Results of Finnish national survey in the chemical industry on EU legislation concerned with risk assessment and safety compliance climate

A questionnaire study about the Finnish chemical industry was devised to explore the implementation of the risk assessment obligations of the EU Chemical Agents Directive (98/24/EC), and the role of risk assessment activities as a part of OSH management. The quantitative method involved an assessment of online questionnaire. The respondents were employers' (N = 49) and workers' (N = 105) OSH representatives from different companies'. The regression analysis of the responses indicated that prioritizations in the risk assessment had a highly significant (p < 0.001) effect both on the prevention measures in the management and on the safe use of chemicals. The present results showed that development measures have to be directed at the most important problems ensuring that sub-contractors carry out hazard identification and arranging their on-the-job training so that it matches the chemical plant enterprise's own workers. Furthermore, the results of risk assessment should be used in the planning and management of the work, in the development of the supervisors' leadership skills as well as when following up the improvements.     

Assessing the impact of CO2 emission control scenarios in Finland on radiative forcing and greenhouse effect

Carbon dioxide emission reduction scenarios for Finland are compared with respect to the radiative forcing they cause (heating power due to the absorption of infrared radiation in the atmosphere). Calculations are made with the REFUGE system model using three carbon cycle models to obtain an uncertainity band for the development of the atmospheric concentration. The future emissions from the use of fossil fuels in Finland are described with three scenarios. In the reference scenario (business-as-usual), the emissions and the radiative forcing they cause would grow continuously. In the scenario of moderate emission reduction, the emissions would decrease annually by 1% from the first half of the next century. The radiative forcing would hardly decrease during the next century, however. In the scenario of strict emission reductions, the emissions are assumed to decrease annually by 3%, but the forcing would not decrease until approximately from the middle of the next century depending on the model used. Still, in the year 2100 the forcing would be considerably higher than the forcing in 1990. Due to the slow removal of CO₂ from the atmosphere by the oceans, it is difficult to reach a decreasing radiative forcing only by limiting fossil CO₂ emissions. The CO₂ emissions from fossil fuels in Finland contribute to the global emissions presently by about 0.2%. The relative contribution of Finnish CO₂ emissions from fossil fuels to the global forcing due to CO₂ emissions is presently somewhat less than 0.2% due to relatively smaller emissions in the past. The impact of the nonlinearity of both CO₂ removal from the atmosphere and of CO₂ absorption of infrared radiation on the results is discussed.     

Passive sampling of PAHs in indoor air in Nepal

PAHs were sampled in ten homes in the Makwanpur region, Nepal. SPMDs and moss bags (Sphagnum girgensohnii) were used as passive samplers. Soot particles on the SPMD surfaces were also analyzed for PAHs. The overall PAH concentrations in SPMDs were significantly higher than those in moss bags. Total PAH mean concentrations of ten houses were 535μg/g lipid for SPMDs and 7.2 μg/g moss (dw) for moss bags. Ratios of phenanthrene/anthracene in indoor SPMDs and particulate matter varied from 2.9 to 3.5 and ratios of fluoranthene/pyrene varied from 1.1 to 1.4. The values for moss bags were respectively 1.7–3.6 and 0.8–2.4. These ratios indicate that the PAHs are from combustion origin. The PAH concentrations in ambient air were estimated as B(a)P TEQs and they were 17–64 times higher than acceptable limit for Finnish community air. Based on PAH levels in the gas phase (SPMD) we may expect PAHs to have an impact on respiratory disease prevalence in Nepalese villages. Both of the sampling methods were feasible in the difficult conditions under which the study was performed.     

Multivariate Statistics of the Pyrolysis Products of High Molecular Components in Pulping Wastewaters to Explain Their Toxicity (6 pp)

Background, Aim and Scope At present, large-scale paper manufacture involves delignification and bleaching by elemental chlorine free (ECF) or totally chlorine free (TCF) processes. The wastewater is purified by secondary treatment (mechanical, chemical and biological) which removes most of the toxic substances from the discharge. However, we found residual toxicity in the high molecular (> 1000 D) matter (HMWM) of the discharge by test of the RET (reverse electronic transfer) inhibition. This fraction consists mainly of polydisperse lignin (LIG) and carbohydrate (CH) macromolecules. Structural units in these molecules are studied by pyrolysis gas chromatography / mass spectrometry (Pyr-GC/MS). In the present work, our aim was to find out those structural units which could explain the RET toxicity of LIG or CH molecules. We compared statistically RET toxicity values of the HMWM samples from treated wastewaters of pilot pulping experiments and intensity variation of the pyrolysis product gas chromatograms of these samples. This application is a novel study procedure. Methods Pyrolysis products (Py-GC/MS results) and inhibition of RET (reverse electronic transport toxicity) as TU50 and TU20 of HMWM (High Molecular Weight Material; Mw > 1000 D) were compared by multivariate statistics. The samples were from laboratory pilot stages of TCF (Totally Chlorine Free) and ECF (Elemental Chlorine Free) manufacture of softwood pulp. Py-GC/MS was done without and with addition of TMAH (Tetra Methyl Ammonium Hydroxide). The name and structure of each abundant fragment compound was identified from its retention time and mass spectrum compared to authentic reference compounds or literature. Four sets of Toxicity Units (TUs) and GC peak areas of the pyrolysis fragments were obtained. The data were normalized by division with LIG (lignin content of each sample). TU values were dependent and the fragment values independent (explanatory) variables in statistical treatments by SPSS system. Separate analyses of correlations, principal components (PCA) and stepwise multiple linear regression (SMLR) were performed from the four sample sets TCF and ECF with and without TMAH. Results and Discussion From the CH fragments, 2-furfural in TCF, and from the LIG fragments, styrene in ECF showed the highest probabilities to originate from source structures of toxicity. Other possible compounds in concern were indicated to be CH fragment 2-methyl-2-cyclopenten-1-one in ECF and LIG fragments 2-methoxy-4-methylphenol, 4,5-dimethoxy-2-methylphenol and 2-methylphenol in TCF.     

Leachate formation and characteristics from gasification and grate incineration bottom ash under landfill conditions

Characteristics and formation of leachates from waste gasification and grate firing bottom ash were studied using continuous field measurements from 112 m³ lysimeters embedded into landfill body for three years. In addition, the total element concentrations of the fresh ash were analysed and laboratory batch tests were performed to study leachate composition. The three-year continuous flow measurement showed that about one fifth of the leachates were formed, when the flow rate was >200 l/d, covering <3.5% of the study time. After three years, the liquid/solid-ratio for the quenched grate ash was 1 (l/kg (d.m.)) and for the initially dry gasification ash 0.4 (l/kg (d.m.)). The low initial water and residual carbon content of the gasification ash kept the leachate pH at a high level (>13) major part of the study. In the grate ash leachate pH was lower (<8) due to the presence of organic carbon and biodegradation indicated by biological oxygen demand and redox potential measurements. In the gasification ash the high pH probably delayed leaching of major elements such as Ca, therefore, raising the need for a longer after-care period. The high pH also explains the higher leaching of As from the gasification ash compared to the grate ash both in the batch test and under landfill conditions.     

Toxicity of waste gasification bottom ash leachate

Toxicity of waste gasification bottom ash leachate from landfill lysimeters (112 m(3)) was studied over three years. The leachate of grate incineration bottom ash from a parallel setup was used as reference material. Three aquatic organisms (bioluminescent bacteria, green algae and water flea) were used to study acute toxicity. In addition, an ethoxyresorufin-O-deethylase (EROD) assay was performed with mouse hepatoma cells to indicate the presence of organic contaminants. Concentrations of 14 elements and 15 PAH compounds were determined to characterise leachate. Gasification ash leachate had a high pH (9.2-12.4) and assays with and without pH adjustment to neutral were used. Gasification ash leachate was acutely toxic (EC(50) 0.09-62 vol-%) in all assays except in the algae assay with pH adjustment. The gasification ash toxicity lasted the entire study period and was at maximum after two years of disposal both in water flea (EC(50) 0.09 vol-%) and in algae assays (EC(50) 7.5 vol-%). The grate ash leachate showed decreasing toxicity during the first two years of disposal in water flea and algae assays, which then tapered off. Both in the grate ash and in the gasification ash leachates EROD-activity increased during the first two years of disposal and then tapered off, the highest inductions were observed with the gasification ash leachate. The higher toxicity of the gasification ash leachate was probably related to direct and indirect effects of high pH and to lower levels of TOC and DOC compared to the grate ash leachate. The grate ash leachate toxicity was similar to that previously reported in literature, therefore, confirming that used setup was both comparable and reliable.     

Environmental assessment of gas management options at the Old Ämmässuo landfill (Finland) by means of LCA-modeling (EASEWASTE)

The current landfill gas (LFG) management (based on flaring and utilization for heat generation of the collected gas) and three potential future gas management options (LFG flaring, heat generation and combined heat and power generation) for the Old Ämmässuo landfill (Espoo, Finland) were evaluated by life-cycle assessment modeling. The evaluation accounts for all resource utilization and emissions to the environment related to the gas generation and management for a life-cycle time horizon of 100 yr. The assessment criteria comprise standard impact categories (global warming, photo-chemical ozone formation, stratospheric ozone depletion, acidification and nutrient enrichment) and toxicity-related impact categories (human toxicity via soil, via water and via air, eco-toxicity in soil and in water chronic).The results of the life-cycle impact assessment show that disperse emissions of LFG from the landfill surface determine the highest potential impacts in terms of global warming, stratospheric ozone depletion, and human toxicity via soil. Conversely, the impact potentials estimated for other categories are numerically-negative when the collected LFG is utilized for energy generation, demonstrating that net environmental savings can be obtained. Such savings are proportional to the amount of gas utilized for energy generation and the gas energy recovery efficiency achieved, which thus have to be regarded as key parameters. As a result, the overall best performance is found for the heat generation option – as it has the highest LFG utilization/energy recovery rates – whereas the worst performance is estimated for the LFG flaring option, as no LFG is here utilized for energy generation.Therefore, to reduce the environmental burdens caused by the current gas management strategy, more LFG should be used for energy generation. This inherently requires a superior LFG capture rate that, in addition, would reduce fugitive emissions of LFG from the landfill surface, bringing further environmental benefits.     

The biodegradation of lactic acid-based poly(ester-urethanes)

The biodegradability of lactic acid based poly(ester-urethanes) was studied using the headspace test method, which was performed at several elevated temperatures. The poly(ester-urethanes) were prepared using a straight two-step lactic acid polymerization process. The lactic acid is first condensation polymerized to a low molecular weight hydroxyl-terminated telechelic prepolymer and then the molecular weight is increased with a chain extender such as diisocyanate. In the biodegradation studies the effect of different stereostructures (different amounts of D-units in the polymer chain), the length of ester units, and the effect of crosslinking on the biodegradation rate were studied. The results indicate that poly(ester-urethanes) do not biodegrade at 25‡C, but at elevated temperatures they biodegrade well. The different stereostructures and crosslinking have a strong influence on the biodegradation rate. The length of ester units in the polymer chain also affects the biodegradation rate, but much less than crosslinking and stereostructure.