Influence of current velocity on cadmium accumulation by an aquatic moss and the consequences for its use as a biomonitor

Aquatic mosses are widely used as biomonitors of contaminant concentrations in running waters. The results of several previous studies suggest that metal concentrations in mosses are influenced by current velocity and that this variable should be taken into account when mosses are used as metal biomonitors. However, in these studies, the purported influence of water velocity was confounded by other uncontrolled variables. We conducted our study to test the influence of current velocity on Cd accumulation by the riverine moss Fontinalis dalecarlica. We found no difference in Cd accumulation over 2 weeks by moss exposed in the laboratory to a constant Cd concentration over a wide range of current velocities (0.01-0.70 m s-1) that occur in the field. Similarly, the results of a field experiment, in which we exposed F. dalecarlica in a Cd-contaminated creek to four current velocities (0.05-0.50 m s-1), confirmed that in nature Cd accumulation by this moss is not influenced by current velocity. We show that a bioaccumulation model that ignores current velocity describes Cd accumulation by F. dalecarlica very well. Our results suggest that current velocity does not have to be considered when using aquatic mosses as metal biomonitors.     

离子交换装置试制及脱除鱿鱼肝脏镉离子的研究

本研究利用大孔阳离子交换树脂脱除鱿鱼肝脏匀浆液中的镉离子。以鱿鱼肝脏匀浆液为原料,镉离子吸附率为评价指标,在试制的离子交换装置基础上研究了大孔强酸性阳离子交换树脂对肝脏匀浆液中镉离子吸附的效果。结果表明,镉离子吸附率随吸附交换时间的增加而升高,当吸附时间为210 min时,离子交换达到平衡状态;降低匀浆液p H,有利于离子交换反应的进行,当p H3.0时,吸附效果较好;树脂用量的增加会提高镉离子的吸附率;镉离子的吸附率在料液比1∶10~3∶10先升高后降低;在25~50℃范围内,升高温度可加快离子交换反应速率。即当树脂用量为20.0 g/L,料液比1∶5,p H3.0,温度为25℃条件下,吸附达平衡状态时,镉离子吸附率可达94.34%。      

微波消解-离子选择性电极法快速检测水产品中镉的研究

以微波消解对样品做前处理,采用多功能水质仪连接镉离子选择性电极测定水产品中镉含量.实验对溶液DH值、总离子强度调节缓冲液用量的选择、电极的性能进行分析探讨,并对鸢乌贼内脏中镉含量进行实样检测.结果表明,方法的加标回收率为94.3%～113.9%,RSD为0.9%～1.3%,准确度与精密度较好,完全适用于水产品中镉的快速检测.     

Formation of aqueous MgUO2(CO3)3(2-) complex and uranium anion exchange mechanism onto an exchange resin

The formation of and stability constants for aqueous Mg-UO2-CO3 complexes were determined using an anion exchange method. Magnesium concentration was varied (up to 20 mmol/L) at constant ionic strength (I = 0.101, 0.202, 0.304, 0.406, and 0.509 mol/kg NaNO3), pH 8.1, total [U(VI)] = 10.4 micromol/L under equilibrium with atmospheric CO2. The results indicate that only the MgUO2(CO3)3(2-) complex is formed. The cumulative formation constant extrapolated to zero ionic strength is similar regardless of the activity correction convention used: logbeta113(0) = 25.8 +/- 0.5 using the Davies equation and = 25.02 +/- 0.08 using specific ion interaction theory (SIT). Uranium sorption onto the exchange resin decreased in the presence of Mg putatively due to the formation of MgUO2(CO3)3(2-) that had a lower affinity for the resin than UO2(CO3)3(4-). Uranium sorption results are consistent with an equivalent anion exchange reaction between NO3- and UO2(CO3)3(4-) species to retain charge neutrality regardless of Mg concentration. No Mg was associated with the anion exchange resin indicating that the MgUO2(CO3)3(2-) complex did not sorb.     

Characterization of freshwater natural aquatic colloids by atomic force microscopy (AFM)

Atomic force microscopy (AFM) has been used to image and quantify riverine colloids in a quantitative and relatively nonperturbing manner. Three main classes of material have been imaged including fibrils (about 10 nm in diameter and 100 nm or more in length), discrete, near-spherical, small colloids primarily below 30-50 nm in diameter, and a surface film, of at least several nanometers thickness, which coatsthe entire mica surface within 30 min of exposure to river water. Colloid structure was found to vary as a function of pH, particularly at high pH. Substantially different structures were observed at high pH values, with the loss of the near-spherical colloids possibly due to rearrangement and aggregation. In addition,film thicknesses of up to 100 nm were estimated on the silicon nitride AFM cantilever after 30 h of deposition in the same water (unperturbed and size fractionated). The observation of these surface films has important implications for understanding the mechanisms by which colloids might bind trace elements. In particular, development of surface coatings implies that binding of pollutants (at least initial surface binding) may be dominated by adsorbed surface layers.     

水产品在消毒水作用下产生呋喃西林代谢物的研究

水产品在加工过程中,残留的消毒水(主要成分为次氯酸钠)与水产品作用能产生呋喃西林代谢物,其含量与消毒水浓度(含量≤3%)、作用时间和接触面积成正比。利用液相色谱串联质谱仪,研究了消毒水浓度、浸泡时间和接触面积与SEM残留量的关系。     

Measurement of cadmium(II) and calcium(II) complexation by fulvic acids using 113Cd NMR

Aquatic and terrestrial fulvic acids are environmentally important in pollution transport because they affect the bioavailability and transport of metal ions. The complexation of the metal ions, Cd(II) and Ca(II), with several fulvic acids is examined in this study using 113Cd NMR. Our results indicate that Cd(II) predominately binds to the oxygen containing functional groups of the fulvic acids. A single 113Cd NMR resonance is observed in NMR spectra of Cd(II)-fulvic acid solutions indicating fast exchange between free and complexed cadmium species. An average association equilibrium constant, K(Cd), is determined from NMR spectra measured for the titration of fulvic acid with Cd(II). The K(Cd) values determined for the four fulvic acids studied range between 1.2 and 3.5 x 10(3) M(-1). Competitive binding between Ca(II) and Cd(II) is used to indirectly determine an average association equilibrium constant, K(Ca), for Ca(II) with each fulvic acid. Overall K(Ca) values range from 4.6 to 7.8 x 10(2) M(-1).     

不同基体改进剂对于石墨炉原子吸收光谱法测定水产干制品中镉的影响

目的寻找最优基体改进剂用于石墨炉原子吸收光谱法(graphite furnace atomic absorption spectrometry,GFAAS)测定水产干制品中痕量镉。方法采用微波消解,塞曼效应扣除背景干扰,分别以不同浓度硝酸铵、磷酸二氢铵、钯、氧化镧和EDTA为基体改进剂,标准曲线法测定水产干制品中镉含量。结果硝酸铵作基体改进剂,可最有效地消除该类食品中的基体干扰,且灵敏度较高。测定的最佳条件为:硝酸铵浓度5 g/L,灰化温度700℃,原子化温度1500℃,测定波长228.8 nm。在0~6μg/L浓度范围内,镉浓度与其吸光度呈良好线性关系,相关系数为0.9995,检出限为2μg/kg,加标回收率在93%~102%之间,相对标准偏差(relative standard deviation,RSD)为2.38%。结论在水产干制品中含盐量较高的情况下,以5 g/L硝酸铵为基体改进剂可较为有效地消除GFAAS测镉的基体干扰,从而使分析结果更加准确可靠。     

Evidence for the aquatic binding of arsenate by natural organic matter-suspended Fe(III)

Dialysis experiments with arsenate and three different NOM samples amended with Fe(lll) showed evidence confirming the formation of aquatic arsenate-Fe(Ill)-NOM associations. A linear relationship was observed between the amount of complexed arsenate and the Fe(lll) content of the NOM. The dialysis results were consistent with complex formation through ferric iron cations acting as bridges between the negatively charged arsenate and NOM functional groups and/or a more colloidal association, in which the arsenate is bound by suspended Fe(lll)-NOM colloids. Sequential filtration experiments confirmed that a significant proportion of the iron present at all Fe/C ratios used in the dialysis experiments was colloidal in nature. These colloids may include larger NOM species that are coagulated by the presence of chelated Fe(lll) and/or NOM-stabilized ferric (oxy)hydroxide colloids, and thus, the solution-phase arsenate-Fe(Ill)-NOM associations are at least partially colloidal in nature.     

Validation of an analytical method for the determination of cadmium (Cd) in fish by atomic absorption spectrometry with electrothermal atomisation

The validation of an analytical method was carried out for the determination of cadmium (Cd) in fish. The method was based on sample digestion in a microwave oven and subsequent reading using an atomic absorption spectrometer with a graphite furnace. The factorial design of experiments was applied to assess method ruggedness using the methodology of Box et al. [Box GEP, Hunter WG, Hunter JS. 1978. Statistics for experiments: an introduction to design, data analysis and model building. New York (NY): Wiley], studying the influence of sample mass, volume and concentration of acid used for sample digestion and the volume of modifier used. To study the possible matrix effect in the determination of Cd, the standard addition method was also performed. The results were treated using the OLS method. For the normality test a homoskedastic distribution was observed for the developed method and the results were adjusted to the statistical model proposed. F-tests and Student's t-tests indicated that there was no matrix effect on the calibration curve between the concentration range 1.0-10.0 μg Cd l(-1). Parameters such as selectivity, precision, decision limit, detection capability and limit of quantification were established by the method of standard addition to blank samples. The limit of quantification was 6.8 μg kg(-1). Accuracy, which was evaluated by using a certified reference material, was 107.0%. The recovery of the spiked analyte was 93.69% for the concentration of 50 μg kg(-1). Precision was defined by the coefficient of variation observed (Horrat value), estimated in terms of repeatability and reproducibility, and the values were below the limit, which is 2.0. The validation procedure confirmed the suitability of the method.     

Dynamic model for the accumulation of cadmium and zinc from water and sediment by the aquatic oligochaete, Tubifex tubifex

In aquatic environments, organisms are exposed to and accumulate metals via waterborne and dietary routes including ingested sediment. A key element in understanding metal uptake and accumulation is information concerning the relative importance of the routes of uptake and the kinetics of the processes. In this work the bioaccumulation of the essential element zinc and the nonessential element cadmium were studied from the aqueous and sediment phase, in the cosmopolitan oligochaete Tubifex tubifex, using the radiotracers 109Cd and 65Zn. A compartmental kinetic model was constructed and parametrized by fitting the model to metal body concentrations. Using the pharmacokinetic modeling approach and taking into account the distribution of the metal between water and sediment, the different routes were quantitatively separated. Under the experimental conditions, the sediment phase accounted for 9.8% of the cadmium and 52% of the zinc uptake. These values are based on the uptake of the radiotracers spiked sediments and therefore likely represent maximal values since it was shown that under the specific conditions this was the most mobile metal fraction. This difference was largely explained by the large difference in assimilation efficiency between cadmium and zinc. Simulations of different conditions showed that both dissolved and sediment-associated metal can be important sources of metal exposure for the worms and that the relative importance strongly depends on the metal and exposure conditions including the lability of the metals in the sediment phase.     

Modeling the potential influence of particle deposition on the accumulation of organic contaminants by submerged aquatic vegetation

Submerged aquatic vegetation can act as both a mitigating factor(e.g., reducing downstream impacts of pesticides following runoff/spray drift) and mobilizing factor (e.g., remobilization of contaminants from sediments) influencing the fate and distribution of organic contaminants in the environment. Consequently, there has been wide scientific and regulatory interest in assessing the role of these plants in different contamination scenarios. Mechanistic models describing the environmental fate of contaminants in submerged aquatic vegetation are useful tools for interpreting laboratory and field measurements in addition to providing valuable information to risk assessors. In this study, we developed a fugacity-based model to investigate the influence of particle deposition to plant surfaces on the fate and distribution of two substances in small ponds. The main motivation for conducting this study was to address the fact that the potential contribution of this process is not typically considered by many types of models describing contaminant dynamics in submerged aquatic vegetation. For the hydrophobic substance included in this evaluation (lambda-cyhalothrin), model performance was greatly improved by including this process. The model was also applied in a generic context to compare the importance of particle deposition versus directwater uptake as a function of chemical properties (log Kow) and concentration of suspended solids in the water column. The generic application demonstrated that contaminant mass transfer is dominated by particle deposition for chemicals with log Kow greater than approximately 5.5--6 across a wide range of suspended solid concentrations and can be important even for low log Kow substances in some circumstances. Further empirical and modeling studies are recommended to explore this process more comprehensively.     

Modeling the inhibition of the bacteral reduction of U(VI) by beta-MnO2(s)

Pyrolusite (beta-MnO2(s)) was used to assess the influence of a competitive electron acceptor on the kinetics of reduction of aqueous uranyl carbonate by a dissimilatory metal-reducing bacterium (DMRB), Shewanella putrefaciens strain CN32. The enzymatic reduction of U(VI) and beta-MnO2(s) and the abiotic redox reaction between beta-MnO2(s) and biogenic uraninite (UO2(s)) were independently investigated to allow for interpretation of studies of U(VI) bioreduction in the presence of beta-MnO2(s). Uranyl bioreduction to UO2(s) by CN32 with H2 as the electron donor followed Monod kinetics, with a maximum specific reduction rate of 110 M/h/10(8) cells/mL and a half-saturation constant of 370 microM. The bioreduction rate of beta-MnO2(s) by CN32 was described by a pseudo-first-order model with respect to beta-MnO2(s) surface sites, with a rate constant of 7.92 x 10(-2) h(-1)/10(8) cells/mL. Uraninite that precipitated as a result of microbial U(VI) reduction was abiotically reoxidized to U(VI) by beta-MnO2(s), with concomitant reduction to Mn(II). The oxidation of biogenic UO2(s) coupled with beta-MnO2(s) reduction was well-described by an electrochemical model. However, a simple model that coupled the bacterial reduction of U(VI) and beta-MnO2(s) with an abiotic redox reaction between UO2(s) and beta-MnO2(s) failed to describe the mass loss of U(VI) in the presence of beta-MnO2(s). Transmission electron microscopy (TEM) and energy dispersive spectroscopy (EDS) revealed that the particle size and spatial distribution of the biogenic UO2(s) changed dynamically in systems with, as compared to without, beta-MnO2(s)). These observations suggested that the surface properties and localization of UO2(s) in relation to the cell and beta-MnO2(s) surfaces was an important factor controlling the abiotic oxidation of UO2(s) and, thus, the overall rate and extent of U(VI) bioreduction. The coupled model that was modified to account for the "effective" contact surface area between UO2(s) and beta-MnO2(s) significantly improved the simulation of microbial reduction of U(VI) in the presence of beta-MnO2(s).     

不同脱除剂对暂养紫贻贝体内重金属Cd2+的脱除效果

重金属镉(Cd2+)污染是影响双壳贝类食用安全的重要因素之一。以紫贻贝为研究对象,探索不同脱除剂对暂养紫贻贝体内重金属Cd2+的脱除效果。将染Cd2+的紫贻贝暂养在含不同脱除剂天然海水中,定期更换暂养水体并取样,采用原子吸收法测定贻贝中Cd2+含量。实验采用硒代蛋氨酸、硒化卡拉胶、亚硒酸钠、EDTA-FeNa、EDTA-ZnNa₂、EDTA、氯化亚铁、氯化铁、氯化锌、β-葡聚糖、肽聚糖及葡萄糖酸钙作为脱除剂,评价暂养过程中其对紫贻贝体内重金属Cd2+的脱除效果。结果显示,60和120 mg/L硒化卡拉胶、160 mg/LEDTA-CaNa₂和500 mg/L β-葡聚糖净化处理后,对紫贻贝体内Cd2+具有良好的脱除效果(p<0.05),其脱除率分别为43.6%、37.2%、41.6%和44.6%。     

石墨湿法消解-电感耦合等离子体质谱法测定云南水产品鱼类中的铅、铬、镉含量

目的 建立石墨湿法消解-电感耦合等离子体质谱法测定云南水产品鱼类中的铅、铬、镉3种金属含量。方法 以云南省8个州市共132件水产品中鱼类样品作为实验对象, 采用石墨湿法消解进行样品前处理, 电感耦合等离子体质谱法定量测定样品中铅、铬、镉的含量。结果 铅、铬、镉三种金属元素在0~ 100 μg/L的浓度范围内线性关系良好, 相关系数均大于0.999。铅、铬、镉3种元素的加标回收率依次为94.9%~98.8%, 98.89%~100.4%, 80.9%~96.6%。测定30 μg/L铅、铬、镉标准溶液得到相对标准偏差依次为0.59%、2.51%、0.08%。132件样品中, 均检出铅、铬、镉3种金属, 其中铅的检出率为79.5%, 铬、镉的检出率为100%。结论 该方法适用于水产品鱼类中的铅、铬、镉含量的检测, 所检测的云南水产品鱼类样品中铅、铬、镉三种金属元素都有检出, 但含量均达到国家标准的要求。     

Lead and cadmium content in cocoa beans (short communication)

The choice of cocoa beans as the experimental and sample material for study of the contamination with lead and cadmium was inspired by high Pb and Cd limits in foods made on its basis (cocoa powder, chocolate) as well as by the relatively high proportion of these foods in human nutrition. For Cd, the limits in food products are within the range of 0.01 mg X kg-1 (milk) to 1.0 mg X kg-1 (kidneys) whereas the limits for lead range between 0.1 mg X kg-1 (e.g. milk) and 10.0 mg X kg-1 (e.g. tea, yeast, crustaceans, molluscs). Limits for Pb and Cd in foods made on cocoa bean basis are given in Table 1.     

石墨炉原子吸收光谱法测定海带中镉含量的不确定度评定

目的:为提高实验室石墨炉原子吸收光谱法测定海带中镉元素含量的准确性。方法:参照GB 5009.15—2014《食品安全国家标准食品中镉的测定》,对海带样品进行微波消解后稀释定容,采用GF-AAS法测定海带中的镉含量;同时结合试验过程和数学模型,识别该测量不确定度的可能来源,计算各影响因素相关的不确定度分量,并将各分量进行合成,评定整个测量过程的不确定度。结果:当海带样品中镉含量为0.202 mg/kg时,其扩展不确定度为0.008 mg/kg (k=2)。结论:影响海带中镉测量不确定度的主要因素为样品溶液中质量浓度的测定,且基本由标准工作溶液配制过程引入,其次加标回收率测定带来的不确定度也较大,今后应加强这两方面的质量控制。     

Depuration of cadmium from blue mussel (Mytilus edulis) by hydrolysis peptides and chelating metal elements

The present experiment was conducted to investigate the effects of prepared hairtail (Lepidopusc audatus) hydrolysis peptide–metal element (Fe^2 +, Zn^2 +, Ca^2 +, or Mg^2 +) complexes (PH–Fe^2 +, PH–Zn^2 +, PH–Ca^2 +, or PH–Mg^2 +) on the depuration of cadmium (Cd) from blue mussel (Mytilus edulis) tissues. Cd concentrations in anterior adductor muscle, posterior adductor muscle, gill, mantle, and visceral mass of mussels were 11.391, 15.323, 63.672, 19.509, and 109.621 μg/g, respectively, after 5 days of exposure to 0.32 mg/L Cd. Five groups of these exposed mussels were then exposed to seawater laced with four different concentrations of the peptide complexes listed above (5, 10, 15, and 20 mg/L) for 8 days. After 8 days of depuration, 5 mg/L of PH–Fe^2 +, PH–Zn^2 +, and PH–Ca^2 + showed no significant (P > 0.05) effects on Cd concentrations in mussel tissues. However, significant differences (P < 0.05) were observed in groups exposed to 20 mg/L of PH–Fe^2 +, PH–Zn^2 +, and PH–Ca^2 +. The Cd concentrations in anterior adductor muscle, posterior adductor muscle, gill, mantle, and visceral mass were significantly (P < 0.05) decreased by 29.56–35.83%, 27.51–33.62%, 31.59–40.34%, 25.83–31.28%, and 33.62–33.97%, respectively. Nevertheless, the variables of Cd concentrations in tissues treated with 5–20 mg/L PH–Mg^2 + showed no significant (P > 0.05) differences from controls at any point during the experimental period. For these reasons, PH–Fe^2 +, PH–Zn^2 +, and PH–Ca^2 + can be recommended as depuration agents in mussel feed to decrease the Cd concentrations in tissues.