Probing the role of the hyper-reactive histidine residue of arginase.

Rat liver arginase (arginase I) is potently inactivated by diethyl pyrocarbonate, with a second-order rate constant of 113M(-1)s(-1) for the inactivation process at pH 7.0, 25 degrees C. Partial protection from inactivation is provided by the product of the reaction, l-ornithine, while nearly complete protection is afforded by the inhibitor pair, l-ornithine and borate. The role of H141 has been probed by mutagenesis, chemical modulation, and X-ray diffraction. The hyper-reactivity of H141 towards diethyl pyrocarbonate can be explained by its proximity to E277. A proton shuttling role for H141 is supported by its conformational mobility observed among the known arginase structures. H141 is proposed to serve as an acid/base catalyst, deprotonating the metal-bridging water molecule to generate the metal-bridging hydroxide nucleophile, and by protonating the amino group of the product to facilitate its departure.

Current-use and legacy pesticide history in the Austfonna Ice Cap, Svalbard, Norway.

The Svalbard archipelago in arctic Norway receives considerable semivolatile organic contaminant (SOC) inputs from the atmosphere. To measure the history of net SOC accumulation there, we analyzed the upper 40 m of an ice core from Austfonna, the largest ice cap in Eurasia, for several legacy organochlorine (OC) compounds and current-use pesticides (CUPs) including organophosphorus (OP), triazine, dinitroaniline, and chloroacetamide compounds. Five OP compounds (chlorpyrifos, terbufos, diazinon, methyl parathion, and fenitrothion), two OCs (methoxychlor and dieldrin), and metolachlor--an herbicide--had historical profiles in the core. The highest OC concentration observed was aldrin (69.0 ng L(-1)) in the surface sample (1992-1998). The most concentrated OP was dimethoate (87.0 ng L(-1)) between 1986 and 1992. The surface sample also had highest concentrations of pendimethalin (herbicide, 18.6 ng L(-1)) and flutriafol, the lone observed fungicide (9.6 ng L(-1)). The apparent atmospheric persistence of CUPs likely results from little or no oxidation by OH* during the dark polar winter and in spring. Long-range atmospheric pesticide transport to Svalbard from Eurasia is influenced by the positive state of the North Atlantic Oscillation Index since 1980 and also by occasional fast-moving summer air masses from northern Eurasian croplands.

Variable air temperature response of gas-phase atmospheric polychlorinated biphenyls near a former manufacturing facility.

Many investigations of gas-phase atmospheric PCB show a strong relationship between concentration and air temperature, especially near PCB sources. Comparative gas-phase atmospheric PCB trends during an annual temperature regime at two sites near a former PCB manufacturing plant and nearby PCB landfills in Anniston, AL, indicate a departure from this trend. The Mars Hill sampling site, located closest to the plant and landfills, shows an annual average sigmaPCB concentration of 27 ng m(-3) (ranging from 8.7 to 82 ng m(-3)) three times the average at Carter, 1.5 km away (9 ng m(-3), ranging from 1.1 to 39). However, total PCB and congener concentrations vary more with air temperature at Carter where PCB are evaporating from surfaces during warmer weather. The slopes of the Clausius-Clapeyron plots of 18 of the most concentrated congeners representing dichloro- through heptachlorobiphenyl homologues are significantly higher at the Carter site. While some of the atmospheric PCB at Mars Hill is derived from ground surface evaporation, the source of much of it apparently is the material buried in the landfills, which has different thermal properties than surface materials and is not in equilibrium with air temperature.