Floodplain storage of sediment contaminated by mercury and
Transcription
Floodplain storage of sediment contaminated by mercury and
Geomorphology 206 (2014) 122–132 Contents lists available at ScienceDirect Geomorphology journal homepage: www.elsevier.com/locate/geomorph Floodplain storage of sediment contaminated by mercury and copper from historic gold mining at Gold Hill, North Carolina, USA Scott A. Lecce a,⁎, Robert T. Pavlowsky b a b Department of Geography, Planning, and Environment, East Carolina University, NC 27858, USA Department of Geography, Geology, and Planning, Missouri State University, Springfield, MO 65804, USA a r t i c l e i n f o Article history: Received 31 July 2012 Received in revised form 16 August 2013 Accepted 2 October 2013 Available online 10 October 2013 Keywords: Mercury Gold mining Floodplains Trace metals North Carolina a b s t r a c t Previous research on the environmental consequences of mining has shown that metal contaminants can have long-lasting impacts on water quality and aquatic ecosystems because of the remobilization of sedimentassociated contaminants that have been stored in floodplains. We examined the magnitude and distribution of mercury (Hg) and copper (Cu) contamination of floodplain deposits associated with nineteenth century gold (Au) mining activities in the Gold Hill mining district, North Carolina. A comparison of post-mining metal concentrations in overbank deposits with sediment quality guidelines indicates that overall about 21% are contaminated above the probable effect concentration (PEC; above which adverse effects are expected to occur more often than not) for both Cu and Hg. The highest contamination occurs upstream near the mine source where 51% of the samples exceed the PEC for Hg and 57% exceed the PEC for Cu. Of the three different methods used to estimate metal mass storage, the most reliable estimate suggests that about 6.8 Mg of Hg and 619 Mg of Cu currently reside in floodplain deposits within this watershed. Although overbank sediment storage increases downstream and with valley width, about 75% of the Hg and Cu mass are stored in the upstream portion of the watershed. Hg mass storage displays a strong negative relationship with cross-sectional stream power, but the relationship between Cu mass storage and stream power is insignificant. We used vertical changes in overbank metal concentrations and the mining history to estimate a mean sedimentation rate of 2.7 cm y−1 during the most intensive period of Au mining at Gold Hill (1842–1856) that is three times the long-term (1842–2007) rate of 0.9cmy−1. Long-term average rates at Gold Hill are comparable to those reported elsewhere in the eastern Piedmont. The downstream increase in long-term rates may indicate a spatial and temporal lag effect where the locus of deposition shifts downstream with time. © 2013 Elsevier B.V. All rights reserved. 1. Introduction Contamination of sediment by trace metals poses significant threats to water quality, aquatic ecosystems, and human health. Numerous studies have shown that floodplains in historically mined watersheds can contain large quantities of sediment contaminated by trace metals (e.g., Knox, 1987; Lewin and Macklin, 1987; Bradley and Cox, 1990; Marron, 1992; Miller, 1997; Ettler et al., 2006; Macklin et al., 2006; Hũrkamp et al., 2009; Žák et al., 2009; Bird et al., 2010; Gosar and Žibret, 2011; Castro-Larragoitia et al., 2013). Although floodplains can store contaminants for hundreds to thousands of years, these sediment sinks remain dynamic because metals can be remobilized from storage through processes such as bank erosion and redistributed downstream to be returned to storage in floodplain and channel deposits (Rang and Schouten, 1989; Bradley and Cox, 1990; Macklin and Klimek, 1992; Lecce and Pavlowsky, 1997, 2001; Bird et al., 2010; Łokas et al., 2010). Consequently, past mining activities can cause trace metal contamination problems in river systems that persist long after mining activities have ⁎ Corresponding author. Tel.: +1 252 328 1047; fax: +1 252 328 6054. E-mail address: [email protected] (S.A. Lecce). 0169-555X/$ – see front matter © 2013 Elsevier B.V. All rights reserved. http://dx.doi.org/10.1016/j.geomorph.2013.10.004 ceased (e.g., Miller, 1997; Walling et al., 2003; Macklin et al., 2006), with present-day contamination primarily controlled by the physical release of metal-contaminated sediments by bank erosion and mass wasting. This paper investigates the magnitude and distribution of metal contamination of floodplain deposits associated with nineteenth century Au-mining activities in the Gold Hill mining district, North Carolina. Previous studies have documented the overall geographic extent and sediment-metal relationships in fluvial sediments within the Dutch Buffalo watershed (Lecce et al., 2008; Pavlowsky et al., 2010). This contribution focuses on understanding the downstream variations of the mass storage of sediment and trace metals in floodplain sinks since the early 1800's and the potential for current and future legacy contamination. Mercury (Hg) has been used to amalgamate gold (Au) for thousands of years (Nriagu, 1994; Malm, 1998). Even today, Au mining is responsible for about 10% of global anthropogenic Hg emissions, and most of the Hg released by Au and silver (Ag) mining during the last 500 years may still be available to the global Hg cycle through the remobilization from abandoned tailings and contaminated deposits (Lacerda, 1997). The environmental impacts of Hg use in Au-mining operations have been well documented in the literature (e.g., Leigh, 1994, 1997; Malm, 1998; S.A. Lecce, R.T. Pavlowsky / Geomorphology 206 (2014) 122–132 Miller et al., 1998, 2003). During mineral ore grinding and amalgamation processing at mill sites, Hg is released to the environment where it can be sorbed to tailings particles or sediments that act as the primary reservoir of Hg in freshwater systems (Ullrich et al., 2001). This Hg can be transformed by microbial processes in aquatic sediments into its more toxic organic form, methylmercury (MeHg), which can bioaccumulate and biomagnify in organisms near the top of the food chain (Gilmour et al., 1992; Holmes and Lean, 2006; Guentzel et al., 2007). Understanding the behavior of Hg in environmental systems is of great interest because this element is toxic at concentrations that are commonly one or two orders of magnitude lower than other toxic metals (MacDonald et al., 2000). The main source of human exposure to this potent neurotoxin is the consumption of Hg-contaminated fish, which has led to worldwide advisories for fish consumption (NAS, 2000; Clarkson, 2002; Guentzel et al., 2007). Spatial variations of sediment and contaminant storage have been explained by a variety of factors such as particle size, valley width, distance from the source, lateral distance from the channel, flood flow hydraulics, the frequency of floodplain inundation, floodplain topography, and stream power (Lecce and Pavlowsky, 1997; Walling and He, 1998; Owens et al., 2001; Walling et al., 2003; Miller and Orbock Miller, 2007; Wyżga and Ciszewski, 2010). A variety of methods have been used to determine how storage changes through time. Geochemical profiles in floodplain cores can be used as stratigraphic tracers to document historical sedimentation trends and pollution histories (Knox, 1987; Macklin and Klimek, 1992; Lecce and Pavlowsky, 2001; Bain and Brush, 2005; Knox, 2006). Geochemical and isotopic tracers have also been used in a fingerprinting approach to determine sources and dispersal pathways for contaminated sediment (Hudson-Edwards et al., 1999; Miller et al., 2002, 2005; Villarroel et al., 2006; Miller and Orbock Miller, 2007). Estimating metal storage in watersheds is important for several reasons. Floodplain cores in contaminated watersheds can be useful for documenting the history of pollution, estimating sediment delivery ratios for polluted sediment, and evaluating the long-term storage and ultimate fate of contaminants (Ongley, 1987; Bradley, 1989). These contaminant profiles can also be used as tracers to understand patterns of sediment transport and deposition (Knox, 1987; Miller, 1997; Lecce and Pavlowsky, 2001; Miller and Orbock Miller, 2007). Metal storage estimates can further be used to evaluate the effectiveness of alluvial storage at attenuating pollutant transport to downstream areas. Understanding the magnitude and spatial distribution of metal pollutants within alluvial deposits, and where they exceed toxic limits, can assist managers in assessing how long contaminants reside in watersheds, identifying hot spots, and focusing future monitoring efforts (Dennis et al., 2009). Gold was first discovered in the USA in 1799 in the Piedmont of North Carolina, USA. Although exploration spread slowly throughout the southern Piedmont in a belt that stretched from Virginia to Alabama, North Carolina produced more Au than any other state in the South and led the nation in Au production until 1848 (Knapp and Glass, 1999). Although the exact date that Hg amalgamation was first used in North Carolina is uncertain, historical accounts suggest that large amounts were being used at Gold Hill in southern Rowan County (northeast of Charlotte, NC) by the mid-1840's (Knapp and Glass, 1999). In a reconnaissance study of Hg contamination in the Dutch Buffalo Creek watershed, Lecce et al. (2008) showed that a strong Cu and Hg mining signal can be detected in overbank sediments at the basin outlet 25 km downstream from the mines at Gold Hill. Pavlowsky et al. (2010) also found high Hg concentrations in active channel sediments even though terrestrial tailings sources at mining sites have been removed, which suggests that metals are being remobilized from overbank storage. In another study of potential Hg contamination in the nearby Cid mining district (located about 30 km to the northeast of Gold Hill), Lecce et al. (2011) found that, although Hg was certainly used to amalgamate Au, Hg concentrations are considerably lower than those found at Gold Hill. 123 Thus, given that mining operations at Gold Hill were more intense than anywhere else in North Carolina (Knapp and Glass, 1999), the floodplains downstream from Gold Hill will likely contain the highest mining-related Hg concentrations in the state. The purpose of this paper is to focus on the magnitude and distribution of metal contamination of historical overbank deposits in the Gold Hill mining district. The primary objectives are (i) to evaluate the degree of contamination by comparing metal concentrations to sediment toxicity guidelines, (ii) to determine the distribution of overbank metal storage and assess geomorphic controls on that distribution, and (iii) to use particle-bound metals as tracers to estimate historical rates of floodplain sedimentation. 2. Study area The Gold Hill mining district is located in the gently rolling topography (140–270 m amsl) of the Piedmont of North Carolina in southern Rowan and northern Cabarrus Counties (Fig. 1). This area was first settled by Europeans between 1730 and 1740 (Merrens, 1964; Powell and Lefler, 1973). When the intensive Au-mining activities began in 1842, this area was occupied primarily by subsistence farmers (Knapp and Glass, 1999). Carpenter (1976) mapped the locations of 13 mines in the Gold Hill district (Fig. 1), all in close proximity to the headwaters of Little Buffalo Creek (39 km2), which is tributary to Dutch Buffalo Creek (254 km2). The upper portion of Dutch Buffalo Creek (above the confluence with Little Buffalo Creek) does not contain any mines. Little Buffalo Creek and Dutch Buffalo Creek are low sinuosity meandering streams with pool-riffle morphology and channel beds consisting primarily of sand, gravel and cobbles. Bedrock is frequently exposed in the channel in the west to east-flowing section of Dutch Buffalo Creek upstream from the confluence with Little Buffalo Creek. The main valleys vary between about 50 m and 450 m in width. Floodplain deposits typically consist of massive, unweathered brown to yellowish-brown vertical accretion sediments (sands and silts) that overlie channel bed gravels. Floodplain surfaces range from 1.5–3 m above the channel bed along Little Buffalo Creek and 3–4 m above the channel bed along Dutch Buffalo Creek. The watershed is underlain by two Au-rich units separated by the SW–NE trending Gold Hill fault, which trends approximately along Little Buffalo Creek and the lower portion of Dutch Buffalo Creek. The igneous intrusive rocks of the Charlotte belt lie to the west, with the metavolcanic and metasedimentary rocks of the Carolina slate belt to the east (Pardee and Park, 1948; Carpenter, 1976; Knapp and Glass, 1999). Most of the Au-bearing ore deposits occur in chlorite–sericite phyllite to the east of the fault line (Carpenter, 1976). Early mining practices were quite crude and focused on excavations above the water table. After the discovery of the primary Au veins in 1842 (Nitze and Wilkins, 1897), mercury was used in Chilean mills and log rockers to amalgamate the Au (Knapp and Glass, 1999). By the mid-1850's the larger mining companies were using steam to power their Cornish pumps and Chilean mills (Knapp and Glass, 1999). Mining in the district continued until about 1915, with peak production for Au in 1856. In addition to Au, the Gold Hill district produced a significant amount of copper (Cu) (Pardee and Park, 1948). Ores rich in Cu-sulfides were encountered as the mines became deeper. These ores had generally been ignored as too difficult to process by amalgamation, but as Au production declined in the 1880's interest in Cu associated with sulfide ores increased (Laney, 1910; Knapp and Glass, 1999). The Union Copper Mine was opened in 1899 and produced large amounts of Cu until its closure in 1906. See Lecce et al. (2008) for a more complete description of the geological setting and mining history of the study area. 3. Methods Background metal concentrations were assessed by collecting soil and sediment samples at 63 surface (i.e., top 10 cm) and subsurface (i.e., B horizons at soil exposures) locations not affected by mining or 124 S.A. Lecce, R.T. Pavlowsky / Geomorphology 206 (2014) 122–132 Fig. 1. Map of the Dutch Buffalo Creek watershed showing the location of the mines and floodplain transect sites. ore processing activities in the watershed. A total of 42 floodplain cores were collected to depths ranging from 78 to 517 cm at nine sites (Fig. 1) using either a 2-cm diameter Oakfield soil probe or a 5-cm diameter, 40-cm long AMS split barrel corer. We collected 783 composite samples from the cores in depth intervals that ranged from 5 cm to 20 cm in thickness, depending on the stratigraphy. These floodplain sites were selected where roads provided access to the floodplain. Sample preparation and physical analyses were performed at the Water and Soil Laboratory of the Ozarks Environmental and Water Resources Institute at Missouri State University. Sediment samples were oven-dried at 60 °C, disaggregated with mortar and pestle, and passed through a 2-mm sieve. Although many studies focus on the b63 μm size fraction, we selected the b2 mm fraction because in mined watersheds sand-sized ore particles and Fe–Mn coatings on sand grains may contain significant amounts of metal (Horowitz, 1991). Geochemical analyses were conducted on the b 2 mm fraction by a commercial laboratory (ALS Chemex, Sparks, NV, USA) where the samples were prepared using an aqua-regia extraction (hot 3:1 nitric– hydrochloric acids) (Mudroch et al., 1997). Mercury levels were determined using cold vapor atomic absorption spectroscopy (AA), while Cu (as part of a 33 element package) was analyzed by inductively coupled plasma–atomic emission spectroscopy (ICP–AES). Although several elements are elevated above background concentrations (i.e., Pb, Zn), we focused on Hg and Cu because they showed the highest contamination levels and were specifically targeted for extraction by the mining operations. Lower detection limits are 0.01 mg/kg for Hg and 1 mg/kg for Cu. ALS Chemex follows quality control procedures involving both batch check standards and duplicate analyses on every 10–20 samples. Duplicate sample analyses are typically within 10%. We have also submitted triplicate geochemical standard materials available from the U.S. Geological Survey to ALS Chemex and found that values are within 15%. A number of different methods have been used to calculate metal budgets in fluvial systems (Dennis et al., 2009). Each of the methods employed to estimate metal storage in floodplains necessarily involves a number of simplifying assumptions that affect the accuracy of the S.A. Lecce, R.T. Pavlowsky / Geomorphology 206 (2014) 122–132 estimates. Because we did not have access to the entire width of the floodplain at most of the sites, we did not collect cores across the entire cross-valley transect. Therefore, we calculated the mass of contaminated deposits as: Σ i¼1 Di 1n Σ i¼1 Ci ð1Þ where M is the metal mass at each site (kg), Afp is the floodplain area between each adjacent site (km2), ρb is the average bulk density of floodplain soils in the watershed (1.5 g cm−3, from McCachren and Woody, 2004), n is the number of cores at each transect, D is the depth that each core is contaminated above background concentrations (cm), and C is the vertically weighted mean metal concentration of each core (mg kg−1). Floodplain area was obtained from the soil surveys for Rowan and Cabarrus Counties (Stephens, 1988; McCachren and Woody, 2004). The area associated with each site was determined by dividing the distance between sites in half and including the area closest to the site in the calculation. This approach assumes that the distal portions of the floodplain (which were seldom cored) contain similar metal concentrations and contaminated depths as the means obtained from the cored portion of each transect. Because our data at sites with several cores across the floodplain suggest that distal floodplain deposits that were not cored are likely thinner and have lower metal concentrations, we believe that Eq. (1) probably overestimates the true metal mass to some degree. Therefore, we also calculated minimum and maximum estimates of metal mass storage to provide some context for the estimates obtained from Eq. (1): n Mmin ¼ L Axs ρb 1n Σ Ci i¼1 ð2Þ where Mmin is the minimum estimate of metal mass at each site (kg), L is the longitudinal distance between each site (km), and Axs is the crosssectional area of the transect that was contaminated above background concentrations (kg). The longitudinal distance associated with each site was determined by bisecting the distance between sites. Eq. (2) provides an estimate of storage only for that portion of the floodplain where we obtained metal concentrations from cores, which ignored the distal portions of each transect lacking core data. Therefore, because these distal areas are likely to contain contaminated sediments, Eq. (2) produced a minimum estimate. We also calculated a maximum estimate of metal storage using the depth of contamination of the one core at each site with the most well defined and abrupt initial peak metal concentration: Mmax ¼ D Afp ρb C ð3Þ where Mmax is the maximum estimate of metal mass at each site (kg). We believe that Eq. (3) produces a maximum estimate of metal storage because the core selected at each site tended to be relatively deep, close to the channel, and more highly contaminated. Nevertheless, this represents the type of sampling that is often used where it is only feasible to collect a single core at each transect location. We used estimates of valley width and stream power to quantify geomorphic controls on sedimentation and metal storage (Lecce, 1997). Valley width was obtained from floodplain soils mapped on the Cabarrus County soil survey. Because the width of floodplain soils was quite variable at the reach scale and therefore sensitive to the exact location of the transects, we estimated an average width over a downvalley distance of 500 m centered on each transit. Cross-sectional stream power has been used as an index of the sediment-transporting capacity of the stream flow (Rhoads, 1987): Ω ¼ γQS slope. The bankfull discharge was estimated using Harman et al.'s (1999) equation developed for North Carolina Piedmont streams. 4. Results n n M ¼ Afp ρb 1 n 125 ð4Þ where Ω is power per unit length (W/m), γ is the specific weight of water (9810 N m−3), Q is discharge (m3 s−1), and S is the energy gradient (m m−1) approximated by field surveys of the channel bed 4.1. Background concentrations Table 1 summarizes metal concentrations for soils in the Gold Hill district that were not contaminated by mining activities. The mean background concentration is 0.06 mg kg−1 for Hg and 46 mg kg−1 for Cu. The mean Hg concentrations is similar to background levels found globally in soils (Reimann and Caritat, 1998), in the National Geochemical Survey for Cabarrus County (USGS, 2004), and by Lecce et al. (2011) in the Cid mining district in nearby Davidson County. The mean background Cu concentration is 12–24 mg kg−1 higher than these other reference levels due to the presence of ore bodies in this watershed that are enriched in Cu sulfides. Concentrations of Hg in surface soils are slightly higher than subsurface soils, probably because of recent airborne inputs. We also used the iterative 2σ technique (Matschullat et al., 2000) to provide the likely upper limit on background values. This procedure essentially eliminates extreme values to obtain a normal distribution around the modal value of the original data set (Zglobicki et al., 2011), producing values of 69 mg kg−1 for Cu and 0.09 mg kg−1 for Hg. 4.2. Downstream contamination trends A large proportion of the post-mining overbank sediment samples we collected had Hg and Cu concentrations above our measured background concentrations in Table 1 (91% for Hg; 80% for Cu) and above thresholds identified using the iterative 2σ technique (88% for Hg; 44% for Cu). Weighted mean concentrations of Cu and Hg decrease downstream from the primary mine sources in the headwaters of Little Buffalo Creek (Fig. 2). This trend is typical of rivers contaminated by point sources of contamination (Miller and Orbock Miller, 2007). Because the upper portion of the Dutch Buffalo Creek watershed was unmined and has a drainage area about three times as large as Little Buffalo Creek, it contributes a significant amount of uncontaminated sediment below the confluence with Little Buffalo Creek. This is reflected in metal concentrations in the lower portion of Dutch Buffalo Creek where mean Hg concentrations are about six times lower and Cu three times lower than those upstream along Little Buffalo Creek. Table 1 Background concentrations. Cu (mg kg−1) Hg (mg kg−1) All (n = 63) Mean Median SD Range 46 40 31 3–144 0.06 0.05 0.04 0.01–0.23 Surface Soils (n = 34) Mean Median SD Range 43 38 31 8–144 0.07 0.06 0.04 0.03–0.23 Subsurface Soils (n = 29) Mean Median SD Range Mean, Davidson Countya Mean, global for soilb Mean, Cid Districtc 51 50 31 3–125 22 25 34 0.05 0.05 0.03 0.01–0.13 0.04 0.05 0.05 a Mean value (N = 9) reported in the National Geochemical Survey for Cabarrus County, North Carolina (USGS, 2004). b Reimann and Caritat (1998). c Lecce et al. (2011). We assessed the overall magnitude of the contamination by comparing our metal concentrations in post-mining floodplain deposits to environmental contamination standards. In order to provide an accurate basis for predicting the presence or absence of sediment toxicity, MacDonald et al. (2000) developed two numerical sediment quality guidelines for freshwater ecosystems: the threshold effect concentration (TEC; below which adverse effects are not expected to occur) and the probable effect concentration (PEC; above which adverse effects are expected to occur more often than not). These guidelines are consensus-based values derived from multiple previously conducted studies. The guidelines we report are the consensus-based value along with the range of values from which it was derived. The PEC for Hg is 1.06 mg kg−1 (0.486–2 mg kg−1), and the PEC for Cu is 149 mg kg−1 (86–197 mg kg−1); while the TEC for Hg is 0.18 mg kg−1 (0.15–0.2 mg kg−1), and the TEC for Cu is 32 mg kg−1 (16–70 mg kg−1). Note that the TEC for Cu is lower than the mean background Cu concentration (46 mg kg−1) in the Dutch Buffalo Creek watershed. About 21% of our samples from floodplain sediments deposited since the onset of mining in the early 1840's at Gold Hill are contaminated above the PEC for both Cu and Hg. Although only 5% of the samples are below the TEC for Cu, 38% of the samples are below the TEC for Hg. The decay of metal concentrations with distance from the mine source causes the percentage of samples above the PEC and below the TEC to change downstream (Fig. 3). The highest contamination occurs along Little Buffalo Creek where 51% of the samples exceed the PEC for Hg and 57% of the samples exceed the PEC for Cu. Only 9% of the samples in the upstream reach had concentrations below the TEC for Hg, while none were below the TEC for Cu. A much lower percentage of the samples below the confluence with Dutch Buffalo Creek exceed the PEC for Hg (6%) and Cu (3%), while 54% of the samples were below the TEC for Hg. This is likely explained by dilution because of inputs of uncontaminated sediment from the upper portion of Dutch Buffalo Creek. In contrast, only 7% of the samples are below the TEC for Cu because background concentrations for Cu in this mineralized watershed are above the TEC for Cu. 4.3. Vertical metal trends Fig. 4 provides examples of vertical trends in Hg, Cu, and the sand content in core profiles in overbank deposits at each of the transect 100 Mercury Concentrations 100 Above PEC Below TEC 80 60 40 20 0 0 5 15 20 25 30 Copper Concentrations 100 Above PEC Below TEC 80 60 40 20 0 0 5 10 15 20 25 Distance downstream (km) 30 Fig. 3. Downstream changes in the percentage of post-mining overbank sediment samples with concentrations above the PEC and below the TEC for Hg and Cu. The arrow indicates the location of the confluence of Little Buffalo Creek and Dutch Buffalo Creek. sites. The down-core trends in sand and comparison of sand-normalized concentrations (Horowitz, 1991) with total element concentrations indicated that grain size exerts a minimal influence on metal trends in the cores. Using metal concentrations as stratigraphic markers assumes that there has been little post-depositional mobilization of the metals. We checked for this by comparing down-core trends in several different metals. Hudson-Edwards (1999) showed that the amount of down-core metal migration was metal specific, with the more strongly bound metals demonstrating the least mobility. We see similar down-core trends in 15 Max = 12.736e-0.09x R² = 0.61; p = 0.013 10 Mean = 3.08e-0.119x R² = 0.71; p = 0.005 Maximum Mean 10 1 5 Mean = 25.04x-0.891 R² = 0.91; p = 0.001 0.1 10 100 0 0 1,000 1000 5 10 15 20 25 30 600 Max = 763.9e-0.077x R² = 0.69; p = 0.006 Mean = 317.5e-0.137x R² = 0.67; p = 0.007 500 Cu (mg/kg) 10 20 Max = 67.78x -0.695 R² = 0.83; p = 0.001 Hg (mg/kg) Percentage of post-mining samples S.A. Lecce, R.T. Pavlowsky / Geomorphology 206 (2014) 122–132 Percentage of post-mining samples 126 100 400 300 Max = 2488x-0.538 R² = 0.76; p = 0.002 Mean = 2830x-0.977 R² = 0.77; p = 0.002 10 1 10 100 Drainage area (km2) 200 100 0 1,000 0 5 10 15 20 25 30 Distance downstream (km) Fig. 2. Downstream trends in mean and maximum concentrations of Hg and Cu. The mean values were obtained by taking the weighted mean of each core at a given transect and then calculating the mean of the weighted means for each site. The maximum represents the sample with the highest concentration in any core at each site. The arrow indicates the location of the confluence of Little Buffalo Creek and Dutch Buffalo Creek. S.A. Lecce, R.T. Pavlowsky / Geomorphology 206 (2014) 122–132 0 Site LB5-35 Site LB3-13.4 Hg (mg/kg) Hg (mg/kg) 2 4 6 8 0 10 2 4 6 8 Site LB6B Hg (mg/kg) 10 12 14 16 0 0 127 0.0 0.5 1.0 1.5 2.0 2.5 0 50 50 50 Depth (cm) 100 150 100 100 200 150 150 Hg Cu % Sand 250 200 300 0 100 200 300 400 200 500 0 100 Cu (mg/kg) 0 20 40 200 60 80 100 0 20 40 3 4 0 50 100 60 80 0 100 20 6 0.0 7 0 50 0.1 0.2 200 250 300 40 60 80 100 0.4 0.5 Sand (%) Site DB7B Hg (mg/kg) 5 150 Cu (mg/kg) Site DB4-52.3 Hg (mg/kg) 2 500 Sand (%) Site LB2-48 1 400 Cu (mg/kg) Sand (%) 0 300 Hg (mg/kg) 0.3 0.4 0.5 0.0 0 0 100 100 200 200 300 300 400 400 0.1 0.2 0.3 Depth (cm) 100 150 200 250 500 300 0 100 200 300 400 500 500 0 600 20 Cu (mg/kg) 0 20 40 40 60 80 0 100 20 0 50 40 60 80 100 0 20 1.6 0 50 0.0 0.5 1.0 1.5 150 200 40 60 80 100 2.0 2.5 Sand (%) Site DB1-55 Hg (mg/kg) Hg (mg/kg) 1.2 100 Cu (mg/kg) Site DB5-24.5 Hg (mg/kg) 0.8 100 Sand (%) Site DB2-50 0.4 80 Cu (mg/kg) Sand (%) 0.0 60 2.0 0.0 2.5 0 0 100 100 200 200 300 300 400 400 0.5 1.0 1.5 Depth (cm) 100 150 200 250 500 300 0 20 40 60 80 100 500 0 20 Cu (mg/kg) 0 20 40 60 Sand (%) 40 60 80 100 120 140 0 20 40 60 80 100 120 140 160 Cu (mg/kg) 80 100 0 20 40 60 Cu (mg/kg) 80 100 0 Sand (%) Fig. 4. Vertical trends in Cu and Hg at each of the floodplain transect sites. 20 40 60 Sand (%) 80 100 S.A. Lecce, R.T. Pavlowsky / Geomorphology 206 (2014) 122–132 concentrations of Pb, Zn, Cu, and Hg, which suggests that these are primary depositional signatures. Furthermore, vertical trends in geochemistry are similar both at a site and among sites, indicating the overall control of physical transport on spatial and temporal variations for Hg and Cu in the cores. In most of the cores the initial upcore increase in the concentration above background levels is abrupt for both Cu and Hg. Concentrations of both Hg and Cu stabilize upcore at levels that are usually at least several times greater than background concentrations. Although these more recently deposited sediments are not nearly as contaminated as those deposited earlier during the peak of mining activity, contamination levels above background suggests that erosion of channel banks is remobilizing metals that had been previously stored in floodplain deposits. At the sites located upstream from the confluence with Dutch Buffalo Creek, most of the cores show an initial increase in Cu at core depths of 30–60 cm before the initial increase in Hg. This suggests that early Au-mining activities and agricultural land disturbance of the Au–Cu-mineralized landscape in the immediate vicinity of the Gold Hill mining area was supplying Cu contaminated sediment to streams prior to the widespread use of Hg amalgamation. The early increase in Cu does not appear in sediment cores from lower Dutch Buffalo Creek probably due to the combined influence of locally high storage rates in floodplain deposits along Little Buffalo Creek and dilution by uncontaminated sediment loads from the larger drainage area of the upper Dutch Buffalo Creek. The release of Cu continued as a by-product of Au-mining activities that incorporated the use of Hg. In the remainder of the cores, the initial peak in Hg generally occurs at the same depth (1–3m) as the initial Cu peak, before decreasing rapidly upcore. Although Fig. 4 suggests that the depth to peak Hg concentrations increases downstream, the trend in all 42 cores is quite variable and depends on factors such as floodplain elevation and distance from the channel. Most of the cores display a second, more recent peak in Cu concentrations as the focus of metal extraction shifted away from Au during a period of Cu-mining at the Union Copper Mine (1899–1907) (Lecce et al., 2008). 4.4. Metal and sediment storage The results of our sediment storage and Hg mass calculations show that Eq. (1), which used multiple cores at each transect to estimate metal storage, produces a Hg mass storage of 6.8 Mg over a floodplain area of 4.9 km2. This value is bracketed on the low side using Eq. (2), which ignores that portion of each floodplain transect lacking core data, to produce a minimum estimate of floodplain Hg storage of 2.0 Mg. Eq. (3), where metal storage is estimated using a single nearchannel core at each site, produces a maximum estimate of floodplain Hg mass storage of 11.7 Mg. Eq. (1) produced a Cu mass storage value of 618Mg, bracketed by a minimum estimate of 173Mg and a maximum estimate of 934Mg. Note that because background metal concentrations were subtracted out, these calculations represent metal mass storage attributed to mining activities. We do not have any historical data on Cu production, but we can compare our estimates of floodplain Hg mass storage to estimates of Hg lost during the amalgamation process in order to assess the importance of floodplains as a sink for Hg. A common rule of thumb used to estimate Hg release is that 1.5kg of Hg was lost for every kilogram of Ag or Au produced (Nriagu, 1994; Lacerda, 1997). However, this ratio can vary from as low as 0.85 for impoverished ores to as high as 4.1 for very rich ores (Nriagu, 1994). Although estimates of the amount of Hg released to the environment can be difficult to obtain, Lacerda (1997) showed that most emission factors (i.e., the amount of Hg emitted to produce 1 kg of Au) fall between 1.0 and 2.0. We use these ratios recognizing that the amalgamation methods from which Lacerda (1997) obtained these values may have been different than those used at Gold Hill. Based on Pardee and Park's (1948) estimates of the total production of Au from the Gold Hill deposits between 1842 and 1935, about 5 Mg of Au was produced. Assuming an emission factor of 1–2 (Lacerda, 1997), then about 5–10 Mg of Hg was lost to the environment. In calculating annual Hg emissions from gold mining, Lacerda (1997) also assumed that approximately 65% of the total Hg emissions go to the atmosphere. This would reduce the Hg available to be stored in floodplains to 1.8–3.5 Mg. Because estimates of Au production in North Carolina were based only on Au received at the mint, and therefore underestimate the true Au production by some unknown amount, this offsets to some degree the amount lost to the atmosphere. Notwithstanding the unknowns discussed above, these estimates based on emission factors and historical accounts of Au production compare favorably with our 6.8 Mg estimate based on core data from floodplains at Gold Hill. Note that our core estimates do not account for channel storage or transport out of the watershed. Spatial variations in Hg and Cu mass storage reflect the interaction of longitudinal trends of both metal concentrations and sediment mass storage. The storage of overbank sediment on floodplains generally increases downstream (Fig. 5), while the highest metal concentrations occur close to the mines along Little Buffalo Creek (Fig. 2). Fig. 6 shows the downstream distribution of Hg and Cu storage. About 77% of the 6.8 Mg of Hg mass storage occurs close to the mines along Little Buffalo Creek. Average Hg mass values in this upstream reach are 3.5 times the average in lower Dutch Buffalo Creek. Similarly, about 75% of the 618 Mg of mining-related Cu is stored in the upstream reach. Thus, while only 32% of the historical sediment is stored along Little Buffalo Creek, this upstream reach contains about 75% of the Hg and Cu storage. Just as most of the mining-related Hg and Cu are stored along Little Buffalo Creek, comparison of metal concentrations to the sediment toxicity guidelines of MacDonald et al. (2000) suggests that the threat of harmful biological effects is also limited to the headwater portion of the watershed closest to the mines. Although we have not sampled downstream from site DB1, there is little reason to believe that elevated Hg or Cu concentrations would be detectable. Dutch Buffalo Creek flows into the much larger Rocky River b1 km downstream from DB1; therefore, further dilution by uncontaminated sediment would likely reduce concentrations to levels indistinguishable from background. Thus, even though the most intensive Au mining in North Carolina took place in the Gold Hill district, potentially harmful metal concentrations are limited to a reasonably small area. Nevertheless, these deposits may be remobilized through bank erosion processes and redistributed downstream. Previous work on active channel sediments in this system suggests that 9% are contaminated to levels that exceed the PEC for Hg, and 30% are contaminated above the PEC for Cu (Pavlowsky et al., 2010). Previous research suggests that it is reasonable to expect that watershed-scale geomorphic factors exert some influence on sediment storage, and therefore, metal storage. Sediment storage tends to increase in wide valleys that favor deposition by decreasing flood depth, flow velocity, and flood power, and decrease where cross-sectional stream Overbank sediment storage (Mg/m) 128 1,000 y = 71.59x 0.393 R² = 0.72; p = 0.004 100 10 100 1,000 Drainage area (km2) Fig. 5. Downstream changes in post-mining floodplain sediment storage in Mg m−1 of reach length. The arrow indicates the location of the confluence of Little Buffalo Creek and Dutch Buffalo Creek. S.A. Lecce, R.T. Pavlowsky / Geomorphology 206 (2014) 122–132 Overbank Sediment Storage (Mg/m) Hg storage (kg/m) 10 y = 1.793x-0.498 R² = 0.62; p = 0.012 1 0.1 0.01 10 100 1,000 129 1,000 a y = 2.98x 0.927 R² = 0.50 p = 0.033 Little Buffalo Cr. Dutch Buffalo Cr. 100 100 1000 Valley Width (m) 100 10 1 10 100 1,000 Drainage area (km2) Fig. 6. Downstream changes in post-mining floodplain Hg and Cu mass storage. Values represent the total Hg and Cu mass storage along valley reaches centered on crossvalley transect locations. The arrow indicates the location of the confluence of Little Buffalo Creek and Dutch Buffalo Creek. power is high (Graf, 1983; Magilligan, 1985, 1992; Lecce, 1997). The results shown in Figs. 7 and 8 are mixed. Although valley width explains 50% of the variance in overbank sediment storage, it is clear that much of the unexplained variance is due to differences between the upper and lower portions of the watershed where higher storage per unit valley width is found downstream along Dutch Buffalo Creek (Fig. 7a). While using data from the entire watershed would suggest a positive relationship between stream power and sediment storage, Fig. 7b shows the expected negative relationship (e.g., Lecce, 1997) along Dutch Buffalo Creek, but an unexpected positive relationship in Little Buffalo Creek. This positive relationship may be due to a combination of factors that include basin shape and valley width. The two most upstream sites have narrow floodplains and low values for stream power. Low stream power values would typically tend to favor deposition, but these narrow valleys lack the space to store sediment. The resulting low storage values produce a positive relationship between stream power and sediment storage in Little Buffalo Creek. Basin shape also affects the difference observed between Little Buffalo Creek and Dutch Buffalo Creek. The basin drained by Little Buffalo Creek is long and narrow so that drainage area and stream power increase dramatically at the confluence with Dutch Buffalo Creek. In addition to the large influx of sediment from upper Dutch Buffalo Creek, the higher discharges produce higher values for stream power along lower Dutch Buffalo Creek. Using stream power as a variable to predict metal storage also produced mixed results. While cross-sectional stream power explains 72% of the variance Hg mass storage in the overbank deposits, the relationship with Cu storage is not statistically significant (Fig. 8). This result may be due to the difference between the timing and magnitude of Hg and Cu contamination. Most of the Hg contamination was associated with the active period of Au mining from 1842 to 1860. Early Cu contamination was also associated with the active Au mining period, but there was also a late period of Cu mining at the Union Copper Mine from 1899 to 1906. This may make the dispersal and ultimate Overbank Sediment Storage (Mg/m) y = 128.69x-0.586 R² = 0.35; p = 0.076 1,000 b y = 37219x-0.61 R² = 0.72; p = 0.071 Little Buffalo Cr. Dutch Buffalo Cr. y = 11.702x0.5467 R² = 0.91; p = 0.046 100 50 500 Cross-sectional Stream Power (W/m) Fig. 7. Relationship between overbank sediment storage and (a) valley width and (b) stream power. distribution of Cu more erratic, and therefore difficult to predict. Stream power can also be an inadequate predictor variable for several reasons. Although we implicitly assume that the modern values for power that we calculated are representative of the magnitude and spatial distribution of power throughout the historical period, stream power can change through time. We also assume that bankfull stream power is an adequate surrogate for overbank flows that deposit contaminated sediment, and yet historical changes in channel/floodplain morphology can complicate this relationship. Despite these difficulties, the relationship between stream power and Hg mass storage is surprising strong. 4.5. Sedimentation rates Sediment-borne contaminants such as Hg and Cu can be used to provide information on historical rates of floodplain sedimentation that may be otherwise difficult to measure in environments that often 1000 100 Hg or Cu (Mg) Cu storage (kg/m) 1,000 Cu = 590.07x- 0.347 R² = 0.21; p = 0.235 10 1 Hg = 63.936x- 0.724 R² = 0.74; p = 0.003 0.1 Hg Cu 0.01 50 500 Cross-sectional stream power (W/m) Fig. 8. Relationship between cross-sectional stream power and Cu and Hg storage. The solid symbols represent sites along Little Buffalo Creek and the open symbols represent site along Dutch Buffalo Creek. S.A. Lecce, R.T. Pavlowsky / Geomorphology 206 (2014) 122–132 Table 2 Summary statistics for sedimentation rates. Sedimentation rate (cm y−1) Mean: SD: Range: N: 1842–1856 1856–1899 1899–2007 1842–2007 2.7 1.3 1.1–7.2 30 0.9 0.5 0.5–1.6 7 1.0 0.4 0.4–1.6 7 0.9 0.4 0.4–1.7 30 Sedimentation rate (cm) 10 y = 2.796x-0.032 R² = 0.01 p = 0.674 1 y = 0.356x0.191 R² = 0.29 p = 0.002 1842-2007 1842-1856 0.1 1 10 100 1,000 Drainage area (km2) Fig. 9. Downstream changes in sedimentation rates. by drainage area (Ad). Fig. 10 shows that sedimentation rates decrease with both distance from the channel and elevation above the channel bed. In a multiple regression analysis Dc is a significant independent variable (p = 0.001) while Ec is not significant (p = 0.159). The significance of Dc, which explains 56% of the variance in the 1842–2007 sedimentation rates, supports much previous work showing decreased vertical accretion with distance from the channel due to sediment transfer by particle diffusion (e.g., Pizzuto, 1987; Walling and He, 1998; Lecce and Pavlowsky, 2004; Wyżga and Ciszewski, 2010). The average sedimentation rates in Table 2 are generally consistent with those reported in the literature (Table 3). Although some studies have reported that Holocene sedimentation rates may vary over a large range (e.g., 0.02–0.65 cm y−1, from Ferring, 1986), Holocene rates are frequently reported to be on the order of tenths of a millimeter per year (e.g., Knox, 1987). Leigh and Webb (2006), for example, reported Holocene rates of 0.03–0.08 cm y−1 in the nearby, but steeper terrain 1842-2007 sedimentation rate (cm) lack datable material or buried soils (e.g., Leigh, 1994; Lecce et al., 2011). Our reconnaissance study (Lecce et al., 2008) reported rates of vertical accretion from near-channel and distal floodplain cores at the DB1 site located at the basin outlet. The mean calculated sedimentation rate during the most intense period of mining at Gold Hill (1842–1856) was 2.5 cm y−1, with a long-term (1842–2006) mean rate of 1.3 cm y−1. Additional coring as part of this study provided the opportunity to further refine rates of vertical accretion where a total of 30 cores had adequate sampling intervals and metal signals to calculate sedimentation rates. Using historical evidence (e.g., Knapp and Glass, 1999) we calculated these rates assuming (i) that the initial rapid increase in Hg concentrations occurred in 1842, (ii) that peak Hg levels occurred in 1856 with the Au production peak, and (iii) that the second rapid increase in Cu concentrations was associated with the opening of the Union Copper Mine in 1899. We acknowledge that the 5–20 cm sampling interval introduces error in the sedimentation rate calculations, but note that the largest intervals of 20 cm were usually used on the deepest cores (e.g., DB1-55) below where the initial contamination occurred. Sedimentation rates during the period of most intense mining (1842–1856) can vary considerably from core to core with a range of 1.1–7.2 cm y−1 (Table 2 and Fig. 9). The rates during this period of intense mining are less reliable because of the short time period. Nevertheless, the mean rate of 2.7 cm y−1 during this early period is three times the long-term (1842–2007) rate of 0.9 cm y−1, suggesting a higher level of landscape disturbance during this period. Rates can also be less reliable where sampling intervals are large. For example, at site LB6B (Fig. 2) the more recent Cu peak associated with the operation of the Union Copper mine (1899–1907) is barely detectable; thus we did not use it in our sedimentation rate calculations. However, not only is it likely that a smaller sampling interval would have produced a more distinct peak, the depth at which it occurred could be located anywhere in the 10–37 cm depth range. Depending upon where the peak actually occurred in this depth-integrated sample, the 1856–1899 sedimentation rate would vary from 0.5–1.2 cm y−1. The long-term sedimentation rates are more consistent, as indicated by the much smaller standard deviation (0.4 cm y−1), and increase downstream as a power function of drainage area (Fig. 9). The downstream increase in long-term rates compared to the rates during the mining period show a spatial and temporal lag effect where the locus of deposition shifts downstream with time (e.g., Knox, 1987; Lecce and Pavlowsky, 2001). This may suggest that upstream channels have become enlarged and are now capable of containing and routing larger magnitude flows downstream to lower capacity channels, leading to higher rates of overbank sedimentation. Variations in the sedimentation rates noted above may be influenced by factors such as inundation frequency, distance from the channel, overbank flow patterns, floodplain topography, and vegetation characteristics on the floodplain (Miller and Orbock Miller, 2007). We assessed two of these factors, distance from the channel (Dc) and the elevation above the channel bed (Eb). Because valley width increases downstream, the locations of our cores tended to increase in distance from the channel bank in the lower portions of the watershed. Likewise, floodplain elevations relative the channel bed also increase systematically downstream. In order to control for these trends, we by divided Dc and Eb 1842-2007 sedimentation rate (cm) 130 10 a y = 0.512x-0.247 R² = 0.57 p = 0.001 1 0.1 0.01 0.1 1 10 10 y = 0.385x-0.226 R² = 0.26 p = 0.005 b 1 0.1 0.01 0.1 Eb/Ad (m/km2) Fig. 10. Relationships between long-term sedimentation rates (1842–2007) and (a) crossvalley distance from the channel (Dc/Ad) and (b) elevation above the channel bed (Eb/Ad). S.A. Lecce, R.T. Pavlowsky / Geomorphology 206 (2014) 122–132 of the southern Blue Ridge Mountains of western North Carolina. In contrast, historical rates are typically one to several orders of magnitude greater than Holocene rates (e.g., 15 cm y−1; from Trimble and Lund, 1982). Long-term rates at Gold Hill are about twice those in the nearby Cid district (Lecce et al., 2011) and southern Blue Ridge Mountains (Leigh and Webb, 2006). Mean rates during the most intensive period of mining at Gold Hill are similar to those in the Dahlonega Au belt of northern Georgia, USA, where hydraulic mining was practiced (Leigh, 1994). Elsewhere in the eastern Piedmont, rates of about 1 cm y−1 (Bain and Brush, 2005; Jackson et al., 2005) are comparable to longterm average rates at Gold Hill. 5. Conclusions Nineteenth century mining activities at Gold Hill introduced substantial quantities of Au and Cu into the Little Buffalo Creek/Dutch Buffalo Creek system. A large proportion (91% for Hg; 80% for Cu) of the post-mining floodplain samples we collected had Hg and Cu concentrations above our measured background concentrations. Comparison of our post-mining floodplain sample concentrations with sediment quality guidelines showed that about 21% are contaminated above the PEC for Cu and for Hg. The highest contamination occurs upstream along Little Buffalo Creek where 51% of the samples exceed the PEC for Hg and 57% of the samples exceed the PEC for Cu, whereas below the confluence with Dutch Buffalo Creek only 6% exceed the PEC for Hg and 3% exceed the PEC for Cu. Our most reliable estimates of mining-related metal mass storage indicate that about 6.8 Mg of Hg and 619 Mg of Cu currently reside in floodplain deposits within this watershed. Our estimate of 6.8 Mg of Hg storage compares favorably with a 5–10 Mg estimate based on emission factors and historical accounts of Au production. Although the storage of post-mining overbank sediment on floodplains increases downstream, the high metal concentrations in upstream reaches close to the mines causes both Hg and Cu storage to decrease downstream. About 77% of the 6.8Mg of Hg and 75% of the 618 Mg of Cu mass storage occurs upstream from the confluence with Dutch Buffalo Creek where average Hg mass values are 3.5 times the average in lower Dutch Buffalo Creek. Efforts to explain sediment and metal storage using geomorphic variables were only moderately successful. Valley width explained 50% of the variance in overbank sediment storage and cross-sectional stream power explained 74% of the variance in Hg mass storage. However, the relationship between cross-sectional stream power and Cu storage was not statistically significant. This result may be due to the more complicated history of Cu dispersal and inadequacies with stream power as an index that accurately reflects spatial patterns of deposition. Basin-wide estimates of rates of floodplain sedimentation compare favorably with a previous estimate at the outlet of the watershed (Lecce et al., 2008). Long-term average rates of about 1 cm y−1 at Gold Hill are comparable to those reported elsewhere in the eastern Piedmont (Bain and Brush, 2005; Jackson et al., 2005). The mean rate of 2.7 cm y−1 Table 3 Regional sedimentation rates. Location Period Sedimentation rate (cm y−1) Source Gold Hill, NC 1842–2006 This study Gold Hill, NC 1842–1856 Cid District, NC 1832–1880 to 2007 Southern Blue Ridge Mtns., NC Eastern Piedmont, ME Historical 0.4–1.7 (mean = 0.9) 1.1–7.2 (mean = 2.7) 0.3–0.9 (mean = 0.5) 0.58–0.65 1820–1880 0.45–1.19 Dahlonega, GA Piedmont, GA 1829–1880 to 1994 1820–2005 1–3 0.87 This study Lecce et al. (2011) Leigh and Webb (2006) Bain and Brush (2005) Leigh (1994) Jackson et al. (2005) 131 during the most intensive period of Au mining at Gold Hill (1842–1856) is similar to rates in the Dahlonega Au belt of north Georgia, USA, where hydraulic mining was used (Leigh, 1994). Furthermore, rates during the peak mining period at Gold Hill are three times the long-term (1842–2007) rate of 0.9 cm y−1, suggesting that during this period the combination of disruptive mining activities, the growth of the mining population, and land-use change associated with agriculture significantly increased the level of landscape disturbance and sediment production. Long-term sedimentation rates decrease with distance from the channel and elevation above the channel bed. The downstream increase in longterm rates may be indicative of a spatial and temporal lag effect where the locus of deposition shifts downstream with time due to the enlargement of upstream channels that route sediment downstream to lower capacity channels that experience more frequent overbank flows (e.g., Knox, 1987; Lecce and Pavlowsky, 2001). Although recently deposited sediments at the floodplain surface contain metal concentrations that are much lower than those deposited during the mining period, these sediments remain contaminated above background concentrations. This study shows that the likely source of these contaminants is the upstream part of the watershed that contains floodplain sediments with high Cu and Hg concentrations that were stored during the period of active mining. These legacy deposits are remobilized primarily by bank erosion. As such, contamination from this period of Au mining is a continuing and dynamic process. 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