High-throughput screening of dioxins in sediment and soil using selective pressurized liquid extraction with immunochemical detection

A high-throughput screening method using selective pressurized liquid extraction (SPLE) and enzyme-linked immunosorbent assay (ELISA) for monitoring dioxins in sediment and soil is described. SPLE conditions were developed by extracting sediment or soil together with alumina, 10% AgNO₃ in silica, and sulfuric acid impregnated silica (acid silica) using dichloromethane (DCM) as the solvent at 100 °C and 2000 psi. Post-extraction cleanups were not required for ELISA. Two reference sediments (National Institute of Standards and Technology SRM 1944 and Wellington Laboratories WMS01) were analyzed by the SPLE–ELISA method. The ELISA utilized a polyclonal antibody and 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) as the calibrant. Recoveries of ELISA-derived TCDD equivalents (EQ) relative to the expected gas chromatography/high resolution mass spectrometry (GC/HRMS) derived dioxin toxic equivalent (TEQ) values were 116 ± 11% for SRM 1944 and 102 ± 13% for WMS01. ELISA TCDD EQs were consistent with the dioxin TEQs as measured by GC/HRMS for 25 soil/sediment samples from seven different contaminated sites. The ELISA had an approximate method detection limit of 10 pg g⁻¹ with a precision of 2.6–29% based on the relative percentage difference (%RPD) for duplicate samples. Estimated sample throughput for the SPLE–ELISA was three times or more than that of the GC/HRMS method employing PLE with a multi-column cleanup.     

A novel source for dioxins present in recycled fat from gelatin production

Within a survey on dioxins in animal fat used as feed ingredient, a sample originating from pigs offal was shown to contain 50 ng Toxic Equivalents (TEQ) PCDD/PCDFs kg(-1) fat. Further investigation revealed fat samples with levels as high as 440 ng TEQ kg(-1) fat and contaminated feed with a highest level of 8.4 ng TEQ kg(-1) feed. The congener pattern was dominated by 1,2,3,7,8-PeCDD and 2,3,7,8-TCDD, and was not recognized from any previous incident or known dioxin source. Remarkably, 2,3,7,8-substituted congeners were much more abundant than their non-2,3,7,8-substituted counterparts. The sampled fat was derived from a gelatin production plant. Broken filters, used to clean the hydrochloric acid (HCl) used in the process, caused the dioxin contamination. The fat was primarily used for pig feed. A new physiologically-based pharmacokinetic (PBPK) model for lipophilic contaminants in growing slaughter pigs predicted levels at slaughter varying between 40 pg TEQ g(-1) fat (worst-case) and 2.5-7pgTEQ g(-1) fat under more realistic scenarios. Almost 300 farms were temporarily blocked. Many fat samples of pigs were analyzed using a combined approach of DR CALUX and GC/HRMS. Levels in contaminated pig fat were around the EU-limit of 1 pg TEQ g(-1) fat, with some samples up to 2-3 pg TEQ g(-1) fat. Of 80 negative samples analyzed by DR CALUX and GC/HRMS no false-negatives were obtained, whereas 36 and 62 of the 80 samples classified suspected with the bioassay had GC/HRMS levels above respectively the tolerance and action limits. It is concluded that novel and unexpected dioxin sources remain a threat to the food chain and require the proper evaluation and monitoring of production processes, including chemicals used therein.     

Historical trends of PCDD/Fs and dioxin-like PCBs in sediments buried in a reservoir in Northern Taiwan

Polychlorinated dibenzo-p-dioxin (PCDD), polychlorinated dibenzofuran (PCDF) and polychlorinated biphenyl (PCB) concentrations were analyzed at 1-2cm intervals in a sediment core collected from a reservoir in Northern Taiwan to evaluate the organic pollution history. The highest PCDD/F (14.4ng TEQ/kg d.w.) and PCB (0.261ng TEQ(WHO)/kg d.w.) concentrations were determined at 13-15cm (estimated year: 1992). The ages of the levels of sediment core were estimated from the sedimentation rate. Analysis results demonstrate that the PCDD/F concentration of the sediment core measured in the reservoir reached their peak when the municipal waste incinerators (MWIs) in the area started to operate. Furthermore, the decrease in sediment core PCDD/F concentration is related to the time of enforcement of the PCDD/F emission limit set by the Environmental Protection Administration (EPA) in Taiwan. Significant distribution of OCDD in homologue profiles was noted in archived soil samples in Taiwan in which the major input of PCDD/Fs was thought to be atmospheric. Major PCB congeners found in the sediment core were the major components of the commercial PCB products. Input fluxes of PCDD/Fs (5.75-158ng-I-TEQ/m(2)-yr) and PCBs (0.248-3.71ng TEQ(WHO)/m(2)yr) into the reservoir of interest are also calculated from the concentration and sedimentation rate of the sediment. The results reveal that considerable amounts of PCDD/Fs and PCBs were carried into the reservoir of interest in the flood stage but not during normal stage.     

Polychlorinated dibenzo-p-dioxins and dibenzofurans in soils and sediments from Daliao River Basin, China

Polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/F) were analyzed in surface sediments and top soils collected from 30 sites in Daliao River Basin. The concentrations of PCDD/F ranged from 0.28 to 29.01 ng TEQ kg(-1) dw (mean value, 7.45 ng TEQ kg(-1)dw) in sediments, and from 0.31 to 53.05 ng TEQ kg(-1)dw (mean value, 7.00 ng TEQ kg(-1)dw) in soils. PCDD/F pollution in sediments from the mid- and downstream sections of Hun River was found to be relatively heavy, and the levels of PCDD/F contamination in paddy soils were generally higher than those of upland soils. Using multivariate statistical analysis, the PCDD/F homologue and congener profiles of all soil and sediment samples were compared with those of suspected PCDD/F sources. The results showed that, PCDD/F contamination in most sediments of Hun River should mainly originated from the production of organochlorine chemicals, while metal smelting was the important potential source of PCDD/F in the drainage area of Taizi River. PCDD/F contamination in paddy soils should be simultaneously attributed to the polluted water irrigation and the organochlorine pesticide application.     

Monitoring of polychlorinated dibenzo-p-dioxins and dibenzofurans, dioxin-like PCBs and polycyclic aromatic hydrocarbons in food and feed samples from Ismailia city, Egypt

Concentrations of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), polychlorinated biphenyl (PCBs) and polycyclic aromatic hydrocarbons (PAHs) have been determined using GC/HRMS in food (butter, seafood and meat) and feed samples (chicken, cattle and fish) purchased from Ismailia city, Egypt. PCDD/F concentrations in food samples ranged between 0.12 and 3.35 pg WHO TEQ/g wet w, while those in feed samples were between 0.08 and 0.2 pg WHO TEQ/g dry w. Levels of PCB TEQ ranged from 0.14 to 3.2 pg/g wet w in the food samples. The feed samples have an average of 0.35 pg PCB TEQ /g dry w. In this study, butter samples showed the highest contamination levels of PCDD/Fs and PCBs. The PCBs contribution to the total TEQ was on average 63% in seafood and on average 49% for meat and butter. The highest contamination levels of PCDD/Fs and PCBs were found in butter samples. The butter TEQ content is several times higher than that reported in all EU countries and exceeded the EU limits, while the PCDD/F levels in seafood and the feed samples is far below the current EU limit. Generally, congener profiles in the food samples reflect the non-industrialized nature of the city and suggest solid waste burning as a significant source of emission. Nevertheless, the profiles for butter suggest an impact from various sources. In the case of the sum of 16 PAH contamination levels in food samples were in the range of 11.7-154.3 ng/g wet w and feed samples had a range of 116-393 ng/g dry w. Benzo(a)pyrene (BaP) has been detected in the range of 0.05-3.29 ng/g wet w in the food samples; butter showed the highest contamination which exceeded the EU standard set for fats and oil. Fingerprints of PAHs suggested both petrogenic and pyrolytic sources of contamination.     

PCDDs, PCDFs, and PCBs concentrations in breast milk from two areas in Korea: body burden of mothers and implications for feeding infants

We determined breast milk concentration of polychlorinated dibenzo-p-dioxins (PCDDs)/polychlorinated dibenzofurans (PCDFs) and polychlorinated biphenyls (PCBs) in 24 mothers living in Korea, and assessed the maternal body burden based on PCDDs/PCDFs and PCBs concentrations in breast milk and an infant intake rate through breast-feeding based on their concentration in breast milk. PCDDs/PCDFs and PCBs levels in breast milk from primipara mothers were found to be higher than those from multipara mothers. For total PCDDs/PCDFs TEQ level, 2,3,4,7,8-PeCDD was the predominant congener, and the proportion of 2,3,7,8-TCDD was less than 3% of total PCDDs/PCDFs TEQ level. For PCBs TEQ level, PCB-126 was the predominant congener. Maternal body burden levels of PCDDs/PCDFs and PCBs based on their concentrations in breast milk were 268-622 TEQ ng. The daily dioxin intakes of mothers were predicted to be 0.78-2.18 TEQ pg/kg/day for PCDDs/PCDFs and 0.34-0.66 TEQ pg/kg/ day for PCBs. For the first year, the body burden of an infant was predicted to be 212 TEQ ng and the daily intake of an infant was predicted to be 85 TEQ pg/kg/day, assuming the mean dioxin-related compounds concentration (27.54 TEQ pg/g fat).     

Preparation of antibodies and development of an enzyme immunoassay for determination of atrazine in environmental samples

An indirect competitive enzyme-linked immunosorbent assay (ELISA) has been developed and optimized for atrazine determination in soil at different depths (0-10, 10-20, and 20-30 cm) before and after 48 h of application, corn shoot and cow milk samples collected from Dina farm, Egypt. This assay was based on a specific polyclonal antibodies (PAb) raised by immunizing New Zealand rabbits with an immunogen prepared by coupling 3-{4-(ethylamino)-6-(isopropylamino)-1,3,5-triazine-2-yl} thiopropanoic acid to bovine serum albumin (BSA) via N-hydroxysuccinimide (NHS) active ester method. The sensitivity (estimated as IC?? value) was 17.5 μg mL?1 with a detection limit of 0.1 ng mL?1. The maximum atrazine concentration was found in soil especially in the deepest layer (325 and 890 μg kg?1 before and after application, respectively). Atrazine concentration in corn shoot was 333.28, μg kg?1 dry plant, while there was no detectable amount in milk. All samples screened by ELISA were validated by gas chromatography mass spectrometer procedure (GC/MS). Good correlation was achieved between the two methods (r = 0.997 for soil and 0.9814 for plant). This study demonstrates the utility and convenience of the simple, practical and cost-effective ELISA method in the laboratory for analysis of environmental samples. The method is ideal for the rapid screening of large numbers of samples in laboratories where access to GC/MS facilities, is limited or lacking.     

Development of dioxin toxicity evaluation method in human milk by enzyme-linked immunosorbent assay--assay validation for human milk

In this study, the development of a toxicity evaluation method for dioxins in human milk by enzyme-linked immunosorbent assay (ELISA) was reported. A total of 17 human milk samples were tested by ELISA and by gas chromatography/mass spectrometry (GC/MS) to assess whether the ELISA performed on samples obtained from primiparas could be considered as reliable enough for identifying a dioxins contamination in human milk. The concept of toxicity equivalent quantity (TEQ) screening was validated by comparing TEQ values for a set of human milk samples to the ELISA responses predicted for those samples. A fairly good correlation (r=0.920) between immunoassay and GC/MS was achieved for human milk. This ELISA should be useful for biological samples monitoring.     

Determination of PCDD/Fs and dioxin-like PCBs in fish oils for feed ingredients by congener-specific chemical analysis and CALUX bioassay

The present research was intended to determine the suitability of the CALUX assay as a screening method for dioxins in fish oil used as a feed ingredient in Japan. Alteration of TEQ in fish oil according to newly proposed toxic equivalency factors (TEF) is also discussed. In the analysis, polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) and dioxin-like polychlorinated biphenyls (DL-PCBs) in 41 fish oil samples were determined by using high-resolution gas chromatography/high-resolution mass spectrometry (HRGC/HRMS) and CALUX bioassay. The mean TEQ values derived from 1998 WHO-TEF of PCDD/Fs and DL-PCBs were 2.6 and 9.9 pg g(-1) (ww), respectively. The levels of TEQ derived from the recently re-evaluated 2005 WHO-TEF were slightly lower than those of the former in both groups. Notably, the contribution of mono-ortho DL-PCBs to total 2005 WHO-TEQ was considerably decreased compared to the case of 1998 WHO-TEQ, resulting from the reduction in its TEF values, while the non-ortho DL-PCBs contribution was increased. The mean TEQ determined by CALUX assay for PCDD/Fs was approximately three times higher, whereas DL-PCBs was approximately two times lower than WHO-TEQ determined by HRGC/HRMS; the sum of PCDD/Fs and DL-PCBs was very similar by both methods. The correlation coefficients of TEQ between the CALUX assay and HRGC/HRMS analysis were 0.84, 0.89, and 0.90 for PCDD/Fs, DL-PCBs, and the sum, respectively. These results suggest that the CALUX assay is a very useful method for the screening of dioxin-related compounds in fish oils.     

Dioxins and furans in the Jordanian environment part 2: Levels of PCDD and PCDF in human milk samples from Jordan

Thirty individual human milk samples were gathered from five main towns in Jordan. They were mixed to six pooled samples and analyzed for PCDD and PCDF. All examined samples were contaminated with 1,2,3,4,6,7,8-HeptaCDD (3.2 – 96.0 n&/kg fat) and OctaCDD (29.0 – 147 ng/kg fat). The calculated TEQ (BGA)-values range between 026 and 60.32 ng TEQ/kg fat, which are all above the calculated tolerable concentration of 019 ng TEQ/kg milk fat.     

Development and validation of a method for analysis of "dioxin-like" PCBs in environmental samples from the steel industry

A method, previously used for determination of 2,3,7,8-substituted polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs), has been modified for quantitative analysis of "dioxin-like" polychlorobiphenyls (PCBs) in environmental samples from the steel industry. The existing sample clean-up procedure, involving liquid chromatography on multi-layered silica and Florisil columns, has been extended to include a third chromatography stage on a basic alumina stationary phase. The additional clean-up stage is required for PCB analysis in order to eliminate interferences from relatively large concentrations of saturated cyclic and aliphatic hydrocarbons. Samples were analysed for WHO-12 congeners using high resolution gas chromatography/high resolution mass spectrometry (HRGC/HRMS) and standard solutions of the method US EPA 1668A. Replicate analysis of method blanks revealed background contamination for PCBs 118, 105 and 77, which are generally abundant in ambient air. These contaminants were taken into account using a subtraction method. The entire procedure was validated by replicate analysis (N = 3) of a certified reference sediment. The RSD for each WHO-12 congener was below 15%, 13C12-labelled PCB internal standard recoveries were in the range 70-95%. A waste dust sample collected in the electrostatic precipitator of a UK sinter plant was analysed for determination of PCDD/Fs and WHO-12 PCBs and exhibited a PCDD/F I-TEQ of 148.5 +/- 21.2 ngkg(-1) and a WHO-TEQ of 7.2 +/- 1.5 ngkg(-1). WHO-12 congeners contributed only 4.6% to the overall TEQ and PCB 126 was the major congener contributing to the WHO-TEQ (96%). The contribution to the overall TEQ of the waste dust sample was mainly attributed to PCDF followed by PCDD, which accounted for 86.6% and 8.7% to the overall TEQ, respectively.     

Residues of dioxins and PCBs in fat of growing pigs and broilers fed contaminated feed

To investigate the kinetics of PCBs and dioxins, 3 week old broilers and 3 month old pigs were fed with a 10-fold diluted feed from the Belgium crisis for one week, followed by a period on clean feed. In the case of broilers this resulted in levels for dioxins, non-ortho and mono-ortho PCBs in fat of 102, 84 and 216 ng TEQ/kg, summarized to 402 ng TEQ/kg. Total levels decreased to 217 and 109 ng TEQ/kg after 1 and 3 weeks on clean feed. Indicator PCB levels decreased from an initial 6.2 mg/kg fat to respectively 3.2 and 1.5 mg/kg. The ratio of indicator PCBs to dioxins TEQs was stable over this period. Levels in back fat of pigs at the end of the exposure period were 26, 15, 82 and 123 ng TEQ/kg for respectively dioxins, non-ortho PCBs, mono-ortho PCBs and the sum. Total TEQ levels decreased to respectively 95, 70, 40, 22 and 12 ng TEQ/kg after 1, 2, 4, 8 or 12 weeks on clean feed. After 12 weeks dioxin levels were around 1 ng TEQ/kg. Indicator PCB levels decreased from 3.48 mg/kg to 2.65, 2.01, 1.25, 0.76 and 0.45 mg/kg fat, again after 1, 2, 4, 8 or 12 weeks on clean feed. Levels of dioxins decreased more rapidly than those of indicator PCBs, also reflected by the ratio of indicator PCBs to dioxins, being 133,000 at the end of the exposure period and 357,000 after week 12. It is concluded that the use of indicator PCBs for dioxins, in the case of a combined exposure, is a safe alternative for screening and in the case of pigs results in an overestimation rather than underestimation of the dioxin levels.     

Characterization of dioxin-like contamination in soil and sediments from the ��hot spot�� area of petrochemical plant in Pancevo (Serbia)

Purpose

Combinatorial bio/chemical approach was applied to investigate dioxin-like contamination of soil and sediment at the petrochemical and organochlorine plant in Pancevo, Serbia, after the destruction of manufacturing facilities that occurred in the spring of 1999 and subsequent remediation actions.

Materials and methods

Soil samples were analyzed for indicator polychlorinated biphenyls (PCBs) by gas chromatography/electron capture detection (GC/ECD). Prioritized soil sample and sediment samples from the waste water channel were analyzed for polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) by high-resolution gas chromatography/high-resolution mass spectrometry (HRGC/HRMS). Microethoxyresorufin o-deethylase (Micro-EROD) and H4IIE?Cluciferase bioassays were used for monitoring of dioxin-like compounds (DLC) and for better characterization of dioxin-like activity of soil samples.

Results

Bioanalytical results indicated high dioxin-like activity in one localized soil sample, while the chemical analysis confirmed the presence of large quantities of DLC: 3.0?×?10⁵ ng/g d.w. of seven-key PCBs, 8.2 ng/g d.w. of PCDD/Fs, and 3.0?×?10⁵ ng/g d.w. of planar and mono-ortho PCBs. In the sediment, contaminant concentrations were in the range 2?C8 ng/g d.w. of PCDD/Fs and 9?C20 ng/g d.w. of PCBs.

Conclusions

This study demonstrates the utility of combined application of bioassays and instrumental analysis, especially for developing and transition country which do not have capacity of the expensive instrumental analysis. The results indicate the high contamination of soil in the area of petrochemical plant, and PCDD/Fs contamination of the sediment from the waste water channel originating from the ethylene dichloride production.     

Effect of backyard burning on dioxin deposition and air concentrations

The influence from open burning of garden and household waste on locally measured dioxin deposition and air concentrations was evaluated in three sets of experiments: the combustion of garden waste in barrels and in open fires, and the incineration of household waste in an empty oil drum. Each set was composed of eight individual experiments over 4 h. Deposition gauges were located 20 m NE, SE, SW and NW with respect to the source and on a background location at 400 m SW. Air samples were taken in the plume with a medium volume sampler equipped with a quartz filter and a polyurethane plug. The results illustrate deposition increments in the wind direction at a distance of 20 m from the source of 0.8 pg TEQ/m2 day for garden waste and 2.5 pg TEQ/m2 day for household waste. Concentrations in the plume were increased by 160-580 fg TEQ/m3 over a period of 12 and 31 h respectively. Expressed at a reference CO2 concentration of 9% this corresponds with a range from 0.8 to 3.6 ng TEQ/m3, which is comparable with a poorly controlled MSWI. Emission factors in the order of magnitude of 4.5 ng TEQ/kg combusted garden waste and 35 ng TEQ/kg burned municipal waste were determined.     

Levels,distribution profile,and risk assessment of polychlorinated biphenyls (PCBs) in water and sediment from two tributaries of the River Chenab,Pakistan

The first study aimed to investigate the polychlorinated biphenyl (PCB) concentration level, spatial distribution pattern, and ecological risk assessment of water and sediment samples from two tributaries (Nullah Aik and Palkhu) of the River Chenab, Punjab Province, Pakistan. A total of 32 PCB congeners were analyzed, and PCB concentration in sediment and water samples ranged between 0.80 and 60 ng/g and 0.20 and 28 ng/L, respectively, where tetra-CBs and tri-CBs dominated over other studied PCB homologs. Dioxin toxicity equivalency (TEQ) was calculated and PCB-126 and PCB-169 showed the higher TEQ values compared with the WHO guidelines, and sediment samples were more toxic than the water samples. The results of the present study should be considered seriously by government authorities to take a proper action against unchecked discharge of contaminants in ecological integrities; otherwise, there may be drastic results in the near future.     

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。     

Exposure to PCBs, through inhalation, dermal contact and dust ingestion at Taizhou, China--a major site for recycling transformers

Air samples containing gaseous and particulate phases were collected from e-waste workplaces and residential areas of an intensive e-waste recycling area and compared with a reference site. The highest total concentration of PCBs was detected at transformer recycling workshops (17.6 ng m(-3)), followed by the residential area (3.37 ng m(-3)) at Taizhou, and the lowest was obtained at the residential area of the reference site, Lin'an (0.46 ng m(-3)). The same trend was also observed with regards to PCB levels in dust samples. The highest average PCBs level of 2824 ng g(-1) (dry wt) was found in the transformer recycling workshops, and was significantly higher than that of residential areas of Taizhou (572 ng g(-1) dry wt) and Lin'an (42.4 ng g(-1) dry wt). WHO-PCB-TEQ level in the workshops of Taizhou was 2216 pg TEQ(1998)g(-1) dry wt or 2159 pg TEQ(2005)g(-1) dry wt, due to the high abundance of PCB 126 (21.5 ng g(-1) dry wt), which contributed 97% or 99% of WHO-PCB-TEQs. The estimated intake of PCBs via dust ingestion and dermal absorption by transformer recycling workers were 77.5×10(-5) and 36.0×10(-5) pg WHO-PCB-TEQ(1998)kg(-1)d(-1), and 67.3×10(-5) and 31.3×10(-5) pg WHO-PCB-TEQ(2005)kg(-1)d(-1), respectively.     

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.     

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.     

Dioxins, metals, and fish toxicity in ash residue from space heaters burning used motor oil

Ash residue, generated from burning used motor oil, is a complex and ubiquitous waste stream. Ash samples were collected from space heaters and analyzed for dioxins (N=10), expressed as toxic equivalents (TEQ), and heavy metals (N=9). TEQ averaged 148-164 ng kg(-1) (standard deviation [SD] 385-416 ng kg(-1)), depending on methods used for non-detects (NDs) and toxic equivalency factors (TEFs). It is notable that median TEQ (2.89-3.49 ng kg(-1)) was about 50 fold lower, reflecting the influence of several high end values on the mean. The proportion of NDs among 17 polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) in each sample averaged 38.2% (range 0-94.1%). Total metals averaged 103,000 mg kg(-1) (SD 26,600 mg kg(-1)), with Zn, Cu, and Pb contributing 89.3%, 6.4%, and 3.0% of the total, respectively. Rainbow trout bioassays resulted in median mortalities of 3.2% and 42.0% (respective SD 25.3% and 43.2%) at ash concentrations of 10 and 100 mg l(-1), respectively. Nominal concentrations of several metals (e.g., Cu, Zn) in the fish bioassay exceeded their reported median lethal concentrations (LC50s) for the test species. Multiple regressions (Bonferroni P<0.05) demonstrated that most of the variance in fish mortality could be accounted for by pH, metals (e.g., As, Cd, Pb), and TEQ. Mean TEQ concentration in used oil ash ranked on the high end of TEQ content in other environmental matrices, including wood ash, cement kiln dust, biosolids, and soils. Overall, these results suggest that suitable disposal methods are needed for ash generated from burning used motor oil.