Endocrine effects generated by photooxidation of coplanar biphenyls in water using titanium dioxide

The oxidative photodegradation behaviors of selected three coplanar polychlorinated biphenyls (PCBs), (CB77, CB81, and CB169) using titanium dioxide (TiO(2)) in water were investigated. The main purposes were to clarify the structural relation between the original PCBs and the intermediates derived by TiO(2) oxidation and to evaluate the estrogenic and thyroid hormonal activity in the treated three coplanar PCBs during the oxidative reactions. Approximately 90% of the three coplanar PCBs decomposed within 180 min. Intermediates from the decomposition of the three coplanar PCBs, such as some hydroxylated-PCBs (OH-PCBs), carboxylic intermediates, phenolic intermediates, and other intermediates produced by the cleavage of a benzene ring were identified and quantified. In the degradation pathways, the produced amounts of OH-PCBs increased within 60 min of irradiation time. The estrogenic activity and thyroid hormonal activity of the intermediates from the three coplanar PCBs in water at 0, 60, 120, 180 and 240 min of irradiation time were assessed by using a yeast two-hybrid assay system for human estrogen receptor alpha (hERalpha) and human thyroid hormone receptor alpha (hTRalpha). The maximal estrogenic activities were induced by the solutions of decomposed PCBs with irradiation time at 60-120 min similar and slightly lower than those after the irradiation time. We found that the solutions occuring during the irradiation times of 60-120 min contained several 4-OH-PCBs substituted with OH and Cl at para- and para'-positions having estrogenic activity. The thyroid hormonal activity was not detected in the decomposed three coplanar PCBs solutions.     

Burrowing behaviour inferred from feeding traces of the opheliid polychaete <Emphasis Type="Italic">Euzonus</Emphasis> sp. as response to beach morphodynamics

The distribution of the opheliid polychate Euzonus sp. and the orientation of its feeding traces were examined in a wave-dominated Pacific sandy beach of central Japan by periodical sampling from June to December 2006. This species occurred constantly within sediments at mid-intertidal level, although its horizontal distributions were variable depending on changes of the beach profiles. These facts indicate that Euzonus sp. moved horizontally seaward or landward within the substratum in response to the shifting beach face due to changes of wave conditions from the ocean. By analysing the orientation of feeding traces, the adaptive burrowing behaviour of this species in response to beach topographical changes was revealed: Euzonus worms burrowed horizontally to various directions in a relatively stable condition of beach topography, whereas they moved preferentially landward under a heavy erosion of the beach face by a storm. These findings indicate that the burrowing behaviour prevents Euzonus sp. from excessive burial and washing out due to the beach morphodynamics.     

Formation of estrogenic products from environmental phthalate esters under light exposure

Phthalate esters (PEs) have been suspected to be environmental endocrine disruptors and the detailed mechanism remains unclear. The activities of these chemicals can be enhanced through chemical modification under the environmental conditions. We demonstrate that PEs acquire unequivocal estrogenic activity by light exposure. Through UV exposure of an aqueous PE solution, one active photoproduct, identified as 4-hydroxyPE (PE-4OH) based on its characteristic UV and mass spectra, was detected in an estrogen receptor alpha-dependent transactivation assay. PE-4OH was effectively generated by UV 290 nm. The PE-4OH production accompanied H2O2 generation in a UV dose-dependent manner. Both PE and UV irradiation were indispensable in the generation of H2O2. Addition of H2O2 to the PE solution increased PE-4OH production under UV irradiation. The PE-4OH production was also observed in the PE reaction with the Fenton reagent generating hydroxyl radical without UV irradiation. The proposed mechanism for PE-4OH production based on these results is such that by PE-mediated photosensitization H2O2 is generated from O2 and H+ and decomposed to hydroxyl radical, thus oxidizing the PE benzene ring. The PEs-4OH are remarkably active estrogenic products of PEs and would be involved in ER-mediated endocrine disruption.     

A study on chest injury mechanism and the effectiveness of a headform impact test for pedestrian chest protection from vehicle collisions

This study was aimed at investigating the injury mechanism of pedestrian chests in collisions with passenger vehicles of various frontal shapes and examining the influence of the local structural stiffness on the chest injury risk by using the headform impact test at the chest contact area of the vehicle. Three simulations of vehicle to pedestrian collisions were conducted using three validated pedestrian finite element (FE) models of three pedestrian heights of 177 (AM50th), 165 and 150 cm and three FE vehicles models representing a one-box vehicle, a minicar and a medium car. The validity of the vehicle models was evaluated by comparing the headform acceleration against the measured responses from headform impact tests. The chest impact kinematics and the injury mechanisms were analyzed in terms of the distribution of the von Mises stress of the ribcage and in terms of the chest deflections. The chest contact locations on the front panel and the bonnet top were identified in connection to the causation of rib fractures. The risk of rib fractures was predicted by using the von Mises stress distribution. The headform impact tests were carried out at the chest contact area on the front panel and bonnet to examine the safety performance with respect to pedestrian chest protection. In simulations of the one-box vehicle to pedestrian collisions, the chest was struck directly by the frontal structure at a high velocity and deformed substantially, since a shear force was generated by the stiff windshield frame. The acceleration of the headform was related to the rib deflections. The injury threshold of the ribcage deflection (42 mm) corresponded to the headform average acceleration of 68 G. In the minicar collision, the chest was struck with the bonnet top and cowl area at a low velocity, and the deformation was small due to the distributed contact force between the chest and the bonnet top. Besides, the ribcage deformation was too small for bridging a relation between the headform accelerations and rib deflections. In the medium car collision, the deformation mode of the chest was similar to that in the minicar collision. The chest collided with the bonnet top at a low velocity and deformed uniformly. The deflection of the ribs had an observable correlation with the headform accelerations measured in the headform impact tests. The frontal shape of a vehicle has a large influence on a pedestrian’s chest loadings, and the chest deformation depends on the size of the pedestrian and the stiffness of the vehicle. The one-box passenger vehicle causes a high chest injury risk. The headform impactor test can be utilized for the evaluation of the local stiffness of a vehicle’s frontal structure. The reduction of the headform acceleration is an effective measure for pedestrian chest protection for specific shapes of vehicles by efficacy in modifying the local structural stiffness.     

Pedestrian head impact conditions depending on the vehicle front shape and its construction--full model simulation

For the evaluation of pedestrian protection, the European Enhanced Vehicle-Safety Committee Working Group 17 report is now commonly used. In the evaluation of head injuries, the report takes into account only the hood area of the vehicle. But recent pedestrian accident data has shown the injury source for head injury changing to the windshield and A-pillar from the hood. The head contact points are considered to fall on a parallel to the front shape of the vehicle along the lateral direction, but the rigidity of the outer side construction is different from the center area. The purpose of this study is to consider the reason for the change in injury source for recent vehicle models. The head contact points and contact conditions, speed and angle, are thought to be influenced not only by the vehicle's geometry, but also its construction (rigidity). In this study, vehicle-pedestrian impact simulations were calculated with a finite element model for several hitting positions, including the outer side areas. Full dummy sled tests were conducted to confirm the simulation results. These results show that, for impacts at the outer sides of the vehicle, the head contact points are more rearward than at the vehicle center. In addition, the speed and angle of the head contact were found to be influenced by the pedestrian height.     

Cervical vertebral motions and biomechanical responses to direct loading of human head

There is little known data characterizing the biomechanical responses of the human head and neck under direct head loading conditions. However, the evaluation of the appropriateness of current crash test dummy head-neck systems is easily accomplished. Such an effort, using experimental means, generates and provides characterizations of human head-neck response to several direct head loading conditions. Low-level impact loads were applied to the head and face of volunteers and dummies. The resultant forces and moments at the occipital condyle were calculated. For the volunteers, activation of the neck musculature was determined using electromyography (EMG). In addition, cervical vertebral motions of the volunteers have been taken by means of X-ray cineradiography. The Ethics Committee of Tsukuba University approved the protocol of the experiments in advance. External force of about 210 N was applied to the head and face of five volunteers with an average age of 25 for the duration of 100 msec or so, via a strap at one of four locations in various directions: (1) an upward load applied to the chin, (2) a rearward load applied to the chin without facial mask, (3) a rearward load applied to the chin with the facial mask, and (4) a rearward load applied to the forehead. The same impact force as those for the human volunteers was also applied to HY-III, THOR, and BioRID. We found that cervical vertebral motions differ markedly according to the difference in impact loading condition. Some particular characteristics are also found, such as the flexion or extension of the upper cervical vertebrae (C0, C1, and C2) or middle cervical vertebrae (C3-C4), showing that the modes of cervical vertebral motions are markedly different among the different loading conditions. We also found that the biofidelity of dummies to neck response characteristics of the volunteers at the low-level impact loads is in the order of BioRID, THOR, and HY-III. It is relevant in this regard that the BioRID dummy was designed for a low-severity impact environment, whereas THOR and HY-III were optimized for higher-severity impacts.     

Finding upper-level sets in cellular surface data using echelons and saTScan

Across a spectrum of contemporary contexts from public health to landscape ecology and natural resources, there is need for objective determination of elevated occurrence in phenomena such as disease incidence and biodiversity. Occurrences of such phenomena constitute response surfaces, but data regarding the surface is typically acquired in a cellular framework. The cells may comprise a regular grid, or may be of irregular shapes such as counties in which statistics are collected. Echelons are a topologically based approach to systematic determination of spatial structure in a step surface. Spatial scan statistics are a probability-based approach to the same issue when interest lies in a rate variable. Here we examine the use of echelons both separately and in conjunction with the SaTScan implementation of spatial scan statistics for purposes of determination and visualization of upper-level sets. Consideration is given to both conventional geographic space and to the cellular pseudo-space of contingency tables for ordered categorical variables. Received: August 2002 / Revised: July 2005     

Reproductive disturbance of Japanese bumblebees by the introduced European bumblebee Bombus terrestris

The European bumblebee, Bombus terrestris, is an invasive eusocial species whose distribution is expanding greatly beyond its native range because numerous colonies are imported to or locally produced in non-native countries for pollination of agricultural crops. Closely related species exist in Japan where the unrestricted import and use of B. terrestris has resulted in the establishment of wild colonies. Laboratory studies previously showed that B. terrestris and Japanese native species can copulate and produce fertilized eggs. Although these eggs do not hatch, the interspecific mating can cause a serious reproductive disturbance to native bumblebees. In this study, we determined the frequencies of interspecies mating between B. terrestris males and native bumblebee queens in the wild on the islands of Hokkaido and Honshu by analyzing the DNA sequences of spermatozoa stored in spermathecae of native queens. We found that 20.2% of B. hypocrita hypocrita queens and 30.2% of B. hypocrita sapporoensis queens had spermatozoa of B. terrestris males in their spermathecae. Given that a Bombus queen generally mates only once in her life, such high frequencies of interspecific mating with B. terrestris pose serious threats to the populations of native bumblebees in Japan.     

Scenario analysis for reduction of pollutant load discharged from a watershed by recycling of treated water for irrigation

A model in which a river model was layered on a distributed model (double-layered model) was developed to analyse the transport of water and pollutants (nitrogen,phosphorus,and BOD as organic matter) in watersheds and rivers.The model was applied to the watershed of Abragafuchi Lake,Japan,where serious water pollution has occurred over three decades,and the applicability of the model was demonstrated.Scenarios of recycling of sewage treated-water into agriculture to reduce pollutant load discharged into the lake were analysed.The results showed that irrigating paddy fields with the sewage-treated water could contribute to conserving water and reducing pollutant load,with reduction rate in BOD,nitrogen,and phosphorus ranging from 6%–36%,16%–46%,and 18%–51%,respectively.Particularly,the results indicated that,irrigating paddy fields with the treated water during non-cropping periods and the accompanying reduction in withdrawn water from the river were more effective in reducing pollutant loads discharged into the lake.Further study is required on the effect of recycled water on crop cultivation and soil conditions for safe implementation.     

Unexpected release of HNO<Subscript>3</Subscript> and related species from UV-illuminated TiO<Subscript>2</Subscript> surface into air in photocatalytic oxidation of NO<Subscript>2</Subscript>

We have discovered that HNO₃ and related species are released from the TiO₂ surface into air in the TiO₂ photocatalytic oxidation of NO₂ (1 ppm) under continuous UV light illumination (1 mW cm⁻²) by dehumidifying the outlet gas of the reaction and analyzing the recovered condensate liquid by ion chromatography. The origin of the HNO₃ recovered in the dehumidifier could not be explained by a simple desorption of HNO₃ overproduced on the TiO₂ surface. The produced HNO₃ must be activated on the TiO₂ surface and causing the unidentified reaction.