PIP25 Index Research Articles

Reconstructing spring sea ice concentration in the Chukchi Sea over recent centuries: insights into the application of the PIP25 index

In this study, we aimed to reconstruct spring (April–June) sea ice changes in the western Arctic Ocean over recent centuries (ca. the last 250 years) by measuring biomarker distributions in a multicore (ARA01B-03MUC) retrieved from the Chukchi Shelf region and to evaluate outcomes against known or modelled estimates of sea ice conditions. Specifically, we analyzed for the Arctic sea ice proxy IP25 and assessed the suitability of a further highly branched isoprenoid (HBI) lipid (HBI III), epi-brassicasterol, and dinosterol as complementary biomarkers for use with the so-called phytoplankton marker-IP25 index (PIP25; PIIIIP25, PBIP25, and PDIP25, respectively). The presence of IP25 throughout core ARA01B-03MUC confirms the occurrence of seasonal sea ice at the study site over recent centuries. From a semi-quantitative perspective, all three PIP25 indices gave different trends, with some dependence on the balance factor c, a term used in the calculation of the PIP25 index. PIIIIP25-derived spring sea ice concentration (SpSIC) estimates using a c value of 0.63, determined previously from analysis of Barents Sea surface sediments, were likely most reliable, since SpSIC values were high throughout the record (SpSIC > 78%), consistent with the modern context for the Chukchi Sea and the mean SpSIC record of the 41 CMIP5 climate models over recent centuries. PBIP25-based SpSIC estimates were also high (SpSIC 108%−127%), albeit somewhat over-estimated, when using a c value of 0.023 obtained from a pan-Arctic distribution of surface sediments. In contrast, PDIP25 values using a pan-Arctic c value of 0.11, and PIP25 data based on the mean biomarker concentrations from ARA01B-03MUC, largely underestimated sea ice conditions (SpSIC as low as 13%), and exhibited poor agreement with instrumental records or model outputs. On the other hand, PBIP25 values using a c factor based on mean IP25 and epi-brassicasterol concentrations exhibited a decline towards the core top, which resembled recent decreasing changes in summer sea ice conditions for the Chukchi Sea; however, further work is needed to test the broader spatial generality of this observation.

Highly branched isoprenoids for Southern Ocean sea ice reconstructions: a pilot study from the Western Antarctic Peninsula

Abstract. Organic geochemical and micropaleontological analyses of surface sediments collected in the southern Drake Passage and the Bransfield Strait, Western Antarctic Peninsula, enable a proxy-based reconstruction of recent sea ice conditions in this climate-sensitive area. We study the distribution of the sea ice biomarker IPSO25, and biomarkers of open marine environments such as more unsaturated highly branched isoprenoid alkenes and phytosterols. Comparison of the sedimentary distribution of these biomarker lipids with sea ice data obtained from satellite observations and diatom-based sea ice estimates provide for an evaluation of the suitability of these biomarkers to reflect recent sea surface conditions. The distribution of IPSO25 supports earlier suggestions that the source diatom seems to be common in near-coastal environments characterized by annually recurring sea ice cover, while the distribution of the other biomarkers is highly variable. Offsets between sea ice estimates deduced from the abundance of biomarkers and satellite-based sea ice data are attributed to the different time intervals recorded within the sediments and the instrumental records from the study area, which experienced rapid environmental changes during the past 100 years. To distinguish areas characterized by permanently ice-free conditions, seasonal sea ice cover and extended sea ice cover, we apply the concept of the PIP25 index from the Arctic Ocean to our data and introduce the term PIPSO25 as a potential sea ice proxy. While the trends in PIPSO25 are generally consistent with satellite sea ice data and winter sea ice concentrations in the study area estimated by diatom transfer functions, more studies on the environmental significance of IPSO25 as a Southern Ocean sea ice proxy are needed before this biomarker can be applied for semi-quantitative sea ice reconstructions.

An assessment of biomarker-based multivariate classification methods versus the PIP25 index for paleo Arctic sea ice reconstruction

The development of various combinative methods for Arctic sea ice reconstruction using the sympagic highly branched isoprenoid (HBI) IP25 in conjunction with pelagic biomarkers has often facilitated more detailed descriptions of sea ice conditions than using IP25 alone. Here, we investigated the application of the Phytoplankton-IP25 index (PIP25) and a recently proposed Classification Tree (CT) model for describing temporal shifts in sea ice conditions to assess the consistency of both methods. Based on biomarker data from three downcore records from the Barents Sea spanning millennial timescales, we showcase apparent and potential limitations in both approaches, and provide recommendations for their identification or prevention. Both methods provided generally consistent outcomes and, within the studied cores, captured abrupt shifts in sea ice regimes, such as those evident during the Younger Dryas, as well as more gradual trends in sea ice conditions during the Holocene. The most significant discrepancies occurred during periods of highly unstable climate change, such as those characteristic of the Younger Dryas–Holocene transition. Such intervals of increased discrepancy were identifiable by significant changes of HBI distributions and correlations to values not observed in proximal surface sediments. We suggest that periods of highly fluctuating climate that are not represented in modern settings may hinder the performance and complementary application of PIP25 and CT-based methods, and that data visualisation techniques should be employed to identify such occurrences in downcore records. Additionally, due to the reliance of both methods on biomarker distributions, we emphasise the importance of accurate and consistent biomarker quantification.

Paleo-sea ice distribution and polynya variability on the Kara Sea shelf during the last 12 ka

The Kara Sea is an important area for paleo-climatic research since sea ice and brine formation take place on its shelf—two processes inducing supra-regional climatic implications and thereby connecting regional environmental variability with global climatic conditions. To gain information about past sea ice coverage and variations, three sediment cores distributed in the southern and central parts of the marginal Sea were investigated. By applying the sea ice biomarker IP25 and the PIP25 index [phytoplankton biomarker (dinosterol)-IP25 index] post-glacial sea ice variability could be detected in the central Kara Sea (Core BP00-36/4), with most intense sea ice cover between 12.4 and 11.8 ka coinciding with the Younger Dryas (12.9–11.6 ka), and reduced sea ice cover between 10 and 8 ka during the Holocene Thermal Maximum. During the last ~ 7 ka, increasing sea ice indicators might indicate a Holocene cooling trend, probably induced by declining summer insolation. Furthermore, temporal changes in the fast ice—polynya distribution in the southern Kara Sea were detected: expanding fast ice during the late Holocene and a cyclic short-term Holocene climate variability documented by abrupt changes in the sea ice coverage at the BP00-07/7 core site. Core BP99-04/7 from the Yenisei estuary recorded consistently seasonal sea ice cover since ~ 9.3 ka, apart from five short phases of fast ice expansion to the core site. The strong influence of river run-off as well as estuary processes might prevent the detection of (short-term) climatic signals at this study site.

Complementary biomarker-based methods for characterising Arctic sea ice conditions: A case study comparison between multivariate analysis and the PIP25 index

The discovery of IP25 as a qualitative biomarker proxy for Arctic sea ice and subsequent introduction of the so-called PIP25 index for semi-quantitative descriptions of sea ice conditions has significantly advanced our understanding of long-term paleo Arctic sea ice conditions over the past decade. We investigated the potential for classification tree (CT) models to provide a further approach to paleo Arctic sea ice reconstruction through analysis of a suite of highly branched isoprenoid (HBI) biomarkers in ca. 200 surface sediments from the Barents Sea. Four CT models constructed using different HBI assemblages revealed IP25 and an HBI triene as the most appropriate classifiers of sea ice conditions, achieving a >90% cross-validated classification rate. Additionally, lower model performance for locations in the Marginal Ice Zone (MIZ) highlighted difficulties in characterisation of this climatically-sensitive region. CT model classification and semi-quantitative PIP25-derived estimates of spring sea ice concentration (SpSIC) for four downcore records from the region were consistent, although agreement between proxy and satellite/observational records was weaker for a core from the west Svalbard margin, likely due to the highly variable sea ice conditions. The automatic selection of appropriate biomarkers for description of sea ice conditions, quantitative model assessment, and insensitivity to the c-factor used in the calculation of the PIP25 index are key attributes of the CT approach, and we provide an initial comparative assessment between these potentially complementary methods. The CT model should be capable of generating longer-term temporal shifts in sea ice conditions for the climatically sensitive Barents Sea.

Short-term variability in late Holocene sea ice cover on the East Greenland Shelf and its driving mechanisms

Arctic sea ice is a critical component of the climate system as it influences the albedo, heat, moisture and gas exchange between ocean and atmosphere as well as the ocean's salinity. An ideal location to study natural sea ice variability during pre-industrial times is the East Greenland Shelf that underlies the East Greenland Current (EGC), the main route of Arctic sea ice and freshwaters from the Arctic Ocean into the northern North Atlantic. Here, we present a new high-resolution biomarker record from the East Greenland Shelf (73°N), which provides new insights into the sea ice variability and accompanying phytoplankton productivity over the past 5.2kyr. Our IP25 based sea ice reconstructions and the inferred PIP25 index do not reflect the wide-spread late Holocene Neoglacial cooling trend that follows the decreasing solar insolation pattern, which we relate to the strong influence of the polar EGC on the East Greenland Shelf and interactions with the adjacent fjord throughout the studied time interval. However, our reconstructions reveal several oscillations with increasing/decreasing sea ice concentrations that are linked to the known late Holocene climate cold/warm phases, i.e. the Roman Warm Period, Dark Ages Cold Period, Medieval Climate Anomaly and Little Ice Age. The observed changes seem to be connected to general ocean atmosphere circulation changes, possibly related to North Atlantic Oscillation and Atlantic Multidecadal Oscillation regimes. Furthermore, we identify a cyclicity of 73–74years in sea ice algae and phytoplankton productivity over the last 1.2kyr, which may indicate a connection to Atlantic Multidecadal Oscillation mechanisms.

Semi-quantitative estimates of paleo Arctic sea ice concentration based on source-specific highly branched isoprenoid alkenes: A further development of the PIP25 index

Previously reported concentration data for highly branched isoprenoid (HBI) alkenes and the sterol 24-methylcholesta-5,22E-dien-3β-ol (brassicasterol or epi-brassicasterol) obtained from 45 Barents Sea surface sediments reflecting contrasting sea ice conditions have been combined together in the form of the PIP25 index, with outcomes compared with recent mean decadal satellite-derived spring and summer sea ice concentrations. Reasonably good positive linear relationships were found between PIP25 indices and spring sea ice concentration, with the strongest correlation found when using a tri-unsaturated HBI (HBI III) as the open-water counterpart to the sea ice biomarker IP25, likely as a result of the greater sensitivity and selectivity of HBI III to the neighbouring sea ice conditions compared to epi-brassicasterol. The quality of the linear fits between PIIIIP25 (i.e., PIP25 based on HBI III) and spring sea ice concentration together with their respective spatial distributions were also far less dependent on the balance factor c, than for PBIP25 (i.e., PIP25 based on epi-brassicasterol), which may have important positive consequences for down-core semi-quantitative sea ice reconstruction, and when making comparisons between outcomes from different Arctic regions or climatic epochs. In contrast, consistently weak linear relationships were observed between individual biomarkers and spring or summer sea ice concentration, and between PIP25 values and summer sea ice concentration. However, we provide evidence that a lower limit threshold for PIIIIP25 might represent a useful qualitative proxy for the past occurrence of summer sea ice. Surface sediment biomarker data from other regions will be needed before the significance of our findings can be fully evaluated.

Identification of paleo Arctic winter sea ice limits and the marginal ice zone: Optimised biomarker-based reconstructions of late Quaternary Arctic sea ice

Analysis of >100 surface sediments from across the Barents Sea has shown that the relative abundances of the mono-unsaturated sea ice diatom-derived biomarker IP25 and a tri-unsaturated highly branched isoprenoid (HBI) lipid (HBI III) are characteristic of the overlying surface oceanographic conditions, most notably, the location of the seasonal sea ice edge. Thus, while IP25 is generally limited to locations experiencing seasonal sea ice, with higher abundances found for locations with longer periods of ice cover, HBI III is found in sediments from all sampling locations, but is significantly enhanced in sediments within the vicinity of the retreating sea ice edge or marginal ice zone (MIZ). The response of HBI III to this well-defined sea ice scenario also appears to be more selective than that of the more generic phytoplankton biomarker, brassicasterol. The potential for the combined analysis of IP25 and HBI III to provide more detailed assessments of past sea ice conditions than IP25 alone has been investigated by quantifying both biomarkers in three marine downcore records from locations with contrasting modern sea ice settings. For sediment cores from the western Barents Sea (intermittent seasonal sea ice) and the northern Norwegian Sea (ice-free), high IP25 and low HBI III during the Younger Dryas (ca. 12.9–11.9 cal. kyr BP) is consistent with extensive sea cover, with relatively short periods of ice-free conditions resulting from late summer retreat. Towards the end of the YD (ca. 11.9–11.5 cal. kyr BP), a general amelioration of conditions resulted in a near winter maximum ice edge scenario for both locations, although this was somewhat variable, and the eventual transition to predominantly ice-free conditions was later for the western Barents Sea site (ca. 9.9 cal. kyr BP) compared to NW Norway (ca. 11.5 cal. kyr BP). For both locations, coeval elevated HBI III (but absent IP25) potentially provides further evidence for increased Atlantic Water inflow during the early Holocene, but this interpretation requires further investigation. In contrast, IP25 and HBI III data obtained from a core from the northern Barents Sea demonstrate that seasonal sea ice prevailed throughout the Holocene, but with a gradual shift from winter ice edge conditions during the early Holocene to more sustained ice cover in the Neoglacial; a directional shift that has undergone a reverse in the last ca. 150 yr according to observational records. Our combined surface and downcore datasets suggest that combined analysis of IP25 and HBI III can provide information on temporal variations in the position of the maximum (winter) Arctic sea ice extent, together with insights into sea ice seasonality by characterisation of the MIZ. Combining IP25 with HBI III in the form of the previously proposed PIP25 index yields similar outcomes to those obtained using brassicasterol as the phytoplankton marker. Importantly, however, some problems associated with use of a variable balance factor employed in the PIP25 calculation, are potentially alleviated using HBI III.

Sea-ice distribution in the modern Arctic Ocean: Biomarker records from trans-Arctic Ocean surface sediments

Records of the spatial and temporal variability of Arctic Ocean sea ice are of significance for understanding the causes of the dramatic decrease in Arctic sea-ice cover of recent years. In this context, the newly developed sea-ice proxy IP25, a mono-unsaturated highly branched isoprenoid alkene with 25 carbon atoms biosynthesized specifically by sea-ice associated diatoms and only found in Arctic and sub-Arctic marine sediments, has been used to reconstruct the recent spatial sea-ice distribution. The phytoplankton biomarkers 24S-brassicasterol and dinosterol were determined alongside IP25 to distinguish ice-free or permanent ice conditions, and to estimate the sea-ice conditions semi-quantitatively by means of the phytoplankton-IP25 index (PIP25). Within our study, for the first time a comprehensive data set of these biomarkers was produced using fresh and deep-frozen surface sediment samples from the Central Arctic Ocean proper (>80°N latitude) characterised by a permanent ice cover today and recently obtained surface sediment samples from the Chukchi Plateau/Basin partly covered by perennial sea ice. In addition, published and new data from other Arctic and sub-Arctic regions were added to generate overview distribution maps of IP25 and phytoplankton biomarkers across major parts of the modern Arctic Ocean. These comprehensive biomarker data indicate perennial sea-ice cover in the Central Arctic, ice-free conditions in the Barents Sea and variable sea-ice situations in other marginal seas. The low but more than zero values of biomarkers in the Central Arctic supported the low in-situ productivity there. The PIP25 index values reflect modern sea-ice conditions better than IP25 alone and show a positive correlation with spring/summer sea ice.When calculating and interpreting PIP25 index as a (semi-quantitative) proxy for reconstructions of present and past Arctic sea-ice conditions from different Arctic/sub-Arctic areas, information of the source of phytoplankton biomarkers and the possible presence of allochthonous biomarkers is needed, and the records of the individual biomarkers always should be considered as well.

Quantitative measurement of the sea ice diatom biomarker IP25 and sterols in Arctic sea ice and underlying sediments: Further considerations for palaeo sea ice reconstruction

The lipid content of sea ice samples collected in 2011 and 2012 from Resolute Passage in the Canadian Arctic Archipelago was measured and compared with related samples obtained from the Amundsen Gulf in 2008. The highly branched isoprenoid (HBI) sea ice biomarker, IP25, was found in sea ice samples from each study, consistent with its formation by diatoms during the spring bloom. Our analysis also revealed the occurrence of a number of sterols in Arctic sea ice and these were rigorously identified and quantified for the first time. Concentrations of IP25 and sterols exhibited some variability between sampling studies, with somewhat higher values in samples from Resolute in 2012 than for the other two datasets, consistent with a general increase in biomass; however, major differences in biomarker concentration between sampling studies were not observed. An estimate of the proportion of Arctic sea ice diatoms that produce IP25 (ca. 1–5%) was obtained by comparison of the concentration of IP25 in the samples with those in laboratory cultures of known HBI-producing diatoms and cell enumeration in selected sea ice samples. The estimate is similar to the proportion of Haslea spp. in the same samples, providing further support to the suggestion that at least some species of the Haslea genus may be responsible for the biosynthesis of IP25 and related HBI diatom lipids in Arctic sea ice and that IP25 is made by a relatively small proportion of sea ice diatoms. In contrast, median sterol/IP25 values were all substantially higher than those in cultures of HBI-producing diatoms, suggesting that sterols are made by the majority of sea ice diatoms. The sterol/IP25 ratio was quite variable between locations and samples, likely as a result of differences in diatom assemblage; however, a comparison of individual and median sterol/IP25 values in sea ice with those from surface sediments from different Arctic regions demonstrated that sterols from sea ice diatoms may, in some cases, have a significant impact on the sedimentary budget. This should be considered carefully for quantitative estimates of palaeo sea ice reconstruction using methods such as the PIP25 index, which are based on the relative concentrations of IP25 and sterols in Arctic marine sediment cores.

Evaluation of the sea ice proxy IP25 against observational and diatom proxy data in the SW Labrador Sea

The recent rapid decline in Arctic sea ice cover has increased the need to improve the accuracy of the sea ice component in climate models and to provide detailed long-term sea ice concentration records, which are only available via proxy data. Recently, the highly branched isoprenoid IP25, identified in marine sediments underlying seasonal sea ice, has emerged as a potential sea ice specific proxy for past sea ice cover. We tested the reliability of this biomarker as a sea ice proxy against observational sea ice data (sea ice concentrations from the global HadISST1 database) and against a more established sea ice proxy (sea ice diatom abundance in sediments) in the South-West (SW) Labrador Sea. Furthermore, our study location at the southern margin of Arctic sea ice drift provided a new environmental setting in which to further test the novel PIP25 index. Our two study sites are located North-East (NE) and South-East (SE) of Newfoundland where box cores covering the last ca 100–150 years were collected. IP25 concentrations are nearly an order of magnitude higher and sea ice diatoms more abundant in sediments from NE of Newfoundland, where sea ice prevails 2–4 months per year compared to the sediments SE of Newfoundland, where conditions are generally ice-free year round. The IP25 fluxes NE of Newfoundland agree well with multi-decadal North Atlantic Oscillation (NAO) trends in the study area, which in previous studies have been shown to affect the climatic and sea ice conditions in the region. When assessed against observational sea ice data, IP25 appears to be a more sensitive indicator of sea ice variability in this setting compared to sea ice diatoms and proved to be a robust and reliable proxy for reconstructing low-frequency variability in past sea ice concentrations. The PIP25 index results clearly differ from the observed sea ice data underlining that caution needs to be exercised when using the index in different environmental settings.

Biomarker distributions in surface sediments from the Kara and Laptev seas (Arctic Ocean): indicators for organic-carbon sources and sea-ice coverage

Studies of spatial and temporal changes in modern and past sea-ice occurrence may help to understand the processes controlling the recent decrease in Arctic sea-ice cover. Here, we determined concentrations of IP25, a novel biomarker proxy for sea ice developed in recent years, phytoplankton-derived biomarkers (brassicasterol and dinosterol) and terrigenous biomarkers (campesterol and β-sitosterol) in the surface sediments from the Kara and Laptev seas to estimate modern spatial (seasonal) sea-ice variability and organic-matter sources. C25-HBI dienes and trienes were determined as additional palaeoenvironmental proxies in the study area. Furthermore, a combined phytoplankton-IP25 biomarker approach (PIP25 index) is used to reconstruct the modern sea-ice distribution more quantitatively. The terrigenous biomarkers reach maximum concentrations in the coastal zones and estuaries, reflecting the huge discharge by the major rivers Ob, Yenisei and Lena. Maxima in phytoplankton biomarkers indicating increased primary productivity were found in the seasonally ice-free central part of the Kara and Laptev seas. Neither IP25 nor PIP25, however, shows a clear and simple correlation with satellite sea-ice distribution in our study area due to the complex environmental conditions in our study area and the transportation process of sea-ice diatom in the water column. Differences in the diene/IP25 and triene/IP25 ratios point to different sources of these HBIs and different environmental conditions. The diene/IP25 ratio seems to correlate positively with sea-surface temperature, while negatively with salinity distributions.

Biomarker proxy shows potential for studying the entire Quaternary Arctic sea ice history

A novel and promising biomarker proxy for reconstruction of Arctic sea ice conditions was developed and is based on the determination of a highly branched isoprenoid with 25 carbons (IP25). IP25 records have been restricted to the last 150kyr BP. We present a biomarker record from Ocean Drilling Program (ODP) Site 912, going back to the Pliocene–Pleistocene boundary and indicating that sea ice of variable extent occurred in the Fram Strait/southern Yermak Plateau area at least since about 2.2Ma. Furthermore, our data support the idea that a combination of IP25 and open water, phytoplankton biomarker data (“PIP25 index”) may give a more reliable and quantitative estimate of past sea ice cover (at least for the study area). The study reveals that the novel IP25/PIP25 biomarker approach has potential for semi-quantitative paleo-sea ice studies covering the entire Quaternary and could motivate further detailed high resolution research on ODP/IODP material using this proxy.