Emission of dioxins/furans and other U-POPs from test burns of non-POP pesticides in a hazardous waste incinerator

This paper presents the results of test burns for obsolete pesticides (OPs) of the permethrin group in a high temperature incinerator (HTI) in Southeast Asia. Three test burn runs were conducted, a baseline run when no OP was fed to the incinerator, and two test runs with different mixtures of OP compounds (formula 1 and 2, refer to Table 1 for detail) containing chlorine in the feeding wastes. The unintentional formed persistent organic pollutants (U-POPs) including 17 dioxins/furans, 12 dioxin-like PCBs and 12 chlorobenzenes (CBs) were monitored in all input materials and all discharges (flue gas, scrubbing liquid and solid residues). The results show relatively high levels of the U-POPs in the flue gas emission with total dioxins/furans of 4.4, 3.4, and 8.4 ng I-TEQ/m³ in the baseline, test run 1 and test run 2, respectively, which are above international acceptable emission levels. The PCB levels in flue gas were, respectively, 0.01, 0.3 and 0.4 ng I-TEQ/m³. The baseline thus had similar U-POPs levels with the OP test runs.In stack emission, approximately 90% of the U-POPs and 100% of CBs were present in gas phase. The emission factors, mass of pollutants per metric ton (tonne) of input waste, of U-POPs associated with fly ash (from bag house) were the highest, followed by flue gas and bottom ash while those associated with scrubbing liquid were relatively low. Among the waste input material only the black toner power contained U-POPs, but at low levels. The profiles of the dioxins/furans and PCBs in the toner waste were significantly different from that in the discharges. Despite the overall good destruction and removal efficiency of permethrin (better than 90%) the high emission of U-POPs and CBs from the test burn is of another more serious concern. To our best knowledge the findings of this study are the first of this kind for the Southeast Asia. The findings emphasize that if not properly conducted a standard destruction technology of a non-POP chemical can lead to a release of a range of more dangerous U-POPs into the environment.     

Formation, release and control of dioxins in cement kilns

Co-processing of hazardous wastes in cement kilns have for decades been thought to cause increased emissions of PCDD/PCDFs--a perception that has been evaluated in this study. Hundreds of PCDD/PCDF measurements conducted by the cement industry and others in the last few years, on emissions and solid materials, as well as recent test burns with hazardous wastes in developing countries do not support this perception. Newer data has been compared with older literature data and shows in particular that many emission factors have to be reconsidered. Early emission factors for cement kilns co-processing hazardous waste, which are still used in inventories, are shown to be too high compared with actual measurements. Less than 10 years ago it was believed that the cement industry was the main contributor of PCDD/PCDFs to air; data collected in this study indicates however that the industry contributes with less than 1% of total emissions to air. The Stockholm Convention on POPs presently ratified by 144 parties, classifies cement kilns co-processing hazardous waste as a source category having the potential for comparatively high formation and release of PCDD/PCDFs. This classification is based on early investigations from the 1980s and 1990s where kilns co-processing hazardous waste had higher emissions compared to those that did not burn hazardous waste. However, the testing of these kilns was often done under worst case scenario conditions known to favour PCDD/PCDF formation. More than 2000 PCDD/PCDF cement kiln measurements have been evaluated in this study, representing most production technologies and waste feeding scenarios. They generally indicate that most modern cement kilns co-processing waste today can meet an emission level of 0.1ngI-TEQ/m(3), when well managed and operated. In these cases, proper and responsible use of waste including organic hazardous waste to replace parts of the fossil fuel does not seem to increase formation of PCDD/PCDFs. Modern preheater/precalciner kilns generally seems to have lower emissions than older wet-process cement kilns. It seems that the main factors stimulating formation of PCDD/PCDFs is the availability of organics in the raw material and the temperature of the air pollution control device. Feeding of materials containing elevated concentrations of organics as part of raw-material-mix should therefore be avoided and the exhaust gases should be cooled down quickly in long wet and long dry cement kilns without preheating. PCDD/PCDFs could be detected in all types of solid samples analysed: raw meal, pellets and slurry; alternative raw materials as sand, chalk and different ashes; cement kiln dust, clinker and cement. The concentrations are however generally low, similar to soil and sediment.     

Distribution of Hg,As and Se in material and flue gas streams from preheater–precalciner cement kilns and vertical shaft cement kilns in China

The aim of this study was to evaluate the behavior of Hg, As, and Se in cement production. Two types of cement plants were studied, including the vertical shaft kiln (VSK) and preheater–precalciner kiln (PPK) processes. Determination of Hg, As, and Se in the main material and gas streams were performed. It was found that recycling of particulate matter captured by an air pollution control device caused a significant enrichment of Hg and As inside both processes. The total quantity of Hg entering the process and the quantity emitted to the atmosphere were found to be 10–109 and 6.3–38 mg, respectively, per ton of clinker produced. The average Hg emission was calculated to be around 41% of the total mercury input. The emissions found complied with the European Union (EU) limit and exceeded partly the U.S. limit. Furthermore, it was found that oxidized mercury was the dominant species in the PPK process, whereas the reduced form was dominant in the VSK process, due to the oxidizing and reducing gas conditions, respectively. Regarding the distribution of As and Se, the major amounts were bound to the solid materials, that is, cement clinker and particulate matter. Based on cement production data in China in 2013, the annual emissions of Hg and As were estimated to be in the range of 8.6–52 and 4.1–9.5 tons, respectively.

Implications: There are fairly limited studies on Hg, As, and Se measurements from cement manufacturing facilities in China, and even more limited studies on the behavior in vertical shaft kilns. The needs for increased emission reduction efforts in energy-intensive industries are globally recognized, and an improved understanding of the processes ongoing in a cement kilns system is decisive. Since the processes are complex and almost impossible to recreate in the laboratory, field measurements are indeed important. The findings in the present study were solely based on field measurements and the data are considered to be valuable for the further development of emission reduction technology.     

Metabolism of DDT in Different Tissues of Young Rats

The bioconcentration and distribution pattern of p,p′-DDT 1,1,1-1trichloro-2,2-bis(2-chlorophenyl-4-chlorophenyl)-ethane] and its main metabolites (p,p′-DDD [1,1-dichloro-2,2-bis (4-chlorophenyl) ethane] and p,p′-DDE [1,1-dichloro-2,2-bis (4-chlorophenyl) in adipose tissue, liver, brain, kidney, thymus, and testis were examined in young rats after 10 days of intraperitoneal injection of 50 and 100 mg of p,p′-DDT/kg of body weight. Analyses were performed by high-resolution gas chromatography. p,p′-DDT was found to be accumulated in a dose-dependent manner with the highest concentration in adipose tissue. However, in brain, the accumulation of pesticide was low and remained unchanged at the higher dose. This difference may relate to the protective role of the blood-brain barrier, which limits the access of the xenobiotic in the cerebral compartment, and to the differential tissue lipid composition. Although tissues concentration of p,p′-DDE and p,p′-DDD correlated positively to total p,p′-DDT levels, the active role in detoxification of pollutants may explain why p,p′-DDD is more abundant in liver than in the rest of organs. On the contrary, in brain, the concentration of p,p′-DDE is higher than that of p,p′-DDD, suggesting that the metabolism of the parent insecticide proceeds via more than one pathway.