Catalytic oxidation of CO over Pt/Fe3O4 catalysts: Tuning O2 activation and CO adsorption

• Strong metal-support interaction exists on Pt/Fe₃O₄ catalysts. • Pt metal particles facilitate the formation of oxygen vacancies on Fe₃O₄. • Fe₃O₄ supports enhance the strength of CO adsorption on Pt metal particles. The self-inhibition behavior due to CO poisoning on Pt metal particles strongly impairs the performance of CO oxidation. It is an effective method to use reducible metal oxides for supporting Pt metal particles to avoid self-inhibition and to improve catalytic performance. In this work, we used in situ reductions of chloroplatinic acid on commercial Fe₃O₄ powder to prepare heterogeneous-structured Pt/Fe₃O₄ catalysts in the solution of ethylene glycol. The heterogeneous Pt/Fe₃O₄ catalysts achieved a better catalytic performance of CO oxidation compared with the Fe₃O₄ powder. The temperatures of 50% and 90% CO conversion were achieved above 260°C and 290°C at Pt/Fe₃O₄, respectively. However, they are accomplished on Fe₃O₄ at temperatures higher than 310°C. XRD, XPS, and H₂-TPR results confirmed that the metallic Pt atoms have a strong synergistic interaction with the Fe₃O₄ supports. TGA results and transient DRIFTS results proved that the Pt metal particles facilitate the release of lattice oxygen and the formation of oxygen vacancies on Fe₃O₄. The combined results of O₂-TPD and DRIFTS indicated that the activation step of oxygen molecules at surface oxygen vacancies could potentially be the rate-determining step of the catalytic CO oxidation at Pt/Fe₃O₄ catalysts. The reaction pathway involves a Pt-assisted Mars-van Krevelen (MvK) mechanism.     

Metal Fractionation Studies in Surfacial and Core Sediments in the Achankovil River Basin in India

The Fractionation of Fe, Zn, Cu, Pb, Mn and Cd in the sediments of the Achankovil River, Western Ghats, India using a sequential extraction method was carried out to understand the metal availability in the basin for biotic and abiotic activities. Spatial distribution of heavy metals has been studied. Sediment grain size has significant control over the heavy metal distribution. The fluctuations in their concentration partly depend upon the lithology of the river basin and partly the anthropogenic activities. The sediments are dominated by sand and are moderately to strongly positively skewed and are very leptokurtotic in nature. The quartzite and feldspars are abundant minerals along with significant amount of mica with low clay content. The core sediments show increasing trend of heavy metal concentration with depth due to the recent addition of anthropogenic sources and post-diagenic activities. Significant amount of Cd (18%) was found in carbonate fraction, which may pose environmental problems due to its toxic nature. Small concentrations of metals, except Cd and Cu, are in exchangeable fraction, which indicate low bio-availability. Enrichment Factor (EF) for individual metals shows the contribution from terrregious and in part from anthropogenic sources. Selective Sequential Extraction (SSE) study shows the variation in specific metal distribution pattern, their distribution in different phases and their bio-availability. Maximum amount of the metals were bound to the non-residual fractions (mainly Fe-oxides). Overall, bio-availability of these micronutrients from sediments seems to be very less. Non-residual phase is the most important phase for majority of heavy metals studied. Among the non-residual fraction, maximum amount of the heavy metals bound to Fe-oxides. The study high lights the need for in-depth study of heavy metals distribution and fractionation in the smaller river basins to get precise information on the behavior and transport of heavy metals in the fluvial environment and their contribution to the world ocean.     

Spatial and Temporal Variations in Trace Metal Concentrations in the Cockle, Austrovenus Stutchburyi from Otago, New Zealand

This is the first comprehensive study of sources of variation in metal concentrations within the whole tissues of a shallow burrowing, filter-feeding intertidal clam, Austrovenus stutchburyi. Samples were collected from 12 sites in April, August, November and February in 1993–1994 in the vicinity of Otago Harbour and Peninsula, New Zealand. Total tissue trace metal concentrations (μg g⁻¹ dry weight) were measured in individual animals for the essential metals : Mn, Cu, Zn, Ni and the non-essential Cr using trace-metal clean acid-digestion and ICP-OAES techniques. Average metal concentrations were 3–60 μg g⁻¹ for Cu, 40–118 μg g⁻¹ for Zn, 2–12 μg g⁻¹ for Mn, 5–35 μg g⁻¹ for Ni and 1–44 μg g⁻¹ for Cr. These levels decreased with body weight and differed amongst sites except for Cr in February (mid-summer). Highest concentrations occurred at sites close to a city (Dunedin) and within the central harbour region although the Cu, Zn, Ni and Cr concentrations did not correlate with the environmental gradient or season. At one coastal site, samples of both the blue mussel Mytilus galloprovincialis and cockles gave similar trends in trace metal levels. These results suggest that the cockle could be a useful trace metal biomonitor within NZ estuaries.     

The use of bioaccumulation, biomarkers and histopathology diseases in shape Procambarus clarkii to establish bioavailability of Cd and Zn after a mining spill

Individuals of the crayfish Procambarus clarkii (males and females) were exposed simultaneously to cadmium and zinc during 21 days. Exposure concentrations were those determined at the Guadiamar river after the Aznalcóllar mining spill (SW, Spain): 10 and 30 μg L⁻¹ of cadmium and 1000 and 3000 μg L⁻¹ of zinc. Three biomarkers (MT: metallothioneins like proteins, VTG: vitellogenin/vitellin like proteins and histopathology) together with heavy metal bioaccumulation were determined in soft tissues of male and female P. clarkii. At the concentrations tested, increasing cadmium exposure resulted in increasing cadmium bioaccumulation and increasing subletal effects (induction of MT, VTG and histopathological damage in tissues). Nevertheless, although increasing zinc exposure showed increasing VTG induction and histopathological damages, not a positive relationship was determined with MT induction. Concerning to responses determined in male and female crayfishes only differences were found between sexes at the highest cadmium exposure concentration related to bioaccumulation in hepatopancreas tissues. Biomarkers responses to heavy metal contamination in this crayfish, even VTG induction not before tested in heavy metal contamination assessment in crustaceans resulted potential tools for the monitoring of heavy metal environmental contamination.     

Comparative Metal Distribution in Hair of Pakistani and Libyan Population and Source Identification by Multivariate Analysis

Using nitric acid-perchloric acid wet digestion based FAAS method ten selected metals (Cd, Co, Cr, Fe, K, Mn, Na, Ni, Pb and Zn) were determined in the scalp hair of male Pakistani and Libyan donors (n = 62), between 3–54 years age and residing in typical urban areas. The study was taken up to identify sources of metal distribution in two diverse population segments exposed to different environments. Sodium emerged with the highest mean hair concentration of 511.0 μg/g and 496.9 μg/g for Libyan and Pakistani donors respectively, followed by K, at 266.2 μg/g and 242.4 μg/g for the two donor categories. Cadmium showed the lowest mean hair concentration for both Pakistani (0.380 μg/g) and Libyan (0.530 μg/g) donors. Levels of Na, K, Pb, Cr and Cd were higher in hair of Libyan donors compared with Pakistani counterparts which showed higher comparative levels of Zn, Fe, Co, Ni and Mn. Strong metal-to-metal correlations were found between Na–K (r = 0.638) and Cd–Co (r = 0.574) for Pakistani donors, while for Libyan donors, Na–K (r = 0.680) and Fe–Mn (r = 0.624) correlations emerged as strongly significant. Only K was found to have a strong positive correlation (r = 0.611) with age for Pakistani donors while this correlation was significantly negative (r = −0.500) for Libyan donors, probably arising from individual food habits. Other metals showed no viable relationship with age. Principal Component Analysis (PCA) and Cluster Analysis (CA) of the data evidenced food, industrial emissions and automobile emissions as possible sources of metal distribution. The results of the present study are compared with those reported for subjects from other regions of the world.     

Fractionation and Sequential Extraction of Heavy Metals in the Soil of Scrapyard of Discarded Vehicles

Chemical and physical size fractionation of heavy metals were carried out on 20 soil samples from the scrap yard area. Tessier method was used in sequential extraction. Cadmium showed the highest levels among the other elements studied in the exchangeable fraction (about 33%), while other elements showed low levels in this fraction (≥1%). Lead and manganese were mostly found in the Fe–Mn oxide fraction, zinc and iron were mostly in residual fraction, while copper was mostly found in the organic fraction of the soil. Soil samples were size-fractionated into four sizes: 1000–500, 500–125, 125–53, and less than 53 μm. The highest levels of Fe, Cu, Pb, Mn, and Cd were found in the medium fraction (500–125 μm), while zinc showed its highest levels in the fine fraction (125–53 μm). The order of heavy metal load in the size fractions was found to be medium > fine > coarse > silt for Fe, Mn, Cu, Pb, and Cd, where it was found as fine > medium > coarse > silt for zinc.     

Integrating Remote Sensing Approach with Pollution Monitoring Tools for Aquatic Ecosystem Risk Assessment and Managment: A Case Study of Lake Victoria(UGANDA)

Aquatic ecosystems around the world, lake, estuaries and coastal areas are increasingly impacted by anthropogenic pollutants through different sources such as agricultural, industrial and urban discharges, atmospheric deposition and terrestrial drainage. Lake Victoria is the second largest lake in the world and the largest tropical lake. Bordered by Tanzania, Uganda, and Kenya, it provides a livelihood for millions of Africans in the region. However, the lake is under threat from eutrophication, a huge decline in the number of native fish species caused by several factors including loss of biodiversity, over fishing and pollution has been recently documented. Increasing usage of pesticides and insecticides in the adjacent agricultural areas as well as mercury contamination from processing of gold ore on the southern shores are currently considered among the most emergent phenomena of chemical contamination in the lake. By the application of globally consistent and comprehensive geospatial data-sets based on remote sensing integrated with information on heavy metals accumulation and insecticides exposure in native and alien fish populations, the present study aims at assessing the environmental risk associated to the contamination of the Lake Victoria water body on fish health, land cover distribution, biodiversity and the agricultural area surrounding the lake. By the elaboration of Landsat 7 TM data of November 2002 and Landsat 7 TM 1986 we have calculated the agriculture area which borders the Lake Victoria bay, which is an upland plain. This process has greatly enhanced nutrient loading to the soil, which is subsequently transported to the lake by rain or as dry fall. All the data has been insert in the Geographical information System (ARCGIS) to be upgraded and consulted. Heavy metals in fish fillets showed concentrations rather low except for mercury being higher than others as already described in previous investigations. In the same tissue, cholinesterases activity (ChE) as an indicator of insecticides exposure showed significant differences among fish species in both activity and sensitivity of selected inhibitor insecticides. This integrated approach aims at identifying and quantifying selected aquatic environmental issues which integrated with monitoring techniques such as contaminant concentrations and biological responses to insecticides exposure in fish populations will provide a scientific basis for aquatic zones management and assist in policy formulations at the national and international levels.     

Trace Metal Levels in Mussels (Mytilus Galloprovincialis L. 1758) from Turkish Aegean Sea Coast

Bio-monitoring of some heavy metal levels (Cd, Pb, Zn, Cu) in whole edible soft parts of Mytilus galloprovincialis (L. 1758) was conducted in Turkish Aegean Sea coast during the period of September 2002–August 2003 seasonally. Moreover, some physico-chemical environmental parameters, also have been analysed in the same region. The values of some physico-chemical environmental parameters in coastal waters of Turkish Aegean Sea were changed between; 9.0–27.0 ^∘C for temperature, 31.93–40.45 psu for salinity, 7.35–8.48 for pH and 4.05–9.50 mg/l for dissolved oxygen. The levels of trace elements in whole edible soft parts including interstitial fluids of Mediterranean mussels M. galloprovincialis (L. 1758), sampled from 6 different regions of Turkish Aegean Sea coast have ranged between; 0.04–0.52 μg Cd/g wet weight, 0.49–1.72 μg Pb/g w.w., 0.95–1.85 Cu/g w.w., 16.11–37.15 μg Zn/g w.w. The highest values for all trace metals (Cd, Pb, Zn, Cu) were measured in inner part of Izmir Bay (station 3) and lowest in Sigacik and Gulluk Bay (station 5, 6). Generally heavy metal levels are lower than the results in soft mussel tissues reported from Mediterranean regions.     

Characterization and Identification of the Sources of Chromium, Zinc, Lead, Cadmium, Nickel, Manganese and Iron in Pm10 Particulates at the Two Sites of Kolkata, India

Monitoring of ambient PM₁₀ (particulate matter which passes through a size selective impactor inlet with a 50% efficiency cut-off at 10 μm aerodynamic diameter) has been done at residential (Kasba) and industrial (Cossipore) sites of an urban region of Kolkata during November 2003 to November 2004. These sites were selected depending on the dominant anthropogenic activities. Metal constituents of atmospheric PM₁₀ deposited on glass fibre filter paper were estimated using Inductively Coupled Plasma Atomic Emission Spectrometer (ICP-AES). Chromium (Cr), zinc (Zn), lead (Pb), cadmium (Cd), nickel (Ni), manganese (Mn) and iron (Fe) are the seven toxic trace metals quantified from the measured PM₁₀ concentrations. The 24 h average concentrations of Cr, Zn, Pb, Cd, Ni, Mn and Fe from ninety PM₁₀ particulate samples of Kolkata were found to be 6.9, 506.1, 79.1, 3.3, 7.4, 2.4 and 103.6 ng/m³, respectively. The 24 h average PM₁₀ concentration exceeded national ambient air quality standard (NAAQS) as specified by central pollution control board, India at both residential (Kasba) and industrial (Cossipore) areas with mean concentration of 140.1 and 196.6 μg/m³, respectively. A simultaneous meteorology study was performed to assess the influence of air masses by wind speed, wind direction, rainfall, relative humidity and temperature. The measured toxic trace metals generally showed inverse relationship with wind speed, relative humidity and temperature. Factor analysis, a receptor modeling technique has been used for identification of the possible sources contributing to the PM₁₀. Varimax rotated factor analysis identified four possible sources of measured trace metals comprising solid waste dumping, vehicular traffic with the influence of road dust, road dust and soil dust at residential site (Kasba), while vehicular traffic with the influence of soil dust, road dust, galvanizing and electroplating industry, and tanning industry at industrial site (Cossipore).     

福建省兴化湾大气重金属的干湿沉降

在兴化湾周围采集1年的大气颗粒物及降雨样品,测定分析了Cd,Pb,Zn和Cu 4种重金属的含量及其大气干湿沉降通量随季节的变化规律,并利用Pb同位素对大气颗粒物的来源进行了解析.结果表明:大气重金属的干沉降通量随季节变化不大,而湿沉降通量随季节变化明显.大气干沉降通量中,Cd,Cu随季节变化很小,而Pb,Zn有一定的季节变化,主要是因为降雨对大气颗粒物的去除作用.大气湿沉降通量中,所有重金属元素受降雨量影响显著,另外还与季节和风速有关.除Pb外,Cd,Zn和Cu的湿沉降通量均大于干沉降通量,说明湿沉降在大气对兴化湾重金属的输入过程中起主导作用.而Pb的输入则以颗粒态为主.根据Pb稳定同位素分析,兴化湾大气颗粒物中的重金属主要来源于工业活动.