A baseline of copper associated with antifouling paint in marinas within a large fjord estuary.

Marinas have been shown to contribute elevated concentrations of copper (Cu) to marine waters. The Cu can come primarily from antifouling paints which are designed to discourage biofouling of boat hulls. Legislation in Washington State, USA is being developed to limit or regulate the amount and rate of diffusion of Cu from antifouling paints. This study provides baseline data for Cu in five marinas of different configuration and size within Puget Sound, a large fjord estuary. Samples were collected over a year from multiple environmental media. We find strong evidence that Cu accumulates inside marinas to higher concentrations than outside marinas. Marinas that are more enclosed accumulated higher concentrations of Cu than more open marinas. Using a power analysis, we assessed the adequacy of the baseline dataset to measure progress as a result of future legislation towards the reduction of Cu to Puget Sound from marinas.

Exploring watershed effects on nutrient concentrations in shallow lakes through stable isotope analysis.

Biogeochemistry patterns in shallow lakes are influenced by both in-lake factors such as ecosystem state as well as watershed-level factors such as land use, but the relative importance of in-lake versus watershed factors is poorly known. This knowledge gap makes it difficult for lake mangers to prioritize efforts on watershed versus in-lake strategies for stabilizing the clear-water state. We studied 48 shallow lakes in Minnesota, USA to assess the relative influence of lake size, land use in watersheds, and ecosystem state (turbid versus clear) on water column total nitrogen (TN) and total phosphorus (TP), as well as δ15N and δ13C in three species of fish. Our land use categories included natural areas, row crop agriculture, and all agriculture (row crops plus alfalfa). A model selection approach revealed different control mechanisms on the behavior of stable isotopes and nutrients. δ13C ratios in fish were most strongly influenced by lake size, while δ15N ratios were influenced by all agriculture in watersheds. In contrast, water column TN and TP concentrations were influenced by the in-lake factor of ecosystem state, with both nutrients lower in the clear state. We detected no effects of land use on TN or TP concentrations, likely due to strong effects of ecosystem state masking watershed effects. However, the strong relationship between agriculture and δ15N in fish indicated that watersheds did influence nutrient processing in shallow lakes, and that effects are not a legacy from past watershed events. Collectively, these observations indicate that lake managers should minimize agricultural intensity in shallow lake watersheds to facilitate the clear-water state, which will, in turn reduce water-column TN and TP relative to the turbid state.

Using a lake sediment record to infer the long-term history of cyanobacteria and the recent rise of an anatoxin producing Dolichospermum sp.

Lakes that experience recurrent toxic cyanobacterial harmful algae blooms (cyanoHABS) are often subject to cultural eutrophication, where landscape development and upland activities increase the nutrient inputs to the water column and fuel cyanoHABS. Few studies have focused on the response of a lake to nutrient inputs for which the natural geomorphic setting predisposes a nutrient-rich water column to already support abundant cyanobacteria. Here, we present a sediment core record from a lake surrounded by parkland that experiences recurrent cyanoHABs which produce dangerous levels of the neurotoxin, anatoxin-a, impacting the recreational use of the lake and park. Using photoautotrophic pigments in the sediment record, we establish cyanobacteria have long been part of the diverse and abundant phytoplankton community within the lake. Despite this long record, shotgun metagenome and other DNA analyses of the sediment record suggest that the current anatoxin-a producer Dolichospermum sp. WA102 only emerged to dominate the cyanobacterial community in the mid-1990s. A period of lakeshore farming that finished in the 1950s-1960s and possibly the stocking of rainbow trout fry (1970-2016) coincide with a progressive shift in primary production, together with a change in bacterial communities. Based on the history of the lake and contemporary ecology of Dolichospermum, we propose that the legacy of nutrient inputs and changes in nutrient cycling within the lake has encouraged the development of an ecosystem where the toxin producing Dolichospermum sp WA102 is highly competitive. Understanding the historical presence of cyanobacteria in the lake provides a context for current-day management strategies of cyanoHABs.

Toxic Burdens of Freshwater Biofilms and Use as a Source Tracking Tool in Rivers and Streams.

Biofilms, composed of periphyton, bacteria, and organic detritus, are the base of the food web in many streams and rivers. This media adsorbs and actively sequesters organic and inorganic contaminants from the water column. Here, we demonstrate the utility of using the contaminant concentrations in the biofilm matrix as an environmental media in source tracking and understanding biological impacts at higher trophic levels. Physical partitioning of polychlorinated biphenyl (PCB) and polybrominated diphenyl ether congeners is the dominant mode of uptake from water to biofilm and bioaccumulation factor: log Kow relationships suggest that PCB uptake is often near equilibrium between log Kow 5-7. We show that the concentrations of metals in biofilms are more effective at delineating and recording spatial and temporal differences in metal inputs than bed sediments and water samples. The burden of metals in the biofilm matrix explained adverse impacts and variability in periphyton metrics and ecological integrity in macroinvertebrates. This work provides new insights into the partitioning of organic chemicals onto biofilms and shows clear linkages between metals in the biofilm matrix and ecological health of invertebrates that depend on biofilms as a food source.

Watershed vs. within-lake drivers of nitrogen: phosphorus dynamics in shallow lakes.

Research on lake eutrophication often identifies variables affecting amounts of phosphorus (P) and nitrogen (N) in lakes, but understanding factors influencing N:P ratios is important given its influence on species composition and toxin production by cyanobacteria. We sampled 80 shallow lakes in Minnesota (USA) for three years to assess effects of watershed size, proportion of watershed as both row crop and natural area, fish biomass, and lake alternative state (turbid vs. clear) on total N : total P (TN : TP), ammonium, total dissolved phosphorus (TDP), and seston stoichiometry. We also examined N:P stoichiometry in 20 additional lakes that shifted states during the study. Last, we assessed the importance of denitrification by measuring denitrification rates in sediment cores from a subset of 34 lakes, and by measuring seston δ15 N in four additional experimental lakes before and after they were experimentally manipulated from turbid to clear states. Results showed alternative state had the largest influence on overall N:P stoichiometry in these systems, as it had the strongest relationship with TN : TP, seston C:N:P, ammonium, and TDP. Turbid lakes had higher N at given levels of P than clear lakes, with TN and ammonium 2-fold and 1.4-fold higher in turbid lakes, respectively. In lakes that shifted states, TN was 3-fold higher in turbid lakes, while TP was only 2-fold higher, supporting the notion N is more responsive to state shifts than is P. Seston δ15 N increased after lakes shifted to clear states, suggesting higher denitrification rates may be important for reducing N levels in clear states, and potential denitrification rates in sediment cores were among the highest recorded in the literature. Overall, our results indicate lake state was a primary driver of N:P dynamics in shallow lakes, and lakes in clear states had much lower N at a given level of P relative to turbid lakes, likely due to higher denitrification rates. Shallow lakes are often managed for the clear-water state due to increased value as wildlife habitat. However, our results indicate lake state also influences N biogeochemistry, such that managing shallow lakes for the clear-water state may also mitigate excess N levels at a landscape scale.

The legacy of large regime shifts in shallow lakes.

Ecological shifts in shallow lakes from clear-water macrophyte-dominated to turbid-water phytoplankton-dominated are generally thought of as rapid short-term transitions. Diatom remains in sediment records from shallow lakes in the Prairie Pothole Region of North America provide new evidence that the long-term ecological stability of these lakes is defined by the legacy of large regime shifts. We examine the modern and historical stability of 11 shallow lakes. Currently, four of the lakes are in a clear-water state, three are consistently turbid-water, and four have been observed to change state from year to year (transitional). Lake sediment records spanning the past 150-200 yr suggest that (1) the diatom assemblage is characteristic of either clear or turbid lakes, (2) prior to significant landscape alteration, all of the lakes existed in a regime of a stable clear-water state, (3) lakes that are currently classified as turbid or transitional have experienced one strong regime shift over the past 150-200 yr and have since remained in a regime where turbid-water predominates, and (4) top-down impacts to the lake food-web from fish introductions appear to be the dominant driver of strong regime shifts and not increased nutrient availability. Based on our findings we demonstrate a method that could be used by lake managers to identify lakes that have an ecological history close to the clear-turbid regime threshold; such lakes might more easily be returned to a clear-water state through biomanipulation. The unfortunate reality is that many of these lakes are now part of a managed landscape and will likely require continued intervention.

Climate change forces new ecological states in tropical Andean lakes.

Air temperatures in the tropical Andes have risen at an accelerated rate relative to the global average over recent decades. However, the effects of climate change on Andean lakes, which are vital to sustaining regional biodiversity and serve as an important water resource to local populations, remain largely unknown. Here, we show that recent climate changes have forced alpine lakes of the equatorial Andes towards new ecological and physical states, in close synchrony to the rapid shrinkage of glaciers regionally. Using dated sediment cores from three lakes in the southern Sierra of Ecuador, we record abrupt increases in the planktonic thalassiosiroid diatom Discostella stelligera from trace abundances to dominance within the phytoplankton. This unprecedented shift occurs against the backdrop of rising temperatures, changing atmospheric pressure fields, and declining wind speeds. Ecological restructuring in these lakes is linked to warming and/or enhanced water column stratification. In contrast to seasonally ice-covered Arctic and temperate alpine counterparts, aquatic production has not increased universally with warming, and has even declined in some lakes, possibly because enhanced thermal stability impedes the re-circulation of hypolimnetic nutrients to surface waters. Our results demonstrate that these lakes have already passed important ecological thresholds, with potentially far-reaching consequences for Andean water resources.

A 200-year perspective on alternative stable state theory and lake management from a biomanipulated shallow lake.

Multiple stressors to a shallow lake ecosystem have the ability to control the relative stability of alternative states (clear, macrophyte-dominated or turbid, algal-dominated). As a consequence, the use of remedial biomanipulations to induce trophic cascades and shift a turbid lake to a clear state is often only a temporary solution. Here we show the instability of short-term manipulations in the shallow Lake Christina (Minnesota, USA) is governed by the long-term state following a regime shift in the lake. During the modern, managed period of the lake, three top-down manipulations (fish kills) were undertaken inducing temporary (5-10 years) unstable clear-water states. Paleoecological remains of diatoms, along with proxies of primary production (total chlorophyll a and total organic carbon accumulation rate) and trophic state (total P) from sediment records clearly show a single regime shift in the lake during the early 1950s; following this shift, the functioning of the lake ecosystem is dominated by a persistent turbid state. We find that multiple stressors contributed to the regime shift. First, the lake began to eutrophy (from agricultural land use and/or increased waterfowl populations), leading to a dramatic increase in primary production. Soon after, the construction of a dam in 1936 effectively doubled the depth of the lake, compounded by increases in regional humidity; this resulted in an increase in planktivorous and benthivorous fish reducing phytoplankton grazers. These factors further conspired to increase the stability of a turbid regime during the modern managed period, such that switches to a clear-water state were inherently unstable and the lake consistently returned to a turbid state. We conclude that while top-down manipulations have had measurable impacts on the lake state, they have not been effective in providing a return to an ecosystem similar to the stable historical period. Our work offers an example of a well-studied ecosystem forced by multiple stressors into a new long-term managed period, where manipulated clear-water states are temporary, managed features.

The altered ecology of Lake Christina: a record of regime shifts, land-use change, and management from a temperate shallow lake.

We collected two sediment cores and modern submerged aquatic plants and phytoplankton from two sub-basins of Lake Christina, a large shallow lake in west-central Minnesota, and used stable isotopic and elemental proxies from sedimentary organic matter to explore questions about the pre- and post-settlement ecology of the lake. The two morphologically distinct sub-basins vary in their sensitivities to internal and external perturbations offering different paleoecological information. The record from the shallower and much larger western sub-basin reflects its strong response to internal processes, while the smaller and deeper eastern sub-basin record primarily reflects external processes including important post-settlement land-use changes in the area. A significant increase in organic carbon accumulation (3-4 times pre-settlement rates) and long-term trends in δ(13)C, organic carbon to nitrogen ratios (C/N), and biogenic silica concentrations shows that primary production has increased and the lake has become increasingly phytoplankton-dominated in the post-settlement period. Significant shifts in δ(15)N values reflect land-clearing and agricultural practices in the region and support the idea that nutrient inputs have played an important role in triggering changes in the trophic status of the lake. Our examination of hydroclimatic data for the region over the last century suggests that natural forcings on lake ecology have diminished in their importance as human management of the lake increased in the mid-1900s. In the last 50 years, three chemical biomanipulations have temporarily shifted the lake from the turbid, algal-dominated condition into a desired clear water regime. Two of our proxies (δ(13)C and BSi) measured from the higher resolution eastern basin record responded significantly to these known regime shifts.

A coherent signature of anthropogenic nitrogen deposition to remote watersheds of the Northern Hemisphere.

Humans have more than doubled the amount of reactive nitrogen (Nr) added to the biosphere, yet most of what is known about its accumulation and ecological effects is derived from studies of heavily populated regions. Nitrogen (N) stable isotope ratios ((15)N:(14)N) in dated sediments from 25 remote Northern Hemisphere lakes show a coherent signal of an isotopically distinct source of N to ecosystems beginning in 1895 ± 10 years (±1 standard deviation). Initial shifts in N isotope composition recorded in lake sediments coincide with anthropogenic CO(2) emissions but accelerate with widespread industrial Nr production during the past half century. Although current atmospheric Nr deposition rates in remote regions are relatively low, anthropogenic N has probably influenced watershed N budgets across the Northern Hemisphere for over a century.

Increased mercury loadings to western Canadian alpine lakes over the past 150 years.

We reconstructed historical trends in mercury (Hg) accumulation over the past ∼ 150 years in nine western Canadian alpine lakes. Recent Hg accumulation rates (fluxes) ranged between ∼ 7 and 75 µg m(-2) yr(-1), which were an average of 1.8 times higher than preindustrial (i.e., pre-1850) fluxes. Increased Hg fluxes in these lakes were less than at lower elevation sites, showing that despite the potential for increased deposition, alpine lakes are no more susceptible to Hg accumulation. Unlike other studies, we found that geographic setting, changes in chlorophyll-inferred algal production, and climate were not significant predictors of [Hg] or Hg flux in lakes. Instead, our findings highlight how a combination of atmospheric deposition and site-specific processes, including organic matter supply and catchment weathering, better explain sequestration of Hg in alpine lakes.

Rapid landscape transformation in South Island, New Zealand, following initial Polynesian settlement.

Humans have altered natural patterns of fire for millennia, but the impact of human-set fires is thought to have been slight in wet closed-canopy forests. In the South Island of New Zealand, Polynesians (Maori), who arrived 700-800 calibrated years (cal y) ago, and then Europeans, who settled ∼150 cal y ago, used fire as a tool for forest clearance, but the structure and environmental consequences of these fires are poorly understood. High-resolution charcoal and pollen records from 16 lakes were analyzed to reconstruct the fire and vegetation history of the last 1,000 y. Diatom, chironomid, and element concentration data were examined to identify disturbance-related limnobiotic and biogeochemical changes within burned watersheds. At most sites, several high-severity fire events occurred within the first two centuries of Maori arrival and were often accompanied by a transformation in vegetation, slope stability, and lake chemistry. Proxies of past climate suggest that human activity alone, rather than unusually dry or warm conditions, was responsible for this increased fire activity. The transformation of scrub to grassland by Europeans in the mid-19th century triggered further, sometimes severe, watershed change, through additional fires, erosion, and the introduction of nonnative plant species. Alteration of natural disturbance regimes had lasting impacts, primarily because native forests had little or no previous history of fire and little resilience to the severity of burning. Anthropogenic burning in New Zealand highlights the vulnerability of closed-canopy forests to novel disturbance regimes and suggests that similar settings may be less resilient to climate-induced changes in the future.

Quantifying recent ecological changes in remote lakes of North America and Greenland using sediment diatom assemblages.

BACKGROUND: Although arctic lakes have responded sensitively to 20(th)-century climate change, it remains uncertain how these ecological transformations compare with alpine and montane-boreal counterparts over the same interval. Furthermore, it is unclear to what degree other forcings, including atmospheric deposition of anthropogenic reactive nitrogen (Nr), have participated in recent regime shifts. Diatom-based paleolimnological syntheses offer an effective tool for retrospective assessments of past and ongoing changes in remote lake ecosystems. METHODOLOGY/PRINCIPAL FINDINGS: We synthesized 52 dated sediment diatom records from lakes in western North America and west Greenland, spanning broad latitudinal and altitudinal gradients, and representing alpine (n = 15), arctic (n = 20), and forested boreal-montane (n = 17) ecosystems. Diatom compositional turnover (beta-diversity) during the 20(th) century was estimated using Detrended Canonical Correspondence Analysis (DCCA) for each site and compared, for cores with sufficiently robust chronologies, to both the 19(th) century and the prior approximately 250 years (Little Ice Age). For both arctic and alpine lakes, beta-diversity during the 20(th) century is significantly greater than the previous 350 years, and increases with both latitude and altitude. Because no correlation is apparent between 20(th)-century diatom beta-diversity and any single physical or limnological parameter (including lake and catchment area, maximum depth, pH, conductivity, [NO(3)(-)], modeled Nr deposition, ambient summer and winter air temperatures, and modeled temperature trends 1948-2008), we used Principal Components Analysis (PCA) to summarize the amplitude of recent changes in relationship to lake pH, lake:catchment area ratio, modeled Nr deposition, and recent temperature trends. CONCLUSIONS/SIGNIFICANCE: The ecological responses of remote lakes to post-industrial environmental changes are complex. However, two regions reveal concentrations of sites with elevated 20(th)-century diatom beta-diversity: the Arctic where temperatures are increasing most rapidly, and mid-latitude alpine lakes impacted by high Nr deposition rates. We predict that remote lakes will continue to shift towards new ecological states in the Anthropocene, particularly in regions where these two forcings begin to intersect geographically.

Reliance on (210)Pb chronology can compromise the inference of preindustrial Hg flux to lake sediments.

Lake sediments are frequently used to reconstruct the rate and magnitude of human impacts on the biogeochemical cycle of mercury (Hg). The vast majority of these studies rely on excess (210)Pb inventories in short cores to temporally constrain recent trends in Hg deposition, revealing an approximately 3-fold increase in Hg deposition since preindustrial times. However, the exhaustion of unsupported (210)Pb and the onset of widespread global Hg pollution converge temporally in the late 19th century, raising the possibility that preindustrial Hg fluxes are poorly constrained. Here, we combine (210)Pb and accelerator mass spectrometry (AMS) (14)C dated lake sediment records from arctic and Andean lakes to assess the reliability of (210)Pb-derived chronologies in the estimation of preindustrial Hg fluxes. For all four studied lakes, relying on (210)Pb chronologies results in an overestimate of preindustrial Hg fluxes, because extrapolated basal (210)Pb sedimentation rates are systematically overestimated in comparison to accumulation models that include (14)C dates. In the Andes, the use of (14)C dates is critical toward assessing the full history of Hg pollution, which extends beyond the industrial era. In the Arctic, (14)C dating suggests that Hg deposition may have increased >10-fold since the Industrial Revolution, rather than the commonly quoted 3-fold increase. The incorporation of (14)C dates may therefore be necessary if accurate Hg flux histories are sought from oligotrophic lake sediments.