The distribution of polychlorinated dibenzo-p-dioxins and dibenzofurans in Jackfish Bay, Lake Superior, in relation to a kraft pulp mill effluent

Samples of whole effluent and effluent suspended solids from a kraft pulp mill and sediments and biota from Jackfish Bay, Lake Superior were analyzed for polychlorinated dibenzo-p-dioxins (CDDs) and dibenzofurans (CDFs). Tetra-CDFs (4CDF) were consistently detected in whole effluent at levels ranging between 0.3 and 1.3 ng/L. Effluent suspended solids also contained 4CDFs as well as traces of 4CDD, 5CDF, 8CDF and 8CDD. The horizontal sediment distribution suggests that the effluent was the only active source of 4CDF in the area but that 8CDD originated from a more general source such as the atmosphere. An abrupt appearance of 4CDF in the more recent sections of a core profile taken in the bay suggests that an operational change at the pulp mill resulted in the formation of 4CDFs in the mill effluent some time after 1973. Moderate values of 4CDF and low values of 4CDD were found in samples of the shrimp confirming the presence of an active source of 4CDF in Jackfish Bay.     

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.     

Levels of PCDDs and PCDFs in products and effluent from the Swedish pulp and paper industry and chloralkali process

Within the Swedish Dioxin Survey various samples from the pulp and paper industry and the chloralkali process have been analyzed by congener specific analytical methods. In addition to the generally discussed “bleaching pattern” of the tetrachlorinated congeners, these samples also contained higher chlorinated congeners like hexa-CDDs, hepta-CDFs, octa-CDD and octa-CDF. Consequently it is recommended that samples from the pulp industry should be analyzed for all PCDDs and PCDFs (tetra- through octa-). Counted as Nordic Toxic Equivalents (NTEQ), the recycled pulp samples had the highest contamination level followed by TMP, unbleached sulfite and bleached softwood and hardwood. In addition to the bleaching process, various chemicals used in the pulping, bleaching and wastewater treatment can contribute to the contamination.     

微库仑法测定新疆棉浆粕企业废水中可吸附有机卤素AOX

建立微库仑滴定法测定水质中可吸附有机卤素AOX的方法,考察3种活性炭柱对于空白的影响。实验结果表明,AOX的检出限为2.19μg/L,相对标准偏差为2.80%,纯水中高、中、低加标回收率在92.5%~107%,新疆棉浆粕企业废水中加标回收率为96.0%~101%。实验室空白也只有新购开封的耶拿原装活性炭小柱能满足标准要求的空白值(<30μg/L)。     

运用模糊层次分析法优选制浆造纸废水深度处理方案

制浆造纸废水最适深度处理方案的选择是一个多准则决策问题,本文通过建立评价指标体系,从经济费用、技术性能、管理效果和社会效益4个方面,对混凝沉淀（气浮）＋过滤、Fenton氧化和生态法3种深度处理方案进行分析;采用层次分析法确定指标体系权重,其中技术性能（0.5333）权重最高;结合模糊数学法开展综合评判,评估各方案的优缺点,最后通过方案总排序确定工程优选方案。同时,针对2个具有代表意义的制浆造纸企业废水深度处理工程案例,在方案隶属度的确定时增加了决策者的期望值和企业的实际情况,分别选取了最适的制浆造纸废水深度处理方案：混凝沉淀（气浮）＋过滤法（A企业）和生态法（B企业）,这样可以更客观地指导决策者选取最合适的制浆造纸废水深度处理方案。     

废弃马铃薯渣改性制备瓦楞纸板粘合剂研究

研究了胶体磨湿法超微粉碎及高压蒸气处理对废弃污染物——马铃薯渣粒径分布及颗粒破坏程度的影响,调节胶体磨齿间隙为12μm处理30 min,并结合高压蒸气121℃处理20 min的条件下,通过显微镜观察和激光粒度分析证明马铃薯渣颗粒粒径明显减小且分布更加均匀,细胞壁和纤维素被破坏,体现出胶粘剂的性质。进而通过氧化变性处理改善其流动性,并添加一系列的助剂,制得了一种瓦楞纸板用粘合剂,其主要性能均接近于目前广泛使用的淀粉基瓦楞纸板粘合剂。     

Fenton/絮凝工艺深度处理制浆造纸废水的工程应用分析

以某制浆造纸厂生化出水Fenton/絮凝深度处理工艺长期运行数据为依据,系统分析了H2O2、废酸液（FeSO4含量约8%）、硫酸铝、PAM及氧化钙等处理药剂用量与水量、进水负荷和COD去除量之间的关系。结果表明,H2O2、废酸液、硫酸铝、PAM及氧化钙的单位水量平均投加量分别为0.05、2.18、0.07、0.0075和0.27 kg/m3,而去除单位COD的药剂平均消耗量分别为0.20、8.48、0.27、0.029和1.06 kg/（kg COD）;H2O2、废酸液、硫酸铝和氧化钙的用量随进水负荷的增大而增加,而PAM随进水负荷的变化较小。H2O2和FeSO4的投加摩尔比（MH2O2/Fe2＋）主要集中在1.0-2.0之间,其中在1.0-1.6之间的累积频率达到93%。该工艺的出水COD和SS分别为65-100 mg/L和20-30 mg/L,达到《制浆造纸工业水污染物排放标准》（GB 3544-2008）排放要求。废水深度处理成本约为1.01元/m3,其中药剂费用约0.58元/m3,占56.98%。     

制浆造纸废水生化出水的混凝处理研究

研究了硫酸铝和三氯化铁对制浆造纸废水生化出水的处理效果.研究发现,不调节原水pH值,硫酸铝投加量为600 mg/L或三氯化铁投加量为300mg/L时,混凝后废水的COD＜150 mg/L,色度＜50倍,出水均符合现阶段排放标准.混凝剂比较发现,在最佳反应条件下,2种混凝剂的处理效果相当,但硫酸铝混凝的成本低于三氯化铁....     

FeSO4/H2O2/UV体系处理化纤厂棉浆粕黑液的研究

Fenton法是处理难降解有毒有机污染物的一种有效的方法.以棉浆粕黑液为研究对象,讨论了H2O2和FeSO4投加量、pH值、搅拌时间等因素对废水CODCr去除率的影响,将紫外光照引入Fenton试剂能提高废水中有毒有机污染物的降解速度,提高氧化能力 .实验确定了最佳工艺条件:pH=7,FeSO4投加量4 g/L,H2O2投加量为1.13%(V/V),搅拌时间15 min,此时CODCr去除率达到66.96%.     

制浆造纸废水生物强化技术研究进展

制浆造纸废水是国内外公认的难处理的工业废水之一,文章介绍了生物强化技术在制浆造纸废水中的应用现状,在分析中,主要从生物强化技术、固定化微生物技术和环境生物制剂等方面,总结了制剂造纸废水生物强化技术的研究进展,并讨论了今后的研究方向。