Nanostructured semiconducting materials for efficient hydrogen generation

Massive production of hydrogen by water decomposition triggered by a solar light active photocatalyst is a major objective in chemistry and a promising avenue to overcome the global energy crisis. The development of efficient, stable, economically viable and eco-friendly photocatalysts for hydrogen production is a challenging task. This article reviews the use of nanocomposite in three combinations: metal oxide–metal oxide semiconductor, metal–metal oxide semiconductor and metal chalcogenide–metal oxide core–shell nanostructures. These core–shell structures occur in two forms: a simple form where the photocatalyst is either in the core or the shell or in a more complex system where the core–shell structure comprises a co-catalyst deposited on a semiconducting material. We discuss the design, synthesis and development of semiconductor-based nanocomposite photocatalysts for hydrogen production. The major points are the role of catalytic active sites, the chemical nature of sacrificial agents, the effect of light sources, the variable light intensity and the energy efficiency calculation. For TiO₂-based nanocomposites, the metal oxide or metal co-catalyst loading of 1.0–3.0 wt% was optimal. TiO₂ nanotube–CuO hybrid nanocomposites produce 1,14,000 µmol h^?1 \({\text{g}}^{ - 1}_{\text{cat}}\), whereas TiO₂/Au nanocomposites display 1,60,000 µmol h^?1 \({\text{g}}^{ - 1}_{\text{cat}}\). For core–shell catalysts, a shell thickness of 2–20 nm was found for the best activity, and its performance is as follows: (a) CdS–NiO system produces around 19,949 µmol h^?1 \({\text{g}}^{ - 1}_{\text{cat}}\) and (b) CuO–Cr₂O₃ as co-catalyst immobilized on TiO₂ system produces around 82,390 µmol h^?1 \({\text{g}}^{ - 1}_{\text{cat}}\).     

Hydrogeochemistry study and groundwater quality assessment in the north of Isfahan,Iran

This study presents the groundwater quality assessment in the north of Isfahan, Iran. In the study area, assessment and measurement of groundwater hydrochemical parameters such as pH, total dissolved solids (TDS), electrical conductivity (EC), sodium absorption ratio (SAR), total hardness, major cations (K⁺, Na⁺, Ca²⁺ and Mg²⁺) and major anions (Cl^?, \({\text{HCO}}_{ 3}^{ - } ,{\text{CO}}_{3}^{2 - }\) and \({\text{SO}}_{4}^{2 - }\)) concentrations were performed. Accordingly, the 66 water samples from different locations were collected during April and May 2015. Water samples collected in the field were analyzed in the laboratory for cations and anions using the standard methods. In this research, the analytical results of physiochemical parameters of groundwater were compared with the standard guideline values as recommended by the world health organization (WHO) for drinking and public health purposes. The pH values of groundwater samples varied from 7.05 to 8.95 with a mean of 7.78, indicating a neutral to slightly alkaline water. TDS values showed that 14% of the samples exceeds the desirable limit given by WHO. EC values varied from 213 to 4320 µS/cm, while 23% of the samples were more than the standard limit. Gibbs diagram had shown that 90% of the samples in the study area fall in the rock weathering zone, and this means that chemical weathering of rock-forming minerals is the main factor controlling the water chemistry in the study area. Irrigation suitability and risk assessment of groundwater are evaluated by measuring EC, %Na, SAR and RSC. According to the dominant cations and anions, five types of water were identified in the water samples: Ca-HCO₃, Ca-SO₄, Na-Cl, Na-HCO₃ and Na-SO₄. The results show that the majority of samples (30 samples, 45%) belongs to the mixed Na-SO₄ water type. Correlation analysis and principal component analysis was used to identify the relationship between ions and physicochemical parameters. Results indicated that 18 stations of the study area had the best quality and can be used for irrigation and drinking purposes in the future.     

Evolution and decay of gravity wavefields in weak-rotating environments: a laboratory study

Gravity waves are prominent physical features that play a fundamental role in transport processes of stratified aquatic ecosystems. In a two-layer stratified basin, the equations of motion for the first vertical mode are equivalent to the linearised shallow water equations for a homogeneous fluid. We adopted this framework to examine the spatiotemporal structure of gravity wavefields weakly affected by the background rotation of a single-layer system of equivalent thickness \(h_{\ell }\), via laboratory experiments performed in a cylindrical basin mounted on a turntable. The wavefield was generated by the release of a diametral linear tilt of the air–water interface, \(\eta _{\ell }\), inducing a basin-scale perturbation that evolved in response to the horizontal pressure gradient and the rotation-induced acceleration. The basin-scale wave response was controlled by an initial perturbation parameter, \({\mathcal{A}}_{*} = \eta _{0}/h_{\ell }\), where \(\eta _{0}\) was the initial displacement of the air–water interface, and by the strength of the background rotation controlled by the Burger number, \({\mathcal{S}}\). We set the experiments to explore a transitional regime from moderate- to weak-rotational environments, \(0.65\le {\mathcal{S}} \le 2\), for a wide range of initial perturbations, \(0.05\le {\mathcal{A}}_{*}\le 1.0\). The evolution of \(\eta _{\ell }\) was registered over a diametral plane by recording a laser-induced optical fluorescence sheet and using a capacitive sensor located near the lateral boundary. The evolution of the gravity wavefields showed substantial variability as a function of the rotational regimes and the radial position. The results demonstrate that the strength of rotation and nonlinearities control the bulk decay rate of the basin-scale gravity waves. The ratio between the experimentally estimated damping timescale, \(T_{d}\), and the seiche period of the basin, \(T_{g}\), has a median value of \(T_{d}/T_{g}\approx 11\), a maximum value of \(T_{d}/T_{g}\approx 10^{3}\) and a minimum value of \(T_{d}/T_{g}\approx 5\). The results of this study are significant for the understanding the dynamics of gravity waves in waterbodies weakly affected by Coriolis acceleration, such as mid- to small-size lakes.     

Environmental impact of CO<Subscript>2</Subscript>, Rn,Hg degassing from the rupture zones produced by Wenchuan <Emphasis Type="Italic">M</Emphasis><Subscript>s</Subscript> 8.0 earthquake in western Sichuan,China

The concentrations and flux of CO₂, ²²²Radon (Rn), and gaseous elemental mercury (Hg) in soil gas were investigated based on the field measurements in June 2010 at ten sites along the seismic rupture zones produced by the May 12, 2008, Wenchuan M _s 8.0 earthquake in order to assess the environmental impact of degassing of CO₂, Rn and Hg. Soil gas concentrations of 344 sampling points were obtained. Seventy measurements of CO₂, Rn and Hg flux by the static accumulation chamber method were performed. The results of risk assessment of CO₂, Rn and Hg concentration in soil gas showed that (1) the concentration of CO₂ in the epicenter of Wenchuan M _s 8.0 earthquake and north end of seismic ruptures had low risk of asphyxia; (2) the concentrations of Rn in the north segment of seismic ruptures had high levels of radon, Maximum was up to level 4, according to Chinese code (GB 50325-2001); (3) the average geoaccumulation index I _geo of soil Hg denoted the lack of soil contamination, and maximum values classified the soil gas as moderately to strongly polluted in the epicenter. The investigation of soil gas CO₂, Rn and Hg degassing rate indicated that (1) the CO₂ in soil gas was characterized by a mean \(\updelta^{13}C_{CO2}\) of ?20.4 ‰ and by a mean CO₂ flux of 88.1 g m^?2 day^?1, which were in the range of the typical values for biologic CO₂ degassing. The maximum of soil CO₂ flux reached values of 399 g m^?2 day^?1 in the epicenter; (2) the soil Rn had higher exhalation in the north segment of seismic ruptures, the maximum reached value of 1976 m Bq m^?2 s^?1; (3) the soil Hg flux was lower, ranging from ?2.5 to 18.7 n g m^?2 h^?1 and increased from south to north. The mean flux over the all profiles was 4.2 n g m^?2 h^?1. The total output of CO₂ and Hg degassing estimated along seismic ruptures for a survey area of 18.17 km² were approximately 0.57 Mt year^?1 and 688.19 g year^?1. It is recommended that land-use planners should incorporate soil gas and/or gas flux measurements in the environmental assessment of areas of possible risk. A survey of all houses along seismic ruptures is advised as structural measures to prevent the ingress of soil gases, including CO₂ and Rn, were needed in some houses.     

Analysis and prediction of $$\mathrm{PM}_{10}$$ concentration levels in Tunisia using statistical learning approaches

Over the past years, the health impact of airborne particulate matter \(\mathrm{PM}_{10}\) has become a very topical subject. Thereby, a lot of research effort in the environmental sciences goes towards the modeling and the prediction of ambient \(\mathrm{PM}_{10}\) concentrations. In this paper, we are interested in the statistical classification of the daily mean \(\mathrm{PM}_{10}\) concentration in Tunisia according to the authority regulation. We consider two monitoring stations: a big industrial station and a traffic station. The main goal of this work is to determine the pertinent predictors of \(\mathrm{PM}_{10}\) concentration within a nonlinear multiclass framework. To do this, we used two popular statistical learning methods; the support vector machines (SVM) and the random forests (RF). The statistical results obtained on the real datasets, show that RF outperform SVM for the purpose of variable selection even with a reduced number of observations compared to the number of explicative variables. It was also demonstrated that the \(\mathrm{PM}_{10}\) concentration measured yesterday is the most relevant predictor of its present-day value. Moreover, we found that the more delayed values of \(\mathrm{PM}_{10}\) concentration may be crucial to get an accurate prediction.     

Direct and indirect effects of pesticides on a benthic grazer during its life cycle

Background

Macroinvertebrates in aquatic ecosystems are repeatedly exposed to pesticides during their life cycle. Effects of consecutive exposure during different life stages and possible synergistic effects are not addressed in the standardized hazard assessment. The present study investigated two environmentally relevant exposure scenarios in batch (microcosm) and artificial indoor stream (mesocosm) experiments using the larvae of the mayfly Rhithrogena semicolorata (grazer) and natural aufwuchs. Grazers were analysed regarding growth, physiological condition, and drift behaviour, while the aufwuchs was analysed in terms of biomass using the particulate organic carbon as well as the chlorophyll a content. The aim was to reveal direct and indirect effects of an herbicide exposure during autumn on juvenile grazers and an insecticide exposure during spring on semi-juvenile grazers.

Results

Direct and indirect effects were found in both exposure scenarios at environmentally relevant concentrations. In the herbicide exposure scenario with terbutryn, clear direct effects on the aufwuchs community with a LOEC of 0.38 µg L^?1 were found. Effect levels of grazers due to indirect effects were equal, with the overnight drift being the most sensitive grazer endpoint. In the insecticide exposure scenario, clear lethal and sub lethal effects of lambda-cyhalothrin were evident. Derived LC₅₀ values for the artificial indoor stream and batch experiment were 2.42 µg g^?1 OC (69 days) and 1.2 µg g^?1 OC (28 days), respectively. Sub lethal effects in terms of increased drift as well-reduced growth and triglyceride levels were found at concentrations of 1.4 and 0.09 µg g^?1 OC (LOECs). These results were confirmed by the batch experiment, which revealed effect values in the similar range. Finally, a clear indirect effect of the insecticide on the aufwuchs was evident in the batch experiment with an LOEC at 0.9 µg g^?1 OC.

Conclusion

Toxicity Exposure Ratios calculated with the derived effect values indicate a risk for the investigated grazer by both pesticides. Moreover, observed indirect effects during the herbicide exposure seem to be able to affect the grazers during a second exposure with an insecticide, due to reduced physiological conditions. We suggest further research with time-shifted exposure scenarios to gain a better understanding of the complex interactions of pesticides with the life cycle and the food webs of macroinvertebrates.

     

On the front conditions for gravity currents in channels of general cross-section

We consider the propagation of a high-Reynolds-number gravity current in a horizontal channel with general cross-section whose width is \(f(z), 0 \le z\le H\), and the gravity acceleration g acts in \(-z\) direction. (The classical rectangular cross-section is covered by the particular case \(f(z) =\) const.) We assume a two-layer system of homogeneous fluids of constant densities \(\rho _{c}\) (current, of height \(h < H \)) and smaller \(\rho _{a}\) (ambient, filling the remaining part of the channel). We focus attention on the calculation and assessment of the nose Froude-number condition \(Fr = U/(g' h)^{1/2}\); here U is the speed of propagation of the current and \(g' = (\rho _{c}/\rho _{a}-1) g\) is the reduced gravity. We first revisit the steady-state current, and derive compact insightful expressions of Fr and energy dissipation as a function of \(\varphi \) (\(=\) area fraction occupied by the current in the cross-section). We show that the head loss \(\delta _0\) on the stagnation line is formally a degree of freedom in the determination of \(Fr(\varphi )\), and we clarify the strong connections with the head loss \(\delta \) in the ambient fluid, and with the overall rate of dissipation \(\dot{{\mathcal{D}}}\). We demonstrate that the closure \(\delta _0 = 0\) [suggested by Benjamin (J Fluid Mech 31, 209–248, 1968) for the rectangular cross-section] produces in general the smallest Fr for a given \(\varphi \); the results are valid for a significant range \([0, \varphi _{\max }]\), in which the current is dissipative, except for the point \(\varphi _{\max }\) where \(\delta = \dot{{\mathcal{D}}} = 0\). We show that imposing the closure \(\delta = \dot{{\mathcal{D}}} = 0\), which corresponds to an energy-conserving or non-dissipative current, produces in general unacceptable restrictions of the range of validity, and large values of Fr; in particular, deep currents (\(\varphi < 0.3\) say) must be excluded because they are inherently dissipative. On the other hand, the compromise closure \(\delta (\varphi ) =\delta _0(\varphi )\) produces the simple \(Fr(\varphi ) = \sqrt{2}(1 - \varphi )\) formula whose values and dissipation properties are very close, and the range of validity is identical, to these obtained with Benjamin’s closure (moreover, we show that this corresponds to circulation-conservation solutions). The results are illustrated for practical cross-section geometries (rectangle, \(\Delta \) and \(\nabla \) triangle, circle, and the general power-law \(f(z) = b z ^\alpha \) (\(b>0, \alpha \ge 0, 0< z \le H\)). Next, we investigate the connection of the steady-state results with the time-dependent current, and show that in a lock-released current the rate of dissipation of the system is equal to, or larger than, that obtained for Fr corresponding to the conditions at the nose of the current. The results and insights of this study cover a wide range of cross-section geometry and apply to both Boussinesq and non-Boussinesq systems; they reveal a remarkable robustness of Fr as a function of \(\varphi \).     

Comparison of chemical compositions in air particulate matter during summer and winter in Beijing,China

The development of industry in Beijing, the capital of China, particularly in last decades, has caused severe environmental pollution including particulate matter (PM), dust–haze, and photochemical smog, which has already caused considerable harm to local ecological environment. Thus, in this study, air particle samples were continuously collected in August and December, 2014. And elements (Si, Al, V, Cr, Mn, Fe, Ni, Cu, Zn, Mo, Cd, Ba, Pb and Ti) and ions (\({\text{NO}}_{3}^{-}\), \({\text{SO}}_{4}^{2-}\), F^?, Cl^?, Na⁺, K⁺, Mg²⁺, Ca²⁺ and \({\text{NH}}_{4}^{+}\)) were analyzed by inductively coupled plasma mass spectrometer and ion chromatography. According to seasonal changes, discuss the various pollution situations in order to find possible particulate matter sources and then propose appropriate control strategies to local government. The results indicated serious PM and metallic pollution in some sampling days, especially in December. Chemical Mass Balance model revealed central heating activities, road dust and vehicles contribute as main sources, account for 5.84–32.05 % differently to the summer and winter air pollution in 2014.     

Thin-layer models for gravity currents in channels of general cross-section area,a review

We present a brief review of the recent investigations on gravity currents in horizontal channels with non-rectangular cross-section area (such as triangle, \(\bigvee \)-valley, circle/semi-circle, trapezoid) which occur in nature (e.g., rivers) and constructed environment (tunnels, reservoirs, canals). To be specific, we discuss the propagation of a gravity current (GC) in a horizontal channel along the horizontal coordinate x, with gravity g acting in the \(-z\) direction, and y the horizontal–lateral coordinate. The bottom and top of the channel are at \(z=0,H\). The “standard” problem is concerned with 2D flow in a channel with rectangular (or laterally unbounded) cross-section area (CSA). Recent investigations have successfully extended the standard knowledge to the channels of CSA given by the quite general \(-f_1(z)\le y \le f_2(z)\) for \(0 \le z \le H\). This includes the practical \(\bigvee \)-valley, triangle, circle/semi-circle and trapezoid; these geometries may be in “up” or “down” setting with respect to gravity, e.g., \(\bigtriangleup \) and \(\bigtriangledown \). The major objective of the extended theory is to predict the height of the interface \(z=h(x,t)\) and the velocity (averaged over the CSA) u(x, t), where t is time; the prediction includes the speed and position of the nose \(u_N(t), x_N(t)\). We show that the motion is governed by a set of simplified equations, called “model,” that provides versatile and insightful solutions and trends. The emphasis in on a high-Reynolds-number current whose motion is dominated by buoyancy–inertia balance; in particular a GC released from a lock, which also contains general effects such as front and internal jumps (shocks), and reflected bore. We discuss two-layer, one-layer, and box models; Boussinesq and non-Boussinesq systems; compositional and particle-driven cases; and the effect of stratification of the ambient fluid. The models are self-contained, and admit realistic initial and boundary conditions. The governing equations are amenable to analytical solutions in some special circumstances. Some salient features of the buoyancy-viscous regime, and the estimate for the length at which transition to this regime takes place, are also presented. Some experimental support to the theory, and open questions for further investigations, are also mentioned. The major conclusions are (1) The CSA geometry has significant influence on the motion of the GC; and (2) The new theory is a useful, very significant, extension of the standard two-dimensional GC problem. The standard current is just a particular case, \(f_{1,2} =\) constants, among many other covered by the new theory.     

In vivo uptake of iodine from a <Emphasis Type="Italic">Fucus serratus</Emphasis> Linnaeus seaweed bath: does volatile iodine contribute?

Seaweed baths containing Fucus serratus Linnaeus are a rich source of iodine which has the potential to increase the urinary iodide concentration (UIC) of the bather. In this study, the range of total iodine concentration in seawater (22–105 µg L^?1) and seaweed baths (808–13,734 µg L^?1) was measured over 1 year. The seasonal trend shows minimum levels in summer (May–July) and maximum in winter (November–January). The bathwater pH was found to be acidic, average pH 5.9 ± 0.3. An in vivo study with 30 volunteers was undertaken to measure the UIC of 15 bathers immersed in the bath and 15 non-bathers sitting adjacent to the bath. Their UIC was analysed pre- and post-seaweed bath and corrected for creatinine concentration. The corrected UIC of the population shows an increase following the seaweed bath from a pre-treatment median of 76 µg L^?1 to a post-treatment median of 95 µg L^?1. The pre-treatment UIC for both groups did not indicate significant difference (p = 0.479); however, the post-treatment UIC for both did (p = 0.015) where the median bather test UIC was 86 µg L^?1 and the non-bather UIC test was 105 µg L^?1. Results indicate the bath has the potential to increase the UIC by a significant amount and that inhalation of volatile iodine is a more significant contributor to UIC than previously documented.     

The effect of hypoxia on behavioural and physiological aspects of lesser sandeel, <Emphasis Type="Italic">Ammodytes tobianus</Emphasis> (Linnaeus, 1785)

Lesser sandeel (Ammodytes tobianus) is abundant in near-shore areas where it is a key prey. It exhibits the behaviour of alternating between swimming in schools and lying buried in the sediment. We first determined the species’ standard metabolic rate (SMR), critical partial pressure of oxygen and maximal oxygen uptake The sandeel were then exposed to an acute stepwise decline in water oxygen pressure (18.4, 13.8, 9.8, 7.5, 5.8, 4.0, and 3.1 kPa ). Swimming speed and routine- and post-experimental blood lactate levels were measured, in addition to levels associated with strenuous exercise. The SMR was 69.0 ± 8.4 mg O₂ kg⁻¹ h⁻¹ and the about seven times as high. The was found to be 4.1 kPa. A rapid decrease (within 1 h) in from 18.4 to 3.1 kPa had no significant effect on routine swimming speed (0.9 ± 0.06 bl s⁻¹), but steady levels at the lowest (3.1 kPa) gradually reduced the swimming speed by 95% after 40 min. The routine blood lactate levels were 2.2 ± 0.6 mmol l⁻¹, while the levels in the strenuously exercised groups were significantly higher with 5.4 ± 1.6 and 5.8 ± 1.3 mmol l⁻¹. The highest levels were observed in post-experimental fish with 7.5 ± 2.7 mmol l⁻¹. We argue that, as sandeel showed no decrease in swimming speed (to offset stress) nor an increased speed to escape the hypoxia, the fish either rely on a low SMR and being a reasonable strong oxygen regulator as a mean to cope when exposed to acute hypoxia, or that the hypoxia simply developed too fast for the fish to decide on an appropriate strategy. Not showing a behavioural response may in the present case be maladaptive, as the consequence was major physiological stress which the fish however appears tolerant towards. The high routine blood lactate levels suggest that anaerobic metabolism is associated with swimming in sandeel, which may be related to the specific lifestyle of the fish where they regularly bury in the sediment.     

Effect of wastewater composition on the calcium carbonate precipitation in upflow anaerobic sludge blanket reactors

Calcium carbonate often precipitates in anaerobic reactors treating wastewater with high calcium content. The aim of this paper is to study the effect of wastewater composition on calcium carbonate precipitation in upflow anaerobic sludge blanket (UASB) reactors. Two laboratory-scale UASB reactors were operated with calcium-containing influents using acetate and carbohydrate as substrate, respectively. There was an obvious accumulation of inorganic precipitate observed in the biogranules. Observations via scanning electron microscope (SEM) and energy dispersive spectroscopy (EDS) showed that the acclimated biogranules in the two reactors differed in microstructure. Calcium carbonate was found to have precipitated on the surface of acetate-degrading biogranules, but precipitated at the core of the carbohydrate-degrading biogranules. The results indicated that substrates had significant influence on the location of calcium carbonate precipitation in anaerobic granular sludge, which was expected due to the different methanogens distribution and pH gradient within the granular sludge degrading various substrates. Moreover, the location of calcium carbonate precipitation substantially affected the specific methanogenic activity (SMA) of the granular sludge. The SMA of the acetate-degrading biogranules dropped from \(1.96 gCOD_{CH_4 } \cdot gVSS^{ - 1} \cdot d^{ - 1} \) to \(0.61 gCOD_{CH_4 } \cdot gVSS^{ - 1} \cdot d^{ - 1} \) after 180-d of operation in the reactor. However, the SMA of the carbohydrate-degrading biogranules was not adversely affected by calcium carbonate precipitation.     

Trace element concentration in fine particulate matter (PM<Subscript>2.5</Subscript>) and their bioavailability in different microenvironments in Agra,India: a case study

Exposure to airborne particulate matter results in the deposition of millions of particle in the lung; consequently, there is need for monitoring them particularly in indoor environments. Case study was conducted in three different microenvironments, i.e., urban, rural and roadside to examine the elemental bioavailability in fine particulate matter and its potential health risk. The samples were collected on polytetrafluoroethylene filter paper with the help of fine particulate sampler during August–September, 2012. The average mass concentration of PM_2.5 was 71.23 µg m^?3 (rural), 45.33 µg m^?3 (urban) and 36.71 µg m^?3 (roadside). Elements in PM_2.5 were analyzed by inductively coupled plasma atomic emission spectroscopy. Percentage bioavailability was determined to know the amount of soluble fraction that is actually taken across the cell membrane through inhalation pathway. Cadmium and lead were found to have cancer risk in a risk evaluation using an Integrated Risk Information system.     

Characteristics of chemical components in PM<Subscript>2.5</Subscript> at a plateau city,South-west China

A sampling campaign including summer, autumn and winter of 2014 and spring of 2015 was accomplished to obtain the characteristic of chemical components in PM_2.5 at three sites of Kunming, a plateau city in South-west China. Nine kinds of water-soluble inorganic ions (WSI), organic and element carbon (OC and EC) in PM_2.5 were analyzed by ion chromatography and thermal optical reflectance method, respectively. Results showed that the average concentrations of total WSI, OC and EC were 22.85±10.95 µg·m^-3, 17.83±9.57 µg·m^-3 and 5.11±4.29 µg·m^-3, respectively. They totally accounted for 53.0% of PM_2.5. Secondary organic and inorganic aerosols (SOA and SIA) were also assessed by the minimum ratio of OC/EC, nitrogen and sulfur oxidation ratios. The annual average concentrations of SOA and SIA totally accounted for 28.3% of the PM_2.5 concentration. The low proportion suggested the primary emission was the main source of PM_2.5 in Kunming. However, secondary pollution in the plateau city should also not be ignorable, due to the appropriate temperature and strong solar radiation, which can promote the atmospheric photochemical reactions.

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Selenium speciation in wheat grain varies in the presence of nitrogen and sulphur fertilisers

This study investigated whether selenium species in wheat grains could be altered by exposure to different combinations of nitrogen (N) and sulphur (S) fertilisers in an agronomic biofortification experiment. Four Australian wheat cultivars (Mace, Janz, Emu Rock and Magenta) were grown in a glasshouse experiment and exposed to 3 mg Se kg^?1 soil as selenate (Se^VI). Plants were also exposed to 60 mg N kg^?1 soil as urea and 20 mg S kg^?1 soil as gypsum in a factorial design (N + S + Se; N + Se; S + Se; Se only). Plants were grown to maturity with grain analysed for total Se concentrations via ICP-MS and Se species determined via HPLC-ICP-MS. Grain Se concentrations ranged from 22 to 70 µg Se g^?1 grain (dry mass). Selenomethionine (SeMet), Se-methylselenocystine (MeSeCys), selenohomolanthionine (SeHLan), plus a large concentration of uncharacterised Se species were found in the extracts from grains. SeMet was the major Se species identified accounting for between 9 and 24 µg Se g^?1 grain. Exposure to different N and S fertiliser combinations altered the SeMet content of Mace, Janz and Emu Rock grain, but not that of Magenta. MeSeCys and SeHLan were found in far lower concentrations (<4 µg Se g^?1 grain). A large component of the total grain Se was uncharacterisable (>30 % of total grain Se) in all samples. When N fertiliser was applied (with or without S), the proportion of uncharacterisable Se increased between 60 and 70 % of the total grain Se. The data presented here indicate that it is possible to alter the content of individual Se species in wheat grains via biofortification combined with manipulation of N and S fertiliser regimes. This has potential significance in alleviating or combating both Se deficiency and Se toxicity effects in humans.     

Variations of bed elevations due to turbulence around submerged cylinder in sand beds

This paper presents the spatio-temporal variations in bed elevations and the near-bed turbulence statistics over the deformed bed generated around the submerged cylindrical piers embedded vertically on loose sediment bed at a constant flow discharge. Experiments were carried out in a laboratory flume for three blockage ratios in the range of 0.04–0.06 using three different sizes of submerged cylinders individually placed vertically at the centerline of the flume. Clear-water experimental conditions were maintained over the smooth sediment bed surface with a constant flow discharge (\(Q = 0.015\,{\rm m}^3/{\rm sec}\)), thereby giving three different cylinder Reynolds numbers \(Re_{D_c} = \frac{U_mD_c}{\nu }\) (=10200, 12750, 15300) away from the cylinder locations, where \(U_m\) is the maximum mean velocity, \(D_c\) is the cylinder diameter and \(\nu\) is the kinematic viscosity of fluid. Instantaneous sand bed elevations around the cylinders were recorded using a SeaTek 5MHz ultrasonic ranging system of net 24 transducers to estimate bed form migration, and the near-bed velocity data at transducer locations over the stable deformed bed around the pier-like structures were collected using down-looking three-dimensional (3D) Micro-acoustic Doppler velocimeter to estimate the bottom Reynolds shear stresses and the contributions of bursting events to the dominant shear stress component. The flow perturbation generated due to relatively lower flow blockage ratio favored to achieve the stable bed condition more rapidly than the others, and larger upstream scour-depth and deformed areas were noticed for greater flow blockage ratio due to larger cylinder diameter. For larger blockage ratio in the upstream of scour-hole near the bed, occurrences of probabilities of both boundary-ward interactions (Q1 and Q3) were the dominant; whereas in the downstream of the scoured region, occurrences of probabilities of second and third quadrant events (Q2 and Q4) were dominant. On the other hand, for the lower blockage ratio, quadrant (Q2) was dominant over Q4 in the downstream of scour-hole, and in the upstream of scour-hole, quadrant Q4 was the dominant.     

Distribution,source apportionment and health risk assessment of polycyclic aromatic hydrocarbons (PAHs) in intertidal sediment of Asaluyeh,Persian Gulf

Surface sediment samples were collected from intertidal zone of Asaluyeh, Persian Gulf, to investigate distribution, sources and health risk of sixteen polycyclic aromatic hydrocarbons (PAHs). Total PAH concentrations ranged from 1.8 to 81.2 μg kg^?1 dry weight, which can be categorized as low level of pollution. Qualitative and quantitative assessments showed that PAHs originated from both petrogenic and pyrogenic sources with slight pyrogenic dominance. Source apportionment using principal component analysis indicated that the main sources of PAHs were fossil fuel combustion (33.59%), traffic-related PAHs (32.77%), biomass and coal combustion (18.54%) and petrogenic PAHs (9.31%). According to the results from the sediment quality guidelines, mean effects range-median quotient (M-ERM-Q) and benzo[a]pyrene toxic equivalents (BaP_eq), low negative ecological risks related to PAH compounds would occur in the intertidal zone of Asaluyeh. The total benzo[a]pyrene (BaP) toxic equivalent quotient (TEQ^carc) for carcinogenic compounds ranged from 0.01 to 7 μg kg^?1-BaP_eq, indicating low carcinogenic risk. The human health risk assessment of PAH compounds via ingestion and dermal pathways suggests low and moderate potential risk to human health, respectively.     

Characteristics,sources and health risk assessment of toxic heavy metals in PM<Subscript>2.5</Subscript> at a megacity of southwest China

Twenty trace elements in fine particulate matters (i.e., PM_2.5) at urban Chengdu, a southwest megacity of China, were determined to study the characteristics, sources and human health risk of particulate toxic heavy metals. This work mainly focused on eight toxic heavy metal elements (As, Cd, Cr, Cu, Mn, Ni, Pb and Zn). The average concentration of PM_2.5 was 165.1 ± 84.7 µg m^?3 during the study period, significantly exceeding the National Ambient Air Quality Standard (35 µg m^?3 in annual average). The particulate heavy metal pollution was very serious in which Cd and As concentrations in PM_2.5 significantly surpassed the WHO standard. The enrichment factor values of heavy metals were typically higher than 10, suggesting that they were mainly influenced by anthropogenic sources. More specifically, the Cr, Mn and Ni were slightly enriched, Cu was highly enriched, while As, Cd, Pb and Zn were severely enriched. The results of correlation analysis showed that Cd may come from metallurgy and mechanical manufacturing emissions, and the other metals were predominately influenced by traffic emissions and coal combustion. The results of health risk assessment indicated that As, Mn and Cd would pose a significant non-carcinogenic health risk to both children and adults, while Cr would cause carcinogenic risk. Other toxic heavy metals were within a safe level.