密相塔烟气脱硫技术试验研究

建立了密相塔烟气脱硫试验装置,并对烧结烟气进行了脱硫试验研究,验证了该工艺的可行性,并研究了主要因素对脱硫效率的影响.结果表明,钙硫比和近绝热饱和温度（approach to adiabatic saturation temperature,AAST）是影响脱硫效率的显著因素,循环灰浓度是保证系统脱硫效率的关键因素.在Ca/S比为1.2、密相塔出口烟气AAST=15℃、循环灰浓度为400g/m3条件下,系统能连续稳定运行,脱硫效率达92.5%以上,系统出口烟气中SO2浓度在150 mg/Nm3以下.     

密相塔烟气脱硫技术试验研究

建立了密相塔烟气脱硫试验装置,并对烧结烟气进行了脱硫试验研究,验证了该工艺的可行性,并研究了主要因素对脱硫效率的影响.结果表明,钙硫比和近绝热饱和温度(approach to adiabatic saturation temperature,AAST)是影响脱硫效率的显著因素,循环灰浓度是保证系统脱硫效率的关键因素.在Ca/S比为1.2、密相塔出口烟气AAST=15℃、循环灰浓度为400g/m3条件下,系统能连续稳定运行,脱硫效率达92.5%以上,系统出口烟气中SO2浓度在150 mg/Nm3以下.     

半干半湿法烟气脱硫主要影响因素分析

建立了半干法气流床烟气脱硫实验反应装置。实验研究了温度、绝对含湿量和飞灰对烟气脱硫的影响。烟气温度在65～130℃之间，绝对含湿量通过改变蒸汽量调节，在0％～10％之间，并且采用飞灰一次加入来模拟返灰，石灰与粉煤灰的比例分别为1：3，1：5和1：8。结果表明，没有水蒸气加入时，温度的升高对脱硫效率影响不大，加入水蒸气后温度为68℃左右时，脱硫效率最高；65℃时，绝对含湿量在7．3％时脱硫效率最高；在T=68℃、Ca／S：1．2时，与不加粉煤灰的脱硫剂相比，利用石灰／粉煤灰=1：8的混合脱硫剂时，脱硫效率提高了12．8％。     

循环灰加湿量对密相塔半干法脱硫效率的影响

为了进一步提高密相塔半干法脱硫工艺的脱硫效率和脱硫剂利用率,研究了系统含湿量对脱硫效率的影响。首先,通过模拟实验探索了系统含湿量与脱硫剂失效时间的关系,然后利用MATLAB编程软件计算了系统中CaO脱硫剂利用率与系统含湿量的关系。结果表明,脱硫剂CaO的失效时间随着系统含湿量的增加而逐渐增大;系统中SO2脱除量和CaO脱硫剂利用率均随着含湿量的增加而显著提高,当系统含湿量为9%时,分别达到1 210 mg和70%。在实际工程中可结合链式搅拌器的使用,进一步提高脱硫剂的利用率和脱硫效率,满足日益严格的排放标准。     

半干半湿法烟气脱硫主要影响因素分析

建立了半干法气流床烟气脱硫实验反应装置。实验研究了温度、绝对含湿量和飞灰对烟气脱硫的影响。烟气温度在65～130℃之间,绝对含湿量通过改变蒸汽量调节,在0%～10%之间,并且采用飞灰一次加入来模拟返灰,石灰与粉煤灰的比例分别为1∶3,1∶5和1∶8。结果表明,没有水蒸气加入时,温度的升高对脱硫效率影响不大,加入水蒸气后温度为68℃左右时,脱硫效率最高;65℃时,绝对含湿量在73%时脱硫效率最高;在T=68℃、Ca/S=12时,与不加粉煤灰的脱硫剂相比,利用石灰/粉煤灰=1∶8的混合脱硫剂时,脱硫效率提高了128%。     

半干法烧结烟气脱硫灰中亚硫酸钙氧化研究

针对半干法烧结烟气脱硫灰因CaSO3含量高难以有效综合利用的问题,采用静态和动态氧化实验,结合热重-差热分析探讨了半干法烧结烟气脱硫灰中CaSO3的氧化效果.实验结果表明,在沮度为45～90℃,以MnO2、Fe2O3、V2O3为催化剂时,脱硫灰中CaSO3的氧化率不超过3%,催化效果好差为MnO2Fe2O3V2O5;在温度为400～500℃、气固比(空气体积流量与脱硫灰质量比)为0.02～0.06m3/(g·h)、反应时间为30～60min、无外加催化剂时.脱硫灰中CaSO,3的氧化率为40.4%～100.0%;温度在450℃以上时,CaSO3氧化率均在80%以上.     

高活性脱硫剂脱硫工艺的实验研究

对以粉煤灰为原料制备的高活性脱硫剂进行了半干法烟气脱硫实验研究，考虑添加剂、脱硫剂加入量、反应温度、烟气流量工艺因素的影响时该活性脱硫剂的脱硫性能；实验结果表明，加入添加剂后，脱硫效率提高1．5％～8．1％；当烟气流量〈2m^3／min，钙硫比取1．5—2．0范围时，脱硫效率较高；一定范围内反应温度变化对脱硫效率影响不大。     

半干半湿法烟气脱硫技术的工业应用研究

探讨了日本半干半湿法脱硫除尘系统和中国环境科学研究院半干半湿法烟气脱硫除尘示范系统的主要差别 ,研究了半干半湿法烟气脱硫技术在出塔烟气温度、钙硫摩尔比和循环粉煤灰返灰等方面对脱硫效率的影响。结果表明 ,在脱硫塔出口烟气温度为 78℃、m(循环粉煤灰返灰 )∶ m(石灰 )为 1∶ 4、n( Ca)∶ n( S) <1.2时 ,脱硫效率达 85 .1%;在 n( Ca)∶ n( S) =1.4时 ,脱硫效率可达 88.3 %。     

高活性脱硫剂脱硫工艺的实验研究

对以粉煤灰为原料制备的高活性脱硫剂进行了半干法烟气脱硫实验研究,考虑添加剂、脱硫剂加入量、反应温度、烟气流量工艺因素的影响时该活性脱硫剂的脱硫性能;实验结果表明,加入添加剂后,脱硫效率提高1.5%～8.1%;当烟气流量＜2 m3/min,钙硫比取1.5～2.0范围时,脱硫效率较高;一定范围内反应温度变化对脱硫效率影响不大.     

半干法烧结烟气脱硫灰的氧化改性

半干法烧结烟气脱硫灰中含有大量CaSO_3,而CaSO_3对于脱硫灰的稳定性具有重要影响,限制了脱硫灰的处理和综合利用。为了解决该问题,采用低温静态氧化改性实验和高温动态焙烧改性实验,在掺加和不掺加催化剂条件下,对含CaSO_3的脱硫灰进行了氧化改性研究,并结合热重实验考察了半干法烧结烟气脱硫灰中CaSO_3的高温动态氧化改性效果。结果表明,在低温为45、75和90℃时,掺入不同催化剂对半干法烧结烟气脱硫灰中CaSO_3进行氧化改性2 h,效果依次为:MnO_2Fe_2O_3不掺催化剂V_2O_5,且CaSO_3的氧化率均低于2.2%;在不掺催化剂的条件下,在350℃以上焙烧30~60 min,CaSO_3的氧化率均可达到85%以上。结合热重分析结果发现,选择合适的焙烧温度和时间对提高CaSO_3的氧化率有重要作用。     

Dioxin- and POP-contaminated sites—contemporary and future relevance and challenges

BACKGROUND, AIM AND SCOPE: Once they have been generated, polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) and other persistent organic pollutants (POPs) can persist in soils and sediments and in waste repositories for periods extending from decades to centuries. In 1994, the US EPA concluded that contaminated sites and other reservoirs are likely to become the major source of contemporary pollution problems with these substances. With this in mind, this article is the first in a new series in ESPR under the title 'Case Studies on Dioxin and POP Contaminated Sites--Contemporary and Future Relevance and Challenges', which will address this important issue. The series will document various experiences from sites contaminated with PCDD/F and other POPs. This article provides an overview of the content of the articles comprising the series. In addition, it provides a review of the subject in its own right and identifies the key issues arising from dioxin/POP-contaminated sites. Additionally, it highlights the important conclusions that can be drawn from these examples. The key aim of this article and of the series as a whole is to provide a comprehensive overview of the types of PCDD/F contaminated sites that exist as a result of historical activities. It details the various processes whereby these sites became contaminated and attempts to evaluate their contemporary relevance as sources of PCDD/Fs and other POPs. It also details the various strategies used to assess these historical legacies of contamination and the concepts developed, or which are under development, to effect their remediation. MAIN FEATURES: Special sessions on 'Contaminated sites--Cases, remediation, risk and policy' were held at the DIOXIN conferences in 2006 and 2007, and this theme will be continued at DIOXIN 2008 to be held in Birmingham. Selected cases from the approximately 70 contributions made to these sessions, together with some additional invited case studies are outlined together with the key issues they raise. By evaluating these cases and adding details of experiences published in the current literature, an overview will be given of the different features and challenges of dioxin and POP-contaminated sites. RESULTS: This article provides a systematic categorisation of types of PCDD/F and POP-contaminated sites. These are categorised according to the chemical or manufacturing process, which generated the PCDD/Fs or POPs and also includes the use and disposal aspects of the product life cycle in question. The highest historical PCDD/F and dioxin-like polychlorinated biphenyl (PCB) contamination burdens have arisen as a result of the production of chlorine and of chlorinated organic chemicals. In particular, the production of chlorinated pesticides, PCBs and the related contaminated waste streams are identified being responsible for historical releases of toxic equivalents (TEQs) at a scale of many tonnes. Along with such releases, major PCDD/F contaminated sites have been created through the application or improper disposal of contaminated pesticides, PCBs and other organochlorine chemicals, as well through the recycling of wastes and their attempted destruction. In some extreme examples, PCDD/F contaminated sites have also resulted from thermal processes such as waste incinerators, secondary metal industries or from the recycling or deposition of specific waste (e.g. electronic waste or car shredder wastes), which often contain chlorinated or brominated organic chemicals. The examples of PCDD/F and dioxin-like PCB contamination of fish in European rivers or the impact of contaminated sites upon fishing grounds and upon other food resources demonstrate the relevance of these historical problems to current and future human generations. Many of the recent food contamination problems that have emerged in Europe and elsewhere demonstrate how PCDD/F and dioxin like PCBs from historical sources can directly contaminate human and animal feedstuffs and indeed highlight their considerable contemporary relevance in this respect. Accordingly, some key experiences and lessons learnt regarding the production, use, disposal and remediation of POPs from the contaminated sites are summarised. DISCUSSION: An important criterion for evaluating the significance and risks of PCDD/Fs and other POPs at contaminated sites is their present or future potential for mobility. This, in turn, determines to a large degree their propensity for off-site transport and environmental accessibility. The detailed evaluation of contaminated site cases reveals different site-specific factors, which influence the varied pathways through which poor water-soluble POPs can be mobilised. Co-contaminants with greater water solubility are also typically present at such sites. Hence, pumping of groundwater (pump and treat) is often required in addition to attempting to physically secure a site. At an increasing number of contaminated sites, securing measures are failing after relatively short time spans compared to the time horizon, which applies to persistent organic pollutant contamination. Due to the immense costs and challenges associated with remediation of contaminated sites 'monitored natural attenuation' is increasingly gaining purchase as a conceptual remediation approach. However, these concepts may well prove limited in their practical application to contaminated sites containing persistent organic pollutants and other key pollutants like heavy metals. CONCLUSIONS: It is inevitable, therefore, that dioxin/POP-contaminated sites will remain of contemporary and future relevance. They will continue to represent an environmental issue for future generations to address. The securing and/or remediation of dioxin/POP-contaminated sites is very costly, generally in the order of tens or hundreds of millions of dollars. Secured landfills and secured production sites need to be considered as constructions not made for 'eternity' but built for a finite time scale. Accordingly, they will need to be controlled, supervised and potentially repaired/renewed. Furthermore, the leachates and groundwater impacted by these sites will require ongoing monitoring and potential further remediation. These activities result in high maintenance costs, which are accrued for decades or centuries and should, therefore, be compared to the fully sustainable option of complete remediation. The contaminated site case studies highlight that, while extensive policies and established funds for remediation exist in most of the industrialised western countries, even these relatively well-regulated and wealthy countries face significant challenges in the implementation of a remediation strategy. This highlights the fact that ultimately only the prevention of contaminated sites represents a sustainable solution for the future and that the Polluter Pays Principle needs to be applied in a comprehensive way to current problems and those which may emerge in the future. RECOMMENDATIONS AND PERSPECTIVES: With the continuing shift of industrial activities in developing and transition economies, which often have poor regulation (and weak self-regulation of industries), additional global challenges regarding POPs and other contaminated sites may be expected. In this respect, a comprehensive application of the "polluter pays principle" in these countries will also be a key to facilitate the clean-up of contaminated areas and the prevention of future contaminated sites. The threats and challenges of contaminated sites and the high costs of securing/remediating the problems highlight the need for a comprehensive approach based upon integrated pollution prevention and control. If applied to all polluting (and potentially polluting) industrial sectors around the globe, such an approach will prove to be both the cheapest and most sustainable way to underpin the development of industries in developing and transition economies.     

Persistence and dissipation kinetics of trifloxystrobin and tebuconazole in onion and soil

The persistence and dissipation kinetics of trifloxystrobin and tebuconazole on onion were studied after application of their combination formulation at a standard and double dose of 75 + 150 and 150 + 300 g a.i. ha^?1. The fungicides were extracted with acetone, cleaned-up using activated charcoal (trifloxystrobin) and neutral alumina (tebuconazole). Analysis was carried out by gas chromatograph (GC) and confirmed by gas chromatograph mass spectrometry (GC-MS). The recovery was above 80% and limit of quantification (LOQ) 0.05 mg kg^?1 for both fungicides. Initial residue deposits of trifloxystrobin were 0.68 and 1.01 mg kg^?1 and tebuconazole 0.673 and 1.95 mg kg^?1 from standard and double dose treatments, respectively. Dissipation of the fungicides followed first-order kinetics and the half life of degradation was 6–6.6 days. Matured onion bulb (and field soil) harvested after 30 days was free from fungicide residues. These findings suggest recommended safe pre-harvest interval (PHI) of 14 and 25 days for spring onion consumption after treatment of Nativo 75 WG at the standard and double doses, respectively. Matured onion bulbs at harvest were free from fungicide residues.     

Sorption and Desorption Behavior of Chloroanilines and Chlorophenols on Montmorillonite and Kaolinite

The bioavailability of pollutants, pesticides and/or their degradation products in soil depends on the strength of their sorption by the different soil components, particularly by the clay minerals. This study reports the sorption-desorption behavior of the environmentally hazardous industrial pollutants and certain pesticides degradation products, 3-chloroaniline, 3,4-dichloroaniline, 2,4,6-trichloroaniline, 4-chlorophenol, 2,4-dichlorophenol and 2,4,6-trichlorophenol on the reference clays kaolinite KGa-1 and Na-montmorillonite SWy-l. In batch studies, 2.0 g of clay were equilibrated with 100.0 mL solutions of each chemical at concentrations ranging from 10.0 to 200.0 mg/L. The uptake of the compounds was deduced from the results of HPLC-UV-Vis analysis. The lipophilic species were best retained by both clay materials. The most lipophilic chemical used in the study, 2,4,6-trichloroaniline, was also the most strongly retained, with sorption of up to 8 mg/g. In desorption experiments, which also relied on HPLC-UV-Vis technique, 2,4,6-trichloroaniline was the least desorbed from montmorillonite. However, on kaolinite all of the compounds under study were irreversibly retained. The experimental data have been modelled according to the Langmuir and Freundlich isotherms. A hypothesis is proposed concerning the sorption mechanism and potential applications of the findings in remediation strategies have been suggested.     

Field and laboratory studies of the fate and enantiomeric enrichment of venlafaxine and O-desmethylvenlafaxine under aerobic and anaerobic conditions

The stereoselectivity of R,S-venlafaxine and its metabolites R,S-O-desmethylvenlafaxine, N-desmethylvenlafaxine, O,N-didesmethylvenlafaxine, N,N-didesmethylvenlafaxine and tridesmethylvenlafaxine was studied in three processes: (i) anaerobic and aerobic laboratory scale tests; (ii) six wastewater treatment plants (WWTPs) operating under different conditions; and (iii) a variety of wastewater treatments including conventional activated sludge, natural attenuation along a receiving river stream and storage in operational and seasonal reservoirs. In the laboratory and field studies, the degradation of the venlafaxine yielded O-desmethylvenalfaxine as the dominant metabolite under aerobic and anaerobic conditions. Venlafaxine was almost exclusively converted to O-desmethylvenlafaxine under anaerobic conditions, but only a fraction of the drug was transformed to O-desmethylvenlafaxine under aerobic conditions. Degradation of venlafaxine involved only small stereoisomeric selectivity. In contrast, the degradation of O-desmethylvenlafaxine yielded remarkable S to R enrichment under aerobic conditions but none under anaerobic conditions. Determination of venlafaxine and its metabolites in the WWTPs agreed well with the stereoselectivity observed in the laboratory studies. Our results suggest that the levels of the drug and its metabolites and the stereoisomeric enrichment of the metabolite and its parent drug can be used for source tracking and for discrimination between domestic and nondomestic wastewater pollution. This was indeed demonstrated in the investigations carried out at the Jerusalem WWTP.     

Synthesis and characterization of m- and p-methylbenzyl-mercapturic acids derived from m- and p-xylenes

Chemical synthesis and physical properties of two mercapturic acids suggested as urinary metabolites of m- and p-xylenes ace described. These compounds may be used for the identification and quantivative determination by high-performance liquid chromatography of the corresponding mercapturic acids in urine.     

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.     

Uptake and translocation of metformin, ciprofloxacin and narasin in forage- and crop plants

Transfer of bioactive organic compounds from soil to plants might represent animal and human health risks. Sewage sludge and manure are potential sources for bioactive compounds such as human- and veterinary drugs. In the present study, uptake of the anti-diabetic compound, metformin, the antibiotic agent ciprofloxacin and the anti-coccidial narasin in carrot (Daucuscarota ssp. sativus cvs. Napoli) and barley (Hordeumvulgare) were investigated. The pharmaceuticals were selected in order to cover various chemical properties, in addition to their presence in relevant environmental matrixes. The root concentration factors (RCF) found in the present study were higher than the corresponding leaf concentration factors (LCF) for the three test pharmaceuticals. The uptake of metformin was higher compared with ciprofloxacin and narasin for all plant compartments analyzed. Metformin was studied more explicitly with regard to uptake and translocation in meadow fescue (Festucapratense), three other carrot cultivars (D.carota ssp. sativus cvs. Amager, Rothild and Nutri Red), wheat cereal (Triticumaestivum) and turnip rape seed (Brassicacampestris). Uptake of metformin in meadow fescue was comparable with uptake in the four carrot cultivars (RCF 2-10, LCF approximately 1.5), uptake in wheat cereals were comparable with barley cereals (seed concentration factors, SCF, 0.02-0.04) while the accumulation in turnip rape seeds was as high as 1.5. All three pharmaceuticals produced negative effects on growth and development of carrots when grown in soil concentration of 6-10 mg kg⁻¹ dry weight.     

Copper-catalyzed chlorination and condensation of acetylene and dichloroacetylene

The chlorination and condensation of acetylene at low temperatures is demonstrated using copper chlorides as chlorinated agents coated to model borosilicate surfaces. Experiments with and without both a chlorine source and borosilicate surfaces indicate the absence of gas-phase and gas-surface reactions. Chlorination and condensation occur only in the presence of the copper catalyst. C₂ through C₈ organic products were observed in the effluent; PCDD/F were only observed from extraction of the borosilicate surfaces. A global reaction model is proposed that is consistent with the observed product distributions. Similar experiments with dichloroacetylene indicate greater reactivity in the absence of the copper catalyst. Reaction is observed in the gas-phase and in the presence of borosilicate surfaces at low temperatures. The formation of hexachlorobenzene is only observed in the presence of a copper catalyst. PCDD/F were only observed from extraction of the borosilicate surfaces. A global reaction model is proposed for the formation of hexachlorobenzene from dichloroacetylene.     

Aerobic and anaerobic degradation of profluralin and trifluralin

Abstract

The degradation of profluralin [N‐(cyclopropylmethyl)‐α,α,α‐trifluoro‐2,6‐dinitro‐N‐propyl‐]p‐toluidine] and trifluralin (α,α,α‐trifluoro‐2,6‐dinitro‐N,N‐dipropyl‐p‐toluidine) was studied under aerobic and anaerobic soil conditions. Three soils (Goldsboro loamy sand, Cecil loamy sand, Drummer clay loam) were each treated with 1 ppmw herbicide; anaerobic conditions were maintained by flooding. Soil samples were extracted monthly and subjected to TLC analysis. No degradation was detected in sterile controls. Aerobic degradation of both herbicides was greatest in the Cecil loamy sand soil over the entire incubation period. Degradation of profluralin in Cecil soil under aerobic conditions was 86 percent after 4 months with three products detected; 83 percent of the trifluralin was degraded with two products detected. Anaerobic degradation accounted for 72 percent of the profluralin and 78 percent of the trifluralin after 4 months. Degradation of both herbicides increased with incubation time for the first 3 months and decreased slightly thereafter. Generally there was more extensive degradation (percent and in number of products formed) of profluralin than trifluralin under the conditions tested. More degradation products were detected for both herbicides under aerobic conditions than under anaerobic conditions.     

Sources and distribution of polychlorinated-dibenzo-p-dioxins and -dibenzofurans in soil and sediment from the Yellow Sea region of China and Korea

Polychlorinated-dibenzo-p-dioxins and -dibenzofurans (PCDD/Fs) were measured in soils and sediments from the Yellow Sea region. Korean soils and sediments mostly contained detectable PCDD/Fs and showed a widespread distribution among locations. Soil and sedimentary PCDD/Fs from China were comparable to or less than those in Korea. The patterns of relative concentrations of individual congeners in soils were different between the two countries, but similar in sediments. Sources of PCDD/Fs in China and Korea were found to be independent of each other and their distributions reflected matrix-dependent accumulation. Spatial distribution indicated some point sources in Korea while Chinese sources were more widespread and diffuse. PCDD/Fs measured in the coastal areas of the Yellow Sea were comparable to or less than those previously reported in for eastern Asia. However, ∑TEQs in soils and sediments were near to or, in some cases exceeded environmental quality guidelines.