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Carbon monoxide (CO) is a naturally occurring atmospheric trace gas, a regulated pollutant, and one of the main components determining the oxidative capacity of the atmosphere. Evaluating climate–chemistry models under different conditions than today and constraining past CO sources requires a reliable record of atmospheric CO mixing ratios ([CO]) that includes data since preindustrial times. Here, we report the first continuous record of atmospheric [CO] for Southern Hemisphere (SH) high latitudes over the past 3 millennia. Our continuous record is a composite of three high-resolution Antarctic ice core gas records and firn air measurements from seven Antarctic locations. The ice core gas [CO] records were measured by continuous flow analysis (CFA), using an optical feedback cavity-enhanced absorption spectrometer (OF-CEAS), achieving excellent external precision (2.8–8.8 ppb; 2σ) and consistently low blanks (ranging from 4.1±1.2 to 7.4±1.4 ppb), thus enabling paleo-atmospheric interpretations. Six new firn air [CO] Antarctic datasets collected between 1993 and 2016 CE at the DE08-2, DSSW19K, DSSW20K, South Pole, Aurora Basin North (ABN), and Lock-In sites (and one previously published firn CO dataset at Berkner) were used to reconstruct the atmospheric history of CO from ∼1897 CE, using inverse modeling that incorporates the influence of gas transport in firn. Excellent consistency was observed between the youngest ice core gas [CO] and the [CO] from the base of the firn and between the recent firn [CO] and atmospheric [CO] measurements at Mawson station (eastern Antarctica), yielding a consistent and contiguous record of CO across these different archives. Our Antarctic [CO] record is relatively stable from −835 to 1500 CE, with mixing ratios within a 30–45 ppb range (2σ). There is a ∼5 ppb decrease in [CO] to a minimum at around 1700 CE during the Little Ice Age. CO mixing ratios then increase over time to reach a maximum of ∼54 ppb by ∼1985 CE. Most of the industrial period [CO] growth occurred between about 1940 to 1985 CE, after which there was an overall [CO] decrease, as observed in Greenland firn air and later at atmospheric monitoring sites and attributed partly to reduced CO emissions from combustion sources. Our Antarctic ice core gas CO observations differ from previously published records in two key aspects. First, our mixing ratios are significantly lower than reported previously, suggesting that previous studies underestimated blank contributions. Second, our new CO record does not show a maximum in the late 1800s. The absence of a [CO] peak around the turn of the century argues against there being a peak in Southern Hemisphere biomass burning at this time, which is in agreement with (i) other paleofire proxies such as ethane or acetylene and (ii) conclusions reached by paleofire modeling. The combined ice core and firn air [CO] history, spanning −835 to 1992 CE, extended to the present by the Mawson atmospheric record, provides a useful benchmark for future atmospheric chemistry modeling studies.

The temperature of the Earth is one of the most important climate parameters. Proxy records of past climate changes, in particular temperature, represent a fundamental tool for exploring internal climate processes and natural climate forcings. Despite the excellent information provided by ice core records in Antarctica, the temperature variability of the past 2000 years is difficult to evaluate from the low-accumulation sites in the Antarctic continent interior. Here we present the results from the Aurora Basin North (ABN) ice core (71∘ S, 111∘ E, 2690 m a.s.l.) in the lower part of the East Antarctic plateau, where accumulation is substantially higher than other ice core drilling sites on the plateau, and provide unprecedented insight into East Antarctic past temperature variability. We reconstructed the temperature of the last 2000 years using two independent methods: the widely used water stable isotopes (δ18O) and by inverse modelling of borehole temperature and past temperature gradients estimated from the inert gas stable isotopes (δ40Ar and δ15N). This second reconstruction is based on three independent measurement types: borehole temperature, firn thickness, and firn temperature gradient. The δ18O temperature reconstruction supports stable temperature conditions within 1 ∘C over the past 2000 years, in agreement with other ice core δ18O records in the region. However, the gas and borehole temperature reconstruction suggests that surface conditions 2 ∘C cooler than average prevailed in the 1000–1400 CE period and supports a 20th century warming of 1 ∘C. A precipitation hiatus during cold periods could explain why water isotope temperature reconstruction underestimates the temperature changes. Both reconstructions arguably record climate in their own way, with a focus on atmospheric and hydrologic cycles for water isotopes, as opposed to surface temperature for gas isotopes and boreholes. This study demonstrates the importance of using a variety of sources for comprehensive paleoclimate reconstructions.

Carbon monoxide (CO) is a regulated pollutant and one of the key components determining the oxidizing capacity of the atmosphere. Obtaining a reliable record of atmospheric CO mixing ratios ([CO]) since preindustrial times is necessary to evaluate climate–chemistry models under conditions different from today and to constrain past CO sources. We present high-resolution measurements of CO mixing ratios from ice cores drilled at five different sites on the Greenland ice sheet that experience a range of snow accumulation rates, mean surface temperatures, and different chemical compositions. An optical-feedback cavity-enhanced absorption spectrometer (OF-CEAS) was coupled with continuous melter systems and operated during four analytical campaigns conducted between 2013 and 2019. Overall, continuous flow analysis (CFA) of CO was carried out on over 700 m of ice. The CFA-based CO measurements exhibit excellent external precision (ranging from 3.3 to 6.6 ppbv, 1σ) and achieve consistently low blanks (ranging from 4.1±1.2 to 12.6±4.4 ppbv), enabling paleoatmospheric interpretations. However, the five CO records all exhibit variability that is too large and rapid to reflect past atmospheric mixing ratio changes. Complementary tests conducted on discrete ice samples demonstrate that these variations are not artifacts of the analytical method (i.e., production of CO from organics in the ice during melting) but are very likely related to in situ CO production within the ice before analysis. Evaluation of the signal resolution and co-investigation of high-resolution records of CO and total organic carbon (TOC) suggest that past atmospheric CO variations can be extracted from the records' baselines with accumulation rates higher than 20 cm w.e.yr-1 (water equivalent per year). Consistent baseline CO records from four Greenland sites are combined to produce a multisite average ice core reconstruction of past atmospheric CO for the Northern Hemisphere high latitudes, covering the period from 1700 to 1957 CE. Such a reconstruction should be taken as an upper bound of past atmospheric CO abundance. From 1700 to 1875 CE, the record reveals stable or slightly increasing values in the 100–115 ppbv range. From 1875 to 1957 CE, the record indicates a monotonic increase from 114±4 to 147±6 ppbv. The ice core multisite CO record exhibits an excellent overlap with the atmospheric CO record from Greenland firn air which spans the 1950–2010 CE time period. The combined ice core and firn air CO history, spanning 1700–2010 CE, provides useful constraints for future model studies of atmospheric changes since the preindustrial period.

Volcanic fallout in polar ice sheets provides important opportunities to date and correlate ice-core records as well as to investigate the environmental impacts of eruptions. Only the geochemical characterization of volcanic ash (tephra) embedded in the ice strata can confirm the source of the eruption, however, and is a requisite if historical eruption ages are to be used as valid chronological checks on annual ice layer counting. Here we report the investigation of ash particles in a Greenland ice core that are associated with a volcanic sulfuric acid layer previously attributed to the 79 CE eruption of Vesuvius. Major and trace element composition of the particles indicates that the tephra does not derive from Vesuvius but most likely originates from an unidentified eruption in the Aleutian arc. Using ash dispersal modeling, we find that only an eruption large enough to include stratospheric injection is likely to account for the sizable (24–85 µm) ash particles observed in the Greenland ice at this time. Despite its likely explosivity, this event does not appear to have triggered significant climate perturbations, unlike some other large extratropical eruptions. In light of a recent re-evaluation of the Greenland ice-core chronologies, our findings further challenge the previous assignation of this volcanic event to 79 CE. We highlight the need for the revised Common Era ice-core chronology to be formally accepted by the wider ice-core and climate modeling communities in order to ensure robust age linkages to precisely dated historical and paleoclimate proxy records.

Volcanic eruptions are a key source of climatic variability, and reconstructing their past impact can improve our understanding of the operation of the climate system and increase the accuracy of future climate projections. Two annually resolved and independently dated palaeoarchives – tree rings and polar ice cores – can be used in tandem to assess the timing, strength and climatic impact of volcanic eruptions over the past ∼ 2500 years. The quantification of post-volcanic climate responses, however, has at times been hampered by differences between simulated and observed temperature responses that raised questions regarding the robustness of the chronologies of both archives. While many chronological mismatches have been resolved, the precise timing and climatic impact of two major sulfate-emitting volcanic eruptions during the 1450s CE, including the largest atmospheric sulfate-loading event in the last 700 years, have not been constrained. Here we explore this issue through a combination of tephrochronological evidence and high-resolution ice-core chemistry measurements from a Greenland ice core, the TUNU2013 record. We identify tephra from the historically dated 1477 CE eruption of the Icelandic Veiðivötn–Bárðarbunga volcanic system in direct association with a notable sulfate peak in TUNU2013 attributed to this event, confirming that this peak can be used as a reliable and precise time marker. Using seasonal cycles in several chemical elements and 1477 CE as a fixed chronological point shows that ages of 1453 CE and 1458 CE can be attributed, with high precision, to the start of two other notable sulfate peaks. This confirms the accuracy of a recent Greenland ice-core chronology over the middle to late 15th century and corroborates the findings of recent volcanic reconstructions from Greenland and Antarctica. Overall, this implies that large-scale Northern Hemisphere climatic cooling affecting tree-ring growth in 1453 CE was caused by a Northern Hemisphere volcanic eruption in 1452 or early 1453 CE, and then a Southern Hemisphere eruption, previously assumed to have triggered the cooling, occurred later in 1457 or 1458 CE. The direct attribution of the 1477 CE sulfate peak to the eruption of Veiðivötn, one of the most explosive from Iceland in the last 1200 years, also provides the opportunity to assess the eruption's climatic impact. A tree-ring-based reconstruction of Northern Hemisphere summer temperatures shows a cooling in the aftermath of the eruption of −0.35 ∘C relative to a 1961–1990 CE reference period and −0.1 ∘C relative to the 30-year period around the event, as well as a relatively weak and spatially incoherent climatic response in comparison to the less explosive but longer-lasting Icelandic Eldgjá 939 CE and Laki 1783 CE eruptions. In addition, the Veiðivötn 1477 CE eruption occurred around the inception of the Little Ice Age and could be used as a chronostratigraphic marker to constrain the phasing and spatial variability of climate changes over this transition if it can be traced in more regional palaeoclimatic archives.

The last glacial period is characterized by a number of millennial climate events that have been identified in both Greenland and Antarctic ice cores and that are abrupt in Greenland climate records. The mechanisms governing this climate variability remain a puzzle that requires a precise synchronization of ice cores from the two hemispheres to be resolved. Previously, Greenland and Antarctic ice cores have been synchronized primarily via their common records of gas concentrations or isotopes from the trapped air and via cosmogenic isotopes measured on the ice. In this work, we apply ice core volcanic proxies and annual layer counting to identify large volcanic eruptions that have left a signature in both Greenland and Antarctica. Generally, no tephra is associated with those eruptions in the ice cores, so the source of the eruptions cannot be identified. Instead, we identify and match sequences of volcanic eruptions with bipolar distribution of sulfate, i.e. unique patterns of volcanic events separated by the same number of years at the two poles. Using this approach, we pinpoint 82 large bipolar volcanic eruptions throughout the second half of the last glacial period (12–60 ka). This improved ice core synchronization is applied to determine the bipolar phasing of abrupt climate change events at decadal-scale precision. In response to Greenland abrupt climatic transitions, we find a response in the Antarctic water isotope signals (δ18O and deuterium excess) that is both more immediate and more abrupt than that found with previous gas-based interpolar synchronizations, providing additional support for our volcanic framework. On average, the Antarctic bipolar seesaw climate response lags the midpoint of Greenland abrupt δ18O transitions by 122±24 years. The time difference between Antarctic signals in deuterium excess and δ18O, which likewise informs the time needed to propagate the signal as described by the theory of the bipolar seesaw but is less sensitive to synchronization errors, suggests an Antarctic δ18O lag behind Greenland of 152±37 years. These estimates are shorter than the 200 years suggested by earlier gas-based synchronizations. As before, we find variations in the timing and duration between the response at different sites and for different events suggesting an interaction of oceanic and atmospheric teleconnection patterns as well as internal climate variability.

The South Pole Ice Core (SPICEcore) was drilled in 2014–2016 to provide a detailed multi-proxy archive of paleoclimate conditions in East Antarctica during the Holocene and late Pleistocene. Interpretation of these records requires an accurate depth–age relationship. Here, we present the SPICEcore (SP19) timescale for the age of the ice of SPICEcore. SP19 is synchronized to the WD2014 chronology from the West Antarctic Ice Sheet Divide (WAIS Divide) ice core using stratigraphic matching of 251 volcanic events. These events indicate an age of 54 302±519 BP (years before 1950) at the bottom of SPICEcore. Annual layers identified in sodium and magnesium ions to 11 341 BP were used to interpolate between stratigraphic volcanic tie points, yielding an annually resolved chronology through the Holocene. Estimated timescale uncertainty during the Holocene is less than 18 years relative to WD2014, with the exception of the interval between 1800 to 3100 BP when uncertainty estimates reach ±25 years due to widely spaced volcanic tie points. Prior to the Holocene, uncertainties remain within 124 years relative to WD2014. Results show an average Holocene accumulation rate of 7.4 cm yr−1 (water equivalent). The time variability of accumulation rate is consistent with expectations for steady-state ice flow through the modern spatial pattern of accumulation rate. Time variations in nitrate concentration, nitrate seasonal amplitude and δ15N of N2 in turn are as expected for the accumulation rate variations. The highly variable yet well-constrained Holocene accumulation history at the site can help improve scientific understanding of deposition-sensitive climate proxies such as δ15N of N2 and photolyzed chemical compounds.

New ice cores retrieved from the Taylor Glacier (Antarctica) blue ice area contain ice and air spanning the Marine Isotope Stage (MIS) 5–4 transition, a period of global cooling and ice sheet expansion. We determine chronologies for the ice and air bubbles in the new ice cores by visually matching variations in gas- and ice-phase tracers to preexisting ice core records. The chronologies reveal an ice age–gas age difference (Δage) approaching 10 ka during MIS 4, implying very low snow accumulation in the Taylor Glacier accumulation zone. A revised chronology for the analogous section of the Taylor Dome ice core (84 to 55 ka), located to the south of the Taylor Glacier accumulation zone, shows that Δage did not exceed 3 ka. The difference in Δage between the two records during MIS 4 is similar in magnitude but opposite in direction to what is observed at the Last Glacial Maximum. This relationship implies that a spatial gradient in snow accumulation existed across the Taylor Dome region during MIS 4 that was oriented in the opposite direction of the accumulation gradient during the Last Glacial Maximum.

In this study, vanillic acid was measured in the Tunu ice core from northeastern Greenland in samples covering the past 1700 years. Vanillic acid is an aerosol-borne aromatic methoxy acid, produced by the combustion of lignin during biomass burning. Air mass trajectory analysis indicates that North American boreal forests are likely the major source region for biomass burning aerosols deposited to the ice core site. Vanillic acid levels in the Tunu ice core range from

Englacial ice contains a significant reservoir of organic material (OM), preserving a chronological record of materials from Earth's past. Here, we investigate if OM composition surveys in ice core research can provide paleoecological information on the dynamic nature of our Earth through time. Temporal trends in OM composition from the early Holocene extending back to the Last Glacial Maximum (LGM) of the West Antarctic Ice Sheet Divide (WD) ice core were measured by fluorescence spectroscopy. Multivariate parallel factor (PARAFAC) analysis is widely used to isolate the chemical components that best describe the observed variation across three-dimensional fluorescence spectroscopy (excitation–emission matrices; EEMs) assays. Fluorescent OM markers identified by PARAFAC modeling of the EEMs from the LGM (27.0–18.0 kyr BP; before present 1950) through the last deglaciation (LD; 18.0–11.5 kyr BP), to the mid-Holocene (11.5–6.0 kyr BP) provided evidence of different types of fluorescent OM composition and origin in the WD ice core over 21.0 kyr. Low excitation–emission wavelength fluorescent PARAFAC component one (C1), associated with chemical species similar to simple lignin phenols was the greatest contributor throughout the ice core, suggesting a strong signature of terrestrial OM in all climate periods. The component two (C2) OM marker, encompassed distinct variability in the ice core describing chemical species similar to tannin- and phenylalanine-like material. Component three (C3), associated with humic-like terrestrial material further resistant to biodegradation, was only characteristic of the Holocene, suggesting that more complex organic polymers such as lignins or tannins may be an ecological marker of warmer climates. We suggest that fluorescent OM markers observed during the LGM were the result of greater continental dust loading of lignin precursor (monolignol) material in a drier climate, with lower marine influences when sea ice extent was higher and continents had more expansive tundra cover. As the climate warmed, the record of OM markers in the WD ice core changed, reflecting shifts in carbon productivity as a result of global ecosystem response.

Wildfires and their emissions have significant impacts on ecosystems, climate, atmospheric chemistry, and carbon cycling. Well-dated proxy records are needed to study the long-term climatic controls on biomass burning and the associated climate feedbacks. There is a particular lack of information about long-term biomass burning variations in Siberia, the largest forested area in the Northern Hemisphere. In this study we report analyses of aromatic acids (vanillic and para-hydroxybenzoic acids) over the past 2600 years in the Eurasian Arctic Akademii Nauk ice core. These compounds are aerosol-borne, semi-volatile organic compounds derived from lignin combustion. The analyses were made using ion chromatography with electrospray mass spectrometric detection. The levels of these aromatic acids ranged from below the detection limit (0.01 to 0.05 ppb; 1 ppb = 1000 ng L−1) to about 1 ppb, with roughly 30 % of the samples above the detection limit. In the preindustrial late Holocene, highly elevated aromatic acid levels are observed during three distinct periods (650–300 BCE, 340–660 CE, and 1460–1660 CE). The timing of the two most recent periods coincides with the episodic pulsing of ice-rafted debris in the North Atlantic known as Bond events and a weakened Asian monsoon, suggesting a link between fires and large-scale climate variability on millennial timescales. Aromatic acid levels also are elevated during the onset of the industrial period from 1780 to 1860 CE, but with a different ratio of vanillic and para-hydroxybenzoic acid than is observed during the preindustrial period. This study provides the first millennial-scale record of aromatic acids. This study clearly demonstrates that coherent aromatic acid signals are recorded in polar ice cores that can be used as proxies for past trends in biomass burning.

Reconstruction of past changes in Arctic sea ice extent may be critical for understanding its future evolution. Methanesulfonate (MSA) and bromine concentrations preserved in ice cores have both been proposed as indicators of past sea ice conditions. In this study, two ice cores from central and north-eastern Greenland were analysed at sub-annual resolution for MSA (CH3SO3H) and bromine, covering the time period 1750–2010. We examine correlations between ice core MSA and the HadISST1 ICE sea ice dataset and consult back trajectories to infer the likely source regions. A strong correlation between the low-frequency MSA and bromine records during pre-industrial times indicates that both chemical species are likely linked to processes occurring on or near sea ice in the same source regions. The positive correlation between ice core MSA and bromine persists until the mid-20th century, when the acidity of Greenland ice begins to increase markedly due to increased fossil fuel emissions. After that time, MSA levels decrease as a result of declining sea ice extent but bromine levels increase. We consider several possible explanations and ultimately suggest that increased acidity, specifically nitric acid, of snow on sea ice stimulates the release of reactive Br from sea ice, resulting in increased transport and deposition on the Greenland ice sheet.

Advances in trace gas analysis allow localised, non-atmospheric features to be resolved in ice cores, superimposed on the coherent atmospheric signal. These high-frequency signals could not have survived the low-pass filter effect that gas diffusion in the firn exerts on the atmospheric history and therefore do not result from changes in the atmospheric composition at the ice sheet surface. Using continuous methane (CH4) records obtained from five polar ice cores, we characterise these non-atmospheric signals and explore their origin. Isolated samples, enriched in CH4 in the Tunu13 (Greenland) record are linked to the presence of melt layers. Melting can enrich the methane concentration due to a solubility effect, but we find that an additional in situ process is required to generate the full magnitude of these anomalies. Furthermore, in all the ice cores studied there is evidence of reproducible, decimetre-scale CH4 variability. Through a series of tests, we demonstrate that this is an artifact of layered bubble trapping in a heterogeneous-density firn column; we use the term “trapping signal” for this phenomenon. The peak-to-peak amplitude of the trapping signal is typically 5 ppb, but may exceed 40 ppb. Signal magnitude increases with atmospheric CH4 growth rate and seasonal density contrast, and decreases with accumulation rate. Significant annual periodicity is present in the CH4 variability of two Greenland ice cores, suggesting that layered gas trapping at these sites is controlled by regular, seasonal variations in the physical properties of the firn. Future analytical campaigns should anticipate high-frequency artifacts at high-melt ice core sites or during time periods with high atmospheric CH4 growth rate in order to avoid misinterpretation of such features as past changes in atmospheric composition.

We present the WD2014 chronology for the upper part (0–2850 m; 31.2 ka BP) of the West Antarctic Ice Sheet (WAIS) Divide (WD) ice core. The chronology is based on counting of annual layers observed in the chemical, dust and electrical conductivity records. These layers are caused by seasonal changes in the source, transport, and deposition of aerosols. The measurements were interpreted manually and with the aid of two automated methods. We validated the chronology by comparing to two high-accuracy, absolutely dated chronologies. For the Holocene, the cosmogenic isotope records of 10Be from WAIS Divide and 14C for IntCal13 demonstrated that WD2014 was consistently accurate to better than 0.5 % of the age. For the glacial period, comparisons to the Hulu Cave chronology demonstrated that WD2014 had an accuracy of better than 1 % of the age at three abrupt climate change events between 27 and 31 ka. WD2014 has consistently younger ages than Greenland ice core chronologies during most of the Holocene. For the Younger Dryas–Preboreal transition (11.595 ka; 24 years younger) and the Bølling–Allerød Warming (14.621 ka; 7 years younger), WD2014 ages are within the combined uncertainties of the timescales. Given its high accuracy, WD2014 can become a reference chronology for the Southern Hemisphere, with synchronization to other chronologies feasible using high-quality proxies of volcanism, solar activity, atmospheric mineral dust, and atmospheric methane concentrations.

The West Antarctic Ice Sheet Divide (WAIS Divide, WD) ice core is a newly drilled, high-accumulation deep ice core that provides Antarctic climate records of the past ∼68 ka at unprecedented temporal resolution. The upper 2850 m (back to 31.2 ka BP) have been dated using annual-layer counting. Here we present a chronology for the deep part of the core (67.8–31.2 ka BP), which is based on stratigraphic matching to annual-layer-counted Greenland ice cores using globally well-mixed atmospheric methane. We calculate the WD gas age–ice age difference (Δage) using a combination of firn densification modeling, ice-flow modeling, and a data set of δ15N-N2, a proxy for past firn column thickness. The largest Δage at WD occurs during the Last Glacial Maximum, and is 525 ± 120 years. Internally consistent solutions can be found only when assuming little to no influence of impurity content on densification rates, contrary to a recently proposed hypothesis. We synchronize the WD chronology to a linearly scaled version of the layer-counted Greenland Ice Core Chronology (GICC05), which brings the age of Dansgaard–Oeschger (DO) events into agreement with the U/Th absolutely dated Hulu Cave speleothem record. The small Δage at WD provides valuable opportunities to investigate the timing of atmospheric greenhouse gas variations relative to Antarctic climate, as well as the interhemispheric phasing of the "bipolar seesaw".

Biomass burning is a major source of greenhouse gases and influences regional to global climate. Pre-industrial fire-history records from black carbon, charcoal and other proxies provide baseline estimates of biomass burning at local to global scales spanning millennia, and are thus useful to examine the role of fire in the carbon cycle and climate system. Here we use the specific biomarker levoglucosan together with black carbon and ammonium concentrations from the North Greenland Eemian (NEEM) ice cores (77.49° N, 51.2° W; 2480 m a.s.l) over the past 2000 years to infer changes in boreal fire activity. Increases in boreal fire activity over the periods 1000–1300 CE and decreases during 700–900 CE coincide with high-latitude NH temperature changes. Levoglucosan concentrations in the NEEM ice cores peak between 1500 and 1700 CE, and most levoglucosan spikes coincide with the most extensive central and northern Asian droughts of the past millennium. Many of these multi-annual droughts are caused by Asian monsoon failures, thus suggesting a connection between low- and high-latitude climate processes. North America is a primary source of biomass burning aerosols due to its relative proximity to the Greenland Ice Cap. During major fire events, however, isotopic analyses of dust, back trajectories and links with levoglucosan peaks and regional drought reconstructions suggest that Siberia is also an important source of pyrogenic aerosols to Greenland.

We present high-resolution measurements of carbon monoxide (CO) concentrations from a shallow ice core of the North Greenland Eemian Ice Drilling project (NEEM-2011-S1). An optical-feedback cavity-enhanced absorption spectrometer (OF-CEAS) coupled to a continuous melter system performed continuous, online analysis during a four-week measurement campaign. This analytical setup generated stable measurements of CO concentrations with an external precision of 7.8 ppbv (1σ), based on repeated analyses of equivalent ice core sections. However, this first application of this measurement technique suffered from a poorly constrained procedural blank of 48 ± 25 ppbv and poor accuracy because an absolute calibration was not possible. The NEEM-2011-S1 CO record spans 1800 yr and the long-term trends within the most recent section of this record (i.e., post 1700 AD) resemble the existing discrete CO measurements from the Eurocore ice core. However, the CO concentration is highly variable (75–1327 ppbv range) throughout the ice core with high frequency (annual scale), high amplitude spikes characterizing the record. These CO signals are too abrupt and rapid to reflect atmospheric variability and their prevalence largely prevents interpretation of the record in terms of atmospheric CO variation. The abrupt CO spikes are likely the result of in situ production occurring within the ice itself, although the unlikely possibility of CO production driven by non-photolytic, fast kinetic processes within the continuous melter system cannot be excluded. We observe that 68% of the CO spikes are observed in ice layers enriched with pyrogenic aerosols. Such aerosols, originating from boreal biomass burning emissions, contain organic compounds, which may be oxidized or photodissociated to produce CO within the ice. However, the NEEM-2011-S1 record displays an increase of ~0.05 ppbv yr−1 in baseline CO level prior to 1700 AD (129 m depth) and the concentration remains elevated, even for ice layers depleted in dissolved organic carbon (DOC). Thus, the processes driving the likely in situ production of CO within the NEEM ice may involve multiple, complex chemical pathways not all related to past fire history and require further investigation.

We present an automated process for determining the annual layer chronology of an ice-core with a strong annual signal, utilising the hydrogen peroxide record from an Antarctic Peninsula ice-core as a test signal on which to count annual cycles and explain the methods. The signal is de-trended and normalised before being split into sections with a deterministic cycle count and those that need more attention. Possible reconstructions for the uncertain sections are determined which could be used as a visual aid for manual counting, and a simple method for assigning probability measures to each reconstruction is discussed. The robustness of this process is explored by applying it to versions of two different chemistry signals from the same stretch of the NGRIP (North Greenland Ice Core Project) ice-core, which shows more variation in annual layer thickness, with and without thinning to mimic poorer quality data. An adapted version of these methods is applied to the more challenging non-sea-salt sulphur signal from the same Antarctic Peninsula core from which the hydrogen peroxide signal was taken. These methods could readily be adapted for use on much longer datasets, thereby reducing manual effort and providing a robust automated layer-counting methodology.