastewater was successfully used for mineralization and biodegradability enhancement required for effluent discharge or subsequent biological treatment, respectively. The influence of the applied current density (30–70 mA/cm2) and the background electrolyte concentration (0–1.5 g/L Na2SO4) on the performance of the electrochemical oxidation was investigated. The supporting electrolyte was required to achieve conductivities that enabled anodic oxidation at the highest current intensities applied. The results indicated that pollutant removal increased with the applied current density, and after 8 h, reductions greater than 90% were achieved for COD, dissolved organic carbon, total phenols and colour. The biodegradability enhancement was from 0.13 to 0.59 and from 0.23 to 0.72 for the BOD/COD ratios with BOD of 5 and 20 days’ incubation period, respectively. The tests without added electrolyte were performed at lower applied electrical charges (15 mA/cm2 or 30 V) with good organic load removal (up to 80%). For an applied current density of 30 mA/cm2, there was a minimum of electric conductivity of 1.9 mS/cm (corresponding to 0.75 g/L of Na2SO4), which minimized the specific energy consumption.

Sugar and volatile fatty acids dynamic during anaerobic treatment of olive mill wastewater

ABSTRACT Biogas production has been the main route used to exploit olive mill wastewater (OMW), after pretreatment and/or in combination with other effluents, but more recently the production of chemicals and biopolymers by biotechnological routes has deserved increasing attention by the scientific community. The present paper aims to explore the potential of fresh OMW as a source of volatile fatty acids (VFAs) and biogas. The time profile of VFAs production and the corresponding sugar consumption was followed by high-performance liquid chromatography, in batch anaerobic assays. The experimental results have revealed the very high potential of the OMW for the production of VFAs, mainly due to the high sugar concentration in the effluent (37.8 g/L) and its complete conversion into VFAs, in a time period of 2–3 days. The most abundant VFAs were acetic (48–50%), n-butanoic (12–27%), iso-pentanoic (12–14%) and propanoic (5–13%). The ratio of VFA containing even and odd carbon chains increased with the reduction in the initial chemical oxygen demand concentration of the samples used in the experiments. The conversion of the VFAs to biogas was inhibited at concentrations of 3.5 g/L of VFAs.

Antibacterial and antioxidant activity of Portuguese Lavandula luisieri (Rozeira) Rivas-Martinez and its relation with their chemical composition.

Lavandula luisieri (Rozeira) Rivas-Martinez is an endemic aromatic Labiatae the Iberian Peninsula, common in semi-arid regions of southern Portugal and southwestern Spain, that produces an active antibacterial essential oil from the leaves and flowers. This work presents the study of the chemical variation in various stages of growth of leaves and flowers of L. luisieri. It has been found that the essential oils are mainly constituted by 1,8-cineol, camphor, linalool and trans-α-necrodil acetate. It was also studied the total phenol content and the antioxidant activity on leaves and flowers. The ethanol extraction from de leaves contents the highest total phenol, important factor for the antioxidant activity of the plant, extract. It has been studied too, the antibacterial activity against Escherichia coli, Salmonella spp. and Staphylococcus aureus. In accordance with the obtained results, the antibacterial activities stand out against Staphylococcus, of the oil of L. luisieri (leaves and flowers).

Investigation of lab-scale horizontal subsurface flow constructed wetlands treating industrial cork boiling wastewater

The feasibility and treatment efficiency of horizontal subsurface flow constructed wetlands (HSFCW) was assessed for the first time for cork boiling wastewater (CBW) through laboratory experiments. CBW is known for its high content of phenolic compounds, complex composition of biorecalcitrant and toxic nature. Two lab-scale units, one planted with Phragmites australis (CWP) and one unplanted (CWC), were used to evaluate the removals of COD, BOD, total phenolic compounds (TPh) and decolourization over a 2.5-years monitoring period under Mediterranean climatic conditions. Seven organic and hydraulic loading rates ranging from 2.6 to 11.5 g COD/m2/d and 5.7-9.1 L/m2/d were tested under average hydraulic retention time (HRT) of 5 ± 1 days required due to the CWB limited biodegradability (i.e., BOD5/COD of 0.19). Average removals of the CWP exceeded those of the CWC and reached 74.6%, 91.7% and 69.1% for COD, BOD5 and TPh, respectively, with respective mass removals rates up to 7.0, 1.7 and 0.5 (in g/m2/d). Decolourization was limited to 35%, since it mainly depends on physical processes rather than biodegradation. CBW concentration of nine phenolic compounds ranged from 1.2 to 38.4 mg/L (for the syringic and ellagic acids, respectively) in the raw CBW, with respective removals in the CWP unit ranging from 41.8 to 76.3%, higher than those in the control unit. Despite CBW high concentration of TPhs (average of 116.3 mg/L), the HSFCW reached organic load removals higher than those of conventional biological treatment methods.