TEMPO-Mediated Oxidation of Norway Spruce and Eucalyptus Pulps: Preparation and Characterization of Nanofibers and Nanofiber Dispersions

This study deals with 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO)-mediated oxidation of cellulose. Softwood and hardwood pulp fibers were suspended in water and oxidized to various extents at pH 10 and 22 °C using sodium hypochlorite in the presence of TEMPO radical and sodium bromide. This reaction system is known to be the most efficient one for the introduction of both surface carboxyl and aldehyde groups. Important relationships between formation of these functional groups and the fibrillation yield, light transmittance of the water dispersions and degree of polymerization of the oxidized softwood and hardwood pulps were established in the present study. A birefringence test confirmed the presence of nanofibers which according to atomic force microscopy analyses had diameters in the 1.6–3.8 nm range.     

Reconstructing the history of 14C discharges from Sellafield: part 1--atmospheric discharges

14C specific activities, above ambient background levels, were determined in individual treerings (corresponding to the years 1950-1999) sectioned from an oak tree that was felled in autumn 1999, from a location 1.5 km east of the Sellafield nuclear fuel reprocessing plant in Cumbria. north-west England. The data were used to produce a new, improved, reconstruction of Sellafield's annual atmospheric 14C discharges between 1951 and 1999, using the most reliable discharge data set (1994-1999) as the primary basis for the determination of a new calibration factor that relates excess 14C activity in individual tree rings to the annual discharge during the corresponding year. The results indicate that the current British Nuclear Fuels plc (BNFL) estimate of total 14C discharges to the atmosphere prior to 1978 is significantly overestimated, while the current estimate of total 14C discharges after 1978 is very similar to that determined in this study. In this study, the total activity of 14C discharged to the atmosphere from Sellafield between 1951 and 1999 is estimated to be 259+/-63 TBq (at 2 std. dev.). The BNFL current estimate is 360TBq.     

Atmospheric monitoring of organochlorine pesticides across some West African countries

Most African countries have ratified the Stockholm Convention on persistent organic pollutants (POPs) and are expected to reduce emissions of POPs such as organochlorine pesticides (OCPs) to the atmosphere. Emerging evidence, however, suggests that there are contemporary sources of OCPs in African countries despite the global ban on these products. This study investigated the atmospheric contamination from OCPs in four West African countries—Togo, Benin, Nigeria, and Cameroon—to ascertain the emission levels of OCPs and the characteristic signatures of contamination. Polyurethane foam (PUF) disk passive air samplers (PAS) were deployed in each country for ca. 55 days in 2012 and analyzed for 25 OCPs. Hexachlorocyclohexanes (HCHs) and DDTs constituted the highest burden of atmospheric OCPs in the target countries, at average concentrations of 441 pg m^?3 (range 23–2718) and 403 pg m^?3 (range 91–1880), respectively. Mirex had the lowest concentration, ranged between 0.1 and 3.3 pg m^?3. The concentration of OCPs in rainy season was higher than in dry season in Cameroon, and presupposed inputs from agriculture during the rainy season. The concentrations of ∑25 OCPs in each country were in the following order: Cameroon > Nigeria > Benin > Togo. There was significant evidence, based on chemical signatures of the contamination that DDT, aldrin, chlordane, and endosulfan were recently applied at certain sites in the respective countries.     

Biological activity of synthetic analogs of tremerogen A-10

The Science of Nature -     

TEMPO-Mediated Oxidation of Hemp Bast Holocellulose to Prepare Cellulose Nanofibrils Dispersed in Water

Hemp bast holocellulose fiber (Cannabis sativa L. Subsp. Sativa) was oxidized by TEMPO (2,2,6,6-tetramethylpiperidine-1-oxyl radical)-mediated oxidation at various NaClO addition levels in water at pH 10. When carboxylate contents of the oxidized products were 1.5–1.7 mmol/g, TEMPO-oxidized cellulose nanofibrils almost completely dispersed at the individual nanofibril were obtained by mechanical disintegration of the TEMPO-oxidized hemp bast holocelluloses in water, where the nanofibrillation yields were 98–100 %. The sugar composition analysis revealed that most of hemicelluloses originally present in the hemp bast holocellulose were degraded and removed from the solid oxidized products, providing almost pure TEMPO-oxidized celluloses. X-ray diffraction patterns of all TEMPO-oxidized hemp bast holocelluloses had the same cellulose I crystal structure and similar crystallinity indices and crystal widths, indicating that carboxylate groups formed by the oxidation were selectively present on the crystalline cellulose microfibril surfaces in the holocellulose. However, the weight recovery ratios and viscosity-average degrees of polymerization of the TEMPO-oxidized hemp bast holocelluloses decreased to 69–59 % and 470–380, respectively, when their carboxylate contents increased to 1.5–1.7 mmol/g by the TEMPO-mediated oxidation. Atomic force microscopy height images showed that the nanofibril widths were 2.7–2.9 nm, and the average nanofibril lengths decreased from 590 to 400 nm as the NaClO addition level was increased from 7.5 to 12.5 mmol/g in the TEMPO-mediated oxidation.