Automated quantitative and isotopic (13C) analysis of dissolved inorganic carbon and dissolved organic carbon in continuous-flow using a total organic carbon analyser

A method for the automated (13)C analysis of dissolved inorganic and organic carbon species has been developed to operate on a continuous-flow isotope ratio mass spectrometer (CF-IRMS). For natural and anthropogenic carbon species, the (13)C stable isotope has proven to be an excellent environmental tracer. Analytical performance tests were carried out on various organic compounds from easily oxidisable (sugar) to difficult (humic acid). A set of natural samples was also analysed to confirm the flexibility of the system. Analytical precision (2sigma) is typically <0.20 per thousand with sample reproducibility from 0.10-0.35 per thousand depending on reactivity of material. We believe this to be the first successful use of a total organic carbon (TOC) analyser for both dissolved inorganic and, specifically, dissolved organic species for (13)C stable isotope analysis in an automated CF-IRMS system. Routine analysis is achieved fairly quickly, is relatively simple with little or no sample manipulation, and will allow new and exciting studies for stable isotope research in both natural abundance and organic tracer studies not easily achieved before.     

New methods for the direct determination of dissolved inorganic, organic and total carbon in natural waters by Reagent-Free Ion Chromatography and inductively coupled plasma atomic emission spectrometry

New methods have been developed and applied successfully for the determination of dissolved inorganic, organic and total carbon in water samples. The new methods utilize two instrumental setups, Reagent-Free™ Ion Chromatography (RF™-IC) and inductively coupled plasma atomic emission spectrometry (ICP-AES). Dissolved inorganic carbon (DIC) was measured in untreated samples along with Cl⁻, F⁻ and SO₄²⁻ using RF™-IC and by in-line mixing with 0.1 M HNO₃ to enhance CO₂ removal in the nebulizer, followed by ICP-AES analysis. Total dissolved carbon (TDC) was measured by in-line mixing with 0.1 M NaOH following ICP-AES analysis. Dissolved organic carbon (DOC) was obtained as the difference between DIC and TDC. Only non-volatile organic carbon could be detected by the present method. The workable limits of detection obtained in the present study were 0.5 mM (RF™-IC) and 0.1 mM (ICP-AES) for dissolved inorganic and organic carbon, respectively. The power of the new methods lies in routine analysis of DIC and DOC in samples of natural waters of variable composition and salinity using analytical techniques and facilities available in most laboratories doing water sample analysis. The techniques are sensitive and precise, can be automated using gas-tight sample vials and auto-samplers, and are independent of most elemental interferences with the exception of chloride overload by saline samples when using RF™-IC. The new methods were successfully applied for analysis of DIC and DOC in selected samples of natural and synthetic waters.     

Simple and accurate method for determining dissolved inorganic carbon in environmental water by reaction headspace gas chromatography

We investigate a simple and accurate method for quantitatively analyzing dissolved inorganic carbon in environmental water by reaction headspace gas chromatography. The neutralization reaction between the inorganic carbon species (i.e. bicarbonate ions and carbonate ions) in environmental water and hydrochloric acid is carried out in a sealed headspace vial, and the carbon dioxide formed from the neutralization reaction, the self‐decomposition of carbonic acid, and dissolved carbon dioxide in environmental water is then analyzed by headspace gas chromatography. The data show that the headspace gas chromatography method has good precision (relative standard deviation ≤ 1.63%) and accuracy (relative differences ≤ 5.81% compared with the coulometric titration technique). The headspace gas chromatography method is simple, reliable, and can be well applied in the dissolved inorganic carbon detection in environmental water.     

Determination of dissolved methane in natural waters using headspace analysis with cavity ring-down spectroscopy

Methane (CH₄) is the third most abundant greenhouse gas (GHG) but is vastly understudied in comparison to carbon dioxide. Sources and sinks to the atmosphere vary considerably in estimation, including sources such as fresh and marine water systems. A new method to determine dissolved methane concentrations in discrete water samples has been evaluated. By analyzing an equilibrated headspace using laser cavity ring-down spectroscopy (CRDS), low nanomolar dissolved methane concentrations can be determined with high reproducibility (i.e., 0.13 nM detection limit and typical 4% RSD). While CRDS instruments cost roughly twice that of gas chromatographs (GC) usually used for methane determination, the process presented herein is substantially simpler, faster, and requires fewer materials than GC methods. Typically, 70-mL water samples are equilibrated with an equivalent amount of zero air in plastic syringes. The equilibrated headspace is transferred to a clean, dry syringe and then drawn into a Picarro G2301 CRDS analyzer via the instrument’s pump. We demonstrate that this instrument holds a linear calibration into the sub-ppmv methane concentration range and holds a stable calibration for at least two years. Application of the method to shipboard dissolved methane determination in the northern Gulf of Mexico as well as river water is shown. Concentrations spanning nearly six orders of magnitude have been determined with this method.     

Conversion efficiency of the high-temperature combustion technique for dissolved organic carbon and total dissolved nitrogen analysis

The measurements of dissolved organic carbon (DOC) and total dissolved nitrogen (TDN) in seawater are key in global change and coastal eutrophication studies. Nowadays, the high-temperature combustion (HTC) technique is a widely used method for DOC and TDN analysis. However, uncertainties exist about the operation of the catalyst in the conversion process of DOC and TDN in the HTC method. In this study, five different ‘catalyst’ materials were tested for their blanks, calibration slopes, and conversion efficiency of DOC and TDN using the Shimadzu TOC 5000A total organic carbon analyser coupled to a Sievers NCD 255 nitrogen chemiluminescence detector. The materials included four metallic catalysts (Shimadzu and Johnson 0.5% Pt–alumina, 13% Cu(II)O–alumina, 0.5% Pd–alumina) and quartz beads. The results indicated that DOC blank signals for the HTC approach using metallic catalysts with an alumina support are higher compared with quartz beads, as a result of the amphoteric nature of the alumina. However, the slopes of the standard calibration graphs were lowest for DOC and TDN determinations on the quartz beads. The DOC recoveries for the metallic catalysts were close to 100% for all compounds tested, with the exception of ammonium pyrrolidine dithiocarbamate. Using quartz beads, poor recoveries were obtained for a range of organic compounds, including the commonly used calibration compounds potassium hydrogen phthalate and glycine. The TDN recoveries for all compounds were typically >90%, with the exception of NaNO₂. Furthermore, analysis using the CuO–alumina and Pd–alumina catalysts and quartz beads showed low recoveries for NH₄Cl. This study showed that catalyst performance should be verified on a regular basis using model compounds and blank checks made during every run, and that the Shimadzu 0.5% Pt–alumina material was an efficient catalyst for DOC and TDN analyses using the coupled total organic carbon–nitrogen chemiluminescence detector (TOC-NCD) analyser.     

A reagent-free SIA module for monitoring of sugar, color and dissolved CO2 content in soft drinks

This work presents a new sequential injection analysis (SIA) method and a module for simultaneous and real-time monitoring of three key parameters for the beverage industry, i.e., the sugar content (measured in Brix), color and dissolved CO₂. Detection of the light reflection at the liquid interface (the schlieren effect) of sucrose and water was utilized for sucrose content measurement. A near infrared LED (890 ± 40 nm) was chosen as the light source to ensure that all the ingredients and dyes in soft drinks will not interfere by contributing light absorption. A linear calibration was obtained for sucrose over a wide concentration range (3.1-46.5 Brix). The same module can be used to monitor the color of the soft drink as well as the dissolved CO₂ during production. For measuring the color, the sample is segmented between air plugs to avoid dispersion. An RGB-LED was chosen as the light source in order to make this module applicable to a wide range of colored samples. The module also has a section where dissolved CO₂ is measured via vaporization of the gas from the liquid phase. Dissolved CO₂, in a flowing acceptor stream of water resulting in the change of the acceptor conductivity, is detected using an in-house capacitively coupled contactless conductivity detector (C⁴D). The module includes a vaporization unit that is also used to degas the carbonated drink, prior the measurements of sucrose and color within the same system. The method requires no chemicals and is therefore completely friendly to the environment.     

Use of GC and equilibrium calculations of CO2 saturation index to indicate whether freshwater bodies in north-eastern Germany are net sources or sinks for atmospheric CO2

The determination of CO₂ saturation by two different methods is described for freshwater bodies of differing trophic states, hydrology and chemistry in the North-East of Germany. Direct measurements were carried out by gas chromatography and values were calculated from the dissolved inorganic carbon concentration and pH. These results were in good agreement. In both cases, the CO₂ saturation index was calculated from the carbon dioxide/carbonate/hydrogencarbonate equilibrium in water. An overestimation of CO₂ saturation index will be caused at pH > 7 by neglecting the calcium forming ion pairs with HCO_{3– and CO}3_{2–. The CO}2 _{saturation patterns exhibited seasonal changes in all the lakes investigated which were variable within each trophic group. A direct relationship was found between the increasing trophic state and undersaturation of CO}2 _{during the periods of high primary production. Thus, with respect to the atmosphere, these freshwater bodies act mostly as sources of CO}2_{. Periods of ice covering and clear-water phases are characterized by high CO}2 _{supersaturation and therefore the surface waters investigated are CO}2 _{sources for short periods only.} Received: 17 October 1997 / Revised: 16 February 1998 / Accepted: 17 February 1998     

Use of GC and equilibrium calculations of CO2 saturation index to indicate whether freshwater bodies in north-eastern Germany are net sources or sinks for atmospheric CO2

The determination of CO₂ saturation by two different methods is described for freshwater bodies of differing trophic states, hydrology and chemistry in the North-East of Germany. Direct measurements were carried out by gas chromatography and values were calculated from the dissolved inorganic carbon concentration and pH. These results were in good agreement. In both cases, the CO₂ saturation index was calculated from the carbon dioxide/carbonate/hydrogencarbonate equilibrium in water. An overestimation of CO₂ saturation index will be caused at pH > 7 by neglecting the calcium forming ion pairs with HCO_{3– and CO}3_{2–. The CO}2 _{saturation patterns exhibited seasonal changes in all the lakes investigated which were variable within each trophic group. A direct relationship was found between the increasing trophic state and undersaturation of CO}2 _{during the periods of high primary production. Thus, with respect to the atmosphere, these freshwater bodies act mostly as sources of CO}2_{. Periods of ice covering and clear-water phases are characterized by high CO}2 _{supersaturation and therefore the surface waters investigated are CO}2 _{sources for short periods only.}     

An assessment of analytical performance of dissolved organic nitrogen and dissolved organic phosphorus analyses in marine environments: a review

To better understand the cycling of marine dissolved organic matter, analytical methods are required allowing for data on dissolved organic nitrogen and phosphorus (DON and DOP) to be acquired with high analytical performance. The coverage of documented DON and DOP analytical performance is very limited; instead analytical data are mostly available for total dissolved N and P (TDN and TDP) analyses. This substitution overestimates analytical performance for DON and DOP measurements due to the cumulative effect of Standard Deviation applied for detection limit and precision evaluations. The little available data obtained by photolytic, chemical, a combination of both, and high temperature combustion methods indicate that current detection limit is 0.30 µM for DON and 0.010 µM for DOP. Precision for both analytes, in general, is ≤4.5%. The data on accuracy is scarce despite availability of Reference Materials for TDN and NO₃^? + NO₂^? analyses, and for the TDN measurement is <5%; even fewer data exist for TDP due to a lack of reference material for this analysis. The Beer–Lambert law is linear up to 200 µM for TDN and 5–6 µM for TDP. Current analytical abilities for DON/DOP measurements are not ready yet to set the level of dissolved organic carbon analysis. The advance in the analytical performance for DON and DOP measurements depends upon the possibility to improve the analytical performance for dissolved inorganic N and P measurements involved in DON and DOP estimations. For the DOP analysis, an international standard method becomes necessary to develop and evaluate collaboratively. The chemical oceanographers’ community should reconsider requirements needed for the coverage of analytical performance for DON and DOP measurements to make this data more shareable and transparent. The lack of these data protracts marine analysts from attaining further methods improvement and development.     

Adsorption equilibria of CO<Subscript>2</Subscript> and CH<Subscript>4</Subscript> in cation-exchanged zeolites 13X

Ion-exchange with different cations (Na⁺, NH₄ ⁺, Li⁺, Ba²⁺ and Fe³⁺) was performed in binderless 13X zeolite pellets. Original and cation-exchanged samples were characterized by thermogravimetric analysis coupled with mass spectrometry (inert atmosphere), X-ray powder diffraction and N₂ adsorption/desorption isotherms at 77 K. Despite the presence of other cations than Na (as revealed in TG-MS), crystalline structure and textural properties were not significantly altered upon ion-exchange. Single component equilibrium adsorption isotherms of carbon dioxide (CO₂) and methane (CH₄) were measured for all samples up to 10 bar at 298 and 348 K using a magnetic suspension balance. All of these isotherms are type Ia and maximum adsorption capacities decrease in the order Li > Na > NH₄–Ba > Fe for CO₂ and NH₄–Na > Li > Ba for CH₄. In addition to that, equilibrium adsorption data were measured for CO₂/CH₄ mixtures for representative compositions of biogas (50 % each gas, in vol.) and natural gas (30 %/70 %, in vol.) in order to assess CO₂ selectivity in such scenarios. The application of the Extended Sips Model for samples BaX and NaX led to an overall better agreement with experimental data of binary gas adsorption as compared to the Extended Langmuir Model. Fresh sample LiX show promise to be a better adsorption than NaX for pressure swing separation (CO₂/CH₄), due to its higher working capacity, selectivity and lower adsorption enthalpy. Nevertheless, cation stability for both this samples and NH₄X should be further investigated.     

Molecular Mechanisms of the Effect of Water on CO<Subscript>2</Subscript>/CH<Subscript>4</Subscript> Mixture Adsorption in Slitlike Carbon Pores

The grand canonical ensemble Monte Carlo method has been used to study adsorption of carbon dioxide, methane, and their mixtures with different compositions in slitlike carbon pores at a temperature of 318 K and pressures below 60 atm. The data obtained have been used to show the effect of fixed amounts of pre-adsorbed water (19, 37, and 70 vol %) on the adsorption capacity and selectivity of carbon micro- and mesopores. The presence of water reduces the adsorption capacity throughout the studied pressure range upon adsorption of gaseous mixtures containing less than 50% CO₂, as well as in narrow micropores (with widths of 8?12 Å). Upon adsorption of mixtures with CO₂ contents higher than 50%, the adsorption capacity of pores with low water contents appears, in some region of the isotherm, to be higher than that in dry pores. In the case of wide pores (16 and 20 Å), this region is located at low and moderate pressures, while for mesopores it is located at high pressures. The analysis of the calculated data has shown that the molecular mechanism of the influence of preadsorbed water on the adsorption capacity is based on the competition between the volume accessible for adsorption (decreases the capacity) and the strength of the interaction between carbon dioxide molecules and water molecules (increases the capacity). Therewith, the larger the surface area of the water–gas contact, the stronger the H₂O–CO₂ interactions.     

Efficiency of CO<Subscript>2</Subscript> Dissociation in a Radio-Frequency Discharge

One possible solution to mitigating the effects of high atmospheric concentrations of carbon dioxide (CO₂) is the use of a plasma source to break apart the molecule into carbon monoxide (CO) and oxygen. This work experimentally investigates the efficiency of dissociation of CO₂ in a 1-kW radio-frequency (rf) plasma source operating at 13.56-MHz in a low-pressure discharge. Mass spectrometry diagnostics are used to determine the species present in the discharge, and these measurements are used to calculate the energy efficiency and conversion efficiency of CO₂ dissociation in the rf plasma source. Experimental results have found that the conversion efficiency of CO₂ to CO can reach values near 90%, however energy efficiency reaches a maximum of 3%. A theoretical energy cost analysis is also given as a method to evaluate the effectiveness of any plasma system designed for CO₂ emissions reduction.     

Conversion of CO<Subscript>2</Subscript> in a trifluoroacetic acid

It is determined that the conversion of carbon dioxide in anhydrous trifluoroacetic acid (TFA) takes place at room temperature and atmospheric pressure, yielding a resinous product. Activation of CO₂ by the oxygen dissolved in a TFA is investigated.     

Effect of oxygen activity and water partial pressure to degradation rate of Ni cermet electrode contacting Zr<Subscript>0.84</Subscript>Y<Subscript>0.16</Subscript>O<Subscript>1.92</Subscript> electrolyte

The time curves of full polarization resistance of Ni cermet electrode modified with CeO_{2 − δ} additive were studied by means of impedance spectroscopy in binary gas mixtures x% H₂ + (100 − x)% H₂O, 10% CO + 90% CO₂ and multicomponent gas mixtures H₂ + CO₂ + H₂O + CO + Ar of various composition at the temperature of 900°C. The Ni cermet electrode degradation rate in binary gas mixtures H₂ + H₂O was shown to increase sharply at the partial water pressure over 45%. The Ni cermet electrode degradation rate in the mixture of 10% CO + 90% CO₂ was significantly lower than that in 10% H₂ + 90% H₂O. The major changes in the electrode characteristics upon long exposure in working conditions were accounted for by changes in the high-frequency partial polarization resistance. In the course of long testing, the electrode microstructure was not significantly changed. In the presence of hydrogen-containing components (H₂ and H₂O), the carbon-containing components (CO and CO₂) were shown to make an insignificant contribution to the current generation processes in Ni cermet electrode. It was suggested that strong degradation of Ni cermet electrode was caused by poisoning its reaction sites with strongly linked adsorption forms of water (hydroxyls) at the positive charge of electrode.     

Determination of total dissolved inorganic carbon in freshwaters by reagent-free ion chromatography

Studies of inorganic carbon cycle in natural waters provide important information on the biological productivity and buffer capacity. Determination of total inorganic carbon, alkalinity and dissolved carbon dioxide gives an indication of the balance between photosynthesis and respiration by biota, both within the water column and sediments, and carbon dioxide transfers from the water column to the atmosphere. There are few methods to measure and distinguish the different forms of inorganic carbon, but all require a measure or an indirect quantification of total inorganic carbon. A direct measurement of TIC in water is made possible by the introduction of electrolytic generated hydroxide eluent in ion chromatography which allows to detect a chromatographic peak for carbonate. The advantage of this method is that all the inorganic forms of carbon are converted in carbonate at eluent pH and can be detected as a single peak by conductivity detection. Repeatability of carbonate peak was evaluated at different levels from 0.02 to 6 mequiv.l(-1) both in high purity water and in real samples and ranged from 1 to 9%. The calibration curve was not linear and has to be fitted by a quadratic curve. Limit of detection was estimated to be 0.02 mequiv.l(-1). Accuracy has been estimated by comparing ion chromatography method with total inorganic carbon calculated from alkalinity and pH. The correlation between the two methods was good (R(2)=0.978, n=141). The IC method has been applied to different typologies of surface waters (alpine and subalpine lakes and rivers) characterised by different chemical characteristics (alkalinity from 0.05 to 2 mequiv.l(-1) and pH from 6.7 to 8.5) and low total organic carbon concentrations. This analytical method allowed to describe the distribution of TIC along the water column of two Italian deep lakes.     

Synthesis of the mixed oxide catalysts based upon the nickel-copper hydrotalcites of the type Ni<Subscript>x</Subscript>Cu<Subscript>6-x</Subscript>Cr<Subscript>2</Subscript>(OH)<Subscript>16</Subscript>(CO<Subscript>3</Subscript>)×4H<Subscript>2</Subscript>O

Summary High resolution TG coupled to a gas evolution mass spectrometer has been used to study the thermal properties of a chromium based series of Ni/Cu hydrotalcites of formulae Ni_xCu_6-xCr₂(OH)₁₆(CO₃)×4H₂O where x varied from 6 to 0. The effect of increased Cu composition results in the increase of the endotherms and mass loss steps to higher temperatures. Evolved gas mass spectrometry shows that water is lost in a number of steps and that the interlayer carbonate anion is lost simultaneously with hydroxyl units. Differential scanning calorimetry was used to determine the heat flow steps for the thermal decomposition of the synthetic hydrotalcites. Hydrotalcites in which M²⁺ consist of Cu, Ni or Co form important precursors for mixed metal-oxide catalysts. The application of these mixed metal oxides is in the wet catalytic oxidation of low concentrations of retractable organics in water. Therefore, the thermal behaviour of synthetic hydrotalcites, Ni_xCu_6-xCr₂(OH)₁₆CO₃×nH₂O was studied by thermal analysis techniques in order to determine the correct temperatures for the synthesis of the mixed metal oxides.     

Adsorption technology for direct recovery of compressed,pure CO<Subscript>2</Subscript> from a flue gas without pre-compression or pre-drying

The effects of the sorption and the regeneration temperatures on the performance of a novel rapid thermal swing chemisorption (RTSC) process (Lee and Sircar in AIChE J. 54:2293–2302, 2008) for removal and recovery of CO₂ from an industrial flue gas without pre-compression, pre-drying, or pre-cooling of the gas were mathematically simulated. The process directly produced a nearly pure, compressed CO₂ by-product stream which will facilitate its subsequent sequestration. Na₂O promoted alumina was used as the CO₂ selective chemisorbent, and the preferred temperatures were found to be, respectively, 150 and 450 °C for the sorption and regeneration steps of the process. The specific cyclic CO₂ production capacity of the process and the pressure of the by-product CO₂ gas were substantially increased over those previously achieved by using the sorption and regeneration temperature of, respectively, 200 and 500 °C (Lee and Sircar in AIChE J. 54:2293–2302, 2008). The net compressed CO₂ recovery from the flue gas (∼92%) did not change. However, substantially different amounts of high and low pressure steam purges were necessary for comparable degree of desorption of CO₂. A first pass estimation of the capital and the operating costs of the RTSC process was carried out for a relatively moderate size application (flue gas clean up and CO₂ recovery from a ∼80 MW coal fired power plant). Both costs were substantially lower than those for a conventional absorption process using MEA as the CO₂ solvent (Desideri and Paolucci in Energy Convers. Manag. 40:1899–1915, 1999).     

Oxygen reduction in acid media by a Ru<Subscript>x</Subscript>Fe<Subscript>y</Subscript>Se<Subscript>z</Subscript>(CO)<Subscript>n</Subscript> cluster catalyst dispersed on a glassy carbon-supported Nafion film

Electrocatalytic oxygen reduction was studied on a Ru_xFe_ySe_z(CO)_n cluster catalyst with Vulcan carbon powder dispersed into a Nafion film coated on a glassy carbon electrode. The synthesis of the electrocatalyst as a mixture of crystallites and amorphous nanoparticles was carried out by refluxing the transition metal carbonyl compounds in an organic solvent. Electrocatalysis by the cluster compound is discussed, based on the results of rotating disc electrode measurements in a 0.5 M H₂SO₄. A Tafel slope of −80.00±4.72 mV dec⁻¹ and an exchange current density of 1.1±0.17×10⁻⁶ mA cm⁻² was calculated from the mass transfer-corrected curve. It was found that the electrochemical reduction reaction follows the kinetics of a multielectronic (n=4e⁻) charge transfer process producing water, i.e. O₂+4H⁺+4e⁻→2H₂O. Electronic Publication     

Fiber-optic microsensor for high resolution pCO2 sensing in marine environment

A fast responding fiber-optic microsensor for sensing pCO₂ in marine sediments with high spatial resolution is presented. The tip diameter varies typically between 20 and 50 μm. In order to make the pH-indicator ¶8-hydroxypyrene-1,3,6-trisulfonate soluble in the ethyl cellulose matrix, it was lipophilized with tetraoctylammonium as the counterion [HPTS-(TOA)₄]. The microsensor was tuned to sense very low levels of dissolved carbon dioxide which are typically present in marine systems. The detection limit is 0.04 hPa pCO₂ which corresponds to 60 ppb CO₂ of dissolved carbon dioxide. A soluble Teflon derivative with an extraordinarily high gas permeability was chosen as a protective coating to eliminate interferences by ionic species like chloride or pH. Response times of less than 1 min were observed. The performance of the new microsensor is described with respect to reproducibility of the calibration curves, dynamic range, temperature behavior, long term stability and storage stability. The effect of hydrogen sulfide as an interferent, which is frequently present in anaerobic sediment layers, was studied in detail.     

Development of solid-phase microextraction to study dissolved organic matter—Polycyclic aromatic hydrocarbon interactions in aquatic environment

Solid-phase microextraction coupled with gas chromatography and mass spectrometry (SPME–GC–MS) was developed for the study of interactions between polycyclic aromatic hydrocarbons (PAHs) and dissolved organic matter (DOM). After the determination of the best conditions of extraction, the tool was applied to spiked water to calculate the dissolved organic carbon water distribution coefficient (K_DOC) in presence of different mixtures of PAHs and Aldrich humic acid. The use of deuterated naphthalene as internal standard for freely dissolved PAH quantification was shown to provide more accuracy than regular external calibration. For the first time, K_DOC values of 18 PAHs were calculated using data from SPME–GC–MS and fluorescence quenching; they were in agreement with the results of previous studies. Competition between PAHs, deuterated PAHs and DOM was demonstrated, pointing out the non-linearity of PAH–DOM interactions and the stronger interactions of light molecular weight PAHs (higher K_DOC values) in absence of high molecular weight PAHs.