基于数字钻进技术和量子遗传-径向基函数神经网络的围岩类别超前识别技术研究

围岩类别超前分类是隧道施工过程中必须开展的一项工作,其直接关系到后续的开挖及施工支护方案。为有效地进行隧道围岩类别超前分类,提出了基于数字钻进技术和量子遗传（QGA）-径向基函数（RBF）神经网络的围岩类别超前分类方法。以数字钻进技术为基础,从钻进参数中提取有用信息,构建围岩类别超前分类指标体系。采用量子计算原理对遗传算法进行改进,通过量子位编码和量子旋转门更新种群,以此来确定RBF神经网络的参数,建立了基于QGA-RBF神经网络的围岩类别超前识别系统。最后将该方法应用于青岛胶州湾海底隧道的围岩类别超前识别中,结果表明,该方法具有较高的准确性,其结果为围岩类别超前分类提供了一种新思路。     

高应力深部洞室模型试验分区破裂现象机制的初步研究

以经典的芬纳公式为手段,以观察到分区破裂现象的模型试验为背景,通过对简化后的圆形巷道围岩应变场和能量场的分析,发现极限平衡区边界存在径向应变的不连续性和弹性变形能的聚集性。认为与开挖洞室呈同心圆的环状断裂的形成,是极限平衡区在边界上由于应变场的不协调而导致的与弹性区的断裂分离。而分区破裂的产生,则是这种断裂分离形成后极限平衡区向深处发展的结果。解释了分区破裂产生时洞周围岩应变和位移随距离洞室增加呈波浪形变化的非单调性规律,给出了分区破裂形成后各破裂区半径的表达式,关系式表明各破裂区之间存在等比关系,比值与地应力状态及围岩力学参数有关。将分区破裂模型试验的参数代入该式,可得,n =1.1左右,与实验完成后剖开模型的各破裂区分布特征基本相符。     

Water Role and Its Influence on Hydrogen Isotopic Composition of Natural Gas during Gas Generation

In order to discuss the role and influence of water during the generation of natural gas, the participation mechanism of water during the evolution of organic matter and its influences were summarized. In addition, we carried out an anhydrous cracking experiment of oil extracted from the Feixianguan Formation source rock in a closed system, which led to the establishment of the kinetic models for describing carbon and hydrogen isotopic fractionation during gas generation from organic matter. The models were calibrated and then applied to the northeastern Sichuan Basin. By combining a series of gas generation experiments from octadecane pyrolysis without water or with distilled water in varying mass proportions, several results were proved: (1) the hydrogen isotopic composition of natural gas becomes lighter with the participation of formation water; (2) we can quantitatively study the hydrogen isotopic fractionation with the kinetic model for describing carbon isotopic fractionation; (3) more abundant and reliable geological information can be obtained through the combined application of carbon and hydrogen isotopic indices.     

Performance of A Combination Process of UV/H2O2/Micro‐Aeration for Oxidation of Dichloroacetic Acid in Drinking Water

The decomposition of dichloroacetic acid (DCAA) in water using a UV/H₂O₂/micro‐aeration process was investigated in this paper. DCAA cannot be removed by UV radiation, H₂O₂ oxidation or micro‐aeration alone, while UV/H₂O₂/micro‐aeration combination processes have proved effective and can degrade this compound completely. With initial concentrations of about 110 μg/L, more than 95.1% of DCAA can be removed in 180 min under UV intensity of 1048.7 μW/cm², H₂O₂ dosage of 30 mg/L and micro‐aeration flow rate of 2 L/min. However, more than 30 μg/L of DCAA was left after 180 min by UV/H₂O₂ combination process without micro‐aeration with the same UV intensity and H₂O₂ dosage. The effects of applied UV radiation intensity, H₂O₂ dose, initial DCAA concentration and pH on the degradation of DCAA have been examined in this study. Degradation mechanisms of DCAA with hydroxyl radical oxidation have been discussed. The removal rate of DCAA was sensitive to operational parameters. There was a linear relationship between rate constant k and UV intensity and initial H₂O₂ concentration, which indicated that a higher removal capacity can be achieved by improvement of both factors. A newly found nitrogenous disinfection by‐product (N‐DBP)‐DCAcAm, which has the potential to form DCAA, was easier to remove than DCAA by UV/H₂O₂ and UV/H₂O₂/micro‐aeration processes. Finally, a preliminary cost comparison revealed that the UV/H₂O₂/micro‐aeration process was more cost‐effective than the UV/H₂O₂ process in the removal of DCAA from drinking water.     

Determination of the Tropospheric Hydroxyl Radical by Liquidphase Scrubbing and HPLC: Preliminary Results

A preliminary study was carried out toexamine the feasibility of measuring tropospherichydroxyl radicals (OH) by liquidphase scrubbing andhigh performance liquid chromatography (HPLC). Thepotential advantages of this approach are itssimplicity, portability, and low expense. Thesampling system employs glass bubblers to trapatmospheric OH into a buffered solution of salicylicacid (o-hydroxybenzoic acid, OHBA). Rapidreaction of OH with OHBA produces a stable fluorescentproduct, 2,5-dihydroxybenzoic acid (2,5-DHBA), whichis determined by reverse-phase HPLC and fluorescencedetection. Our preliminary field results indicatethat this method is most suitable for OH measurementsin clean tropospheric air, where interferences fromother atmospheric species appear to be negligible orminor relative to polluted air. In clean air, thesampling period is about 45–90 minutes, which yieldsa detection limit of approximately 3–6 ×10⁵ radicalscm^-3. During an OHintercomparison experiment at the Caribou samplingsite in Colorado, our liquidphase scrubber method wascompared with the ion-assisted mass spectrometry (MS)method. Our results were within the same range asthose of the ion-assisted MS method (1–5 ×10⁶ radicals cm^-3) within our precision atthat time (about ±30–50%). Preliminary testsin Pullman, WA indicated that the method might alsofunction in moderately polluted air by acidifying thescrubbing solution or by adding a scavenger tosuppress interferences. In Pullman, mid-day OHconcentrations were usually in the range of 2–20 ×10⁶ radicals cm^-3. Nighttime OHconcentrations were always low, either at or slightlyabove the detection limit.     

Study on the Free Radical Scavenging Activity of Sea Cucumber(Paracaudina chinens var.) Gelatin Hydrolysate

Gelatin from the sea cucumber(Paracaudina chinens var.) was hydrolyzed by bromelain and the hydrolysate was found to have a high free radical scavenging activity. The hydrolysate was fractionated through an ultrafiltration membrane with 5 kDa molecular weight cutoff(MWCO). The portion(less than 5 kDa) was further separated by Sephadex G-25. The active peak was col-lected and assayed for free radical scavenging activity. The scavenging rates for superoxide anion radicals(O2·-) and hydroxyl radi-cals(·OH) of the fraction with the highest activity were 29.02% and 75.41%,respectively. A rabbit liver mitochondrial free radical damage model was adopted to study the free radical scavenging activity of the fraction. The results showed that the sea cucumber gelatin hydrolysate can prevent the damage of rabbit liver and mitochondria.     

Expression of the Phycoerythrin Gene of Gracilaria lemaneiformis (Rhodophyta) in E. coli and Evaluation of the Bioactivity of Recombinant PE

Phycoerythrin (PE) is one of the most important proteins involved in light capturing during photosynthesis in red algae. Its potential biological activities had gained wide concerns. In the present study, tumor cytotoxic and hydroxyl radical assay were preformed to detect the bioactivity of recombinant PE. Recombinant plasmids pGEX-PE and pBGL were transformed into E.coli BL21 to make two recombinant strains BEX (pGEX-PE) and BGL (pBGL). PE expressing in BEX (pGEX-PE) was validated by SDS-PAGE and Western blotting analysis. SDS-PAGE analysis indicated that the PE-GST fusion protein was mostly inclusion bod- ies. Specific expression of PE was confirmed by Western blotting analysis. The recombinant E. coli BEX (pGEX-PE) cells were col- lected and sonicated. The supernatants were reserved for the tumor cytotoxic experiments. The result of tumor cytotoxic assay indi- cated that the supernatants containing PE had the activity of inhibiting the growth of Hela cells and with the increase of protein con- centration, the inhibiting rate increased from 37.31% to 63.26%, which showed significant difference from the control. Hydroxyl radical scavenging effect was tested with supernatants of BEX (pGEX-PE) and BGL (pBGL) cell lysates treated with sonication and heating. For the sonication samples, the scavenging rates of the supernatants of BEX (pGEX-PE) and BGL (pBGL) cell lysates were significantly higher than the negative control BL21(pGEX-4T) (P<0.02), and the scavenging rates increased slowly following the increase of the protein content. For the heating samples, except for the 0.2 mg mL-1 BGL (pBGL) products, the scavenging effects of the supernatants of BEX (pGEX-PE) and BGL (pBGL) cell lysates were stronger than that of negative control BL21(pGEX-4T). However, the effect intensity was not positively correlated with the increase of the protein concentration. Though a partially de- creased hydroxyl radical scavenging activity was led by heating, the biological activity was still retained and conspicuous. This re- search showed that phycoerythrin protein expressing in E. coli has the potential medical and sanitarian value.     

Formation of hydroxyl radicals catalyzed by clay surfaces

 The formation of superoxide and hydroxyl radicals at the surface of smectite clays due to oxygen reduction is demonstrated by electron paramagnetic resonance spectroscopy. The yield of hydroxyl radicals is mainly a function of particle size of the clays and depends, to a lesser extent, on the clay lattice iron. Synthetic laponite clay with small platelet size (∼20 nm) and without lattice iron is leading in the formation of hydroxyl radicals followed by montmorillonite (∼200 nm). Fluorohectorite (∼2000 nm) was inactive to hydroxyl radical formation by oxygen reduction. Received: 20 January 2001 / Accepted: 7 August 2001     

Mineral oxygen isotope and hydroxyl content changes in ultrahigh-pressure eclogite–gneiss contacts from Chinese Continental Scientific Drilling Project cores

A combined study of mineral O isotopes and hydroxyl contents was carried out for the contacts between ultrahigh‐pressure eclogite and gneiss from main hole of the Chinese Continental Scientific Drilling Project in the Sulu orogen. While there is a large δ¹⁸O variation from ?8.3 to 7.3‰ for all minerals, different styles of mineral‐pair fractionation occur at the boundaries of different lithologies. Both equilibrium and disequilibrium O isotope fractionations are observed between quartz and the other minerals, with reversed fractionations between omphacite and garnet in some samples of eclogite. This suggests that both eclogite and gneiss acquired their negative δ¹⁸O values by meteoric‐hydrothermal alteration of their protoliths at high temperatures before subduction, and that fluid‐assisted O isotope exchange did take place across the boundary of different lithologies at local scales during amphibolite‐facies retrogression. Fourier Transform Infrared Spectroscopy analysis yielded H₂O concentrations of 50 to 1144 p.p.m. (by weight) for garnet and 139 to 751 p.p.m. for omphacite. The state of equilibrium or disequilibrium O isotope fractionations between omphacite and garnet are correlated with variations in their water content at local scales, indicating that the internally derived fluid plays a critical role in retrograde metamorphism during exhumation. The retrograde metamorphism results in mineral reactions and O isotope disequilibria between some of the minerals, but the fluid for retrogression was derived from the decompression exsolution of structural hydroxyl and thus internally buffered in the O isotope composition. A quantitative estimate suggests that a hand specimen (3 × 6 × 9 cm) of eclogite composed of 70% garnet and 30% omphacite can release 0.316 g water by the decompression exsolution of structural hydroxyl, which can form 14.4 g amphibole during exhumation. This provides sufficient amounts of water for the amphibolite‐facies retrogression.     

The effect of gas-phase chemistry on aqueous-phase sulfur dioxide oxidation rates

The rates and mechanisms of both gas and liquid phase reactions for the oxidation of sulfur dioxide play an important role in the production of atmospheric acids and aerosol particles. Rhodeet al. (1981) concluded that sulfate production rates were highly non-linear functions of sulfur dioxide emission rates. Their modelling study used an HO _x termination mechanism for the HO—SO₂ reaction in the gas-phase. Stockwell and Calvert (1983) determined that one of the products of the overall reaction of HO with sulfur dioxide was an HO₂ radical. The National Research Council (1983) using a version of the Rhodeet al. (1981) model modified to include HO₂ production from the HO—SO₂ reaction concluded that sulfate production becomes much more linear with respect to reductions in sulfur dioxide emissions. However, the cause of this increased linearity was not explained by the National Research Council report. It is demonstrated that the increased linearity is due to the coupling of gas-phases and aqueous phase chemistry. The gas-phase sulfur dioxide oxidation mechanism has a very significant effect on hydrogen perodide production rates.