Evaluation of yeast strains as possible agents for trace enrichment of metal ions in aquatic environments

Sorption properties of six yeast strains were evaluated for trace enrichment of metal ions; Cd²⁺, Cr³⁺, Cr⁶⁺, Cu²⁺, Pb²⁺, and Zn²⁺ from aqueous environments. Metal concentration was determined by flame atomic absorption spectrometry (FAAS). The results showed that trace enrichment of the metals under study with yeast, was dependent on the pH and available metal ions. Enrichment time of 30 min gave an optimum metal uptake. The presence of Na⁺, K⁺, and Ca²⁺ suppressed the uptake of Pb by less than 5%, but suppressed the uptake of Zn by between 15 and 25%. Mg²⁺, Cu⁺, Cu²⁺, Cr³⁺ Cr⁶⁺, Cd²⁺, and Zn²⁺ suppressed the uptake of Pb by between 25 and 35%, and that of Zn by between 15 and 25%. For both Pb and Zn, Cd had the highest suppression of 35 and 30%, respectively for baker's yeast (Saccharomyces cerevisiae). Baker's yeast achieved enrichment factors (EF) of 23, 4, 100, and 1 for dam water, stream water, treated wastewater, and industrial effluent samples for Cu, Pb, Zn, and Cr, respectively. The recoveries of optimised Cd and Cr samples spiked with 2 μg ml⁻¹ of the metal could reach up to 90%, but never exceeded 66% for 10 μg ml⁻¹ samples. For Cu and Pb, the recoveries generally increased independent of concentration, however they were not as high as those for Zn, which exceeded 90% for all the samples spiked with 10 μg ml⁻¹ of the metal. S. cerevisiae PR 61/3 had the highest EF for Cr as compared to the other yeast strains. S. cerevisiae PRI 60/78 was the only yeast strain which was able to enrich Cd in all the samples. Baker's yeast had the highest EFs for Cu and Zn as compared to the other yeast strains without pH adjustment of the water samples. Candida tropicalis attained the highest EFs for Pb as compared to the other yeast strains. The results indicate that all the yeast strains used had a high affinity for Zn based on the EF values achieved. The results from these studies demonstrate that yeast is a viable trace metal enrichment agent that can be used freely suspended in solution to enrich metal ions at relatively low concentrations. This has ramifications on the traditional methods of sampling, sample collection, and transportation from remote sampling sites.     

高效液相色谱法测定水产品中的红霉素残留量

建立了以高效液相色谱法测定水产品中红霉素残留量的方法。提出了以乙腈为提取剂,经过液-液萃取、固相萃取、反萃取等步骤对样品进行分离净化的样品处理方法。测定下限为200μg/kg,回收率70%,批内精密度和批间精密度均小于10%。     

Occurrence and spatial distribution of statins,fibrates and their metabolites in aquatic environments

Due to widespread occurrence of lipid lowering drugs such as statins, fibrates and their metabolites in the aquatic environments, there is a worldwide growing concern in their role in water quality and aquatic biota. However, this concern is limited by ability to address their occurrence, distribution, fate and eco-toxicological effects. This study focuses on the quantification of the levels of statins, fibrates and their metabolites in the aquatic environments using Ultra-High Performance Liquid Chromatography coupled to high resolution quadrupole time-of-flight mass spectrometry (UHPLC-QTOF-MS). The developed UHPLC–QTOF–MS based method was successfully applied to the analysis of statins, fibrates and metabolites in real water samples collected from Daspoort WWWs influent and effluent and Apies River. A series of statin compounds (mevastatin, simvastatin, pravastatin, rosuvastatin, fluvastatin, atorvastatin), fibrates (gemfibrozil, fenofibrate) and the corresponding metabolites (clofibric and fenofibric acids) were detected and quantified in the range of 0.56–19.90 µg/L in both waste and River water samples. In general, the results of the present study are an indication of pollution hazards from wastewater treatment processes and these levels poses a huge risk to the growth and reproduction of aquatic organisms. Thus, regulating the limit levels of statins, fibrates and metabolites in any type of water is paramount as it will provide the vital information on the toxic risks associated with organic pollutants of pharmaceutical origin.     

反相高效液相色法测定水产品中三聚氰胺

采用反相高效液相色谱法(RP-HPLC) 测定了水产品中的三聚氰胺. 色谱柱为Symmetry C18 (5 μm, 4.6 mm×250 mm), 流动相为含有0.01 mol/L庚烷磺酸钠和0.01 mol/L柠檬酸的乙腈(1+4)水溶液, 检测器为紫外检测器, 检测波长240 nm. 线性范围为1～50 μg/mL, 相关系数为0.9998, 最低检出限为0.24 μg/mL, 样品平均加标回收率为78.8%～96.1%, 相对标准偏差为3.7%～6.4%. 方法可用于水产品中三聚氰胺的测定.     

高效液相色谱法检测水产品中硝基呋喃类代谢物残留量

建立了水产品中硝基呋喃类代谢物残留量测定的样品处理方法和高效液相色谱分析方法.样品经酸解、2.氯苯甲醛衍生后用乙酸乙酯萃取、SPE柱净化,经高效液相-紫外检测器测定.本方法4种硝基呋喃类代谢物的定量限均为1.0μg/kg,在5.0～500μg/L质量浓度范围内,4种硝基呋喃类代谢物的工作曲线均呈良好线性,在2个添加浓度水平的平均回收率为76%～102%,相对标准偏差均小于10%(n=6).该方法适用于定性定量水产品中硝基呋喃类代谢物的残留分析.     

Trace enrichment of metal ions in aquatic environments by Saccharomyces cerevisiae

Sorption properties of baker’s yeast cells, characterised as Saccharomyces cerevisiae were evaluated for trace enrichment of metal ions: Cd²⁺, Cr³⁺, Cr⁶⁺, Cu²⁺, Pb²⁺ and Zn²⁺ from aqueous environments. Metal concentration was determined by flame atomic absorption spectrometry (FAAS). Parameters affecting metal uptake such as solution pH, incubation time, amount of yeast biomass and effect of glucose concentration (energy source) were optimised. Further studies were carried out to evaluate the effects on metal uptake after treating yeast with glucose as well as with an organic solvent. The results showed that trace enrichment of the metals under study with yeast, depends upon the amount of yeast biomass, pH and incubation time. Treatment of yeast cells with 10-20 mM glucose concentration enhanced metal uptake with exception to Cr⁶⁺, whose metal enrichment capacity decreased at glucose concentration of 60 mM. Of the investigated organic solvents THF and DMSO showed the highest and lowest capacity, respectively, to enhance metal uptake by yeast cells. Trace enrichment of metal ions from stream water, dam water, treated wastewater from a sewage plant and wastewater from an electroplating plant achieved enrichment factors (EF) varying from 1 to 98, without pre-treatment of the sample. pH adjustment further enhanced the EF for all samples. The results from these studies demonstrate that yeast is a viable trace metal enrichment media that can be used freely suspended in solution to achieve very high EF in aquatic environments.     

Monitoring and effects of nicosulfuron in aquatic mesocosms: development of a simple analytical procedure and evidence for low toxicity to phytoplankton communities

A new analytical procedure is proposed for monitoring nicosulfuron (sulfonylurea herbicide) in aquatic mesocosms derived from complex ecosystems. The approach is based on alternate use of the anionic and molecular forms of the pesticide during the procedure. It also takes into account the sensitivity of the molecule to hydrolysis. The procedure involves solid-phase extraction on a polystyrene–divinylbenzene support followed by a conventional high-performance liquid chromatographic analysis with UV-diode array detection. Recovery tests on samples from natural waters demonstrated that the performances obtained were convenient for monitoring aquatic mesocosms (recoveries of 91±12% at 0.5 g L^–1). The method was used to monitor nicosulfuron in mesocosms initially spiked at 2 or 30 g L^–1 . The evolution curves were compared to those obtained from mesocosms contaminated with atrazine at the same initial doses. The sensitivity of phytoplankton communities to nicosulfuron in aquatic mesocosms was found to be very limited.     

Organic UV filters in marine environments: An update of analytical methodologies,occurrence and distribution

Ultraviolet filters (UV Filters) are compounds that are widely employed in personal care products such as sunscreens to protect the skin from sun damage, but they are also added to other products, such as food packaging, plastics, paints, textiles, detergents, etc. The continuous use of these products causes the release of a substantial amount of these products into the marine environment through direct input or wastewater discharge, and thus they are becoming an important class of contaminants of emerging concern. A correlation between their occurrence and different negative effects on marine biota has been reported.Taking into account all the possible impacts on the environment, knowledge of their presence and distribution in the different compartments of the ecosystems, ranging from waters and sediments to aquatic organisms, which potentially suffer from bioaccumulation and biomagnification processes, is essential. High concentrations of ultraviolet filters have been found in samples collected from across the entire planet, even in polar regions, revealing their global distribution.Therefore, interest in the sensitive determination of ultraviolet filters in several marine matrices has increased. In this article, an overall review of the more recently reported analytical chemistry methods for identifying and quantifying these compounds in marine environmental samples is presented. We compare and discuss the potential advantages and disadvantages of every step involved in the analytical procedure, including the pre-treatment, treatment and extraction processes that are required to avoid matrix effects. Moreover, we describe the worldwide occurrence and distribution of those most important UV filters.     

Biomonitoring: an appealing tool for assessment of metal pollution in the aquatic ecosystem

Wide occurrence of aquatic metal pollution has caused much attention. Biomonitoring offers an appealing tool for the assessment of metal pollution in aquatic ecosystem. The bioindicators including algae, macrophyte, zooplankton, insect, bivalve mollusks, gastropod, fish, amphibian and others are enumerated and compared for their advantages and disadvantages in practical biomonitoring of aquatic metal pollution. The common biomonitoring techniques classified as bioaccumulation, biochemical alterations, morphological and behavior observation, population- and community-level approaches and modeling are discussed. The potential applications of biomonitoring are proposed to mainly include evaluation of actual aquatic metal pollution, bioremediation, toxicology prediction and researches on toxicological mechanism. Further perspectives are made for the biomonitoring of metal pollution in aquatic ecosystem.     

固相萃取/高效液相色谱荧光法测定水产品中苯并芘

采用Florisil固相萃取柱纯化样品,建立了高效液相色谱(HPLC)荧光法测定水产品中苯并(a)芘的方法.样品以正己烷为提取剂,净化、蒸发浓缩后用流动相溶解.荧光检测器激发波长297 nm,发射波长405 nm.流动相为V(乙腈):V(水)=75:25,流速1.0 mL/min,外标法定量.苯并(a)芘在0～200 ng/mL浓度范围内线性关系良好,相关系数r=0.99990;在5个空白样品中添加0.5μg/kg浓度水平的标准品,回收率在81.9%～89.5%之间,相对标准偏差为4.1%(n=5);日内、日间精密度分别为0.7%(n=5)、2.4%(n=3);最低检测限为90 ng/kg.     

Study of the Linear Range in HPLC Analyses with UV Detection: Methodology and Experimental Application to the Influence of the Analyte UV Spectrum

Determination of the linear range is one of the main concerns in validation of an HPLC analysis method. It is particularly important since single point calibration will be then used routinely. We proposed an iterative methodology to handle this problem. The idea was, at each step, to test statistically whether the following point belonged to the same regression line. The methodology was then used to evaluate quantitatively the effect on linear range of a shift in detection wavelength or of the detector bandwidth. Although experimental results were globally in accordance with spectroscopic theory, magnitudes observed were rather large. So the linear range could vary by a factor of over 2 with changes in conditions that remained within the range of current practical values. Changes in detection wavelength were limited to about fifteen nm around λ_max and the detector used was considered to be representative of modern high-performance UV detectors. The question of how to take consequences in method validation into account was raised. The solution proposed recommended that the validation was undertaken in conditions as close as possible to those where the method would be conducted routinely. This means with the same instrumentation and on the product of interest for analyses.     

Liquid chromatography methodologies for the determination of steroid hormones in aquatic environmental systems

Steroid hormones are a diverse group of natural and synthetic compounds. Their wide use in human and veterinary medicine results in their continual introduction into the environment. In recent years, environmental concern over steroids that act as endocrine disruptors has increased because of their adverse effects on organisms or their progeny. Moreover, as these compounds are not totally removed from sewage in wastewater treatment plants, they can reach the aquatic environment and persist due to their physicochemical characteristics.For this reason, a major trend in analytical chemistry is the development of rapid and efficient procedures for the extraction, determination and quantification of steroid hormones in environmental samples. Over the past few decades, the significant expansion of liquid chromatography technology utilizing mass spectrometry detection has led to applications with increased selectivity and sensitivity. Optimized extraction and microextraction techniques combined to these liquid chromatography techniques have lowered detection and quantification limits to the ng L⁻¹–μg L⁻¹ range, which is the concentration of steroid hormones in liquid, solid and biota samples.In this paper, the state-of-the-art techniques for the analysis of steroid hormones focused mainly in based liquid chromatography methods in liquid and aquatic solid and biota samples are reviewed. Handling, storage, extraction and detection methodologies are reviewed and compared for all families of steroid hormones.     

紫外/臭氧法在脱除沸石有机模板剂中的应用

选取LTA, FAU, BETA, MFI和MEL型沸石, 研究紫外/臭氧法在沸石有机模板剂脱除中的应用, 并与传统高温焙烧法比较, 考察两种方法对有机模板剂的脱除能力. 采用XRD, FT-IR, BET等方法对脱除模板剂前后的沸石样品进行表征, 结果表明紫外/臭氧法是一种低温有效除去沸石模板剂的方法. Beta, silicalite-1和silicalite-2沸石在紫外光照后相应的模板剂四乙基氢氧化铵、四丙基氢氧化铵和四丁基氢氧化铵已彻底脱除, A和Y型沸石中分别有27.5和6.2 wt%的四甲基氢氧化铵模板剂残留, 这主要是受其特殊β笼结构的限制而引起的.     

Adjusting timing of weathering test to account for seasonal variations in UV exposure

Satellite-derived UV climatology has been used to design a timetable for the outdoor UV exposure of polymeric material specimens. By pre-exposure computation, fixed time increments are transformed into a schedule with a predicted average accumulation of UV dose. The method was applied to produce a timetable for an ongoing exposure programme in a network of seven European test sites over the latitude range 28.5-67.4°N. The effect of the average seasonal variability of solar UV irradiance on the predicted accumulated UV exposure is shown to be notably diminished by the method. Relative underestimations of 5-82% of cumulative UV stress are estimated to be avoided by extensions of 6-167 days exposure durations as suggested by the adjustment procedure. Hence, more reproducible degradation data are expected to be obtainable for exposures that are not multiples of the full annual cycle of UV, especially for those with a duration <1 year.     

LC-MS/MS内标法测定水产品中三聚氰胺残留量

建立了高效液相色谱-电喷雾串联质谱(LC-MS/MS)测定水产品中残留的三聚氰胺的方法.以13C,15N标记三聚氰胺为内标,样品经三氯乙酸溶液沉淀蛋白,提取目标分析物,经SCX-C18均匀混合填装的反相色谱柱分离,选择反应监测(SRM)正离子模式测定.LC-MS/MS的检测低限为10 μg/kg;在10.0～500 ng/mL时峰强度与质量浓度的线性关系良好(r>0.99).方法的平均回收率为78%～118%.     

高效毛细管电泳-紫外检测法测定饮料等包装材料中的双酚A

建立了饮料等包装材料中双酚A的高效毛细管电泳-紫外检测法.以无水乙醇为提取溶剂,采用硼砂-十二烷基硫酸钠-乙腈溶液为运行缓冲液(pH 9.5);分离毛细管为50cm×50μm,有效长度41cm的熔融石英毛细管;电泳温度为20℃;检测波长为195n m;重力进样,进样时间为15s.以相对迁移时间定性,标准曲线法定量.方法...     

紫外导数光谱法在含苯乙烯链节共聚物组成测定中的应用

人们利用苯环在260nm区域的特征紫外吸收测定共聚物中聚苯乙烯(PS)链节含量时,常假设共聚物的紫外吸收仅来源于PS链节,且共聚物和PS均聚物具有相同的摩尔吸光系数.这些假定并不一定正确,即使共聚单体单元在260nm处不存在特征吸收,对共聚物吸收峰的位置和强度也有明显影响.不少研究者发现苯乙烯-甲基丙烯酸甲酯共聚物中,PS含量和吸光度不存在线性关系.E.J.Mechan发现丁二烯-苯乙烯共聚物中聚丁二烯链节在250～300nm范围内有一个宽的背景吸收.我们也发现在聚苯乙烯-g-十八烷基聚氧乙烯(PS-g-SPEO)接枝共聚物中,SPEO的背景吸收严重干扰了PS链节在260nm处的紫外吸收.为     

Occurrence of pharmaceutical metabolites and transformation products in the aquatic environment of the Mediterranean area

The presence of pharmaceutically active substances (PhACs) in aquatic ecosystems is of great concern due to their constant occurrence in different water systems and potential negative effects on the quality of water and living organisms. After consumption, PhACs are excreted as the parent compound, and/or as free or conjugated metabolites, which might finally arrive to surface and ground waters after their incomplete removal (and possible degradation) in the wastewater treatment plants (WWTP). A large amount of data about parent PhACs in water has been reported in the literature in the last decade; however, there is a lack of information about the presence of their metabolites and transformation/degradation products (TPs). Recent publications report that PhACs found in water are only the “top of the iceberg” in relation to the environmental impact associated to the consumption of PhACs. From a scientific-technological point of view, the overall study of PhACs is a challenge and requires to advance with respect to current knowledge and analytical capacities, considering several key aspects, such as the reliable identification and quantification of the compounds, the improvement of the removal efficiency by the WWTPs, the study of their behaviour in the environment (e.g. persistence and biodegradability), and the environmental risk assessment, considering not only the parent PhACs but also their transformation/metabolism products. In this work, it is intended to delve into this problem, presenting a detailed overview on metabolites and TPs of PhACs in environmental waters from the Mediterranean area. Analytical and environmental problems associated to the determination of these compounds are briefly commented, ending the paper with the main conclusions and expected future trends in relation to this field.     

Study on the nanoscale current of ZnO film by photoassisted peak force tunnel atomic force: A novel technique for UV detection

ZnO film-based ultraviolet (UV) detector was fabricated by photoassisted peak force tunnel atomic force (PFTUNA) on fluorine tin oxide (FTO) substrate. The PFTUNA current in dark and in UV light was ~0.1 and 2.0 nA, respectively. The UV sensitivity (photocurrent/dark current) is more than 20. The response time and the recovery time are ~0.12 and 0.32 s, respectively. The UV sensing mechanism is that the holes will transport to the ZnO surface to capture the adsorbed oxygen ions to weaken the depletion layer under UV illumination. The PFTUNA current between the tip and the ZnO film is consistent with the Richardson–Schottky (RS) thermionic emission model.     

Detection of benzaldehyde and formaldehyde in the UV photolysis of gas-phase methyl benzoate

The excitation of gas-phase methyl benzoate at 240 nm leads to the observation of phosphorescence. The dispersed phosphorescence spectrum has an assigned origin of 25 270 cm⁻¹ and a prominent C=O progression of 1720 cm⁻¹, consistent with literature reports of gas-phase benzaldehyde spectroscopy. Weaker bands, which correspond to formaldehyde ν₁₇ and ν₂₅, are also evident. Time-resolved IR diode laser absorption spectroscopy has been used to probe formaldehyde. Excitation of methyl benzoate at 222 nm clearly indicates the generation of formaldehyde as a photoproduct. The temporal profile of the formaldehyde signal is consistent with significant nascent vibrational excitation in this product. The ratio of formaldehyde initially in the ground vibrational state to that in the excited vibrational states is estimated to be 0.6 ± 0.1. The proposed elimination mechanisms are analogous to those postulated for the formation of CO₂ and acetaldehyde from pyruvic acid.