Estimating and simulating the degree of serpentinization of peridotites using hyperspectral remotely sensed imagery

The mineral products resulting from the process of serpentinization, by which primary magnesium silicate minerals in peridotites are replaced by hydrous serpentine-group minerals, are of economic importance since Alpine-type peridotites are the host rocks for virtually all large asbestos deposits, which may be attributed mainly to the serpentine-group mineral chrysotile. Conventional field mapping of the distribution of highly serpentinized areas is time consuming and requires detailed sampling and laboratory analysis. In 0.4- to 2.5-m reflectance spectra of serpentinized peridotites, serpentinization is responsible for a decrease in contrast of olivine-pyroxene iron absorption features and an appearance and increase in OH^– absorption features near 1.4 m and 2.3 m associated with serpentine minerals. The degree of serpentinization is positively correlated with the depth of the 1.4-m and 2.3-m absorption features for samples containing more than 55 weight percent serpentine minerals. Small amounts of magnetite in a sample obscure the spectral contrast and decrease the overall brightness of weakly serpentinized samples. A methodology is used for mapping serpentine minerals in ultrabasic rocks from imaging spectrometer data, which includes (1) vegetation masking, (2) calculating the absorption band depth of the 2.3-m absorption feature in unmasked pixels, (3) translating this value into percent serpentine minerals using an empirical linear model, and (4) estimating the degree of serpentinization at the remaining locations using conditional simulation techniques or ordinary block kriging. From the results of this study, it can be concluded that mapping the degree of serpentinization from high-spectral resolution imagery is possible within marginal statistical fluctuations. Conditional simulation reproduces the spatial and statistical variability of the data set; however, it sacrifices the local accuracy. Direct estimation using ordinary kriging provides a better local estimate but does not honor the statistics and spatial dispersion of the original data.The spectral analyses presented in this publication were carried out at the Jet Propulsion Laboratory in Pasadena, California. The author would like to thank Mrs. Cindy Grove for her help in processing the samples. Dr. Harold Lang is thanked for advice in interpreting the spectra. The article benefitted from critical comments by Dr. Roger Clark and Dr. John Mustard, and various discussions with Prof. Salemon Kroonenberg and Prof. Andrea Fabbri. The Spectral Image Processing System (SIPS) developed at the Center for the Study of Earth from Space (CSES) of the University of Colorado, Boulder, was used for the GERIS data calibration. This article benefitted from a critical review by Dr. Daniel H. Knepper, Jr.     

Climatic and anthropogenic influence on the stable isotope record from bulk carbonates and ostracodes in Lake Neuchâ, Switzerland, during the last two millennia

Lake Neuchåtel is a medium sized, hard-water lake, lacking varved sediments, situated in the western Swiss Lowlands at the foot of the Jura Mountains. Stable isotope data (18O and 13C) from both bulk carbonate and ostracode calcite in an 81 cm long, radiocarbon-dated sediment core represent the last 1500 years of Lake Neuchåtel's environmental history. Comparison between this isotopic and other palaeolimnologic data (mineralogical, geochemical, palynological, etc.) helps to differentiate between anthropogenic and natural factors most recently affecting the lake. An increase in lacustrine productivity (450–650AD ca), inferred from the positive trend in 13C values of bulk carbonate, is related to medieval forest clearances and the associated nutrient budget changes. A negative trend in both the bulk carbonate and ostracode calcite 18O values between approximately 1300 and 1500AD, is tentatively interpreted as due to a cooling in mean air temperature at the transition from the Medieval Warm Period to the Little Ice Age. Negative trends in bulk carbonate 18O and 13C values through the uppermost sediments, which have no equivalent in ostracode calcite isotopic values, are concomitant with the recent onset of eutrophication in the lake. Isotopic disequilibrium during calcite precipitation, probably due to kinetic factors in periods of high productivity is postulated as the mechanism to explain the associated negative isotopic trends, although the effect of a shift of the calcite precipitation towards the warmer months cannot be excluded.     

A diatom-based inference model for autumn epilimnetic total phosphorus concentration and its application to a presently eutrophic boreal lake

A diatom transfer function to infer epilimnetic total phosphorus (TP) concentration was derived using surface sediment diatom data from 68 medium-sized (10–1000 ha) lakes in Southern Finland. Publicly available monitoring records were used in lake selection to avoid gradients caused by pH and humic substances. Constrained and partially constrained ordinations indicated that TP was an important variable influencing diatom assemblages. A long floristic gradient in relation to TP was also apparent and therefore an inference model was developed for TP using unimodal-based regression and calibration methods. The final model included 61 lakes with epilimnetic TP concentrations between 3 and 89 g P l^–1, measured during the autumnal circulation period. It has a jackknifed-estimated root mean squared error of prediction of 0.16 log g P l^–1, a maximum bias of 0.28 log g P l^–1, and an r² _jack of 0.76.The model was tested in the presently eutrophic Lake Valkjärvi (epilimnetic [TP] 60–85 g P l^–1), located in Southern Finland. It successfully predicted the measured autumnal epilimnetic TP concentration for the past twenty years and the changes in inferred [TP] reflected disturbances known to have occurred before that time. The diatom-based inferences show that Lake Valkjärvi was oligo-mesotrophic as late as the 1930's and has become eutrophic because of nutrient inputs from agriculture and, especially, municipalities. However, epilimnetic TP concentration has not increased further.     

Abrupt changes in climatic conditions across the late-glacial/Holocene transition on the N. E. Tibet-Qinghai Plateau: evidence from Lake Qinghai, China

A multi-proxy investigation of two sediment cores from the large closed-basin Lake Qinghai provides evidence of abrupt changes in paleolimnological conditions across the late-glacial/Holocene transition. The chronology of the lacustrine sediment sequence is framed by four AMS ¹⁴C ages for aquatic-plant macrofossil seeds. Four distinct stratigraphic units are identified on the basis of abrupt shifts in lithology, carbonate composition, ¹⁸O of authigenic carbonates, magnetic susceptibility characteristics, and total nitrogen content. These units represent four environmental stages that were each initiated by three abrupt changes in hydro-climatic regime at 11,600, 10,700, and 10,000 ¹⁴C yrs B.P. Each of the four environmental stages thus represents a characteristic precipitation-to-evaporation balance for the lake catchment. The paleoenvironmental evidence indicates that the lake before 11,600 ¹⁴C yrs B.P. was very shallow with carbonate production and organic productivity much lower than in the Holocene, suggesting a much colder and drier climate than in the Holocene. From 11,600 to 10,700 ¹⁴C yrs B.P., the presence of clastic laminations and Ruppia fossil seeds suggests an increased inflow of sediment-laden waters into the lake. Between 10,700 and 10,000 ¹⁴C yrs B.P., the development of a carbonate playa lake indicates that a negative water balance persisted. From 10,000 ¹⁴C yrs B.P. an abrupt increase in rainfall is suggested by a sudden termination of the playa lake environment and the diluted lake waters, as evidenced by negative shift in both total carbonate content and ¹⁸O values of mineral carbonate. However, the lake level during the early Holocene was about 20 m shallower than today, indicating that the effective moisture then was much lower than it is today. The multi-proxy record suggests a step-wise pattern of climatic change across the late-glacial/Holocene transition along with abrupt shifts in P-E balance on the N. E. Tibet-Qinghai Plateau. This pattern is characterized by reorganization of Asian monsoon circulation, which probably was determined by increasing summer insolation and changes in surface boundary conditions accompanying regional deglaciation. The arid event at 10,700–10,000 ¹⁴C yrs B.P. is interpreted as a Younger Dryas equivalent, although climatic cooling is not indicated by the evidence at hand.     

Development of paleolimnological inference models for pH, total nitrogen and specific conductivity based on planktonic diatoms

Canonical correspondence analysis (CCA was used to explore and identify statistically significant relationships between the distributions of planktonic diatoms and the physical and chemical properties of 50 Connecticut lakes. Six variables (pH, total nitrogen, calcium, sulfate, potassium and chlorophyll- a concentrations) were found to be significantly correlated with either or both of the first two extracted axes. The pH and calcium concentration, and to a lesser extent total nitrogen concentrations, were the most important variables controlling the distributions of planktonic diatoms in this suite of lakes. Paleolimnological inference models were developed for pH, total nitrogen (TN) and specific conductivity. Weighted averaging with (WAtol) and without (WA) tolerance downweighting, with and without bootstrap resampling techniques, and using either classical or inverse deshrinking methods were used to develop inference models for each variable. The pH and TN yielded sufficiently high 1/2 ratios and a highly significant first (constrained) axis when entered as single variables in both constrained and partially constrained CCA analyses, supporting the idea that reliable inference models could be developed for these variables. The r2 and RMSE of prediction values ranged from 0.73 to 0.86 and 0.37 to 0.6, respectively for pH, and from 0.4 to 0.64 and 59 g/l to 95 g/l, respectively for TN. Inference models for specific conductivity also yielded significant goodness-of-fit statistics. However, because specific conductivity was removed from the CCA analysis due to its high variance inflation factor and did not yield a significant relationship when entered as the sole variable in a partial constrained CCA, inference models for this variable will probably not yield any additional environmental information. The use of only planktonic diatoms in construction of inference models is discussed.     

Morphological variation of Stephanodiscus niagarae Ehrenb. (Bacillariophyta) in a Lake Ontario sediment core

Stephanodiscus niagarae populations in a core from Lake Ontario show systematic variation in radial puncta number and mean valve diameter. Puncta number is stable in specimens from samples deposited between 1720 and 1844. Puncta number gradually increases in samples deposited between 1860 and 1947, then increases rapidly to high numbers in samples deposited after 1964. Mean valve diameter is relatively high in specimens from samples deposited between 1720 and 1959. Diameter of specimens deposited during this period fluctuates around a mean of 63.2 m. Mean diameter of specimens deposited from 1959 to 1980 is only 42.5 m. We conclude that the trend in puncta number reflects the time course of eutrophication in Lake Ontario. We interpret the precipitous decline in mean diameter as an indication that conditions in the lake after the late 1950's did not permit sexual reproduction in this species.     

Relationships between environmental variables and zooplankton subfossils in the surface sediments of 36 shallow coastal brackish lakes with special emphasis on the role of fish

Subfossil zooplankton assemblages (Cladocera 22 taxa, Rotifera 1 taxon) were identified from the surface sediments of 36 shallow (median depth = 0.7 m) Danish coastal brackish lakes differing in epilimnic salinity (SAL, range 0.2–17.4), summer-mean total phosphorus (TP, 27–327 g l^–1) and total nitrogen (TN, 0.850–2.629 mg l^–1), as well as in submerged macrophyte coverage and planktivorous fish density (PL-CPUE). Cladoceran species richness declined significantly with increasing SAL, TP and TN, while no significant correlation was found to either PL-CPUE, macrophyte coverage or lake surface area. Bonferroni-adjusted forward selection within canonical correspondence analysis (CCA) showed that 22.1% of the variation in zooplankton data was explained by PL-CPUE, SAL and TP uniquely; each variable explaining an almost equally significant amount of variation in the zooplankton data. Predictive models to infer PL-CPUE, SAL and TP were developed using variance weighted-averaging (WA) procedures. Almost similar values of boot-strapped coefficient of determination (r²_{boot-strapped} 0.22–0.38) were produced by the WA inference models of PL-CPUE, SAL and TP, while the inference models of TP produced the lowest boot-strapped root-mean-squared-error of prediction (RMSEP_{boot-strapped} 0.29–0.36 log(TP + 1), g l^–1). Yet, zooplankton TP and SAL optima (WA) were strongly correlated (r² = 0.46), while PL-CPUE optima (WA) were independent of both TP and SAL optima, indicating that only the PL-CPUE inference models are suitable for making reconstructions.     

Lacustrine oxygen isotope record of 20th-century climate change in central EuropeL evaluation of climatic controls on oxygen isotopes in precipitation

We report oxygen isotope data from a 108-yr (1885–1993) sequence with annual laminae of bio-induced authigenic calcite in a frozen core from Baldeggersee, a small lake in Central Switzerland. These isotope results provide proxy data on the isotopic composition of past precipitation in the Baldeggersee catchment region and are quantitatively compared with instrumental climate data (i.e. mean annual air temperature and atmospheric circulation pattern indices) to evaluate climatic controls on oxygen isotopes in precipitation.Monitoring the isotope hydrology of Baldeggersee demonstrates that the oxygen isotopic composition of the lake water is controlled by the isotopic composition of local atmospheric precipitation (¹⁸O_p) and that the isotopic signal of precipitation is preserved, albeit damped, in the lake calcite oxygen isotope record (¹⁸O_c). Comparison of the calcite oxygen isotope proxy for ¹⁸O_p in the catchment with historical mean annual air temperature measurements from Bern, Switzerland confirms that authigenic calcite reliably records past annual air temperature in the region. This ¹⁸O_c/temperature relationship is calculated to be 0.39/°C for the period 1900–1960, based on an isotope mass-balance model for Baldeggersee. An exception is a 0.8 anomalous negative shift in calcite ¹⁸O values since the 1960s. Possible explanations for this recent ¹⁸O_c shift, as it is not related to mean annual air temperature, include changes in ¹⁸O_p due to synoptic circulation patterns. In particular, the 0.8 negative shift coincides with a trend towards a more dominant North Atlantic Oscillation (NAO) index. This circulation pattern would tend to bring more isotopically more negative winter precipitation to the region and could account for the 0.8 offset in ¹⁸O_c data.     

Processes affecting deposition of sediment in a small, morphologically complex lake

Devil Lake is morphologically complex as a result of Pleistocene glacial erosion of the Frontenac Axis of the Canadian Shield. In order to assess the processes causing highly variable sedimentation in the lake, we monitored currents, suspended sediment and temperature in the lake before and during autumn overturn in 2002. Strong summer thermal stratification (stability number to 0.11 s^–1 declining with the approach of overturn) was insufficient to prevent a dynamic response in the hypolimnion to wind forcing. Superimposed on a gradual increase in suspended sediment concentration in the last weeks of stratification from less than 2 g/l to about 30 g/l were shorter-term rises lasting up to several days. Associated with these events was an increase in particle size of the sediment from a mode of 40–50 to 150–200 m ascribed to flocculation from primary particles. These events culminated in rapid (<1 h) clearing of the water associated with strong, sustained winds over the lake, especially from the southwest. After overturn, the events were more frequent, and flocculation was unable to develop as well in the more vigorous circulation. However, currents in the hypolimnion occurred throughout the period before, during and after overturn with speed related to wind speed, but direction largely independent of wind direction. The results represent an approach to understanding the nature of sedimentary processes and thus to strengthening the use of sedimentary records as proxy in environmental and paleoenvironmental assessment.     

Lead analysis of sediment cores from seven Connecticut lakes

Lead analyses were performed on sediment cores from seven Connecticut lakes by dilute acid leaching. The absolute concentrations of lead varied from core to core, but the lead profiles were similar in all of the cores, and each depicted a point where the concentration of lead sharply increased above background levels. The background lead concentrations observed in the bottom portions of the cores ranged from 12-54 g Pb/g sediment with a mean of 30 g Pb/g, and increased to a mean maximum of 310 g Pb/g. In six of the lakes significant increases above background levels were not noted until between 1924 and 1952, suggesting that, at least for Connecticut lakes, the point in a lake sediment core where the concentration of lead began to increase was after ca. 1924, and on average about 1930. Lead concentrations declined in the surface sediments of only three of the lakes, mostly since the 1980's, and presumably in response to the phasing out of leaded gasoline. However, significant declines in lead concentrations were not observed in the remaining cores, possibly due to increased motor vehicle use within the airshed of the lakes and/or changes in the export of lead to the lakes from their watersheds.     

Authigenic clays in East Africa: Regional trends and paleolimnology at the Plio–Pleistocene boundary, Olduvai Gorge, Tanzania

Ultrafine clays (<0.1 m) from six East African basins show wide chemical variability that can be conveniently described as the octahedral cation index (OCI), calculated as octahedral element ratio Mg/(Al+Fe). Values range from dioctahedral clays with OCI < 0.1 (upland soils/detrital sources) to trioctahedral clays with OCI > 4 (saline, alkaline lake deposits). The association of Mg-rich clays with saline, alkaline conditions provides a paleochemical proxy in sedimentary contexts. The octahedral chemistry of central-basin clays from paleolake Olduvai (1.79 Ma) records two lake expansions, with an intervening lake contraction, over 18,000 years. The initial lake expansion correlates well with the marine record of increased African humidity, but the subsequent drying episode does not, suggesting that some high-frequency environmental oscillations in East Africa may occur independent of obliquity and precession control. The clay record correlates well with the fossiliferous and archaeologically rich stratigraphy of the lake margin, and suggests that fossils and artifacts accumulated on the exposed lake margin over <4000 years. The chemistry of clays is a potentially powerful tool to add to multi-proxy studies in basins with alkaline waters, particularly in stratigraphic intervals that lack pollen, calcareous, or siliceous microfossils.     

The role of fluid inclusions in mineral exploration—An attempt on the Bihar Mica Belt of India

Fluid inclusions and melt inclusions have been considered as possible guides for mineral exploration by many researchers. However, the minuteness of the fluid inclusions and the multiplicity of generations within the same deposit have always posed serious problems in the proper utilization of fluid-inclusion data in prospecting.Fluid inclusions preserve a valid and comprehensive record of the fluids coexisting with host minerals at the time of crystallization. A careful comparison of fluid-inclusion parameters and deposit characteristics enables one to distinguish between economically significant and insignificant zones of pegmatites.A systematic study of different pegmatites in an area of about 100 km² in the central part of the Bihar Mica Belt, India, was made. Mineralogical, fluid-inclusion, and melt-inclusion data of the principal mineral constituents like quartz, beryl, and apatite were collected. Thirty-three occurrences were chosen for the study. Pegmatites were grouped into economically significant (commercial) and barren (noncommercial) types. The fluid-inclusion parameters used in this study are size, population, presence of liquid carbon dioxide, salinity, and temperature of homogenization.Economically significant pegmatites and barren pegmatites have distinctly different populations of fluid inclusions. Economic pegmatites show a preponderance of highly saline, polyphase fluid inclusions, commonly with liquid carbon dioxide; these fluid inclusions homogenize over a wide range of temperature. Their size ranges from 50 m to 10 m. On the other hand, quartz of barren pegmatites is characterized by the preponderance of vapor-rich biphase inclusions, which homogenize at a relatively narrower but higher range of temperature. Fluid inclusions that contain halite daughter crystals are rare. The average size of the fluid inclusions in barren pegmatites is smaller (5 m to 20 m). Melt inclusions are more abundant in the barren pegmatites.     

Lacustrine ostracodes as hydrochemical indicators in lakes of the north-central United States

The modern ostracode distribution in lakes of the north-central United States shows how ostracode abundances are related to concentrations of major ions such as calcium, sulfate, and bicarbonate. These relationships are quantified for species living in lakes that range from fresh water (200 S cm^-1) to saline water (17 000 S cm^-1). Lakes located in the Minnesota forests have different ostracode assemblages and different water chemistry than lakes located on the prairie of North Dakota and South Dakota. These differences are attributed to differences in precipitation and rock-water interactions. Multivariate analyses of the ostracode and water chemistry data set indicate that different ostracode species are associated with different water types. For example, Limnocythere sappaensis and Heterocypris glaucus are found in bicarbonate-enriched sulfate-dominated waters, whereas Limnocythere staplini is found in bicarbonate-depleted sulfate-dominated waters. Candona ohioensis and Limnocythere itasca are found in fresh water, and Candona rawsoni is eurytopic and found in both bicarbonate-enriched and bicarbonate-depleted sulfate-dominated waters. Ostracodes can be used to identify changes in both ionic composition (solutes) and ionic concentration.This publication is the second of a series of papers presented at the Conference on Sedimentary and Paleolimnological Records of Saline Lakes. This Conference was held August 13–16, 1991 at the University of Saskatchewan, Saskatoon, Canada. Dr Evans is serving as Guest Editor for this series.     

Calibration of diatoms along a nutrient gradient in Florida Everglades Water Conservation Area-2A, USA

The relationship between diatom taxa preserved in surface soils and environmental variables at 31 sites in Water Conservation Area 2A (WCA-2A) of the Florida Everglades was explored using multivariate analyses. Surface soils were collected along a phosphorus (P) gradient and analyzed for diatoms, total P, % nitrogen (N), %carbon (C), calcium (Ca), and biogenic silica (BSi). Phosphorus varied from 315-1781 g g^-1, and was not found to be correlated with the other geochemical variables. Canonical correspondence analysis (CCA) was used to examine which environmental variables correlated most closely with the distributions in diatom taxa. Canonical correspondence analysis with forward selection, constrained and partial CCA, and Monte Carlo permutation tests of significance show the most significant changes in diatom assemblages along the P gradient (p < 0.01), with additional species differences correlated with soil C, N, Ca, and BSi.Weighted-averaging (WA) regression and calibration models of diatom assemblages to P and BSi were developed. The diatom-based inference model for soil [P] had a high apparent r² (0.86) with RMSE_boot = 218 g g^-1. Indicator diatom species identified by assessing species WA optima and WA tolerance to [P], such as Nitzschia amphibia and N. palea for high [P] (~1300-1400 g^-1) and Achnanthes minutissima var. scotica and Mastogloia smithii for low [P] (~400-600 g g^-1), may be useful as monitoring tools for eutrophication in WCA-2A as well as other areas of the Everglades. Diatom assemblages analyzed by cluster analysis were related to location within WCA-2A, and dominant taxa within clusters are discussed in relation to the geochemical variables measured as well as hydrology and pH. Diversity of diatom assemblages and a Disturbance Index based on diatom data are discussed in relation to the historically P-limited Everglades ecosystem. Diatom assemblages should be very useful for reconstructions of [P] through time in the Florida Everglades, provided diatoms are well preserved in soil cores.     

Chrysophyte cysts as paleolimnological indicators of environmental change due to cottage development and acidic deposition in the Muskoka-Haliburton region, Ontario, Canada

Chrysophyte cysts preserved in recent and pre-industrial lake sediment samples from 54 Muskoka-Haliburton (Ontario) lakes were used in a paleolimnological study to determine the impact of acidic precipitation and cottage development on water quality. A total of 246 cyst morphotypes were identified. Ecological preferences of cyst morphotypes were determined using multivariate statistical analysis, cluster analysis, and species-environment correlations. Recent cyst assemblages were related to water chemistry and lake morphometric variables using Redundancy Analysis (RDA). The distribution of morphotypes was related to a gradient of acid neutralising capacity (ANC), expressed through the association of variables related to buffering (i.e. longitude, watershed area, and ionic concentration) with the first axis (₁ = 0.29). Cyst assemblages were also defined, to a lesser extent (₂ = 0.06), by a trophic status gradient, created through the combination of total nitrogen (TN), total phosphorus (TP), volume-weighted cottage density, and lake depth variables. The identification of lakewater pH and trophic status as important determinants of cyst assemblage structure allowed for the reconstruction of acidification and eutrophication related water chemistry changes using fossil cyst assemblages. The reconstruction of pre-industrial (pre-1850) water quality conditions with fossil cyst assemblages indicated that pH significantly decreased in 24.1% of the study lakes and increased in 16.7% of the lakes. Increases in pH in more alkaline drainage basins are attributed to alkalinity generation processes induced by acidic precipitation as has been shown in other studies. Total phosphorus (TP) concentrations significantly declined in 12.9% of the lakes and increased in 16.6% of lakes. Increases in [TP] were linked to cottage development. Decreases in trophic status may be due to landuse changes, the result of the acidification occurring in the area, or warmer and drier climates. A comparison of chrysophyte cyst and diatom water quality inferences show similar trends in pH changes. There is a good agreement between diatom and chrysophyte bioindicators with respect to [TP] changes in oligotrophic lakes (< 10 g/L); however, diatom inferences suggest that lakes with current [TP] values greater than 10 g/L have decreased in trophic status over time, while chrysophyte reconstructions suggest that these same lakes have become more productive systems.     

Paleoecological investigation of recent lake acidification in the Adirondack Mountains,N.Y.

Paleoecological analysis of the sediment record of 12 Adirondack lakes reveals that the 8 clearwater lakes with current pH < 5.5 and alkalinity < 10 eq l^-1 have acidified recently. The onset of this acidification occurred between 1920 and 1970. Loss of alkalinity, based on quanitative analysis of diatom assemblages, ranged from 2 to 35 eq l^-1. The acidification trends are substantiated by several lines of evidence including stratigraphies of diatom, chrysophyte, chironomid, and cladoceran remains, Ca:Ti and Mn:Ti ratios, sequentially extracted forms of Al, and historical fish data. Acidification trends appear to be continuing in some lakes, despite reductions in atmospheric sulfur loading that began in the early 1970s. The primary cause of the acidification trend is clearly increased atmospheric deposition of strong acids derived from the combustion of fossil fuels. Natural processes and watershed disturbances cannot account for the changes in water chemistry that have occurred, but they may play a role. Sediment core profiles of Pb, Cu, V, Zn, S, polycyclic aromatic hydrocarbons, magnetic particles, and coal and oil soot provide a clear record of increased atmospheric input of materials associated with the combustion of fossil fuels beginning in the late 1800s and early 1900s. The primary evidence for acidification occurs after that period, and the pattern of water chemistry response to increased acid inputs is consistent with current understanding of lake-watershed acidification processes.This is the second of a series of papers to be published by this journal which is a contribution of the Paleoecological Investigation of Recent Lake Acidification (PIRLA) project. Drs. D.F. Charles and D.R. Whitehead are guest editors for this series.     

Development of a diatom-based model for inferring total phosphorus in southeastern Australian water storages

Diatom-based transfer functions for inferring epilimnetic total phosphorus (TP) have been developed from a data set of 33 southeastern Australian water storages. Regular institutional monitoring of these sites has allowed comparison of models developed from TP data covering different time periods. A model based on mean annual TP performs better than models derived from winter maximum TP, spring minimum TP or TP nearest the time of diatom sampling. A mean annual TP model (WA-PLS 2 component) has a jack-knifed diatom-inferred versus measured TP correlation coefficient (r ² _jack) of 0.69 and a root-mean-square-error of prediction (RMSEP) of 0.246 log₁₀g TP l^–1, while alternative models have RMSEP > 0.27. Deletion of two samples with uncharacteristic species composition and environmental conditions improved performance of the mean annual TP model (r ² _jack= 0.74; RMSEP = 0.233 log₁₀g TP l^–1). Comparison with other published diatom-TP calibration models indicates that this model performs relatively well, with possible contributing factors including the extensive characterisation of TP (with an average 15 determinations making up the annual mean) and the dominance of planktonic diatoms in most sites. Downcore application of the model will allow the reconstruction of reservoir nutrient histories since commissioning, and thus provide a basis for understanding and management of reservoirs.     

Sediment heavy metal record in Lake Baikal: natural and antrhopogenic sources

Geochemical analysis of six radiometrically dated short cores of recent sediment from Lake Baikal shows clear evidence of enhanced Pb supply. However, the sediment concentration increases are very small; the average Pb concentration rises from a baseline value of 10.9 g g^-1 to a peak value of only 14.8 g g^-1. In contrast to the more polluted lakes commonly studied in Europe and North America, variation in Pb concentration is far more strongly influenced by natural variation than by pollution. In sediment deposited over the last 150–200 years 73% of the variance in the sediment Pb concentration can be accounted for by variation in bulk composition of the sediment, and by atmospheric pollution. Factors influencing Pb concentrations over this time period are, in order of decreasing average importance (fraction of total variance explained), catchment supply (indicated by ²²⁶Ra activity variation) (43%), anthropogenic Pb emissions (24%), and dilution by ferromanganese hydroxides (6%). On longer (1000s of years) time scales dilution by biogenic silica is probably more important.The recent enhanced supply of catchment Pb correlates with accelerating accumulation rates, indicating a link with enhanced erosion. Anthropogenic sources dominate only in the southern basin, where local fossil-fuel burning industry is situated. The evidence for a local industrial source for the Pb pollution is strengthened by the high correlation between the inventories for Pb and for spheroidal carbonaceous particles. The absence of detectable anthropogenic Pb enrichment in the northern part of the lake suggests that long-distance Pb pollution is small compared with the local natural supply.     

Determination of orthophosphate in highly saline waters

Standard methods for the determination of phosphorus as phosphate ion are now well established for fresh and marine waters. In highly saline waters, however, salt effects due to ionic strength, or to particular ions present, may result in method interferences. Three methods of analysis of phosphate based on the formation of phosphomolybdenum blue complexes have been evaluated here for hypersaline waters. Stannous chloride reduction in aqueous media exhibits a substantial salt effect and its use is not recommended. Stannous chloride reduction following extraction into non aqueous solvents shows a significant salt effect (up to 30 per cent) in solutions of salinity >100 g L^–1. Dilution of hypersaline waters to below this salinity may overcome the salt effect but the method suffers from other disadvantages involving resource constraints and health and safety considerations. Ascorbic acid reduction, catalysed by antimony (III) ions, appears to offer the most promise for hypersaline waters. Turbidity in samples having high salinity (> 100 g L^–1) and high phosphorus concentrations (> 500 g P L^–1) changes the spectral characteristics of solutions but linear calibration curves still result for concentrations in the range 400 to 1,000 g P L^–1. The occurrence of turbidity is also affected by the ionic composition of hypersaline waters since solutions made from sea salt give different results to those made from sodium chloride. Dilution of samples, to give salinities less than 100 g L^–1 prior to reduction is recommended to avoid turbidity. The salt effect in these lower salinity waters is less than 3 per cent up to 100 g L^–1.     

Relationship of Mn-carbonates in varved lake-sediments to catchment vegetation in Big Watab Lake, MN, USA

Mn-carbonates are documented in the late-glacial varved sediments from Big Watab Lake, Minnesota, USA. The Mn-carbonate is authigenic and forms rims around contemporaneous epilimnetic calcite. Although such carbonates are found in minor amounts throughout the entire late-glacial sequence, significant quantities of Mn-carbonate are associated mainly with laminated intervals.Because of the suspected difference in isotopic fractionation between different carbonate minerals, the stable-isotopic compositions of bulk carbonate samples are used as a proxy for relative amounts of the Mn-carbonate in the sediment. High ¹⁸O and low ¹³C values are associated with abundant Mn-carbonates. Low ¹⁸O and high ¹³C values are associated with only minor concentrations of Mn-carbonates.The oxygen-18 record is correlated with fluctuations in the vegetation assemblage based on pollen spectra using a multiple regression model with backward elimination. The proposed link between the sedimentary archive and local vegetation is the mediation of advective mixing in the lake by forest composition. In this model, periods of forest closure resulted in a well-stratified water column that was anoxic at the sediment/water interface, permitting the formation of authigenic Mn-carbonates. Openings of Artemisia in the forest allowed wind shear to mix oxygen to depth, causing bioturbation of the laminations and preventing the formation of Mn-carbonate.