Dioxin formation in pulp and paper mills of India

Samples of effluents, sludge, pulp, final products (paper) and soil were collected from the identified pulp and paper mills in India. The samples were analysed for 2,3,7,8-tetrachloro-dibenzo-p-dioxin (2,3,7,8-TCDD) and other dioxin congeners and precursors. Pulp and paper mills using chlorine for the bleaching process showed the presence of 2,3,7,8-TCDD in effluent samples. In the effluent and pulp samples from mills where chlorine dioxide was used as a bleaching agent, the 2,3,7,8-TCDD congener ranged from below the detection limit 0.05 to 0.12 ngL⁻¹/ngg⁻¹. The relative standard deviation of reproducibility and the percent recovery of 2,3,7,8-TCDD were 2.07 and 82.4% in pulp and 2.8 and 92% in effluent, respectively. The 1,3,6,8-TCDD was the only other major dioxin congener found in the treated and untreated effluent and sludge samples. However, dichlorobenzene, trichlorophenyl, and hexachlorobiphenyl were detected in all samples. The formation of dioxins can be minimised by replacing chlorine with chlorine dioxide in bleaching processes in pulp and paper mills.     

草制浆造纸中段废水处理及回用技术分析研究

中段废水是制浆造纸工业的主要污染源之一,从工程设计的角度出发,对草制浆造纸中段废水处理及回用提出一套可行适用的工艺方案;对主要工艺环节参数、设备备有说明,以供同行借鉴.     

草制浆造纸中段废水处理及回用技术分析研究

中段废水是制浆造纸工业的主要污染源之一，从工程设计的角度出发，对草制浆造纸中段废水处理及回用提出一套可行适用的工艺方案；对主要工艺环节参数、设备备有说明，以供同行借鉴。     

Lime as the source of PCDD/F contamination in citrus pulp pellets from Brazil and status of the monitoring program

After an exhaustive investigation, in 1997 the source of the milk contamination in Germany was traced to citrus pulp pellets originating from Brazil. It has been shown that lime was the source of the PCDD/F contamination of these products. After this conclusion, a continuous monitoring program has been performed over a two year period and the results are presented in this paper. Standard isotope dilution techniques were used for all samples, which were analyzed by selected ion monitoring high resolution GC–MS.     

Identification and level estimation of chlorinated neutral aromatic sulfur compounds and their alkylated derivatives in pulp mill effluents and sediments

Seven effluent samples from a modern pulp mill, in which chlorine and chlorine dioxide bleaching is used, and five sediment samples from the recipient watercourse were investigated for polychlorinated dibenzothiophenes (PCDBTs), polychlorinated thianthrenes (PCTAs), polychlorinated diphenylsulfides (PCDPSs) and for alkylated derivatives of these. Mainly di-, tri-, tetra- and pentachlorinated congeners were studied. Particles and filtrates from the effluents were analyzed separately. The concentration levels of the nonalkylated compounds were found to be higher in the filtrates than in the particles. Trichlorinated dibenzothiophenes and thianthrenes were found as the major congeners. Pentachlorinated derivatives were not found. Alkylated di- and trichlorodibenzothiophenes were detected in some samples, while alkylated chlorinated thianthrenes and diphenylsulfides were nondetectable. The estimated concentration levels of the compounds detected were in the range of 40–2700 pg/L in the pulp mill effluents and in the range of 2–40 pg/g dry weight in the sediments. Mixtures of methylated di- and trichlorodibenzothiophenes used as references in analyses were prepared from methylchlorobiphenyls. Some new pure model compounds were obtained by HPLC fractionation of the chlorination mixture of dibenzothiophene. Structures of these were determined by ¹H NMR.     

PCBs, dioxins and furans in Hooded Merganser (Lophodytes cucullatus), Common Merganser (Mergus merganser) and mink (Mustela vison) collected along the St. Maurice River near La Tuque, Quebec

A pulp and paper mill located in La Tuque on the St.Maurice River, Quebec, and using the kraft bleaching process was historically the largest pulp and paper industry point source of chlorinated dibenzo-p-dioxins and dibenzofurans in Quebec. A study was undertaken to document the bioaccumulation of PCBs, dioxins and furans in piscivorous birds and mammals in this area. Hooded and Common Merganser eggs were collected in nest boxes along the St.Maurice River and Common Merganser fledglings were collected at two sites on the river. Wild minks were trapped along the St.Maurice River and in a control area upstream. Analysis of pooled merganser eggs showed contamination with dioxins, furans and PCBs. Liver samples of fledglings were contaminated with 2,3,7,8-tetrachlorodibenzofuran at the downstream site. Analysis of mink livers showed a significant higher contamination with dioxins and furans in some downstream samples compared with the upstream samples.     

木聚糖酶在硫酸盐木浆辅助漂白中的应用研究

结合某木浆厂的实际运行数据,对采用木聚糖酶辅助漂白前后的木浆质量、主要物料消耗量及产生废水的污染物指标进行了详细分析.结果表明,在工艺运行参数不变条件下,使用木聚糖酶辅助漂白能够显著提高生产纸浆质量等级,降低原木、二氧化氯和能源消耗量,减轻漂后废水的污染负荷,对于降低纸浆生产成本,保护水环境具有重要意义.     

Fingerprint of polychlorinated biphenyl congeners in samples of human subcutaneous adipose tissue

The concentrations of various PCB congeners as well as the fingerprint of their composition were determined for samples of human subcutaneous adipose tissue. The results indicate the presence of several inducers of MFO activity which are prevalently of PB- and mixed-type inducers. We discuss the possibility that this tissue may represent a “reservoir” which causes a chronic exposure to the organism.     

Levels, profile and pattern of PCDDs and PCDFs in samples related to the production and use of chlorine

Analyses of sludge from graphite electrodes used in the chloralkali process show total levels of PCDFs as high as 650000 pg/g sludge. The levels of tetra-, penta-and hexaCDFs were found to be approximately the same. The levels for the corresponding PCDDs were below the detection level. The dominating congeners within each group are the toxic 2,3,7,8-substituted PCDFs at levels of 340000 pg/g, This typical pattern, called the “chloralkali pattern” can also be found in soil samples taken at another chloralkali plant. The typical pattern can also be identified in a solution of ferric chloride. Traces of “chloralkali pattern” are identified in a sludge sample from the drinking water purification plant, the source for PCDFs in the sludge is unknown.     

Chlorinated components in lime used in production contaminated citrus pulp pellets from Brazil

In order to further understand the contamination of the citrus pulp pellets (CPP) that were exported to Europe in 1997 we examined both contaminated lime and CPP samples for the distribution of polychlorinated biphenyls (PCBs) and chlorinated benzenes (tri–hexa). Standard isotope dilution techniques were applied for all samples, which were analysed by selected ion monitoring high resolution GC–MS. Lime that is used in the production of CPP product is highly contaminated with PCBs and chlorobenzenes.     

Determination of PCBs, PCDDs and PCDFs in insulating oil samples from stored Chinese electrical capacitors by HRGC/HRMS

Homologue and congener profiles of polychlorinated biphenyls (PCBs), polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) in commercial PCBs formulations are key information for the source identification of PCBs contamination as well as for the risk assessment caused by potential exposure. The isotope dilution technology in combination with high resolution gas chromatography-high resolution mass spectrometry (HRGC/HRMS) has made the accurate determination of such profiles possible. So far, various commercial PCB formulations except Chinese products have been successfully determined. Two PCBs containing insulating oil samples from stored Chinese electrical capacitors have been determined with the same methodology for comparability. The total concentration PCBs in two oil samples were 790 000 μg g⁻¹ and 720 000 μg g⁻¹, respectively. TriCBs, TetraCBs, and DiCBs were found to be most abundant. Concentration of dioxins contamination in two samples is 650-670 ngTEQ g⁻¹, of which 69-71 ngTEQ g⁻¹ from PCDD/Fs with the predominant congeners of 1,2,7,8-TeCDF; 2,3,7,8-TeCDF; 2,3,4,7,8-PeCDF and 1,2,3,7,8-PeCDF. The contributions of DL-PCBs in total TEQ in both samples were more than 85%. The dioxin-like toxicity in insulating oils contained in electrical capacitors could be considered receive attention as an important dioxins source if such wastes are not managed in an environmentally sound manner.     

Polychlorinated biphenyls (PCBs) and Polybrominated Diphenyl Ethers (PBDEs) in surface sediments from Monastir Bay (Tunisia,Central Mediterranean): Occurrence,distribution and seasonal variations

An assessment of PCB and PBDE contamination of surface sediments in Monastir Bay was carried out in two contrasted seasons of the year. Samples were collected from 5 sites and analyzed for the ∑₇ marker PCBs (i.e. PCBs 28, 52, 101, 118, 138, 153 and 180) and ∑₄ PBDE congeners (PBDEs 47, 99, 119 and 153) by GC/ECD. Concentrations of both PCBs and PBDEs showed seasonal variations. PCB concentrations were in the range of 3.1–9.3 ng g⁻¹ and 1.1–8.1 ng g⁻¹ in wet and dry season respectively, and sediments were considered moderately contaminated with PCBs. All PCBs analyzed were detected in surface sediments. PCB 153 and 52 congeners showed the highest relative abundance in both winter and summer. PBDE concentrations ranged from not detect to 0.1 ng g⁻¹, with only BDE-47 congener detected in sediments and only in winter. Analysis of spatial and seasonal variations indicated that PCB distribution is governed by hydrodynamics and temporal variability of inputs. While the PCB contamination appeared to be mainly land-based, PBDEs are suspected to originate from atmospheric deposition.     

Distribution of PCDDs and PCDFs in Soils Collected from the Denver Front Range - Principal Components Analysis of Diffuse Dioxin Sources (10 pp)

Background, Aims and Scope The Rocky Mountain Arsenal (RMA) is a US Army facility located northeast of Denver, Colorado that has been listed on the National Priorities List (NPL). It is currently being re-mediated under the authority of the Comprehensive Environmental Response, Compensation, and Liability Act of 1980 (CERCLA) and the Superfund Amendments and Reauthorization Act of 1986 (SARA). As part of the remediation activities at RMA, indications were found that a source of polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) had existed on the RMA. As a result, investigations were undertaken to assess the possible nature and extent of any potential sources of PCDDs and PCDFs on the RMA site. In addition, other studies were conducted that examined PCDD/PCDF contamination in the Denver area. The goal of these studies was to examine nature and extent of PCDD/PCDF contamination both on the RMA as well as in the surrounding Denver area. The intent of this study was to characterize sources of dioxins (PCDDs) and dibenzofurans (PCDFs) at low environmental concentrations which might have originated from diffuse sources in the Denver Colorado area and in particular, the Rocky Mountain Arsenal (RMA) using Principal Component Analysis (PCA). Methods Over 200 soil samples were collected from the RMA and the Denver area. From the RMA, soil was collected as part of three studies that included a (1) random site-wide sampling of the RMA, (2) soils from the Western Tier Parcel (WTP), and (3) soils from Historic Use areas. Denver area soil samples were collected from five different land use categories: Residential, Agricultural, Open Space, Commercial, and Industrial. PCA was conducted on concentrations of 17 2,3,7,8-substuituted PCDD and PCDF congeners in 220 soil samples collected from the RMA and the Denver Front Range region. Results and Discussion PCA demonstrated the presence of possible minor sources of dioxins on the RMA. Current remediation efforts on RMA will result in the removal of these sources. Samples from the RMA were identified by the presence of a congener profile containing higher chlorinated PCDFs while the Denver Front Range areas were characterized by the presence of higher chlorinated PCDD congeners. The presence of a PCDF signature for the RMA samples does not necessarily indicate a major source of these contaminants on-site. Indeed, the relatively diffuse nature of the sample clusters would argue strongly against the presence of a single large source. Instead, the predominance of the PCDF congeners probably indicates the mixed industrial activities that took place on and near the site. Conclusion PCA results indicate that PCDD/PCDF profiles in soils collected from the RMA differed from those collected from the outlying Denver areas but that a major source of these contaminants was not present. Rather, the diffuse nature of sample clusters from the PCA indicated that the congener profile of RMA samples was most likely a result of the mixed industrial activities that historically have taken place on and near the site. PCA also indicated that many of the 'open area' (peripheral site-wide) RMA soils samples did not differ from Denver are reference congener profiles. This finding was also true for samples collected from the WTP that were essentially indistinguishable from Off-RMA reference samples. In addition, total TEQ concentrations in soils collected from WTP were similar to those measured in soils collected from the Denver Front Range areas indicating that lack of a major source of PCDD/PCDF within the WTP zones of the RMA. Recommendation and Outlook Analytical as well as statistical results of the soil congener data indicate that the WTP soils are indistinguishable from soils collected from non-industrial areas in the Denver area. This finding would support the recent 'de-listing' of the WTP from the other RMA areas and its' transfer to other authorities in the Denver area.     

Contamination of human milk in Middle Hesse, Germany--a cross-sectional study on the changing levels of chlorinated pesticides, PCB congeners and recent levels of nitro musks

Human milk samples from women in Middle Hesse, Germany were chemically analyzed for contamination levels of alpha-, beta- and gamma-HCH, HCB, p,p'-DDE and p,p'-DDT as well as the PCB-congeners no. 28, 31, 49, 52, 101, 118, 138, 153, 156, 170 and 180. Changes in concentrations of these compounds in human milk over an extended time period were studied by comparing samples from 1984/85, 1990/91 and 1995. In addition, concentrations of the nitro-aromatic compounds musk xylene and musk ketone were determined in the 1995 samples. The study showed statistically highly significant (p<0.001) reductions in levels of beta- and gamma-HCH, HCB, p,p'-DDE and p,p'-DDT, in human milk from 1995 compared to samples from 1984/85. A weakly significant reduction (p<0.05) of alpha-HCH was also observed. For low-chlorinated PCB congeners, on the other hand, a highly significant increase of PCB no. 28 was detected and concentrations of congeners no. 31, 49 and 52 remained unchanged. Concentrations of the high-chlorinated congeners no. 101, 138, 153 and 180 dropped (highly significant). A highly significant reduction of PCB no. 118 and 156 occurred between 1990/91 and 1995, but a highly significant increase was found for no. 170. Lower levels of hydrocarbon contamination of human milk samples from 1995 than were found in samples from 1984/85 and 1990/91 can be seen to result partially from voluntary reductions, but primarily reflect restrictive environmental legislation in the Federal Republic of Germany. Mean concentrations of musk xylene and musk ketone in samples from 1995 were 41 microg/kg and 10 microg/kg milk fat, respectively.     

Lipophilic extractives in process waters during manufacturing of totally chlorine free kraft pulp from eucalypt wood

The chemical composition of lipophilic extractives from process waters throughout a totally chlorine free (TCF) bleaching sequence after kraft pulping of eucalypt wood has been studied. These compounds are among the most problematic wood constituents for both TCF and zero liquid effluent (ZLE) processes, since they tend to accumulate in circuits resulting in the formation of the so-called pitch deposits causing serious problems in the pulp and paper industry. Pitch deposits collected at different parts of the pulp mill were also characterized and their composition compared with that of lipophilic compounds in process waters and Eucalyptus globulus wood. The identification of these compounds from process waters, wood and pitch deposits was performed by gas chromatography and gas chromatography-mass spectrometry using short- and medium-length high temperature capillary columns. Sterols, sterol esters, steroid ketones and steroid hydrocarbons were the main compounds identified. These chemical species arise from eucalypt wood extractives that survive the pulping and are released from pulp into the process waters during the bleaching process. Finally, they can deposit in pulp and on different parts of the mill or remain suspended in process waters being discharged in effluents.     

Analysis and evaluation of chlorinated persistent organic compounds and PAHs in sludge in Korea

The concentrations of 12 POPs listed in the Stockholm convention, chlorophenols (CPs) and PAHs were investigated in sludge samples from wastewater and sewage treatment plants (WWTPs and STPs). The concentrations of PCDD/Fs in the wastewater sludge ranged from 0.189 to 1092 ng-TEQkg(-1) dry wt., and most of the sludge samples had levels below the EU guideline for the land application of PCDD/Fs (<100 ng-TEQkg(-1) dry wt.) except one sample. Co-PCB congeners were analyzed from four WWTPs, with total concentrations ranging from 0.265 to 26.6 ng-TEQkg(-1) dry wt., which were similar to the results obtained from previous studies. The levels of PCDD/Fs and Co-PCBs varied according to the main source of the influent to each WWTP and the paper industry was the main source of these compounds in the sludge due to the chlorine bleaching process. In case of OCPs, HCB and p,p'-DDE were detected at relatively high levels in the sludge samples compared to other target compounds, ranging from 1.30 to 21.5 microg kg(-1) dry wt. and 0.758 to 14.8 microg kg(-1) dry wt., respectively. Different OCP distribution patterns were observed according to sludge types, with HCB and DDTs being dominant in the sludge from WWTPs and STPs, respectively. The total levels of PAHs and CPs ranged from 1.24 to 44.9 mg kg(-1) dry wt. and 0.340 to 3.85 mg kg(-1) dry wt., respectively. The PAHs and CPs were also shown to have various distribution patterns, possibly due to the different wastewater sources to the WWTPs.     

Semipermeable membrane device (SPMD) for monitoring PCDD and PCDF levels from a paper mill effluent in the Androscoggin River, Maine, USA

Paper mill effluents may contain polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) that are normally generated due to chlorinated bleaching of pulp and paper. We used the semipermeable membrane device (SPMD) to monitor PCDD/F levels upstream and downstream of a paper mill on the Androscoggin River, in Jay (ME). Following the 36 day deployment, SPMD dialysis and cleanup, the samples were analyzed by HRGC/HRMS. Total concentrations of PCDD/Fs in SPMDs (sum of all tetra-through octachlorinated congeners) ranged from 4.71 pg g(-1) to 26.26 pg g(-1). Five out of the targeted 17 toxic congeners were detected, including: 2,3,7,8-TCDF; 1,2,3,7,8-PeCDF; 2,3,4,7,8-PeCDF; 1,2,3,4,6,7,8-HpCDD and OCDD. Permeability reference compounds (PRCs) were used for in situ calibration of the SPMD sampling rate (Rs). In all sites, water concentrations were the highest for OCDD (0.081-0.103 pg l(-1)), and the lowest for 1,2,3,7,8-PeCDF (0.005-0.009 pg l(-1)). There was not a consistent pattern of upstream-downstream gradient in the PCDD/F levels. This suggested that processes other than the mill in Jay (multiple sources, river dynamics) governed the flux of PCDD/Fs in the sampling locations. The SPMD results were validated by comparison to other studies on the Androscoggin River and elsewhere, confirming the potential of the device as a useful monitoring technique for PCDD/Fs in large river systems.     

GC-profiles of chlorinated terpenes (Toxaphenes) in some Finnish environmental samples

The profiles of chlorinated terpenes in Finnish environmental samples were compared by GLC-SIM technique with those of toxaphene and Eastern European “dark”. The profiles in the seal blubber in the Northern and in the Eastern Baltic Sea proved to be similar. Chlorinated terpenes were found to be present in Finnish human milk.The spent bleach liquor of pine kraft pulp mill contained components having similar retention times and responses to those from toxaphene components.     

蔗渣浆酶促漂白预处理对纤维形态性质和污染物发生的影响

采用Pulpzyme HC木聚糖酶对蔗渣纸浆进行酶促漂白处理。试验结果表明,酶处理的最佳纸浆浓度为5％,处理时间为60min．酶用量为1．0IU／g。酶处理后纸浆的得率下降不多．强度略有升高,但纸浆白度增加。试验结果还表明,酶处理对纸浆纤维不具有破坏性。对酶处理后纸浆的扫描电镜观察说明,随酶处理时间和酶用量的增加,蔗渣中木聚糖的溶出量加大。酶处理使木聚糖降解溶出,使木质素充分暴露出来,有利于后续漂白剂与之反应．同时可减少后续化学漂白剂的使用量,从而减少有毒氯化有机污染物的产生。随处理时间增长和酶用量增加,处理液中CODcr,和BOD5呈上升趋势。酶用量超过1．5IU／g后．BOD5增长较缓慢,表明酶的作用对纤维表面生物可降解成分的溶出较彻底。     

碱法麦草浆漂白废水脱色白腐菌的筛选及脱色研究

从腐木上采集,经多次分离纯化筛选出2株具有较高漂白废水脱色能力的菌株F7、F9,与Phanerochaete Chrysosporium在相同的条件下处理碱法麦草浆CE段混合漂白废水,培养4d脱色率分别为74．44％,46．67％和62．22％。延长培养时间至第8d,F7菌脱色效果不明显,而F9菌脱色可增至67．58％。