快速液相色谱-串联质谱法测定环境空气中的全氟化合物

不同研究报道的空气中离子型全氟化合物(PFCs)的分析方法各不相同,本文的目的在于对比和优化不同分析条件。通过对比不同流动相(甲醇和乙腈)、不同色谱柱(C8和C18)、不同梯度洗脱条件下目标化合物的分离效果,确定了以甲醇为流动相、C18色谱柱为分离柱和最佳梯度淋洗液分离的仪器分析条件。比较了甲醇和正已烷/丙酮混合溶剂萃取气相(PUF)和颗粒相(GFF)样品的效果,确定以甲醇为萃取溶剂。建立了空气中PFCs的LC-MS/MS优化分析方法,方法线性范围在0.1~50 ng·m L~(-1)之间,PUF与GFF样品方法检出限分别为0.02~0.35 pg·m~(-3)和0.02~0.26 pg·m~(-3)。同时将方法用于大气实际样品分析。     

Consumer safety evaluation after monitoring of endocrine disruptor pesticide residues: a case study of Thessaly,Central Greece

Abstract

A large number of pesticides used in agricultural practice has been characterized or suspected to be Endocrine Disruptors, with dietary intake to be the major route of consumer’s exposure. In the present study the safety to consumer after the consumption of pome fruits and fruiting vegetables originated from the area of Thessaly, Central Greece was assessed. Objective samplings of 110 samples were conducted in local retail markets in an effort to quantify potential residues of targeted pesticides, previously characterized as endocrine disruptors. For the determination of residues, a QuEChERs-based multiresidue method coupled with liquid and gas chromatographic systems was applied and fully validated in accordance with the European Unions’s requirements in apples and tomatoes in three fortification levels. Acceptable results were obtained for all the validation parameters studied and the limit of quantification of 0.01?mg/kg and limit of detection of 0.0033?mg/kg were achieved. Based on the determined results, the most frequently determined pesticide was chlorpyrifos with a maximum concentration of 0.32?mg/kg in tomato samples. Cypermethrin and dimethoate were also determined in tomatoes and aubergines. The EFSA PRIMo rev.3.1 model was applied for all positive samples and acute risk for consumers was confirmed only in the case of determination of chlorpyrifos in tomatoes.     

基于分散固相萃取-超高效液相色谱串联质谱法测定沉积物中大环内酯类抗生素

采用分散固相萃取与超高效液相色谱串联质谱技术,建立了快速测定沉积物中9种大环内酯类抗生素(螺旋霉素、阿奇霉素、替米考星、竹桃霉素、红霉素、泰乐菌素、吉他霉素、罗红霉素和交沙霉素)的检测方法。沉积物经磷酸盐缓冲液和乙腈混合液浸提,再经过石墨化炭黑和C18硅胶分散固相萃取材料净化。采用超高效液相色谱串联质谱仪(UPLC-MS/MS)测定,以0.1%甲酸和乙腈为流动相,梯度洗脱,采用多反应监测(MRM)离子模式进行测定。结果表明,沉积物中9种大环内酯类回收率范围为67.6%—96.2%,相对标准偏差3.8%—13.6%(n=6),方法检出限介于0.005—0.01μg·kg^-1(R²>0.995)。以太湖湖区典型沉积物样品作为验证,该方法满足实际样品的检测需求。     

Polycyclic aromatic hydrocarbons in Syrian olive oils and their likely daily intakes

The levels of 16 US Environmental Protection Agency polycyclic aromatic hydrocarbons (16 EPA PAHs) in Syrian olive oils have been determined. Forty-two samples including commercial extra virgin and virgin olive oils, and virgin olive oils from olive mills were analyzed. Only naphthalene (NAP) was detected in all olive oil samples under investigation. Among the studied 16 EPA PAHs, the highest maximum concentration was also observed for NAP (120 μg kg^?1). Moreover, three samples exceeded the European Union (EU) maximum level of 2 μg kg^?1 for benzo[a]pyrene (BaP) in oils and fats, and only one sample exceeded the EU maximum level of 10 μg kg^?1 for the sum of benz[a]anthracene, chrysene, BaP, and benzo[b]fluoranthene (PAH4). The likely daily intakes of the total sum of 16 EPA PAHs, the sum of eight genotoxic PAHs, the sum of PAH4, the BaP, and the BaP equivalent through consumption of Syrian olive oils were estimated.     

Pyrolysis of WEEE plastics using catalysts produced from fly ash of coal gasification

Catalytic pyrolysis of thermoplastics extracted from waste electrical and electronic equipment (WEEE) was investigated using various fly ash-derived catalysts. The catalysts were prepared from fly ash by a simple method that basically includes a mechanical treatment followed by an acid or a basic activation. The synthesized catalysts were characterized using various analytical techniques. The results showed that not treated fly ash (FA) is characterized by good crystallinity, which in turn is lowered by mechanical and chemical treatment (fly ash after mechanical and acid activation, FAMA) and suppressed almost entirely down to let fly ash become completely amorphous (fly ash after mechanical and basic activation FAMB). Simultaneously, the surface area resulted increased. Subsequently, FA, FAMB and FAMA were used in the pyrolysis of a WEEE plastic sample at 400°C and their performance were compared with thermal pyrolysis at the same temperature. The catalysts principally improve the light oil yield: from 59 wt.% with thermal pyrolysis to 83 wt.% using FAMB. The formation of styrene in the oil is also increased: from 243 mg/g with thermal pyrolysis to 453 mg/g using FAMB. As a result, FAMB proved to be the best catalyst, thus producing also the lowest and the highest amount of char and gas, respectively.

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A simple and robust method for determination of neem (Azadirachta indica A. Juss) oil in neem oil coated urea

The production of neem oil coated urea (NOCU), a technology developed by the Indian Agricultural Research Institute, has been grown to over 2.0 million tons per year. The estimation of neem oil content in NOCU is important due to its significance in ensuring agronomic efficiency. Therefore, this study was taken up to develop a simple method for the determination of neem oil in NOCU. The procedure involves extraction of neem oil from NOCU; saponification of extracted oil; oxidation of released glycerol to formaldehyde, and subsequent conversion of formaldehyde to a dihydrolutidine derivative. Its concentration was determined spectrophotometrically. The recoveries of neem oil from NOCU with oil load of 500 and 1000?ppm were 87.6?±?3.0% and 90.0?±?4.8% respectively with direct method; and improved to 92.6?±?4.0% and 96.7?±?3.8% after including the in situ purification. A simple method based on the Hantzsch reaction was developed for the determination of neem oil in NOCU. This method is superior to earlier methods in terms of sensitivity, simplicity, and time required.     

Biodegradation of aromatic hydrocarbon in marine sediments of three North Sea oil fields

On a survey around three North Sea oil fields in 1980 the biodegradation of the hydrocarbons ¹⁴C-naphthalene and ¹⁴C-benzo[a]pyrene was measured. An amino acid mixture was taken as reference substrate for total heterotrophic activity. The rate of uptake of naphthalene was found to increase with decreasing distance from the oil platform at all fields with maximum values at stations 0.5 miles (ca 0.8 km) from the centre of oil activity. Data on naphthalene uptake parallel GC-MS data for aromatic hydrocarbons and allow an estimation of the actual uptake velocity of naphthalene in the sediment to be made. A significant mineralisation of benzo[a]pyrene could only occasionally be detected. The respiration of amino acids did not show any pattern related to the oil field activities.     

A steam dried municipal solid waste gasification and melting process

Considering high-moisture municipal solid waste (MSW) of China, a steam dried MSW gasification and melting process was proposed, the feasibility was tested, and the mass and energy balance was analyzed. Preliminary experiments were conducted using a fixed-bed drying apparatus, a 200 kg per day fluidized-bed gasifier, and a swirl melting furnace. Moisture percentage was reduced from 50% to 20% roughly when MSW was dried by slightly superheated steam of 150°C?C350°C within 40 min. When the temperature was less than 250°C, no incondensable gas was produced during the drying process. The gasifier ran at 550°C?C700°Cwith an air equivalence ratio (ER) of 0.2?C0.4. The temperature of the swirl melting furnace reached about 1240°C when the gasification ER was 0.3 and the total ER was 1.1. At these conditions, the fly ash concentration in the flue gas was 1.7 g·(Nm³)^?1, which meant over 95% fly ash was trapped in the furnace and discharged as slag. 85% of Ni and Cr were bound in the slag, as well as 60% of Cu. The mass and energy balance analysis indicates that the boiler heat efficiency of an industrial MSW incineration plant reaches 86.97% when MSW is dried by steam of 200°C. The boiler heat efficiency is sensitive to three important parameters, including the temperature of preheated MSW, the moisture percentage of dried MS Wand the fly ash percentage in the total ash.     

Hepatotoxic and haematological effects of Nigerian Bonny light crude oil in male albino rats

The effect of Bonny light crude oil was assessed in adult albino rats. The rats were administered with 200, 400, and 800?mg/kg of the crude oil orally for 7 days. Fluid intake was measured daily, and the initial and final animal body weight recorded. Oral crude oil at these doses produced no effect on feed and fluid intake between the test groups and the control group. There was a significant decrease in body weight compared to the control group after 7 days of treatment with the different doses of crude oil.

The toxic effects of the liver and hematological effects were assessed. The packed cell volume (PCV) and total white blood cell (WBC) of the 200?mg/kg group were significantly decreased compared to the respective control values. Administration of 200, 400, and 800 mg/kg of Bonny light crude oil, caused a significant dose-dependent increase in glutamic oxaloacetic transaminase (GOT) and glutamic pyruvic transaminase (GPT) levels, but a significant decrease in the alkaline phosphatase (AP) level compared to the control. Histological examination indicates that crude oil induced severe pathologic changes in the forms of necrosis and oedema.     

Reagenzienfreie Bestimmung von Quecksilberspuren in Wasserproben

A comprehensive ecological monitoring of hazardous substances is indispensable to preserve our health and environment. Therefore, fast and inexpensive techniques for routine analysis of pollutants are essential. However, in the measuring procedure itself often toxic reagents are used producing hazardous waste. Omitting environmentally hazardous substances in the analysis procedure is an important contribution to a more sustainable and green analytical chemistry. A reagent-free method for ultra-trace (pg to ng?L^-1) mercury determination in water samples was developed and validated. An active nanogold collector integrated in a fully automated flow injection system is the core of this new method. All mercury species dissolved in the water sample are adsorbed and preconcentrated on the nano-structured gold surface of the collector. After rinsing and drying of the collector, the enriched mercury is thermally desorbed and finally measured by atomic fluorescence spectrometry. This method was optimized and validated for the determination of mercury in natural waters. The influence of various water constituents was investigated and only high contents of dissolved organic carbon (DOC) showed interferences of mercury preconcentration due to the strong complexation of mercury by DOC. This restriction can be solved by UV-irradiation, i.?e. reagent-free digestion of DOC rich samples prior to the preconcentration procedure. Mercury concentration of several natural river and sea waters and water from the discharge of a waste water treatment plant were determined with this new analytical method. Accuracy and precision of the method were demonstrated by several recovery experiments in natural water samples (recoveries: 96–102?%) and by analysis of the certified reference material BCR-579 (Mercury in Coastal Sea Water; recovery: 101?±?1?%). With a detection limit of only 80?pg?Hg?L^–1 the proposed method is highly sensitive. Furthermore the method avoids potential contamination of the sample by reagent addition and is due to the reagent-free procedure environment-friendly. Hence this work is an important contribution to sustainable environmental analysis and at the same time improves accurate routine mercury trace analysis.     

Population dynamic studies on phytoplankton cultures

The use of ozone as an oxidative supplement to biological filtration and to control epizootic microbial outbreaks coincident with maintaining a biological filter was investigated in a 2,271-1 (600 gallon) closed marine-water system. Under conditions of a relatively large biomass load (1.82 kg/3801), filter-bed effluent levels of total ammonia (0.135±0.01 ppm), un-ionized ammonia (0.0074±0.0006 ppm) and nitrite (0.17±0.01 ppm) were maintained within acceptable limits. Reservoir ozonation (100 mg/h/380 l) further significantly reduced (P<0.005) these levels. Nitrates were significantly elevated (P<0.005) with ozonation. Cessation of ozonation elevated total ammonia, un-ionized ammonia and nitrite levels above acceptable limits within 24 h. Resuming ozonation rapidly reversed this trend. Ozone reduced the microbial content of the culture water. Ozonation is suggested as a means of maintaining oxidative flexibility when used as a supplement to biological filtration. Further, prevention of epizootic microbial outbreaks may be accomplished without danger to the biological filter provided a proper system design is utilized.Contribution No. 342, Department of Biology.     

杭州市居室空气中芳香族化合物污染研究

用热解吸/气质联用技术研究了杭州市居室空气中芳香族化合物的组成。结果表明:杭州市居室空气中共存在60种芳香族化合物,其中苯系化合物48种,非苯芳香族化合物12种,检出率大于50%的23种;在10种非苯芳香族化合物,茚、二氢甲基-1H-茚、二氢二甲基-1H-茚、六氢四甲基亚甲基奥、戊基呋喃等5种化合物的总含量之比为77%-96%,是主要的非苯芳香族化合物污染物,在48种苯系化合物中,苯、甲苯、乙苯、苯乙烯、邻二甲苯、间(对)二甲苯、1,2,4-三甲苯、1,3,5-三甲苯、乙基甲苯、丙烯基苯、乙基二甲苯、二乙基苯、萘等13种的总含量之比大于97%,是室内空气中最主要的苯系污染物。     

Utilization of MSWI fly ash as partial cement or sand substitute with focus on cementing efficiency and health risk assessment

• Washed MSWI fly ash was used as partial cement or sand substitute. • Sand replacing is beneficial for strength, while cement replacement reduces strength. • Cementing efficiency factor and mortar pore structure explain the strength results. • Health risk assessment was conducted for MSWI fly ash blended cement mortar. • CR and HI contributed by different exposures and heavy metals were analyzed. The strength of cement substituted mortar decreases with the increase in fly ash amount, whereas the strength increases when the fly ash is blended as sand substitute. A mortar with highest strength (compressive strength= 30.2 Mpa; flexural strength= 7.0 Mpa) was obtained when the sand replacement ratio was 0.75%. The k value (cementing efficiency) of fly ash varied between 0.36 and 0.15 for the fly ash fraction in binder between 5% and 25%. The k values of fly ash used for sand replacement were all significantly above that used for cement substitution. The macropores assigned to the gaps between particles decreased when the fly ash was used as sand replacement, providing an explanation for the strength enhancement. The waste-extraction procedure (toxicity-sulphuric acid and nitric acid method (HJ/T 299-2007)) was used to evaluate metal leaching, indicating the reuse possibility of fly ash blended mortar. For the mortar with the mass ratio of fly ash to binder of 0.5%, the carcinogenic risks (CR) and non-carcinogenic hazard quotient (HQ) in sensitive scenario for blended mortar utilization were 9.66 × 10^-7 and 0.06, respectively; these results were both lower than the threshold values, showing an acceptable health risk. The CR (9.89 × 10^-5) and HQ (3.89) of the non-sensitive scenario for fly ash treatment exceeded the acceptable threshold values, indicating health risks to onsite workers. The main contributor to the carcinogenic and non-carcinogenic risk is Cr and Cd, respectively. The CR and HQ from inhalation was the main route of heavy metal exposure.     

Effect of nitrification inhibitor on plant biomass and N2O emission rates in alpine meadows on the Tibetan Plateau

ABSTRACT

Treatment with nitrification inhibitors, such as dicyandiamide (DCD) and 3,4-dimethylpyrazole phosphate (DMPP) have been strongly indicated to increase grassland biomass and mitigate soil N₂O emission rates. However, the responses of both alpine meadow aboveground biomass and N₂O emission rates to nitrification inhibitors remains unclear. We separately applied three doses of DCD and DMPP to alpine grassland soils with three duplicates. The biomass and N₂O emission rates were subsequently measured by a clear-cut method and in-situ static chamber gas chromatography during the growing season. Our findings indicated that aboveground biomass increased significantly, and N₂O emission rate decreased significantly at 6.8?kg?ha^?1 DCD and DMPP. Furthermore, the biomass increase effect was more significant than the N₂O emission rate mitigation effect (p?<?0.05). The highest ratios of DCD treatments on meadow production increase and N₂O emission rate decrease were 27.2% and 36.3%, respectively. Our findings provide insight into the enhanced grassland primary production and decreased N₂O flux by nitrification inhibitor treatment in alpine meadows, which may be beneficial to help mitigate global warming.     

Persistence of carbaryl and its risk assessment through consumption of treated grapes

The average initial deposits of carbaryl were observed to be 1.4 and 3.1?mg?kg^?1, respectively, following four applications of the insecticide at 4.95 and 9.9?kg active ingredient per hectare. Residues of carbaryl dissipated below its limit of quantification of 50?µg?kg^?1 after 7 and 10 days at single and double the application dosage, respectively. The half-life values (t _1/2) of carbaryl were worked out to be 1.3 and 0.7 days, respectively, at single and double dosages. The acceptable daily intake (ADI) for carbaryl has been fixed at 8?µg?kg^?1 body weight per day. Keeping in view the residues of carbaryl observed one day after the last application, a child of 10?kg and an adult of 60?kg will have an intake of 77 and 154?µg carbaryl after consumption of 100 and 200?g grapes, in comparison to its ADI of 80 and 480?µg; thus, no health risk is to be expected. Therefore, a waiting period of 1 day has been suggested for the safe consumption of carbaryl-treated grapes to avoid any health hazards.     

Ecotoxicological assessment of sediment from Texcalac River and agricultural soil of riverside area,in Tlaxcala,Mexico

This study assesses the potential risk of Texcalac River and riparian area. The p,p′ DDT and ∑DDTs levels in agricultural soils (3.9–208.0?µg/kg) and in surface sediments (0.6–137?µg/kg) surpassing the guidelines for protection of aquatic life (75% > TEC). The ∑PCBs concentration oscillated from 135 to 93941?µg/kg; the half of sediments exceeded the international guidelines (PEL, PEC), as well as two soils (SQGE?=?500?µg/kg). The TEQ concentration of four PCB-DL varied between 0.1 and 24.9?µg TEQ/kg, chiefly affected by PCB 169. Five sediments were lethal for E. foetida, two resulted to be cytotoxic and the 58% produced genotoxicity higher than negative control (A?=?0.28?±?0.05; DICA?=?72.5?±?16.9 au). Likewise, 31.6% of samples increased the micronuclei frequency in V. faba in comparison with negative control. The analytical data and the bioassays results suggest a significant and immediate risk to exposed biota of this region, highlighting a specific area in Texcalac River and other one in Sambrano Ravine. It is necessity assess the dispersion of pollutants and perform biomonitoring studies that display the exposure levels in biota with the goal to characterise the ecotoxicological risk.     

Analyses of phenolic compounds occurring in olive oil mill wastewaters by GC–MS

Phenolic compounds in olive oil mill wastewaters were analysed by HRGC–MS after extracting the acidified solution with ethyl acetate and derivatization with N,O-bis(trimethylsilyl)trifluoroacetamide. Both simple and complex phenols were detected with the latter being the most abundant. 1,2-dihydroxybenzene (catechol), p-hydroxyphenyl ethanol (tyrosol), 3,4-dihydroxyphenyl ethanol (hydroxytyrosol) and 4-hydroxy-3-methoxyphenyl ethanol (homovanillyl alcohol) predominated among the simple phenols using a gas chromatograph coupled with a mass selective detector.     

Analytical studies on the pollution of argeş river

Using two analytical techniques (ICP‐AES and ASV) the heavy metal pollution of Arge? River was studied. These techniques are characterized by similar analytical performances.

The samples were collected from 13 sites starting from Capra Lake (altitude 2241 m) and finishing at Oltenita city (altitude 10 m).

Arge? River is the fifth longest river in Romania after Siret, Mure?, Olt and Some?, its length is 340 km and the river flows through four cities, Curtea de Arge?, Pite?ti, Gae?ti and Oltenita.

The results of the determinations of Cu, Cd, Zn and Pb, indicate that the Arge? River shows relatively low pollution.     

Microwave-assisted synthesized zinc nanoparticles attenuate cisplatin-induced testicular toxicity in mice

Abstract

The purpose of this study was to investigate the protective effects of zinc nanoparticles against cisplatin-induced testicular toxicity in mice. Zinc nanoparticles were produced by microwave-assisted synthesis using Lavandula vera extract as reducing agent. Single doses of cisplatin (7?mg/kg, intraperitoneally) and ZnSO₄ (10?mg/kg, orally), and various doses of zinc nanoparticles (10???50?mg/kg, orally) and vitamin E (100?mg/kg, interaperitoneally) were administered. The protective role of zinc nanoparticles was determined biochemically and histologically. Gradual reduction in malondialdehyde levels and elevation in glutathione levels and in the activities of superoxide dismutase and catalase upon administration of zinc nanoparticles were observed. The pathology of mice treated with cisplatin/vitamin E and cisplatin/zinc nanoparticles were apparently equal, but vitamin E treatment was more effective in lowering oxidative stress markers than zinc nanoparticles. These findings suggest that co-administration of zinc nanoparticles with cisplatin could prevent adverse effects on the male reproductive system via their potential antioxidant properties.     

厌氧好氧一体化生物反应器处理发酵废水的研究

采用新型厌氧好氧一体化生物反应器对发酵废水进行了中试处理研究.试验结果表明,系统总有机负荷最高可达到8.88kg(COD)m-3d-1,系统去除率稳定在88.10%~96.88%,说明反应器处理效率高,抗冲击能力强.反应器结构合理,利于保持丰富、高活性的微生物,反应器厌氧区颗粒污泥TS高达83.9gL-1,VS/TS为56.9%~57.4%,比产甲烷活性为280~350mL(CH4)gvss-1d-1;好氧区固定化微生物TS高达64.03gL-1载体,VS/TS为94.02%~94.30%.反应器各功能区对废水的降解过程分析,说明反应器厌氧区和好氧区一体化结构合理,可将废水逐级降解,从而保证整个系统的处理效果.图8表4参11