Multivariate statistics of the pyrolysis products of high molecular components in pulping wastewaters to explain their toxicity.
OBJECTIVE
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.


CONCLUSIONS
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.
Paasivirta
Jaakko
J
Department of Chemistry, University of Jyväskylä, Finland. jpta@cc.jyu.fi
Kukkola
Jukka
J
Knuutinen
Juha
J
Pessala
Piia
P
Schultz
Eija
E
Herve
Sirpa
S
D000477:Alkylating Agents; D002241:Carbohydrates / Q000032:analysis / Q000737:chemistry*; D004579:Electron Transport; D008401:Gas Chromatography-Mass Spectrometry; D007220:Industrial Waste / Q000009:adverse effects*; D008031:Lignin / Q000032:analysis / Q000737:chemistry*; D016014:Linear Models; D008970:Molecular Weight; D010209:Paper; D025341:Principal Component Analysis; D000644:Quaternary Ammonium Compounds; D018675:Toxicity Tests / Q000379:methods*; D014865:Waste Disposal, Fluid; D014874:Water Pollutants, Chemical / Q000633:toxicity
D000477:Alkylating Agents; D002241:Carbohydrates; D007220:Industrial Waste; D000644:Quaternary Ammonium Compounds; D014874:Water Pollutants, Chemical; D008031:Lignin; C027917:tetramethylammonium