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Soluble reactive phosphorus (SRP) concentrations in agricultural headwaters can display pronounced seasonal variability at low flow, often with the highest concentrations occurring in summer. These SRP concentrations often exceed eutrophication levels, but their main sources, spatial distribution, and temporal dynamics are often unknown. The purpose of this study is therefore to differentiate between potential SRP losses and releases from soil drainage, anoxic riparian wetlands, and stream sediments in an agricultural headwater catchment. To identify the dominant SRP sources, we carried out three longitudinal stream sampling campaigns for SRP concentrations and fluxes. We used salt dilution tests and natural 222Rn to determine water fluxes in different sections of the stream, and we sampled for SRP, Fe, and 14C dissolved organic carbon (DOC) to examine possible redox-mediated mobilization from riparian wetlands and stream sediments. The results indicate that a single short section in the upper headwater reach was responsible for most of the SRP fluxes to the stream. Analysis of samples taken under summer low-flow conditions revealed that the stream water SRP concentrations, the fraction of SRP within total dissolved P (TDP), and DOC radiocarbon ages matched those in the groundwater entering the gaining section. Pore water from the stream sediment showed evidence of reductive mobilization of SRP, but the exchange fluxes were probably too small to contribute substantially to SRP stream concentrations. We also found no evidence that shallow flow paths from riparian wetlands contributed to the observed SRP loads in the stream. Combined, the results of this campaign and previous monitoring suggest that groundwater is the main long-term contributor of SRP at low flow, and agricultural phosphorus is largely buffered in the soil zone. We argue that the seasonal variation of SRP concentrations was mainly caused by variations in the proportion of groundwater present in the streamflow, which was highest during summer low-flow periods. Accurate knowledge of the various input pathways is important for choosing effective management measures in a given catchment, as it is also possible that observations of seasonal SRP dilution patterns stem from increased mobilization in riparian zones or from point sources.

Mercury accumulation in lake sediments is a widespread environmental problem due to the biomagnification of Hg in the aquatic food chain. Soil Hg concentrations, catchment vegetation, erosion, and lake productivity are major factors controlling the accumulation of Hg in lakes. However, their influence on the Hg mass balance in lakes with different catchment characteristics and trophic state is poorly understood. In this multilake study, we decipher the effects of catchment vegetation (coniferous vs. deciduous forest), soil Hg content, and trophic state on Hg sedimentation at six lakes in Germany. We investigated Hg concentrations in leaves, soils, and the lake's water phase. Soils under coniferous stands show slightly higher Hg concentrations than under deciduous forest. Hg concentrations in the water phase were higher in the oligotrophic brown water lakes (8.1 ± 5.6 ng L−1 vs. 3.0 ± 1.9 ng L−1). Lower Hg concentrations in sediment trap material indicate dilution by algae organic matter in the mesotrophic lakes (0.12–0.17 μg g−1 vs. 0.57–0.89 μg g−1). However, Hg accumulation rates in sediment traps were up to 14‐fold higher in the mesotrophic lakes (113–443 μg m−2 yr−1) than in the brown water lakes (32–144 μg m−2 yr−1), which could not be explained by higher Hg fluxes to the productive lakes. Hg mass balance calculation reveals that water phase Hg scavenging by algae is the major reason for the intense Hg export to the sediments of productive lakes which makes them significantly larger sedimentary sinks than oligotrophic brown water lakes., Deutsche Forschungsgemeinschaft http://dx.doi.org/10.13039/501100001659

Understanding groundwater–surface water (GW–SW) interactions is vital for water management in karstic catchments due to its impact on water quality. The objective of this study was to evaluate and compare the applicability of seven environmental tracers to quantify and localize groundwater exfiltration into a small, human‐impacted karstic river system. Tracers were selected based on their emission source to the surface water either as (a) dissolved, predominantly geogenic compounds (radon‐222, sulphate and electrical conductivity) or (b) anthropogenic compounds (predominantly) originating from wastewater treatment plant (WWTP) effluents (carbamazepine, tramadol, sodium, chloride). Two contrasting sampling approaches were compared (a) assuming steady‐state flow conditions and (b) considering the travel time of the water parcels (Lagrangian sampling) through the catchment to account for diurnal changes in inflow from the WWTP. Spatial variability of the concentrations of all tracers indicated sections of preferential groundwater inflow. Lagrangian sampling techniques seem highly relevant for capturing dynamic concentration patterns of WWTP‐derived compounds. Quantification of GW inflow with the finite element model FINIFLUX, based on observed in‐stream Rn activities led to plausible fluxes along the investigated river reaches (0.265 m3 s−1), while observations of other natural or anthropogenic environmental tracers produced less plausible water fluxes. Important point sources of groundwater exfiltration can be ascribed to locations where the river crosses geological fault lines. This indicates that commonly applied concepts describing groundwater–surface water interactions assuming diffuse flow in porous media are difficult to transfer to karstic river systems whereas concepts from fractured aquifers may be more applicable. In general, this study helps selecting the best suited hydrological tracer for GW exfiltration and leads to a better understanding of processes controlling groundwater inflow into karstic river systems., Karst aquifers represent an increased complexity when aiming to measure the interaction between groundwater and river water. Combining field‐based measurements on catchment scale and modelling, the applicability of ‘classical’ environmental groundwater tracers was compared to selected organic (micro)pollutants often considered as conservative and originally arising from a wastewater treatment plant. This study demonstrates that the choice of an appropriate tracer is crucial when either aiming to quantify groundwater exfiltration into karstic river systems, or indicating hydrological processes, applying (globally) omnipresent pollutants., German Research Foundation (DFG) http://dx.doi.org/10.13039/501100001659

International audience; Key Points: Lumped parameter modeling of hyporheic nitrate removal by applying the exposure time concept.  Exposure time distributions are derived from analytical residence time distributions and reaction kinetics for hyporheic oxygen consumption.  Using exposure times rather than residence times is likely to lead to more realistic estimates for nutrient removal in the hyporheic zone Abstract The rate of biogeochemical processing associated with natural degradation and transformation processes in the hyporheic zone (HZ) is one of the largest uncertainties in predicting nutrient fluxes. We present a lumped parameter (LPM) model that can be used to quantify the mass loss for nitrate in the HZ operating at the scale of river reaches to entire catchments. The model is based on using exposure times (ET) to account for the effective timescales of reactive transport in the HZ. Reach scale ET distributions are derived by removing the portion of hyporheic residence times (RT) associated with flow through the oxic zone. The model was used to quantify nitrate removal for two scenarios: 1) a 100 m generic river reach and 2) a small agricultural catchment in Brittany (France). For the field site hyporheic RT are derived from measured in-stream 222 Rn activities and mass balance modelling. Simulations were carried out using different types of RT distributions (exponential, power-law and gamma type) for which ET were derived. Mass loss of nitrate in the HZ for the field site ranged from 0-0.45 kg d-1 depending on the RT distribution and the availability of oxygen in the streambed sediments. Simulations with power law ET distribution models only show very little removal of nitrate due to the heavy weighting towards shorter flow paths that are confined to the oxic sediments. Based on the simulation results, we suggest that ET likely lead to more realistic estimates for nutrient removal.

23 pags., 10 figs., 4 tabs., In this work, we describe the compilation and homogenization of an extensive data set of aerosol iodine field observations in the period between 1963 and 2018 and we discuss its spatial and temporal dependences by comparison with CAM-Chem model simulations. A close to linear relationship between soluble and total iodine in aerosol is found (∼80% aerosol iodine is soluble), which enables converting a large subset of measurements of soluble iodine into total iodine. The resulting data set shows a distinct latitudinal dependence, with an enhancement toward the Northern Hemisphere (NH) tropics and lower values toward the poles. This behavior, which has been predicted by atmospheric models to depend on the global distribution of the main oceanic iodine source (which in turn depends on the reaction of ozone with aqueous iodide on the sea water-air interface, generating gas-phase I2 and HOI), is confirmed here by field observations for the first time. Longitudinally, there is some indication of a waveone profile in the tropics, which peaks in the Atlantic and shows a minimum in the Pacific. New data from Antarctica show that the south polar seasonal variation of iodine in aerosol mirrors that observed previously in the Arctic, with two equinoctial maxima and the dominant maximum occurring in spring. While no clear seasonal variability is observed in NH middle latitudes, there is an indication of different seasonal cycles in the NH tropical Atlantic and Pacific. Long-term trends cannot be unambiguously established as a result of inhomogeneous time and spatial coverage and analytical methods, Juan Carlos Gómez Martín acknowledges financial support from the State Agency for Research of the Spanish MCIU through the “Center of Excellence Severo Ochoa” award to the Instituto de Astrofísica de Andalucía (SEV-2017-0709) and the Ramon y Cajal Program (RYC-2016-19,570). Alfonso Saiz-Lopez acknowledges financial support from the European Research Council Executive Agency under the European Union’s Horizon 2020 Research and Innovation program (Project “ERC-2016-COG 726349 CLIMAHAL”). Rafael P. Fernandez would like to thank financial support from ANPCyT (PICT 2015-0714), UNCuyo (SeCTyP M032/3853), and UTN (PID 4920-194/2018).

Understanding the controls on event-driven DOC export is crucial, as DOC is an important link between the terrestrial and the aquatic carbon cycles. We hypothesize that topography is a key driver of DOC export because it influences hydrologic connectivity, which can inhibit or facilitate DOC mobilization. To test this we studied the mechanisms controlling DOC mobilization and export in the Große Ohe catchment, a forested headwater in a mid-elevation mountainous region in Southeastern Germany. Discharge and stream DOC concentrations were continuously measured using in-situ UV-Vis spectrometry from June 2018 until October 2020 at two topographically contrasting sub-catchments of the same stream: at a steep hillslope (888 m.a.s.l.) and in a flat and wide riparian zone (771 m.a.s.l). We focus on four events with contrasting antecedent hydrological conditions and event size. During events, in-stream DOC concentrations increased up to 19 mg L−1 in comparison to 2–3 mg L−1 during baseflow. The concentration-discharge relationships exhibited pronounced but almost exclusively anti-clockwise hysteresis loops, which were generally wider in the lower catchment than in the upper catchment due to a delayed DOC mobilization in the flat riparian zone. The riparian zone released considerable amounts of DOC, which led to a total DOC load up to 522 kg per event. The total DOC load increased with the total catchment wetness. We found a disproportionally high contribution to the total DOC export of the upper catchment during events following a long dry period. We attribute this to the lack of hydrological connectivity in the lower catchment during drought, which inhibited DOC mobilization, especially at the beginning of the events. Our data show that not only event size but also antecedent hydrological conditions strongly influence the hydrological connectivity during events, leading to a varying contribution to DOC export of different catchment parts depending on topography. As the frequency of prolonged drought periods is predicted to increase, the relative contribution of different catchment parts to DOC export may change in the future, when hydrological connectivity will occur less often.

Investigation of river water/groundwater interaction aims generally at: (i) localizing water migration pathways, and (ii) quantifying water and associated matter exchange between the two natural water resources. Related numerical models generally rely on model-specific parameters that represent the physical conditions of the catchment and suitable aqueous tracer data. A generally applicable approach for this purpose is based on the finite element model FINIFLUX that is using the radioactive noble gas radon-222 as naturally occurring tracer. During the study discussed in this paper, radon and physical stream data were used with the aim to localize and quantify groundwater discharge into a well-defined section of a small headwater stream. Besides site-specific results of two sampling campaigns, the outcomes of the study reveal: (i) the general difficulties of conducting river water/groundwater interaction studies in small and heterogeneous headwater catchments, and (ii) the particular challenge of defining well constrained site- and campaign-specific values for both the groundwater radon endmember and the radon degassing coefficient. It was revealed that determination of both parameters should be based on as many data sources as possible and include a critical assessment of the reasonability of the gathered and used datasets. The results of our study exposed potential limitations of the approach if executed in small and turbulent headwater streams. Hence, we want to emphasize that the project was not only executed as a case study at a distinct site but rather aimed at evaluating the applicability of the chosen approach for conducting river water/groundwater interaction studies in heterogeneous headwater catchments.

Identifying groundwater discharge zones to lakes is important because the groundwater system can contribute a significant flux of water and solutes and potentially influence lake chemistry and ecology. We present a new instrument, Temperature Mapper (TM), to map groundwater discharge zones in lakes via temperature anomalies along the lake bottom, tested in Lake Constance at 2 former sand and gravel extraction sites. TM is essentially a 4 m wide sled with an array of 19 high-resolution sensors attached to an aluminum lattice towed along the lake bed behind a boat. It is able to map spatial temperature patterns representing groundwater discharge zones at a resolution of 20 cm laterally and 2.5 m in path direction. We conducted 2 field campaigns in February 2016 and February 2017, during which TM identified several temperature anomalies interpreted as groundwater discharging zones. Radon-222 was also analyzed at selected locations as an independent indicator of groundwater discharge. Overall, when comparing the different methods and different years, we observed similar spatial patterns of preferential groundwater discharge. TM offers a useful qualitative tool to identify and map potential groundwater discharge zones in lakes or coastal areas that can then be further studied by more quantitative, small-scale methods such as chemical tracers or seepage meters.

The potentially detrimental impact of groundwater discharge into rivers on the ecosystem services provided by the river makes the localization of groundwater discharge areas as well as the quantification of the associated mass fluxes an issue of major interest. However, localizing groundwater discharge zones and evaluating their impact are challenging tasks because of (i) the limited number of suitable tracers and (ii) the high spatio-temporal variability of groundwater/river water interaction in general. In this study, we applied the ubiquitous naturally occurring radioactive noble gas radon (&sup2, &sup2, Rn) as an aqueous tracer to localize and quantify groundwater discharge along a 60 km reach of the upper German part of the major river Elbe under drought conditions. All radon data processing was executed with the numerical implicit finite element model FINIFLUX, a radon mass balance-based approach, which has been developed specifically to quantify the groundwater flux into rivers. The model results were compared to the tritium (3H) distribution pattern in the studied river reach. The results of the study proved the applicability of both (i) the methodical approach (i.e., radon as tracer) and (ii) the application of FINIFLUX to drought conditions (with river discharge rates as low as 82 m3/s vs. a long time mean of 300 m3/s). Applying the model, the recorded dataset allowed differentiating between groundwater baseflow, on the one hand, and interflow and surface water runoff distributions to the river, on the other. Furthermore, the model results allowed assessing the location and the intensity of groundwater discharge into the river under low flow conditions. It was also shown that analysing discrete river water samples taken from distinct points in a major stream might lead to slightly incorrect results because of an incomplete mixing of river water and locally discharging groundwater. An integrating sampling approach (as applied for radon) is preferable here.

Knowledge of groundwater residence times and recharge locations is vital to the sustainable management of groundwater resources. Here we investigate groundwater residence times and patterns of recharge in the Gellibrand Valley, southeast Australia, where outcropping aquifer sediments of the Eastern View Formation form an "aquifer window" that may receive diffuse recharge from rainfall and recharge from the Gellibrand River. To determine recharge patterns and groundwater flow paths, environmental isotopes (3H, 14C, δ13C, δ18O, δ2H) are used in conjunction with groundwater geochemistry and continuous monitoring of groundwater elevation and electrical conductivity. The water table fluctuates by 0.9 to 3.7 m annually, implying recharge rates of 90 and 372 mm yr−1. However, residence times of shallow (11 to 29 m) groundwater determined by 14C are between 100 and 10 000 years, 3H activities are negligible in most of the groundwater, and groundwater electrical conductivity remains constant over the period of study. Deeper groundwater with older 14C ages has lower δ18O values than younger, shallower groundwater, which is consistent with it being derived from greater altitudes. The combined geochemistry data indicate that local recharge from precipitation within the valley occurs through the aquifer window, however much of the groundwater in the Gellibrand Valley predominantly originates from the regional recharge zone, the Barongarook High. The Gellibrand Valley is a regional discharge zone with upward head gradients that limits local recharge to the upper 10 m of the aquifer. Additionally, the groundwater head gradients adjacent to the Gellibrand River are generally upwards, implying that it does not recharge the surrounding groundwater and has limited bank storage. 14C ages and Cl concentrations are well correlated and Cl concentrations may be used to provide a first-order estimate of groundwater residence times. Progressively lower chloride concentrations from 10 000 years BP to the present day are interpreted to indicate an increase in recharge rates on the Barongarook High.

Radon ( R 86 222 n ) as a hydrological tracer offers a method for studying short to medium term groundwater - surface water interactions. These high frequency processes play an important role in wetland hydrology and biogeochemistry and may influence their contribution to the global carbon cycle. Therefore, there is a definite need for robust methods to measure high resolution 222Rn time series in-situ. In this study we adapted and improved a membrane system to measure 222Rn continuously with a primary focus on a rapid response time and low power consumption. The membrane system was constructed using a hydrophobic capillary membrane and laboratory experiments were conducted to quantify the systems' response time to predefined 222Rn pulses. It was then deployed in a stream draining a riparian wetland. The new membrane system could reduce the response time by ≈ 60 % in comparison to the established silicone membrane. We could identify the behaviour of the system in response to dynamically changing 222Rn activities and suggest a new method using simple linear regression to quantify the systems’ response when the response time concept is inapplicable. Finally, we were able to measure high temporal resolution 222Rn activities reliably over an extended field deployment (68 d). We conclude that the improved system fills a gap ensuring high temporal resolution while maintaining extended maintenance intervals. This allows the user to study high frequency hydrological processes in remote areas. This new membrane system can be used to detect fast changes in 222Rn activities improving the comprehension of the underlying hydrological processes.

The interaction between groundwater and surface water along the Tambo and Nicholson rivers, southeast Australia, was investigated using 222Rn, Cl, differential flow gauging, head gradients, electrical conductivity (EC) and temperature profiles. Head gradients, temperature profiles, Cl concentrations and 222Rn activities all indicate higher groundwater fluxes to the Tambo River in areas of increased topographic variation where the potential to form large groundwater–surface water gradients is greater. Groundwater discharge to the Tambo River calculated by Cl mass balance was significantly lower (1.48 × 104 to 1.41 × 103 m3 day−1) than discharge estimated by 222Rn mass balance (5.35 × 105 to 9.56 × 103 m3 day−1) and differential flow gauging (5.41 × 105 to 6.30 × 103 m3 day−1) due to bank return waters. While groundwater sampling from the bank of the Tambo River was intended to account for changes in groundwater chemistry associated with bank infiltration, variations in bank infiltration between sample sites remain unaccounted for, limiting the use of Cl as an effective tracer. Groundwater discharge to both the Tambo and Nicholson rivers was the highest under high-flow conditions in the days to weeks following significant rainfall, indicating that the rivers are well connected to a groundwater system that is responsive to rainfall. Groundwater constituted the lowest proportion of river discharge during times of increased rainfall that followed dry periods, while groundwater constituted the highest proportion of river discharge under baseflow conditions (21.4% of the Tambo in April 2010 and 18.9% of the Nicholson in September 2010).

Iodine has recently been of interest in atmospheric chemistry due to its role in tropospheric ozone depletion, modification of the HO/HO(2) ratio and aerosol nucleation. Gas-phase iodine chemistry is tightly coupled to the aerosol phase through heterogeneous reactions, which are dependent on iodine concentrations and speciation in the aerosol. To date, the only method available for total iodine determination in aerosols is collection on filters by impaction and quantification by neutron activation analysis (NAA). NAA is not widely available to all working groups and is costly to commission. Here, we present a method to determine total iodine concentrations in aerosol impact filter samples by combustion of filter sub-samples (approximately 5 cm(2)) at 1,000 degrees C, trapping in deionised water and quantification by UV/Vis spectroscopy. Both quartz and cellulose filters were analysed from four separate sampling campaigns. The method proved to be sensitive (3sigma = 6 ng absolute iodine approximately 3 pmol m(-3)) precise (RSD approximately 5%) and accurate, as determined by external and standard addition calibrations. Total iodine concentrations ranged from 10 pmol m(-3) over the Southern Ocean to 100 pmol m(-3) over the tropical Atlantic, in agreement with previous estimates. The soluble iodine concentration (extracted with water and measured by ICP-MS) was then subtracted from the total iodine to yield non-water-soluble iodine (NSI). The NSI fraction ranged from 20% to 53% of total iodine, and thus can be significant in some cases.

Iodine is a vital micronutrient for all mammals, including humans. Despite iodine's listing by the WHO as the world's most easily preventable cause of brain damage, there is very little known about iodine cycling in terrestrial freshwaters, particularly regarding temporal changes in speciation. This study presents iodine speciation (measured by IC-ICP-MS) data from one year of monthly sampling of a dimictic humic lake in the Black Forest (Mummelsee). Total soluble iodine (TSI) levels in the Mummelsee's water column averaged 1.9 ± 0.3 μg L-1. Soluble organically bound iodine (SOI) accounted for the majority of TSI in the lake (85 ± 7%) and inflow (76 ± 6%). SOI showed few changes throughout the year, despite stratification, anoxia in the hypolimnion and ice cover. Iodide was lost from the epilimnion during the summer, autumn and winter, which may be related to (micro)biological uptake and sedimentation of dead organic matter. Efficient biological uptake was also suggested by a sediment core, where we found high total iodine concentrations (av. 11.8 ± 1.7 mg kg-1) and a significant correlation with organic carbon content (p

Iodine oxides, such as iodate, should be the only thermodynamically stable sink species for iodine in the troposphere. However, field observations have increasingly found very little iodate and significant amounts of iodide and soluble organically bound iodine (SOI) in precipitation and aerosols. The aim of this study was to investigate iodine speciation, including the organic fraction, in rain, snow, and aerosols in an attempt to further clarify aqueous phase iodine chemistry. Diurnal aerosol samples were taken with a 5 stage cascade impactor and a virtual impactor (PM2.5) from the Mace Head research station, Ireland, during summer 2006. Rain was collected from Australia, New Zealand, Patagonia, Germany, Ireland, and Switzerland and snow was obtained from Greenland, Germany, Switzerland, and New Zealand. Aerosols were extracted from the filters with water and all samples were analysed for total soluble iodine (TSI) by inductively coupled plasma mass spectrometry (ICP-MS) and iodine speciation was determined by coupling an ion chromatography unit to the ICP-MS. The median concentration of TSI in aerosols from Mace Head was 222 pmol m−3 (summed over all impactor stages) of which the majority was associated with the SOI fraction (median day: 90±4%, night: 94±2% of total iodine). Iodide exhibited higher concentrations than iodate (median 6% vs. 1.2% of total iodine), and displayed significant enrichment during the day compared to the night. Interestingly, up to 5 additional, presumably anionic iodo-organic peaks were observed in all IC-ICP-MS chromatograms, composing up to 15% of the TSI. Soluble organically bound iodine was also the dominant fraction in all rain and snow samples, with lesser amounts of iodide and iodate (iodate was particularly low in snow). Two of the same unidentified peaks found in aerosols were also observed in precipitation from both Southern and Northern Hemispheres. This suggests that these species are transferred from the aerosols into precipitation and that they have either a relatively long lifetime or are rapidly recycled. It is thought that SOI is formed by reactions between HOI or I2 and organic matter derived from the ocean surface layer. SOI may then photolytically decompose to yield iodide and the unidentified species. The data in this study show that iodine oxides are the least abundant species in rain, snow, and aerosols and therefore considerably more effort is required on aqueous phase iodine chemistry for a holistic understanding of the iodine cycle.

This study compares geochemical and physical methods of estimating baseflow in the upper reaches of the Barwon River, southeast Australia. Estimates of baseflow from physical techniques such as local minima and recursive digital filters are higher than those based on chemical mass balance using continuous electrical conductivity (EC). Between 2001 and 2011 the baseflow flux calculated using chemical mass balance is between 1.8 × 103 and 1.5 × 104 ML yr−1 (15 to 25% of the total discharge in any one year) whereas recursive digital filters yield baseflow fluxes of 3.6 × 103 to 3.8 × 104 ML yr−1 (19 to 52% of discharge) and the local minimum method yields baseflow fluxes of 3.2 × 103 to 2.5 × 104 ML yr−1 (13 to 44% of discharge). These differences most probably reflect how the different techniques characterise baseflow. Physical methods probably aggregate much of the water from delayed sources as baseflow. However, as many delayed transient water stores (such as bank return flow or floodplain storage) are likely to be geochemically similar to surface runoff, chemical mass balance calculations aggregate them with the surface runoff component. The mismatch between geochemical and physical estimates is greatest following periods of high discharge in winter, implying that these transient stores of water feed the river for several weeks to months. Consistent with these interpretations, modelling of bank storage indicates that bank return flows provide water to the river for several weeks after flood events. EC vs. discharge variations during individual flow events also imply that an inflow of low EC water stored within the banks or on the floodplain occurs as discharge falls. The joint use of physical and geochemical techniques allows a better understanding of the different components of water that contribute to river flow, which is important for the management and protection of water resources.

Iodine undergoes several redox changes in the natural environment, existing as iodate, iodide, and covalently bound to organic matter. While considerable attention has been given to iodine speciation and cycling in the marine environment, very little is known about iodine cycling and speciation in terrestrial fresh water systems. Here we show iodine speciation (measured by IC-ICP-MS) data from one year of monthly sampling of a small humic rich lake in the Black Forest (Mummelsee) under varying redox conditions. The aim was to elucidate the seasonal cycles of iodine species in the lake water column and to quantify both inorganic and organic iodine species. A sediment core was also collected for iodine analysis. Total iodine levels in the Mummelsee averaged 1.93±0.3 μg l−1. Organo-I was the dominant species in the lake, making up on average 85±7% of the total iodine. No strong seasonal variation in organo-I was observed, with only small variations occurring in the epi- and hypolimnion. Iodide was scavenged from the epilimnion during the summer and autumn, which could be related to (micro)biological uptake and co-precipitation. This was also suggested by the high iodine levels in the sediment core (av. 11.8±1.7 mg kg −1). In the hypolimnion, a strong flux of iodide was observed from the sediments into the water column during anoxic and hypoxic conditions, observed during the summer, autumn and, in the bottom 2 m, the winter. This iodide flux and is thought to occur during decomposition of biological material. Iodate levels in the epilimnion increased consistently over the year, whereas it was reduced below detection limits in the hypolimnion during low oxygen conditions. The winter partial turnover lead to reintroduction of oxygen into the hypolimnion and the formation of iodate and organo-I, as well as removal of iodide. In conclusions, iodine cycling in the Mummelsee was controlled by organo-I, although redox conditions and perhaps biological activity were also important, particularly in the hypolimnion during stratification.

Iodine in soils and sediments is a difficult element to analyze due to its volatility in acidic conditions. Traditionally it has been quantified using neutron activation analysis techniques, which, unfortunately, requires access to a nuclear reactor. We present here a simple method for solid-phase iodine analysis by thermo extraction at 1000 degrees C and quantification by UV/Vis photometry. Samples are combusted in an oxygen stream and trapped in Milli-Q water. The extracts are then quantified by an As3+-Ce4+ spectrometric method whereby iodide catalyzes the oxidation of As3+ to As5+ and reduction of Ce4+ to Ce3+. Three standard reference materials were analyzed with excellent recoveries (97-113%) and RSDs (5%). Moreover, the detection limit was less than 50 ng absolute iodine with a confidence limit of 95%. When applied to carbonate-rich samples from sediment traps deployed in Lake Constance we found very low iodine levels (0.8-2 mg kg(-1)). Despite the low concentrations, the precision of the method was consistently better than 5% RSD. However, the method needed to be slightly modified for organic and iodine-rich sediments (20-30% organic carbon) from a lake in the Black Forest by increasing the oxygen flow rate and decreasing the combustion time. Using the modified method we were able to achieve RSDs lower than 5%.

International audience; Iodine is an essential trace element for all mammals and may also influence climate through new aerosol formation. Atmospheric bromine cycling is also important due to its well-known ozone depletion capabilities. Despite precipitation being the ultimate source of iodine in the terrestrial environment, the processes effecting its distribution, speciation and transport are relatively unknown. The aim of this study was to determine the effect of orographically induced precipitation on iodine concentrations in snow and also to quantify the inorganic and organic iodine and bromine species. Snow samples were collected over an altitude profile (~840 m) from the northern Black Forest and were analysed by ion-chromatography - inductively coupled plasma mass spectrometry (IC-ICP-MS) for iodine and bromine species and trace metals (ICP-MS). All elements and species concentrations in snow showed significant (r2>0.65) exponential decrease relationships with altitude despite the short (5 km) horizontal distance of the transect. In fact, total iodine more than halved (38 to 13 nmol/l) over the 840 m height change. The results suggest that orographic lifting and subsequent precipitation has a major influence on iodine concentrations in snow. This orographically induced removal effect may be more important than lateral distance from the ocean in determining iodine concentrations in terrestrial precipitation. The microphysical removal process was common to all elements indicating that the iodine and bromine are internally mixed within the snow crystals. We also show that organically bound iodine is the dominant iodine species in snow (61?75%), followed by iodide. Iodate was only found in two samples despite a detection limit of 0.3 nmol/l. Two unknown but most likely anionic organo-I species were also identified in IC-ICP-MS chromatograms and comprised 2?10% of the total iodine. The majority of the bromine was inorganic bromide with a max. of 32% organo-Br.