A model for inferring dissolved organic carbon (DOC) in lakewater from visible-near-infrared spectroscopy (VNIRS) measures in lake sediment

We developed an inference model to infer dissolved organic carbon (DOC) in lakewater from lake sediments using visible-near-infrared spectroscopy (VNIRS). The inference model used surface sediment samples collected from 160 Arctic Canada lakes, covering broad latitudinal (60–83°N), longitudinal (71–138°W) and environmental gradients, with a DOC range of 0.6–39.6 mg L⁻¹. The model was applied to Holocene lake sediment cores from Sweden and Canada and our inferences are compared to results from previous multiproxy paleolimnological investigations at these two sites. The inferred Swedish and Canadian DOC profiles are compared, respectively, to inferences from a Swedish-based VNIRS-total organic carbon (TOC) model and a Canadian-based diatom-inferred (Di-DOC) model from the same sediment records. The 5-component Partial Least Squares (PLS) model yields a cross-validated (CV) R_CV² R_{CV}^{2}  = 0.61 and a root mean squared error of prediction (RMSEP _CV ) = 4.4 mg L⁻¹ (11% of DOC gradient). The trends inferred for the two lakes were remarkably similar to the VNIRS-TOC and the Di-DOC inferred profiles and consistent with the other paleolimnological proxies, although absolute values differed. Differences in the calibration set gradients and lack of analogous VNIRS signatures in the modern datasets may explain this discrepancy. Our results corroborate previous geographically independent studies on the potential of using VNIRS to reconstruct past trends in lakewater DOC concentrations rapidly.     

Fourier-transform Infrared Spectroscopy (FTIRS), a New Method to Infer Past Changes in Tree-line Position and TOC using Lake Sediment

This study tests the hypothesis that Fourier-transform infrared spectroscopy (FTIRS) of lake sediments can be used to infer past changes in tree-line position and total organic carbon (TOC) content of lake water. A training set of 100 lakes from northern Sweden spanning a broad altitudinal and TOC gradient from 0.7 to 14.9 mg/l was used to assess whether vegetation zones and TOC can be modelled from FTIR spectra of surface sediments (0–1 cm) using principal component analysis (PCA) and partial least squares (PLS) regression. Preliminary results show that FTIRS of lake sediments can be used to reconstruct past changes in tree line and the TOC content of lake water, which is hardly surprising since FTIRS registers the properties of organic and minerogenic material derived from the water mass and the drainage area. The FTIRS model for TOC gives a root mean squared error (RMSECV) of calibration of 1.4 mg/l (10% of the gradient) assessed by internal cross-validation (CV) yielding an R_cv² of 0.64. This should be compared with a near-infrared spectroscopy (NIRS) and diatom transfer function for TOC from the same set of lakes, which have a R_cv² of 0.61 and 0.31, and RMSECV of 1.6 and 2.3 mg/l, respectively. The FTIRS-TOC model was applied to a Holocene sediment core from a tree-line lake and the results show similar trends as inferences from NIRS and pollen from the same core. Overall, the results indicate that changes in FTIR spectra from lake sediments reflect differences in catchment vegetation and TOC, and that FTIRS-models based on surface-sediment samples can be applied to sediment cores for retrospective analysis.     

Arsenic contamination of lake sediments in Florida: evidence of herbicide mobility from watershed soils

Organic arsenical herbicides, which include monosodium methylarsonate (MSMA), have been applied to golf courses and lawns throughout Florida, USA, since the 1950s. These products convert rapidly to inorganic forms of arsenic (As) in soils and are mobilized readily. Leachates have been known to contaminate groundwater and surface waters, although past studies have not examined whether use of these products has led to significant As accumulation in lake sediments. We used paleolimnological methods to document the depositional history and inventories of total As in sediments and porewaters of Little Lake Jackson in Florida, which is adjacent to three golf courses. Six sediment cores, four of which were ²¹⁰Pb dated, showed porewater total As concentrations as high as 435 μg l⁻¹, and dry-sediment total As concentrations as high as 148 mg kg⁻¹. Approximately 537 kg of total As is present in >19,000 metric tons of sediment (dry mass), and an additional 18 kg of As is dissolved in 10.8 × 10⁴ m³ of porewaters. Total As content in surface sediments (mean = 47.3 mg kg⁻¹) exceeds the consensus-based sedimentary concentration for probable toxicity effects in freshwater benthic fauna. Surface and subsurface waters flow to the lake from topographically higher areas to the west, where golf courses and residential areas are located. Total As concentrations were elevated highly in monitoring wells and in a stream that flows between the golf courses and lake, but As was below detection limits in wells that were located at the distal perimeter of the golf courses. Subsurface and surface waters exit the lake towards topographically lower areas to the east. Nearly all As in sediments remains bound in the solid phase, indicating that As sedimentary profiles largely reflect depositional history. Sedimentary As concentrations are correlated strongly with aluminum and iron, which suggests that As was scavenged from lake waters during the past. Sedimentary As concentrations increased until the 1980s, then declined somewhat to the present time. Dissolved As was scavenged efficiently from the water column when hypolimnetic waters were oxygenated persistently, but after eutrophication led to a seasonally anoxic hypolimnion in the 1980s, apparently less As was co-precipitated, and more was lost to hydrological outflow. Arsenic accumulation in sediments might be common in areas where As derived from organic arsenical herbicide applications is directed by shallow water tables towards adjacent lakes.     

A caveat regarding diatom-inferred nitrogen concentrations in oligotrophic lakes

Atmospheric deposition of reactive nitrogen (Nr) has enriched oligotrophic lakes with nitrogen (N) in many regions of the world and elicited dramatic changes in diatom community structure. The lakewater concentrations of nitrate that cause these community changes remain unclear, raising interest in the development of diatom-based transfer functions to infer nitrate. We developed a diatom calibration set using surface sediment samples from 46 high-elevation lakes across the Rocky Mountains of the western US, a region spanning an N deposition gradient from very low to moderate levels (<1 to 3.2 kg Nr ha⁻¹ year⁻¹ in wet deposition). Out of the fourteen measured environmental variables for these 46 lakes, ordination analysis identified that nitrate, specific conductance, total phosphorus, and hypolimnetic water temperature were related to diatom distributions. A transfer function was developed for nitrate and applied to a sedimentary diatom profile from Heart Lake in the central Rockies. The model coefficient of determination (bootstrapping validation) of 0.61 suggested potential for diatom-inferred reconstructions of lakewater nitrate concentrations over time, but a comparison of observed versus diatom-inferred nitrate values revealed the poor performance of this model at low nitrate concentrations. Resource physiology experiments revealed that nitrogen requirements of two key taxa were opposite to nitrate optima defined in the transfer function. Our data set reveals two underlying ecological constraints that impede the development of nitrate transfer functions in oligotrophic lakes: (1) even in lakes with nitrate concentrations below quantification (<1 μg L⁻¹), diatom assemblages were already dominated by species indicative of moderate N enrichment; (2) N-limited oligotrophic lakes switch to P limitation after receiving only modest inputs of reactive N, shifting the controls on diatom species changes along the length of the nitrate gradient. These constraints suggest that quantitative inferences of nitrate from diatom assemblages will likely require experimental approaches.     

Hydrogeochemistry of Groundwater and Its Suitability for Drinking and Agricultural Use in Nahavand,Western Iran

Groundwater is the major source of drinking water in Nahavand city. However, the groundwater quality at the agricultural areas has been deteriorating in recent years. Ground water quality monitoring is a tool which provides important information for water management and sustainable development of the water resources in Nahavand. Hydrochemical investigations were carried out in an agricultural area in Nahavand, western Iran, to assess chemical composition of groundwater. In this study, 64 representative groundwater samples were collected from different irrigation wells and analyzed for pH, electrical conductivity, major ions, and nitrate. The results of the chemical analysis of the groundwater showed that concentrations of ions vary widely and the most prevalent water type is Ca–Mg–HCO₃, followed by other water types: Ca–HCO₃, Ca–Na–HCO₃, and Na–Cl, which is in relation with their interactions with the geological formations of the basin, dissolution of feldspars and chloride and bicarbonate minerals, and anthropogenic activities. Thirty-seven percent of the water samples showed nitrate (NO₃ ⁻) concentrations above the human affected value (13 mg L⁻¹). The phosphorous (P) concentration in groundwater was between 0.11 and 0.90 mg L⁻¹, with an average value of 0.30 mg L⁻¹, with all of the samples over 0.05 mg L⁻¹. The most dominant class C2-S1 (76.5%) was found in the studied area, indicating that sodicity is very low and salinity is medium, and that these waters are suitable for irrigation in almost all soils. Agronomic practices, such as cultivation, cropping, and irrigation water management may decrease the average NO₃ ⁻ concentration in water draining from the soil zone.     

The use of diatom records to establish reference conditions for UK lakes subject to eutrophication

A knowledge of pre-disturbance conditions is important for setting realistic restoration targets for lakes. For European waters this is now a requirement of the European Council Water Framework Directive where ecological status must be assessed based on the degree to which present day conditions deviate from reference conditions. Here, we employ palaeolimnological techniques, principally inferences of total phosphorus from diatom assemblages (DI-TP) and classification of diatom composition data from the time slice in sediment cores dated to ~1850 AD, to define chemical and ecological reference conditions, respectively, for a range of UK lake types. The DI-TP results from 169 sites indicate that reference TP values for low alkalinity lakes are typically <10 μg L⁻¹ and in many cases <5 μg L⁻¹, whilst those for medium and high alkalinity lakes are in the range 10–30 and 20–40 μg L⁻¹, respectively. Within the latter two alkalinity types, the deeper waters (>3 m mean depth) generally had lower reference TP concentrations than the shallow sites. A small group of shallow marl lakes had concentrations of ~30 μg L⁻¹. Cluster analysis of diatom composition data from 106 lakes where the key pressure of interest was eutrophication identified three clusters, each associated with particular lake types, suggesting that the typology has ecological relevance, although poor cross matching of the diatom groups and the lake typology at type boundaries highlights the value of a site-specific approach to defining reference conditions. Finally the floristic difference between the reference and present day (surface sample) diatom assemblages of each site was estimated using the squared chord distance dissimilarity coefficient. Only 25 of the 106 lakes experienced insignificant change and the findings indicate that eutrophication has impacted all lake types with >50% of sites exhibiting significant floristic change. The study illustrates the role of the sediment record in determining both chemical and ecological reference conditions, and assessing deviation from the latter. Whilst restoration targets may require modification in the future to account for climate induced alterations, the long temporal perspective offered by palaeolimnology ensures that such changes are assessed against a sound baseline.     

Use of sedimentary pigments to infer past phosphorus concentration in lakes

We propose a palaeolimnological method for inferring past total phosphorus (TP) concentrations in lake water from spectrophotometrically-measured sedimentary pigments, particularly total carotenoids (TC). Our approach is based on a highly significant statistical correlation (P < 0.0001) between pigment concentrations (total carotenoids) in the surface sediment of 28 Italian lakes (subalpine, large, deep, shallow, volcanic) and TP concentrations measured in these lakes at overturn when the core was collected. A transfer function was developed from this “training” set, and used to estimate past TP concentrations from pigment concentrations in sediment cores. The results generally agreed with TP values as measured by long-term water quality monitoring programs. Contrasting results were obtained by a comparison with diatom-inferred TP. While the diatom model showed a tendency to overestimate TP values higher than 100 μg l⁻¹, the pigment model correctly estimated TP in lakes when TP was <100 μg l⁻¹, but not when lakes were rich in macrophytes. In fact, lakes with extensive populations of aquatic submersed macrophytes and epiphytes are outliers in terms of the TC versus TP relationship. The root mean square error of prediction of the pigment model is lower than those derived from certain diatom—based inference models. The predicted and residual values are not related to the estimated values and their average is not statistically different from zero. Errors were estimated via a ‘leave-one-out’ re-sampling technique. The proposed method permits rapid and relatively inexpensive determination of reference trophic conditions.     

Determination of carbon, carbonate, nitrogen, and phosphorus in freshwater sediments by near-infrared reflectance spectroscopy: Rapid analysis and a check on conventional analytical methods

Sediments are typically analyzed for C, N, and P for characterization, sediment quality assessment, and in nutrient and contaminant studies. Cost and time required for analysis of these constituents by conventional chemical techniques can be limiting factors in these studies. Determination of these constituents by near-infrared reflectance spectroscopy (NIRS) may be a rapid, cost-effective method provided the technology can be applied generally across aquatic ecosystems. In this study, we explored the feasibility of using NIRS to predict total C, CO₃ ^–2 organic C, N, and P in deep-water sediment cores from four Canadian lakes varying over 19 degrees of latitude. Concentration ranges of constituents in the samples (dry weight basis) were total C, 12-55; CO₃ ^–2, 6-26; organic C, 7-31; N, 0.6-3.1; and P, 0.22-2.1 mg g^–1. Coefficients of determination, r2, between results from conventional chemical analysis and NIR-predicted concentrations, based on calibrations across all the four lakes, were 0.97-0.99 for total C, organic C, and N. Prediction for CO₃ ^–2 was good for the hard water lake from a calibration across all four lakes, but this constituent in the three soft water lakes was better predicted by a calibration across the soft water lakes. The NIR calibration for P fell below acceptable levels for the technique, but proved useful in the identification of outliers from the chemical method that were later removed with the re-analysis of several samples. This study demonstrated that NIRS is useful for rapid, simultaneous, cost-effective analysis of total C, CO₃ ^–2, organic C, N, and P in dried sediments from lakes at widely varying latitudes. Also, this study showed that NIRS is an independent analytical tool useful for the identification of outliers that may be due to error during the analysis or to distinctive composition of the samples.     

Landscape-scale patterns of sediment sulfur accumulation in Swedish lakes

Sulfur has played a central role in the acidification of many lakes in Scandinavia and other regions. As part of the research into sulfur cycling, numerous studies have analyzed the sediment record in order to develop insights into past in-lake cycling of sulfur, particularly in the context of reconstructing past deposition rates. Although many of these studies have shown that it is not easy to interpret the sediment record in terms of past sulfur deposition rates, analyses of sulfur in sediment still provide valuable information on the response of lakes to anthropogenic sulfur deposition. Here, we have analyzed sulfur in top and bottom samples from short surface cores (25–35 cm, representing ≥250 years) as well as bulk cores from ∼110 lakes located throughout Sweden, which were collected during 1986, as well as in more-detailed profiles from six lakes. The lakes with the highest surface sediment concentrations (9–24 mg S g⁻¹ dry mass) and the highest calculated inventories of ‘excess’ sulfur (20–180 g S m⁻²) are found in southern Sweden and around one industrial area along the northeastern coast where sulfur deposition rates and lake-water concentrations have been highest. For many lakes in the central and northern inland region it is common that the sediment cores exhibit either no enrichment or even a decline in sulfur concentrations in near-surface sediments, which we suggest was the pre-pollution norm for lakes. Although interpreting sulfur sediment profiles is problematic for reconstructing deposition, a more-comprehensive spatial sampling approach shows that there is a good geographic agreement between sulfur deposition, lake-water chemistry and sediment sulfur accumulation.     

Biogeochemical records of paleoenvironmental changes in Nainital Lake,Kumaun Himalayas,India

Rapid urbanization and increased tourism around Nainital Lake in the Kumaun Himalayan region in north India has raised concerns about sediment and water pollution. Lead-210 dated sediment cores from the lake represent ~95 years of accumulation and yield a mean sedimentation rate of ~4.7 mm year⁻¹. Total organic carbon (TOC), percent N and S and their atomic C/N and C/S ratios, stable isotopes (δ¹³C, δ¹⁵N, and δ³⁴S), and specific biomarkers (n-alkanes and pigments) were measured in the core. Organic matter is primarily derived from in-lake algal production and TOC flux varies from 1.0 to 3.5 g m⁻² year⁻¹. Sediments are anoxic (Eh −328 to −187 mV) and have low (0.10–0.30 g m⁻² year⁻¹) N, but high (0.37–1.0 g m⁻² year⁻¹) S flux. Shifts in δ¹³C, δ¹⁵N, and δ³⁴S suggest in-lake microbial processes dominated by denitrification and sulfate reduction. The sediments are dominated by short-chain hydrocarbons with low Carbon Preference Index values. The pigments indicate a gradual shift to cyanobacterial domination of the phytoplankton community in recent years. Despite an increase in external input of nutrients, the trophic state of the lake has remained largely unchanged, and the perceived human-induced impacts are limited.     

Biomonitoring past salinity changes in an athalassic subarctic lake

A short sediment core was taken from a small saline lake located on an intermontane plateau in the central Yukon Territory, Canada. In July 1990, chemical analyses indicated that, although the lake was shallow (Z_max=1.1 m), it was also chemically stratified, with hyposaline (9.9 to 10.0 g L⁻¹) surface waters and slightly mesosaline (22.0 g L⁻¹) deeper waters. The surface water was dominated by Na⁺ and HCO ₃ ⁻ . To our knowledge, this is the northernmost athalassic saline lake yet recorded. Quantification of algal (diatom, chrysophyte, and pigment) and invertebrate (chironomid, ceratopogonid, andChaoborus) fossils at four stratigraphic levels indicated that the lake sediments preserved numerous biological indicators that could be used to infer recent lake development. Many of the taxa are found in other athalassic salt lakes. The most striking stratigraphic change was a remarkable drop in the species richness of diatoms and invertebrates in the recent sediments, which parallels the elimination of species characteristic of less saline conditions. Halophilous taxa dominate the most recent sediments, indicating the development of more saline conditions. At the same time, a significant shift in chrysophyte cyst composition was observed. Fossil carotenoids and chlorophylls indicated a decrease in total algal abundance in recent sediments, as green and blue-green algae replaced diatoms and chrysophytes. Together, these paleolimnological data suggest a recent shift to drier conditions or increased evaporation in the central Yukon Territory.     

Evaporative enrichment of oxygen-18 and deuterium in lake waters on the Tibetan Plateau

Stable isotopes (δ¹⁸O and δD) are useful tracers for investigating hydrologic and climatic variability on a variety of temporal and spatial scales. Since the early isotopic studies on mountainous glaciers in the late 1960s, a great deal of information has been generated on the isotopic composition of rainfall, snow, ice, surface waters, and lake carbonate sediments across the Tibetan Plateau. However, measurements of δ¹⁸O and δD values of lake water are scarce. Here we present a new dataset of δ¹⁸O and δD values of lake waters collected from 27 lakes across the plateau during a reconnaissance survey in summer 2009. δ¹⁸O and δD values of lake water range from −19.9 to 6.6‰ and from −153 to −16‰, respectively. The average values of δ¹⁸O and δD are −6.4 and −72‰, considerably greater than those of precipitation observed in this region. The derived Tibetan lake water line, δD = 5.2δ¹⁸O − 38.9, is significantly different from the global meteoric water line. Most of the lakes, including some freshwater lakes, contain water with negative values of d-excess (d). There is a negative correlation between d and total dissolved solids (TDS). Each of these findings indicates that evaporation-induced isotopic enrichment prevails in Tibetan lakes. Moreover, we develop an isotope modeling scheme to calculate E/P ratios for Tibetan lakes, using a combination of existing isotopic fractionation equations and the Rayleigh distillation model. We use the intersection of the local evaporation line and GMWL as a first approximation of δ¹⁸O and δD values of lake water inputs to infer an E/P ratio for each lake. Our modeling calculations reveal that although variable from lake to lake, the water budget across the plateau is positive, with an average E/P of 0.52. This is in good agreement with other observational and model data that show varying degrees of increases in lake size from satellite imagery and significant decreases in lake salinity in many lakes on the plateau over the last several decades. Together with the new isotopic dataset, the proposed modeling framework can be used to examine and quantify past changes in a lake’s hydrologic balance from the isotopic record of downcore carbonate sediments in the region.     

Stable isotope (δ<Superscript>13</Superscript>C and δ<Superscript>15</Superscript>N) values of sediment organic matter in subtropical lakes of different trophic status

Lake sediments contain archives of past environmental conditions in and around water bodies and stable isotope analyses (δ¹³C and δ¹⁵N) of sediment cores have been used to infer past environmental changes in aquatic ecosystems. In this study, we analyzed organic matter (OM), carbon (C), nitrogen (N), phosphorus (P), and δ¹³C and δ¹⁵N values in sediment cores from three subtropical lakes that span a broad range of trophic state. Our principal objectives were to: (1) evaluate whether nutrient concentrations and stable isotope values in surface deposits reflect modern trophic state conditions in the lakes, and (2) assess whether stratigraphic changes in the measured variables yield information about shifts in trophic status through time, or alternatively, diagenetic changes in sediment OM. Three Florida (USA) lakes of very different trophic status were selected for this study. Results showed that both δ¹³C and δ¹⁵N values in surface sediments of the oligo-mesotrophic lake were relatively low compared to values in surface sediments of the other lakes, and were progressively lower with depth in the sediment core. Sediments of the eutrophic lake had δ¹³C values that declined upcore, whereas δ¹⁵N values increased toward the sediment surface. The eutrophic lake displayed δ¹³C values intermediate between those in the oligo-mesotrophic and hypereutrophic lakes. Sediments of the hypereutrophic lake had relatively higher δ¹³C and δ¹⁵N values. In general, we found greater δ¹³C and δ¹⁵N values with increasing lake trophic state.     

Impacts of Coal-Fired Power Plants on Trace Metals and Polycyclic Aromatic Hydrocarbons (PAHs) in Lake Sediments in Central Alberta, Canada

Trace metals and polycyclic aromatic hydrocarbons (PAH) were analyzed in sediment cores from three central Alberta lakes to determine the contributions of local coal-fired power plants to contaminant loadings. In Wabamun Lake, with four power plants built since 1950 within a 35-km radius, sediment concentrations of mercury, copper, lead, arsenic and selenium have increased by 1.2- to 4-fold. Trace metal enrichments were less pronounced in Lac Ste. Anne and Pigeon Lake, situated 20 km north and 70 km south of Wabamun Lake, respectively. Total Hg flux to Wabamun Lake sediments (21–32μg m⁻² yr⁻¹) has increased 6-fold since 1950, compared to 2- and 1.5-fold increases in Lac Ste. Anne and Pigeon Lake, respectively, since circa 1900. Total PAH flux to surface sediments was 730–1100μg m⁻² yr⁻¹ in Wabamun Lake, 290–420μg m⁻² yr⁻¹ in Lac Ste. Anne, and 140–240μg m⁻² yr⁻¹ in Pigeon Lake. Without adoption of pollution-abatement technology that compensates for increases in generating capacity, continued expansion of coal-burning industry in Alberta will result in increased contaminant deposition, primarily from local sources.     

Cladocera as indicators of trophic state in Irish lakes

We examined the impact of lake trophic state on the taxonomic and functional structure of cladoceran communities and the role of nutrient loading in structuring both cladoceran and diatom communities. Surface sediment assemblages from 33 Irish lakes were analysed along a gradient of total phosphorus concentration (TP; 4.0–142.3 μg l⁻¹), using a variety of statistical approaches including ordination, calibration and variance partitioning. Ordination showed that the taxonomic structure of the cladoceran community displayed the strongest response to changes in lake trophic state, among 17 measured environmental variables. Trophic state variables chlorophyll-a and TP explained about 20% of the variance in both cladoceran and diatom assemblages from a set of 31 lakes. Procrustes analysis also showed significant concordance in the structure of cladoceran and diatom communities (P < 0.001). Thus, lake trophic state affects the taxonomic structure of both primary and secondary producers in our study lakes. We also found a significant decrease in relative abundance of taxa associated with both macrophytes and sediments, or sediments only, along the TP gradient (r = −0.49, P = 0.006, n = 30), as well as an increase in the proportion of the planktonic group (r = 0.43, P = 0.017, n = 30). This suggests that cladoceran community structure may also be shaped by lake trophic state indirectly, by affecting habitat properties. We found no relationship between lake trophic state and the relative abundance of each of three cladoceran groups that display different body size. We compared community structure between bottom and top sediment samples in cores from six Irish lakes. Results revealed similar trajectories of nutrient enrichment over time, as well as a strong shift in cladoceran functional structure in most systems. This study confirms that Cladocera remains in lake sediments are reliable indicators of lake trophic state. This study also highlights the fact that taxonomic and functional structure should both be considered to account for the multiple factors that shape cladoceran communities.     

Geochemical and biological consequences of groundwater augmentation in lakes of west-central Florida (USA)

We studied sediment cores from four Florida (USA) lakes that have received groundwater hydrologic supplements (augmentation) for >30 years to maintain lake stage. Top samples (0–4 cm) from sediment cores taken in Lakes Charles, Saddleback, Little Hobbs, and Crystal had ²²⁶Ra activities of 44.9, 17.5, 7.6, and 8.5 dpm g⁻¹, respectively, about an order of magnitude greater than values in deeper, older deposits. The surface sample from Lake Charles yielded the highest ²²⁶Ra activity yet reported from a Florida lake core. Several lines of evidence suggest that groundwater augmentation is responsible for the high ²²⁶Ra activities in recent sediments: (1) ²²⁶Ra activity in cores increased recently, (2) the Charles, Crystal, and Saddleback cores display ²²⁶Ra/²¹⁰Pb disequilibrium at several shallow depths, suggesting ²²⁶Ra entered the lakes in dissolved form, (3) cores show recent increases in Ca, which, like ²²⁶Ra, is abundant in augmentation groundwater, and (4) greater Sr concentrations are associated with higher ²²⁶Ra activities in recent Charles and Saddleback sediments. Sr concentrations in Eocene limestones of the deep Floridan Aquifer are high relative to Sr concentrations in surficial quartz sands around the lakes. Historical water quality inferences for the lakes were based on diatom assemblages in sediments. Recent alkalization in Lakes Charles, Saddleback, Little Hobbs, and Crystal was inferred from weighted-averaging calibration (WACALIB). The lakes also show recent trophic state increases based on WACALIB-derived estimates for limnetic total P. Although residential and agricultural sources might contribute to increased P loading, P in augmentation waters probably has had significant influence on eutrophication. Dystrophic diatoms were abundant in the early history of Lakes Saddleback, Little Hobbs, and Crystal, which suggests that these lakes contained more tannic waters during the past than at present, perhaps as a consequence of greater inflows from surrounding wetlands. Ionic content of lake waters increased, as indicated by diatom autecological analysis. Recent geochemical and biological changes detected in cores from these lakes probably are a result of deliberate groundwater augmentation, although inputs of groundwater pumped for agricultural and residential development in the watersheds also might have contributed to limnological changes.     

Sediment accumulation rates in European lakes since AD 1850: trends,reference conditions and exceedence

Sediment accumulation rate (SAR) is an important physical parameter in all lakes and increases have been observed in many over the last c.100 years. This has been ascribed to changes in land-use and land-management causing accelerated catchment soil erosion and an increase in autochthonous organic matter production. The EU Water Framework Directive requires that assessment of biological, hydromorphological and chemical elements of water quality should be based on the degree to which present day conditions deviate from those expected in the absence of significant anthropogenic influence, termed reference conditions. Currently however, the reference condition for sediment accumulation rate for lakes of different types is undefined. To improve our understanding of the controls on SARs we compiled SAR and lake typology data for 207 European lakes derived from ²¹⁰Pb dated cores to assess how rates have changed through time (in 25 year classes) both overall and for lakes of different types. Seventy-one percent of these sediment cores showed surface SARs higher than “basal” (mainly nineteenth century) rates, 11% showed no change while 18% showed a decline. Lakes were then classified into lake-types using four variables: alkalinity (3 classes), altitude (3 classes), maximum depth (2 classes) and lake area (2 classes). This generated a possible 36 lake classes of which 25 were represented in the dataset. Nine lake-types contained >10 lakes. Little change in SAR occurred prior to 1900 and most increases occurred in more recent periods, in particular 1950–1975 and post-1975. This indicates a general acceleration in SAR in European lakes during the second half of the twentieth century. Reference SARs were estimated for six lake-types with the highest number of sites. European mountain lakes had the lowest reference SAR (0.005 ± 0.003 g cm⁻² yr⁻¹) while lowland, high alkalinity sites had the highest (0.03–0.04 g cm⁻² yr⁻¹). SARs for other lake-types ranged between 0.012 and 0.024 g cm⁻² yr⁻¹. Using the mountain lake-type as an example, the 1850 reference SAR appears to show good agreement with available data for lakes beyond Europe indicating these values may be more broadly applicable. Contemporary SARs in lakes of all classes showed exceedence over their defined reference SAR. This may be partly due to diagenetic processes. Greatest exceedences were found in shallow, low altitude lakes and these are considered to be the ones under the greatest threat from continued elevation of SAR. It is considered that climate change may play a progressively more important role in driving SAR in the future.     

Diatom-based total phosphorus (TP) and pH transfer functions for the Irish Ecoregion

A 72-lake diatom training set was developed for the Irish Ecoregion to examine the response of surface sediment diatom assemblages to measured environmental variables. A variety of multivariate data analyses was used to investigate environmental and biological data structure and their inter-relationships. Of the variables used in determining a typology for lakes in the Irish Ecoregion, alkalinity was the only one found to have a significant effect on diatom assemblages. A total of 602 diatom taxa were identified, with 233 recorded at three or more sites with abundances ≥1%. Generally diatom data displayed a high degree of heterogeneity at the species level and non-linear ecological responses. Both pH and total phosphorus (TP) (in the ranges of 5.1–8.5 and 4.0–142.3 μg l⁻¹ respectively) were shown to be the most significant variables in determining the surface sediment diatom assemblages. The calibration models for pH and TP were developed using the weighted averaging (WA) method; data manipulation showed strong influences on model performances. The optima WA models based on 70 lakes produced a jack-knifed coefficient of determination (r ² _jack) of 0.89 with a root mean squared error (RMSEP) of 0.32 for pH and r ² _jack of 0.74 and RMSEP of 0.21 (log₁₀ μg l⁻¹) for TP. Both models showed strong performances in comparison with existing models for Ireland and elsewhere. Application of the pH and TP transfer functions developed here will enable the generation of quantitative water quality data from the expanding number of palaeolimnological records available for the Irish Ecoregion, and thus facilitate the use of palaeolimnological approaches in the reconstruction of past lake water quality, ecological assessment and restoration.     

Lead pollution history from 256 BC to AD 2005 inferred from the Pb isotope ratio (<Superscript>206</Superscript>Pb/<Superscript>207</Superscript>Pb) in a varve record of Lake Korttajärvi in Finland

The lead pollution history, based on the accumulation rate of total Pb and ratio of stable isotopes (²⁰⁶Pb/²⁰⁷Pb), was studied in the annually laminated sediment of a small lake in Finland (62°20′ N; 25°41′ E). The sediment chronology based on varve counting provided a unique opportunity to explore and date signals of Pb emissions, including the ancient metallurgical activities of the Roman Empire at the beginning of the Current Era. Changes in the ratio of stable isotopes gave a pronounced signal of the atmospheric Pb fallout in AD 32–392, although this was not distinguishable in the accumulation rate of total Pb, as it was observed in previous work. Calculated accumulations of the ancient pollution Pb were low, the highest values being 0.2–0.3 mg m² a⁻¹ in AD 144–392, corresponding 14–21% of the accumulation of total Pb. The accumulation of pollution Pb collapsed in the fifth century and remained at or close to the background level up to the eleventh century. After this, the accumulation rate of pollution Pb began to increase and reached 1.2 mg m² a⁻¹ in AD 1420–1439, corresponding to 44% of the total Pb accumulation. During five centuries, from AD 1420–1895, the average accumulation of pollution Pb was 2.6 mg m² a⁻¹, the variation being from 0.8 to 4.8 mg m² a⁻¹. The accumulation of Pb started to increase exponentially in the early twentieth century, and the highest accumulations of pollution Pb (11–22 mg m² a⁻¹, corresponding 50–76% of the annual accumulation of total Pb) were dated to AD 1926–1985. The banning of the use of leaded fuel has led to a pronounced decrease in the accumulation of pollution Pb since the 1980s, and the present accumulation rate represents the level that prevailed 80–120 years ago.