Efficiency of Moso Bamboo Charcoal and Activated Carbon for Adsorbing Radioactive Iodine

Preventing radioactive pollution is a troublesome problem but an urgent concern worldwide because radioactive substances cause serious health‐related hazards to human being. The adsorption method has been used for many years to concentrate and remove radioactive pollutants; selecting an adequate adsorbent is the key to the success of an adsorption‐based pollution abatement system. In Taiwan, all nuclear power plants use activated carbon as the adsorbent to treat radiation‐contaminated air emission. The activated carbon is entirely imported; its price and manufacturing technology are entirely controlled by international companies. Taiwan is rich in bamboo, which is one of the raw materials for high‐quality activated carbon. Thus, a less costly activated carbon with the same or even better adsorptive capability as the imported adsorbent can be made from bamboo. The objective of this research is to confirm the adsorptive characteristics and efficiency of the activated carbon made of Taiwan native bamboo for removing ¹³¹I gas from air in the laboratory. The study was conducted using new activated carbon module assembled for treating ¹³¹I‐contaminated air. The laboratory results reveal that the ¹³¹I removal efficiency for a single‐pass module is as high as 70%, and the overall efficiency is 100% for four single‐pass modules operated in series. The bamboo charcoal and bamboo activated carbon have suitable functional groups for adsorbing ¹³¹I and they have greater adsorption capacities than commercial activated carbons. Main mechanism is for trapping of radioiodine on impregnated charcoal, as a result of surface oxidation. When volatile radioiodine is trapped by potassium iodide‐impregnated bamboo charcoal, the iodo‐compound is first adsorbed on the charcoal surface, and then migrates to iodide ion sites where isotope exchange occurs.     

Study of the Contributions of Non‐Specific and Specific Interactions during Fluoxetine Adsorption onto Activated Carbons

The adsorption of fluoxetine onto activated carbons (ACs) prepared from almond tree pruning by steam and CO₂ activation under different temperature conditions (650–950°C), was studied. In both series increasing the temperature caused an increase in the BET apparent surface area, yielding ACs with S_BET up to 870 and 710 m² g^?1 after steam and CO₂ activation, respectively. Also, a slight widening of the porosity was found in both cases. In order to modify the functionality of the ACs, two of them were impregnated with triethylenediamine (TEDA) prior to the adsorption process, which caused a decrease in the AC apparent surface mainly due to micropore blockage. The fluoxetine adsorption isotherms at 25°C showed maximum adsorption capacities between 110 and 224 mg g^?1. The adsorption isotherms were analyzed using Langmuir and Freundlich models. Although the impregnation reduced the pore volume, it did not cause a decrease in the fluoxetine maximum adsorption capacity, but a modification in the adsorption mechanism was observed.     

Removal of Copper,Nickel and Zinc Ions from Aqueous Solution by Chitosan‐8‐Hydroxyquinoline Beads

In this work, 8‐hydroxyquinoline is used as the active sites in cross‐linked chitosan beads with epichlorohydrin (CT‐8HQ). The CT‐8HQ material was shaped in bead form and used for heavy metal removal from aqueous solution. The study was carried out at pH 5.0 with both batch and column methods and the maximum adsorption capacity of metal ions by the CT‐8HQ was attained in 4 h in the batch experiment. The adsorption capacity order was: Cu²⁺ > Ni²⁺ > Zn²⁺ for both mono‐ and multi‐component systems with batch conditions. From breakthrough curves with column conditions, the adsorption capacity followed the order Cu²⁺ > Zn²⁺ > Ni²⁺ for both mono‐ and multi‐component systems. The CT‐8HQ beads maintained good metal adsorption capacity for all five cycles with absorbent restoration achieved with the use of 1.0 mol L^–1 HCl solution, with 90% regeneration.     

Spectroscopic Characterization of Organic Structures and Organic‐Inorganic Interactions in Paper Mill Sludge

The organic composition and organic‐inorganic interaction in paper mill sludge (PS) solvent extracts (hexane, ethyl acetate, acetone and ethanol) and humic fractions, humic acid (HA) and humin (HU) were studied by electron paramagnetic resonance spectroscopy (EPR), proton and carbon‐13 nuclear magnetic resonance spectroscopy (¹H NMR; ¹³C NMR), Fourier‐transformed infrared spectroscopy (FTIR), and ultraviolet‐visible spectroscopy (UV‐vis). The strategy of fractionating the PS, sequentially, with organic solvents of increasing polarity is a reliable analytical procedure for humic substance sample separation because it results in more purified fractions. FTIR, ¹H NMR and ¹³C NMR results showed that hexane extract consisted mainly of aliphatic hydrocarbon structures. Their contents in the extracts decreased as the polarity of the extracting solvent increased and the content of oxygen functional groups increased. Carboxylic and carboxylate functional groups were found in the acetone extract, and ester and ether functions were predominantly found in the ethanol extract. EPR spectra revealed some Fe³⁺ complexes with rhombic structure (g₁ = 4.3; g₂ = 9.0) in the humic fractions and in all solvent extracts, except hexane. Quasi‐octahedral Fe³⁺ complexes (g = 2.3; ΔH_pp ≤ 400 G) were found in the HU fraction and in the acetone extract. The organic free radical content in the HA fraction was higher than the non‐fractionated PS sample and HU fraction.     

Designing Iron‐Amended Biosand Filters for Decentralized Safe Drinking Water Provision

There are ongoing efforts to render conventional biosand filters (BSF) more efficient for safe drinking water provision. One promising option is to amend BSF with a reactive layer containing metallic iron (Fe⁰). The present communication presents some conceptual options for efficient Fe⁰‐amended BSF in its fourth generation. It is shown that a second fine‐sand layer should be placed downwards from the Fe⁰‐reactive layer to capture dissolved iron. This second fine‐sand layer could advantageously contain adsorbing materials (e.g. activated carbons, wooden charcoals). An approach for sizing the Fe⁰‐reactive layer is suggested based on 3 kg Fe⁰ per filter. Working with the same Fe⁰ load will ease comparison of results with different materials and the scaling up of household BSF to large scale community slow sand filters (SSF).     

Evaluation of Two Low‐Cost–High‐Performance Adsorbent Materials in the Waste‐to‐Product Approach for the Removal of Pesticides from Drinking Water

This study evaluates the performance of two low cost and high performance adsorption materials, i.e., activated carbon produced from two natural waste products: Bamboo and coconut shell, in the removal of three pesticides from drinking water sources. Due to the fact that bamboo and coconut shell are abundant and inexpensive materials in many parts of the world, they respond to the “low‐cost” aspect. The adsorption capacities of two local adsorbents have been compared with commercial activated carbon to explore their potential to respond to the “high quality” aspect. Two pesticides were selected, namely dieldrin and chlorpyrifos, because they are commonly used in agriculture activities, and may remain in high concentrations in surface water used as drinking water sources. The results indicate that the adsorption of pesticides on activated carbons is influenced by physico‐chemical properties of the activated carbon and the pesticides such as the presence of an aromatic ring, and their molar mass. The activated carbon produced from bamboo can be employed as low‐cost and high performance adsorbent, alternative to commercial activated carbon for the removal of pesticides during drinking water production. The performance of activated carbon from bamboo was better due to its relatively large macroporosity and planar surface. The effect of adsorbent and pesticide characteristics on the performance was derived from batch experiments in which the adsorption behavior was studied on the basis of Freundlich isotherms.     

Degradation and Leaching of Napropamide in BRIS Soil Amended with Chicken Dung and Palm Oil Mill Effluent

The degradation and leaching of napropamide were compared between Beach Ridges Interspersed with Swales (BRIS) soil samples, and the same soil samples amended with 20 mg ha^?1 of either chicken dung (CD) or palm oil mill effluent (POME). The effects of removing dissolved organic carbon (DOC) from the soil samples on napropamide degradation and leaching were also studied. The addition of CD and POME to BRIS soil increased the napropamide half‐life values to 69 and 49.5 days, respectively. Sterilization of the soil samples resulted in partial inhibition of napropamide degradation in all soil samples. The half‐lives of napropamide in BRIS soils receiving 0, 20, 100, and 200 mg kg^?1 of DOC derived from CD were 43, 46.2, 53.4, and 63 days, respectively. The napropamide half‐lives in soil samples treated with 0, 20, 100, and 200 mg kg^?1 of DOC derived from POME were 43, 49.2, 57.7, and 69 days, respectively. However, in the sterilized soil samples, there were no significant effects of adding DOC derived from either CD or POME on napropamide half‐lives. Incorporating either CD or POME decreased napropamide leaching and total amounts of napropamide remained in the soil columns after two pore volumes of water has been leached were higher in the amended than the non‐amended soil. The CD was more effective in decreasing napropamide leaching than the POME. There were no effects of DOC on napropamide leaching in all soil treatments.     

Quantification of TCE Co‐Oxidation in Groundwater Using a 14C–Assay

Bacteria that degrade natural organic matter in groundwater contain oxygenase enzymes that can co‐oxidize trichloroethene (TCE). This degradation pathway is promising for large dilute plumes, but its evaluation is limited because the density of the bacteria with oxygenase enzymes has not been correlated to field scale rates of degradation. A ¹⁴C–TCE assay was developed to determine pseudo first‐order rate constants for the aerobic co‐oxidation of TCE in groundwater. The assay involved incubating ¹⁴C–TCE in samples of groundwater contained in 160 mL serum bottles, and monitoring the accumulation of radiolabel in degradation products. A first‐order rate constant for co‐oxidation was extracted from the rate of accumulation of ¹⁴C in products, accounting for volumetric changes in the serum bottles due to sampling and subsequent changes to the distribution of TCE between the aqueous and gaseous phases. Of the groundwater samples evaluated from 19 wells at five sites, eight samples at three sites had ¹⁴C product accumulation rates that exceeded the accumulation rate in filter‐sterilized groundwater controls. First‐order rate constants ranged from 2.65 to 0.0066 year^?1, which is equivalent to half‐lives of 0.26 to 105 years. Groundwater samples from a few of the wells in which co‐oxidation occurred had volatile organic contaminants in addition to TCE; their presence may have induced the oxygenase enzymes that are needed for TCE co‐oxidation. ¹⁴CO₂ represented ~37% to 97% of the ¹⁴C products that accumulated; the balance of the products was soluble and non‐volatile.     

Solid-state nuclear magnetic resonance and infrared spectroscopy of alkali feldspars

²⁹Si,²⁷Al MAS NMR and IR spectra of rnonophase K-feldspars (sanidine, orthoclase and microcline) and Na-feldspars (monalbite, anorthoclase and low albite) in different structural states have been studied. The NMR and IR spectra of K-feldspars and Na-feldspars vary regularly along with their degrees of Si/Al ordering evolution. Si in orthoclase occupiesT _2m,T2o andT1m, and the high-temperature Na-feldspar (monalbite and anorthoclase) coincides in²⁹Si,²⁷Al NMR and IR spectra. Moreover, all the high-temperature Na-feldspars and sanidine have the same²⁷Al NMR and IR spectra. Project supported by the Foundation of Laboratory of Magnetic Resonance and Atom and Molecular Physics, Wuhan Institute of Physics, Chinese Academy of Sciences.     

Removal of Arsenic from Simulated Groundwater Using GAC‐Ca in Batch Reactor: Kinetics and Equilibrium Studies

This paper deals with kinetics and equilibrium studies on the adsorption of arsenic species from simulated groundwater containing arsenic (As(III)/As(V), 1:1), Fe, and Mn in concentrations of 0.188, 2.8, and 0.6 mg/L, respectively, by Ca²⁺ impregnated granular activated charcoal (GAC‐Ca). Effects of agitation period and initial arsenic concentration on the removal of arsenic species have also been described. Although, most of the arsenic species are adsorbed within 10 h of agitation, equilibrium reaches after ～24 h. Amongst various kinetic models investigated, the pseudo second order model is more adequate to explain the adsorption kinetics and film diffusion is found to be the rate controlling step for the adsorption of arsenic species on GAC‐Ca. Freundlich isotherm is adequate to explain the adsorption equilibrium. However, empirical polynomial isotherm gives more accurate prediction on equilibrium specific uptakes of arsenic species. Maximum specific uptake (q_max) for the adsorption of As(T) as obtained from Langmuir isotherm is 135 µg/g.     

Runoff‐generating processes in hydromorphic soils on a plot scale: free gravity‐driven versus pressure‐controlled flow

Draining soil water is an important runoff generator. This study aims to describe runoff‐generating processes on a plot scale (1 m²) in hydromorphic soils with different initial soil water contents. We irrigated 16 hydromorphic soils in the northern Pre‐Alps in Switzerland and recorded the variations in water content with time domain reflectometry (TDR) at five different depths per plot. Sprinkling was repeated three times at approximately 23‐h intervals and lasted for 1 h with a volume flux density of 70 mm h^?1. The comparison between the measured water content of the drainages with two physically based models revealed which of the flow processes dominated during water recessions. We distinguished between vertical drainage, lateral outflow and infiltration without drainage. Approximately 45% of all recorded time series of soil water content did not drain within approximately 20 h after the end of irrigation, about 25% drained laterally and 10% of the outflow was vertical. The drainage of the remaining 20% was the result of both lateral and vertical water flow (≈12%), or was not interpretable with the approaches applied (≈8%). Vertical flow was only observed in layers without any or with just a few hydromorphic features. Lateral draining horizons had approximately half the storage capacity and amplitude of water recession of those with vertical flow. Vertical flow was only observed in the upper soil horizons. Thus, vertical flow transmitted water to layers with lateral outflow and did not delay runoff by deep percolation. Increasing initial soil moisture increased the percentage of water content recordings according to a lateral outflow slightly, while vertical flow was less frequent. Copyright © 2010 John Wiley & Sons, Ltd.     

Use of Nitrogen‐15‐Enriched Escherichia coli as a Bacterial Tracer in Karst Aquifers

Karst aquifers are susceptible to contamination by microorganisms, but relatively few studies have used bacteria as tracers. We demonstrate the utility of Escherichia coli enriched in the stable isotope nitrogen‐15 (¹⁵N) as a novel bacterial tracer. Nonpathogenic E. coli from two springs in central Kentucky were grown on ¹⁵N‐enriched media. Survival of E. coli and persistence of the isotopic signal were assessed in two sets of laboratory experiments conducted with sterilized spring water in dark microcosms at 14 °C. First, isotopically labeled bacteria survived for 130 d at concentrations within one log unit of the average initial value, and there was no significant difference in δ¹⁵N values from Day 1 to Day 130. Second, water samples with E. coli were inoculated with either of two different species of protozoa (Tetrahymena pyriformis or Colpoda steinii). During 7 d, δ¹⁵N values increased in T. pyriformis while bacterial populations decreased. In a field test, following a 2.1‐cm rainfall, ¹⁵N‐labeled E. coli, solutes (rhodamine WT dye and bromide), and latex microspheres were injected into a sinkhole approximately 530 m upgradient of a spring. Breakthrough of all tracers coincided, but microspheres were remobilized by subsequent storms, unlike other tracers. Enriched E. coli exhibited more tailing than solute tracers during the initial storm‐flow recession. These results indicate that ¹⁵N‐enriched E. coli is a viable tracer of bacterial transport in karst aquifers, although predation may attenuate the isotopic signal in systems that are not rapidly flushed.     

Bi‐Solute Sorption of Estrogens at Low Concentration: Two‐ and Three‐Parametric Analysis

Competitive sorption of estriol (E3) and 17α‐ethinylestradiol (EE2) was studied on activated charcoal. Better sorption of E3 (88.9%) and EE2 (69.5%) was observed with single‐solute sorption system than with bi‐solute sorption system. Single‐solute sorption kinetics of E3 and EE2 were evaluated with two (Langmuir and Freundlich) and three (dual mode and Song) parameter models. Freundlich model (R², 0.9915 (E3); 0.9875 (EE2)) showed good prediction compared to other models for single‐solute sorption. Adsorption capacity documented reduced efficacy (86.4% (E3); 65.9% (EE2)) due to induced competitive behavior between the estrogens in aqueous phase. Bi‐solute adsorption kinetics of E3 and EE2 were described by IAST with two and three parameter models. Among these models, IAST‐Freundlich model (R², 0.9765 (E3); 0.9985 (EE2)) was best in predicting bi‐solute sorption of E3 and EE2 by activated charcoal. All these models showed favorable representation of both single‐ and bi‐solute sorption behaviors.     

Push‐Pull Tests for Estimating RDX and TNT Degradation Rates in Groundwater

In situ bioremediation is being considered to optimize an existing pump‐and‐treat remedy for treatment of explosives‐contaminated groundwater at the Umatilla Chemical Depot. Push‐pull tests were conducted using a phased approach to measure in situ hexahydro‐1,3,5‐trinitro‐1,3,5‐triazine (RDX) and 2,4,6‐trinitrotoluene (TNT) degradation rates associated with various carbon substrates. Phase I included short‐duration transport tests conducted in each well to determine dilution rates and retardation factors for RDX and TNT. Phase II included aquifer “feedings” conducted by injecting 150 gallons of treated site groundwater amended with ethanol, corn syrup, lactose or emulsified oil (concentrations 10, 25 and 27 mM, respectively; 12% by volume for emulsified oil). Wells received up to 6 substrate “feedings” over the course of 3 months followed by monitoring dissolved oxygen, nitrate, Fe(II), and sulfate to gauge in situ redox conditions as indicators of anaerobic microbial activity. Phase III included push‐pull tests conducted by injecting 150 gallons of site groundwater amended with approximately 1000 µg/L RDX, 350 µg/L TNT, carbon substrate and a conservative tracer, followed by sampling over 8 d. Corn syrup resulted in the best RDX removal (82% on average) and the largest RDX degradation rate coefficient (1.4 ± 1.1 d^?1). Emulsified oil resulted in the best TNT removal (99%) and largest TNT degradation rate coefficient (5.7 × 10^?2 d^?1). These results will be used to simulate full‐scale in situ bioremediation scenarios at Umatilla and will support a go/no‐go decision to initiate full‐scale bioremediation remedy optimization.     

Removal of Cadmium from Aqueous Solution Using Castor Seed Hull: A Kinetic and Equilibrium Study

The effects of various parameters such as initial concentration, adsorbent loading, pH, and contact time on kinetics and equilibrium of adsorption of Cd²⁺ metal ion from its aqueous solution by castor seed hull (CSH) and also by activated carbon have been investigated by batch adsorption experiments. The amount of adsorption increases with initial metal ion concentration, contact time, solution pH, and the loading of adsorbent for both the systems. Kinetic experiments indicate that adsorption of cadmium metal ion on both CSH and on activated carbon consists of three steps – a rapid adsorption of cadmium metal ion, a transition phase, and an almost flat plateau region. This has also been confirmed by the intraparticle diffusion model. The lumped kinetic results show that the cadmium adsorption process follows a pseudo‐second order rate law. The kinetic parameters including the rate constant are determined at different initial metal ion concentrations, pH, amount, and type of adsorbent, respectively. The Langmuir and Freundlich adsorption isotherm models are used to describe the experimental data. The Langmuir model yields a better correlation coefficient than the other model. A comparison of the monolayer adsorption capacity (q_m) of CSH, activated carbon, and several other reported adsorbents has been provided. The value of separation factor (R_L) calculated from the Langmuir equation also gives an indication of favorable adsorption of the metal ion. From comparative studies, it has been found that CSH is a potentially attractive adsorbent than commercial activated carbon for cadmium metal ion (Cd²⁺) removal.     

Structure of volcanic glasses from the NMR-EPR perspective: a preliminary application to the Neapolitan Yellow Tuff

Glass samples from alkali-trachytic pumice of the Lower Member (LM, level LM1) and Upper Member (UM) of the Neapolitan Yellow Tuff at Campi Flegrei Caldera were studied by nuclear magnetic resonance (NMR) and electron paramagnetic resonance (EPR) spectroscopy. The EPR data show that the relative occupancy of the different iron sites varies in samples from the Lower Member LM1 and Upper Member of the eruptive sequence. The LM1 glasses are characterized by a more homogeneous distribution of the cationic site population of iron compared with UM and by a different Fe³⁺/Al³⁺ substitution in the C_2v symmetrical sites of the silicate framework. ²⁹Si MAS NMR spectra on glasses indicate that LM1 glasses are more depolymerized than UM glasses, indicating the existence of structurally distinct magma batches. ²⁷Al MAS NMR spectra indicate the occurrence in UM glasses of aluminum in both tetrahedral and octahedral coordination; the observed Al^VI is believed to be a primary feature of the glass, since ²⁷Al CP-MAS NMR experiments do not reveal detectable esa-hydrated Al. The Al in sixfold coordination could be ascribed either to the more abundant alkali–OH terminations in UM, in which alkalies would be extracted from their charge-balance role for Al, thus altering its fourfold structural position, or to permanent compaction during fast cooling and decompression of high-pressure melts. ²³Na CP-MAS NMR experiments indicate the existence of Na–OH groups in both LM1 and UM glasses, relatively more abundant in the latter. Although preliminary, the results indicate the possible application of atomic-scale studies to variables that determine the regimes of explosive volcanism. Received: 1 July 1998 / Accepted: 1 October 1998     

Sensitivity analysis of temperature‐index melt simulations to near‐surface lapse rates and degree‐day factors at Vestari‐Hagafellsjökull,Langjökull,Iceland

The performance of temperature‐index melt models is particularly affected by the choice of near‐surface lapse rate used to determine the sum of positive daily temperatures at different elevations, and by the choice of factor used to relate this sum to the rate of melting. Data from the Langjökull ice cap are used in this study to quantify the influence of lapse‐rate and degree‐day factor variation on temperature‐index melt simulations. The lapse rate was significantly lower during summer than in spring or autumn, as a result of diabatic cooling, reducing boundary‐layer sensitivity to free‐air temperature change. The summer lapse rate was also significantly lower than the saturated adiabatic lapse rate. A sensitivity of approximately 600 mm water equivalent (w.e.) cumulative June–August melt per 0.1 °C 100 m^–1 change in lapse rate was found across a 500‐m altitude range. The sensitivity to a 1‐mm w.e. °C^–1 day^–1 change in degree‐day factors varied more: from approximately 500 mm w.e. cumulative summer melt at low elevation to approximately 200 mm w.e. at high elevation, reflecting the decline in melt rates associated with the greater persistence of snow with increasing altitude. The determination of a degree‐day factor for snow is complicated by the densification of the ageing snowpack, but the application of a parameterization for near‐surface density on the basis of albedo helped account for the development of snow water equivalence. Lapse rate was parameterized as a function of standardized anomalies in 750 hPa reanalysis temperature and significantly improved the simulation of cumulative summer melt compared with models applying the saturated adiabatic lapse rate. Copyright © 2012 John Wiley & Sons, Ltd.     

Biofilm Detection in a Model Well‐Bore Environment Using Low‐Field NMR

This research addresses the challenges of the lack of non‐invasive methods and poor spatiotemporal resolution associated with monitoring biogeochemical activity central to bioremediation of subsurface contaminants. Remediation efforts often include growth of biofilm to contain or degrade chemical contaminants, such as nitrates, hydrocarbons, heavy metals, and some chlorinated solvents. Previous research indicates that nuclear magnetic resonance (NMR) is sensitive to the biogeochemical processes of biofilm accumulation. The current research focuses on developing methods to use low‐cost NMR technology to support in situ monitoring of biofilm growth and geochemical remediation processes in the subsurface. Biofilm was grown in a lab‐scale radial flow bioreactor designed to model the near wellbore subsurface environment. The Vista Clara Javelin NMR logging device, a slim down‐the‐borehole probe, collected NMR measurements over the course of eight days while biofilm was cultivated in the sand‐packed reactor. Measured NMR mean log T₂ relaxation times decreased from approximately 710 to 389 ms, indicating that the pore environment and bulk fluid properties were changing due to biofilm growth. Destructive sampling employing drop plate microbial population analysis and scanning electron and stereoscopic microscopy confirmed biofilm formation. Our findings demonstrate that the NMR logging tool can detect small to moderate changes in T₂ distribution associated with environmentally relevant quantities of biofilm in quartz sand.     

Assessing DOC export from a Sphagnum‐dominated peatland using δ13C and δ18O–H2O stable isotopes

Dissolved organic carbon (DOC) originating in peatlands can be mineralized to carbon dioxide (CO₂) and methane (CH₄), two potent greenhouse gases. Knowledge of the dynamics of DOC export via run‐off is needed for a more robust quantification of C cycling in peatland ecosystems, a prerequisite for realistic predictions of future climate change. We studied dispersion pathways of DOC in a mountain‐top peat bog in the Czech Republic (Central Europe), using a dual isotope approach. Although δ¹³C_DOC values made it possible to link exported DOC with its within‐bog source, δ¹⁸O_H2O values of precipitation and run‐off helped to understand run‐off generation. Our 2‐year DOC–H₂O isotope monitoring was complemented by a laboratory peat incubation study generating an experimental time series of δ¹³C_DOC values. DOC concentrations in run‐off during high‐flow periods were 20–30 mg L^?1. The top 2 cm of the peat profile, composed of decaying green moss, contained isotopically lighter C than deeper peat, and this isotopically light C was present in run‐off in high‐flow periods. In contrast, baseflow contained only 2–10 mg DOC L^?1, and its more variable C isotope composition intermittently fingerprinted deeper peat. DOC in run‐off occasionally contained isotopically extremely light C whose source in solid peat substrate was not identified. Pre‐event water made up on average 60% of the water run‐off flux, whereas direct precipitation contributed 40%. Run‐off response to precipitation was relatively fast. A highly leached horizon was identified in shallow catotelm. This peat layer was likely affected by a lateral influx of precipitation. Within 36 days of laboratory incubation, isotopically heavy DOC that had been initially released from the peat was replaced by isotopically lighter DOC, whose δ¹³C values converged to the solid substrate and natural run‐off. We suggest that δ¹³C systematics can be useful in identification of vertically stratified within‐bog DOC sources for peatland run‐off.     

Characterisation of Fulvic Acids and Glycyrrhizic Acid by Time‐of‐Flight Secondary Ion Mass Spectrometry

Fulvic acids of different origin, spray deposited on polished silicon after dissolution in high‐purity water without any additives, were analysed by time‐of‐flight secondary ion mass spectrometry (TOF‐SIMS) in combination with oblique 24...36 keV SF₅⁺ ion bombardment. The observed, highly reproducible mass spectra cover more than five orders of magnitude in dynamic range, without background subtraction. Apart from lines due to atomic ions and low‐mass ion fragments, the mass spectra exhibit broad maxima between m/z 200...350, mainly due to a beat‐like superposition of lines at every single mass number, up to at least m/z 400. In the negative ion spectra the beats have a spacing of m/z 14, corresponding to a CH₂‐unit. The high‐mass tails of the spectra extend well beyond m/z 5000, with similar slopes in the positive and the negative ion mass spectra. The negative spectra appear to be less affected by fragmentation products than the positive spectra. Fulvic acids (FAs) of different origin show distinctly different spectra, with mean masses ranging between m/z ≈ 450 and 580 (for a low‐mass cut‐off m/z 150). To further verify the ability of TOF‐SIMS to detect molecules and clusters with masses significantly above the maxima of the FA spectra, samples of glycyrrhizic acid (GA, as GA ammonium salt with molecular weight 840) were also analysed. Parent ions as well as multimers (GA)_n were observed as positive and negative ions, up to n = 4 (m/z 3320). The results are compared with spectra recently obtained by other mass spectrometric techniques.