Physical characteristics of small ions and their interaction with ultrafine particles in the urban environment

In recent years, the effect of ions and ultrafine particles on ambient air quality and human health has been well documented, however, knowledge about their sources, concentrations and interactions within different types of urban environments remains limited. This thesis presents the results of numerous field studies aimed at quantifying variations in ion concentration with distance from the source, as well as identifying the dynamics of the particle ionisation processes which lead to the formation of charged particles in the air. In order to select the most appropriate measurement instruments and locations for the studies, a literature review was also conducted on studies that reported ion and ultrafine particle emissions from different sources in a typical urban environment. The initial study involved laboratory experiments on the attachment of ions to aerosols, so as to gain a better understanding of the interaction between ions and particles. This study determined the efficiency of corona ions at charging and removing particles from the air, as a function of different particle number and ion concentrations. The results showed that particle number loss was directly proportional to particle charge concentration, and that higher small ion concentrations led to higher particle deposition rates in all size ranges investigated. Nanoparticles were also observed to decrease with increasing particle charge concentration, due to their higher Brownian mobility and subsequent attachment to charged particles. Given that corona discharge from high voltage powerlines is considered one of the major ion sources in urban areas, a detailed study was then conducted under three parallel overhead powerlines, with a steady wind blowing in a perpendicular direction to the lines. The results showed that large sections of the lines did not produce any corona at all, while strong positive emissions were observed from discrete components such as a particular set of spacers on one of the lines. Measurements were also conducted at eight upwind and downwind points perpendicular to the powerlines, spanning a total distance of about 160m. The maximum positive small and large ion concentrations, and DC electric field were observed at a point 20 m downwind from the lines, with median values of 4.4×103 cm-3, 1.3×103 cm-3 and 530 V m-1, respectively. It was estimated that, at this point, less than 7% of the total number of particles was charged. The electrical parameters decreased steadily with increasing downwind distance from the lines but remained significantly higher than background levels at the limit of the measurements. Moreover, vehicles are one of the most prevalent ion and particle emitting sources in urban environments, and therefore, experiments were also conducted behind a motor vehicle exhaust pipe and near busy motorways, with the aim of quantifying small ion and particle charge concentration, as well as their distribution as a function of distance from the source. The study found that approximately equal numbers of positive and negative ions were observed in the vehicle exhaust plume, as well as near motorways, of which heavy duty vehicles were believed to be the main contributor. In addition, cluster ion concentration was observed to decrease rapidly within the first 10-15 m from the road and ion-ion recombination and ion-aerosol attachment were the most likely cause of ion depletion, rather than dilution and turbulence related processes. In addition to the above-mentioned dominant ion sources, other sources also exist within urban environments where intensive human activities take place. In this part of the study, airborne concentrations of small ions, particles and net particle charge were measured at 32 different outdoor sites in and around Brisbane, Australia, which were classified into seven different groups as follows: park, woodland, city centre, residential, freeway, powerlines and power substation. Whilst the study confirmed that powerlines, power substations and freeways were the main ion sources in an urban environment, it also suggested that not all powerlines emitted ions, only those with discrete corona discharge points. In addition to the main ion sources, higher ion concentrations were also observed environments affected by vehicle traffic and human activities, such as the city centre and residential areas. A considerable number of ions were also observed in a woodland area and it is still unclear if they were emitted directly from the trees, or if they originated from some other local source. Overall, it was found that different types of environments had different types of ion sources, which could be classified as unipolar or bipolar particle sources, as well as ion sources that co-exist with particle sources. In general, fewer small ions were observed at sites with co-existing sources, however particle charge was often higher due to the effect of ion-particle attachment. In summary, this study quantified ion concentrations in typical urban environments, identified major charge sources in urban areas, and determined the spatial dispersion of ions as a function of distance from the source, as well as their controlling factors. The study also presented ion-aerosol attachment efficiencies under high ion concentration conditions, both in the laboratory and in real outdoor environments. The outcomes of these studies addressed the aims of this work and advanced understanding of the charge status of aerosols in the urban environment.

Corona ions from high-voltage power lines : nature of emission and dispersion

Positive and negative small ions, aerosol ion and number concentration and dc electric fields were monitored at an overhead high-voltage power line site. We show that the emission of corona ions was not spatially uniform along the lines and occurred from discrete components such as a particular set of spacers. Maximum ion concentrations and atmospheric dc electric fields were observed at a point 20 m downwind of the lines. It was estimated that less than 7% of the total number of aerosol particles was charged. The electrical parameters decreased steadily with further downwind distance but remained significantly higher than background.

The relationship between airborne small ions and particles in urban environments

Ions play an important role in affecting climate and particle formation in the atmosphere. Small ions rapidly attach to particles in the air and, therefore, studies have shown that they are suppressed in polluted environments. Urban environments, in particular, are dominated by motor vehicle emissions and, since motor vehicles are a source of both particles and small ions, the relationship between these two parameters is not well known. In order to gain a better understanding of this relationship, an intensive campaign was undertaken where particles and small ions of both signs were monitored over two week periods at each of three sites A, B and C that were affected to varying degrees by vehicle emissions. Site A was close to a major road and reported the highest particle number and lowest small ion concentrations. Precursors from motor vehicle emissions gave rise to clear particle formation events on five days and, on each day this was accompanied by a suppression of small ions. Observations at Site B, which was located within the urban airshed, though not adjacent to motor traffic, showed particle enhancement but no formation events. Site C was a clean site, away from urban sources. This site reported the lowest particle number and highest small ion concentration. The positive small ion concentration was 10% to 40% higher than the corresponding negative value at all sites. These results confirm previous findings that there is a clear inverse relationship between small ions and particles in urban environments dominated by motor vehicle emissions.

Investigation on bioactivity of titanium dioxide thin films fabricated by electron cyclotron resonance plasma aided pulsed laser deposition

Titanium dioxide thin films with a rutile crystallinite size around 20 nm were fabricated by pulsed laser deposition (PLD) aided with an electron cyclotron resonance (ECR) plasma. With annealing treatment, the crystal size of the rutile crystallinite increased to 100 nm. The apatite-forming ability of the films as deposited and after annealing was investigated in a kind of simulated body fluid with ion concentrations nearly equal to those of human blood plasma. The results indicate that ECR aided PLD is an effective way both to fabricate bioactive titanium dioxide thin films and to optimize the bioactivity of titanium dioxide, with both crystal size and defects of the film taken into account.

Suppression of cluster ions during particle formation events in the atmosphere

Cluster ions and charged and neutral nanoparticle concentrations were monitored using a neutral cluster and air ion spectrometer (NAIS) over a period of one year in Brisbane, Australia. The study yielded 242 complete days of usable data, of which particle formation events were observed on 101 days. Small, intermediate and large ion concentrations were evaluated in real time. In the diurnal cycle, small ion concentration was highest during the second half of the night while large ion concentrations were a maximum during the day. The small ion concentration showed a decrease when the large ion concentration increased. Particle formation was generally followed by a peak in the intermediate ion concentration. The rate of increase of intermediate ions was used as the criteria for identifying particle formation events. Such events were followed by a period of growth to larger sizes and usually occurred between 8 am and 2 pm. Particle formation events were found to be related to the wind direction. The gaseous precursors for the production of secondary particles in the urban environment of Brisbane have been shown to be ammonia and sulfuric acid. During these events, the nanoparticle number concentrations in the size range 1.6 to 42 nm, which were normally lower than 1x104 cm-3, often exceeded 5x104 cm-3 with occasional values over 1x105 cm-3. Cluster ions generally occurred in number concentrations between 300 and 600 cm-3 but decreased significantly to about 200 cm-3 during particle formation events. This was accompanied by an increase in the large ion concentration. We calculated the fraction of nanoparticles that were charged and investigated the occurrence of possible overcharging during particle formation events. Overcharging is defined as the condition where the charged fraction of particles is higher than in charge equilibrium. This can occur when cluster ions attach to neutral particles in the atmosphere, giving rise to larger concentrations of charged particles in the short term. Ion-induced nucleation is one of the mechanisms of particle formation in the atmosphere, and overcharging has previously been considered as an indicator of this process. The possible role of ions in particle formation was investigated.

Charged particles and cluster ions produced during cooking activities

Previous studies showed that a significant number of the particles present in indoor air are generated by cooking activities, and measured particle concentrations and exposures have been used to estimate the related human dose. The dose evaluation can be affected by the particle charge level which is usually not considered in particle deposition models. To this purpose, in this paper we show, for the very first time, the electric charge of particles generated during cooking activities and thus extending the interest on particle charging characterization to indoor micro-environments, so far essentially focused on outdoors. Particle number, together with positive and negative cluster ion concentrations, was monitored using a condensation particle counter and two air ion counters, respectively, during different cooking events. Positively-charged particle distribution fractions during gas combustion, bacon grilling, and eggplant grilling events were measured by two Scanning Mobility Particle Sizer spectrometers, used with and without a neutralizer. Finally, a Tandem Differential Mobility Analyzer was used to measure the charge specific particle distributions of bacon and eggplant grilling experiments, selecting particles of 30, 50, 80 and 100 nm in mobility diameter. The total fraction of positively-charged particles was 4.0%, 7.9%, and 5.6% for gas combustion, bacon grilling, and eggplant grilling events, respectively, then lower than other typical outdoor combustion-generated particles.

Mortality and blood loss by blue swimmer crabs (Portunus pelagicus) after simulated capture and discarding from gillnets

Two laboratory experiments were carried out to quantify the mortality and physiological responses of juvenile blue swimmer crabs (Portunus pelagicus) after simulated gillnet entanglement, air exposure, disentanglement, and discarding. In both experiments, all but control blue swimmer crabs were entangled in 1-m(2) gillnet panels for 1 h, exposed to air for 2 min, subjected to various treatments of disentanglement ranging between the forceful removal of none, one, two, and four appendages, then "discarded" into individual experimental tanks and monitored for 10 d. In Experiment 1, mortalities were associated with the number of appendages removed and the occurrence of unsealed wounds. In Experiment 2, live blue swimmer crabs were sampled for blood at 2 min and 6, 24, and 72 h post-discarding to test for the effects of disentanglement and appendage removal on total haemocyte counts, clotting times, protein levels (by refractive index), and blood ion concentrations. Compared with blue swimmer crabs that had sealed or no wounds, those with unsealed wounds had lower total haemocyte counts, protein, and calcium concentrations and increased clotting ties and magnesium and sodium levels. Induced autotomy, as opposed to the arbitrary, forceful removal of a appendages has the potential to minimize the mortality and stress of discarded, juvenile blue swimmer crabs.

Cat's claw creeper vine, Macfadyena unguis-cati (Bignoniaceae), invasion impacts: comparative leaf nutrient content and effects on soil physicochemical properties

Macfadyena unguis-cati (L.) Gentry (Bignoniaceae) is a major environmental weed in coastal Queensland, Australia. There is a lack of quantitative data on its leaf chemistry and its impact on soil properties. Soils from infested vs uninfested areas, and leaves of M. unguis-cati and three co-occurring vine species (one exotic, two native) were collected at six sites (riparian and non-riparian) in south-eastern Queensland. Effects of invasion status, species, site and habitat type were examined using univariate and multivariate analyses. Habitat type had a greater effect on soil nutrients than on leaf chemistry. Invasion effect of M. unguis-cati on soil chemistry was more pronounced in non-riparian than in riparian habitat. Significantly higher values were obtained in M. unguis-cati infested (vs. uninfested) soils for ~50% of traits. Leaf ion concentrations differed significantly between exotic and native vines. Observed higher leaf-nutrient load (especially nitrogen, phosphorus and potassium) in exotic plants aligns with the preference of invasive plant species for disturbed habitats with higher nutrient input. Higher load of trace elements (aluminium, boron, cadmium and iron) in its leaves suggests that cycling of heavy-metal ions, many of which are potentially toxic at excess level, could be accelerated in soils of M. unguis-cati-invaded landscape. Although inferences from the present study are based on correlative data, the consistency of the patterns across many sites suggests that M. unguis-cati may improve soil fertility and influence nutrient cycling, perhaps through legacy effects of its own litter input.

Major Cellular and Physiological Impacts of Ocean Acidification on a Reef Building Coral

As atmospheric levels of CO2 increase, reef-building corals are under greater stress from both increased sea surface temperatures and declining sea water pH. To date, most studies have focused on either coral bleaching due to warming oceans or declining calcification due to decreasing oceanic carbonate ion concentrations. Here, through the use of physiology measurements and cDNA microarrays, we show that changes in pH and ocean chemistry consistent with two scenarios put forward by the Intergovernmental Panel on Climate Change (IPCC) drive major changes in gene expression, respiration, photosynthesis and symbiosis of the coral, Acropora millepora, before affects on biomineralisation are apparent at the phenotype level. Under high CO2 conditions corals at the phenotype level lost over half their Symbiodinium populations, and had a decrease in both photosynthesis and respiration. Changes in gene expression were consistent with metabolic suppression, an increase in oxidative stress, apoptosis and symbiont loss. Other expression patterns demonstrate upregulation of membrane transporters, as well as the regulation of genes involved in membrane cytoskeletal interactions and cytoskeletal remodeling. These widespread changes in gene expression emphasize the need to expand future studies of ocean acidification to include a wider spectrum of cellular processes, many of which may occur before impacts on calcification.

Analysis of forest soil chemistry and hydrology with a dynamic model ACIDIC.

In this study we analyze how the ion concentrations in forest soil solution are determined by hydrological and biogeochemical processes. A dynamic model ACIDIC was developed, including processes common to dynamic soil acidification models. The model treats up to eight interacting layers and simulates soil hydrology, transpiration, root water and nutrient uptake, cation exchange, dissolution and reactions of Al hydroxides in solution, and the formation of carbonic acid and its dissociation products. It includes also a possibility to a simultaneous use of preferential and matrix flow paths, enabling the throughfall water to enter the deeper soil layers in macropores without first reacting with the upper layers. Three different combinations of routing the throughfall water via macro- and micropores through the soil profile is presented. The large vertical gradient in the observed total charge was simulated succesfully. According to the simulations, gradient is mostly caused by differences in the intensity of water uptake, sulfate adsorption and organic anion retention at the various depths. The temporal variations in Ca and Mg concentrations were simulated fairly well in all soil layers. For H+, Al and K there were much more variation in the observed than in the simulated concentrations. Flow in macropores is a possible explanation for the apparent disequilibrium of the cation exchange for H+ and K, as the solution H+ and K concentrations have great vertical gradients in soil. The amount of exchangeable H+ increased in the O and E horizons and decreased in the Bs1 and Bs2 horizons, the net change in whole soil profile being a decrease. A large part of the decrease of the exchangeable H+ in the illuvial B horizon was caused by sulfate adsorption. The model produces soil water amounts and solution ion concentrations which are comparable to the measured values, and it can be used in both hydrological and chemical studies of soils.

Interaction of rhodium(III) with DNA

The nature of interaction of Rh(III) with DNA was studied using viscometry and ultraviolet, visible and infrared spectroscopy. The rate of interaction was found to be very slow at room temperature taking several days for completion. The time needed to attain equilibrium is dependent on the concentrations of metal ion, higher the concentration shorter the period required for equilibration. Visible spectra of Rh(III) were found to alter considerably in the presence of DNA. An increase in absorbance and a red shift were observed in the ultraviolet spectra of DNA in the presence of Rh(III). The specific viscosity of DNA solution was found to decrease asymptotically with time and concentrations of metal ion. The melting temperature of DNA was found to increase at lower metal ion concentrations, whereas at higher values a decrease was obtained. At still higher metal ion concentrations (Image ) a ‘nonmeltable state’ of DNA was observed. These results seem to indicate that Rh(III) binds both with the phosphate and the bases of the DNA.

Metal-metal charge transfer and interfacial charge transfer mechanism for the visible light photocatalytic activity of cerium and nitrogen co-doped TiO2

Nanosized cerium and nitrogen co-doped TiO2 (Ce-TiO2-xNx) was synthesized by sol gel method and characterized by powder X-ray diffraction (PXRD), X-ray photoelectron spectroscopy (XPS), FESEM, Fourier transform infrared, N-2 adsorption and desorption methods, photoluminescence and ultraviolet-visible (UV-vis) DRS techniques. PXRD analysis shows the dopant decreases the crystallite sizes and slows the crystallization of the titania matrix. XPS confirm the existence of cerium ion in +3 or +4 state, and nitrogen in -3 state in Ce-TiO2-xNx. The modified surface of TiO2 provides highly active sites for the dyes at the periphery of the Ce-O-Ti interface and also inhibits Ce particles from sintering. UV-visible DRS studies show that the metal-metal charge transfer (MMCT) of Ti/Ce assembly (Ti4+/Ce3+ -> Ti3+/Ce4+) is responsible for the visible light photocatalytic activity. Photoluminescence was used to determine the effect of cerium ion on the electron-hole pair separation between the two interfaces Ce-TiO2-xNx and Ce2O3. This separation increases with the increase of cerium and nitrogen ion concentrations of doped samples. The degradation kinetics of methylene blue and methyl violet dyes in the presence of sol gel TiO2, Ce-TiO2-xNx and commercial Degussa P25 was determined. The higher visible light activity of Ce-TiO2-xNx was due to the participation of MMCT and interfacial charge transfer mechanism.

Sol-gel matrix modified microstructured optical fibre towards a fluoride sensitive optical probe

In this article, we report an optical fluoride probe based on microstructured polymer optical fibers (MPOFs) which is modified with morin-Al complex doped silica gel film. This probe is fabricated by sol-gel fluxion coating process. Sol solution doped with morin-Al is directly inhaled into array holes of MPOF and then forms morin-Al-gel matrix film in them. The sensing probe shows different fluorescence intensity to different fluoride ion concentrations in the aqueous solution. The range of response is 550 mmol/L, under the condition of pH 4.6. Crown Copyright (C) 2009 Published by Elsevier B.V. All rights reserved.

白腐菌选择性降解木质素的研究

对15株白腐真菌进行了以玉米秸秆为基质的初步筛选，从中获得一株选择性系数较高的菌株Y10，并对其降解玉米秸秆的情况进行了研究。结果表明，在30天的培养过程中菌株Y10对玉米秸秆降解的选择性系数都大于1，第15天选择性系数最高为3.88。对未经降解和降解过的玉米秸秆分别作了紫外光谱和红外光谱分析，结果表明，经该菌降解后玉米秸秆的化学成分发生了很大变化，且木质素的降解程度要大于纤维素的降解程度。对菌株Y10进行了ITS-5.8S rDNA序列鉴定，初步判定其为Cerrena sp.。 为了考查不同的外源添加物对菌株Y10降解玉米秸秆的影响，在以玉米秸秆为基质的固态发酵培养基中分别添加了7种金属离子、8种碳源、6种氮源。结果显示，这7种金属离子均能促进木质素的降解，并且一定浓度的某些离子明显抑制纤维素的降解；其中添加0.036%的MnSO4·H2O和0.36%的MgSO4·7H2O对纤维素降解的抑制作用比较强，降解率分别为0.96%和1.31%，木质素的选择性系数分别达到了34.40和20.17。8种碳源中除麦芽糖外都能促进木质素的降解，除微晶纤维素外都明显促进纤维素的降解。6种氮源中酒石酸铵、硫酸铵、草酸铵和氯化铵的添加都会使该菌生长变慢，而且氮源浓度越高菌丝生长越慢。外加碳源和金属离子对半纤维素降解和选择性系数的影响不大。 同时对菌株Y10在液态培养下产木质素降解酶的条件和培养基做了优化。结果表明，在初始产酶培养基中，菌株Y10的漆酶酶活在第10d达到最高，锰过氧化物酶酶活在第11d达到最高，基本上检测不到木质素过氧化物酶。菌株Y10产漆酶的最适温度为32℃，最适PH为6.0；产锰过氧化物酶的最适温度为32℃，最适PH为6.5。菌株Y10产漆酶的最佳碳源为甘露糖，最佳氮源为酒石酸铵，最适诱导剂VA浓度为3 mmol/L，最适表面活性剂TW-80浓度为1%。 利用响应面法对其产漆酶的培养基进行优化，优化后的培养基配方为葡萄糖10.00 g/L，酒石酸铵0.50 g/L，大量元素296.50 ml/L，微量元素100.00 ml/L，NTA 1.40 g/L，VA 5.00 mmol/L，吐温-80加入量为0.10%。进行了菌株Y10产漆酶的验证实验，实测酶活为5282.56 U/L，与预测酶活5162.73 U/L接近。在优化后培养基中，菌株Y10在第14 d达到生长的最高峰，第20 d时，漆酶酶活最高，为11325.00 U/L；第16 d时，锰过氧化物酶酶活最高，为30.77 U/L。 对菌株Y10的漆酶酶学性质做了初步的研究，结果显示，酶反应的最适温度为40℃-65℃，最适PH为3.0。在40℃，PH=3.0时，漆酶催化ABTS反应的米氏方程为 。 Fifteen white-rot fungi based on corn stalk were screened. One white-rot fungus Y10 with high selectivity value was obtained. The degradation of corn stalk was initially studied. The results indicated that the selectivity value was above 1 during the 30 day-cultivation and the highest was 3.88 after 15 days. The composition of untreated and treated stalk was analyzed through ultraviolet spectroscopy and infrared spectroscopy. It was found that the composition of treated stalk was greatly altered and the degree of the degradation of lignin is greater than the cellulose. Y10 was identified as Cerrena sp. by ITS -5.8S rDNA sequence analysis. The influence of metal ions, carbon sources and nitrogen sources on corn stalk degradation by white-rot fungus was studied. While all seven metal ions could promote lignin degradation, the cellulose degradation was best inhibited at certain ion concentrations. Notably, when 0.036% MnSO4·H2O and 0.36% MgSO4·7H2O were added into the medium, the cellulose degradation was restrained to the extents that the coefficients of lignin selectivity rose to 34.40 and 20.17 respectively. It was also found that all carbon sources except maltose can promote lignin degradation. The addition of carbon sources other than microcrystalline cellulose significantly promoted cellulose degradation. The addition of the nitrogen sources, ammonium tartrate, ammonium sulfate, oxalate, ammonium chloride, resulted in remarkable inhibition to mycelium growth; the larger the concentrations of nitrogen sources are, the slower the mycelium grew. The addition of carbon sources and metal ions had less impact on the degradation of hemicellulose and selectivity value. Meanwhile, we optimized the conditions and culture medium of the lignin-degrading enzyme production of strain Y10. The results showed that in the initial culture medium, the Lac activity was highest at the 10th day, the MnP activity was highest at the 11th day and the LiP could not be detected. The optimum condition of Lac was at temperature 32 and PH =6.0 and the optimum condition of MnP was at temperature 32 and PH =6.5. The optimum carbon source for Lac was seminose, the optimum nitrogen source was ammonium tartrate, the optimum content of VA was 3 mmol/L, the optimum content of TW-80 was 1%. PB and RSM were used to optimize the culture medium of laccase by white-rot fungus Y10. The optimum culture medium was consist of glucose 10.00 g/L, ammonium tartrate 0.50 g/L, macro elements 296.50 ml/L, trace elements 100.00 ml/L, NTA 1.40 g/L, VA 5.00 mmol/L, TW-80 0.10%. Under the optimal conditions, the activity of laccase was 5282.56 U/L and the experimental value agreed with the predicted value 5162.73 U/L. The biomass was highest at the 14th day, the Lac activity was highest at the 20th day, the MnP activity was highest at the 16th day. The results of the studies on the characteristics of Lac showed that the optimum temperature for Lac activity is 40℃-65℃ ; the optimum PH for Lac activity is 3.0 and under 40℃，PH=3.0, the Michaelis-menten equation of Lac catalized ABTS oxidation was .

Mass transfer of Er(III) between HBTMPTP dissolved in n-heptane and HAc-NaAc

The rate of extraction of Er(III) from aqueous acetate solutions at 0. 2 mol/L ionic strength by HBTMPTP in n-heptane was studied by using a constant interfacial area cell with laminar flow at (30+/- 0. 5)degrees C. The interfacial activity of HBTMPTP was investigated at n-heptane/0. 2 mol/L (H, Na)Ac (pH=5. 00) interface, The rate of Er(III) extraction was measured at different chemical compositions by varying hydrogen ion, HBTMPTP, Cyanex 302 and chlorine ion concentrations, The effect of stirring speed, temperature and special interfacial area on the rate of extraction was also studied. The results showed that, under the conditions of the experiments, the overall rate is diffusion controlled, that the impurities of Cyanex 302 have the effect of synergistic extraction.