Elemental lead (Pb) contamination is recognized as a major environmental concern, with binational policy actions taken to reduce its impact across North America (
Nriagu 1990). As such, several studies have utilized sediment cores to investigate metal contamination in lacustrine systems across Canada (e.g.,
Michelutti et al. 2010;
Roberts et al. 2019), including a data synthesis approach by
Dunnington et al. (2020a). Herein we build on these earlier efforts and synthesize available elemental Pb data across the Canadian boreal zone. In addition, with warming and eutrophication expected to strongly impact higher latitude areas including the boreal zone, we chose to investigate trends in sedimentary chlorophyll
a (which includes its main diagenetic products) as an indicator of nutrient enrichment in lakes.
Case study 1: time series investigation of sedimentary Pb records
To assess how temporal trends in metal enrichment have varied across the Canadian boreal zone, we assembled a dataset of 62 boreal and hemiboreal lake sediment cores from existing paleolimnological literature. We indexed the Web of Science Core Collection in January 2022 with the following search terms:
CU (Country/Region) =Canada AND (TS (Topic) =lake* OR TS =lacustrine*) AND TS =sediment* AND (TS =lead contamina* OR TS =lead pollut* OR TS =lead emission* OR TS =element*leadOR TS =element*Pb)
We sought to include studies that presented time series data of elemental Pb concentrations or fluxes for Canadian boreal zone lake sediment records and covered the time period of at least 1900–1990 CE (for details on our inclusion process and reasons for exclusion, see Supplemental material S1). Our search identified 487 sources whose titles and abstracts were reviewed by at least two study authors. This narrowed the number of articles down to 118, and then full-text articles were reviewed by a single study author for potential inclusion in our synthesis. Our search ultimately included 37 studies, but we added one more study suggested by a co-author that did not appear in our search (
Meyer-Jacob et al. 2019). This additional study focused on DOC rather than elemental Pb, but nevertheless presented Pb concentrations through time.
To extract elemental Pb records from the studies included in our data synthesis, we first looked to the Supplemental materials for downloadable data used in the study. In the absence of open data, we used the “DigitizeIt” software (
Bormann 2012;
Rakap et al. 2016) to convert Pb records presented in figures into a usable format, a method which shows a high degree of reliability and validity (
Rakap et al. 2016). In some cases, digitization was not possible without risking significant error (e.g., due to overlapping data points, data presented as averages or ratios, inconsistent axis labelling) and so these records were removed from our database. In total, we obtained data for 62 boreal zone lake sediment records from our 38 included studies; for further details on their analytical methodologies, please refer to Supplemental material S2 or the original studies.
Our study was limited to the use of Pb concentrations to investigate trends in elemental Pb, rather than Pb flux. Pb flux normalizes elemental concentrations to their respective sedimentation rates, and this approach is recommended for generating mass balances (
Engstrom and Rose 2013). However,
Dunnington et al. (2020b) recently compared numerous geochemical metrics for two sediment cores (i.e., fluxes, tracer element ratios, enrichment factors, excess measures, and centred log-ratios and concentrations) and found that Pb concentrations were reasonable indicators of Pb pollution in all cases. In our data synthesis, only 12 of the 62 sites presented elemental Pb fluxes. For studies that did not present Pb fluxes, we considered digitizing
210Pb chronologies to calculate flux, but
210Pb sediment chronologies and measurement errors were often absent, making it difficult or impossible to do so with confidence. We therefore opted to focus on concentrations and examined overall trends on a per-site basis.
We used segmented linear regressions to identify significant breakpoints in elemental Pb trends. We subset Pb records to only consider data from 1850 CE to present day, as
210Pb dating is best suited to recent sediments (
Baud et al. 2022). We performed regressions in the R software environment (
R Core Team 2022) using the package “segmented” (
Muggeo 2022). To determine the ideal number of breakpoints for each record, we assessed segmented models using the Akaike Information Criterion (AIC) and Bayesian Information Criterion (BIC) (
Akaike 1974;
Schwarz 1978). AIC and BIC measure the fit of parameterized models, with BIC more highly penalizing additional model parameters, and are best applied together (
Kuha 2004). When the AIC/BIC of two models were within two criterion units (
Burnham and Anderson 2002), or in cases of disagreement between AIC and BIC in the number of breakpoints, we selected the model with fewer breakpoints as the best fitting segmented model. For each record, we used analysis of variance to compare the best fitting segmented model to a simple linear fit (
Dunnington et al. 2020a) and in most cases, the segmented model significantly outperformed a simple linear fit (
p < 0.05). When the segmented model did not provide a significant improvement (
n = 15 cases), we did not report a breakpoint. Visualized fitted models are available in the Supplemental material S3.
We split our time series into before and after the identified breakpoint (i.e., historical vs. modern trends, respectively) and quantified trends using the nonparametric Mann–Kendall (M-K) test from the package “trend” (
Pohlert 2020). When our breakpoint analysis identified two significant breakpoints, we split the time series into historical and modern trends by the most recently identified breakpoint. The M-K test is based on the Kendall rank correlation and returns a tau (
τ) value for each time series between −1 and + 1, with −1 showing a monotonic decreasing trend and +1 showing a monotonic increasing trend. In the absence of a statistically significant breakpoint, we applied the M-K test to the entire time series, identified these instances as “Full M-K tests”, and presented them as a modern trend. Occasionally, splitting time series by breakpoint meant that they did not meet the mandatory three data points to apply a M-K test; in these instances, no trend is presented. We visualized the results of our M-K tests using the ArcMap™ 10.8.1 ArcGIS® software by Esri. For further details on M-K trend results and associated p-values see Supplemental material S4.
The mean timing of the most recent breakpoint identified across all of the elemental Pb profiles was 1973 CE ± 14.6 years (
n = 47). Trends in elemental Pb before the most recent breakpoint (i.e., historical trends) suggest a widespread increase across the boreal zone around the onset of industrialization, with all lakes demonstrating either a slightly increasing (M-K τ = 0.01–0.49, n = 6) or strongly increasing (M-K
τ = 0.5–1.0,
n = 41) trend (
Fig. 2). A total of 15 sediment cores had no significant breakpoint detected and thus no historical trend was determined. Conversely, modern trends in elemental Pb (i.e., after the most recent breakpoint) exhibited more heterogeneity relative to historical trends, but many decreased across the boreal zone (
Fig. 3). A total of 46 lakes had a strongly negative trend (M-K
τ = −1 to −0.5;
n = 36) or a slightly negative trend (M-K
τ = −0.49 to −0.01;
n = 10), while 13 lakes slightly increased during the modern period (M-K
τ = 0.01–0.49;
n = 7) or strongly increased (M-K
τ = 0.5–1;
n = 6). Three sediment cores have no trend reported because there were not enough points post-breakpoint to calculate the M-K trend.
One of the primary pathways for elemental Pb to enter lacustrine systems is through atmospheric deposition, enabling lead to traverse long distances before entering the landscape (
Marx et al. 2016;
Dunnington et al. 2020a). Given that leaded gasoline was a primary contributor to atmospheric Pb until the mid-1970s, legislated efforts to remove Pb from gasoline that began in 1975 appear to have contributed to the declining trends observed (
Nriagu 1990). Other environmental regulations and policies including the phasing out of coal appear to have contributed to declining Pb levels in some areas as well (
Weiss et al. 2002;
Gallon et al. 2005). The increasing historical trends we observed across the boreal zone are congruent with these earlier studies. In addition, the timing of the push toward unleaded gasoline agrees well with the average breakpoint year identified in our lakes that were best described by a segmented linear model (∼1973 CE). With 74% of boreal zone lakes exhibiting a decreasing modern trend, it seems likely that elemental Pb concentrations have generally declined across boreal lakes in response to policy efforts to reduce Pb emissions. Still, 13 lakes included in our synthesis exhibited an increasing trend during the modern period, with six of these sites strongly increasing (M-K
τ = 0.5–1.0).
Strongly increasing modern M-K trends were found in three Northwest Territories lakes (
Fig. 3, red box), likely caused by nearby gold mining operations at Giant Mine. Wind direction is one possible explanation for why this increase was observed in some, but not all lakes. Several lakes at an equivalent distance from Giant Mine exhibited decreasing trends in Pb enrichment. However, these lakes were in a non-dominant wind direction and researchers posited that the terrestrial supply of legacy metals was therefore lower (
Jasiak et al. 2021;
Kay et al. 2023). The importance of wind direction is further emphasized in a Pb isotope study from nearby Yellowknife Bay which found that downwind legacy metals stored in the terrestrial environment were responsible for the metal enrichment of modern sediments (
Pelletier et al. 2020). Metal enrichment of lacustrine systems can thus persist following the cessation of mining activities, particularly in areas downwind of mining sites. However, of the 42 study lakes that original authors identified as being in close proximity to mines, only 21% showed continued increases in Pb. It is possible that the other 79% of lakes are impacted, but only exhibit elevated levels of other heavy metals; however, as Pb is almost always a co-product of metal mining operations (
Brown et al. 2009), we would generally still expect to see Pb enrichment in response to mining, regardless of the type of mine. This reinforces the importance of local factors, such as wind direction, terrestrial legacy metal supply, and surface and groundwater flow direction, that need to be investigated when evaluating the impact of mining on lake ecosystems. In anticipation of increased resource exploitation across the boreal zone and the need to determine reference conditions, lakes nearby and downwind from mining sites should be studied to adequately assess the impact of mining activities on lake ecosystems, along with modulating factors.
Case study 2: snapshot comparison of pre- and post-industrial sedimentary chlorophyll a
To investigate trends in lake primary production across the boreal zone, we leveraged samples that were collected as part of the NSERC Canadian Lake Pulse Network (hereafter referred to as LakePulse;
Huot et al. 2019). LakePulse sampled 664 lakes across Canada between 2017 and 2019; sediments from a 145-lake subset were analyzed for sedimentary chlorophyll
a as part of a national assessment of primary production (
Griffiths et al. 2022). Here, we present a subset of these data for sites within the Canadian boreal zone (
n = 76; for site details see Supplemental material S2).
Griffiths et al. (2022) measured sedimentary chlorophyll
a and its diagenetic products as a proxy for historical primary production using visible reflectance spectroscopy (VRS). VRS-inferred chlorophyll
a, determined according to the methods described by
Wolfe et al. (2006) and
Michelutti et al. (2010), has been shown to reflect changes in primary production and lake trophic status (
Michelutti et al. 2010;
Michelutti and Smol 2016). Briefly, sediments were freeze-dried, homogenized, and sieved through a sub-125 µm mesh to attain a relatively even particle size, before analysing with a FOSS NIRSystem Model 6500 at Queen's University in the Paleoecological Environmental Assessment and Research Laboratory. Sediment intervals were selected for chlorophyll
a analysis using a top-bottom approach, whereby the top sample represents recent conditions and the bottom sample represents pre-disturbance conditions. Sediment ages of bottom samples were verified with
210Pb dating to ensure that most cores extended into the pre-industrial era (pre ∼1850 CE) (see
Griffiths et al. (2022) for a detailed description).
To partly account for any minor diagenetic loss or inorganic carbon dilution (
Rydberg et al. 2020), we normalized VRS-inferred sedimentary chlorophyll
a to organic carbon concentrations measured by
Griffiths et al. (2022). To assess the magnitude of change in sedimentary chlorophyll
a since baseline conditions, we calculated % change in top (modern) chlorophyll
a relative to bottom (historical) chlorophyll
a (Supplemental material S4).
We observed a general increase in chlorophyll
a across the boreal zone since pre-industrial times. VRS-inferred sedimentary chlorophyll
a (normalized to organic carbon) increased in 76% of lakes, with 29 lakes displaying a marginal increase (0.1%–50%), and another 29 that showed a large increase (>50%) (
Fig. 4). Of the 18 lakes that showed a relative decrease in chlorophyll
a in the modern interval, 13 were modest decreases (i.e., less than 49.9% declines), and just 5 showed a large decrease (i.e., greater than 50% declines). We found that the widespread increases in chlorophyll
a held true without correcting for organic carbon concentration, with 84% of lakes showing an increasing trend (Supplemental material S4). The correction caused 10 records to shift their trajectories from displaying an increasing to a decreasing trend, most of which were modest changes except for one lake. Decreasing trends in chlorophyll
a may be related to the organic carbon correction, reflecting site specific factors such as the amount and type of allochthonous carbon inputs. For example, an increase in inorganic material entering the lake (possibly driven by increased erosion from land-use, precipitation, or hydrological changes) can cause an apparent decrease in the amount of chlorophyll
a preserved in sediment. Similarly, increased inputs of organic material into the system (possibly driven by increased agricultural and pastoral runoff) can also appear as a decrease in the amount of chlorophyll
a, as chlorophyll
a values are normalized to organic carbon. The latter mechanism is possible in lakes of the Boreal Plains and Prairies, whose watersheds have undergone extensive agricultural and pastoral development since pre-industrial times (some observed declines in lakes of these regions disappear when chlorophyll
a values are left uncorrected; Supplemental material S4). Decreasing trends in chlorophyll
a may also be explained by pollution or management strategies and policies that mitigate nutrient inputs and algal blooms (
Wilkinson et al. 2022). Despite these factors, our study highlights a general increase of primary production across boreal zone lakes since pre-industrial conditions.
The widespread increase in inferred lake primary production has been observed globally in several large-scale studies (e.g.,
Taranu et al. 2015;
Summers et al. 2016;
Griffiths et al. 2022). Notably,
Griffiths et al. (2022) found significant increases in primary production in 80% of their sampled lakes across Canada (
n = 145). This extensive and increasing trend may be related to a number of factors. Increasing chlorophyll
a concentrations often reflect eutrophication, which in many cases can be driven by land-use changes, longer growing seasons and/or changes in water column mixing patterns (
Moser et al. 2002;
Schindler et al. 2008). Further, eutrophication and its effects are exacerbated by regional climate warming that has been observed in the boreal region (
Summers et al. 2016;
Favot et al. 2019). Additionally, reduced ice cover, lengthening of the growing season, and enhanced thermal stability provide favourable conditions for increased primary production. Detecting temperature-mediated effects in the boreal zone may be easier than in sites further south as their watersheds tend to be less altered and the rate of climate change in the North is accentuated. For example, with the absence of anthropogenic eutrophication,
Favot et al. (2019) identified regional climate warming as an important factor promoting algal blooms in a remote, oligotrophic lake. Similarly, in Lake of the Woods,
Paterson et al. (2017) found that sedimentary chlorophyll
a continued to rise despite long-term declining nutrient inputs inferred using diatoms. In particular, they noted that increased sedimentary chlorophyll
a was positively correlated to mean annual air temperature and total precipitation. Furthermore, the widespread increase observed across such a broad geographic area may indicate a larger-scale stressor, such as climate, may be responsible for the apparent trends (
Griffiths et al. 2022;
Fig. 4). Given that higher latitude areas are expected to warm at an increased rate, we might expect to see continued increases in primary production and sedimentary chlorophyll
a in boreal lakes.