A deactivating behavior of TiO2 photocatalysts in NO2 oxidation to HNO3 was studied with use of TiO2 nanoparticulate thin films (0.5−1.5 μm thick) under UV light illumination over 10 h. The photocatalytic activity was decreased with accumulation of HNO3 on the TiO2 surface. For thicker TiO2 films, the deactivation rate was found to be slower. The amount of HNO3 trapped on the TiO2 surface was increased and finally saturated, at which the largest amount of HNO3 was proportional to the thickness of the film. On the basis of the results, we concluded that the produced HNO3, inhibiting the reaction as a physical barrier, must be able to diffuse on the TiO2 surface at a rate of at least more than 1.5 μm h−1, and finally distributes homogeneously on the whole film. The maximum density of HNO3 accumulated on the TiO2 surface was estimated to be ∼2 molecules nm−2 under standard conditions. Finally, when the steady state is reached, the photocatalytic activity remained ∼8% of the initial one.

Recent single-gene-based surveys of deep continental aquifers demonstrated the widespread occurrence of archaea related to Candidatus Methanoperedens nitroreducens (ANME-2d) known to mediate anaerobic oxidation of methane (AOM). However, it is unclear whether ANME-2d mediates AOM in the deep continental biosphere. In this study, we found the dominance of ANME-2d in groundwater enriched in sulfate and methane from a 300-m deep underground borehole in granitic rock. A near-complete genome of one representative species of the ANME-2d obtained from the underground borehole has most of functional genes required for AOM and assimilatory sulfate reduction. The genome of the subsurface ANME-2d is different from those of other members of ANME-2d by lacking functional genes encoding nitrate and nitrite reductases and multiheme cytochromes. In addition, the subsurface ANME-2d genome contains a membrane-bound NiFe hydrogenase gene putatively involved in respiratory H oxidation, which is different from those of other methanotrophic archaea. Short-term incubation of microbial cells collected from the granitic groundwater with C-labeled methane also demonstrates that AOM is linked to microbial sulfate reduction. Given the prominence of granitic continental crust and sulfate and methane in terrestrial subsurface fluids, we conclude that AOM may be widespread in the deep continental biosphere.

Many kinds of proteins have been found in the sieve element–companion cell complexes by the analyses of phloem sap and microscopic observations. The cDNAs, which encode some of these sieve-tube proteins, have already been cloned. As mature sieve elements lack nuclei and most ribosomes, sieve-tube proteins have been hypothesized to be synthesized in the companion cells and then transported to the lumina of the functional sieve tubes through the plasmodesmata connecting the companion cells and sieve elements. Soluble proteins present in the sieve tubes can be collected by several techniques, such as incision or the aphid technique. The composition of the proteins in the phloem sap is unique compared with that of tissue extract, suggesting these proteins have important roles for the development and functions of sieve tubes.