RESUMO
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 paper machine process waters was quantitatively determined. The measured quality parameters, such as selectivity, linearity, precision, and accuracy, clearly indicated that, compared with traditional gas chromatographic techniques, the simple method developed provided a faster chromatographic analysis with almost real-time monitoring of these acids.
Assuntos
Cromatografia Líquida de Alta Pressão/métodos , Ácidos Graxos/química , Espectrometria de Massas/métodos , Papel , Resinas Vegetais/química , Água/química , Limite de DetecçãoRESUMO
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 functional groups in lignin may be of importance regarding the biological effects.
Assuntos
Lignina/química , Lignina/toxicidade , Papel , Eliminação de Resíduos Líquidos/métodos , Poluentes Químicos da Água/toxicidade , Animais , Bioensaio/métodos , Citocromo P-450 CYP1A1/metabolismo , Daphnia/efeitos dos fármacos , Transporte de Elétrons/efeitos dos fármacos , Finlândia , Hepatócitos/efeitos dos fármacos , Oncorhynchus mykiss/metabolismo , Testes de Toxicidade , Vibrio/efeitos dos fármacos , Poluentes Químicos da Água/análiseRESUMO
We examined the acute effects of a 1-h strength training session (STS) on plasma amino acid concentration following orally ingestion of leucine, branched-chain amino acids (BCAAs) or glutamine in nine physically active men who participated in double-blinded and randomised experiments. The subjects took placebo, leucine, BCAAs, or glutamine capsules (50 mg/kg) in either rest (REST) or STS condition. Blood samples were taken before and at 30, 60, 90, and 120 min after the beginning of the treatment and they were assayed for plasma amino acids with HPLC. Following both leucine and BCAA ingestion the peak concentration of leucine was similar at rest (524 +/- 46 and 530 +/- 29 nmol/ml, respectively) and similar after STS (398 +/- 43 and 387 +/- 46 nmol/ml, respectively) but the rest and STS concentrations differed from each other (P < 0.01-0.001). The modelled polynomial data for the leucine treatment showed that the peak concentration of leucine occurred at 67 min at rest and at 90 min in STS (difference between REST and STS: P = 0.012). For the BCAA treatment the polynomial data showed that the peak concentration of leucine occurred at 72 min at rest and at 78 min in STS (P = 0.067). The peak concentration of glutamine was similar in both rest and STS condition and occurred at 60 min at rest and at 57 min in STS. In conclusion, 1-h of STS slows the increase in the peak concentration of plasma leucine similarly after oral ingestion of leucine or BCAAs but after oral ingestion of glutamine it has no slowing effect on glutamine concentration.
Assuntos
Glutamina/sangue , Glutamina/farmacocinética , Leucina/sangue , Leucina/farmacocinética , Treinamento Resistido , Adulto , Método Duplo-Cego , Humanos , Masculino , Taxa de Depuração Metabólica , Resistência Física/efeitos dos fármacos , Descanso/fisiologiaRESUMO
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 the sampling results, and, e.g. the roles of various properties of lake dynamics and photodegradation were identified. The new model also enables simultaneous assessment of transformation products. Environmentally formed transformation product concentrations were estimated to be at highest an order of magnitude lower than those of the parent compounds, and unlikely to reach a detectable level. However, a possibility that conjugates of ibuprofen are present at higher levels than the parent compound was identified. Simulation results suggest that environmental degradation half-lives of the inspected contaminants under stratified lake conditions are in the range of some weeks to months.
Assuntos
Modelos Químicos , Poluentes Químicos da Água/análise , Carbamazepina/análise , Carbamazepina/química , Diclofenaco/análise , Diclofenaco/química , Monitoramento Ambiental/métodos , Finlândia , Ibuprofeno/análise , Ibuprofeno/química , Lagos/química , Fotólise , Águas Residuárias/química , Poluentes Químicos da Água/químicaRESUMO
Sewage sludge is the largest by-product generated during the wastewater treatment process. Since large amounts of sludge are being produced, different ways of disposal have been introduced. One tempting option is to use it as fertilizer in agricultural fields due to its high contents of inorganic nutrients. This, however, can be limited by the amount of trace contaminants in the sewage sludge, containing a variety of microbiological pollutants and pathogens but also inorganic and organic contaminants. The bioavailability and the effects of trace contaminants on the microorganisms of soil are still largely unknown as well as their mixture effects. Therefore, there is a need to analyze the sludge to test its suitability before further use. In this article, a variety of sampling, pretreatment, extraction, and analysis methods have been reviewed. Additionally, different organic trace compounds often found in the sewage sludge and their methods of analysis have been compiled. In addition to traditional Soxhlet extraction, the most common extraction methods of organic contaminants in sludge include ultrasonic extraction (USE), supercritical fluid extraction (SFE), microwave-assisted extraction (MAE), and pressurized liquid extraction (PLE) followed by instrumental analysis based on gas or liquid chromatography and mass spectrometry.
Assuntos
Compostos Orgânicos/análise , Esgotos/química , Animais , Cromatografia Líquida/métodos , Humanos , Espectrometria de Massas , Micro-OndasRESUMO
The presence of five selected pharmaceuticals, consisting of four anti-inflammatory drugs, diclofenac, ibuprofen, ketoprofen, naproxen, and an antiepileptic drug carbamazepine, was determined at four municipal wastewater treatment plants (WWTPs) and in the receiving waterway in central Finland. The samples were taken from influents and effluents of the WWTPs and from surface water of six locations along the water way, including northern Lake Päijänne. In addition, seasonal variation in the area was determined by comparing the concentrations in the winter and summer. The samples were analyzed by liquid chromatography coupled to tandem mass spectrometry (LC-MS/MS) in the multiple reaction monitoring mode. The concentrations in the influents and effluents ranged from hundreds of nanogram per liter to microgram per liter while ranged from tens of nanogram per liter in northern parts of the waterway to hundreds of nanogram per liter in northern Lake Päijänne near the city area. In addition, the concentrations were higher in the winter compared to summer time in surface water due to decreased temperature and solar irradiation. On the other hand, higher concentrations of ibuprofen, ketoprofen, and naproxen were found in summer at the WWTPs, possibly due to seasonal variations in consumption. In conclusion, there are considerable amounts of pharmaceuticals not only in influents and effluents of the WWTPs but also in lake water along the waterway and in northern Lake Päijänne.
Assuntos
Monitoramento Ambiental/métodos , Lagos/química , Preparações Farmacêuticas/análise , Águas Residuárias/química , Poluentes Químicos da Água/análise , Purificação da Água/métodos , Anti-Inflamatórios/análise , Anticonvulsivantes/análise , Finlândia , Estações do Ano , Espectrometria de Massas em TandemRESUMO
The occurrence of five pharmaceuticals, consisting of four anti-inflammatory and one antiepileptic drug, was studied by passive sampling and grab sampling in northern Lake Päijänne and River Vantaa. The passive sampling was performed by using Chemcatcher® sampler with a SDB-RPS Empore disk as a receiving phase. In Lake Päijänne, the sampling was conducted during summer 2013 at four locations near the discharge point of a wastewater treatment plant and in the years 2013 and 2015 at four locations along River Vantaa. The samples were analyzed by liquid chromatography coupled to tandem mass spectrometry (LC-MS/MS) in the multiple reaction monitoring mode. The concentrations of carbamazepine, diclofenac, ibuprofen, ketoprofen, and naproxen in Lake Päijänne determined by passive sampling ranged between 1.4-2.9 ng L(-1), 15-35 ng L(-1), 13-31 ng L(-1), 16-27 ng L(-1), and 3.3-32 ng L(-1), respectively. Similarly, the results in River Vantaa ranged between 1.2-40 ng L(-1), 15-65 ng L(-1), 13-33 ng L(-1), 16-31 ng L(-1), and 3.3-6.4 ng L(-1). The results suggest that the Chemcatcher passive samplers are suitable for detecting pharmaceuticals in lake and river waters.
Assuntos
Monitoramento Ambiental/instrumentação , Lagos/química , Preparações Farmacêuticas/análise , Rios/química , Poluentes Químicos da Água/análise , Calibragem , Carbamazepina/análise , Cromatografia Líquida , Diclofenaco/análise , Monitoramento Ambiental/métodos , Finlândia , Ibuprofeno/análise , Cetoprofeno/análise , Naproxeno/análise , Estações do Ano , Espectrometria de Massas em Tandem , Águas Residuárias/análiseRESUMO
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 2,3,4,4',5,6-hexabromodiphenyl ether, based on energy maps calculated by semiempirical AM1 method, may indicate that all PBDE congeners except those with the tetra-ortho-bromination are conformationally flexible (or soft) due to low energy barriers for interconversion of stable conformers. The results of the conformational analyses are in conformity with recently published X-ray crystallographic data. For comparison with the results of the semiempirical method, higher level ab initio and DFT models were applied as well. The optimized geometries all lie well inside low energy regions on the maps and thus also ascertain the semiempirical calculations. According to computed geometric parameters and net atomic charges, the model B3LYP/3-21G* seemed to give better results than B3LYP/6-31G* and HF/6-31G*.
Assuntos
Técnicas de Química Analítica/métodos , Retardadores de Chama , Modelos Moleculares , Éteres Fenílicos/química , Bifenil Polibromatos/química , Conformação MolecularRESUMO
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 reactions of BDEs was predicted. Furthermore, satisfactory quantitative structure-activity (property) relationship (QSAR and QSPR) models were derived to calculate gas chromatographic and ultraviolet spectral properties and luciferase induction activities from the AM1-computed electronic parameters.
Assuntos
Técnicas de Química Analítica/métodos , Retardadores de Chama , Éteres Fenílicos/química , Bifenil Polibromatos/química , Relação Quantitativa Estrutura-Atividade , Cromatografia Gasosa , Luciferases/metabolismo , Espectrometria de Massas , Conformação Molecular , Éteres Fenílicos/metabolismo , Bifenil Polibromatos/metabolismo , Hormônios Tireóideos/metabolismoRESUMO
BACKGROUND, AIM AND SCOPE: At present, large-scale paper manufacture involves delignification and bleaching by elemental chlorine free (ECF), or totally chlorine free (TCF) processes. The wastewater is purified by secondary treatment (mechanical, chemical and biological) which removes most of the toxic substances from the discharge. However, we found residual toxicity in the high molecular (> 1000 D) matter (HMWM) of the discharge by test of the RET (reverse electronic transfer) inhibition. This fraction consists mainly of polydispersed lignin (LIG) and carbohydrate (CH) macromolecules. Structural units in these molecules are studied by pyrolysis gas chromatography/mass spectrometry (Pyr-GC/MS). In the present work, our aim was to find out those structural units which could explain the RET toxicity of LIG or CH molecules. We compared statistically RET toxicity values of the HMWM samples from treated wastewaters of pilot pulping experiments and intensity variation of the pyrolysis product gas chromatograms of these samples. This application is a novel study procedure. METHODS: Pyrolysis products (Py-GC/MS results) and inhibition of RET (reverse electronic transport toxicity) as TU50 and TU20 of HMWM (High Molecular Weight Material; Mw > 1000 D) were compared by multivariate statistics. The samples were from laboratory pilot stages of TCF (Totally Chlorine Free) and ECF (Elemental Chlorine Free) manufacture of softwood pulp. Py-GC/MS was done without and with the addition of TMAH (Tetra Methyl Ammonium Hydroxide). The name and structure of each abundant fragment compound was identified from its retention time and mass spectrum compared to authentic reference compounds or literature. Four sets of Toxicity Units (TUs) and GC peak areas of the pyrolysis fragments were obtained. The data were normalized by division with LIG (lignin content of each sample). TU values were dependent and the fragment values independent (explanatory) variables in statistical treatments by SPSS system. Separate analyses of correlations, principal components (PCA) and stepwise multiple linear regression (SMLR) were performed from the four sample sets TCF and ECF with and without TMAH. RESULTS AND DISCUSSION: From the CH fragments, 2-furfural in TCF, and from the LIG fragments, styrene in ECF showed the highest probabilities of originating from source structures of toxicity. Other possible compounds in concern were indicated to be CH fragment 2-methyl-2-cyclopenten-1-one in ECF and LIG fragments 2-methoxy-4-methylphenol, 4,5-dimethoxy-2-methylphenol and 2-methylphenol in TCF.
Assuntos
Carboidratos/química , Resíduos Industriais/efeitos adversos , Lignina/química , Papel , Testes de Toxicidade/métodos , Alquilantes , Carboidratos/análise , Transporte de Elétrons , Cromatografia Gasosa-Espectrometria de Massas , Lignina/análise , Modelos Lineares , Peso Molecular , Análise de Componente Principal , Compostos de Amônio Quaternário , Eliminação de Resíduos Líquidos , Poluentes Químicos da Água/toxicidadeRESUMO
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 wastewaters, including aerobic and anaerobic processes. However, some fractions of organic material, such as lignin and its derivatives, are difficult to degrade. Therefore, novel chemical methods, including electrochemical and oxidation processes, have been developed for separate use or in combination with biological treatment processes.
Assuntos
Substâncias Perigosas/análise , Resíduos Industriais/análise , Compostos Orgânicos/análise , Papel , Águas Residuárias/química , Análise da Demanda Biológica de Oxigênio , Desinfetantes/análise , Lignina , Compostos Orgânicos/toxicidade , Eliminação de Resíduos Líquidos , Águas Residuárias/análise , Águas Residuárias/toxicidadeRESUMO
The presence of five different pharmaceuticals, consisting of four anti-inflammatory and one antiepileptic drug, was determined in influent and effluent of a municipal wastewater treatment plant (WWTP) near the city of Jyväskylä, Finland, and in the receiving water, northern Lake Päijänne. In addition, samples of sedimented particles were collected among water samples from five locations near the discharge point of the treated wastewater. The solid phase extracts (SPEs) of water samples were analyzed by liquid chromatography coupled to tandem mass spectrometry (LC-MS/MS) in the multiple reaction monitoring mode. The studied pharmaceuticals were detected from influent, effluent, and lake water but also in the sedimented particles. The concentrations of carbamazepine, diclofenac, ibuprofen, ketoprofen, and naproxen in Lake Päijänne ranged from 1 to 21 ng L(-1), 4 to 209 ng L(-1), 5 to 836 ng L(-1), 9 to 952 ng L(-1), and 2 to 129 ng L(-1), respectively. The concentrations of ketoprofen in sedimented particles ranged from 79 to 135 µg g(-1) while only trace amounts of other selected pharmaceuticals were detected. The results indicate that the concentrations of pharmaceuticals are affected by the biological and chemical reactions occurring in the wastewater treatment processes but also by the UV light in the photic layer of Lake Päijänne. It can be concluded that considerable amount of selected pharmaceuticals are present in the influent and effluent of municipal WWTP but also in the water phase and sedimented particles of northern Lake Päijänne.
Assuntos
Sedimentos Geológicos/química , Lagos/química , Preparações Farmacêuticas/análise , Águas Residuárias/análise , Poluentes Químicos da Água/análise , Purificação da Água/métodos , Cromatografia Líquida , Cidades , Finlândia , Extração em Fase Sólida , Espectrometria de Massas em TandemRESUMO
PURPOSE: 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. METHODS: 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) and muscle samples from the VL muscle. The enrichment was analyzed by GC/MS and leg muscle amino acid kinetics determined by three-pool compartment model between FA, FV, and VL. RESULTS: During recovery at 60 min after RES, there was no difference in muscle protein synthesis or muscle protein breakdown between the groups, but at 195 min, both muscle protein synthesis (P < 0.05) and muscle protein breakdown (P < 0.05) were increased in EG compared with CG. The protein net balance was negative and similar in both groups. Simultaneously in serum concentrations, there was a decrease in leucine (P < 0.05) associated with an increase in aspartate (P < 0.05). Furthermore, the exercise-induced increase in alanine concentration decreased both in serum and muscle. CONCLUSION: In fasting conditions, protein net balance is negative and RES induces an increase in muscle protein synthesis and breakdown at 195 min but not yet at 60 min of recovery.
Assuntos
Aminoácidos Essenciais/metabolismo , Exercício Físico/fisiologia , Perna (Membro)/irrigação sanguínea , Proteínas Musculares/metabolismo , Músculo Esquelético/metabolismo , Levantamento de Peso , Adulto , Aminoácidos Essenciais/sangue , Transporte Biológico , Estudos de Casos e Controles , Humanos , Masculino , Análise Multivariada , Proteínas Musculares/sangue , Músculo Esquelético/fisiologia , Consumo de Oxigênio/fisiologia , Fenilalanina/sangue , Fenilalanina/metabolismo , Esforço Físico/fisiologia , Probabilidade , Valores de Referência , Fluxo Sanguíneo Regional , Sensibilidade e EspecificidadeRESUMO
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, 126.6Jg(-1) and 171.3 degrees C for d-sucrose, 146.5 degrees C, 185.4Jg(-1) and 152.0 degrees C for d-glucose and 112.7 degrees C, 154.1Jg(-1) and 113.9 degrees C for d-fructose. The same parameters at 10 degrees Cmin(-1) rate of heating were 188.9 degrees C, 134.4Jg(-1) and 189.2 degrees C for d-sucrose, 155.2 degrees C, 194.3Jg(-1) and 170.3 degrees C for d-glucose and 125.7 degrees C, 176.7Jg(-1) and 136.8 degrees C d-fructose. At slow rates of heating, there were substantial differences between the different samples of the same sugar. The melting point determination is a sensitive method for the characterization of crystal quality but it cannot be used alone for the identification of sugar samples in all cases. Therefore, the melting point method should be validated for different sugars.
Assuntos
Frutose/química , Glucose/química , Sacarose/química , Varredura Diferencial de Calorimetria , TermodinâmicaRESUMO
The main aim of the European Union Water Framework Directive (WFD) (2000/60/EC) is to protect rivers, lakes, coastal waters and groundwaters (EC 2000). The implementation of the WFD requires monitoring the concentration levels of several priority pollutants such as nonylphenol ethoxylates (NPEOs) and nonylphenol (NP) in the area of EU. The present practices for determining the concentration levels of various pollutants are, in many respects, insufficient, and there is an urgent need to develop more cost-effective sampling methods. A passive sampling tool named Chemcatcher was tested for monitoring NPEOs and NP in aqueous media. These environmentally harmful substances have been widely used in different household and industrial applications, and they affect aquatic ecosystems, for example, by acting as endocrine disrupting compounds. The suitability of different receiving phases which were sulfonated styrene-divinylbenzene reversed phase polymer (SDB-RPS), standard styrene-divinyl benzene polymer (SDB-XC) and C-18 (octadecyl) was assessed in laboratory and field trials. The effect of a diffusion membrane on the accumulation of studied compounds was also investigated. The SDB-XC and C-18 receiving phases collected the NPEOs and NP most effectively. The water flow affected the accumulation factor of the studied substances in the field trials, and the water concentrations calculated using sampling rates were tenfold lower than those measured with conventional spot sampling. The concentration of the analytes in spot samples taken from the sampling sites might be higher because in that case, the particle-bound fraction is also measured. The NPEOs readily attach to suspended matter, and therefore, the total concentration of such compounds in water is much higher. Also, the spot samples were not taken daily but once a week, while the passive samplers collected the compounds continuously for 2- or 4-week time periods. This may cause differences when comparing the results of those two methods as well. Both techniques can be applied for monitoring the concentration levels at different sampling sites, but the calculated and measured analyte concentrations in surrounding water are not necessarily comparable with each other. More experiments are still needed to study the effect of hydrological issues and humic substances on the accumulation of chemicals. However, the Chemcatcher passive sampler gives valuable information about the mean concentration levels of studied compounds during 2- or 4-week sampling period. This is important for comparison of annual monitoring results, especially in sampling sites with rapidly fluctuating concentrations.
Assuntos
Monitoramento Ambiental , Etilenoglicóis/química , Fenóis/química , Poluentes Químicos da Água/química , Ecossistema , Disruptores Endócrinos/química , Lagos/química , Estrutura Molecular , Rios/química , Água do Mar/químicaRESUMO
The European Union Water Framework Directive (WFD; 2000/60/EC) is an important piece of environmental legislation that protects rivers, lakes, coastal waters and groundwaters (EC 2000). The implementation of the WFD requires the establishment and use of novel and low-cost monitoring programmes, and several methods, e.g. passive sampling, have been developed to make the sampling process more representative compared to spot sampling. This review considers passive sampling methods focusing mainly on a passive sampler named Chemcatcher®, which has been used for monitoring several harmful compounds in aquatic environments. Also, the sample treatment and analysis of nonylphenol ethoxylates (NPEOs) and nonylphenol (NPs) from water using solid phase extraction (SPE) is briefly summarized. The procedure of Chemcatcher passive sampling is quite similar to that of the SPE extraction since it concentrates the studied compounds from water as well. After sampling, the accumulated substances are extracted from the receiving phase of the sampler. The concentrations of NPEOs and NPs are currently monitored by taking conventional spot samples; SPE can be successfully used as a pretreatment procedure. Chemcatcher® passive sampling technique is a simple and useful monitoring tool and can be applied to new chemicals, such as NPEOs and NPs in aquatic environments.
Assuntos
Monitoramento Ambiental/métodos , Etilenoglicóis/análise , Fenóis/análise , Extração em Fase Sólida/métodos , Poluentes Químicos da Água/análise , Calibragem , Monitoramento Ambiental/instrumentação , Membranas Artificiais , Extração em Fase Sólida/instrumentação , Água/análiseRESUMO
The formation of perfluorooctanoate (PFOA) from 1H,1H,2H,2H-perfluorodecanol (8:2 FTOH) was studied for the first time in laboratory experiments with brackish water. The water samples were collected from the Baltic Sea, which is one of the largest brackish water areas in the world and is polluted with PFOA and other perfluorinated compounds. The formation of PFOA was studied in closed-bottle experiments at different water temperatures. As a reference experiment, a modified OECD 310 test was conducted with sludge from a wastewater treatment plant and with brackish water. The PFOA and 8:2 FTOH were concentrated from water samples by solid-phase extraction (SPE) and were analysed using liquid chromatography-mass spectrometry. The effect of oxygen concentration on the formation of PFOA was studied using surface water samples with high and low oxygen contents. Other experiments were performed with oxygen-rich surface water and oxygen-deficient bottom water. The formation of PFOA was observed in all experiments; it was higher in the trial performed with brackish water than in the reference test carried out with sludge. Clear temperature dependence was observed in the formation of PFOA in brackish water tests; after a 30-day test period, a sixfold increase was observed in the amount of PFOA in surface water between the temperatures of 15 and 20 °C. Microbes were suggested as the major cause of the formation of PFOA, but other environmental characteristics, such as oxygen, could also affect the formation potential of PFOA.
Assuntos
Caprilatos/análise , Fluorocarbonos/análise , Países Bálticos , Cromatografia Líquida , Água Doce/química , Espectrometria de Massas , Modelos Químicos , Oceanos e Mares , Salinidade , Água do Mar/química , Esgotos/química , Extração em Fase SólidaRESUMO
BACKGROUND, AIMS, AND SCOPE: Currently, elemental chlorine-free (ECF) and totally chlorine-free (TCF) bleaching systems are widely used for pulp production. Low and medium molecular weight lignin break-down products are known to have harmful effects on the environment. According to some recent results, also high molecular weight (HMW) material consisting mainly of lignin and carbohydrates may cause toxic effects to the environment. For these reasons, toxicity and structure studies of HMW materials are of great importance. This investigation is a part of a larger project to obtain more structure information of HMW materials and toxicity of ECF and TCF bleaching effluents. Size-exclusion chromatography (SEC) has been commonly used for the characterization of organic macromolecules such as lignin, but to our knowledge, no reports have appeared dealing with the comparison of SEC of ECF and TCF bleaching liquors. The aim of the present study was to get more information about the molecular weight distribution (MWD) of HMW fractions of waste liquors from ECF and TCF bleaching sequences by SEC. METHODS: The MWDs of organic materials dissolved during different stages of ECF bleaching (O-D-EOP-D-ED) and TCF bleaching (O-Z-Q-P-Z-Q-P-P) of softwood (Pinus sylvestris) kraft pulp were determined and compared by SEC. All effluent samples from the above bleaching stages were ultrafiltrated using a membrane with a cutoff value of 1,000 Da. SEC was performed on high and also low molecular weight fractions and non-fractionated effluents. In the SEC experiments, a Superdex 75 column was used with 0.1 M NaOH solution as the eluent. Standards used for calibrating the SEC system were albumin, carboanhydrase, cytochrome C, tannic acid, dehydrodiacetovanillone, and vanillin. RESULTS AND DISCUSSION: The chromatograms of liquors from TCF bleaching stages vary more than those from ECF bleaching. Peroxide and chelating stages contained mostly high molecular weight (HMW) matter whereas chlorine dioxide and ozone stages had more low molecular weight compounds. The lignin content in HMW matter was higher than in stages that consisted of low molecular matter. Bleaching effluents contained the highest amounts of HMW material, mainly lignin, in the beginning of the sequences; the amounts decreased towards the end of the bleaching sequence. CONCLUSION: Determinations of MWD by the SEC method showed that effluents from the TCF sequence contained more HMW material than those from the ECF stage. This might be due to peroxide stages (P) that dissolve HMW lignin effectively. However, the molecular weights of ozone stages (Z) were very low compared to other stages. Chlorine dioxide stages also dissolved mostly low molecular weight lignin. Ultrafiltration of bleaching liquors showed that high molecular weight fraction also included some low molecular weight compounds and vice versa. High polydispersity and high lignin content correlated with the amount of HMW material in ECF and TCF bleaching stages. RECOMMENDATION AND OUTLOOK: Our liquor samples were studied by using a UV detector commonly used for lignin preparations; in upcoming investigations, it will be interesting to determine carbohydrates such as hemicelluloses. The results are applicable in papermaking in order to improve commonly used bleaching procedures, to test new potential bleaching systems, and to study chemical behavior of HMW materials in various bleaching liquors. The present results also form a good basis for toxicity measurements of ECF and TCF bleaching effluents and for more comprehensive spectroscopic and chromatographic experiments with samples taken from various bleaching stages. From the behavior of liquors studied, it appears that our other structure investigations by spectroscopic and chromatographic (NMR, Py-GC/MS, etc.) methods mostly correlate well with the present results.
Assuntos
Cloro/química , Cromatografia em Gel/métodos , Lignina/isolamento & purificação , Eliminação de Resíduos Líquidos/métodos , Madeira , Carboidratos/química , Carboidratos/isolamento & purificação , Carboidratos/toxicidade , Cloro/farmacologia , Lignina/química , Lignina/toxicidade , Peso Molecular , PapelRESUMO
BACKGROUND, AIM, AND SCOPE: In papermaking, there is a continuous interest both to minimize fresh water consumption and to reduce discharges into the environment. These general trends mean an increase in the amounts of detrimental substances, such as resin and fatty acids, in papermaking process waters. Resin acids, in particular, are responsible for much of the toxicity typically present in paper mill effluents and, for this reason, the routine and rapid monitoring of these compounds in various process streams is necessary. This also means that there is a continuous need to develop straightforward offline and online techniques to clarify problems occurring, for example, as a result of the introduction of more intensively closed systems of water circulation. In the present study, we describe the use of a novel, online, sample enrichment technique followed by atmospheric pressure chemical ionization-mass spectrometry (APCI-MS) suitable for monitoring the concentration levels of common resin and fatty acids in papermaking process waters. MATERIALS AND METHODS: The representative process water samples were taken from the grinding zone of a thermomechanical pulping mill. The samples were first preconcentrated in a precolumn C18, and the analytes were transferred online to MS. The high intensive [M-H](-) ion was used for the identification of each analyte since, according to the present ionization method, no other fragmentation was observed. Laboratory-scale, online measurements with an online sample feed were carried out by connecting a centrifugal pump and a ceramic filter to the APCI-MS. RESULTS: Quality parameters, such as repeatability, linearity, and limit of detection (LOD), were determined by using dehydroabietic acid (DHAA) in order to evaluate the suitability of the method for the rapid screening of concentration levels. This method provided satisfactory linearity and a good correlation between analyte concentration and peak area. The suitability of the system for the continuous analysis of the same acids was evaluated in laboratory-scale, online experiments. In all cases, the response to changes in the analyte concentration was linear, and the repeatability of the system was also satisfactory. DISCUSSION: Only a few studies have been published on the analysis of resin and fatty acids with MS techniques. The present method was applied to the monitoring of dehydroabietic, oleic, and stearic acids. The quality parameters were highly comparable with those reported earlier, and the LOD values of the DHAA were below the levels usually encountered in process waters. The quality parameters were only slightly higher than those obtained by the traditional methods of analysis, probably due to the absence of an effective sample clean-up before analysis. CONCLUSIONS: The results of the laboratory-scale, online experiments indicated that the online enrichment APCI-MS system is a suitable alternative for monitoring the concentration levels of selected resin and fatty acids in papermaking process waters. The method can be used, for example, to provide useful information about the concentration levels of these acids in different stages of the process, thus signaling possibly impending problems. In general, faster and simpler measurements are needed to meet the requirements for a reduction in fresh water usage in papermaking. RECOMMENDATIONS AND PERSPECTIVES: Compared to the conventional methods used for this purpose, the main benefits of the method are rapidity of measurement, simplicity of use, and absence of the need for multistage sample treatments (short analysis time). For this reason, this online method is more suitable for the control of papermaking by analyzing the concentration levels of interfering substances (i.e., selected resin and fatty acids) than an offline analysis detailing all the individual extractives-based compounds in process streams. It is also obvious that the technique can easily be modified for other environmental pollutants as well.