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Global research is showing that coastal blue carbon ecosystems are vulnerable to climate change driven threats including accelerated sea-level rise and prolonged periods of drought. Furthermore, direct anthropogenic impacts present immediate threats through deterioration of coastal water quality, land reclamation, long-term impact to sediment biogeochemical cycling. These threats will invariably alter the future efficacy of carbon (C) sequestration processes and it is imperative that currently existing blue carbon habitats be protected. Knowledge of underlying biogeochemical, physical and hydrological interactions occurring in functioning blue carbon habitats is essential for developing strategies to mitigate threats, and promote conditions to optimise C sequestration/storage. In this current work, we investigated how sediment geochemistry (0–10 cm depth) responds to elevation, an edaphic factor driven by long-term hydrological regimes consequently exerting control over particle sedimentation rates and vegetation succession. This study was performed in an anthropogenically impacted blue carbon habitat along a coastal ecotone encompassing an elevation gradient transect from intertidal sediments (un-vegetated and covered daily by tidal water), through vegetated salt marsh sediments (periodically covered by spring tides and flooding events), on Bull Island, Dublin Bay. We determined the quantity and distributions of bulk geochemical characteristics in sediments through the elevation gradient, including total organic carbon (TOC), total nitrogen (TN), total metals, silt, clay, and also, 16 individual polyaromatic hydrocarbon’s (PAH’s) as an indication of anthropogenic input. Elevation measurements for sample sites were determined on this gradient using a LiDAR scanner accompanied by an IGI inertial measurement unit (IMU) on board a light aircraft. Considering the gradient from the Tidal mud zone (T), through the low-mid marsh (M) to the most elevated upper marsh (H), there were significant differences between all zones for many measured environmental variables. The results of significance testing using Kruskal–Wallis analysis revealed, that %C, %N, PAH (µg/g), Mn (mg/kg), TOC:NH4+ and pH are significantly different between all zones on the elevation gradient. The highest values for all these variables exists (excluding pH which followed a reverse trend) in zone H, decreasing in zone M and lowest in the un-vegetated zone T. TC content is 16 fold higher overall in vegetated (3.43 -21.84%) than uninhabited (0.21–0.56%) sediments. TN was over 50 times higher (0.24–1.76%), more specifically increasing in % mass on approach to the upper salt marsh with distance from the tidal flats sediments zone T (0.002–0.05%). Clay and silt distributions were greatest in vegetated sediments, increasing in % content towards upper marsh zones The retention of water, metals, PAHs, mud, chloride ions, NH4+, PO43− and SO42− increased with elevated C concentrations, concurrently where pH significantly decreased. Sediments were categorized with respect to PAH contamination where all SM samples were placed in the high polluted category. The results highlight the ability of Blue C sediments to immobilise increasing levels of C, N, and metals, and PAH with over time and with both lateral and vertical expansion. This study provides a valuable data set for an anthropogenically impacted blue carbon habitat predicted to suffer from sea-level rise and exponential urban development. Graphical abstract Summarized results from this study demonstrating the geochemical changes through an elevation gradient, with a transect encompassing intertidal sediments through supratidal salt marsh sediments within Bull Island’s blue carbon lagoon zones.

Coastal wetlands are highly efficient ‘blue carbon’ sinks which contribute to mitigating climate change through the long-term removal of atmospheric CO2 and capture of carbon (C). Microorganisms are integral to C sequestration in blue carbon sediments and face a myriad of natural and anthropogenic pressures yet their adaptive responses are poorly understood. One such response in bacteria is the alteration of biomass lipids, specifically through the accumulation of polyhydroxyalkanoates (PHAs) and alteration of membrane phospholipid fatty acids (PLFA). PHAs are highly reduced bacterial storage polymers that increase bacterial fitness in changing environments. In this study, we investigated the distribution of microbial PHA, PLFA profiles, community structure and response to changes in sediment geochemistry along an elevation gradient from intertidal to vegetated supratidal sediments. We found highest PHA accumulation, monomer diversity and expression of lipid stress indices in elevated and vegetated sediments where C, nitrogen (N), PAH and heavy metals increased, and pH was significantly lower. This was accompanied by a reduction in bacterial diversity and a shift to higher abundances of microbial community members favouring complex C degradation. Results presented here describe a connection between bacterial PHA accumulation, membrane lipid adaptation, microbial community composition and polluted C rich sediments. Graphical Abstract Geochemical, microbiological and polyhydroxyalkanoate (PHA) gradient in a blue carbon zone.

We provide an updated sea level dataset for Dublin for the period 1938–2016 at yearly resolution. Using a newly collated sea level record for Dublin Port, as well as two nearby tide gauges at Arklow and Howth Harbour, we perform data quality checks and calibration of the Dublin Port record by adjusting the biased high water level measurements that affect the overall calculation of mean sea level (MSL). To correct these MSL values, we use a novel Bayesian linear regression that includes the mean low water values as a predictor in the model. We validate the re-created MSL dataset and show its consistency with other nearby tide gauge datasets. Using our new corrected dataset, we estimate a rate of sea level rise of 1.1 mm yr−1 during 1953–2016 (95 % credible interval from 0.6 to 1.6 mm yr−1), and a rate of 7 mm yr−1 during 1997–2016 (95 % credible interval from 5 to 8.8 mm yr−1). The overall sea level rise is in line with expected trends, but large multidecadal variability has led to higher rates of rise in recent years.

Total alkalinity (TA) is one of the four main carbonate system variables and is a conventionally measured parameter used to characterise marine water carbonate chemistry. It is an important indicator of a waterbody's buffering capacity and a measure of its ability to resist acidification, a matter of growing concern in the marine environment. Although TA is primarily associated with the inorganic components of seawater such as bicarbonate, there is a growing consensus that dissolved organic matter (DOM) can significantly contribute to TA in coastal waters. This organic fraction of TA (OrgAlk) is typically deemed negligible and is not accounted for in conventional TA expressions. However, omission of OrgAlk can lead to the propagation of errors in subsequent carbonate system calculations and to misinterpretation of key carbonate chemistry descriptors such as calcium carbonate saturation states. Here we provide an overview of OrgAlk contributions to TA and investigate the implications of its omission in carbonate system studies conducted in coastal waters. We examine the prevalence of OrgAlk across both coastal and pelagic waters using publicly available carbonate system data products, such as GLODAP and GOMECC. Current measures to account for, incorporate and characterise the contribution of OrgAlk to TA are also critically examined.

We provide an updated sea level dataset for Dublin for the period 1938 to 2016 at yearly resolution. Using a newly collated sea level record for Dublin Port, as well as two nearby tide gauges at Arklow and Howth Harbour, we perform data quality checks and calibration of the Dublin Port record by adjusting the biased high water level measurements that affect the overall calculation of mean sea level (MSL). To correct these MSL values, we use a novel Bayesian linear regression that includes the Mean Low Water values as a predictor in the model. We validate the re-created MSL dataset and show its consistency with other nearby tide gauge datasets. Using our new corrected dataset, we estimate a rate of 1.08 mm/yr sea level rise at Dublin Port between 1953–2016 (95 % CI from 0.62 to 1.55 mm/yr), and a rate of 6.48 mm/yr between 1997–2016 (95 % CI 4.22 to 8.80 mm/yr). Overall sea level rise is in line with expected trends but large multidecadal varaibility has led to higher rates of rise in recent years.

There is remarkable potential for research at the interface between the earth sciences and environmental microbiology that may lead to advances in our understanding of the role of bacterial communities in the surface or subsurface environment of our planet. One mainstay of sedimentary classification is the concept of differential soil and/or paleosol horizons being the result of primarily physical and chemical weathering, with relatively little understanding of how microbial communities between these stratified horizons differ, if at all. In this study we evaluate the differences in microbial community taxonomy and biogeochemical functional potential between stratified soil horizons in an alpine paleosol environment using next-generation sequencing (NGS) shotgun sequencing. Paleosols represent a unique environment to study the effect of differences soil horizon environments on the microbial community due to their relative isolation, and the fact that three distinct stratified soil horizons can be identified within the top 30 cm of the soil. This enables us to assess variation in microbial community composition that will be relatively distinct from variation due to distance alone. We test the hypothesis that variation in soil community composition is linked to variation in the physical and chemical parameters that define stratigraphy. Multivariate statistical analysis of sequencing reads from soil horizons across five sampling sites revealed that 1223 microbial genera vary significantly and consistently in abundance across stratified soil horizons at class level. Specifically Ktedonobacter, Bacilli and Betaproteobacteria responded most strongly to soil depth. Alpha diversity showed a positive correlation with soil depth. Beta diversity, however, did not differ significantly between horizons. Genes involved in carbohydrate and nitrogen metabolism were found to be more abundant in Ah horizon samples. Closer inspection of carbohydrate metabolism genes revealed that genes involved in CO2 fixation, fermentation and saccharide metabolism decreased in abundance with depth while one‑carbon metabolism increased down profile.

Marine pockmarks are globally widespread seabed depressions, conventionally thought to be formed by the accumulation and expulsion of microbial and thermogenic gas. However, other putative fluids and processes have been implicated in pockmark formation and gas escape to the atmosphere may be underestimated. Given the complex spectrum of aquatic settings, morphologies and sizes, there may also exist a spectrum of physical, chemical and biological processes that form pockmarks. Pockmarks in shallow coastal waters are now understood to be widespread, but the influence of physical dynamics (e.g. tides, storms, etc.), terrestrial processes and anthropogenic activities add considerable spatiotemporal complexity and uncertainty to our understanding of these features. Here, we revisit a field of small (ca. 2 m diameter), shallow (

Commercial composting of the mechanically separated organic fraction of municipal solid waste (MS-OFMSW) is employed to stabilize municipal organic waste. Its feasibility is linked to process efficacy and compost stability. Threshold values for stability are imposed by regulatory frameworks. Limited reuse options exist for this material often due to the presence of organic pollutants. The optimisation of the composting process is required to reach stability in a viable timeframe. We evaluated the effects on compost stability and the degradation of organic contaminates by using wood shavings as a bulking agent and increasing the turning frequency in a pilot scale process. The use of wood shavings decreased the time required for compost stability while turning frequency had no impact. The addition of wood shavings to the initial feedstock stimulated microbial activity that in turn decreased the time to compost stability and enhanced the degradation of detected PAHs and short-chain phthalates.

We analysed multiple tide gauges from the east coast of Ireland over the period 1938–2018. We validated the different time series against each other and performed a missing value imputation exercise, which enabled us to produce a homogenised record. The recordings of all tide gauges were found to be in good agreement between 2003–2015, though this was markedly less so from 2016 to the present. We estimate the sea level rise in Dublin port for this period at 10 mm yr−1. The rate over the longer period of 1938–2015 was 1.67 mm yr−1 which is in good agreement with the global average. We found that the rate of sea level rise in the longer term record is cyclic with some extreme upward and downward trends. However, starting around 1980, Dublin has seen significantly higher rates that have been always positive since 1996, and this is mirrored in the surrounding gauges. Furthermore, our analysis indicates an increase in sea level variability since 1980. Both decadal rates and continuous time rates are calculated and provided with uncertainties in this paper.

The formation, fate, and toxicology of oxy-, hydroxy-, and carboxy- substituted PAH (OPAH, OHPAH, COOHPAH, respectively) alongside PAH in contaminated soils have received increasing attention over the past two decades; however, there are still to date no standardized methods available for their identification and quantitation in soil. Here we investigated and developed the first method using aminopropylsilica solid phase extraction (SPE) for these compounds. We further investigated the efficacy of the developed method for three soils representing a range of contamination levels and soil textural characteristics and evaluated the impact of different sample preparation steps on the recovery of targeted compounds. Average recovery of PAH, OPAH, and OHPAH standards were 99%, 84%, and 86%, respectively for the SPE method. In contrast, COOHPAH exhibited the lowest recovery (0–82%) and poor inter-batch reproducibility. Soil texture and contamination levels influenced full method efficiency. Specifically, soils with higher proportion of clay contributed to the loss of the higher molecular weight OHPAH prior to SPE. Soil with the highest contamination showed enhanced recovery of some lower-concentration mid weight PAH and OPAH, while the least contaminated soil showed greater sensitivity to evaporative losses during sample preparation. Recommendations for reducing matrix effects as well as the practice of using deuterated PAH surrogate standards for OPAH analysis are further discussed. Quantitation of recovered PAH and oxygenated PAH across the three soils showed high reproducibility (

It is estimated that up to 138 million tonnes of bio-waste are produced in Europe annually, with only 25% being recycled into high-quality compost and digestate. Currently, residual organic waste is generated as by-product of municipal solid waste treatment. Its reuse options vary across EU countries, due to the lack of clear guidance at European level. In some countries, compost derived from municipal solid waste (MSW – compost) is restricted to being used as landfill cover or in land reclamation, under the premises of meeting national legal criteria. Other countries, have regulated its used as marketable compost if it meets defined compost standards. However, for many countries the value-added use of MSW derived compost is uncertain.The restricted use of MSW - compost is linked to the organic and inorganic contamination associated with such a heterogeneous material. Despite this, under the European view of the Circular Economy, MSW-compost has great potential to be reused and recycled for the benefit of all. Controlled use on land would off-set carbon emissions by diverting the material from a waste that is largely incinerated or added to landfill to a carbon positive soil additive that increases soil quality particularly in restoration sites. Our study aims to risk-assess the use of MSW-compost as a soil amendment by monitoring resulting water run-off for metal and nutrient content. Leaching trials, conducted over 6 months were performed in a forest soil (20 cm depth) with a history of Sitka Spruce plantation (c.a 20 years). Adapted water storage tanks were set-up to conduct the trials. Leachate was collected weekly in the first two months, and monthly thereafter. Four treatments 1) control, 2) sewage sludge chemically stabilized (10 t/ha), 3) MSW-compost (10 t/ha) and 4) MSW-compost (25 t/ha) were established in duplicate. Sewage sludge was used as a comparison material, due to its current legal status allowing for controlled land spreading. Leachate samples were analysed for nitrate, ammonium and the metals aluminium, cadmium, copper, total chromium, mercury, nickel, zinc and lead. Preliminary results from the first 6 weeks show that metals concentrations in the leachate from all trials were below threshold criteria in surface water quality regulations. Levels of ammonium above detection limits were only detected at week one and surpassed 0.2 mg/L. Nitrate concentration in the leachates was found to be below 50 mg/L and it peaked in the sewage sludge and MSW-compost (25 t/ha) at week 2.Results gathered so far show that the use MSW-compost in land compares to sewage sludge application in relation to their potential for water pollution. MSW-compost could be used as a soil improver under a regulatory alignment similar to the sewage sludge regulations, aligned with the current European Circular Economy goals.

Nearshore bathymetric data are used in many coastal monitoring applications, but acquisition conditions can be challenging. Shipborne surveys are prone to the risk of grounding in shallow waters, and scheduled airborne surveys often fail to coincide with optimal atmospheric and water conditions. As an alternative, since its launch in 2018, ICESat-2 satellite laser profile altimetry data provide free and readily available data on a 91-day repeat cycle, which may contain incidental bathymetric returns when suitable environmental conditions prevail. In this paper, the vertical accuracy of extracted, refraction-adjusted ICESat-2 nearshore marine bathymetric data is evaluated at four test sites in a Northern hemisphere, temperate latitude location. Multiple ICEsat-2 bathymetric values that occurred in close horizontal proximity to one another were averaged at a spatial scale of 1 m and compared with Multibeam Echosounder bathymetric survey data and Global Navigation Satellite System reference data. Mean absolute errors of less than 0.15 m were observed up to depths of 5 m, with errors of less than 0.24 m (to 6 m), 0.39 m (to 7 m) and 0.52 m (to 10 m). The occurrence of larger bathymetric errors with depth, which increase to 0.54 m at maximum photon depths of 11 m, appears to be primarily related to reduced numbers of geolocated photons with depth. The accuracies achieved up to 6 m suggest that the manual extraction, refraction adjustment and bathymetric filtering steps were effective. Overall, the results suggest that ICESat-2 bathymetric data accuracy may be sufficient to be considered for use in nearshore coastal monitoring applications where shipborne and airborne bathymetric data might otherwise be applied.

Previous evidence for fragments of a cosmic airburst in the Western Alps has been shown to reside in weathering rinds in surface clasts of Late Glacial (LG) (mid-LG-post Allerod) deposits and in Ah horizons of several associated paleosols. In contrast to outlying strata, Younger Dryas (YD) paleosol horizons contain minor reworked airburst evidence that includes melted quartz/pyroxene grains, carbon spherules, glass-like carbon, and with minor differences in microbial populations. New data from LG paleosol profiles show REEs elevated above crustal abundance in several profiles of mid-Late Glacial age, along with elevated Pt concentrations, similar to those found at the YD Boundary in the Greenland Ice Sheet. Pt/Pd ratios that are elevated above background suggest an exogenic influx of Pt from meteoritic ablation and/or airbursts. An increasing number of localities with sedimentary time lines coeval with an airburst (12.8 ka) indicate the event was intercontinental, producing widespread conflagrations archived in local sediment sequences. This is the first instance worldwide in which evidence of the black mat event has been found both in weathering rinds and in paleosols in the Alps, with such information being applicable to reconnaissance beyond Earth such as in the case of Mars.

Bull Island (BI) is a coastal sand spit that formed as an unintended consequence of the construction of two walls, built over 200 years ago in Dublin Port, Ireland to alleviate silting of the shipping route. A large lagoon, on the land side of the island was separated in 1964 by the construction of a causeway to produce two separate lagoons that are now impacted by different water sources. Here we investigate the influence of riverine inputs on the two adjacent but unconnected tidal wetland lagoons. The South lagoon (SL) is supplied by tidal water passing through the eutrophic R. Liffey and R. Tolka estuary zones, while the North Lagoon (NL) is supplied by seawater and to a lesser degree, freshwater from the R. Liffey plume. Within each of these zones a clear ecotone exists between the mudflats (MF) and vegetated saltmarshes (SM). We determined the quantity and distributions of bulk geochemical characteristics across BI’s sediments, including total organic carbon (TOC), total nitrogen (TN), metals, and also, 16 individual polyromantic hydrocarbon’s (PAH’s) as an indication of anthropogenic input. Primary focus was placed on studying the blue carbon sediments of the lagoon zones. Significant differences in analytical results showed major influences exerted on sediment geochemistry within each lagoon. This study highlights the ability of a functioning coastal wetland to flourish and sequester elevated levels of carbon, metals and pollutants under the constraints of increasing anthropogenic impact. As the inadvertent result of geo-engineering, BI and its environs is a very important site to investigate the potential of artificially constructed wetlands to act as blue carbon reservoirs.

Understanding the mechanism associated with rates of weathering and evolution of rocks→sediment→soil→paleosol in alpine environments raises questions related to the impact of microbial mediation versus various diverse abiotic chemical/physical processes, even including the overall effect of cosmic impact/airburst during the early stage of weathering in Late Glacial (LG) deposits. This study is of a chronosequence of soils/paleosols, with an age range that spans the post–Little Ice Age (post-LIA

As a primary decomposition process in terrestrial biosystems, biodegradation has been extensively studied with regard to its impact on soil organic matter transformation. However, the biotransformation of soil microbial biomass (a primary source of soil organic carbon) remains poorly understood, and even less is known about the fate of microbial-derived carbon under photodegradation. Here, we combine infrared and diffusion editing NMR spectroscopies to provide molecular-level information on the photodegradation of major biochemical components in soil microbial biomass and leachates over time. Results indicate a considerable enrichment in aliphatic components, presumably polymethylenic-C [(C–H2)n] and the simultaneous loss of carbohydrate and protein structures in the biomass. An immediate conclusion is that photodegradation increased the conversion of macromolecular carbohydrates and proteins to smaller components. However, further analysis reveals that macromolecular carbohydrates and proteins may be more resistant to photodegradation than initially thought and are found in the leachates. Although attenuated, there is also evidence to suggest that some aliphatic structures persist in the leachates. Overall, the photodegradation pathway reported here is remarkably similar to that of biodegradation, suggesting that under rapidly expanding anthropogenic land disturbances, photodegradation could be an important driver of the transformation of microbial-derived organic matter in terrestrial biosystems.

International audience; An integrated geophysical, geological, and geochemical investigation of seabed fluid venting was carried out in upper Bantry Bay, a large marine inlet on the southwest coast of Ireland. The results provide evidence of the seafloor venting of gas rich fluids, resulting in the formation of a pockmark field identified here for the first time. The pockmarks occur in an area where sub-bottom profiles provide evidence of chimney-like features interpreted to record upward gas migration through Quaternary sediments to the seafloor. Three vibrocores up to 6 m long were acquired in water depths of 24-34 m, two from the pockmark field and one from outside. Methane of predominantly biogenic origin was quantified in all three cores by headspace analysis of sediment sub-samples. Well-defined sulfate methane transition zones (SMTZs) were observed in two of the cores, the shallowest (1.25 m) inside the pockmark field and the other (3.75 m) outside. It is likely that an SMTZ occurs at the location of the third core, also within the pockmark field, although beneath the samples obtained during this study. Gas release possibly from a combination of various faulting mechanisms and shallow methanogenesis appears to drive diffuse pore fluid migration across wide areas, while focused flow through the pockmarks may be related to gas originating from the Owenberg River Fault and methanogenesis of pre-glacial lacustrine sediments preserved in a bedrock basin. Analysis of phospholipid fatty acids (PLFAs) and archaeal isoprenoid hydrocarbons was used to investigate the microbial ecology of these sediments. Anaerobic oxidation of methane (AOM) may play a role in controlling release of CH4 to the water column and atmosphere in this shallow gas setting, potentially mediated by syntrophic sulfate reducing bacteria (SRB) and anaerobic methanotrophic archaea (ANME).

Bacterial laccases are now known to be abundant in soil and to function outside of the cell facilitating the bacterial degradation of lignin. In this study we wanted to test the hypotheses that: i) Such enzymes can be identified readily in stratified paleosols using metagenomics approaches, ii) The distribution of these genes as potential ‘public good’ proteins in soil is a function of the soil environment, iii) Such laccase genes can be readily retrieved and expressed in E. coli cloning systems to demonstrate that de novo assembly processes can be used to obtain similar metagenome-derived enzyme activities. To test these hypotheses, in silico gene-targeted assembly was employed to identify genes encoding novel type B two-domain bacterial laccases from alpine soil metagenomes sequenced on an Illumina MiSeq sequencer. The genes obtained from different strata were heterologously cloned, expressed and the gene products were shown to be active against two classical laccase substrates. The use of a metagenome-driven pipeline to obtain such active biocatalysts has demonstrated the potential for gene mining to be applied systematically for the discovery of such enzymes. These data ultimately further demonstrate the application of soil pedology methods to environmental enzyme discovery. As an interdisciplinary effort, we can now establish that paleosols can serve as a useful source of novel biocatalytic enzymes for various applications. We also, for the first time, link soil stratigraphy to enzyme profiling for widespread functional gene activity in paleosols.

The bacterial community composition and biomass abundance from a depositional mud belt in the western Irish Sea and regional sands were investigated by phospholipid ester-linked fatty acid profiling, denaturing gradient gel electrophoresis and barcoded pyrosequencing of 16S rRNA genes. The study area varied by water depth (12–111 m), organic carbon content (0.09–1.57% TOC), grain size, hydrographic regime (well-mixed vs. stratified), and water column phytodetrital input (represented by algal polyunsaturated PLFA). The relative abundance of bacterial-derived PLFA (sum of methyl-branched, cyclopropyl and odd-carbon number PLFA) was positively correlated with fine-grained sediment, and was highest in the depositional mud belt. A strong association between bacterial biomass and eukaryote primary production was suggested based on observed positive correlations with total nitrogen and algal polyunsaturated fatty acids. In addition, 16S rRNA genes affiliated to the classes Clostridia and Flavobacteria represented a major proportion of total 16S rRNA gene sequences. This suggests that benthic bacterial communities are also important degraders of phytodetrital organic matter and closely coupled to water column productivity in the western Irish Sea.

A small gas pockmark field in Dunmanus Bay, SW Ireland was surveyed and ground-truthed to assess its activity, geomorphology, explore its formation mechanisms and to investigate its potential influence on the benthic community. The field consisted of 121 circular, shallow units ranging from 5 to 17 m in diameter and not exceeding 1 m in relief. Sub-bottom profiles revealed broad acoustic signatures typical of shallow gas accumulation in the subsurface in addition to vertically elongated signals of ascending bubbles captured in the echo sounder data. The pockmarks show strong correlation with the depth of sub-surface gas fronts. However methane concentrations in the water column and directly above the features were close to typical marine, background values and did not exceed 15 nM. This suggests a very mild, periodic venting scenario. Sediment core samples revealed permeable sandy layers with slightly elevated methane concentrations indicative of stratified, diffusive flow. Pore-water sulphate and chloride data show no sign of pore water freshening and thus suggest that methane gas is the sole fluid responsible for formation of these pockmarks. Benthic infauna distributions showed reduced diversity in pockmarked regions, primarily influenced by the sediment composition. Few species utilising chemosymbiotic associations were identified, and there was little indication of a community influenced by methane venting in Dunmanus Bay.

Following a period of unusually strong winds and high seas in the spring of 2014, a blanket peat bog formerly covered by a beach comprised of fine sand and large rocks was uncovered at a coastal site in Spiddal, Co. Galway, Ireland. The surface of the bog was littered with standing tree stumps, the remnants of a Holocene forest that had succumbed to a relatively sudden drowning. A combination of inorganic and organic geochemical techniques was applied to determine the cause of this rapid submersion and to glean palaeoclimatic information from the preserved record within the peat. The study represents the first use of a multiproxy lipid biomarker approach to investigate palaeoclimate conditions from a peat bog in Ireland. The results provide evidence of climatic variation throughout a ca. 3400 yr timeframe during the mid-Holocene. Biomarker proxies displaying the relative contribution of Sphagnum spp. vs. higher plants were used to show changes in precipitation and temperature during peat formation. The data correlate with described events, including the 4.2 ka event and the Subboreal-Subatlantic transition and show the benefit of a lipid biomarker method for investigating Ireland’s peatland resources. In particular, the indication of colder/wetter conditions coinciding with the 4.2 ka event implies the possibility that its effects were felt in Ireland, contrary to some reports. The results suggest that a combination of warm and dry conditions followed by a rapid rise in sea level led to the growth and subsequent drowning of the ancient forest landscape.

The presence of Mn-Fe nodules in the epipedons (surface horizons) of paleosols of presumed Upper Neogene age in the northwestern Venezuelan Andes have been interpreted as products of inorganic oxidation and reduction processes operating over the full range of glacial and interglacial cycles that affected paleosol morphogenesis. New microscopic/chemical data from combined SEM-EDS-FIB analyses of representative Mn-Fe nodules indicate microbes play an important role in Mn/Fe precipitation leading to their genesis in alpine Mollisols (Argiustolls). Although the prevailing new data are based mainly on fossil forms of filamentous bacteria and fungi and other biogenic pseudomorphs that may represent the former resident bacteria, the presence of extant microbes must await field experiments/collection, followed by a molecular microbiology approach to determine the biological drivers of metal precipitation. As in other terrestrial niche environments, microbes are seen here to play a role, perhaps a key one, in the ...

Methane-derived authigenic carbonate (MDAC) mound features at the Codling Fault Zone (CFZ), located in shallow waters (50–120 m) of the western Irish Sea were investigated and provide a comparison to deep sea MDAC settings. Carbonates consisted of aragonite as the major mineral phase, with δ13C depletion to − 50‰ and δ18O enrichment to ~ 2‰. These isotope signatures, together with the co-precipitation of framboidal pyrite confirm that anaerobic oxidation of methane (AOM) is an important process mediating methane release to the water column and the atmosphere in this region. 18O-enrichment could be a result of MDAC precipitation with seawater in colder than present day conditions, or precipitation with 18O-enriched water transported from deep petroleum sources. The 13C depletion of bulk carbonate and sampled gas (− 70‰) suggests a biogenic source, but significant mixing of thermogenic gas and depletion of the original isotope signature cannot be ruled out. Active seepage was recorded from one mound and together with extensive areas of reduced sediment, confirms that seepage is ongoing. The mounds appear to be composed of stacked pavements that are largely covered by sand and extensively eroded. The CFZ mounds are colonized by abundant Sabellaria polychaetes and possible Nemertesia hydroids, which benefit indirectly from available hard substrate. In contrast to deep sea MDAC settings where seep-related macrofauna are commonly reported, seep-specialist fauna appear to be lacking at the CFZ. In addition, unlike MDAC in deep waters where organic carbon input from photosynthesis is limited, lipid biomarkers and isotope signatures related to marine planktonic production (e.g. sterols, alkanols) were most abundant. Evidence for microbes involved in AOM was limited from samples taken; possibly due to this dilution effect from organic matter derived from the photic zone, and will require further investigation.

One of the most cost effective methods of pollution remediation is through natural attenuation where the resident microorganisms are responsible for the breakdown of pollutants (Dou et al. 2008). Other forms of bioremediation – such as analogue enrichment, composting and bio-venting – also use the microbes already present in a contaminated site to enhance the remediation process. In order for these approaches to be successful, in an industrial setting, some form of monitoring needs to take place enabling conclusions to be drawn about the degradation processes occurring. In this review we look at some key molecular biology techniques that have the potential to act as a monitoring tool for industries dealing with contaminated land.

Ion-exchange chromatography with pulsed amperometric detection (IEC-PAD) was employed to investigate dissolved neutral sugars and their microbial conversion in both artificially prepared dissolved organic matter (ADOM), and naturally occurring dissolved organic matter (DOM) obtained from seawater and freshwater sources. The analysis of ADOM and naturally occurring DOM samples using IEC-PAD resulted in chromatograms suggesting very similar composition, each characterised by three early eluting peaks, the latter of which being a broad co-elution of multiple compounds. For naturally occurring DOM, several sugars, including arabinose, glucose, galactose, xylose and ribose, could also be identified. The three distinctive peaks obtained from IEC-PAD of ADOM were collected and further analysed by means of reversed-phase high performance liquid chromatography-high resolution mass spectrometry (RPLC-HRMS), the latter showing that glucose was totally consumed during microbial production of ADOM and potentially transformed into higher molecular weight materials and CO2.

A suite of lipid biomarkers were investigated from surface sediments and particulate matter across hydrographically distinct zones associated with the western Irish Sea gyre and the seasonal bloom. The aim was to assess the variation of organic matter (OM) composition, production, distribution and fate associated with coastal and southern mixed regions and also the summer stratified region. Based on the distribution of a suite of diagnostic biomarkers, including phospholipid fatty acids, source-specific sterols, wax esters and C25 highly branched isoprenoids, diatoms, dinoflagellates and green algae were identified as major contributors of marine organic matter (MOM) in this setting. The distribution of cholesterol, wax esters and C20 and C22 polyunsaturated fatty acids indicate that copepod grazing represents an important process for mineralising this primary production. Net tow data from 2010 revealed much greater phytoplankton and zooplankton biomass in well-mixed waters compared to stratified waters. This appears to be largely reflected in MOM input to surface sediments. Terrestrial organic matter (TOM), derived from higher plants, was identified as a major source of OM regionally, but was concentrated in proximity to major riverine input at the Boyne Estuary and Dundalk Bay. Near-bottom residual circulation and the seasonal gyre also likely play a role in the fate of TOM in the western Irish Sea.

Normal-phase high-performance counter-current chromatography (HPCCC) is used to obtain a preliminary fractionation of components in dissolved organic matter (DOM) from a freshwater source. The HPCCC solvent system involved a normal-phase approach with water/methanol (1:1) as the lower stationary phase and hexane/ethyl acetate (1:1) as the upper mobile phase. The critical experiment parameters were optimised: revolution speed 1800 rpm and flow rate 0.15 mL/min. Under these conditions 50 μL of a 0.50 mg/mL DOM solution was loaded. The detection wavelength was monitored at 330 nm in order to isolate the main portion of DOM, which includes substances such as carboxyl-rich alicyclic molecules. By optimising this system it was possible to isolate materials that, according to GC–MS, can be related to molecules with an analogous structural background. Where fraction analysis was not suitable for GC–MS, RP-HPLC with UV absorbance detection was used, showing unique chromatograms for each fraction at both 210 and 330 nm.

International audience; The microbial contribution to soil organic matter (SOM) has recently been shown to be much larger than previously thought and thus its role in carbon sequestration may also be underestimated. In this study we employ 13C (13CO2) to assess the potential CO2 sequestration capacity of soil chemoautotrophic bacteria and combine nuclear magnetic resonance (NMR) with stable isotope probing (SIP), techniques that independently make use of the isotopic enrichment of soil microbial biomass. In this way molecular information generated from NMR is linked with identification of microbes responsible for carbon capture. A mathematical model is developed to determine real-time CO2 flux so that net sequestration can be calculated. Twenty-eight groups of bacteria showing close homologies with existing species were identified. Surprisingly, Ralstonia eutropha was the dominant group. Through NMR we observed the formation of lipids, carbohydrates, and proteins produced directly from CO2 utilized by microbial biomass. The component of SOM directly associated with CO2 capture was calculated at 2.86 mg C (89.21 mg kg-1) after 48 h. This approach can differentiate between SOM derived through microbial uptake of CO2 and other SOM constituents and represents a first step in tracking the fate and dynamics of microbial biomass in soil.

A marine sediment core obtained from a methane seepage site off the northern coast of Irelandwas analysed, at 3 depths, for catabolic genes associated with the aerobic and anaerobic degradation of aromatic compounds. Catabolic gene copy numbers varied through the core peaking at 2.1 meters below sediment surface (mbsf)-just above the sulphate boundary. Beyond the sulphate boundary gene copy numbers fell considerably, suggesting the boundary may be a critical factor in the degradation of aromatic compounds within marine sediments. At the 2.1 mbsf depth our data also suggest that known benzoyl CoA reductase utilizing bacteria are readily detectable.

Soil microbial biomass is a primary source of soil organic carbon (SOC) and soil organic nitrogen (SON) and therefore plays a fundamental role in carbon and nitrogen cycling. However, little is known about the fate and transformation of the magnitude of microbial components in the soil. Here we employ Fourier Transform Infrared (FT-IR) spectroscopy and allied techniques to analyze kaolinite–microbial interactions to determine; the spatial distribution of organic structures on clay mineral surfaces, which organic structures preferentially associate with these surfaces, which may be accessible to microbial heterotrophs, and which are physically protected during decomposition. Results indicate that microbial biomass and microbial-derived OM adsorbed solely on the external surfaces of kaolinite and that these interactions are dominated by aliphatic structures. Similarly, aliphatic species remained dominant after acid hydrolysis, the possible harshest condition that such complexes will experience in the environment. This is consistent with the expectation of the preferential adsorption and stabilization off aliphatic lipids, in particular, polymethylenic lipids [(CH 2 ) n ] by clay minerals. Protein and carbohydrate structures most likely from microbial exudate and cell wall components such as peptidoglycan also adsorbed strongly to kaolinite and are physically protected from acid hydrolysis.

Living (LM) and non-living maerl (NLM) rhodoliths of the species Lithothamnion coral- lioides (Crouan & Crouan, 1867) from Kingstown Bay, Galway, were sampled and compared in rela- tion to their physical structure and lipid and low molecular weight carbohydrate (LMWC) composi- tion. Saturated (SATFA) and polyunsaturated fatty acids (PUFA) were dominant, in particular 16:0, 20:4n-6 and 20:5n-3, but a diverse range of fatty acids were identified. The abundance of n-alkanals was high, and sterol composition was simple, with cholesterol accounting for over 90% of the total sterols. Mono-, di-, and trisaccharides, with galactose units being dominant, and floridoside were present in high abundance. Notably, the fatty acid and LMWC profiles varied little between NLM and LM. The relatively high abundance of PUFA and floridoside, in particular, suggests that NLM may have further potential for research and commercial purposes in a variety of food, biomedical and industrial applications. Previously reported unidentified 'globular inclusions' were more abundant in NLM and exhibited a crystalline morphology. Together with the bacterial fatty acid composition of LM and NLM, the results indicate that these structures are not bacterial in nature.

Bulk paleosol samples collected from a Middle to Early Miocene moraine in the New Mountain area of the Dry Valleys, Antarctica, yielded Coleoptera exoskeletons and occasional endoskeletons showing considerable diagenetic effects along with several species of bacteria, all lodged in a dry-frozen but salt-rich horizon at shallow depth to the land surface. The till is at the older end of a chronologic sequence of glacial deposits, thought to have been deposited before the transition from wet-based to cold-based ice (∼15 Ma), and hence, entirely weathered in contact with the subaerial atmosphere. It is possible, though not absolutely verifiable, that the skeletons date from this early stage of emplacement having undergone modifications whenever light snowmelt occurred or salt concentrations lowered the freezing temperature to maintain water as liquid. Correlation of the Coleoptera species with cultured bacteria in the sample and the likelihood of co-habitation with Beauveria bassiani found in two adjacent, although younger paleosols, leads to new questions about the antiquity of the Coleoptera and the source of N and glucose from chitinase derived from the insects. The skeletons in the 831 section may date close to the oldest preserved chitin (Oligocene) yet found on Earth. While harsh Martian conditions make it seemingly intolerable for complex, multicellular organisms such as insects to exist in the near-surface and subaerially, life within similar cold, dry paleosol microenvironments (Cryosols) of Antarctica point to life potential for the Red Planet, especially when considering the relatively diverse microbe (bacteria and fungi) population.

Soil microbial biomass is a primary source of soil organic carbon (SOC) and therefore plays a fundamental role in carbon and nitrogen cycling. However, little is known about the fate and transformations of microbial biomass in soil. Here we employ HR-MAS NMR spectroscopy to monitor 13C and 15N labeled soil microbial biomass and leachate degradation over time. As expected, there is a rapid loss of carbohydrate structures. However, diffusion edited HR-MAS NMR data reveals that macromolecular carbohydrates are more resistant to degradation and are found in the leachate. Aromatic components survive as dissolved species in the leachate while aliphatic components persist in both the biomass and leachate. Dissolved protein and peptidoglycan accumulate in the leachate and recalcitrant amide nitrogen and lipoprotein persists in both the degraded biomass and leachate. Cross-peaks that appear in 1H–15N HR-MAS NMR spectra after degradation suggest that specific peptides are either selectively preserved or used for the synthesis of unknown structures. The overall degradation pathways reported here are similar to that of decomposing plant material degraded under similar conditions suggesting that the difference between recalcitrant carbon from different sources is negligible after decomposition.

The Dry Valleys of Antarctica are one of the coldest and driest environments on Earth with paleosols in selected areas that date to the emplacement of tills by warm-based ice during the Early Miocene. Cited as an analogue to the martian surface, the ability of the Antarctic environment to support microbial life-forms is a matter of special interest, particularly with the upcoming NASA/ESA 2018 ExoMars mission. Lipid biomarkers were extracted and analyzed by gas chromatography--mass spectrometry to assess sources of organic carbon and evaluate the contribution of microbial species to the organic matter of the paleosols. Paleosol samples from the ice-free Dry Valleys were also subsampled and cultivated in a growth medium from which DNA was extracted with the explicit purpose of the positive identification of bacteria. Several species of bacteria were grown in solution and the genus identified. A similar match of the data to sequenced DNA showed that Alphaproteobacteria, Gammaproteobacteria, Bacteriodetes, and Actinobacteridae species were cultivated. The results confirm the presence of bacteria within some paleosols, but no assumptions have been made with regard to in situ activity at present. These results underscore the need not only to further investigate Dry Valley cryosols but also to develop reconnaissance strategies to determine whether such likely Earth-like environments on the Red Planet also contain life.

The use of municipal biosolids as agricultural fertilisers has raised significant concerns in recent years. As part of this, the presence of complex mixtures of pharmaceutical residues and their effects on soil ecosystems remains particularly under-researched. This study focuses on the transfer of a selection of pharmaceutical residues from municipal sewage sludge to agricultural topsoils and their fate therein after an accelerated 6-month rainfall event. Twelve pharmaceuticals encompassing antibiotics, analgesics, anti-inflammatories, beta-blockers, hyperlipidaemics and stimulants were invesigated by employing a combination of extraction techniques and liquid chromatography-tandem mass spectrometry. Both liquid- and solid-phase pharmaceutical contents were analysed and pharmaceutical and personal care products quantified at defined timepoints to elucidate transport behaviour and transformation potential. Results show the distribution and separation of pharmaceuticals over a 100-mm soil depth following typical biosolid enrichment. Using experimentally determined solid-water partition coefficients (K (d)) and hydrophobicity distribution ratios (D (ow)), mobility and modes of interaction under dynamic conditions are discussed. Finally, a brief study into the susceptibility of soil microbes is also presented. To our knowledge, this is the first investigation of pharmaceutical and personal care products release from amended biosolids to soils to include the factors and mechanisms governing their distribution and transformation even over relatively shallow depths. It applies multicompartmental and mass-balanced chemical analyses as well as microbiological approaches for a holistic view of these complex processes.

The substantial heterogeneity of dissolved organic matter (DOM) inhibits detailed chromatographic analysis with conventional detectors as little structural information can be obtained in the presence of extensive coelution. Here we examine the direct hyphenation of high-performance size exclusion chromatography (HPSEC) with nuclear magnetic resonance (NMR) spectroscopy to determine how size-distinguished fractions differ in composition. The results support the applicability of using HPSEC to generate more homogeneous fractions of DOM prior to NMR analysis and demonstrate that structure is significantly altered with size. The largest fractions are enriched in carbohydrate- and aromatic-type structures. The midsized material is substantial and is representative of carboxyl-rich alicyclic molecules (CRAMs). The smallest material has strong signatures of material derived from linear terpenoids (MDLT). Both CRAMs and MDLT have been recently hypothesized as major components of DOM, and detection by HPSEC-NMR confirms their existence as unique and separable entities. This preliminary work focuses on NMR hyphenation to HPSEC due to widespread use of HPSEC to characterize DOM. Online hyphenation is useful not only for time-efficient analysis of DOM but also for that of other highly complex samples such as those found in many environmental analyses.

Since the isolation of soil organic matter in 1786, tens of thousands of publications have searched for its structure. Nuclear magnetic resonance (NMR) spectroscopy has played a critical role in defining soil organic matter but traditional approaches remove key information such as the distribution of components at the soil-water interface and conformational information. Here a novel form of NMR with capabilities to study all physical phases termed Comprehensive Multiphase NMR, is applied to analyze soil in its natural swollen-state. The key structural components in soil organic matter are identified to be largely composed of macromolecular inputs from degrading biomass. Polar lipid heads and carbohydrates dominate the soil-water interface while lignin and microbes are arranged in a more hydrophobic interior. Lignin domains cannot be penetrated by aqueous solvents even at extreme pH indicating they are the most hydrophobic environment in soil and are ideal for sequestering hydrophobic contaminants. Here, for the first time, a complete range of physical states of a whole soil can be studied. This provides a more detailed understanding of soil organic matter at the molecular level itself key to develop the most efficient soil remediation and agricultural techniques, and better predict carbon sequestration and climate change.

Soil microbes are central to many soil processes, but due to the structural complexity of soil organic matter, the accurate quantification of microbial biomass contributions continues to pose a significant analytical challenge. In this study, microbes from a range of soils were cultured such that their molecular profile could be compared to that of soil organic matter and native vegetation. With the use of modern NMR spectroscopy, the contributions from microbial species can be discerned in soil organic matter and quantified. On the basis of these studies, the contributions of microbial biomass to soil organic matter appear to be much higher than the 1-5% reported by other researchers. In some soils, microbial biomass was found to contribute >50% of the extractable soil organic matter fractions and approximately 45% of the humin fraction and accounted for >80% of the soil nitrogen. These findings are significant because organic matter is intimately linked to nutrient release and transport in soils, nitrogen turnover rates, contaminant fate, soil quality, and fertility. Therefore, if in some cases soil organic matter and soil organic nitrogen are predominately of microbial origin, it is likely that this fraction, whether in the form of preserved material or living cells, plays an underestimated role in several soil processes.

Sediments recovered from 0 to 27 + meters below the seafloor (mbsf) of a gas-hydrate and gas-venting active area in the Gulf of Mexico were added to a hydrate growth test cell to determine the influence of the organic and inorganic sedimentary components on hydrate induction times and formation rates. Induction times were sixteen times shorter in the presence of sediment from approximately 18 mbsf (relative to sediment from 1 mbsf), and remained stable in the presence of sediment from 18 to 27 mbsf. Formation rates increased by a factor of 2.5 in the presence of sediments from approximately 18 mbsf and decreased somewhat in the presence of sediment from 18 to 27 mbsf. Selected samples (surface, 18 and 27 mbsf) were density fractionated and subjected to bulk elemental and X-ray photoelectron spectroscopy (XPS) analysis. XPS revealed the presence of iron in various chemical environments at depths of 18 and 27 mbsf. High Resolution Magic Angle Spinning Nuclear Magnetic Resonance (HR-MAS NMR) was used to characterize the organic component of sediments from selected depths. The discovery of intact proteinaceous material in the surface sediment was surprising due to the labile nature of these biopolymers, and potentially reflects microbial activity in these surface layers. This material was less abundant in sediment from increasing depths, where more lipid-like compounds were prominent. The results suggest that hydrate growth is inhibited by the presence of proteinaceous material but enhanced by lipid-like compounds associated with iron-bearing mineral surfaces.

This review presents an overview of the separation techniques applied to the complex challenge of dissolved organic matter characterisation. The review discusses methods for isolation of dissolved organic matter from natural waters, and the range of separation techniques used to further fractionate this complex material. The review covers both liquid and gas chromatographic techniques, in their various modes, and electrophoretic based approaches. For each, the challenges that the separation and fractionation of such an immensely complex sample poses is critically reviewed.

Plant litter decomposition plays a fundamental role in carbon and nitrogen cycles, provides key nutrients to the soil environment and represents a potentially large positive feedback to atmospheric CO2. However, the full details of decomposition pathways and products are unknown. Here we present the first application of HR-MAS NMR spectroscopy on 13C and 15N labeled plant materials, and apply this approach in a preliminary study to monitor the environmental degradation of the pine and wheatgrass residues over time. In HR-MAS, is it possible to acquire very high resolution NMR data of plant biomass, and apply the vast array of multidimensional experiments available in conventional solution-state NMR. High levels of isotopic enrichment combined with HR-MAS significantly enhance the detection limits, and provide a wealth of information that is unattainable by any other method. Diffusion edited HR-MAS NMR data reveal the rapid loss of carbohydrate structures, while two-dimensional (2-D) HR-MAS NMR spectra demonstrate the relatively fast loss of both hydrolysable and condensed tannin structures from all plant tissues studied. Aromatic (partially lignin) and aliphatic components (waxes, cuticles) tend to persist, along with a small fraction of carbohydrate, and become highly functionalized over time. While one-dimensional (1-D)13C HR-MAS NMR spectra of fresh plant tissue reflect compositional differences between pine and grass, these differences become negligible after decomposition suggesting that recalcitrant carbon may be similar despite the plant source. Two-dimensional 1H–15N HR-MAS NMR analysis of the pine residue suggests that nitrogen from specific peptides is either selectively preserved or used for the synthesis of what appears to be novel structures. The amount of relevant data generated from plant components in situ using HR-MAS NMR is highly encouraging, and demonstrates that complete assignment will yield unprecedented structural knowledge of plant cell components, and provide a powerful tool with which to assess carbon sequestration and transformation in the environment.

The influence of montmorillonite intercalated with representatives of three major classes of biological molecules-lysine (amino acid), α–glucose (carbohydrate) and rhamnolipid (lipid) on the catalytic activity of acid phosphatase was investigated. In comparison to pure clay, the presence of the organic intercalates preserves residual activity at extreme pH values of 3 and 11 and temperatures as low as 10 °C. Thermodynamic parameters of free energy, enthalpy and entropy, suggest that catalytic activity on the lysine and rhamnolipid intercalated surfaces is more spontaneous and favorable than that of pure clay. Michaelis-constants (Km values) and maximum reaction velocities (Vmax values) were determined and confirmed the enhancement of activity on the organo-mineral surfaces. The catalytic reaction product was measured as a function of time and the data fitted to equations describing the behavior of first and second order rates of reaction. All processes apart from the glucose-intercalated clay (second order) could be described by first order reactions. Catalytic activity was generally less on the glucose-mineral surface compared to the other organo-mineral surfaces and the pure clay. However, when all surfaces were saturated with acid phosphatase the glucose complex exhibited the highest level of catalytic activity.

Protease, a common extracellular enzyme in soils, was adsorbed onto smectite and bentonite clays exchanged with both Na and Ca cations. Initial concentrations and residual activity of the enzyme were studied together with a new approach to adsorption modeling and an introduction to the technique of phase plane analysis. Protease adsorption reached a maximum level of 0.34 mg mg-1 on the Na-exchanged smectite and a minimum of 0.20 mg mg-1 on the Ca-exchanged bentonite. The inhibition study of protease activity within the clay matrix showed that the enzyme retained a maximum of 9.9% (Na-exchanged smectite) and a minimum of 0% (Ca-exchanged bentonite) of its original activity. As opposed to the classic Langmuir and Freundlich model description, a general form, the Langmuir−Freundlich isotherm in combination with phase plane analysis, was used. The model appeared to agree well with the adsorption data of all four of the enzyme/clay complexes. The use of phase plane analysis was shown to be a powerful tool in e...

Combustion studies of poultry litter alone or mixed with peat by 50% on weight basis were undertaken in an atmospheric bubbling fluidised bed. Because of high moisture content of poultry litter, there was some uncertainty whether the combustion could be sustained on 100% poultry litter and as peat is very available in Ireland; its presence was considered to help to improve the combustion. However, the results showed that, as long as the moisture content of poultry litter was kept below 25%, the combustion did not need the addition of peat. The main parameters that were investigated are (i) moisture content, (ii) air staging, and (iii) variations in excess air levels along the freeboard. The main conclusions of the results are (i) combustion was influenced very much by the conditions of the fuel supply, (ii) the steady fuel supply was strongly dependent on the moisture content of the poultry litter, (iii) temperature appeared to be still very influential in reducing the levels of unburned carbon and hydrocarbons released from residues, (iv) the air staging in the freeboard improved combustion efficiency by enhancing the combustion of volatiles released from residues in the riser and (vi) NOx emissions were influenced by air staging in the freeboard. Particles collected from the bed and the two cyclones were analysed to determine the levels of heavy metals and the leachability tests were carried out with ashes collected to verify whether or not they could safely be used in agricultural lands.

Glasses from a complex SiO2-Al2O3-P2O5-CaO-CaF2 glass series, known as 'ionomer glasses' were investigated. For comparison, a sodium-boro-silicate (s-b-s) glass system, which is known to undergo amorphous phase separation was also investigated. Scanning Electron Microscopy (SEM), Energy Dispersive X-ray Analysis (EDX) and BET surface area and pore distribution analysis were the principal analytical techniques used in this study. SEM analysis of the ionomer glass compositions revealed smooth spherical droplets of 2–15 nm while the background morphology appeared rough and speckled. A classic interconnected structure was observed for the s-b-s glass. EDX analysis of the s-b-s glass confirmed that the sodium-borate phase was removed by leaching with 0.3 M HNO3, leaving behind a silica-rich structure. EDX analysis of ionomer glasses leached with 10% NaOH showed that the calcium and phosphate phases were being removed, although not to completion. For the base s-b-s glass a surface area of m 82 g−1 was recorded. However, the base glass after extraction with 0.3 M HNO3 of the sodium borate rich phase gave a BET surface area of 330 m2 g−1 indicating that it had already undergone phase separation on quenching from the melt, giving rise to a fine scale interconnected structure. The leached s-b-s glasses exhibited type 4 adsorption/desorption isotherms characteristic of mesoporous materials. Glasses which had been heat treated at 580°C for 4 h exhibited a surface area of 62 m2 g−1. This indicates that the as-quenched glass is already phase separated and that the phase separated microstructure is coarsening on heat treatment. A surface area of 4 m2 g−1 was measured for the base ionomer glasses. After leaching with 10% NaOH this value rose 10-fold with a maximum surface area of 44.1 m2 g−1 being recorded. The ionomer glasses also exhibited adsorption/desorption isotherms characteristic of mesoporous materials.

N-methylformamide (NMF) and 1-methyl-2-pyrrolidone (NMP) were intercalated with kaolinite, characterized, and deintercalated for analysis (the NMP was intercalated after expansion of the kaolinite layers with NMF). The dynamics of guest molecules within the kaolinite lamellae was studied by means of FT-IR and liquid state (1)H and (13)C NMR on the NMF and NMP before intercalation and also on the deintercalated solutions. Both compounds were deintercalated using water. The FT-IR spectra show no significant differences before and after intercalation, for either NMF or NMP, indicating that there is no change in molecular arrangement as a result of intercalation. (1)H and (13)C NMR investigations supported the findings of the FT-IR and indicated that structural arrangement and orientation of the guest species remain the same after deintercalation. This work provides evidence that intercalation is due to weak physical bonding.