Toxic Equivalent Quantity Research Articles

Occurrence and Source Identification of Polychlorinated Dibenzo-p-dioxins and Dibenzofurans and Polychlorinated Biphenyls in Surface Sediments from Liangshui River in Beijing, China

Polychlorinated dibenzo-p-dioxins and dibenzofurans and polychlorinated biphenyls were measured in the surface sediments of Liangshui River, the second largest drainage river in Beijing, China. The sum concentrations of polychlorinated dibenzo-p-dioxins and dibenzofurans and polychlorinated biphenyls ranged from 3.5 to 3019 (mean value: 184) pg g-1 dry weight and from 319 to 5949 (mean value: 1958) pg g-1 dry weight, and the corresponding World Health Organization toxic equivalent quantity values were 0.0011-5.1 pg TEQ g-1 dry weight and 0.0074-1.4 pg TEQ g-1 dry weight, respectively. The spatial distributions of polychlorinated dibenzo-p-dioxins and dibenzofurans and polychlorinated biphenyls showed increasing trends from urban area and development area to suburb. Principal component analysis revealed that polychlorinated dibenzo-p-dioxins and dibenzofurans contamination in the sediments may originate from pentachlorophenol and sodium pentachlorophenate and municipal solid waste incineration. Regarding polychlorinated biphenyls, the steel industry, combustion processes and usage of some commercial polychlorinated biphenyl products were identified as the major sources. The emission from a former steel plant could be the main contributor to polychlorinated biphenyls in urban areas. The mean value of the total toxic equivalent quantities in the sediment samples exceeded the Canadian interim sediment quality guidelines. Long-term wastewater irrigation increases the load of sediment-bound pollutants in agricultural soil and may pose potential ecological risks to crops and human health.

Rapid Determination of Oxygenated and Parent Polycyclic Aromatic Hydrocarbons in Milk Using Supercritical Fluid Chromatography-Mass Spectrometry.

Liquid milks are consumed worldwide in large amounts, especially by adolescents and infants. Thus, their health quality linked with polycyclic aromatic hydrocarbon (PAH) contamination has attracted great concern. This study developed a rapid and sensitive supercritical fluid chromatography (SFC)-MS method to determine two typical oxygenated PAHs (OPAHs) and EU 15+1PAHs except for benzo[k]fluoranthene (BkF) in three types of liquid milks: 10 ultra heat treated (UHT) milks, 8 pasteurized milks, and 4 extended-shelf-life pasteurized milks. The instrumental analysis was 15 min with a recovery of 67.66-118.46%, a precision of 1.45-14.68%, detection limits of 0.04-0.24 μg/kg, and quantification limits of 0.13-0.78 μg/kg. We found 9-fluorenone, anthraquinone, 15 EU priority PAHs, and benzo[a]pyrene toxic equivalent quantity (BaPeq) in the 22 milk samples, which were 0.32-1.56 μg/kg, 0.40-1.74 μg/kg, 0.57-8.48 μg/kg, and 0.01-17.42 μg/kg, respectively. The UHT milks and whole fat milks showed higher PAH concentrations than other investigated samples, where the maximum levels of BaP and PAH4 were 0.77 and 3.61 μg/kg, respectively. PAH4 dominantly contributed to the PAH8 concentration and was detected in 73% and 32% of samples at more than 1.0 and 2.0 μg/kg, respectively. The results suggest that raw milks should be strictly monitored and extensively investigated for PAH4 and BaP concentrations for future risk assessment, limitations, and dietary guidance.

Spatial distribution, source identification, and human health risk assessment of PAHs and their derivatives in soils nearby the coke plants

The coking industry can generate large amounts of polycyclic aromatic hydrocarbons (PAHs) and their derivatives, which may negatively impact the environment and human health. In this study, soils nearby a typical coking plant were sampled to assess the impact of coke production on the surrounding residential areas and human health. The mean concentration of PAHs and their derivatives in residential area soils nearby the coke plant was 4270 ng/g dw, which was 1 order of magnitude higher than that observed in areas far from the coke plant and approximately 4 times lower than that revealed the coke plant. In addition, the results showed that coking processing area was the most contaminant area of the coke plant (mean: 74.4 μg/g dw), where was also the main source of pollutants in residential areas. In terms of vertical soils in coking plant, the maximum levels of chemicals (mean: 205 μg/g dw) were presented at the leakage of underground pipelines, where were much higher than those in surface soils, and decreased with the increase of depth. The analysis of variance (ANOVA) results showed obvious differences in the concentrations of 6-nitrochrysene between the plant, residential areas and control areas. Meanwhile, 6-nitrochrysene had potential cancer risk (CR) for human in the coking site. Thus, 6-nitrochrysene was the most noteworthy PAH derivatives. Furthermore, the CR (mean: 5.94 × 10−5) and toxic equivalent quantities (TEQs) (mean: 14.8 μg·TEQ/g) of PAHs and their derivatives was assessed in this study. This finding suggested that PAHs and their derivatives especially those extremely toxic chemicals (Nitro-PAHs (NPAHs) and Br/Cl-PAHs (XPAHs)) might pose a potential health risk to residents nearby the coke plant. The current study provides further insights into the pollution characteristics of PAHs and their derivatives in coke plants and potential risks to the workers and surrounding residents.

Polybrominated dibenzo-p-dioxins/furans and their chlorinated analogues in sediments from a historical hotspot for both brominated flame retardants and organochlorine pesticides

Polybrominated dibenzo-p-dioxin/furans (PBDD/Fs) and polychlorinated dibenzo-p-dioxin/furans (PCDD/Fs) in the environment are closely related to their precursors, brominated flame retardants (BFRs) and organochlorine pesticides (OCPs). However, their change trends following the regulation of BFRs and OCPs remain incompletely characterized. Here, we examined PBDD/Fs and PCDD/Fs in sediments from a historical hotspot for both BFRs and OCPs, namely the Pearl River Delta (PRD), China. PBDD/Fs showed ubiquity in these samples but significantly lower concentrations than PCDD/Fs. Spatially, the occurrence of PBDD/Fs was positively correlated with local development levels and sediments from highly urbanized/industrialized areas showed higher and increasing PBDD/F concentrations. Polybrominated diphenyl ether (PBDE)-related products/industries were the greatest PBDD/F contributors to the PRD, followed by bromo-phenol/benzene-related products/industries. PCDD/Fs in PRD sediments showed significant positive correlations with local grain planting area, yield, and pesticide consumption. The historical use of pentachlorophenol (PCP)/PCP-Na and biomass open-burning were the leading PCDD/F sources of the PRD agricultural/rural areas, where the concentrations and toxic equivalent quantities (TEQs) of PCDD/Fs in sediments changed very little over the past decade. Anthropogenic thermal processes involved in metallurgy, waste incineration, and vehicles were the greatest PCDD/F contributors in the PRD urban/industrial areas, where the PCDD/F concentrations in sediments almost doubled over the last decade. This finding indicates the increasing PCDD/F contributions of industrial and municipal activities in the PRD, despite the implementation of strict emission standards. Over sixty percent of the samples showed TEQs that surpassed the low-risk threshold specified for mammalian life by the U.S. EPA (2.5 pg TEQ g−1) and warrant continuous attention.

Breastfed infants’ exposure to polychlorinated biphenyls, polychlorinated dibenzo-p-dioxins and dibenzofurans, and per- and polyfluoroalkyl substances: A cross-sectional study of a municipal waste incinerator in China

A municipal waste incinerator (MWI) in Zhejiang, China, operating since 2008 was completely reconstructed from 2016 to 2019. In 2013, we conducted a cross-sectional study of breastfeeding mothers living near the MWI. We evaluated the concentrations of polychlorinated biphenyls (PCBs) and polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) in the mothers' breast milk and their infants' estimated daily intake (EDI). To investigate the temporal variations of these pollutants, we conducted a cross-sectional study of 29 mothers in 2019. We assessed the levels of 18 PCB congeners, 17 PCDD/F congeners, and 21 per- and polyfluoroalkyl substance (PFAS) congeners in breast milk and estimated the EDI. The mean total concentrations of PCDD/Fs (ΣPCDD/Fs) and PCBs (ΣPCBs) were 81.2 and 4.90 ng/g lipid, respectively, while the toxic equivalent quantity (TEQ) levels of ΣPCDD/Fs and dioxin-like PCBs (ΣDL-PCBs) were 2.7 and 1.4 pg WHO-TEQ/g lipid, respectively. Compared to our 2013 measurements, the mass concentrations of ΣPCDD/Fs and ΣPCBs decreased by 13% and 35%, respectively (3.361 vs. 2.915 pg/g wet weight [ww] and 269.1 vs. 175.0 pg/g ww, respectively). The TEQ-ΣPCDD/F levels decreased by 67% (0.241 vs. 0.080 pg/g ww), but the TEQ-ΣDL-PCB levels increased by 11% (0.046 vs. 0.051 pg WHO-TEQ/g ww). The median concentration of PFASs was 0.250 ng/mL, ranging from 0.151 to 0.833 ng/mL. The infants’ mean EDI of total PCDD/Fs and DL-PCBs was 17.7 pg TEQ/kg body weight [bw], representing a 20% decline compared to 2013. The average EDI levels of PFOS, PFOA, and PFNA were 5.8, 17.9, and 1.7 ng/kg bw, respectively. A comprehensive comparison of the results with studies from around the world showed that the potential health risks posed by legacy PCDD/F and PCB pollutants were not as grave for mothers and infants living near this MWI, but the emerging PFAS pollutants represented a new cause for concern. Main findingsThe potential health risks posed by legacy PCDD/F and PCB pollutants were not particularly serious for mothers and infants living near the MWI, but the emerging PFAS pollutants raised new concerns.

Sources and composition of natural and anthropogenic hydrocarbons in sediments from an impacted estuary.

Hydrocarbons in estuarine sediments provide information on sources of sedimentary organic matter (OM), and they are thus useful for tracing natural and anthropogenic OM inputs to the estuary. Here, we assessed the amounts, compositions and sources of natural and anthropogenic hydrocarbons from the sediments of a large, ecologically important estuary, Mobile Bay in Southeast USA. TOC/TN ratios and δ13C of organic carbon suggest that the bulk natural OM was sourced from marine phytoplankton and bacteria mixed with marsh and terrigenous C3 plants. Normal alkanes show high proportions of long-chain compounds with a high Carbon Preference Index, indicating the importance of C3 plants-derived OM in Mobile Bay. High concentrations of biogenic hopanes and perylene indicate microbial sources and degradation played an important role in shaping OM compositions. Anthropogenic hydrocarbons, αβ-hopanes and polycyclic aromatic hydrocarbons (PAHs), were widely detected in Mobile Bay sediments. The source diagnostic ratios of hopanes and steranes suggest they were sourced from coal and diesel combustions. The source diagnostic ratios of PAHs, together with a positive correlation between PAHs and total mercury, suggests that PAHs originated primarily from coal combustion. We proposed two ratios, αβ-hopanes/(ββ-hopanes+hopenes) and 16 PAHs/perylene, to evaluate anthropogenic versus natural contributions of hydrocarbons. These ratios were higher in the western estuary than in the eastern estuary, suggesting elevated anthropogenic hydrocarbon inputs to the western estuary. Correspondingly, the toxic equivalent quantity (TEQBaQ) of PAHs showed a higher ecological risk for the western estuary. This spatially uneven distribution of hydrocarbon pollutants can be attributed to more concentrated urban and industrial areas on the western shore, suggesting the importance of adjacent pollution sources. Collectively, our results provide new insights into the origins and dynamics of natural and anthropogenic OM and highlight the significance of coal combustion in contributing hydrocarbon pollutants in Mobile Bay sediments.

Seasonal congener survey for polychlorinated biphenyls in sediments of south-western rivers, Nigeria: Occurrence, sources, and ecotoxicological risks

In this work, sediment samples from major rivers within southwestern Nigeria were collected to study the seasonal distribution, transport, and ecological risk assessment of polychlorinated biphenyls (PCB) using gas chromatography coupled with an electron capture detector (GC–ECD). The ΣPCB concentrations ranged from 9.86–77.56 μg/kg and 11.88–80.76 μg/kg in dry and wet seasons respectively. The most predominant PCBs congener in all the sediments was 2,2’,4,5,5’-PeCB(#101) with mean concentrations of 4.35 ± 2.96 and 6.10±3.38μg/kg across all locations in dry and wet seasons respectively. Relevant guidelines including sediments quality guidelines (SQGs) mean effect range-median quotient (m-ERM-Q), and toxic equivalent factor (TEF) were used for risk assessment and to evaluate the ecological risks of PCBs across the rivers. The toxic equivalent quantity (TEQ) ranged from 0.044–0.807 μg-TEQ/kg and 0.055–0.825 μg-TEQ/kg for the dry and wet seasons respectively. The non-ortho PCBs congeners constituted ≥ 99.8% of the ∑TEQ values. The seven indicators PBCs for evaluating non-dioxin-like PCBs ranged from 3.70–32.69 μg/kg across the seasons and accounted for 33.4%, 39.8%, 36.8%, 37.9%, 41.4%, and 40.4% of the ∑PCBs at Asejire, Odo Ona, Ogbese, Ogun, Ikorodu rivers and Third Mainland Bridge Ocean respectively. In two out of six rivers, the ∑PCBs exceeded the Canadian SQG threshold effect level of 21.5 and 34.1μg/kg for fresh and marine sediments respectively. The results of the study call for a concerted effort toward holistic monitoring of PCB residues in rivers in Nigeria to ensure ecological integrity and the protection of human health.

Contamination and sources of polychlorinated naphthalenes in the surface sediments of Chaobai River, China

In aquatic systems, sediment is both a sink for persistent organic pollutants (POPs) and a potential source of POPs release. Consequently, it is important to understand the pollution characteristics and sources of polychlorinated naphthalenes (PCNs) as POPs of Stockholm Convention in sediment for control of the ecological risk. Atmospheric deposition is a potential source of PCNs in sediment. However, there is no clear report on the contribution of atmospheric deposition to PCNs in sediments. In this study, the Chaobai River in China was selected because it is an important drinking water source that is not affected by wastewater discharge. Surface sediments from the river were analyzed for 75 PCN congeners by using high resolution gas chromatography combined with high resolution mass spectrometry. The total PCNs concentration ranged from 54 to 2266 (mean: 402) pg/g. The toxic equivalent quantity of 19 PCNs in surface sediments was 9.69 × 10−2, and CN73, CN66/CN67, and CN63 had the largest contributions to this value. Dichlorinated and trichlorinated naphthalenes were the dominant homologs. The PCN data from the sediment samples in this study were combined with data for PCNs in ambient air from a literature, which has a good match with this study in both temporal and spatial scales. The contribution of atmospheric deposition to PCNs in the surface sediment was evaluated by comparing congener characteristics and correlation analysis. Our study indicated atmospheric transportation and deposition are important pathways for transport of PCNs into surface sediments.

Source apportionment and health risk assessment of polycyclic aromatic hydrocarbons (PAHs) in the coastal ecosystem of the Brunei Bay, Brunei

Pollution characteristics and associated ecological risks of PAHs in sediments from Brunei Bay, Brunei were investigated. The concentrations of ∑16 PAHs ranged from 826.7 to 2955.3 μg kg−1, indicating moderate to high level of pollution. Source apportionment of PAHs by molecular isomeric ratios and positive matrix factorization model indicated impact of potential anthropogenic PAH sources including combustion of biomass and fossil fuels. The data indicated relatively no significant ecotoxicological risk for most of PAH compounds. To estimate the individual c-PAH toxicity, the toxic equivalent quantity (c-TEQ) was calculated. Results of the TEQ analysis showed that BaP followed by DBA and BaA are the most carcinogenic of PAHs examined in the study area. The evaluation of human health risk of PAHs revealed that the cancer risk of PAHs for adults and children was higher than the USEPA threshold (<1E−06) and lower than 1E-3, implying low to moderate risk.

Source identification and toxicity apportionment of polycyclic aromatic hydrocarbons in surface soils in Beijing and Tianjin using a PMF-TEQ method.

Beijing and Tianjin are two of the largest cities in northern China with high population densities and highly developed manufacturing industries. In the past decade, some authors have reported their PAH concentrations in surface soils, identified their sources and quantitatively reported their health risks. However, the contributions of different PAH sources to their toxicity have not been reported thus far. In this study, we reviewed the PAH concentrations, contributions of different sources to the toxicity, and cancer risks in soils from different land use types found within Beijing and Tianjin from data gathered by 41 studies. The total PAH concentration varied in the range of 175.7–1989.0 ng g-1 with a higher median PAH concentration detected in urban soils (789.7 ng g-1), followed by suburban soils (647.3 ng g-1) and rural soils (390.8 ng g-1). Source identification using diagnostic ratios and principal component analysis (PCA) suggested that the PAHs in all three land use types mainly originated from biomass and coal combustion, vehicular emissions, and petrogenic processes with contributions varying from 13% to 62%. Furthermore, results from a positive matrix factorization (PMF) model suggested that vehicular emissions and coal combustion in urban soils, and the vehicular emissions, coal combustion and biomass combustion in suburban and rural soils dominated the total PAH concentrations (>85%). These results were consistent with those of the PCA model. Results of the additional toxicity apportionment performed using the PMF model suggested that vehicular emissions and coal combustion contributed the most to the toxic equivalent quantity for Benzo(a)Pyrene (BaPTEQ) and, by extension, to the carcinogenic potencies. The incremental lifetime cancer risk (ILCR) values suggested a low risk level for adults exposed to PAHs in the different land use types found within Beijing and Tianjin.

Comparative Analysis of Polycyclic Aromatic Hydrocarbons and Halogenated Polycyclic Aromatic Hydrocarbons in Different Parts of Perilla frutescens (L.) Britt.

Perilla frutescens (L.) Britt., a medicinal herb and edible plant, is very popular among East Asian countries. The perilla leaves, stems and seeds can be used as traditional medicines and foods. Polycyclic aromatic hydrocarbons (PAHs) and halogenated PAHs (HPAHs) are organic pollutants that are widely present in the environment, such as in water, air and soil, and are harmful to humans. In this study, the contents of 16 PAHs and 4 HPAHs in perilla leaves, stems and seeds were determined by gas chromatography tandem mass spectrometry (GC-MS). A total of 12 PAHs were detected in all samples, and no HPAHs were detected. The total contents of PAHs in perilla leaves, stems and seeds varied from 41.93 to 415.60 ng/g, 7.02 to 51.52 ng/g and 15.24 to 180.00 ng/g, respectively. The statistical analyses showed that there were significant differences in the distribution of PAHs in perilla leaves, stems and seeds. On the basis of the toxic equivalent quantity (TEQ) and incremental lifetime cancer risk (ILCR) model, the cancer risks of the intake of perilla leaves, stems and seeds were assessed to be from 3.30 × 10−8 to 2.11 × 10−5, 5.52 × 10−9 to 5.50 × 10−8 and 1.20 × 10−8 to 1.41 × 10−7, respectively. These were lower than 10−4 (the priority risk level of the EPA) and suggested that there may be almost no cancer risk from the intake of these traditional Chinese medicines (TCMs).

Comprehensive Evaluation of Dietary Exposure and Health Risk of Polychlorinated Naphthalenes.

Intake from food is considered an important route of human exposure to polychlorinated naphthalenes. To our knowledge, several studies have quantified dietary exposure but only in European countries and measuring only a few of the 75 congeners. In addition, the influence of source diversity on human exposure has seldom been assessed. We analyzed 192 composite food samples composed of 17,280 subsamples from 24 provinces in China to measure the concentrations of polychlorinated naphthalenes and estimate their daily intake and potential health risks on a national scale. The estimated cancer risk was in the range of 6.8 × 10-8 to 4.6 × 10-7. We compared our findings for 75 congeners with reports in the literature that quantified only 12 congeners. We estimate that these 12 congeners contribute only approximately 4% to the total mass daily intake of polychlorinated naphthalenes and 70% to the total toxic equivalent quantity, indicating underestimation of dietary exposure. The contributions of combustion-associated congeners to the total concentrations of polychlorinated naphthalenes were in the range of 31-52%, suggesting that the ongoing unintentional release of these compounds from industrial thermal processes is an important factor in polychlorinated naphthalene contamination and human exposure in China.

Emission Characteristics of Polychlorinated Dibenzo-p-Dioxins/Dibenzofurans (PCDD/DFs) in Commercial Bio-SRF and SRF Incineration Plants

Incineration plants using solid refused fuel (SRF) should control their air pollution materials to minimize environmental impact. This study evaluated the emission of polychlorinated dibenzo-p-dioxin/dibenzofurans (PCDD/DFs) congener patterns in seven commercial incineration plants in Korea using SRF and biomass SRF (bio-SRF). We examined the reduction rate differences of PCDD/DFs, depending on the air pollutant control device. All seven incineration plants sufficiently managed their dioxin emissions. However, both SRF and bio-SRF incineration plants showed active chlorination reactions and resulted in a large amount of highly chlorinated dioxins. The average dioxin concentration was 0.02 ng international toxic equivalency quantity (I-TEQ)/Sm3. Ratios of 1,2,3,4,6,7,8-HpCDF and 1,2,3,7,8-PeCDF were high in the waste heat boilers of both SRF and bio-SRF incineration plants. The octachlorinated dibenzofuran (OCDF) ratio was only high in the SRF incineration plants. Octachlorodibenzo-p-dioxin (OCDD) and OCDF exhibited high dioxin ratios. SRF incineration plants had a low ratio of OCDF to 1,2,3,4,6,7,8-HpCDF. In addition, the reduction rate of PCDD/DFs was substantially high after treatment with the air pollutant control device.

Effects of physical and chemical aging on polycyclic aromatic hydrocarbon (PAH) content and potential toxicity in rice straw biochars.

Polycyclic aromatic hydrocarbons in biochars threaten their environmental application. The aging process may affect the concentration of PAHs, potential toxicity, and the properties of biochar. In this study, the aged biochars were obtained by simulated physical aging method (freeze-thaw treatment) and chemical aging method (H2O2 chemical oxidation). The PAH contents in biochars were measured, and their potential toxicity was assessed. Meanwhile, the influence of aging process on the physicochemical properties of biochar was also investigated. This study shows that the change of PAH content of aged biochars depended on pyrolysis temperature, ambient temperature, and oxidant concentration. Furthermore, physical and chemical aging process influenced the distribution of different ring PAHs in biochars. High-ring-number PAHs (four, five, six-ring PAHs) appeared in some aged biochar. Aging at ±20 °C and 0.01 M H2O2 increased the toxic equivalent quantity of all biochars which may be attributed to the change of the physicochemical properties influencing the different PAH ring distribution in biochars. The contribution of PAHs with different rings to TEQ varied in pristine and aged biochars. Physical and chemical aging process significantly affected the properties of biochars, such as element content, ash content, surface area, pore volume, pH, functional groups, and surface morphology. Correlation analysis confirmed that surface area and pore volume are dominant factors determining the PAH content in the biochars. Therefore, the aging process indeed affected the PAH concentration and toxicity of PAHs in biochar. Assessing PAH behavior in biochar over long timescales should not be overlooked.

Fingerprint analysis reveals sources of petroleum hydrocarbons in soils of different geographical oilfields of China and its ecological assessment

The distribution and characteristics of petroleum in three different geographic oilfields in China: Shengli Oilfield (SL), Nanyang Oilfield (NY), and Yanchang Oilfield (YC) were investigated. The average concentration of the total petroleum hydrocarbons (TPHs) conformed to be in the following law: SL Oilfield > NY Oilfield > YC Oilfield. Fingerprint analysis on the petroleum contamination level and source was conducted by the geochemical indices of n-alkanes and PAHs, such as low to high molecular weight (LMW/HMW) hydrocarbons, n-alkanes/pristine or phytane (C17/ Pr, C18/Ph), and ratio of anthracene/ (anthracene + phenanthrene) [Ant/(Ant + Phe)]. Soils adjacent to working well oils indicated new petroleum input with higher ratio of low to high molecular weight (LMW/HMW) hydrocarbons. The oil contamination occurred in the grassland soils might result of rainfall runoff. Petroleum source, petroleum combustion source, and biomass combustion were dominant PAHs origination of soils collected from oil exploitation area, petrochemical-related sites, farmland and grassland, respectively. The suggestive petroleum control strategies were proposed in each oilfield soils. Ecological potential risk of PAHs was assessed according to the toxic equivalent quantity (TEQ) of seven carcinogenic PAHs. The results showed that high, medium, and low ecological risk presented in petro-related area, grassland soils, and farmland soils, respectively. High ecological risk was persistent in abandoned oil well areas over abandoned time of 15 years, and basically stable after 5 years. This study can provide a critical insight to ecological risk management and source control of the petroleum contamination.

A comprehensive emission inventory of hazardous air pollutants from municipal solid waste incineration in China

The Hazardous air pollutants (HAPs) released from increasing municipal solid waste incineration (MSWI) plants have drawn great concerns in China. However, a full picture of their emission characteristics is still urgently needed, especially after the implementation of stricter emission limits on MSWI. In this study, a comprehensive historical emission inventory of HAPs emitted from MSWI plants in China during the period of 2006–2017 was dedicatedly established by integrating with detailed plant-level activity data and renewed localized emission factors. Overall, HAPs emissions initially increased with years, then peaked or slowed increase in the year 2014, but leveled off after 2016 due to the gradually and fully implementing of newly revised national emission standard (GB18485–2014) applied to mainland China and much stricter local standards for several provinces and cities. It was estimated that totally 50,716 tons (t) of NOx, 13,026 t of CO, 7988 t of SO2, 4399 t of PM, 1943 t of HCl, 9916 kg of Pb, 5901 kg of Mn, 4805 kg of Cu, 3574 kg of Cr, 3329 kg of Ni, 2154 kg of Hg, 1168 kg of Cd, 862 kg of As, 409 kg of Co, 216 kg of Sb, 13 kg of Tl, and 19 g toxic equivalent quantity of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans were emitted from 337 MSWI plants scattered in 30 provinces of mainland China in 2017, respectively. HAPs emissions were heavily concentrated in developed coastal provinces and cities. Scenario analysis highlighted the importance of continuous improvement and upgrade on advanced air pollution control devices and MSWI management to meet the future ultra-low emission limits and minimize the harmful impacts of HAPs on atmospheric environment and public health.

Phase distribution, migration and relationship of polychlorinated dibenzo-p-dioxins and dibenzofurans and heavy metals in a large-scale hazardous waste incinerator

Polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/F) and heavy metals emitted from hazardous waste incinerators have aroused public concern due to the risks to the environment and human health. In the study, phase distribution, migration, and relationship of PCDD/F and heavy metals (arsenic, cadmium, chromium, copper, mercury, nickel, plumbum, zinc) are investigated in a typical hazardous waste incinerator. The PCDD/F mass concentrations and toxic equivalent quantity are reduced to 3.26 ng/Nm3 and 0.0484 ng/Nm3 by air control pollution devices, with 93.1% remove efficiency. High sulfur content in hazardous waste results in low PCDD/F and heavy metals emissions. Moreover, migration analysis of PCDD/F mass concentrations indicates that vast PCDD/F migrates to the mixtures with sodium bicarbonate and activated carbon (52.4%), followed by fly ash (21.8%), sodium hydroxide solution (19.3%), and atmosphere (6.49%). Furthermore, TCDF isomers (37%) dominate among the PCDD/F congeners, while 1,2,3,4,6,7,8-HpCDF (20%) dominates among 2,3,7,8-substituted congeners. Deduced by the ratio of PCDF/PCDD, the dominant mechanism of PCDD/F is de novo synthesis and chlorobenzene route synthesis. Based on the relative enrichment index, heavy metals are classified into three types: volatile heavy metals (plumbum, zinc, cadmium, mercury), medium volatile heavy metals (copper, chromium, arsenic), involatile heavy metals (nickel). Additionally, copper is inclined to deposit into the bottom slag as CuSO4 rather than the volatile substance due to high levels of sulfur dioxide (3000 parts per million). The migration behavior of heavy metals is dependent on the volatility properties of these metals. Statistically, PCDD/F emissions have the highest correlation coefficient with plumbum (r = 0.815), followed by nickel (r = −0.798). Besides, the PCDD/F formation is promoted by the volatile heavy metal, prevented by medium volatile heavy metals. The study not only provides a comprehensive understanding of PCDD/F and heavy metals characteristics but also effective and feasible strategies to reduce the toxic pollutants emissions in large-scale hazardous waste incinerators.

Contribution of atmospheric deposition to halogenated polycyclic aromatic hydrocarbons in surface sediments: A validation study

Surface sediments are both sinks and sources of chlorinated and brominated polycyclic aromatic hydrocarbons (Cl/Br-PAHs) in the environment. It is important to study the source of Cl/Br-PAHs in the surface sediment for controlling the ecological risk of Cl/Br-PAHs. Clues from the previous research suggested that atmospheric deposition may be one of the main sources of Cl/Br-PAHs in sediment. However, due to the lack of matched sediment and atmospheric Cl/Br-PAHs data, the contribution of atmospheric deposition to Cl/Br-PAHs in sediment has not been confirmed. This study investigated the characteristics of 37 Cl/Br-PAHs and validated the contribution of atmospheric sedimentation to Cl/Br-PAHs in sediment by a case study in the surface sediments of the Chaobai River, China. To the best of our knowledge, four Cl-PAHs and eleven Br-PAHs were found in the sediments for the first time. The total concentrations of 18 Cl-PAH species were 76–2301 pg/g, while those of Br-PAHs were 6–238 pg/g. The toxic equivalent quantities (TEQ) of the Cl-PAHs in surface sediments in the water conservation area and in the urban comparison area were 0.73 pg TEQ/g and 2.21 pg TEQ/g, respectively. The TEQ of the Br-PAHs in surface sediments in the water conservation area and in the urban comparison area were 2.85 × 10−2 pg TEQ/g and 6.6 × 10−2 pg TEQ/g, respectively. Based on the characteristics comparison and correlation analysis of Cl/Br-PAHs in both sediment and ambient air, it was initially confirmed the contribution of atmospheric deposition to Cl-PAHs in sediments. However, there was no conclusion of Br-PAHs in sediment similar to Cl-PAHs in sediment. It was inferred that the sources of Br-PAHs in sediment were different from Cl-PAHs in sediment.

Effect of magnetite on the catalytic oxidation of polycyclic aromatic hydrocarbons in fly ash from MSW incineration: A comparative study of one-step and two-step hydrothermal processes

Polycyclic aromatic hydrocarbons (PAHs), many of which are carcinogenic, teratogenic, and mutagenic, exist in fly ash (FA) produced from municipal solid waste incineration (MSWI). Hydrothermal treatment (HT) is an efficient approach to remove PAHs from MSWI FA. Here, magnetite (Fe3O4) was used as the catalyst and hydrogen peroxide (H2O2) as the oxidant for one-step and two-step catalytic hydrothermal methods. When the magnetite dosage increased to 15 wt%, the maximum degradation rates of PAHs were 84.36% and 92.51%, respectively; however, the toxicity equivalent quantity (TEQ) degradation rates of the PAHs both increased upon increasing the magnetite dose. At 20 wt% Fe3O4, the maximum TEQ degradation rates of the PAHs were 93.29% and 97.76%, respectively. The reaction between OH and PAHs is non-selective, which means that LMW, MMW, and HMW PAHs were all degraded. The decrease in TEQ was mainly due to the degradation of HMW PAHs, i.e., those with five rings. Under the same Fe3O4 dose, oxidant dose, and reaction time, the detoxification of PAHs by the two-step method was significantly better than that of the one-step method, possibly because the two-step method more effectively produced OH. The first step degraded more than 90% of PAHs, and the residual PAHs in the HT products of the first step limited the utilization of the oxidant during the second step. The minerals in the HT products implied that the two-step hydrothermal method not only produced more OH, which reacted with PAHs, but also generated metal-magnetite substitution, which affected its surface reactivity during heavy metal adsorption and catalysis. These results revealed that both magnetite and the two-step hydrothermal treatment degraded PAHs. 20 wt% magnetite was the optimal amount during the two-step hydrothermal catalytic oxidation of MSWI FA.

Polybrominated dibenzo-p-dioxins/furans (PBDD/Fs) in soil around municipal solid waste incinerator: A comparison with polychlorinated dibenzo-p-dioxins/furans (PCDD/Fs)

Polybrominated dibenzo-p-dioxins/furans (PBDD/Fs) and polychlorinated dibenzo-p-dioxins/furans (PCDD/Fs) share similar toxicities and thermal origins, e.g., municipal solid waste incinerator (MSWI). Recently, PBDD/Fs from MSWI attracted rising concern because their important precursors, i.e., brominated flame retardants (BFRs), were frequently found in various wastes for landfill or MSWI feedstock. So far, however, little is known about PBDD/Fs and their associated risks in the vicinal environments of MSWI. Here we analyzed PBDD/Fs and PCDD/Fs in 29 soil samples collected around a multiyear large-scale MSWI, and compared their spatial distributions, sources and risks. PBDD/Fs demonstrated comparable concentrations and toxic equivalent quantities (TEQs) to PCDD/Fs in these samples. Spatially, both the concentrations of PBDD/Fs and PCDD/Fs decreased outwards from the MSWI, and exhibited significant linear correlations with the distances from the MSWI in the southeast downwind soil, suggesting the influence of the MSWI on its vicinal soil environment. However, the existence of other dioxin sources concealed its influence beyond 6 km. PBDD/Fs in the soils were characterized by highly-brominated PBDFs, especially Octa-BDF, and their sources were diagnosed as the MSWI and diesel exhaust; PCDD/Fs, however, were dominated by highly-chlorinated PCDDs, particularly Octa-CDD, and were contributed individually or jointly by the MSWI, automobile exhaust and pentachlorophenol (PCP)/Na-PCP. The non-carcinogenic risks of dioxins in all the soil samples were acceptable, but their carcinogenic risks in 17% of the samples were unacceptable. These samples were all located close to the MSWI and highways, therefore, the land use of these two high-risk zones should be cautiously planed.