Size-exclusion chromatographic study of ECF and TCF softwood kraft pulp bleaching liquors

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.     

Risk Assessment in the Working Environment in Estonia

The first step to chart hazards in the working environment in Estonia (labour force: 0.65 million) was taken by the National Board of Health Protection in the beginning of 1996.

The existing chemical, physical, and biological agents in the working environment were investigated with the help of local health inspectors in all counties. An identification of hazards and workers at risk was carried out. The results of the analysis showed that 16% of Estonian industrial workers are exposed to different hazards: 20,000 persons are exposed to noise, 11,000 are working in the conditions of vibration, 10,000 are affected by unsatisfactory microclimate, 6,000 complain about long-lasting work in a compulsory posture, the overexertion of eyes is suffered by 5,500 persons, and physical overload by 3,500 workers. In the group of chemical hazards the greatest numbers of workers are exposed to organic dust (6,500) and welding aerosols (5,400), followed by petroleum products (2,700), and oil-shale dust (4,300). The measurements of working conditions showed that an average of 30.3% of the results are above the standards. Proposals for the improvement of the situation in occupational safety and health are presented.     

A Simple and Flexible Risk Assessment Method in the Work Environment

The existing risk assessment models in the work environment (on the basis of Standard No. BS 8800:1996; British Standards Institution, 1996) contain the need to determine the probability of the occurrence and the severity of consequences of the influence of hazardous factors on the worker. The determination of the probabilities of the influence of hazards (noise, vibration, chemicals, etc.) is complicated.

The authors of this article have developed a simple risk assessment method that does not contain the probabilities. The method is based on a 2-step model that could be enlarged into a 6-step model.

The implementation possibilities of the model are presented. The existing norms in the work environment in Estonia were analysed and the safety level of a wood-processing factory was determined.     

Biodegradation of chemicals in a standardized test and in environmental conditions

The estimation of biodegradation rates is an important source of uncertainty in chemical risk assessment. The existing OECD tests for ready biodegradability have been developed to devise screening methods to determine whether a chemical is potentially easily biodegradable, rather than to predict the actual rate, of biodegradation in the environment. However, risk assessment needs degradation rates. In practice these rates are often estimated (default values) from ready biodegradability tests. These tests have many compromising arbitrary features compared to the situation in the real environment. One important difference is the concentration of the chemical. In wastewater treatment or in the environment many chemicals are present at ng l(-1) to microg l(-1) levels whereas in the tests the concentrations exceed 10-400 mg carbon per litre. These different concentrations of the chemical will lead to different growth kinetics and hence different biodegradation rates. At high concentrations the chemical, if it is degradable, can serve as a primary substrate and competent microorganisms will grow exponentially, resulting in a sigmoid biodegradation curve. At low environmental concentrations the chemical does not serve as a primary substrate, and therefore does not support significant growth of the degraders, and the substrate has a linear biodegradation rate. In this study the biodegradation rates of two reference chemicals, aniline and 4-chloroaniline, were compared in a standard method and in more realistic conditions at low concentrations, using 14C-labelled substances and different sources of inocula. Biomass evolution during the tests was monitored by adenosine triphosphate measurement and also on the basis of the residual 14C-activity in the particulate matter. The results partly support the thesis that low concentrations lead to different biodegradation kinetics compared to the concentrations used in the standard tests. Furthermore the biodegradation rates of the chemicals studied, particularly of 4-chloroaniline, in Finnish natural waters appeared to be lower than those reported in some other countries.     

Bioluminescent yeast assays for detecting estrogenic and androgenic activity in different matrices

In this paper we describe the construction and use of a set of bioluminescent yeast strains for the detection of compounds that can affect androgen or estrogen receptor mediated hormonal signalling. The set includes Saccharomyces cerevisiae strains expressing human androgen receptor (AR), estrogen receptor alpha (ERalpha) or estrogen receptor beta (ERbeta), along with firefly luciferase controlled by a respective hormone responsive promoter. A constitutively luminescent strain was included in the set for determining the cytotoxicity of the sample. Yeast cells were incubated with pure chemicals or complex samples for 2.5 h, after which the signal could be detected from the cell-sample mixture after simply adding the D-luciferin substrate. The assays could be completed in one day and they required no cell lysis or centrifugation steps, which makes them suitable for high-throughput analysis of samples. Due to a short incubation time the assays are directly applicable to different sample matrices, requiring no pretreatment of the samples. The assays were used to assess the hormonal activity in moisturizing lotions as an example of a complex sample matrix known to contain endocrine disrupting chemicals. Six out of eight tested moisturisers showed high estrogenic activity, whereas no androgenic activity was observed in the samples.     

Multivariate Statistics of the Pyrolysis Products of High Molecular Components in Pulping Wastewaters to Explain Their Toxicity (6 pp)

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 polydisperse 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 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 to originate 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.     

Evaluation of resin and fatty acid concentration levels by online sample enrichment followed by atmospheric pressure chemical ionization-mass spectrometry (APCI-MS)

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.