Influence of pesticides contamination on the emission of PCDD/PCDF to the land from open burning of corn straws

Open burning of crop residues has been identified as an important emission source of PCDD/PCDF to the environment. This paper presents the first known data on the emission of PCDD/PCDF to the land considering the influence of pesticides applied in crops planting. Emission factor for PCDD/PCDF to the land from open burning of corn straw with pesticides contamination ranged from 0.07 to 0.57 ng WHO₂₀₀₅-TEQ/kg straw burned with a mean value of 0.24 ng WHO₂₀₀₅-TEQ/kg straw burned and median value of 0.20 ng WHO₂₀₀₅-TEQ/kg straw burned, respectively. The concentration was 35 to 270 times higher than that without additional pesticide contaminated. Initial observation was that emission factor for PCDD/PCDF from open burning of crop residues was overestimated in the former UNEP Dioxin Toolkit. Pesticides contamination should be considered in some hotpots where special and over dosed pesticides has been sprayed especially in developing countries.     

PCDD/F enviromental impact from municipal solid waste bio-drying plant

The present work indentifies some environmental and health impacts of a municipal solid waste bio-drying plant taking into account the PCDD/F release into the atmosphere, its concentration at ground level and its deposition. Four scenarios are presented for the process air treatment and management: biofilter or regenerative thermal oxidation treatment, at two different heights. A Gaussian dispersion model, AERMOD, was used in order to model the dispersion and deposition of the PCDD/F emissions into the atmosphere. Considerations on health risk, from different exposure pathways are presented using an original approach. The case of biofilter at ground level resulted the most critical, depending on the low dispersion of the pollutants. Suggestions on technical solutions for the optimization of the impact are presented.     

Polychlorinated dibenzo-p-dioxins and dibenzofurans emissions from open burning of crop residues in China between 1997 and 2004

Annual emissions of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) from open burning of crop residues in each province of China mainland between 1997 and 2004 were estimated to be ranged from 1.38x10(3) to 1.52x10(3) g I-TEQ/yr, with the average of 1.50+/-0.08x10(3) g I-TEQ/yr, which contributed to approximately 10% approximately 20% of the total emissions in China. The PCDD/F emissions mainly occurred in the largest crop-producing provinces, especially in those of higher economic levels. The major sources of PCDD/F emissions from open burning in China were found to be cereal residues (i.e. rice, wheat, and corn), which accounted about 70% of the total emissions. Moreover, the first-order one-variable grey differential equation model (GM (1,1) model) for annual emissions of PCDD/Fs was established based on grey system theory. The GM (1,1) model was proved to be robust to predict the annual PCDD/F emissions from crop residue field burning in forthcoming years.     

Open burning of household waste: Effect of experimental condition on combustion quality and emission of PCDD, PCDF and PCB

Open burning for waste disposal is, in many countries, the dominant source of polychlorinated dibenzodioxins, dibenzofurans and biphenyls (PCDD/PCDF/PCB) release to the environment. To generate emission factors for open burning, experimental pile burns of about 100 kg of household waste were conducted with emissions sampling. From these experiments and others conducted by the same authors it is found that less compaction of waste or active mixing during the fire - “stirring” - promotes better combustion (as evidenced by lower CO/CO₂ ratio) and reduces emissions of PCDD/PCDF/PCB; an intuitive but previously undemonstrated result. These experiments also support previous results suggesting PCDD/PCDF/PCB generation in open burning - while still highly variable - tends to be greater in the later (smoldering) phases of burning when the CO/CO₂ ratio increases.     

Quality control for sampling of PCDD/PCDF emissions from open combustion sources

Both long duration (>6 h) and high temperature (up to 139 °C) sampling efforts were conducted using ambient air sampling methods to determine if either high volume throughput or higher than ambient air sampling temperatures resulted in loss of target polychlorinated dibenzodioxins/dibenzofurans (PCDDs/PCDFs) from a polyurethane foam (PUF) sorbent. Emissions from open burning of simulated military forward operating base waste were sampled using EPA Method TO-9A for 185 min duration using a filter/PUF/PUF in series combination. After a 54 m³ sample was collected, the sampler was removed from the combustion source and the second PUF was replaced with a fresh, clean PUF. An additional 6 h of ambient air sampling (171 m³) was conducted and the second PUF was analyzed to determine if the PCDD/PCDF transferred from the filter and the first PUF. Less than 4.4% of the initial PCDD/PCDF was lost to the second PUF. To assess the potential for blow off of PCDD/PCDF analytes during open air sampling, the mobility of spiked mono- to hepta-PCDD/PCDF standards across a PUF sorbent was evaluated from ambient air temperatures to 145 °C with total volumes between 600 L and 2400 L. Lower molecular weight compounds and higher flow amounts increased release of the spiked standards consistent with vapor pressure values. At 600 L total sampled volume, the release temperature for 1% of the tetra-CDD (the lowest chlorinated homologue with a toxic compound) was 87 °C; increasing the volume fourfold reduced this temperature to 73 °C.     

Emission characterization of unintentionally produced persistent organic pollutants from iron ore sintering process in China

Emission of unintentionally produced persistent organic pollutants (Unintentional POPs), including polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), polychorinated biphenyls (PCBs), hexachlorobenzene (HxCBz) and pentachlorobenzene (PeCBz), were investigated in four typical iron ore sintering plants in China. The emission factors and annual mass releases of the Unintentional POPs were calculated. The results indicated that PCDFs contributed more than 60% to the overall toxic equivalent quantity (TEQ) values, while the contribution of the dl-PCBs is relatively low, and only in the range of 8-9%. The dominant congeners of PCDD/Fs and dl-PCBs contributing most to the total TEQ were 1,2,3,7,8-PeCDD, 2,3,4,7,8-PeCDF and PCB-126. With regard to the TEQ contributions, the most abundant homologues were PeCDFs and HxCDD/Fs, followed by PeCDDs and non-ortho dl-PCB, whereas HpCDD/Fs, OCDD/Fs and mono-ortho dl-PCBs almost made no contributions. Due to the massive use of recycled waste in the feeding materials, the average emission factor of PCDD/Fs and dl-PCBs of the four plants was 3.95 μg WHO-TEQ ton⁻¹. Based on the results, the annual release of PCDD/Fs and dl-PCBs in 2007-2009 were estimated to be 2070 g, 2212 g, and 2307 g WHO-TEQ, respectively.     

Air pollutant emissions from rice straw open field burning in India, Thailand and the Philippines

Rice is a widely grown crop in Asia. China (30%) and India (21%) contribute to about half of the world's total rice production. In this study, three major rice-producing countries in Asia are considered, India, Thailand and the Philippines (the later two contributing 4% and 2% of the world's rice production). Rice straw is one of the main field based residues produced along with this commodity and its applications vary widely in the region. Although rice production practises vary from one country to another, open burning of straw is a common practice in these countries.In this study, an approach was followed aiming at (a) determining the quantity of rice straw being subject to open field burning in those countries, (b) congregating pollutant specific emissions factors for rice straw burning, and (c) quantifying the resulting air pollutant emissions. Uncertainties in the results obtained as compared to a global approach are also discussed.     

采用循环流化床技术焚烧城市生活垃圾

根据目前我国城市生活垃圾热值偏低的实际情况 ,提出以煤为辅助燃料 ,采用循环流化床焚烧技术处理生活垃圾 ,可大幅度降低运行成本 ,符合国情。阐述了循环流化床焚烧技术在降低NOx、SO2 和二噁等方面的优越性。尾气处理建议采用喷活性碳 +布袋除尘组合工艺 ,飞灰处理建议采用高温熔融处理     

Using stochastic risk assessment in setting information priorities for managing dioxin impact from a municipal waste incinerator

The objectives of this study were to assess site-specific carcinogenic risk of incinerator-emitted dioxins in a manner reflecting pollutant transfer across multimedia and multi-pathways. The study used site-specific environmental and exposure information and combined the Monte Carlo method with multimedia modeling to produce probability distributions of risk estimates. The risk estimates were further categorized by contaminated environmental media and exposure pathways that are experienced by human receptors in order to pinpoint significant sources of risk. Rank correlation coefficients were also calculated along with the Monte Carlo sampling to identify key factors that influenced estimation of risk. The results showed that ingestion accounted for more than 90% of the total risk and that risk control on ingestion of eggs, aboveground vegetables, and poultry should receive priority. It was also found that variation of parameters with variability accounted for around 35% of the total risk variance, while uncertainty contributed to the remaining 65%. Intake rates of aboveground vegetables, eggs, and poultry were the key parameters with the largest contribution to variance. In addition, sufficient sampling and analysis of dioxin contents in eggs, aboveground vegetables, poultry, soil, and fruit should be performed to improve risk estimation because the variation in concentrations in these media accounted for the largest overall risk variance. Finally, focus should be placed on reduction of uncertainty associated with the risk estimation through ingestion of aboveground vegetables, eggs, poultry, fruit, and soil because the risk estimates associated with these exposure pathways had the largest variance.     

Dechlorination and destruction of PCDD,PCDF and PCB on selected fly ash from municipal waste incineration

The potential of fly ash to dechlorinate and destroy PCDD, PCDF and PCB was tested under oxygen deficient conditions in the laboratory. Specifically, two types of fly ash were compared, originating either from a fluidized bed incinerator using Ca(OH)₂ spray (FA1), or a stoker incinerator without Ca(OH)₂ impact (FA2).

Results from the present study indicate that on FA2 type fly ash, the degradation processes of OCDD, OCDF and D₁₀CB occurred primarily via dechlorination/hydrogenation up to temperature settings of 340 °C. In contrast, FA1 type fly ash was found to effect both dechlorination and destruction of these compounds already at temperature settings of 260 °C.

The dechlorination velocity of PCDD and PCDF did not differ significantly. However, the first dechlorination step of OCDF in the 1,9-position occurred faster compared to the first dechlorination step of OCDD.

The isomer pattern resulting from the dechlorination processes was quite similar on both FA1 and FA2, indicating that differences in alkalinity or elemental composition of the two types of fly ashes do not have a significant influence on the position of dechlorination. PCDD and PCDF dechlorination of the 2,3,7,8-positions was not favoured over dechlorination of the 1,4,6,9-positions on either type of fly ash. In contrast, dechlorination of PCB occurred predominantly on the toxicological relevant 3- and 4-positions.

The dechlorination/destruction processes were completed on both types of fly ash at 380 °C within one hour, which correlates well with results obtained from actual plant operation practices.     

Aerostat-lofted instrument and sampling method for determination of emissions from open area sources

An aerostat-borne instrument and sampling method was developed to characterize air samples from area sources, such as emissions from open burning. The 10 kg battery-powered instrument system, termed “the Flyer”, is lofted with a helium-filled aerostat of 4 m nominal diameter and maneuvered by means of one or two tethers. The Flyer can be configured variously for continuous CO₂ monitoring, batch sampling of semi-volatile organic compounds (SVOCs), volatile organic compounds (VOCs), black carbon, metals, and PM by size. The samplers are controlled by a trigger circuit to avoid unnecessary dilution from background sampling when not within the source plume. The aerostat/Flyer method was demonstrated by sampling emissions from open burning (OB) and open detonation (OD) of military ordnance. A carbon balance approach was used to derive emission factors that showed excellent agreement with published values.     

Elimination of persistent organic pollutants from fish oil with solid adsorbents

Fish oils are one of the main sources of ω-3 fatty acids in animal and human diet. However, they can contain high concentrations of persistent organic pollutants due to their lipophilic properties. The aim of this study is the reduction of persistent organic pollutants in fish oil using silicon-based and carbon-based solid adsorbents. A wide screening study with different commercially available adsorbents was carried out, in order to determine their capacity of pollutant removal from fish oil. Moreover, adsorption conditions were evaluated and optimized with using an experimental design and adjustment of the experimental results to response surfaces, obtaining removals rates of more than 99% of PCDD/Fs, 81% of dioxin-like PCBs, 70% of HCB, 41% of DDTs, 16% of marker PCBs and 10% of PBDEs. Finally, fish oil fatty acids were analyzed before and after the treatment with solid adsorbents, confirming that it did not affect its nutritive properties.     

流化床垃圾焚烧炉产生的有毒二噁英同类物分布研究

测定了流化床垃圾焚烧炉焚烧产生的飞灰、烟尘和烟气中的2，3，7，8位氯取代二噁英同类物的含量及其毒性当量。结果表明，产生的二噁英主要存在于飞灰中，烟气中的含量很少。飞灰中二噁英总浓度和毒性当量分别为8.44ng／g和0．80ng／g，经过布袋除尘器后的烟尘和烟气中二噁英的浓度之和与毒性当量之和分别为0．34ng／m^3和0．02ng／m^3，而布袋除尘器前的烟尘和烟气中二噁英的浓度之和与毒性当量之和分别为40．78ng／m^3和3．0ng／m^3。飞灰和烟尘中2，3，7，8位氯取代二噁英同类物的分布相似，但是与烟气中2，3，7，8位氯取代二噁英同类物的分布差别较大。通过了解有毒二噁英同类物的分布，可以进一步优化流化床垃圾焚烧炉的焚烧条件，降低二噁英的排放量，减少垃圾焚烧对环境的污染。     

Simultaneous sampling of PCDD/PCDF inside the combustion chamber and on four boiler levels of a waste incineration plant

At a MSWI (municipal solid waste incinerator) plant PCDD/PCDF samples (gasphase and particulates) were taken simultaneously be a shock-freezing method in the incinerator combustion chamber at approx. 800°C and in four sampling sections in the boiler at about 490°C, 370°C, 330°C and 270°C. In this way PCDD/PCDF-formation in the flow through the boiler was determined. Two data sets were evaluated. A considerable PCDD/PCDF-formation had occurred already at boiler temperatures of about 490°C; the highest concentration, however, was found at the end of the boiler at about 300°C. The accompanying measuring program of plant parameters made the calculation of the PCDD/PCDF mass flows possible, which allowed the inclusion of the PCDD/PCDF-content in the ESP dust in the mass flow calculations.     

城市生活垃圾焚烧过程中二次污染物的生成与控制

在我国 ,采用焚烧法处理城市固体垃圾 ,逐渐得到推广和应用。然而焚烧带来的二次污染物 ,如二、细颗粒、重金属、HCl以及SOx、NOx 等也随之引起了广泛关注。对垃圾焚烧过程中各种二次污染物的产生机理及其控制方法进行了综述。并且指出近期我国城市固体垃圾焚烧烟气污染物的重点控制对象应为颗粒物、HCl、SOx 和NOx。     

Historical estimation of carbonaceous aerosol emissions from biomass open burning in China for the period 1990-2005

Multi-year inventories of carbonaceous aerosol emissions from biomass open burning at a high spatial resolution of 0.5° × 0.5° have been constructed in China using GIS methodology for the period 1990-2005. Black carbon (BC) emissions have increased by 383.03% at an annual average rate of 25.54% from 14.05 Gg in 1990 to 67.87 Gg in 2005; while organic carbon (OC) emissions have increased by 365.43% from 57.37 Gg in 1990 to 267.00 Gg in 2005. Through the estimation period, OC/BC ratio for biomass burning was averagely 4.09, suggesting that it was not the preferred control source from a climatic perspective. Spatial distribution of BC and OC emissions were similar, mainly concentrated in three northeastern provinces, central provinces of Shandong, Jiangsu, Anhui and Henan, and southern provinces of Guangxi, Guangdong, Hunan and Sichuan basin, covering 24.89% of China’s territory, but were responsible for 63.38% and 67.55% of national BC and OC emissions, respectively.     

The emissions of heavy metals and persistent organic pollutants from modern coal-fired power stations

Extensive research for establishing the emissions of heavy metals from coal-fired power stations is performed in the Netherlands for the past 25 years. In the Netherlands coal is fired from all over the world. This means that the emissions are established for coal of various origins. In the eighties, the emissions of installations equipped with ESPs (electrostatic precipitators) were measured. In the nineties, the influence of wet FGD (flue gas desulphurisation) on the emissions was studied. The effect of co-combustion of biomass and other secondary fuels is the main item for the last 10 years.Fifty-five elements were measured in the solid state and eight elements in the gaseous phase. It appeared that at low particulate concentration the influence of calcium containing evaporated water droplets downstream the wet FGD on the emissions of heavy metals is bigger than the composition of the coal. Also it appeared that at modern coal-fired power stations the emissions are hardly influenced by co-combustion of biomass. All the results are used for modelling, resulting in the KEMA TRACE MODEL^®, by which the emissions can be predicted. The established emission factors are for most elements in good agreement with literature values for comparable modern installations.Persistence organic pollutants (POPs) that were detected in the flue gases of coal-fired power stations are polycyclic aromatic hydrocarbons (PAH) and dioxins/furans. Measurements during full coal-firing and during co-firing of biomass have indicated that these emissions are negligible.     

Partitioning of persistent organic pollutants (POPs) between human serum and breast milk: A literature review

The literature was reviewed to assess the relationship between the lipid adjusted concentration in human serum and breast milk (expressed as the serum/milk ratio) of a broad range of POPs in paired samples. Thirteen studies were identified, including seven studies that reported serum/milk ratios for polychlorinated dibenzo-dioxins and -furans (PCDD/Fs), ten for polychlorinated biphenyls (PCBs), five for polybrominated diphenyl ethers (PBDEs), and five for organochlorine pesticides (OCPs). Mean serum/milk ratios ranged between 0.7 and 25 depending on the compound and congener. For PCDD/Fs, PCBs and PBDEs, a clear trend of increasing mean serum/milk ratio by increasing molar volume, hydrophobicity and number of halogen substitutes was observed. The mean serum/milk ratios reported by the 13 studies summarized here will aid comparison between human POPs exposure studies using either serum or milk samples. More studies are needed to allow a valid comparison between data obtained from analysis of breast milk and serum samples for a broader range of POPs. Furthermore such studies may shed light on compound specific factors as well as other determinants that may affect the partitioning and partition kinetics of POPs between serum and breast milk.     

PCDD/Fs atmospheric deposition fluxes and soil contamination close to a municipal solid waste incinerator

Bulk depositions and surface soil were collected in a suburban area, near the Adriatic Sea, in order to assess the contribution of a municipal solid waste incinerator to the area’s total contamination with polychlorinated dibenzodioxins and polychlorinated dibenzofurans (PCDDs and PCDFs). Samples were collected at two sites, situated in the area most affected by plant emissions (according to the results of the Calpuff air dispersion model), and at an external site, considered as a reference. Results show that the studied area is subject to low contamination, as far as these compounds are concerned. Deposition fluxes range from 14.3 pg m⁻² d⁻¹ to 89.9 pg m⁻² d⁻¹ (0.75 pg-TEQ m⁻² d⁻¹ to 3.73 pg-TEQ m⁻² d⁻¹) and no significant flow differences are observed among the three monitored sites. Total soil concentration amounts to 93.8 ng kg⁻¹ d.w. and 1.35 ng-TEQ kg⁻¹ d.w, on average, and confirms a strong homogeneity in the studied area. Furthermore, from 2006 to 2009, no PCDD/Fs enrichment in the soil was noticed. Comparing the relative congener distributions in environmental samples with those found in stack emissions from the incineration plant, significant differences are observed in the PCDD:PCDF ratio and in the contribution of the most chlorinated congeners. From this study we can conclude that the incineration plant is not the main source of PCDD/Fs in the studied area, which is apparently characterized by a homogeneous and widespread contamination situation, typical of an urban area.