Comparison of mercury mass loading in streams to atmospheric deposition in watersheds of Western North America: Evidence for non-atmospheric mercury sources.

Annual stream loads of mercury (Hg) and inputs of wet and dry atmospheric Hg deposition to the landscape were investigated in watersheds of the Western United States and the Canadian-Alaskan Arctic. Mercury concentration and discharge data from flow gauging stations were used to compute annual mass loads with regression models. Measured wet and modeled dry deposition were compared to annual stream loads to compute ratios of Hg stream load to total Hg atmospheric deposition. Watershed land uses or cover included mining, undeveloped, urbanized, and mixed. Of 27 watersheds that were investigated, 15 had some degree of mining, either of Hg or precious metals (gold or silver), where Hg was used in the amalgamation process. Stream loads in excess of annual Hg atmospheric deposition (ratio>1) were observed in watersheds containing Hg mines and in relatively small and medium-sized watersheds with gold or silver mines, however, larger watersheds containing gold or silver mines, some of which also contain large dams that trap sediment, were sometimes associated with lower load ratios (<0.2). In the non-Arctic regions, watersheds with natural vegetation tended to have low ratios of stream load to Hg deposition (<0.1), whereas urbanized areas had higher ratios (0.34-1.0) because of impervious surfaces. This indicated that, in ecosystems with natural vegetation, Hg is retained in the soil and may be transported subsequently to streams as a result of erosion or in association with dissolved organic carbon. Arctic watersheds (Mackenzie and Yukon Rivers) had a relatively elevated ratio of stream load to atmospheric deposition (0.27 and 0.74), possibly because of melting glaciers or permafrost releasing previously stored Hg to the streams. Overall, our research highlights the important role of watershed characteristics in determining whether a landscape is a net source of Hg or a net sink of atmospheric Hg.

Pesticides in Mississippi air and rain: a comparison between 1995 and 2007.

A variety of current-use pesticides were determined in weekly composite air and rain samples collected during the 1995 and 2007 growing seasons in the Mississippi Delta (MS, USA) agricultural region. Similar sampling and analytical methods allowed for direct comparison of results. Decreased overall pesticide use in 2007 relative to 1995 generally resulted in decreased detection frequencies in air and rain; observed concentration ranges were similar between years, however, even though the 1995 sampling site was 500 m from active fields whereas the 2007 sampling site was within 3 m of a field. Mean concentrations of detections were sometimes greater in 2007 than in 1995, but the median values were often lower. Seven compounds in 1995 and 5 in 2007 were detected in ≥50% of both air and rain samples. Atrazine, metolachlor, and propanil were detected in ≥50% of the air and rain samples in both years. Glyphosate and its degradation product, aminomethyl-phosphonic acid (AMPA), were detected in ≥75% of air and rain samples in 2007 but were not measured in 1995. The 1995 seasonal wet depositional flux was dominated by methyl parathion (88%) and was >4.5 times the 2007 flux. Total herbicide flux in 2007 was slightly greater than in 1995 and was dominated by glyphosate. Malathion, methyl parathion, and degradation products made up most of the 2007 nonherbicide flux.

Volatilization of polycyclic aromatic hydrocarbons from coal-tar-sealed pavement.

Coal-tar-based pavement sealants, a major source of PAHs to urban water bodies, are a potential source of volatile PAHs to the atmosphere. An initial assessment of volatilization of PAHs from coal-tar-sealed pavement is presented here in which we measured summertime gas-phase PAH concentrations 0.03 m and 1.28 m above the pavement surface of seven sealed (six with coal-tar-based sealant and one with asphalt-based sealant) and three unsealed (two asphalt and one concrete) parking lots in central Texas. PAHs also were measured in parking lot dust. The geometric mean concentration of the sum of eight frequently detected PAHs (ΣPAH(8)) in the 0.03-m samples above sealed lots (1320 ng m(-3)) during the hottest part of the day was 20 times greater than that above unsealed lots (66.5 ng m(-3)). The geometric mean concentration in the 1.28-m samples above sealed lots (138 ng m(-3)) was five times greater than above unsealed lots (26.0 ng m(-3)). Estimated PAH flux from the sealed lots was 60 times greater than that from unsealed lots (geometric means of 88 and 1.4 µg m(-2) h(-1), respectively). Although the data set presented here is small, the much higher estimated fluxes from sealed pavement than from unsealed pavement indicate that coal-tar-based sealants are emitting PAHs to urban air at high rates compared to other paved surfaces.

Pesticides in rain in four agricultural watersheds in the United States.

Rainfall samples were collected during the 2003 and 2004 growing seasons at four agricultural locales across the USA in Maryland, Indiana, Nebraska, and California. The samples were analyzed for 21 insecticides, 18 herbicides, three fungicides, and 40 pesticide degradates. Data from all sites combined show that 7 of the 10 most frequently detected pesticides were herbicides, with atrazine (70%) and metolachlor (83%) detected at every site. Dacthal, acetochlor, simazine, alachlor, and pendimethalin were detected in more than 50% of the samples. Chlorpyrifos, carbaryl, and diazinon were the only insecticides among the 10 most frequently detected compounds. Of the remaining pesticide parent compounds, 18 were detected in fewer than 30% of the samples, and 13 were not detected. The most frequently detected degradates were deethylatrazine; the oxygen analogs (OAs) of the organophosphorus insecticides chlorpyrifos, diazinon, and malathion; and 1-napthol (degradate of carbaryl). Deethylatrazine was detected in nearly 70% of the samples collected in Maryland, Indiana, and Nebraska but was detected only once in California. The OAs of chlorpyrifos and diazinon were detected primarily in California. Degradates of the acetanilide herbicides were rarely detected in rain, indicating that they are not formed in the atmosphere or readily volatilized from soils. Herbicides accounted for 91 to 98% of the total pesticide mass deposited by rain except in California, where insecticides accounted for 61% in 2004. The mass of pesticides deposited by rainfall was estimated to be less than 2% of the total applied in these agricultural areas.

A regional atmospheric fate and transport model for atrazine. 2. Evaluation.

The Community Multiscale Air Quality (CMAQ) modeling system has been adapted to simulate the regional fate and transport of atrazine. Model modifications and simulations spanning April to mid-July 1995 are described in a previous paper. CMAQ results for atrazine concentrations in air and rainfall are evaluated against field observations taken along the Mississippi River and the shores of Lake Michigan in 1995. CMAQ results agree within 10% of published annual wet deposition load estimates for Lake Michigan and predicted annual dry deposition lies within published error bounds. Comparisons of weekly observed and predicted air and rainfall concentrations along the Mississippi River yield order-of-magnitude differences. Precipitation weighting of concentrations in rainfall good agreement for seasonal time frames. Weekly ambient gas form concentrations tend to be overpredicted by the CMAQ and semivolatile particulate fractons are underpredicted. Uncertainty in CMAQ predictions of air and rainfall concentrations for atrazine appear to derive primarily from uncertainty in emissions estimates, simulated precipitation, and spatial scale.