Andrew L. Macumber

Organic matter control on the distribution of arsenic in lake sediments impacted by ~ 65 years of gold ore processing in subarctic Canada

Climate change is profoundly affecting seasonality, biological productivity, and hydrology in high northern latitudes. In sensitive subarctic environments exploitation of mineral resources led to contamination and it is not known how cumulative effects of resource extraction and climate warming will impact ecosystems. Gold mines near Yellowknife, Northwest Territories, subarctic Canada, operated from 1938 to 2004 and released >20,000t of arsenic trioxide (As2O3) to the environment through stack emissions. This release resulted in elevated arsenic concentrations in lake surface waters and sediments relative to Canadian drinking water standards and guidelines for the protection of aquatic life. A meta-analytical approach is used to better understand controls on As distribution in lake sediments within a 30-km radius of historic mineral processing activities. Arsenic concentrations in the near-surface sediments range from 5mg·kg-1 to over 10,000mg·kg-1 (median 81mg·kg-1; n=105). Distance and direction from the historic roaster stack are significantly (p<0.05) related to sedimentary As concentration, with highest As concentrations in sediments within 11km and lakes located downwind. Synchrotron-based μXRF and μXRD confirm the persistence of As2O3 in near surface sediments of two lakes. Labile organic matter (S1) is significantly (p<0.05) related to As and S concentrations in sediments and this relationship is greatest in lakes within 11km from the mine. These relations are interpreted to reflect labile organic matter acting as a substrate for microbial growth and mediation of authigenic precipitation of As-sulphides in lakes close to the historic mine where As concentrations are highest. Continued climate warming is expected to lead to increased biological productivity and changes in organic geochemistry of lake sediments that are likely to play an important role in the mobility and fate of As in aquatic ecosystems.

Geochemistry of lakes across ecozones in the Northwest Territories and implications for the distribution of arsenic in the Yellowknife region. Part 1.

We obtained near total element geochemistry on 211 near-surface sediment samples from lakes along a transect across the Western Interior Platform to the central portion of the Slave Geological Province with a focus near the City of Yellowknife, Northwest Territories, to document regional concentrations of arsenic (As) and other elements in lake sediments. Concentrations of major and trace elements, including elements of potential human and ecological concern (As, Cd, Cr, Cu, Pb, Zn), were extracted from sediments using a modified aqua regia digestion. Concentrations of As exceed Canadian federal guidelines for the protection of aquatic life in most of the lakes sampled in the Slave Geological Province. Seventy one percent (n=149) of all sediment samples contain As concentrations higher than the Canadian Council of Ministers of the Environment (CCME) Interim Freshwater Sediment Quality Guideline of 5.9 mg/kg and 54% (n=114) of the samples contain As concentrations that exceed the CCME Probable Effect Level of 17 mg/kg. Sediments with the highest As concentrations are from lakes near the City of Yellowknife and likely reflect a combination of contamination associated with past industrial activity and geogenic input from mineralized bedrock and derived surficial materials (median As concentration 107.9 mg/kg, range 6.30->10,000+, n=95). Arsenic concentrations in lake sediments sampled elsewhere in the central Northwest Territories are lower (Ingraham Trail, median As concentration 10.6 mg/kg, range 1.9-101.6, n=27; Tibbitt to Contwoyto Winter Road, median As concentration 7.9 mg/kg, 0.3-101.4, n=52; Western Interior Platform, median As concentration 1.1 mg/kg, 0.1-7.1, n=37). Based on our data and a review of existing literature, background As concentration in lake sediments appear to ~25 mg/kg for the Yellowknife region, and lower for other regions in the central NWT. Other elements (Cr, Cu, Pb, Zn) are below sediment quality guidelines in the majority of lake sediments sampled.

Sequential sample reservoirs for Itrax-XRF analysis of discrete samples

AbstractGeochemical analysis of sediment samples can be used to characterize between- and within-lake variability and provide insights into lake chemistry, depositional processes and contamination sources. The number of samples for geochemical studies is restricted by cost, sample volume required, and the destructive nature of inductively coupled plasma mass spectrometry, instrumental neutron activation analysis, or wavelength dispersive x-ray fluorescence. Core scanners that incorporate energy dispersive x-ray fluorescence spectrometry, such as the Cox Itrax-XRF core scanner, have high through-put and can be used to produce high-quality geochemical datasets at low cost without destroying sample material. Here we describe a new analysis vessel that enables rapid, non-destructive Itrax-XRF analysis of discrete sediment samples.

Reconstruction of Holocene hydroclimatic variability in subarctic treeline lakes using lake sediment grain-size end-members:

Current climate trends are expected to result in the northward expansion of the subarctic treeline leading to changes in vegetation cover and permafrost distribution, as they did during the Holocene Climate Optimum when the treeline was 150 km north of its current position. The impacts of these changes on the region’s hydrology are still poorly understood. The grain-size distributions of treeline lake sediments provide an important proxy related to spring melt conditions that can be used to reconstruct hydroclimatic variability. End-member mixing analysis was used to model depositional end-members in 55 modern lake sediment samples and two sediment cores spanning the mid- to late Holocene collected from above and below the treeline in the central Northwest Territories, Canada. Cold climatic intervals (e.g. ‘Dark Ages Cold Period’, ‘Little Ice Age’) were characterised by an increase in the very coarse silt and the fine sand end-members. This was interpreted to be a response to degradation of vegetation cover and/or permafrost development. We observed increases in fine and coarse silt end-members during warmer climatic intervals (e.g. Medieval Climate Anomaly) and over the past c. 300 yr BP. This pattern is probably the result of extended melt seasons, with greater losses to evaporation and increased infiltration. The most pronounced palaeo-hydroclimatological change over the past c. 8000 yr BP was the abrupt increase in a very coarse silt end-member (mode = 50–200 µm) at c. 6300 yr BP. We interpreted the sedimentological change as an increase in winter precipitation and more energetic spring melt conditions, leading to the spring melt becoming the dominant lacustrine sediment delivery mechanism. These results place modern hydrological changes in a millennial context and show that analysis of temporal changes in the hydroclimatological system can provide insight into the future states of these sensitive subarctic ecosystems.

Late Holocene climatic variability in Subarctic Canada: insights from a high-resolution lake record from the central Northwest Territories.

We examined late Holocene (ca. 3300 yr BP to present-day) climate variability in the central Northwest Territories (Canadian Subarctic) using a diatom and sedimentological record from Danny’s Lake (63.48ºN, 112.54ºW), located 40 km southwest of the modern-day treeline. High-resolution sampling paired with a robust age model (25 radiocarbon dates) allowed for the examination of both lake hydroecological conditions (30-year intervals; diatoms) and sedimentological changes in the watershed (12-year intervals; grain size records) over the late Holocene. Time series analysis of key lake ecological indicators (diatom species Aulacoseira alpigena, Pseudostaurosira brevistriata and Achnanthidium minutissimum) and sedimentological parameters, reflective of catchment processes (coarse silt fraction), suggests significant intermittent variations in turbidity, pH and light penetration within the lake basin. In the diatom record, we observed discontinuous periodicities in the range of ca. 69, 88–100, 115–132, 141–188, 562, 750 and 900 years (>90% and >95% confidence intervals), whereas the coarse silt fraction was characterized by periodicities in the >901 and <61-year range (>95% confidence interval). Periodicities in the proxy data from the Danny’s Lake sediment core align with changes in total solar irradiance over the past ca. 3300 yr BP and we hypothesize a link to the Suess Cycle, Gleissberg Cycle and Pacific Decadal Oscillation via occasional inland propagation of shifting air masses over the Pacific Ocean. This research represents an important baseline study of the underlying causes of climate variability in the Canadian Subarctic and provides details on the long-term climate variability that has persisted in this region through the past three thousand years.

Hydrology of the North Klondike River: carbon export, water balance and inter-annual climate influences within a sub-alpine permafrost catchment

ABSTRACT Arctic and sub-arctic watersheds are undergoing significant changes due to recent climate warming and degrading permafrost, engendering enhanced monitoring of arctic rivers. Smaller catchments provide understanding of discharge, solute flux and groundwater recharge at the process level that contributes to an understanding of how larger arctic watersheds are responding to climate change. The North Klondike River, located in west central Yukon, is a sub-alpine permafrost catchment, which maintains an active hydrological monitoring station with a record of >40 years. In addition to being able to monitor intra-annual variability, this data set allows for more complex analysis of streamflow records. Streamflow data, geochemistry and stable isotope data for 2014 show a groundwater-dominated system, predominantly recharged during periods of snowmelt. Radiocarbon is shown to be a valuable tracer of soil zone recharge processes and carbon sources. Winter groundwater baseflow contributes 20 % of total annual discharge, and accounts for up to 50 % of total river discharge during the spring and summer months. Although total stream discharge remains unchanged, mean annual groundwater baseflow has increased over the 40-year monitoring period. Wavelet analysis reveals a catchment that responds to El Niño and longer solar cycles, as well as climatic shifts such as the Pacific Decadal Oscillation. Dedicated to Professor Peter Fritz on the occasion of his 80th birthday