Umeå universitets logga

The widespread use of chlorinated phenols (CPs) as a wood preservative has led to numerous contaminated sawmill sites. However, it remains challenging to assess the extent of in situ degradation of CPs. We evaluated the use of compound-specific chlorine and carbon isotope analysis (Cl- and C-CSIA) to assess CP biotransformation. In a laboratory system, we measured isotopic fractionation during oxidative 2,4,6-trichlorophenol dechlorination by representative soil enzymes (C. fumago chloroperoxidase, horseradish peroxidase, and laccase from T. versicolor). Using a mathematical model, the validity of the Rayleigh approach to evaluate apparent kinetic isotope effects (AKIE) was confirmed. A small but significant Cl-AKIE of 1.0022 ± 0.0006 was observed for all three enzymes, consistent with a reaction pathway via a cationic radical species. For carbon, a slight inverse isotope effect was observed (C-AKIE = 0.9945 ± 0.0019). This fractionation behavior is clearly distinguishable from reported reductive dechlorination mechanisms. Based on these results we then assessed degradation and apportioned different types of technical CP mixtures used at two former sawmill sites. To our knowledge, this is the first study that makes use of two-element CSIA to study sources and transformation of CPs in the environment.

Coralline algal (maerl) beds are widespread, slow-growing, structurally complex perennial habitats that support high biodiversity, yet are significantly understudied compared to seagrass beds or kelp forests. We present the first eddy covariance (EC) study on a live maerl bed, assessing the community benthic gross primary productivity (GPP), respiration (R), and net ecosystem metabolism (NEM) derived from diel EC time series collected during 5 seasonal measurement campaigns in temperate Loch Sween, Scotland. Measurements were also carried out at an adjacent (similar to 20 m distant) permeable sandy habitat. The O-2 exchange rate was highly dynamic, driven by light availability and the ambient tidally-driven flow velocity. Linear relationships between the EC O-2 fluxes and available light indicate that the benthic phototrophic communities were light limited. Compensation irradiance (E-c) varied seasonally and was typically similar to 1.8-fold lower at the maerl bed compared to the sand. Substantial GPP was evident at both sites; however, the maerl bed and the sand habitat were net heterotrophic during each sampling campaign. Additional inputs of similar to 4 and similar to 7 mol m(-2) yr(-1) of carbon at the maerl bed and sand site, respectively, were required to sustain the benthic O-2 demand. Thus, the 2 benthic habitats efficiently entrap organic carbon and are sinks of organic material in the coastal zone. Parallel deployment of 0.1 m(2) benthic chambers during nighttime revealed O-2 uptake rates that varied by up to similar to 8-fold between replicate chambers (from -0.4 to -3.0 mmol O-2 m(-2) h(-1); n = 4). However, despite extensive O-2 flux variability on meter horizontal scales, mean rates of O-2 uptake as resolved in parallel by chambers and EC were typically within 20% of one another.

Inorganic geochemistry is a powerful tool in paleolimnology. It has become one of the most commonly used techniques to analyze lake sediments, particularly due to the development and increasing availability of XRF core scanners during the last two decades. It allows for the reconstruction of the continuous processes that occur in lakes and their watersheds, and it is ideally suited to identify event deposits. How earth surface processes and limnological conditions are recorded in the inorganic geochemical composition of lake sediments is, however, relatively complex. Here, we review the main techniques used for the inorganic geochemical analysis of lake sediments and we offer guidance on sample preparation and instrument selection. We then summarize the best practices to process and interpret bulk inorganic geochemical data. In particular, we emphasize that log-ratio transformation is critical for the rigorous statistical analysis of geochemical datasets, whether they are obtained by XRF core scanning or more traditional techniques. In addition, we show that accurately interpreting inorganic geochemical data requires a sound understanding of the main components of the sediment (organic matter, biogenic silica, carbonates, lithogenic particles) and mineral assemblages. Finally, we provide a series of examples illustrating the potential and limits of inorganic geochemistry in paleolimnology. Although the examples presented in this paper focus on lake and fjord sediments, the principles presented here also apply to other sedimentary environments.

Introduction: Thousands of halogenated natural products (HNPs) are generated in the ocean and on land. A subset of these, halomethoxybenzenes (HMBs), are released from both natural and anthropogenic sources. Here we consider: 1. Brominated anisoles (BAs), transformation products of bromophenols. 2. Drosophilin A methyl ether (DAME: 1,2,4,5-tetrachloro-3,6-dimethoxybenzene), a secondary metabolite of terrestrial fungi. 3. Tetrachloroveratrole (TeCV: 1,2,3,4-tetrachloro-5,6-dimethoxybenzene), a lignin byproduct found in bleached kraft mill effluent. 4. Pentachloroanisole (PeCA), a metabolite of the wood preservative pentachlorophenol.

Methods: We examined several ecosystem compartments to determine sources and exchange processes for these HMBs: air, precipitation, rivers, forest fungi and litter, and water from northern Baltic estuaries and offshore. Samples were analyzed for HMBs by capillary gas chromatography – quadrupole mass spectrometry.

Results and discussion: All four types of HMBs were found in air, and BAs, DAME and TeCV were also present in precipitation. BAs and DAME were common in rivers and estuaries, whereas TeCV was low and PeCA was below detection. DAME was identified in several species of fungi and in forest litter; TeCV was occasionally present, but BAs and PeCA were below detection. Concentrations of BAs were higher in estuaries than in rivers or offshore waters, showing that estuaries are hot spots for production. BAs were negatively or not correlated with chlorophyll-a, suggesting contribution by heterotrophic bacteria as well as known production by phytoplankton and macroalgae. DAME was negatively or not correlated with BAs and did not appear to be produced in the estuaries; fungi and forest litter containing fungal mycelia are suggested as sources. HMBs volatilize from sea and land, disperse through the atmosphere, and return via precipitation and rivers. Production and biogeochemical cycles are influenced by climate change and we suggest BAs and DAME for following partitioning and exchange processes.

Seaweed and seagrass communities in the northeast Atlantic have been profoundly impacted by humans, and the rate of change is accelerating rapidly due to runaway CO2 emissions and mounting pressures on coastlines associated with human population growth and increased consumption of finite resources. Here, we predict how rapid warming and acidification are likely to affect benthic flora and coastal ecosystems of the northeast Atlantic in this century, based on global evidence from the literature as interpreted by the collective knowledge of the authorship. We predict that warming will kill off kelp forests in the south and that ocean acidification will remove maerl habitat in the north. Seagrasses will proliferate, and associated epiphytes switch from calcified algae to diatoms and filamentous species. Invasive species will thrive in niches liberated by loss of native species and spread via exponential development of artificial marine structures. Combined impacts of seawater warming, ocean acidification, and increased storminess may replace structurally diverse seaweed canopies, with associated calcified and noncalcified flora, with simple habitats dominated by noncalcified, turf-forming seaweeds.

This report provides an overview of the progress and results of the VR:KFI infrastructure projects 2007-7494 and (825-)2010-5976. It should be considered as a status report in an on-going long-term research infrastructure development project.

Significant warming and acidification of the oceans is projected to occur by the end of the century. CO2 vents, areas of upwelling and downwelling, and potential leaks from carbon capture and storage facilities may also cause localised environmental changes, enhancing or depressing the effect of global climate change. Cold-water coral ecosystems are threatened by future changes in carbonate chemistry, yet our knowledge of the response of these corals to high temperature and high CO2 conditions is limited. Dimethylsulphoniopropionate (DMSP), and its breakdown product dimethylsulphide (DMS), are putative antioxidants that may be accumulated by invertebrates via their food or symbionts, although recent research suggests that some invertebrates may also be able to synthesise DMSP. This study provides the first information on the impact of high temperature (12 A degrees C) and high CO2 (817 ppm) on intracellular DMSP in the cold-water coral Lophelia pertusa from the Mingulay Reef Complex, Scotland (56A degrees 49'N, 07A degrees 23'W), where in situ environmental conditions are meditated by tidally induced downwellings. An increase in intracellular DMSP under high CO2 conditions was observed, whilst water column particulate DMS + DMSP was reduced. In both high temperature treatments, intracellular DMSP was similar to the control treatment, whilst dissolved DMSP + DMS was not significantly different between any of the treatments. These results suggest that L. pertusa accumulates DMSP from the surrounding water column; uptake may be up-regulated under high CO2 conditions, but mediated by high temperature. These results provide new insight into the biotic control of deep-sea biogeochemistry and may impact our understanding of the global sulphur cycle, and the survival of cold-water corals under projected global change.

Free-living coralline algae lay down growth bands formed by areas of more and less calcified cells which, in certain species, are associated with winter and summer growth respectively. Band width and cell calcification of Lithothamnion glaciale from Scotland were compared to annual and seasonal cloud cover and sea surface temperature (SST). There was a negative relationship between summer calcification (the degree of cellular carbonate infilling) and winter cloud cover. Annual and summer SST were also negatively related to summer calcification. This indicates that summer calcification may be affected by the previous winter's cloud cover and that summer's/year's SST. No relationships between band width and cloud cover were observed. A cloud cover hindcast using summer calcification and SST indicated a modest rise in cloud cover trends from 1910 to 2006 and a 12 (mean) year cyclicity in cloud cover, however, the latter may be associated with other site-specific factors. This study demonstrates the utility of densitometric algochronology in understanding marine temperature and cloud cover histories. 

The release of dimethylsulphoniopropionate (DMSP) by marine algae has major impacts on the global sulphur cycle and may influence local climate through the formation of dimethylsulphide (DMS). However, the effect of global change on DMSP/DMS (DMS(P)) production by algae is not well understood. This study examined the effect of low pH on DMS(P) production and epithelial cell morphology of the free-living red coralline alga Lithothamnion glaciale. Three pH treatments were used in the 80-day experiment: (1) current pH level (8.18, control), (2) low, chronic pH representing a 2100 ocean acidification (OA) scenario (7.70) and (3) low, acute pH (7.75, with a 3-day spike to 6.47), representing acute variable conditions that might be associated with leaks from carbon capture and storage infrastructure, at CO2 vent sites or in areas of upwelling. DMS(P) production was not significantly enhanced under low, stable pH conditions, indicating that red coralline algae may have some resilience to OA. However, intracellular and water column DMS(P) concentrations were significantly higher than the control when pH was acutely spiked. Cracks were observed between the cell walls of the algal skeleton in both low pH treatments. It is proposed that this structural change may cause membrane damage that allows DMS(P) to leak from the cells into the water column, with subsequent implications for the cycling of DMS(P) in coralline algae habitats.

Oceanic pH is projected to decrease by up to 0.5 units by 2100 (a process known as ocean acidification, OA), reducing the calcium carbonate saturation state of the oceans. The coastal ocean is expected to experience periods of even lower carbonate saturation state because of the inherent natural variability of coastal habitats. Thus, in order to accurately project the impact of OA on the coastal ocean, we must first understand its natural variability. The production of dimethylsulphoniopropionate (DMSP) by marine algae and the release of DMSP's breakdown product dimethylsulphide (DMS) are often related to environmental stress. This study investigated the spatiotemporal response of tropical macroalgae (Padina sp., Amphiroa sp. and Turbinaria sp.) and the overlying water column to natural changes in reefal carbonate chemistry. We compared macroalgal intracellular DMSP and water column DMSP+DMS concentrations between the environmentally stable reef crest and environmentally variable reef flat of the fringing Suleman Reef, Egypt, over 45-hour sampling periods. Similar diel patterns were observed throughout: maximum intracellular DMSP and water column DMS/P concentrations were observed at night, coinciding with the time of lowest carbonate saturation state. Spatially, water column DMS/P concentrations were highest over areas dominated by seagrass and macroalgae (dissolved DMS/P) and phytoplankton (particulate DMS/P) rather than corals. This research suggests that macroalgae may use DMSP to maintain metabolic function during periods of low carbonate saturation state. In the reef system, seagrass and macroalgae may be more important benthic producers of dissolved DMS/P than corals. An increase in DMS/P concentrations during periods of low carbonate saturation state may become ecologically important in the future under an OA regime, impacting larval settlement and increasing atmospheric emissions of DMS.

Marine algae are key sources of the biogenic sulfur compound dimethylsulphoniopropionate (DMSP), a vital component of the marine sulfur cycle. Autotrophic ecosystem engineers such as red coralline algae support highly diverse and biogeochemically active ecosystems and are known to be high DMSP producers, but their importance in the global marine sulfur cycle has not yet been appreciated. Using a global sampling approach, we show that red coralline algae are a globally significant pool of DMSP in the oceans, estimated to be similar to 110x10(12) moles worldwide during the summer months. Latitude was a major driver of observed regional-scale variations, with peaks in polar and tropical climate regimes, reflecting the varied cellular functions for DMSP (e.g., as a cryoprotectant and antioxidant). A temperate coralline algal bed was investigated in more detail to also identify local-scale temporal variations. Here, water column DMSP was driven by water temperature, and to a lesser extent, cloud cover; two factors which are also vital in controlling coralline algal growth. This study demonstrates that coralline algae harbor a large pool of dimethylated sulfur, thereby playing a significant role in both the sulfur and carbon marine biogeochemical cycles. However, coralline algal habitats are severely threatened by projected climate change; a loss of this habitat may thus detrimentally impact oceanic sulfur and carbon biogeochemical cycling.

Mid- to high-latitude fjordic coastal environments experience naturally variable salinity regimes. Climate projections suggest that freshwater input into the coastal ocean will increase in the future, exposing coastal organisms to further periods of reduced salinity. This study investigated the effect of low salinity on Lithothamnion glaciale, a red coralline alga found in mid- to high-latitude fjordic regions, during a 21-day experiment. Specific measurements included: the intracellular concentration of dimethylsulphoniopropionate (DMSP, an algal secondary metabolite and major precursor to the climatically active gas dimethylsulphide), pigment composition and photosynthetic characteristics. No significant difference in intracellular DMSP concentrations was observed between treatments, suggesting that the primary function for DMSP in L. glaciale is not as a compatible solute, perhaps favouring an antioxidant role . Photosynthetic parameters (including pigment composition) exhibited a mixed response, suggesting some degree of photosynthetic resilience to reduced salinity. This study provides evidence of intracellular mechanisms adopted by L. glaciale in response to reduced salinity. This has significant implications for the survival of L. glaciale under a projected freshening scenario and provides organism-level detail to ecosystem-level projected changes should lower-salinity conditions become more frequent and more intense in the future.

The deep porewater of northern peatlands stores large amounts of carbon dioxide (CO2). This store is viewed as a stable feature in the peatland CO2 cycle. Here, we report large and rapid fluctuations in deep porewater CO2 concentration recurring every autumn over four consecutive years in a boreal peatland. Estimates of the vertical diffusion of heat indicate that CO2 diffusion occurs at the turbulent rather than molecular rate. The weakening of porewater thermal stratification in autumn likely increases turbulent diffusion, thus fostering a rapid diffusion of deeper porewater CO2 towards the surface where net losses occur. This phenomenon periodically decreases the peat porewater CO2 store by between 29 and 90 g C m−2 throughout autumn, which is comparable to the peatland’s annual C-sink. Our results establish the need to consider the role of turbulent diffusion in regularly destabilizing the CO2 store in peat porewater.

Neurotoxic methylmercury (MeHg) is formed by microbial methylation of inorganic divalent Hg (HgII) and constitutes severe environmental and human health risks. The methylation is enabled by hgcA and hgcB genes, but it is not known if the associated molecular-level processes are rate-limiting or enable accurate prediction of MeHg formation in nature. In this study, we investigated the relationships between hgc genes and MeHg across redox-stratified water columns in the brackish Baltic Sea. We showed, for the first time, that hgc transcript abundance and the concentration of dissolved HgII-sulfide species were strong predictors of both the HgII methylation rate and MeHg concentration, implying their roles as principal joint drivers of MeHg formation in these systems. Additionally, we characterized the metabolic capacities of hgc+ microorganisms by reconstructing their genomes from metagenomes (i.e., hgc+ MAGs), which highlighted the versatility of putative HgII methylators in the water column of the Baltic Sea. In establishing relationships between hgc transcripts and the HgII methylation rate, we advance the fundamental understanding of mechanistic principles governing MeHg formation in nature and enable refined predictions of MeHg levels in coastal seas in response to the accelerating spread of oxygen-deficient zones.

The use of lake sedimentary DNA to track the long-term changes in both terrestrial and aquatic biota is a rapidly advancing field in paleoecological research. Although largely applied nowadays, knowledge gaps remain in this field and there is therefore still research to be conducted to ensure the reliability of the sedimentary DNA signal. Building on the most recent literature and seven original case studies, we synthesize the state-of-the-art analytical procedures for effective sampling, extraction, amplification, quantification and/or generation of DNA inventories from sedimentary ancient DNA (sedaDNA) via high-throughput sequencing technologies. We provide recommendations based on current knowledge and best practises.

Birnessite is a layered MnO₂ mineral capable of intercalating nanometric water films in its bulk. With its variable distributions of Mn oxidation states (Mn^IV, Mn^III, and Mn^II), cationic vacancies, and interlayer cationic populations, birnessite plays key roles in catalysis, energy storage solutions, and environmental (geo)chemistry. We here report the molecular controls driving the nanoscale intercalation of water in potassium-exchanged birnessite nanoparticles. From microgravimetry, vibrational spectroscopy, and X-ray diffraction, we find that birnessite intercalates no more than one monolayer of water per interlayer when exposed to water vapor at 25 °C, even near the dew point. Molecular dynamics showed that a single monolayer is an energetically favorable hydration state that consists of 1.33 water molecules per unit cell. This monolayer is stabilized by concerted potassium–water and direct water–birnessite interactions, and involves negligible water–water interactions. Using our composite adsorption–condensation–intercalation model, we predicted humidity-dependent water loadings in terms of water intercalated in the internal and adsorbed at external basal faces, the proportions of which vary with particle size. The model also accounts for additional populations condensed on and between particles. By describing the nanoscale hydration of birnessite, our work secures a path for understanding the water-driven catalytic chemistry that this important layered manganese oxide mineral can host in natural and technological settings.

The fractionation factor in the magnesium-isotope fractionation between aqueous solutions of magnesium and brucite changes sign with increasing temperature, as uncovered by recent experiments. To understand this behavior, the Reduced Partition Function Ratios and isotopic fractionation factors (Δ^26/24Mg_{brucite-Mg(aq)}) are calculated using molecular models of aqueous [Mg(OH₂)₆]²⁺ and the mineral brucite at increasing levels of density functional theory. The calculations were carried out on the [Mg(OH₂)₆]²⁺·12H₂O cluster, along with different Pauling-bond-strength-conserving models of the mineral lattice of brucite. Three conclusions were reached: (i) all levels of theory overestimate 〈Mg‒O〉 bond distances in the aqua ion complex relative to Tutton’s salts; (ii) the calculations predict that brucite at 298.15 K is always enriched in the heavy isotope, in contrast with experimental observations; (iii) the temperature dependencies of Wimpenny et al. (2014) and Li et al. (2014) could only be achieved by fixing the 〈Mg‒O〉 bond distances in the [Mg(OH₂)₆]²⁺·12H₂O cluster to values close to those observed in crystals that trap the hydrated ion.

Reconstructing pH from biogenic carbonates using boron isotopic compositions relies on the assumption that only borate, and no boric acid, is present. Red coralline algae are frequently used in palaeoenvironmental reconstruction due to their widespread distribution and regular banding frequency. Prior to undertaking pH reconstructions using red coralline algae we tested the boron composition of the red coralline alga Lithothamnion glaciale using high field NMR. In bulk analysed samples, thirty percent of boron was present as boric acid. We suggest that prior to reconstructing pH using coralline algae 1) species-specific boron compositions and 2) within-skeleton special distributions of boron are determined for multiple species. This will enable site selective boron analyses to be conducted validating coralline algae as palaeo-pH proxies based on boron isotopic compositions.

The shell of the gastropod mollusc, abalone, is comprised of nacre with an outer prismatic layer that is composed of either calcite or aragonite or both, depending on the species. A striking characteristic of the abalone shell is the row of apertures along the dorsal margin. As the organism and shell grow, new apertures are formed and the preceding ones are filled in. Detailed investigations, using electron backscatter diffraction, of the infill in three species of abalone: Haliotis asinina, Haliotis gigantea and Haliotis rufescens reveals that, like the shell, the infill is composed mainly of nacre with an outer prismatic layer. The infill prismatic layer has identical mineralogy as the original shell prismatic layer. In H. asinina and H. gigantea, the prismatic layer of the shell and infill are made of aragonite while in H. rufescens both are composed of calcite. Abalone builds the infill material with the same high level of biological control, replicating the structure, mineralogy and crystallographic orientation as for the shell. The infill of abalone apertures presents us with insight into what is, effectively, shell repair. 

Approximately 40% of earth's carbon (C) stored in land vegetation and soil is within the boreal region. This large C pool is subjected to substantial removals and transformations during periodic wildfire. Fire-altered C, commonly known as pyrogenic carbon (PyC), plays a significant role in forest ecosystem functioning and composes a considerable fraction of C transport to limnic and oceanic sediments. While PyC stores are beginning to be quantified globally, knowledge is lacking regarding the drivers of their production and transport across ecosystems. This study used the chemo-thermal oxidation at 375°C (CTO-375) method to isolate a particularly refractory subset of PyC compounds, here called black carbon (BC), finding an average increase of 11.6 g BC m⁻² at 1 year postfire in 50 separate wildfires occurring in Sweden during 2018. These increases could not be linked to proposed drivers, however BC storage in 50 additional nearby unburnt soils related strongly to soil mass while its proportion of the larger C pool related negatively to soil C:N. Fire approximately doubled BC stocks in the mineral layer but had no significant effect on BC in the organic layer where it was likely produced. Suppressed decomposition rates and low heating during fire in mineral subsoil relative to upper layers suggests potential removals of the doubled mineral layer BC are more likely transported out of the soil system than degraded in situ. Therefore, mineral soils are suggested to be an important storage pool for BC that can buffer short-term (production in fire) and long-term (cross-ecosystem transport) BC cycling.

We present two cases of incoherent-scatter ion line enhancements in conjunction with auroral arcs drifting through the radar beam. The up- and downshifted ion line shoulders as well as the spectral region between them are enhanced equally and simultaneously. The power enhancements are one order of magnitude above the thermal level and are concentrated in less than 15 km wide altitude ranges at the ionospheric F region peak. The auroral arc passages are preceded by significantly enhanced ion temperatures in the E region, which are shown to generate high velocity shears. We use a Hall MHD model of velocity shears perpendicular to the geomagnetic field and show that a Kelvin-Helmholtz instability will grow for the two presented cases. We assess the possibility that the subsequently generated low frequency turbulence can explain the observed spectrally uniform ion line power enhancements.

The aim of the study was to map the extent of Fe, Cu, Pb, As, Zn and S contamination in the area surrounding the Nasa silver mine. The mine operated between 1635 and 1810 with some prospecting performed in 1889, and has become infamous for the gruesome ways that the indigenous people were treated during the early years of operation. This study tested three hypotheses through a geochemical survey: 1) sulfide oxidation is still active in the abandoned mine, 2) the soil downslope of the mine is contaminated by mine drainage, and 3) the stream downslope of the mine is affected in the same way. All three hypotheses were valid, as the results showed that still, >200 years after mining operations ceased, signs of the historical mining are clearly visible in the surrounding environment. Acidic conditions were discovered in surface waters close to the waste rock piles, which indicates active sulfide oxidation. In addition, elevated levels of Fe, Cu, Pb, As, Zn and S were found in both soil and stream sediment downslope of the mines, as compared to reference localities upstream the mine (p <0.05). These results suggest that previous assessments of the mine being no threat to the environment may not be entirely correct. This study illustrates how mining waste can continue to affect the local, sub-arctic environment long after mining operations have ceased.

Biomineral production in marine organisms employs transient phases of amorphous calcium carbonate (ACC) in the construction of crystalline shells. Increasing seawater pCO(2) leads to ocean acidification (OA) with a reduction in oceanic carbonate concentration which could have a negative impact on shell formation and therefore survival. We demonstrate significant changes in the hydrated and dehydrated forms of ACC in the aragonite and calcite layers of Mytilus edulis shells cultured under acidification conditions (1000 mu atm pCO(2)) compared to present day conditions (380 mu atm pCO(2)). In OA conditions, Mytilus edulis has more ACC at crystalisation sites. Here, we use the high-spatial resolution of synchrotron X-ray Photo Emission Electron Microscopy (XPEEM) combined with X-ray Absorption Spectroscopy (XAS) to investigate the influence of OA on the ACC formation in the shells of adult Mytilus edulis. Electron Backscatter Diffraction (EBSD) confirms that OA reduces crystallographic control of shell formation. The results demonstrate that OA induces more ACC formation and less crystallographic control in mussels suggesting that ACC is used as a repair mechanism to combat shell damage under OA. However, the resultant reduced crystallographic control in mussels raises concerns for shell protective function under predation and changing environments.

Global climate change threatens the oceans as anthropogenic carbon dioxide causes ocean acidification and reduced carbonate saturation. Future projections indicate under saturation of aragonite, and potentially calcite, in the oceans by 2100. Calcifying organisms are those most at risk from such ocean acidification, as carbonate is vital in the biomineralisation of their calcium carbonate protective shells. This study highlights the importance of multi-generational studies to investigate how marine organisms can potentially adapt to future projected global climate change. Mytilus edulis is an economically important marine calcifier vulnerable to decreasing carbonate saturation as their shells comprise two calcium carbonate polymorphs: aragonite and calcite. M. edulis specimens were cultured under current and projected pCO(2) (380, 550, 750 and 1000 mu atm), following 6 months of experimental culture, adults produced second generation juvenile mussels. juvenile mussel shells were examined for structural and crystallographic orientation of aragonite and calcite. At 1000 mu atm pCO(2), juvenile mussels spawned and grown under this high pCO(2) do not produce aragonite which is more vulnerable to carbonate under-saturation than calcite. Calcite and aragonite were produced at 380, 550 and 750 mu atm pCO(2). Electron back scatter diffraction analyses reveal less constraint in crystallographic orientation with increased pCO(2). Shell formation is maintained, although the nacre crystals appear corroded and crystals are not so closely layered together. The differences in ultrastructure and crystallography in shells formed by juveniles spawned from adults in high pCO(2) conditions may prove instrumental in their ability to survive ocean acidification. 

Ocean acidification is altering the oceanic carbonate saturation state and threatening the survival of marine calcifying organisms. Production of their calcium carbonate exoskeletons is dependent not only on the environmental seawater carbonate chemistry but also the ability to produce biominerals through proteins. We present shell growth and structural responses by the economically important marine calcifier Mytilus edulis to ocean acidification scenarios (380, 550, 750, 1000 mu atm pCO(2)). After six months of incubation at 750 matm pCO(2), reduced carbonic anhydrase protein activity and shell growth occurs in M. edulis. Beyond that, at 1000 matm pCO(2), biomineralisation continued but with compensated metabolism of proteins and increased calcite growth. Mussel growth occurs at a cost to the structural integrity of the shell due to structural disorientation of calcite crystals. This loss of structural integrity could impact mussel shell strength and reduce protection from predators and changing environments.

Ocean acidification threatens organisms that produce calcium carbonate shells by potentially generating an under-saturated carbonate environment. Resultant reduced calcification and growth, and subsequent dissolution of exoskeletons, would raise concerns over the ability of the shell to provide protection for the marine organism under ocean acidification and increased temperatures. We examined the impact of combined ocean acidification and temperature increase on shell formation of the economically important edible mussel Mytilus edulis. Shell growth and thickness along with a shell thickness index and shape analysis were determined. The ability of M.edulis to produce a functional protective shell after 9months of experimental culture under ocean acidification and increasing temperatures (380, 550, 750, 1000atm pCO(2), and 750, 1000atm pCO(2)+2 degrees C) was assessed. Mussel shells grown under ocean acidification conditions displayed significant reductions in shell aragonite thickness, shell thickness index, and changes to shell shape (750, 1000atm pCO(2)) compared to those shells grown under ambient conditions (380atm pCO(2)). Ocean acidification resulted in rounder, flatter mussel shells with thinner aragonite layers likely to be more vulnerable to fracture under changing environments and predation. The changes in shape presented here could present a compensatory mechanism to enhance protection against predators and changing environments under ocean acidification when mussels are unable to grow thicker shells. Here, we present the first assessment of mussel shell shape to determine implications for functional protection under ocean acidification.

Ocean acidification (OA) and the resultant changing carbonate saturation states is threatening the formation of calcium carbonate shells and exoskeletons of marine organisms. The production of biominerals in such organisms relies on the availability of carbonate and the ability of the organism to biomineralize in changing environments. To understand how biomineralizers will respond to OA the common blue mussel, Mytilus edulis, was cultured at projected levels of pCO(2) (380, 550, 750, 1000 mu atm) and increased temperatures (ambient, ambient plus 2 degrees C). Nanoindentation (a single mussel shell) and microhardness testing were used to assess the material properties of the shells. Young's modulus (E), hardness (H) and toughness (K-IC) were measured in mussel shells grown in multiple stressor conditions. OA caused mussels to produce shell calcite that is stiffer (higher modulus of elasticity) and harder than shells grown in control conditions. The outer shell (calcite) is more brittle in OA conditions while the inner shell (aragonite) is softer and less stiff in shells grown under OA conditions. Combining increasing ocean pCO(2) and temperatures as projected for future global ocean appears to reduce the impact of increasing pCO(2) on the material properties of the mussel shell. OA may cause changes in shell material properties that could prove problematic under predation scenarios for the mussels; however, this may be partially mitigated by increasing temperature.

The ASPERA-3 experiment on Mars Express provides the first measurements of energetic neutral atoms (ENAs) from Mars. These measurements are used to study the global structure of the interaction of the solar wind with the Martian atmosphere. In this study we describe the tailward ENA flow observed at the nightside of Mars. After characterizing energy spectra of hydrogen ENA signals, we present composite images of the ENA intensities and compare them to theoretical predictions (empirical and MHD models). We find that the tailward flow of hydrogen ENAs is mainly generated by shocked solar wind protons. Despite intensive search, no oxygen ENAs above the instrument threshold are detected. The results challenge existing plasma models and constrain the hydrogen exospheric densities and atmospheric hydrogen and oxygen loss rates at low solar activity.

Under the gradients of salinity and redox, the transportation and distribution of dissolved, particulate, and sedimentary arsenic present differences from estuary to bay. Samples of water, suspended particulate sediment (SPS), and sediment from the Jiaozhou Bay were analyzed. The concentrations of arsenic decreased significantly from the estuaries toward the bay. The sedimentary arsenic mostly existed as hydrous oxide-bound and residual fractions and tended to be attached to smaller particles. Sedimentary particles were more capable of absorbing arsenic than SPS and the capacity increased from the estuaries toward the bay. The spatial distribution of arsenic was impacted by the residual currents, resulting in higher contents of dissolved arsenic in the eastern coastal zone and higher concentrations of sedimentary arsenic in the inner bay. In water, total phosphorus (TP), dissolved organic carbon (DOC), and alkalinity had significant positive correlations with the dissolved arsenic. In sediments, Fe oxides and sediment organic matter (SOM) would promote adsorption of arsenic. The significant correlation between non-residual fractions and enrichment factors of arsenic indicated that the sedimentary arsenic was more likely to originate from anthropogenic sources, mainly impacted by riverine transport from the eastern urban regions and agricultural production in the western farmland.

The biogenic methylation of inorganic, divalent mercury (Hg(II)) by methylating microorganisms leads to formation and bioaccumulation of monomethyl mercury (MeHg) in the environment and can cause severe damage to ecosystems and human health. Diverse microorganisms carry the gene sequence hgcAB and are able to methylate Hg(II) intracellularly. The interplay of biological, chemical and physical parameters is driving mercury (Hg) transformation by microorganisms. The chemical speciation of Hg(II) with thiol compounds, both with dissolved low molecular mass (LMM) thiols and thiols present on microbial membrane surfaces, is one key factor for Hg availability and transformation. In this work the role of thiol compounds with respect to Hg speciation, uptake and transformation was studied by the iron-reducing model organisms Geobacter sulfurreducens. The turnover of dissolved thiols and the role of outer and inner membrane thiols was studied with novel experimental strategies.

In Paper I and II the formation of thiol compounds was studied under varying nutrient conditions. It was shown that the formation of LMM-thiol compounds was impacted by divalent iron, Fe(II). Furthermore, we showed the turnover of the small LMM-thiol cysteine to the branched LMM-thiol penicillamine, which was further amplified by the addition of exogenous cysteine or nutrients. This turnover of small to branched LMM-thiols impacted the Hg(II) speciation in methylation assays and the relative contribution between cysteine and penicillamine was important for Hg(II) availability, uptake and methylation. In addition, the partition of Hg(II) between the cell-adsorbed and dissolved phase was shifted towards the latter at higher LMM-thiol concentrations. Nutrient concentrations impacted cell physiology due to a shift to an active metabolism and a faster metabolization of LMM-thiols. We concluded that the interplay between thiol metabolism, Hg(II) speciation and cell physiology are key parameters for Hg(II) methylation by G. sulfurreducens. In Paper III The outer and inner membrane was characterized independently by two X-ray absorption spectroscopy techniques. The determination of the Hg speciation by both X-ray absorption spectroscopy techniques showed coherent results for both the outer and inner membrane of G. sulfurreducens. The concentration of thiol membrane groups was higher on the inner compared to the outer membrane. The differences between the outer and inner membrane suggested that thiol concentration and Hg coordination environment likely impact the Hg(II) internalization. The role of membrane thiols for Hg(II) uptake and transformation was further investigated in Paper IV by selectively blocking these functional groups. Partitioning and uptake of Hg was not affected by blocking the outer and inner membrane thiols of whole cell and spheroplast samples, respectively. However, the Hg(II) methylation was decreased by blocking thiols at the outer membrane, but no effect was observed by blocking thiols at the inner membrane. Blocking of membrane surface thiols changed the physiology in whole cells but not in spheroplasts. This result suggested weaknesses of the applied blocking approach. In addition, Hg(II) reduction was studied on the outer and inner membrane and showed the formation of liquid and gaseous elemental Hg, Hg(0), in Paper III and IV, respectively.

Overall, this work showed the central role of dissolved and cell-associated thiol compounds for Hg(II) uptake and the transformation reactions. Herby, concentration, compositions and distribution of thiols are crucial and impact the Hg(II) speciation, partitioning, uptake and availability for Hg(II) methylation and reduction. In addition, cell physiology is impacting the methylation potential and the turnover of LMM-thiol compounds. The role of membrane surface thiols for Hg(II) uptake was not fully identified, however such thiols were for the first time characterized selectively for the outer and inner membrane by X-ray absorption spectroscopy.

The chemical and biological factors controlling microbial formation of methylmercury (MeHg) are widely studied separately, but the combined effects of these factors are largely unknown. We examined how the chemical speciation of divalent, inorganic mercury (Hg(II)), as controlled by low-molecular-mass thiols, and cell physiology govern MeHg formation by Geobacter sulfurreducens. We compared MeHg formation with and without addition of exogenous cysteine (Cys) to experimental assays with varying nutrient and bacterial metabolite concentrations. Cysteine additions initially (0–2 h) enhanced MeHg formation by two mechanisms: (i) altering the Hg(II) partitioning from the cellular to the dissolved phase and/or (ii) shifting the chemical speciation of dissolved Hg(II) in favor of the Hg(Cys)₂ complex. Nutrient additions increased MeHg formation by enhancing cell metabolism. These two effects were, however, not additive since cysteine was largely metabolized to penicillamine (PEN) over time at a rate that increased with nutrient addition. These processes shifted the speciation of dissolved Hg(II) from complexes with relatively high availability, Hg(Cys)₂, to complexes with lower availability, Hg(PEN)₂, for methylation. This thiol conversion by the cells thereby contributed to stalled MeHg formation after 2–6 h Hg(II) exposure. Overall, our results showed a complex influence of thiol metabolism on microbial MeHg formation and suggest that the conversion of cysteine to penicillamine may partly suppress MeHg formation in cysteine-rich environments like natural biofilms.

Pharmaceutical substances present at low concentrations in the environment may cause effects on biological systems such as microbial consortia living on solid riverbed substrates. These consortia are an important part of the river ecosystem as they form part of the food chain. This case study aims to contribute to an increased understanding of how low levels of pharmaceuticals in freshwater streams may influence sessile bacterial consortia. An important point source for pharmaceutical release into the environment is treated household sewage water. In order to investigate what types of effects may occur, we collected water samples as well as riverbed substrates from a small stream in the south of Sweden, Knivstaån, upstream and downstream from a sewage treatment plant (STP). Data from these samples formed the base of this case study where we investigated both the presence of pharmaceuticals in the water and bacterial composition on riverbed substrates. In the water downstream from the STP, 19 different pharmaceuticals were detected at levels below 800 ng/dm3. The microbial composition was obtained from sequencing 16S rRNA genes directly from substrates as well as from cultivated isolates. The cultivated strains showed reduced species variability compared with the data obtained directly from the substrates. No systematic differences were observed following the sampling season. However, differences could be seen between samples upstream and downstream from the STP effluent. We further observed large similarities in bacterial composition on natural stones compared to sterile stones introduced into the river approximately two months prior to sampling, giving indications for future sampling methodology of biofilms.

Aluminum (Al) is the most common metal in the Earth's crust, and exists mainly in the form of silicates, oxides and hydroxides, or in complexes with natural organic matter (NOM) or inorganic ligands. Since speciation is a key factor for understanding the environmental impact of Al, it is important to determine the chemical forms of Al that predominate in different natural media and under varying geochemical conditions. This study investigated how complexation with NOM influenced the speciation of Al(III) in different environmental samples (isolated aquatic NOM, organic soils and stream waters) using X-ray absorption spectroscopy (XAS) and Infrared (IR) spectroscopy. The combined spectroscopic results showed that Al(III) formed mononuclear complexes with carboxylic functional groups in NOM that were sufficiently stable to suppress the hydrolysis and polymerization of Al(III). These organic Al complexes were favored at slightly acidic pH values between pH 3 and 6 and at decreasing Al concentrations. The XAS results of the organic soils and the stream water samples indicated a variation in the speciation from a predominance of organically complexed Al in the stream waters to a mixture of Al-NOM complexes and precipitated Al phases (Al hydroxides and/or Al silicates) in the organic soils. Although the presented XAS results were limited by relatively low signal-to-noise caused by the low K-edge energy of Al, the combined spectroscopic results provided new and useful information about Al in different environmental samples and showed that NOM and pH are important parameters controlling the speciation of Al.

Analysis of sediment samples in the visible to mid infrared (IR) region requires small amounts of sample material and enables rapid and cost efficient geochemical analysis of mineral and organic sediment components. Here we use geochemical properties (total organic and inorganic carbon, biogenic silica, total nitrogen) from the ICDP deep drilling project PASADO to compare three different IR spectroscopy techniques: Diffuse Reflectance Fourier Transform IR Spectrometry (DRIFTS), Attenuated Total Reflectance Fourier Transform IR Spectroscopy (ATR-FTIRS) and Visible Near IR Spectroscopy (VNIRS). ATR-FTIRS and VNIRS are more rapid techniques compared to DRIFTS. Results show that calibration models developed using DRIFTS are most robust (correlation coefficient: R = 0.92 for TIC, R = 0.84 for BSi, R = 0.97 for TOC, R = 0.95 for TN). However, good statistical performance was also obtained by using ATR-FTIRS and VNIRS. When time and costs are limiting factors, these tools may be given preference for rapid biogeochemical screening.

The purpose of this study was to evaluate the spatial distribution of geochemistry in Swedish till and whether interpolations could predict unknown values of geochemistry between samples at a national spatial level, Sweden, and a regional, the county of Västerbotten. The information of the spatial distribution of the elements and the interpolations accurateness has several applications. For example, the establishing of infrastructure.  Which, in Sweden, is regulated by Naturvårdsverkets guidelines for sensitive land management (KM) and less sensitive land management (MKM) since elements can be harmful for the environment and health above certain levels. The guidelines for waste disposal of soil with levels of less than slight risk (MRR) does also acquire knowledge about the background levels of an area which are found in the C-horizon. The aim of the study was therefore to answer the following questions 1) Which interpolation method provides the most accurate prediction for the various elements at the national and regional level? 2) How does the calculated levels of geochemistry differ from the sampled ones for the two spatial levels? The study was conducted by studying the levels of ten elements in the C-horizon at the two spatial levels were the regional had greater sample density than the national. The interpolations that were used for these elements were the local interpolation methods kriging, inverse distance weighting (IDW), natural neighbour, thiessen polygons and triangular irregular network (TIN). Samples were gathered from Sweden’s geological Surveys (SGU) for the elements that are regulated by Naturvårdsverkets guidelines which was why these ten elements were studied: arsenic, barium, cobalt, chromium, copper, nickel, lead, antimony, vanadium, and zinc. The interpolations were done with two thirds of  the data. A validation was done with the remaining third by calculating root mean square error (RMSE). For the interpolation method with the lowest RMSE, the mean absolute square error (MAPE) was calculated for all the validation points to see how the calculated levels differed from the samples. The result showed that kriging and IDW were the most accurate interpolation methods for the data but that some of the studied elements need even greater sample density to become more correct. This can be solved by doing a cross-validation of the existing data. Furthermore, the interpolations were more accurate at the regional level for elements except antimony. The higher accuracy can be explained by the higher sample density at the regional level. At the national level the interpolations worked better in the north of Sweden than in the south which needs further studying. Overall, the interpolations were the least accurate when the levels of the elements were low, which may be the reason why antimony showed higher RMSE at the regional level. In conclusion the study showed that it is possible to use interpolations to predict values at unknown places with different accurateness.

Accumulation records of pollutant metals in peat have been frequently used to reconstruct past atmospheric deposition rates. While there is good support for peat as a record of relative changes in metal deposition over time, questions remain whether peat archives represent a quantitative or a qualitative record. Several processes can potentially influence the quantitative record of which downwashing is particularly pertinent as it would have a direct influence on how and where atmospherically deposited metals are accumulated in peat. The aim of our study was two-fold: first, to compare and contrast the retention of dissolved Pb, Cu, Zn and Ni in peat cores; and second, to test the influence of different precipitation intensities on the potential downwashing of metals. We applied four 'rainfall' treatments to 13 peat cores over a 3-week period, including both daily (2 or 5.3 mm day(-1)) and event-based additions (37 mm day(-1), added over 1 h or over a 10 h rain event). Two main trends were apparent: 1) there was a difference in retention of the added dissolved metals in the surface layer (0-2 cm): 21-85% for Pb, 18-63% for Cu, 10-25% for Zn and 10-20% for Ni. 2) For all metals and both peat types (sphagnum lawn and fen), the addition treatments resulted in different downwashing depths, i.e., as the precipitation-addition increased so did the depth at which added metals could be detected. Although the largest fraction of Pb and Cu was retained in the surface layer and the remainder effectively immobilized in the upper peat (<= 10 cm), there was a smearing effect on the overall retention, where precipitation intensity exerts an influence on the vertical distribution of added trace metals. These results indicate that the relative position of a deposition signal in peat records would be preserved, but it would be quantitatively attenuated. 

Several factors can affect the integrity of natural archives such as peat records, e.g., decomposition and nutrient cycling, and it has also been hypothesized that some rapid downward transport of atmospherically derived elements may occur. We test this hypothesis by analyzing the short-lived, natural tracer beryllium-7 (tA1/2A = 53.4 days) in five cores from two peatlands. In triplicate hummock cores from a raised bog in southern Sweden, Be-7 could be measured to 20, 18 and 8 cm depth, and in a nutrient-poor mire in northern Sweden to a depth of 16 cm in a Sphagnum lawn core, but only 4 cm in the dominant, more-decomposed fen peat, indicating some spatial variability both within and between sites. Total Be-7 inventories were 320-450 Bq m(-2) in the bog, and 150 Bq m(-2) (lawn) and 240 Bq m(-2) (fen peat) in the mire. 25-79 % of the total inventory of Be-7 was located in the upper 2-cm layer. To further test downwashing, in the laboratory we applied a CuBr-solution to two cores and a Cu-solution to one core taken from the mire Sphagnum lawn, all with low water table conditions. About 50 % of the added Cu and similar to 35 % of the added Br were retained in the surface (2 cm) layer; 1-3 % of the Cu was found at 8-12 cm depth and similar to 1 % of the Br was measured in the lowest level (20-22 cm). Based on our novel approach using Be-7 and experimental work we show that short-term downwashing can occur in peatlands and we suggest the depth of this will depend on the properties of the peat, e.g., bulk density and decomposition, as well as hydrology.

Accurate dating of peat accumulation is essential for quantitatively reconstructing past changes in atmospheric metal deposition and carbon burial. By analyzing fallout radionuclides Pb-210, Cs-137, Am-241, and Be-7, and total Pb and Hg in 5 cores from two Swedish peatlands we addressed the consequence of estimating accumulation rates due to downwashing of atmospherically supplied elements within peat. The detection of Be-7 down to 18-20 cm for some cores, and the broad vertical distribution of Am-241 without a well-defined peak, suggest some downward transport by percolating rainwater and smearing of atmospherically deposited elements in the uppermost peat layers. Application of the CRS age-depth model leads to unrealistic peat mass accumulation rates (400-600 g m(-2) yr(-1)), and inaccurate estimates of past Pb and Hg deposition rates and trends, based on comparisons to deposition monitoring data (forest moss biomonitoring and wet deposition). After applying a newly proposed IP-CRS model that assumes a potential downward transport of Pb-210 through the uppermost peat layers, recent peat accumulation rates (200-300 g m(-2) yr(-1)) comparable to published values were obtained. Furthermore, the rates and temporal trends in Pb and Hg accumulation correspond more closely to monitoring data, although some off-set is still evident. We suggest that downwashing can be successfully traced using Be-7, and if this information is incorporated into age-depth models, better calibration of peat records with monitoring data and better quantitative estimates of peat accumulation and past deposition are possible, although more work is needed to characterize how downwashing may vary between seasons or years.

The past decade has seen a rapid increase in interest in the biogeochemical record preserved in peat, particularly as it relates to carbon dynamics and environmental change. Importantly, recent studies show that carbon dynamics, that is, organic matter decomposition, can influence the record of atmospherically derived elements such as halogens and mercury. Most commonly, bulk density, light transmission, or carbon/nitrogen (C/N) ratios are used as a proxy to qualitatively infer the degree of decomposition in peat, but do these three proxies reflect the same patterns? Furthermore, how do each of these proxies relate to other geochemical data? To address these questions, we analyzed bulk density, light transmission, and C/N ratios, as well as multielement geochemistry (wavelength-dispersive x-ray fluorescence (WD-XRF)), in three hummock cores (70 cm in length, c. 500 years) from an ombrotrophic Swedish bog. To compare the proxies, we applied principal component analysis (PCA) to identify how the proxies relate to and interact with the geochemical matrix. This was coupled with changepoint modeling to identify and compare statistically significant changes for each proxy. Our results show differences between the proxies within and between cores, indicating each responds to a different part of the decomposition process. This is supported by the PCA, where the three proxies fall on different principal components. Changepoint analysis also showed that the inferred number of changepoints and their depths vary for each proxy and core. This suggests that decomposition is not fully captured by any one of these commonly used proxies, and thus, more than one proxy should be included.

The ability of coral reefs to engineer complex three-dimensional habitats is central to their success and the rich biodiversity they support. In tropical reefs, encrusting coralline algae bind together substrates and dead coral framework to make continuous reef structures, but beyond the photic zone, the cold-water coral Lophelia pertusa also forms large biogenic reefs, facilitated by skeletal fusion. Skeletal fusion in tropical corals can occur in closely related or juvenile individuals as a result of non-aggressive skeletal overgrowth or allogeneic tissue fusion, but contact reactions in many species result in mortality if there is no 'self-recognition' on a broad species level. This study reveals areas of 'flawless' skeletal fusion in Lophelia pertusa, potentially facilitated by allogeneic tissue fusion, are identified as having small aragonitic crystals or low levels of crystal organisation, and strong molecular bonding. Regardless of the mechanism, the recognition of 'self' between adjacent L. pertusa colonies leads to no observable mortality, facilitates ecosystem engineering and reduces aggression-related energetic expenditure in an environment where energy conservation is crucial. The potential for self-recognition at a species level, and subsequent skeletal fusion in framework-forming cold-water corals is an important first step in understanding their significance as ecological engineers in deep-seas worldwide.

Cold-water corals are associated with high local biodiversity, but despite their importance as ecosystem engineers, little is known about how these organisms will respond to projected ocean acidification. Since preindustrial times, average ocean pH has decreased from 8.2 to similar to 8.1, and predicted CO2 emissions will decrease by up to another 0.3 pH units by the end of the century. This decrease in pH may have a wide range of impacts upon marine life, and in particular upon calcifiers such as cold-water corals. Lophelia pertusa is the most widespread cold-water coral (CWC) species, frequently found in the North Atlantic. Here, we present the first short-term (21 days) data on the effects of increased CO2 (750 ppm) upon the metabolism of freshly collected L pertusa from Mingulay Reef Complex, Scotland, for comparison with net calcification. Over 21 days, corals exposed to increased CO2 conditions had significantly lower respiration rates (11.4 +/- 1.39 SE, gmol O-2 g(-1) tissue dry weight h(-1)) than corals in control conditions (28.6 +/- 7.30 SE mu mol O-2 g(-1) tissue dry weight h(-1)). There was no corresponding change in calcification rates between treatments, measured using the alkalinity anomaly technique and C-14 uptake. The decrease in respiration rate and maintenance of calcification rate indicates an energetic imbalance, likely facilitated by utilisation of lipid reserves. These data from freshly collected L pertusa from the Mingulay Reef Complex will help define the impact of ocean acidification upon the growth, physiology and structural integrity of this key reef framework forming species. 

Cold-water corals, such as Lophelia pertusa, are key habitat-forming organisms found throughout the world's oceans to 3000 m deep. The complex three-dimensional framework made by these vulnerable marine ecosystems support high biodiversity and commercially important species. Given their importance, a key question is how both the living and the dead framework will fare under projected climate change. Here, we demonstrate that over 12 months L. pertusa can physiologically acclimate to increased CO2, showing sustained net calcification. However, their new skeletal structure changes and exhibits decreased crystallographic and molecular-scale bonding organization. Although physiological acclimatization was evident, we also demonstrate that there is a negative correlation between increasing CO2 levels and breaking strength of exposed framework (approx. 20-30% weaker after 12 months), meaning the exposed bases of reefs will be less effective load-bearers', and will become more susceptible to bioerosion and mechanical damage by 2100.

A polymeric ion-exchange resin, incorporating methyl-amino-phosphonic (TP260) functionalities, and a solvent impregnated resin (SIR) incorporating tri-methylpentylphosphinic acid (TP272), were evaluated for the selective separation of Rare Earth Elements (REE) from Transition (TE), post -Transition (PTE), and Alkaline Earth (AE) Elements in acidic mine waters (AMW). The influence of the functional groups nature and the acidity dependence were studied and their effects on efficiencies for REE removal and separation from TE/PTE were analysed Both resins provided good separation factors of REE from TE/PTE by acidity control of the treated effluent once Fe (III), the major component in AMW, had been removed by precipitation. The TP272 resin, containing trimethylpentylphosphinic acid (Cyanex 272) onto the polymeric network, showed higher affinity towards Heavy REE (HRRE) than for Light REE (LRRE) by acidity control (pH > 4). Higher pre-concentration factors were achieved for TP272 impregnated resin (e.g., 20-30) in comparison with the TP260 phosphonic resin (2-5), as the pH extraction window is in the moderate pH region (1-5). The integration in series of both resins could be used to separate and recover HREE and LREE from TE/PTE from AMW generated concentrates could be used to recover REE as secondary resources for the clean energy technology industry.

Abstract Because of heterogeneous properties, dissolved organic matter (DOM) is known to control the environmental fate of a variety of organic pollutants and trace metals in aquatic systems. Here we report absorptive and fluorescence properties of DOM, in concurrence with concentrations of dissolved mercury (Hg), along the Xiaoqing River-Laizhou Bay estuary system located in the Bohai Sea of China. A mixing model consisting of the two end-members terrestrial and aquatic DOM demonstrated that terrestrial signatures decreased significantly from the river into the estuary. Quasi-conservative mixing behavior of DOM sources suggests that the variations in the average DOM composition were governed by physical processes (e.g., dilution) rather than by new production and/or degradation processes. In contrast to some previous studies of river-estuary systems, the Xiaoqing River-Laizhou Bay estuary system displayed a non-significant correlation between DOM and Hg quantities. Based on this and the variation of Hg concentration along the salinity gradient, we concluded that Hg showed a non-conservative mixing behavior of suggested end-member sources. Thus, rather than mixing, Hg concentration variations seemed to be controlled by biogeochemical processes.

Neurotoxic methylmercury (MeHg) formed from inorganic divalent mercury (HgII) accumulates in aquatic biota and remains at high levels worldwide. It is poorly understood to what extent different geochemical Hg pools contribute to these levels. Here we report quantitative data on MeHg formation and bioaccumulation, in mesocosm water-sediment model ecosystems, using five HgII and MeHg isotope tracers simulating recent Hg inputs to the water phase and Hg stored in sediment as bound to natural organic matter or as metacinnabar. Calculations for an estuarine ecosystem suggest that the chemical speciation of HgII solid/adsorbed phases control the sediment Hg pool's contribution to MeHg, but that input of MeHg from terrestrial and atmospheric sources bioaccumulates to a substantially greater extent than MeHg formed in situ in sediment. Our findings emphasize the importance of MeHg loadings from catchment runoff to MeHg content in estuarine biota and we suggest that this contribution has been underestimated.

Schwertmannite precipitated from acid mine drainage at the Kristineberg Zn-Cu mine in northern Sweden has been characterised regarding elemental composition, phase transformation as a function of pH and time. SO42- release and speciation of SO42- associated with the solid. The elemental analysis gave the composition FeSOS(OH)(5.02)(-SO4)(1.49) . 0.5H(2)O where approximately 1/3 of the SO42- is adsorbed to the surface. The conversion of schwertmannite to goethite at pH 9 was complete within 187 days; at pH 6. the conversion was still incomplete after 514 days. Lower pH and relatively high SO42- concentration decreased the conversion even further. Also temperature was shown to be an important parameter for this process and low temperature (+4 degreesC) effectively stopped the transformation at pH 3. The release of SO42- was linear with pH and X-ray photoelectron spectroscopy measurements confirming that the surface bound SO42- was released before bulk SO42-. Zeta potential measurements indicate a pH(IEP) of 7.2 for the schwertmannite sample. Prior to conversion into goethite, the SO42- associated with schwertmannite was indicated by attenuated total reflectance FTIR spectroscopy to be present both as bulk and surface species. Furthermore: the speciation of surface SO42- was shown to vary with pH and two predominating species were detected. As pH increases. SO42- is increasingly Coordinated in an outer sphere mode whereas a stronger. possibly inner sphere, complex dominates. at low pH.