Cu／A1-Ce-PILC在丙烯选择性催化还原NO反应中的失活研究

采用聚合羟基复合阳离子合成交联黏土A1-Ce-PILC，经SO4^2-改性后，以浸渍法制备了铜基交联黏土催化剂Cu／A1-Ce-PILC，并将其应用于C3H6选择性催化还原NO的反应，350℃时NO转化率达到最大值56％，700℃时下降至22％．为探究催化剂高温失活的原因，采用XPS、TPR、TGA、Py-IR和DSC对反应前后催化剂的物化性能进行了表征．结果表明，经过H2预处理活化后活性组分Cu物种以Cu^＋形式存在，而高温反应后Cu物种除以Cu^＋和Cu^2＋ 2种形式存在外，还出现了少量CuO物种；高温反应过程中A1-Ce-PILC上结构羟基和SO4^2-流失导致催化剂表面酸性减弱；此外，还存在表面积炭覆盖了部分活性中心并堵塞了催化剂孔道的现象．这三者的共同影响促进了C3H6深度氧化，抑制了NO还原，从而导致催化剂的失活．     

Carbon isotope ratios in logged and unlogged boreal forests: Examination of the potential for determining wildlife habitat use

Due to assimilation of recycled CO₂ from litter decomposition and photosynthetic changes in carbon fractionation at low light levels, the foliage at the base of a forest is often more depleted in¹³C compared to that exposed to the atmosphere in either the canopy or in open clearings. This is referred to as the canopy effect. African research has indicated that these habitat differences in foliar ¹³C can be substantial enough to affect the carbon isotope ratios of resident fauna. Previous work documenting a 30-year chronology on moose teeth from Isle Royale National Park indicated a progressive depletion in¹³C and suggested that this could be due to forest regrowth following extensive burning. The present study examined the assumption implicit in this hypothesis that foliar ¹³C varies between open and closed boreal forest sites. I found a marginal canopy effect of 2 ¹³C difference between upper canopy and ground flora for a forest in northwestern Ontario and an average difference of 1.2 in under- and mid-story vegetation between closed forests and open clear-cuts. Because of these small differences, the utility of carbon isotope analysis in quantifying temporally integrated exploitation of deforested habitats will be low for northern boreal locations. In denser forests, such as those in the tropics or western North American where the canopy effect can be expected to be much greater, ¹³C analysis may still offer some promise for determining selection by wildlife of disturbed habitats.     

Synthesis and biodegradation of poly(γ-butyrolactone-co-l-lactide)

Biodegradable polyesters were synthesized by ring-opening copolymerization of -butyrolactone (BL) and its derivatives withl-lactide (LLA). Although tetraphenyl tin was the main catalyst used, other organometallic catalysts were used as well.¹H and¹³C NMR spectra showed that poly(BL-co-LLA)s were statistical and that their number-average molecular weights were as high as 7×10⁴. The maximum BL content obtained from copolymerization BL/LLA was around 17%. TheT _m andT _g values of the copolymers showed a gradual depression with an increase in BL content. NoT _m was obtained for the copolymers containing more than 13 mol% BL. The biodegradability of the copolyesters was evaluated by enzymatic hydrolysis and nonenzymatic hydrolysis tests. The enzymatic hydrolysis was carried out at 37°C for 24 h using lipases fromRhizopus arrhizus andR. delemar. Hydrolyses by both lipases showed that an increase in BL content of the copolymer resulted in enhanced biodegradability. Nonenzymatic accelerated hydrolysis of copolymers at 70°C was found to increase proportionally to their exposure time. The hydrolysis rate of these copolymers was considerably faster than that of PLLA. The higher hydrolyzability was recorded for the BL-rich copolymers. The copolymerization of -methyl--butyrolactone (MBL) or -ethyl--butyrolactone (EBL) with LLA resulted in relatively LA-rich copolymers.     

Enzymatic degradation of poly([R,S] β-hydroxybutyrate)

The synthetic analogue of a bacterially produced polyester, poly(-hydroxybutyrate) (PHB) was synthesized from racemic -butyrolactone using anin situ trimethyl aluminum-water catalyst. The polymer was fractionated into samples differing in molecular weight and isotactic diad content. The latter was closely related to degree of crystallinity. The biodegradation of these fractions were examined by monitoring mass loss over time in the presence of anAlcaligenes faecalis T1 extracellular bacterial poly(-hydroxybutyrate) depolymerase. The fraction with high isotactic diad tacticity content showed little or no degradation over a 50 hour incubation period, whereas the fraction of intermediate isotactic diad content degraded in a continuous steady fashion at a rate that was less than that for bacterial PHB. The low isotactic diad fraction underwent a rapid initial degradation, followed by no further mass loss. The presence of stereoblocks in the polymer structure of the various fractions was an influence on the degree of susceptibility towards degradation and is related to sample crystallinity.     

BUILDUP,WASHOFF, AND EVENT MEAN CONCENTRATIONS1

ABSTRACT: Most watershed water quality simulation models require the user to specify pollutant buildup and washoff rate parameters for pollutants, by land use. Buildup and washoff rates are difficult to measure directly, and only limited guidance and few observed data are available from the literature. Many studies, however, report storm event mean concentrations (EMCs). These EMCs must arise as a result of the buildup and washoff processes, but typically represent the net contribution from a variety of pervious and impervious surfaces. This paper explores the relationship between EMCs and buildup/washoff parameters. An assumption of the mathematical form of the buildup/washoff relationship gives an algebraic expression for the EMC consistent with model assumptions. This yields techniques to separate observed EMCs into contributions from different land uses and from pervious and impervious surfaces. Given this relationship, numerical optimization may be used to estimate site specific values of buildup and washoff parameters from observed storm EMCs for use in modeling. Use of this approach helps ensure that model parameters are consistent with observed data, providing a rational starting point for final model calibration. Several site examples demonstrate use of the method.     

INTEGRATING SERVICE‐LEARNING INTO WATERSHED MANAGEMENT PROGRAMS: OPPORTUNITIES AND CHALLENGES1

ABSTRACT: The objective of this article is to open a dialogue on integrating service‐learning into community based watershed management programs and to discuss opportunities and challenges that a service‐learning program presents to universities and communities. The article presents the concept and definition of service‐learning, and arguments concerning why institutions of higher education and university faculty and students should be involved with community based watershed management programs. The article describes a case study for developing a service‐learning program for watershed management at Virginia Tech and discusses lessons learned from the case study. The paper concluded that to make a service‐learning program sustainable, there should be a long term plan, regular and effective communication with the stakeholders, and some incentives for faculty and students for long term commitment to the community based watershed management programs.     

COLD WATER PATCHES IN WARM STREAMS: PHYSICOCHEMICAL CHARACTERISTICS AND THE INFLUENCE OF SHADING1

ABSTRACT: Discrete cold water patches within the surface waters of summer warm streams afford potential thermal refuge for cold water fishes during periods of heat stress. This analysis focused on reach scale heterogeneity in water temperatures as influenced by local influx of cooler subsurface waters. Using field thermal probes and recording thermistors, we identified and characterized cold water patches (at least 3°C colder than ambient streamflow temperatures) potentially serving as thermal refugia for cold water fishes. Among 37 study sites within alluvial valleys of the Grande Ronde basin in northeastern Oregon, we identified cold water patches associated with side channels, alcoves, lateral seeps, and floodplain spring brooks. These types differed with regard to within floodplain position, area, spatial thermal range, substrate, and availability of cover for fish. Experimental shading cooled daily maximum temperatures of surface waters within cold water patches 2 to 4°C, indicating a strong influence of riparian vegetation on the expression of cold water patch thermal characteristics. Strong vertical temperature gradients associated with heating of surface layers of cold water patches exposed to solar radiation, superimposed upon vertical gradients in dissolved oxygen, can partially restrict suitable refuge volumes for stream salmonids within cold water patches.     

IMPLICATIONS OF C.A.R.E. VS. SOUTHVIEW FARM ON THE U.S. LIVESTOCK AND POULTRY INDUSTRY1

ABSTRACT: On May 19, 1993, a jury in the U.S. District Court for the Western District of New York found Southview Farm and Richard H. Popp guilty of violating the Clean Water Act on five occasions. The violations were the result of storm water runoff from a site used for disposal of dairy cattle manure from an unpermitted concentrated animal feeding operation. The presiding District Court judge later dismissed the jury verdict, and subsequently a U.S. Court of Appeals for the Second Circuit reversed the dismissal. The Court of Appeals concluded that the discharges were not exempt as agricultural storm water discharges, and that the manure spreaders involved were point sources. Because the use of animal manures in crop production activities will result, unavoidably, in the discharge of some pollutants to adjacent surface waters, a rational and universally applicable basis is needed to determine when such discharges are point versus nonpoint source. Current statutes and regulations do not delineate clearly such a boundary. To address this lack of specificity, I propose that application rates be based on recommended crop nutrient needs.     

TEMPORAL AND GEOMORPHIC VARIATIONS OF STREAM STABILITY AND MORPHOLOGY: MAHOGANY CREEK,NEVADA1

ABSTRACT: Detailed studies of long-term management impacts on rangeland streams are few because of the cost of obtaining detailed data replicated in time. This study uses government agency aquatic habitat, stream morphologic, and ocular stability data to assess land management impacts over four years on three stream reaches of an important rangeland watershed in northwestern Nevada. Aquatic habitat improved as riparian vegetation reestablished itself with decreased and better controlled livestock grazing. However, sediment from livestock disturbances and road crossings and very low stream flows limited the rate of change. Stream type limited the change of pool variables and width/depth ratio, which are linked to gradient and entrenchment. Coarse woody debris removal due to previous management limited pool recovery. Various critical-element ocular stability estimates represented changes with time and differences among reaches very well. Ocular stability variables tracked the quantitative habitat and morphologic variables well enough to recommend that ocular surveys be used to monitor changes with time between more intensive aquatic surveys.