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.     

Aerosol particle number concentration measurements in five European cities using TSI-3022 condensation particle counter over a three-year period during health effects of air pollution on susceptible subpopulations

In this study, long-term aerosol particle total number concentration measurements in five metropolitan areas across Europe are presented. The measurements have been carried out in Augsburg, Barcelona, Helsinki, Rome, and Stockholm using the same instrument, a condensation particle counter (TSI model 3022). The results show that in all of the studied cities, the winter concentrations are higher than the summer concentrations. In Helsinki and in Stockholm, winter concentrations are higher by a factor of two and in Augsburg almost by a factor of three compared with summer months. The winter maximum of the monthly average concentrations in these cities is between 10,000 cm(-3) and 20,000 cm(-3), whereas the summer min is approximately 5000-6000 cm(-3). In Rome and in Barcelona, the winters are more polluted compared with summers by as much as a factor of 4-10. The winter maximum in both Rome and Barcelona is close to 100,000 cm(-3), whereas the summer minimum is > 10,000 cm(-3). During the weekdays the maximum of the hourly average concentrations in all of the cities is detected during the morning hours between 7 and 10 a.m. The evening maxima were present in Barcelona, Rome, and Augsburg, but these were not as pronounced as the morning ones. The daily maxima in Helsinki and Stockholm are close or even lower than the daily minima in the more polluted cities. The concentrations between these two groups of cities are different with a factor of about five during the whole day. The study pointed out the influence of the selection of the measurement site and the configuration of the sampling line on the observed concentrations.     

Gas-phase degradation of CCl<Subscript>4</Subscript>, CHCl<Subscript>3</Subscript> and CH<Subscript>2</Subscript>Cl<Subscript>2</Subscript> over metallic Fe

We studied the hydrolysis of gas-phase carbon tetrachloride (CCl₄), chloroform (CHCl₃), and dichloromethane (CH₂Cl₂) over a metallic Fe surface for its application in combination with air stripping and soil vapour extraction. The effects of chlorocarbon concentration, type and preparation of the iron-containing material, humidity, and temperature on process performance are reported. The hydrolysis of chlorinated methane derivatives is catalysed by metallic iron resulting in a noticeable decrease of the reaction temperature. The reaction kinetics were found to be consistent with the Langmuir-Hinshelwood model.     

Diversifying forest expertise: forest journals narrating policy change

ABSTRACT

During policy change, the role of the actors communicating the change to different audiences is accentuated. The media plays an increasing role, either as an actor or by providing a stage for other actors. In particular, specialised journals represent an influential, albeit understudied, sphere of policy studies. We use the narrative policy framework complemented with frame analysis to trace how specialised media can affect policy implementation through implicit suggestions for action. Using this combined approach, we analyse how specialised forest journals, which are the most important forest information source for Finnish forest owners, have conveyed the renewal of forest legislation in Finland. The core message of the journals is that forest owners should, despite their new freedom granted by the reform, rely on experts rather than experimenting when managing their forests. This suggests that the media contributes to a path-dependent continuation of a forest policy that is based on a rationalistic exploitation ethos. The innovative potential, which the policy change aimed at encouraging, is thereby partially undermined. However, the analysis of the narratives also reveals that forest expertise and professionalism are diversifying. This notion is important as diversity can eventually lead to narratives supporting more fundamental change in forests management.     

Geographic variation in maternal investment: acidity affects egg size and fecundity in Rana arvalis

Environmental-stress-mediated geographic variation in reproductive parameters has been little studied in natural vertebrate populations outside the context of climatic variation. Based on life-history theory, an increase in the degree of environmental stress experienced by a population should lead to (1) a shift in reproductive allocation from fecundity to offspring quality, (2) stronger trade-offs between reproductive parameters, and (3) changes in the relationship between female phenotype and maternal investment. To test these predictions, we investigated geographic variation in maternal investment of moor frogs (Rana arvalis) in relation to breeding site acidity (pH 4-8). We found that mean egg size increased and clutch size and total reproductive output (TRO) decreased with increasing acidity among 19 Swedish moor frog populations. Tests for variation and co-variation in maternal investment and female size and age in 233 females from a subset of four acid origin (AO) and four neutral origin (NO) populations revealed that clutch size and TRO increased with female size in both acid and neutral environments. However, in AO populations, egg size also increased with female size, and clutch size and TRO with female age, whereas in NO populations, egg size increased with female age. The strength of the egg-size-clutch-size tradeoff tended to be stronger in AO than in NO females as expected if the former experience stronger environmental constraints. All in all, these results suggest that environmental acidification selects for investment in larger eggs at a cost to fecundity, imposes negative effects on reproductive output, and alters the relationship between female phenotype and maternal investment.     

Changes in Lumbriculus variegatus metabolites under hypoxic exposure to benzo(a)pyrene,chlorpyrifos and pentachlorophenol: Consequences on biotransformation

The regulation of endogenous metabolites is still not fully understood in aquatic invertebrates exposed concurrently to toxicants and hypoxia. Despite the prevalence of hypoxia in the aquatic environment, toxicity estimations seldom account for multiple stressors thereby differing from natural conditions. In this study, we examined the influence of hypoxia (<30% O₂) on contaminant uptake and the composition of intracellular metabolites in Lumbriculus variegatus exposed to benzo(a)pyrene (B(a)P, 3 μg L⁻¹), chlorpyrifos (CPF, 100 μg L⁻¹) or pentachlorophenol (PCP, 100 μg L⁻¹). Tissue extracts of worms were analyzed for 123 metabolites by gas chromatography–mass spectrometry and metabolite levels were then related to treatments and exposure time. Hypoxia markedly increased the accumulation of B(a)P and CPF, which underlines the significance of oxygen in chemical uptake. The oxygen effect on PCP uptake was less pronounced. Succinate and glycerol-3-phosphate increased significantly (p < 0.0001) following hypoxic treatment, whereas sugars, cysteine, and cholesterol were effectively repressed. The buildup of succinate coupled with the corresponding decline in intracellular 2-oxo- and 2-hydroxy glutaric acid is indicative of an active hypoxia inducible factor mechanism. Glutamate, and TCA cycle intermediates (fumarate, and malate) were disturbed and evident in their marked suppression in worms exposed concurrently to hypoxia and PCP. Clearly, hypoxia was the dominant stressor for individuals exposed to B(a)P or CPF, but to a lesser extent upon PCP treatment. And since oxygen deprivation promotes the accumulation of different toxicants, there may be consequences on species composition of metabolites in natural conditions.     

Potential biodiversity benefits from international programs to reduce carbon emissions from deforestation

Deforestation is the second largest anthropogenic source of carbon dioxide emissions and options for its reduction are integral to climate policy. In addition to providing potentially low cost and near-term options for reducing global carbon emissions, reducing deforestation also could support biodiversity conservation. However, current understanding of the potential benefits to biodiversity from forest carbon offset programs is limited. We compile spatial data on global forest carbon, biodiversity, deforestation rates, and the opportunity cost of land to examine biodiversity conservation benefits from an international program to reduce carbon emissions from deforestation. Our results indicate limited geographic overlap between the least-cost areas for retaining forest carbon and protecting biodiversity. Therefore, carbon-focused policies will likely generate substantially lower benefits to biodiversity than a more biodiversity-focused policy could achieve. These results highlight the need to systematically consider co-benefits, such as biodiversity in the design and implementation of forest conservation programs to support international climate policy.     

Gene expression responses of paper birch (Betula papyrifera) to elevated CO2 and O3 during leaf maturation and senescence

Gene expression responses of paper birch (Betula papyrifera) leaves to elevated concentrations of CO₂ and O₃ were studied with microarray analyses from three time points during the summer of 2004 at Aspen FACE. Microarray data were analyzed with clustering techniques, self-organizing maps, K-means clustering and Sammon's mappings, to detect similar gene expression patterns within sampling times and treatments. Most of the alterations in gene expression were caused by O₃, alone or in combination with CO₂. O₃ induced defensive reactions to oxidative stress and earlier leaf senescence, seen as decreased expression of photosynthesis- and carbon fixation-related genes, and increased expression of senescence-associated genes. The effects of elevated CO₂ reflected surplus of carbon that was directed to synthesis of secondary compounds. The combined CO₂ + O₃ treatment resulted in differential gene expression than with individual gas treatments or in changes similar to O₃ treatment, indicating that CO₂ cannot totally alleviate the harmful effects of O₃.     

First Europe-wide correlation analysis identifying factors best explaining the total nitrogen concentration in mosses

In this study, the indicative value of mosses as biomonitors of atmospheric nitrogen (N) depositions and air concentrations on the one hand and site-specific and regional factors which explain best the total N concentration in mosses on the other hand were investigated for the first time at a European scale using correlation analyses. The analyses included data from mosses collected from 2781 sites across Europe within the framework of the European moss survey 2005/6, which was coordinated by the International Cooperative Programme on Effects of Air Pollution on Natural Vegetation and Crops (ICP Vegetation). Modelled atmospheric N deposition and air concentration data were calculated using the Unified EMEP Model of the European Monitoring and Evaluation Programme (EMEP) of the Convention on Long-range Transboundary Air Pollution (CLRTAP). The modelled deposition and concentration data encompass various N compounds. In order to assess the correlations between moss tissue total N concentrations and the chosen predictors, Spearman rank correlation analysis and Classification and Regression Trees (CART) were applied. The Spearman rank correlation analysis showed that the total N concentration in mosses and modelled N depositions and air concentrations are significantly correlated (0.53 ≤ r_s ≤ 0.68, p < 0.001). Correlations with other predictors were lower than 0.55. The CART analysis indicated that the variation in the total N concentration in mosses was best explained by the variation in NH₄⁺ concentrations in air, followed by NO₂ concentrations in air, sampled moss species and total dry N deposition. The total N concentrations in mosses mirror land use-related atmospheric concentrations and depositions of N across Europe. In addition to already proven associations to measured N deposition on a local scale the study at hand gives a scientific prove on the association of N concentration in mosses and modelled deposition at the European scale.     

Dependence of home outdoor particulate mass and number concentrations on residential and traffic features in urban areas

The associations between residential outdoor and ambient particle mass, fine particle absorbance, particle number (PN) concentrations, and residential and traffic determinants were investigated in four European urban areas (Helsinki, Athens, Amsterdam, and Birmingham). A total of 152 nonsmoking participants with respiratory diseases, not exposed to occupational pollution, were included in the study, which comprised a 7-day intensive exposure monitoring period of both indoor and home outdoor particle mass and number concentrations. The same pollutants were also continuously measured at ambient fixed sites centrally located to the studied areas (fixed ambient sites). Relationships between concentrations measured directly outside the homes (residential outdoor) and at the fixed ambient sites were pollutant-specific, with substantial variations among the urban areas. Differences were more pronounced for coarse particles due to resuspension of road dust and PN, which is strongly related to traffic emissions. Less significant outdoor-to-fixed variation for particle mass was observed for Amsterdam and Birmingham, predominantly due to regional secondary aerosol. On the contrary, a strong spatial variation was observed for Athens and to a lesser extent for Helsinki. This was attributed to the overwhelming and time-varied inputs from traffic and other local sources. The location of the residence and traffic volume and distance to street and traffic light were important determinants of residential outdoor particle concentrations. On average, particle mass levels in suburban areas were less than 30% of those measured for residences located in the city center. Residences located less than 10 m from a street experienced 133% higher PN concentrations than residences located further away. Overall, the findings of this multi-city study, indicated that (1) spatial variation was larger for PN than for fine particulate matter (PM) mass and varied between the cities, (2) vehicular emissions in the residential street and location in the center of the city were significant predictors of spatial variation, and (3) the impact of traffic and location in the city was much larger for PN than for fine particle mass.