Polychlorinated dibenzo-p-dioxins,polychlorinated dibenzofurans and non-ortho,mono-ortho chlorine substituted biphenyls in Japanese human liver and adipose tissue

We measured PCDDs/DFs levels in Japanese human livers and adipose tissues in 1999, and TEQ were calculated with WHO TEF. The mean total levels of PCDDs/DFs in livers and adipose tissues were 57 pg TEQ/g on a lipid basis and 49 pg TEQ/g on a lipid basis, respectively. 1,2,3,6,7,8-HxCDD, 1,2,3,4,6,7,8-HpCDD, OCDD, 2,3,4,7,8-PeCDF, 1,2,3,4,7,8-HxCDF, 1,2,3,6,7,8-HxCDF, 2,3,4,6,7,8-HxCDF, 1,2,3,7,8,9-HxCDF and 1,2,3,4,6,7,8-HpCDF concentrations in livers considerably differed from those in 1989 (p < 0.05). The mean non-ortho-chlorine substituted biphenyls levels showed 20 pg TEQ/g on a lipid basis and 17 pg TEQ/g on a lipid basis in livers and adipose tissues, respectively. In livers, the mean of 3,3',4,4'-TCB concentrations was 131 pg/g on a lipid basis, and 7.7-fold higher than that in 1989. The mean total mono-ortho-chlorine substituted biphenyls level was 13.0 pg TEQ/g on a lipid basis in livers and 21.6 pg TEQ/g on a lipid basis in adipose tissues. 3,3',4,4',5-PeCB and 3,3',4,4',5,5'-HxCB levels decreased in adipose tissues, and 3,3',4,4',5-PeCB level only decreased in livers. PCDDs, PCDFs, and mono- and non-ortho-chlorine substituted biphenyls levels may have decreased in livers and adipose tissues because of a governmental policy on dioxins discharge for the decade. Then, we estimated the correlations of PCDDs, PCDFs and the related compound levels between livers and adipose tissues. The correlative PCDDs congeners may have had a similar behavior to that between liver and adipose tissue. On the contrary, most PCDFs isomers may have different behavior between liver and adipose tissue, while 2',3,4,4',5-PeCB (IUPAC No. 123) may also have a different behavior between liver and adipose tissue.     

Stabilities of 58 volatile organic compounds in fused-silica-lined and SUMMA polished canisters under various humidified conditions

Fused-silica-lined (FSL) canisters and SUMMA polished (SUMMA) canisters were compared for the recoveries and the stabilities of 58 volatile organic compounds (VOCs) at low ppbv (volume/volume) levels under various humidified conditions using a three-stage preconcentration method followed by GC-MS analysis. The target VOCs included non-polar VOCs (e.g. halogenated hydrocarbons and aromatic hydrocarbons) and polar VOCs (e.g. alcohols, ketones, esters, ethers, nitriles and thiols). The three-stage preconcentration method was initially optimized for simultaneous analysis of non-polar and polar VOCs because determination of canister stability is dependent on the accuracy of analytical measurements. The method showed good linearity over the concentration range from 1 to 25 ppbv for all target analytes, and the correlation coefficients were higher than 0.9974. The method detection limits ranged from 0.023 to 0.39 ppbv. The test mixtures loaded in both type of canisters (n = 3) had concentrations of 1.7-2.5 ppbv per compound at ambient pressure under various humidified conditions (%RH = 1.6, 8.0, 27, 39, 53 and >99% with excess water present). All canister samples were initially analyzed on day 0 (after 6-12 h). The effect of competitive adsorption of water vapor and polar VOCs on active sites of interior surface was remarkably observed for SUMMA canisters. Polar VOCs had a greater requirement for water vapor to be present. The RH percentages that ensured good recovery on day 0 were RH > 8% for non-polar VOCs and RH > 27% for polar VOCs (except alcohols under the condition of RH > 99%). All thiols were not recovered from SUMMA canisters under all conditions. FSL canisters showed good recoveries of more than 86% for all VOCs under all conditions on day 0 (except alcohols under the condition of RH > 99%). The recoveries of alcohols in both canisters under the condition of RH > 99% displayed relatively low recoveries in the range 25-76% because of the partitioning effect into condensed water. The canister samples under the conditions of RH 8.0, 27, 53 and > 99% were analyzed for the stability test on days 3, 7, 14 and 28 after loading. All non-polar VOCs were reasonably stable in the FSL canisters under all examined conditions over 28 days. However, several polar VOCs that have relatively lower vapor pressure, e.g. MIBK, butyl acetate and alcohols except ethanol, showed unstable characteristics under relatively dry conditions (RH 8 and 27%) during 28 days. RH > 53% was needed to ensure good stabilities of all analytes except thiols with the recoveries of > 80% over 28 days for both canisters. Although the FSL canister showed good recoveries of more than 86% for thiols on day 0, drastic degradations were observed after day 3 and they were not detected after day 14.     

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.     

Experimental assessment of factors influencing microhabitat selection by the two tidepool fishes Oligocottus maculosus and O. snyderi

Oligocottus maculosus Girard and O. snyderi Greeley are two similar tidepool fishes with differing, but overlapping, intertidal distribution patterns. The factors influencing microhabitat selection and distribution patterns were experimentally assessed to elucidate the mechanisms by which the two species partition the resources of the intertidal environment. O. snyderi displays a much more rigid substrate-cover requirement. This, combined with its stenothermal nature serve to strongly restrict the intertidal distribution of this species. O. maculosus has a more generalized substrate-cover requirement and is also known to be eurythermal and euryhaline. Thus, O. maculosus is a ubiquitous intertidal species. Other behavioral attributes of O. maculosus, such as its tide-related locomotor activity and preference for shallow water, facilitate its particular intertidal distribution pattern. Similar depth preferences or tide-related activity were not observed in O. snyderi. Interspecific competition and related agonistic behavior were absent from both species and are probably not important to their microhabitat selection and intertidal distribution patterns.Based on a portion of a dissertation submitted in partial fulfillment of the requirements for the Ph.D. degree at the University of British Columbia, Vancouver, B.C., Canada     

Formation of PCDDs and PCDFs during the combustion of polyvinylidene chloride and other polymers in the presence of HCl

PVDC and three non-chlorinated polymers (PP, PET, and PA) were incinerated at 700-850 degrees C in a laboratory-scale quartz tubular furnace in the presence of HCl (ca. 500 ppm congruent with 0.8 mg/l), and the gas-phase formation of PCDD/Fs, their putative precursors and their homologue profiles were investigated. The addition of HCl had little or no apparent effect on the level of PCDD/Fs formation during PVDC combustion, and their homologue profiles were quite different from those of the three non-chlorinated polymers. With PVDC, O8CDD and particularly O8CDF were by far most prevalent, apparently as a result of the selective formation of the precursors. With each of the three non-chlorinated polymers, combustion at 800 degrees C or higher in the presence of HCl resulted in PCDD/Fs formation at levels equaling or exceeding those observed with PVDC. In trials made with one of them (PP) under the same conditions but using a large polymer sample (100 mg vs 20 mg in all other trials), the level of PCDD/Fs formation was far higher than with the smaller polymer samples, and thus demonstrated the importance of appropriate combustion conditions for polymer incineration.     

Degradation of organophosphoric esters in leachate from a sea-based solid waste disposal site

Degradation of organophosphoric esters (OPEs) in leachate from a sea-based solid waste disposal site was investigated by laboratory experiment. Aryl-phosphates, tricresyl phosphate and triphenyl phosphate, in leachate rapidly decreased to less than the detection limit within 20 days under aerobic condition, suggesting high biodegradability. These phosphates also decreased in sterilized leachate, which suggested a contribution to degradation by reactions (adsorption and chemical degradation) with chemicals in the leachate. Concerning alkyl-phosphates, tributyl phosphate decreased rapidly after one week, which is considered to have been caused by biodegradation. Tris-2-ethylhexyl phosphate and tris-2-butoxyethyl phosphate decreased slowly in all samples but that of sterilized distilled water. This however, suggested contribution of biodegradation because the velocity of decrease in the leachate was higher than in control samples. Among chloro alkylphosphates, decrease of tris-2-chloroethyl phosphate and tris-dichloropropyl phosphate were observed though it was not obvious whether by biodegradation or not. Decrease of tris-2-chloropropyl phosphate (TCPP) was not observed for 80 days suggesting that TCPP remains in the leachate over a long period of time. Except for aryl-phosphates decrease of OPEs was not observed under anaerobic condition. It was considered that the composition ratio and the behavior of OPEs in leachate in the field reflects the biological and chemical degradation as well as the chemical properties of OPEs.     

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.