The aqueous solubility of twenty‐seven insecticides and related compounds.

Abstract

The aqueous solubilities of 27 insecticides and related compounds were determined. Diazinon, fensulfothion and paraoxon had solubilities greater than reported in the literature. The presence of impurities and/or additional components in the mixture altered the measured solubility values. Addition of acetone in amounts up to 1% (volume) produced increases in parathion solubility up to 11%. The pH values of the equilibrated solubility systems were, in most instances, acidic and, in several instances, were in the pH 3–4 range.     

Effect of fluoride on pH, organic matter and solubility of elements in soils

The effect of NaF addition on pH, organic matter and the solubilities of fifteen elements was investigated on twenty-eight surface soil samples. Four concentrations of NaF were added: 0, 10(-2.7), 10(-1.7) and 10(-1.0)m F in solution. Addition of NaF increased the pH and the solubility of organic matter for all soils. The magnitude of these increases was higher for acid than for alkaline soils. Aluminum, Fe and Ca showed the greatest increases in solubility while Mg, K, Mn and P showed intermediate increases. The elements Cd, Cr, Ni, Cu, Zn, B, Mo and Ba showed only slight increases in solubility. Another experiment was conducted to test whether the effects of NaF on pH, organic matter and the solubilities of various elements were due to F or Na. Four levels of NaCl similar to those for NaF were added to three acid and two alkaline soils. The results confirmed the effects of F on soil pH, organic matter and the solubilities of all elements investigated except those of K, Ca and Mg. Addition of Na as NaF resulted in release of K, Ca and Mg from the exchange sites on solid surfaces into solution.     

Evaluation of the dependence of aqueous solubility of nitro compounds on temperature and salinity: a COSMO-RS simulation

The solubility in pure and saline water at various temperatures was calculated for selected nitro compounds (nitrobenzene, 1,3,5-trinitrobenzene, 2-nitrotoluene, 3-nitrotoluene, 4-nitrotoluene, 2,4-dinitrotoluene, 2,6-dinitrotoluene, 2,3-dinitrotoluene, 3,4-dinitrotoluene, 2,4,6-trinitrotoluene) using the Conductor-like Screening model for Real Solvents (COSMO-RS). The results obtained were compared with experimental values. The COSMO-RS predictions have shown high accuracy in reproducing the trends of aqueous solubilities for both temperature and salinity. The proposed methodology was then applied to predict the aqueous solubilities of 19 nitro compounds in the temperature range of 5-50 °C in saline solutions. The salting-out parameters of the Setschenow equation were also calculated. The predicted salting-out parameters were overestimated when compared to the measured values, but these parameters can still be used for qualitative estimation of the trends.     

Fat solubility — A property of environmental relevance?

Solubilities in fats ranging from 0.88 g l^?1 to completely miscible are reported for twelve organic chemicals. Comparison of these and other literature values with bioconcentration factors and octanol: water partition coefficients indicate that fat solubility is not a reliable predictor for either parameter. The results for the solubilities of seven chemicals in eight different fats cover a restricted range, indicating that the composition of the fat is not a critical parameter in determining the solubility.     

Evaluation of solubilizing ability of humic aggregate basing on the phase-separation model

Solubilizing abilities of aggregates of humic acid (HA) to chlorinated benzenes (CBs) were investigated by means of the apparent water solubility enhancement. Both the water solubilities of 1,4-dichlorobenzene (DCB) and 1,2,4,5-tetrachlorobenzene (TeCB) linearly increased with increasing concentration of HA above the critical micelle concentration (CMC). Such solubilization behavior of CBs for HA was compatible with those for sodium dodecyl sulfate (SDS). These results indicate that the solubilization of CBs in the aqueous solution of HA above the CMC can be interpreted on the basis of the phase-separation model. Thus, the partition coefficients (K(mic)) of CBs between water and HA aggregate phases were calculated by assuming this model. The fact that the K(mic) value increased with increasing K(ow) of CBs supported the partition into the HA aggregate phase by hydrophobic interaction. The estimated K(mic) values of DCB were not dependent on the solution pH. Both K(mic) values of DCB and TeCB for the HA aggregate were found to be 4-5-fold lower than those of SDS.     

Further water solubility determinations of insecticidal compounds

Abstract

The aqueous solubility of 39 insecticidal and related compounds was determined at 20±1.5°C, using a previously described shaking and centrifugation method. Fenamiphos, fenthion and methi‐dathion produced values substantially less than those reported in the literature whereas, aminocarb, diazinon, dicapthon, pirimiphos‐ethyl and pirimiphos‐methyl gave solubilities substantially greater than reported literature values.     

Behavior and stability of organic contaminant droplets in aqueous solutions

The behavior of several hydrophobic organic compounds (HOCs) in water at concentrations close to and above their maximum solubility values was studied. For this purpose, solutions of benzene, toluene, xylene, trichloroethylene (TCE) and a mixture of them were prepared in excess in freshwater and in saltwater, and solution stability was examined. High organic concentrations were found to remain stable in both freshwater and saltwater. In saltwater, for example, toluene and xylene concentrations remained as high as 14 and 26 times their solubilities, respectively, over a period of 6 days, while in freshwater, their concentrations remained 8 and 30 times their solubilities over the same period. This phenomenon is attributed to the presence of stable organic droplets, which were observed using optical microscopy. In addition, the transport of HOC droplets through sand is demonstrated, using an experimental system consisting of a saltwater source reservoir connected by a porous inactive sand layer to a freshwater collector reservoir.     

Aqueous solubility, Henry's law constants and air/water partition coefficients of n-octane and two halogenated octanes

New data on the aqueous solubility of n-octane, 1-chlorooctane and 1-bromooctane are reported between 1 degree C and 45 degrees C. Henry's law constants, K(H), and air/water partition coefficients, K(AW), were calculated by associating the measured solubility values to vapor pressures taken from literature. The mole fraction aqueous solubility varies between (1.13-1.60)x10(-7) for n-octane with a minimum at approximately 23 degrees C, (3.99-5.07)x10(-7) for 1-chlorooctane increasing monotonically with temperature and (1.60-3.44)x10(-7) for 1-bromooctane with a minimum near 18 degrees C. The calculated air-water partition coefficients increase with temperature and are two orders of magnitude lower for the halogenated derivatives compared to octane. The precision of the results, taken as the average absolute deviations of the aqueous solubility, the Henry's law constants, or the air/water partition coefficients, from appropriate smoothing equations as a function of temperature is of 3% for n-octane and of 2% and 4% for 1-chlorooctane and 1-bromooctane, respectively. A new apparatus based on the dynamic saturation column method was used for the solubility measurements. Test measurements with n-octane indicated the capability of measuring solubilities between 10(-6) and 10(-10) in mole fraction, with an estimated accuracy better than +/-10%. A thorough thermodynamic analysis of converting measured data to air/water partition coefficients is presented.     

Solubility of lead, zinc and copper added to mineral soils

Elevated levels of heavy metals in soils are a result of industrial activities, atmospheric deposition, and the land application of sewage sludges and industrial by-products. Their persistence in the soil environment has created interest in the possible changes in solubility. In this study, total dissolved concentrations of Pb, Zn, and Cu were monitored in seven metal-amended soils (a calcareous and six acid mineral soils). Single metal solutions were added to soils and equilibrated (aged) for 40 days. During the 40 days the soil was allowed to air-dry and was rewetted in cycles of about 5 days. At the end of this reaction period, metal solubility was measured (by atomic absorption spectrometry and direct current plasma spectrometry) at the initial soil pH and at decreased pH values which were induced by addition of small aliquots of acid. As expected, solubility of added Pb, Zn, and Cu increased with a decrease in pH. Furthermore, the results showed that the solubility relationship with pH was similar in all non-calcareous soils. This suggests that metal solubility may be controlled by similar soil components, presumably involving soil characteristics such as pH, organic matter content, and soil mineralogy. For each metal, an approximate pH value was found at which solubility deviated from the solubility of metals when they occur in soils at typical (natural) values. This pH was about (pH+/-0.2): 5.2 for Pb, 6.2 for Zn, and 5.5 for Cu. Thus, pH values below these thresholds may enhance metal mobility, biological availability and toxicity in soils. Metals dissolved at higher pH in the calcareous soil (18.8 g kg(-1) inorganic carbon, initial pH 8.2). In a calcareous soil, a significant fraction of these metals react with carbonates, and decreased pH results in much higher metal dissolution. Yet, metal solubility in soils is not determined by the formation and dissolution of single metal compounds.     

Vapour pressures, aqueous solubility, Henry's law constants and air/water partition coefficients of 1,8-dichlorooctane and 1,8-dibromooctane

New data on the vapour pressures and aqueous solubility of 1,8-dichlorooctane and 1,8-dibromooctane are reported as a function of temperature between 20 °C and 80 °C and 1 °C and 40 °C, respectively. For the vapour pressures, a static method was used during the measurements which have an estimated uncertainty between 3% and 5%. The aqueous solubilities were determined using a dynamic saturation column method and the values are accurate to within ±10%. 1,8-Dichlorooctane is more volatile than 1,8-dibromooctane in the temperature range covered (p_sat varies from 3 to 250 Pa and from 0.53 to 62 Pa, respectively) and is also approximately three times more soluble in water (mole fraction solubilities at 25 °C of 5.95 × 10⁻⁷ and 1.92 × 10⁻⁷, respectively). A combination of the two sets of data allowed the calculation of the Henry’s law constants and the air water partition coefficients. A simple group contribution concept was used to rationalize the data obtained.     

Solubilities of selected organic electronic materials in pressurized hot water and estimations of aqueous solubilities at 298.15 K

Increasing production and disposal of organic light-emitting diode (OLED) displays for smartphones and tablets may have impact on the environment depending on the aqueous solubility of the pertinent chemicals. Here, aqueous solubilities are presented for several compounds, mostly aromatic amines, used as hole transport materials in the OLED displays. Solute selection includes 1,4-bis(diphenylamino)benzene, tetra-N-phenylbenzidine, 4,4′-bis(N-carbazolyl)-1,1′-biphenyl, 1,3,5-tris(diphenylamino)benzene, and 9,10-bis(phenylethynyl)anthracene. The solubilities are those in pressurized hot water (PHW), i.e., measured at elevated temperature (up to 260 °C) and pressure. The semi-quantitative estimates of room-temperature solubilities of the solutes have been obtained from extrapolations of the solubilities in PHW. For the compounds studied, the estimated aqueous solubilities at room temperature do not exceed 2 × 10^?11 g of the solute per 1 kg of water. Aqueous solubilities of triphenylamine have also been measured and used to upgrade a recent group-contribution model of aqueous solubilities of organic nonelectrolytes with the parameters for the nitrogen atom in aromatic amines.     

Aqueous solubility, effects of salts on aqueous solubility, and partitioning behavior of hexafluorobenzene: experimental results and COSMO-RS predictions

The aqueous solubility of hexafluorobenzene has been determined, at 298.15 K, using a shake-flask method with a spectrophotometric quantification technique. Furthermore, the solubility of hexafluorobenzene in saline aqueous solutions, at distinct salt concentrations, has been measured. Both salting-in and salting-out effects were observed and found to be dependent on the nature of the cationic/anionic composition of the salt. COSMO-RS, the Conductor-like Screening Model for Real Solvents, has been used to predict the corresponding aqueous solubilities at conditions similar to those used experimentally. The prediction results showed that the COSMO-RS approach is suitable for the prediction of salting-in/-out effects. The salting-in/-out phenomena have been rationalized with the support of COSMO-RS σ-profiles. The prediction potential of COSMO-RS regarding aqueous solubilities and octanol-water partition coefficients has been compared with typically used QSPR-based methods. Up to now, the absence of accurate solubility data for hexafluorobenzene hampered the calculation of the respective partition coefficients. Combining available accurate vapor pressure data with the experimentally determined water solubility, a novel air-water partition coefficient has been derived.     

Temperature dependent properties of environmentally important synthetic musks

Environmental fate determining physical properties including their temperature dependence for five nitro musks and for seven polycyclic musks were estimated. The properties evaluated were vapor pressure in a solid and liquid state (PS and PL), solubility in water (S), Henry's law coefficient (H = PL/S) and log octanol-water partition coefficient (log KOW). Gas chromatography for starting values of vapor pressure estimation and HPLC experiments at 5-20 degrees C for comparison of the theoretical versus experimental solubilities in water were performed. The values of temperature (T) dependence coefficients (Ai and Bi) in equations: log (Property)i = Ai - Bi/T were determined. Values of properties were compared with literature-based data, and an example of their use in environmental hazard estimation by fate modeling was given.     

Determination of the temperature dependence of water solubilities of polycyclic aromatic hydrocarbons by a generator column-on-line solid-phase extraction-liquid chromatographic method

An improved dynamic coupled column liquid chromatographic (DCCLC) technique for determining water solubility data of hydrophobic compounds is presented. The technique is based on pumping water through a thermostated generator column in order to generate emulsion-free, saturated aqueous solutions of the compound under study. Through a switching valve system the solute in the aqueous solution is extracted and concentrated by an on-line solid-phase extraction process and subsequently eluted and analyzed by high performance liquid chromatography (fluorescence detection coupled to photodiode array detection). The improvements carried out to the original DCCLC technique have given rise to savings in time for the experimental work and increased sensitivity during the detection and quantification stage. Applicability of the method for studying highly hydrophobic substances is demonstrated by determining water solubility of anthracene and pyrene in the temperature range of 8.9-49.9 and 8.5-32.2 degrees C, respectively. The measured water solubilities are in good agreement with the best available literature data. The method has also been applied to the determination of water solubility of m-terphenyl, 9, 10-dihydrophenanthrene and guaiazulene, in the temperature range of 4.8-49.9, 4.8-25.0, and 4.5-29.9 degrees C, respectively. The uncertainty in the Sw values determined in this work ranged from 0.7% to 4.6%. The experimental water solubility data, as a function of temperature, are fitted to the equation In Sw = A + B/T; where Sw and T are given in mole fraction and Kelvin, respectively.     

Comparison of solubility databases used for HLW performance assessment

Elemental solubility limits are employed in many performance assessment studies of the disposal of high-level radioactive waste. A comparison of solubility databases used in a number of recent assessments from Canada, Finland, Japan, Sweden, Switzerland and the U.S.A. is presented. Despite similarities in the chemical conditions under which such solubilities are defined, there are very large ranges in the values selected for most elements (several orders of magnitude). In some cases, differences in solubilities can be attributed to differences in the thermodynamic databases used but, due to generally incomplete documentation, both of such databases and the criteria for data selection, detailed analysis of the reason for such discrepancies is precluded. A key factor, however, is the fairly subjective choice of the solid phase considered to be “solubility-limiting”. Procedures are recommended which would increase the transparency of solubility database compilation in future analyses.     

Prediction of seawater solubility of aromatic compounds

The salting-out effect by seawater constituents on the water solubilities of 11 aromatic compounds, anthracene, pyrene, phenanthrene, biphenyl, naphthalene, p-nitrotoluene, p-toluidine, o-nitrophenol, m-nitrophenol, p-nitrophenol and phenol was investigated. A best fit equation (r = 0.965) for the salting-out parameters, K, and distilled water solubilities, S_o, at 20°C was found to be K = ?0.0298 log S_o + 0.114. Seawater solubilities, S, predicted for solutions of ionic strength, I, using the equation log S = (0.0298 I + 1) log S_o ? 0.114 I were in agreement with observed values within 13 % (average 4.8 %) and there were no significant differences between values from the Pacific Ocean seawater and those from 35 o/oo NaCl solutions. It was concluded that dissolved organic matter in seawater had an insignificant effect for the test chemicals.     

Effect of calcite on Pb-doped solidified waste forms in leaching

The alkalinity of cementitious materials rectifies a low pH of leachant to be over 12 in leaching. The rapid change of leachant pH produces the remarked variation of solubility of heavy metals in the toxicity characteristic leaching procedure. The release of lead on cementitious solid waste forms in leaching was observed in the pH range of particularly 12. The release of lead is significant dependant on the changed values of leachant pH. The pH static leaching procedure (PSLP) was implemented for assessing a quantitative measurement of total potential leachability with the continuing addition of acidic leachant up to the point of no change of leachant pH. The release of lead on Pb-doped solidified waste forms (SWF), in the PSLP, was 27.0% of initial concentration at the maximum meq CH₃COOH (about 24.0) added to g dry solidified wastes. In this study, the immobilization effect of calcite on SWF was investigated in the acidic condition by the PSLP. Calcite additions to SWF make a good fixation efficiency of about 92%. Calcite addition abundantly provides the acid neutralization capacity to protect SWF from the attack of acid, with the marked development of hydrated minerals (mainly portlandite and C–S–H) in accordance with the accelerating effect of cement hydration.     

Biosurfactant-enhanced solubilization of NAPL mixtures

Remediation of nonaqueous phase liquids (NAPLs) by conventional pump-and-treat methods (i.e., water flushing) is generally considered to be ineffective due to low water solubilities of NAPLs and to mass-transfer constraints. Chemical flushing techniques, such as surfactant flushing, can greatly improve NAPL remediation primarily by increasing the apparent solubility of NAPL contaminants. NAPLs at hazardous waste sites are often complex mixtures. However, the equilibrium and nonequilibrium mass-transfer characteristics between NAPL mixtures and aqueous surfactant solutions are not well understood. This research investigates the equilibrium solubilization behavior of two- and three-component NAPL mixtures (containing akylbenzenes) in biosurfactant solutions. NAPL solubilization is found to be ideal in water (i.e., obeys Raoult's Law), while solubilization in biosurfactant solutions was observed to be nonideal. Specifically, the relatively hydrophobic compounds in the mixture experienced solubility enhancements that were greater than those predicted by ideal enhanced solubilization theory, while the solubility enhancements for the relatively hydrophilic compounds were less than predicted. The degree of nonideality is shown to be a nonlinear function of the NAPL-phase mole fraction. Empirical relationships based on the NAPL-phase mole fraction and/or micelle-aqueous partition coefficients measured in single-component NAPL systems are developed to estimate values for the multicomponent partition coefficients. Empirical relationships that incorporate both the NAPL-phase mole fraction and single-component partition coefficients yield much improved estimates for the multicomponent partition coefficient.     

Accumulation and elimination of C-PCBs by daphnia magna straus 1820

The accumulation of chlorinated biphenyls in shows a tendency to increase with decreasing water solubility. The depuration times of PCBs from daphnia depend on the temperature of the test water and possibly on the water solubility of the substance. The water solubilities of 2,2′-dichlorobiphenyl, 2,5,4′-trichlorobiphenyl, 2,4,6,2′-tetrachlorobiphenyl and 2,4,6,2′,4′-pentachlorobiphenyl have been determined using ¹⁴C-labelled substances.     

PTR-MS measurements and analysis of models for the calculation of Henry's law constants of monosulfides and disulfides

Sulfides are known for their strong odor impact even at very low concentrations. Here, we report Henry’s law constants (HLCs) measured at the nanomolar concentration range in water for monosulfides (dimethylsulfide, ethylmethylsulfide, diethylsulfide, allylmethylsulfide) and disulfides (dimethyldisulfide, diethylsulfide, dipropylsulfide) using a dynamic stripping technique coupled to Proton Transfer Reaction-Mass Spectrometry (PTR-MS). The experimental data were compared with literature values and to vapor/solubility calculations and their consistency was confirmed employing the extra-thermodynamic enthalpy-entropy compensation effect. Our experimental data are compatible with reported literature values, and they are typically lower than averaged experimental literature values by about 10%. Critical comparison with other freely available models (modeled vapor/solubility; group and bond additivity methods; Linear Solvation Energy Relationship; SPARC) was performed to validate their applicability to monosulfides and disulfides. Evaluation of theoretical models reveals a large deviation from our measured values by up to four times (in units of M atm⁻¹). Two group contribution models were adjusted in view of the new data, and HLCs for a list of sulfur compounds were calculated. Based on our findings we recommend the evaluation and adaption of theoretical models for monosulfides and disulfides to lower values of solubility and higher values of fugacity.