Cost–benefit analysis of using sewage sludge as alternative fuel in a cement plant: a case study

Background, aim, and scope  To enforce the implementation of the Kyoto Protocol targets, a number of governmental/international institutions have launched emission trade schemes as an approach to specify CO₂ caps and to regulate the emission trade in recent years. These schemes have been basically applied for large industrial sectors, including energy producers and energy-intensive users. Among them, cement plants are included among the big greenhouse gas (GHG) emitters. The use of waste as secondary fuel in clinker kilns is currently an intensive practice worldwide. However, people living in the vicinity of cement plants, where alternative fuels are being used, are frequently concerned about the potential increase in health risks. In the present study, a cost–benefit analysis was applied after substituting classical fuel for sewage sludge as an alternative fuel in a clinker kiln in Catalonia, Spain. Materials and methods  The economical benefits resulting in the reduction of CO₂ emissions were compared with the changes in human health risks due to exposure to polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) and carcinogenic metals (As, Cd, Co, and Cr) before and after using sewage sludge to generate 20% of the thermal energy needed for pyro-processing. The exposure to PCDD/Fs and metals through air inhalation, soil ingestion and dermal absorption was calculated according to the environmental levels in soil. The carcinogenic risks were assessed, and the associated cost for the population was estimated by considering the DG Environment’s recommended value for preventing a statistical fatality (VPF). In turn, the amount of CO₂ emitted was calculated, and the economical saving, according to the market prices, was evaluated. Results  The use of sewage sludge as a substitute of conventional energy meant a probability cancer decrease of 4.60 for metals and a cancer risk increase of 0.04 for PCDD/Fs. Overall, a net reduction of 4.56 cancers for one million people can be estimated. The associated economical evaluation due to the decreasing cancer for 60,000 people, the current population living near the cement plant, would be of 0.56 million euros (US$ 0.83 million). In turn, a reduction of 144,000 tons of CO₂ emitted between 2003 and 2006 was estimated. Considering a cost of 20 euros per ton of CO₂, the global saving would be 2.88 million euros (US$ 4.26 million). Discussion  After the partial substitution of the fuel, the current environmental exposure to metals and PCDD/Fs would even mean a potential decrease of health risks for the individuals living in the vicinity of the cement plant. The total benefit of using sewage sludge as an alternative fuel was calculated in 3.44 million euros (US$ 5.09 million). Environmental economics is becoming an interesting research field to convert environmental benefits (i.e., reduction of health risks, emission of pollutants, etc.) into economical value. Conclusions  The results show, that while the use of sewage sludge as secondary fuel is beneficial for the reduction in GHG emissions, no additional health risks for the population derived from PCDD/F and metal emissions are estimated. Recommendations and perspectives  Cost–benefit analysis seems to be a suitable tool to estimate the environmental damage and benefit associated to industrial processes. Therefore, this should become a generalized practice, mainly for those more impacting sectors such as power industries. On the other hand, the extension of the study could vastly be enlarged by taking into account other potentially emitted GHGs, such as CH₄ and N₂O, as well as other carcinogenic and non-carcinogenic micropollutants.     

Emission characteristics for co-combustion of leather wastes,sewage sludge,and coal in a laboratory-scale entrained flow tube furnace

Four different mixed fuels consisted of leather waste, coal, and sewage sludge were combusted in a lab-scale entrained flow fluidized bed furnace. The influence of blending ratio on emission characteristics of SO₂, NO_x, HCl, particulate matter (PM), heavy metals, and polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs) was studied. Results showed that the mixing of coal with sewage sludge had a complex effect on the emission characteristics. On the one hand, with more sewage sludge blending in the mixed fuel, the acid gas pollutant (SO₂, NO_x) decreased a lot, and the recovery of volatile heavy metals (Cd, Pb) increased at the same time. Furthermore, the leaching toxicity of Cr in the fly ash and bottom ash went down below the national standard with the adding of sewage sludge. On the other hand, the mixing of sewage sludge which consisted of more ash content resulted in the increase of the PM emission. Moreover, the high content of Cu and chlorine in the sewage sludge can promote the formation of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs) when the fuel 3 and 4 were combusted. Most importantly, the concentration of toxic PCDD/Fs in the flue gas produced from fuel 3 and fuel 4 was successfully controlled down below 0.20 ng I-TEQ/Nm³ by the active carbon.

     

PCDD/F, PAH and heavy metals in the sewage sludge from six wastewater treatment plants in Beijing, China

In order to better understand land application of sewage sludge, the characterization of heavy metals, PCDD/F and PAHs in sewage sludge was investigated from six different wastewater treatment plants (WWTP) in Beijing City, China. It was found that the total concentrations of Zn in Wujiacun (WJC) sewage sludge, and Cd and Hg in sewage sludge generated from all of the six different places are higher than Chinese regulation limit of pollutants for sludge to be used for agriculture (GB18918-2002). The levels of 16 PAHs that have been categorized as priority pollutants by US EPA in the sewage sludge samples varied from 2467 to 25923 microg/kg (dry weight), the highest values of 25923 microg/kg being found in WJC WWTP. The concentrations of Benzo[a]pyrene were as high as 6.1mg/kg dry weight in WJC sewage sludge, exceeding the maximum permitted content by GB18918-2002. Individual PAH content varies considerably with sewage samples. The ratios of anthracene to anthracene plus phenanthrene (An/178), benz[a]anthracene to benz[a]anthracene plus chrysene (BaA/228), indene[1,2,3-cd]pyrene to indene[1,2,3-cd]pyrene plus benzo[g,h,i]perylene (In/In+BP), and fluoranthene to fluoranthene plus pyrene (Fl/Fl+Py) suggest that petroleum and combustion of fossil fuel were the dominant contributions for the PAHs in sewage sludge. The concentrations of total PCDD/F in the sewage sludge ranged from 330 to 4245 pg/g d.w. The toxicity equivalent concentrations is between 3.47-88.24 pg I-TEQ according to NATO/CCMS, which is below Chinese legislation limit value proposed for land application. The PCDD/F congener/homologue profiles found in the Beijing samples indicated that the high chlorinated PCDD/F contamination might originate mainly from PCP-related source and depositional sources while the low chlorinated PCDD/F homologues could be originating from incineration or coal combustion. The major source of PCDD/Fs in Beijing sludge is still unclear.     

A study of the influence of sewage sludge fertilization on the concentrations of PCDD/F and PCB in soil and milk

The influence of the agricultural use of sewage sludge on the concentrations of PCBs and PCDD/Fs in soil, feed and milk was investigated on four dairy farms. Evidence of contaminant accumulation in the soil was found on both farms that fertilized with sewage sludge. The concentrations in feed and milk from one of these farms were similar to the concentrations in the matched control, while the concentrations in the samples from the second sludge user were elevated. The study demonstrates that the agricultural use of sewage sludge does under some conditions lead to higher levels of PCBs and PCDD/Fs in food products.     

Emissions behavior and distribution of polychlorinated dibenzo-p-dioxins and furans (PCDD/Fs) from cement kilns in China

The production of cement in China is accompanied by various emissions, such as fine particulate matter, heavy metals, nitrogen oxides, sulfur oxides, carbon dioxide…. Moreover, cement kiln presents a potential health risk to its surroundings, linking to emissions of persistent organic pollutants (POPs), such as polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), in brief dioxins. Flue gas samples were collected from five typical cement kilns during twelve runs and were used to evaluate the levels and distribution of PCDD/Fs in the emissions from cement kilns. The PCDD/Fs concentrations (136 congeners) and I-TEQ values ranged from 2.3 to >40 ng/m³ and 9.3?～?90.8?×?10^?3 ng I-TEQ/m³, respectively, which were lower than the emission standard in China (0.1 ng I-TEQ/m³). In weight units, the dominant congeners were OCDD, 1,2,3,4,6,7,8-HpCDF, and OCDF; 2,3,4,7,8-PeCDF is the largest contributor (36–66 %) to the total I-TEQ value of twelve runs. HxCDF and TCDF were the first two most abundant homologue groups (12–85 and 4–52 %), and the homologue concentration decreased with rising chlorine number for PCDDs. In addition, there was no marked difference in homologue profiles when solid wastes (refuse-derived fuel and municipal solid waste) and hazardous wastes (DDT and POPs) were combusted as supplemental fuels. The use of various supplemental fuels had no obvious effect on the fingerprint of PCDD/F homologues. Moreover, there was no significant difference in levels of PCDD/Fs emission due to the diversity of production capacity, which were consistent with reported previously. Air pollution control device had effect on the homologue profiles, and cement system with electrostatic precipitators (ESP) had more fractions of octachloro congeners to the total.     

The influence of sewage sludge applications to agricultural land on human exposure to polychlorinated dibenzo-p-dioxins (PCDDs) and -furans (PCDFs)

Polychlorinated dibenzo-p-dioxins and furans (PCDD/Fs) are organic chemicals of suspected extreme toxicity. PCDD/Fs are ubiquitous in the environment and relatively enriched in sewage sludges. The deliberate application of sewage sludge to agricultural land can therefore potentially increase exposure of the human population to these compounds via transfers through the foodchain. This paper presents a protocol for assessing the background human exposure to all seventeen 2,3,7,8-substituted PCDD/Fs for which toxic equivalent factors (TEFs) are available. Background daily human exposure in the UK to 2,3,7,8-T(4)CDD and I-TEQ are calculated to be 0.0239 ng and 0.203 ng, respectively. The potential increases in crop plant and livestock tissue PCDD/F concentrations, and hence in human exposure, following applications of sewage sludge to agricultural land are quantified for different sludge application scenarios. The key role of PCDD/F transfer into livestock via ingestion of sludge adhered to vegetation in determining increases in human exposure is demonstrated.     

PCDDs and PCDFs in sewage sludges from two wastewater treatment plants in Beijing, China

The levels of polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) were analyzed by an isotope-dilution high-resolution mass spectrometric in 16 sewage sludges, sampled from 2004 to 2009, from two municipal wastewater treatment plants (WWTPs) in Beijing. Total toxicity equivalent (TEQ) values were evaluated using the toxicity equivalent factors proposed by International for PCDD/Fs. The I-TEQs for these sewage sludges were from 0.97 to 15.0 pg g⁻¹ dry weight (dw) with a mean value 4.43 pg g⁻¹ dw, indicating that all I-TEQs were below Chinese legislation limit value regulated for agricultural use in soils.The results from limited samples (16 samples) showed that the levels of PCDD/Fs might be correlated with the sludge age. Meanwhile, the temporal trends of PCD/Fs suggested that the I-TEQs may correlate with rainfall in the present study.     

Quantification of PCDD/F concentrations in animal manure and comparison of the effects of the application of cattle manure and sewage sludge to agricultural land on human exposure to PCDD/Fs

PCDD/Fs were quantified in samples of cattle, pig, sheep and chicken manure. TEQs ranged from 0.19 ng TEQ/kg dw for the pig manure to 20 ng TEQ/kg dw for one cattle manure sample. Exposure assessments were carried out to compare the effect of various sewage sludge and cattle manure land application scenarios on human PCDD/F exposure. Background exposure was estimated at 4.9 pg TEQ/kg bw/day and it was found that land application of sewage sludge and cattle manure at contemporary rates did not increase PCDD/F TEQ background exposure. It was concluded that the application of sewage sludge, under the new UK guidelines, and cattle manure to agricultural land, do not make a significant contribution to human exposure to PCDD/Fs.     

Fish products available in Polish market – Assessment of the nutritive value and human exposure to dioxins and other contaminants

Chemical analyses were performed on one hundred and twenty of the most popular varieties of fish products (smoked fish, salted fish, and marinated fish) of the fish market in Poland. The contents of the nutritive substances of fish products (protein, micro- and macronutrients, vitamins A₁, D₃, E, and fatty acids) and the chosen contaminant (toxic metals – mercury, cadmium, lead, arsenic; dioxin/furans – PCDDFs; dioxin-like PCB – dl-PCBs; seven congeners of polybrominated diphenyl ethers – PBDEs; organochlorine pesticides – ΣDDT, HCB, ΣHCH and marker polychlorinated biphenyls – PCB₇) levels were determined. It was confirmed that fish products are a good source of digestible proteins, iodine, selenium, and vitamin D₃. The fundamental nutritive benefit of processed fish lies in its highly beneficial fatty acid composition, which is what imparts them healthy nutritive qualities. The high content of long-chain polyunsaturated fatty acids (LC-PUFAs), which is not noted in other food products, is particularly important.The majority of contaminants studied were present in low levels. The possible threats, particularly in the case of pregnant/nursing women and young children, can pose the levels of dioxin/furans (PCDD/Fs) and dioxin-like (dl-PCBs) in smoked Baltic salmon and smoked sprat, elevated in a relation to particular requirements concerning the content of sum of PCDD/Fs and dl-PCBs in fish (8 pg WHO-TEQ g⁻¹).The health benefits and risks stemming from consumption of fish products were determined according to the Provisional Tolerable Weekly Intake (PTWI) for chosen contaminants (Cd, Hg, As, PCDD/Fs + dl-PCB) and the quantity of ingredients that render a fish diet healthy based on data from the EFSA Journal [EFSA (European Food Safety Authority), 2005. Opinion of the scientific panel on contaminants in the food chain on a request from the European Parliament related to the safety assessment of wild and farmed fish. EFSA J. 236, 1–118]. In regard of high content of LC-PUFAa and other nutritive ingredients, fish products available in Polish market may be considered as healthy food.However, many authors point at contaminants (methylmercury, PCDD/Fs) occurring in fish and fish products as on potential health problem, and emphasize that the amount of that hazardous substances should be limited in human diet.     

Dioxin-like compounds in Australian sewage sludge--review and national survey

An Australian survey of dioxin-like compounds in sewage sludge was conducted in two parts (a) a national survey, and (b) a time-study. All sewage sludge samples analysed as part of these studies had low overall concentrations of dioxin-like compounds. Out of 37 samples, all except one, were within the reported concentration range of soil within the Australian environment. The mean concentration of dioxin-like compounds in the Australian sewage sludge survey of 2006 was found to be 5.6 (s.d. 4.5) ng WHO(05) TEQkg(-1) (n=14) and were within the range of 1.2-15.3 ng WHO(05) TEQ kg(-1). All the Australian sewage sludge samples cited in these studies were below the Victorian EPA "investigation limit" of 50 ng WHO(98) TEQ kg(-1), and well below the European proposed guidelines of 100 ng I-TEQ kg(-1). The burden of dioxin-like compounds in Australian sewage sludge is low and its land application as biosolids is not likely to pose a problem. A general positive relationship was found between population of the town producing the waste and both dioxin-like PCDD/Fs and dioxin-like PCBs. The one exception to this trend was sludge from a town that had a history of smelting and had a relatively high burden of dioxin-like compounds. Sludge from one rural WWTP also had a higher burden of dioxin-like compounds. The treatment plant services a geographically isolated town with a low population and no known emitters of dioxin-like compounds. However, this sample also had a relatively high burden of dioxin-like PCBs, which could be the source of the dioxin-like PCDD/Fs found in this sludge. The time study analyzing sludges from three WWTP from the same city between the years 2002 and 2006 found no apparent difference between WWTPs, but a statistically significant decline of 1.49 ng WHO(05) TEQ kg(-1) per year. Also, a comprehensive review of the scientific literature, presents typical levels and sources of dioxin-like compounds in international sewage sludges.     

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.     

Long-term environmental monitoring of persistent organic pollutants and metals in a chemical/petrochemical area: human health risks

Organic pollutants such as polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), polychlorinated biphenyls (PCBs), polychlorinated naphthalenes (PCNs) and polycyclic aromatic hydrocarbons (PAHs), as well as some metals are periodically monitored in soil and vegetation samples collected in Tarragona County (Spain). We here report the temporal trends of the concentrations of the above pollutants between the initial survey (2002) and that recently (2009) performed. The area under evaluation was divided into 4 sections (chemical, petrochemical, urban/residential and unpolluted). In general terms, urban soils presented the highest concentrations of PCDD/Fs, PCNs and PAHs, confirming that traffic is a very important emission source of these pollutants. In addition, substantially higher levels of PAHs and some metals were found in vegetation samples from the petrochemical complex. The assessment of health risks of these contaminants indicated that the current concentrations of micropollutants did not mean additional non-carcinogenic or cancer risks for the population living in the zone.     

Polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), dioxin-like polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) in waterbird eggs of Hong Kong, China

Concentrations of PCDD/Fs, PCBs and PBDEs were measured in 56 egg samples collected from waterbirds of different species (Great Egret, Little Egret, Night Heron and Chinese Pond Heron) from different regions of Hong Kong (Ho Sheung Heung, Mai Po Village and Mai Po Lung Village) during 2000 and 2006. Dominance of 2,3,4,7,8-PeCDF indicates a signature associated with commercial usage of PCBs. Although no significant variations were observed within- and between-site in the levels of PCDD/Fs, coplanar PCBs and PBDEs, the concentrations of coplanar PCBs were much higher than PCDD/Fs. Similarity in composition profiles of PCDD/F and coplanar PCBs from different egretries is possibly associated with non-point sources of these contaminants to Hong Kong. Predominant accumulation of BDE-47, BDE-99 and BDE-100 suggested the penta-BDE technical mixtures usage in Hong Kong and its vicinity. Toxic equivalency and Monte Carlo simulation technique showed potential risks on waterbirds due to their exposure to PCDD/Fs.     

Distribution characteristics and source analysis of dioxins in sediments and mussels from Qingdao coastal sea

Seven of surface sediments, one sediment core and two mussel samples were collected from the Qingdao coastal sea of the western Yellow Sea and analyzed to determine the horizontal distribution, deposition flux, and toxicity equivalency (TEQs) of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs). The total PCDD/Fs concentrations in the surface sediments ranged between 10.7 and 428 ng kg(-1) dry wt. The horizontal distribution of PCDD/F congeners in the sediments was characterized by elevated concentrations at the locations in the east of Jiaozhou Bay with the highest concentration occurring near the Haibo River mouth. Physical parameters (total organic carbon contents and sediment types) and the current circulation systems in Jiaozhou Bay can be important factors controlling the horizontal distribution pattern of PCDD/Fs in the bay. The influence of the Haibo River as a source of pollution was evidenced by PCDD/F homologue profiles, indicating a contribution from sewage sludge in addition to other possible sources. Records from the sediment core revealed that the total PCDD/Fs in the Qingdao coastal sea were nearly constant since 1951 till 1980s and increased remarkably after 1980s. The total 2,3,7,8-substituted PCDD/Fs and total TEQs of PCDD/Fs on the lipid basis in the mussel sample inside the bay were significantly higher than in the adjacent sediment. The homologue profiles of PCDD/Fs in the mussels were quite different from those of the sediments, characterized by high TCDF (50% of the total PCDD/Fs).     

Improvements to the UK PCDD/F and PCB atmospheric emission inventory following an emissions measurement programme

PCDD/F data are presented from 75 samples of primary emissions sampled between 1995-97 as part of the compliance monitoring survey undertaken by the UK Environment Agency. Municipal solid waste (MSW), chemical waste and clinical waste incinerators, cement kilns, sinter plants and sewage sludge incinerators were the source categories monitored and reported here. Based on this monitoring programme, the previous national UK emission estimates by Eduljee and Dyke (1) of 560-1100 g I-TEQ a(-1) for 1993 have been revised downwards to 220-660 g I-TEQ a(-1). Despite source reduction measures, MSW incinerators remain a significant source of PCDD/Fs to the atmosphere, contributing between 30-50% of the EPCDD/F I-TEQ emission, rather than the approximately 80% they were estimated to contribute in 1993. 2,3,7,8-substituted PCDD/F congener profile data are presented for some of the source categories and generally support the view that differences in the mixtures ('fingerprints') of PCDD/Fs emitted from different sources are observed. New data on the dioxin-like PCB emissions are presented for cement kilns and sinter plants. These show that TEQ-rated PCBs can make an important contribution to the I-TEQ emitted from certain combustion sources. High concentrations of a full range of PCB congeners/homologues have been measured in the atmosphere close to sintering strands, although the precise source of PCBs from this process remains unclear.     

Assessment of characteristic distribution of PCDD/Fs and BFRs in sludge generated at municipal and industrial wastewater treatment plants

The presence of polychlorinated dibenzo-p-dioxins and furan (PCDD/Fs) and brominated flame retardants (BFRs) in sludge generated at municipal wastewater treatment plants (MWTPs) and industrial wastewater treatment plants (IWTPs) was investigated. The concentrations of these pollutants were in the following ranges: 5.38-7947 ng kg⁻¹ dw (0.02-49.9 ng WHO-TEQ kg⁻¹ dw) for 17 PCDD/Fs, 17.5-66 761 μg kg⁻¹ dw for 27 polybrominated diphenyl ethers (PBDEs), 1.55-29 604 μg kg⁻¹ dw for hexabromocyclododecanes (HBCDs) (α-, β-, and γ-diastereomers), and 4.01-618 μg kg⁻¹ dw for tetrabromobisphenol A (TBBPA). Generally, the levels of each compound in the sewage-sludge samples were higher than those in the industrial-sludge samples with some exceptions. The characteristic distribution profiles of target compounds were observed for different types of sludge and different sources of wastewater. High-chlorinated PCDD/Fs were dominant in all samples except those from the textile industry. The distribution of the BFRs in industrial-sludge samples varied, whereas that of the BFRs in sewage-sludge samples was consistent. The proportion of penta-BDEs in sewage sludge was higher than that in industrial sludge, even though BDE-209 was the most dominant congener in all the samples. For HBCDs, the distribution of diastereomers (α-, β-, and γ-HBCD) was similar across sludge samples that had the same source of wastewater and treatment processes.     

PCDD/Fs-induced oxidative damage and antioxidant system responses in tobacco cell suspension cultures

Polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs) are ubiquitous contaminants and can be considerably accumulated by natural plants. In order to elucidate the biochemical and physiological responses of plant to PCDD/Fs, tobacco Bright Yellow-2 (BY-2) cells were selected as model plant and treated with time- and concentration-dependent PCDD/Fs. The toxic effect and oxidative stress caused by PCDD/Fs were evident, which could be indicted by the reduction in fresh mass, the increase in malondialdehyde (MDA) content, and the damage of tobacco cell ultrastructure. PCDD/Fs tolerance was correlated with changes in antioxidant system and hormones of tobacco cells. Superoxide dismutase (SOD) and peroxidase (POD) exhibited peak enzyme activities at the PCDD/Fs concentration of 1000 ng WHO₉₈-TEQ g⁻¹ fresh weight. Glutathione reductase (GR) enzyme activity increased monotonically at high level PCDD/Fs, but the activity of catalase (CAT) was only slightly affected at all treatment. Meanwhile, the exposure to PCDD/Fs resulted in the changes of hormones content. With the increase of exposure concentration of PCDD/Fs, the levels of indole-3-acetic acid (IAA) and abscisic acid (ABA) increased, whereas the concentration of jasmonates (JAs) decreased. The above results suggest that tobacco cells had the ability to cope with the oxidative stress induced by low concentration of PCDD/Fs through increasing the activities of antioxidant enzymes and alternating plant hormones levels. However, oxidative stress and toxicity would burst out when plant cells were exposed to the high levels of PCDD/Fs.     

Heavy metals, PCDD/F and PCB in sewage sludge samples from two wastewater treatment facilities in Rio de Janeiro State, Brazil

Two sewage sludge samples collected from an urban as well as a rural area in Brazil and one sludge sample originating from the city of Balingen, Baden-Württemberg, South Germany, were investigated in respect to contamination with heavy metals, PCDD/F and PCB. The results were compared to PCDD/F and indicator-PCB mean values found in the region of Baden-Württemberg. The observed toxicity equivalents of PCDD/F found in the Brazilian samples, were below the upper limit specified by German legislation for final disposal or agricultural use in soils. Both the PCB and heavy metal values exceeded this limit. The PCDD/F congener/homologue profiles found in the Brazilian samples indicated that the urban sewage sludge shows a contamination where both chlorophenols and depositional sources appear to be contributing to the contamination pool. The enrichment of highly chlorinated PCDD/F groups in the sludge of semi-rural origin is probably due to transport phenomena effects. For the German sludge sample, depositional sources seem to be the main PCDD/F contamination pathway. Regarding PCB, both Brazilian samples show a homologue profile that indicates a contamination stemming from technical PCB formulations like Clophen A50 and Clophen A60 or equivalent.     

Source identification of PCDD/Fs in a sewage treatment plant of a German village

The PCDD/F levels in the sewage sludge of a village in North-East Germany were substantially above the limit of 100 pg I-TEq/g for sludge applied to land. A study was initiated to identify the PCDD/F sources in the sewage of this treatment plant. It was found that the PCDD/F contamination entered the plant through the faecal inlet, where the content of faecal storage tanks was emptied into the treatment plant. The isomeric patterns of the higher chlorinated homologues were similar to that of PCP, while incineration showed some influence on the lower chlorinated homologues. Cluster analysis revealed a profile similar to that of PCP.     

Nationwide monitoring of atmospheric PCDD/Fs and dioxin-like PCBs in South Korea

Polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) and dioxin-like polychlorinated biphenyls (DL-PCBs) were measured in ambient air samples collected from different parts of South Korea in 2008, and the measured levels were used for assessing the spatial and temporal distribution of atmospheric PCDDFs and DL-PCBs in South Korea. The average concentrations of atmospheric PCDD/Fs and DL-PCBs among the 37 sites were 28 fg I-TEQ m⁻³ (ND ∼ 617) and 1 fg WHO-TEQ m⁻³ (ND ∼ 0.016). Elevated atmospheric levels of PCDD/Fs and DL-PCBs observed at residential/industrial sites and in the north-west of Korea, indicated a potential contribution and impacts of anthropogenic sources of PCDD/Fs and DL-PCBs. These levels were similar or lower than those previously reported in other ambient air surveys. Average concentrations of PCDD/Fs showed small seasonal variations (ANOVA analysis, p = 0.144). The highest concentrations of PCDD/Fs were observed during winter, followed by spring, autumn and summer. Atmospheric PCDD/Fs and DL-PCBs in South Korea rapidly decreased during the last 10 years (1998-2008), demonstrating the efficiency of stricter regulations and the application of best available technologies/best environmental practices at emission sources. Comparison of the congener profiles and principal component analysis showed that current atmospheric PCDD/Fs are mostly influenced by industrial sources and PCBs from old commercial PCB uses. Nationwide POPs monitoring will continue and allows an effective evaluation of the implementation of the Stockholm Convention on POPs.