Measuring binding and speciation of hydrophobic organic chemicals at controlled freely dissolved concentrations and without phase separation

The binding and speciation of hydrophobic organic chemicals (HOCs) in aqueous solutions were determined by controlling chemical activity and measuring total concentrations. Passive dosing was applied to control chemical activities of HOCs in aqueous solutions by equilibrium partitioning from a poly(dimethylsiloxane) polymer preloaded with the chemicals. The HOC concentrations in the equilibrated solutions [C(solution(eq))] and water [C(water(eq))] were then measured. Free fractions of the HOCs were determined as C(water(eq))/C(solution(eq)), whereas enhanced capacities (E) of the solutions for HOCs were determined as C(solution(eq))/C(water(eq)). A mixture of polycyclic aromatic hydrocarbons served as model analytes, while humic acid, sodium dodecyl sulfate, hydroxypropyl-β-cyclodextrin, and NaCl served as model medium constituents. The enhanced capacities were plotted versus the concentrations of medium constituents, and simple linear regression provided precise partition ratios, salting out constants, and critical micelle concentrations. These parameters were generally in good agreement with published values obtained by solid phase microextraction and fluorescence quenching. The very good precision was indicated by the low relative standard errors for the partition ratios of 0.5-8%, equivalent to 0.002-0.03 log unit. This passive dosing approach allows binding and speciation of HOCs to be studied without any phase separation steps or mass balance assumptions.     

Equilibrium sampling through membranes of freely dissolved copper concentrations with selective hollow fiber membranes and the spectrophotometric detection of a metal stripping agent

A sensitive spectrophotometric method for the determination of freely dissolved copper concentrations in aqueous samples after preconcentration with hollow fiber membrane extraction has been developed. The method is based on the equilibrium sampling through a selective membrane into an acceptor solution containing 4-(pyridyl-2-azo)resorcinol (PAR), which serves as stripping agent and metal indicator. Negligible extraction of interferences and equilibrium enrichment of copper allowed for selective spectrophotometric determination of the Cu-PAR complex. Some important extraction parameters such as acceptor composition, shaking, equilibrium time, and sample volume were studied. The optimized methodology showed good linearity in the range of 5-100 microg/L, an enrichment factor of 93, good repeatability and reproducibility (RSDs < 6%, n = 6), and a detection limit of 4 microg/L. The cationic metals Ni2+, C(2+, Cd2+, Fe3+, Pb2+, Zn2+, and Mn2+ were shown not to interfere with the measurement of Cu2+. Measurements on samples containing mixtures of various ligands and cations were in good agreement with theoretically calculated concentrations, and the method was also applied to environmental samples. The developed technique requires less labor and less sophisticated equipment than conventional methods typically based on atomic absorption spectrometry or ICP.     

Direct determination of lead isotopes (206Pb, 207Pb, 208Pb) in arctic ice samples at picogram per gram levels using inductively coupled plasma-sector field MS coupled with a high-efficiency sample introduction system

Adopting strict cleanroom procedures, ice samples from the Canadian High Arctic have been analyzed for Pb concentrations and Pb isotopes (206Pb, 207Pb, 208Pb) using ICP-SMS. The detection limit for Pb (0.06 pg g(-1)) was approximately 2 orders of magnitude lower than the lowest concentration of Pb in the ice samples (range, 4.3-1660 pg g(-1); median, 45 pg g(-1)). Acidification of ice samples with high-purity HNO3 for stabilization purposes contributed only 0.004 pg of Pb g(-1), which is an insignificant source of Pb. Using a new sample introduction system consisting of a heated (140 degrees C) minicyclonic spray chamber and a Peltier cooled condenser (2 degrees C) and by replacing the conventional sample cone with a high-performance cone, signal intensities for Pb were increased by approximately 1 order of magnitude. Thus, it was possible not only to measure Pb isotope ratios directly using ICP-SMS but also to achieve reasonable precision (approximately 0.2%) at low picogram per gram concentrations of total Pb. This precision is comparable to that achievable by thermal ionization mass spectrometry at such low Pb concentrations, but the ICP-SMS requires much less sample volume (approximately 2 mL), needs no sample pretreatment, and therefore is considerably faster and less expensive than the conventional approach. Even though absolute Pb concentrations in two ice samples dating from 1974 and 1852 were very similar (9 and 6 pg g(-1)) their fundamentally different isotopic signature (206Pb/207Pb: 1.169 +/- 0.002 vs 1.147 +/- 0.003) clearly indicates different sources of Pb. The analytical procedures described here, therefore, offer great promise for fingerprinting the predominant sources of atmospheric Pb in polar snow and ice.     

Tertiary treatment of textile wastewater with combined media biological aerated filter (CMBAF) at different hydraulic loadings and dissolved oxygen concentrations

An up-flow biological aerated filter packed with two layers media was employed for tertiary treatment of textile wastewater secondary effluent. Under steady state conditions, good performance of the reactor was achieved and the average COD, NH(4)(+)-N and total nitrogen (TN) in the effluent were 31, 2 and 8mg/L, respectively. For a fixed dissolved oxygen (DO) concentration, an increase of hydraulic loading resulted in a decrease in substrate removal. With the increase of hydraulic loadings from 0.13 to 0.78m(3)/(m(2)h), the removal efficiencies of COD, NH(4)(+)-N and TN all decreased, which dropped from 52 to 38%, from 90 to 68% and from 45 to 33%, respectively. In addition, the results also confirmed that the increase of COD and NH(4)(+)-N removal efficiencies resulted from the increase of DO concentrations, but this variation trend was not observed for TN removal. With the increase of DO concentrations from 2.4 to 6.1mg/L, the removal efficiencies of COD and NH(4)(+)-N were 39-53% and 64-88%, whenas TN removal efficiencies increased from 39 to 42% and then dropped to 35%.     

Preconcentration of U(VI), Th(IV), and REE(III) from nitric acid solutions using carbon nanotubes modified with bis(dioctylphosphinylmethyl)phosphinic acid

The extraction of microamounts of U(VI) and Th(IV) from HNO₃ solutions in the form of complexes with bis(dioctylphosphinylmethyl)phenylphosphinic acid was studied. The stoichiometry of the extractable complexes was studied, and the influence of the extractant structure on the efficiency and selectivity of the U(VI) and Th(IV) extraction was examined. U(VI), Th(IV), and REE(III) can be preconcentrated from nitric acid solutions with a complexing sorbent prepared by noncovalent immobilization of bis(dioctylphosphinylmethyl) phosphinic acid on the surface of carbon nanotubes.     

Performance prediction of a specific wear rate in epoxy nanocomposites with various composition content of polytetrafluoroethylen (PTFE), graphite,short carbon fibers (CF) and nano-TiO2 using adaptive neuro-fuzzy inference system (ANFIS)

Specific wear rate of composite materials plays a significant role in industry. The processes to measure it are both time and cost consuming. It is essential to suggest a modeling method to predict and analyze the effectiveness of parameters of specific wear rate. Nowadays, computational methods such as Artificial Neural Network (ANN), Fuzzy Inference System (FIS) and adaptive neuro-fuzzy inference system (ANFIS) are mainly considered as applicable tools from modeling point of view. ANFIS present integrate performance of neural network (NN) and fuzzy system (FS). Present paper investigates performance prediction of a specific wear rate of epoxy composites with various composition using ANFIS. The obtained results showed that ANFIS is a powerful tool in modeling specific wear rate. The obtained mean of squared error (MSE) for testing sets in present paper obtained 0.0071.