A critical step in determining soil-to-atmosphere nitrous oxide (N2 O) exchange using non-steady-state chambers is converting collected gas concentration versus time data to flux values using a flux calculation (FC) scheme. It is well documented that different FC schemes can produce different flux estimates for a given set of data. Available schemes differ in their theoretical basis, computational requirements, and performance in terms of both accuracy and precision. Nonlinear schemes tend to increase accuracy compared with linear regression but can also decrease precision. The chamber bias correction method can be used if soil physical data are available, but this introduces additional sources of error. Here, the essential theoretical and practical aspects of the most commonly used FC schemes are described as a basis for their selection and use. A gold standard approach for application and selection of FC schemes is presented, as well as alternative approaches based on availability of soil physical property data and intensity of sample collection during each chamber deployment. Additional criteria for scheme selection are provided in the form of an error analysis tool that quantifies performance with respect to both accuracy and precision based on chamber dimensions and sampling duration, soil properties, and analytical measurement precision. Example error analyses are presented for hypothetical conditions illustrating how such analysis can be used to guide FC scheme selection, estimate bias, and inform design of chambers and sampling regimes.

Concentrations of polybrominated diphenyl ethers (PBDEs), pesticides, polychlorinated biphenyls (PCBs), and polycyclic aromatic hydrocarbons were measured in 136 fish from 14 remote lakes in 8 western U.S. National Parks/Preserves between 2003 and 2005 and compared to human and wildlife contaminant health thresholds. A sensitive (median detection limit--18 pg/g wet weight), efficient (61% recovery at 8 ng/g), reproducible (4.1% relative standard deviation (RSD)), and accurate (7% deviation from standard reference material (SRM)) analytical method was developed and validated for these analyses. Concentrations of PCBs, hexachlorobenzene, hexachlorocyclohexanes, DDTs, and chlordanes in western U.S. fish were comparable to or lower than mountain fish recently collected from Europe, Canada, and Asia. Dieldrin and PBDE concentrations were higher than recent measurements in mountain fish and Pacific Ocean salmon. Concentrations of most contaminants in western U.S. fish were 1-6 orders of magnitude below calculated recreational fishing contaminant health thresholds. However, lake average contaminant concentrations in fish exceeded subsistence fishing cancer thresholds in 8 of 14 lakes and wildlife contaminant health thresholds for piscivorous birds in 1 of 14 lakes. These results indicate that atmospherically deposited organic contaminants can accumulate in high elevation fish, reaching concentrations relevant to human and wildlife health.

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