Ann Chalmers

The effect of frozen soil on snowmelt runoff at Sleepers River, Vermont†

Soil frost depth has been monitored at the Sleepers River Research Watershed in northeastern Vermont since 1984. Soil frost develops every winter, particularly in open fields, but its depth varies greatly from year to year in inverse relation to snow depth. During the 15 years of record at a benchmark mid-elevation open site, the annual maximum frost depth varied from 70 to 390 mm. We empirically tested the hypothesis that frozen soil prevents infiltration and recharge, thereby causing an increased runoff ratio (streamflow/(rain + snowmelt)) during the snowmelt hydrograph rise and a decreased runoff ratio during snowmelt recession. The hypothesis was not supported at the 111 km 2 W-5 catchment; there was no significant correlation of the runoff ratio with the seasonal maximum frost depth for either the pre-peak or post-peak period. In an analysis of four events, however, the presence of frost promoted a large and somewhat quicker response to rainfall relative to the no-frost condition, although snow cover caused a much greater time-to-peak regardless of frost status. For six years of flow and frost depth measured at the 59 ha agricultural basin W-2, the hypothesis appeared to be supported. The enhancement of runoff due to soil frost is evident on small plots and in extreme events, such as rain on frozen snow-free soil. In the northeastern USA rind eastern Canada, the effect is often masked in larger catchments by several confounding factors, including storage of meltwater in the snowpack, variability in snowmelt timing due to elevational and aspect differences, interspersed forested land where frost may be absent, and the timing of soil thawing relative to the runoff peak.

Comparison of total mercury and methylmercury cycling at five sites using the small watershed approach

The small watershed approach is well-suited but underutilized in mercury research. We applied the small watershed approach to investigate total mercury (THg) and methylmercury (MeHg) dynamics in streamwater at the five diverse forested headwater catchments of the US Geological Survey Water, Energy, and Biogeochemical Budgets (WEBB) program. At all sites, baseflow THg was generally less than 1ng L(-1) and MeHg was less than 0.2ng L(-1). THg and MeHg concentrations increased with streamflow, so export was primarily episodic. At three sites, THg and MeHg concentration and export were dominated by the particulate fraction in association with POC at high flows, with maximum THg (MeHg) concentrations of 94 (2.56)ng L(-1) at Sleepers River, Vermont; 112 (0.75)ng L(-1) at Rio Icacos, Puerto Rico; and 55 (0.80)ng L(-1) at Panola Mt., Georgia. Filtered (<0.7microm) THg increased more modestly with flow in association with the hydrophobic acid fraction (HPOA) of DOC, with maximum filtered THg concentrations near 5ng L(-1) at both Sleepers and Icacos. At Andrews Creek, Colorado, THg export was also episodic but was dominated by filtered THg, as POC concentrations were low. MeHg typically tracked THg so that each site had a fairly constant MeHg/THg ratio, which ranged from near zero at Andrews to 15% at the low-relief, groundwater-dominated Allequash Creek, Wisconsin. Allequash was the only site with filtered MeHg consistently above detection, and the filtered fraction dominated both THg and MeHg. Relative to inputs in wet deposition, watershed retention of THg (minus any subsequent volatilization) was 96.6% at Allequash, 60% at Sleepers, and 83% at Andrews. Icacos had a net export of THg, possibly due to historic gold mining or frequent disturbance from landslides. Quantification and interpretation of Hg dynamics was facilitated by the small watershed approach with emphasis on event sampling.

Ultraviolet absorbance as a proxy for total dissolved mercury in streams

Stream water samples were collected over a range of hydrologic and seasonal conditions at three forested watersheds in the northeastern USA. Samples were analyzed for dissolved total mercury (THg(d)), DOC concentration and DOC composition, and UV(254) absorbance across the three sites over different seasons and flow conditions. Pooling data from all sites, we found a strong positive correlation of THg(d) to DOC (r(2)=0.87), but progressively stronger correlations of THg(d) with the hydrophobic acid fraction (HPOA) of DOC (r(2)=0.91) and with UV(254) absorbance (r(2)=0.92). The strength of the UV(254) absorbance-THg(d) relationship suggests that optical properties associated with dissolved organic matter may be excellent proxies for THg(d) concentration in these streams. Ease of sample collection and analysis, the potential application of in-situ optical sensors, and the possibility for intensive monitoring over the hydrograph make this an effective, inexpensive approach to estimate THg(d) flux in drainage waters.

Mercury trends in fish from rivers and lakes in the United States, 1969-2005

A national dataset on concentrations of mercury in fish, compiled mainly from state and federal monitoring programs, was used to evaluate trends in mercury (Hg) in fish from US rivers and lakes. Trends were analyzed on data aggregated by site and by state, using samples of the same fish species and tissue type, and using fish of similar lengths. Site-based trends were evaluated from 1969 to 2005, but focused on a subset of the data from 1969 to 1987. Data aggregated by state were used to evaluate trends in fish Hg concentrations from 1988 to 2005. In addition, the most recent Hg fish data (1996–2005) were compared to wet Hg deposition data from the Mercury Deposition Network (MDN) over the same period. Downward trends in Hg concentrations in fish from data collected during 1969–1987 exceeded upward trends by a ratio of 6 to 1. Declining Hg accumulation rates in sediment and peat cores reported by many studies during the 1970s and 1980s correspond with the period when the most downward trends in fish Hg concentrations occurred. Downward Hg trends in both sediment cores and fish were also consistent with the implementation of stricter regulatory controls of direct releases of Hg to the atmosphere and surface waters during the same period. The southeastern USA had more upward Hg trends in fish than other regions for both site and state aggregated data. Upward Hg trends in fish from the southeastern USA were associated with increases in wet deposition in the region and may be attributed to a greater influence of global atmospheric Hg emissions in the southeastern USA. No significant trends were found in 62% of the fish species from six states from 1996 to 2005. A lack of Hg trends in fish in the more recent data was consistent with the lack of trends in wet Hg deposition at MDN sites and with relatively constant global emissions during the same time period. Although few significant trends were observed in the more recent Hg concentrations in fish, it is anticipated that Hg concentrations in fish will respond to changes in atmospheric Hg deposition, however, the magnitude and timing of the response is uncertain.

Concentrations of hormones, pharmaceuticals and other micropollutants in groundwater affected by septic systems in New England and New York

Septic-system discharges can be an important source of micropollutants (including pharmaceuticals and endocrine active compounds) to adjacent groundwater and surface water systems. Groundwater samples were collected from well networks tapping glacial till in New England (NE) and sandy surficial aquifer New York (NY) during one sampling round in 2011. The NE network assesses the effect of a single large septic system that receives discharge from an extended health care facility for the elderly. The NY network assesses the effect of many small septic systems used seasonally on a densely populated portion of Fire Island. The data collected from these two networks indicate that hydrogeologic and demographic factors affect micropollutant concentrations in these systems. The highest micropollutant concentrations from the NE network were present in samples collected from below the leach beds and in a well downgradient of the leach beds. Total concentrations for personal care/domestic use compounds, pharmaceutical compounds and plasticizer compounds generally ranged from 1 to over 20 μg/L in the NE network samples. High tris(2-butoxyethyl phosphate) plasticizer concentrations in wells beneath and downgradient of the leach beds (>20 μg/L) may reflect the presence of this compound in cleaning agents at the extended health-care facility. The highest micropollutant concentrations for the NY network were present in the shoreline wells and reflect groundwater that is most affected by septic system discharges. One of the shoreline wells had personal care/domestic use, pharmaceutical, and plasticizer concentrations ranging from 0.4 to 5.7 μg/L. Estradiol equivalency quotient concentrations were also highest in a shoreline well sample (3.1 ng/L). Most micropollutant concentrations increase with increasing specific conductance and total nitrogen concentrations for shoreline well samples. These findings suggest that septic systems serving institutional settings and densely populated areas in coastal settings may be locally important sources of micropollutants to adjacent aquifer and marine systems.

Streamwater fluxes of total mercury and methylmercury into and out of Lake Champlain.

From 2000 to 2004, we sampled for total mercury (THg) and methylmercury (MeHg) in inlet streams to Lake Champlain, targeting high flow periods to capture increases in THg and MeHg concentrations with increasing flow. We used these data to model stream THg and MeHg fluxes for Water Years 2001 through 2009. In this mountainous forested basin with a high watershed-to-lake area ratio of 18, fluvial export from the terrestrial watershed was the dominant source of Hg to the lake. Unfiltered THg and MeHg fluxes were dominated by the particulate fraction; about 40% of stream THg was in the filtered (<0.4 μm) phase. THg flux from the watershed to the lake averaged 2.37 μg m(-2) yr(-1), or about 13% of atmospheric Hg wet and dry deposition to the basin. THg export from the lake represented only about 3% of atmospheric Hg input to the basin.

Influence of a chlor-alkali superfund site on mercury bioaccumulation in periphyton and low-trophic level fauna

In Berlin, New Hampshire, USA, the Androscoggin River flows adjacent to a former chlor-alkali facility that is a US Environmental Protection Agency Superfund site and source of mercury (Hg) to the river. The present study was conducted to determine the fate and bioaccumulation of methylmercury (MeHg) to lower trophic-level taxa in the river. Surface sediment directly adjacent to the source showed significantly elevated MeHg (10-40× increase, mean ± standard deviation [SD]: 20.1 ± 24.8 ng g(-1) dry wt) and total mercury (THg; 10-30× increase, mean ± SD: 2045 ± 2669 ng g(-1) dry wt) compared with all other reaches, with sediment THg and MeHg from downstream reaches elevated (3-7× on average) relative to the reference (THg mean ± SD: 33.5 ± 9.33 ng g(-1) dry wt; MeHg mean ± SD: 0.52 ± 0.21 ng g(-1) dry wt). Water column THg concentrations adjacent to the point source for both particulate (0.23 ng L(-1)) and dissolved (0.76 ng L(-1)) fractions were 5-fold higher than at the reference sites, and 2-fold to 5-fold higher than downstream. Methylmercury production potential of periphyton material was highest (2-9 ng g(-1) d(-1) dry wt) adjacent to the Superfund site; other reaches were close to or below reporting limits (0. 1 ng g(-1) d(-1) dry wt). Total Hg and MeHg bioaccumulation in fauna was variable across sites and taxa, with no clear spatial patterns downstream of the contamination source. Crayfish, mayflies, and shiners showed a weak positive relationship with porewater MeHg concentration.

Effects of urbanization on mercury deposition and accumulation in New England

We compare total mercury (HgT) loading and methylmercury (MeHg) accumulation in streams and lakes from an urbanized area (Boston, Massachusetts) to rural regions of southern New Hampshire and Maine. The maximum HgT loading, as indicated by HgT atmospheric deposition, HgT emissions, and sediment HgT concentrations, did not coincide with maximum MeHg concentrations in fish. Urbanized ecosystems were areas of high HgT loading but had low MeHg concentrations in fish. Controls on MeHg production and accumulation appeared to be related primarily to HgT loading in undeveloped areas, while ecosystem sensitivity to MeHg formation appeared to be more important in regulating accumulation of MeHg in the urban area.