Enhancement of association of organic molecules on silica gel by surface water: surface photoreaction of stilbene

Here, we show that association of stilbene molecules is facilitated by water on silica gel because of hydrophobic interaction and photodimerization becomes the main photochemical process. Irradiation of trans-stilbene (t-1) on silica gel gives cis-stilbene (c-1), phenanthrene (2), benzaldehyde (3), and dimers r-ctt-4 and r-tct-4. The yields of the dimers increase and those of 2 and 3 decrease with an increase in the amount of t-1 loaded on silica gel. Atmospheric oxygen is responsible for the formation of 2 and 3. The yields of the dimers also increase with an increase in the water on a silica-gel surface and change drastically at the point where the percentage of water to silica gel is around 25 wt%. All active sites on a silica-gel surface would be covered completely with 25 wt% of water.     

Deoxyribonuclease activity in seawater and sediment

This paper describes a fluorometric method for assaying deoxyribonuclease (DNase) activity in natural seawater and sediment. DNase activity was detected in a sea-water sample taken from Tokyo Bay (Japan), and in various sediment samples taken from Suruga, Sagami and Tokyo Bays, and from Aburatsubo Inlet. Much more DNase occurred in seawater in a state bound to suspended particles or microbial cells than dissolved free in seawater. Although viable DNA-hydrolyzing bacteria were found to be widely distributed in seawater and sediment, poor correlation existed between the bacterial population and the intensity of DNase activity in the sediments examined. In addition, intensities of DNase activity in various surface sediments had no apparent correlation with the DNA contents and the sediment types. However, a close correspondence was found between the vertical variation of DNase activities and the gradient of DNA contents and of Eh in the core sediment at Aburatsubo Inlet.     

Prediction of physico-chemical properties for PCs/DFs using the UNIFAC model with an alternative approximation for group assignment

The original-type UNIFAC model was used to predict the environmentally important physico-chemical properties of PCDDs/DFs, such as aqueous solubility, Henry's law constant, and 1-octanol/water partition coefficient, through the UNIFAC-derived infinite dilution activity coefficient. In this application, we suggest an alternative approximation that the aromatic ether group AC-O in PCDD/DF molecules is replaced with the aliphatic ether group CH-O, because the AC-O group is not available in the conventional UNIFAC model. With this approximation, the ability of the UNIFAC model to predict those properties was examined by comparing with experimental data. The UNIFAC model provided comparatively good estimation results. From these results, it is shown that the alternative approximation is useful for the UNIFAC estimation of physico-chemical properties for PCDDs/DFs. Furthermore, the predicted solubilities of 2,3,7,8-T4CDD and O8CDD in organic solvents and the co-solvency effect on solubility of PCDDs in methanol/water mixture indicate that the UNIFAC calculation presented here could well predict the physico-chemical properties of PCDDs/DFs in various solution conditions.     

Non-sterile simultaneous saccharification and fermentation of corn leaves and stalks to <Emphasis Type="SmallCaps">l</Emphasis>-lactic acid without external nutrient addition

Fermentation of lignocellulosic biomass requires auxiliary materials, including nutrients, to ensure the proliferation of microorganisms. Nutrients are usually inexpensive, but their contribution to the cost is considerable because of the very low prices of fermentation products, such as bio-ethanol. Using substances present in native lignocellulosic biomass as nutrients for fermentation was proposed and demonstrated. Leaves and stalks of corn plants were used as biomass, and nutrients were recovered as a nutrient solution by soaking them in water before alkaline peroxide pretreatment. Pretreated biomass and the nutrient solution derived from the same lot were used for non-sterile simultaneous enzymatic saccharification and thermophilic l-lactic acid fermentation (SSF). Using the nutrient solution in the saccharification step did not impact sugar recovery, and instead improved sugar yields because of the presence of eluted sugars in the solution. The l-lactic acid yield of 0.33 g g^?1 based on native biomass weight indicated that the nutrient solution functioned as a source of nutrients and sugars, especially as a source of essential phosphorus. Comparatively, autoclaved SSF yielded less or no l-lactic acid, indicating an apparent inhibitive effect derived from the nutrient solution on bacterial growth.     

Potential utilization of riverbed sediments by hydrothermal solidification and its hardening mechanism

Hydrothermal solidification of riverbed sediments (silt) has been carried out in a Teflon (PTFE) lined stainless steel hydrothermal apparatus, under saturated steam pressure at 343–473 K for 2–24 h by calcium hydrate introduction. Tobermorite was shown to be the most important strength-producing constituent of the solidified silt. A longer curing time or a higher curing temperature was shown to be favorable to the tobermorite formation, thus promoting strength development; however, overlong curing time (24 h) seemed to affect the strength development negatively. The hardening mechanism consisted of the crystal growth/morphology evolution during the hydrothermal process. The species dissolved from the silt were precipitated first as fine particles, and then some of the particles seemed to build up the rudimental morphology of calcium silicate hydrate (CSH) gel. The CSH gel, with precipitated particles, appeared to cause some reorganization within the matrix, which made the matrix denser and thus gave an initial strength development. Tobermorite, transformed inevitably from the CSH gel, reinforced the matrix with its interlocked structure, and thus further promoted the strength development.     

Physicochemical properties of selected polybrominated diphenyl ethers and extension of the UNIFAC model to brominated aromatic compounds

The aqueous solubilities (S(w)) at various temperatures from 283 K to 308 K and 1-octanol/water partition coefficients (K(ow)) for four polybrominated diphenyl ethers (PBDEs: 4,4'-dibromodiphenyl ether (BDE-15), 2,2',4,4'-tetrabromodiphenyl ether (BDE-47), 2,2',4,4',5-pentabromodiphenyl ether (BDE-99), and 2,2',4,4',5,5'-hexabromodiphenyl ether (BDE-153)) were measured by the generator column method. The S(w) and K(ow) data revealed the effect of bromine substitution and basic structure on S(w) and K(ow). To estimate the infinite dilution activity coefficients (gamma(i)(w,infinity)) of the PBDEs in water from the S(w) data, enthalpies of fusion and melting points for those compounds were measured with a differential scanning calorimeter. Henry's Law constants (H(w)) of the PBDEs were derived from the determined gamma(i)(w,infinity) and literature vapor pressure data. Some physicochemical characteristics of PBDEs were also suggested by comparing the present property data with that of polychlorinated dibenzo-p-dioxins, brominated phenols and brominated benzenes in past studies. Furthermore, in order to represent different phase equilibria including solubility and partition equilibrium for other brominated aromatic compounds using the UNIFAC model, a pair of UNIFAC group interaction parameters between the bromine and water group were determined from the S(w) and K(ow) data of PBDEs and brominated benzenes. The ability of the determined parameters to represent both properties of brominated aromatics was evaluated.     

Biologically induced Po emission from fresh water

Behavior of Po in fresh waters was examined in laboratory culture experiments using fresh water collected from a small pool, Xi river and Xiqing lake, showing formation of volatile Po compounds followed by emission to air. Addition of tryptone to the fresh water cultures increased the emission of Po considerably along with a growth of microorganisms, suggesting a connection of chemoheterotrophs to Po emission. Participation of photoautotrophs was also considered because Po emission was increased when NaHCO3 was added to the fresh water cultures. The emission behavior of Po and S in these experiments appeared in different ways. The quantity of Po emitted was comparable to the previous culture experiments (Momoshima, Song, Osaki & Maeda, Environ. Sci. Technol., 35, 2956-2960, 2001) in which artificial culture medium containing 3% NaCl was used and inoculated with sea sediment extract. The biological support for Po emission, thus, would be a general phenomenon in fresh water as well as a seawater environment and is possibly a source for atmospheric Po.     

Formation of cyanide ion or cyanogen chloride through the cleavage of aromatic rings by nitrous acid or chlorine. IX. On the reactions of chlorinated, nitrated, carboxylated or methylated benzene derivatives with hypochlorous acid in the presence of ammonium ion

Chlorinated, nitrated, carboxylated or methylated benzenes, phenols and anilines reacted with chloramine to give cyanogen chloride, independently of the positions and the numbers of the substituents. Among these compounds, 2,4,6-trichlorophenol afforded cyanogen chloride in a relatively high yield of 13.3%, and the intermediates in the reaction were 2,6-dichloro-1,4-benzoquinone-4-(N-chloro)imine and 4,6-dichloro-1,2-benzoquinone-2-(N-chloro)-imine, of which the latter was the main intermediate.     

Personal exposure monitoring to nitrogen dioxide

Measurement of personal exposure to nitrogen dioxide for short and long term was made with a sensitive NO₂ passive sampler by volunteer housewives and office workers in different seasons. These measurements were compared with the simultaneous measurement of outdoor and indoor concentration of the participants. A common result over all the measurements is the potential effect of using an unvented space heater to increase personal exposure. Mean personal exposure and indoor concentration are higher than outdoor levels elevated by the samples exposed to pollutant produced from the heater. Without an NO₂ source indoors, the mean outdoor concentrations are always highest among the data of measurement. A time-weighted indoor/outdoor activity model gives modestly improved estimates of personal exposure over those predicted from measured indoor concentrations alone.     

Thermal neutron fluence from ultra low-level γ-ray spectrometry of spoons activated during the JCO criticality accident at Tokai-mura in 1999

During the JCO-accident in Tokai-mura in 1999, the surrounding village was irradiated by an uncontrolled neutron flux. At some locations in that village, the thermal neutron flux was determined retrospectively by measurement of the very low activity of ⁵¹Cr and ⁶⁰Co in stainless-steel spoons using γ-ray spectrometry in underground laboratories. Activities determined in the HADES underground facility are presented here, together with calibrations performed using a well-defined thermal neutron flux to directly estimate the fluence of thermal neutrons independent of most assumptions. The results show measurable ⁵¹Cr in three samples and ⁶⁰Co in four samples taken from locations at distances of up to 430 m from the accident location despite the elapse of 4 half-lives of ⁵¹Cr before measurement. Effects of air transport of the samples were considered and shown to be negligible.