Base-catalyzed amination of olefins: an example of an environmentally friendly synthesis of amines

The base-catalyzed amination of aromatic olefins is described as an environmentally friendly synthesis of various beta-arylethylamines. Primary and secondary aliphatic amines as well as aromatic amines react with styrene derivatives to give the corresponding beta-arylethylamines in high yield up to 99%. While aliphatic amines react with styrenes in the presence of n-BuLi as the pre-catalyst, anilines can be olefinated using KOtBu as the catalyst.     

Application of photocatalysis as a post treatment method of a heterotrophic-autotrophic denitrification reactor effluent

The aim of this study is the application of photocatalysis as an effective post treatment scheme for the removal of the organic matter and bacteria released by an innovative biological denitrification process referred to as heterotrophic-autotrophic denitrification, which combines heterotrophic and autotrophic denitrification processes. Photocatalytic treatment was applied using TiO2 as a photocatalyst in the loading range of 0.25-2.00 g l(-1) for irradiation periods up to 60 min using a black light fluorescent lamp with an intensity of I(0)=1309 microW cm(-2). The photocatalytic inactivation data were modelled to pseudo first order kinetics as well as by the areal rates to evaluate the photocatalyst loading effect. Chlorination was used as a final disinfection step to attain an overall inactivation of total coliforms as well as to the formation of very low level of trihalomethanes.     

Strategies of maintaining the natural purification potential of rivers and lakes

Surface waters have a great impact on ecology and life of man. Because of their current use and exploitation, chemical and biological pollution, as well as physical changes of rivers and lakes are common. Natural self-purification potential helps to compensate harms to a certain degree. Proposals are given to detect restrictions of the purification potential in time as well as to support and to enhance the natural purification potential.     

Investigation of the characteristics of the reflectivity of clouds

This paper investigates some of the reflectivity characteristics that clouds (when modelled as solid bodies) must exhibit to be compatible with observations that the reflecting surface of a cloud (i) appears almost equally bright across its face, (ii) is brightest when the cloud is opposite to the Sun but decreases in brightness as the cloud moves to other positions and (iii) increases in brightness with increasing optical thickness of the cloud in the observer's line of sight. These observations, respectively, are shown to imply that the peak value of the bidirectional total reflectivity from a cloud surface (i) increases in inverse proportion to the cosine of the angle between the Sun and the normal to the cloud surface, as the incident angle increases, (ii) appears to be directed back in the direction of the incident radiation, and (iii) increases as optical thickness of the cloud in the observer's line of sight increases. The results could have application in many fields (e.g. modelling diffuse radiance distributions for cloudy skies).     

The evolution of mass balance models of persistent organic pollutant fate in the environment

Current approaches to modelling the fate of persistent organic pollutants (POPs) in the environment have evolved in response to four dominant characteristics of these substances; namely: (1) the presence of POPs in virtually all environmental phases and the ease with which they move from one to the other requires multi-compartmental modelling. Describing transport across phase boundaries becomes as, or even more, important as quantifying transport within the phases; (2) POPs may persist in the environment for many decades. For chemicals that 'have time', concepts such as equilibrium partitioning and steady-state become more important than for short-lived substances whose fate is more controlled by the rates of transformation; (3) measuring POPs is difficult and expensive and observed concentrations of POPs are not available in high spatial or temporal resolution. Consequently, high resolution tends not to be a high priority in POP models; and (4) detrimental effects of POPs often manifest themselves in top predators, which has led to a focus on modelling biotic uptake and transfer within food chains. The task of building a POPs model is viewed as combining the four 'building blocks' of partitioning, transport, transformation and source data with the help of the law of the conservation of mass. Process models, evaluative models, models of real local, regional and global fate, as well as biological uptake models are presented and references to numerous examples are provided. An attempt is made to forecast future directions in the field of POPs modelling. It is expected that modelling techniques that do not rely on quantitative emission estimates as well as approaches that take into account spatial, temporal and climatic variability as well as parameter uncertainty will increase in importance. Finally, the relationship between modelling POPs and models of other pollutant issues is addressed, as are potential interactions between POPs and pollutant issues such as eutrophication, acidification and global climate change.     

Structural Dependence of Diurnal Fluctuations of Radon Progeny in Residential Buildings

Movement of radon progeny inside houses is a complex process that depends both on atmospheric conditions and on building structure. The indoor working level (WL) monitored in four houses of differing structures shows regular diurnal fluctuations related to solar warming of the atmosphere. In the two houses with full basements, radon is removed by indoor/outdoor pressure-driven airflow, and basement WL varies inversely with outdoor temperature. In the two houses with half basements open to crawl spaces, radon is drawn into the basement faster than it is removed, so that basement WL varies directly with outside temperature. Average WL's in basements are about twice as high as first floor WL's and as much as 18 times as high as outdoor WL's. Each house shows an individual pattern of radon progeny movement throughout the building.     

A preliminary assessment of the potential environmental and human health impact of unsymmetrical dimethylhydrazine as a result of space activities

A preliminary assessment of the potential environmental and human health impact of UDMH as a result of space activities has been carried out applying a theoretical approach in comparison with selected experimental data. The theoretical framework includes QSAR, ADME and PASS modelling as well as studies on the possible atmospheric dispersion of UDMH as calculated applying the OML-Multi model. The possible impact on the environment and the human health has been elucidated and it has been concluded that UDMH especially inside the fall region of burned-out rocket stages constitute a significant threat to both environmental and human health, the latter as a results of the carcinogenic, mutagenic, convulsant, teratogenic and embryotoxic characteristics of UDMH in addition to the general toxic characteristics of the compound.     

膜萃取邻甲酚废水的传质特性研究

构造了卷绕式及管束式两种膜组件,采用均质硅橡胶膜,以氢氧化钠溶液为萃取液来萃取邻甲酚废水.通过考察邻甲酚初始浓度、两相流动状态、两相压差(△P)和温度等因素对传质过程的影响,研究了邻甲酚废水的膜萃取过程与机制.结果表明,初始质量浓度为21.93 g/L的邻甲酚废水很适合直接进行膜萃取;当△P<0.07 MPa时,总传质系数(Kov)随△P的增大而略有减小.当△P>0.07 MPa时,Kov随△P增大而显著增大,由实验数据拟合得到总的膜萃取传质模型.且该模型的实验值与理论值的相对误差在5%以内,满足工业设计要求.     

生活垃圾仓式静态好氧发酵供风系统工艺设计

生活垃圾堆肥厂的核心——发酵系统对堆肥产品的质量和成本起着决定性的作用,所以其设计显得至关重要。结合多年的科研及工程实践经验,就垃圾仓式静态好氧发酵供风系统工艺设计中供风形式、方式选择,风量、风压计算以及供风控制形式选择等几个关键部分做了详细介绍。     

Effect of fatty acids and oils on photodegradation of azadirachtin-A

Azadirachtin-A on exposure to UV-light (254 nm) as a thin film on glass surface gave a isomerised (Z)-2-methylbut-2-enoate product. Half-life of azadirachtin-A as thin film under UV light was found to be 48 min. Azadirachtin-A was irradiated along with saturated and unsaturated fatty acids, and fatty oils under ultra-violet light as thin film. Saturated fatty acid increased the rate of photodegradation of azadirachtin-A, whereas unsaturated fatty acids such as oleic, linoleic and elaidic acid reduced the rate of degradation. Castor, linseed and olive oil accelerated the rate of degradation, whereas neem oil showed no or little change in the rate of degradation of azadirachtin-A. None of these fatty acids and fatty oils were effective in controlling the rate of degradation of azadirachtin-A under UV-light as thin film.     

Simulated and experimental evaluation of factors affecting the rate and extent of reductive dehalogenation of chloroethenes with glucose

Carbohydrates such as molasses are being added to aquifers to serve as electron donors for reductive dehalogenation of chloroethenes. Glucose, as a model carbohydrate, was studied to better understand the processes involved and to evaluate the effectiveness for dehalogenation of different approaches for carbohydrate addition. A simulation model was developed and calibrated with experimental data for the reductive dehalogenation of tetrachloroethene to ethene via cis-1,2-dichloroethene. The model included fermentors that convert the primary donor (glucose) into butyrate, acetate and hydrogen, methanogens, and two separate dehalogenator groups. The dehalogenation groups use the hydrogen intermediate as an electron donor and the different haloethenes as electron acceptors through competitive inhibition. Model simulations suggest first that the initial relative population size of dehalogenators and H(2)-utilizing methanogens greatly affects the degree of dehalogenation achieved. Second, the growth and decay of biomass from soluble carbohydrate plays a significant role in reductive dehalogenation. Finally, the carbohydrate delivery strategies used (periodic versus batch addition and the time interval between periodic addition) greatly affect the degree of dehalogenation that can be obtained with a given amount of added carbohydrate.     

Administration of Local Air Pollution Control Programs (Salaries and Qualifications of Personnel)

An attempt to develop medical air quality guides are recently made in Sweden. Even if air pollution is present in only fairly small amounts, problems frequently arise especially concerning nuisance reactions. Present regulations do not provide a basis for a standardized treatment of air pollution problems. The national air pollution situation was discussed and a survey of the literature was performed to collect data concerning current air pollutants. For sulfur dioxide a 30 day value of eight pphm and a two hour value of 25 pphm was recommended. It was further recommended to keep the carbon monoxide concentration as low as possible with an eight hour value of 30 ppm as an absolute maximum. For carcinogenic and mutagenic substances it was also recommended to keep the values as low as possible. Although available data did not support complete medical guides in all cases it was decided rather to have the above approximations than to leave the air pollution situation uncontrolled.     

Desulfurization of Caribbean Fuel

An American Petroleum Institute study of desulfurization of Caribbean fuel oil was completed in February 1967. The report is unique in that proprietary information was made available to the contractor, the Bechtel Corp., by task force members and licensors of desulfurization processes. Thus confidential information never before available to a single organization was used to develop feasibility and incremental costs of various processes for desulfurization. The report provides needed guideposts for decision-making by governmental units as well as by industry. Incremental costs are presented for intermediate levels of desulfurization from the normal level for Caribbean heavy fuel oil of 2.6% down to 0.5%, as well as the sensitivity of costs to sulfur credits and to rate of recovery of invested capital. Degree of justifiable confidence in the various data is discussed. Effects of desulfurization on other characterisics of the fuel oil are also discussed.     

Assessment of Bacillus subtilis spores as a possible bioindicator for evaluation of the microbicidal efficacy of radiation processing of water.

Gamma and electron-beam irradiation of Bacillus subtilis spores suspended in different types of water was studied to evaluate the inactivation of the spores and assess their possible use as a bioindicator for radiation processing. We found that the inactivation proceeded endogenously, being dose-rate-dependent and affected by oxygen. The radiation resistance of the suspended spores was found to be rather high; therefore, B. subtilis spores used as a bioindicator for efficiency of water treatment by radiation under practical conditions might result in the spores being overly conservative surrogates for pathogenic microorganisms. Moreover, the doserate dependency impedes the use of the spores as a bioindicator. Thus, B. subtilis spores cannot be recommended as a bioindicator for evaluation of the microbicidal efficacy of ionizing radiation processing of water.     

Removal of hexafluoroarsenate from waters

Arsenic predominantly occurs in natural ground and surface waters as arsenate and arsenite. Other arsenic species can also be present in anthropogenically influenced waters. By means of a newly-developed speciation technique an arsenic compound was identified as hexafluoroarsenate at high concentration (about 0.8mgl(-1) as As) in a lake polluted by waste water from a former crystal glass factory. This compound shows a completely different behavior than common arsenite and arsenate in waters. However, respective literature data were little found regarding its environmental behavior as well as the applicable remediation technologies. Conventional arsenic treatment mechanisms, such as the well-known sorption to iron hydroxides, can not be used to remediate water with this compound. Hence, an effective method to remove hexafluoroarsenate from water was developed using its strong affinity to anion exchangers (strong basic exchangers with quaternary ammonium groups). The sorption can be described by a Langmuir isotherm and first-order kinetics with a half-life of about 10min. Interferences by sulphate and fluoride, present at much higher concentrations in the polluted lake water, might be expected due to the anion exchange mechanism, but were shown to be of minor importance.     

Causes and Consequences of Backdrafting of Vented Gas Appliances

Abstract

House depressurization occurs when household equipment such as a kitchen or bathroom fan or a fireplace exhausts air from the house and lowers the pressure indoors with respect to the outside. The operation of air handlers for forced-air heating or cooling systems also can have a depressurization effect. This depressurization can hinder the natural draft from vented combustion appliances and lead to backdrafting, which in turn can result in combustion gases spilling into the indoor airspace. Extensive spillage can cause elevated indoor levels of combustion products such as carbon dioxide (CO2) and water vapor, as well as contaminants such as carbon monoxide (CO) and nitrogen dioxide (NO2).

The focus of this paper is to review studies on depressurization- induced backdrafting and spillage from gas-fired, drafthood equipped furnaces and domestic hot water heaters. Qualitative and quantitative techniques that were used in depressurization and backdrafting studies conducted in Canada, Europe, and the United States are analyzed. These studies have shown that exhaust fans operated simultaneously with fireplaces depressurize houses by 3 to 8 Pa on average. The CO indoor concentrations due to spillage, as reported in these studies, generally have been lower than 5 ppm. However, such low CO concentrations do not necessarily imply that a potential problem associated with backdrafting does not exist. Other combustion products, such as NO2, rarely have been measured in prior backdrafting studies.

It can be concluded from the literature review that causes of house depressurization are well understood. However, more comprehensive research is needed to better understand the frequency, duration, and severity of depressurization-induced spillage in a broad cross section of houses. Efforts in this direction have begun recently in the United States through a workshop to define research issues, pilot studies to develop comprehensive measurement protocols, and consensus standard development activities to prepare standardized methods and protocols.     

Mobility of adsorbed arsenic in two calcareous soils as influenced by water extract of compost

The mobility of arsenic (As) in soil affects both the bio-toxicity of As and the groundwater quality, which in turn indirectly affects the quality of edible part of crops and human health, if the crops were irrigated with As contaminated groundwater. A vertical soil column simulates the depth of a soil profile in a real soil environment. Thus soil column experiment is much more pertinent to soil environment than a batch experiment to simulate solute movement as well as leaching through soil profile. A laboratory soil column experiment was conducted to determine the extent of As leaching from soil percolated with influent that contained organic substances. The water extract of compost (WEC) was used as the source of organic substances. The results of As breakthrough curves (BTCs) showed that less pore volumes of influents were required to reach the relative concentration ratio of 1 (C/C0=1) for the two calcareous soils treated with influent that contained WEC. The concentrations of As in the column effluents of soils percolated with 0.01M KCl in WEC were significantly higher than those percolated with 0.01M KCl with the same volumes of effluents collected. This clearly indicates that dissolved as well as deprotonated organic substances which are negatively charged have higher potential for competing the adsorption sites with As on soils, leading to increasing mobility of As in soil and associated environments. Further, it is observed that the characteristics of soil components related to As adsorption affected the adsorption as well as desorption processes and subsequent mobility of As in soil environment as influenced by organic substances.     

Toxicologic Appraisal of Particulate Matter,Oxides of Sulfur,and Sulfuric Acid

An examination of the available toxicological literature indicates that sulfur dioxide itself would be properly classified as a mild respiratory irritant, the main portion of which is absorbed in the upper respiratory tract. The reported industrial experience of symptoms of mild chronic respiratory irritation from exposures at or above 5 ppm is compatible with what would have been predicted on the basis of available toxicological data. The basic physiological response to inhalation of pure SO₂ appears to be a mild degree of bronchoconstriction reflected in a measurable increase in flow resistance. Although the response is highly variable, most individuals tested have responded to 5 ppm and levels of 5 to 10 ppm have upon occasion produced severe bronchospasm in sensitive individuals. This serves to point up the fact that experience with the industrial Threshold Limit Value (5 ppm) is not applicable as a guide for the general population. Although the majority of individuals tested have shown no detectable response to levels of 1 ppm, there are again sensitive individuals who have responded. It is not known whether these individuals would have responded to concentrations lower than this. The response of these more sensitive individuals to 1 ppm would be classified as detectable response, not as severe bronchospasm. An examination of the available toxicological literature also indicates that sulfuric acid and irritant sulfates, to the extent that the latter have been examined, are more potent irritants than sulfur dioxide. This has been demonstrated in studies using morality and lung pathology as criteria as well as in studies using alterations in pulmonary function in experimental animals and human subjects. The irritant potency of these substances is affected by particle size and by relative humidity, which factors are probably interrelated. It is unfortunate that these substances have not been as yet studied in as great detail as has the less irritant sulfur dioxide. There is evidence which cannot be ignored, even though it is based entirely on animal experiments of one investigator, indicating that the presence of particulate material capable of oxidizing sulfur dioxide to sulfuric acid caused a three to fourfold potentiation of the irritant response. The aerosols causing this potentiation were soluble salts of ferrous iron, manganese and vanadium all of which would become droplets upon inhalation. Insoluble aerosols such as carbon, iron oxide fume, triphenylphosphate or fly ash did not cause a potentiation of the irritant action of SO₂ even when used at higher concentrations. The concentrations of SO₂ used in these various experiments were in some cases as low as 0.16 ppm. The catalytic aerosols were used at concentrations of 0.7 to 1 mg/m³ which is above any reported levels of these metals in urban air. If the SO₂ present as an air pollutant remained unaltered until removed by dilution, there would be no evidence in the toxicological literature suggesting that it would be likely to have any effects on man at prevailing levels. Studies of atmospheric chemistry have shown that SO₂ does not remain unaltered in the atmosphere, especially under onditions of high humidity and in the presence of particulate material, but is converted to H₂SO₄. Such a conversion increases its irritant potency. On this basis the toxicological literature combined with the literature of atmospheric chemistry suggest that sulfur dioxide levels be controlled in terms of the potential formation of irritant particles. This means that control measures as far as feasible should be aimed at both SO₂ and particulate material and not against either alone.     

Evaluation of a novel carbon adsorbent for fractionation and treatment of halogenated organic wastes

A carbon adsorbent obtained by a procedure analogous to reverse burn coal gasification is being evaluated in our laboratory. This low surface area carbon adsorbent shows considerable promise as a fractionation medium for a variety of organics. The performance of the adsorbent compares favorably to the highly specialized carbon adsorbents such as PX-21 (Amoco Corp.). The adsorbent also has considerable potential for treatment of wastes containing organochlorine compounds. The adsorbent shows good adsorption capacity and can hold as much as 50% (w/w basis) of organic sludge while maintaining a relatively dry, granular character. Furthermore, this waste-loaded adsorbent is amenable to highly efficient self-sustained thermal degradation. Degradation efficiencies approaching 99.99 percent have been achieved for such recalcitrant organics as polychlorinated biphenyls and tetrachlorodibenzo-p-dioxins.