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.     

Characteristics of biotic and abiotic removals of dissolved organic carbon in wastewater effluents using soil batch reactors.

Biodegradable dissolved organic carbon (BDOC) analyses and abiotic adsorption of dissolved organic carbon (DOC) from different wastewater effluent were conducted to evaluate biotic and abiotic removal mechanisms as a function of the initial DOC concentration and source of DOC using soil batch reactors. To obtain high DOC concentrations, a laboratory-scale reverse osmosis unit was used. It was found that BDOC fraction was independent of the initial DOC concentration and was dependent on the source of wastewater and/or the types of wastewater treatment. The BDOC fractions varied from 9 to 73%. Trickling filter effluent (Tucson, Arizona) showed the highest BDOC, ranging from 65 to 73% biodegradable, while wastewater treated by the soil aquifer treatment (SAT) (NW-4) was found to be most refractory, with DOC removals of 9 to 14%. For nitrified/denitrified tertiary effluent (Mesa, Arizona) and secondary effluent (Scottsdale, Arizona), 36 to 42% removal of DOC was observed during the BDOC test. The amount of BDOC in the wastewater depended not on the concentration of DOC, but on the effectiveness of pretreatment. Abiotic adsorption capacity of wastewater effluent varied from 6 to 18%. Molecular weight distribution analyses showed that more than 50% of DOC in the Scottsdale concentrate had a molecular weight of less than 1000 Da, and no significant change in distribution profiles occurred after approximately 12% abiotic adsorption with both soils with acclimated microorganisms (SAT soil) and soils without acclimated microorganisms (non-SAT soils). Hence, preferential adsorption was not observed and the presence of acclimated microbes did not influence adsorption.     

Inter-laboratory comparison study on measuring semi-volatile organic chemicals in standards and air samples

Measurements of semi-volatile organic chemicals (SVOCs) were compared among 21 laboratories from 7 countries through the analysis of standards, a blind sample, an air extract, and an atmospheric dust sample. Measurement accuracy strongly depended on analytes, laboratories, and types of standards and samples. Intra-laboratory precision was generally good with relative standard deviations (RSDs) of triplicate injections <10% and with median differences of duplicate samples between 2.1 and 22%. Inter-laboratory variability, measured by RSDs of all measurements, was in the range of 2.8-58% in analyzing standards, and 6.9-190% in analyzing blind sample and air extract. Inter-laboratory precision was poorer when samples were subject to cleanup processes, or when SVOCs were quantified at low concentrations. In general, inter-laboratory differences up to a factor of 2 can be expected to analyze atmospheric SVOCs. When comparing air measurements from different laboratories, caution should be exercised if the data variability is less than the inter-laboratory differences.     

Methods for the analysis of PCBs in human food, faeces and serum.

A method was developed to determine trace concentrations of a range of individual PCB congeners in biological samples (serum, food and faeces) using GC-MS, to prepare a mass balance of PCBs in humans. A simple method for the analysis of PCBs in human serum, which excluded an extraction step, was first employed. Results indicated that the recoveries of 13C12 PCB spikes were variable. A soxhlet extraction step was added and was found to be efficient and reproducible. A quality control routine and method validation results are presented. In batch tests of the methods presented it was found that the serum analysis method gave within batch mean 13C12 spike recoveries of 98-120% and standard deviations between 6 and 20%. The food/faeces analysis method gave within-batch mean 13C12 spike recoveries of 88-100%, and within batch standard deviations between 4 and 12%. The batch to batch mean recovery for serum analysis was 100%, with an RSD of 9% for high spikes and 10% for low spikes. For food/faeces analysis the batch to batch average recovery was 110%, with an RSD of 5% for high spikes and 9% for low spikes.     

Activated sludge deflocculation in response to chlorine addition: the potassium connection.

Chlorination is often used to control filamentous bulking in activated sludge systems. Pure culture and mixed-liquor experiments showed that soluble potassium (K+) concentrations increased by 2.4 mg/L (80%) and 1.5 to 3.6 mg/L (11 to 30%) in the bulk liquid phase of pure and activated sludge cultures that were exposed to chlorine, relative to unchlorinated controls. Effluent turbidity and total suspended solids from settled mixed liquor increased significantly in both short-term batch and sequencing batch reactor experiments when chlorine mass load increased above 6 milligrams of chlorine per gram mixed liquor volatile suspended solids (mg Cl2/g MLVSS) in a single dose, which correlated with a localized chlorine concentration at the dose point of 10 mg/L as Cl2 or greater. The results support the hypothesis that the glutathione-gated potassium efflux (GGKE) bacterial stress response may contribute to increased effluent turbidity associated with high doses of mixed-liquor chlorination. It is suggested that potassium is a useful parameter to monitor at full-scale facilities when determining chlorine mass doses that should be used to control filaments and minimize increases in effluent turbidity.     

An intercalibration study on organobromine compounds: Results on polybrominated diphenylethers and related dioxin-like compounds

An intercalibration study on organobromine compounds has been conducted to evaluate the accuracy and reliability in the analysis of brominated flame retardants (BFRs) such as polybrominated diphenyl ethers (PBDEs) and their related compounds like polybrominated and monobromo-polychlorinated dibenzodioxins and -furans (PBDDs/DFs, MoBPCDDs/DFs). This paper reports the results for these compounds in 'Mixed Standard Solutions' and 'Air-Dried Sediment'. The relative standard deviations (RSDs) for PBDEs, PBDDs/DFs and MoBPCDDs/DFs in mixed standard solutions ranged from 9% to 24%, 4% to 20% and 8% to 27%, respectively. The results of this study are better than those reported in earlier international interlaboratory studies due to general improvement in analytical methods and an increasing number of available authentic standards, particularly for PBDEs. In the analysis for higher brominated compounds such as octabromodibenzodioxin, the participants were advised to optimize the calibration curves befitting the range of concentrations found in samples because variation of relative response factors was noted. The results for 'Air-Dried Sediment' were also reasonable with RSDs from 10% to 38% for PBDEs, 8% to 38% for PBDDs/DFs and 17% to 36% for MoBPCDDs/DFs. In the sediment sample, possible errors in the sample pretreatment and/or interference by other compounds/impurities were indicated. The concentrations of pentabromodiphenylether, BDE100, varied more than the other PBDE isomers due to its poor separation in some chromatographic conditions. In addition, interference by PBDEs was observed in the analysis for PBDFs. Potential degradation/secondary formulation of PBDEs and PBDFs during the Soxhlet extraction were suggested when copper powder was added into the sediment samples. Inspite of these observations, the results in this study are better than those reported in other interlaboratory studies due to the advice given to participants for improving the results. Compared with the results for PCDDs/DFs (5-23% RSDs) and Co-PCBs (6-24% RSDs), the RSDs for most of the organobromine compounds were high, indicating an immature QA/QC approach for the analysis of PBDEs and related compounds in comparison to common chlorinated dioxins.     

Fenton氧化对制浆造纸废水分子量及可生化性变化的影响

以制浆造纸废水的初沉池出水为研究对象,对不同剂量的Fenton氧化试剂处理制浆造纸厂初沉废水的效果进行了研究,初沉废水中的分子量大于10 000的有机污染物含量占到83%,废水可生化性较差;在Fe2+与H2O2的摩尔比为1∶5,废水pH为3.5的条件下,H2O2(30%)投加量小于3.25 mL/L时,Fenton试剂的氧化效率更高;H2O2(30%)投加量为6.50 mL/L时,废水中污染物的去除率更高,其中废水COD的去除率为79.5%,AOX的去除率为75.3%,色度去除率为97.5%,同时处理后废水中分子量在500~3 000之间的有机物含量占到82.98%,废水的BOD5/COD值提高到0.56。Fenton氧化作为前置技术处理制浆造纸废水,可以降低废水中的有机物分子量,减少废水的生物毒性,增加废水生物降解性,有助于后续生物处理的正常运行。     

城市污水厂污水污泥的热值测定分析方法研究

建立热力学指标是污水生物处理过程热力学分析的基础工作，目前仍缺乏污水污泥化学能测试的标准方法。采用IKA C5000型自动热量计对某城市二级污水处理厂进水、出水、初沉污泥、剩余污泥、混合污泥和脱水污泥进行了热值测定，样品前处理采用103～105℃烘干获得干燥基，用苯甲酸进行加标回收。参照煤的发热量测定方法得到样品的高位热值。试验结果显示：出水干燥基的热值为05 kJ/g，进水干燥基的热值为4 kJ/g以上，各工艺段的污泥干燥基热值较高，基本都在12 kJ/g以上，接近右江褐煤水平。测定结果的标准偏差≤±0.452%，相对标准偏差≤±0.136%。通过同一批样品的元素分析及Dulong公式理论推算，发现2种方法可得到相似的结果。     

Interlaboratory study for the polychlorinated naphthalenes (PCNs): phase 1 results

An interlaboratory study was initiated to investigate consistency in reported concentrations of polychlorinated naphthalenes (PCNs). Results are reported from the first phase of a study that examined the variability associated with different quantification methodologies, instrumentation and standards. Nine participating labs from seven countries quantified individual homolog groups, summation operator PCN (the sum of 2-8 chlorinated homologs), and selected congeners in two test solutions derived from Halowax 1014. The means of the reported summation operator PCN values were within less than 15% of the known concentrations of the two test solutions and the relative standard deviation among laboratories was 11%. However, the among laboratory variability was in the range 20-40% for individual PCN homologs and individual PCN congeners. These results suggest the need for additional interlaboratory studies and for the development of reference materials for PCN analysis. Future PCN interlaboratory comparison exercises are discussed that will utilize control materials and unknowns consisting of suitable environmental matrices.     

Comparative toxicity of effluents processed by different treatments in V79 fibroblasts and the algae Selenastrum capricornutum

The efficacy of ozonation and of photocatalysis processing in the treatment of pulp mill ECF (elementary chlorine free) bleaching and textile effluents was evaluated by determining total organic carbon reduction (TOC) and the toxicity. The chronic toxicity of the effluents was evaluated by the ability to inhibit the growth of algae Selenastrum capricornutum. Cultured hamster V79 fibroblasts were used to assess the cytotoxicity of effluents submitted to different detoxification processes. Two endpoints were measured in V79 cells: 3-(4,5-dimethylthiazole-2-yl)-2,5-biphenyl tetrazolium bromide (MTT) reduction and neutral red uptake (NRU). Both treatment processes were able to reduce the TOC, although ozonization was less effective for pulp mill ECF bleaching. The pulp mill ECF bleaching and textile effluents reduced the growth of S. capricornutum by 39% and 27%, respectively. However, at the highest concentration tested, the textile effluents treated by photochemical process for 60 min showed increased cytotoxicity in V79 cells compared to the untreated effluent when assessed by the NRU and MTT reduction assays (increases of 30% and 40%, respectively). Pulp mill ECF bleaching effluent treated by ozonization had a similar cytotoxicity to that of untreated effluent in the NRU assay. In contrast, the MTT reduction assay indicated that effluents treated with ozone were around 20% more cytotoxic than untreated effluents. These results show that cultured fibroblasts may be useful for studying cellular responses to pollutants and may be included in tests to monitor the efficiency of effluent detoxification processes.     

Decolorization of palm oil mill effluent using growing cultures of Curvularia clavata

Agricultural wastewater that produces color are of environmental and health concern as colored effluent can produce toxic and carcinogenic by-products. From this study, batch culture optimization using response surface methods indicated that the fungus isolated from the pineapple solid waste, Curvularia clavata was able to decolorize sterile palm oil mill effluent (POME) which is mainly associated with polyphenol and lignin. Results showed successful decolorization of POME up to 80 % (initial ADMI [American Dye Manufacturing Index] of 3,793) with 54 % contributed by biosorption and 46 % by biodegradation after 5 days of treatment. Analysis using HPLC and GC-MS showed the degradation of color causing compound such as 3-methoxyphenyl isothiocynate and the production of new metabolites. Ecotoxicity test indicated that the decolorized effluent is safe for discharge. To determine the longevity of the fungus for a prolonged decolorization period, sequential batch decolorization studies were carried out. The results showed that lignin peroxidase and laccase were the main ligninolytic enzymes involved in the degradation of color. Carboxymethyl cellulase (CMCase) and xylanase activities were also detected suggesting possible roles of the enzymes in promoting growth of the fungus which consequently contributed to improved decolorization of POME. In conclusion, the ability of C. clavata in treating color of POME indicated that C. clavata is of potential use for decolorization and degradation of agricultural wastewater containing polyphenolic compounds.     

Coupling of solar-assisted advanced oxidative and biological treatment for degradation of agro-residue-based soda bleaching effluent

This study evaluates the effect of integrated solar-assisted advanced oxidation process (AOP) and biological treatment on the extent of degradation of effluents from chlorination (C) and first alkaline extraction (E₁) stages of soda pulp bleaching in agro-residue-based pulp and paper mill. Biodegradation of the effluents was attempted in suspended mode using activated sludge from the functional pulp and paper industry effluent treatment plant acclimatized to effluents in question. The photocatalytic treatment was employed using zinc oxide (ZnO) in slurry mode for decontamination of effluents in a batch manner and the degradation was evaluated in terms of reduction in chemical oxygen demand. The biological treatment (24?h) of C and E₁ effluent resulted in 30 and 57?% of degradation, respectively. Solar-induced AOP of C and E₁ effluents resulted in 53 and 43?% degradation under optimized conditions (2.5?g?L^?1 ZnO at pH?8.0) after 6?h of exposure. For C effluent, a short duration of solar/ZnO (1?h) prior to biological treatment reduced the time required at biological step from 24 to 12?h for almost same extent (92?%) of degradation. However, sequential biological treatment (24?h) followed by solar/ZnO (2?h) resulted in 85.5?% degradation. In contrast, in the case of E₁ effluent, sequential biological (24?h)?Csolar/ZnO (2?h) system effectively degrades effluent to 95.4?% as compared to 84.8?% degradation achieved in solar/ZnO (2?h)?Cbiological treatment (24?h) system. In the present study, the sequencing of photocatalysis with the biological treatment is observably efficient and technically viable process for the complete mineralization of the effluents.     

Determining algal-available phosphorus in pulp and paper mill effluents: algal assays vs routine phosphorus analyses

We determined the potentially algal-available P (P(aa)) in pulp and paper mill effluents by two bioassay techniques (a dual-culture assay and a batch approach) and compared it with chemically analysed P (total P, total dissolved P, reactive P, dissolved reactive P and dissolved hydrolysable P). The mean P(aa) given by the dual-culture assay was within a 40% range of that given by the batch approach. The P(aa) obtained by both bioassays differed from total P. Dissolved reactive P appeared to be the most readily available chemical P fraction, but other P fractions also contributed to P(aa). The analysis of reactive P, which involves direct staining of an unfiltered sample, best approximated the P(aa) given by the dual-culture assay (relative error 9%). The results suggest that assessment of eutrophying effluent P can be improved by analysing simple chemical P fractions in wastewater. The fractions to be analysed, however, may be site specific.     

Assessing the biological status of fish in a river receiving pulp and paper mill effluents

This study compared the use of sentinel species- and community-based field approaches for assessing the biological status of fish living in a river receiving pulp and paper mill effluents. Three approaches were compared. Two approaches used sentinel species. One of these involved an internal/external examination of the fish that leads to the calculation of a fish health assessment index (HAI) and the other involved biochemical measurements of hepatic mixed function oxidase (MFO) activity and plasma steroid levels. The third approach characterized the fish community structure according to an index of biotic integrity (IBI). The comparison focused on how the methods respond to the hypothesis that recent process modifications/effluent treatment changes, resulting in demonstrable improvements in effluent quality, have beneficial effects on fish. Neither of the approaches using sentinel fish indicated clear mill-related influences either before or after the process modifications/effluent treatment changes. There was no evidence of depressed plasma steroids and increased MFO activity in fish frequently associated with mill effluent exposure in previous studies. While the HAI was higher at stations downstream from two mills, this could not be linked to effluent exposure alone. In contrast, the study of community structure showed a substantial improvement in fish assemblages at all the mill sites.     

ASBBR-二级SBBR-化学除磷组合工艺处理榨菜腌制废水

针对榨菜腌制废水高盐高氮磷高有机物浓度的特征,提出"厌氧序批式生物膜反应器(ASBBR)-二级序批式生物膜反应器(SBBR)-化学除磷"组合处理工艺,在前期对组合工艺中单元工艺的关键工况参数研究的基础上,考察组合工艺的处理效能。实验结果表明,采用该组合工艺,可使进水COD、NH4+-N、TN及PO43--P分别为10 000、345、550和38.5mg/L的榨菜腌制废水,处理出水COD、NH4+-N、TN及PO43--P分别达到93.6、12.3、18和0.1 mg/L,去除率分别为99.1%、96.4%、96.7%和99.9%,出水达到污水综合排放一级标准。     

序批式膜生物反应器(SMBR)处理生活污水的研究

实验模拟生活污水,考察了连续式膜生物反应器(continuous membrane bioreactor,CMBR)和序批式膜生物反器(sequencing batch membrane bioreactor,SMBR)的膜污染和污染物去除效果.结果表明CMBR和SMBR出水COD的平均浓度分别为15.42 mg/L和...     

Transport of Escherichia coli bacteria through laboratory columns of glacial-outwash sediments: estimating model parameter values based on sediment characteristics

Bacterial transport through cores of intact, glacial-outwash aquifer sediment was investigated with the overall goal of better understanding bacterial transport and developing a predictive capability based on the sediment characteristics. Variability was great among the cores. Normalized maximum bacterial-effluent concentrations ranged from 5.4x10(-7) to 0.36 and effluent recovery ranged from 2.9x10(-4) to 59%. Bacterial breakthrough was generally rapid with a sharp peak occurring nearly twice as early as the bromide peak. Bacterial breakthrough exhibited a long tail of relatively constant concentration averaging three orders of magnitude less than the peak concentration for up to 32 pore volumes. The tails were consistent with non-equilibrium detachment, corroborated by the results of flow interruption experiments. Bacterial breakthrough was accurately simulated with a transport model incorporating advection, dispersion and first-order non-equilibrium attachment/detachment. Relationships among bacterial transport and sediment characteristics were explored with multiple regression analyses. These analyses indicated that for these cores and experimental conditions, easily-measurable sediment characteristics--median grain size, degree of sorting, organic-matter content and hydraulic conductivity--accounted for 66%, 61% and 89% of the core-to-core variability in the bacterial effective porosity, dispersivity and attachment-rate coefficient, respectively. In addition, the bacterial effective porosity, median grain size and organic-matter content accounted for 76% of the inter-core variability in the detachment-rate coefficient. The resulting regression equations allow prediction of bacterial transport based on sediment characteristics and are a possible alternative to using colloid-filtration theory. Colloid-filtration theory, used without the benefit of running bacterial transport experiments, did not as accurately replicate the observed variability in the attachment-rate coefficient.     

Fish community responses to pulp and paper mill effluents at the southern Lake Saimaa, Finland.

The fish community in sublittoral and profundal waters, at stony shores, and densities of vendace larvae were studied in the southern Lake Saimaa, Finland. The objective was to investigate the possible recovery of fish populations after modernizations at the pulp and paper mills discharging into the lake. Sublittoral and profundal waters were studied by gill net trial fishings, stony shores by electrofishing, and vendace larvae by beach seine. The research area was divided in a polluted (0.5-4.0% effluent), an intermediate (0.1-0.5%) and a 'clean' reference area. The fish community in sublittoral and profundal waters in the lake was dominated (> 60%) by perch and roach. Relative abundance of fish was highest in the polluted area, and lowest in the reference area. The number of species caught was similar among areas. The abundance of bleak and ruffe was highest in the polluted area, while the abundance of vendace and whitefish was highest in the intermediate and reference area. The fish fauna of stony shores in the lake was dominated by bullhead, stone loach and minnow, densities were lowest at polluted shores and highest in the intermediate area. Minnow, apparently a more sensitive species to pulp mill effluents, were not caught at the most polluted shores. The catch of vendace larvae was similar among areas, larvae were also caught in the vicinity of the mills. Compared with before the modernization at the mills, the relative abundance of perch in the polluted area was increased, ruffe decreased, while populations of whitefish and vendace showed signs of recovery. These changes may be explained by the reduced nutrient load and toxicicity of pulp mill effluents. At present, the fish community in the polluted area can be considered typical for a moderate eutrophication.     

A comparison of hourly with annual air pollutant emissions: Implications for estimating acute exposure and public health risk

Health risks from air pollutants are evaluated by comparing chronic (i.e., an average over 1 yr or greater) or acute (typically 1-hr) exposure estimates with chemical- and duration-specific reference values or standards. When estimating long-term pollutant concentrations via exposure modeling, facility-level annual average emission rates are readily available as model inputs for most air pollutants. In contrast, there are far fewer facility-level hour-by-hour emission rates available for many of these same pollutants. In this report, we first analyze hour-by-hour emission rates for total reduced sulfur (TRS) compounds from eight kraft pulp mill operations. This data set is used to demonstrate discrepancies between estimating exposure based on a single TRS emission rate that has been calculated as the mean of all operating hours of the year, as opposed to reported hourly emission rates. A similar analysis is then performed using reported hourly emission rates for sulfur dioxide (SO₂) and oxides of nitrogen (NO_x) from three power generating units from a U.S. power plant. Results demonstrate greater variability at kraft pulp mill operations, with ratios of reported hourly to average hourly TRS emissions ranging from less than 1 to greater than 160 during routine facility operations. Thus, if fluctuations in hourly emission rates are not accounted for, over- or underestimates of hourly exposure, and thus acute health risk, may occur. In addition to this analysis, we also demonstrate an additional challenge when assessing health risk based on hourly exposures: the lack of human health reference values based on 1-hr exposures.

Implications: Largely due to the lack of reported hourly emission rate data for many air pollutants, an hourly average emission rate (calculated from an annual emission rate) is often used when modeling the potential for acute health risk. We calculated ratios between reported hourly and hourly average emission rates from pulp and paper mills and a U.S. power plant to demonstrate that if not considered, hourly fluctuations in emissions could result in an over- or underestimation of exposure and risk. We also demonstrate the lack of 1-hr human health reference values meant to be protective of the general population, including children.     

不同再生水处理工艺出水水质回用途径适应性分析

为分析典型再生水处理工艺出水的回用途径适应性,采用标准指数法评价了4座不同处理工艺的再生水厂出水质量,为再生水处理工艺选择和安全回用提供参考。结果表明,4种再生水处理工艺出水用于市政杂用水时基本是安全的;除反渗透(RO)工艺外,其他工艺出水回用于景观环境用水时都存在氮磷指标超标问题;膜处理工艺的出水可以满足工业用水标准,但是常规絮凝过滤工艺出水用作工业用水应注意氮磷等指标的进一步处理;各种再生水处理工艺出水质量均不能满足地下水回灌用水标准,主要是氨氮和环境激素DBP超标问题,用作地下水回灌用水时存在一定的环境风险。