An Overview of Sediment Organic Matter Records of Human Eutrophication in the Laurentian Great Lakes Region

The isotopic and molecular compositions of organic matter buried in lake sediments provide information that helps to reconstruct past environmental conditions and to assess impacts of humans on local ecosystems. This overview of sedimentary records from the North American Great Lakes region describes examples of applications of organic geochemistry to paleolimnological reconstructions. These lakes experienced a succession of human-induced environmental changes that started after completion of the Erie Canal in 1825. Agricultural deforestation in the mid-nineteenth century released soil nutrients that increased algal productivity and caused an associated increase in algal biomarkers in sediment records. Eutrophication that accompanied magnified delivery of municipal nutrients to the lakes in the 1960s and 1970s created excursions to less negative δ¹³C values in sediment organic matter. Increased organic carbon mass accumulation rates mirror the isotopic evidence of eutrophication in the Great Lakes.     

Temporal Trends in Mercury Accumulation in Lake Sediments in Sweden

Lake sediment cores were analyzedto study the history of mercury (Hg) pollution andparticularly to determine whether recent sedimentconcentrations have declined in response todeclining atmospheric deposition of Hg. Sedimentcores from 6 forest lakes distributed fromsouthern to northern Sweden and 3 northernmountain lakes were analyzed for Hg using CVAAS. A400 cm sediment profile from Måkevatten insouthwest Sweden indicates that the onset of Hgpollution occurred in the 18th century. Anindisputable increase in Hg concentrationsoccurred concurrent with the appearance ofspheroidal carbonaceous flyash particles (SCP)derived from fossil-fuel combustion, in themid-19th century. There is a strong correlationbetween Hg and SCP concentrations in the sedimentcores (r=0.67 to 0.91), which suggests a strongrelationship between historical Hg pollution andfossil fuel burning. In contrast to sediment corestaken in 1979, maximum Hg concentrations are nowobserved below the sediment surface and declinetowards the sediment surface. This study confirmsthat reductions in atmospheric deposition of Hgover Sweden have resulted in a decreased transferof total Hg to aquatic environments as reflectedby lake sediments, and that lake sediment profilesof Hg concentrations reflect relative trends inthe atmospheric deposition of Hg rather thanpost-depositional diagenetic processes.     

Distribution of Redox-sensitive Elements in Bottom Waters,Porewaters and Sediments of Rogoznica Lake (Croatia) in Both Oxic and Anoxic Conditions

Geochemical, mineralogical and sedimentological analyses were carried out to contrast two different sites (respectively characterized by permanently oxic and anoxic conditions) in a small, meromictic, seawater lake. In fact, due to relatively high organic matter content, and reduced water exchange, the Rogoznica Lake has almost permanent anoxic conditions below the depth of 12 m, where sediment can be considered an anoxic–sulphidic sedimentary environment. Different water column and sediments redox conditions affect the distribution and speciation of major redox-sensitive metals (Fe, Mn, Mo), reduced sulphur species (RSS) and dissolved organic C (DOC). Trace metals, especially those that accumulate in anoxic–sulphidic environments (Fe, Mo) showed a marked enrichment in the solid phase, whereas the low solubility of sulphides leads to low porewater concentrations. The relatively high sedimentary enrichment of Mo (up to 81 mg/kg) also confirms highly anoxic conditions within the Rogoznica Lake sediments. Results clearly show that chemical species within the sediments will tend towards equilibrium between porewater and solid phase according the prevailing environment conditions such as redox, pH, salinity, DOC.     

Recent Sediment of Lake Bled (NW Slovenia): Sedimentological and Geochemical Properties

Sediment cores collected in eutrophic subalpine Lake Bled (NW Slovenia) were analyzed sedimentologically in terms of grain size, mineralogy and sedimentation rates, and geochemically in terms of metals and nutrients. Surficial sediment is composed of dark gyttya type clayey silt with 5%–10% of organic matter. The sediment below is fine laminated and composed of homogenous silt and clayey silt: Mineralogically, low-Mg calcite prevails, followed by dolomite, quartz, partially of diatomaceous origin, and feldspar. Clay minerals are composed of muscovite/illite and chlorite. Authigenic minerals are pyrite and ‘lake chalk’ (low-Mg calcite). Lake sediment is especially polluted by Pb, Zn and P. Higher contents were found in the northwestern and eastern parts due to the particle input by local inflows. Increasing eutrophication and pollution, indicated by Cd, Cu, V, Cr, Co and total N and P enrichment in the top layers of the cores, started almost 100 years B.P., and especially 50 years ago.     

Metal Concentrations in Pore Water of the Lusatian Lignite Mining Sediments and Internal Metal Distribution in Juncus bulbosus

The aim of this study was to determine a suite of four metals (Fe, Mn, Zn, Cu) in the sediment, porewater and a pioneer plant (Juncus bulbosus) of Lusatian lignite mining lakes in eastern Germany. An attempt was made to understand the factors which affect element concentrations in the above- and below-ground biomass of Juncus bulbosus in an extreme environment. Water samples, sediments, porewater and plant material collected from two different mining lakes dominated by Juncus bulbosus species were analyzed for their elemental content. Additionally, scanning electron microscopy (SEM) and an energy-dispersive X-ray (EDX) detector were used to follow the internal metal distribution in the roots of Juncus plant. Results showed that sediment and porewater element concentrations in the lakes decreased in the order Fe > Mn > Zn and Cu. All the four elements were higher in the roots than in above-ground tissues, suggesting that iron plaque induced on roots under anaerobic conditions served as a metal reservoir, but not as an ultimate mechanism to control metal concentrations in the above-ground tissues. SEM and EDX analyses revealed that the rhizodermis, exodermis and endodermis cells regulate the traffic of transition metals and therefore avoid excess levels that are toxic to the plant in acidic mining-impacted lake sediments.     

Assessment of the Ecological Integrity of Traunsee (Austria) Via Analysis of Sediments and Benthic Microbial Communities

Since nearly one hundred years Traunsee experiences the import of tons of liquid and solid waste originating from salt and soda production. Today, the lake exhibits chloride concentrations of up to 170 mg L^-1 and 19% of the lake floor are directly or indirectly influenced by industrial deposits (ID). Based on the comparison of several microbial parameters in unaffected, directly affected and intermediate lake bottom sediments, the ecological integrity of the lake was evaluated. The highly alkaline ID, which were exclusively colonized by microorganisms, harbored a bacterial community reduced by a factor of 10 in abundance and biomass compared to undisturbed sediment areas within the lake. The bacterial community of ID was furthermore characterized by a reduced content of actively respiring cells (INT-formazan reduction), a lower frequency of dividing cells (FDC) and a significantly reduced cell and biomass production. A 80 to 90% reduction in carbon recycling is estimated for the area exclusively covered by ID. Protists, although occasionally absent from the industrial sediments, were in general found to be less sensitive to the contaminant stress. Differences in alkalinity and dissolved organic carbon (DOC) concentrations of sediment porewaters as well as the total organic content and C/N ratios of sediments partly explain the microbial pattern observed at the various sampling sites. Possible consequences of the continuous industrial tailings for the whole lake ecosystem and the validation of the ecological integrity are discussed.     

Dissolved Oxygen and Nutrient Fluxes Across the Sediment–Water Interface of the Neckar River,Germany: In Situ Measurements and Simulations

A benthic in situ flume and a 1D biogeochemical sediment model to evaluate solute fluxes across the sediment–water interface have been developed. The flume was successfully used to determine oxygen and nutrient fluxes at various locations of the Neckar River in Germany. The experimental results were linked with vertical pore water concentration profiles and independently verified with the model. By combining experimental and model results we assessed the influence of dissolved oxygen concentrations in the water column and the availability of degradable organic matter on sediment oxygen demand. The results and the derived relations can be used to parameterize the sediment module of large scale water quality models, allowing one to assess the influence of sediment–water interactions on various aspects of river water quality. Moreover, the biogeochemical sediment model can help to improve the general understanding of the processes governing solute concentrations and fluxes in sediments and across their interfaces.     

Spatial and Temporal Comparison of Polycyclic Aromatic Hydrocarbons and Spheroidal Carbonaceous Particles in Remote European Lakes

Spheroidal carbonaceous particles (SCP) and polycyclicaromatic hydrocarbons (PAH) have been measured in the dated sediment cores of 10 remote lakes distributed across Europe. The geographic trends were evaluated by examination of the superficial sediment fluxes and total sediment inventories. The highest levels of both markers were observed in the Eastern European lakes whereas the minimal values corresponded to the lake located in the Arctic. However, this SCP-PAH correlation was not observed after exclusion of the end member lakes from the series. The temporal trends of both pollutant markers are consistent with the history of pyrolytic emissions over Europe. However, the downcore SCP distributions are shorter than the PAH profiles in nearly all lakes. The differences are probably related to the different size particle fractions involved in the measurement of each marker, >5 and >1 m for SCP and PAH, respectively. Thus, the two proxies probably reflect pollution inputs from closer (SCP) and more distant sites (PAH).     

Total Lead and Stable Lead Isotopes in Stockholm Sediments

Lead (Pb) in the environment is derived from both naturaland anthropogenic sources. The aim of this study is to estimate the isotopic signature of anthropogenic Pb in sediments from a highly contaminated area (Stockholm), to discuss the influence of different sources on this signature, and to suggest natural Pb background concentrations. Also distribution patterns and differences between different water areas in Stockholm have been studied, both by total Pb and stable Pb isotopes. In 1993, sediment samples were collected at 24 stations in the Stockholm area and analysed for total Pb, zirconium (Zr), scandium (Sc) and stable Pb isotopes (^{204, 206-208}Pb). Total Pb data show that the Stockholm sediments are severely contaminated by Pb. The contamination seems to be rather local since the small lakes surrounding the central parts of Stockholm are much less effected than the central parts. Stockholm is clearly influenced by anthropogenic and natural sources, but in some of the small lakes also by Pb in zircons from the geological basement. The anthropogenic Pb in Stockholm has typical ²⁰⁷Pb/²⁰⁶Pb ratios of 0.85–0.89 and ²⁰⁸Pb/²⁰⁴Pb ratios of 36–38, which are distinct from natural sources. Pb/Sc ratios suggest that the natural background Pb concentration is 10–20 mg kg^-1 d.w.     

The Influence of Chironomus plumosus Larvae on Nutrient Fluxes and Phosphorus Fractions in Aluminum Treated Lake Sediment

One of the methods to diminish the internal phosphorus (P) loading is inactivation of P by aluminum (Al). After addition of Al to lake water an Al(OH)₃ floc is formed, which settles to the bottom and initially form a lid on the sediment surface. The effects of Chironomus plumosus larvae on sediment nutrient fluxes and P binding-sites in the sediment after addition of Al were tested. C. plumosus larvae were added to sediment cores in which sediment–water fluxes of nutrients were measured four times. After one month, the sediment was sectioned with depth and P fractions were measured by sequential chemical extraction. The chironomids created burrows through the Al layer which caused a significantly increased efflux of P from the Al treated sediment, because the P had only limited contact to the added Al. The chironomids also affected the P fractions in the sediment by their bioturbating activity. Thus, they caused increased Al concentrations in the upper part of the Al treated sediment. This created an enhanced contact between Al and P in the upper 7 cm of the sediment and, as a result, an increased binding of P to Al and a lowered porewater P. The DIP efflux is therefore expected to be lowered after the initial phase. Al had no effects on the nitrogen fluxes, but the chironomids enhanced the release, and decreased the release or increased the uptake by the sediments.     

Lead Speciation in the Sediments of the Heavily Polluted Western Harbor of Alexandria

The Western Harbor (WH) became under stress in the past decades, following successive increase in population. This study deals with local distribution of total lead and its species in the WH sediments. The lead content was high and there was a relationship between its enrichment and oil dispersed from ships. The lowest total lead value was found in the harbor middle far from direct effects of pollution. A five-step sequential extraction scheme was applied to illustrate the contribution shared by each individual fraction in the total lead concentration in the WH sediments. The exchangeable fraction (F1) was very low. The bound to carbonate fraction (F2), the bound to iron-manganese oxide fraction (F3) and the bound to organic matter—sulfide fraction (F4) ranked fourth, second and third in abundance. Oxygen was the main factor controlling the value of F2. F3 gave a direct relationship with total lead. The high levels of F4 occurred at locations of low salinity and enriched with organic matter. The residual fraction (F5) dominated other lead species, reflecting the sediment composition and the amounts of discharged pollutants.     

Composite Biofilms grown in Acidic Mining Lakes and assessed by Electron Microscopy and Molecular Techniques

Microbial consortia of composite biofilms, grown in surface water of acidicmining lakes near Lauchhammer, Germany, were investigated. The red-brown colored lake water was acidic (pH 2.5), had high concentrations of Fe(III), Al(III), and sulphate and low concentrations of dissolved organic matter. As a result the abundance of bacteria in the lake is with 10⁴ cells mL^-1 rather low. One input of organic material into the lake are autumnal leaves from trees, growing in the lakeside area. From aliquots of unfixed birch leave biofilms the 16S rRNA genes were amplified by PCR and community fingerprints were determined by single-strand conformation polymorphism (SSCP) analysis. Specific bands within the fingerprints were extracted from SSCP gels and sequenced for the taxonomical affiliation.These results were compared with those from the second type of biofilms which were grown on sterile substrata, floating submersed in surface waters of the lakes. By excising the bands from the gel and sequencing the individual bands bacterial taxa, common to both types of biofilms, were found but also some, which were only present in one type of biofilm. Ultrathin sectioned biofilms often showed bacteria associated with electron dense particles as main inorganic constituents. Elemental microanalysis by energy dispersive X-ray analysis (EDX) revealed them to contain iron, sulfur and oxygen as main elemental fractions and electron diffraction ring pattern analysis classified them to be schwertmannite. These bacteria and their interactions with each other as well as with the inorganic minerals formed in this lake generally is of great interest, in order to use these results for bioremediation applications.     

Functions of Straw for In Situ Remediation of Acidic Mining Lakes

The addition of straw in combination with Carbokalk, a by-product from the sugar-industry, was successfully used to stimulate microbial alkalinity generation in an acidic mining lake. To get detailed information about functions of straw, anenclosure experiment was carried out. Straw bundles were placedat the sediment surface of an acidic mining lake (ML 111) and thephysiochemical conditions and the microbiology of the sediment-water contact zone were studied. Straw was degraded by anaerobic microorganisms and dissolved organic carbon (DOC) leached from straw bundles. Pigmented flagellates responded to the DOC supply in the water column anda considerable amount of algal carbon was transported to the sediment. Straw addition led to microbial reduction of iron andsulfate in the sediment. Sulfate reduction was observed at a pHof 5.5. The pH, however, was not high enough to precipitate H₂S completely. Thus, some H₂S diffused into the watercolumn, where it was reoxidized. Straw did not create orstabilize an anoxic water body above the sediment. Microbial sulfate reduction and pyrite formation only took place in the sediment,whereas iron reduction also took place in the straw. Straw, however, altered the flow conditions above the sediment surfaceand prevented complete mixing of the profundal water. Straw didnot serve as a substratum for a reactive biofilm. We conclude that the most important function of straw for mining lake remediation is to be a long-term nutrient source for microbialalkalinity generation in the sediment.     

Finnish Lake Survey: The Role of Catchment Attributes in Determining Nitrogen, Phosphorus, and Organic Carbon Concentrations

This study is based on a Finnish lake survey conducted in 1995, a dataset of 874 statistically selected lakes from the national lake register. The dataset was divided into subgroups to evaluate lake water-catchment relationships in different geographical regions and in lakes of different size. In the three southernmost regions, the coefficients of determination in multiple regression equations varied between 0.40 and 0.53 for total nitrogen (TN) and between 0.37 and 0.53 for total phosphorus (TP); the best interpreters were agricultural land and water area in the catchment. In the two northernmost regions, TN concentrations in lake water were best predicted by the proportion of peatlands in the catchment, the catchment slope, and TP concentrations by lake elevation and latitude. Coefficients of determination in multiple regression equations in these northern regions varied between 0.39 and 0.67 for TN and between 0.41 and 0.52 for TP. For all the subsets formed, the best coefficients of determination explaining TN, TP, and total organic carbon (TOC) were obtained for a subset of large lakes (>10 km²), in which 72–83% of the variation was explained. This was probably due to large heterogeneous catchments of these lakes.     

Quantification of the Erosion Resistance of Undisturbed and Remoulded Cohesive Sediments

Cohesive sediments besides their typical heterogeneity are characterised by structural discontinuity. Particularly, organic consolidated muds are a good example of sediments that consist of vast aggregates, pore water and gaseous products. The texture of a cohesive sediment bed is a result of a number of mutually affecting factors, such as deposition history, mineral and organic composition, kind of biota and oxygen uptake. The presented work attempts to quantify the effect of sediment physical properties and sediments structure on the sediment erosion potential, considering incipient motion and erosion rate. This quantification is made on the basis of comparative testing of both unremoulded and remoulded samples of a river mud. Due attention is paid to sediment handling to preserve the delicate structure of the sediment for the laboratory experiments. Mud with two degrees of consolidation has been examined in a tilting flume under different flow situations. The test results show a typical increase of erosion strength with dry matter concentration of the mud. It has also been found that the structural properties increase the erosion strength for the less consolidated mud. An opposite effect has been recorded for a more consolidated deposit. As a consequence, due to the sediment structure, the original beds differ much less in erosion resistance in relation to the dry mass concentration than their disturbed analogues. Finally, the erosion resistance of the examined mud is compared with data from the literature.     

Spatial and Temporal Variations in the Sediment Habitat of Ranunculus spp. in Lowland Chalk Streams – Implications for Ecological Status?

Ranunculus spp. are the dominant plants of lowland chalk stream habitats in England. The spatial variability of sediment characteristics (silt–clay, organic matter, total phosphorus and total nitrogen content) within stands of Ranunculus spp. was investigated in 12 rivers in lowland England. Variability was found to be high and there were no discernible differences between samples taken from within Ranunculus and a limited number of samples from bare substrate. For two of these rivers, comparisons were also made between reaches upstream and downstream of waste water treatment works outfalls in terms of the characteristics of the sediments within Ranunculus stands. In one river a clear increase in sediment nutrient, fine and organic material content was observed downstream but in the other there was no consistent difference. Temporal variability was considered for two rivers in the Frome catchment, Dorset, by analysing the monthly variability in sediment organic matter and silt–clay content beneath Ranunculus stands over an annual cycle of growth and die-back. Whilst a clear pattern of fine and organic material retention consistent with seasonal plant growth patterns was evident at one site, the three sites displayed different temporal patterns. This inconsistency is believed to reflect differences in sediment supply at the three sites.     

Atmospheric Metal Pollutants-Archives, Methods, and History

Pollution of the atmosphere with cadmium (Cd), mercury (Hg), and lead (Pb) is a consequence of human activities. Natural archives are necessary to reconstruct the long-term history of metal deposition because accurate measurement of atmospheric deposition is a recent accomplishment. Reconstructions require: (1) accurate determination of concentrations of elements and isotopes, (2) accurate chronology of archives, and (3) archives that faithfully record atmosphere deposition. The most useful long-term archives are accumulations of ice and snow, peat, and lake sediment. Quantification of Cd deposition is uncommon because of its low concentration and substantial chemical mobility. Nonetheless, trends in peat and lake sediment are similar to those of Hg and Pb since ca. 1800 a.d. Both Hg and Pb are relatively chemically immobile and thus the peat and lake archives are believed to record historic trends of atmospheric deposition. Isotopic and concentration studies of Pb indicate a history of northern hemisphere atmospheric pollution extending back prior to 0 a.d. Although measurements of Hg concentration are now routine, isotopic measurements are in their infancy. Some Hg pollution sources have unique isotopic ratios, thereby contributing unique signals to the total Hg. Maximum accumulation rates of Hg and Pb occur up to 10 years later than for Cd (1970s versus 1960s in eastern North America, perhaps slightly later in Europe). By 2004, deposition of Cd, Hg, and Pb had declined from peak values in eastern North America more than 75, 75, and 90%, respectively.     

Use of Natural 35S to Trace Sulphate Cycling in Small Lakes,Flattops Wilderness Area,Colorado, U.S.A.

Measurements of the cosmogenically-produced ³⁵S, a radioisotope of sulphur (t_1/2 = 87 days), are reported for the Ned Wilson Lake watershed in Colorado. The watershed contains two small lakes and a flowing spring presumed to be representative of local ground water. The watershed is located in the Flattops Wilderness Area and the waters in the system have low alkalinity, making them sensitive to increases in acid and sulphate deposition. Time series of ³⁵S measurements were made during the summers of 1995 and 1996 (July–September) at all three sites. The system is dominated by melting snow and an initial concentration of 16–20 mBq L^-1 was estimated for snowmelt based on a series of snow samples collected in the Rocky Mountains. The two lakes had large initial ³⁵S concentrations in July, indicating that a large fraction of the lake water and sulphate was introduced by meltwater from that year's snowpack. In 1995 and 1996, ³⁵S concentrations decreased more rapidly than could be accounted for by decay, indicating that other processes were affecting ³⁵S concentrations. The most likely explanation is that exchange with sediments or the biota was removing ³⁵S from the lake and replacing it with older sulphate devoid of ³⁵S. In September of 1995 and 1996, ³⁵S concentrations increased, suggesting that atmospheric deposition is important in the sulphate flux of these lakes in late summer. Sulphur-35 concentrations in the spring water were highly variable but never higher than 3.6 mBq L^-1 and averaged 2 mBq L^-1. Using a simple mixing model, it was estimated that 75% of the spring water was derived from precipitation of previous years.     

Microbial Fe(III) Reduction in Acidic Mining Lake Sediments after Addition of an Organic Substrate and Lime

To elucidate the role of Fe(III) reduction in mining lake sediments amended with organic substrates, we performed a large (10 m diameter) enclosure experiment in which sediments were amended with Carbokalk, a waste product from sugar industry containing organic carbon and lime. Fe(III) reduction rates were determined monthly by measuring the accumulation of Fe(II) in the sediments in the field. Fe(III) reduction rates were also determined by incubating sediment samples with synthetic Fe(III) oxyhydroxide under in situ temperature in the laboratory. Sulfate reduction was selectively inhibited in the Fe(III) reduction experiments by addition of sodium molybdate. Sulfate reduction was measured by accumulation of reduced inorganic sulfides in the field and by ³⁵S radiotracer using a core injection technique. Sediment incubation and determination of sulfate reduction rates with radiotracer showed that sulfate reduction and direct microbial Fe(III) reduction occured simultaneously in the upper centimeters of the sediments and that both processes contributed to alkalinity generation. However, Fe(III) reduction was the initial process and rates were at least 3.5 fold higher than sulfate reduction rates. The results indicate that the presence of suitable anions for Fe(II) precipitation as carbonate or sulfide is needed in order to prevent loss of potential alkalinity by Fe(II) diffusion and reoxidation in the water column.