Rate constants for the reactions of the NO3 radical with HCOOH/HCOO− and CH3COOH/CH3COO− in aqueous solution between 278 and 328 K

The kinetics of the aqueous phase reactions of NO₃ radicals with HCOOH/HCOO^– and CH₃COOH/CH₃COO^– have been investigated using a laser photolysis/long-path laser absorption technique. NO₃ was produced via excimer laser photolysis of peroxodisulfate anions (S₂O ₈ ^2– ) at 351 nm followed by the reactions of sulfate radicals (SO ₄ ^– ) with excess nitrate. The time-resolved detection of NO₃ was achieved by long-path laser absorption at 632.8 nm. For the reactions of NO₃ with formic acid (1) and formate (2) rate coefficients ofk ₁=(3.3±1.0)×10⁵ l mol^–1 s^–1 andk ₂=(5.0±0.4)×10⁷ l mol^–1 s^–1 were found atT=298 K andI=0.19 mol/l. The following Arrhenius expressions were derived:k ₁(T)=(3.4±0.3)×10¹⁰ exp[–(3400±600)/T] l mol^–1 s^–1 andk ₂(T)=(8.2±0.8)×10¹⁰ exp[–(2200±700)/T] l mol^–1 s^–1. The rate coefficients for the reactions of NO₃ with acetic acid (3) and acetate (4) atT=298 K andI=0.19 mol/l were determined as:k ₃=(1.3±0.3)×10⁴ l mol^–1 s^–1 andk ₄=(2.3±0.4)×10⁶ l mol^–1 s^–1. The temperature dependences for these reactions are described by:k ₃(T)=(4.9±0.5)×10⁹ exp[–(3800±700)/T] l mol^–1 s^–1 andk ₄(T)=(1.0±0.2)×10¹² exp[–(3800±1200)/T] l mol^–1 s^–1. The differences in reactivity of the anions HCOO^– and CH₃COO^– compared to their corresponding acids HCOOH and CH₃COOH are explained by the higher reactivity of NO₃ in charge transfer processes compared to H atom abstraction. From a comparison of NO₃ reactions with various droplets constituents it is concluded that the reaction of NO₃ with HCOO^– may present a dominant loss reaction of NO₃ in atmospheric droplets.     

三江平原旱田耕作对湿地土壤理化性质的累积影响初探

在中国科学院三江平原湿地生态试验站综合实验场,对不同耕作年限的湿地土壤(0~20 cm)进行环境累积效应分析。结果表明,随着开垦时间的增加,土壤的理化性质发生渐变,物理性质方面,土壤容重和比重逐渐增大,而孔隙度和田间持水量逐年减少;化学性质方面,土壤pH值随开垦时间的增加而增加,有机质和其他养分则随开垦时间的增加而逐年降低。弃耕后土壤性质有所恢复。土壤性质在开垦初期变化较明显,而后逐渐变缓。     

Performance of Mortar and Chemical Grout Injection into Surrounding Soil When Slurry Pipe-jacking Method is Used

Small-diameter shallow tunnels are often being built by using the slurry pipe-jacking method. This system involves the pushing or thrusting of a drivage machine and concrete pipes into the ground. Chemical grout injection into the surrounding soil around the tunnel is carried out after the drivage and pushing processes are finished. The purpose of the chemical grout injection is to maintain permanent stability of the surrounding soil. However, the behavior of the chemical grouting material in the surrounding soil around the tunnel and the amount of optimum injection is not clearly understood. From these points of view, this paper discusses the performance of the chemical grouting material, when it is injected into the surrounding soil around the tunnel, by means of 2-D Eulerian–Lagrangian seepage analysis. Moreover, the effectiveness of the chemical grout injection was evaluated by using the non-linear finite element method. This investigation show when the range of the grouted zone is designed; it is necessary that the relationship between Young’s modulus of the soil/grouted zone and the confining stress be taken into consideration in order to establish effective, economical and safe chemical grout injection system. Understanding the performance of the seepage/dispersion behavior of the chemical grout and the characteristics of soil/ grouted zone is also important.     

Lake Sediment Core Records of Sulphur Accumulation and Sulphur Isotopic Composition in Central Ontario, Canada Lakes

Stable isotopic compositions and concentrations of total sedimentary sulphur (S) were determined in cores from 6 lakes in the acid-sensitive Muskoka-Haliburton region of south-central Ontario. The isotopic composition of S in deep sediment (> ~ 20 cm) was approximately constant in all lakes, and indicated a pre-industrial δ ³⁴S value between +4.0 and +5.3‰, which is similar to current bulk deposition. Similarly, total S concentrations in deep sediment were relatively low (1.9–5 mg S g⁻¹ dwt) and approximately constant with depth within cores. All lakes exhibited up-core increases in total S and decreases in δ ³⁴S at a depth corresponding to the beginning of industrialization in the Great Lakes region ( ~ 1900), resulting in a generally reciprocal depth pattern between total S concentration and δ ³⁴S ratios. While initial shifts in total S and δ ³⁴S were likely due to enhanced SO₄ reduction of newly available anthropogenic SO₄, both the magnitude and pattern of up-core S enrichment and shifts in δ ³⁴S varied greatly among lakes, and did not match changes in S deposition post 1900. Differences between lakes in total S and δ ³⁴S were not related to any single hydrologic (e.g., residence time) or physical (e.g., catchment-area-to-lake area ratio) lake characteristic. This work indicates that sediment cores do not provide consistent records of changes in post-industrial S deposition in this region, likely due to redox-related mobility of S in upper sediment.     

Reply to comment by Y. Park and J.-H. Ree on 'Chemical remagnetization of the Upper Carboniferous-Lower Triassic Pyeongan Supergroup in the Jeongseon area, Korea: fluid migration through the Ogcheon Fold Belt'

In their comment, Park & Ree have raised several points against the interpretation by Park et al. , and argued that the remagnetization in the Jeongseon area was caused by the thermal effects of a Late Cretaceous pluton and/or associated short-range hydrothermal fluids, rather than by long-range fluids advocated by us.
We disagree with most points raised by Park & Ree and we make a case that these are invalid because of what we believe is incorrect geologic evidence. Hence, our model—that the fluids causing the chemical remagnetization might migrate through the fault system within the Ogcheon Fold Belt—is the most plausible scenario. We recognize that our model needs to be tested in a future study and we welcome new interpretations for or against our model based on reliable geologic or geophysical data.     

要十分重视另一类型地质灾害的防治

文章提出另一类型地质灾害,即化学型地质灾害的定义及其分类。并认为化学型地质灾害不像物理型地质灾害那样发生瞬时灾害,而有一个延缓过程,但是一旦发生,难于挽救。化学型地质灾害体的主体是化学元素,开展地球化学调查,研究化学元素的赋存规律、土壤及沉积物承受各类元素的极限、各类元素活化的条件是揭示诱发化学型地质灾害机理的关键。因此要十分重视与加强化学型地质灾害的调查、研究、监测与治理工作。     

Chemical characterization of the Neogene Aquifer, Belgium

The evolution of groundwater chemistry along the direction of groundwater flow was studied using hydrochemical data from samples collected along a flow line in the Neogene Aquifer, Belgium. Infiltrating water was found to have a very low mineral content and low pH because the sediments are strongly decalcified. Increasing SiO₂ and cation concentrations along the groundwater flow line indicate silicate-weathering processes, confirmed with the aid of saturation indices, calculated with PHREEQC, and stability diagrams. A classification system based on redox sensitive species was developed and shows that an extensive redox sequence is present in the aquifer. At a shallow depth, pyrite oxidation has caused an increase in sulphate, while iron is precipitated as hydroxides. Elevated arsenic concentrations are related to the reduction of these iron hydroxides at a relatively shallow depth and to the dissolution of siderite at greater depth. Dissolution of carbonate in the aquifer material, present in deep layers and to the north, has lead to increased Ca²⁺ and HCO₃ ^? concentrations. The Ca²⁺ from the groundwater is exchanged for Na⁺, Mg²⁺ and K⁺ adsorbed to the clay surfaces at the bottom of the groundwater reservoir. Although the Neogene Aquifer is well flushed, there are still some marine influences present in the deepest parts.     

Toxicities of p-nitrotoluenes and their effects on blood corpuscles and ovaries in Crusian carps (Carassius auratus)

p-nitrotoluene is an important organic intermediate widely used in pesticide, foamed plastics, dyestuff and medicine industries. In this paper, Crusian carps (Carassius auratus) were exposed to dilute p-nitrotoluene solutions with different concentrations of 0, 20, 40, 80, 120, 160, 240 and 320 μg/L; the subsequent physiological responses to the chemical were observed, and the variation characteristics of blood corpuscles, ovaries and oocytes were studied by bio-microscopy. Results showed that even very low concentrations of p-nitrotoluene would lead to toxicosis and even the death of Carassius auratus. The bio-microscopic structures revealed that, compared with the compartment of Carassius auratus growing in the p-nitrotoluene-free water (the control group), the lower concentrations of p-nitrotoluene (for example no more than 80 μg/L) would result in the faster disintegration of erythrocytes and the significant enlargement of oocytes, while the higher contents of p-nitrotoluene (no less than 240 μg/L in this case) would inhibit the division of cells and their further growth, even degenerate blood corpuscles and ovaries, suggesting stronger estrogenic activities. The study is financially supported by the Development Foundation of Science and Technology under Shandong Provincial Education Department (No. J05D51).     

Experimental research on a new encapsulated heat-generating hydraulic fracturing fluid system

1 IntroductionFracturing plays an important role in increasingthe production and injection and enhancing the final re-covery of oil and gas. At present, the use of ahydroxypropyl guar gum, borate-crosslinked, hydraulicfracturing fluid systemhas become ext…     

旧供水井化学处理方法介绍--以加德满都市旧供水井修复为例

本文以加德满都市旧供水井修复项目为例,针对因滤水管缝隙被化学物质堵塞,导致井出水量逐年减少的旧供水井。通过井下电视摄像系统检查,采用六偏磷酸钠、氨基黄酸等有机酸,结合刷洗、高压喷射等机械方法进行处理,使旧供水井出水量得到明显提高。