Exploratory study on modification of sludge-based activated carbon for nutrient removal from stormwater runoff.

Nutrients (P, N) in stormwater runoff are a major cause of eutrophication and algal blooms. A promising solution to this problem is to amend the rain garden growing medium (RGGM) with sewage sludge-based activated carbon (SBAC). To optimize the SBAC production process, different metals, pyrolysis conditions (temperature, heating time, carrier gas), and post-treatments were explored. When pyrolyzed at 400 °C for two hours, Zn-activated SBAC removed up to 41% of PO4-P (initial concentration of 1 mg/L) and 72% of NO3-N (initial concentration of 2 mg/L), at a dose of 1 g sorbent/L of nutrient-spiked distilled water. When the same dosage was applied to stormwater leachate made from RGGM and spiked with nutrients, the removal efficiencies were reduced to 20% for PO4-P and 38% for NO3-N. These reductions were probably caused by competition from other leachate components. Increasing the dosage to 3 g/L leachate improved PO4-P removal to 31% and NO3-N to 72%, while also resulting in the removal of 46% of total organic carbon. The major energy cost of producing such sorbents is estimated to be ∼$0.76 CAD/kg SBAC.

Selecting reliable physicochemical properties of perfluoroalkyl and polyfluoroalkyl substances (PFASs) based on molecular descriptors.

Perfluoroalkyl and polyfluoroalkyl substances (PFASs) are a class of global environmental pollutants whose environmental fate and adverse effects are of concern. However, data on the basic physicochemical properties of PFASs are scarce. To fill part of the data gaps, improved quantitative structure -property relationship (QSPR) models for prediction of PFAS properties are developed based on the correlation between reported experimental data and molecular descriptors (fluorine number, molar volume and total surface area). Properties include vapor pressure, aqueous solubility, octanol/water partition coefficient, air/water partition coefficient and octanol/air partition coefficient. The fluorine number-descriptor model is based on good statistical results. However, this model cannot distinguish among PFASs with the same number of attached fluorines. Setting aside the fluorine number-descriptor models, models based on molar volume are statistically better than those based on total surface area.Therefore, The PFAS data obtained from the molar volume descriptor model are more reliable than from fluorine number and total surface area descriptor models. These results are intended to improve the understanding of the behavior and fate of PFASs in the environment, at contaminated sites and during remediation.

Filling the gap: estimating physicochemical properties of the full array of polybrominated diphenyl ethers (PBDEs).

Physicochemical properties of PBDE congeners are important for modeling their transport, but data are often missing. The quantitative structure-property relationship (QSPR) approach is utilized to fill this gap. Individual research groups often report piecemeal properties through experimental measurements or estimation techniques, but these data seldom satisfy fundamental thermodynamic relationships because of errors. The data then lack internal consistency and cannot be used directly in environmental modeling. This paper critically reviews published experimental data to select the best QSPR models, which are then extended to all 209 PBDE congeners. Properties include aqueous solubility, vapor pressure, Henry's law constant, octanol-water partition coefficient and octanol-air partition coefficient. Their values are next adjusted to satisfy fundamental thermodynamic equations. The resulting values then take advantage of all measurements and provide quick references for modeling and PBDE-contaminated site assessment and remediation. PCBs are also compared with respect to their properties and estimation methods.

Compositional effects in Ru, Pd, Pt, and Rh-doped mesoporous tantalum oxide catalysts for ammonia synthesis.

A series of early metal-promoted Ru-, Pd-, Pt-, and Rh-doped mesoporous tantalum oxide catalysts were synthesized using a variety of dopant ratios and dopant precursors, and the effects of these parameters on the catalytic activity of NH3 synthesis from H2 and N2 were explored. Previous studies on this system supported an unprecedented mechanism in which N-N cleavage occurred at the Ta sites rather than on Ru. The results of the present study showed, for all systems, that Ba is a better promoter than Cs or La and that the nitrate is a superior precursor for Ba than the isopropoxide or the hydroxide. 15N-labeling studies showed that residual nitrate functions as the major ammonia source in the first hour but that it does not account for the ammonia produced after the nitrate is completely consumed. Ru3(CO)12 proved to be a better Ru precursor than RuCl(3).3H2O, and an almost linear increase in activity with increasing Ru loading level was observed at 350 degrees C (623 K). However, at 175 degrees C (448 K), the increase in Ru had no effect on the reaction rate. Pd functioned with comparable rates to Ru, while Pt and Rh functioned far less efficiently. The surprising activities for the Pd-doped catalysts, coupled with XPS evidence for low-valent Ta in this catalyst system, support a mechanism in which cleavage of the N-N triple bond occurs on Ta rather than the precious metal because the Ea value for N-N cleavage on Pd is 2.5 times greater than that for Ru, and the 9.3 kJ mol-1 Ea value measured previously for the Ru system suggests that N-N cleavage cannot occur at the Ru surface.

Electroactive mesoporous tantalum oxide catalysts for nitrogen activation and ammonia synthesis.

A new mesoporous Ta oxide catalyst for conversion of dinitrogen to ammonia shows strong evidence for a novel mechanism involving low valent Ta on the surface, supporting recent work in organometallic chemistry using low valent early transition metals for dinitrogen cleavage.