Formation of chlorinated estrones via hypochlorous disinfection of wastewater effluent containing estrone

Chlorinated derivatives of estrone (E1) in the effluent of a municipal sewage treatment plant located in Shizuoka prefecture, Japan were detected by gas chromatography/mass spectrometry using electron impact in selected ion monitoring (GC/MS-EI-SIM) analysis. The concentrations of E1, 2-chloroestrone, 4-chloroestrone and 2,4-dichloroestrone in the effluent sample collected in December 2005 were 60.0 ng l(-1), 4.0 ng l(-1), 14.5 ng l(-1), and 9.8 ng l(-1), respectively. In the effluent sample taken in June 2005, 2,4-dichloroestrone was detected at 5.6 ng l(-1) along with 17.6 ng l(-1) of E1. However, only E1 was detected at 5.9 ng l(-1) in the sample in May 2005. To elucidate the behavior of E1 during the disinfection process with sodium hypochlorite in the sewage treatment plant, we carried out a reaction of E1 with sodium hypochlorite in buffer solutions at pH 7 and 9. As E1 was consumed rapidly, chlorinated estrones were produced and relatively fast formation of 2-chloroestrone, 4-chloroestrone, and 2,4-dichloroestrone was observed. Furthermore, 1,4-estradiene-3,17-dione derivatives were formed from the reaction between 2,4-dichloroestrone and sodium hypochlorite.     

Dioxins in human milk and smoking of mothers

BACKGROUND: The relation between the levels of dioxins in human breast milk and the smoking habits of the mothers is controversial. To clarify this relationship, we analyzed data from the human milk survey in Japan. METHODS: The human milk survey has been conducted in Japan since 1997. Healthy pregnant women aged 20-39 years were recruited and 50 ml of breast milk was collected from them at 30 days after delivery. PCDDs, PCDFs, and dioxin-like PCBs were measured by using GC/MS. The smoking habits of the mothers were established by interviewing them soon after delivery and were classified into four categories: current smokers, ever smokers who quit smoking at the pregnancy, ever smokers who quit smoking before the pregnancy, and never smokers. The levels of dioxins in breast milk were compared in the four categories of smoking among 853 primiparas. In addition, we analyzed the association between dioxin levels and passive smoking among never smokers. The geometric means of the dioxin concentrations were calculated in order to compare the differences between dioxins. RESULTS: The geometric means of dioxin-like PCBs in milk of never smokers was the highest (9.2 pg TEQ/g fat); followed by ever smokers who quit smoking before the pregnancy, ever smokers who quit smoking at the pregnancy, and current smokers (7.5, 7.2, and 6.6 pg TEQ/g fat, respectively). The differences between these levels were statistically significant (ANOVA, p<0.001). No significant difference was observed between the level of dioxins in milk from never smokers subjected to passive smoking status and those who had not experienced passive smoking. CONCLUSION: The levels of dioxin-like PCBs in human milk were negatively related to the smoking habits of mothers.     

Ontogenetic shift in foraging habit of ocean sunfish Mola mola from dietary and behavioral studies

The ocean sunfish (Mola mola) is typically considered to feed on gelatinous zooplankton, but reports in the literature describe various benthic organisms being found in their stomachs. This might reflect ontogenetic dietary shift, as little was known about the foraging habit of this species. We examined their foraging habits using dietary analyses in combination with a behavioral study in Iwate, Japan (39°22′N, 141°58′E) from 2009 to 2010. Our stomach content analyses (n = 17, 31–250 cm total length) suggested that small sunfish (<50 cm) feed on benthic crustaceans, but large sunfish (>200 cm) feed on jellyfish. Larger sunfish showed higher values of both carbon and nitrogen stable isotope ratios. Deployment of accelerometers and animal-borne cameras on small sunfish in July (49–58 cm, n = 5) suggested their possibility of feeding, while they stayed near the seabed. This indicates that small sunfish might feed on benthic preys. Deployment of accelero-magnetometers on large sunfish in July (84–164 cm, n = 4) clarified that the large sunfish in July swam back and forth between the surface and deep water (>100 m). Temporary decelerations, which were considered to be associated with feeding of planktonic prey, were observed in deep water. Whereas deployment of accelero-magnetometers on large sunfish in November (105 cm, n = 3) showed several bursts, they swam within the mixed layer (0–100 m), which might be associated with chasing of rapid prey. These results suggest that ocean sunfish have heterogeneous diets depending on their body size and possibly season.     

Hydrogen sulfide removal by iron containing activated carbon

Activated carbon modified by impregnation with iron (III) chloride solution (Fe‐ACs) were studied to try to raise their adsorption capacity for hydrogen sulfide, a malodorous substance.

The surface area and pore volume of activated carbon were decreased by impregnation, but the amount of hydrogen sulfide adsorbed onto Fe‐AC was larger than that onto raw activated carbon (R‐AC). In particular, a large increase of the amount adsorbed onto Fe‐AC was noted at low equilibrium pressure. It was assumed that the increase of amount of hydrogen sulfide adsorbed onto Fe‐AC was due to the chemical interaction between iron (III) chloride on the pores in addition to the physical adsorption onto pores of activated carbon. Fe‐AC shows a high selectivity for hydrogen sulfide.     

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.     

Manganese toxicity as indicated by visible foliar symptoms of Japanese white birch (Betula platyphylla var. japonica)

For the purpose of a field diagnosis of Mn toxicity, we showed the possibility of using visible foliar symptoms of Japanese white birch (Betula platyphylla var. japonica Hara) as indicator. To examine the relationship between the expression of visible symptoms and leaf Mn concentrations, white birch seedlings were grown under four different Mn levels: 1 mg Mn l-1 as control, 10, 50 and 100 mg Mn l-1. Foliar symptoms of Mn toxicity for white birch were: (1) chlorosis at entire young leaves in the 50 and 100 mg Mn l-1 treatments; and (2) brown speckles at the leaf marginal and interveinal area for old leaves in the treatments greater than 1 mg Mn l-1. Mn preferably accumulated into the leaf marginal and interveinal area, where the brown speckles were observed. The mechanism determining the expression of symptoms seems to be associated with the physiological state related to leaf age as well as Mn distribution and concentration within a leaf.     

Geology-dependent impacts of forest conversion on stream fish diversity

Forest conversion is one of the greatest global threats to biodiversity, and land-use change and subsequent biodiversity declines sometimes occur over a variety of underlying geologies. However, how forest conversion and underlying geology interact to alter biodiversity is underappreciated, although spatial variability in geology is considered an integral part of sustaining ecosystems. We aimed to examine the effects of forest conversion to farmland, the underlying geology, and their interaction on the stream fishes’ diversity, evenness, and abundance in northeastern Japan. We disentangled complex pathways between abiotic and biotic factors with structural equation modeling. Species diversity of stream fishes was indirectly shaped by the interaction of land use and underlying geology. Diversity declined due to nutrient enrichment associated with farmlands, which was mainly the result of changes in evenness rather than by changes in species richness. This impact was strongest in streams with volcanic geology with coarse substrates probably because of the differential responses of abundant stream fishes to nutrient enrichment (i.e., dominance) and the high dependency of these fishes on large streambed materials during their life cycles. Our findings suggest that remediation of deforested or degraded forest landscapes would be more efficient if the interaction between land use and underlying geology was considered. For example, the negative impacts of farmland on evenness were larger in streams with volcanic geology than in other stream types, suggesting that riparian forest restoration along such streams would efficiently provide restoration benefits to stream fishes. Our results also suggest that land clearing around such streams should be avoided to conserve species evenness of stream fishes.     

Role of the bivalveCorbicula japonica in the nitrogen cycle in a mesohaline lagoon

The effect of the bivalveCorbicula japonica on the nitrogen cycle in Lake Shinji, a mesohaline brackish lagoon in Japan, was examined quantitatively based on field surveys and laboratory experiments carried out in the summer of 1982 and 1983. The biomass of the flesh ofC. japonica comprised 97% of the total biomass of the macrozoobenthos in summer. Total biomass ofC. japonica in the lake was estimated 30 986 t fresh wt. The concentration of suspended solids immediately above the lake bottom, whereC. japonica filters the water, was 1.5 to 4 times higher than that in the surface water. In laboratory experiments, the filtration rate was 5.0 litres g dry flesh wt^-1 h^-1, the excretion rates of ammonia and of feces and pseudofeces ofC. japonica were 200×10^-6 g N g dry flesh wt^-1 h^-1 and 33.4 mg dry wt g dry flesh wt^-1 h^-1, respectively at 27°C, the average summer water temperature in the lake. From our study, we estimated thatC. japonica filters almost the same amounts of particulate organic nitrogen produced in the lake by phytoplankton and that supplied from rivers, and that it excretes 30% of filtered nitrogen as feces or pseudofeces and 18% as ammonia.     

Algal growth inhibition by river water pollutants in the agricultural area around Lake Biwa, Japan

An ecotoxicological study of river water discharged from the agricultural area around Lake Biwa was performed by using algal bioassays to guide chemical analysis. Water samples were collected once a week, at least, for 1 year starting in April 1997 and continuing until April 1998. The toxicities of the dissolved and particulate-adsorbed extracts of water samples were evaluated by the algal growth inhibition test and concentrations of individual pesticides were determined. Most of the river water that was collected during the periods when pesticides were applied to the paddy fields caused algal growth inhibition. Some extracts were found to contain herbicides (molinate, mefenacet, simetryn, or esprocarb) as major compounds. According to chemical assay and bioassay, simetryn was identified as the most toxic compound that caused algal growth inhibition.     

Decolorization of mixtures of different reactive textile dyes by the white-rot basidiomycete Phanerochaete sordida and inhibitory effect of polyvinyl alcohol

We tried to decolorize mixtures of four reactive textile dyes, including azo and anthraquinone dyes, by a white-rot basidiomycete Phanerochaete sordida. P. sordida decolorized dye mixtures (200 mg l-1 each) by 90% within 48 h in nitrogen-limited glucose-ammonium media. Decolorization of dye mixtures needed Mn2+ and Tween 80 in the media. Manganese peroxidase (MnP) played a major role in dye decolorization by P. sordida. Decolorization of dye mixtures by P. sordida was partially inhibited by polyvinyl alcohol (PVA) that wastewaters from textile industries often contain. This was caused by an inhibitory effect of PVA on the decolorization of Reactive Red 120 (RR120) with MnP reaction system. Second addition of Tween 80 to the reaction mixtures in the presence of PVA improved the decolorization of RR120. These results suggest that PVA could interfere with lipid peroxidation or subsequent attack to the dye.