Emerging iron-based mesoporous materials for adsorptive removal of pollutants: Mechanism, optimization, challenges, and future perspective.

Iron-based materials (IBMs) have shown promise as adsorbents due to their unique physicochemical properties. This review provides an overview of the different types of IBMs, their synthesis methods, and their properties. Results found in the adsorption of emerging contaminants to a wide range of IBMs are discussed. The IBMs used were evaluated in terms of their maximum uptake capacity, with special consideration given to environmental conditions such as contact time, solution pH, initial pollutant concentration, etc. The adsorption mechanisms of pollutants are discussed taking into account the results of kinetic, isotherm, thermodynamic studies, surface complexation modelling (SCM), and available spectroscopic data. A current overview of molecular modeling and simulation studies related to density functional theory (DFT), surface response methodology (RSM), and artificial neural network (ANN) is presented. In addition, the reusability and suitability of IBMs in real wastewater treatment is shown. The review concludes with the strengths and weaknesses of current research and suggests ideas for future research that will improve our ability to remove contaminants from real wastewater streams.

Characterisation of bushfire residuals in source water and removal by coagulation.

A bushfire is a spontaneous vegetation fire that can fundamentally affect lives, property, the environment, and even the global climate. Ash from fire carries hazardous pollutants like metal oxides/hydroxides, minerals, black carbons, and by-products of partial combustion, such as hydrocarbons and colloidal charcoal. Bushfire gases and residues can heavily pollute surface and groundwater resources. This paper focuses on the impact of bushfire residue on water quality and explores methods to remediate impacted water supplies. Soils burned in controlled furnace conditions between 150 °C, and 600 °C were characterised, suspended in water, and changes in water quality was measured following leaching from the burned residues. Results indicate that once the soil is burned at temperatures above 300 °C, there is little evidence of leached organic matter. At temperatures below 300 °C, the water discolouration was evident after 24 h leaching, and much higher quantities of leached organic matter were measured. Higher burning temperatures resulted in more alkaline residues. Leachate and charred sample characterisation data shows that the charcoal is highly porous and mainly consists of- amorphous material. The ash is a heterogeneous concoction of smaller particles and comprises significant mineral content. The results also indicate that the primary pollutant among the brushfire residuals is ash which increases pH, alkalinity, turbidity, and UV254. Coagulation experiments reveal that dual coagulation systems with metal salts- organic polyelectrolyte reduced the turbidity by 84 %, and dissolved organic carbon (DOC) reduced by 68 % of water containing ash residues. However, some other treatments are needed to reduce the alkalinity.

Nitrous oxide emission in altered nitrogen cycle and implications for climate change.

Natural processes and human activities play a crucial role in changing the nitrogen cycle and increasing nitrous oxide (N2O) emissions, which are accelerating at an unprecedented rate. N2O has serious global warming potential (GWP), about 310 times higher than that of carbon dioxide. The food production, transportation, and energy required to sustain a world population of seven billion have required dramatic increases in the consumption of synthetic nitrogen (N) fertilizers and fossil fuels, leading to increased N2O in air and water. These changes have radically disturbed the nitrogen cycle and reactive nitrogen species, such as nitrous oxide (N2O), and have impacted the climatic system. Yet, systematic and comprehensive studies on various underlying processes and parameters in the altered nitrogen cycle, and their implications for the climatic system are still lacking. This paper reviews how the nitrogen cycle has been disturbed and altered by anthropogenic activities, with a central focus on potential pathways of N2O generation. The authors also estimate the N2O-N emission mainly due to anthropogenic activities will be around 8.316 Tg N2O-N yr-1 in 2050. In order to minimize and tackle the N2O emissions and its consequences on the global ecosystem and climate change, holistic mitigation strategies and diverse adaptations, policy reforms, and public awareness are suggested as vital considerations. This study concludes that rapidly increasing anthropogenic perturbations, the identification of new microbial communities, and their role in mediating biogeochemical processes now shape the modern nitrogen cycle.

Synthesis and biological evaluation of 4H-benzo[e][1,3]oxazin-4-ones analogues of TGX-221 as inhibitors of PI3Kß.

A novel series of TGX-221 analogues was prepared that include isosteric replacement of the 4H-pyrido[1,2-a]pyrimidin-4-one with a 4H-benzo[e][1,3]oxazin-4-one scaffold. The compounds that included an CH(CH3)NH type linker showed comparable activity to TGX-221 analogues with the isosterism supported by the comparative SAR analysis. The analogues containing an CH(CH3)O linker were less active but still showed useful SAR including a favoured o-methyl substitution.

Semi-Solid and Solid Dosage Forms for the Delivery of Phage Therapy to Epithelia.

The delivery of phages to epithelial surfaces for therapeutic outcomes is a realistic proposal, and indeed one which is being currently tested in clinical trials. This paper reviews some of the known research on formulation of phages into semi-solid dosage forms such as creams, ointments and pastes, as well as solid dosage forms such as troches (or lozenges and pastilles) and suppositories/pessaries, for delivery to the epithelia. The efficacy and stability of these phage formulations is discussed, with a focus on selection of optimal semi-solid bases for phage delivery. Issues such as the need for standardisation of techniques for formulation as well as for assessment of efficacy are highlighted. These are important when trying to compare results from a range of experiments and across different delivery bases.

The effect of inositol hexaphosphate on cadmium sorption to gibbsite.

HYPOTHESIS: Oxides, hydrous oxides and hydroxides of aluminium and iron are important in determining the availability of trace and heavy metals in soil systems. The presence of complexing anions is also known to affect the binding of these metals in soils. Since organophosphates, such as inositol hexaphosphate (IP6), are present in most soil systems they are expected to affect the nature of the interaction between metal ions and metal (hyr)oxides. EXPERIMENTS: Both adsorption edge and isotherm experiments were conducted on Cd(II)-gibbsite and Cd(II)-IP6-gibbsite systems. In addition, solid-state (31)P MAS NMR measurements were performed on the ternary system. All results were used to develop Extended Constant Capacitance surface complexation models of both the Cd(II)-gibbsite and IP6-Cd(II)-gibbsite sorption systems. FINDINGS: The presence of IP6 significantly increased sorption of Cd(II) to gibbsite below pH 8 especially at higher concentrations of Cd(II) and IP6. The (31)P MAS NMR spectra, together with surface complexation modeling, indicated the presence of two outer-sphere ternary complexes with the first, [(SOH2)3(3+)(LHCd)(9-)](6-), important at relatively low concentrations, while the second, [SLH3(8-)Cd(2+)](6-), dominated sorption at higher sorbate concentrations. Thus the presence of organophosphates in soil systems increases sorption and may therefore decrease the availability of trace and heavy metals to plants.

Synthesis, structure elucidation, DNA-PK and PI3K and anti-cancer activity of 8- and 6-aryl-substituted-1-3-benzoxazines.

The synthesis of 6-aryl, 8- aryl, and 8-aryl-6-chloro-2-morpholino-1,3-benzoxazines with potent activity against PI3K and DNA-PK is described. Synthesis of thirty one analogues was facilitated by an improved synthesis of 3-bromo-2-hydroxybenzoic acid 13 by de-sulphonation of 3-bromo-2-hydroxy-5-sulfobenzoic acid 12 en route to 2-methylthio-substituted-benzoxazine intermediates 17-19. From this series, compound 20k (LTURM34) (dibenzo[b,d]thiophen-4-yl) (IC50 = 0.034 µM) was identified as a specific DNA-PK inhibitor, 170 fold more selective for DNA-PK activity compared to PI3K activity. Other compounds of the series show markedly altered selectivity for various PI3K isoforms including compound 20i (8-(naphthalen-1-yl) a potent and quite selective PI3Kδ inhibitor (IC50 = 0.64 µM). Finally, nine compounds were evaluated and showed antiproliferative activity against an NCI panel of cancer cell lines. Compound 20i (8-(naphthalen-1-yl) showed strong anti-proliferative activity against A498 renal cancer cells that warrants further investigation.

Walnuts (Juglans regia) Chemical Composition and Research in Human Health.

Walnuts are among the most widely consumed commercially grown tree nuts in the world. Many health benefits have been claimed for the consumption of these, including reduced risk of cardiovascular disease, coronary heart disease, type II diabetes treatment, and prevention and treatment of certain cancers, and the lessening of symptoms attributed to age-related and other neurological disorders. The health-promoting benefits of walnut consumption are ascribed to its fatty acid profile, which is rich in polyunsaturated fatty acids with a particularly high ω3:ω6 ratio-the highest among all the tree nuts. The content of polyphenols and other phytochemicals in walnuts, with their claimed cytotoxic properties, also make them an attractive candidate for research for the prevention of free radical-induced nucleic acid damage. Research of walnut consumption in humans and animals employing a range of data sets and statistical methods suggest that walnuts may be considered a safe potential nutraceutical or possibly pharmaceutical substance. Nevertheless, few reviews of scientific research on the proposed benefits of these nuts exist, in spite of the numerous claims attributed to them in the lay media. This brief review article attempts to disseminate much of the information surrounding walnut consumption, and human health benefits, to other scientists and the interested general reader.

Surface complexation modeling of inositol hexaphosphate sorption onto gibbsite.

The sorption of Inositol hexaphosphate (IP6) onto gibbsite was investigated using a combination of adsorption experiments, (31)P solid-state MAS NMR spectroscopy, and surface complexation modeling. Adsorption experiments conducted at four temperatures showed that IP6 sorption decreased with increasing pH. At pH 6, IP6 sorption increased with increasing temperature, while at pH 10 sorption decreased as the temperature was raised. (31)P MAS NMR measurements at pH 3, 6, 9 and 11 produced spectra with broad resonance lines that could be de-convoluted with up to five resonances (+5, 0, -6, -13 and -21ppm). The chemical shifts suggest the sorption process involves a combination of both outer- and inner-sphere complexation and surface precipitation. Relative intensities of the observed resonances indicate that outer-sphere complexation is important in the sorption process at higher pH, while inner-sphere complexation and surface precipitation are dominant at lower pH. Using the adsorption and (31)P MAS NMR data, IP6 sorption to gibbsite was modeled with an extended constant capacitance model (ECCM). The adsorption reactions that best described the sorption of IP6 to gibbsite included two inner-sphere surface complexes and one outer-sphere complex: ≡AlOH + IP6¹²â» + 5H⁺ ↔ ≡Al(IP6H4)7⁻ + H2O, ≡3AlOH + IP6¹²â» + 6H⁺ ↔ ≡Al3(IP6H3)6⁻ + 3H2O, ≡2AlOH + IP6¹²â» + 4H⁺ ↔ (≡AlOH2)2²âº(IP6H2)¹°â». The inner-sphere complex involving three surface sites may be considered to be equivalent to a surface precipitate. Thermodynamic parameters were obtained from equilibrium constants derived from surface complexation modeling. Enthalpies for the formation of inner-sphere surface complexes were endothermic, while the enthalpy for the outer-sphere complex was exothermic. The entropies for the proposed sorption reactions were large and positive suggesting that changes in solvation of species play a major role in driving the sorption process.

Synthesis, DNA-PK inhibition, anti-platelet activity studies of 2-(N-substituted-3-aminopyridine)-substituted-1,3-benzoxazines and DNA-PK and PI3K inhibition, homology modelling studies of 2-morpholino-(7,8-di and 8-substituted)-1,3-benzoxazines.

A number of new 2-(pyridin-3-ylamino)-4H-(substituted) benz[e]-1,3-oxazin-4-ones were synthesized 10a-g. These were then reacted with the hydro-halogen salt of 2, 3 and 4-(halo-methyl) pyridine in the presence of Cs(2)CO(3) to give eighteen new 2-(N-substituted (pyridin-3-ylmethyl) amino)-substituted-1,3-benzoxazines (compounds 11a-i, 13a-c, and 15a-f). X-ray crystallography was used to confirm that the 2-N-substituted structures 11 and 13 were formed rather than the 3-N-substitution analogues 12 and 14. Eleven of the new compounds were tested for their effect on collagen induced platelet aggregation and it was found that the most active inhibitory compound was 8-methyl-2-(pyridin-3-yl(pyridin-3-ylmethyl)amino)-7-(pyridin-3-ylmethoxy)-4H-benz[e]-1,3-oxazin-4-one 15e with an IC(50) of 10 ± 2 µM. DNA-dependent protein kinase (DNA-PK) inhibition data for 12 previously prepared 2-morpholino substituted-1,3-benzoxazines (compounds 19-31) were measured and showed high to moderate activity where the most active compound was compound 27 with an IC(50) of 0.28 µM. Furthermore DNA-PK inhibition data for six newly prepared 2-(N-substituted (pyridin-3-ylmethyl) amino)-substituted-1,3-benzoxazines (compounds 11b, 13a-b, 15a-b and 15e) and 8-methyl-7-(pyridin-3-ylmethoxy)-3-(pyridin-3-ylmethyl)-2H-benz[e]-1,3-oxazin-2,4(3H)-dione 17d were measured and moderate to low inhibitory activity was observed, with the most active of the compounds in this series being 8-methyl-2-(pyridin-3-yl(pyridin-3-ylmethyl)amino)-7-(pyridin-3-ylmethoxy)-4H-benz[e]-1,3-oxazin-4-one 15e with an IC(50) of 2.5 µM. PI3K inhibition studies revealed that compound 27 is highly potent (IC(50) for PI3Kα = 0.13 µM, PI3Kß = 0.14 µM, PI3Kγ = 0.72 µM, PI3Kδ = 2.02 µM). Compound 22 with 7-[2-(4-methylpiperazin-1-yl)ethoxy] group shows greater inhibition of DNA-PK over PI3K. Docking of some 2-morpholino-substituted-1,3-benzoxazine compounds 19-31 within the binding pocket and structure-activity relationships (SAR) analyses were performed with results agreeing well with observed activities.

Inhibition of uranium(VI) sorption on titanium dioxide by surface iron(III) species in ferric oxide/titanium dioxide systems.

Uranium (U(VI)) sorption in systems containing titanium dioxide (TiO(2)) and various Fe(III)-oxide phases was investigated in the acidic pH range (pH 2.5-6). Studies were conducted with physical mixtures of TiO(2) and ferrihydrite, TiO(2) with coprecipitated ferrihydrite, and with systems where Fe(III) was mostly present as crystalline Fe(III) oxides. The presence of ferrihydrite resulted in decreased U(VI) sorption relative to the pure TiO(2) systems, particularly below pH 4, an unexpected result given that the presence of another sorbent would be expected to increase U(VI) uptake. In mixtures of TiO(2) and crystalline Fe(III) oxide phases, U(VI) sorption was higher than for the analogous mixtures of TiO(2) with ferrihydrite, and was similar to U(VI) sorption on TiO(2) alone. X-ray absorption spectroscopy of the TiO(2) system with freshly precipitated Fe(III) oxides indicated the presence of an Fe(III) surface phase that inhibits U(VI) sorption-a reaction whereby Fe(III) precipitates as lepidocrocite and/or ferrihydrite effectively blocking surface sorption sites on the underlying TiO(2). Competition between dissolved Fe(III) and U(VI) for sorption sites may also contribute to the observed decrease in U(VI) sorption. The present study demonstrates the complexity of sorption in mixed systems, where the oxide phases do not necessarily behave in an additive manner, and has implications for U(VI) mobility in natural and impacted environments where Fe(III) (oxyhydr)oxides are usually assumed to increase the retention of U(VI).

An investigation of the mode of sorption of inositol hexaphosphate to goethite.

Adsorption of inositol hexaphosphate (IP(6)) on goethite has been studied as a function of pH and concentration, and by use of Attenuated Total Reflectance-Fourier Transform Infrared Spectroscopy (ATR-FTIR). While adsorption was highest at low pH, a significant amount remained adsorbed above pH 10 where, in the absence of IP(6), the surface is expected to have a net negative charge. The adsorption isotherm at pH 5.5 indicated strong binding to the surface with each adsorbed species occupying about 2.5 nm(2). ATR-FTIR spectra of IP(6) solutions in the pH range from 2 to 12 were fitted with a single set of IR bands which were assigned primarily by analogy with phosphate spectra. From its variation in intensity with pH the band at 1040 cm(-1) was assigned to the effect of hydrogen bonding on the PO vibration. No additional bands were required to fit the spectra of IP(6) adsorbed to goethite, indicating that adsorption occurs by outer-sphere complexation in this system. At all pH values studied the band associated with hydrogen bonding was more intense for the adsorbed species than in solution at the corresponding pH indicating that hydrogen bonding plays an important role in binding IP(6) to goethite.

Synthesis, structural elucidation, DNA-PK inhibition, homology modelling and anti-platelet activity of morpholino-substituted-1,3-naphth-oxazines.

A number of new angular 2-morpholino-(substituted)-naphth-1,3-oxazines (compound 10b), linear 2-morpholino-(substituted)-naphth-1,3-oxazines (compounds 13b-c), linear 6, 7 and 9-O-substituted-2-morpholino-(substituted)-naphth-1,3-oxazines (compounds 17-22, 24, and 25) and angular compounds 14-16 and 23 were synthesised. The O-substituent was pyridin-2yl-methyl (15, 18, and 21) pyridin-3yl-methyl (16, 19, and 22) and 4-methylpipreazin-1-yl-ethoxy (23-25). Twelve compounds were tested for their inhibitory effect on collagen induced platelet aggregation and it was found that the most active compounds were compounds 19 and 22 with IC(50)=55±4 and 85±4 µM, respectively. Furthermore, the compounds were also assayed for their ability to inhibit DNA-dependent protein kinase (DNA-PK) activity. The most active compounds were 18 IC(50)=0.091 µM, 24 IC(50)=0.191 µM, and 22 IC(50)=0.331 µM. Homology modelling was used to build a 3D model of DNA-PK based on the X-ray structure of phosphatidylinositol 3-kinases (PI3Ks). Docking of synthesised compounds within the binding pocket and structure-activity relationships (SAR) analyses of the poses were performed and results agreed well with observed activity.

Measuring 'hydrophobicity' of filamentous bacteria found in wastewater treatment plants.

Attempts to measure the hydrophobicity of the cell surfaces of Gordonia amarae and Rhodococcus erythropolis, filamentous bacteria found in wastewater treatment plants, by several methods--microbial adhesion to hydrocarbons (MATH) or bacterial adhesion to hydrocarbons (BATH), contact angle, and micro-sphere adhesion to cells (MAC)--were unsuccessful. The results were erratic and inconsistent. This was in part because of the filamentous growth habit of G. amarae, but it was also a consequence of the fact that the 'hydrophobicity' of bacterial cells is not a clearly defined quantity. A technique is introduced in which bacteria are suspended in solutions of synthetic surfactants (non-ionic, cationic and anionic), and the suspensions aerated under defined conditions. The partitioning of bacterial cells between the foam and liquid phases was reproducible. The method was tested in model systems in which the bacteria were replaced by silica particles with defined surface modifications. Although this technique is not a direct measure of 'hydrophobicity', the partitioning of cells depends in part upon their surface hydrophobicity. In addition, qualitative information is gained about ionic interactions between the bacteria and the bubble surface. The results are pertinent to the problem of foaming in wastewater treatment plants.

The effect of filamentous bacteria on foam production and stability.

Bacteria have been implicated in the formation of viscous brown foams that can appear suddenly on wastewater treatment plants. Three strains of the filamentous bacterium Gordonia amarae, isolated from wastewater treatment plants, were investigated to determine their effect on foam formation and stabilisation. During the exponential phase of the bacterial growth a biosurfactant was formed, causing a significant drop in the surface tension of the filtered medium and the formation of persistent foam. Foaming tests in the presence and absence of bacteria showed that bacteria increased foam persistence, most probably by reducing the drainage from the lamellae between bubbles. Experiments showed that > or =55% of the three bacterial strains partitioned into the foam produced by the biosurfactant, indicating that their surfaces were hydrophobic. The extent of partitioning was independent of the growth stage, suggesting that the cell surface hydrophobicity did not change with age, or with cell viability. This work shows that, although the G. amarae cells themselves do not cause foaming, they do produce biosurfactant, which aids foam formation, and they stabilise the foam by reducing the rate of drainage from the foam lamellae.

Sorption of chlorpyrifos to selected minerals and the effect of humic acid.

Sorption of chlorpyrifos (CPF) from 2.85 microM (1 mg/L) aqueous solutions in 0.01 M NaCl to montmorillonite, kaolinite, and gibbsite was investigated at 25 degrees C. Uptake of CPF by kaolinite and gibbsite was generally <10%, with pH having at most a small effect. Sorption to montmorillonite was significantly greater, with approximately 50% of the initial CPF being removed from solution below pH 5. Above pH 5 the sorption decreased to about 30%. About 70% of CPF was sorbed to kaolinite and gibbsite after 30 min, whereas on montmorillonite only 50% sorbed in an initial rapid uptake (approximately 30 min) followed by slower sorption, with a maximum achieved by 24 h. Although CPF desorbed completely from kaolinite in methanol, only about two-thirds was desorbed from montmorillonite. CPF has only a weak affinity for the surfaces of kaolinite and gibbsite. In the case of montmorillonite, sorption is significantly stronger and may involve a combination of sorption to external surfaces and diffusion into microporous regions. At pH >6 increased negative surface charge results in a lower affinity of CPF for the external surface. In the presence of 50 mg/L humic acid (HA) the amount of CPF sorbed on gibbsite and kaolinite was 3-4 times greater than that in the binary systems. The HA forms an organic coating on the mineral surface, providing a more hydrophobic environment, leading to enhanced CPF uptake. The HA coating on montmorillonite may reduce access of CPF to microporous regions, with CPF tending to accumulate within the HA coating.

31P solid-state nuclear magnetic resonance study of the sorption of phosphate onto gibbsite and kaolinite.

Sorption of phosphate onto gibbsite (gamma-Al(OH)3) and kaolinite has been studied by both macroscopic and 31P solid-state NMR measurements. Together these measurements indicate that phosphate is sorbed by a combination of surface complexation and surface precipitation with the relative amounts of these phases depending on pH and phosphate concentration. At low pH and high phosphate concentrations sorption is dominated by the presence of both amorphous and crystalline precipitate phases. The similarity between the single-pulse and CP/MAS NMR spectra suggests that the precipitate phases form a thin layer on the surface of the particles in close contact with protons from surface hydroxyl groups or coordinated water molecules. While the crystalline phase is only evident on samples below pH 7, amorphous AlPO4 was found at all pH and phosphate concentrations studied. As pH was increased the fraction of phosphate sorbed as an inner-sphere complex increased, becoming the dominant surface species by pH 8. Comparison of sorption and NMR results suggests that the inner-sphere complexes form by monodentate coordination to singly coordinated Al-OH sites on the edges of the gibbsite and kaolinite crystals. Outer-sphere phosphate complexes, which are readily desorbed, are also present at high pH.

Influence of temperature on the adsorption of mellitic acid onto kaolinite.

The adsorption of mellitic acid (benzene-1,2,3,4,5,6-hexacarboxylic acid) onto kaolinite was investigated at five temperatures between 10 and 70 degrees C. Mellitic acid adsorption increased with increasing temperature at low pH (below pH 5.5), but at higher pH, the effect of increasing temperature was to reduce the amount adsorbed. Potentiometric titrations were conducted, adsorption isotherms were measured over the same temperature range, and the data obtained were used in conjunction with adsorption edge and ATR-FTIR spectroscopic data to develop an extended constant capacitance surface complexation model of mellitic acid adsorption. A single set of reactions was used to model all data at the five temperatures studied. The model indicates that mellitic acid sorbs via outer-sphere complexation to surface hydroxyl (SOH) groups on the kaolinite surface rather than to permanent charge sites. The reactions proposed are SOH + L6- + 2H+ <-->[(SOH2)+(LH)5-]4- and SOH + L(6-) <--> [(SOH)(L)6-]6-. Thermodynamic parameters calculated from the temperature dependence of the equilibrium constants for these reactions indicate that the adsorption of mellitic acid onto kaolinite is accompanied by a large entropy increase.

Optimization of silylation using N-methyl-N-(trimethylsilyl)-trifluoroacetamide, N,O-bis-(trimethylsilyl)-trifluoroacetamide and N-(tert-butyldimethylsilyl)-N-methyltrifluoroacetamide for the determination of the estrogens estrone and 17alpha-ethinylestradiol by gas chromatography-mass spectrometry.

This paper reports an improved silylation procedure for simultaneous determination of the steroid hormones 17alpha-ethinylestradiol (EE2) and estrone (E1) using gas chromatography-mass spectrometry (GC-MS). This follows a re-assessment of some of the popular silylation procedures using N-methyl-N-trimethylsilyltrifluoroacetamide (MSTFA), N-O-bis-(trimethylsilyl)-trifluoroacetamide (BSTFA) and N-(tert-butyldimethylsilyl)-N-methyltrifluoroacetamide (MTBSTFA), which lead to the formation of trimethylsilyl (TMS) and tert-butyldimethylsilyl (TBS) derivatives. Silylation of EE2 using MSTFA or BSTFA+1% TMCS in ethyl acetate, acetonitrile and dichloromethane solvents produced multiple peaks corresponding to TMS-E1, and 3-mono-TMS-EE2 and/or 3,17-di-TMS-EE2 in variable proportions depending on the solvent used. When pyridine or dimethyl formamide solvents were used in the silylation of EE2 under the same reaction conditions, only 3,17-di-TMS-EE2 derivative was formed. Derivatization using MTBSTFA reagents using ethyl acetate, acetonitrile, dichloromethane, pyridine and dimethyl formamide resulted in almost 100% conversion of mono-TBS-EE2 to the TBS-E1. Therefore, typical methods used in some previous GC-MS determinations of E1 and EE2 in environmental water and/or sediment samples are subject to speculation. However, we can confirm that any of the TMS reagents can be used with either pyridine or dimethyl formamide under suitable reaction conditions.

The influence of temperature on the adsorption of mellitic acid onto goethite.

The adsorption of mellitic acid (benzene-1,2,3,4,5,6-hexacarboxylic acid) onto goethite was investigated at five temperatures between 10 and 70 degrees C. Mellitic acid adsorption increased with increasing temperature below pH 7.5, but at higher pH the effect of increasing temperature was to reduce the amount adsorbed. Potentiometric titrations were conducted and adsorption isotherms were measured over the same temperature range, and the data obtained were used in conjunction with adsorption edge data to develop an Extended Constant Capacitance Surface Complexation Model of mellitic acid adsorption. A single set of reactions was used to model the adsorption for the three different experiment types at the five temperatures studied. The adsorption reactions proposed for mellitate ion (L(6-)) adsorption at the goethite surface (SOH) involved the formation of two outer-sphere complexes: SOH + L(6-) + 3H+ <==> [(SOH2)+ (LH2)(4-)]3-, 2SOH + L(6-) + 2H+ <==> [(SOH2)2(2+) (L)(6-)]4-. This mechanism is consistent with recent ATR-FTIR spectroscopic measurements of the mellitate-goethite system. Thermodynamic parameters calculated from the temperature dependence of the equilibrium constants for these reactions indicate that the adsorption of mellitic acid onto goethite is accompanied by a large entropy increase.