变蛋中微量铅的催化示波极谱法测定

用催化示波极谱法测定变蛋中微量铅 ,提出在HCl-酒石酸 -KI -抗坏血酸体系中 ,用催化示波极谱法测定变蛋中微量铅。在此体系中 ,Pb(ⅠⅠ )于 -0 54V处产生一个非常灵敏的吸附催化波。铅含量在 0 0 2 5～ 3 μg·mL-1 范围内波高与浓度呈良好线型关系 ,相关系数r为 0 9976,检测限为0 0 2 5μg·mL-1 。样品经HNO3 -HClO4消化和分解 ,蒸至近干后 ,再用HCl溶解 ,在HCl-酒石酸 -KI体系中测定 ,回收率为 ( 98± 2 ) %。此方法具有灵敏、准确、快速等特点 ,适用于变蛋及其他食品、人发等样品中微量铅的测定     

Lipid Distribution in Marine Sediments from the Northern South China Sea and Association with Gas Hydrate

The distributions of lipids in surface and subsurface sediments from the northern South China Sea were determined. The n-alkanes were in bimodal distribution that is characterized by a centre at n-C16 –n-C20 with maximum at C18(or C19) and n-C27 –n-C31 as well as at C29(or C31). The short-chain alkanes suffered from significant losses due to their slow deposition in the water column, and their presence with a slight even carbon predominance in shallow seafloor sediments was ascribed mainly to the direct input from the benthos. The long-chain alkanes with odd predominance indicate transportion of terrigenous organic matter. Immature hopanoid biomarkers reflect the intense microbial activity for bacteria–derived organic matter and the gradual increase of maturity with burial depth. Abundant n-fatty acid methyl esters(n-FAMEs) that are in distributions coincident with fatty acids were detected in all samples. We proposed that the observed FAMEs originated from the methyl esterification of fatty acids; methanol production by methanotrophs and methanogenic archaea related to the anaerobic oxidation of methane, and sulfate reduction provided an O–methyl donor for methylation of fatty acids. The CH4 released from hydrate dissociation at oxygen isotope stage II of Cores ZD3 and ZS5, which had been confirmed by the occurrence of negative δ13C excursion and spherical pyrite aggregates, could have accelerated the above process and thus maximized the relative content of FAMEs at ZD3-2(400–420 cm depth) and ZS5-2(241–291 cm depth).     

Bacterial wax esters in recent fluvial sediments

We investigated the molecular inventory of River Danube sediments and identified wax esters with 28–36 carbons, with C₃₀, C₃₁ and C₃₂ homologs the most abundant. They consist of various combinations of n-, iso- and anteiso-aliphatic acid and alcohol moieties, with different isomer distributions for the esters with odd and even carbon numbers. The short chain length (C₂₈–C₃₆), high proportion of methyl moieties and presence of monounsaturated esters together suggest a bacterial origin for the wax esters. The concentration in surface sediments varied from 0 to 741 μg/kg, being significantly enriched at locations with high nutrient concentration and high primary productivity. Cluster analysis of denaturing gradient gel electrophoresis (DGGE) band patterns revealed different bacterial communities in surface sediments from the stream and surface sediments from the reservoir. The concentration in a 70 cm core of rapidly deposited sediments decreased significantly with depth, following first order kinetics, suggesting a loss of the esters within ca. 3 years following burial and hence a low probability for preservation in the geological record. Wax esters in rivers have rarely been investigated; our results suggest that they represent a bacterial response to enhanced primary production, triggered by higher nutrient supply.     

Occurrence of phthalate diesters in rivers of the Paris district (France)

The occurrence and fate of six phthalate esters were investigated in the River Seine and two tributaries in the Paris area, at six sites from upstream to downstream, throughout different seasons, with special attention given to a flood episode. At all sites, except the River Marne, whatever the period, diethylhexyl phthalate (DEHP) displayed the highest concentration (0·323–0·779 µg l^?1 as mean values), followed by di‐n‐butyl phthalate (DnBP; 0·211–0·526 µg l^?1 as mean values), which is consistent with the production pattern. High phthalate concentrations appeared to be related to population density and industrial distribution. The strongest values were located downstream from wastewater treatment plant effluent inputs. Seasonal variations were closely related to river flow and air and water temperature. The annual evolution of phthalates was linked to the hydrological conditions. During the flood episode at Paris, the DEHP concentration displayed a sharp increase (260 to 1123 ng l^?1) occurring 9 days before the flood peak. The simultaneous fluctuations of NH₄, typical of domestic origin, and of DEHP suggests a similar origin from combined sewer overflows for both compounds. Other elevated values corresponded to the highest precipitation amounts, and demonstrated the contribution of non‐point‐source runoff and wastewater overflow to DEHP inputs. The DEHP concentration relationship with river flow displayed a clockwise hysteresis loop, corresponding to a ‘first‐flush’ effect in which the finite supplies are swept along in the early stage of the flood. Annual fluxes for 2004 at Paris were 2257 kg of DEHP and 1613 kg of DnBP. The flood period seemed to have a minor impact on annual phthalate transport (29·5% and 41% of the total for DEHP and for DnBP, respectively), which is contrary to annual suspended solids transport (69%). Copyright © 2007 John Wiley & Sons, Ltd.     

Occurrence of phthalate esters in the Seine River estuary (France)

The rigin and fate of six phthalate esters (dimethyl phthalate (DMP), diethyl phthalate (DEP), di‐n‐butyl phthalate (DnBP), butyl benzyl phthalate (BBP), di (2‐ethylhexyl) phthalate (DEHP) and di‐n‐octyl phthalate (DnOP)), were investigated during 2005 and 2006 in the densely populated Seine river estuary. Four compounds, DMP, DEP, DnBP and DEHP were detected at all the stations with DEHP (160–314 ng L^?1), followed by DEP (71–181 ng L^?1) and next DnBP (67–319 ng L^?1), except at la Bouille, where DnBP was the second most important compound. BBP and DnOP concentrations remained low and were not found at all the stations. Considering all six phthalates, Caudebec‐en‐Caux (beginning of the salinity gradient) was the least polluted station (464 ng L^?1), whereas Honfleur (771 ng L^?1) and La Bouille (716 ng L^?1) displayed the highest contamination levels, probably related to important industrial plants. From Caudebec‐en‐Caux to Honfleur (maximum turbidity), variation of DEHP concentration was related to that of suspended matter. In addition, the salinity rise in that area might have facilitated DEHP sorption upon particles. A significant correlation between flow magnitude and DEHP concentration was found (P < 0·01, n = 12), supporting the influence of the hydrological cycle upon contamination. Runoff contribution (56·9 kg d^?1) to river contamination was confirmed by the annual evolution of phthalate concentrations in the Seine river at Poses. Concentrations of DEHP in the tributaries were in the same range as those of the Seine River (100–350 ng L^?1), except for two in densely populated and industrialized areas: Robec (800 ng L^?1) and Cailly (970 ng L^?1). The treatment plant discharge fluxes were in the same range as those of tributaries (30·4–250 g d^?1). During high flow periods, the influence of tributaries and of treatment plants seemed to play a minor part in the contamination level of the Seine river estuary. Copyright © 2009 John Wiley & Sons, Ltd.     

The Reaction of Unsaturated Aliphatic Oxygenates with Ozone

The reaction of ozone with unsaturated aliphatic oxygenates has been studied at ambient T (287–297 K) and p = 1 atm. of air (RH = 55 ± 10%) with sufficient cyclohexane added to scavenge the hydroxyl radical. Reaction rate constants, in units of 10-18 cm3 molecule-1 s-1, are 10.7 ± 1.4 for methyl trans-3-methoxy acrylate, 63.7 ± 9.9 for 4-hexen-3-one (predominantly the trans isomer), 125 ± 17 for trans-4-methoxy-3-buten-2-one, 148 ± 13 for cis-4-heptenal, 439 ± 37 for 3- methyl-2-buten-1-ol and 585 ± 132 for (cis + trans)-ethyl 1-propenyl ether. The influence of the oxygen-containing substituents on reactivity toward ozone is examined. Unsaturated ethers react with ozone faster than their alkene structural homologues; the reverse is observed for unsaturated esters and unsaturated carbonyls. Major reaction products have been identified by liquid chromatography with ultraviolet detection (LC-UV), particle beam-mass spectrometry (PB- MS) and gas chromatography-mass spectrometry (GC-MS) and are methyl formate and methyl glyoxylate from methyl trans-3-methoxy acrylate, acetaldehyde and 2-oxobutanal from 4-hexen-3-one, propanal and succinic dialdehyde from cis-4-heptenal, hydroxyacetaldehyde and acetone from 3-methyl-2-buten-1-ol, and ethyl formate and acetaldehyde from (cis + trans)-ethyl 1-propenyl ether. PB-MS and GC- MS were also employed to identify new reaction products and to confirm the structure of products tentatively identified in a previous study of the reaction of ozone with five unsaturated oxygenates (Grosjean and Grosjean, 1997a): formic acid and methyl glyoxylate from methyl acrylate, formic acid and formic acetic anhydride from vinyl acetate, 2-oxoethyl acetate and 3-oxopropyl acetate from cis-3-hexenyl acetate, ethyl formate and formic acid from ethyl vinyl ether, and methyl formate from trans-4-methoxy-3- buten-2-one. The nature and formation yields of the reaction products are consistent with (and supportive of) the reaction mechanism: O3 + R1R2C=CR3X (R1COR2 + R3C(X)OO) + (1 - )(R3COX + R1C(R2)OO), where R1, R2 and R3 = H or alkyl, X is the oxygen-containing substituent, R1COR2 and R3COX are the primary products and R1C(R2)OO and R3C(X)OO are the carbonyl oxide biradicals. The variations of the coefficient , which ranges from 0.25 to 0.61, are discussed in terms of the number and nature of alkyl and oxygen-containing substituents. Subsequent reactions of the alkyl-substituted biradicals R1C(R2)OO and of the biradicals R3C(X)OO that bear the oxygen-containing substituent are discussed. For the biradical CH3CHOO, the ratio ka/kb for the competing pathways of rearrangement to acetic acid (CH3CHOO CH3C(O)OH, reaction (a) and formation of an unsaturated hydroperoxide (CH3CHOO CH2=CH(OOH), reaction (b) is <0.25 for ethyl 1-propenyl ether and <0.27 for 4-hexen-3-one. Concentrations measured in co- located samples, one downstream of a water impinger and the other without water impinger, show the uptake in water impingers to be high (from 83.2 to >99.9%) and comparable to that for formaldehyde (98.4%) for formic acetic anhydride and for difunctional oxygenated compounds. Uptake in water impingers was lower (19–78%) for monofunctional aldehydes and ketones.     

酞酸酯类物质污染及其危害性研究进展

酞酸酯类化合物是环境中一类极其重要的污染物,它分布广,难降解。详细介绍了酞酸酯物质的概念,环境中该物质的来源,在环境中的分布情况,以及它的危害,尤其侧重介绍了对人体生殖系统的危害。最后介绍了目前国内外酞酸酯污染物分布和危害的研究情况。     

Occurrence and distribution of phthalate esters in riverine sediments from the Pearl River Delta region,South China

Sixty-eight sediment samples collected from Dongjiang River, Xijiang River, Beijiang River and Zhujiang River in the Pearl River Delta (PRD) region, Southern China, were analyzed for 16 phthalate esters (PAEs). PAEs were detected in all riverine sediments analyzed, which indicate that PAEs are ubiquitous environmental contaminants. The Σ₁₆PAEs concentrations in riverine sediments in the PRD region ranged from 0.567 to 47.3 μg g⁻¹ dry weight (dw), with the mean and median concentrations of 5.34 μg g⁻¹ dw and 2.15 μg g⁻¹ dw, respectively. Elevated PAEs concentrations in riverine sediments in the PRD region were found in the highly urbanized and industrialized areas. Of the 16 PAEs, diisobutyl phthalate (DiBP), di-n-butyl phthalate (DnBP) and di(2-ethylhexyl) phthalate (DEHP) dominated the PAEs, with the mean and median concentrations of 1.12 μg g⁻¹ dw, 0.420 μg g⁻¹ dw and 3.72 μg g⁻¹ dw, and 0.429 μg g⁻¹ dw, 0.152 μg g⁻¹ dw and 1.55 μg g⁻¹ dw, respectively, and accounted for 94.2–99.7% of the Σ₁₆PAEs concentrations. Influenced by local sources and the properties of PAEs, a gradient trend of concentrations and a fractionation of composition from more to less industrialized and urbanized areas were discovered. As compared to the results from other studies, the riverine sediments in the PRD region were severely contaminated with PAEs. Information about PAEs contamination status and its effect on the aquatic organisms in the PRD region may deserve further attention.     

Toxic effects of several phthalate esters on the embryos and larvae of abalone Haliotis diversicolor supertexta

As the most widely used plasticizers in the world, phthalate esters (PAEs) are potential endocrine disruption compounds (EDCs). In the present study, the toxicity of dimethyl phthalate (DMP), diethyl phthalate (DEP), dibutyl phthalate (DBP), di (2-ethylhexyl) phthalate (DEHP) on embryogenesis and larvae development of the marine univalve Haliotis diversicolor supertexta was examined in laboratory. The results show that the malformation of embryos appeared during the experiment, such as embryos died or lysed, small transparent flocculent rings studded on the periphery of the embryo, and the larvae could failed to hatch. In embryo toxic test, embryos incubated at the highest concentration of DMP, DEP and DBP solutions showed significantly high abnormal rate compared with the control, while DEHP solutions displayed no significant difference. In larval toxic test, in all concentrations of DMP, DEP and DBP solutions, larval settlement rates were low significantly than that of the control. Similarly, DEHP solutions show nearly no effect on the larval settlement. The order of toxicity on embryos and larvae is DBP>DEP>DMP>DEHP. Being a simple and easy stimulation to indoor spawn, sensitive to environmental factors, and short culture time, the embryos of H. diversicolor supertexta can be used to indicate toxicity of the PAEs. Supported by National Natural Science Foundation of China (No. 40476057)