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Landscape heterogeneity impacts community assembly in animals and plants, but it is not clear if this ecological concept extends to microbes. To examine this question, we chose to investigate polar soil environments from the Antarctic and Arctic, where microbes often form the major component of biomass. We examined soil environments that ranged in connectivity from relatively well-connected slopes to patchy, fragmented landforms that comprised isolated frost boils. We found landscape connectedness to have a significant correlation with microbial community structure and connectivity, as measured by co-occurrence networks. Soils from within fragmented landforms appeared to exhibit less local environmental heterogeneity, harboured more similar communities, but fewer biological associations than connected landforms. This effect was observed at both poles, despite the geographical distances and ecological differences between them. We suggest that microbial communities inhabiting well-connected landscape elements respond consistently to regional-scale gradients in biotic and edaphic factors. Conversely, the repeated freeze thaw cycles that characterize fragmented landscapes create barriers within the landscape and act to homogenize the soil environment within individual frost boils and consequently the microbial communities. We propose that lower microbial connectivity in the fragmented landforms is a function of smaller patch size and continual disturbances following soil mixing.

Mitchell Peninsula is located towards the East of the Windmill Islands in eastern Antarctica. It is an ice-free polar desert, and knowledge of its soil microbial taxonomic composition is limited. In this study, we investigated the soil microbial taxonomic composition using multiplex 454 pyrosequencing targeting the bacterial 16S rRNA and the fungal ITS genes; and the bacterial and fungal abundances were estimated using quantitative PCR. In total, 40 bacterial and five fungal phyla were identified comprising 111 bacterial and 22 fungal classes, respectively. Mitchell Peninsula soil exhibited a unique bacterial taxonomic profile. In contrast to the usual dominance of Proteobacteria, Firmicutes, Actinobacteria and Bacteroidetes in polar and temperate soils, Mitchell Peninsula was rich in the poorly studied Chloroflexi (31.7 %), candidate divisions WPS-2 (8.1 %) and AD3 (5.1 %), while the commonly observed Bacteroidetes and Firmicutes were present in relative abundances below 1 %. The fungal community consisted of Ascomycota (77 %) and Basidiomycota (10 %), and was dominated by the lichenous fungal class Lecanoromycetes (46.4 %). Network analysis revealed the presence of several microbial clusters that each potentially occupied a different environmental niche, and fewer numbers of correlations were identified between bacteria within each cluster compared with the lichen community, where extensive community dynamics may be present. As Mitchell Peninsula exhibits a unique microbial taxonomic composition, not previously observed in any reported polar or temperate ecosystem, we believe it is a potential microbial biodiversity “hotspot”, which warrants further investigation to examine the role of the dominance of these uncharacterised candidate divisions in this extreme ecosystem.

Microbial activities in Arctic and Antarctic soils are of particular interest due to uncertainty surrounding the fate of the enormous polar soil organic matter (SOM) pools and the potential to lose unique and vulnerable micro-organisms from these ecosystems. We quantified richness, evenness and taxonomic composition of both fungi and bacteria in 223 Arctic and Antarctic soil samples across 8 locations to test the global applicability of hypotheses concerning edaphic drivers of soil microbial communities that have been primarily developed from studies of bacteria in temperate and tropical systems. We externally validated our model's conclusions with an independent dataset comprising 33 Arctic heath samples. We also explored if our system was responding to large scale climatic or biogeographical processes that we had not measured by evaluating model stability for one location, Mitchell Pennisula, that had been extensively sampled. Soil Fertility (defined as organic matter, nitrogen and chloride content) was the most important edaphic property associated with measures of α-diversity such as microbial richness and evenness (especially for fungi), whereas pH was primarily associated with measures of β-diversity such as phylogenetic structure and diversity (especially for bacteria). Surprisingly, phosphorus emerged as consistently the second most important driver of all facets of microbial community structure for both fungi and bacteria. Despite the clear importance of edaphic factors in controlling microbial communities, our analyses also indicated that fungal/bacterial interactions play a major, but causally unclear, role in structuring the soil microbial communities of which they are a part.

Browning Peninsula is an ice-free polar desert situated in the Windmill Islands, Eastern Antarctica. The entire site is described as a barren landscape, comprised of frost boils with soils dominated by microbial life. In this study, we explored the microbial diversity and edaphic drivers of community structure across this site using traditional cultivation methods, a novel approach the soil substrate membrane system (SSMS), and culture-independent 454-tag pyrosequencing. The measured soil environmental and microphysical factors of chlorine, phosphate, aspect and elevation were found to be significant drivers of the bacterial community, while none of the soil parameters analyzed were significantly correlated to the fungal community. Overall, Browning Peninsula soil harbored a distinctive microbial community in comparison to other Antarctic soils comprised of a unique bacterial diversity and extremely limited fungal diversity. Tag pyrosequencing data revealed the bacterial community to be dominated by Actinobacteria (36%), followed by Chloroflexi (18%), Cyanobacteria (14%), and Proteobacteria (10%). For fungi, Ascomycota (97%) dominated the soil microbiome, followed by Basidiomycota. As expected the diversity recovered from culture-based techniques was lower than that detected using tag sequencing. However, in the SSMS enrichments, that mimic the natural conditions for cultivating oligophilic “k-selected” bacteria, a larger proportion of rare bacterial taxa (15%), such as Blastococcus, Devosia, Herbaspirillum, Propionibacterium and Methylocella and fungal (11%) taxa, such as Nigrospora, Exophiala, Hortaea, and Penidiella were recovered at the genus level. At phylum level, a comparison of OTU's showed that the SSMS shared 21% of Acidobacteria, 11% of Actinobacteria and 10% of Proteobacteria OTU's with soil. For fungi, the shared OTUs was 4% (Basidiomycota) and

On polar coasts, seasonal sea-ice duration strongly influences shallow marine environments by affecting environmental conditions, such as light, sedimentation, and physical disturbance. Sea-ice dynamics are changing in response to climate, but there is limited understanding of how this might affect shallow marine environments and benthos. Here we present a unique set of physical and biological data from a single region of Antarctic coast, and use it to gain insights into factors shaping polar benthic communities. At sites encompassing a gradient of sea-ice duration, we measured temporal and spatial variation in light and sedimentation and hard-substrate communities at different depths and substrate orientations. Biological trends were highly correlated with sea-ice duration, and appear to be driven by opposing gradients in light and sedimentation. As sea-ice duration decreased, there was increased light and reduced sedimentation, and concurrent shifts in community structure from invertebrate to algal dominance. Trends were strongest on shallower, horizontal surfaces, which are most exposed to light and sedimentation. Depth and substrate orientation appear to mediate exposure of benthos to these factors, thereby tempering effects of sea-ice and increasing biological heterogeneity. However, while light and sedimentation both varied spatially with sea-ice, their dynamics differed temporally. Light was sensitive to the site-specific date of sea-ice breakout, whereas sedimentation fluctuated at a regional scale coincident with the summer phytoplankton bloom. Sea-ice duration is clearly the overarching force structuring these shallow Antarctic benthic communities, but direct effects are imposed via light and sedimentation, and mediated by habitat characteristics.

Transient white and grey mats were observed in depressions and enclosed basins in marine sediment in the Windmill Islands, East Antarctica. These patches have not been described in the Antarctic marine environment previously although a similar phenomenon has been described in the Arctic. Our aim was to describe the sediment geochemical and biological properties inside the patches and to determine their similarity to each other. We compared the benthic infaunal communities and the chemical properties of the sediment in the white patches to nearby sediment without white mats. We observed differences in sediment pH, Eh and elemental concentrations inside and outside patches. The benthic infaunal communities inside the patches were significantly different, lower in abundance and diversity, compared to outside the patches. The structure of the microbial communities within the mats was described by constructing clone libraries from four different patches. These clone libraries were dominated by bacteria from the bacteroidetes phylum. Clones closely related to sulphur-oxidising bacteria from the gammaproteobacteria and/or the epsilonproteobacteria were present in all libraries. This is the first detailed description of these patches in the Antarctic and demonstrates the link between physico-chemical factors and microbial and infaunal community structure. It appears that this phenomenon may be driven by the formation and persistence of sea-ice, and as both the spatial extent of sea-ice and its persistence in polar regions are likely to change under predicted climate change scenarios, we suggest this is a previously undocumented mechanism for climate change to impact polar ecosystems.

Sediment profiles for pH, Eh, 28 elements, water and organic content are presented here for human impacted and reference locations in the Windmill Islands, East Antarctica. Variations in element concentrations are observed with increasing depth, especially at Brown Bay where the impact of past human activities is most pronounced in the top 10 cm. Spatial differences were observed between sediment profiles at reference and impacted locations and were largely explained by Pb variability in the top 5 cm. Median element concentrations from surface, middle and bottom regions of the sediment profile were compared to composite sample medians (no depth stratigraphy) for 11 elements at O'Brien Bay (reference) and Brown Bay (impacted). Pronounced differences were observed for Brown Bay, particularly surface and middle sections, implying that composite samples dilute the near surface anthropogenic signal by mixing with deeper uncontaminated sediment.

Previous studies of impacted sites near Casey Station, Antarctica, have revealed elevated concentrations of metals and metalloids, particularly Cd, Cu, Fe, Pb, Sn and Zn in marine sediments. However, attempts to understand the availability and mobility of contaminant elements have not provided a true understanding of speciation. The current work shows, for the first time, that sediments in Brown Bay, an embayment adjacent to the Thala Valley waste disposal site, have elevated concentrations of sulfide, well in excess of that required to bind contaminant metals such as Cd, Cu, Pb and Zn. Furthermore, sediment characterisation using the BCR sequential extraction scheme has shown metal partitioning consistent with sulfides being the controlling factor in metal availability, thus explaining the low porewater concentrations of these metals. The speciation of Sn in Brown Bay, however, is still unclear with the BCR sequential extraction scheme partitioning Sn predominantly into the residual fraction despite Sn being readily extracted by dilute HCl.

The Antarctic Treaty permits the discharge of wastewater into Antarctic marine waters providing that conditions exist for initial dilution and rapid dispersal. We investigated the dilution and dispersal of macerated wastewater around Australia's Davis Station in East Antarctica and examined sediments for evidence of contaminants. Methods used to examine hydrodynamic conditions included current meters, dye release experiments and measurement of sewage-associated microbial markers and surfactants in the water column. We measured marine sediments for metals, nutrients, PBDEs, hydrocarbons and faecal sterols. We propose that if there is adequate dilution and dispersal there would be no significant difference in contaminant concentrations in sediments around the outfall compared to distant control sites. Currents were strongly correlated with prevailing wind conditions. Modelling indicated that diffusivity of wastewater had the greatest effect on dilution factors and that neither discharge rates nor local currents had as much effect. During summer conditions of open water, wastewater is likely to be constrained in a narrow plume close to the coast. Concentrations of sewage bacteria were high around the outfall and detected up to 1.5 km away, along with dye. There were significant differences in sediment concentrations of metals, PBDEs, hydrocarbons, nutrients and faecal sterols between sites within 2 km of the outfall and control sites. We conclude that dilution and dispersal conditions at the Davis outfall are insufficient to prevent the accumulation of contaminants in local sediments and that microbial hazards posed by wastewater are an environmental risk to local wildlife.

Landscape heterogeneity impacts community assembly in animals and plants, but it is not clear if this ecological concept extends to microbes. To examine this question, we chose to investigate polar soil environments from the Antarctic and Arctic, where microbes often form the major component of biomass. We examined soil environments that ranged in connectivity from relatively well-connected slopes to patchy, fragmented landforms that comprised isolated frost boils. We found landscape connectedness to have a significant correlation with microbial community structure and connectivity, as measured by co-occurrence networks. Soils from within fragmented landforms appeared to exhibit less local environmental heterogeneity, harboured more similar communities, but fewer biological associations than connected landforms. This effect was observed at both poles, despite the geographical distances and ecological differences between them. We suggest that microbial communities inhabiting well-connected landscape elements respond consistently to regional-scale gradients in biotic and edaphic factors. Conversely, the repeated freeze thaw cycles that characterize fragmented landscapes create barriers within the landscape and act to homogenize the soil environment within individual frost boils and consequently the microbial communities. We propose that lower microbial connectivity in the fragmented landforms is a function of smaller patch size and continual disturbances following soil mixing.

Explosive volcanic eruptions can inject large quantities of sulphur dioxide into the stratosphere. the aerosols that result from oxidation of the sulphur dioxide can produce significant cooling of the troposphere by reflecting or absorbing solar radiation. It is possible to obtain an estimate of the relative stratospheric sulphur aerosol concentration produced by different volcanoes by comparing sulphuric acid fluxes determined by analysis of polar ice cores. Here,we use a non-sea-salt sulphate time series derived from three well-dated Law Dome ice cores to investigate sulphuric acid flux ratios for major eruptions over the period AD 1301–1995. We use additional data from other cores to investigate systematic spatial variability in the ratios. Only for the Kuwae eruption (Law Dome ice date AD 1459.5) was the H2SO4 flux larger than that deposited by Tambora (Law Dome ice date AD 1816.7).

A series of ice cores from sites with different snow-accumulation rates across Law Dome, East Antarctica, was investigated for methanesulphonic acid (MSA) movement. the precipitation at these sites (up to 35 km apart) is influenced by the same air masses, the principal difference being the accumulation rate. At the low-accumulation-rate W20k site (0.17m ice equivalent), MSAwas completely relocated from the summer to winter layer. Moderate movement was observed at the intermediate-accumulation-rate site (0.7m ice equivalent), Dome Summit South (DSS), while there was no evidence of movement at the high-accumulation-rate DE08 site (1.4m ice equivalent). the main DSS record of MSA covered the epoch AD 1727–2000 and was used to investigate temporal post-depositional changes. Co-deposition of MSA and sea-salt ions was observed in the surface layers, outside of the main summer MSA peak,which complicates interpretation of these peaks as evidence of movement in deeper layers. A seasonal study of the 273 year DSS record revealed MSA migration predominantly from summer into autumn (in the up-core direction), but this migration was suppressed during the Tambora (1815) and unknown (1809) volcanic eruption period, and enhanced during an epoch (1770–1800) with high summer nitrate levels. A complex interaction between the gradients in nss-sulphate, nitrate and sea salts (which are influenced by accumulation rate) is believed to control the rate and extent of movement of MSA.

A record of volcanic activity over the period A.D. 1301–1995 has been extracted from three Law Dome ice cores (East Antarctica). The record dating is unambiguous at the annual level from A.D. 1807 to 1995 and has an uncertainty of ±1 year at A.D. 1301. Signals from 20 eruptions are preserved in the record, including those of two unknown eruptions with acid deposition beginning in A.D. 1810.8 and A.D. 1685.8. The beginning of the ice core signal from the A.D. 1815 Tambora eruption is observed in the austral summer of A.D. 1816/1817. The mean observed stratospheric transport and deposition time to Law Dome from the eruption site is 1.5 years (σ = 0.6 years) from 11 well-dated eruptions. The largest eruption observed in the Law Dome record has its maximum in A.D. 1460 with volcanic sulfate deposition beginning in the austral winter of A.D. 1459. This event is also observed in other ice core records and is attributed to the volcano Kuwae, with an eruption date in the range A.D. 1455.9–1459.9 if all sources of error are considered. This is at least three years later than the date previously ascribed by dendrochronological and historical studies.

The concentration of trace ionic species in snow and ice samples was determined using suppressed ion chromatography (IC) with conductivity detection and ultra-clean sample preparation techniques. Trace anion species were determined in a single 24-min run by combining sample preconcentration with gradient elution using Na2B4O7 eluent. The detection limits (ranging from 0.001 to 0.006 microM) are the lowest reported in the literature. Cation species were analysed by direct injection of 0.25 ml and isocratic elution with a H2SO4 eluent. The clean preparation techniques showed no evidence of a difference (Student's t-test) between Milli-Q water samples analysed directly and processed Milli-Q ice samples. These robust, ultra-clean IC methods were routinely applied to the analysis of large number of samples to produce a high-resolution trace ion ice core record from Law Dome, East Antarctica.

A precision-dated ice-core nitrate record from Law Dome, coastal East Antarctica is compared to the timing of known solar proton events and geomagnetic storms over the period 1888 to 1995. We find statistical evidence for a significant (P < 0.03) but small elevation in mean nitrate concentrations following the solar events (∼11% over the 12 months beginning 3 months post-event). While some solar events are identifiable in the nitrate record, most are not distinguishable from the background noisy signal (which has numerous large peaks), and some solar events show no nitrate elevation above even mean levels.

Despite decreasing costs, generating large-scale, well-replicated and multivariate microbial ecology investigations with sequencing remains an expensive and time-consuming option. As a result, many microbial ecology investigations continue to suffer from a lack of appropriate replication. We evaluated two fingerprinting approaches – terminal restriction fragment length polymorphism (T-RFLP) and automated ribosomal intergenic spacer analysis (ARISA) against 454 pyrosequencing, by applying them to 225 polar soil samples from East Antarctica and the high Arctic. By incorporating local and global spatial scales into the dataset, our aim was to determine whether various approaches differed in their ability and hence utility, to identify ecological patterns. Through the reduction in the 454 sequencing data to the most dominant OTUs, we revealed that a surprisingly small proportion of abundant OTUs (< 0.25%) was driving the biological patterns observed. Overall, ARISA and T-RFLP had a similar capacity as sequencing to separate samples according to distance at a local scale, and to correlate environmental variables with microbial community structure. Pyrosequencing had a greater resolution at the global scale but all methods were capable of significantly differentiating the polar sites. We conclude fingerprinting remains a legitimate approach to generating large datasets as well as a cost-effective rapid method to identify samples for elucidating taxonomic information or diversity estimates with sequencing methods.

Sensitive analytical techniques are typically required when dealing with samples from Antarctica as even low concentrations of contaminants can have detrimental environmental effects. Magnetic Sector ICP-MS is an ideal technique for environmental assessment as it offers high sensitivity, multi-element capability and the opportunity to determine isotope ratios. Here we consider the Pb isotope record of five marine sediment cores collected from three sites in the Windmill Islands area of East Antarctica: Brown Bay adjacent to the current Australian station Casey, Wilkes near the abandoned US/Australian Station and McGrady Cove lying midway between the two. Two sediment pre-treatment approaches were considered, namely partial extraction with 1 M HCl and total dissolution involving HF. Lead isotope ratio measurements made following sediment partial extraction provided a more sensitive indication of Pb contamination than either Pb concentrations alone (irrespective of sample pre-treatment method) or isotope ratios made after HF digestion, offering greater opportunity for discrimination between impacted and natural/geogenic samples and sites. Over 90% of the easily extractable Pb from sediments near Casey was anthropogenic in origin, consisting of Pb from major Australian deposits. At Wilkes impact from discarded batteries with a unique isotopic signature was found to be a key source of Pb contamination to the marine environment with ~ 70–80% of Pb being anthropogenic in origin. The country and source of origin of these batteries remain unknown. Little evidence was found suggesting contamination at Wilkes by Pb originating from the major US source, Missouri. No definitive assessment could be made regarding Pb impact at McGrady Cove as the collected sediment core was of insufficient depth. Although Pb isotope ratio signatures may indicate anthropogenic input, spatial concentration gradients at nearby Brown Bay suggest contamination at McGrady Cove is unlikely. We recommend Pb isotopic analysis following 1 M HCl partial extraction pre-treatment as a powerful and sensitive method for tracing Pb contamination in marine sediments.

The effect of oxidation of anoxic sediment upon the extraction of 13 elements (Cd, Sn, Sb, Pb, Al, Cr, Mn, Fe, Co, Ni, Cu, Zn, As) using the optimised Community Bureau of Reference of the European Commission (BCR) sequential extraction procedure and a dilute acid partial extraction procedure (4h, 1 molL(-1) HCl) was investigated. Elements commonly associated with the sulfidic phase, Cd, Cu, Pb, Zn and Fe exhibited the most significant changes under the BCR sequential extraction procedure. Cd, Cu, Zn, and to a lesser extent Pb, were redistributed into the weak acid extractable fraction upon oxidation of the anoxic sediment and Fe was redistributed into the reducible fraction as expected, but an increase was also observed in the residual Fe. For the HCl partial extraction, sediments with moderate acid volatile sulfide (AVS) levels (1-100 micromolg(-1)) showed no significant difference in element partitioning following oxidation, whilst sediments containing high AVS levels (100 micromolg(-1)) were significantly different with elevated concentrations of Cu and Sn noted in the partial extract following oxidation of the sediment. Comparison of the labile metals released using the BCR sequential extraction procedure (SigmaSteps 1-3) to labile metals extracted using the dilute HCl partial extraction showed that no method was consistently more aggressive than the other, with the HCl partial extraction extracting more Sn and Sb from the anoxic sediment than the BCR procedure, whilst the BCR procedure extracted more Cr, Co, Cu and As than the HCl extraction.

A number of extraction methods are currently used to characterise metals in marine sediments. These include total digestion involving HF, extraction with concentrated acid, partial extraction with weak acid, or a more complicated multiple stage sequential extraction scheme (e.g. BCR) (Mudroch et al., 1999). Partial extraction methods are attractive because they are simple, fast, relatively safe, and they target labile phases and reservoirs containing metals

Remediation of the Thala Valley waste disposal site near Casey Station, East Antarctica was conducted in the austral summer of 2003/2004. Biomonitoring of the adjacent marine environment was undertaken using the gammaridean amphipod Paramoera walkeri as a sentinel species [Stark, J.S., Johnstone, G.J., Palmer, A.S., Snape, I., Larner, B.L., Riddle, M.J., in press, doi:10.1016/j.marpolbul.2006.05.020. Monitoring the remediation of a near shore waste disposal site in Antarctica using the amphipod Paramoera walkeri and diffusive gradients in thin films (DGTs). Marine Pollution Bulletin and references therein]. Determination of uptake of metals and hypothesis testing for differences that could be attributed to contamination required the establishment of baseline metal concentrations in P. walkeri. Baseline metal concentrations from two reference locations in the Windmill Islands are presented here. P. walkeri was a found to be a sensitive bioaccumulating organism that recorded spatial and temporal variability at the reference sites. Measurement of metals in P. walkeri required the development of a simple digestion procedure that used concentrated nitric acid. For the first time, rare earth metals were determined with additional clean procedures required to measure ultra low concentrations using magnetic sector ICP-MS. Certified and in-house reference materials were employed to ensure method reliability.

The water quality of a marine embayment (Brown Bay) was monitored during the remediation of an abandoned waste disposal site at Casey Station, East Antarctica, using a combination of biomonitoring and chemical methods. The Antarctic amphipod Paramoera walkeri, in field mesocosms suspended in the water column, was deployed adjacent to the site and at two reference sites for periods of 14 days, repeated three times during the remediation period (December to February). Diffusive gradients in thin film (DGT) samplers were deployed for the same periods to provide estimates of dissolved metals. No difference in mortality of amphipods was observed between Brown Bay and reference sites. There were significant differences, however, in accumulated metal concentrations between amphipods from Brown Bay and reference sites, with greater concentrations of antimony, copper, cadmium, lead, iron and tin at Brown Bay. The melt water/runoff treatment strategy employed for the remediation was successful in preventing acute toxic effects, but water quality was reduced at Brown Bay, where increased metal bioavailability may have been high enough to induce chronic effects in some biota. DGT samplers were less sensitive than amphipods in detecting differences in metal concentrations between sites, indicating that metals bound to suspended particulates were a potentially significant source of contamination.

Mineral dust from the Saharan desert can be transported across the Mediterranean towards the Alpine region several times a year. When coinciding with snowfall, the dust can be deposited on Alpine glaciers and then appears as yellow or red layers in ice cores. Two such significant dust events were identified in an ice core drilled at the high-accumulation site Piz Zupó in the Swiss Alps (46°22' N, 9°55' E, 3850 ma.s.l.). From stable oxygen isotopes and major ion concentrations, the events were approximately dated as October and March 2000. In order to link the dust record in the ice core to the meteorological situation that led to the dust events, a novel methodology based on back-trajectory analysis was developed. It allowed the detailed analysis of the specific meteorologic flow evolution that was associated with Saharan dust transport into the Alps, and the identification of dust sources, atmospheric transport paths, and wet deposition periods for both dust events. Differences in the chemical signature of the two dust events were interpreted with respect to contributions from the dust sources and aerosol scavenging during the transport. For the October event, the trajectory analysis indicated that dust deposition took place during 13–15 October 2000. Mobilisation areas of dust were mainly identified in the Algerian and Libyan deserts. A combination of an upper-level potential vorticity streamer and a midlevel jet across Algeria first brought moist Atlantic air and later mixed air from the tropics and Saharan desert across the Mediterranean towards the Alps. The March event consisted of two different deposition phases which took place during 17–19 and 23–25 March 2000. The first phase was associated with an exceptional transport pathway past Iceland and towards the Alps from northerly directions. The second phase was similar to the October event. A significant peak of methanesulphonic acid associated with the March dust event was most likely caused by incorporation of biogenic aerosol while passing through the marine boundary layer of the western Mediterranean during a local phytoplankton bloom. From this study, we conclude that for a detailed understanding of the chemical signal recorded in dust events at Piz Zupó, it is essential to consider the whole transport sequence of mineral aerosol, consisting of dust mobilisation, transport, and deposition at the glacier.

[1] In July 2001, a 140 m long ice core was recovered from the Belukha glacier (49°48′26″N, 86°34′43″E, 4062 m a.s.l.) in the Siberian Altai. The ion chemistry of the upper 86 m, covering the last two centuries, is characterized by biogenic emissions (ammonium and formate), aeolian dust (calcium, magnesium, chloride, and sodium) and anthropogenic species (sulfate, nitrate, and ammonium). Particularly high ammonium and formate concentrations indicate pronounced emissions from Siberian forests. The inferred fire frequency does not show a long-term trend but distinct periods of enhanced activity. Sulfate has the highest industrial to preindustrial ratio and an anthropogenic contribution of more than 80%. Variations in this record reflect sulfur dioxide emissions in Siberia and Kazakhstan. Sulfate concentrations remained low until 1950, then sharply increased and peaked in the 1970s. The decrease in the 1980s is attributed to the economic, political, and social crises and to the replacement of coal with gas. Rising nitrate concentrations since 1960 reflect traffic growth and enhanced fertilizer application. Increasing ammonium concentrations since the 1950s are attributable to population inflow in southern Siberia with the associated enhancement of agricultural activity. A nitrate peak of short duration in 1908 is thought to be the atmospheric signature from the Tunguska event on 30 June 1908.

The instrumental record of Antarctic sea ice in recent decades does not reveal a clear signature of warming despite observational evidence from coastal Antarctica. Here we report a significant correlation ( P < 0.002) between methanesulphonic acid (MSA) concentrations from a Law Dome ice core and 22 years of satellite-derived sea ice extent (SIE) for the 80°E to 140°E sector. Applying this instrumental calibration to longer term MSA data (1841 to 1995 A.D.) suggests that there has been a 20% decline in SIE since about 1950. The decline is not uniform, showing large cyclical variations, with periods of about 11 years, that confuse trend detection over the relatively short satellite era.

A solid-phase extraction method based on an ion-exchange retention mechanism has been used for in-line preconcentration of inorganic anions prior to their separation by capillary electrophoresis (CE). A single capillary containing a preconcentration and a separation zone has been used in a commercial CE instrument without instrumental modification. Analyte anions were retained on a preconcentration zone comprising an adsorbed layer of cationic latex particles, while separation was achieved in a separation zone comprising fused silica modified by adsorption of a cationic polymer. Elution of the adsorbed analytes was achieved using an eluotropic gradient formed by a transient isotachophoretic boundary between a fluoride electrolyte and a naphthalenedisulfonate electrolyte. Optimization of the electrolyte concentrations, sample injection times, and back-flushing times allowed the successful separation of sub-ppb levels of inorganic anions using a 100-min injection at 2 bar pressure, introducing over 40 capillary volumes of sample. A method based on a 10-min injection allowed a 100-fold increase in sensitivity over conventional hydrodynamic injection for Br-, I-, NO3-, CrO4(2-), and MoO4(2-) with a total analysis time of 25 min. Detection limits were dependent on the injection time but were in the range 2.2-11.6 ppb for a 10-min injection time. This approach was used to determine NO3- in Antarctic ice cores where the analysis could be performed using a sample volume 100 times less than that used for ion chromatography.

[1] A 700-year, high-resolution, multivariate ice core record from Dome Summit South (DSS) (66°46′S, 112°48′E; 1370 m), Law Dome, is used to investigate sea level pressure (SLP) variability in the region of East Antarctica. Empirical orthogonal function (EOF) analysis reveals that the first EOF (LDEOF1) of the combined glaciochemical, oxygen isotope ratio, and accumulation rate record from DSS represents most of the variability in sea salt seen in the record. LDEOF1 is positively correlated (at least 95% confidence level) to instrumental June mean SLP across most of East Antarctica. Over the last 700 years, LDEOF1 levels at Law Dome were the highest during the nineteenth century, suggesting an increase in intensification of winter circulation during this period. The Law Dome DSS oxygen isotope ratio series also indicates that the nineteenth century had the coldest winters of any century in the record. In contrast, LDEOF1 levels were the lowest at Law Dome during the eighteenth century, suggesting a significant shift in the patterns and/or intensity of East Antarctic atmospheric circulation between the eighteenth and the nineteenth centuries. The LDEOF1 sea salt record is characterized by significant decadal-scale variability with a strong 25-year periodic structure.