Clam shell catalyst for continuous production of biodiesel

Continuous flow transesterification of waste frying oil (WFO) with methanol for the biodiesel production was tested in a laboratory scale jacketed reactive distillation (RD) unit packed with clam shell based CaO as solid catalyst. The physiochemical properties of the clam shell catalysts were characterized by X-ray Diffraction (XRD), Brunauer–Emmett–Teller (BET), Scanning Electron Microscopy (SEM), and Energy Dispersive Atomic X-ray Spectrometry (EDAX). The effects of the reactant flow rate, methanol-to-oil ratio, and catalyst bed height were studied to obtain the maximum methyl ester conversion. Reboiler temperature of 65°C was maintained throughout the process for product purification and the system reached the steady state at 7 hr. The experimental results revealed that the jacketed RD system packed with clam shell based CaO showed high catalytic activity for continuous production of biodiesel and a maximum methyl ester conversion of 94.41% was obtained at a reactant flow rate of 0.2 mL/min, methanol/oil ratio of 6:1, and catalyst bed height of 180 mm.     

Optimizing mixture properties of biodiesel production using genetic algorithm-based evolutionary support vector machine

Nowadays, biodiesel is used as one of the alternative renewable energy due to the increasing energy demand. However, optimum production of biodiesel still requires a huge number of expensive and time-consuming laboratory tests. To address the problem, this research develops a novel Genetic Algorithm-based Evolutionary Support Vector Machine (GA-ESIM). The GA-ESIM is an Artificial Intelligence (AI)-based tool that combines K-means Chaotic Genetic Algorithm (KCGA) and Evolutionary Support Vector Machine Inference Model (ESIM). The ESIM is utilized as a supervised learning technique to establish a highly accurate prediction model between the input--output of biodiesel mixture properties; and the KCGA is used to perform the simulation to obtain the optimum mixture properties based on the prediction model. A real biodiesel experimental data is provided to validate the GA-ESIM performance. Our simulation results demonstrate that the GA-ESIM establishes a prediction model with better accuracy than other AI-based tool and thus obtains the mixture properties with the biodiesel yield of 99.9%, higher than the best experimental data record, 97.4%.     

固体废物全过程管理中固体废物鉴别研究

对固体废物应进行全过程管理,固体废物鉴别是固体废物全过程管理的基础和关键,包括依据产生来源鉴别和过程鉴别两种方法,依据产生来源鉴别包括丧失原有利用价值的物质、在生产过程中产生的副产物、环境治理和污染控制过程中产生的物质、其他物质四类,在每一类中详细地列举了属于该产生来源的具体固体废物种类名称,便于理解和增强可操作性。过程鉴别包括在固体废物再生利用过程和处置过程中的固体废物鉴别两类,其中在再生利用过程的固体废物鉴别中明确指出了固体废物再生利用产物只有同时满足产品质量标准要求、国家污染控制标准要求以及有实际市场需求、固定用户等条件时,才不作为固体废物管理,在处置过程的固体废物鉴别中具体地列出了处置固体废物全过程中仍然作为固体废物管理的国际惯用处置方式。同时,给出了清晰的"原料—产品—固体废物—处置或产品"全过程中固体废物的产生节点和相应的固体废物类别图,为固体废物鉴别工作提供参考,使固体废物全过程管理有的放矢,有效防止固体废物对环境和人体健康造成的危害。     

Variability of pesticide residues in cauliflower units collected from a field trial and market places in Greece

To estimate the variability of pesticide residue levels present in cauliflower units, a total of 142 samples were collected from a field trial of a cooperative farmer, and 120 samples were collected from different market places in Thessaloniki, Greece. The collected samples were extracted using the quick, easy, cheap, effective, rugged, and safe (QuEChERS) extraction technique, and the residues were determined by liquid chromatography–tandem mass spectrometry. The developed method was validated by evaluating the accuracy, precision, linearity, limit of detection (LOD), and limit of quantification (LOQ). The average recoveries for all the analytes, derived from the data of control samples fortified at 0.01, 0.05, 0.1, and 0.2 mg/kg, ranged from 74 to 110% with a relative standard deviation of ≤8%. The correlation coefficient (R²) was ≥0.997 for all the analytes using matrix-matched calibration standards. The LOD values ranged from 0.001 to 0.003 mg/kg, and the LOQ was determined at 0.01 mg/kg for all the sought analytes. The matrix effect was found to be at a considerable level, especially for cypermethrin and deltamethrin, amounting to +90% and +145%, respectively. For the field samples, the unit-to-unit variability factors (VFs) calculated for cypermethrin and deltamethrin were 2.38 and 2.32, respectively, while the average VF for the market basket samples was 5.11. In the market basket samples, residues of cypermethrin, deltamethrin, chlorpyrifos, and indoxacarb were found at levels ≥LOQ and their respective VFs were 7.12, 5.67, 5.28, and 2.40.     

Effects of humic acids derived from lignite and cattle manure on antioxidant enzymatic activities of barley root

To investigate the effects of humic acids (HAs) on the ability of plants to defend themselves against oxidative stress, barley was hydroponically cultured in the absence and presence of HAs, and the antioxidant enzymatic activities (catalase, superoxide dismutase, ascorbate and glutathione peroxidases) of root tissue were evaluated. Auxin-like structures in HAs, which were extracted from an oxidation product of lignite (LHA) and compost derived from cattle manure (CHA), were identified by pyrolysis-gas chromatography/mass spectrometry (GC/MS) with tetramethylammonium hydroxide. The LHA, which had the lower molecular weight, was more effective in promoting the growth of barley root than CHA. However, the amounts of auxin-like structures in the CHA were much higher than those for LHA. The antioxidant enzymatic activities were initially decreased in the presence of LHA and CHA at the first day after refreshing the culture solution, but were significantly increased on the second day. The CHA sample, which contained relatively high levels of phenolic acids that contained auxin-like structures, was effective in increasing four types of enzymatic activities, while the activities of catalase and ascorbate peroxidase were increased in the presence of LHA, which contains naphthalene derivatives. These results indicate that using HAs as a supplement can be effective in enhancing antioxidation enzymatic activities, while the appearance of the effects is retarded because of the decomposition and release of auxin-like compounds from HAs by organic acids from the plant roots.     

Determination of neonicotinoids in Estonian honey by liquid chromatography–electrospray mass spectrometry

The aim of the study was to provide a comprehensive overview of neonicotinoid pesticide residues in honey samples for a single country and compare the results with the import data for neonicotinoid pesticides. The levels of four neonicotinoid pesticides, namely thiamethoxam, imidacloprid, acetamiprid, and thiacloprid, were determined in 294 honey samples harvested from 2005 to 2013 from more than 200 locations in Estonia. For the analyzed honey samples, 27% contained thiacloprid, and its levels in all cases were below the maximum residue level set by the European Union. The other neonicotinoids were not detected. The proportion of thiacloprid-positive samples for different years correlates well with the data on thiacloprid imports into Estonia, indicating that honey contamination with neonicotinoids can be estimated based on the import data.     

Impact of European legislation on marketed pesticides — A view from the standpoint of health impact assessment studies

The very significant impact of European legislation (Directive 91/414/EEC) on the authorization of plant protection products is reviewed herein, which has resulted in withdrawal of 704 active substances (AS) out of 889 assessed so far. The list of currently approved 276 AS includes 194 AS “existing” in the market before 1993 and 82 “new” AS introduced during the last 15 years. Results of toxicity characterization of the approved AS are also summarized, utilizing several well-known databases. Although significant data gaps exist for a rather large part of the approved AS, it is found that 84 AS are positive for at least one health effect (after chronic and/or acute exposure) including carcinogenicity, reproductive and neuro-developmental disorders, as well as endocrine disruption. The toxicity characterization results of this study are compared to those of recent assessments by other organizations (KemI, the Swedish Chemicals Agency, and the Pesticide Safety Directorate of the UK), where interpretation and use is made of AS “cut-off” criteria foreseen in new EU legislation. These studies report a comparatively smaller AS number with positive toxicity characterization. The possibility of some additional AS withdrawal in the near future, combined with the rather small rate of new AS introduction (approx. 5 per year) suggest that the list of approved AS over the next 10–15 years may not change very drastically. Consideration of the above trends is necessary and instructive in evaluating results of existing health impact assessment (HIA) studies, as well as in planning new ones. Due to the very drastic change in the number and type of marketed AS, that took place within the past 8–9 years, it is suggested that new HIA studies (based on epidemiological data after year 2000) should focus on a rather short time frame and, therefore, on appropriate cohort groups, e.g. young children. For the same reason, results of epidemiological studies of the past (involving banned AS) should be carefully interpreted and used with caution.     

Levels of PCDD/F in adipose tissue on non-occupationally exposed subjects living near a hazardous waste incinerator in Catalonia, Spain

The potential adverse effects on human health of hazardous waste incinerators (HWIs) are a subject of concern. The construction of the first and till now only HWI in Spain finished in 1999. In 2007, after approximately 9 years of regular operations in the facility, the concentrations of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/F) were determined by HRGC/HRMS in samples of adipose tissue of 15 autopsied subjects living in the area under potential impact of the HWI (Constantí, Tarragona County, Catalonia). These data were compared with the levels found in two previous surveys performed in 1998 (baseline) and 2002. The current mean PCDD/F concentration in adipose tissue was 14.6 pg WHO-TEQ/g of fat (range: 3.3–55.4 pg WHO-TEQ/g of fat). It means significant changes (a reduction of 64% and an increase of 47%) in the mean PCDD/F levels in comparison to those found in 1998 and 2002: 40.1 and 9.9 pg WHO-TEQ/g of fat, respectively. Women showed higher levels of PCDD/F than men (23.8 vs 11.2 pg WHO-TEQ/g of fat). The increase in the last 5 years would not be directly attributable to exposure to PCDD/F emitted by the HWI, as other biological monitors such as human plasma and milk decreased during the same period.     

The food-print of Paris: long-term reconstruction of the nitrogen flows imported into the city from its rural hinterland

Between the tenth and twentieth century the population of Paris city increased from a few thousand to near 10 million inhabitants. In response to the growing urban demand during this period, the agrarian systems of the surrounding rural areas tremendously increased their potential for commercial export of agricultural products, made possible by a surplus of agricultural production over local consumption by humans and livestock in these areas. Expressed in terms of nitrogen, the potential for export increased from about 60 kg N/km2/year of rural territory in the Middle Ages, to more than 5,000 kg N/km2/year from modern agriculture. As a result of the balance between urban population growth and rural productivity, the rural area required to supply Paris (i.e. its food-print) did not change substantially for several centuries, remaining at the size of the Seine watershed surrounding the city (around 60,000 km2). The theoretical estimate of the size of the supplying hinterland at the end of the eighteenth century is confirmed by the figures deduced from the analysis of the historical city toll data (octroi). During the second half of the twentieth century, the ‘food-print’ of Paris reduced in size, owing to an unprecedented increase in the potential for commercial export associated with modern agricultural systems based on chemical N fertilization. We argue that analysing the capacity of territories to satisfy the demand for nitrogen-containing food products of local or distant urban population and markets might provide new and useful insights when assessing world food resource allocation in the context of increasing population and urbanization.     

GC/MS法测定润滑油基础油中多环芳烃

对润滑油基础油中多环芳烃的气相色谱/质谱(GC/MS)测定方法进行了研究,探讨了样品的提取,固相萃取柱净化等前处理方法,同时也对仪器测定条件进行了优化.结果表明,在检测润滑油基础油中多环芳烃时,经优化的GC/MS法的加标回收率和精密度均达到较满意的水平.