Effect of hydroxyl and amino groups on electrochemiluminescence activity of tertiary amines at low tris(2,2 '-bipyridyl)ruthenium(II) concentrations

ECL of several amines containing different numbers of hydroxyl and amino groups was investigated. N-butyldiethanolamine is found to be more effective than 2-(dibutylamino)ethanol at gold and platinum electrodes, and is the most effective coreactant reported until now. Surprisingly, ECL intensities of monoamines, such as 2-(dibutylamino)ethanol and N-butyldiethanolamine, are much stronger than that of diamines including N,N,N',N'-tetrakis-(2-hydroxyethyl)-ethylenediamine and N,N,N',N'-tetrakis-(2-hydroxypropyl)ethlenediamine. The striking contrast between ECL signals of the investigated monoamines and diamines may result from more significant side reactions of diamines, such as the intramolecular side reactions between oxidative amine cation radicals and reductive amine free radicals.

Determination of ultra-trace concentrations of elements in high purity tellurium by inductively coupled plasma mass spectrometry after Fe(OH)(3) coprecipitation

In this work, a method was established for the determination of impurities in high purity tellurium by inductively coupled plasma mass spectrometry (ICP-MS) after Fe(OH)(3) coprecipitation. After comparison of coprecipitation ability and separation efficiency between Fe(OH), and Al(OH)(3), Fe(OH)(3) was chosen as the precipitate. A separation factor of 160 for 200 mg tellurium was obtained under conditions of pH 9 and 2 mg of Fe3(+). The 13 elements, such as Bi, Sn, Pb, In, Tl, Cd, Cu, Co, Ni, Zn, Ti, Be and Zr, could be almost completely coprecipitated under these conditions. In addition, Te memory effect imposed on the ICP-MS instrument was assessed, as well as Te matrix effect that caused the low recovery of Ga, As, Sb and V in real sample was discussed. Finally, the method was evaluated through recovery test and was applied to practical sample analysis, with detection limits of most of the elements being below 0.15 mug g(-1) and R.S.D. below or at approximately 10%, which indicated that this method could fully satisfy the requirements for analysis of 99.999% similar to 99.9999% high purity Te.

Effect of storage time and cryoprotectant concentrations on the fertilization rate and hatching rate of cryopreserved sperm in red seabream (Pagrus major Temminck & Schlegel, 1843)

This study examined the effects of storage time and cryoprotectant concentrations on the post-thaw sperm of red seabream, Pagrus major. Sperm treated with 12%, 15%, 18% and 21% DMSO were cryopreserved for 10, 30, 60 and 360 days, and fertilization and hatching rates were analysed. For all groups, there were no differences in the fertilization rates and hatching rates between sperm cryopreserved for < 60 days and fresh sperm (98.8 +/- 0.8%, 96.4 +/- 1.3%). However, for sperm cryopreserved for 360 days, both fertilization rates (88.6 +/- 3.0% to 7.0 +/- 1.9%) and hatching rates (79.4 +/- 7.2% to 3.3 +/- 0.8%) decreased drastically. Furthermore, the cryoprotectant concentrations affected sperm quality significantly (P < 0.05). When cryopreserved for 360 days, sperm treated with 15% DMSO obtained the best results compared with other concentrations. We suggest that 15% DMSO may be an effective cryoprotectant for long-term sperm cryopreservation of red seabream.

Resuspension and advection processes affecting suspended particulate matter concentrations in the central English Channel

Suspended particulate matter (SPM) measurements obtained along a cross-section in the central English Channel (Wight-Cotentin transect) indicate that the area may be differentiated into: (1) an English coastal zone, associated with the highest concentrations; (2) a French coastal zone, with intermediate concentrations; and (3) the offshore waters of the Channel, characterised by a very low suspended-sediment load. The SPM particle-size distribution was modal close to the English coast (main mode 10-12 mu m); the remainder of the area was characterised by flat SPM distributions. Examination of the diatom communities in the SPM suggest:; that material resuspended in the intertidal zone and the estuarine environments was advected towards the offshore waters of the English Channel. Considerable variations in SPM concentrations occurred during a tidal cycle: maximum concentrations were sometimes up to 3 times higher than the minimum concentrations, Empirical orthogonal function (EOF) analysis of the SPM concentration time series indicates that, although the bottom waters were more turbid than the surficial waters, this was not likely to be the result of in situ sediment resuspension. Instead, the observed variations appear to be controlled mainly by advective mechanisms. The limited resuspension was probably caused by: (1) the limited availability of fine-grained material within the bottom sediments, and (2) 'bed-armouring' processes which protect the finer-grained fractions of the seabed material from erosion and entrainment within the overlying flow during the less energetic stages of the tide.

Estimation of suspended sediment concentrations using Pulse-coherent Acoustic Doppler Profiler (PCADP)

The objective of the study is to investigate the suitability of using Pulse-coherent Acoustic Doppler Profiler (PCADP) to estimate suspended sediment concentration (SSC). The acoustic backscatter intensity was corrected for spreading and absorption loss, then calibrated with OBS and finally converted to SSC. The results show that there is a good correlation between SSC and backscatter intensity with R value of 0.74. The mean relative error is 22.4%. Then the time span of little particle size variation was also analyzed to exclude the influence of size variation. The correlation coefficient increased to 0.81 and the error decreased to 18.9%. Our results suggest that the PCADP can meet the requirement of other professional instruments to estimate SSC with the errors between 20% and 50%, and can satisfy the need of dynamics study of suspended particles.

Concentrations and distribution of organochlorine pesticides in shellfish from Changjiang estuary

To analyze and evaluate the status of organochlorine pollutants in the Changjiang (Yangtze River) estuary and adjacent waters, the concentrations of hexachlorocyclohexane (HCHs) and dichlorodiphenyltrichloroethane (DDTs) in shellfish collected in study area from 2006 to 2007 were determined with gas chromatography (GC). The concentration range of HCHs was (ND-12.13)x10(-3) mg/kg wet weight and averaged at 0.54x10(-3) mg/kg while the concentration of DDTs was in the range of (4.06-281.73) x10(-3) mg/kg with a mean of 57.52x10(-3) mg/kg in the survey areas. The concentrations of DDTs in the shellfish were higher than HCHs', so that DDTs could be considered as typical organochlorine pollutants in the areas. The concentrations of DDTs in the shellfish were higher than HCHs', so that DDTs could be considered as typical organochlorines pollutants. The HCHs in all the shellfish conformed to the first level of criterion (0.02 mg/kg) of the Marion Biology Quality (GB 18421-2001), and that of DDTs in most samples were beyond the first level (0.01 mg/kg) but conformed to the second level (0.10 mg/kg). On average, alpha-HCH and delta-HCH occupied the most part of HCHs, while O,P'-DDT and P,P'-DDT occupied the most part of DDTs. The concentrations of organocholorine pesticides in shellfish samples varied in site and in species. The highest level occurred at the Shengsi (SS), followed by Yangkougang (YKG), Lvsi (LS), Dongyuan (DY) and Beibayao (BBY), low concentrations were observed at Changsha (CS), Beidaodi (BDD), and Gouqi (GQ). The concentration of HCHs and DDTs in most sites decreased clearly from 2006 to 2007 except for YKG, DY, BDD, LYS, and SS. All of above results suggested that the study area was slightly affected by organochlorine pesticide, special by DDTs.

Concentrations of Cadmium and Zinc in Seawater of Bohai Bay and Their Effects on Biomarker Responses in the Bivalve Chlamys farreri

Both in-field chemical investigation and in the laboratory toxic tests were carried out to systematically understand the pollution status of cadmium (Cd) and zinc (Zn) in Bohai Bay. Samples collected from surface seawater were determined to describe the distributions of Cd and Zn in Bohai Bay. The average values in our study of Cd and Zn were 0.15 mu g/L and 19.68 mu g/L, respectively. Both of them were lower than the first class limit of seawater quality standard in China. In the laboratory, antioxidant enzymes [SOD (Cu/Zn-SOD, Mn-SOD), CAT], lipid peroxidation (MDA), phase I and phase II enzymes (CYP4501A and GST) were investigated in the bivalves Chlamys farreri exposed to Cd and Zn at the concentration levels of Bohai Bay seawater, which were obtained from our in-field investigation. The reduced SOD, CAT, and EROD (7-ethoxyresorufin-O-deethylase) activities (with the inhibitory rate of 16.8%, 31.5%, and 51.6%, respectively) in Cd treatment were observed and resulted in obvious lipid peroxidation damage. However, treatment of Zn showed elevations in SOD and GST by 13.3% and 29.9%, respectively, and with no influence on lipid peroxidation. In summary, seawater quality in Bohai Bay seawater was ranked as good in general, but it seemed that Cd might possess a potential environmental risk by effecting pro-oxidant/antioxidant balance and phase I detoxification in C. farreri.

Trace metal concentrations in suspended particles, sediments and clams (Ruditapes philippinarum) from Jiaozhou Bay of China

Suspended particulate matter (SPM), sediments and clams were collected at three sites in Jiaozhou Bay to assess the magnitude of trace metal pollution in the area. Metal concentrations in SPM (Cu: 40.11-203; Zn: 118-447; Pb: 50.1-132; Cd: 0.55-4.39; Cr: 147.6-288; Mn: 762-1670 mu g/g), sediments (Cu: 17.64-34.26; Zn: 80.79-110; Pb: 24.57-49.59; Cd: 0.099-0.324; Cr: 41.6-88.1; Mn: 343-520 mu g/g) and bivalves (Cu: 6.41-19.76; Zn: 35.5-85.5; Pb: 0.31-1.01; Cd: 0.51-0.67; Mn: 27.45-67.6 mu g/g) are comparable to those reported for other moderately polluted world environments. SPM showed a less clear pattern. Metal concentrations in sediments displayed a clear geographical trend with values increasing with proximity to major urban centers. The clams (on dry weight) showed a complex pattern due to the variability introduced by age-related factors. Cd showed an apparent reverse industrial trend with higher concentrations in clams collected at distant stations. Zn, Pb and Mn showed no clear geographical pattern, whereas Cu increased in the clams collected in the most industrialized area. In addition, the bioaccumulation factors (BAF) were calculated. The result indicated that the studied Ruditapes philippinarum in Jiaozhou Bay possessed different bioaccumulation capacities for Cd, Zn, Cu, Pb and Mn, and Cd, Zn had a relatively high assimilation of those metals from sediment particles. A significant relationship with clam age was observed for Zn (positive) and Cu (negative) suggesting different physiological requirements for both metals with age. Trace metal concentrations measured in the tissue of the investigated clam were in the range considered safe by the WHO for human use.

Radioactivity Concentrations in Soils in the Qingdao Area, China

The specific activity concentrations of radionuclides U-238, Th-212, and K-40 of 2300 sampling points in the Qingdao area were measured by an FD-3022 gamma-ray spectrometer. The radioactivity concentrations of U-238, Th-232, and K-40 ranged from 3.3 to 185.3, from 6.9 to 157.2, and from 15.8 to 7834.4 Bq kg(-1), respectively. The air-absorbed dose at I meter above ground, effective annual dose, external hazard index, and radium equivalent activity were also calculated to systematically evaluate the radiological hazards of the natural radioactivity in Qingdao. The air-absorbed dose, effective annual dose, external hazard index, and radium equivalent activity in the study area were 98.6 nGy h(-1), 0.12 mSv, 0.56, 197 Bq kg(-1), respectively. Compared with the worldwide value, the air-absorbed dose is slightly high, but the other factors are all lower than the recommended value. The natural external exposure will not pose significant radiological threat to the population. In conclusion, the Qingdao area is safe with regard to the radiological level and suitable for living.

Seasonal regulations of energetics, serum concentrations of leptin, and uncoupling protein 1 content of brown adipose tissue in root voles (Microtus oeconomus) from the Qinghai-Tibetan plateau

Survival of small mammals in winter requires proper adjustments in physiology, behavior and morphology. The present study was designed to examine the changes in serum leptin concentration and the molecular basis of thermogenesis in seasonally acclimatized root voles (Microtus oeconomus) from the Qinghai-Tibetan plateau. In January root voles had lower body mass and body fat mass coupled with higher nonshivering thermogenesis (NST) capacity. Consistently, cytochrome c oxidase activity and mitochondrial uncoupling protein-1 (UCP1) protein contents in brown adipose tissues were higher in January as compared to that in July. Circulating level of serum leptin was significantly lower in winter and higher in July. Correlation analysis showed that serum leptin levels were positively related with body mass and body fat mass while negatively correlated with UCP1 protein contents. Together, these data provided further evidence for our previous findings that root voles from the Qinghai-Tibetan plateau mainly depend on higher NST coupled with lower body mass to enhance winter survival. Further, fat deposition was significantly mobilized in cold winter and leptin was potentially involved in the regulation of body mass and thermogenesis in root voles. Serum leptin might act as a starvation signal in winter and satiety signal in summer.

湘西地区上震旦统上部－下寒武统底部黑色岩系沉积学及地球化学

Widespread black chert-shales occur in the Ediacaran-Cambrian(E-C) boundary successions along the flank of Yangtze Platform, South China, remarkable changes in sedimentology, geochemistry and biology were recorded. Although extensive studies were carried out upon this boundary succession, the origin of black chert-shales still remain controversial. This paper focuses on the E-C black chert-shales in western Hunan, South China, upon which detailed depositional and geochemical changes are documented, accordingly a depositional model for black chert-shales is proposed. Stratigraphic anatomy across the depositional strike demonstrates that the shallow-water Dengying dolostone along the platform margin sharply pass basinward into the Liuchapo chert successions, which indicate syndepositional extensional faulting at depth could have occurred along the platform margin. The deep-water Niutitang phosphorite-rich black shales are either underlain by the Dengying dolostones on the platform margin toward platform interior or directly by the Liuchaopo chert successions farther basinwards. By detailed investigation, silica chimneys are firsly identified approximately in the chert along platform margin; two types of silica chimneys, including mounded and splayed/funnelized chert(generally brecciated) bodies are further sorted out. The mounded chert are exitbited by domed or hummocky surfaces on the top and irregular spongy to digitiform internal fabrics; within the silica mounds, abundant original vesicles/voids and/or channels were mostly plugged by initial chalcedony, quartze crystals with minor dolomite and bladed barite crystals. Splayed/funnelized brecciated chert “intrusion” cross-cut the uppermost dolostones capping to the horizon underneath, and are directly overlain by the Niutitang phosphorite-rich black shales. Their similarities to the silica chimneys reported from the oceanic spreading centres suggest a similar origin responsible for these unique silica bodies which is also supported by the microthermonmetric data and element geochemistry. High P, Ba, Fe contents and positive correlation between Fe and TOC concentrations in the Niutitang black shales indicate a high palaeo-productivity in the Early Cambrian ocean. The low Th/U and the high V/Cr, V/Sc, V/(V+Ni) ratios in the black shales suggest an anoxic water condition during this interval. Furthermore, Positive Eu anomalies and high Ba contents in the sediments also imply a hydrothermal influence on the formation of Niutitang black shales. To better constrain the placement of deep-water successions straddling the E-C boundary and the timing of hydrothermal silica chimneys, sensitive high-resoluton ion microprobe(SHRIMP) U-Pb dating of zircon grains from tuffs within the chert succession of Liuchapo Formation at Ganziping was conducted and yields a weighted-mean 206Pb/238Pb age at 536.6±5.5Ma, younger than E-C boundary age(542.0±0.3Ma). This age combined with carbon isotopic data is then proposed to correspond to the U-Pb age of zircons(538.2±1.5Ma) from the Zhongyicun member of Meishucun Formation at Meishucun in eastern Yunna, thus, the E-C boundary in Gazngziping was placed between the Dengying formations and Liuchapo formatioms. therefore, the silica chimneys took place at the beginning of the Cambrian period. The temporal coincidence of silica chimneys and negative excursions of δ13C and δ34Spy pairs suggest hydrothermal activities were likely responsible for the isotopic changes. Under such a circumstance, vast amounts of greenhouse gases(CO2, CH4, H2S), with highly 13C-depleted carbon and 34S-depleted sulfur would be released into the ocean and atmosphere. A positive shift in δ34Scas and Δ34S values from the late Ediacaran to the Early Cambrian could be a reflection of enhanced bacterial sulfate reduction(BSR), strengthened by the intensified oceanic anoxia stimulated by hydrothermal activities. Based on the analyses of sedimentology and geochemistry, a model- “oceanic anoxia induced by hydrothermal–volcanic activies” was proposed to responsible for the formation of black chert-shales during this E-C transition. Under this case, hydrothermal-volcanic activies could release large large amount of greenhouse into atmosphere and metal micronutrients into the ocean, which may lead to global warming, stratified ocean, thereby a high palaeoproductivity; on the other hand, the massive releasing of reduced hydrothermal fluids with abundant H2S, could have in turn enhanced the ocean anoxia. All of these were favourable the for preservation of organic matter, and subsequent extensive deposition of black silica-shales.