Differential global profiling as a new analytical strategy for revealing micropollutant treatment by-products: application to ethinylestradiol and chlorination water treatment

The detection and structural elucidation of micropollutants treatment by-products are major issues to estimate efficiencies of the processes employed for drinking water production versus endocrine disruptive compounds contamination. This issue was mainly investigated at the laboratory scale and in high concentration conditions. However, potential by-products generated after chlorination can be influenced by the dilution factor employed in real conditions. The present study proposes a new methodology borrowed to the metabolomic science, using liquid chromatography coupled to high-resolution mass spectrometry, in order to reveal potential chlorination by-products of ethinylestradiol in spiked real water samples at the part-per-billion level (5 μg L⁻¹). Conventional targeted measurements first demonstrated that chlorination with sodium hypochlorite (0.8 mg L⁻¹) led to removals of ethinylestradiol over 97%. Then, the developed differential global profiling approach permitted to reveal eight chlorination by-products of EE2, six of them being described for the first time. Among these eight halogenated compounds, five have been structurally identified, demonstrating the potential capabilities of this new methodology applied to environmental samples.     

PCDD/Fs and dioxin-like PCBs in sediment and biota from the Mondego estuary (Portugal)

The concentrations of 17 polychlorinated dibenzo-p-dioxins and furans (PCDD/Fs), and 12 dioxin-like polychlorinated biphenyls (dl-PCBs) were measured in sediment and key species as an initial investigation on PCDD/Fs and dl-PCBs contamination in the Mondego estuary (Portugal). The results demonstrated that the values of the total PCDD/Fs (∑PCDD/Fs) concentrations were considerably lower than those of the sum of dl-PCBs (∑dl-PCBs) in all the studied samples. Regarding the contribution of individual congeners, OCDD was the predominant PCDD/F and the mono-ortho PCB 118 and PCB 105 were the dominant PCBs in the majority of the samples. Our results suggest that PCDD/Fs and PCBs behave quite differently along the aquatic food web: ∑PCDD/Fs concentrations were lower in higher trophic-level organisms with fish presenting a distinct PCDD/Fs congeners profile; on the contrary, the higher ∑dl-PCBs values were found in upper-level biota, although not exclusively, and quite similar dl-PCBs congener profiles were observed in nearly all the studied species.     

Effect of Reprocessing and Accelerated Weathering on ABS Properties

The feasibility of reprocessing has been investigated as a possible alternative for acrylonitrile–butadiene–styrene terpolymer (ABS) recycling. Up to 10 reprocessing cycles have been performed by both extrusion and injection techniques and their effect on thermal and mechanical properties have been studied. Moreover, the effect of the combined reprocessing and accelerated weathering has been analyzed. Measurements collected after each molding cycle indicated virtually complete retention of thermal properties. The same behaviour has been observed from accelerated weathering tests. With respect to the mechanical properties, neither the flow index nor the tensile strength were affected by the number of reprocessing cycles though the impact strength decreased slightly. However, the studies based on the accelerated weathering show that there is an important influence of the number of reprocessing cycles on the tensile strength.     

Accumulation and leaching potential of some pharmaceuticals and potential endocrine disruptors in soils irrigated with wastewater in the Tula Valley, Mexico

The reuse of wastewater for irrigation of agricultural land is a well established practice but introduces many contaminants into the terrestrial environment including pharmaceuticals and personal care products. This study reports the persistence and leaching potential of a group of acidic pharmaceuticals, carbamazepine, and three endocrine disruptors in soils from the Tula Valley in Mexico, one of the largest irrigation districts in the world that uses untreated wastewater. After irrigation of soil columns with fortified wastewater over the equivalent of one crop cycle, between 0% and 7% of the total added amounts of ibuprofen, naproxen, and diclofenac and between 0% and 25% of 4-nonylphenol, triclosan, and bisphenol-A were recovered from the soil profiles. Carbamazepine was more persistent, between 55% and 107% being recovered. Amounts in leachates suggested that movement through the soil was possible for all of the analytes, particularly in profiles of low organic matter and clay content. Analysis of soil samples from the Tula Valley confirmed the general lack of accumulation of the acidic pharmaceuticals (concentrations from below the limit of detection to 0.61 μgkg(-1)) and endocrine disruptors (concentrations from below the limit of detection to 109 μgkg(-1)) despite continual addition through regular irrigation with untreated wastewater; there was little evidence of movement through the soil profiles. In contrast, carbamazepine was present in horizon A of the soil at concentrations equivalent to several years of additions by irrigation (2.6-7.5 μgkg(-1)) and was also present in the deeper horizons. The persistence and mobility of carbamazepine suggested a potential to contaminate groundwater.     

Synthesis of chromium-doped malayaite pigments from wastewater containing low chromium(VI)

A malayaite pigment was synthesized with wastewater containing low chromium (Cr)(VI) by a novel liquid-phase reaction method. The effects of the particle size of the precursor and calcination temperature on the final product are examined. The result of scanning electron microscopy shows that the obtained precursor is amorphous and the particle size is approximately 250 nm. The results of X-ray diffraction and differential scanning calorimetry show that the complete transformation temperature was approximately 1050 degrees C. Furthermore, the Commission International de l'Eclairage laboratory shows that the red color of as-prepared pigments is more saturated with a high a* value at 34.1. This process of malayaite pigment preparation via reuse of the Cr(VI)-containing wastewater is quite simple, economical, and energy-saving for the industry, and the products have a saturated red color. There is considerable foreground for the industrial application of this work.     

大型活动拥挤踩踏事故BP神经网络安全评估方法应用分析

根据大型活动拥挤踩踏事故是一个极其复杂的多因素、多变量、多层次的人-机-环境系统,利用数学建模的思路,引入人工神经网络评估方法;以沈阳世博会开幕式为例,通过前馈型BP网络训练和测试,将开幕式举办过程中的人员拥挤踩踏事故风险系统划分为人的因素、物的因素、环境因素、管理因素4个子系统和拥挤踩踏事故综合评估总系统,分别对其进行拟合分析,在各个系统的拟合残差满足条件的情况下,得出量化的评估预测值及BP神经网络的使用范围。研究实例表明,BP神经网络评估结果直观易懂,可操作性强,是值得推广运用的一种评估方法。     

Composting anaerobic and aerobic sewage sludges using two proportions of sawdust

Sawdust has been proven to be a good bulking agent for sludge composting; however, studies on the most suitable ratio of sludge:sawdust for sludge composting and on the influence of the sludge nature (aerobic or anaerobic) on the composting reaction rate are scarce. In this study two different sewage sludges (aerobic, AS, and anaerobic, ANS) were composted with wood sawdust (WS) as bulking agent at two different ratios (1:1 and 1:3 sludge:sawdust, v:v). Aerobic sludge piles showed significantly higher microbial activity than those of anaerobic sludge, organic matter mineralization rates being higher in the AS mixtures. The lowest thermophilic temperatures during composting were registered when the anaerobic sludge was mixed with sawdust at 1:1 ratio, suggesting the presence of substances toxic to microorganisms. This mixture also showed the lowest decreases of ammonium during composting. All this matched with the inhibitory effect on the germination of Lepidium sativum seeds of this mixture at the first stages of composting, and with its low values of microbial basal respiration. However, the ANS+WS 1:3 compost developed in a suitable way; the higher proportion of bulking agent in this mixture appeared to have a diluting effect on these toxic compounds. Both the proportions assayed allowed composting to develop adequately in the case of the aerobic sludge mixture, yielding suitable composts for agricultural use. However, the ratio 1:1 seems more suitable because it is more economical than the 1:3 ratio and has a lower dilution effect on the nutritional components of the composts. In the case of the anaerobic sludge with its high electrical conductivity and ammonium content, and likely presence of other toxic and phytotoxic substances, the 1:3 ratio is to be recommended because of the dilution effect.     

Trifluralin: photolysis under sunlight conditions and reaction with HO* radicals

The gas phase atmospheric degradation of trifluralin (a widely used herbicide) has been investigated at the EUPHORE facility. Its photolysis has been studied under sunlight conditions and its reaction rate constant with HO() radicals was measured using the relative rate method. Using 1,3,5-trimethylbenzene as reference compound, the rate constant of HO() reaction with trifluralin was obtained to be [formula: see text] The mean photolysis rate measured under solar radiation was [formula: see text] . The photolysis of trifluralin was found to generate organic aerosols with a yield of (20 +/-10)%. The data obtained enabled us to discuss the atmospheric fate of trifluralin in the gas phase.     

Mineralization of CCl4 by the UVC-photolysis of hydrogen peroxide in the presence of methanol

A method for a photochemically induced mineralization of CCl4 is described in which use is made of reductive radicals. The UVC-photolysis (254 nm) of H2O2 added to aqueous solutions of CCl4 is leading to the homolysis of the oxidant yielding hydroxyl radicals (HO) that subsequently react with added methanol to generate hydroxymethyl radicals (CH2OH). The latter radicals initiate mineralization of CCl4 by reductive C-Cl bond splitting. CHCl3, C2Cl4 and C2Cl6 were found as reaction intermediates, but are quantitatively depleted in a parallel oxidative reaction manifold leading to mineralization. Carbon dioxide radical anion, CO2(-), an intermediate in the mineralization pathway of methanol, is also shown to initiate the mineralization of CCl4 by reductive dechlorination. A reaction mechanism is proposed and validated with computer simulations of all the experimental results.     

Radio-acoustic positioning as a tool for studying site-specific behavior of the white shark and other large marine species

We describe a method, radio-acoustic-positioning (RAP), for continuously monitoring the movements and behavior of large marine animals. An ultrasonic transmitter on the animal can be localized with high spatial accuracy (2 to 10?m) within an area of 1?km², based on when the same pulse arrives at three hydrophones on sonobuoys aligned in a triangular array. Radio transceivers communicate with the base station, where the x and y coordinates of the subject are calculated using hyperbolic equations. The base station plots the individual's position and displays information from the tag's sensors in real time on a computer monitor before saving the data on a disk. The base station must be situated either on land or on a vessel within the reception range of the three buoys. We used a RAP system to monitor the movements and behavior of white sharks (Carcharodon carcharias) near the elephant seal rookery at Año Nuevo Island in central California. This type of system is an ideal tool to study the predatory behavior of the white shark because individuals patrol for seal prey within a zone <1300?m from shore. We describe the operation of the system, including acoustic triangulation, range of detection and positioning, data acquisition and analysis, and positional accuracy. We illustrate the implementation of the method and its advantages and disadvantages by describing an ongoing study of white shark hunting-behavior. Sample data from this study are presented to illustrate specific points. We describe the movements of five sharks within the receiving range and their behavior relative to each other. The RAP system is compared to other complementary tracking methods. We conclude that this system has great potential for monitoring the movements and behavior of large marine animals within a relatively small zone, where feeding or reproduction takes place.