RESUMEN

Dissolved arsenic in drinking water is a global concern as it causes serious health problems. The purpose of this research was to study the applicability of an industrial intermediate product, a mixture of titanium hydroxide and titanium dioxide for removing aqueous arsenic. The material is common, inexpensive, and non-toxic, making it an attractive choice for drinking water purification. The kinetics and equilibrium of removing both primary inorganic arsenic forms, As(III) and As(V), were studied by separate batch experiments. The tested material functioned well in removing both of these arsenic forms. The apparent values for Langmuir monolayer sorption capacities were 31.8 mg/g for As(III) and 33.4 mg/g for As(V) at pH 4. The studied TiO(2) performed the best in acidic conditions, but also reasonably well in other pH conditions.

RESUMEN

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.

Asunto(s)

RESUMEN

Up to 20 million tons of waste wood biomass per year is left unused in Finland, mainly in the forests during forestry operations, because supply and demand does not meet. As a consequence of high heat energy prices, the looming threat of climate change, the greenhouse effect, and due to global as well as national demands to considerably increase the proportion of renewable energy, there is currently tremendous enthusiasm in Finland to substantially increase pellet production. As part of this European objective to increase the eco- and cost-efficient utilization of bio-energy from the European forest belt, the aim of our research group is - by means of multidisciplinary research, especially through chemical methods - to promote the development of Nordic wood-based pellet production in both the qualitative and the quantitative sense. Wood-based pellets are classified as an emission-neutral fuel, which means that they are free from emission trading in the European Union. The main fields of pellet research and the chemical toolbox that has been developed for these studies, which includes a new specific staining and optical microscope method designed to determine the cross-linking of pellets in the presence of various binding compounds, are described in this paper. As model examples illustrating the benefits of this toolbox, experimental data is presented concerning Finnish wood pellets and corresponding wood-based pellets that include the use of starch-containing waste potato peel residue and commercial lignosulfonate as binding materials. The initial results concerning the use of the developed and optimized specific staining and microscopic method using starch-containing potato peel residue as binding material are presented.

Asunto(s)

RESUMEN

A five-stage sequential extraction procedure was used to determine the distribution of 11 metals (Cd, Cr, Cu, Mo, Pb, Zn, As, Co, V, Ni, Ba), and sulphur (S) in bottom ash and in fly ash from a fluidized bed co-combustion (i.e. wood and peat) boiler of Stora Enso Oyj Oulu Mill at Oulu, Northern Finland, into the following fractions: (1) water-soluble fraction (H2O); (2) exchangeable fraction (CH3COOH); (3) easily reduced fraction (NH2OH-HCl); (4) oxidizable fraction (H2O2 + CH3COONH4); and (5) residual fraction (HF + HNO3 + HCl). Although metals were extractable in all fractions, the highest concentrations of most of the metals occurred in the residual fraction. From the environmental point of view, this fraction is the non-mobile fraction and is potentially the least harmful. The Ca concentrations of 29.3 g kg(-1) (dry weight) in bottom ash and of 68.5 g kg(-1) (dry weight) in fly ash were correspondingly approximately 18 and 43 times higher than the average value of 1.6 g kg(-1) (dry weight) in arable land in Central Finland. The ashes were strongly alkaline pH (approximately 12) and had a liming effects of 9.3% (bottom ash) and 13% (fly ash) expressed as Ca equivalents (dry weight). The elevated Ca concentrations indicate that the ashes are potential agents for soil remediation and for improving soil fertility. The pH and liming effect values indicate that the ashes also have a pH buffering capacity. From the environmental point of view, it is notable that the heavy metal concentrations in both types of ash were lower than the Finnish criteria for ash utilization.

Asunto(s)

RESUMEN

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.

Asunto(s)

RESUMEN

From the utilization point of view, it is notable that the total element concentrations in the precipitated calcium carbonate (PCC) waste were significantly lower than the maximal allowable heavy metal concentrations for fertilizers used in agriculture and in forestry, set on the basis of the EU and Finnish legislation. The easily soluble Ca concentration of 168.5g kg(-1) (d.w.) in PCC waste was 105 times higher than the typical value of 1.6g kg(-1) (d.w.) in the coarse mineral soil in Finland indicates that the PCC waste is a potential agent for soil remediation and for improving soil fertility if it is used as fertilizer. According to a five-stage sequential extraction procedure, the highest concentrations of most of the elements occurred either in HF+HNO3+HCl or H2O2+CH3COONH4 fraction. This means that the major part of the elements retained in the PCC waste are not easy to extract (leach) under conditions normally found in nature. This is beneficial since, if inorganic materials and by-products are utilized in earth construction, the content of harmful compounds must be low and the harmful components must be tightly bound to the matrix.

Asunto(s)

RESUMEN

The aim of this research was to study the suitability of a manometric respirometric test (OECD 301F) for the determination of biological oxygen demand (BOD) in domestic wastewater. This was done by comparing four different BOD tests (a manometric respirometric test, oxygen sensor determination, iodometric titration, and UV absorption measurement) and by evaluating the BOD(7) value after a short-term measurement applying the manometric respirometric test. Measurements were done in three different laboratories. The respirometric test was performed well on municipal sewage, and the precision of results was good. There were minor deviations between BOD(7) values as determined by the different methods, but the deviations were not essentially big enough to have a practical impact. Evaluation of the BOD(7) value after two or three days' incubation by the respirometric method was shown to work well; average deviations between measured and evaluated values after three days' incubation were 5-18%. Hence, the manometric respirometric test proved to be a rapid and suitable tool for process control purposes.

RESUMEN

The biodegradability of certain biofuels was studied in the case of forest soils using the manometric respirometric technique, which was proved to be very suitable for untreated, fertilized as well as pH adjusted soils. Experiments carried out in infertile sandy forest soil gave a BOD/ThOD value of 45.1% for a typical model substance, that is, sodium benzoate after a period of 30 days and mineral addition improved the BOD/ThOD value to a value of 76.2%. Rapeseed oil-based chain oil almost did not biodegrade at all in 30 days in nonprocessed soil, and when pH was adjusted to 8.0, the BOD/ThOD value increased slightly to a value of 7.4%. Mineral addition improved the BOD/ThOD value on average to 43.2% after 30 days. The combined mineral addition and pH adjustment together increased the BOD/ThOD value to 75.8% in 30 days. The observations were similar with a rapeseed oil-based lubricating oil: after 30 days, the BOD/ThOD value increased from 5.9% to an average value of 51.9%, when the pH and mineral concentrations of the soil were optimized. The mineral addition and pH adjustment also improved the precision of the measurements significantly.

RESUMEN

A five-stage sequential leaching procedure was used to fractionate 13 heavy metals (Cd, Cu, Pb, Cr, Zn, Fe, Mn, Al, Ni, Co, As, V, Ba) and sulphur (S) in lime waste from the lime kiln at the causticizing plant of Stora Enso Oyj Veitsiluoto Pulp Mills at Kemi, Northern Finland, into the following fractions: (1) water-soluble fraction (H(2)O), (2) exchangeable fraction (CH(3)COOH), (3) easily reduced fraction (HONH(3)Cl), (4) oxidizable fraction (H(2)O(2)+CH(3)COONH(4)), and (5) residual fraction (HF+HNO(3)+HCl). Although metals were leachable in all fractions, the highest concentrations for most of the metals were observed in the residual fraction (stage 5). It was also notable that the total heavy metal concentrations in lime waste did not exceed the maximal allowable heavy metal concentrations for soil conditioner agents set by the ministry of the Agricultural and Forestry in Finland. The heavy metals concentrations in lime waste were also lower than the maximal allowable heavy metals concentrations of the European Union Directive 86/278/EEC on the protection of environment, and in particular of the soil, when sewage sludge is used in agriculture. The Ca concentration (420 g kg(-1); d.w.) was about 262 times higher than the typical value of 1.6 g kg(-1) (d.w.) in arable land in Central Finland. However, the concentration Mg (0.2 g kg(-1); d.w.) in lime waste was equal to the Mg concentration in arable land in the Central Finland. The lime waste has strongly alkaline pH ( approximately 12.8) and a neutralizing value (i.e. liming effect) of 47.9% expressed as Ca equivalents (d.w.). This indicates lime waste to be a potential soil conditioner and improvement as well as a pH buffer.

Asunto(s)

RESUMEN

The biological oxygen demand (BOD) test is widely used in many wastewater treatment plants. The conventional BOD tests are usually time-consuming and the results are often out of date for process control purposes. The aim of this research was to compare the manometric respirometric test with common chemical methods in the determination of BOD of wastewater from a pulp and paper mills as well as to evaluate the BOD (7) values of both wastewaters from the short-term respirometric measurements. The results showed that there were differences in the BOD(7) values of paper mill samples measured by conventional and respirometric methods. The main cause was found to be the dilution solution used in the conventional BOD tests. Using the same mineral solution in the respirometric measurements diminished the difference remarkably. Evaluation of the BOD(7) value after two or three days incubation was proved to work very well and the estimated results were close to measured values (deviations 1%-12%).

RESUMEN

Certain wear metals (Fe, Cr, Ni, Cu and Zn) of various lubrication oils were determined by means of ICP-OES and FAAS. The kerosene dilution method, which is used widely together with ICP-OES, was applied with both methods here. Calibration standards were made from a commercial organo-metallic standard. Our aim was to clarify the possibility of using the quick kerosene dilution method together with FAAS for a rapid check for certain indicator metals. Metal determinations with FAAS were accurate enough for quantitative work in machine condition diagnostics and waste oil characterization, when compared with those with ICP-OES.

Asunto(s)

RESUMEN

A new infrared spectroscopic method suitable for determining total fatty alcohol and fatty acid ester concentrations in industrial oils has been developed. Oil samples were diluted with toluene (1:3 w/w), the toxicity and volatility of which are relatively low compared with more commonly used IR solvents, like carbon tetrachloride or carbon disulfide. Mixture standards were prepared from dodecanol, tetradecanol, octadecanol, methyl stearate and methyl palmitate. Some analytical and statistical tests were performed on the developed method. The recoveries and the repeatability of the method proved to be sufficient for the quantitative determination of fatty alcohol and fatty acid ester additives in industrial oils. Reproducibility testing in another laboratory also produced satisfactory results. The developed method also proved to be relatively quick and simple. This method was developed to satisfy industry's need to determine the concentrations of these oil additives, and it has already been applied successfully in machinery oil analysis.

Asunto(s)

RESUMEN

A five-stage sequential leaching procedure was used to fractionate heavy metals (Cd, Cu, Pb, Cr, Zn, Fe, Mn, Ni, Co, As, V, Ba and Ti) in green liquor dregs into the following fractions: (1) water-soluble fraction (H2O), (2) exchangeable fraction (CH3COOH), (3) easily reduced fraction (HONH3Cl), (4) oxidizable fraction (H2O2 + CH3COONH4), and (5) residual fraction (HF + HNO3 + HCl). The green liquor dregs were derived from a causticizing process at a pulp mill at Kemi, Northern Finland. According to the leaching studies, the leachability of heavy metals in the water-soluble fraction varied between 0.5 and 2 mg kg(-1) expressed on a dry weight (d.w.) basis, indicating relatively low bioavailability of the metals. However, the concentration of Mn (2065 mg kg(-1); d.w.) showed a strong and of Zn (17.6 mg kg(-1); d.w.), Ni (39.7 mg kg(-1); d.w.) and Ba (32.0 mg kg(-1); d.w.) slightly tendency to be extracted in the exchangeable fraction. In addition, Zn, Mn, Ni, Co, V and Ba showed clear leachability in the easily reduced fraction, as well as Cd, Cu, Cr, Zn, Mn, As and Ba in the oxidizable fraction. For Cd, Cu, Cr, Zn, Mn, Ni, Co, Ba and Ti, the sum of leachable heavy metal concentrations in fractions 1-5 agreed relatively well with the "total" heavy metal concentrations. Recoveries of the sum of fractions 1-5 were 84-56% of those obtained by the US EPA method 3052 (i.e. concentrations obtained after microwave oven digestion with a mixture of HF and HNO3).

Asunto(s)

RESUMEN

The respirometric BOD OxiTop method was used to monitor the biodegradation of different chain oils (mineral, rapeseed and tall oils) over 28 days in groundwater, as well as in standard conditions described by OECD 301 F. The aim of the study was to gather more information about the biodegradability of forestry oils in groundwater, as well as about the suitability of the automatic OxiTop method for biodegradation measurements. The BOD OxiTop method proved to be a precise and reliable technique for determining the biodegradations of different oils. Some comparative studies were also made using a traditional IR method in order to clarify the total oil concentrations. The results show that if biodegradation only is to be monitored, the OxiTop method is preferable. This is due to the influence of other reactions aside from biodegradation on total hydrocarbon concentrations when using the IR method.

Asunto(s)