Analysis of munitions constituents in groundwater using a field-portable GC-MS.

The use of munitions constituents (MCs) at military installations can produce soil and groundwater contamination that requires periodic monitoring even after training or manufacturing activities have ceased. Traditional groundwater monitoring methods require large volumes of aqueous samples (e.g., 2-4 L) to be shipped under chain of custody, to fixed laboratories for analysis. The samples must also be packed on ice and shielded from light to minimize degradation that may occur during transport and storage. The laboratory's turn-around time for sample analysis and reporting can be as long as 45 d. This process hinders the reporting of data to customers in a timely manner; yields data that are not necessarily representative of current site conditions owing to the lag time between sample collection and reporting; and incurs significant shipping costs for samples. The current work compares a field portable Gas Chromatograph-Mass Spectrometer (GC-MS) for analysis of MCs on-site with traditional laboratory-based analysis using High Performance Liquid Chromatography with UV absorption detection. The field method provides near real-time (within ~1 h of sampling) concentrations of MCs in groundwater samples. Mass spectrometry provides reliable confirmation of MCs and a means to identify unknown compounds that are potential false positives for methods with UV and other non-selective detectors.

Mobility and sorption of bis-2-chloroethyl ether in an aquifer material.

Active treatment of BCEE (bis-2-chloroethyl ether) is being currently performed in the on-site Cohansey Aquifer at the Lipari Superfund Site. Remediation of BCEE in the underlying Kirkwood aquifer is being considered, necessitating investigations of BCEE geochemistry in aquifer material from the site. It is currently unknown to what extent BCEE is present in the dissolved, sorbed, or free-product phase in the Kirkwood Sand aquifer material. A series of partition coefficient sorption, column leach, and column loading tests were conducted to determine BCEE sorption to, and mobility in, the Kirkwood Sand aquifer material. The leach studies indicated that up to 50% of BCEE spiked (as free-phase product) onto two aquifer material column designs could be leached in approximately 18h, due to the high aqueous solubility of BCEE. Dissolved BCEE concentrations then began to plateau as sorption reactions hindered further leaching, resulting in up to 80% removal after 48h. Column loading and batch sorption experiments suggest that BCEE mobility is limited by sorption rather than solubility factors. Tracer tests in both column loading and batch sorption tests indicate sorption hinders leaching of BCEE from the Kirkwood Sand material.

Comparison of standard and reaction cell inductively coupled plasma mass spectrometry in the determination of chromium and selenium species by HPLC-ICP-MS.

Elemental speciation is becoming a common analytical procedure for geochemical investigations. The various redox species of environmentally relevant metals can have vastly different biogeochemical properties, including sorption, solubility, bioavailability, and toxicity. The use of high performance liquid chromatography (HPLC) coupled to elemental specific detectors, such as inductively coupled plasma mass spectrometry (ICP-MS), has become one of the most important speciation methods employed. This is due to the separation versatility of HPLC and the sensitive and selective detection capabilities of ICP-MS. The current study compares standard mode ICP-MS to recently developed reaction cell (RC) ICP-MS, which has the ability to remove or reduce many common polyatomic interferences that can limit the ability of ICP-MS to quantitate certain analytes in complex matrices. Determination of chromium and selenium redox species is achieved using ion-exchange chromatography with elemental detection by standard and RC-ICP-MS, using various chromium and selenium isotopes. In this study, method performance and detection limits for the various permutations of the method (isotope monitored or ICP-MS detection mode) were found to be comparable and generally less than 1 microg L(-1). The method was tested on synthetic laboratory samples, surface water, groundwater, and municipal tap water matrices.

Physical, photophysical and structural properties of ruthenium(II) complexes containing a tetradentate bipyridine ligand.

The focus of this report is the synthesis and properties of two new analogues of ruthenium(ii) tris-bipyridine, a monomer and dimer. The complexes contain the ligand 6,6'-(ethan-1,2-diyl)bis-2,2'-bipyridine (O-bpy) which contains two bipyridine units bridged in the 6,6' positions by an ethylene bridge. Crystal structures of the two complexes formulated as [Ru(bpy)(O-bpy)](PF6)2 and [(Ru(bpy)2)2(O-bpy)](PF6)4 reveal structures of lower symmetry than D3 which affects the electronic properties of the complexes as substantiated by density functional theory (DFT) and time dependent density functional theory (TDDFT) calculations. The HOMO lies largely on the ruthenium center; the LUMO spreads its electron density over the bipyridine units, but not equally in the mixed O-bpy-bpy complexes. Calculated Vis/UV spectra using TDDFT methods agree with experimental spectra. The lowest lying triplet excited state for [Ru(bpy)(O-bpy)](PF6)2 is 3MC resulting in a low emission quantum yield and a large chloride ion photosubstitution quantum yield.

Computational study of iron(II) systems containing ligands with nitrogen heterocyclic groups.

Density functional theory (DFT) calculations show the higher energy HOMO (highest occupied molecular orbital) orbitals of four iron(II) diimine complexes are metal centered and the lower energy LUMO (lowest unoccupied molecular orbitals) are ligand centered. The energy of the orbitals correlates with electrochemical redox potentials of the complexes. Time-dependent density functional theory (TDDFT) calculations reveal ligand centered (LC) and metal-to-ligand charge transfer (MLCT) at higher energy than experimentally observed. TDDFT calculations also reveal the presence of d-d transitions which are buried under the MLCT and LC transitions. The difference in chemical and photophysical behavior of the iron complexes compared to that of their ruthenium analogues is also addressed.