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.

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.

Sorption of bisphenol A, 17alpha-ethynylestradiol and estrone to mineral surfaces.

Sorption of the endocrine disrupting chemicals (EDCs) bisphenol A (BPA), 17alpha-ethynylestradiol (EE2) and estrone (E1) from 3 microM aqueous solutions in 10 mM KNO3 to goethite, kaolinite and montmorillonite was investigated at 25 degrees C. Uptake of the EDCs by goethite and kaolinite suspensions was <20%, and little affected by pH. Sorption by montmorillonite was greater, ranging from 20 to 60%, and steadily increased from about pH 7. The amount of EDC sorbed to the mineral phases generally increased in the order of decreasing solubility (BPA

Surface complexation modeling of the sorption of 2-, 3-, and 4-aminopyridine by montmorillonite.

The sorption of 2-, 3-, and 4-aminopyridine on K-saturated Wyoming (SWy-K) and Texas (STx-K) and Ca-enriched Texas (STx-Ca) montmorillonite was measured at 25 degrees C with 10 mM KNO(3) or 3.3 mM Ca(NO(3))(2) as the background electrolyte. The aminopyridines adsorbed to montmorillonite at low pH, but not at high pH. Extended constant capacitance surface complexation models (ECCMs) and attenuated total reflectance-FTIR data indicate that aminopyridines sorb to the silica-like faces by cation exchange, forming outer-sphere complexes between aminopyridinium ions and permanent negatively charged surface sites (X(-)). X-ray diffraction data and sorption kinetics suggest that sorption occurs not only at external X(-) sites but also at those in the interlayer spaces. Differences in the sorption behaviors of 2-, 3-, and 4-aminopyridine result from differences in their pK(a)s. The extent of sorption of aminopyridines by the montmorillonite samples (SWy-K>STx-K>STx-Ca) results from the higher cation-exchange capacity of SWy-K, and from the fact that Ca(2+) is much more effective than K(+) in competing with protonated aminopyridines for the X(-) sites.

Cosorption of Zn(II) and 2-, 3-, or 4-aminopyridine by montmorillonite.

Data from acid-base titrations at 25 degrees C of Zn(NO(3))(2) and 2-, 3-, or 4-aminopyridine in 10 mM KNO(3) as background electrolyte suggested that soluble complexes ZnL(2+) and Zn(OH)L(+) form, where L represents aminopyridine. Zinc-hydroxyaminopyridine complexes have not been reported previously. The cosorption of Zn(II) with each of the aminopyridines to K-saturated Wyoming (SWy-K) and Texas (STx-K), and Ca-enriched Texas (STx-Ca) montmorillonites was measured at 25 degrees C, with 10 mM KNO(3) or 3.3 mM Ca(NO(3))(2) as background electrolyte. Comparison with previous data for sorption of Zn(II) and the aminopyridines separately and surface complexation modeling of the cosorption data showed that under acid conditions competition between Zn(2+) and aminopyridinium ions for the permanent negatively charged sites of montmorillonite results in suppression of the uptake of each sorbate by the other, but only when a large excess of the competing sorbate is present. Under alkaline conditions the sorption of Zn(II) was not affected by the presence of even a large excess of aminopyridine, but the sorption of 4-aminopyridine in particular was slightly enhanced when a large excess of Zn(II) was present. The enhancement was attributed to the formation of metal-bridged ternary surface complexes at the variable-charge sites on the edges of the montmorillonite crystals.

Adsorption of aspartic acid on kaolinite.

The interaction of aspartic acid with kaolinite was studied by potentiometric titrations and by adsorption measurements both at constant aspartate concentration (but varying pH) and at a constant pH of 5.5. The temperature was 25 degrees C, and the ionic medium 5 mM KNO3. Aspartic acid dissociation constants estimated from titrations agreed with those from the literature. The adsorption of aspartic acid to kaolinite was weak and varied only slightly with pH; 10-18% of 100 microM aspartic acid adsorbed to kaolinite at 100 m(2)L(-1) between pH 3 and 10. Data from the titrations and adsorption experiments were fitted closely by an extended constant-capacitance surface complexation model, in which monodentate outer-sphere complexes formed between deprotonated aspartic acid molecules and protonated sites on the variable-charge edges of the kaolinite crystals. There appeared to be no adsorption to the permanently charged crystal faces.

The effect of aspartic acid on the binding of transition metals to kaolinite.

The effect of aspartic acid on the adsorption of Pb(II), Cu(II), Zn(II), Co(II), and Mn(II) on kaolinite at 25 degrees C in the presence of 5 mM KNO3 was investigated by means of potentiometric titrations and adsorption measurements over a range of pH and concentration. Data were modeled by extended constant capacitance models. Aspartic acid slightly enhanced the adsorption of Pb(II), Zn(II), and Co(II) at low pH, but inhibited the adsorption of all the metal ions at higher pH. Adsorption of Cu(II) and Co(II) was inhibited strongly. Because aspartic acid is adsorbed only weakly by kaolinite, inhibition of metal ion adsorption depends on the ability of aspartic acid to form complexes with the various metal ions together with the adsorption characteristics of these complexes. In particular suppression of adsorption at high pH arises from competition between surface sites and dissolved aspartate ions for the available metal ions. Cu(II) and Co(II) form complexes with aspartic acid more strongly than the other metals. As these complexes do not adsorb, Cu(II) and Co(II) suffer greater suppression from aspartic acid than the other metals. There was no evidence of adsorption of aspartic acid complexes to the permanently charged kaolinite faces.

Suitability of N,O-bis(trimethylsilyl)trifluoroacetamide and N-(tert-butyldimethylsilyl)-N-methyltrifluoroacetamide as derivatization reagents for the determination of the estrogens estrone and 17alpha-ethinylestradiol by gas chromatography-mass spectrometry.

This paper describes apreviously unreported problem with the use of N,O-bis-(trimethylsilyl)trifluoroacetamide (BSTFA) and N-(tert-butyldimethylsilyl)-N-methyltrifluoroacetamide (MTBSTFA) to derivatise the natural hormone estrone (E1) and the synthetic estrogen 17alpha-ethinylestradiol (EE2). The resulting trimethylsilyl (TMS) and t-butyldimethylsilyl (TBS) derivatives of EE2 were partially converted to their respective El derivatives. Therefore, these reagents may not be suitable for simultaneous determination of estrogens in environmental samples, which raises questions about the reliability of results from some earlier studies.

Modeling the adsorption of Cd(II) onto kaolinite and Muloorina illite in the presence of citric acid.

The adsorption of cadmium onto kaolinite and Muloorina illite in the presence of citric acid has been measured as a function of pH and cadmium concentration at 25 degrees C. When citric acid is present in the systems cadmium adsorption is slightly enhanced below pH 5, but significantly suppressed between pH 5 and 8, for both substrates. At higher citric acid concentrations very little cadmium adsorbs onto kaolinite from pH 5 to 8. Above pH 8 adsorption of Cd(II) onto illite is enhanced in the presence of citric acid, especially at lower concentrations, but this does not occur for kaolinite. Adsorption and potentiometric titration data were fitted by simple extended constant-capacitance surface complexation models for the two substrates. Enhancement of adsorption at lower pH values was ascribed to the ternary reaction [X(-)--K(+)](0)+Cd(2+)+L(3-)+2H(+) right arrow over left arrow (0)+K(+) involving outer-sphere complexation with permanently charged X(-) sites on the "silica" faces of both clay minerals. The models suggested that suppression of adsorption in the intermediate pH range was due to the formation of a strong CdL(-) solution complex which adsorbed neither on the permanently charged sites nor on the surface hydroxyl groups at the edges of the clay crystals. At higher pH values the dominant solution complex, CdLOH(2-), apparently adsorbed as an outer-sphere complex at surface hydroxyl groups on illite, SOH+2Cd(2+)+L(3-) right arrow over left arrow [SOCd(+)--CdOHL(2-)](-)+2H(+), but not on kaolinite. This difference in behavior results from the presence of =FeOH groups on the illite surface which can form surface complexes with CdLOH(2-), while the =AlOH groups on the kaolinite surface cannot.

Modeling the adsorption of Cd(II) onto goethite in the presence of citric acid.

The adsorption of cadmium onto goethite in the presence of citric acid was measured as a function of pH and cadmium concentration at 25 degrees C. Potentiometric titrations were also performed on the system. Cadmium adsorption onto goethite was enhanced above pH 4 in the presence of 50 microM, 100 microM and 1 mM citric acid. While there was little difference between the enhancements caused by 50 and 100 microM citric acid below pH 6, above pH 6 further enhancement is seen in the presence of 100 microM citric acid. When 1 mM citric acid was present, the enhancement of cadmium adsorption was greater below pH 6, with increased Cd(II) adsorption down to pH 3.5. However, above pH 6, 1 mM of citric acid caused slightly less enhancement than the lower citric acid concentrations. ATR-FTIR spectra of soluble and adsorbed citrate-cadmium species were measured as a function of pH. At pH 4.6 there was very little difference between the ternary Cd(II)-citric acid-goethite spectrum and the binary citric acid-goethite spectrum. However, spectra of the ternary system at pH 7.0 and 8.7 indicated the presence of additional surface species. Further analysis of the spectra suggested that these were metal-ligand outer-sphere complexes. Data from the adsorption experiments and potentiometric titrations of the ternary Cd(II)-citric acid-goethite system were fitted by an extended constant-capacitance surface complexation model. The spectroscopic data were used to inform the choice of surface species. Three reactions in addition to those for the binary Cd(II)-goethite and citric acid-goethite systems were required to describe all of the data. They were [formula in text], [formula in text], and [formula in text]. Neither the spectroscopy nor the modeling suggested the formation of a ternary inner-sphere complex or a surface precipitate under the conditions used in this study.

Modeling the adsorption of citric acid onto Muloorina illite and related clay minerals.

The adsorption of citric acid onto goethite, kaolinite, and illite was measured as a function of pH (adsorption edges) and concentration (adsorption isotherms) at 25 degrees C. The greatest adsorption was onto goethite and the least onto illite. Adsorption onto goethite was at a maximum below pH 5 and decreased as the pH was increased to pH 9. For kaolinite, maximum adsorption occurred between pH 4.5 and pH 7, decreasing below and above this pH region, while for illite maximum adsorption occurred between about pH 5 and pH 7, decreasing at both lower and higher pH. ATR-FTIR spectra of citrate adsorbed to goethite at pH 4.6, pH 7.0, and pH 8.8 were compared with those of citrate solutions between pH 3.5 and pH 9.1. While the spectra of adsorbed citrate resembled those of the fully deprotonated solution species, there were significant differences. In particular the C[bond]O symmetric stretching band of the adsorbed species at pH 4.6 and 7.0 changed shape and was shifted to higher wave number. Further spectral analysis suggested that citrate adsorbed as an inner-sphere complex at pH 4.6 and pH 7.0 with coordination to the surface most probably via one or more carboxyl groups. At pH 8.8 the intensity of the adsorbed bands was much smaller but their shape was similar to those from the deprotonated citrate solution species, suggesting outer-sphere adsorption. Insufficient citric acid adsorbed onto illite or kaolinite to provide spectroscopic information about the mode of adsorption onto these minerals. Data from adsorption experiments, and from potentiometric titrations of suspensions of the minerals in the presence of citric acid, were fitted by extended constant-capacitance surface complexation models. On the goethite surface a monodentate inner-sphere complex dominated adsorption below pH 7.9, with a bidentate outer-sphere complex required at higher pH values. On kaolinite, citric acid adsorption was modeled with a bidentate outer-sphere complex at low pH and a monodentate outer-sphere complex at higher pH. There is evidence of dissolution of kaolinite in the presence of citric acid. For illite two bidentate outer-sphere complexes provided a good fit to all data.

Sorption of 17beta-estradiol onto selected soil minerals.

Sorption of the endocrine-disrupting chemical 17beta-estradiol (E(2)) from aqueous solutions to goethite, an iron oxide, and the clay minerals kaolinite, illite, and montmorillonite (K and Ca forms) was measured at 25 degrees C. The clay minerals sorbed more E(2) than the oxide, with sorption capacity increasing in the order goethite

Characterization of carbonaceous combustion residues. I. Morphological, elemental and spectroscopic features.

Scanning electron microscopy, surface area determination, elemental analysis, organic matter extraction and solid-state cross polarization/magic angle spinning and Bloch decay/magic angle spinning 13C nuclear magnetic resonance (NMR) spectroscopy were used to investigate distinctive features among carbonaceous combustion residues. Black carbon (BC) samples included diesel soot, urban dust, carbon black, chimney soot, vegetation fire residues, wood and straw charcoals. Particles varied from small spheres (<50 nm) in fossil BC (>100 m(2)/g), to large layered structures in plant-derived BC (generally <8 m(2)/g). Chimney soot also included large (>1 micrometer) liquid-like structures, while spherules >100 nm were unique to urban dust. The ratios of amorphous to soot carbon (SC) (isolated by thermal degradation) were not necessarily correlated with the degree of aromaticity estimated from H/C ratios. In particular, values of SC in diesel soot were clearly overestimated. Solvent-extractable organic matter (SEOM) was <2% for charcoals and carbon black, but >13% for urban dust, chimney and diesel soot. SEOM is thought to clog pores or to form large waxy globules, hence reducing surface areas. The ratio of polar/nonpolar SEOM was generally <7 for fossil BC, but >30 for plant-derived BC. NMR analysis revealed essentially one chemical shift in the aromatic C region of charcoals, while diesel soot also showed important aliphatic contributions. Aliphatic and oxygenated C predominated over aryl C in urban dust and chimney soot. These morphological and chemical characteristics of the BC samples are discussed in terms of their environmental implications.

Modeling the adsorption of Cd(II) onto Muloorina illite and related clay minerals.

The adsorption of Cd(II) onto goethite, kaolinite, and illite was measured as a function of pH (adsorption edges) and concentration (adsorption isotherms) at 25 degrees C. As the pH was increased, adsorption onto goethite occurred mainly in the pH range 5.5-8, whereas adsorption onto kaolinite occurred in two stages, separated by a plateau in the pH region 5.5 to 7. Adsorption onto illite increased steadily as the pH was increased, with far less Cd(II) adsorbing onto illite than onto goethite or kaolinite per m(2) of mineral surface area. Potentiometric titrations of suspensions of each mineral, with and without Cd(II) present, were also completed. Results from all three types of experiments were modeled using an extended constant- capacitance surface complexation model. The reactions [Formula: see text] [Formula: see text] and [Formula: see text] best described Cd(II) adsorption onto goethite, while [Formula: see text] and [Formula: see text] best described Cd(II) adsorption onto kaolinite. A combination of the first, second, and fourth of these reactions best fitted the data for Cd(II) adsorption onto illite. In each case the model fitted all experimental data well. The results suggest that adsorption onto the variable charge (SOH) sites on illite more closely resembles adsorption onto goethite than onto kaolinite.

Intracoronal sealing ability of two dental cements.

The purpose of this study was to compare the efficacy of sealing the coronal 2-mm of the root canals versus covering the entire pulpal floor with one of two dental-resin cements (Principle or C&B Metabond). Sixty-two molars with the occlusal half of the crowns and the apical half of the roots removed were used. Each canal was enlarged by using a #3 Gates Glidden bur and obturated with unsealed gutta-percha cones. The teeth were randomly assigned to four groups, each containing 15 teeth, plus a negative and a positive control. In group 1, 2 mm of Principle were placed over the entire pulpal floor. In group 2, Principle was placed 2 mm into each canal orifice. Groups 3 and 4 were the same as groups 1 and 2, except C&B Metabond cement was used. After the cement set, the gutta-percha was removed and the integrity of the seal was tested by fluid filtration at a pressure of 20 cm H2O at 1 h and at 1, 2, and 4 weeks. The data were analyzed by a three-way ANOVA and the Student-Newman-Keuls tests at alpha = 0.05. The controls behaved as expected. Results showed that there were no statistically significant differences among the materials used or the location (p > 0.05), but there was a significant difference with respect to time. Principle leaked significantly more than C&B Metabond at 1 h (p < 0.05), but the seal became tighter over time. C&B Metabond leaked less early (p < 0.05) but increased in leakage at 4 weeks. Both materials sealed well over the 4-week study. Principle was easier to use, and sealing the entire pulpal floor was easier than sealing only the canal orifice.