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.     

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-M...     

分散固相萃取-超高效液相色谱-串联质谱联用快速检测大豆及土壤中氟磺胺草醚残留

采用分散固相萃取(QuEChERS)样品前处理方法,建立了超高效液相色谱-串联质谱(UPLC-MS/MS)快速检测大豆和土壤中氟磺胺草醚的残留分析方法.大豆和土壤样品采用乙腈(含0.5%甲酸)提取,N-丙基乙二胺(PSA)或石墨化碳黑(GCB)净化,UPLC-MS/MS外标法检测定量.在0.005—0.5 mg.kg-1添加范围内,氟磺胺草醚在土壤、大豆和大豆植株中的平均回收率在79.4%—109.0%之间,变异系数在3.6%—10.1%之间.在山东、河南、吉林进行了氟磺胺草醚在大豆植株和土壤中的降解动态研究,结果表明,试验点中氟磺胺草醚在土壤中的降解半衰期为8.5—23.7 d;在大豆植株中的降解半衰期为2.7—9.8 d.     

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.     

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.     

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.     

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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Improved liquid chromatographic photo diode array mass spectrometric determination of 5-hydroxymethylfurfural and related furfurals in honey

5-Hydroxymethylfurfural is found in several food commodities, including honey. Its concentration is used as one of honey's quality indicators since elevated 5-hydroxymethylfurfural levels indicate overheating and aging of the product. In this context, the European Commission and Codex Alimentarius established the maximum tolerable level for 5-hydroxymethylfurfural, for general type honeys intended for human consumption, at 40 mg kg^?1. In this study, 5-hydroxymethylfurfural, 2-furfural, and the furfuralic derivative 5-methyl-2-furfural were investigated in Greek honey samples, through a high performance liquid chromatographic photo diode array mass spectrometric method developed and validated. Sample preparation was based on a modification of the ‘Quick, Easy, Cheap, Effective, Rugged, and Safe’ procedure. The method was sensitive, exhibiting limit of detection for 5-hydroxymethylfurfural at 0.1 mg kg^?1, far below the permissible level of 40 mg kg^?1. Levels of 5-hydroxymethylfurfural in 28 honey samples varied from 0.5 to 23.5 mg kg^?1, thus, not worrying for consumers. Traces of 2-furfural were detected in limited samples.     

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.     

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.     

Supramolecular complex formation,a possible antigenotoxic mechanism of glucomannan against aflatoxin B1

Abstract

Glucomannan is a highly branched polysaccharide with glycosidic linkages, constituted of mannoses and glucoses. In recent years, its usefulness due to its immunological, antioxidant and antimutagenic activity has been recognized. The aim of the study was to determine the antigenotoxic ability of glucomannan extracted from Candida utilis orally administered (100–700?mg/kg) to mice, which subsequently received 1?mg/kg aflatoxin B₁. Hepatocytes obtained from these animals 4–16?h post administration were examined by means of the comet assay. The antigenotoxic effect was found to be higher than that observed in previous studies with α-mannan and β-D-glucan isolated from Saccharomyces cerevisiae., In order to explore the possibility of formation of a supramolecular complex between glucomannan and aflatoxin B₁, both compounds were co-crystallized, their melting points determined, and the complex analyzed through ultraviolet spectroscopy. The spectroscopy data suggest that the protective effect of glucomannan is related to the formation of a supramolecular complex between the two compounds.     

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.     

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.     

Oral bioaccessibility of inorganic contaminants in waste dusts generated by laterite Ni ore smelting

The laterite Ni ore smelting operations in Niquelândia and Barro Alto (Goiás State, Brazil) have produced large amounts of fine-grained smelting wastes, which have been stockpiled on dumps and in settling ponds. We investigated granulated slag dusts (n = 5) and fly ash samples (n = 4) with a special focus on their leaching behaviour in deionised water and on the in vitro bioaccessibility in a simulated gastric fluid, to assess the potential exposure risk for humans. Bulk chemical analyses indicated that both wastes contained significant amounts of contaminants: up to 2.6 wt% Ni, 7580 mg/kg Cr, and 508 mg/kg Co. In only one fly ash sample, after 24 h of leaching in deionised water, the concentrations of leached Ni exceeded the limit for hazardous waste according to EU legislation, whereas the other dusts were classified as inert wastes. Bioaccessible fractions (BAF) of the major contaminants (Ni, Co, and Cr) were quite low for the slag dusts and accounted for less than 2 % of total concentrations. In contrast, BAF values were significantly higher for fly ash materials, which reached 13 % for Ni and 19 % for Co. Daily intakes via oral exposure, calculated for an adult (70 kg, dust ingestion rate of 50 mg/day), exceeded neither the tolerable daily intake (TDI) nor the background exposure limits for all of the studied contaminants. Only if a higher ingestion rate is assumed (e.g. 100 mg dust per day for workers in the smelter), the TDI limit for Ni recently defined by European Food Safety Authority (196 µg/day) was exceeded (324 µg/day) for one fly ash sample. Our data indicate that there is only a limited risk to human health related to the ingestion of dust materials generated by laterite Ni ore smelting operations if appropriate safety measures are adopted at the waste disposal sites and within the smelter facility.     

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.     

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.     

Airborne fine particulate matter (PM2.5) at industrial,high- and low-density residential sites in a Nigerian megacity

Abstract

Airborne particulate matter PM_2.5 was collected in an industrial, a low-density, and a high-density residential area of Lagos from December 2010 to November 2011, and elemental composition was determined by proton-induced X-ray emission. Across the months, mass concentrations ranged from 13 to 237?µg?m^?3, exceeding the World Health Organization guideline value of 10?µg?m^?3. Data on 24 elements were obtained, with maximum values during Harmattan season months; source identification and apportionment studies by positive matrix factorization suggested that petroleum oil combustion (70%) was the major source of PM_2.5 and could pose a great hazard to Lagos receptors.