Independent measurement of biogenic silica in sediments by FTIR spectroscopy and PLS regression

We present an independent calibration model for the determination of biogenic silica (BSi) in sediments, developed from analysis of synthetic sediment mixtures and application of Fourier transform infrared spectroscopy (FTIRS) and partial least squares regression (PLSR) modeling. In contrast to current FTIRS applications for quantifying BSi, this new calibration is independent from conventional wet-chemical techniques and their associated measurement uncertainties. This approach also removes the need for developing internal calibrations between the two methods for individual sediments records. For the independent calibration, we produced six series of different synthetic sediment mixtures using two purified diatom extracts, with one extract mixed with quartz sand, calcite, 60/40 quartz/calcite and two different natural sediments, and a second extract mixed with one of the natural sediments. A total of 306 samples—51 samples per series—yielded BSi contents ranging from 0 to 100 %. The resulting PLSR calibration model between the FTIR spectral information and the defined BSi concentration of the synthetic sediment mixtures exhibits a strong cross-validated correlation ( R2cv = 0.97) and a low root-mean square error of cross-validation (RMSECV = 4.7 %). Application of the independent calibration to natural lacustrine and marine sediments yields robust BSi reconstructions. At present, the synthetic mixtures do not include the variation in organic matter that occurs in natural samples, which may explain the somewhat lower prediction accuracy of the calibration model for organic-rich samples.

Spring temperature variability and eutrophication history inferred from sedimentary pigments in the varved sediments of Lake Żabińskie, north-eastern Poland, AD 1907–2008

Varved lake sediments are excellent natural archives providing quantitative insights into climatic and environmental changes at very high resolution and chronological accuracy. However, due to the multitude of responses within lake ecosystems it is often difficult to understand how climate variability interacts with other environmental pressures such as eutrophication, and to attribute observed changes to specific causes. This is particularly challenging during the past 100 years when multiple strong trends are superposed. Here we present a high-resolution multi-proxy record of sedimentary pigments and other biogeochemical data from the varved sediments of Lake Żabińskie (Masurian Lake District, north-eastern Poland, 54°N–22°E, 120 m a.s.l.) spanning AD 1907 to 2008. Lake Żabińskie exhibits biogeochemical varves with highly organic late summer and winter layers separated by white layers of endogenous calcite precipitated in early summer. The aim of our study is to investigate whether climate-driven changes and anthropogenic changes can be separated in a multi-proxy sediment data set, and to explore which sediment proxies are potentially suitable for long quantitative climate reconstructions. We also test if convoluted analytical techniques (e.g. HPLC) can be substituted by rapid scanning techniques (visible reflectance spectroscopy VIS-RS; 380–730 nm). We used principal component analysis and cluster analysis to show that the recent eutrophication of Lake Żabińskie can be discriminated from climate-driven changes for the period AD 1907–2008. The eutrophication signal (PC1 = 46.4%; TOC, TN, TS, Phe-b, high TC/CD ratios total carotenoids/chlorophyll-a derivatives) is mainly expressed as increasing aquatic primary production, increasing hypolimnetic anoxia and a change in the algal community from green algae to blue-green algae. The proxies diagnostic for eutrophication show a smooth positive trend between 1907 and ca 1980 followed by a very rapid increase from ca. 1980 ± 2 onwards. We demonstrate that PC2 (24.4%, Chl-a-related pigments) is not affected by the eutrophication signal, but instead is sensitive to spring (MAM) temperature (r = 0.63, pcorr < 0.05, RMSEP = 0.56 °C; 5-yr filtered). Limnological monitoring data (2011–2013) support this finding. We also demonstrate that scanning visible reflectance spectroscopy (VIS-RS) data can be calibrated to HPLC-measured chloropigment data and be used to infer concentrations of sedimentary Chl-a derivatives {pheophytin a + pyropheophytin a}. This offers the possibility for very high-resolution (multi)millennial-long paleoenvironmental reconstructions.

A chrysophyte-based quantitative reconstruction of winter severity from varved lake sediments in NE Poland during the past millennium and its relationship to natural climate variability

Chrysophyte cysts are recognized as powerful proxies of cold-season temperatures. In this paper we use the relationship between chrysophyte assemblages and the number of days below 4 °C (DB4 °C) in the epilimnion of a lake in northern Poland to develop a transfer function and to reconstruct winter severity in Poland for the last millennium. DB4 °C is a climate variable related to the length of the winter. Multivariate ordination techniques were used to study the distribution of chrysophytes from sediment traps of 37 low-land lakes distributed along a variety of environmental and climatic gradients in northern Poland. Of all the environmental variables measured, stepwise variable selection and individual Redundancy analyses (RDA) identified DB4 °C as the most important variable for chrysophytes, explaining a portion of variance independent of variables related to water chemistry (conductivity, chlorides, K, sulfates), which were also important. A quantitative transfer function was created to estimate DB4 °C from sedimentary assemblages using partial least square regression (PLS). The two-component model (PLS-2) had a coefficient of determination of View the MathML sourceRcross2 = 0.58, with root mean squared error of prediction (RMSEP, based on leave-one-out) of 3.41 days. The resulting transfer function was applied to an annually-varved sediment core from Lake Żabińskie, providing a new sub-decadal quantitative reconstruction of DB4 °C with high chronological accuracy for the period AD 1000–2010. During Medieval Times (AD 1180–1440) winters were generally shorter (warmer) except for a decade with very long and severe winters around AD 1260–1270 (following the AD 1258 volcanic eruption). The 16th and 17th centuries and the beginning of the 19th century experienced very long severe winters. Comparison with other European cold-season reconstructions and atmospheric indices for this region indicates that large parts of the winter variability (reconstructed DB4 °C) is due to the interplay between the oscillations of the zonal flow controlled by the North Atlantic Oscillation (NAO) and the influence of continental anticyclonic systems (Siberian High, East Atlantic/Western Russia pattern). Differences with other European records are attributed to geographic climatological differences between Poland and Western Europe (Low Countries, Alps). Striking correspondence between the combined volcanic and solar forcing and the DB4 °C reconstruction prior to the 20th century suggests that winter climate in Poland responds mostly to natural forced variability (volcanic and solar) and the influence of unforced variability is low.

Local formation of varved sediments in a karstic collapse depression of Lake Banyoles (NE Spain)

Banyoles is the largest and deepest lake of karstic-tectonic origin in the Iberian Peninsula. The lake comprises several circular sub-basins characteri- zed by different oxygenation conditions at their hypolimnions. The multiproxy analysis of a > 5 m long sediment core combined with high resolution seis- mic stratigraphy (3.5 kHz pinger and multi-frequency Chirp surveys), allow a precise reconstruction of the evolution of a karstic depression (named B3) until present times. Local meromictic conditions in this sub-basin have been conducive to deposition and preservation of ca. 85 cm of varved sediments since the late 19th century. The onset of these conditions is likely related to lake waters eutrophication caused by increasing farming activities in the wa- tershed. Increasing clastic input and organic productivity during the second half of the 20th century have also been recorded within the laminated sedi- ments, revealing an intensification of human impact and warmer water tem- peratures.

Sediments of Lake Vens (SW European Alps, France) record large-magnitude earthquake events

We studied sediment cores from Lake Vens (2,327 m asl), in the Tinée Valley of the SW Alps, to test the paleoseismic archive potential of the lake sediments in this particularly earthquake-sensitive area. The historical earthquake catalogue shows that moderate to strong earthquakes, with intensities of IX–X, have impacted the Southern Alps during the last millennium. Sedimentological (X-ray images, grain size distribution) and geochemical (major elements and organic matter) analyses show that Lake Vens sediments consist of a terrigenous, silty material (minerals and organic matter) sourced from the watershed and diatom frustules. A combination of X-ray images, grain-size distribution, major elements and magnetic properties shows the presence of six homogenite-type deposits interbedded in the sedimentary background. These sedimentological features are ascribed to sediment reworking and grain sorting caused by earthquake-generated seiches. The presence of microfaults that cross-cut the sediment supports the hypothesis of seismic deposits in this system. A preliminary sediment chronology is provided by 210Pb measurement and AMS 14C ages. According to the chronology, the most recent homogenite events are attributable to damaging historic earthquakes in AD 1887 (Ligure) and 1564 (Roquebillière). Hence, the Lake Vens sediment recorded large-magnitude earthquakes in the region and permits a preliminary estimate of recurrence time for such events of ~400 years.

A 600 years warm-season temperature record from varved sediments of Lago Plomo, Northern Patagonia, Chile (47°S)

High-resolution records of calibrated proxy data for the past millennium are fundamental to place current changes into the context of pre-industrial natural forced and unforced variability. Although the need for regional spatially-explicit comprehensive reconstructions is widely recognized, the proxy data sources are still scarce, particularly for the Southern Hemisphere and especially for South America. We present a 600-year long warm season temperature record from varved sediments of Lago Plomo, a proglacial lake of the Northern Patagonian Ice field in Southern Chile (46°59′S, 72°52′W, 203 m a.s.l.). The thickness of the bright summer sediment layer relative to the dark winter layer (measured as total brightness; % reflectance 400–730 nm) is calibrated against warm season SONDJF temperature (1900–2009; r = 0.58, p(aut) = 0.056, RE = 0.52; CE = 0.15, RMSEP = 0.28 °C; five-year triangular filtered data). In Lago Plomo, warm summer temperatures lead to enhanced glacier melt and suspended sediment transport, which results in thicker light summer layers and to brighter sediments. Although Patagonia shows pronounced regional differences in decadal temperature trends and variability, the 600 years temperature reconstruction from Lago Plomo compares favourably with other regional/continental temperature records, but also emphasizes significant regional differences for which no data and information existed so far. These regional differences seem to be real as they are also reflected in modern climate data sets (1900–2010). The reconstruction shows pronounced subdecadal – multidecadal variability with cold phases during parts of the Little Ice Age (16th and 18th centuries) and in the beginning of the 20th century. The most prominent warm phase is the 19th century which is as warm as the second half of the 20th century. The exceptional summer warmth AD 1780–1810 is also found in other archives of Northern Patagonia and Central Chile. Our record shows the delayed 20th century warming in the Southern Hemisphere. The comparison between winter precipitation and summer temperature (inter-seasonal coupling) from Lago Plomo reveals alternating phases with parallel and contrasting decadal trends of winter precipitation and summer temperature (positive and negative running correlations Rwinter PP; summer TT). This observation from the sediment proxy data is also confirmed by two sets of reanalysis data for the 20th century. Reanalysis data show that phases with negative correlations between winter precipitation and summer temperature (e.g., dry winters and warm summers) at Lago Plomo are characteristic for periods when circumpolar Westerly flow is displaced southward and enhanced around 60°S.

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.

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.

Reconnaissance survey of Galveston Bay sediments for selective nonresidual trace metals

The nonresidual concentrations of five trace metals were determined for 322 sediments that were the product of a systematic sampling program of the entire Galveston Bay system. The nonresidual component of the trace metal concentration (e.g. that fraction of the metals that can be relatively easily removed from the sediments without complete destruction of the sediment particle) was considered to be more indicative of the anthropogenic metal pollution that has impacted the Galveston Bay ecosystem.^ For spatial analysis of the metal concentrations, the Galveston Bay system was divided into nine bay-areas, based on easily definable geological and geographical characteristics. Isopleth mapping analyses of these metal concentrations indicated a direct relationship with the $<$63$\mu$m fraction of the sediment (%FINE) in all of the bay areas. Covariate regression analyses indicated that position of the sediment within the Galveston Bay system (e.g. bay-area) was a better predictor of metal concentration than %FINE. Analysis of variance of the metals versus the bay-areas indicated that the five metals maintained a relatively constant order and magnitude of concentration for all the bay-areas.^ The major shipping channels of the Galveston Bay system, with their associated vessels and transported materials, are a likely source of metal pollution. However, these channels were not depositional corridors of high metal concentration. All metal concentration highs were found to be located away from the channels and associated with %FINE highs in the deeper portions of the bay-areas.^ Disturbance of the sediments, by the proposed widening and deepening of these channels, is not predicted to remobilize the trace metals. A more likely adverse effect on the health of the Galveston Bay ecosystem would come from the increase in turbidity of the water due to the dredging and in an extension of the salt water wedge farther north into the bay system. ^