重庆南山酸雨与马尾松衰亡的关系

1985—1986年对重庆南山马尾松林衰亡与酸雨的关系进行了研究。四个月的雨水监测表明南山酸雨况情严重。酸雨频率百分之百,平均pH4.2—4.4,最低pH3.6—4.0。土壤酸化程度较重(pH3.7—4.0)。土壤酸化的主要原因是酸雨的输入。濒死树针叶中锰和钴元素大为减少,与土壤中这两种元素的减少相对应。濒死树针叶中铝大量积累,土壤中活性铝增多和铝钙比增大。初步肯定酸雨是南山马尾松衰亡的重要原因之一。     

Infiltration and redistribution of LNAPL into unsaturated layered porous media

Enhanced understanding of light non-aqueous phase liquid (LNAPL) infiltration into heterogeneous porous media is important for the effective design of remediation strategies. We used a 2-D experimental facility that allows for visual observation of LNAPL contours in order to study LNAPL redistribution in a layered porous medium. The layers are situated in the unsaturated zone near the watertable and they are inclined to be able to observe the effect of discontinuities in capillary forces and relative permeabilities. Two experiments were performed. The first experiment consisted of LNAPL infiltration into a fine sand matrix with a coarse sand layer, and the second experiment consisted of a coarse sand matrix and a fine sand layer. The numerical multi-phase flow model STOMP was validated with regard to the experimental results. This model is able to adequately reproduce the experimental LNAPL contours. Numerical sensitivity analysis was also performed. The capillarity contrast between sands was found to be the main controlling factor determining the final LNAPL distribution.     

Kinetic study of the gas-phase reaction of O3 with three unsaturated alcohols

Rate constants for the reactions of ozone with 1-octen-3-ol, 1-nonen-3-ol and 1-nonen-4-ol have been determined at 298 ± 1 K and atmospheric pressure for the first time. The experiments were performed in a 100-L FEP Teflon film bag using absolute rate method; the rate constants were(1.91 ± 0.19) × 10~(-17),(1.89 ± 0.20) × 10~(-17), and(0.83 ± 0.08) × 10~(-17)cm~3/(molecule·sec) for 1-octen-3-ol, 1-nonen-3-ol, and 1-nonen-4-ol, respectively. The rate constants have been compared with those of unsaturated alcohols structural homologs, and used to estimate the reaction reactivity. The electronegativity of carbon–carbon double bond was calculated by atomic charges analysis. The calculated results show that the electronic effect of the lone pair electrons of hydroxyl oxygen is the main cause of the difference in rate coefficient. According to the obtained rate constants, the atmospheric lifetimes of studied unsaturated alcohols were also estimated, which indicates that the reaction with ozone is an important loss pathway in the atmosphere, especially in polluted areas.     

氧化还原电位对土壤中重金属环境行为的影响研究进展

E_h（redox potential,氧化还原电位）代表土壤氧化性和还原性的相对程度,是以电位反映土壤所处氧化还原状态的指标.由于重金属易与对E_h敏感的组分发生吸附、络合、沉淀等化学反应,因此E_h的变化会直接/间接影响重金属形态从而决定其毒性和活性.E_h变化对重金属活性往往存在双向影响:①淹水环境使E_h降低,引发反硝化反应、铁锰氧化物和硫酸盐还原,使pH向中性靠拢,从而间接导致酸性土壤中游离态重金属沉淀或碱性土壤中吸附态重金属释放.②厌氧条件在使E_h发生变化的同时,会引起铁锰氧化物、有机质、硫化物的形态或含量发生改变,如铁锰氧化物还原、大分子有机质分解,分解产物与重金属离子结合增加了可溶性重金属的浓度,但厌氧条件也可以使重金属离子和硫化物产生沉淀,且还原Cr、Hg等元素,降低毒性;在氧化条件下,硫化物氧化形成硫酸盐促进了重金属释放;但铁锰离子沉淀及其氧化物形态变化形成的具有强吸附力的无定形铁锰氧化物可重新吸附游离态金属离子.这些复杂的化学变化对定量化研究E_h对重金属的影响造成困难,从而降低了E_h波动环境（水稻土、周期性覆水潮滩沉积物等）中重金属污染风险评价的准确性,也限制了通过改变E_h来原位修复重金属污染土壤的方法实施.因此,需进一步对E_h诱导下土壤颗粒界面上发生的与重金属行为相关的反应进行深入研究,并开发检测分析技术,如无损伤的物理探测方法或同位素稀释技术等,建立不同土壤中E_h与重金属形态、活性的定量关系,以揭示E_h对重金属形态的影响机制.      

高锰酸盐指数分析时加标回收率的测定

高锰酸盐指数分析一般不进行加标回收实验,因为加标回收率的实施对一个综合指标来说不易找到现成的标准物质,且容量法做加标回收存在一定困难,为加强高锰酸盐指数分析时准确度的控制,文章在加标回收率的测定方面做了积极的探索。     

论CODMn测定方法的改进

从理论和试验两方面论证了现行高锰酸钾法测定化学需氧量的不足，提出在水浴加热过程中增加回流冷凝装置的改进建议。     

旋转填充床中催化氧化脱硫的试验研究

对在新型强化传质设备－旋转填充床中用Mn^2 催化氧化脱除烟气中SO2的工艺进行了试验研究,其脱硫率可达99％,比传统设备的氧化脱硫率提高4％－69％。该设备体积小,操作简单,具有工业化应用前景。     

Tritium and Cl as constraints on fast fracture flow and percolation flux in the unsaturated zone at Yucca Mountain

An analysis of tritium and ³⁶Cl data collected at Yucca Mountain, Nevada suggests that fracture flow may occur at high velocities through the thick unsaturated zone. The mechanisms and extent of this “fast flow” in fractures at Yucca Mountain are investigated with data analysis, mixing models and several one-dimensional modeling scenarios. The model results and data analysis provide evidence substantiating the weeps model [Gauthier, J.H., Wilson, M.L., Lauffer, F.C., 1992. Proceedings of the Third Annual International High-level Radioactive Waste Management Conference, vol. 1, Las Vegas, NV. American Nuclear Society, La Grange Park, IL, pp. 891–989] and suggest that fast flow in fractures with minimal fracture–matrix interaction may comprise a substantial proportion of the total infiltration through Yucca Mountain. Mixing calculations suggest that bomb-pulse tritium measurements, in general, represent the tail end of travel times for thermonuclear-test-era (bomb-pulse) infiltration. The data analysis shows that bomb-pulse tritium and ³⁶Cl measurements are correlated with discrete features such as horizontal fractures and areas where lateral flow may occur. The results presented here imply that fast flow in fractures may be ubiquitous at Yucca Mountain, occurring when transient infiltration (storms) generates flow in the connected fracture network.     

Spatial variability of arsenic and chromium in the soil water at a former wood preserving site

Contamination of industrial sites by wood preservatives such as chromated copper arsenate (CCA) may pose a serious threat to groundwater quality. The objective of this study was to characterise the spatial variability of As and Cr concentrations in the solid phase and in the soil water at a former wood impregnation plant and to reveal the fundamental transport processes. The soil was sampled down to a depth of 2m. The soil water was extracted in situ from the vadose zone over a period of 10 months at depths of 1 and 1.5m, using large horizontally installed suction tubes. Groundwater was sampled from a depth of 4.5m. Results showed that arsenic and chromium had accumulated in the upper region of the profile and exhibited a high spatial variability (As: 21-621 mg kg(-1); Cr: 74-2872 mg kg(-1)). Concentrations in the soil water were high (mean As 167 microg L(-1); Cr: 62 microg L(-1)) and also showed a distinct spatial variability, covering concentration ranges up to three orders of magnitude. The variability was caused by the severe water-repellency of the surface soil, induced by the concurrent application of creosote wood preservatives, which leads to strong preferential flow as evident from a dye experiment. In contrast to soil water concentrations, only low As concentrations (<12 microg L(-1)) were detected in the groundwater. High Cr concentrations in the groundwater (approx. 300 microg L(-1)), however, illustrated the pronounced mobility of chromium. Our study shows that at sites with a heterogeneous flow system in the vadose zone a disparity between flux-averaged and volume-averaged concentrations may occur, and sampling of soil water might not be adequate for assessing groundwater concentrations. In these cases long-term monitoring of the groundwater appears to be the best strategy for a groundwater risk assessment.     

Operator-splitting errors in coupled reactive transport codes for transient variably saturated flow and contaminant transport in layered soil profiles

One possible way of integrating subsurface flow and transport processes with (bio)geochemical reactions is to couple by means of an operator-splitting approach two completely separate codes, one for variably-saturated flow and solute transport and one for equilibrium and kinetic biogeochemical reactions. This paper evaluates the accuracy of the operator-splitting approach for multicomponent systems for typical soil environmental problems involving transient atmospheric boundary conditions (precipitation, evapotranspiration) and layered soil profiles. The recently developed HP1 code was used to solve the coupled transport and chemical equations. For steady-state flow conditions, the accuracy was found to be mainly a function of the adopted spatial discretization and to a lesser extent of the temporal discretization. For transient flow situations, the accuracy depended in a complex manner on grid discretization, time stepping and the main flow conditions (infiltration versus evaporation). Whereas a finer grid size reduced the numerical errors during steady-state flow or the main infiltration periods, the errors sometimes slightly increased (generally less than 50%) when a finer grid size was used during periods with a high evapotranspiration demand (leading to high pressure head gradients near the soil surface). This indicates that operator-splitting errors are most significant during periods with high evaporative boundary conditions. The operator-splitting errors could be decreased by constraining the time step using the performance index (the product of the grid Peclet and Courant numbers) during infiltration, or the maximum time step during evapotranspiration. Several test problems were used to provide guidance for optimal spatial and temporal discretization.