Small molecules dominate organic phosphorus in NaOH-EDTA extracts of soils as determined by 31P NMR.

Understanding the composition of organic phosphorus (P) in soils is relevant to various disciplines, from agricultural sciences to ecology. Despite past efforts, the precise nature of soil organic P remains an enigma, especially that of the orthophosphate monoesters, which dominate 31P NMR spectra of NaOH-EDTA extracts of soils worldwide. The monoester region often exhibits an unidentified, broad background believed to represent high molecular weight (MW) P. We investigated this monoester background using 1D 31P NMR and 2D 1H31P NMR, as well as 31P transverse relaxation (T2) measurements to calculate its intrinsic linewidth and relate it to MW. Analyzing seven soils from different ecosystems, we observed linewidths of 0.5 to 3 Hz for resolved monoester signals and the background, indicating that it consists of many, possibly >100, sharp signals associated with small (<1.5 kDa) organic P molecules. This result was further supported by 2D 1H31P NMR spectra revealing signals not resolved in the 1D spectra. Our findings align with 31P NMR studies detecting background signals in soil-free samples and modern evidence that alkali-soluble soil organic matter consists of self-assemblies of small organic compounds mimicking large molecules.

Catchment characteristics control boreal mire nutrient regime and vegetation patterns over ~5000 years of landscape development.

Vegetation holds the key to many properties that make natural mires unique, such as surface microtopography, high biodiversity values, effective carbon sequestration and regulation of water and nutrient fluxes across the landscape. Despite this, landscape controls behind mire vegetation patterns have previously been poorly described at large spatial scales, which limits the understanding of basic drivers underpinning mire ecosystem services. We studied catchment controls on mire nutrient regimes and vegetation patterns using a geographically constrained natural mire chronosequence along the isostatically rising coastline in Northern Sweden. By comparing mires of different ages, we can partition vegetation patterns caused by long-term mire succession (<5000 years) and present-day vegetation responses to catchment eco-hydrological settings. We used the remote sensing based normalized difference vegetation index (NDVI) to describe mire vegetation and combined peat physicochemical measures with catchment properties to identify the most important factors that determine mire NDVI. We found strong evidence that mire NDVI depends on nutrient inputs from the catchment area or underlying mineral soil, especially concerning phosphorus and potassium concentrations. Steep mire and catchment slopes, dry conditions and large catchment areas relative to mire areas were associated with higher NDVI. We also found long-term successional patterns, with lower NDVI in older mires. Importantly, the NDVI should be used to describe mire vegetation patterns in open mires if the focus is on surface vegetation, since the canopy cover in tree-covered mires completely dominated the NDVI signal. With our study approach, we can quantitatively describe the connection between landscape properties and mire nutrient regime. Our results confirm that mire vegetation responds to the upslope catchment area, but importantly, also suggest that mire and catchment aging can override the role of catchment influence. This effect was clear across mires of all ages, but was strongest in younger mires.

Wide-spread microbial sulfate reduction (MSR) in northern European freshwater systems: Drivers, magnitudes and seasonality.

Microbial sulfate reduction (MSR), which transforms sulfate into sulfide through the consumption of organic matter, is an integral part of sulfur and carbon cycling. Yet, the knowledge on MSR magnitudes is limited and mostly restricted to snap-shot conditions in specific surface water bodies. Potential impacts of MSR have consequently been unaccounted for, e.g., in regional or global weathering budgets. Here, we synthesize results from previous studies on sulfur isotope dynamics in stream water samples and apply a sulfur isotopic fractionation and mixing scheme combined with Monte Carlo simulations to derive MSR in entire hydrological catchments. This allowed comparison of magnitudes both within and between five study areas located between southern Sweden and the Kola Peninsula, Russia. Our results showed that the freshwater MSR ranged from 0 to 79 % (interquartile range of 19 percentage units) locally within the catchments, with average values from 2 to 28 % between the catchments, displaying a non-negligible catchment-average value of 13 %. The combined abundance or deficiency of several landscape elements (e.g., the areal percentage of forest and lakes/wetlands) were found to indicate relatively well whether or not catchment-scale MSR would be high. A regression analysis showed specifically that average slope was the individual element that best reflected the MSR magnitude, both at sub-catchment scale and between the different study areas. However, the regression results of individual parameters were generally weak. The MSR-values additionally showed differences between seasons, in particular in wetland/lake dominated catchments. Here MSR was high during the spring flood, which is consistent with the mobilization of water that under low-flow winter periods have developed the needed anoxic conditions for sulfate-reducing microorganisms. This study presents for the first time compelling evidence from multiple catchments of wide-spread MSR at levels slightly above 10 %, implying that the terrestrial pyrite oxidation may be underestimated in global weathering budgets.

The missing pieces for better future predictions in subarctic ecosystems: A Torneträsk case study.

Arctic and subarctic ecosystems are experiencing substantial changes in hydrology, vegetation, permafrost conditions, and carbon cycling, in response to climatic change and other anthropogenic drivers, and these changes are likely to continue over this century. The total magnitude of these changes results from multiple interactions among these drivers. Field measurements can address the overall responses to different changing drivers, but are less capable of quantifying the interactions among them. Currently, a comprehensive assessment of the drivers of ecosystem changes, and the magnitude of their direct and indirect impacts on subarctic ecosystems, is missing. The Torneträsk area, in the Swedish subarctic, has an unrivalled history of environmental observation over 100 years, and is one of the most studied sites in the Arctic. In this study, we summarize and rank the drivers of ecosystem change in the Torneträsk area, and propose research priorities identified, by expert assessment, to improve predictions of ecosystem changes. The research priorities identified include understanding impacts on ecosystems brought on by altered frequency and intensity of winter warming events, evapotranspiration rates, rainfall, duration of snow cover and lake-ice, changed soil moisture, and droughts. This case study can help us understand the ongoing ecosystem changes occurring in the Torneträsk area, and contribute to improve predictions of future ecosystem changes at a larger scale. This understanding will provide the basis for the future mitigation and adaptation plans needed in a changing climate.

Stream metabolism controls diel patterns and evasion of CO2 in Arctic streams.

Streams play an important role in the global carbon (C) cycle, accounting for a large portion of CO2 evaded from inland waters despite their small areal coverage. However, the relative importance of different terrestrial and aquatic processes driving CO2 production and evasion from streams remains poorly understood. In this study, we measured O2 and CO2 continuously in streams draining tundra-dominated catchments in northern Sweden, during the summers of 2015 and 2016. From this, we estimated daily metabolic rates and CO2 evasion simultaneously and thus provide insight into the role of stream metabolism as a driver of C dynamics in Arctic streams. Our results show that aquatic biological processes regulate CO2 concentrations and evasion at multiple timescales. Photosynthesis caused CO2 concentrations to decrease by as much as 900 ppm during the day, with the magnitude of this diel variation being strongest at the low-turbulence streams. Diel patterns in CO2 concentrations in turn influenced evasion, with up to 45% higher rates at night. Throughout the summer, CO2 evasion was sustained by aquatic ecosystem respiration, which was one order of magnitude higher than gross primary production. Furthermore, in most cases, the contribution of stream respiration exceeded CO2 evasion, suggesting that some stream reaches serve as net sources of CO2 , thus creating longitudinal heterogeneity in C production and loss within this stream network. Overall, our results provide the first link between stream metabolism and CO2 evasion in the Arctic and demonstrate that stream metabolic processes are key drivers of the transformation and fate of terrestrial organic matter exported from these landscapes.

Industrial and natural compounds in filter-feeding black fly larvae and water in 3 tundra streams.

We report concentrations of polychlorinated biphenyls, polybrominated diphenyl ethers, novel flame retardants, and naturally occurring bromoanisoles in water and filter-feeding black fly (Simuliidae) larvae in 3 tundra streams in northern Sweden. The results demonstrate that black fly larvae accumulate a wide range of organic contaminants and can be used as bioindicators of water pollution in Arctic streams. Environ Toxicol Chem 2018;37:3011-3017. © 2018 SETAC.

Emissions from thaw ponds largely offset the carbon sink of northern permafrost wetlands.

Northern regions have received considerable attention not only because the effects of climate change are amplified at high latitudes but also because this region holds vast amounts of carbon (C) stored in permafrost. These carbon stocks are vulnerable to warming temperatures and increased permafrost thaw and the breakdown and release of soil C in the form of carbon dioxide (CO2) and methane (CH4). The majority of research has focused on quantifying and upscaling the effects of thaw on CO2 and CH4 emissions from terrestrial systems. However, small ponds formed in permafrost wetlands following thawing have been recognized as hotspots for C emissions. Here, we examined the importance of small ponds for C fluxes in two permafrost wetland ecosystems in northern Sweden. Detailed flux estimates of thaw ponds during the growing season show that ponds emit, on average (±SD), 279 ± 415 and 7 ± 11 mmol C m-2 d-1 of CO2 and CH4, respectively. Importantly, addition of pond emissions to the total C budget of the wetland decreases the C sink by ~39%. Our results emphasize the need for integrated research linking C cycling on land and in water in order to make correct assessments of contemporary C balances.

Global change-driven effects on dissolved organic matter composition: Implications for food webs of northern lakes.

Northern ecosystems are experiencing some of the most dramatic impacts of global change on Earth. Rising temperatures, hydrological intensification, changes in atmospheric acid deposition and associated acidification recovery, and changes in vegetative cover are resulting in fundamental changes in terrestrial-aquatic biogeochemical linkages. The effects of global change are readily observed in alterations in the supply of dissolved organic matter (DOM)-the messenger between terrestrial and lake ecosystems-with potentially profound effects on the structure and function of lakes. Northern terrestrial ecosystems contain substantial stores of organic matter and filter or funnel DOM, affecting the timing and magnitude of DOM delivery to surface waters. This terrestrial DOM is processed in streams, rivers, and lakes, ultimately shifting its composition, stoichiometry, and bioavailability. Here, we explore the potential consequences of these global change-driven effects for lake food webs at northern latitudes. Notably, we provide evidence that increased allochthonous DOM supply to lakes is overwhelming increased autochthonous DOM supply that potentially results from earlier ice-out and a longer growing season. Furthermore, we assess the potential implications of this shift for the nutritional quality of autotrophs in terms of their stoichiometry, fatty acid composition, toxin production, and methylmercury concentration, and therefore, contaminant transfer through the food web. We conclude that global change in northern regions leads not only to reduced primary productivity but also to nutritionally poorer lake food webs, with discernible consequences for the trophic web to fish and humans.

Persistent nitrogen limitation of stream biofilm communities along climate gradients in the Arctic.

Climate change is rapidly reshaping Arctic landscapes through shifts in vegetation cover and productivity, soil resource mobilization, and hydrological regimes. The implications of these changes for stream ecosystems and food webs is unclear and will depend largely on microbial biofilm responses to concurrent shifts in temperature, light, and resource supply from land. To study those responses, we used nutrient diffusing substrates to manipulate resource supply to biofilm communities along regional gradients in stream temperature, riparian shading, and dissolved organic carbon (DOC) loading in Arctic Sweden. We found strong nitrogen (N) limitation across this gradient for gross primary production, community respiration and chlorophyll-a accumulation. For unamended biofilms, activity and biomass accrual were not closely related to any single physical or chemical driver across this region. However, the magnitude of biofilm response to N addition was: in tundra streams, biofilm response was constrained by thermal regimes, whereas variation in light availability regulated this response in birch and coniferous forest streams. Furthermore, heterotrophic responses to experimental N addition increased across the region with greater stream water concentrations of DOC relative to inorganic N. Thus, future shifts in resource supply to these ecosystems are likely to interact with other concurrent environmental changes to regulate stream productivity. Indeed, our results suggest that in the absence of increased nutrient inputs, Arctic streams will be less sensitive to future changes in other habitat variables such as temperature and DOC loading.

Multiple sources and sinks of dissolved inorganic carbon across Swedish streams, refocusing the lens of stable C isotopes.

It is well established that stream dissolved inorganic carbon (DIC) fluxes play a central role in the global C cycle, yet the sources of stream DIC remain to a large extent unresolved. Here, we explore large-scale patterns in δ13C-DIC from streams across Sweden to separate and further quantify the sources and sinks of stream DIC. We found that stream DIC is governed by a variety of sources and sinks including biogenic and geogenic sources, CO2 evasion, as well as in-stream processes. Although soil respiration was the main source of DIC across all streams, a geogenic DIC influence was identified in the northernmost region. All streams were affected by various degrees of atmospheric CO2 evasion, but residual variance in δ13C-DIC also indicated a significant influence of in-stream metabolism and anaerobic processes. Due to those multiple sources and sinks, we emphasize that simply quantifying aquatic DIC fluxes will not be sufficient to characterise their role in the global C cycle.

Boreal Forests Sequester Large Amounts of Mercury over Millennial Time Scales in the Absence of Wildfire.

Alterations in fire activity due to climate change and fire suppression may have profound effects on the balance between storage and release of carbon (C) and associated volatile elements. Stored soil mercury (Hg) is known to volatilize due to wildfires and this could substantially affect the land-air exchange of Hg; conversely the absence of fires and human disturbance may increase the time period over which Hg is sequestered. Here we show for a wildfire chronosequence spanning over more than 5000 years in boreal forest in northern Sweden that belowground inventories of total Hg are strongly related to soil humus C accumulation (R2 = 0.94, p < 0.001). Our data clearly show that northern boreal forest soils have a strong sink capacity for Hg, and indicate that the sequestered Hg is bound in soil organic matter pools accumulating over millennia. Our results also suggest that more than half of the Hg stock in the sites with the longest time since fire originates from deposition predating the onset of large-scale anthropogenic emissions. This study emphasizes the importance of boreal forest humus soils for Hg storage and reveals that this pool is likely to persist over millennial time scales in the prolonged absence of fire.

Plant and microbial responses to nitrogen and phosphorus addition across an elevational gradient in subarctic tundra.

Temperature and nutrients are major limiting factors in subarctic tundra. Experimental manipulation of nutrient availability along elevational gradients (and thus temperature) can improve our understanding of ecological responses to climate change. However, no study to date has explored impacts of nutrient addition along a tundra elevational gradient, or across contrasting vegetation types along any elevational gradient. We set up a full factorial nitrogen (N) and phosphorus (P) fertilization experiment in each of two vegetation types (heath and meadow) at 500 m, 800 m, and 1000 m elevation in northern Swedish tundra. We predicted that plant and microbial communities in heath or at lower elevations would be more responsive to N addition while communities in meadow or at higher elevations would be more responsive to P addition, and that fertilizer effects would vary more with elevation for the heath than for the meadow. Although our results provided little support for these predictions, the relationship between nutrient limitation and elevation differed between vegetation types. Most plant and microbial properties were responsive to N and/or P fertilization, but responses often varied with elevation and/or vegetation type. For instance, vegetation density significantly increased with N + P fertilization relative to the other fertilizer treatments, and this increase was greatest at the lowest elevation for the heath but at the highest elevation for the meadow. Arbuscular mycorrhizae decreased with P fertilization at 500 m for the meadow, but with all fertilizer treatments in both vegetation types at 800 m. Fungal to bacterial ratios were enhanced by N+ P fertilization for the two highest elevations in the meadow only. Additionally, microbial responses to fertilization were primarily direct rather than indirect via plant responses, pointing to a decoupled response of plant and microbial communities to nutrient addition and elevation. Because our study shows how two community types differ in their responses to fertilization and elevation, and because the temperature range across this gradient is approximately 3 degrees C, our study is informative about how nutrient limitation in tundra may be influenced by temperature shifts that are comparable to those expected under climate change during this century.

Bioavailable soil phosphorus decreases with increasing elevation in a subarctic tundra landscape.

Phosphorus (P) is an important macronutrient in arctic and subarctic tundra and its bioavailability is regulated by the mineralization of organic P. Temperature is likely to be an important control on P bioavailability, although effects may differ across contrasting plant communities with different soil properties. We used an elevational gradient in northern Sweden that included both heath and meadow vegetation types at all elevations to study the effects of temperature, soil P sorption capacity and oxalate-extractable aluminium (Alox) and iron (Feox) on the concentration of different soil P fractions. We hypothesized that the concentration of labile P fractions would decrease with increasing elevation (and thus declining temperature), but would be lower in meadow than in heath, given that N to P ratios in meadow foliage are higher. As expected, labile P in the form of Resin-P declined sharply with elevation for both vegetation types. Meadow soils did not have lower concentrations of Resin-P than heath soils, but they did have 2-fold and 1.5-fold higher concentrations of NaOH-extractable organic P and Residual P, respectively. Further, meadow soils had 3-fold higher concentrations of Alox + Feox and a 20% higher P sorption index than did heath soils. Additionally, Resin-P expressed as a proportion of total soil P for the meadow was on average half that in the heath. Declining Resin-P concentrations with elevation were best explained by an associated 2.5-3.0 °C decline in temperature. In contrast, the lower P availability in meadow relative to heath soils may be associated with impaired organic P mineralization, as indicated by a higher accumulation of organic P and P sorption capacity. Our results indicate that predicted temperature increases in the arctic over the next century may influence P availability and biogeochemistry, with consequences for key ecosystem processes limited by P, such as primary productivity.

Atmospheric deposition of persistent organic pollutants and chemicals of emerging concern at two sites in northern Sweden.

Bimonthly bulk atmospheric deposition samples (precipitation + dry particle) were taken for one year at an arctic (Abisko, 68°20' N, 19°03' E) and a sub-arctic (Krycklan 64°14' N, 19°46' E) location in northern Sweden using Amberlite IRA-743 as an absorbent for hydrophobic pollutants. The samples were analyzed by gas chromatography-high resolution mass spectrometry (GC-HRMS) for polychlorinated biphenyls (PCBs), legacy organochlorine pesticides (OCPs = hexachlorocyclohexanes and chlordane-related compounds), polybrominated diphenyl ethers (PBDEs) and emerging chemicals. Higher deposition rates of most compounds were observed at the more northern site despite its receiving less precipitation and being more remote. HCHs and PCBs made up the bulk of the total deposition at both sites. Five emerging chemicals were detected: the current-use pesticides trifluralin and chlorothalonil; and non-BDE flame retardants 1,2-dibromo-4-(1,2-dibromoethyl)cyclohexane (TBECH), 1,2-bis(2,4,6-tribromophenoxy) ethane (BTBPE), and Dechlorane Plus (DP). A decrease in the fraction of the anti isomer of DP was observed at the arctic site, indicating isomer-selective degradation or isomerization during long range transport. Air parcel back trajectories revealed a greater influence from air originating over the ocean at the more northern site. The differences in these air sources were reflected in higher ∑HCH to ∑PCB ratios compared to the more southern site, as HCHs are related to volatilization from the ocean and Abisko is located <100 km from the Norwegian coast, while PCBs are emitted from continental sources.

Surface complexes of monomethyl phosphate stabilized by hydrogen bonding on goethite (α-FeOOH) nanoparticles.

Typically, a significant fraction of phosphorus in soils is composed of organic phosphates, and this fraction thus plays an important role in the global phosphorus cycle. Here we have studied adsorption of monomethyl phosphate (MMP) to goethite (α-FeOOH) as a model system in order to better understand the mechanisms behind adsorption of organic phosphates to soil minerals, and how adsorption affects the stability of these molecules. The adsorption reactions and stability of MMP on goethite were studied at room temperature as a function of pH, time and total concentration of MMP by means of quantitative batch experiments, potentiometry and infrared spectroscopy. MMP was found to be stable at the water-goethite interface within the pH region 3-9 and over extended periods of time, as well as in solution. The infrared spectra indicated that MMP formed three predominating pH-dependent surface complexes on goethite, and that these interacted monodentately with surface Fe. The complexes differed in hydrogen bonding interactions via the auxiliary oxygens of the phosphate group. The presented surface complexation model was based on the collective spectroscopic and macroscopic results, using the Basic Stern approach to describe the interfacial region. The model consisted of three monodentate inner sphere surface complexes where the MMP complexes were stabilized by hydrogen bonding to a neighboring surface site. The three complexes, which had equal proton content and thus could be defined as surface isomers, were distinguished by the distribution of charge over the 0-plane and ß-plane. In the high pH-range, MMP acted as a hydrogen bond acceptor whereas it was a hydrogen bond donor at low pH.

High-resolution characterization of organic phosphorus in soil extracts using 2D 1H-31P NMR correlation spectroscopy.

Organic phosphorus (P) compounds represent a major component of soil P in many soils and are key sources of P for microbes and plants. Solution NMR (nuclear magnetic resonance spectroscopy) is a powerful technique for characterizing organic P species. However, (31)P NMR spectra are often complicated by overlapping peaks, which hampers identification and quantification of the numerous P species present in soils. Overlap is often exacerbated by the presence of paramagnetic metal ions, even if they are in complexes with EDTA following NaOH/EDTA extraction. By removing paramagnetic impurities using a new precipitation protocol, we achieved a dramatic improvement in spectral resolution. Furthermore, the obtained reduction in line widths enabled the use of multidimensional NMR methods to resolve overlapping (31)P signals. Using the new protocol on samples from two boreal humus soils with different Fe contents, 2D (1)H-(31)P correlation spectra allowed unambiguous identification of a large number of P species based on their (31)P and (1)H chemical shifts and their characteristic coupling patterns, which would not have been possible using previous protocols. This approach can be used to identify organic P species in samples from both terrestrial and aquatic environments increasing our understanding of organic P biogeochemistry.

Enzymatic hydrolysis of organic phosphates adsorbed on mineral surfaces.

Esters of phosphoric acid constitute a sizable fraction of the total phosphorus supply in the environment and thus play an important role in the global phosphorus cycle. Enzymatic hydrolysis of these esters to produce orthophosphate is often a required reaction preceding phosphorus uptake by plants and microorganisms. Generally, adsorption to environmental particles is assumed to limit this process. Here we show, however, that the rate of enzymatic hydrolysis of glucose-1-phosphate (G1P) adsorbed on goethite by acid phosphatase (AcPase) can be of the same order of magnitude as in aqueous solution. The surface process releases carbon to the solution whereas orthophosphate remains adsorbed on goethite. This hydrolysis reaction is strictly an interfacial process governed by the properties of the interface. A high surface concentration of substrate mediates the formation of a catalytically active layer of AcPase, and although adsorption likely reduces the catalytic efficiency of the enzyme, this reduction is almost balanced by the fact that enzyme and substrate are concentrated at the mineral surfaces. Our results suggest that mineral surfaces with appropriate surface properties can be very effective in concentrating substrates and enzymes thereby creating microchemical environments of high enzymatic activity. Hence, also strongly adsorbed molecules in soils and aquatic environments may be subjected to biodegradation by extracellular enzymes.

Within- and across-species responses of plant traits and litter decomposition to elevation across contrasting vegetation types in subarctic tundra.

Elevational gradients are increasingly recognized as a valuable tool for understanding how community and ecosystem properties respond to climatic factors, but little is known about how plant traits and their effects on ecosystem processes respond to elevation. We studied the response of plant leaf and litter traits, and litter decomposability across a gradient of elevation, and thus temperature, in subarctic tundra in northern Sweden for each of two contrasting vegetation types, heath and meadow, dominated by dwarf shrubs and herbaceous plants respectively. This was done at each of three levels; across species, within individual species, and the plant community using a community weighted average approach. Several leaf and litter traits shifted with increasing elevation in a manner consistent with greater conservation of nutrients at all three levels, and the most consistent response was an increase in tissue N to P ratio. However, litter decomposition was less directly responsive to elevation because the leaf and litter traits which were most responsive to elevation were not necessarily those responsible for driving decomposition. At the community level, the response to elevation of foliar and litter traits, and decomposability, varied greatly among the two vegetation types, highlighting the importance of vegetation type in determining ecological responses to climatic factors such as temperature. Finally our results highlight how understanding the responses of leaf and litter characteristics of functionally distinct vegetation types, and the processes that they drive, to temperature helps provide insights about how future climate change could affect tundra ecosystems.

Lichen responses to nitrogen and phosphorus additions can be explained by the different symbiont responses.

• Responses to simulated nitrogen (N) deposition with or without added phosphorus (P) were investigated for three contrasting lichen species - the N-sensitive Alectoria sarmentosa, the more N-tolerant Platismatia glauca and the N(2) -fixing Lobaria pulmonaria- in a field experiment. • To examine whether nutrient limitation differed between the photobiont and the mycobiont within the lichen, the biomass responses of the respective bionts were estimated. • The lichenized algal cells were generally N-limited, because N-stimulated algal growth in all three species. The mycobiont was P-limited in one species (A. sarmentosa), but the growth response of the mycobionts was complex, as fungal growth is also dependent on a reliable carbon export from the photobiont, which may have been the reason for the decrease of the mycobiont with N addition in P. glauca. • Our findings showed that P availability was an important factor when studying effects of N deposition, as P supply can both mitigate and intensify the negative effects of N on epiphytic lichens.

Adsorption mechanisms of glucose in aqueous goethite suspensions.

The adsorption of glucose and polysaccharides onto solid surfaces is important in several areas of science and engineering including soil chemistry and mineral processing. In this work we have studied the adsorption of D-glucose at the water-goethite (α-FeOOH) interface as a function of pH using batch adsorption measurements and a simultaneous infrared and potentiometric technique. Molecular orbital calculations were also performed in order to support interpretations of the infrared spectroscopic data. Infrared spectroscopy has shown that glucose adsorbs at the water-goethite interface with an intact ring structure and that the ß-form is favored relative to the α isomer. The collective spectroscopic and macroscopic results were fully consistent with an adsorption mechanism where glucose interacts with goethite surface sites via hydrogen bonding interactions. Specific infrared peak shifts indicated that glucose primarily acts as a hydrogen bond donor and that it interacts with acceptor sites that become increasingly more prevalent as the surface is deprotonated. These results are in general agreement with the acid/base model for mono- and polysaccharide interactions at metal oxide surfaces, but contradict the inner sphere hypothesis that was proposed based on ex situ spectroscopic measurements.