广西象州与横县碳酸盐岩分布区土壤中Cd形态分布特征及影响因素

广西壮族自治区碳酸盐岩分布面积为96 372 km2,约占全区陆地国土面积的407%。由碳酸盐岩风化形成的土壤中Cd、Pb、Hg等重金属元素普遍富集。初步评价发现,农作物籽实对Cd的吸收量与土壤Cd含量无对应关系,农作物Cd超标多出现在土壤Cd含量较低的地区。进一步研究发现,Cd高含量的土壤中普遍含有铝土矿、Fe Mn结核等颗粒。为了探索土壤中Cd存在形态及其影响因素,选择了含铝土矿和铁锰结核的横县土壤和无铝土矿与铁锰结核的象州土壤,系统研究了土壤Cd形态差异及其影响因素。结果表明：(1)象州土壤中Cd主要以活动态形式存在,生物可利用性高,横县土壤中Cd主要以稳定态形式存在,生物可利用性低。(2)pH值为60是象州土壤Cd活动态含量的突变点,pH值在60处含量达到最大值;而在横县,pH降低使活动态Cd比例增加。(3)象州土壤中活动态Cd随有机质增加而增加,表明Cd被有机质弱吸附;而横县土壤有机质含量与Cd形态无明显相关性。(4)由铝土矿导致的土壤高Cd含量,多以残渣态形式存在,不会对动植物造成危害。     

膜去溶-电感耦合等离子体质谱法测定环境地质样品中的镉

应用电感耦合等离子体质谱法(ICP-MS)分析环境地质样品中的Cd时,Zr、Mo元素的氧化物和氢氧化物会对Cd造成严重干扰,导致结果有明显的偏差。针对此问题,本文建立了膜去溶-ICP-MS直接测定环境地质样品中微量Cd的分析方法,该方法可有效地消除Zr、Mo氧化物和氢氧化物对Cd的干扰,保证结果准确、可靠。膜去溶-ICP-MS相比于常规ICP-MS测定Cd的方法,可将Zr、Mo氧化物和氢氧化物对Cd的干扰降低到0.001%,检测灵敏度提高3.5倍左右。在给定条件下,Cd的检出限为0.28 ng/L,测定下限为2.2 ng/L,精密度(RSD,n=12)为2.2%。利用该方法分析20种岩石、土壤和沉积物国家标准物质的测定值与标准值相符,表明膜去溶-ICP-MS法直接测定环境地质样品中痕量或超痕量Cd时具有一定的应用潜力。同时,用该方法对2016年中核集团组织的实验室间两个比对样品中的Cd进行测定,稳健Z比分数分别为0.500和-0.964,Z的绝对值都小于2。     

Biochemical and Physiological Responses in Atlantic Salmon (Salmo salar) Following Dietary Exposure to Copper and Cadmium

Three experiments were conducted with Atlantic salmon (Salmo salar) to assess the effects of dietary exposure to copper and cadmium. The results presented here provide an overview, details of each experiment will be published in full elsewhere. In the first experiment, salmon parr exposed for four weeks to 35 and 700 mg Cu kg⁻¹ diet had significantly elevated intestinal copper concentrations, cell proliferation (PCNA) and apoptosis rates compared to control fish. No differences were observed in gill or plasma copper concentrations among the groups. In contrast to the controls, the Cu exposed groups did not grow significantly during the exposure period. The second experiment (three months exposure) was conducted to assess the effects of dietary copper (control, 35, 500, 700, 900 or 1750 mg Cu kg⁻¹ diet) on growth and feed utilization in salmon fingerlings. Growth was significantly reduced after three months exposure to dietary Cu concentrations above 500 mg kg⁻¹. Similarly, copper body burdens were significantly higher in fish exposed to elevated dietary copper concentrations (above 35 mg Cu kg⁻¹ diet). In the third experiment, salmon parr were exposed to one of six dietary cadmium concentrations (0, 0.5, 5, 25, 125 or 250 mg Cd kg⁻¹ diet) for four months. Cadmium accumulated in the liver>intestine>gills of exposed fish. Rates of apoptosis and cell proliferation in the intestine increased following exposure to dietary cadmium. Exposure to elevated concentrations of dietary cadmium had no effect on growth in salmon parr. Results from these studies indicate that cellular biomarkers have potential as early warning signs of negative effects on the overall fitness of an organism.     

外源鸟氨酸对菹草(Potamogeton crispus L.)抗镉胁迫能力的影响

本文以组织培养技术培养的菹草无菌苗为实验材料,研究了2 mmol/L外源鸟氨酸(L-Orn)对40μmol/L镉(Cd)胁迫下菹草体内Cd含量、光合色素水平、超氧阴离子(O·-2)产生速率、过氧化氢(H2O2)、丙二醛(MDA)与可溶性蛋白含量以及脯氨酸和多胺代谢的影响.结果显示:(1)在单一Cd胁迫下,菹草体内的Cd大量积累,达到335.00μg/g,并诱导了明显的氧化胁迫,具体表现为O·-2产生速率以及H2O2和MDA含量显著升高,可溶性蛋白以及光合色素含量明显下降.外源L-Orn的添加很大程度上抑制了菹草体内Cd的积累,Cd含量降至232.50μg/g,并降低了活性氧(ROS)水平,减轻了膜脂过氧化程度,减缓了光合色素和可溶性蛋白的分解.(2)在单一Cd胁迫下,伴随着吡咯啉-5-羧酸合成酶(P5CS)活性的增加和脯氨酸脱氢酶(ProDH)活性的下降,菹草体内的脯氨酸含量轻微增加,仅为对照组的1.91倍,而外源L-Orn显著增强了P5CS和δ-鸟氨酸转氨酶(OAT)的活性,使脯氨酸含量大幅度升高,为对照组的8.36倍.(3)单一Cd胁迫分别通过激活精氨酸脱羧酶(ADC)、鸟氨酸脱羧酶(ODC)和多胺氧化酶(PAO)的活性,使腐胺(Put)的含量增加,亚精胺(Spd)和精胺(Spm)含量减少.而施用外源L-Orn后,ADC和ODC的活性进一步增强,Put的含量大幅增加,并促进Put向Spd和Spm的转化,同时PAO的活性下降,使Spd和Spm含量增加,从而使总多胺含量增加.由此可见,外施L-Orn可通过抑制Cd的进入和参与调节脯氨酸以及多胺代谢,抑制ROS的积累、膜脂过氧化、光合色素以及蛋白质的分解,一定程度上增强菹草对Cd胁迫的抗性.     

Adsorption of cadmium on riverine sediments: quantitative treatment of the large particles

The effects of solution pH, sediment dose, contact time, and particle size on the adsorption of cadmium ions on bed sediments have been studied for a highly polluted river in western Uttar Pradesh, India. The role of the coarser sediment and the clay and silt fractions has been examined. The optimum contact time needed to reach equilibrium is of the order of 30 and 60 min for 0–75 μm and 210–250 μm sediment size, respectively. The extent of cadmium adsorption increases with increasing pH and adsorbent doses and decreases with adsorbent particle size. The important geochemical phases, iron and manganese oxide, provide the active support material for the adsorption of cadmium. The competitive experiments conducted in the presence of lead and zinc ions indicate that both the ions suppress the ability of cadmium to adsorb on to sediments. The Langmuir and Freundlich adsorption models were used to determine the mechanistic parameters associated with the adsorption process. Copyright © 2000 John Wiley & Sons, Ltd.     

纳米TiO2对菲律宾蛤仔消化腺中Cd的蓄积与生化响应的影响

随着纳米科技的发展及纳米颗粒在纺织、食品、太阳能及水处理等各行业的应用,进入水生环境的纳米颗粒对其中痕量金属的生物地球化学循环及其生物学效应的影响受到关注。本文研究了水环境中分布最广泛的纳米二氧化钛(n-TiO2)对镉(100μg·L^-1)在海洋双壳类菲律宾蛤仔体内生物利用性及生物效应的影响,通过14d的暴露实验,在环境真实浓度下研究Cd在蛤仔体内的蓄积量及毒性。暴露期间测定了蛤仔消化腺中超氧化物歧化酶(SOD)、过氧化氢酶(CAT)、谷胱甘肽S-转移酶(GST)、丙二醛(MDA)和金属硫蛋白(MT)等生物标志物的活性或含量,同时分析了消化腺中Cd的蓄积。暴露3d后,Cd处理组及n-TiO2+Cd处理组均观测到蛤仔消化腺内Cd含量显著升高(p<0.05),并随时间延长而不断升高。各处理组SOD活性在整个暴露周期内与同期对照组相比均无显著差异。CAT(3d)和GST(7、14d)活性仅在Cd处理组出现显著升高(p<0.05)。Cd处理组在暴露结束时出现MDA含量的显著增加;n-TiO2单独及联合处理组MDA含量显著上升出现在7d后,至暴露结束时与对照组无显著差异。随暴露时间的延长,只有Cd处理组中蛤仔消化腺MT的含量呈现显著升高。结果表明,相同浓度条件下,Cd对蛤仔的亚致死毒性高于n-TiO2,而n-TiO2能够通过抑制Cd的生物积累而减轻后者对蛤仔的毒性,这种影响与n-TiO2对Cd的吸附作用有关。     

海洋站总氮自动监测仪的研制

基于海洋监测站无人值守自动监测要求,通过控制程序,实现微波-过硫酸盐消解,镉柱还原,流动注射紫外分光光度法连续测定近岸海域海水中总氮。在设计改进仪器模块的条件下,通过试验,优化测定条件。实验结果证明,海水中总氮浓度与吸光度呈良好线性关系,总氮质量浓度为0.010～10 mg/L时,线性方程为y=0.185x+0.043,相关系数r=0.9990。标准样品检验,实验相对标准偏差(RSD)为0.89%,样品的加标回收率在98%～102%。方法稳定性:零点漂移在?0.5%之内,量程漂移在?3%之内,符合《近岸海域水质自动监测技术规范》(HJ731-2014)要求。该方法测定实际海水样品总氮质量浓度为0.1927mg/L,与国标法测定结果 0.209 4mg/L无显著性差异。实现了近岸海域总氮的实时监测和预警监测。     

Improving estuarine net flux estimates for dissolved cadmium export at the annual timescale: Application to the Gironde Estuary

Dissolved Cd (Cd_D) concentrations along the salinity gradient were measured in surface water of the Gironde Estuary during 15 cruises (2001–2007), covering a wide range of contrasting situations in terms of hydrology, turbidity and season. During all situations dissolved Cd concentrations displayed maximum values in the mid-salinity range, reflecting Cd addition by chloride-induced desorption and complexation. The daily net Cd_D fluxes from the Gironde Estuary to the coastal ocean were estimated using Boyle's method. Extrapolating Cd_D concentrations in the high salinity range to the freshwater end member using a theoretical dilution line produced 15 theoretical Cd concentrations (Cd_D⁰), each representative of one distinct situation. The obtained Cd_D⁰ concentrations were relatively similar (201 ± 28 ng L⁻¹) when freshwater discharge Q was >500 m³ s⁻¹ (508 ≤ Q ≤ 2600 m³ s⁻¹), but were highly variable (340 ± 80 ng L⁻¹; 247–490 ng L⁻¹) for low discharge situations (169 ≤ Q ≤ 368 m³ s⁻¹). The respective daily Cd_D net fluxes were 5–39 kg day⁻¹, mainly depending on freshwater discharge. As this observation invalidates the existing method of estimating annual Cd_D net fluxes, we proposed an empirical model, using representative Cd_D⁰ values and daily freshwater discharges for the 2001–2007 period. Subsequent integration produced reliable Cd_D net flux estimates for the Gironde Estuary at the annual timescale that ranged between 3.8–5.0 t a⁻¹ in 2005 and 6.0–7.2 t a⁻¹ in 2004, depending on freshwater discharge. Comparing Cd_D net fluxes with the incoming Cd_D fluxes suggested that the annual net Cd_D addition in the Gironde Estuary ranged from 3.5 to 6.7 t a⁻¹, without any clear temporal trend during the past seven years. The annual Cd_D net fluxes did not show a clearly decreasing trend in spite of an overall decrease by a factor 6 in Cd gross fluxes during the past decade. Furthermore, in six years out of seven (except 2003), the annual Cd_D net fluxes even exceeded river borne total (dissolved + particulate) gross Cd fluxes into the estuary. These observations were attributed to progressive Cd desorption from both suspended particles and bottom sediment during various sedimentation–resuspension cycles induced by tidal currents and/or continuous dredging (navigation channel) and diverse intra-estuarine sources (wet deposition, urban sources, and agriculture). Provided that gross fluxes remain stable over time, dissolved Cd exportation from the Gironde Estuary to the coastal ocean may remain at the present level for the coming decade and the estuarine sedimentary Cd stock is forecast to decrease slowly.     

Speciation of dissolved copper and cadmium in the Loire estuary and over the North Biscay continental shelf in spring

Dissolved cadmium and copper species were measured in the Loire estuary and the North Biscay Bay continental shelf (France) in spring 2002. Metal behaviours along the salinity gradient, metal fluxes from the Loire system and surface distributions on the continental shelf were described and compared with the ones obtained at a period of higher discharge (i.e., winter 2001). Vertical distributions at different stations were also examined with the aim to assess whether the Loire inputs affect the Cu and Cd speciation over the continental shelf. In the Loire estuary, different metal behaviours were observed from winter. Cu and its various species mostly followed a theoretical dilution line whereas a Cd addition composed of chloro- and organic complexes was observed. According to our estimations, the Cu flux was composed, as in winter, of 40% hydrophobic organic complexes. On the other hand, Cd organic complexes accounted for less in the total dissolved metal flux than they did in winter (55 and 78% for spring and winter, respectively). On the continental shelf, a C₁₈Cu-to-TDCu ratio of 40% was observed in the stratified area under Loire influence. For Cd, the organic fraction was relatively important in the surface waters near the mouth of the estuary and decreased deeper and seaward. Thus, the Cu and Cd speciation on the North Biscay Bay continental shelf are firstly determined by the extent of the estuarine plume. Beyond the estuarine influence, biological processes appeared to be the origin of the observed variations.     

马尔可夫模型在洞庭湖区Cd的生态地球化学评价中的应用

根据马尔可夫链模型,定量地探讨了湖南省洞庭湖区农田生态系统中Cd的迁移转化问题,计算了Cd在土壤-水-稻谷-大气系统中的滞留时间和环境允许量,进而探讨了系统的生态承载力,得到系统中Cd的最大允许排放量CdA与生态承载力M人口之间的关系式:CdA=3.56×10-4M人口,为生态环境地球化学评价提供了一种新的方法和途径。