Mechanism and catalytic performance for direct dimethyl ether synthesis by CO2 hydrogenation over CuZnZr/ferrierite hybrid catalyst

Direct synthesis of dimethyl ether(DME) by CO_2 hydrogenation has been investigated over three hybrid catalysts prepared by different methods:co-precipitation,sol-gel,and solid grinding to produce mixed Cu,ZnO,ZrO_2 catalysts that were physically mixed with a commercial ferrierite(FER) zeolite.The catalysts were characterized by N_2 physisorption,X-ray diffraction(XRD),transmission electron microscopy(TEM),X-ray photoelectron spectroscopy(XPS),temperature programmed desorption of CO_2(CO_2-TPD),temperature programmed desorption of NH_3(NH_3-TPD),and temperature programmed H2 reduction(H_2-TPR).The results demonstrate that smaller CuO and Cu crystallite sizes resulting in better dispersion of the active phases,higher surface area,and lower reduction temperature are all favorable for catalytic activity.The reaction mechanism has been studied using in situ diffuse reflectance infrared Fourier transform spectroscopy(DRIFTS).Methanol appears to be formed via the bidentate-formate(b-HCOO) species undergoing stepwise hydrogenation,while DME formation occurs from methanol dehydration and reaction of two surface methoxy groups.     

Incorporating natural capital into economy-wide impact analysis: a case study from Alberta

Traditionally, decision-makers have relied on economic impactestimates derived from conventional economy-wide models. Conventional models lack the environmental linkages necessary for examining environmental stewardship and economic sustainability, and in particular the ability to assess the impact of policies on natural capital. This study investigatesenvironmentally extended economic impact estimation on a regionalscale using a case study region in the province of Alberta knownas the Foothills Model Forest (FMF). Conventional economic impactmodels are environmentally extended in pursuit of enhancingpolicy analysis and local decision-making. It is found that theflexibility of the computable general equilibrium (CGE) modelingapproach offers potential for environmental extension, with a solid grounding in economic theory. The CGE approach may be the tool of the future for more complete integrated environment andeconomic impact assessment.     

Interlaboratory evaluation of endotoxin analyses in agricultural dusts--comparison of LAL assay and mass spectrometry

Endotoxin exposure is associated with wheeze and asthma morbidity, while early life exposure may reduce risk of allergy and asthma. Unfortunately, it is difficult to compare endotoxin results from different laboratories and environments. We undertook this study to determine if lipopolysaccharide (LPS) extraction efficiency could account for differences among laboratories. We generated and collected aerosols from chicken and swine barns, and corn processing. We randomly allocated side-by-side filter samples to five laboratories for Limulus assay of endotoxin. Lyophilized aliquots of filter extracts were analyzed for 3-hydroxy fatty acids (3-OHFAs) as a marker of LPS using gas chromatography-mass spectrometry. There were significant differences in endotoxin assay and GC-MS (LPS) results between laboratories for all dust types (p < 0.01). Patterns of differences between labs varied by dust type. Relationships between assay and GC/MS results also depended on dust type. The percentages of individual 3-OHFA chain lengths varied across labs (p < 0.0001) suggesting that each lab recovered a different fraction of the LPS available. The presence of large amounts of particle associated LPS and absence of a freezing thawing cycle were associated with lower correlations between LPS and bioactivity, consistent with an absence of Limulus response to cell-bound endotoxin. These data suggest that extraction methods affect endotoxin measurements. The LAL methods may be most suitable when comparing exposures within similar environments; GC-MS offers additional information helpful in optimizing sample treatment and extraction. GC-MS may be of use when comparing across heterogeneous environments and should be considered for inclusion in future studies of human health outcomes.     

An Evaluation of Selenium Concentrations in Water, Sediment, Invertebrates, and Fish from the Republican River Basin: 1997–1999

The Republican River Basin of Colorado,Nebraska, and Kansas lies in a valley which contains PierreShale as part of its geological substrata. Selenium is anindigenous constituent in the shale and is readily leached intosurrounding groundwater. The Basin is heavily irrigated throughthe pumping of groundwater, some of which is selenium-contaminated, onto fields in agricultural production. Water,sediment, benthic invertebrates, and/or fish were collected from46 sites in the Basin and were analyzed for selenium to determinethe potential for food-chain bioaccumulation, dietary toxicity,and reproductive effects of selenium in biota. Resultingselenium concentrations were compared to published guidelines orbiological effects thresholds. Water from 38% of the sites (n = 18) contained selenium concentrations exceeding 5 g L^-1, which is reported to be a high hazard for selenium accumulation into the planktonic food chain. An additional 12 sites (26% of the sites) contained selenium in water between 3–5 g L^-1, constituting a moderate hazard. Selenium concentrations in sedimentindicated little to no hazard for selenium accumulation fromsediments into the benthic food chain. Ninety-five percent ofbenthic invertebrates collected exhibited selenium concentrationsexceeding 3 g g^-1, a level reported as potentially lethal to fish and birds that consume them. Seventy-five percent of fish collected in 1997, 90% in 1998, and 64% in 1999 exceeded 4 g g^-1selenium, indicating a high potential for toxicity andreproductive effects. However, examination of weight profilesof various species of collected individual fish suggestedsuccessful recruitment in spite of selenium concentrations thatexceeded published biological effects thresholds for health andreproductive success. This finding suggested that universalapplication of published guidelines for selenium may beinappropriate or at least may need refinement for systems similarto the Republican River Basin. Additional research is needed todetermine the true impact of selenium on fish and wildliferesources in the Basin.     

Characterization of microbial communities from coastal waters using microarrays

Molecular methods, including DNA probes, were used to identify and enumerate pathogenic Vibrio species in the Chesapeake Bay; our data indicated that Vibrio vulnificus exhibits seasonal fluctuations in number. Our work included a characterization of total microbial communities from the Bay; development of microarrays that identify and quantify the diversity of those communities; and observation of temporal changes in those communities. To identify members of the microbial community, we amplified the 16S rDNA gene from community DNA isolated from a biofilm sample collected from the Chesapeake Bay in February, 2000. The resultant 75 sequences were 95% or more similar to 7 species including two recently described Shewanella species, baltica and frigidimarina, that have not been previously isolated from the Chesapeake. When the genera of bacteria from biofilm after culturing are compared to those detected by subcloning amplified 16S fragments from community DNA, the cultured sample exhibited a strong bias. In oysters collected in February, the most common bacteria were previously unknown. Based on our 16S findings, we are developing microarrays to detect these and other microbial species in these estuarine communities. The microarrays will detect each species using four distinct loci, with the multiple loci serving as an internal control. The accuracy of the microarray will be measured using sentinel species such as Aeromonas species, Escherichia coli, and Vibrio vulnificus. Using microarrays, it should be possible to determine the annual fluctuations of bacterial species (culturable and non-culturable, pathogenic and non-pathogenic). The data may be applied to understanding patterns of environmental change; assessing the health of the Bay; and evaluating the risk of human illness associated with exposure to and ingestion of water and shellfish.     

The effect of the introduction of prenatal diagnosis on the reproductive history of women at increased risk from neural tube defects

The reproductive history of 45 couples at increased risk for neural tube defect (NTD) who came for genetic counselling in 1970 and 1971 were compared with a similar number counselled in 1975 and 1976, when prenatal diagnostic tests were freely offered. They were subsequently interviewed in their homes and had their reproductive history recorded to the end of 1973 and 1978 respectively. Nearly all had a previous child with an NTD and none of the women were pregnant at the time of counselling. The effect of prenatal diagnosis was to speed somewhat the decision about further pregnancies, but the number of couples deciding on no further children and on having further pregnancies were almost identical in the two groups. The average number of pregnancies was 2·8 per family, with only 1·2 surviving children. The pregnancy outcomes are discussed as are the reasons for not attempting further pregnancies in both groups, which included very high risk of recurrence, a surviving spina bifida child, inability to accept the tests or its implications. Ninety per cent of the second group had tests. Their reactions to the tests were favourable but all complained of the waiting time between amniocentesis and obtaining the results. They all would have tests again in any future pregnancy. The reason for women not having prenatal diagnostic tests included inability to accept termination. It is concluded that couples in South Wales decide either to have no more children or to have further pregnancies regardless of tests. but tests speed a decision and enable the women to enjoy the pregnancy after obtaining the results, and that an NTD greatly reduces the number of children per family. A termination for an NTD is much more acceptable to most than an NTD at term. The reasons for this are discussed.     

Flow rate and particle concentration within the house of the pelagic tunicate Oikopleura vanhoeffeni

The food-concentrating filter within the house of Oikopleura vanhoeffeni Lohmann consists of three layers, upper and lower fine-mesh layers and an intermediate coarse-mesh layer. The filter is a natural analogue of man-made tangential, or cross-flow, filters that are used to concentrate fine particulate and colloidal material by the exclusion of water. Flow analysis using video microscopy of O. vanhoeffeni, collected in 1989 and 1990 at Logy Bay, insular Newfoundland, indicates concentration of particles of 74 to 1089 times that of ambient seawater ( ,n=23), for individuals 1.8 to 5.4 mm long. The smallest individuals had the highest concentration factors. Flow through the house is predominately affected by viscous forces and values of Reynolds numbers are 1. Flow rates through the house of O. vanhoeffeni indicate a maximum filtration capacity of ca. 1.4 to 26 liters d^-1 and clearance rates (assuming ca. 50% of the time is spent not actively pumping) of 0.7 to 13 liters d^-1, depending on body size. The estimated thickness of the boundary layer around individual fibers of the food-concentrating filter is 0.08 m, which is less than the pore width. The estimated concentration factors suggest that colloidal and fine particulate material may aggregate into larger particles within the food-concentrating filter and food tube during feeding.     

Thermal treatment and non-thermal technologies for remediation of manufactured gas plant sites

More than 1500 manufactured gas plant (MGP) sites exist throughout the U.S. Many are contaminated with coal tar from coal-fueled gas works which produced ‘town gas’ from the mid-1800s through the 1950s.^1,2 Virtually all old U.S. cities have such sites. Most are in downtown areas as they were installed for central distribution of manufactured gas. While a few sites are CERCLA/Superfund, most are not. However, the contaminants and methods used for remediation are similar to those used for Superfund clean-ups of coal tar contamination from wood-treating and coke oven facilities. Clean-up of sites is triggered by regulatory pressure, property transfers and re-development as well as releases to the environment — in particular, via groundwater migration. Due to utility de-regulation, site clean-ups may also be triggered by sale of a utility or of a specific utility site to other utilities. Utilities have used two approaches in dealing with their MGP sites. The first is ‘do nothing and hope for the best’. History suggests that, sooner or later, these sites become a bigger problem via a release, citizen lawsuit or regulatory/public service commission intervention. The second, far better approach is to define the problem now and make plans for waste treatment or immobilization. This paper describes recent experience with a high capacity/low cost thermal desorption process for this waste and reviews non-thermal technology, such as bio-treatment, capping, recycling, and dig and haul. Cost data is provided for all technologies, and a case study for thermal treatment is also presented.