Lignin structural variation in hardwood species

A comprehensive lignin structure analysis of ten industrially relevant hardwood species is presented. Milled wood lignin (MWL) was isolated from each species using a modified protocol and all milled wood lignin preparations were analyzed through quantitative (13)C NMR spectroscopy, elemental analysis, methoxyl analysis, sugar analysis, and nitrobenzene oxidation. Nitrobenzene oxidation and ozonation were carried out on extractive-free wood, alkali-extracted wood, milled wood lignin, and alkali-extracted lignin. Milled wood lignin isolated by the modified protocol was found to be representative of the total lignin in alkali-extracted wood. Significant variations in lignin structures, such as syringylpropane/guaiacylpropane ratio (S/G ratio), arylglycerol-β-aryl ether (β-O-4), degree of condensation, and elemental and methoxyl contents, were found among the hardwood species studied. These structural variations among species appear to be correlated to a single factor, the syringyl/guaiacyl ratio. A new method to predict the S/G ratio of total lignin in wood was developed, using a calibration line established by the syringaldehyde/vanillin (S/V) ratio (nitrobenzene oxidation) and the S/G ratio ((13)C NMR) of milled wood lignin (MWL).     

Pollution impacts on bird population density and species diversity at four non-ferrous smelter sites

Non-ferrous smelters pose a potential hazard for breeding bird populations, but comprehensive analyses of the impacts on bird population densities around smelter sites are currently lacking. We measured with point counts bird population densities around four smelter sites in Russia (Monchegorsk, Karabash and Revda) and Finland (Harjavalta) to explore the relationships between bird population density/species diversity and exposure level quantified by the potentially bioavailable copper concentrations in forest litter. Total bird densities, bird biomasses and species diversities decreased in the vicinity of all three Russian smelters. In Harjavalta, there were no pollution-related trends in total bird density or biomass, although species diversity (species number and Shannon’s index) decreased towards the pollution source. In general, the four smelters showed negative effects on bird populations in decreasing order of impact as follows: Monchegorsk > Karabash > Revda > Harjavalta, reflecting the amount of current and past emissions and consequent habitat change at each site. Our results suggest that around copper–nickel and copper smelters the pollution impact on bird diversity is accelerated when the litter copper level exceeds 1000 μg/g. However, even though bird densities and diversities reflected the exposure levels in our study, they were not associated with litter copper concentrations in a strictly dose-dependent manner, indicating that copper itself is not a primary cause for the changes in bird communities, but rather the combined effect of multiple pollutants on birds and especially on the resources necessary for breeding, such as food and suitable habitat.     

Bolometric infrared photoresponse of suspended single-walled carbon nanotube films

The photoresponse in the electrical conductivity of a single-walled carbon nanotube (SWNT) film is dramatically enhanced when the nanotube film is suspended in vacuum. We show here that the change in conductivity is bolometric (caused by heating of the SWNT network). Electron-phonon interactions lead to ultrafast relaxation of the photoexcited carriers, and the energy of the incident infrared (IR) radiation is efficiently transferred to the crystal lattice. It is not the presence of photoexcited holes and electrons, but a rise in temperature, that results in a change in resistance; thus, photoconductivity experiments cannot be used to support the band picture over the exciton model of excited states in carbon nanotubes. The photoresponse of suspended SWNT films is sufficiently high that they may function as the sensitive element of an IR bolometric detector.     

Quantitative characterization of a hardwood milled wood lignin by nuclear magnetic resonance spectroscopy

The structure of Eucalyptus grandis milled wood lignin (MWL) was investigated by 2D 1H-13C HSQC, HMQC, and 1H-1H TOCSY correlation NMR techniques and by quantitative 13C NMR as well as by the permanganate oxidation degradation technique. The combination of 2D NMR and quantitative 13C NMR spectroscopy of nonacetylated and acetylated lignin preparations allowed reliable identification and calculation of the amount of different lignin structures. About 85% of side-chain moieties were estimated on the structural level. This information was substantiated by data on the quantity of various functional groups and interunit linkages as a whole. A modified method for calculation of the h:g:s ratio has been suggested and compared with previously suggested approaches. E. grandis MWL has been determined to have an h:g:s ratio of 2:36:62. The amounts of various phenolic/etherified noncondensed/condensed guaiacyl and syringyl moieties were approximately estimated. E. grandis MWL contained approximately 0.60/Ar of beta-O-4 moieties along with small amounts of other structural units such as pino/syringyresinol (0.03/Ar), phenylcoumaran (0.03/Ar), and spirodienone (0.05/Ar). The degree of condensation was estimated at approximately 21%; the main condensed structures are 4-O-5 moieties (approximately 0.09/Ar). The structure of E. grandis MWL was compared with those of other lignin preparations isolated from various hardwoods.     

Does Impact of Point Polluters Affect Growth and Reproduction of Herbaceous Plants?

Sedimentprofiles of the last 4,000–14,000 years are presented from three dimictic lakes in Mecklenburg-Vorpommern (North-eastern Germany). Sedimentological composition, major trace elements and nutrients as well as parameter for core chronology (palynology, ¹⁴C-AMS) were investigated in order to reconstruct the historical development of the lakes during the Holocene. Palynological results reflect different human settlement phases and environmental changes from the late Pleistocene to the Subatlantic. Since the Middle Ages, a permanent settlement in the catchment area resulted in higher sedimentation rates in the three lakes. Variations in sediment composition like organic matter, carbonate and mineral content were caused by different land management techniques and natural changes in the catchment area. The phosphorus accumulation increased in the upper sediment layers, but the highest phosphorus accumulations were not found in the industrial phase, but in older sediments associated with human settlement activities in the catchment area. The heavy metals lead and zinc increase in the uppermost part of all three lakes reflecting the atmospheric anthropogenic input during the last 150–200 years.     

Organic phosphorus species in humic acids of mountain soils along a toposequence in the Northern Caucasus

Organic P was investigated in humic acids extracted from mountain soils developed in the subalpine, upper subalpine and alpine zones of the Northern Caucasus. P contents of humic acids varied between 3.4 and 14.2 g P kg^?1, depending on P contents of the parent vegetation and on site conditions. Organic P was accumulated at sites where microbial activity is restrained due to soil acidity, low soil temperature and hydromorphy.³¹ P NMR spectroscopy revealed that orthophosphate monoesters were the dominent P species (72–85% of extract- able P), orthophosphate diesters amounted to 12–21%, and phospho- nates ranged between 0 and 9%. Humic acids of soils under cold and wet climatic conditions showed highest concentrations in phospho- nates and orthophosphate diesters. Hence, the accumulation of organo-P in the Caucasian mountain soils was partly due to increasing proportions of potentially available organic P species.     

Critical Loads of Acidity for Forest Ecosystems of North Asia

Critical loads of acidity were calculated using the PROFILE model to assess the forest ecosystem sensitivity to acid deposition in the Asian part of Russia — Siberia. The main input parameters and the output were mapped. At present atmospheric inputs of acid forming pollutants to the study territory are mainly related to transregional and transboundary pollution from Europe. It was shown that the most sensitive to acid loading are ecosystems of the Tundra zone and of the East Sayan mountains' coniferous forests with dystric cambisols and gleysoils, critical loads of actual acidity (CL(Ac)) = 0–0.3 keq/ha/yr. The most tolerant ecosystems are ecosystems of deciduous forests with podsoluvisols, luvisols and humic luvisols of South Taiga zone in West Siberia, CL(Ac) = 3.5–7.0 keq/ha/yr. Generally the values of critical loads are increasing from the North to the South and from the East to the West following the bioproductivity, annual soil temperature and alkalinity of deposition increases.     

A comprehensive approach for quantitative lignin characterization by NMR spectroscopy

A detailed approach for the quantification of different lignin structures in milled wood lignin (MWL) has been suggested using a combination of NMR techniques. 1H-13C heteronuclear multiple quantum coherence and quantitative 13C NMR of nonacetylated and acetylated spruce MWL have been found to have a synergetic effect, resulting in significant progress in the characterization of lignin moieties by NMR. About 80% of side chain moieties, such as different beta-O-4, dibenzodioxocin, phenylcoumaran, pinoresinol, and others, have been identified on the structural level. The presence of appreciable amounts of alpha-O-alkyl and gamma-O-alkyl ethers has been suggested. Although the quantification of various condensed moieties was less precise than for side chain structures, reliable information can be obtained. Comparison of the calculated results with known databases on spruce MWL structure shows that the suggested approach is rather informative and comparable with the information obtained from the combination of various wet chemistry methods. Discrepancies between the results obtained in this study and those previously published are discussed.