Evaluation of the health risk of platinum group metals emitted from automotive catalytic converters

A health risk assessment of platinum (Pt) emitted from automotive catalytic converters is presented. Following a stepwise approach, the relevant literature is discussed in order to characterize Pt emissions as well as the toxic potential of Pt and its compounds. In an exposure assessment, ambient Pt concentrations in air are predicted to range from approximately 4 pg/m3 (street canyon, typical conditions) up to approximately 112 pg/m3 (express motorway, severe conditions). These values agree well with the few measured concentrations, which are also in the low pg/m3 range. Pt is emitted from catalytic converters in very small amounts (ng/km range), mainly in the (0)-oxidation state (elemental Pt). The nanocrystalline Pt particles are attached to microm-sized aluminum oxide particles. Whether free ultrafine Pt particles may be emitted and result in biological effects has not been studied sufficiently. Hence, risk assessment can only be based on the respiratory sensitizing potential of halogenated Pt salts. The presence of such compounds in automotive Pt emissions cannot definitely be excluded. From recent occupational studies conducted in catalytic converter production, a conservative no-effect level (NOEL) of 1.5 ng/m3 can be derived for the sensitizing effect of halogenated Pt salts. In a (reasonable) worst case approach, it is assumed that such compounds comprise 1% (0.1%) of the total Pt emissions. Applying a safety factor of 10 to account for interindividual variability, a guidance value of 15 (150) ng/m3 is derived for catalyst-borne Pt. The exposure to Pt in ambient air as measured or predicted is at least two orders of magnitude below this guidance range. Rhodium is also contained in automotive catalysts, palladium has increasingly substituted Pt, and iridium-based catalysts have recently been introduced. Although the database on these platinum group metals is rather small, there is no evidence that they pose a health risk to the general population.     

Environmental risk of particulate and soluble platinum group elements released from gasoline and diesel engine catalytic converters

A comparison of platinum-group element (PGE) emission between gasoline and diesel engine catalytic converters is reported within this work. Whole raw exhaust fumes from four catalysts of three different types were examined during their useful lifetime, from fresh to 80,000 km. Two were gasoline engine catalysts (Pt-Pd-Rh and Pd-Rh), while the other two were diesel engine catalysts (Pt). Samples were collected following the 91441 EUDC driving cycle for light-duty vehicle testing, and the sample collection device used allowed differentiation between the particulate and soluble fractions, the latter being the most relevant from an environmental point of view. Analyses were performed by inductively coupled plasma-mass spectrometry (ICP-MS) (quadrupole and high resolution), and special attention was paid to the control of spectral interference, especially in the case of Pd and Rh. The results obtained show that, for fresh catalysts, the release of particulate PGE through car exhaust fumes does not follow any particular trend, with a wide range (one-two orders of magnitude) for the content of noble metals emitted. The samples collected from 30,000-80,000 km present a more homogeneous PGE release for all catalysts studied. A decrease of approximately one order of magnitude is observed with respect to the release from fresh catalysts, except in the case of the diesel engine catalyst, for which PGE emission continued to be higher than in the case of gasoline engines. The fraction of soluble PGE was found to represent less than 10% of the total amount released from fresh catalysts. For aged catalysts, the figures are significantly higher, especially for Pd and Rh. Particulate PGE can be considered as virtually biologically inert, while soluble PGE forms can represent an environmental risk due to their bioavailability, which leads them to accumulate in the environment.     

散流器半受限分散射流的数学模型及分析

建立了数学模型,通过数值求解得到了散流器在不同半锥顶角下的射流轨迹,分析了锥体顶角对射流的影响,建议锥体顶角为110°～130°。     

Palladium and platinum concentration in soils from the Napoli metropolitan area,Italy: possible effects of catalytic exhausts

Soils from the Napoli metropolitan area (Italy) were evaluated for Pt and Pd concentrations. One hundred and ninety-five (195) samples were collected from residual soils and non-residual soils from flower-beds in a 120 km(2) area on a 0.5 km grid in the downtown-urbanized area and on 1 km grid in suburban zones. The soils <100 mesh size fraction (150 microm) was analyzed for Pt, Pd and 37 other elements by ICP-ES and ICP-MS after aqua regia digestion. Pt and Pd contents range between <2 and 52 microg/kg and between <10 and 110 microg/kg, respectively. A large number of samples from the metropolitan area were characterized by anomalous values for Pt (>6 microg/kg) and Pd (>17 microg/kg). Non-residual soils from flower-beds are located mainly in the urbanized downtown areas subject to heavy traffic and have higher Pt and Pd contents than residual soils from suburban areas. Geochemical maps show a strong correlation between roads with major traffic flow and high Pt and Pd concentrations. In addition, data from most of the downtown flower-beds fall within the three-way catalytic converters (TWC) field identified by [Ely JC, et al. Environ Sci Technol; 35:3816-3822]. This suggests that emissions of abraded fragments from vehicle exhausts may be the source of the high values and geographic distributions of Pd and especially Pt in urban soils of Napoli. Catalytic converters (Pt/Pd/Rh) have been mandatory for gasoline-powered vehicles in Europe since 1993. Italy permitted the use of non-catalytic motor until January, 2002. This is responsible for the high values for both Pt and Pd in the non-residual soils of the urban areas of Napoli.     

Amphibians as a model to study endocrine disruptors: I. Environmental pollution and estrogen receptor binding

Many chemicals released into the environment without toxicological risks have the capacities to disrupt the function of endocrine systems. These endocrine disruptors disturb normal endocrine mechanisms and have been observed in nearly all classes of vertebrates. The aim of this research is to develop a comprehensive model to study endocrine disruption using the amphibian Xenopus laevis. The assessment of estrogenic potencies of endocrine disruptors includes several levels of investigation: (I) binding to liver estrogen receptor, (II) estrogenic activity in vitro by inducing vitellogenin synthesis in primary cultured hepatocytes, and (III) in vivo effects on sexual development caused by exposure of larvae. The present paper is focused on the first part by establishing a radioreceptorassay for [3H]17 beta-estradiol ([3H]E2) binding using liver cytosol fraction. In order to get optimum binding conditions we performed kinetic, saturation, and competitive displacement experiments. Association of [3H]E2 to estrogen receptor revealed that maximum specific binding is achieved between 18 and 48 h of incubation. Scatchard analyses of saturation experiments resulted in a homogenous saturable population of estrogen receptors having no significant differences of binding parameters between both sexes. The values of Kd (dissociation constant) in males and females were 22.4 +/- 6.0 and 15.0 +/- 2.8 nM (mean +/- S.E.M.; n = 5), respectively, while corresponding Bmax (maximum binding capacity) revealed 89 +/- 46 and 136 +/- 46 fmol [3H]E2/mg protein. The specificity of estrogen receptors as shown by competitive displacement experiments demonstrated receptors being highly specific just for estrogens, but not for other endogenous steroids having the following ranking of binding affinities: E2 > estrone > dehydroepiandrosterone > aldosterone > or = testosterone > or = corticosterone > or = progesterone. The affinity ranking of environmental chemicals compared to E2 was: E2 > tetrachlorbiphenyl > diethylphthalate > 2,2-bis-(4-hydroxyphenyl)-propan (bisphenol A) > or = 4-nonylphenol > or = 3-t-butyl-4-hydroxyanisole > or = 4-octylphenol > dichlor-diphenyl-trichlor-ethan (4,4'-DDT). Analyses of five sewage effluents for displacement of [3H]E2 binding resulted in three samples displacing more than 50% of specific binding at their original concentration. Taken together the established radioreceptorassay for [3H]E2 binding in Xenopus laevis liver cytosol is useful to screen estrogen receptor binding of pure compounds or complex mixtures of them, which is the prerequisite for causing either estrogenic or antiestrogenic effects.     

The cadmium and lead content of suspended particulate matter emitted from a U.K. refuse incinerator

Suspended particulate matter (SPM), sampled from the stack of a large refuse incinerator in the U.K., contained markedly elevated levels of Cd (approximately 1600 micrograms g-1) and Pb (approximately 3%). These values were similar to those previously reported for several other incinerators in Europe, but the Pb concentrations were lower than in the SPM from three American incinerators. Calculation of the metal concentration ratio SPM/fly ash for the U.K. incinerator revealed a three-fold enrichment of the two metals on the SPM. Similar ratios were obtained for several other European incinerators; this correspondence in metal partitioning was linked to the use of electrostatic precipitators in these facilities. The SPM metal data obtained in this study were used to estimate atmospheric emissions of 0.5 t Cd year-1 and 11 t Pb year-1 from the incinerator. Extrapolation of the Cd and Pb emission factors derived from this study to the quantity of refuse incinerated in the U.K. results in atmospheric discharges of 6 t Cd year-1 and 115 t Pb year-1. These estimates are in good agreement with those previously reported by an emissions inventory which identified incineration as the single largest source of airborne Cd in the U.K.     

Determination of emitted airborne microorganisms from a BIO-PAK wastewater treatment plant

Results of a study conducted to assess the degree of airborne microbial contamination generated by a wastewater treatment plant (WWTP) with bioreactor “BIO-PAK” closed treatment system and evaluation of the dispersion of potential pathogens are described. Over the year aerosol samples were collected simultaneously with sedimentation and impact methods from several plant sites and the surroundings. External upwind sites were used as control. Total colony-forming counts of heterotrophic psychrophilic, psychrotrophic, mesophilic, haemolytic bacteria, as well as members of the Enterobacteriaceae family, Staphylococcus, Enterococcus and Pseudomonas genera, actinomycetes and fungi (moulds, yeasts and yeast-like fungi) were determined. Their highest concentrations ranged up to 10¹-10³ CFU/m³ (with the exception of moulds exceeding 2 × 10⁴) were determined in air sampled inside the bioreactor, its vicinity, and near the grate chamber. Higher species diversity of the family Enterobacteriaceae (including Shigella spp., Yersinia enterocolitica, Escherichia coli, Klebsiella pneumoniae ozaenae) in the air sampled inside or near the bioreactor may imply a health risk for staff exposed for longer periods of time. Notwithstanding, no increased emission of the analysed groups of microorganisms, including faecal bacteria, were found outside the WWTP.     

A computational and experimental study of ultra fine water mist as a total flooding agent

Computational fluid dynamics (CFD) calculations were carried out to design total flooding fire tests in a 28 m³ compartment for an ultra fine water mist (<10 μm). The exit momentum of the mist produced by a proprietary ultrasonic generator technology was extremely low with a mist discharge velocity below 1 m/s. The mist was discharged with multiple floor outlets equally spaced around the centrally located 120 kW pool-like gas fire. The transport of mist and its interaction with the fire was simulated by Fluent, a commercial CFD model. Lagrangian Discrete Phase Model (DPM) was used for droplets. Simulation predicted extinguishment within 10 s with a mist delivery rate of 1 l/min. However, in total flooding fire tests conducted, extinction times were more than 5 min. Additional computations approximating the ultra fine mist (UFM) as a dense gas agreed well with the observed transport timescales of minutes indicating that UFM behaves like a gas. Further, the mist–fire interaction needs a multi-phase Euler–Euler approach with a droplet vaporization model.     

Bioavailability as an issue in risk assessment and management of food cadmium: a review

The bioavailability of cadmium (Cd) from food is an important determinant of the potential risk of this toxic element. This review summarizes the effects of marginal deficiencies of the essential nutrients zinc (Zn), iron (Fe), and calcium (Ca) on the enhancement of absorption and organ accumulation and retention of dietary Cd in laboratory animals. These marginal deficiencies enhanced Cd absorption as much as ten-fold from diets containing low Cd concentrations similar to that consumed by some human populations, indicating that people who are nutritionally marginal with respect to Zn, Fe, and Ca are at higher risk of Cd disease than those who are nutritionally adequate. Results from these studies also suggest that the bioavailability of Cd is different for different food sources. This has implications for the design of food safety rules for Cd in that if the dietary source plays such a significant role in the risk of Cd, then different foods would require different Cd limits. Lastly, the importance of food-level exposures of Cd and other potentially toxic elements in the study of risk assessment are emphasized. Most foods contain low concentrations of Cd that are poorly absorbed, and it is neither relevant nor practical to use toxic doses of Cd in experimental diets to study food Cd risks. A more comprehensive understanding of the biochemistry involved in the bioavailability of Cd from foods would help resolve food safety questions and provide the support for a badly needed advance in international policies regarding Cd in crops and foods.     

Soil sealing footprint as an indicator of dispersed urban growth: a multivariate statistics approach

The present study introduces a set of indicators derived from high-resolution land-use maps with the aim to illustrate the spatial distribution, intensity, and diversity of sealed soils in a Mediterranean region (Rome, Italy) shifting from a mono-centric spatial organization toward a dispersed urban agglomeration. A multivariate approach provides a comprehensive assessment of Rome ‘sealing footprint’, classifying local districts according to different imperviousness profiles. Results illustrate the rearrangement of the land-use structure determined by suburbanization with higher soil consumption and lower land-use efficiency. The approach is considered a promising tool to inform policies for a spatially balanced and land-saving urban development.     

火灾中吸毒及抑制技术分析研究

本文介绍了火灾中烟气的产生、组成、危害性,烟毒的检测及相关标准,提出了烟毒的抑制方法,对我国抑烟技术现状进行了分析探讨.     

十四集总催化重整反应动力学模型研究

提出一个包含十四集总组分、25个反应的催化重整动力学模型,以较少的集总和较高的预测精度适应实际催化重整生产的需要;根据在催化重整微型反应实验装置上获得的实验数据,得到重整反应动力学模型的参数;用该模型预测产物组成和催化重整装置的模拟。结果表明:预测的最大绝对偏差为2.30%,偏差大部分小于2.0%;模拟得到产物中各组分及温度在反应器中分布与催化重整反应机理吻合;模型集总划分适中,使用方便,能够用于催化重整装置的预测。     

Bioavailability of iron from spinach using an in vitro/human Caco-2 cell bioassay model

Spinach (Spinacia oleracea) cv Whitney was tested for iron bioavailabilty using an in vitro human intestinal cell culture ferritin bioassay technique previously developed. Spinach was cultured in a growth chamber for 33 days, harvested, and freeze-dried. Total iron in the samples was an average of 71 micrograms/g dry weight. Spinach was digested in vitro (pepsin and 0.1 M HCl followed by pancreatin and 0.1 M NaHCO3) with and without the addition of supplemental ascorbic acid. Caco-2 cell cultures were used to determine iron bioavailability from the spinach mixtures. Production of the iron-binding protein ferritin in the Caco-2 cells showed the supplemental ascorbic acid doubled bioavailability of iron from spinach. The data show fresh spinach is a poor source of iron, and emphasize the importance of evaluation of whole meals rather than single food items. The data support the usefulness of the in vitro/Caco-2 cell ferritin bioassay model for prescreening of space flight diets for bioavailable iron.     

Characterization of indoor sources of fine and ultrafine particles: a study conducted in a full-scale chamber

Humans and their activities are known to generate considerable amounts of particulate matter indoors. Some of the activities are cooking, smoking and cleaning. In this study 13 different particle sources were for the first time examined in a 32 m3 full-scale chamber with an air change rate of 1.7 +/- 0.1/h. Two different instruments, a condensation particle counter (CPC) and an optical particle counter (OPC) were used to quantitatively determine ultrafine and fine particle emissions, respectively. The CPC measures particles from 0.02 microm to larger than 1.0 microm. The OPC was adjusted to measure particle concentrations in eight fractions between 0.3 and 1.0 microm. The sources were cigarette side-stream smoke, pure wax candles, scented candles, a vacuum cleaner, an air-freshener spray, a flat iron (with and without steam) on a cotton sheet, electric radiators, an electric stove, a gas stove, and frying meat. The cigarette burning, frying meat, air freshener spray and gas stove showed a particle size distribution that changed over time towards larger particles. In most of the experiments the maximum concentration was reached within a few minutes. Typically, the increase of the particle concentration immediately after activation of the source was more rapid than the decay of the concentration observed after deactivation of the source. The highest observed concentration of ultrafine particles was approximately 241,000 particles/cm3 and originated from the combustion of pure wax candles. The weakest generation of ultrafine particles (1.17 x 10(7) particles per second) was observed when ironing without steam on a cotton sheet, which resulted in a concentration of 550 particles/cm3 in the chamber air. The highest generation rate (1.47 x 10(10) particles per second) was observed in the radiator test. PRACTICAL IMPLICATIONS: Humans and their activities are known to generate substantial amounts of particulate matter indoors and potentially they can have a strong influence on short-term exposure. In this study a quantitative determination of the emissions of fine and ultrafine particles from different indoor sources was performed. The aim is a better understanding of the origin and fate of indoor particles. The results may be useful for Indoor Air Quality models.     

陶瓷细骨料再生混凝土抗压强度试验研究

研究了以建筑废弃陶瓷为再生细集料取代天然河砂生产混凝土时取代率对再生混凝土抗拉、抗压强度的影响.通过试验,初步得出了再生混凝土立方体抗压强度、劈裂抗拉强度与细骨料取代率的关系.试验表明,再生混凝土的抗压强度、劈裂抗拉强度与普通混凝土没有明显区别.试验还表明,再生混凝土抗压强度与抗拉强度之间的换算与普通混凝土不同.建立了再生混凝土抗压强度随陶瓷取代率变化的关系式;引入取代率R,提出了劈裂抗拉强度与抗压强度、R之间的强度指标换算关系.     

Cardboard as a construction material: a case study

A small cardboard building with a 25-year intended lifetime was developed as a live innovation project to explore and resolve the practical problems surrounding the design, fabrication and construction, costs, and use of an alternative building material. The primary aim to reduce environmental impacts was based on developing the potential of a recycled material as the main structural and cladding component that could be further recycled at the end of its working life. This case study of a small school building presents both the research and development undertaken by the project team and the practical implications of realizing this as a building for a client.     

Cardboard as a construction material: a case study

A small cardboard building with a 25-year intended lifetime was developed as a live innovation project to explore and resolve the practical problems surrounding the design, fabrication and construction, costs, and use of an alternative building material. The primary aim to reduce environmental impacts was based on developing the potential of a recycled material as the main structural and cladding component that could be further recycled at the end of its working life. This case study of a small school building presents both the research and development undertaken by the project team and the practical implications of realizing this as a building for a client.     

Performance of high strength concrete made with copper slag as a fine aggregate

This research study was conducted to investigate the performance of high strength concrete (HSC) made with copper slag as a fine aggregate at constant workability and to study the effect of superplasticizer addition on the properties of HSC made with copper slag. Two series of concrete mixtures were prepared with different proportions of copper slag. The first series consisted of six concrete mixtures prepared with different proportions of copper slag at constant workability. The water content was adjusted in each mixture in order to achieve the same workability as that for the control mixture. Twelve concrete mixtures were prepared in the second series. Only the first mixture was prepared using superplasticizer whereas the other eleven mixtures were prepared without using superplasticizer and with different proportions of copper slag used as sand replacement. The results indicated that the water demand reduced by almost 22% at 100% copper slag replacement compared to the control mixture. The strength and durability of HSC were generally improved with the increase of copper slag content in the concrete mixture. However, the strength and durability characteristics of HSC were adversely affected by the absence of the superplasticizer from the concrete paste despite the improvement in the concrete strength with the increase of copper content. All concrete mixtures did not meet the strength and durability design requirements due to the segregation and dryness of the concrete paste. Therefore it can be concluded that the use of copper slag as sand substitution improves HSC strength and durability characteristics at same workability while superplasticizer is very important ingredient in HSC made with copper slag in order to provide good workability and better consistency for the concrete matrix.     

以废砖粉和废砂浆为细骨料的再生混凝土受力性能试验研究

通过81个以废砖粉和废砂浆为细骨料、废混凝土为粗骨料的再生混凝土试块作正交抗压强度试验,研究不同取代率及不同水灰比等强度影响参数,同时利用RMT-201岩石与混凝土力学电液伺服试验系统研究这种混凝土的应力-应变曲线,分析了这种再生混凝土强度变化规律及其变形发展的特点,提出了以废砖粉和废砂浆为细骨料、以废混凝土为粗骨料的再生混凝土强度影响因素和特征.