Measurement of the first neutron diffraction peak of D2O flowing in a 2 mm diameter aluminium tube as a function of temperature

A pilot experiment was performed using the WOMBAT powder diffraction instrument at ANSTO in which the first neutron diffraction peak (Q0) was measured for D2O flowing in a 2 mm internal diameter aluminium tube. Measurements of Q0 were made at -9, 4.3, 6.9, 12, 18.2 and 21.5 °C. The D2O was circulated using a siphon with water in the lower reservoir returned to the upper reservoir using a small pump. This enabled stable flow to be maintained for several hours. For example, if the pump flow increased slightly, the upper reservoir level rose, increasing the siphon flow until it matched the return flow. A neutron wavelength of 2.4 Å was used and data integrated over 60 minutes for each temperature. A jet of nitrogen from a liquid N2 Dewar was directed over the aluminium tube to vary water temperature. After collection of the data, the d spacing of the aluminium peaks was used to calculate the temperature of the aluminium within the neutron beam and therefore was considered to be an accurate measure of water temperature within the beam. Sigmaplot version 12.3 was used to fit a Weibull five parameter peak fit to the first neutron diffraction peak. The values of Q0 obtained in this experiment showed an increase with temperature consistent with data in the literature [1] but were consistently higher than published values for bulk D20. For example at 21.5 °C we obtained a value of 2.008 Å-1 for Q0 compared to a literature value of 1.988 Å-1 for bulk D2O at 20 °C, a difference of 1%. Further experiments are required to see if this difference is real or artifactual.

Nanohybrids of silver particles on clay platelets delaminate Pseudomonas biofilms

Aim To evaluate the effectiveness of novel nanohybrids, composed of silver nanoparticles and nanoscale silicate platelets, to clear Pseudomonas aeruginosa biofilms. Materials & methods The nanohybrids were manufactured from an in situ reduction of silver salts in the silicate platelet dispersion, and then applied to biofilms in vitro and in vivo. Results In reference to the biocidal effects of gentamycin, the nanohybrids mitigated the spreading of the biofilms, and initiated robust cell death and exfoliation from the superficial layers of the biofilms in vitro. In vivo, the nanohybrids exhibited significant therapeutic effects by eliminating established biofilms from infected corneas and promoting the recovery of corneal integrity. Conclusion All of the evaluations indicate the high potency of the newly developed silver nanoparticle/nanoscale silicate platelet nanohybrids for eliminating biofilms.

Mechanochemical synthesis of aluminium nanoparticles and their deuterium sorption properties to 2 kbar

A mechanochemical synthesis process has been used to synthesise aluminium nanoparticles. The aluminium is synthesised via a solid state chemical reaction which is initiated inside a ball mill at room temperature between either lithium (Li) or sodium (Na) metal which act as reducing agents with unreduced aluminium chloride (AlCl3). The reaction product formed consists of aluminium nanoparticles embedded within a by-product salt phase (LiCl or NaCl, respectively). The LiCl is washed with a suitable solvent resulting in aluminium (Al) nanoparticles which are not oxidised and are separated from the byproduct phase. Synthesis and washing was confirmed using X-ray diffraction (XRD). Nanoparticles were found to be ∼25–100nm from transmission electron microscopy (TEM) and an average size of 55nm was determined fromsmall angle X-ray scattering (SAXS) measurements. As synthesised Al/NaCl composites, washed Al nanoparticles, and purchased Al nanoparticles were deuterium (D2) absorption tested up to 2 kbar at a variety of temperatures, with no absorption detected within system resolution.

Handmade clay balls and recycled crush glass as alternative media in water filtration

For many years materials such as quarried sand, anthracite, and granular activated carbon have been the principal media-products traditionally used in water and wastewater filtration plants. Pebble Matrix Filtration (PMF) is a novel non-chemical, sustainable pre-treatment method of protecting Slow Sand Filters (SSF) from high turbidity during heavy monsoon periods. PMF uses sand and pebbles as the filter media and the sustainability of this new technology might depend on availability and supply of pebbles and sand, both finite resources. In many countries there are two principal methods of obtaining pebbles and sand, namely dredging from rivers and beaches, and due to the scarcity of these resources in some countries the cost of pebbles is often 4-5 times higher than that of sand. In search for an alternative medium to pebbles after some preliminary laboratory tests conducted in Colombo-Sri Lanka, Poznan-Poland and Cambridge-UK, a 100-year-old brick factory near Sudbury, Suffolk, has produced hand-made clay pebbles satisfying the PMF quality requirements. As an alternative to sand, crushed recycled glass from a UK supplier was used and the PMF system was operated together with hand-made clay balls in the laboratory for high turbidity removal effectively. The results of laboratory experiments with alternative media are presented in this paper. There are potential opportunities for recycled crushed glass and clay ball manufacturing processes in some countries where they can be used as filter media.

Preparation, characterization of surfactants modified clay minerals and nitrate adsorption

Organic surfactants modified clay minerals are usually used as adsorbents for hydrophobic organic contaminants remediation; this work however has shown organoclays can also work as adsorbents for hydrophilic anionic contaminant immobilization. Organoclays were prepared based on halloysite, kaolinite and bentonite and used for nitrate adsorption, which are significant for providing mechanism for the adsorption of anionic contaminants from waste water. XRD was used to characterize unmodified and surfactants modified clay minerals. Thermogravimetric analysis (TG) was used to determine the thermal stability and actual loading of surfactant molecules. Ion chromatography (IC) was used to determine changes of nitrate concentration before and after adsorption by these organoclays. These organoclays showed different removal capacities for anionic ions from water and adsorption mechanism was investigated.

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).

Transition metal layered double hydroxides for energy storage

Various types of layered double hydroxides, a type of clay, were synthesised. They were then electrochemically tested to determine whether the samples would be suitable to store energy as supercapacitors. A manganese aluminium layered double hydroxide was electrochemically tested for the first time and found to have a large capacitance.

Strength properties of composite clay balls containing additives from industry wastes as new filter media in water treatment

Pebble matrix filtration (PMF) is a water treatment technology that can remove suspended solids in highly turbid surface water during heavy storms. PMF typically uses sand and natural pebbles as filter media. Hand-made clay pebbles (balls) can be used as alternatives to natural pebbles in PMF treatment plants, where natural pebbles are not readily available. Since the high turbidity is a seasonal problem that occurs during heavy rains, the use of newly developed composite clay balls instead of pure clay balls have the advantage of removing other pollutants such as natural organic matter (NOM) during other times. Only the strength properties of composite clay balls are described here as the pollutant removal is beyond the scope of this paper. These new composite clay balls must be able to withstand dead and live loads under dry and saturated conditions in a filter assembly. Absence of a standard ball preparation process and expected strength properties of composite clay balls were the main reasons behind the present study. Five different raw materials from industry wastes: Red Mud (RM), Water Treatment Alum Sludge (S), Shredded Paper (SP), Saw Dust (SD), and Sugar Mulch (SM) were added to common clay brick mix (BM) in different proportions. In an effort to minimize costs, in this study clay balls were fired to 1100 0C at a local brick factory together with their bricks. A comprehensive experimental program was performed to evaluate crushing strength of composite hand-made clay balls, using uniaxial compression test to establish the best material combination on the basis of strength properties for designing sustainable filter media for water treatment plants. Performance at both construction and operating stages were considered by analyzing both strength properties under fully dry conditions and strength degradation after saturation in a water bath. The BM-75% as the main component produced optimum combination in terms of workability and strength. With the material combination of BM-75% and additives-25%, the use of Red Mud and water treatment sludge as additives produced the highest and lowest strength of composite clay balls, with a failure load of 5.4 kN and 1.4 kN respectively. However, this lower value of 1.4 kN is much higher than the effective load on each clay ball of 0.04 kN in a typical filter assembly (safety factor of 35), therefore, can still be used as a suitable filter material for enhanced pollutant removal.

Are there generalizable trends in the release of airborne synthetic clay nanoparticles from a jet milling process?

Despite recent efforts to assess the release of nanoparticles to the workplace during different nanotechnology activities, the existence of a generalizable trend in the particle release has yet to be identified. This study aimed to characterize the release of synthetic clay nanoparticles from a laboratory-based jet milling process by quantifying the variations arising from primary particle size and surface treatment of the material used, as well as the feed rate of the machine. A broad range of materials were used in this study, and the emitted particles mass (PM2.5) and number concentrations (PNC) were measured at the release source. Analysis of variance, followed by linear mixed-effects modeling, was applied to quantify the variations in PM2.5 and PNC of the released particles caused by the abovementioned factors. The results confirmed that using materials of different primary size and surface treatment affects the release of the particles from the same process by causing statistically-significant variations in PM2.5 and PNC. The interaction of these two factors should also be taken into account as it resulted in variations in the measured particles release properties. Furthermore, the feed rate of the milling machine was confirmed to be another influencing parameter. Although this research does not identify a specific pattern in the release of synthetic clay nanoparticles from the jet milling process generalizable to other similar settings, it emphasizes that each tested case should be handled individually in terms of exposure considerations.

Field performance of in-service cast iron water reticulation pipe buried in reactive clay

Field monitoring is an important means for understanding soil behaviour and its interaction with buried structures such as pipeline. This paper details the successful instrumentation of a section of an in-service cast iron water main buried in an area of reactive clay where frequent water pipe breakage has been observed. The instrumentation included measurement of pipe strain; pipe water pressure and temperature; soil pressure, temperature, moisture content and matric suction, as well as the meteorological conditions on site. The data generally indicated that changes in soil temperature, suction and moisture content were directly related to the local climatic variations. The suction and moisture content data indicated that the soil profile at the site down to around 700 mm, and probably down to 1000 mm, is affected by changes in surface weather, while soil conditions below this depth appear to be more stable. Analysis of pipe strain indicated that the pipe behaves like a cantilever beam, with the top experiencing predominantly tensile strains during summer. Subsequently, these trends reduce to compressive strains as soil swelling occurs due to increase of moisture content with the onset of winter.

Are we getting accurate measurements of Ksat for sodic clay soils?

In this paper we discuss the use of a series of column experiments to improve understanding of the effect irrigation water chemistry (saline solutions) has on measurements of saturated hydraulic conductivity (Ksat) of a sodic clay soil. We highlight in particular the use of extended leaching periods to determine whether the duration of leaching affects the results. In the experiments, mixed cation solutions of two different salinity levels, 50 meq/L and 100 meq/L, were applied under constant head to columns of a repacked sodic clay soil using three replicates for each treatment. The maximum Ksat measured during leaching with the 100 meq/L solution was approximately double the maximum Ksat measured during leaching with the 50 meq/L solution. Measured flow rates were found to increase rapidly after flow commenced then decrease gradually until flow rates became stable. The final, stable flow rate was roughly 80% less than the maximum flow rate measured. Reasons for these changes in saturated hydraulic conductivity are discussed. The key finding from these experiments is that long term leaching, involving significantly more pore volumes than is commonly reported in the literature, is required to obtain a ‘stable’ Ksat. We recommend that further studies be carried out to (1) determine whether similar behaviour in Ksat occurs in a wide range of sodic clay soils and (2) to help build a better understanding of the causes and implications of the observed behaviour in Ksat.

Applying HYDRUS to flow in a sodic clay soil with solution composition–dependent hydraulic conductivity

Management of sodic soils under irrigation often requires application of chemical ameliorants to improve permeability combined with leaching of excess salts. Modeling irrigation, soil treatments, and leaching in these sodic soils requires a model that can adequately represent the physical and chemical changes in the soil associated with the amelioration process. While there are a number of models that simulate reactive solute transport, UNSATCHEM and HYDRUS-1D are currently the only models that also include an ability to simulate the impacts of soil chemistry on hydraulic conductivity. Previous researchers have successfully applied these models to simulate amelioration experiments on a sodic loam soil. To further gauge their applicability, we extended the previous work by comparing HYDRUS simulations of sodic soil amelioration with the results from recently published laboratory experiments on a more reactive, repacked sodic clay soil. The general trends observed in the laboratory experiments were able to be simulated using HYDRUS. Differences between measured and simulated results were attributed to the limited flexibility of the function that represents chemistry-dependent hydraulic conductivity in HYDRUS. While improvements in the function could be made, the present work indicates that HYDRUS-UNSATCHEM captures the key changes in soil hydraulic properties that occur during sodic clay soil amelioration and thus extends the findings of previous researchers studying sodic loams.

Hydraulic conductivity increases in a sodic clay soil in response to gypsum applications impacts of bulk density and cation exchange

Amelioration of sodic soils is commonly achieved by applying gypsum, which increases soil hydraulic conductivity by altering soil chemistry. The magnitude of hydraulic conductivity increases expected in response to gypsum applications depends on soil properties including clay content, clay mineralogy, and bulk density. The soil analyzed in this study was a kaolinite rich sodic clay soil from an irrigated area of the Lower Burdekin coastal floodplain in tropical North Queensland, Australia. The impact of gypsum amelioration was investigated by continuously leaching soil columns with a saturated gypsum solution, until the hydraulic conductivity and leachate chemistry stabilized. Extended leaching enabled the full impacts of electrolyte effects and cation exchange to be determined. For the columns packed to 1.4 g/cm3, exchangeable sodium concentrations were reduced from 5.0 ± 0.5 mEq/100 g to 0.41 ± 0.06 mEq/100 g, exchangeable magnesium concentrations were reduced from 13.9 ± 0.3 mEq/100 g to 4.3 ± 2.12 mEq/100 g, and hydraulic conductivity increased to 0.15 ± 0.04 cm/d. For the columns packed to 1.3 g/cm3, exchangeable sodium concentrations were reduced from 5.0 ± 0.5 mEq/100 g to 0.51 ± 0.03 mEq/100 g, exchangeable magnesium concentrations were reduced from 13.9 ± 0.3 mEq/100 g to 0.55 ± 0.36 mEq/100 g, and hydraulic conductivity increased to 0.96 ± 0.53 cm/d. The results of this study highlight that both sodium and magnesium need to be taken into account when determining the suitability of water quality for irrigation of sodic soils and that soil bulk density plays a major role in controlling the extent of reclamation that can be achieved using gypsum applications.

Environmental applications of inorganic-organic clays for recalcitrant organic pollutants removal: Bisphenol A

Bisphenol-A (BPA) adsorption onto inorganic-organic clays (IOCs) was investigated. For this purpose, IOCs synthesised using octadecyltrimethylammonium bromide (ODTMA, organic modifier) and hydroxy aluminium (Al13, inorganic modifier) were used. Three intercalation methods were employed with varying ODTMA concentration in the synthesis of IOCs. Molecular interactions of clay surfaces with ODTMA and Al13 and their arrangements within the interlayers were determined using Fourier transform infrared spectroscopy (FTIR). Surface area and porous structure of IOCs were determined by applying Brunauer, Emmett, and Teller (BET) method to N2 adsorption-desorption isotherms. Surface area decreased upon ODTMA intercalation while it increased with Al13 pillaring. As a result, BET specific surface area of IOCs was considerably higher than those of organoclays. Initial concentration of BPA, contact time and adsorbent dose significantly affected BPA adsorption into IOCs. Pseudo-second order kinetics model is the best fit for BPA adsorption into IOCs. Both Langmuir and Freundlich adsorption isotherms were applicable for BPA adsorption (R2 > 0.91) for IOCs. Langmuir maximum adsorption capacity for IOCs was as high as 109.89 mg g‒1 and it was closely related to the loaded ODTMA amount into the clay. Hydrophobic interactions between long alkyl chains of ODTMA and BPA are responsible for BPA adsorption into IOCs.

What are the driving factors influencing the size distribution of airborne synthetic clay particles emitted from a jet milling process?

In the field of workplace air quality, measuring and analyzing the size distribution of airborne particles to identify their sources and apportion their contribution has become widely accepted, however, the driving factors that influence this parameter, particularly for nanoparticles (< 100 nm), have not been thoroughly determined. Identification of driving factors, and in turn, general trends in size distribution of emitted particles would facilitate the prediction of nanoparticles’ emission behavior and significantly contribute to their exposure assessment. In this study, a comprehensive analysis of the particle number size distribution data, with a particular focus on the ultrafine size range of synthetic clay particles emitted from a jet milling machine was conducted using the multi-lognormal fitting method. The results showed relatively high contribution of nanoparticles to the emissions in many of the tested cases, and also, that both surface treatment and feed rate of the machine are significant factors influencing the size distribution of the emitted particles of this size. In particular, applying surface treatments and increasing the machine feed rate have the similar effect of reducing the size of the particles, however, no general trend was found in variations of size distribution across different surface treatments and feed rates. The findings of our study demonstrate that for this process and other activities, where no general trend is found in the size distribution of the emitted airborne particles due to dissimilar effects of the driving factors, each case must be treated separately in terms of workplace exposure assessment and regulations.