珠江口表层水中多环芳烃的分布特征及健康风险评估

分别于2015年2、5、8、11月在珠江八大入海口采集表层水体样品,应用固相萃取富集法对该区域表层水体中16种USEPA优控多环芳烃(PAHs)的时空分布特征进行分析,并利用终生致癌风险增量模型(ILCR)对该区域的饮水健康风险进行评价。结果表明:珠江口4个季度所采集的水样中,∑15PAHs的浓度范围为18.0~50.3 ng/L,含量处于中等水平。其中7种强致癌性∑7PAHs的浓度范围为1.53~3.73 ng/L,占∑15PAHs的5.89%~11.1%,∑15PAHs和∑7PAHs在枯水期(2、11月)样品中明显高于丰水期(5、8月)。就组成特征而言,各采样点PAHs以3、4环为主。珠江口表层水中非致癌类PAHs的危害商数值为0.99×10~(-5)~2.73×10~(-5),远低于USEPA规定的阈值(1);致癌类PAHs产生的健康风险为6.50×10~(-8)~2.37×10~(-7),其中Ba P导致的饮水途径健康风险最高,所有点位致癌类PAHs的健康风险均低于USEPA推荐的对致癌物质最大可接受风险水平(10~(-6)),表明珠江口表层水中PAHs尚不具备严重的致癌风险,但是仍然存在潜在的健康风险,需要重点控制和管理。     

A two-stage cyclone using microcentrifuge tubes for personal bioaerosol sampling

Personal aerosol samplers are widely used to monitor human exposure to airborne materials. For bioaerosols, interest is growing in analyzing samples using molecular and immunological techniques. This paper presents a personal sampler that uses a two-stage cyclone to collect bioaerosols into disposable 1.5 ml Eppendorf-type microcentrifuge tubes. Samples can be processed in the tubes for polymerase chain reaction (PCR) or immunoassays, and the use of multiple stages fractionates aerosol particles by aerodynamic diameter. The sampler was tested using fluorescent microspheres and aerosolized fungal spores. The sampler had first and second stage cut-off diameters of 2.6 microm and 1.6 microm at 2 l min(-1)(geometric standard deviation, GSD = 1.45 and 1.75), and 1.8 microm and 1 microm at 3.5 l min(-1)(GSD = 1.42 and 1.55). The sampler aspiration efficiency was >or=98% at both flow rates for particles with aerodynamic diameters of 3.1 microm or less. For 6.2 microm particles, the aspiration efficiency was 89% at 2 l min(-1) and 96% at 3.5 l min(-1). At 3.5 l min(-1), the sampler collected 92% of aerosolized Aspergillus versicolor and Penicillium chrysogenum spores inside the two microcentrifuge tubes, with less than 0.4% of the spores collecting on the back-up filter. The design and techniques given here are suitable for personal bioaerosol sampling, and could also be adapted to design larger aerosol samplers for longer-term atmospheric and indoor air quality sampling.     

Fungicidal values of bio-oils and their lignin-rich fractions obtained from wood/bark fast pyrolysis

Pine wood, pine bark, oak wood and oak bark were pyrolyzed in an auger reactor. A total of 16 bio-oils or pyrolytic oils were generated at different temperatures and residence times. Two additional pine bio-oils were produced at the National Renewable Energy Laboratory in a fluidized-bed reactor at different temperatures. All these bio-oils were fractionated to obtain lignin-rich fractions which consist mainly of phenols and neutrals. The pyrolytic lignin-rich fractions were obtained by liquid-liquid extraction. Whole bio-oils and their lignin-rich fractions were studied as potential environmentally benign wood preservatives to replace metal-based CCA and copper systems that have raised environmental concerns. Each bio-oil and several lignin-rich fractions were tested for antifungal properties. Soil block tests were conducted using one brown-rot fungus (Gloeophyllum trabeum) and one white-rot fungus (Trametes versicolor). The lignin-rich fractions showed greater fungal inhibition than whole bio-oils for a impregnation solution 10% concentration level. Water repellence tests were also performed to study wood wafer swelling behavior before and after bio-oil and lignin-rich fraction treatments. In this case, bio-oil fractions did not exhibit higher water repellency than whole bio-oils. Comparison of raw bio-oils in soil block tests, with unleached wafers, at 10% and 25% bio-oil impregnation solution concentration levels showed excellent wood preservation properties at the 25% level. The good performance of raw bio-oils at higher loading levels suggests that fractionation to generate lignin-rich fractions is unnecessary. At this more effective 25% loading level in general, the raw bio-oils performed similarly. Prevention of leaching is critically important for both raw bio-oils and their fractions to provide decay resistance. Initial tests of a polymerization chemical to prevent leaching showed some success.     

Changes in plasma thyroid hormones and cortisol levels in crucian carp (Carassius auratus) exposed to the extracted microcystins

The endocrine response of crucian carp injected intraperitoneally with extracted microcystins (MC) was investigated in this study. Fish were injected intraperitoneally either with 0.75% NaCl (control) and Microcystis extract corresponding to 150 and 600 microg microcystins per kg body weight. The plasma levels of triiodothyronine (T(3)), thyroxine (T(4)), free triiodothyronine (FT(3)), free thyroxine (FT(4)), and cortisol were determined at 0, 1, 3, 12, 24, and 48h post-administration of MC-containing extract. Treated fish displayed abnormal behaviors, such as a startle response and disoriented swimming, as well as changes in ventilation rates. Plasma cortisol concentrations of fish in both dose groups significantly increased after administration of extracted MC and remained high throughout the experiment, which suggested that MC elicited a stress response in treated fish. The profiles of cortisol changes in treated fish appeared to be dose dependent, indicating that fish in the high dose group experienced greater MC-induced disturbance. Mortality occurred after 12h in the high dose group. Plasma levels of T(4), T(3), FT(4), and FT(3) did not vary significantly between the control fish. In contrast to this, fish exposed to MC-containing extract showed significant declines in T(3), FT(4), and FT(3) levels in a dose-dependent manner throughout the experiment. Plasma T(4) levels, however, did not vary significantly in the low dose group, whereas they decreased significantly at 48h post injection in the high dose group. This study demonstrates that administration of microcystins-containing extract causes a stress response and reduces the plasma levels of thyroid hormones in crucian carp. These results illustrate that microcystins exerted potent effects on the endocrine system of crucian carp, through activating their hypothalamus-pituitary- interrenal axis and disturbing thyroid function.     

Pre-concentration and separation of heavy metal ions by chemically modified waste paper gel

Iminodiacetic acid was immobilized on waste paper by chemical modification in order to develop a new type of adsorption gel for heavy metal ions. Adsorption behavior of the gel was investigated for a number of metal ions, specifically Cu(II), Pb(II), Fe(III), Ni(II), Cd(II), and Co(II) at acidic pH. From batch adsorption tests, the order of selectivity was found to be as follows: Cu(II)  Fe(III) > Pb(II) > Ni(II)  Co(II) > Cd(II). Column tests were carried out for pairs of metal ions to understand the separation and pre-concentration behavior of the gel. It was found that mutual separation of Ni(II) from Co(II) and that of Pb(II) from Cd(II) can be achieved at pH 3. Similarly, selective separation of Cu(II) from Cu(II)–Fe(III) and Cu(II)–Pb(II) mixtures at pH 1.5 and 2, respectively, was observed by using this new adsorption gel. In all cases, almost complete recovery of the adsorbed metal was confirmed by elution tests with HCl.     

Feasibility study of preparation and certification of reference materials for nitrogen dioxide and sulfur dioxide in diffusive samplers

This paper presents the results of a feasability study for the preparation and certification of reference materials (RMs) for nitrogen dioxide (NO(2)) and sulfur dioxide (SO(2)) in diffusive samplers. RMs for NO(2) were prepared by exposure to gas mixtures in a chamber while the RMs for SO(2) were prepared by liquid spiking. Certification of RMs for NO(2) was found feasible with a certified uncertainty of 5.8% and a proposed shelf life of 5 years. The uncertainty was calculated with contribution from the homogeneity of preparation, stability and transport of the CRMs and from an external verification of the certified value. To reach 5.8% of uncertainty, the contribution of the differences between the results of analysis by ion chromatography and colorimetry must be eliminated. It is proposed to solve this by pre-extracting the samplers with water before analysis. The results of this study indicate that the samplers are stable for at least two years before and after exposure when stored in a refrigerator. By contrast, the certification of RMs for SO(2) was found to not be feasible due to instability problems. This instability was attributed to reaction of sulfate on the walls of the samplers. Alternatively, the preparation of RMs by simultaneous exposure to SO(2) and NO(2) has been tested. Satisfying homogeneities has been reached both for NO(2) and SO(2).     

港口工程对沿海环境的影响

海洋的许多生态参数,如溶解氧浓度和温度等均与环流有关,所以环流的流态对海洋环境的影响十分显著。在海中建造各种建筑物必然会妨碍水体运动,从而影响海洋环境。本文旨在研究港口建筑物对环流运动的影响和由此而引起的环境影响。 文中提出一个可供估算水文参数和废水耗氧量变化的简易数学模型。对于废水引起的富营养化效应也做了分析研究。 在港口工程规划设计阶段,必须进行环境生态影响的研究,如果港口附近有污水排放口,进行环境影响分析尤为重要。 本文介绍的方法,曾应用于靠近雅典城市污水排放区的比雷埃夫斯港的扩建工程。分析表明,如果按照原来的设计进行施工,而忽视工程引起的环境影响,其结果必然导致明显的生态变化。     

Contaminant exposure in terrestrial vertebrates

Here we review mechanisms and factors influencing contaminant exposure among terrestrial vertebrate wildlife. There exists a complex mixture of biotic and abiotic factors that dictate potential for contaminant exposure among terrestrial and semi-terrestrial vertebrates. Chemical fate and transport in the environment determine contaminant bioaccessibility. Species-specific natural history characteristics and behavioral traits then play significant roles in the likelihood that exposure pathways, from source to receptor, are complete. Detailed knowledge of natural history traits of receptors considered in conjunction with the knowledge of contaminant behavior and distribution on a site are critical when assessing and quantifying exposure. We review limitations in our understanding of elements of exposure and the unique aspects of exposure associated with terrestrial and semi-terrestrial taxa. We provide insight on taxa-specific traits that contribute, or limit exposure to, transport phenomenon that influence exposure throughout terrestrial systems, novel contaminants, bioavailability, exposure data analysis, and uncertainty associated with exposure in wildlife risk assessments. Lastly, we identify areas related to exposure among terrestrial and semi-terrestrial organisms that warrant additional research.     

Conversion of rice husk ash to zeolite beta

White rice husk ash (RHA), an agriculture waste containing crystalline tridymite and alpha-cristobalite, was used as a silica source for zeolite Beta synthesis. The crystallization of zeolite Beta from RHA at 150 degrees C in the presence of tetraethylammonium hydroxide was monitored by XRD, FTIR and (29)Si MAS NMR techniques. It was found that zeolite Beta started to form after 12h and the complete crystallization of zeolite Beta phase was achieved after 2d. XRD, (29)Si MAS NMR and solid yield studies indicate that the transformation mechanism of silica present in RHA to zeolite Beta involves dissolution of the ash, formation of an amorphous aluminosilicate after 6h of crystallization, followed by dissolution in the mother liquor and final transformation to pure zeolite Beta crystals.     

Mineralogical characterization of the Tournemire argillite after in situ interaction with concretes

This study aims to investigate, through mineralogical characterization (SEM, XRD) and mass-balance calculations, the effects of contact time, concrete types and presence of free water on the Tournemire argillite under in situ conditions. Three sampling zones from Excavation Disturbed Zone (EDZ) areas have been chosen: (1) dry contacts, collected at the tunnel masonry/argillite interface (contact time - 125 years), (2) wet contacts, taken close to drained areas below the tunnel roadbed in contact with the canal draining the Cernon fault water (contact time - 15 and 7 years) and at the tunnel masonry/argillite interface over 70 m from the Cernon fault (contact time - 125 years). This study shows that: in the absence of water, no significant modification of argillite is observed after 125 years, except for pyrite dissolution and gypsum precipitation; in the presence of water, precipitation of gypsum, recrystallization of mixed-layer clays, neoformation of zeolites and K-feldspars overgrowths are observed. At the concrete/argillite interface near the Cernon fault, important dolomite neoformation and leaching of chlorite and kaolinite occur. These processes are enhanced with contact time, low flow rate and the nature of the concrete (compound cement Portland CEM II 32.5). Evidence for oxidation processes linked to the EDZ (pyrite oxidation, Fe-oxy-hydroxide and gypsum precipitation) is observed.