Do aerosols act as catalysts in the OH radical initiated atmospheric oxidation of volatile organic compounds?

Smog chamber/FTIR techniques were used to study the relative reactivity of OH radicals with methanol, ethanol, phenol, C₂H₄, C₂H₂, and p-xylene in 750 Torr of air diluent at 296±2 K. Experiments were performed with, and without, 500–8000 μg m⁻³ (4000–50 000 μm² cm⁻³ surface area per volume) of NaCl, (NH₄)₂SO₄ or NH₄NO₃ aerosol. In contrast to the recent findings of Oh and Andino (Atmospheric Environment 34 (2000) 2901, 36 (2002) 149; International Journal of Chemical Kinetics 33 (2001) 422) there was no discernable effect of aerosol on the rate of loss of the organic compounds via reaction with OH radicals. Gas kinetic theory arguments cast doubt upon the findings of Oh and Andino. The available data suggest that the answer to the title question is “No”. As part of this work the rate constants for reactions of OH radicals with methanol, ethanol, and phenol in 750 Torr of air at 296 K were determined to be: k_OH+CH3OH=(8.12±0.54)×10⁻¹³, k_OH+C2H5OH=(3.47±0.32)×10⁻¹² and k_OH+phenol=(3.27±0.31)×10⁻¹¹ cm³ molecule⁻¹ s⁻¹.     

Diffusion scrubber technique used for measurements of atmospheric ammonia

A diffusion scrubber (DS) was developed to measure trace levels of gaseous ammonia in ambient air. The sampling resolution time for this method is 10 min and the detection limit is estimated to be 0.01 ppbv. The response to the NI-I₃ concentrations is found to be dependent on the relative humidity in the ambient air and the temperature. The method is calibrated by using a diluted NH₃ cylinder gas, and the concentrations of the calibration gas were in the range 0.02–2 ppbv during the test. Sampling performed with the DS-method is compared to sampling performed by a filter pack and a continuous flow denuder (AMANDA). The DS-method shows good agreement with the continuous flow denuder and the filter pack.     

Packaging waste measurement—A key element in digital's total quality program

Measurement of packaging waste is a key element of the Total Quality Management program at Digital Equipment Corporation. This case study shows how the company uses measurement techniques to set priorities for which areas of packaging waste should be addressed first and to track improvements over time. To date, an 1,800-ton annual reduction in packaging waste has been achieved, with associated annual savings of $2.7 million.     

A conspicuous H<Subscript>2</Subscript>S-oxidizing microbial mat from a high-latitude Arctic fjord (Young Sound,NE Greenland)

A several centimeter thick, H₂S-oxidizing microbial mat was encountered in a high-latitude Arctic fjord. Microscopic investigations revealed that the mat contained numerous filamentous bacteria, and fluorescence in situ hybridization showed that the vast majority of these belonged to -Proteobacteria and that Thiothrix spp. was present. The mat grew on a layer of accumulated decaying macroalgae and was characterized by a complex three-dimensional structure consisting of numerous holes, voids and chimney-like structures. Microsensor measurements performed in situ and in a laboratory-established mesocosm showed a highly dynamic O₂, pH and H₂S distribution, especially around protruding structures of the mat. Detailed microsensor investigations documented that anoxic sulfidic water emerged trough the chimneys and indicated a microcirculation, replenishing the emerging water with oxygenated water in areas were the mat was absent. This governed an efficient advective exchange of solutes and presumably allowed the mat to grow to the extensive thickness of several centimeters.Communicated by M. Kühl, Helsingør     

Transformation products of 2-benzoxazolinone (BOA) in soil

Three degradation experiments were performed to examine the formation of transformation products from 2-benzoxazolinone (BOA) in different soil types and concentrations. In two experiments using BOA in low concentration (400 microgkg(-1)) only one unidentified transformation product was found, whereas in the degradation experiment in high concentration (400 mgkg(-1)) several metabolites occurred. Two of these metabolites, 2-amino-(3H)-phenoxazin-3-one (APO); and 2-acetylamino-(3H)-phenoxazin-3-one (AAPO) were synthesized to prove their identity. This is the first time that the successive formation of these types of compounds from BOA is shown in soil. A number of other APO related transformation products were detected and provisionally characterized. The formation of APO, which is a much more biologically active compound than BOA, and the concurrent formation of a number of other APO-related metabolites in soil underline the importance of performing transformation studies as part of the evaluation of the effect of allelochemicals on weeds and soil-borne diseases.     

Mantle buffering of the early oceans

Archean calcites and dolomites, if compared to their Phanerozoic counterparts, are enriched in Sr²⁺, Ba²⁺, Mn²⁺, Fe²⁺, depleted in ¹⁸O, (Na⁺), and contain mantle-like ⁸⁷Sr/⁸⁶Sr and, in associated S phases, mantle-like ³⁴S/³²S. This may be a consequence of massive seawater pumping through, and equilibration with, the coeval basaltic oceanic crust. The exponential decline of oceanic geothermal gradient in the course of terrestrial evolution led to a waning of this “mantle” flux and to the enhancement of the continental river discharge as the controlling factor of seawater composition; the major transition occurring probably during the late Archean — early Proterozoic time interval. Such evolution is consistent with the observed tectonic, sedimentological, geochemical and metallogenic secular patterns and may also provide an alternative, or complementary, inorganic explanation for the development of the post-Archean oxygenic atmosphere.