超声技术降解对氯苯酚的研究

研究了超声降解对氯苯酚(4-cp)溶液的规律和超声波对其降解效果的影响因素。实验结果说明溶液的初始浓度、辐射时间、作用频率和作用功率、pH值等因素对对氯苯酚降解效果有明显影响。实验的最佳方案是:溶液的初始浓度为50.30mg/L、超声辐射时间为360min、作用频率为59kHz和作用功率为90W。     

海洋平台圆柱体坠落运动轨迹及落点分析

传统的角度偏差经验值方法导致落物风险评价过程中的落点和危险区预测存在较大误差,科学化、立体化、完整化、多因素概化的落物轨迹和落点分析方法及工具缺位。为此,以海洋平台圆柱体落物为研究对象开展先导研究,在2D运动理论模型基础上,考虑3维、6度受力与运动参数,引入粘性拖曳力系数经验公式、海流运动、旋转升力和力矩项,建立了具有普适性的落物水下3D运动轨迹预测模型,并以现场实验数据校验表明模型方法可行、结果更可信;据此以Matlab 2016为程序设计平台编制了海洋平台圆柱体坠落运动预测分析工具（MREDP）,分析了坠落运动落点分布规律。研究结果表明:随着初始倾斜角度的增大,落点偏移距离呈现先增后降的趋势,于62°时达到最大值,运动轨迹整体呈现螺线曲率减小、向轨迹曲线外开口侧偏移趋势;落点分布变化可分为Y轴偏移稳定主导阶段、X轴偏移实力型快速主导阶段和X轴偏移机会型主导阶段3个阶段;相对MREDP预测结果,DNVGL-RP-F107经验性角度偏差推荐结果较为保守,MREDP可为DNVGL-RP-F107提供更加准确、可信的轨迹曲线和落点取值。基于分析结果,提出了采用Monte Carlo方法表征实际工程中起始运动参数随机性和入水撞击产生的不确定性等建议。     

可见光响应型CuO/BiVO4的光催化活性研究

采用浸渍法制备了CuO/BiVO4光催化剂,通过X射线衍射(XRD)、热重/差示扫描量热(TG/DSC)和傅立叶红外光谱(FTIR)对其进行了表征,并在可见光照射下考察了其光催化氧化亚甲基蓝(MB)的动力学特性。结果表明,Cu的掺杂并未改变BiVO4的晶型结构;Cu(NO3)2/BiVO4在热处理(30～300℃)过程中,NO3-已经完全分解,Cu最终以CuO的形式存在于CuO/BiVO4光催化剂体系中;掺杂不同量Cu的CuO/BiVO4中的Cu2+/Bi+(摩尔比)实测值与理论值相近,该系列光催化剂的合成过程具有较高的可信度;在可见光照射下,CuO/BiVO4光催化降解MB反应符合表观一级反应动力学特征;当Cu2+/Bi+为0.050时,反应动力学速率常数(k)达到最高值(0.4334h-1),此时的k比单体BiVO4作用下的提高了1.04倍;由于异质结的存在,CuO/BiVO4与单体BiVO4相比,电子和空穴的利用率大大增加,使得CuO/BiVO4的光催化活性较单体BiVO4有了大幅度提高。     

Monod kinetics rather than a first-order degradation model explains atrazine fate in soil mini-columns: Implications for pesticide fate modelling

Pesticide transport models commonly assume first-order pesticide degradation kinetics for describing reactive transport in soil. This assumption was assessed in mini-column studies with associated batch degradation tests. Soil mini-columns were irrigated with atrazine in two intermittent steps of about 30 days separated by 161 days application of artificial rain water. Atrazine concentration in the effluent peaked to that of the influent concentration after initial break-through but sharply decreased while influx was sustained, suggesting a degradation lag phase. The same pattern was displayed in the second step but peak height and percentage of atrazine recovered in the effluent were lower. A Monod model with biomass decay was successfully calibrated to this data. The model was successfully evaluated against batch degradation data and mini-column experiments at lower flow rate. The study suggested that first-order degradation models may underestimate risk of pesticide leaching if the pesticide degradation potential needs amplification during degradation.     

4A沸石去除水中Pb2＋的研究

在静态条件下,研究了4A沸石对废水中Pb2＋的吸附性能,并探讨了影响吸附的因素。实验表明：当温度为30℃,废水pH为5～6,0．01g4A沸石对100mg／LPb2＋溶液10mL吸附20min,Pb2＋的去除率可达到99％以上。在实验研究条件下,4A沸石对Pb2＋的吸附符合Langmuir和Freundlich等温吸附方程,相关系数为0．9819和0．9998。经计算,4A沸石对Pb2＋的饱和吸附量为125mg／g。4A沸石吸附水中Pb2＋达到吸附平衡的时间较短;溶液pH值的变化对吸附效果影响不显著;温度从室温略微升高,Pb2＋的去除率略有增大。吸附在4A沸石上的Pb“可回收利用,处理后的4A沸石可以再生,且重复使用性能较好。     

Tell the truth or not? The montero mechanism for emissions control at work

We experimentally test the truth-telling mechanism proposed by Montero (2008) for eliciting firms' abatement costs. We compare this mechanism with two well-known alternative allocation mechanisms, free and costly allocation of permits at the Pigouvian price. Controlling for the number of firms and the firms' maximal emissions, we find that, in line with the theoretical predictions, firms over-report their maximal emissions under free allocation of permits and under-report these under costly allocation of permits. Under Montero's mechanism, by contrast, firms almost always report their maximal emissions truthfully. However, in terms of efficiency, the difference between Montero's mechanism and costly allocation disappears with industries including more than one firm.     

Changes in TcpA gene frequency explain 2,4,6-trichlorophenol degradation in mesocosms

Soils are often polluted by chlorophenols in timber production areas in the northern hemisphere. The tcpA gene encodes the first step of 2,4,6-trichlorophenol (246-TCP) degradation. We tested tcpA gene frequency in three natural pristine soils with different 246-TCP degradation capacity. Gene tcpA frequency increased more in spiked than non-spiked 10-L pails containing coniferous humus soil with high degradation capacity, in contrast to soils where degradation was slower. As the soil in each mesocosm originated from a spatially separate field plot, changes in tcpA gene frequency affected 246-TCP degradation over a range of soil origins. This indicates that the abundance of and changes in tcpA gene frequency could be utilized in estimating the efficacy of natural attenuation and biostimulation treatments in controlled conditions.     

Metabolism of the Nonylphenol Isomer [Ring-U-14c]-4-(3′,5′-Dimethyl-3′-Heptyl)-Phenol by Cell Suspension Cultures of Agrostemma githago and Soybean

Abstract

The biotransformation of the nonylphenol isomer [ring-U-¹⁴C]-4-(3′,5′-dimethyl-3′-heptyl)-phenol (4-353-NP, consisting of two diastereomers) was studied in soybean and Agrostemma githago cell suspension cultures. With the A. githago cells, a batch two-liquid-phase system (medium/n-hexadecane 200:1, v/v) was used, in order to produce higher concentrations and amounts of 4-353-NP metabolites for their identification; 4-353-NP was applied via the n-hexadecane phase. Initial concentrations of [¹⁴C]-4-353-NP were 1 mg L^?1 (soybean), and 5 and 10 mg L^?1 (A. githago). After 2 (soybean) and 7 days (A. githago) of incubation, the applied 4-353-NP was transformed almost completely by both plant species to four types of products: glycosides of parent 4-353-NP, glycosides of primary 4-353-NP metabolites, nonextractable residues and unknown, possibly polymeric materials detected in the media. The latter two products emerged especially in soybean cultures. Portions of primary metabolites amounted to 19–22% (soybean) and 21–42% of applied ¹⁴C (A. githago). After liberation from their glycosides, the primary 4-353-NP metabolites formed by A. githago were isolated by HPLC and examined by GC-EIMS as trimethylsilyl derivatives. In the chromatograms, eight peaks were detected which due to their mass spectra, could be traced back to 4-353-NP. Seven of the compounds were side-chain monohydroxylated 4-353-NP metabolites, while the remaining was a (side-chain) carboxylic acid derivative. Unequivocal identification of the sites of hydroxylation/oxidation of all transformation products was not possible. The main primary metabolites produced by A. githago were supposed to be four diastereomers of 6′-hydroxy-4-353-NP (about 80% of all products identified). It was concluded that plants contribute to the environmental degradation of the xenoestrogen nonylphenol; the toxicological properties of side-chain hydroxylated nonylphenols remain to be examined.     

The effects of triclopyr on 2,4‐D mineralization in two soils

Abstract

The effects of the herbicide triclopyr (3,5,6‐trichloro‐2‐pyridinyloxyacetic acid) on the mineralization of 2,4‐D (2,4‐dichlorophenoyxacetic acid) in two soils which differed in their histories of prior exposure to the two herbicides were investigated. The relative effects of triclopyr on 2,4‐D mineralization and most probable numbers of 2,4‐D degraders were dependent upon the soil. Triclopyr was shown to increase 2,4‐D mineralization rates in a soil which had been exposed to both 2,4‐D and triclopyr, but decreased the mineralization rate of 2,4‐D and inhibited the increase of most probable numbers of 2,4‐D degraders in a soil that had not been directly exposed to either herbicide.     

Rain‐washing of foliar deposits of Dimilin®WP‐25 formulated in four different carrier liquids

Abstract

Dimilin^® WP‐25, a wettable powder formulation of diflubenzuron (DFB) [1‐(4‐chlorophenyl)‐3‐(2,6‐difluorobenzoyl) urea], was formulated in four different carrier liquids, viz., water; a light petroleum paraffinic oil, ID 585; a heavy paraffinic oil, Sunspray^® 7N; and a 1:2 mixture of a light petroleum aromatic solvent (Cyclosol^® 63) and canola oil; to provide four end‐use mixtures, Dim‐W, Dim‐585, Dim‐7N and Dim‐Cy‐C respectively, each containing 28 g of DFB per litre. Balsam fir branch tips clipped from greenhouse‐grown seedlings, and sugar maple branch tips clipped from field‐grown young trees, were exposed to uniform‐sized droplets (ranging in diameters from 135 to 190 μm) of the four end‐use mixtures which were atomized using a monodispersed droplet generator. Droplets were collected on the fir and maple branch tips and the initial residue per g fresh weight of foliage was determined by high‐performance liquid chromatography (HPLC). The branch tips were exposed to cumulative rainfall of 3, 6 and 10 mm at an intensity of 5 mm/h and at time intervals of 1, 12, 36 and 72 h after DFB treatment, to test the influence of ‘ageing’ of foliar residues on rainfastness. Foliar samples were collected for residue determination just before the onset of rainfall, and at 0.5 h post‐rain. DFB was quantified by the HPLC method. In the case of fir foliage, the Dim‐W formulation was the most susceptible to rain‐washing and the rainfastness did not increase with the ageing period of foliar deposits. In contrast, the three oil‐based mixtures showed greater rainfastness depending upon the carrier liquid and the ageing period. Rainfastness decreased in the order of Dim‐Cy‐C > Dim‐7N > Dim‐585 > Dim‐W. In contrast, the data on maple foliage indicated that the ageing of deposits increased the rainfastness of all the 4 end‐use mixtures. Dim‐585 was the most susceptible to rain washing, and rainfastness decreased in the order of Dim‐W > Dim‐Cy‐C > Dim‐7N > Dim‐585.