Sequential Determination of Trace Metals in Sea Water by Inductively Coupled Plasma Mass Spectrometry After Electrothermal Vaporization of their Dithiocarmabamate Complexes in Methyl Isobutyl Ketone

A sensitive method for sequential determination of V, Mn, Fe, Co, Ni, Cu, Zn, Mo and Sb in sea water using an inductively coupled plasma mass spectrometry (ICP-MS) after electrothermal vaporization of their dithiocarbamate complexes in methyl isobutyl ketone (MIBK) has been investigated. All analyte elements were simultaneously concentrated 20 fold in a single extract and introduced into the plasma using a graphite rod electrothermal vaporizer (ETV). A sensitivity enhancement due to a chemical modification using a mixed modifier of palladium nitrate and magnesium nitrate was observed for all analyte elements. The limits of detection of the method ranged from 2 ng l-1 for Co to 329 ng l-1 for V. For the replicate determinations of the analyte elements in a sea water sample, the repeatability was within 10% (as a coefficient variation), except for V (12.8%). The recovery test performed on a sea water sample resulted in values ranging from 87% for Sb to 119% for V. With the exception of Mo, the application of this method for the determination of the analyte elements in sea water samples collected from the surface to the depth of 5000 m at the sampling station of 34°12.08N, 141°57.50E (Oct. 12, 1994) in the northwest Pacific Ocean resulted in vertical distributions and concentration ranges which were in a good agreement with those reported in literatures.     

An Urban Atmospheric Diffusion Model for Traffic-Related Emission Based on Mass-Conservation and Advection-Diffusion Equations

This paper proposes an atmospheric diffusion model for traffic-related emission in urban areas within a few hundred meters from relevant roads. The model adopts the mass-conservation (MC) principle for the velocity calculation and the advection-diffusion (AD) equation for the concentration calculation. This MC+AD combination was chosen to achieve fast calculation for complex geometries. To compensate for the inherent deficiencies of MC and AD, as many known properties possible of turbulent boundary-layer flow over obstacles are incorporated into the MC calculation, and the diffusivity in AD is derived from the velocity spectrum as a function of distance from the emission source. The model is evaluated against wind-tunnel experiments ranging from point-source emission in uniform urban canopy to along-road emission in real city geometries. The model performs well in relatively simple configurations, but the performance deteriorates considerably as the complexity increases. However, in real city geometries, the model exhibits distinctly better performance in terms of statistical indices than a conventional Gaussian-plume model that neglects the effect of individual buildings. The model is therefore a viable option for environmental assessment.     

Removal of PCDDs/DFs and dl-PCBs in MWI fly ash by heating under vacuum

Temperature dependence of PCDD/DF and dioxin-like polychlorinated biphenyl (dl-PCB) concentrations in fly ash from a municipal waste incinerator (MWI) heated under vacuum has been investigated as a function of sample temperature ranging from T(s)=425 to 800 K to find out if PCDDs/DFs in fly ash evaporate and are trapped in a liquid nitrogen-cooled trap. The results show that more than 99.98% of PCDDs/DFs in TEQ is removed from fly ash by vacuum heat treatment at T(s)>650 K for 4 h. Almost no PCDDs/DFs were detected in the liquid nitrogen-cooled trap. Homologue distributions indicate that dechlorination/hydrogenation (DCH) reactions proceed in fly ash at T(s)>450 K. Arrhenius rate parameters for the DCH reactions have been determined for each homologue assuming that only DCH reactions occur. The fly ash heated under vacuum at 650 or 800 K was reheated at 573 K (300 degrees C) in a stream of dry or humid air to see how much PCDDs/DFs and dl-PCBs are regenerated. We have found that (1) PCDDs/DFs are regenerated in both 650 K and 800 K treated fly ash, whereas dl-PCBs are regenerated in 650 K treated fly ash, (2) formation of PCDFs predominates over that of PCDDs or dl-PCBs, and (3) less chlorinated homologues are abundant for PCDDs/DFs and dl-PCBs.     

Accumulation of polychlorinated naphthalenes in domestic animal related samples

Concentrations of polychlorinated naphthalene (PCN) congeners were measured in domestic animal related samples such as feed ingredients, mixed feed and animal fat. Mean concentrations of total PCNs in feed ingredients ranged from 500 to 1500 pg g(-1) lipid wt with a high concentration found in fish meal. Total PCN concentrations were similar among mixed feeds, which ranged from 98 to 110 pg g(-1) lipid wt. The total PCN concentration in chickens was more than twice the amount in pigs. Tetra-CNs were the predominant homologues in all samples. Biomagnification of higher chlorinated PCN congeners, especially penta- and hexa-CNs, was a few fold greater in chickens compared to pigs. The estimated concentrations of 2,3,7,8-tetrachloro dibenzo-p-dioxin equivalents (TEQs) of some selected PCNs in feed ingredients, mixed feeds, chickens and pigs were 0.008 to 0.063, 0.001 to 0.002, 0.033 and 0.011 pg g(-1) lipid wt, respectively. Based on predicted luciferase inducing potency for each PCN congener, the estimated PCN-TEQs in feed ingredients and animal fat were similar to those that were estimated from selected PCNs.     

Determination of PCDD/Fs and dioxin-like PCBs in fish oils for feed ingredients by congener-specific chemical analysis and CALUX bioassay

The present research was intended to determine the suitability of the CALUX assay as a screening method for dioxins in fish oil used as a feed ingredient in Japan. Alteration of TEQ in fish oil according to newly proposed toxic equivalency factors (TEF) is also discussed. In the analysis, polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) and dioxin-like polychlorinated biphenyls (DL-PCBs) in 41 fish oil samples were determined by using high-resolution gas chromatography/high-resolution mass spectrometry (HRGC/HRMS) and CALUX bioassay. The mean TEQ values derived from 1998 WHO-TEF of PCDD/Fs and DL-PCBs were 2.6 and 9.9 pg g(-1) (ww), respectively. The levels of TEQ derived from the recently re-evaluated 2005 WHO-TEF were slightly lower than those of the former in both groups. Notably, the contribution of mono-ortho DL-PCBs to total 2005 WHO-TEQ was considerably decreased compared to the case of 1998 WHO-TEQ, resulting from the reduction in its TEF values, while the non-ortho DL-PCBs contribution was increased. The mean TEQ determined by CALUX assay for PCDD/Fs was approximately three times higher, whereas DL-PCBs was approximately two times lower than WHO-TEQ determined by HRGC/HRMS; the sum of PCDD/Fs and DL-PCBs was very similar by both methods. The correlation coefficients of TEQ between the CALUX assay and HRGC/HRMS analysis were 0.84, 0.89, and 0.90 for PCDD/Fs, DL-PCBs, and the sum, respectively. These results suggest that the CALUX assay is a very useful method for the screening of dioxin-related compounds in fish oils.     

Regional-specific emission inventory for NH3, N2O, and CH4 via animal farming in South, Southeast, and East Asia

Ammonia, nitrous oxide, and methane emission from animal farming of South, Southeast, and East Asia, in 2000, was estimated at about 4.7 Tg NH₃–N, 0.51 Tg N₂O–N, and 29.9 Tg CH₄, respectively, using the FAO database and countries’ statistic databases as activity data, and emission factors taking account of regional characteristics. Most of these atmospheric components, up to 60–80%, were produced in China and India. Pakistan, Bangladesh, and Indonesia, which were large source countries next to China and India, contributed more than a few percent of total emission of each atmospheric component. The largest emission livestock were cattle whose contribution was considerably high in South, Southeast, and East Asia; more than one-fourth of ammonia and nitrous oxide emissions: more than half of methane emission. The other major livestock for nitrous oxide and ammonia emissions were pigs. For methane emission, buffaloes were second source livestock. To provide spatial distributions of these gases, the emissions of county and district level were allocated into each 0.5° grid by means of the weighting by high-resolution land cover datasets. The regions with considerable high emissions of all components were able to be found at the Ganges delta and the Yellow River basin. The spatial distributions for ammonia and nitrous oxide emissions were similar but had a substantial difference from methane distribution.     

A global analysis of residential heating and cooling service demand and cost-effective energy consumption under different climate change scenarios up to 2050

Climate change and energy service demand exert influence on each other through temperature change and greenhouse gas emissions. We have consistently evaluated global residential thermal demand and energy consumption up to the year 2050 under different climate change scenarios. We first constructed energy service demand intensity (energy service demand per household) functions for each of three services (space heating, space cooling, and water heating). The space heating and cooling demand in 2050 in the world as a whole become 2.1–2.3 and 3.8–4.5 times higher than the figures for 2010, whose ranges are originated from different global warming scenarios. Cost-effective residential energy consumption to satisfy service demand until 2050 was analyzed keeping consistency among different socio-economic conditions, ambient temperature, and carbon dioxide (CO₂) emission pathways using a global energy assessment model. Building shell improvement and fuel fuel-type transition reduce global final energy consumption for residential thermal heating by 30% in 2050 for a 2 °C target scenario. This study demonstrates that climate change affects residential space heating and cooling demand by regions, and their desirable strategies for cost-effective energy consumption depend on the global perspectives on CO₂ emission reduction. Building shell improvement and energy efficiency improvement and fuel fuel-type transition of end-use technologies are considered to be robust measures for residential thermal demand under uncertain future CO₂ emission pathways.     

Perfluorinated organic compounds in human blood serum and seminal plasma: a study of urban and rural tea worker populations in Sri Lanka

Concentrations and accumulation of 13 fluorinated organic compounds (FOCs) in human sera and seminal plasma were measured in an Asian developing country, Sri Lanka. Six of the FOCs, PFOS (perfluorooctanesulfonate), PFHS (perfluorohexanesulfonate), PFUnA (perfluoroundecanoic acid), PFDA (perfluorodecanoic acid), PFNA (perfluorononanoic acid) and PFOA (perfluorooctanoic acid), were detected in all of the sera samples. Measurable quantities of two main perfluorosulfonates, PFOS and PFHS, were found in all seminal plasma samples. The detection frequency of the predominant perfluoroalkylcarboxylate, PFOA, in seminal plasma was >70%. Accumulation of PFOS in sera was significantly positively correlated with PFOA, PFHS and PFNA. Positive linear regressions were also found between PFNA and PFUnA and PFNA and PFDA suggesting that these compounds may have a similar origin of exposure and accumulation. Significantly positive associations were observed for partitioning of both PFOS and PFNA between sera and seminal plasma. The accumulation of FOCs was not significantly different in sera from Colombo (urban population) and Talawakele (rural conventional tea workers). However, the Haldummulla population (rural organic tea workers) had relatively lower exposure to FOCs compared to the other two groups, urban and rural conventional tea workers. Concentrations of FOCs in Sri Lanka were similar to those reported for industrialized countries suggesting that human exposure to such chemicals is widespread even in developing countries. The novel finding of FOCs in human seminal plasma implies that further studies are needed to determine whether long-term exposure in humans can result in reproductive impairments.     

Site selection in CO2 ocean sequestration: Dependence of CO2 injection rate on eddy activity distribution

Site selection in CO₂ ocean sequestration is examined based on the idea that a site where injected CO₂ is efficiently diluted is favourable in reducing/avoiding biological impacts. Simulations of CO₂ injection into several sites by an eddy-resolving oceanic general circulation model (OGCM) show that the maximum CO₂ concentration differs by a factor of 10 among sites. The distribution of eddy activity is the most important causative factor producing the geographical differences in CO₂ dilution. Based on the relationship between the maximum CO₂ concentration and eddy activity, we estimated the distribution of the maximum CO₂ injection rate by a proposed method, which does not cause chronic impacts on biota. Around Japan, extensive ocean volume has the potential to dilute 20 million tonnes per year without chronic impacts, and some areas can be injected with 80 million tonnes per year.