Mercury mobilization and episodic stream acidification during snowmelt: Role of hydrologic flow paths, source areas, and supply of dissolved organic carbon

Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/95317/1/wrcr11826.pd

Taking the pulse of snowmelt: in situ sensors reveal seasonal, event and diurnal patterns of nitrate and dissolved organic matter variability in an upland forest stream

Highly resolved time series data are useful to accurately identify the timing, rate, and magnitude of solute transport in streams during hydrologically dynamic periods such as snowmelt. We used in situ optical sensors for nitrate (NO3 −) and chromophoric dissolved organic matter fluorescence (FDOM) to measure surface water concentrations at 30 min intervals over the snowmelt period (March 21–May 13, 2009) at a 40.5 hectare forested watershed at Sleepers River, Vermont. We also collected discrete samples for laboratory absorbance and fluorescence as well as δ18O–NO3 − isotopes to help interpret the drivers of variable NO3 − and FDOM concentrations measured in situ. In situ data revealed seasonal, event and diurnal patterns associated with hydrological and biogeochemical processes regulating stream NO3 − and FDOM concentrations. An observed decrease in NO3 − concentrations after peak snowmelt runoff and muted response to spring rainfall was consistent with the flushing of a limited supply of NO3 − (mainly from nitrification) from source areas in surficial soils. Stream FDOM concentrations were coupled with flow throughout the study period, suggesting a strong hydrologic control on DOM concentrations in the stream. However, higher FDOM concentrations per unit streamflow after snowmelt likely reflected a greater hydraulic connectivity of the stream to leachable DOM sources in upland soils. We also observed diurnal NO3 − variability of 1–2 μmol l−1 after snowpack ablation, presumably due to in-stream uptake prior to leafout. A comparison of NO3 − and dissolved organic carbon yields (DOC, measured by FDOM proxy) calculated from weekly discrete samples and in situ data sub-sampled daily resulted in small to moderate differences over the entire study period (−4 to 1% for NO3 − and −3 to −14% for DOC), but resulted in much larger differences for daily yields (−66 to +27% for NO3 − and −88 to +47% for DOC, respectively). Despite challenges inherent in in situ sensor deployments in harsh seasonal conditions, these data provide important insights into processes controlling NO3 − and FDOM in streams, and will be critical for evaluating the effects of climate change on snowmelt delivery to downstream ecosystems

Measuring soil frost depth in forest ecosystems with ground penetrating radar

Soil frost depth in forest ecosystems can be variable and depends largely on early winter air temperaturesand the amount and timing of snowfall. A thorough evaluation of ecological responses to seasonallyfrozen ground is hampered by our inability to adequately characterize the frequency, depth, durationand intensity of soil frost events. We evaluated the use of ground penetrating radar to nondestructivelydelineate soil frost under field conditions in three forest ecosystems. Soil frost depth was monitoredperiodically using a 900 MHz antenna in South Burlington, Vermont (SB), Sleepers River Watershed,North Danville, Vermont (SR) and Hubbard Brook Experimental Forest, New Hampshire (HBEF) duringwinter 2011–2012 on plots with snow and cleared of snow. GPR-based estimates were compared to datafrom thermistors and frost tubes, which estimate soil frost depth with a color indicating solution. In theabsence of snow, frost was initially detected at a depth of 8–10 cm. Dry snow up to 35 cm deep, enhancednear-surface frost detection, raising the minimum frost detection depth to 4–5 cm. The most favorablesurface conditions for GPR detection were bare soil or shallow dry snow where frost had penetrated to theminimum detectable depth. Unfavorable conditions included: standing water on frozen soil, wet snow,thawed surface soils and deep snow pack. Both SB and SR were suitable for frost detection most of thewinter, while HBEF was not. Tree roots were detected as point reflections and were readily discriminatedfrom continuous frost reflections. The bias of GPR frost depth measurements relative to thermistors wassite dependent averaging 0.1 cm at SB and 1.1 cm at SR, and was not significantly different than zero. Whenseparated by snow manipulation treatment at SR, overestimation of soil frost depth (5.5 cm) occurredon plots cleared of snow and underestimation (−1.5 cm) occurred on plots with snow. Despite somelimitations posed by site and surface suitability, GPR could be useful for adding a spatial component topre-installed soil frost monitoring networks

Spatial patterns of soil nitrification and nitrate export from forested headwaters in the northeastern United States

Nitrogen export from small forested watersheds is known to be affected by N deposition but with high regional variability. We studied 10 headwater catchments in the northeastern United States across a gradient of N deposition (5.4 - 9.4 kg ha-1 yr-1) to determine if soil nitrification rates could explain differences in stream water NO 3- export. Average annual export of two years (October 2002 through September 2004) varied from 0.1 kg NO3--N ha-1 yr-1 at Cone Pond watershed in New Hampshire to 5.1 kg ha-1 yr-1 at Buck Creek South in the western Adirondack Mountains of New York. Potential net nitrification rates and relative nitrification (fraction of inorganic N as NO3-) were measured in Oa or A soil horizons at 21-130 sampling points throughout each watershed. Stream NO3- export was positively related to nitrification rates (r2 = 0.34, p = 0.04) and the relative nitrification (r2 = 0.37, p = 0.04). These relationships were much improved by restricting consideration to the 6 watersheds with a higher number of rate measurements (59-130) taken in transects parallel to the streams (r 2 of 0.84 and 0.70 for the nitrification rate and relative nitrification, respectively). Potential nitrification rates were also a better predictor of NO3- export when data were limited to either the 6 sampling points closest to the watershed outlet (r2 = 0.75) or sampling points \u3c250 m from the watershed outlet (r2 = 0.68). The basal area of conifer species at the sampling plots was negatively related to NO3- export. These spatial relationships found here suggest a strong influence of near-stream and near-watershed-outlet soils on measured stream NO3- export. Copyright 2012 by the American Geophysical Union

Tropical river suspended sediment and solute dynamics in storms during an extreme drought

Droughts, which can strongly affect both hydrologic and biogeochemical systems, are projected to become more prevalent in the tropics in the future. We assessed the effects of an extreme drought during 2015 on stream water composition in the Luquillo Mountains of Puerto Rico. We demonstrated that drought base flow in the months leading up to the study was sourced from trade-wind orographic rainfall, suggesting a resistance to the effects of an otherwise extreme drought. In two catchments (Mameyes and Icacos), we sampled a series of four rewetting events that partially alleviated the drought. We collected and analyzed dissolved constituents (major cations and anions, organic carbon, and nitrogen) and suspended sediment (inorganic and organic matter (particulate organic carbon and particulate nitrogen)). The rivers appeared to be resistant to extreme drought, recovering quickly upon rewetting, as (1) the concentration-discharge (C-Q) relationships deviated little from the long-term patterns; (2) “new water” dominated streamflow during the latter events; (3) suspended sediment sources had accumulated in the channel during the drought flushed out during the initial events; and (4) the severity of the drought, as measured by the US drought monitor, was reduced dramatically after the rewetting events. Through this interdisciplinary study, we were able to investigate the impact of extreme drought through rewetting events on the river biogeochemistry

Soil Aggregates as a Source of Dissolved Organic Carbon to Streams: An Experimental Study on the Effect of Solution Chemistry on Water Extractable Carbon

Over the past two decades, headwater streams of the northern hemisphere have shown increased amounts of dissolved organic carbon (DOC), coinciding with decreased acid deposition. The exact nature of the mechanistic link between precipitation composition and stream water DOC is still widely debated in the literature. We hypothesize that soil aggregates are the main source of stream water DOC and that DOC release is greater in organic rich, riparian soils vs. hillslope soils. To test these hypotheses, we collected soils from two main landscape positions (hillslope and riparian zones) from the acid-impacted Sleepers River Research Watershed in northeastern Vermont. We performed aqueous soil extracts with solutions of different ionic strength (IS) and composition to simulate changes in soil solution. We monitored dynamic changes in soil particle size, aggregate architecture and composition, leachate DOC concentrations, dissolved organic matter (DOM) characteristics by fluorescence spectroscopy and trends in bioavailability. In low IS solutions, extractable DOC concentrations were significantly higher, particle size (by laser diffraction) was significantly smaller and organic material was separated from mineral particles in scanning electron microscope observations. Furthermore, higher DOC concentrations were found in Na+ compared to Ca2+ solutions of the same IS. These effects are attributed to aggregate dispersion due to expanding diffuse double layers in decreased IS solutions and to decreased bridging by divalent cations. Landscape position impacted quality but not quantity of released DOC. Overall, these results indicate that soil aggregates might be one important link between Critical Zone inputs (i.e., precipitation) and exports in streams

Deposition of mercury in forests across a montane elevation gradient: Elevational and seasonal patterns in methylmercury inputs and production

Global mercury contamination largely results from direct primary atmospheric and secondary legacy emissions, which can be deposited to ecosystems, converted to methylmercury, and bioaccumulated along food chains. We examined organic horizon soil samples collected across an elevational gradient on Whiteface Mountain in the Adirondack region of New York State, USA to determine spatial patterns in methylmercury concentrations across a forested montane landscape. We found that soil methylmercury concentrations were highest in the midelevation coniferous zone (0.39 ± 0.07 ng/g) compared to the higher elevation alpine zone (0.28 ± 0.04 ng/g) and particularly the lower elevation deciduous zone (0.17 ± 0.02 ng/g), while the percent of total mercury as methylmercury in soils decreased with elevation. We also found a seasonal pattern in soil methylmercury concentrations, with peak methylmercury values occurring in July. Given elevational patterns in temperature and bioavailable total mercury (derived from mineralization of soil organic matter), soil methylmercury concentrations appear to be driven by soil processing of ionic Hg, as opposed to atmospheric deposition of methylmercury. These methylmercury results are consistent with spatial patterns of mercury concentrations in songbird species observed from other studies, suggesting that future declines in mercury emissions could be important for reducing exposure of mercury to montane avian species.Key PointsTotal mercury and methylmercury concentrations and fluxes are examined across an elevational gradient on an Adirondack, New York mountainMethylmercury concentrations across the elevational gradient are greatest in midelevation coniferous zonesSoil methylmercury concentrations are driven by the internal processing of mercury, rather than external inputs of methylmercuryPlain Language SummaryOnce mercury is emitted into the atmosphere by anthropogenic sources, it can be deposited onto the Earth’s surface. This mercury can then be converted to its toxic form of methylmercury by microbes in the soil and can accumulate in birds, altering physiology, behavior, and reproduction. We examined soils from Whiteface Mountain in the Adirondack region of New York State, USA to determine patterns in the production of methylmercury. We found that methylmercury in soils was highest in the mid‐elevation coniferous forests of the mountain and that the concentration appeared to be driven by soil microbes rather than direct deposition of mercury from the atmosphere. The finding of peak methylmercury at mid‐elevations was consistent with previous studies showing peak bird mercury concentrations at the same elevation. Thus, reductions in methylmercury concentrations in these forests is important to reducing bird mercury concentrations.Peer Reviewedhttps://deepblue.lib.umich.edu/bitstream/2027.42/138300/1/jgrg20832_am.pdfhttps://deepblue.lib.umich.edu/bitstream/2027.42/138300/2/jgrg20832-sup-0001-2016JG003721-SI.pdfhttps://deepblue.lib.umich.edu/bitstream/2027.42/138300/3/jgrg20832.pd

Does stream water composition at sleepers river in vermont reflect dynamic changes in soils during recovery from acidification?

Stream water pH and composition are widely used to monitor ongoing recovery from the deposition of strong anthropogenic acids in many forested headwater catchments in the northeastern United States. However, stream water composition is a function of highly complex and coupled processes, flowpaths, and variations in soil and bedrock composition. Spatial heterogeneity is especially pronounced in headwater catchments with steep topography, potentially limiting stream water composition as an indicator of changes in critical zone (CZ) dynamics during system recovery. To investigate the link between catchment characteristics, landscape position, and stream water composition we used long-term data (1991–2015) from the Sleepers River Research Watershed (SRRW) in northeastern Vermont. We investigated trends with time in stream water and trends with time, depth, and landscape position (upslope, midslope, and riparian zone) in groundwater (GW) and soil solution. We further determined soil elemental composition and mineralogy on archived (1996) and modern (2017) soil samples to assess changes in composition with time. SRRW is inherently well-buffered by calcite in bedrock and till, but soils had become acidified and are now recovering from acidification. Although base cations, especially Ca, decrease progressively with time in GW, riparian soils have become more enriched in Ca, due to a mixture of lateral and vertical transfers. At the same time stream water Ca fluxes increased over the past two decades, likely due to the leaching of (transient) legacy Ca from riparian zones and increased water fluxes. The stream water response therefore reflects the dynamic changes in soil chemistry, flow routing and water inputs

Recent advances in understanding and measurement of mercury in the environment: Terrestrial Hg cycling

This review documents recent advances in terrestrial mercury cycling. Terrestrial mercury (Hg) research has matured in some areas, and is developing rapidly in others. We summarize the state of the science circa 2010 as a starting point, and then present the advances during the last decade in three areas: land use, sulfate deposition, and climate change. The advances are presented in the framework of three Hg "gateways" to the terrestrial environment: inputs from the atmosphere, uptake in food, and run off with surface water. Among the most notable advances:The Arctic has emerged as a hotbed of Hg cycling, with high stream fluxes and large stores of Hg poised for release from permafrost with rapid high-latitude warming.The bi-directional exchange of Hg between the atmosphere and terrestrial surfaces is better understood, thanks largely to interpretation from Hg isotopes; the latest estimates place land surface Hg re-emission lower than previously thought.Artisanal gold mining is now thought responsible for over half the global stream flux of Hg.There is evidence that decreasing inputs ofHg to ecosystems may bring recovery sooner than expected, despite large ecosystem stores of legacy Hg.Freshly deposited Hg is more likely than stored Hg to methylate and be incorporated in rice.Topography and hydrological connectivity have emerged as master variables for explaining the disparate response of THg and MeHg to forest harvest and other land disturbance.These and other advances reported here are of value in evaluating the effectiveness of theMinamata Convention on reducing environmental Hg exposure to humans and wildlife. (C) 2020 The Authors. Published by Elsevier B.V

A novel protamine variant reversal of heparin anticoagulation in human blood in vitro

AbstractPurpose: Protamine reversal of heparin anticoagulation during cardiovascular surgery may cause severe hypotension and pulmonary hypertension. A novel protamine variant, [+18RGD], has been developed that effectively reverses heparin anticoagulation without toxicity in canine experiments. Heretofore, human studies have not been undertaken. This investigation hypothesized that [+18RGD] would effectively reverse heparin anticoagulation of human blood in vitro. Methods: Fifty patients who underwent anticoagulation therapy during vascular surgery had blood sampled at baseline and 30 minutes after receiving heparin (150 IU/kg). Activated clotting times were used to define specific quantities of [+18RGD] or protamine necessary to completely reverse heparin anticoagulation in the blood sample of each patient. These defined amounts of [+18RGD] or protamine were then administered to the heparinized blood samples, and percent reversals of activated partial thromboplastin time, thrombin clotting time, and antifactor Xa/IIa levels were determined. In addition, platelet aggregation assays, as well as platelet and white blood cell counts were performed. Results: [+18RGD] and protamine were equivalent in reversing heparin as assessed by thrombin clotting time, antifactor Xa, antifactor IIa levels, and white blood cell changes. [+18RGD], when compared with protamine, was superior in this regard, as assessed by activated partial thromboplastin time (94.5 ± 1.0 vs 86.5 ± 1.3%δ, respectively; p < 0.001) and platelet declines (–3.9 ± 2.9 vs –12.8 ± 3.4 per mm3, respectively; p = 0.048). Platelet aggregation was also decreased for [+18RGD] compared with protamine (23.6 ± 1.5 vs 28.5 ± 1.9%, respectively; p = 0.048). Conclusions: [+18RGD] was as effective as protamine for in vitro reversal of heparin anticoagulation by most coagulation assays, was statistically more effective at reversal than protamine by aPTT assay, and was associated with lesser platelet reductions than protamine. [+18RGD], if less toxic than protamine in human beings, would allow for effective clinical reversal of heparin anticoagulation. (J Vasc Surg 1997;26:1043-8.