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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.

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 (

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 (

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.

The microbial contribution to soil organic matter has been shown to be much larger than previously thought and thus it plays a major role in carbon cycling. Among soil microorganisms, chemoautotrophs can fix CO2 without sunlight and can glean energy through the oxidation of reduced elements such as sulfur. Here we show that the addition of sulfur to soil results in an initial surge in production of CO2 through microbial respiration, followed by an order of magnitude increase in the capture of carbon from the atmosphere as elemental sulfur is oxidised to sulfate. Thiobacillus spp., take advantage of specific conditions to become the dominant chemoautotrophic group that consumes CO2. We discern the direct incorporation of atmospheric carbon into soil carbohydrate, protein and aliphatic compounds and differentiate these from existing biomass. These results suggest that chemoautotrophs can play a large role in carbon cycling and that this carbon is heavily influenced by land management practises.

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.

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.

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...

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.

Fly ash, from the combustion of poultry litter, was assessed as an adsorbent for chromium(III) from aqueous solution. The adsorption process was studied as a function of temperature and time. Adsorption was best described by the Langmuir model. The adsorption of chromium(III) on the fly ash was endothermic and kinetic studies suggest that the overall rate of adsorption was pseudo-second order. At low initial concentrations film diffusion effects contribute to limiting the overall rate of adsorption while at higher initial chromium(III) concentrations pore diffusion becomes more important. An adsorption capacity of 53 mg dm−3 was reached at 20 °C. © 2002 Society of Chemical Industry

Waste kaolinite from a fertilizer industry was intercalated with n-methylformamide (NMF) under ambient conditions. The complex was washed, characterized and then reacted with benzamide (dissolved in ethanol) under similar conditions. Using X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR) and differential thermal analysis (DTA), clear evidence of benzamide intercalation was observed after a reaction time of 48 h. The FTIR and DTA analysis also confirmed that the ethanol was not involved in the intercalation and that both NMF and benzamide are present in the interlayer region.

International audience; Soils are amongst the largest organic carbon reservoirs on earth containing approximately three times the carbon contained in all living systems and roughly double the amount present in the atmosphere. Soil organic matter is central to agriculture, carbon cycling, and contaminant sequestration, but due to its extreme heterogeneity it is challenging to study with most modern analytical approaches. As such 13C NMR spectroscopy has emerged as an indispensable technique for the characterization of soil organic matter in the solid-state. Single pulse (SP) 13C NMR approaches theoretically provide the highest level of quantitation for soil organic matter, however, due to its relative insensitivity, sample analysis can take a prohibitively long time. Consequently, for routine studies the more sensitive approach of cross-polarization under magic angle spinning conditions (CP/MAS) is more commonly utilized. In particular, 13C CP is extremely useful when low organic carbon content samples are compared and is normally used to reveal the nature, transformations and fate of organic matter in soils. Here, the performance of a novel NMR scheme, which so far has not yet been applied to soils samples, is investigated. The ramp-CPSP scheme adds a SP block to a ramp-CP scheme, taking advantage of both techniques without extending the experimental time. This method shows enhancements higher than 100% for key regions of the 13C spectra and also provides 13C profiles that are closer to quantitative when compared to the widely used ramp-CP scheme. In addition, a critical analysis of these enhancements is presented. Even under the worst case scenario, when the SP element adds little additional signal, the result still reflects the conventional ramp-CP experiment. As such the ramp-CPSP approach can be implemented in a routine fashion without drawback. The results shown here suggest replacing conventional ramp-CP with the ramp-CPSP sequence for routine soil analysis in the solid-state since it can save considerable experimental time and provide a more representative 13C spectrum of the soil in general.

Biomass gasification is a possible alternative to the direct use of fossil fuel energy. Biomass, a CO2 neutral source of renewable fuel, can contribute to the demand for heat, electricity and synthesis gas. However, there are inefficiencies in the technology, which at present render biomass gasification economically unviable. The presence of condensable organic compounds and methane in the product gas renders the gas unsuitable for specific applications. Elimination of the condensable organic compounds and methane by a suitably cheap technology will enhance the economic viability of biomass gasification. This paper contains an extensive literature review of the three main groups of catalysts, which have been evaluated for the elimination of these hydrocarbons. These three groups of catalysts are dolomite, alkali metals and nickel.

A cubic mesoporous silicate (CMS) was prepared, characterised, and assessed as an adsorbent for tetramethyl ammonium hydroxide (TMAH) from aqueous solution. The adsorption process was studied as a function of temperature and time. Sorption closely followed the Langmuir model. The adsorption of TMAH on CMS was endothermic and kinetic studies suggest that the overall rate of adsorption was pseudo-second-order. Pore diffusion effects contribute to limiting the overall rate of adsorption while at lower initial TMAH concentrations, film diffusion becomes more important. Desorption studies were carried out using water and methanol. Methanol was the superior desorbing agent. © 2001 Society of Chemical Industry

An optimised and validated method for the determination of pharmaceutical residues in blue mussels (Mytilus spp.) is presented herein, as well as an investigation of the effect of cooking (by steaming) on any potential difference in human exposure risk. Selected pharmaceuticals included two non-steroidal anti-inflammatory drugs (diclofenac and mefenamic acid), an antibiotic (trimethoprim), an anti-epileptic (carbamazepine) and a lipid regulator (gemfibrozil). An in vivo exposure experiment was set up in the laboratory in which mussels were exposed either directly by injection (10 ng) or daily through spiked artificial seawater (ASW) over 96 h. In liquid matrices, pharmaceutical residues were either determined using liquid chromatography-tandem mass spectrometry (LC-MS/MS) directly, or in combination with solid-phase extraction (SPE) for analyte concentration purposes. The extraction of pharmaceuticals from mussel tissues used an additional pressurised liquid extraction step prior to SPE and LC-MS/MS. Limits of quantification of between 2 and 46 ng L(-1) were achieved for extracted cooking water and ASW, between 2 and 64 μg L(-1) for ASW in exposure tanks, and between 4 and 29 ng g(-1) for mussel tissue. Method linearities were achieved for pharmaceuticals in each matrix with correlation coefficients of R (2) 0.975. A selection of exposed mussels was also cooked (via steaming) and analysed using the optimised method to observe any effect on detectable concentrations of parent pharmaceuticals present. An overall increase in pharmaceutical residues in the contaminated mussel tissue and cooking water was observed after cooking.

Sequestration of CO2 via biological sinks is a matter of great scientific importance due to the potential lowering of atmospheric CO2. In this study, a custom built incubation chamber was used to cultivate a soil microbial community to instigate chemoautotrophy of a temperate soil. Real-time atmospheric CO2 concentrations were monitored and estimations of total CO2 uptake were made. After careful background flux corrections, 4.52 +/- 0.05 g CO2 kg I dry soil was sequestered from the chamber atmosphere over 40 h. Using isotopically labelled (CO2)-C-13 and GCMS-IRMS, labelled fatty acids were identified after only a short incubation, hence confirming CO2 sequestration for soil. The results of this in vivo study provide the ground work for future studies intending to mimic the in situ environment by providing a reliable method for investigating CO2 uptake by soil microorganisms.(C) 2012 Elsevier Ltd. All rights reserved.

Sequestration of CO2 via biological sinks is a matter of great scientific importance due to their potential to lower atmospheric CO2 levels. In this study a custom built incubation chamber was used to cultivate a soil microbial community, under ideal conditions, to investigate soil chemoautotrophy. The internal atmospheric CO2 concentrations were monitored and used to estimate the mass of CO2 uptake. It was found after careful background corrections that 256.4 μg CO2 kg−1 dry soil was removed from the chamber atmosphere over 16 h. Comparisons were made to photosynthetic controls (i.e. grass and soil algae) whereupon it was observed that the chemoautotrophic fraction sequestered 2.6 and 5.4 % of that taken up by grass and soil algae respectively. Using isotopically labelled 13CO2 and GCMS-IRMS it was also possible to extract and identify labelled fatty acids after a short incubation time, hence confirming the CO2 uptake potential of the soil slurry. Provided with favourable conditions, chemoautotrophic soil bacteria have the potential to make a significant impact on inorganic carbon sequestration within the environment. The results of this in vivo study have provided ground work for future studies intending to mimic the in situ environment by providing a reliable method for investigating CO2 uptake by soil microorganisms.

International audience; Pyrophosphate-extractable Al has been used to establish the presence of organically-complexed compounds in middle latitude and tropical soils and paleosols on Earth. As proxy data used to establish the presence of organic molecules and trace movement within profiles, it has proved an accurate indicator of downward translocation in Spodosols (podzols). Antarctic paleosols, dating from Middle to Early Miocene age (15-20 Ma), are mineralic weathering profiles lacking A and B horizons. These profiles exhibit pavement/Cox/Cz/Cu horizons, largely with sandy silt textures, little clay, and exceedingly low concentrations of organic matter. Recent chemical investigations of 33 soil samples from the New Mountain and Aztec Mountain areas near the Inland Ice, adjacent to the Taylor Glacier, show that pyrophosphate-extractable Al concentrations vary in phase with organic carbon as determined by loss-on-ignition. While Al-extract concentrations in selected samples are low (< 0.15%), increasing values above nil approximately correlate positively with increases in bacterial populations of several common phylum, the extreme high numbers with more advanced biota including fossil Coleoptera. Available data suggest Alp extracts may target samples which may have undergone minor chelation, and which over long periods of time might have a cumulative weathering effect resulting in the accumulation of small concentrations of organic matter.

Environmental contextFreshwater dissolved organic matter is a complex chemical mixture central to many environmental processes, including carbon and nitrogen cycling. Questions remain, however, as to its chemical characteristics, sources and transformation mechanisms. We studied the nature of dissolved organic matter in a lake system and found that it is influenced by anthropogenic activities. Human activities can therefore influence the huge amounts of carbon sequestered in lakes as dissolved organic matter. AbstractFreshwater dissolved organic matter (DOM) is a complex mixture of chemical components that are central to many environmental processes, including carbon and nitrogen cycling. However, questions remain as to its chemical characteristics, sources and transformation mechanisms. Here, we employ 1- and 2-D nuclear magnetic resonance (NMR) spectroscopy to investigate the structural components of lacustrine DOM from Ireland, and how it varies within a lake system, as well as to assess potential sources. Major components found, such as carboxyl-rich alicyclic molecules (CRAM) are consistent with those recently identified in marine and freshwater DOM. Lignin-type markers and protein/peptides were identified and vary spatially. Phenylalanine was detected in lake areas influenced by agriculture, whereas it is not detectable where zebra mussels are prominent. The presence of peptidoglycan, lipoproteins, large polymeric carbohydrates and proteinaceous material supports the substantial contribution of material derived from microorganisms. Evidence is provided that peptidoglycan and silicate species may in part originate from soil microbes.

Humic substances (HS) are an operationally defined fraction of soil organic matter, and they represent the largest pool of recalcitrant organic carbon in the terrestrial environment. It has traditionally been thought that extractable HS consist of novel categories of cross-linked macromolecular structures. In this study, advanced nuclear magnetic resonance approaches were used to study the major components (proteins, carbohydrates, aliphatic biopolymers, and lignin) that are known to be present in HS, and to identify their fingerprints in humic mixtures. Theoretically, once all known components have been identified, the remaining signals should be from materials with novel structures, themselves forming a distinct chemical category of humic materials. Surprisingly, nearly all of the NMR signals in traditional HS fractions could be assigned to intact and degrading biopolymers. We therefore suggest that the vast majority of operationally defined humic material in soils is a very complex mixture of microbial and plant biopolymers and their degradation products but not a distinct chemical category. It is important to note this work in no way rules out the existence of a distinct category of humic macromolecules, either at low abundance in the soluble fraction from young soils, in diagenetically evolved samples (for example lignites, etc.), or in the nonextractable humin fraction.

The preferential sorption of model compounds to calcium-exchanged montmorillonite surfaces was investigated using 1H high-resolution magic-angle spinning (HR-MAS) and liquid-state NMR. Synthetic mixtures, representing the major structural categories abundant in natural organic matter (NOM), and two soil extracts were sorbed to montmorillonite. The NMR spectra indicate that, of the organic components observable by 1H HR-MAS NMR, aliphatic components preferentially sorb to the clay surface, while carbohydrates and amino acids mainly remain in the supernatant. These results may help explain the highly aliphatic nature of organic matter associated with clay fractions in natural soils and sediments. Investigations using the synthetic mixtures demonstrate a specific interaction between the clay surface and the polar region in 1-palmitoyl-3-stearoyl-rac-glycerol. Similar observations were obtained with natural soil extracts. The results presented have important implications for understanding the role of organoclay complexes in natural processes, and provides preliminary evidence that HR-MAS NMR is a powerful analytical technique for the investigation of organoclay complex structure and conformation.

Non-living natural organic matter (NOM) is ubiquitous in the oceans, atmosphere, sediments, and soils, and represents the most abundant organic carbon reserves on earth. However, a large proportion is considered to be “molecularly uncharacterized” because the inherent complexity of NOM is problematic when applying conventional analytical techniques. This manuscript presents initial applications of LC-NMR (1H) and LC-SPE-NMR (1H) to the studies of NOM isolated from water and soil. LC-NMR is applied to dissolved natural organic matter (DNOM) collected from freshwater environments, and both LC-NMR and LC-SPE-NMR are applied to an alkaline soil extract. The polar and complex nature of the DNOM samples limits conventional reversed phase separation, which can be partially overcome with the use of an ion pair reagent, although such an approach further complicates the NMR detection. LC-SPE-NMR of the soil alkaline extract was encouraging, and specific components in the mixture could be assigned. This work demonstrates that it is both possible to separate and concentrate specific components in NOM such that NMR detection is possible. As NMR information will be critical in unraveling the novel and/or complex structures in NOM this represents a key analytical hurdle in this area.

This paper describes procedures for the generation of 2D NMR databases containing spectra predicted from chemical structures. These databases allow flexible searching via chemical structure, substructure or similarity of structure as well as spectral features. In this paper we use the biopolymer lignin as an example. Lignin is an important and relatively recalcitrant structural biopolymer present in the majority of plant biomass. We demonstrate how an accurate 2D NMR database of approximately 600 2D spectra of lignin fragments can be easily constructed, in approximately 2 days, and then subsequently show how some of these fragments can be identified in soil extracts through the use of various search tools and pattern recognition techniques. We demonstrate that once identified in one sample, similar residues are easily determined in other soil extracts. In theory, such an approach can be used for the analysis of any organic mixtures.

Four cubic mesoporous silicates (CMS), one unmodified and three grafted with amine, carboxylic and cyano surface functional groups, were prepared, characterised and compared as adsorbents for tetramethyl ammonium hydroxide (TMAH) from aqueous solution. The adsorption process was studied as a function of molecular size and CMS pore volume. Sorption on the unmodified, cyano- and carboxylic-grafted adsorbents closely followed the Langmuir model while adsorption on the amine-treated silicate conformed to the Freundlich model. A comparison of the adsorbent pore volume and the volume of sorbed TMAH molecules suggested that monolayer sorption occurred, there being some evidence that surface functional groups influenced the adsorption process. The presence or absence of structural order, as defined by X-ray diffraction analysis, had no significant influence on the adsorption, as all materials, both ordered and disordered, had relatively high adsorption capacities.

A cubic mesoporous silicate (CMS) was prepared, characterised and assessed as an adsorbent for quaternary ammonium hydroxides (QAHs) from aqueous solution. The adsorption process was studied as a function of molecular size and CMS pore volume. Sorption closely followed the Langmuir model. A comparison of the CMS pore volume and the volume of the sorbed molecules suggested that monolayer sorption occurred and that the number of molecules sorbed was a function of the size of the quaternary ammonium hydroxide molecule and the threshold area capable of being occupied by this molecule.

A gasification test rig was designed in which peat was gasified under nitrogen over a temperature range 25–550°C at 5° C min −1 . The gasification unit resulted in 35.5 wt% of the carbon present in the peat being converted to a volatile fraction. The volatile fraction was transferred to a secondary catalytic reforming reactor at 800°C. The thermal effect of the second reactor resulted in an increase in the CO, CO2 and CH4 content of the volatile fraction, a syngas ratio of 0.75 and a higher heating value (HHV) of 26.5 MJ kg −1 . Several nickel-supported catalysts were investigated with the intention that they should give an increase in the conversion of the condensable hydrocarbons in the volatile fraction to CO, CO2 and CH4, and a resultant gas stream suitable for use in an integrated gasification combined cycle plant (IGCC) (i.e. syngas ratio 2:1, low methane content and better HHV). Alumina-supported nickel catalysts investigated gave the highest activities and co-precipitated Ni/Al catalysts were most active. A Ni/Al 3:17 catalyst increased the conversion of the hydrocarbons to 91.5%, gave a syngas ratio of 1.81:1, increased the HHV by a factor of 5.3 and completely eliminated methane from the gas stream.

Erythrocyte folates are commonly extracted for assay by 10-fold dilution of EDTA-anticoagulated blood (EDTA-WB) in 10 g/L ascorbic acid. It is assumed that this procedure achieves two goals: the complete lysis of erythrocytes and the exposure of intracellular folate polyglutamates to plasma conjugase enzyme (γ-glutamyl hydrolase) at a pH near 4.5, which favors their conversion to assayable folate. These EDTA-WB hemolysates require a further 20-fold (or more) dilution before analysis by microbiological assay with Lactobacillus rhamnosus . A recent study of red cell folate extraction (1), using a microbiological assay, challenged these assumptions. The authors noted that adjusting the pH of a 10 g/L ascorbic acid diluent from pH 2.7 to pH 4 or 4.25 with 1 mol/L NaOH before EDTA-WB dilution (1 in 10) and incubation produced significantly increased whole-blood folate (WBF) yields (>10%) from fresh, unfrozen hemolysates. They also recommended the inclusion of a cell-lysing agent in extraction diluents, noting that saponin (100 mg/L) could substantially increase WBF yields, depending on hemolysate pH (1). We evaluated these findings using our “in house” microbiological assay …

A comprehensive analytical investigation of the sorption behaviour of a large selection of over-the-counter, prescribed pharmaceuticals and illicit drugs to agricultural soils and freeze-dried digested sludges is presented. Batch sorption experiments were carried out to identify which compounds could potentially concentrate in soils as a result of biosolid enrichment. Analysis of aqueous samples was carried out directly using liquid chromatography-tandem mass spectrometry (LC-MS/MS). For solids analysis, combined pressurised liquid extraction and solid phase extraction methods were used prior to LC-MS/MS. Solid-water distribution coefficients (K(d)) were calculated based on slopes of sorption isotherms over a defined concentration range. Molecular descriptors such as log P, pK(a), molar refractivity, aromatic ratio, hydrophilic factor and topological surface area were collected for all solutes and, along with generated K(d) data, were incorporated as a training set within a developed artificial neural network to predict K(d) for all solutes within both sample types. Therefore, this work represents a novel approach using combined and cross-validated analytical and computational techniques to confidently study sorption modes within the environment. The logarithm plots of predicted versus experimentally determined K(d) are presented which showed excellent correlation (R(2)0.88), highlighting that artificial neural networks could be used as a predictive tool for this application. To evaluate the developed model, it was used to predict K(d) for meclofenamic acid, mefenamic acid, ibuprofen and furosemide and subsequently compared to experimentally determined values in soil. Ratios of experimental/predicted K(d) values were found to be 1.00, 1.00, 1.75 and 1.65, respectively.