Performance characterisation of a stormwater treatment bioretention basin

Treatment performance of bioretention basins closely depends on hydrologic and hydraulic factors such as rainfall characteristics and inflow and outflow discharges. An in-depth understanding of the influence of these factors on water quality treatment performance can provide important guidance for effective bioretention basin design. In this paper, hydraulic and hydrologic factors impacting pollutant removal by a bioretention basin were assessed under field conditions. Outcomes of the study confirmed that the antecedent dry period plays an important role in influencing treatment performance. A relatively long antecedent dry period reduces nitrite and ammonium concentrations while increasing the nitrate concentration, which confirms that nitrification occurs within the bioretention basin. Additionally, pollutant leaching influences bioretention basin treatment performance, reducing the nutrients removal efficiency, which was lower for high rainfall events. These outcomes will contribute to a greater understanding of the treatment performance of bioretention basins, assisting in the design, operation and maintenance of these systems.

Mesoporous silica spheres from colloids

A novel method has been developed to synthesize mesoporous silica spheres using commercial silica colloids (SNOWTEX) as precursors and electrolytes (ammonium nitrate and sodium chloride) as destabilizers. Crosslinked polyacrylamide hydrogel was used as a temporary barrier to obtain dispersible spherical mesoporous silica particles. The influences of synthesis conditions including solution composition and calcination temperature on the formation of the mesoporous silica particles were systematically investigated. The structure and morphology of the mesoporous silica particles were characterized via scanning electron microscopy (SEM) and N2 sorption technique. Mesoporous silica particles with particle diameters ranging from 0.5 to 1.6 μm were produced whilst the BET surface area was in the range of 31-123 m2 g-1. Their pore size could be adjusted from 14.1 to 28.8 nm by increasing the starting particle diameter from 20-30 nm up to 70-100 nm. A simple and cost effective method is reported that should open up new opportunities for the synthesis of scalable host materials with controllable structures.

Investigation into chemistry of new particle formation and growth in subtropical urban environment

The role of different chemical compounds, particularly organics, involved in the new particle formation (NPF) and its consequent growth are not fully understood. Therefore, this study was conducted to investigate the chemistry of aerosol particles during NPF events in an urban subtropical environment. Aerosol chemical composition was measured along with particle number size distribution (PNSD) and several other air quality parameters at five sites across an urban subtropical environment. An Aerodyne compact Time-of-Flight Aerosol Mass Spectrometer (c-TOF-AMS) and a TSI Scanning Mobility Particle Sizer (SMPS) measured aerosol chemical composition and PNSD, respectively. Five NPF events, with growth rates in the range 3.3-4.6 nm, were detected at two sites. The NPF events happened on relatively warmer days with lower humidity and higher solar radiation. Temporal percent fractions of nitrate, sulphate, ammonium and organics were modelled using the Generalised Additive Model (GAM), with a basis of penalised spline. Percent fractions of organics increased after the NPF events, while the mass fraction of ammonium and sulphate decreased. This uncovered the important role of organics in the growth of newly formed particles. Three organic markers, factors f43, f44 and f57, were calculated and the f44 vs f43 trends were compared between nucleation and non-nucleation days. f44 vs f43 followed a different pattern on nucleation days compared to non-nucleation days, whereby f43 decreased for vehicle emission generated particles, while both f44 and f43 decreased for NPF generated particles. It was found for the first time that vehicle generated and newly formed particles cluster in different locations on f44 vs f43 plot and this finding can be used as a tool for source apportionment of measured particles.

Synthesis of organoclays: A critical review and some unresolved issues

The synthesis of organoclays (OC) by intercalation of quaternary ammonium cation (QAC) into expanding clay minerals, notably montmorillonite (Mt), has attracted a great deal of attention during the past two decades. The OC have also found applications in the manufacture of clay polymer nanocomposites (CPN) and environmental remediation. Despite the wealth of information that exists on the formation and properties of OC, some problems remain to be resolved. The present contribution is an attempt at clarifying two outstanding issues, based on the literature and experimental data obtained by the authors over the past years. The first issue concerns the relationship between the cation exchange capacity (CEC) of the Mt and the basal spacing of the OC which, in turn, is dependent on the concentration and the nature of the added QAC. At a concentration less than 1 CEC, organo-Mt (OMt) formed using the QAC with a short alkyl chain length with nc < 16 (e.g., dodecyl trimethylammonium) gives basal spacings of 1.4–1.6 nm that are essentially independent of the CEC. However, for long-chain QAC with nc ≥ 16 (e.g., hexadecyl trimethylammonium), the basal spacing varies with the QAC concentration. For Mt with a CEC of 80–90 meq/100 g, the basal spacing of the OC increases gradually with the CEC and shows a sudden (stepwise) increase to 3.2–3.8 nm at a QAC concentration of 1.5 CEC and to 3.5–4.0 nm at a concentration of 2.0 CEC. The second issue pertains to the “locking” effect in QAC- and silane-modified pillared interlayered clays (PILC) and Mt. For silylated Mt, the “locking” effect results from the covalent bonding of silane to two adjacent layers within a single clay mineral particle. The same mechanism can operate in silane-grafted PILC but in this case, the “locking” effect may primarily be ascribed to the pillaring of adjacent basal surfaces by metal hydr(oxides).

Anodized nanoporous WO3 Schottky contact structure for hydrogen and ethanol sensing

This paper reports the development of nanoporous tungsten trioxide (WO3) Schottky diode-based gas sensors. Nanoporous WO3 films were prepared by anodic oxidation of tungsten foil in ethylene glycol mixed with ammonium fluoride and a small amount of water. Anodization resulted in highly ordered WO3 films with a large surface-to-volume ratio. Utilizing these nanoporous structures, Schottky diode-based gas sensors were developed by depositing a platinum (Pt) catalytic contact and tested towards hydrogen gas and ethanol vapour. Analysis of the current–voltage characteristics and dynamic responses of the sensors indicated that these devices exhibited a larger voltage shift in the presence of hydrogen gas compared to ethanol vapour at an optimum operating temperature of 200 °C. The gas sensing mechanism was discussed, associating the response to the intercalating H+ species that are generated as a result of hydrogen and ethanol molecule breakdowns onto the Pt/WO3 contact and their spill over into nanoporous WO3.

Effect of nitrification inhibitors (DMPP and 3MP+ TZ) on soil nitrous oxide emissions from a sub-tropical vegetable production system in Queensland, Australia

The use of nitrification inhibitors, in combination with ammonium based fertilisers, has been promoted recently as an effective method to reduce nitrous oxide (N2O) emissions from fertilised agricultural fields, whilst increasing yield and nitrogen use efficiency. Vegetable cropping systems are often characterised by high inputs of nitrogen fertiliser and consequently elevated emissions of nitrous oxide (N2O) can be expected. However, to date only limited data is available on the use of nitrification inhibitors in sub-tropical vegetable systems. A field experiment investigated the effect of the nitrification inhibitors (DMPP & 3MP+TZ) on N2O emissions and yield from a typical vegetable production system in sub-tropical Australia. Soil N2O fluxes were monitored continuously over an entire year with a fully automated system. Measurements were taken from three subplots for each treatment within a randomized complete blocks design. There was a significant inhibition effect of DMPP and 3MP+TZ on N2O emissions and soil mineral N content directly following the application of the fertiliser over the vegetable cropping phase. However this mitigation was offset by elevated N2O emissions from the inhibitor treatments over the post-harvest fallow period. Cumulative annual N2O emissions amounted to 1.22 kg-N/ha, 1.16 kg-N/ha, 1.50 kg-N/ha and 0.86 kg-N/ha in the conventional fertiliser (CONV), the DMPP treatment, the 3MP+TZ treatment and the zero fertiliser (0N) respectively. Corresponding fertiliser induced emission factors (EFs) were low with only 0.09 - 0.20% of the total applied fertiliser lost as N2O. There was no significant effect of the nitrification inhibitors on yield compared to the CONV treatment for the three vegetable crops (green beans, broccoli, lettuce) grown over the experimental period. This study highlights that N2O emissions from such vegetable cropping system are primarily controlled by post-harvest emissions following the incorporation of vegetable crop residues into the soil. It also shows that the use of nitrification inhibitors can lead to elevated N2O emissions by storing N in the soil profile that is available to soil microbes during the decomposition of the vegetable residues over the post-harvest phase. Hence the use of nitrification inhibitors in vegetable systems has to be treated carefully and fertiliser rates need to be adjusted to avoid excess soil nitrogen during the postharvest phase.

Purification of the major group 1 allergen from bahia grass pollen, Pas n 1

Background Group 1 grass pollen allergens are glycoproteins of the β-expansin family. They are a predominant component of pollen and are potent allergens with a high frequency of serum IgE reactivity in grass pollen-allergic patients. Bahia grass is distinct from temperate grasses and has a prolonged pollination period and wide distribution in warmer climates. Here we describe the purification of the group 1 pollen allergen, Pas n 1, from Bahia grass (Paspalum notatum), an important subtropical aeroallergen source. Methods Pas n 1 was purified from an aqueous Bahia grass pollen extract by ammonium sulphate precipitation, hydrophobic interaction and size exclusion chromatography, and assessed by one- and two-dimensional gel electrophoresis, immunoblotting and ELISA. Results Pas n 1 was purified to a single 29-kDa protein band containing two dominant isoforms detected by an allergen-specific monoclonal antibody and serum IgE of a Bahia grass pollen-allergic donor. The frequency of serum IgE reactivity with purified Pas n 1 in 51 Bahia grass pollen-allergic patients was 90.6%. Serum IgE reactivity with purified Pas n 1 was highly correlated with serum IgE reactivity with Bahia grass pollen extract and recombinant Pas n 1 (r = 0.821 and 0.913, respectively). Conclusions Pas n 1 is a major allergen reactive at high frequency with serum IgE of Bahia grass pollen-allergic patients. Purified natural Pas n 1 has utility for improved specific diagnosis and immunotherapy for Bahia grass pollen allergy.

The dominant 55kDa allergen of the subtropical Bahia grass (Paspalum notatum) pollen is a group 13 pollen allergen, Pas n 13

Bahia grass, Paspalum notatum, is an important pollen allergen source with a long season of pollination and wide distribution in subtropical and temperate regions. We aimed to characterize the 55. kDa allergen of Bahia grass pollen (BaGP) and ascertain its clinical importance. BaGP extract was separated by 2D-PAGE and immunoblotted with serum IgE of a grass pollen-allergic patient. The amino-terminal protein sequence of the predominant allergen isoform at 55. kDa had similarity with the group 13 allergens of Timothy grass and maize pollen, Phl p 13 and Zea m 13. Four sequences obtained by rapid amplification of the allergen cDNA ends represented multiple isoforms of Pas n 13. The predicted full length cDNA for Pas n 13 encoded a 423 amino acid glycoprotein including a signal peptide of 28 residues and with a predicted pI of 7.0. Tandem mass spectrometry of tryptic peptides of 2D gel spots identified peptides specific to the deduced amino acid sequence for each of the four Pas n 13 cDNA, representing 47% of the predicted mature protein sequence of Pas n 13. There was 80.6% and 72.6% amino acid identity with Zea m 13 and Phl p 13, respectively. Reactivity with a Phl p 13-specific monoclonal antibody AF6 supported designation of this allergen as Pas n 13. The allergen was purified from BaGP extract by ammonium sulphate precipitation, hydrophobic interaction and size exclusion chromatography. Purified Pas n 13 reacted with serum IgE of 34 of 71 (48%) grass pollen-allergic patients and specifically inhibited IgE reactivity with the 55. kDa band of BaGP for two grass pollen-allergic donors. Four isoforms of Pas n 13 from pI 6.3-7.8 had IgE-reactivity with grass pollen allergic sera. The allergenic activity of purified Pas n 13 was demonstrated by activation of basophils from whole blood of three grass pollen-allergic donors tested but not control donors. Pas n 13 is thus a clinically relevant pollen allergen of the subtropical Bahia grass likely to be important in eliciting seasonal allergic rhinitis and asthma in grass pollen-allergic patients.

Isostructural co-crystals derived from molecules with different supramolecular topologies

In this article, we report the crystal structures of five halogen bonded co-crystals comprising quaternary ammonium cations, halide anions (Cl– and Br–), and one of either 1,2-, 1,3-, or 1,4-diiodotetrafluorobenzene (DITFB). Three of the co-crystals are chemical isomers: 1,4-DITFB[TEA-CH2Cl]Cl, 1,2-DITFB[TEA-CH2Cl]Cl, and 1,3-DITFB[TEA-CH2Cl]Cl (where TEA-CH2Cl is chloromethyltriethylammonium ion). In each structure, the chloride anions link DITFB molecules through halogen bonds to produce 1D chains propagating with (a) linear topology in the structure containing 1,4-DITFB, (b) zigzag topology with 60° angle of propagation in that containing 1,2-DITFB, and (c) 120° angle of propagation with 1,3-DITFB. While the individual chains have highly distinctive and different topologies, they combine through π-stacking of the DITFB molecules to produce remarkably similar overall arrangements of molecules. Structures of 1,4-DITFB[TEA-CH2Br]Br and 1,3-DITFB[TEA-CH2Br]Br are also reported and are isomorphous with their chloro/chloride analogues, further illustrating the robustness of the overall supramolecular architecture. The usual approach to crystal engineering is to make structural changes to molecular components to effect specific changes to the resulting crystal structure. The results reported herein encourage pursuit of a somewhat different approach to crystal engineering. That is, to investigate the possibilities for engineering the same overall arrangement of molecules in crystals while employing molecular components that aggregate with entirely different supramolecular connectivity.

Insights into the growth of newly formed particles in a subtropical urban environment

The role of different chemical compounds, particularly organics, involved in the new particle formation (NPF) and its consequent growth are not fully understood. Therefore, this study was conducted to investigate the chemical composition of aerosol particles during NPF events in an urban subtropical environment. Aerosol chemical composition was measured along with particle number size distribution (PNSD) and several other air quality parameters at five sites across an urban subtropical environment. An Aerodyne compact Time-of-Flight Aerosol Mass Spectrometer (c-TOF-AMS) and a TSI Scanning Mobility Particle Sizer (SMPS) measured aerosol chemical composition (particles above 50 nm in vacuum aerodynamic diameter) and PNSD (particles within 9-414 nm in mobility diameter), respectively. Five NPF events, with growth rates in the range 3.3-4.6 nm, were detected at two of the sites. The NPF events happened on relatively warmer days with lower condensation sink (CS). Temporal percent fractions of organics increased after the particles grew enough to have a significant contribution to particles volume, while the mass fraction of ammonium and sulphate decreased. This uncovered the important role of organics in the growth of newly formed particles. Three organic markers, factors f43, f44 and f57, were calculated and the f44 vs f43 trends were compared between nucleation and non-nucleation days. K-means cluster analysis was performed on f44 vs f43 data and it was found that they follow different patterns on nucleation days compared to non-nucleation days, whereby f43 decreased for vehicle emission generated particles, while both f44 and f43 decreased for NPF generated particles. It was found for the first time that vehicle generated and newly formed particles cluster in different locations on f44 vs f43 plot and this finding can be potentially used as a tool for source apportionment of measured particles.

Dynamics of nitrate-nitrogen removal in experimental stormwater biofilters under intermittent wetting and drying

High concentrations of nitrate-nitrogen degrade the quality of aquatic environments. The primary mechanism by which nitrate-nitrogen is removed (denitrification) requires anoxic conditions and electron donors. While removal of total and ammonium-nitrogen is often high in stormwater biofilters, poor removal or even the release of nitrate-nitrogen in the outflow has often been observed. Five Perspex biofilter columns (94 mm internal diameter) were fabricated with a filter layer that contained 8% organic material. Columns were operated at 875  mm/h 875  mm/h and fed with simulated stormwater with different antecedent dry days (ADDs) and concentrations of nitrate-nitrogen. Samples were collected from the outflow at different time intervals between 2 and 150 min and were tested for nitrate-nitrogen. The removal of nitrate-nitrogen varied during an event from a high removal percentage (60–90%) in the initial outflow that gradually decreased in the first 30 min and settled at 0–15% removal thereafter. This remained consistent during all simulated events independent of the number of ADDs or inflow concentrations. ADDs and previous event feed concentrations affected the outflow nitrate-nitrogen concentration in the first 30 min of the current event. Therefore, from this study it is concluded that denitrification within stormwater biofilters occurs mainly during drying periods rather than wetting periods.

The ambient aerosol characterization during the prescribed bushfire season in Brisbane 2013

Prescribed burnings are conducted in Queensland each year from August until November aiming to decrease the impact of bushfire hazards and maintain the health of vegetation. This study reports chemical characteristics of the ambient aerosol, with a focus on source apportionment of the organic aerosol (OA)fraction, during the prescribed biomass burning (BB) season in Brisbane 2013. All measurements were conducted within the International Laboratory for Air Quality and Health (ILAQH) located in Brisbane’s Central Business District. Chemical composition, degree of ageing and the influence of BB emission on the air quality of central Brisbane were characterized using a compact Time of Flight Aerosol Mass Spectrometer (cToF-AMS). AMS loadings were dominated by OA (64 %), followed by, sulfate (17 %), ammonium (14 %) and nitrates (5 %). Source apportionment was applied on the AMS OA mass spectra via the multilinear engine solver (ME-2) implementation within the recently developed Source Finder (SoFi) interface. Six factors were extracted including hydrocarbon-like OA (HOA), cooking-related OA (COA), biomass burning OA (BBOA), low-volatility oxygenated OA (LV-OOA), semivolatile oxygenated OA (SV-OOA), and nitrogen-enriched OA (NOA). The aerosol fraction that was attributed to BB factor was 9 %, on average over the sampling period. The high proportion of oxygenated OA (72 %), typically representing aged emissions, could possess a fraction of oxygenated species transformed from BB components on their way to the sampling site.