The aim of this research was to study the effects of chemical spills on activated sludge metabolic activity and settleability. On-site, laboratory-scale tests were carried out at three pulp and paper mill activated sludge plants. Oxygen uptake rate (OUR) and dissolved organic carbon (DOC) removal were used for monitoring of metabolic inhibition. The effects of chemicals on 30-min settled sludge volume were studied. Accidental release reports from five pulp and paper mills were analysed. Thirty-four chemicals were selected to the laboratory tests. Of the tested chemicals 2 biocides, monochloro acetic acid, soft soap and turpentine inhibited the OUR of the sludge and thus, had an acute toxic effect on the activated sludge. The biocides and disperging agent reduced DOC removal. Aluminium sulphate and optical brightener had a negative effect on sludge settleability and thus, they may cause losses of activated sludge from treatment plant. In conclusion, maximum possible spill of the five chemicals may reduce the performance of the activated sludge.

Nafion membranes were shown to be suitable substrates for atomic layer deposition (ALD) process.ALD utilising trimethyl aluminum as a precursor leads to well reproducible formation of smooth single-sided Al2O3 coating on the membranes. Physicochemical and mechanical properties of the coated membranes were compared to those of the unmodified ones. The coating reduced water uptake and thus also conductivity. Moreover, the Al2O3 coating decreased the oxygen permeability of the membrane by 10 % and the methanol permeability 30-50 %. The mechanical properties of the Nafion ® membrane were improved. The resulting membranes were successfully applied in hydrogen fuel cells, direct methanol fuel cells and microbial fuel cells. In the microbial fuel cell, the Al2O3 coated membrane showed stable performance during long-term measurements of more than 100 d and doubled power densities in comparison to a cell equipped with a pristine membrane. The membrane modification strategy has potential for improving the performance of various types of membrane fuel cells and could be used for several types of functional membranes containing active groups for ALD growth.Keywords atomic layer deposition, aluminum oxide coating, ion exchange membrane, reactant crossover, microbial fuel cell Revised manuscript No. JMS-15-8873

High suspended solids concentrations are typical for pulp and paper industry treated effluents. A new clarifier model was developed to find the reasons for this problem. The model clarifier is divided into four different zones: inlet, settling, thickening and separation. In the inlet zone sludge is transported by water flow and neither thickening nor settling will happen. When water velocity decreases the main part of the sludge will settle until it reaches the thickening zone. Thickening will continue until the sludge is pumped away from the clarifier. Concentration increase depends on sludge concentration, time and specific thickening coefficient. The minor part, which is specific to the sludge, enters the separation zone and will either settle in the thickening zone or stay in the effluent. In intensive field studies on 12 different activated sludge processes sludge volume in the clarifier, effluent suspended solids concentrations and sludge settling qualities were examined. Modelled sludge blanket volumes were verified with blanket measurements. Modelled effluent suspended solids were also verified by concentration measurements. Sludge thickening characteristics can be estimated by DSVI. From the data collected two empirical relationships were noticed between sludge settling properties and process operation. Solids concentration in clarified water depends on settling number, which is the mean number of sludge settling during its residence time in the process (sludge age). Sludge settling properties seem to depend on collision load, which is defined as COD-load divided by return sludge biomass flow.

Sludge thickening is modeled dynamically and results of simulations are compared to observations of sludge blanket in different clarifier types. Thickening is described to depend on the inverse of thickening factor and solids concentration. Thickening factor can be measured in test cylinder or estimated on DSVI. Short circuiting inside the sludge blanket is modeled by combination of PFR- and CSTR-blocks of thickening. The results indicate that sludge blanket behavior can be explained by thickening.

Efficiency improvement in a pulp mill includes minimisation of environmental discharges simultaneously with the development of pulp quality and production economy. Material balances in production processes, including fate of sidestreams, are key in proceeding these matters. Different approaches of determining the material balances increase understanding of process behaviour. We have focused on measuring sidestream (carryovers, washing water, filtrate) dissolved organic matter (DOM) in fibreline unit process blocks of softwood ECF bleached kraft production. The DOM was analysed by traditional wastewater methods (volatile solids, organic carbon, chemical oxygen demand). The measured data was combined with primarily simulated water balances and routine operational mill data in a simulation model. From this balance, yield estimate included, lost organic matter through complete degradation (CD) and volatile organic compounds (VOC) can be calculated throughout the fibreline. The sensitivity of this considerable amount (23-35 kgDVS/adt in total) to various factors is discussed in this paper.