Determination of irradiated reactor uranium in soil samples in Belarus using 236U as irradiated uranium tracer

This work presents experimental results on the distribution of irradiated reactor uranium from fallout after the accident at Chernobyl Nuclear Power Plant (NPP) in comparison to natural uranium distribution in different soil types. Oxidation processes and vertical migration of irradiated uranium in soils typical of the 30 km relocation area around Chernobyl NPP were studied using 236U as the tracer for irradiated reactor uranium and inductively coupled plasma mass spectrometry as the analytical method for uranium isotope ratio measurements. Measurements of natural uranium yielded significant variations of its concentration in upper soil layers from 2 x 10(-7) g g(-1) to 3.4 x 10(-6) g g(-1). Concentrations of irradiated uranium in the upper 0-10 cm soil layers at the investigated sampling sites varied from 5 x 10(-12) g g(-1) to 2 x 10(-6) g g(-1) depending on the distance from Chernobyl NPP. In the majority of investigated soil profiles 78% to 97% of irradiated "Chernobyl" uranium is still contained in the upper 0-10 cm soil layers. The physical and chemical characteristics of the soil do not have any significant influence on processes of fuel particle destruction. Results obtained using carbonate leaching of 236U confirmed that more than 60% of irradiated "Chernobyl" uranium is still in a tetravalent form, ie. it is included in the fuel matrix (non-oxidized fuel UO2). The average value of the destruction rate of fuel particles determined for the Western radioactive trace (k = 0.030 +/- 0.005 yr(-1)) and for the Northern radioactive trace (k = 0.035 + 0.009 yr(-1)) coincide within experimental errors. Use of leaching of fission products in comparison to leaching of uranium for study of the destruction rate of fuel particles yielded poor coincidence due to the fact that use of fission products does not take into account differences in the chemical properties of fission products and fuel matrix (uranium).     

基于脉冲电晕放电技术的硫氰化物分解与氮转化

针对含高浓度硫氰酸盐的废水/废液,采用高效的物化技术实现化学转化,避免生物过程因毒性抑制所需要的稀释作用,作为预处理工艺提供厌氧氨氧化的水质条件.以配制的硫氰酸盐模拟废水作为研究对象,采用自主搭建的脉冲电晕放电(PCD)装置,从构建厌氧氨氧化适配条件的目的出发,考察了不同pH条件下含氮污染物经PCD处理随时间的动态转化规律,以及SCN~--N降解副产物(SO_4~(2-)和HCO~-_3浓度)对NH~+_4-N降解的影响,并拟合了不同条件下NH~+_4-N的降解动力学.结果表明,PCD技术利用原位产生的O_3和·OH能氧化包括SCN~--N和NH~+_4-N在内的还原态含氮化合物为NO~-_3-N,pH的增高有利于氧化反应的进行;反应过程中产生的SO_4~(2-)和HCO~-_3对NH~+_4-N的氧化具有显著的抑制作用,HCO~-_3的抑制效应要高于SO_4~(2-).研究表明,对于高SCN~-废水的处理,PCD技术可作为厌氧氨氧化工艺的预处理技术,在规避毒性抑制与构造水质特征方面表现出优越性.     

The last polar dinosaurs: high diversity of latest Cretaceous arctic dinosaurs in Russia

A latest Cretaceous (68 to 65 million years ago) vertebrate microfossil assemblage discovered at Kakanaut in northeastern Russia reveals that dinosaurs were still highly diversified in Arctic regions just before the Cretaceous–Tertiary mass extinction event. Dinosaur eggshell fragments, belonging to hadrosaurids and non-avian theropods, indicate that at least several latest Cretaceous dinosaur taxa could reproduce in polar region and were probably year-round residents of high latitudes. Palaeobotanical data suggest that these polar dinosaurs lived in a temperate climate (mean annual temperature about 10°C), but the climate was apparently too cold for amphibians and ectothermic reptiles. The high diversity of Late Maastrichtian dinosaurs in high latitudes, where ectotherms are absent, strongly questions hypotheses according to which dinosaur extinction was a result of temperature decline, caused or not by the Chicxulub impact.     

Development and comparison of methods using MS scan and selective ion monitoring modes for a wide range of airborne VOCs

Adsorbent sampling with analysis by thermal desorption, gas chromatography and mass spectrometry (TD/GC/MS) offers many advantages for volatile organic compounds (VOCs) and thus is increasingly used in many applications. For environmental samples and other complex mixtures, the MS detector typically is operated in the scan mode to aid identification of co-eluting compounds. However, scan mode does not achieve the optimal sensitivity, thus compounds occurring at low concentrations may not be detected. This paper develops and evaluates the application of a more sensitive TD/GC/MS method using selective ion monitoring (SIM) that is applicable to VOC mixtures found in ambient and indoor air. Based on toxicity and prevalence, 94 VOCs (including terpenes, aromatic, halogenated and aliphatic compounds) were selected as target compounds. Two analytical methods were developed: a conventional full scan method for ions from 29 to 270 m/z; and a SIM method using 16 time windows and different ions selected for the compounds in each window. Both methods used the same Tenax GR adsorbent sampling tubes, TD and GC parameters, and target and qualifier ions. Laboratory tests determined calibrations, method detection limits (MDLs), precisions, recoveries and storage stability. Field tests compared scan and SIM mode analyses for duplicate samples of indoor air in 51 houses and outdoor air at 41 sites. Statistical analyses included the development of error/precision models. The laboratory tests showed that most compounds demonstrated excellent precision (<10% for concentrations exceeding approximately 0.5 microg m(-3)), good linearity, near identical calibrations for scan and SIM modes, a wide dynamic range (up to 1500 microg m(-3)), and negligible storage losses after 1 month (7 compounds showed moderate losses). SIM mode MDLs ranged from 0.004 to 0.27 microg m(-3), representing a modest (1.1 to 22-fold) improvement compared to scan mode. However, in field tests the SIM method detected significantly more compounds (e.g., styrene and chloroform). Error models fit most compounds and allow quantification of errors at selected percentiles. Overall, while the new SIM method is somewhat time-consuming to develop, it offers greater sensitivity and maintains the high selectivity of traditional scan methods.     

Trends of brominated diphenyl ethers in fresh and archived Great Lakes fish (1979-2005)

While few environmental measurements of brominated diphenyl ethers (BDEs) were completed prior to the mid-1990s, analysis of appropriately archived samples might enable the determination of contaminant trends back to the introduction of these chemicals. In this paper, we first investigate the stability of BDEs in archived frozen and extracted fish samples, and then characterize trends of these chemicals in rainbow smelt (Osmerus mordax) and lake trout (Salvelinus namaycush) in each of the Great Lakes between 1979 and 2005. We focus on the four most common congeners (BDE-47, 100, 99 and 153) and use a change-point analysis to detect shifts in trends. Analyses of archived fish samples yielded precise BDE concentration measurements with only small losses (0.8% per year in frozen fish tissues, 2.2% per year in refrigerated extracts). Trends in fish from all Great Lakes showed large increases in BDE concentrations that started in the early to mid-1980s with fairly consistent doubling times (generally 2-4 years except in Lake Erie smelt where levels increased very slowly), though concentrations and trends show differences by congener, fish species and lake. The most recent data show that accumulation rates are slowing, and concentrations of penta- and hexa-congeners in trout from Lakes Ontario and Michigan and smelt from Lake Ontario started to decrease in the mid-1990s. Trends in smelt and trout are evolving somewhat differently, and trout concentrations in the five lakes are now ranked as Michigan>Superior=Ontario>Huron=Erie, and smelt concentrations as Michigan>Ontario>Huron>Superior>Erie. The analysis of properly archived samples permits the reconstruction of historical trends, congener distributions, biomagnification and other information that can aid the understanding and management of these contaminants.     

Catalytic TiO2 oxidation of ethanethiol for environmentally begnin air pollution control of sulphur compounds

Volatile organic compounds containing reduced sulphur such as thiols and thioethers are released mostly from biological activities and a number of manufacturing processes, such as papermaking and petroleum refining. Environmentally benign and cost-effective air pollution control technology for reduced sulphur compounds is still a topic of research, e.g., in pulp and paper industry. Due to its advantages, photocatalytic oxidation over titanium dioxide presents a potential alternative for the air treatment strategies. The temperature influence on the reaction pathway and kinetics of gas-phase photocatalytic oxidation and thermal catalytic decomposition of ethanethiol over Degussa P25 TiO₂ was established by a continuous flow method in a simple tubular reactor at temperatures from 373 to 453 K. Kinetic parameters for ethanethiol were: adsorption enthalpy −45 kJ mol⁻¹ and activation energy 42 kJ mol⁻¹. Sulphur dioxide, carbon monoxide, carbon dioxide, acetic acid and water were identified as by-products.     

Biomarkers of carcinogenic contaminants in baltic flounder (Platichthys flesus)

In order to study effects of environmental contamination, a suite of biomarkers were measured over the period 1996 to 1999 in livers of flounder (Platichthys flesus) from two urban embayments and one non-urban reference site of the Gulf of Finland in the vicinity of Tallinn, Estonia. Total cytochrorne P450 (CYP) level, aryl hydrocarbon hydroxylase (AHH), 5-amino-levulinic acid synthetase (ALA-S), and heme synthetase (HEM-S) activities were quantified by means of spectrophotometry. These data were compared to results obtained in 1994 for the same biomarkers at one of the urban embayments and the non-urban site, as measured by the same protocols. For the flounder collected from the non-urban site, changes occurred in AHH activity and the total CYP level, which were significantly lower in 1996 and 1999 compared with 1994 (p< 0.05). Activity of ALA-S de-creased slightly over this same period. The activity of HEM-S increased between 1996 and 1999. In the urban site first investigated in 1994, the activities of AHH and ALA-S, as well as the total level of CYP in flounder liver were significantly higher compared with 1999 (p< 0.05). HEM-S activities did not show any significant changes over this time period. AHH activities of flounder collected in another urban site decreased slightly between 1996 and 1999, in contrast to data on the total CYP level which diminished drastically over these years (p< 0.05). Activities of HEM-S increased significantly (p< 0.05) during the period investigated, while activities of ALA-S remained unchanged. These findings suggest that contamination of the marine environments by PAHs has gone down everywhere in the Tallinn area during the last 3 to 5 years. However, the results indicate that the area is still contaminated, as indicated by elevated heme synthesis enzymes and the total CYP content, and that monitoring of contaminants and their effects should be continued in this region.     

Ozone artifacts and carbonyl measurements using Tenax GR, Tenax TA, Carbopack B, and Carbopack X adsorbents

Four popular thermally desorbable adsorbents used for air sampling (Tenax TA, Tenax GR, Carbopack B, and Carbopack X) are examined for the potential to form artifacts with ozone (O3) at environmental concentrations. The performance of these adsorbents for the ketone and aldehyde species identified as O3-adsorbent artifacts was also characterized, including recovery, linearity, and method detection limits (MDLs). Using gas chromatography/mass spectrometry, 13 different artifacts were identified and confirmed for both Tenax TA and Tenax GR, 9 for Carbopack B, but none for Carbopack X. Several O3 artifacts not reported previously were identified, including: pentanal, 3-hexanone, 2-hexanone, hexanal, 3-heptanone, and heptanal with Tenax TA; pentanal, 3-hexanone, 2-hexanone, hexanal, and 3-heptanone on Tenax GR; and 1-octene and 1-nonene with Carbopack B. Levels of straight-chain aldehyde artifacts rapidly diminished after a few cycles of adsorbent conditioning/O3 exposure, and concentrations could be predicted using a first-order model. Phenyl-substituted carbonyl artifacts (benzaldehyde and acetophenone) persisted on Tenax TA and GR even after 10 O3 exposure-conditioning cycles. O3 breakthrough through the adsorbent bed was most rapid in adsorbents that yielded the highest levels of artifacts. Overall, artifact composition and concentration are shown to depend on O3 concentration and dose, conditioning method, and adsorbent type and age. Calibrations showed good linearity, and most compounds had reasonable recoveries, for example, 90 +/- 15% for Tenax TA, 97 +/- 23% for Tenax GR, 101 +/- 24% for Carbopack B, and 79 +/- 25% (91 +/- 9% for n-aldehydes) for Carbopack X. Benzeneacetaldehyde recovery was notably poorer (22-63% across the four adsorbents). MDLs for several compounds were relatively high, up to 5 ng. By accounting for both artifact formation and method performance, this work helps to identify which carbonyl compounds can be measured using thermally desorbable adsorbents and which may be prone to bias because of the formation of O3-adsorbent artifacts.     

Spatial assessment of the economic feasibility of short rotation coppice on radioactively contaminated land in Belarus, Ukraine, and Russia. II. Monte Carlo analysis

A Monte Carlo analysis of two sequential GIS-embedded submodels, which evaluate the economic feasibility of short rotation coppice (SRC) production and energy conversion in areas contaminated by Chernobyl-derived (137)Cs, was performed to allow for variability of environmental conditions that was not contained in the spatial model inputs. The results from this analysis were compared to the results from the deterministic model presented in part I of this paper. It was concluded that, although the variability in the model results due to within-gridcell variability of the model inputs was considerable, the prediction of the areas where SRC and energy conversion is potentially profitable was robust. If the additional variability in the model input that is not contained in the input maps is also taken into account, the SRC production and energy conversion appears to be potentially profitable at more locations for both the small scale and large scale production scenarios than the model predicted using the deterministic model.