Characterization of Chlorolignins in Bleached Kraft Pulp Mill Effluents Using Elemental Analysis and Fingerprinting by CuO Oxidation And Hplc

Abstract Elemental analyses and chemical degradation techniques were applied to characterize lignin compounds in different stages of the chlorine bleaching process and in total mill effluent. Ultrafiltration was used for separation of chlorolignins into three nominal molecular weight fractions. Alkaline CuO oxidation products were analyzed by HPLC with diode array detection. Major compounds were identified by reference to authentic compounds. For comparison, native lignins (MWL), kraft lignins, and humic substances were studied as well. The oxygen, carbon and organic chlorine contents were closely similar in the various mill samples and their fractions. In all mill samples, vanillin and 6-c…

17O NMR study of isomeric monochloro- and monohydroxy-benzaldehydes and chlorinated salicylaldehydes

The 17O NMR chemical shifts of isomeric monochloro- and monohydroxy-benzaldehydes and chlorinated salicylaldehydes were measured at 40°C for 0.25 M CDCI3 solutions. The 17O NMR chemical shift of the carbonyl oxygen of the compounds studied varies from 506 to 573 ppm measured from external D2O. The observed variation is probably mainly due to the intramolecular hydrogen bonding between the adjacent carbonyl and hydroxyl groups. The 17O NMR chemical shift range of the hydroxyl oxygen is from 80 to 98 ppm.

Acute toxicity of some chlorinated phenolic compounds toSelenastrum capricornutum and phytoplankton

Acute toxicity of several chlorinated phenolic compounds detected in waste waters of bleached pulp was determined forSelenastrum capricornutum and indigenous phytoplankton using bioassays. Five of the phenolic compounds were chlorocatechols, four were chloroguaiacols and one was chlorosyringol. The response ofSelenastrum capricornutum to chemicals was measured by cell counting and phytoplankton14C-uptake. Chlorinated catechols inhibited the growth ofSelenastrum cultures in lower concentrations than chlorinated guaiacols. The increasing number of chlorine substituents on the phenolic ring increased the toxicity of both chlorinated catechols and guaiacols. The EC50-values (0-96 hr) of the com…

Pyrolysis of humic acids from digested and composted sewage sludge

Humic acids (HAs) were extracted from four digested sewage sludge samples composted for four months, one, two and four years. HAs were pyrolyzed at three different temperatures applying both conventional and in situ methylation (ISM) pyrolysis. The pyrolysates were analyzed using gas chromatography-mass spectrometry (GC/MS). Derivatization (ISM) and pyrolysis temperature had dramatic effects on the composition and relative amounts of the pyrolysates. Among the derivatized HA fragments aliphatic compounds prevailed under all the pyrolysis conditions tested. Aromatic substances consisting mainly of guaiacyl-type compounds were detected in higher abundances only at elevated temperatures. Witho…

Gas chromatographic separation of acetylated chlorinated phenols, guaiacols and catechols on an SE-30 quartz capillary column

Mass spectra of chlorinated aromatics formed in pulp bleaching: I—chlorinated catechols

The fragmentation of chlorinated guaiacols (2-methoxyphenols) on electron impact has been studied. The most common fragmentation processes are interpreted and in some cases the small differences between spectra of positional isomers are explained. In addition to the well-known alkyl-oxygen fission (loss of methyl radical), metastable ion studies and deuterium labelling have indicated several new fragmentation pathways. The most characteristic are the formation of [MCH3HCl]+ and [MCH3Cl]+· ions. In general, however, the spectra of positional isomers are shown to be very similar.

Refractory organic pollutants and toxicity in pulp and paper mill wastewaters

This review describes medium and high molecular weight organic material found in wastewaters from pulp and paper industry. The aim is to review the versatile pollutants and the analysis methods for their determination. Among other pollutants, biocides, extractives, and lignin-derived compounds are major contributors to harmful effects, such as toxicity, of industrial wastewaters. Toxicity of wastewaters from pulp and paper mills is briefly evaluated including the methods for toxicity analyses. Traditionally, wastewater purification includes mechanical treatment followed by chemical and/or biological treatment processes. A variety of methods are available for the purification of industrial w…

Molecular orbital studies on brominated diphenyl ethers. Part II—reactivity and quantitative structure–activity (property) relationships

Polybrominated diphenyl ethers (PBDEs) are widely used as flame retardants and are increasingly turning up in the environment. Their structural similarities to polychlorinated biphenyls and thyroid hormones suggest they may be a risk to human health. The present study examines the reactivity of brominated diphenyl ethers (BDEs) on the basis of the electronic structures as calculated by semiempirical AM1 self-consistent field molecular orbital (SCF-MO) method. Frontier orbital energies were used to elucidate the reactivity of BDEs in electrophilic, nucleophilic and photolytic reactions. From an examination of the frontier electron densities, the regioselectivity, or orientation, of metabolic…

Melting behaviour of d-sucrose, d-glucose and d-fructose

The melting behaviour of d-sucrose, d-glucose and d-fructose was studied. The melting peaks were determined with DSC and the start of decomposition was studied with TG at different rates of heating. In addition, melting points were determined with a melting point apparatus. The samples were identified as d-sucrose, alpha-d-glucopyranose and beta-d-fructopyranose by powder diffraction measurements. There were differences in melting between the different samples of the same sugar and the rate of heating had a remarkable effect on the melting behaviour. For example, T(o), DeltaH(f) and T(i) (initial temperature of decomposition) at a 1 degrees Cmin(-1) rate of heating were 184.5 degrees C, 126…

Bioaccumulation of organochlorine compounds in earthworms

Abstract Bioaccumulation of chlorophenolic wood preservatives 2,3,4,6-tetrachlorophenol (2346-TeCP) and pentachlorophenol (PeCP) and their metabolites in earthworms were studied in the laboratory, and by taking worm samples from the contaminated soil of a sawmill which was abandoned 28 yr ago. In two laboratory experiments 2346-TeCP (containing PeCP as impurity) was added into the soil, and samples were taken at certain intervals both from the soil and the earthworms ( Lumbricus rubellus in experiment 1 and Aporrectodea caliginosa tuberculata in experiment 2). Considerable amounts of chlorophenols were found in field samples. Soil concentrations ranged from 157 to 338 μg 2346-TeCP g −1 dry …

Analysis of Trace Pharmaceuticals and Related Compounds in Municipal Wastewaters by Preconcentration, Chromatography, Derivatization, and Separation Methods

A significant portion of pharmaceuticals and other organic chemicals consumed by people and animals are released into municipal wastewater treatment plants. Most of them are degraded during the wastewater treatment processes, but some of them degrade only partially and may be widely transported and dispersed into the aquatic environment. This is why efficient and fast analytical methods are needed for detection of organic compounds in wastewaters at trace levels. Because wastewaters often consist of complex matrices and high-molecular mass materials, e.g., lignocellulosic biomass, which may bring challenges to the sample preparation procedures, efficient pre-concentration methods such as so…

Gas-liquid chromatographic analyses

A mixture of all nine chlorinated 4-hydroxybenzaldehydes and the parent homologue was separated on a non-polar SE-30 capillary column using various isothermal and temperature-programmed operating conditions. The relative retention data for the compounds are given and the retention indices together with the retention index increments for each position of chlorine substitution are examined. The retention order 3-Cl<parent<2,5-di-Cl<2,3-di-Cl<3,5-di-Cl<2-Cl<2,3,5-tri-Cl<2,3,6-tri-Cl<2,6-di-Cl<tetra-Cl isomer obtained indicates that the effect of the position of substitution on the retention behaviour is greater than that of the number of chlorine atoms. The retention is maximal with 2-Cl and 2…

Chemical degradation products of lignin and humic substances part I Synthesis, structure verification and gas chromatographic separation of chlorinated vanillins and syringaldehydes

Abstract Chlorinated vanillins (4-hydroxy-3-methoxybenzaldehydes) and syringaldehydes (3,5-dimethoxy-4-hydroxy-benzaldehydes) were synthesized and their purities and structures were examined by quartz capillary gas chromatography and mass spectrometry. The detailed procedures for the synthesis, gas chromatographic separation and mass spectroscopic features are presented.

Molecular orbital studies on brominated diphenyl ethers. Part I—conformational properties

Polybrominated diphenyl ethers (PBDEs) are widely used as additive flame retardants and quantities in the environment are on the rise. Because they are structurally related to polychlorinated biphenyls and also to thyroid hormones, there is serious concern that PBDEs may pose a danger to human health. Knowledge of their conformational properties is key to assessing their environmental fate and risk. The conformational properties of PBDEs were investigated by quantum chemical methods including semiempirical self-consistent field molecular orbital (SCF-MO), ab initio SCF-MO and density functional theory (DFT). Conformational analyses of model congeners 2,2',4,6'-tetrabromodiphenyl ether and 2…

Gas chromatographic study of acetyl derivatives of chlorinated 4-hydroxybenzaldehydes

The GC retention times of 4-hydroxybenzaldehyde and its chloro derivatives have been measured on three nonpolar capillary columns. Multiple linear regression analysis has been used to explain the mobility of chlorinated compounds relative to the reference compound 4-hydroxybenzaldehyde. The most important effects have shown to be due to the number of chlorine atoms and the substituents ortho to the formyl group. Other effects have also been observed but found to be unable to explain the GC data.

13C NMR study on the methoxy carbon chemical shifts in chloro-substituted anisoles and guaiacols

The 13C NMR chemical shifts of methoxy carbons in chlorinated anisoles and guaiacols have been measured for acetone-d6 solutions. Multiple linear regression analysis, and also ‘simple sum rule’ calculations, have been used to estimate the effects of the chlorine atoms (the position and degree of substitution) on the chemical shifts. The most important effects have shown to be due to the chlorine atoms adjacent to the methoxy and hydroxy substituents. For chlorinated guaiacols, the greatest effect is due to the chlorine atom adjacent to the methoxy group. For chlorinated anisoles, the substituents adjacent to the methoxy group (2,6-disubstitution) cause large effects. For both groups of comp…

Polychlorinated phenols and their metabolites in soil and earthworms of sawmill environment

Abstract Topsoil and earthworm samples collected from three Finnish sawmill environments were analysed for polychlorinated phenols, 2,3,4,6-tetrachloro- and pentachlorophenol, and their metabolites. Analyses were carried out by gas chromatography/mass spectrometry using a selected ion monitoring technique and by dual-channel gas chromatography using quartz capillary columns and two electron capture detectors. The total chlorophenol concentrations ranged from ca. 260 to 480 μg/g (dry weight) in soil and from ca. 140 to 3500 μg/g fat in earthworms. The most important metabolites in soil were chlorinated dihydroxy-benzenes (also at ppm level); only traces of chlorinated anisoles were detected …

Biological effects of high molecular weight lignin derivatives

Abstract A number of high molecular weight (HMW) lignin derivatives possessing varied chemical properties were screened for their biological effects in order to obtain more information on the possible structural features of HMW lignin-related effects. The studied compounds were both commercial and in-house extracted lignin derivatives. Bioassays used include reverse electron transport (RET), Vibrio fischeri, Daphnia magna , and juvenile rainbow trout ( Oncorhynchus mykiss) hepatocytes. The studied lignin derivatives inhibited the in vitro systems and luminescence of V. fischeri bacteria to some extent–daphnids were not affected. It seems that, at least in the RET assay, certain pH-dependent…

Gas chromatographic-mass spectrometric analysis of chlorinated phenoxyphenols in the technical chlorophenol formulation ky-5′

Abstract The content of polychlorinated phenoxyphenol (PCPP) impurities in the technical chlorophenol formulation Ky-5 (wood preservative) was studied. The phenolic fraction was shown to contain predioxins and isopredioxins, the structures of the components being verified by gas chromatography mass spectrometry of non-derivatized, methylated and acetylated fractions. 2,6-Dichloro-4-(2,4,6-trichlorophenoxy)phenol and 2,6-dichloro-4-(2,3,4,6-tetrachlorophenoxy)phenol were identified by the comparison of their retention times and the mass spectra of their methyl and acetyl derivatives with those of authentic specimens. The amounts of the above components in Ky-5 were ca. 0.8 and 0.2%, respecti…

13C and17O NMR study of methoxy groups in chlorinated Di- and trimethoxybenzenes

13C and 17O NMR data [chemical shifts and 1J(CH) values] for the methoxy groups in isomeric 1,2-, 1,3- and 1,4-dimethoxybenzenes, 1,2,3-trimethoxybenzenes and most of their chlorinated derivatives and some related brominated compounds were measured for CDCl3 solutions. The 17O NMR chemical shifts show up to 60 ppm dispersion. Comparison between the compounds with and without adjacent chlorine atoms (2,6-di- and 2,4,6-tri-substitution) also showed a clear methoxy carbon chemical shift change. The number and position of the chlorine atoms in the aromatic ring give small but observable effects on the 17O NMR chemical shifts of the methoxy group if it is coplanar with the aromatic plane. Simila…

17O NMR study of chlorinated anisoles

The 17O NMR chemical shifts of anisole and all 19 chlorinated anisoles measured in CDCI3 at ambient temperature show a dispersion of approximately 40 ppm. The substituent chemical shifts (SCS) of di- or more highly chlorinated compounds cannot be reproduced by addition of single substituent effects. Theoretical calculations of the 17O NMR chemical shifts have been attempted by molecular mechanical and semi-empirical molecular orbital methods at the INDO level, but the results are not satisfactory.

Interactions between cationic amylose derivatives and a pulp fiber model surface studied by molecular modelling

This study was performed in order to obtain more information about the interactions between pulp fibers and acetylated cationic starch derivatives on a molecular scale. The adsorption of the polymers on the fiber surface was studied by simulating polymers on a fiber model surface at 300 K. Fractional atomic coordinates of regenerated cellulose II were used to generate a cellulose fiber surface model. Carboxylate groups were added on the cellulose surface to represent the anionic charge of pulp fiber which originates from hemicelluloses. Amylose chains cationized and acetylated atom by atom were chosen to represent four different starch derivatives. Atomic charges used in simulations were ca…

Direct injection analysis of fatty and resin acids in papermaking process waters by HPLC/MS

A novel HPLC-atmospheric pressure chemical ionization/MS (HPLC-APCI/MS) method was developed for the rapid analysis of selected fatty and resin acids typically present in papermaking process waters. A mixture of palmitic, stearic, oleic, linolenic, and dehydroabietic acids was separated by a commercial HPLC column (a modified stationary C(18) phase) using gradient elution with methanol/0.15% formic acid (pH 2.5) as a mobile phase. The internal standard (myristic acid) method was used to calculate the correlation coefficients and in the quantitation of the results. In the thorough quality parameters measurement, a mixture of these model acids in aqueous media as well as in six different pape…

Quartz-capillary gas chromatography of chlorinated phenols and catechols

The gas chromatography of all chlorinated phenols and catechols on a non-polar SE-30 quartz-capillary column has been studied. The relative retention times of the individual components are given and the elution order is discussed. All of the chlorophenols and chlorocatechols can be separated under appropriate operating conditions but simultaneous determination of all the compounds studied resulted in overlapping peaks. Theortho-effect in catechols is stronger than that in phenols. A different order of elution for the compounds studied to that of the corresponding acetate esters is found. Generally, longer retention times for the latter are observed.

1H and13C NMR spectroscopy of brominated diphenyl ethers. A multiple linear regression analysis

The 1H and 13C NMR chemical shifts and 1H, 1H coupling constants of 27 brominated diphenyl ethers are reported. The increment models for the bromine substituent effects on the 1H and 13C NMR chemical shifts were constructed based on a multiple linear regression analysis. In addition to the single substituent effects, two particle increments and corrective terms for conformational effects are included in these models in order to obtain a reliable prediction of chemical shifts. Copyright © 2000 John Wiley & Sons, Ltd.

Free amino acid pool and muscle protein balance after resistance exercise.

The aim of this study was to assess the effects of a resistance exercise session (RES) on free amino acid concentrations and protein synthesis and breakdown of the vastus lateralis (VL) muscle during recovery in male subjects.Both the exercise group (EG) and the control group (CG) consisted of six healthy physically active men. On the experiment day in fasting conditions, a stable isotopic tracer of L-[ring-2H(5)] phenylalanine was infused and EG started a heavy 50-min hypertrophic RES for lower extremities after 55 min of infusion. At the same time, CG was at rest. During recovery of 195 min after RES, several blood samples were drawn from the femoral artery (FA) and the femoral vein (FV) …

Thin-layer chromatography of chlorinated cresols

Abstract The thin-layer chromatography of four chlorinated cresols was studied on five layer materials using eleven solvent systems. Sharp spots were obtained except on Kieselguhr G layers. The best separation of the individual compounds occurred on silica gel-containing layers with dichloromethane as the solvent. Each solvent system was found to cause a different separation on different layers.

Pharmaceuticals in processing of municipal sewage sludge studied by grab and passive sampling

Abstract Concentrations of pharmaceuticals, consisting of four anti-inflammatory and one antiepileptic drug, were studied in the aqueous and solid phase of municipal sewage sludge, collected from a wastewater treatment plant (WWTP) in central Finland. The samples included untreated municipal sludge from the biological wastewater treatment, digested sludge and sludge before and after composting. First, samples were taken as grab samples to study the bioavailable part in aqueous phase but also the part in solid fraction. Later, the long-term concentrations were studied by passive sampling with styrene divinylbenzene-reverse phase sulfonated (SDB-RPS) disks. In the untreated solid sludge, the …

Chloroanisoles in soils and earthworms

One important group of metabolites of chlorophenols in Finnish soils is their methylation products, i.e. chloroanisoles. Bioaccumulation of chloroanisoles into the biomass of earthworms was studied both in laboratory and by taking earthworm samples from contaminated soils. Concentrations of these compounds in the soils were also analysed. In the laboratory experiment, concentrations of 2,3,4,6-tetrachloroanisole (2346-TeCA) and pentachloroanisole (PeCA) were high in earthworms 1 week after introduction (approx. 50 μ/g fat). Later on, the concentrations decreased to a low level at a considerable rate, bcth in soil and in earthworms. The higher the concentration of chloroanisoles in the soil …

Thin-layer chromatography of chlorinated catechols on a silica gel 60 layer

NMR Study of Kraft Pulp Mill Waste and Natural Humic Substances

High field proton NMR spectroscopy in DMSO-d6 solution is applied for structural analysis of main high molecular fractions of natural humus and waste lignin from kraft pulp mill. The spectra are similar in great part. Main differences appear in p-disubstituted benzene proton and -CH2 -CO-proton signals which are absent in spectrum of waste lignin obviously due to chlorination. A new observation of 51 Hz 1:1:1 triplet in both spectra is discussed.

Mass spectra of chlorinated veratroles (1,2-dimethoxybenzenes)

The behaviour of all nine chlorinated veratroles (1,2-dimethoxybenzenes) under electron impact has been investigated. The most common fragmentation processes are interpreted using metastable ion analysis and deuterium labelled compounds. For all compounds studied, the most common fragmentation route seems to be the primary loss of a methyl radical followed by loss of carbon monoxide. The ion formed has a well-known quinonoid structure and fragments by several routes elucidated by metastable ion analysis. In general, the spectra of the positional isomers are shown to be practically similar and it is apparent that e.g. the 3- and 4-chloro isomers can be differentiated only from the abundance …

Mass spectra of methoxychlorobenzenes (chloroanisoles)

Electron impact mass of all 19 ring-substituted chloroanisoles have been investigated. The fragmentation pathways were elucidated with the aid of the 1st field-free region metastable ions. The greatest disparity between the spectra of the positional isomers is shown with the [M−CH 3 ] + and [M−CH 2 O] +• ions, i.e., the ortho and para isomers preferentially lose • CH 3 , whereas the meta isomers generally show both loss of • CH 3 and elimination of formaldehyde, the latter process being more dominant with the meta-monochloro and di- and trichloro isomers having two meta-chlorine atoms. Characteristic for all isomers is also the abundant M +• and [M−CH 3 −CO] + ions, the other fragmentation …

Toxicity of 5- chloro- 3- methyl- catechol to rat: Chemical observations and light microscopy of the tissue

5-chloro-3-methyl-catechol was first time described by GAUNT and EVANS (1961) as a metabolite of MCPA (4-chloro-2-methylphenoxyacetic aci~which is the most widely used herbicide in the Nordic countries. The toxicity of the metabolite 5-chloro-3-methylcatechol bas hot been studied so far. Other catechols like 3,5dichlorocatechol has been shown to be a metabollte of 2,4-D (BOLLAG et ai. 1968a, BOLLAG et ai. 1968b), and it has been proven to be toxic to cells by HORVATH (1971). The catechols are metabolized by bacteria finally to muconic semialdehyde (HORVATH 1970, HORVATH and ALEXANDER 1970). In this work the toxicity of 5-chloro-3-methyl-catechol to maie rats was studied in acute and subchro…

Organic chlorine compounds in lake sediments. III. Chlorohydrocarbons, free and chemically bound chlorophenols

Abstract Chlorohydrocarbons and free and chemically bound chlorophenols, catechols and guaiacols were measured from lake sediments in Central Finland. Chlorohydrocarbons occurred at low backround levels except chlorocymenes from pulp mills and PCBs near the city of Aanekoski, where a local leakage occurrs. Free chlorophenols (hexane extractables) were found in all 18 areas studied, but the bound ones (extracted with strong alkali) only in the pulp mill reciepient lakes where they dominated. Preliminary analyses of chemically bound chlorophenols in high molecular fractions of spent bleach liquors and pulp mill effluents indicated that majority of chlorocatechols and guaiacols are bound alrea…

Thin-layer chormatography of chlorinated guaiacols

Transport of high molecular mass lignin material in the receiving water system of a mechanical pulp mill

High molecular mass material (HMM) of water samples collected from the receiving water system of a mechanical pulp mill was characterized applying cupric oxide oxidation combined with GC and HPLC analysis of the oxidation products. This qualitative method was used to follow the transport of organic HMM discharged by the mill. The interpretation of results was complicated by degradation reactions of HMM in the water system and the assimilation of HMM produced by the mill to natural humic compounds. The analytical data was subjected to the principal component analysis (PCA) to verify the results obtained.

Resin and fatty-acid analysis by solid-phase extraction coupled to atmospheric pressure chemical ionization–mass spectrometry

Using gas-chromatographic analysis, the suitability of liquid–liquid extraction and solid-phase extraction (SPE) methods was studied for the rapid separation of resin and fatty-acid fractions from papermaking process waters. In the second phase of this study, a novel procedure (correlation coefficient >0.99 and repeatability RSD <8%) for on-line monitoring of selected individual acid components (limits of detection 11–78 µg L−1) by SPE combined with atmospheric pressure chemical ionization–mass spectrometry was developed. The suitability of this technique for quality control of papermaking process waters was tested by means of industrial samples. The method was also found suitable for the a…

A statistical study of the additivities of substituent effects in the13C NMR chemical shifts of hydroxy- and chloro-substituted benzenes

The 13C NMR spectra of six hydroxybenzenes, all chlorobenzenes, all chlorophenols and eight chlorocatechols are measured and assigned. The additivity of the substituent effects and the usefulness of some corrective parameters are studied with regression analysis. The order of the chemical shifts is most efficiently predicted by the simplest substituent effect model, containing only the direct effects of the substituents, although the 95% confidence limits of the calculated shifts are as high as 5.6 ppm. If the chemical shifts need to be predicted within the measuring errors (approximately 0.05–0.10 ppm, in the present data), the number of necessary corrections is very impractical. The corre…

Potential Off-Flavour Compounds from Chloro-Bleaching of Pulp and Chlorodisinfection of Water

Chlorobleaching of pulp is the most important source of organochlorine pollutants in the Finnish aquatic ecosystems. Similar types of pollutants are formed during chlorodisinfection of water. The model compound approach employed in our laboratory has revealed the structures and amounts of pollutants formed and has made the interpretation and assay of individual organochlorine compounds in the environment possible. Tainting of fish near chlorination plants is frequently observed. Especially chlorinated phenols and anisoles (microbial metabolites of the former) are chlorination products which are known to have a strong odour and taste at very low concentrations. Other chlorinated products, wh…

The effect of chlorine substituent(s) on the primary loss of a methyl radical from chlorinated veratroles (1,2-dimethoxybenzenes)

OVERVIEW OF ANALYTICAL PROCEDURES FOR FATTY AND RESIN ACIDS IN THE PAPERMAKING PROCESS

This review describes the role of wood extractives, especially fatty and resin acids, in papermaking, as well as the importance of their removal from process waters. One of the main aims is also to illustrate versatile analysis methods for this purpose and highlight recent developments in corresponding applications. Most of the current methods require time-consuming and laborious sample pretreatment procedures prior to gas chromatography coupled either with flame ionization or mass selective detection. However, some faster, even online techniques with minimum sample pretreatment, are also available, mainly including high performance liquid chromatography coupled with mass spectrometry. The …

Ab initio study of halogenated diphenyl ethers. NMR chemical shift prediction

Molecular modeling studies of interactions between sodium polyacrylate polymer and calcite surface

Abstract The interactions between calcite pigment and sodium polyacrylate dispersing agent, widely used in papermaking as paper coating components, were investigated using classical force field and quantum chemical approaches. The objective was to understand interactions between the calcite surface and sodium polyacrylate polymer at 300 K using molecular dynamics simulations. A quantum mechanical ab initio Hartree–Fock method was also used to obtain detailed information about the sodium polyacrylate polymer structure. The effect of water molecules (moisture) on the interactions was also examined. Calculations showed that molecular weight, branching and the orientation of sodium polyacrylate…

Chemometric investigation on structural changes in pine kraft lignin during pulping

Abstract Various structural changes which take place in dissolved lignin during the laboratory-scale kraft pulping of Scots pine (Pinus sylvestris) were studied. Lignin samples were subjected to the alkaline cupric oxide oxidation and the analytical data further processed by various multivariate chemometric techniques (principal component analysis, PCA; principal component regression, PCR; and projection to latent structures, PLS). Several models applicable to the indirect measurement of common pine kraft pulp properties (i.e., total cooking yield, kappa number and ISO brightness) were produced.

Identification of fish species by reversed-phase high-performance liquid chromatography with photodiode-array detection

A method for the separation of sarcoplasmic fish proteins by RP-HPLC is described. The procedure revealed significant differences useful for reliable identification of fish species. Sixteen of the most common Finnish freshwater fish species were differentiated by species-specific HPLC chromatograms obtained using photodiode-array detection (PAD) at 200-350 nm. The analytical column was a Hi-Pore RP-304 reversed-phase column. The separation was performed by a linear gradient of acetonitrile and water with a small amount of trifluoracetic acid (TFA). Star-symbol plots were constructed from the chromatograms to visualize the data. Clearly different HPLC protein profiles for most fish species w…

Evaluation of biodegradation of nonylphenol ethoxylate and lignin by combining toxicity assessment and chemical characterization.

Abstract The aerobic biodegradation of commercial nonylphenol ethoxylate (NPE) mixture and alkali lignin was studied using the OECD headspace test accompanied by the simultaneous measurement of ecotoxicity directly from the biodegradation liquors and by the follow-up of the chemical composition of the studied chemicals. NPE degradation was dependent on the inoculum source: approximately 40% of NPE was mineralized into CO2 during the 4-week experiment when inoculum from Helsinki City wastewater treatment plant (WWTP) was used, and only 12% was mineralized when inoculum from Jyvaskyla City WWTP was used. Chemical analyses revealed a shift in the ethoxylate chain length from longer to shorter …

Pyrolysis-GC-MS and CuO-oxidation-HPLC in the characterization of HMMs from sediments and surface waters downstream of a pulp mill

Abstract High molecular mass fractions of lignin and humic compounds in sediments and waters downstream of a pulp mill were characterized applying pyrolysis-gas chromatography-mass spectrometry. The results were compared to those obtained using reversed phase HPLC on the cupric oxide oxidation products. The chromatographic data of both pyrolysis and cupric oxide oxidation were also subjected to the principal component analysis (PCA). The sediment samples and fractions obtained by ultrafiltration of river water samples were freeze dried prior to characterization. The sediment samples were also extracted using 2 M sodium hydroxide solution. The extracts were ultrafiltrated, freeze dried and c…

Thin-layer chromatography of chlorinated anisoles and veratroles

The thin-layer chromatography of chlorinated anisoles (methoxybenzenes) and veratroles (1,2-dimethoxybenzenes) has been examined on silica gel G60 and RP-18 thin-layer plates. More than fifty solvent systems were screened and some of them recommended for particular separations. Acetone was shown to be suitable for group separation of both chlorinated anisoles and veratroles on a silica gel G60 stationary phase having a very narrow range of RF values. On the other hand, benzene, dichloromethane and the various mixtures of light petroleum (b.p. 40–60°C) and a more polar eluent (such as diethyl ether, acetone or ethyl acetate) were recommended for separation of certain individual isomers. The …

Characterization of high molecular mass material in ECF and TCF bleaching liquors by Py-GC/MS with and without TMAH methylation

Abstract High molecular weight (HMW) fractions (MW > 1000) of effluents were obtained by ultrafiltration of elemental chlorine-free (ECF) bleaching (O-D-EOP-D-ED) and totally chlorine-free (TCF) bleaching (O-Z-Q-P-Z-Q-P-P) liquors of softwood (Pinus sylvestris) pulp. The fractions were studied by analytical pyrolysis coupled to gas chromatography/mass spectrometry (Py-GC/MS) with and without TMAH (tetramethyl ammonium hydroxide) derivatization. The pyrograms showed a number of pyrolysis products mainly derived from lignin and carbohydrates. The comparison of 4-hydroxyphenyl (H), guaiacyl (G) and syringyl (S) lignin units in both bleaching effluents showed that the G unit content was clearly…

1H,13C and17O NMR study of chlorovanillins and some related compounds

1H, 13C and 17O NMR chemical shifts and nJ(H,H), 1J(C,H) and 3J(C-6, H-formyl) spin—spin coupling constants of chlorinated vanillins (3-methoxy-4-hydroxybenzaldehydes) were determined. The variation in the long-range 4J(H,H) value between the formyl proton and an ortho-proton suggests that the ortho-substituent strongly forces the formyl group out of the aromatic plane. This can also be observed by considering the 3J(C-6,H-formyl) values and the 13C and 17O NMR chemical shifts. The 17O NMR chemical shifts show a linear correlation with the torsion angle of the formyl group calculated by molecular mechanics. The 13C and 17O NMR chemical shifts of the methoxyl group also possess strong predic…

A fugacity model assessment of ibuprofen, diclofenac, carbamazepine, and their transformation product concentrations in an aquatic environment

An updated version of FATEMOD, a multimedia fugacity model for environmental fate of organic chemicals, was set up to assess environmental behaviour of three pharmaceuticals in northern Lake Päijänne, Finland. Concentrations of ibuprofen, diclofenac, and carbamazepine were estimated at various depths at two sites: near a wastewater treatment plant and 3.5 km downstream the plant. When compared with environmental sampling data from corresponding depths and sites, the predicted concentrations, ranging from nanograms to hundreds of nanograms per litre, were found to be in good agreement. Weather data were utilised with the model to rationalise the effects of various environmental parameters on…

Chemical characterization of peat fulvic acid fractions

Abstract Milled peat fulvic acid (FA) preparation was fractionated by XAD-8 and conventional extraction methods. The fractions were further analyzed by IR and NMR and subjected to cupric oxide (CuO) oxidation. Carbohydrates of polydisperse FA were mostly not retained in the XAD-8 fractionation. The intensity of the signals due to double bonded carbons was much greater in the 13 C and proton NMR spectrum of the XAD-8 retained fraction than in the spectra of the XAD-8 non-retained or XAD-8 non-treated fractions. In CuO oxidation the main products of all FA fractions were 4-hydroxybenzaldehyde and 4-hydroxyacetophenone, both indicators of 4-hydroxyphenylpropane building blocks. Their concentra…

Gas chromatographic and gas chromatographic-mass spectrometric studies of acetate esters of chlorinated phenols

Gas chromatographic and mass spectrometric analysis of chlorinated catechols occurring in pulp bleach liquors

Chlorination step (C-step), spent bleach liquor from a kraft pulp mill and the product from the chlorination of guaiacol in aqueous solution have been investigated for their content of chlorinated catechols. After separation the samples were derivatized with diazoethane and analysed by glass capillary gas chromatography with an electron capture detector. The external standard mixture of all ethylated chlorocatechols was used in the measurements. The structures of the compounds identified were confirmed by gas chromatography/mass spectrometry. Eight chlorinated catechols were identified from a sample prepared by chlorination of guaiacol with Cl2 in aqueous solution. However, only four of the…

A statistical study of the additivity of substituent effects on the5J(HH) long-range coupling constant of the formyl proton in substituted benzaldehydes

The additivity of chloro and hydroxy substituent effects on the formyl proton spin-spin coupling constants with the meta ring proton, 5J(HH), has been tested with 15 chlorinated benzaldehydes and hydroxybenzaldehydes by multiple linear regression analysis. No general additivity rule was detected with whole data. Using benzaldehyde as the reference substance, a good correlation was achieved for p-hydroxybenzaldehydes. The same reference compound was not suitable for o-hydroxy derivatives; a much better correlation was observed using o-hydroxybenzaldehyde as a reference compound in the latter case.

Methylation products of chlorophenols, catechols and hydroquinones in soil and earthworms of sawmill environments

Abstract Soil samples and earthworms collected from one noncleaned and two cleaned sawmill environments were analysed for their content of chlorinated anisoles (methoxybenzenes), veratroles (1,2-dimethoxybenzenes) and 1,4-dimethoxybenzenes. 2,3,4,6-tetrachloroanisole and pentachloroanisole were observed in all soil samples studied, in maximum combined amount about 1.5 μg/g dry soil. Small amounts (ca. 1–110 ng/g dry mass) of 3,4,5-trichloroveratrole, tetrachloroveratrole and tetrachloro-1,4-dimethoxybenzene were found in the most polluted soil samples. Only 2,3,4,6-tetrachloroanisole and pentachloroanisole were found in earthworms, where concentrations of each were ca. 0.1–20 μg/g fat. In g…

Gas—liquid chromatographic analyses

Abstract The gas choromatographic retention behaviour of veratrole and all nine chlorinated veratroles was studied on SE-30 and OV-351 capillary columns. Temperature programming from 100°C at 6°C min−1 and isothermal operation at 140, 160, 180 and 200°C were used. The complete separation of a mixture was obtained on SE-30, the isomers being eluted in order of their degree of chlorination. On OV-351, however, the 3,4,5-trichloro and tetrachloro isomers overlap with temperature programming, being separated at 140, 160 and 200°C. Retention indices and increments of retention indices for each position of substitution are examined and the effect of increasing temperature on retention is discusse…

Molecular modeling studies of interactions between styrene–butadiene latex and sodium polyacrylate polymer surface

Abstract The interaction between two important paper coating ingredients, sodium polyacrylate polymer dispersing agent and styrene–butadiene latex binder, was studied using classical force field and quantum chemical methods. The objective was to understand the adsorption of styrene–butadiene latex on the sodium polyacrylate polymer model surfaces at 300 K using molecular dynamics simulations. A quantum mechanical ab initio Hartree–Fock method was also used to obtain detailed information about the above interactions. In addition, the effect of moisture was investigated. Calculations showed that the conformation and orientation of styrene–butadiene latex, the number of carboxylate groups in t…

High-Performance Liquid Chromatographic Study on Oxidation Products of Lignin and Humic Substances

We describe a convenient method of preparing samples and characterizing the mixture of degradation products obtained from alkaline cupric oxide oxidation of water samples containing lignin and humic substances. The method was applied to one unpolluted humic water sample and a total mill effluent of a kraft pulp mill. The fractions (Mr &amp;gt; 1000) obtained by ultrafi1tration were oxidized and the products (mixtures of degradation products) were analyzed by reversed-phase high-performance liquid chromatography (Spherisorb 5 ODS column). Acetonitrile-0.01 M phosphate buffer (pH 2) was used as the eluent in a gradient system and UV (set at 280 nm) as the detection system. Differences in the …