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.     

Relationship between different size classes of particulate matter and meteorology in three European cities

Evidence on the correlation between particle mass and (ultrafine) particle number concentrations is limited. Winter- and spring-time measurements of urban background air pollution were performed in Amsterdam (The Netherlands), Erfurt (Germany) and Helsinki (Finland), within the framework of the EU funded ULTRA study. Daily average concentrations of ambient particulate matter with a 50% cut off of 2.5 microm (PM2.5), total particle number concentrations and particle number concentrations in different size classes were collected at fixed monitoring sites. The aim of this paper is to assess differences in particle concentrations in several size classes across cities, the correlation between different particle fractions and to assess the differential impact of meteorological factors on their concentrations. The medians of ultrafine particle number concentrations were similar across the three cities (range 15.1 x 10(3)-18.3 x 10(3) counts cm(-3)). Within the ultrafine particle fraction, the sub fraction (10-30 nm) made a higher contribution to particle number concentrations in Erfurt than in Helsinki and Amsterdam. Larger differences across the cities were found for PM2.5(range 11-17 microg m(-3)). PM2.5 and ultrafine particle concentrations were weakly (Amsterdam, Helsinki) to moderately (Erfurt) correlated. The inconsistent correlation for PM2.5 and ultrafine particle concentrations between the three cities was partly explained by the larger impact of more local sources from the city on ultrafine particle concentrations than on PM2.5, suggesting that the upwind or downwind location of the measuring site in regard to potential particle sources has to be considered. Also, relationship with wind direction and meteorological data differed, suggesting that particle number and particle mass are two separate indicators of airborne particulate matter. Both decreased with increasing wind speed, but ultrafine particle number counts consistently decreased with increasing relative humidity, whereas PM2.5 increased with increasing barometric pressure. Within the ultrafine particle mode, nucleation mode (10-30 nm) and Aitken mode (30-100 nm) had distinctly different relationships with accumulation mode particles and weather conditions. Since the composition of these particle fractions also differs, it is of interest to test in future epidemiological studies whether they have different health effects.     

Quantitative analysis of environmental factors in differential weighing of blank Teflon filters

Mass differences less than 100 microg must be correctly measured in gravimetric analysis of particles collected on filters. Even small variations in mass measurement may contribute significant errors to calculated concentrations. In addition to the collected particles, a number of other factors affect the observed mass difference between the measurements before and after sampling. The most often controlled of these factors are static charge, temperature, and humidity. Using 951 laboratory blank filter weights, we have statistically analyzed these and other factors that affect the observed filter weight. Some of these are controllable or correctable; others are not and enter into the final results as errors. The standard deviation of differential blank filter weighing after applying all corrections was 2.7 microg. The most important correctable factors are air buoyancy variation and filter storage time. When weighing blank Teflon filters at relative humidity < 50%, these are an order of magnitude more important than weighing-room humidity. Using field blank filters in each weighing batch could control these three factors but also doubles the errors caused by balance random variation and filter handling contamination, because four weighing measurements and the handling of two filters are needed to obtain one corrected differential mass result.     

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.     

Effects of Land Use Changes on the Landscape Composition: A Comparison Between Finnish and Russian Karelia

During the last 50 years the practising and intensity of agriculture and forestry have differed considerably between Finnish and Russian Karelia. We studied the effects of different land use practices on the landscape composition in the two countries using the road transect sampling along four study routes (99-121 km) between 1997 and 1999. Effective environmental management in Finland has resulted in more distinct agricultural land types, more even distribution of the different age classes of forests, and the higher abundance of coniferous forests. Fields (mean percentage of the landscape: Finland 28%, Russia 13%), clearcuts and sapling stands (15%, 6%), and young forests (23%, 9%) were more typical elements of the Finnish landscape, whereas settlements (9%, 13%), semi-natural grasslands (3%, 7%), and mature forests (20%, 49%) were more characteristic of the Russian landscape. Landscape-level differences between the two countries may have various effects on the diversity of fauna and flora inhabiting Finnish and Russian Karelia.     

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.     

Silver nanoparticles: behaviour and effects in the aquatic environment

This review summarises and evaluates the present knowledge on the behaviour, the biological effects and the routes of uptake of silver nanoparticles (Ag NPs) to organisms, with considerations on the nanoparticle physicochemistry in the ecotoxicity testing systems used. Different types of Ag NP syntheses, characterisation techniques and predicted current and future concentrations in the environment are also outlined. Rapid progress in this area has been made over the last few years, but there is still a critical lack of understanding of the need for characterisation and synthesis in environmental and ecotoxicological studies. Concentration and form of nanomaterials in the environment are difficult to quantify and methodological progress is needed, although sophisticated exposure models show that predicted environmental concentrations (PECs) for Ag NPs in different environmental compartments are at the range of ng L(-1) to mg kg(-1). The ecotoxicological literature shows that concentrations of Ag NPs below the current and future PECs, as low as just a few ng L(-1), can affect prokaryotes, invertebrates and fish indicating a significant potential, though poorly characterised, risk to the environment. Mechanisms of toxicity are still poorly understood although it seems clear that in some cases nanoscale specific properties may cause biouptake and toxicity over and above that caused by the dissolved Ag ion. This review concludes with a set of recommendations for the advancement of understanding of the role of nanoscale silver in environmental and ecotoxicological research.     

Air emissions of ammonia and methane from livestock operations: valuation and policy options

The animal husbandry industry is a major emitter of ammonia (NH3), which is a precursor of fine particulate matter (PM2.5)--arguably, the number-one environment-related public health threat facing the nation. The industry is also a major emitter of methane (CH4), which is an important greenhouse gas (GHG). We present an integrated process model of the engineering economics of technologies to reduce NH3 and CH4 emissions at dairy operations in California. Three policy options are explored: PM offset credits for NH3 control, GHG offset credits for CH4 control, and expanded net metering policies to provide revenue for the sale of electricity generated from captured methane (CH4) gas. Individually these policies vary substantially in the economic incentives they provide for farm operators to reduce emissions. We report on initial steps to fully develop the integrated process model that will provide guidance for policy-makers.