Quantifying the spatial and temporal variation of ground-level ozone in the rural Annapolis Valley, Nova Scotia, Canada using nitrite-impregnated passive samplers.

The spatiotemporal variability of ground-level ozone (GLO) in the rural Annapolis Valley, Nova Scotia was investigated between August 29, 2006, and September 28, 2007, using Ogawa nitrite-impregnated passive diffusion samplers (PS). A total of 353 PS measurements were made at 17 ambient and 1 indoor locations over 18 sampling periods ranging from 2 to 4 weeks. The calculated PS detection limit was 0.8 +/- 0.02 parts per billion by volume (ppbv), for a 14-day sampling period. Duplicate samplers were routinely deployed at three sites and these showed excellent agreement (R2 values of 0.88 [n = 11], 0.95 [n = 17], and 0.96 [n = 17]), giving an overall PS imprecision value of 5.4%. Comparisons between PS and automated continuous ozone analyzers at three sites also demonstrated excellent agreement with R2 values of 0.82, 0.95, and 0.95, and gradients not significantly different from unity. The minimum, maximum, and mean (+/- 1 sigma) ambient annual GLO concentrations observed were 7.7, 72.1, and 34.3 +/- 10.1 ppbv, respectively. The three highest sampling sites had significantly greater (P = 0.032) GLO concentrations than three Valley floor sites, and there was a strong correlation between concentration and elevation (R2 = 0.82). Multivariate models were used to parameterize the observed GLO concentrations in terms of prevailing meteorology at an elevated site found at Kejimkujik National Park and also at a site on the Valley floor. Validation of the multivariate models using 30 months of historical meteorological data at these sites yielded R2 values of 0.70 (elevated site) and 0.61 (Valley floor). The mean indoor ozone concentration was 5.4 +/- 3.3 ppbv and related to ambient GLO concentration by the equation: indoor = 0.34 x ambient - 5.07. This study has demonstrated the suitability of PS for long-term studies of GLO over a wide geographic area and the effect of topographical and meteorological influences on GLO in this region.

Abiotic production of methylmercury by solar radiation.

Methylmercury [MeHg(I) in the aerobic surface water of lakes is thought to be rapidly degraded, but contrary to expectations, we show that MeHg(I) concentrations often increase during sunlight hours or remain relatively constant. We hypothesized that there were water column processes that generated MeHg(I) and that these processes were linked to dissolved organic matter (DOM) and solar radiation. A 2-day diurnal pattern of MeHg(I) in surface water with corresponding bottled controls was assessed for two contrasting lakes in Kejimikujik, Nova Scotia, Canada. Following this study, a tangential ultrafiltrator was used to size-fractionate and generate a concentration gradient of DOM from four different lakes located near Lac Berthelot, Quebec, Canada. The watersheds of two of these lakes were not substantially logged whereas the other two had been extensively logged. Different size fractions of DOM as well as different concentrations of DOM were exposed to sunlight for varying periods of time. We observed that, in Keiimikujik, the concentration of MeHg(I) in surface waters peaked in the early afternoon. Furthermore, this also occurred in bottled water for one of the lakes, Puzzle, eliminating the possibility that in-lake mixing played a role in this pattern. The formation of MeHg(I) was found to be dependent on the size fraction and amount of DOM present in the water. Specifically, DOM less than 5 kDa or between 30 and 300 kDa generated MeHg(I) when exposed to sunlight, but larger fractions did not. Furthermore, although data are limited, we found that water from lakes with logged watersheds generated MeHg(I) when exposed to sunlight, whereas water from lakes with low levels of logging in the undisturbed watersheds did not. Our results demonstrate that MeHg(I) can be formed in freshwaters of certain lakes in response to solar radiation. This photoproduction of MeHg(I) is dependent on DOM concentrations and type, with the importance of water chemistry not yet clear. The significance of this process to freshwater lakes and the mechanism responsible for MeHg(I) photoproduction is still unclear, but a correction in the conventional wisdom that MeHg(I) is rapidly photodegraded is timely.

Continuous analysis of dissolved gaseous mercury (DGM) and mercury flux in two freshwater lakes in Kejimkujik Park, Nova Scotia: evaluating mercury flux models with quantitative data.

Diurnal patterns for dissolved gaseous mercury (DGM) concentration, mercury flux, several water variables (pH, oxidation reduction potential (ORP), water temperature), and meteorological variables (wind speed, air temperature, % relative humidity, solar radiation) were measured in two lakes with contrasting dissolved organic carbon (DOC) concentrations in Kejimkujik Park, Nova Scotia. A continuous analysis system made it possible to measure quick changes in DGM over time. Consistently higher DGM concentrations were found in the high DOC lake as compared to the low DOC lake. An examination of current mercury flux models using this quantitative data indicated some good correlations between the date and predicted flux (r ranging from 0.27 to 0.83) but generally poor fit (standard deviation of residuals ranging from 0.97 to 3.39). Cross-correlation analysis indicated that DGM dynamics changed in response to solar radiation with lag-times of 65 and 90 min. This relationship with solar radiation was used to develop new predictive models of DGM and mercury flux dynamics for each lake. We suggest that a generalized approach using time-shifted solar radiation date to predict DGM can be incorporated into existing mercury flux models. It is clear from the work presented that DOC and wind speed may also play important roles in DGM and mercury flux dynamics, and these roles have not been adequately accounted for in current predictive models.