Loss on ignition as a method for estimating organic and carbonate content in sediments: reproducibility and comparability of results

Five test runs were performed to assess possible bias when performing the loss on ignition (LOI) method to estimate organic matter and carbonate content of lake sediments. An accurate and stable weight loss was achieved after 2 h of burning pure CaCO3 at 950 °C, whereas LOI of pure graphite at 530 °C showed a direct relation to sample size and exposure time, with only 40-70% of the possible weight loss reached after 2 h of exposure and smaller samples losing weight faster than larger ones. Experiments with a standardised lake sediment revealed a strong initial weight loss at 550 °C, but samples continued to lose weight at a slow rate at exposure of up to 64 h, which was likely the effect of loss of volatile salts, structural water of clay minerals or metal oxides, or of inorganic carbon after the initial burning of organic matter. A further test-run revealed that at 550 °C samples in the centre of the furnace lost more weight than marginal samples. At 950 °C this pattern was still apparent but the differences became negligible. Again, LOI was dependent on sample size. An analytical LOI quality control experiment including ten different laboratories was carried out using each laboratory's own LOI procedure as well as a standardised LOI procedure to analyse three different sediments. The range of LOI values between laboratories measured at 550 °C was generally larger when each laboratory used its own method than when using the standard method. This was similar for 950 °C, although the range of values tended to be smaller. The within-laboratory range of LOI measurements for a given sediment was generally small. Comparisons of the results of the individual and the standardised method suggest that there is a laboratory-specific pattern in the results, probably due to differences in laboratory equipment and/or handling that could not be eliminated by standardising the LOI procedure. Factors such as sample size, exposure time, position of samples in the furnace and the laboratory measuring affected LOI results, with LOI at 550 °C being more susceptible to these factors than LOI at 950 °C. We, therefore, recommend analysts to be consistent in the LOI method used in relation to the ignition temperatures, exposure times, and the sample size and to include information on these three parameters when referring to the method.

Pollen and charcoal in lake sediments compared with historically documented forest fires in southern Switzerland since AD 1920

Charcoal in unlaminated sediments dated by 210Pb was analysed by the pollen-slide and thin-section methods. The results were compared with the number and area of forest fires on different spatial scales in the area around Lago di Origlio as listed in the wildfire database of southern Switzerland since AD 1920. The influx of the number of charcoal particles > 75 µm2 in pollen slides correlates well with the number of annual forest fires recorded within a distance of 20-50 km from the coring site. Hence a size-class distinction or an area measurement by image analysis may not be absolutely necessary for the reconstruction of regional fire history. A regression equation was computed and tested against an independent data set. Its use makes it possible to estimate the charcoal area influx (or concentration) from the particle number influx (or concentration). Local fires within a radius of 2 km around the coring site correlate well with the area influx of charcoal particles estimated by the thin-section method measuring the area of charcoal particles larger than 20 000 µm2 or longer than 50 µm. Pollen percentages and influx values suggest that intensive agriculture and Castanea sativa cultivation were reduced 30-40 years ago, followed by an increase of forest area and a development to more natural woodlands. The traditional Castanea sativa cultivation was characterized by a complete use of the biomass produced, so abandonment of chestnut led to an increasing accumulation of dead biomass, thereby raising the fire risk. On the other hand, the pollen record of the regional vegetation does not show any clear response to the increase of fire frequency during the last three decades in this area.

Global pulses of organic carbon burial in deep-sea sediments during glacial maxima

The burial of organic carbon in marine sediments removes carbon dioxide from the ocean–atmosphere pool, provides energy to the deep biosphere, and on geological timescales drives the oxygenation of the atmosphere. Here we quantify natural variations in the burial of organic carbon in deep-sea sediments over the last glacial cycle. Using a new data compilation of hundreds of sediment cores, we show that the accumulation rate of organic carbon in the deep sea was consistently higher (50%) during glacial maxima than during interglacials. The spatial pattern and temporal progression of the changes suggest that enhanced nutrient supply to parts of the surface ocean contributed to the glacial burial pulses, with likely additional contributions from more efficient transfer of organic matter to the deep sea and better preservation of organic matter due to reduced oxygen exposure. These results demonstrate a pronounced climate sensitivity for this global carbon cycle sink.

Towards science-based sediment quality standards-Effects of field-collected sediments in rainbow trout (Oncorhynchus mykiss).

Sediments can act as long-term sinks for environmental pollutants. Within the past decades, dioxin-like compounds (DLCs) such as polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), polychlorinated biphenyls (PCBs), and polycyclic aromatic hydrocarbons (PAHs) have attracted significant attention in the scientific community. To investigate the time- and concentration-dependent uptake of DLCs and PAHs in rainbow trout (Oncorhynchus mykiss) and their associated toxicological effects, we conducted exposure experiments using suspensions of three field-collected sediments from the rivers Rhine and Elbe, which were chosen to represent different contamination levels. Five serial dilutions of contaminated sediments were tested; these originated from the Prossen and Zollelbe sampling sites (both in the river Elbe, Germany) and from Ehrenbreitstein (Rhine, Germany), with lower levels of contamination. Fish were exposed to suspensions of these dilutions under semi-static conditions for 90 days. Analysis of muscle tissue by high resolution gas chromatography and mass spectrometry and of bile liquid by high-performance liquid chromatography showed that particle-bound PCDD/Fs, PCBs and PAHs were readily bioavailable from re-suspended sediments. Uptake of these contaminants and the associated toxicological effects in fish were largely proportional to their sediment concentrations. The changes in the investigated biomarkers closely reflected the different sediment contamination levels: cytochrome P450 1A mRNA expression and 7-ethoxyresorufin-O-deethylase activity in fish livers responded immediately and with high sensitivity, while increased frequencies of micronuclei and other nuclear aberrations, as well as histopathological and gross pathological lesions, were strong indicators of the potential long-term effects of re-suspension events. Our study clearly demonstrates that sediment re-suspension can lead to accumulation of PCDD/Fs and PCBs in fish, resulting in potentially adverse toxicological effects. For a sound risk assessment within the implementation of the European Water Framework Directive and related legislation, we propose a strong emphasis on sediment-bound contaminants in the context of integrated river basin management plans.

Human–climate interactions in the central Mediterranean region during the last millennia: The laminated record of Lake Butrint (Albania)

Lake Butrint (39°47 N, 20°1 E) is a ca. 21 m deep, coastal lagoon located in SW Albania where finely-laminated sediments have been continuously deposited during the last millennia. The multi-proxy analysis (sedimentology, high-resolution elemental geochemistry and pollen) of a 12 m long sediment core, supported by seven AMS radiocarbon dates and 137Cs dating, enable a precise reconstruction of the environmental change that occurred in the central Mediterranean region during the last ∼4.5 cal kyrs BP. Sediments consist of triplets of authigenic carbonates, organic matter and clayey laminae. Fluctuations in the thickness and/or presence of these different types of seasonal laminae indicate variations in water salinity, organic productivity and runoff in the lake's catchment, as a result of the complex interplay of tectonics, anthropogenic forcing and climate variability. The progradation of the Pavllo river delta, favoured by variable human activity from the nearby ancient city of Butrint, led to the progressive isolation of this hydrological system from the Ionian Sea. The system evolved from an open bay to a restricted lagoon, which is consistent with archaeological data. An abrupt increase in mass-wasting activity between 1515 and 1450 BC, likely caused by nearby seismic activity, led to the accumulation of 24 homogenites, up to 17 cm thick. They have been deposited during the onset of finely laminated sedimentation, which indicates restricted, anoxic bottom water conditions and higher salinity. Periods of maximum water salinity, biological productivity, and carbonate precipitation coincide with warmer intervals, such as the early Roman Warm Period (RWP) (500 BC–0 AD), the Medieval Climate Anomaly (MCA) (800–1400 AD) and recent times (after 1800 AD). Conversely, lower salinity and more oxic conditions, with higher clastic input were recorded during 1400–500 BC, the Late Roman and the Early Medieval periods (0–800 AD) and during the Little Ice Age (1400–1800 AD). Hydrological fluctuations recorded in Butrint are in phase with most central and western Mediterranean records and correlate with NAO variability. In contrast, opposite hydrological patterns have been recorded in the Eastern Balkans and the Levant during the last millennium, emphasizing a complex spatial variability in the region. Phases of maximum settlement intensity in Butrint (Roman-Late Antique) coincide with warmer and/or stable climate periods (0–800 AD and MCA, respectively), indicating a long-term influence of climatic conditions on human activities. The Late Holocene sedimentary record of Lake Butrint demonstrates the complex interplay of climate variability, tectonics and human impact in the recent evolution of coastal Mediterranean regions.

Apatite as an indicator of fluid salinity: An experimental study of chlorine and fluorine partitioning in subducted sediments

In order to constrain the salinity of subduction zone fluids, piston-cylinder experiments have been conducted to investigate the partitioning behaviour of Cl and F in subducted sediments. These experiments were performed at H2O-undersaturated conditions with a synthetic pelite starting composition containing 800 ppm Cl, over a pressure and temperature range of 2.5–4.5 GPa and 630–900 °C. Repetitive experiments were conducted with 1900 ppm Cl + 1000 ppm F, and 2100 ppm Cl. Apatite represents the most Cl-abundant mineral phase, with Cl concentration varying in the range 0.1–2.82 wt%. Affinity for Cl decreases over the following sequence: aqueous fluid > apatite ⩾ melt > other hydrous minerals (phengite, biotite and amphibole). It was found that addition of F to the Cl-bearing starting composition significantly lowers the Cl partition coefficients between apatite and melt (DClAp–melt) and apatite and aqueous fluid (DClAp–aq). Cl–OH exchange coefficients between apatite and melt (KdCl–OHAp–melt) and apatite and aqueous fluid (KdCl–OHAp–aq) were subsequently calculated. KdCl–OHAp–melt was found to vary from 1 to 58, showing an increase with temperature and a decrease with pressure and displaying a regular decrease with increasing H2O content in melt. Mole fractions of Cl and OH in melt were calculated based on an ideal mixing model for H2O, OH, O, Cl and F. The Cl contents of other hydrous minerals (phengite, biotite and amphibole) fall between 200 and 800 ppm, with resultant Cl partition coefficients from 0.02 to 0.49, appearing independent of the bulk Cl and F content. Preliminary data from this study show that the partitioning behaviour of F is strongly in favour of apatite relative to melt and phengite, with DFAp–melt = 15–51. Apatites from representative eclogite facies metasediments were examined and found to have low Cl contents close to ∼100 ppm. Calculations using our experimentally determined KdCl–OHAp–aq of 0.004 at 2.5 GPa, 630 °C indicate a low salinity character (0.5–2 wt% NaCleq) for the fluid formed during dehydration of subducted oceanic sediment at ∼80 km depth.

Late-glacial and Holocene vegetation history and dynamics as shown by pollen and plant macrofossil analyses in annually laminated sediments from Soppensee, central Switzerland

The palynostratigraphy of two sediment cores from Soppensee, Central Switzerland (596 m asl) was correlated with nine regional pollen assemblage zones defined for the Swiss Plateau. This biostratigraphy shows that the sedimentary record of Soppensee includes the last 15 000 years, i.e. the entire Late-glacial and Holocene environmental history. The vegetation history of the Soppensee catchment was inferred by pollen and plant-macrofossil analyses on three different cores taken in the deepest part of the lake basin (27 m). On the basis of a high-resolution varve and calibrated radiocarbonchronology it was possible to estimate pollen accumulation rates, which together with the pollen percentage data, formed the basis for the interpretation of the past vegetation dynamics. The basal sediment dates back to the last glacial. After reforestation with juniper and birch at ca. 12 700 B.P., the vegetation changed at around 12 000 B.P. to a pine-birch woodland and at the onset of the Holocene to a mixed deciduous forest. At ca. 7000 B.P., fir expanded and dominated the vegetation with beech becoming predominant at ca. 50014C-years later until sometime during the Iron Age. Large-scale deforestation, especially during the Middle Ages, altered the vegetation cover drastically. During the Late-glacial period two distinct regressive phases in vegetation development are demonstrated, namely, the Aegelsee oscillation (equivalent to the Older Dryas biozone) and the Younger Dryas biozone. No unambiguous evidence for Holocene climatic change was detected at Soppensee. Human presence is indicated by early cereal pollen and distinct pulses of forest clearance as a result of human activity can be observed from the Neolithic period onwards.