EOX concentrations in sediment in the part of the Bothnian Bay affected by effluents from the pulp and paper mills at Kemi, Northern Finland

The Bothnian Bay, which is the northernmost part of the Gulf of Bothnia in Northern Finland, is affected by effluents discharged from point sources such as the pulp and paper mills of Stora Enso Oyj Veitsiluoto Mill and Oy Metsä-Botnia Ab Kemi Mill at Kemi, and the Kemi municipal sewage plant, as well as the River Kemijoki. In this paper we discuss, how modernisation of the wastewater treatment plant at the mills, and process investments in the Best Available Techniques (BAT) for effluent treatment, have decreased the effluent discharges of biological oxygen demand (BOD), chemical oxygen demand (COD), total phosphorus (Tot-P), total nitrogen (TOT-N), total suspended solids (TSS) and adsorbable organically bound halogens (AOX) from the mills since 1988. One specific aim of the study was to determine the EOX (Extractable Organically Bound Halogens) concentrations in bottom sediment of the Bothnian Bay in order to assess whether the EOX concentrations reflect the reduction in discharges of chlorinated compounds. According to the monitoring program carried out every third year between 1997–2006, the decreasing trend in EOX concentrations in the top 2 cm of the bottom sediment reflect the decrease in organochlorine discharges (AOX) from the mills. In 1997 the EOX concentrations in bottom sediment varied between 3–70 μg of Cl g^?1 (dry weight), and in 2006 between 3.3–32 μg of Cl g^?1 (dry weight).     

Analysis of mixed halogenated dibenzo-p-dioxins and dibenzofurans (PXDD/PXDFs) in soil by gas chromatography tandem mass spectrometry (GC-MS/MS)

Mixed halogenated dibenzo-p-dioxins and dibenzofurans (PXDD/PXDFs, X = Br, Cl) are formed through combustion processes, and may be more toxic than their corresponding chlorinated and brominated analogues. With 4600 potential congeners, limited analytical standards, and complex environmental matrices, PXDD/PXDFs present a significant analytical challenge. Gas chromatography tandem mass spectrometry (GC-MS/MS) offers both selectivity and sensitivity through multiple reaction monitoring of unique transitions in a novel approach to PXDD/PXDF congener identification. Method validation was performed through analysis of soil samples obtained from a recycling plant fire. Of the PXDD/PXDFs examined, monobromo-dichlorodibenzofuran was the most prevalent, ranging in concentration from 8.6 ng g⁻¹ to 180 ng g⁻¹. Dibromo-dichlorodibenzo-p-dioxin, a compound of toxicological concern, ranged from 0.41 ng g⁻¹ to 10 ng g⁻¹. Concentrations of PXDD/PXDFs were between 6% and 10% that of the corresponding polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/PCDFs), with the exception of dibromo-dichlorodibenzo-p-dioxin concentrations, which were 36% that of tetrachlorodibenzo-p-dioxins. Higher levels of polybrominated PXDD/PXDFs may indicate a significant bromine source was present during combustion.     

Aromatization of waste polyolefin pyrolysate over H-ZSM-5 zeolite-supported gallium oxide catalysts

H-ZSM-5 zeolite-supported gallium oxides were studied as aromatization catalysts for polyolefin pyrolysate. The catalysts were prepared by a conventional physical mixing method with a gallium content of 1.0 and 4.5 wt% and were reduced in flowing hydrogen at 585°C. To test their activity, a polyolefin sample was pyrolyzed and passed over a heated catalyst layer; the product was analyzed by gas chromatography/mass spectrometry. A continuous-flow fixed-bed reactor was used for aromatization of a model gas of polyolefin pyrolysate. For chlorine-free sources at 450°C, the catalyst with only 1.0 wt% gallium exhibited activity comparable to a gallium silicate catalyst. For chlorine-contaminated sources, the catalyst with 4.5 wt% gallium sustained catalytic activity for long periods. From the activity test results, it was found that zeolite-supported gallium catalysts prepared by the physical mixing method are suitable for converting polyolefin into aromatic hydrocarbons.     

Molten hydroxide for detoxification of chlorine-containing waste: Unraveling chlorine retention efficiency and chlorine salt enrichment

Hazardous waste dechlorination reduces the potential of creating dioxins during the incineration process. To investigate the salt effect on waste dechlorination, molten hydroxides with a low melting temperature were utilized for the pre-dechlorination and decomposition of chlorine-containing organic wastes(COWs) including trichlorobenzene(TCB),perchloroethylene, hexachlorobenzene and chlordane. The results showed that a eutectic mixture of caustic sodium and potassium hydroxides(41 wt.% NaOH and 59 wt.% KOH) led to a low melting point below 300°C and a relatively high chlorine retention efficiency(CRE) with TCB as a representative COWs. The amounts of hydroxides, reaction time, and temperature all had notable influence on CRE. When the mass ratio of hydroxides to TCB reached 30:1,approximately 98.1% of the TCB was destroyed within 2.5 hr at 300°C with CRE of 71.6%.According to the residue analysis, the shapes of reaction residues were irregular with particles becoming swollen and porous. The benzene ring and C–Cl bonds disappeared, while carboxyl groups formed in the residues. The stripped chlorine was retained and condensed to form chloride salts, and the relative abundance of the chloride ions associated with the mass of TCB in residues increased from 0 to 75.0% within the 2.5 hr reaction time. The observed concentration of dioxins in residues was 5.6 ngTEQ/kg. A reaction pathway and possible additional reactions that occur in this dechlorination system were proposed. Oxidizing agents may attack TCB and facilitate hydrogenation/dechlorination reactions, making this process a promising and environmentally friendly approach for chlorine-containing organic waste treatment.     

Impact of combining chlorine dioxide and chlorine on DBP formation in simulated indoor swimming pools

The main objective of this study was to assess the combined use of chlorine dioxide (ClO2) and chlorine (Cl2) on the speciation and kinetics of disinfection by-product (DBP) formation in swimming pools using synthetic pool waters prepared with a body fluid analog (BFA) and/or fresh natural water. At 1:25 (mass ratio) of ClO2 to Cl2, there was no significant reduction in the formation of trihalomethanes (THMs) and haloacetic acids (HAAs) for both BFA solution and natural water compared to the application of Cl2 alone. When the mass ratio of ClO2 to Cl2 increased to 1:1, substantial decreases in both THMs and HAAs were observed in the natural water, while there was almost no change of DBP formations in the BFA solution. Haloacetonitriles and halonitromethanes levels in both water matrices remained similar. In the presence of bromide, the overall DBP formation increased in both BFA solution and natural water. For the DBP formation kinetics, after 72 hr of contact time, very low formation of THMs and HAAs was observed for the use of ClO2 only. Compared to Cl2 control, however, applying the 1:1 mixture of ClO2/Cl2 reduced THMs by > 60% and HAAs by > 50%. Chlorite was maintained below 1.0 mg/L, while the formation of chlorate significantly increased over the reaction time. Finally, in a bench-scale indoor pool experiment, applying ClO2 and Cl2 simultaneously produced less THMs compared to Cl2 control and kept chlorite at < 0.4 mg/L, while HAAs and chlorate accumulated over 4-week operation period.     

两段式处理药用辛醇废水的研究

以辛醇废水为研究对象,采用空气催化氧化-ClO2助氧化相结合的方法,探讨了药用辛醇废水的处理方法.结果表明,该方法能有效的去除废水中的有机污染物,实现废水处理的资源化回收利用.处理后的废水中CODCr浓度达到国家排放标准(CODCr≤1 50 mg/L).     

二氧化氯处理印染废水的研究

二氧化氯是一种性能很好的氧化剂和杀菌消毒剂,本文介绍了二氧化氯的化学性质及在印染废水中的应用,表明二氧化氯与有机物反应具有选择性.     

二氧化氯制备方法研究进展

二氧化氯是一种具有高氧化性和强消毒性的化合物,介绍了二氧化氯制备的化学法、电解法以及电化学法,并对几种工艺方法的优缺点进行了分析和比较,适合工业化生产的工艺主要是化学法中的氯酸钠法和亚氯酸钠法。     

The formation and fate of chlorinated organic substances in temperate and boreal forest soils

Background, aim and scope  Chlorine is an abundant element, commonly occurring in nature either as chloride ions or as chlorinated organic compounds (OCls). Chlorinated organic substances were long considered purely anthropogenic products; however, they are, in addition, a commonly occurring and important part of natural ecosystems. Formation of OCls may affect the degradation of soil organic matter (SOM) and thus the carbon cycle with implications for the ability of forest soils to sequester carbon, whilst the occurrence of potentially toxic OCls in groundwater aquifers is of concern with regard to water quality. It is thus important to understand the biogeochemical cycle of chlorine, both inorganic and organic, to get information about the relevant processes in the forest ecosystem and the effects on these from human activities, including forestry practices. A survey is given of processes in the soil of temperate and boreal forests, predominantly in Europe, including the participation of chlorine, and gaps in knowledge and the need for further work are discussed. Results  Chlorine is present as chloride ion and/or OCls in all compartments of temperate and boreal forest ecosystems. It contributes to the degradation of SOM, thus also affecting carbon sequestration in the forest soil. The most important source of chloride to coastal forest ecosystems is sea salt deposition, and volcanoes and coal burning can also be important sources. Locally, de-icing salt can be an important chloride input near major roads. In addition, anthropogenic sources of OCls are manifold. However, results also indicate the formation of chlorinated organics by microorganisms as an important source, together with natural abiotic formation. In fact, the soil pool of OCls seems to be a result of the balance between chlorination and degradation processes. Ecologically, organochlorines may function as antibiotics, signal substances and energy equivalents, in descending order of significance. Forest management practices can affect the chlorine cycle, although little is at present known about how. Discussion  The present data on the apparently considerable size of the pool of OCls indicate its importance for the functioning of the forest soil system and its stability, but factors controlling their formation, degradation and transport are not clearly understood. It would be useful to estimate the significance and rates of key processes to be able to judge the importance of OCls in SOM and litter degradation. Effects of forest management processes affecting SOM and chloride deposition are likely to affect OCls as well. Further standardisation and harmonisation of sampling and analytical procedures is necessary. Conclusions and perspectives  More work is necessary in order to understand and, if necessary, develop strategies for mitigating the environmental impact of OCls in temperate and boreal forest soils. This includes both intensified research, especially to understand the key processes of formation and degradation of chlorinated compounds, and monitoring of the substances in question in forest ecosystems. It is also important to understand the effect of various forest management techniques on OCls, as management can be used to produce desired effects.     

二氧化氯杀菌处理石化循环冷却水

以硫酸盐还原菌,铁细菌以及异养菌数为指标,研究二氧化氯对石化厂循环冷却水的杀菌效果。考察了二氧化氯投加量,杀菌时间,温度及pH以及余氯量随时间的变化。结果表明,在CLO2投加量为3mg／L、灭菌时间为90min时,出水细菌数即可达到化工行业循环冷却水处理标准,并且余氯可在0．5-1．0mg／L范围内维持2h。温度和pH的改变对杀菌效果影响不大。