Chemical components of bleached eucalypt kraft pulp effluent COD and treatment removal efficiency during normal mill operation and maintenance shutdowns.

In order to meet increasingly strict Brazilian COD emissions limits, mills must understand the components that contribute to effluent COD, how these vary between normal mill operation and maintenance shutdowns, and how this variation affects treatment efficiency. To this end, primary and secondary effluents from a Brazilian bleached eucalypt kraft pulp mill activated sludge system were analyzed for COD, lignin, extractives, carbohydrates and AOX over a sixth month period that included two general maintenance shutdowns and four months of normal operation. Primary effluent presented significantly different compositions during periods of normal operation and mill shutdowns. During normal operation, the main components of effluent COD (909 mg/l average) were carbohydrates, followed by lignin. However, the lignin fraction was the main component of secondary effluent COD during both normal operation and mill shutdowns. Higher removal efficiencies for COD carbohydrates and AOX were observed during normal operation compared to shutdowns, while no difference in removal efficiencies of lignin and extractives was observed. Carbohydrate removal efficiency was significantly lower in one of the parallel treatment lines. The different removal efficiencies reflect not only variations in effluent composition, but possibly differences in system operational control which should be explored in greater detail.

Removing textile mill effluent recalcitrant COD and toxicity using the H2O2/UV system.

The potential of the H2O2/UV process for improving quality of an industrial textile effluent before biological treatment was evaluated in the laboratory using a multivariate experimental design to determine the effects of pH, H2O2 dose and reaction time on colour, COD and toxicity removal efficiencies. Increasing reaction time (from 10 to 120 min) and H2O2 dose (from 0 to 5 mmol L(-1)) significantly improved removal efficiencies, while increasing pH (from 4 to 10) had a negative effect on colour and toxicity removals. Laboratory H2O2/UV treatment of the mill effluent under optimum conditions (pH 7, 5 mmol L(-1) H2O2, 120 min) resulted in decreases in colour (70%), COD (21%) and toxicity (67%), without lowering BOD. H2O2 was consumed within the first 30-60 min, while the effluent average oxidation state stabilized after 60 min. Decreasing reaction time to 60 min resulted in similar colour (63%) and COD (20%) removals but lower toxicity removal (44%). Spectrophotometric monitoring of the optimized reaction indicated partial destruction of residual aromatic azo dyes. H2O2 and residual peroxide and average oxidation state of the effluent Effluent biodegradability (BOD/COD) increased by 28% after the H2O2/UV treatment. Improvements observed in effluent quality are expected to enhance combined AOP-biological treatment efficiency of the mill effluent.

Effect of hot acid hydrolysis and hot chlorine dioxide stage on bleaching effluent biodegradability.

The hot acid hydrolysis followed by chlorine dioxide (A/D*) and hot chlorine dioxide (D*) technologies have proven very useful for bleaching of eucalyptus kraft pulp. Although the characteristics and biodegradability of effluents from conventional chlorine dioxide bleaching are well known, such information is not yet available for effluents derived from hot acid hydrolysis and hot chorine dioxide bleaching. This study discusses the characteristics and biodegradability of such effluents. Combined whole effluents from the complete sequences DEpD, D*EpD, A/D*EpD and ADEpD, and from the pre-bleaching sequences DEp, D*Ep, A/D*Ep and ADEp were characterized by quantifying their colour, AOX and organic load (BOD, COD, TOC). These effluents were also evaluated for their treatability by simulation of an activated sludge system. It was concluded that treatment in the laboratory sequencing batch reactor was efficient for removal of COD, BOD and TOC of all effluents. However, colour increased after biological treatment, with the greatest increase found for the effluent produced using the AD technology. Biological treatment was less efficient at removing AOX of effluents from the sequences with D*, A/D* and AD as the first stages, when compared to the reference D stage; there was evidence of the lower treatability of these organochlorine compounds from these sequences.

Advanced oxidation of bleached eucalypt kraft pulp mill effluent.

In this study a poorly biodegradable (BOD/COD = 0.3) industrial alkaline ECF bleaching filtrate was treated using different advanced oxidation processes to evaluate their use in combined chemical-biological treatment aimed at increasing recalcitrant COD removal and improving final effluent quality. Oxidative treatments included ozonation combined with hydrogen peroxide (2, 5, 10, 20 mmol L(-1) O3/0.7, 2, 5, 10 mmol L(-1) H2O2) and photocatalysis with hydrogen peroxide (UV/2, 4 and 8 mmolL(-1) H2O2) and with TiO2 (UV/TiO2/0.7 and 4 mmol L(-1) H2O2). The O3/H2O2 process increased effluent biodegradability by up to 68% as a result of increasing BOD and decreasing COD. Increasing the O3 dose had a greater effect on biodegradability improvement and lignin and colour removal efficiencies than increasing the H2O2 dose. A combined oxidant dose of 5 mmol L(-1) O3 and 2 mmol L(-1) H2O2 resulted in 75% lignin removal, 40% colour removal and 6% carbohydrate loss without mineralizing the organic carbon. The photocatalytic processes led to a decrease in effluent biodegradability through combined decrease in BOD and increase in COD and did not result in efficient lignin or colour removal. Photocatalytic oxidation was apparently inhibited by the high chloride and COD levels in the alkaline filtrate, and may be more efficient in recalcitrant COD removal if performed after biological.

Combined chemical biological treatment of bleached eucalypt kraft pulp mill effluent.

Effectiveness of ozonation before and after biological treatment for removal of recalcitrant organic matter in bleached kraft pulp effluents was compared. Two industrial ECF bleached eucalypt kraft pulp effluents (E1 and E2) were pretreated with 100 mg O3/L. Raw and pretreated effluents were treated biologically in bench-scale sequencing batch reactors, under constant conditions. Following biological treatment, effluents were post-treated with 100 and 200 mg O3/L. Effluent pretreatment increased effluent biodegradability by 10% in E1 and 24% in E2. Combined O3-biological treated led to small but significant increases in COD, BOD and lignin removal over biological treatment alone, but pretreatment had no significant effect on effluent colour and carbohydrate removal. Ozone pretreatment did not affect biological activity during treatment of effluent E1 but resulted in a 38% lower specific oxygen uptake rate in effluent E2. At an equivalent dose of 100 mg/L, pre-ozonation produced better quality effluent than post-ozonation, especially with regard to COD and colour. Likewise, when an equivalent dose of 200 mg/L was applied, splitting the dose equally between pre- and post-treatments was more efficient than applying the entire dose in the post-treatment. The potential for combined chemical-biological treatment to improve effluent quality has been confirmed in this study.

Potential for enhancement of aerobic biological removal of recalcitrant organic matter in bleached pulp mill effluents.

Increasingly stringent effluent quality limits for bleached kraft pulp mills pose a great challenge to mill wastewater system managers since these limits can require levels of chemical oxygen demand (COD) removal efficiency rarely reported for biological treatment of these types of effluents. The present study was therefore undertaken to better understand the nature of recalcitrant COD in bleached kraft pulp effluents that persists through the biological treatment system. Bleaching effluents from a Brazilian eucalypt bleached kraft pulp mill were collected and treated in a bench-scale sequencing batch reactor. Organic matter in raw and treated effluents was characterized before and after separation into low and high molecular mass fractions. Biological treatment removed 71% of the COD, with 83% removal of the low molecular mass COD but only 36% removal of the high molecular mass COD. Microorganisms capable of degrading the recalcitrant COD were isolated from enrichment cultures of the original activated sludge fed on fractions of the bleaching effluent that presented low biodegradabilities. Use of a microbial consortium composed of ten of these isolates to treat the biologically treated effluent removed a further 12% of the effluent COD, all from the high molecular mass fraction. Results of this research indicate that microorganisms with potential for degrading recalcitrant COD are present in activated sludge, but that these are not metabolically active during normal activated sludge treatment of mill effluents. The use of biological selectors in the treatment system to promote growth of such microorganisms may enhance removal of recalcitrant organic matter.

Isolation and characterization of biosurfactant/bioemulsifier-producing bacteria from petroleum contaminated sites.

Biosurfactant-producing bacteria were isolated from terrestrial and marine samples collected in areas contaminated with crude oil or its byproducts. Isolates were screened for biosurfactant/bioemulsifier production in different carbon sources (glucose, fructose, sucrose and kerosene) using the qualitative drop-collapse test. Glucose produced the highest number of positive results (17 of 185 isolates). All 17 isolates produced emulsions with kerosene and 12 exhibited high emulsion-stabilizing capacity, maintaining 50% of the original emulsion volume for 48 h. Eight of the 17 isolates reduced the growth medium surface tension below 40 mN m(-1) with 5 exhibiting this capacity in cell-free filtrates. Onset of biosurfactant production differed among the isolates, with some initiating synthesis during the exponential growth phase and others after the stationary phase was reached. Increasing temperature from 25 to 35 degrees C accelerated onset of biosurfactant production in only two isolates while pH (6.5-7.6) had no effect in any isolate tested. Isolation from petroleum contaminated sites using the screening protocol presented proved to be a rapid and effective manner to identify bacterial isolates with potential industrial applications.