On‐line Solid Phase Extraction of Copper in Water Samples with Flow Injection Flame Atomic Absorption Spectrometry

An on‐line solid phase extraction method for the preconcentration and determination of Cu(II) by flame atomic absorption spectrometry has been described. The procedure is based on the retention of Cu(II) ions at pH 6.0 on a minicolumn packed with Amberlite XAD‐1180 resin impregnated with chrome azurol S. After preconcentration, Cu(II) ions adsorbed on the impregnated resin were eluted by 1 mol L^?1 HNO₃ solution. Several parameters, such as pH, type of eluent, flow rates of sample and eluent solutions, amount of resin were evaluated. At optimized conditions, for 3.5 min of preconcentration time, the system achieved a detection limit of 1.0 µg L^?1, and a relative standard deviation of 1.2% at 0.2 µg mL^?1 copper. An enrichment factor of 56‐fold was obtained with respect to the copper determination. The proposed method was successfully validated by the analysis of standard reference material (TMDA 54.4 lake water) and recovery studies. The method was applied to the preconcentration of Cu(II) in natural water samples.     

Preparation,Characterization of a Novel Chelating Resin Functionalized with o‐Hydroxybenzamide and Its Application for Preconcentration of Trace Metal Ions

A stable extractor of metal ions was synthesized through azo linking of o‐hydroxybenzamide (HBAM) with Amberlite XAD‐4 (AXAD‐4) and was characterized by elemental analyses, IR spectral, and thermal studies. Its water regain value and hydrogen ion capacity were found to be 12.93 and 7.68 mmol g^?1, respectively. The optimum pH range (with the half‐loading time [min], t_1/2) for Cu(II), Cr(III), Ni(II), Co(II), Zn(II), and Pb(II) ions were 2.0–4.0 (5.5), 2.0–4.0 (7.0), 2.0–4.0 (8.0), 4.0–6.0 (9.0), 4.0–6.0 (12.0), and 2.0–4.0 (15.0), respectively. Comparison of breakthrough and overall capacities of the metals ascertains the high degree of column utilization (>70%). The overall sorption capacities for Cu(II), Cr(III), Ni(II), Co(II), Zn(II), and Pb(II) ions were found to be 0.29, 0.22, 0.20, 0.16, 0.13, and 0.11 mmol g^?1 with the corresponding preconcentration factor of 400, 380, 380, 360, 320, and 320, respectively. The limit of preconcentration was in the range of 5.0–6.3 ng mL^?1. The detection limit for Cu(II), Cr(III), Ni(II), Co(II), Zn(II), and Pb(II) were found to be 0.39, 0.49, 0.42, 0.59, 0.71, and 1.10 ng mL^?1, respectively. The AXAD‐4‐HBAM has been successfully applied for the analysis of natural water, multivitamin formulation, infant milk substitute, hydrogenated oil, urine, and fish.     

A Multi‐Element Ion‐Pair Extraction for Trace Metals Determination in Environmental Samples

A multi‐element ion‐pair extraction method was described for the preconcentration of Cd(II), Co(II), Cr(III), Cu(II), Fe(III), Mn(II), Ni(II), Pb(II), and Zn(II) ions in environmental samples prior to their determinations by flame atomic absorption spectrometry (FAAS). As an ion‐pair ligand 2‐(4‐methoxybenzoyl)‐N′‐benzylidene‐3‐(4‐methoxyphenyl)‐3‐oxo‐N‐phenyl‐propono hydrazide (MBMP) was used. Some analytical parameters such as pH of sample solution, amount of MBMP, shaking time, sample volume, and type of counter ion were investigated to establish optimum experimental conditions. No interferences due to major components and some metal ions of the samples were observed. The detection limits of the proposed method were found in the range of 0.33–0.9 µg L^?1 for the analyte ions. Recoveries were found to be higher than 95% and the relative standard deviation (RSD) was less than 4%. The accuracy of the procedure was estimated by analyzing the two certified reference materials, LGC6019 river water and RTC‐CRM044 soil. The developed method was applied to several matrices such as water, hair, and food samples.     

Coprecipitation with Cu(II)‐4‐(2‐Pyridylazo)‐resorcinol for Separation and Preconcentration of Fe(III) and Ni(II) in Water and Food Samples

The coprecipitation method is widely used for the preconcentration of trace metal ions prior to their determination by flame atomic absorption spectrometry (FAAS). A simple and sensitive method based on coprecipitation of Fe(III) and Ni(II) ions with Cu(II)‐4‐(2‐pyridylazo)‐resorcinol was developed. The analytical parameters including pH, amount of copper (II), amount of reagent, sample volume, etc., were examined. It was found that the metal ions studied were quantitatively coprecipitated in the pH range of 5.0–6.5. The detection limits (DL) (n = 10, 3s/b) were found to be 0.68 µg L^?1 for Fe(III) and 0.43 µg L^?1 for Ni(II) and the relative standard deviations (RSD) were ≤4.0%. The proposed method was validated by the analysis of three certified reference materials (TMDA 54.4 fortified lake water, SRM 1568a rice flour, and GBW07605 tea) and recovery tests. The method was successfully applied to sea water, lake water, and various food samples.     

Selective Separation and Preconcentration of Fe(III) and Zn(II) Ions by Solvent Extraction Using a New Triketone Reagent

A simple, rapid, and accurate method was developed for separation and preconcentration of trace levels of iron(III) and zinc(II) ions in environmental samples. Methyl‐2‐(4‐methoxy‐benzoyl)‐3‐(4‐methoxyphenyl)‐3‐oxopropanoylcarbamate (MMPC) has been proposed as a new complexing agent for Fe(III) and Zn(II) ions using solvent extraction prior to their determination by flame atomic absorption spectrometry (FAAS). Fe(III) and Zn(II) ions can be selectively separated from Fe(II), Pb(II), Co(II), Cu(II), Mn(II), Cr(III), Ni(II), Cd(II), Ag(I), Au(III), Pd(II), Cr(VI), and Al(III) ions in the solution by using the MMPC reagent. The analytical parameters such as pH, sample volume, shaking time, amount of MMPC reagent, volume of methyl isobutyl ketone (MIBK), effect of ionic strength, and type of back extractant were investigated. The recovery values for Fe(III) and Zn(II) ions were greater than 95% and the detection limits for Fe(III) and Zn(II) ions were 0.26 and 0.32 µg L^?1, respectively. The precision of the method as the relative standard deviation changed between 1.8 and 2.1%. Calibration curves have a determination coefficient (r²) of at least 0.997 or higher. The preconcentration factor was found to be 100. Accuracy of the method was checked by analyzing of a certified reference material and spiked samples. The developed method was applied to several matrices such as water, hair, and food samples.     

Selective Preconcentration of Trace Amounts of Cu(II) With Surface‐Imprinted Multiwalled Carbon Nanotubes

In this study, a new sorbent is synthesized using surface imprinting technique. Cu(II)‐imprinted multiwalled carbon nanotube sorbent (Cu(II)‐IMWCNT) is used as the solid phase in the solid‐phase extraction method. After the preconcentration procedure, Cu(II) ions are determined by high‐resolution continuum source atomic absorption spectrometry. A total of 0.1 mol L^?1 ethylenediaminetetraacetic acid (EDTA) is used to remove Cu(II) ions from the sorbent surface. The optimum experimental conditions for effective preconcentration of Cu(II), parameters such as pH, eluent type and concentration, flow rate, sample volume, sorbent capacity, and selectivity are investigated. The synthesized solid phase is characterized by Fourier transform infrared spectroscopy and scanning electron microscopy. The maximum adsorption capacities of Cu(II)‐IMWCNT and non‐imprinted solid phases are 270.3 and 14.3 mg g^?1 at pH 5, respectively. Under optimum experimental conditions for Cu(II) ions, the limit of detection is 0.07 μg L^?1 and preconcentration factor is 40. In addition, it is determined to be reusable without significant decrease in recovery values up to 100 adsorption–desorption cycles. Cu(II)‐IMWCNT have a high stability. To check the accuracy of the developed method, certified reference materials, and water samples are analyzed with satisfactory analytical results.     

Determination of Cu,Fe, and Ni in Spices after Preconcentration on Diaion‐HP 20 Resin as Their Zincon Complexes

In this work, a new separation–preconcentration method was developed for the determination of trace amounts of Cu(II), Ni(II), and Fe(III) by flame atomic absorption spectrometry (FAAS). Analytes were complexed by using zincon (2‐[2‐[alpha(2‐hydroxy‐5‐sulfophenylazo) benzylidene] hydrazino] benzoic acid sodium salt). The analyte ions were quantitatively adsorbed on a Diaion HP‐20 resin at pH 5. The retained metal ions on the resin were eluted by acetone. The analytical parameters such as pH of the sample, eluent type and volume, sample volume, and flow rates of the solution and the eluent were investigated. The influences of concomitant ions on the recoveries of the analytes were also examined. The instrumental detection limits for the analytes after application of the presented solid‐phase extraction procedure were in the range of 0.72–1.41 µg/L. The validation of the presented procedure was checked by analyzing certified reference material of SRM1515 Apple Leaves. The procedure was performed by analyzing some spice samples.     

Fractionation of Ni,Cr and Cu from Soil by Sequential Extraction Procedure and Determination by Inductively Coupled Plasma Optical Emission Spectrometry

Five‐step sequential extractions were employed to fractionation of Ni, Cr and Cu in soil polluted by anthropogenic activities and determine the mobility of the metals. Twelve samples were collected on an agricultural area that was located near an airport and intercity roads in Elazig‐Turkey. Exchangeable, organically bounded, carbonate bounded, adsorbed species on Fe and Mn oxides and residual species (except silicates) of Ni, Cr and Cu were extracted into solution by using CaCl₂, Na₄P₂O₇, Na₂EDTA, NH₂OH–HCl and HNO₃–H₂O₂, respectively. Mobile metal concentrations in fractions and total recoverable in soils were determined by using inductively coupled plasma‐optical emission spectrometry (ICP‐OES). Total recoverable Ni, Cr and Cu concentrations were in the range of 40–119, 45–126 and 23–72 mg kg^?1, respectively. It was observed that total concentrations of metals in some of the samples were higher than the permitted values. The sum of the mobile percentages of metals was found to be lower than 50%. The Ni, Cr and Cu percentages for exchangeable species are in the ranges of 0.18–1.64, 0.03–0.59 and 0.42–2.53%, respectively.     

Separation and Preconcentration of Cobalt Using a New Schiff Base Derivative on Amberlite XAD‐7

In this study, a new solid‐phase extraction procedure has been developed for preconcentration and determination of Co ions in different water samples by flame atomic absorption spectrometry (FAAS). Cobalt was preconcentrated as N,N′‐bis(pyridine‐2‐yl‐methyl)benzene‐1,4‐diamine (Co‐BPMBDA) from sample solutions using a column containing Amberlite XAD‐7 and was determined. In order to achieve the best performance for the method, effects of several parameters such as pH, concentrations of ligand, sample flow rate, eluent, and matrix ions on the method efficiency were investigated. Under optimum conditions, the preconcentration factor was found to be 200 for 1000 mL waters samples. Detection limit based on the 3S_b criterion was calculated as 0.24 µg/L for 100 mL of sample solution and relative standard deviation was found to be 1.8%. The method was applied to determine the trace amounts of cobalt in water samples.     

Selective Separation/Preconcentration of Silver Ion in Water by Multiwalled Carbon Nanotubes Microcolumn as a Sorbent

The present paper proposes the application of multiwalled carbon nanotubes (MWCNTs) as a solid adsorbent for selective separation/preconcentration of silver(I) in water samples prior to flame atomic absorption spectrometry. The procedure is based on the solid phase extraction of Ag(I)–2‐mercaptobenzothiazole chelate on MWCNTs. The elution step is carried out with 5 mL of 2 mol L^?1 HNO₃ in acetone solution at a flow rate of 1.0 mL min^?1. The influences of the various analytical parameters including pH of the solution, eluent type, sample volume, flow rates of eluent, matrix ions were investigated for optimization of the presented procedure. Tests of addition/recovery for analyte ion in real samples were performed with satisfactory results. Preconcentration factor and limit of detection for Ag(I) were 160 and 0.21 µg L^?1, respectively. The synthesized MWCNT exhibited excellent stability in eluent solution and its adsorption capacity was 5.4 mg of silver per gram of sorbent. The proposed method was successfully applied to trace silver determination in a variety of environmental water samples.     

Selective Solid Phase Extraction for Separation and Preconcentration of Palladium from Gold Ore and Anode Slime after Complexation with a N4O2 Mixed Donor Ligand Derivative

A selective and sensitive method for the preconcentration, separation, and determination of palladium with flame atomic absorption spectrometry using 4,15‐bis[(4‐methylphenyl)sulfonyl]‐20,21‐dinitro‐2,3,4,5,6,7,9,10,12,13,14,15,16,17‐tetradecahydro‐8,11‐ethano‐1,18,4,8,11,15‐benzodioxa tetraaza cycloicosine (TNACIN) on XAD‐2010 was developed. TNACIN–Pd(II) complex formed acidic aqueous solution (0.075–0.100 M HNO₃) was accumulated on XAD‐2010 and then eluted with 1 M HCl in acetone. The effects of some analytical parameters including pH, TNACIN amount, sample volume, eluent type, and concentration, sample flow rate and matrix ions were studied for optimization of the method. Detection limit and precision were calculated for Pd(II). This method was also verified with CRM and internal standard, and satisfactory results were obtained.     

Dispersive Liquid–Liquid Microextraction for Preconcentration and Determination of Nickel in Water

A method for the determination of nickel in water was developed. The procedure involves preconcentration of nickel by using dispersive liquid–liquid microextraction. The Ni(II) ions were extracted in chloroform in the form of complex with the reagent 2‐(2′‐benzothiazolylazo)‐p‐cresol. Ethanol was used as the disperser solvent. After injection of the extracting mixture in a solution of nickel, a cloudy mixture was observed. A quick centrifugation induces phase separation and thus the settling of rich phase. The nickel content in the rich phase is measured by flame atomic absorption spectrometry. Under optimal conditions, the limit of detection and quantification obtained were 1.4 and 4.7 µg L^?1, respectively. Some parameters used to characterize preconcentration systems, such as enrichment factor and consumption index were calculated and resulted in 29 and 0.34 mL, respectively. After optimization of variables and determination of analytical characteristics, the method was used for the analysis of certified reference materials (BCR‐713: wastewater, effluent and BCR‐414: plankton) and real water samples.     

Removal of Ni(II) Using Cation Exchange Resins in Packed Bed Column: Prediction of Breakthrough Curves

Sorptive removal of Ni(II) from electroplating rinse wastewaters by cation exchange resin Dueolite C 20 was investigated at the temperature of 30°C under dynamic conditions in a packed bed. The effects of sorbent bed length 0.1–0.2 m, fixed flow rate 6 dm³ min^?1, and the initial rinse water concentration (C₀) 53.1 mg L^?1 on the sorption characteristics of Dueolite C 20 were investigated at an influent pH of 6.5. More than 94.5% of Ni(II) was removed in the column experiments. The column performance was improved with increasing bed height and decreasing the flow rate. The Thomas, Yoon–Nelson, Clark, and Wolborska models were applied to the experimental data to represent the breakthrough curves and determine the characteristic design parameters of the column. The sorption performance of the Ni(II) ions through columns could be well described by the Thomas, Yoon–Nelson, and Wolborska models at effluent‐to‐influent concentration ratios (C/C₀) >0.03 and <0.99. Among the all models, the Clark model showed the least average percentage time deviation. The sorptive capacity of electroplating rinse water using Ni(II) was found to be 45.98 mg g^?1.     

Preconcentration of trace multi-elements in water samples using Dowex 50W-x8 and Chelex-100 resins prior to their determination using inductively coupled plasma atomic emission spectrometry (ICP-OES)

This work presents a solid phase extraction (SPE) method for simultaneous preconcentration of trace elements in water samples prior to their ICP-OES determination. Dowex 50W-x8 and Chelex-100 resins were used as SPE sorbent materials for preconcentration of trace Cd, Co, Cr, Cu, Fe, Ni, Pb and Zn. The optimum sample pH, eluent concentration and sample flow rates were found to 6, 3.0 mol L⁻¹ and 3.0 mL min⁻¹, respectively. In terms of multi-element preconcentration capabilities, Dowex 50W-x8 appeared to be a better sorbent. The recoveries for all the tested analytes were >95%. However, Chelex-100 showed a better performance in terms of recovery (>95%) towards Cu, Fe and Zn. Under optimized conditions using Dowex 50W-x8, the relative standard deviations for different metals were <3%. The limits of detection and limits of quantification ranged from 0.01–0.39 μg L⁻¹ and 0.05–0.1.3 μg L⁻¹, respectively. The accuracy of the preconcentration method was confirmed by spike recovery test and the analysis of certified reference materials. The SPE method was applied for preconcentration of the analyte ions in tap water, bottled water and wastewater samples.     

The Adsorption Behavior of Functional Particles Modified by Polyvinylimidazole for Cu(II) Ion

In this paper, a novel composite material the silica grafted by poly(N‐vinyl imidazole) (PVI), i.e., PVI/SiO₂, was prepared using 3‐methacryloxypropyl trimethoxysilane (MPS) as intermedia through the “grafting from” method. The adsorption behavior of metal ions by PVI/SiO₂ was researched by both static and dynamic methods. Experimental results showed that PVI/SiO₂ possessed very strong adsorption ability for metal ions. For different metal ions, PVI/SiO₂ exhibited different adsorption abilities with the following order of adsorption capacity: Cu²⁺ > Cd²⁺ > Zn²⁺. The adsorption material PVI/SiO₂ was especially good at adsorbing Cu(II) ion and the saturated adsorption capacity could reach up to 49.2 mg/g. The empirical Freundlich isotherm was found to describe well the equilibrium adsorption data. Higher temperatures facilitated the adsorption process and thus increased the adsorption capacity. The pH and grafting amount of PVI had great influence on the adsorption amount. In addition, PVI/SiO₂ particles had excellent eluting and regenerating property using diluted hydrochloric acid solution as eluent. The adsorption ability trended to steady during 10 cycles.     

Cloud Point Extraction for the Preconcentration of Silver and Palladium in Real Samples and Determination by Atomic Absorption Spectrometry

A cloud point extraction procedure is presented for the preconcentration and simultaneous determination of Ag⁺ and Pd²⁺ in various samples. After complexation with 2‐((2‐((1H‐benzo[d]imidazole‐2‐yl)methoxy)phenoxy)methyl)‐1H‐benzo[d]imidazol (BIMPI), which was used as a new chelating agent, analyte ions were quantitatively extracted to a phase rich in Triton X‐114 following centrifugation, and determination was carried out by flame atomic absorption spectrometry (FAAS). Under the optimum experimental conditions (i. e., pH = 7.0, 15.0·10^–5 mol/L BIMPI and 0.036% (w/v) Triton X‐114), calibration graphs were linear in the range of 28.0–430.0 μg/L and 57.0–720.0 μg/L with detection limits of 10.0 and 25.0 μg/L for Ag⁺ and Pd²⁺, respectively. The enrichment factors were 35.0 and 28.0 for Ag⁺ and Pd²⁺, respectively. The method has been successfully applied to evaluate these metals in some real samples, including waste water, soil and hydrogenation catalyst samples.     

Removal of Copper,Nickel, and Zinc Ions from Electroplating Rinse Water

Removal of copper, nickel, and zinc ions from synthetic electroplating rinse water was investigated using cationic exchange resin (Ceralite IR 120). Batch ion exchange studies were carried out to optimize the various experimental parameters (such as contact time, pH, and dosage). Influence of co‐existing cations, chelating agent EDTA on the removal of metal ion of interest was also studied. Sorption isotherm data obtained at different experimental conditions were fitted with Langmuir, Freundlich, Redlich–Peterson, and Toth models. A maximum adsorption capacity of 164 mg g^?1 for Cu(II), 109 mg g^?1 for Ni(II), and 105 mg g^?1 for Zn(II) was observed at optimum experimental conditions according to Langmuir model. The kinetic data for metal ions adsorption process follows pseudo second‐order. Presence of EDTA and co‐ions markedly alters the metal ion removal. Continuous column ion exchange experiments were also conducted. The breakeven point of the column was obtained after recovering effectively several liters of rinse water. The treated rinse water could be recycled in rinsing operations. The Thomas and Adams–Bohart models were applied to column studies and the constants were evaluated. Desorption of the adsorbed metal ions from the resin column was studied by conducting a model experiments with Cu(II) ions loaded ion exchange resin column using sulfuric acid as eluant. A novel lead oxide coated Ti substrate dimensionally stable (DSA) anode was prepared for recovery of copper ions as metal foil from regenerated liquor by electro winning at different current densities (50–300 A cm^?2).     

Adsorption Kinetic and Equilibrium Studies on Removal of Lead(II) onto Glutamic Acid/Sepiolite

In this study, a modified method was used to increase the adsorption of lead ions from aqueous solutions by using modified clay mineral on the laboratory scale. Adsorption experiments have been carried out on the use of both thermal activated sepiolite (TAS) and their glutamate/sepiolite modification (GS) as adsorbents. The experimental data was analyzed using adsorption kinetic models (pseudo first‐ and second‐order equations). The pseudo second‐order kinetic model fitted well to the kinetic data (R² ≥ 0.99). Then, the Freundlich and Langmuir models were applied to describe the uptake of Pb(II) on GS and the Langmuir isotherm model agrees well with the equilibrium experimental data (R² ≥ 0.97). The maximum adsorption capacity was observed to be 128.205 mg/g by GS according to the Langmuir equation. Desorption efficiency of the GS was studied by the batch method using EDTA, HCl, and HNO₃ solutions. Desorption of 69.18, 74.55, and 80% of Pb(II) from GS was achieved with 0.1 M EDTA, 0.1 M HCl, and 0.1 M HNO₃ solutions, respectively. FTIR analysis suggests the importance of functional groups such as amino, hydroxyl, and carboxyl during Pb(II) removal. SEM observations demonstrated that an important interaction at the lead‐modified sepiolite interface occurred during the adsorption process. In addition, the thermodynamic constants was calculated that the values of the Gibbs free energy (ΔG*), enthalpy (ΔH*), and entropy (ΔS*) of modification were 86.79 kJ/mol, ?18.91 kJ/mol, and ?354.70 J/mol/K, respectively. The negative value of ΔH* shows exothermic nature of adsorption.     

Assessment of Metal Pollution in Water and Surface Sediments of the Seyhan River,Turkey, Using Different Indexes

The aim of this study was to assess the level of heavy metals (Al, Cd, Cr, Cu, Fe, Mn, Ni, Pb, and Zn) contamination and enrichment in the surface sediments of the Seyhan River, which is the receiving water body of both treated and untreated municipal and industrial effluents as well as agricultural drainage waters generated within Adana, Turkey. Sediment and water samples were taken from six previously determined stations covering the downstream of the Seyhan dam during both wet and dry seasons and the samples were then analyzed for the heavy metals of concern. When both dry and wet seasons were considered, metal concentrations varied significantly within a broad range with Al, 7210–33 967 mg kg^?1 dw; Cr, 46–122 mg kg^?1 dw; Cu, 6–57 mg kg^?1 dw; Fe, 10 294–26 556 mg kg^?1 dw; Mn, 144–638 mg kg^?1 dw; Ni, 82–215 mg kg^?1 dw; Pb, 11–75 mg kg^?1 dw; Zn, 34–146 mg kg^?1 dw in the sediments while Cd was at non‐detectable levels for all stations. For both seasons combined, the enrichment factor (EF) and the geo‐accumulation index (I_geo) for the sediments in terms of the specified metals ranged from 0.56 to 10.36 and ?2.92 to 1.56, respectively, throughout the lower Seyhan River. The sediment quality guidelines (SQG) of US‐EPA suggested the sediments of the Seyhan River demonstrated “unpolluted to moderate pollution” of Cu, Pb, and Zn, “moderate to very strong pollution” of Cr and Ni. The water quality data, on the other hand, indicated very low levels of these metals suggesting that the metal content in the surface sediments were most probably originating from fine sediments transported along the river route instead of water/wastewater discharges with high metal content.     

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.