Russell Schumann

Properties of activated carbon controlling 2-Methylisoborneol adsorption

2-Methylisoborneol (MIB) is one of the most common taste and odour molecules found in water supplies. The use of activated carbons is known to be effective in removing MIB from water. In this work, it was found that the selection of an appropriate carbon for removing MIB from water depends on the carbon surface hydrophilicity, which can be determined via water adsorption analysis or elemental analysis. Provided the carbons used are microporous, the less hydrophilic carbons adsorb more MIB.

The influence of surface chemistry on activated carbon adsorption of 2-methylisoborneol from aqueous solution

Abstract An activated carbon with a relatively high oxygen content was heated at various temperatures in an argon atmosphere to produce a series of carbons with decreasing oxygen content. A second activated carbon with a relatively low oxygen content was treated with an ozone–oxygen mixture to produce a series of carbons with increasing oxygen content. In both cases, the pore size distribution and pore volume were unaffected by the treatment conditions. Adsorption isotherm and enthalpy of water displacement measurements were made for adsorption of 2-methylisoborneol (MIB) by these carbons in water. Both measurements show the importance of the oxygen content on the adsorption of MIB from aqueous solution. Increasing surface oxygen content at a constant pore volume leads to a decrease in both the amount adsorbed and the enthalpy of adsorption. To test the role of the solvent in this adsorption process, a relatively non-polar solvent, dichloromethane (DCM), was used to make adsorption measurements. Adsorption isotherms show that the amount of MIB adsorbed from DCM solution is independent of the oxygen content. These results indicate that the solvent plays an important role in the control of the adsorption from solution of a sparingly soluble solute.

Determination of geosmin and 2-methylisoborneol in water using solid-phase microextraction and gas chromatography-chemical ionisation/electron impact ionisation-ion-trap mass spectrometry

A method for the determination of geosmin and 2-methylisoborneol (MIB) in water by solid-phase microextraction (SPME) is presented. Various SPME fibre chemistries have been compared for their efficiency in extracting MIB from water. Extraction conditions including the extraction time and temperature have been optimised. A 30 ml water sample is extracted for 20 min at 60 degrees C using a divinylbenzene fibre, and the extract analysed by gas chromatography with ion-trap mass spectrometry detection. d5-Geosmin and d3-MIB are added as internal standards to compensate for any variability in the SPME process which is not carried out to equilibrium. Chemical ionisation, using acetonitrile as the reagent gas, was found to give superior sensitivity to electron impact ionisation (EI) for the detection of MIB. EI was used as the ionisation mode for detection of geosmin. The method shows good linearity over the concentration range 5-40 ng l-1 and gives detection limits of 1 ng l-1 for both geosmin and MIB. Recovery (93-110%) and precision (3-12%) over this concentration range, for both raw and treated drinking waters, are comparable to currently employed methods such as closed-loop stripping analysis (CLSA). The method offers the advantage of being simple to use, with much shorter analysis times in comparison to CLSA.

Field methods for sampling and storing nectar from flowers with low nectar volumes

BACKGROUND AND AIMS Although several methods of sampling and storing floral nectar are available, little information exists on sampling and storing nectar from flowers with low nectar volumes. Methods for sampling and storing nectar from the flowers of species with low floral nectar volumes (<1 microL) were investigated using the flowers of Eucalyptus species. METHODS Sampling with microcapillary tubes, blotting up with filter paper, washing and rinsing were compared to determine masses of sugars recovered and differences in sugar ratios. Storage methods included room temperature, refrigeration and freezing treatments; the addition of antimicrobial agents benzyl alcohol or methanol to some of these treatments was also evaluated. Nectar samples were analysed using high-performance liquid chromatography and the masses of sucrose, glucose and fructose in each sample were determined. KEY RESULTS Masses of sugars varied significantly among sampling treatments, but the highest yielding methods, rinsing and washing, were not significantly different. A washing time of 1 min was as effective as one of 20 min. Storage trials showed that the sugar concentration measurements of nectar solutions changed rapidly, with the best results achieved for refrigeration with no additive (sucrose and fructose were stable for at least 2 weeks). Sugar ratios, however, remained relatively stable in most treatments and did not change significantly across 4 weeks for the methanol plus refrigerator and freezing treatments, and 2 weeks for the refrigeration treatment with no additive. CONCLUSIONS Washing is recommended for nectar collection from flowers with low nectar volumes in the field (with the understanding that one wash underestimates the amounts of sugars present in a flower), as is immediate analysis of sugar mass. In view of the great variation in results depending on nectar collection and storage methods, caution should be exercised in their choice, and their accuracy should be evaluated. The use of pulsed amperometric detection, more specific than refractive index detection, may improve the accuracy of nectar sugar analysis.

Floral nectar sugar composition and flowering phenology of the food plants used by the western pygmy possum, Cercartetus concinnus, at Innes National Park, South Australia.

The western pygmy possum (Cercartetus concinnus) is a small nocturnal marsupial that relies primarily on the nectar and pollen of myrtaceous species at Innes National Park and may occasionally also ingest invertebrates. This study confirmed plant utilization by C. concinnus using scat samples and pollen swabs, and investigated the flowering phenology of dietary plants to determine resource availability. We compared nectar composition between day and night and analyzed nectar sugar production for dietary species. Pollen swabs and scats suggested that C. concinnus relied primarily on the nectar and pollen of Kingscote mallee, Eucalyptus rugosa (76.8% of grains counted in combined scat samples) at Innes National Park, when available; only one of 30 scat samples contained numerous moth scales. The nectars of the species investigated showed marked differences in their composition, but only Melaleuca gibbosa and M. halmaturorum sugar composition changed between day and night. The nectar sugar ratio of E. rugosa differed from those of most other species investigated. C. concinnus may select this plant’s flowers because its nectar is relatively high in hexose sugars. Although E. diversifolia was abundant, its flowers were mostly ignored by possums, perhaps because the nectar in these flowers was proportionately much richer in sucrose than other species’. E. rugosa’s flowering index (calculated from flower load and canopy size) was greatest in December. Six of the seven eucalypt species flowered between November and April; for half of the year pygmy possums must find other resources.

Dehydration products of 2-methylisoborneol

Abstract 2-Methylenebornane and 2-methyl-2-bornene have previously been identified as dehydration or degradation products of 2-methylisoborneol (MIB), a compound responsible for taste and odour problems in various water environments. Previously, the identification of these products has been based on mass spectral analysis only. The dehydration of MIB under a variety of conditions was reinvestigated and the products fully characterised by 1 H and 13 C n.m.r. and GC-MS. Comparison of EI mass spectra of the dehydration products of MIB with those published previously indicate that earlier assignments of MIB dehydration products are incorrect.

Acid-base accounting assessment of mine wastes using the chromium reducible sulfur method.

The acid base account (ABA), commonly used in assessment of mine waste materials, relies in part on calculation of potential acidity from total sulfur measurements. However, potential acidity is overestimated where organic sulfur, sulfate sulfur and some sulfide compounds make up a substantial portion of the sulfur content. The chromium reducible sulfur (CRS) method has been widely applied to assess reduced inorganic sulfur forms in sediments and acid sulfate soils, but not in ABA assessment of mine wastes. This paper reports the application of the CRS method to measuring forms of sulfur commonly found in mine waste materials. A number of individual sulfur containing minerals and real waste materials were analyzed using both CRS and total S and the potential acidity estimates were compared with actual acidity measured from net acid generation tests and column leach tests. The results of the CRS analysis made on individual minerals demonstrate good assessment of sulfur from a range of sulfides. No sulfur was measured using the CRS method in a number of sulfate salts, including jarosite and melanterite typically found in weathered waste rocks, or from dibenzothiophene characteristic of organic sulfur compounds common to coal wastes. Comparison of ABA values for a number of coal waste samples demonstrated much better agreement of acidity predicted from CRS analysis than total S analysis with actual acidity. It also resulted in reclassification of most samples tested from PAF to NAF. Similar comparisons on base metal sulfide wastes generally resulted in overestimation of the acid potential by total S and underestimation of the acid potential by CRS in comparison to acidity measured during NAG tests, but did not generally result in reclassification. In all the cases examined, the best estimate of potential acidity included acidity calculated from both CRS and jarositic S.

Nectar collected with microcapillary tubes is less concentrated than total nectar in flowers with small nectar volumes

Previous research indicated that microcapillary tubes greatly underestimated sugar present in flowers with low nectar volumes, but it was unclear whether tubes missed liquid nectar or whether sugar concentration in nectar they collected did not represent total sugar concentration in a flower. We determined the suitability of microcapillary tubes to estimate the energetic value of Acrotriche patula R.Br. (Ericaceae) nectar from total sugar mass. We collected a standing crop of nectar from individual flowers with microcapillary tubes and subsequently washed the flowers to recover putatively any residual sucrose, glucose, and fructose. We assessed microcapillary nectar volume as a predictor for total sugar mass in a flower by regression analysis, identified the percentage of sugar missed by microcapillary tubes, and compared sugar ratios between microcapillary samples and total nectar. Nectar volume collected with microcapillary tubes cannot be used to predict total nectar sugar contents in a flower. Microcapillary tubes missed 71% of the floral sugar on average, but not a large volume, indicating that sugar is not evenly distributed in a flower’s nectar. Proportions of different sugars did not differ significantly between microcapillary samples and total samples. Animals with different tongue morphologies and feeding behaviours may obtain different energetic rewards from the same flower with low nectar volume. Variation in a flower’s nectar at one point in time is likely to favour the generalisation of pollination systems.

The Formation of Silicate-Stabilized Passivating Layers on Pyrite for Reduced Acid Rock Drainage

Acid and metalliferous release occurring when sulfide (principally pyrite)-containing rock from mining activities and from natural environments is exposed to the elements is acknowledged as a major environmental problem. Acid rock drainage (ARD) management is both challenging and costly for operating and legacy mine sites. Current technological solutions are expensive and focused on treating ARD on release rather than preventing it at source. We describe here a viable, practical mechanism for reduced ARD through the formation of silicate-stabilized iron oxyhydroxide surface layers. Without silicate, oxidized pyrite particles form an overlayer of crystalline goethite or lepidocrocite with porous structure. With silicate addition, a smooth, continuous, coherent and apparently amorphous iron oxyhydroxide surface layer is observed, with consequent pyrite dissolution rates reduced by more than 90% at neutral pH. Silicate is structurally incorporated within this layer and inhibits the phase transformation from amorphous iron (oxy)hydroxide to goethite, resulting in pyrite surface passivation. This is confirmed by computational simulation, suggesting that silicate-doping of a pseudoamorphous iron oxyhydroxide (ferrihydrite structure) is thermodynamically more stable than the equivalent undoped structure. This mechanism and its controlling factors are described. As a consequence of the greatly reduced acid generation rate, neutralization from on-site available reactive silicate minerals may be used to maintain neutral pH, after initial limestone addition to achieve neutral pH, thus maintaining the integrity of these layers for effective ARD management.

Method for distinctive estimation of stored acidity forms in acid mine wastes.

Jarosites and schwertmannite can be formed in the unsaturated oxidation zone of sulfide-containing mine waste rock and tailings together with ferrihydrite and goethite. They are also widely found in process wastes from electrometallurgical smelting and metal bioleaching and within drained coastal lowland soils (acid-sulfate soils). These secondary minerals can temporarily store acidity and metals or remove and immobilize contaminants through adsorption, coprecipitation, or structural incorporation, but release both acidity and toxic metals at pH above about 4. Therefore, they have significant relevance to environmental mineralogy through their role in controlling pollutant concentrations and dynamics in contaminated aqueous environments. Most importantly, they have widely different acid release rates at different pHs and strongly affect drainage water acidity dynamics. A procedure for estimation of the amounts of these different forms of nonsulfide stored acidity in mining wastes is required in order to predict acid release rates at any pH. A four-step extraction procedure to quantify jarosite and schwertmannite separately with various soluble sulfate salts has been developed and validated. Corrections to acid potentials and estimation of acid release rates can be reliably based on this method.