Tiina Leiviskä

Effect of biological wastewater treatment on the molecular weight distribution of soluble organic compounds and on the reduction of BOD, COD and P in pulp and paper mill effluent.

Pulp and paper mill wastewater was characterizated, before (influent) and after (effluent) biological wastewater treatment based on an activated sludge process, by microfiltration (8, 3, 0.45 and 0.22microm) and ultrafiltration (100, 50, 30 and 3kDa) of the wastewater samples into different size fractions. Various parameters were measured on each fraction: molecular weight distribution (MWD) using high performance size exclusion chromatography (HPSEC), total organic carbon (TOC), biochemical oxygen demand (BOD), chemical oxygen demand (COD), total phosphorus (Tot-P), phosphate phosphorus (PO(4)-P), electrical conductivity, pH, turbidity, charge quantity and zeta potential. The MWD, TOC and COD(Cr) results indicated that the majority of the material present in both the influent and effluent was in the medium molecular weight (MW) range (i.e. MW<10kDa) with three main MW sub-fractions. There were no significant differences in the range of the MWD between the influent and effluent samples. The magnitude of the MWD in the effluent was about one half that in the influent, the greatest reduction being in the 6kDa fraction. The 3kDa fractions of both the influent and effluent showed a considerable increase in BOD(7), probably due to the removal of compounds harmful to bacteria in 3kDa ultrafiltration. Influent turbidity decreased considerably in microfiltration (8-0.22microm). As the turbidity was removed by 0.22microm filtration, the anionic charge quantity started to decrease. Particles in the influent and effluent contained 19-29% and 14-20% of the total phosphorus, respectively. The major phosphorus fraction was in the form of soluble phosphate.

Size fractionation of wood extractives, lignin and trace elements in pulp and paper mill wastewater before and after biological treatment.

Integrated kraft pulp and paper mill wastewater was characterized before (influent) and after (effluent) the activated sludge process by microfiltration (8, 3, 0.45 and 0.22 microm) and ultrafiltration (100, 50, 30 and 3 kDa) into different size fractions. Wood extractives, lignin, suspended solids and certain trace elements were determined in each fraction. Forty four percent of the resin and fatty acids in the influent (12.8 mg/L) occurred in particles (>0.45 microm), 20% as colloids (0.45 microm-3 kDa) and 36% in the <3 kDa fraction. The corresponding values for sterols (1.5 mg/L) were 5, 46 and 49%. In the effluent, resin and fatty acids (1.45 mg/L) and sterols (0.26 mg/L) were mainly present in the <3 kDa fraction, as well as a small proportion in particles. beta-sitosterol was present in particles in the effluent (88+/-50 microg/L). Lignin in the influent was mainly in the colloidal and <3 kDa fractions, whereas in the effluent it was mainly in the <3 kDa fraction. Thus the decrease of lignin in the biological treatment was concentrated on the colloidal fraction. In the influent, Mn, Zn and Si were mainly present in the <3 kDa fraction, whereas a significant proportion of Fe and Al were found also in the particle and colloidal fractions. In the effluent, Fe and Al were mainly present in the colloidal fraction; in contrast, Mn, Zn and Si were mainly in the <3 kDa fraction. The results indicated that the release of certain compounds and elements into the environment could be significantly decreased or even prevented simply by employing microfiltration as a final treatment step or by enhancing particle removal in the secondary clarifier.

Removal of nitrate by modified pine sawdust: Effects of temperature and co-existing anions

The effect of temperature, sulphate and phosphate, and the initial nitrate concentration on nitrate removal was studied with synthetic solutions. Chemically modified pine sawdust (Pinus sylvestris) anion exchange resin (MPSD) was used in the sorption studies. The resin was synthesized by reacting pine sawdust with epichlorohydrin, ethylenediamine and triethylamine in the presence of N,N-dimethylformamide. Nitrate removal was successful at 5-70 °C. Higher temperatures caused nitrate removal to decrease moderately, but sorption capacities of 22.2-32.8 mg/g for NO3-N were achieved. The removal of nitrate in the presence of sulphate or phosphate was studied at concentrations of 30 mg N/l, 10-500 mg S/l and 1-50 mg P/l. A significant decrease in nitrate reduction was observed at sulphate and phosphate concentrations of 100 mg S/l and 50 mg P/l, respectively. The effect of initial nitrate concentration was studied in column. Nitrate sorption was clearly dependent on the initial concentration. Desorption of nitrate in column was completed using about 80 bed volumes of 0.1 M NaCl solution. The sorption data were fitted to the Langmuir, Freundlich and Redlich-Peterson adsorption models. The Redlich-Peterson and Langmuir models gave the best fit, which suggests monolayer sorption. Thermodynamic studies revealed that the sorption of nitrate was spontaneous and exothermic in nature. The results imply that modified pine sawdust could be a feasible alternative in the treatment of real industrial wastewaters.

Removal of nickel and vanadium from ammoniacal industrial wastewater by ion exchange and adsorption on activated carbon

AbstractNickel and vanadium were removed from real ammoniacal industrial wastewater (Ni 2–4, V 40–50 mg/L) obtained from a synthesis gas scrubber. The aim of the study was to develop an industrial application for simultaneous removal of nickel and vanadium. The studied methods were adsorption (activated carbon (AC), AquaSorb® 2000), anion exchange (Amberjet™ 4200 Cl) and cation exchange (Amberjet™ 1200 H). AC removed > 95% of nickel at pH 5.5–9 (dose > 2 g/L) but the vanadium uptake remained poor. In batch cation exchange, all nickel was removed (optimum pH 4–7) and 70–75% of vanadium was removed at pH 7 (5–10 g/L). All nickel was removed in batch anion exchange (optimum pH 5.5–9, 2–10 g/L). Over 89% of vanadium was removed in batch anion exchange at pH 7 (1–10 g/L). Adsorption capacities of 4.36 and 48.9 mg/g were obtained for nickel and vanadium in anion exchange at pH 7. In column anion exchange, all nickel and 92–98% of vanadium were removed in all three ion exchange cycles at pH 7–9. In regeneration,...

Vanadium(V) removal from aqueous solution and real wastewater using quaternized pine sawdust.

Cross-linked and quaternized pine sawdust was tested for vanadium removal from a synthetic aqueous solution as well as from real industrial wastewater which had a considerable amount of vanadium and other ions such as sulphate, ammonium and nickel. The maximum vanadium sorption capacity of the modified pine sawdust was found to be 130 mg/g in synthetic solution and 103 mg/g in real wastewater. Modified pine sawdust worked well over a wide range of pH. Column studies with real wastewater proved that vanadium was efficiently desorbed from the material with 2 M NaOH and that the material could be reused.

Coagulation of humic waters for diffused pollution control and the influence of coagulant type on DOC fractions removed.

This study examined the suitability of organic coagulants for treatment of typically humic peat extraction runoff water by comparing their performance with that of ferric sulphate (FS). The influence of coagulant type on dissolved organic carbon (DOC) fractions removed was analysed in detail using LC-OCD-OND (size exclusion liquid chromatography coupled with organic carbon and organic nitrogen detection) fractionation techniques. In general, lower coagulant dosage was needed under acidic (pH 4.5) than neutral (pH 6.5) conditions. Chitosan (Chit) and poly (diallyldimethyl) ammonium chloride (pDMAC) required significantly lower dosage (40-55%) than FS for acceptable purification, while a tannin-based coagulant (Tan2) required substantially higher dosage (55-75%) independent of water pH. FS demonstrated the best removal of DOC (<81%) and phosphorus (<93%) followed by pDMAC, while Chit and Tan2 achieved the highest removal of suspended solids (SS) (<58%), with flocs formed by Tan2 presenting the best settling properties. Higher molecular weight (MW) DOC fractions were more efficiently removed by all coagulants, with FS being the most efficient (biopolymers 69% and humic substances 91%), followed by Tan2. FS also displayed satisfactory removal of lower MW fractions (building blocks ∼46% and low MW neutrals 62%). Overall, FS was the best performing coagulant. Nevertheless, the organic polymers demonstrated satisfactory overall performance, achieving purification rates mostly inside the requirements set by Finnish environmental authorities.

Quaternized pine sawdust in the treatment of mining wastewater.

ABSTRACT Mining wastewater was treated using quaternized pine sawdust (QPSD) anion exchanger. The wastewater contained heavy metals (e.g. Sb, As, Co, Cr, Ni, V, U), NO3−, among others, and a high concentration of SO42−. A series of column cycles imitating a real treatment process was conducted (three sorption/desorption cycles, a maintenance cycle with HCl and two sorption/desorption cycles). The effects of contact time and temperature (5°C and 23°C) were studied to assess the applicability of QPSD in the treatment of cold mining effluents. At 5°C, 85% of nickel was removed but the sorption was slower than at 23°C (initial Ni concentration was about 39 µg/l). Nickel was also removed in column efficiently (85–100% reduction). Treatment with HCl during the maintenance cycles did not hinder nickel sorption. Nickel was desorbed with both NaCl and HCl. Contrary to expectations, nitrate was not sorbed. QPSD showed selectivity towards nickel. However, uptake of uranium and cobalt was detected in column. Neutron activation analysis was used to detect metals sorbed onto the QPSD, and uptake of several metals was confirmed. GRAPHICAL ABSTRACT

Characteristics and settling behaviour of particles from blast furnace flue gas washing

A lot of particles from iron-making are removed with blast furnace off-gas and routed to the gas cleaning system. As water is used for cleaning the gas, the produced wash water contains a large amount of particles such as valuable Fe and C. However, the presence of zinc prevents recycling. In addition, the high amount of calcium results in uncontrolled scaling. Therefore, the properties of the wash water from scrubber and sludge, from the Finnish metal industry (SSAB Raahe), were evaluated in this study. Size fractionation of wash water revealed that Fe, Zn, Al, Mn, V, Cr and Cd appeared mainly in the larger fractions (>1.2 μm) and Na, Mg, Si, Ni, K, Cu and As appeared mainly in the smaller fractions (<1.2 μm) or in dissolved form. Calcium was found both in the larger fractions and dissolved (∼60 mg/L). Most of the particles in wash water were included in the 1.2-10 μm particle size and were settled effectively. However, a clear benefit was observed when using a chemical to enhance particle settling. In comparison to 2.5 h of settling without chemical, the turbidity was further decreased by about 94%, iron 85% and zinc 50%. Coagulation-flocculation experiments indicated that both low and high molecular weight cationic polymers could provide excellent purification results in terms of turbidity. Calcium should be removed by other methods. The particles in sludge were mostly in the 2-4 μm or 10-20 μm fractions. Further sludge settling resulted in high solids removal.

Preparation of cationized pine sawdust for nitrate removal: Optimization of reaction conditions

Anion exchange materials were prepared from pine sawdust (Pinus sylvestris, PSD) through cationizing treatment with N-(3-chloro-2-hydroxypropyl) trimethyl ammonium chloride (CHMAC) in the presence of NaOH. Response surface methodology (RSM) was used to find the optimal reaction conditions. Three factors were chosen: reaction temperature (26-94 °C), reaction time (0.32-3.7 h) and NaOH/CHMAC molar ratio (0.19-2.2). Product yield (%) was used as a response. A quadratic model was fitted to the experimental data. The optimal conditions were: a reaction temperature of 57 °C, a reaction time of 1.8 h and a NaOH/CHMAC molar ratio of 1.32. A maximum nitrogen content of 2.6% was obtained at 60 °C, 3.7 h and a molar ratio of 1.2. The molar ratio had the greatest impact on the response. Regression analysis revealed that over 95% of the variance can be explained by the model. A maximum nitrate sorption capacity of 15.3 ± 1.4 mg N/g was achieved. The effect of CHMAC dose was also studied (a NaOH/CHMAC molar ratio of 1.2): 0.064 mol/g PSD was found to be near the optimum. Nitrate-contaminated groundwater (27.5 mg/l NO3) was treated with CPSD. Doses of 3-6 g/l resulted in 59-71% nitrate reduction.

Utilization of Industrial Microbe Side Streams for Biosorption of Heavy Metals from Wastewaters

The present report reviews the potential and applicability of industrial microbe side streams produced in Finnish bioprocess industries for biosorption of heavy metals from waste waters. Microbial side stream biomasses are formed worldwide in e.g. food, brewing, biofuel, pharmaceuticals, wood processing and enzyme manufacturing industries. Although these streams are typically used for low-valued animal feed or biogas production, they would also have potential for biosorbent materials to be used in in situ water treatment. Since major challenges have been recognized, especially regarding the availability of biomass, and to logistic and processing cost, biosorption is not the most economically attractive option for the use of these biomasses at the moment. However, in the future the situation may change due to new incentives or more cost-efficient biosorbent preparation technologies. This report will provide a knowledge basis for the consideration of biosorption applications for industrial microbe side streams.