Processes involved in uptake and release of nitrogen dioxide from soil and building stones into the atmosphere

Atmospheric NO₂ was taken up by samples of various soils and building stones. The NO₂ uptake rate constants were highest in soil samples taken during the summer months. However, the NO₂ uptake rate constants of the soils and building stones were not significantly correlated with any of the following variables: moisture, pH, ammonium, nitrite, or nitrate. NO₂ uptake by soil and stone was not abolished by autoclaving indicating a chemical uptake process. NO₂ uptake by acidic and air-dry soils and stones resulted in nearly stoichiometric reduction of NO₂ to NO. This reduction was enhanced by the addition of ferrous iron and was further enhanced by incubation under 1 ppmv SO₂. The results suggest that NO₂ reduction may be coupled to oxidation of ferrous to ferric iron which may be reduced again by atmospheric SO₂ thus regenerating the ferrous iron content of the soil or stone. Conversion of NO₂ to NO was not observed in neutral or/and moist soils and stones. NO₂ was also taken up by purified and sterilized quartz sand moistend with water. This uptake was enhanced by addition of humic material but not by addition of bacteria which both had been extracted from genuine soil. Under most conditions, only uptake but no release of NO₂ was observed. However, NO₂ was released in air-dry soils that were heated to 45–65°C, or in ammonium-fertilized soil or stone that was drying up at room temperature. Under the latter conditions mimicking field practice, the NO₂ release reached rates that were similar to the NO release rates.     

Estimates of animal methane emissions

The enteric methane emissions into the atmospheric annually from domestic animals total about 77 Tg. Another 10 to 14 Tg are likely released from animal manure disposal systems. About 95% of global animal enteric methane is from ruminants, a consequence of their large populations, body size and appetites combined with the extensive degree of anaerobic microbial fermentation occurring in their gut. Accurate methane estimates are particularly sensitive to cattle and buffalo census numbers and estimated diet consumption. Since consumption is largely unknown and must be predicted, accuracy is limited often by the information required, i.e., distribution of animals by class, weight and productivity. Fraction of the diet lost as enteric methane mostly falls into the range of 5.5–6.5% of gross energy intake for the world's cattle, sheep and goats. Manure methane emissions are heavily influenced by fraction of disposal by anaerobic lagoon. Non-ruminants, i.e., swine, become major contributors to these emissions.     

A view from the countryside

Guest Editorial

A view from the countryside     

Interlaboratory evaluation of endotoxin analyses in agricultural dusts--comparison of LAL assay and mass spectrometry

Endotoxin exposure is associated with wheeze and asthma morbidity, while early life exposure may reduce risk of allergy and asthma. Unfortunately, it is difficult to compare endotoxin results from different laboratories and environments. We undertook this study to determine if lipopolysaccharide (LPS) extraction efficiency could account for differences among laboratories. We generated and collected aerosols from chicken and swine barns, and corn processing. We randomly allocated side-by-side filter samples to five laboratories for Limulus assay of endotoxin. Lyophilized aliquots of filter extracts were analyzed for 3-hydroxy fatty acids (3-OHFAs) as a marker of LPS using gas chromatography-mass spectrometry. There were significant differences in endotoxin assay and GC-MS (LPS) results between laboratories for all dust types (p < 0.01). Patterns of differences between labs varied by dust type. Relationships between assay and GC/MS results also depended on dust type. The percentages of individual 3-OHFA chain lengths varied across labs (p < 0.0001) suggesting that each lab recovered a different fraction of the LPS available. The presence of large amounts of particle associated LPS and absence of a freezing thawing cycle were associated with lower correlations between LPS and bioactivity, consistent with an absence of Limulus response to cell-bound endotoxin. These data suggest that extraction methods affect endotoxin measurements. The LAL methods may be most suitable when comparing exposures within similar environments; GC-MS offers additional information helpful in optimizing sample treatment and extraction. GC-MS may be of use when comparing across heterogeneous environments and should be considered for inclusion in future studies of human health outcomes.     

Changes in levels of organochlorines in woodcock wings from 1971 to 1975

Wings from woodcock (Philohela minor) were first monitored for organochlorine pesticides and polychlorinated biphenyls (PCBs) in the eastern U.S. in 1971. Regional differences in these compounds were clearly demonstrated and baseline residue levels were obtained for later comparisons. An expanded sampling of wings in 1972 revealed that residues in wings of adult woodcock may differ significantly from those in immatures, and that residues of several important agricultural insecticides and PCBs had declined significantly. More extensive sampling was undertaken in 1975 to determine if changes in residue levels had taken place in the intervening years. PCBs, mirex, and heptachlor epoxide increased significantly between 1972 and 1975 in adult woodcock wings. In immature woodcock wings mirex, dieldrin, and PCBs increased significantly between 1972 and 1975, but DDT residues decreased significantly.     

Ambient air concentrations of PCDDs,PCDFs, coplanar PCBs,and PAHs at the Mississippi Sandhill Crane National Wildlife Refuge,Jackson County,Mississippi

Our objective was to determine the levels of selected airborne contaminants in ambient air at the Mississippi Sandhill Crane National Wildlife Refuge, Mississippi, that might be affecting the health of endangered cranes living there. Two high-volume air samplers were operated at separate locations on the Refuge during May–September 1991. The sampling media were micro-quartz filters in combination with polyurethane foam plugs. Composite bimonthly samples from each station were analyzed for polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs), coplanar polychlorinated biphenyls (PCBs), and polycyclic aromatic hydrocarbons (PAHs). Overall, residue concentrations were low. The toxic PCDD isomer 2,3,7,8-tetra-CDD was not detected, nor was penta-CDD. There was no difference (P>0.05) in residue concentrations between stations or over time and meteorological parameters were not correlated with residue concentrations. Because contaminant levels and patterns may differ seasonally, we recommend that air samples collected during winter months also be analyzed for these same chemical groups.     

24 h diffusive sampling of toxic VOCs in air onto Carbopack X solid adsorbent followed by thermal desorption/GC/MS analysis-laboratory studies

Diffusive sampling of a mixture of 42 volatile organic compounds (VOCs) in humidified, purified air onto the solid adsorbent Carbopack X was evaluated under controlled laboratory conditions. The evaluation included variations in sample air temperature, relative humidity and ozone concentration. Linearity of samples with loading was examined both for a constant concentration with time varied up to 24 h and for different concentrations over 24 h. Reverse diffusion and its increase with accumulation of sample were determined for all compounds. Tubes were examined for blank levels, change of blanks with storage time, and variability of blanks. Method detection limits were determined based on seven replicate samples. Based on this evaluation, 27 VOCs were selected for quantitative monitoring in the concentration range from approximately 0.1 to 4 ppbv. Comparison results of active and diffusive samples taken over 24 h and under the same simulated ambient conditions at a constant 2 ppbv were interpreted to estimate the effective diffusive sampling rates (ml min(-1)) and their uncertainties and to calculate the corresponding diffusive uptake rates (ng ppmv(-1) min(-1)).     

Measurement of atmospheric concentrations of common household pesticides: A pilot study

Air concentrations of 28 of the most commonly used household pesticides were measured inside nine homes in Jacksonville, Florida, and compared with corresponding outdoor levels. The households selected were sorted into three categories according to the degree of pesticide indoor usage. Personal air monitoring was also performed on one resident of each household by means of a portable sampler, which was kept with the person at all times. Five of the pesticides were found in the air inside of the majority of the homes at concentrations as high as 15 gm^–3 (average concentrations, 12 ngm^–3 to 2.4 gm^–3). Indoor levels were generally one to two ordrrs of magnitude higher than surrounding outdoor air levels and personal air measurements were within ± 50% of corresponding indoor values. All samples were collected over 24-hr periods on polyurethane foam and analyzed by capillary colum gas chromatography with mass spectrometric and/or electron capture detection.