Levels and distribution of Dechlorane Plus in coastal sediments of the Yellow Sea, North China

Dechlorane Plus (DP) has been determined in surface sediments from three Chinese coastal bays, e.g. Jiaozhou, Sishili and Taozi Bay in North China. DP concentrations ranged from <1.2 to 187 pg g⁻¹ dry weight (dw) (mean: 24.7 pg g⁻¹ dw) in Jiaozhou Bay, <1.2 to 135 pg g⁻¹ dw (mean 69.9 pg g⁻¹ dw) in Sishili Bay and <1.2 to 66.7 pg g⁻¹ dw (mean: 40.4 pg g⁻¹ dw) in Taozi Bay, respectively. Additionally, two dechlorinated species were quantified, which accounted for 0.6-5.1% of the ∑DP concentration.The f_syn values (syn-isomer/(syn- + anti-isomer)) in sediments from Jiaozhou Bay (mean 0.29) were close to the technical DP mixture (0.2-0.4), probably indicating local inputs of DP. In contrast, sediments in Sishili and Taozi Bay showed much lower f_syn values (mean 0.16). During transportation the DP isomers are subject to stereo selective degradation which partly resulted in the relative enrichment of anti-DP in coastal sediments.     

Tissue distribution of Dechlorane Plus and its dechlorinated analogs in contaminated fish: high affinity to the brain for anti-DP

Information on tissue distribution of Dechlorane Plus (DP) and its dechlorinated analogs in wildlife is scarce. DP isomers and two dechlorinated compounds, anti-Cl₁₁-DP and anti-Cl₁₀-DP, were examined in the muscle, liver, and brain tissues of two bottom fish species collected from an electronic waste recycling site, South China. The median levels of syn-, anti-, and anti-Cl₁₁-DP isomers in the tissues ranged 0.18-39.1, 0.22-52.9, and 0.01-5.63 ng/g wet wt, respectively. Anti-Cl₁₀-DP was only detected in one muscle sample of mud carp (0.01 ng/g wet wt), although it was consistently detected in the sediments (0.42-0.83 ng/g dry wt). Preferential distribution in liver relative to muscle was observed for syn-DP and anti-Cl₁₁-DP. However, a high persistent retention in the brain compared to the liver was observed for anti-DP, suggesting that this isomer can across the blood-brain barrier of fish, and may cause adverse effects to the nervous system in the exposed biota.     

Levels and isomer profiles of Dechlorane Plus in the surface soils from e-waste recycling areas and industrial areas in South China

Dechlorane Plus (DP) is a highly chlorinated flame retardant. Levels of DP were measured in surface soils from e-waste recycling areas and industrial areas in South China. Higher DP levels were found in e-waste recycling areas (undetectable-47.4 ng/g) than those in industrial areas (0.0336-4.65 ng/g) in South China. The highest DP concentration (3327 ng/g) was found at the e-waste recycling site in Qingyuan, while DP levels fell dramatically with increasing distance away from the recycling site, suggesting that the e-waste recycling activities are an important source of DP emissions. The mean ratios of anti-DP to total DP (f_anti) for different sampling areas ranged from 0.58 to 0.76 and showed no significant difference from the ratio for the technical DP products (t-test, p > 0.05). Further intensive studies are needed to investigate the process of DP degradation and its degradation products.     

Detection of Dechlorane Plus and brominated flame retardants in marketed fish in Japan

Fish samples purchased from Japanese markets were analyzed for Dechlorane Plus (DP)(syn-, anti-), polybrominated diphenyl ether (PBDE), and hexabromocyclododecane (HBCD)(α, γ). Twenty fish were analyzed using gas chromatography-mass spectrometry for DP and PBDE, and using liquid chromatography-tandem mass spectrometry for HBCD. DP was detected in 18 samples and ∑DP concentrations were <0.2-14.2 pg g⁻¹ wet wt. Among the DP isomers, anti-DP was the dominant residue observed in this study. PBDE was detected in all samples. Concentrations of ∑PBDE ranged from 2.2 to 878 pg g⁻¹ wet wt. HBCD was detected in 18 samples, and ∑HBCD concentrations were <0.02-21.9 ng g⁻¹ wet wt. In fish landed near the East China Sea and the Sea of Japan, we detected relatively high concentrations of DP, PBDE, and HBCD. These results indicate that the seawaters around East Asia are contaminated with flame retardants. This study demonstrates the presence of DP in fish marketed in Japan for the first time.     

Dechlorane Plus (DP) in air and plants at an electronic waste (e-waste) site in South China

Air and foliage samples (Eucalyptus spp. and Pinus massoniana Lamb.) were collected from e-waste and reference sites in South China and analyzed for Dechlorane Plus (DP) and two dechlorinated DPs. DP concentrations in the air were 13.1-1794 pg/m³ for the e-waste site and 0.47-35.7 pg/m³ for the reference site, suggesting the recycling of e-waste is an important source of DP to the environment. Plant DP, with concentrations of 0.45-51.9 ng/g dry weight at the e-waste site and 0.09-2.46 ng/g at the reference site, exhibited temporal patterns similar to the air DP except for pine needle at the reference site. The air-plant exchange of DP could be described with the two-compartment model. Anti-Cl₁₁ DP was measured in most air and plant samples from the e-waste site. The ratios of anti-Cl₁₁ DP to anti-DP in the air and plants may indicate the preferential uptake of dechlorinated DP by plant compared with DP.     

An international survey of decabromodiphenyl ethane (deBDethane) and decabromodiphenyl ether (decaBDE) in sewage sludge samples

Decabromodiphenyl ethane (deBDethane) is an additive flame retardant marketed as a replacement for decabromodiphenyl ether (decaBDE). The structures of the two chemicals are similar, and hence deBDethane may also become an environmental contaminant of concern. Environmental data on deBDethane are scarce. Since sewage sludge is an early indicator of leakage of these chemicals into the environment, an international survey of deBDethane and decaBDE levels in sludge was conducted. Samples were collected from 42 WWTPs in 12 different countries and analyzed with GC/LRMS. DeBDethane was present in sludge from all countries and may therefore be a worldwide concern. The levels of deBDethane in sludge samples from the Ruhr area of Germany were the highest so far reported in the literature (216 ng g⁻¹ d.wt.). The [deBDethane]/[decaBDE] quotient for the whole data set ranged from 0.0018 to 0.83. High ratios were found in and around Germany where deBDethane imports are known to have been high and substitution of decaBDE with deBDethane is likely to have occurred. Low ratios were found in the USA and the UK, countries that have traditionally been large users of decaBDE. An estimate of the flux of deBDEthane from the technosphere via WWTPs to the environment within the European Union gave 1.7 ± 0.34 mg annually per person. The corresponding value for decaBDE was 41 ± 22 mg annually per person.     

Biodegradation of nonylphenol in sewage sludge

We investigated the effects of various factors on the aerobic degradation of nonylphenol (NP) in sewage sludge. NP (5 mg/kg) degradation rate constants (k₁) calculated were 0.148 and 0.224 day⁻¹ for the batch experiment and the bioreactor experiment, respectively, and half-lives (t_1/2) were 4.7 and 3.1 days, respectively. The optimal pH value for NP degradation in sludge was 7.0 and the degradation rate was enhanced when the temperature was increased and when yeast extract (5 mg/l) and surfactants such as brij 30 or brij 35 (55 or 91 μM) were added. The addition of aluminum sulfate (200 mg/l) and hydrogen peroxide (1 mg/l) inhibited NP degradation within 28 days of incubation. Of the microorganism strains isolated from the sludge samples, we found that strain CT7 (identified as Bacillus sphaericus) manifested the best degrading ability.     

Species- and tissue-specific accumulation of Dechlorane Plus in three terrestrial passerine bird species from the Pearl River Delta, South China

Little data is available on the bioaccumulation of Dechlorane Plus (DP) in terrestrial organisms. Three terrestrial passerine bird species, light-vented bulbul, long-tailed shrike, and oriental magpie-robin, were collected from rural and urban sites in the Pearl River Delta to analyze for the presence of DP and its dechlorinated products in muscle and liver tissues. The relationships between trophic level and concentration and isomeric composition of DP in birds were also investigated based on stable nitrogen isotope analysis. DP levels had a wide range from 3.9 to 930 ng g⁻¹ lipid weight (lw) in muscle and from 7.0 to 1300 ng g⁻¹ lw in liver. Anti-Cl₁₁-DP and syn-Cl₁₁-DP, two dechlorinated products of DP, were also detected in bird samples with concentrations ranged between not detected (nd)-41 and nd-7.6 ng g⁻¹ lw, respectively. DP preferentially accumulated in liver rather than in muscle for all three bird species. Birds had significantly higher concentrations of DP in urban sites than in rural sites (mean, 300 vs 73 ng g⁻¹ lw). The fractions of anti-DP (f_anti) were higher in birds collected in rural sites than in urban sites. Significant positive correlation between DP levels and δ¹⁵N values but significant negative correlation between f_anti and δ¹⁵N values were found for birds in both urban and rural sites, indicating that trophic level of birds play an important role in determining DP level and isomeric profile.     

Occurrence and environmental implications of pharmaceuticals in Chinese municipal sewage sludge

The presence of pharmaceuticals in aquatic environment has become a topic of concern because of their potential adverse effects on human health and wildlife species. A total of 45 dewatered sewage sludge samples were collected throughout China and analyzed for 30 commonly consumed pharmaceutical residues. Ofloxacin was found to be the dominant contaminant with concentrations up to 24 760 μg kg⁻¹, followed by oxytetracycline (5280 μg kg⁻¹), norfloxacin (5280 μg kg⁻¹) and ketoprofen (4458 μg kg⁻¹). The concentration of pharmaceutical residues varied greatly depending on the operation conditions of wastewater treatment plants and sampling locations. Poor agreement was found between the predicted (calculation based on the annual consumption and coefficient of sludge water partition) and detected concentrations of the pharmaceuticals indicating that the occurrence of pharmaceutical residues was affected by various factors such as loading rates, sewage properties and the chemical properties such as the contribution from polar groups. National wide fate and ecotoxicity study is required for the development of control strategies.     

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.     

Feedstock quality and growth of bioenergy crops fertilized with sewage sludge

Sewage sludge is rich in essential plant nutrients, but its use is restricted for crop production due to the pollutants it contains, such as metalloids and heavy metals. Sludge is also very sticky and compact. Therefore, the objectives of this work were to evaluate (1) the impact of various amounts of sludge on bioenergy crop productivity and quality and (2) the use of peat as an adjuvant to reduce the stickiness, density and nutrient richness of the sludge. Three different applications of sludge were examined, high, low (50% of high) and low mixed with an equal volume of peat. The sludge-peat mix increased significantly leaf area and biomass accumulation of maize and hemp. High sludge and sludge-peat mix applications increased significantly the leaf area and biomass accumulation as well as the net photosynthesis of oilseed rape. High sludge application resulted in the highest heavy metal and metalloid accumulation in maize and hemp. Sludge-peat mix resulted in the highest heavy metal and metalloid accumulation in oilseed rape. However, the sludge-peat mix application provided the best feedstock quality in all three crops, since chloride, silicon and sulfur concentrations and ash content in plant material were the lowest of the three sludge treatments.     

城市生活污泥和矿化垃圾中氮磷淋失的模拟研究

通过模拟土柱实验,分析了城市生活污泥和矿化垃圾中氮磷的迁移对地下水的影响以及矿化垃圾对氮磷的去除特性.测定项目包括总磷、总氮、硝态氮、pH和电导率(EC).结果表明:施用污泥和矿化垃圾后淋滤液的pH呈下降趋势;EC和总氮都有显著增加;硝态氮增加特别明显,容易造成地下水污染;总磷变化不大,污染地下水的可能性较小.矿化垃圾对氮的去除作用不明显,反而增加了淋滤液中的氮素含量,但对磷的去除效果明显.因此,在利用矿化垃圾取代土壤时,应注意矿化垃圾中氮特别是硝态氮的污染.     

Extraction of raw sewage sludge containing iron phosphate for phosphorus recovery

The objective of the present study was to establish an alkali extraction technology for FePO₄-containing sewage sludge obtained from a wastewater treatment system that includes phosphorous removal by iron electrolysis. By clarifying the extraction properties of phosphorous, organic matter, and inorganic matter, conditions for alkali extraction were optimized. As a result, it was suggested that unheated phosphorous extraction would be superior for FePO₄-containing sewage sludge. And, extraction methods and sewage sludge properties were also compared, and the noteworthy result that extraction of metals can be suppressed to extremely low amounts with alkali extraction as compared with acid extraction was obtained. A new insight was also gained that, as compared with the use of incinerated ash reported in previous studies, alkali extraction was more efficient when raw sewage sludge was used.     

城市生活垃圾和污水处理厂剩余污泥混合发酵的原料配比优化研究

以城市生活垃圾和污水处理厂的剩余污泥为混合原料,研究了混合原料的不同配比对厌氧发酵过程及产气的影响。结果表明:城市生活垃圾与剩余污泥以挥发性固体(VS)质量比为2∶1混合后,厌氧发酵效果最好,累计产气量最高,达到8 721mL,发酵后的总固体(TS)、VS、COD去除率分别达43.65%、35.98%、47.88%;各实验组在发酵过程中的pH、氨氮浓度和碱度均在合理范围内,未对厌氧发酵反应造成影响;以适当配比的城市生活垃圾和剩余污泥为混合原料,进行中温联合厌氧发酵是可行的,联合厌氧发酵可以弥补单一原料的缺陷,在一定程度上改善厌氧发酵效果。     

Long-term study of palladium in road tunnel dust and sewage sludge ash

The present work summarizes data about palladium contents of road tunnel dust from 1994 to 2007 and sewage sludge ash from 1972 to 2006. Since palladium is emitted from automotive catalytic converters as elemental particles, road dust is quiet useful to study traffic-related Pd emissions. Very high Pd values of up to 516 μg Pd kg⁻¹ were found in the road dust samples collected in 2007. Heavy metals of all urban emissions, also dental practice effluent, are enriched in sewage sludge ash and thus this matrix is useful for the documentation of palladium emission caused by the use of Pd alloys in dental medicine. In sewage sludge ash highest Pd contents of maximum 460 μg Pd kg⁻¹ were found in the years 1986-1997. In both matrices correlations of Pd content to Pd demand of industry are discussed.     

Effects of sewage sludge blending on the coal combustion: a thermogravimetric assessment

Combustion of urban sewage sludge together with coal in existing infrastructures may be a sustainable management option energetically interesting for these materials, usually considered wastes. Thermogravimetric analysis was used to study the combustion of a semianthracite coal and the modifications undergone when adding a small percentage (2%, 5%, 10%) of sewage sludge. Both Differential Scanning Calorimetric analysis and Differential Thermogravimetry burning profiles showed differences between coal and sewage sludge combustion. However, the effects of adding a percentage of sewage sludge equal or smaller than 10% was hardly noticeable in terms of heat release and weight loss during the coal combustion. This was further proved by non-isothermal kinetic analysis, which was used to evaluate the Arrhenius activation energy corresponding to the co-combustion of the blends. This work shows that thermogravimetric analysis may be used as an easy rapid tool to asses the co-combustion of sewage sludge together with coal.     

Effects of sewage sludge biochar on plant metal availability after application to a Mediterranean soil

Pyrolytic conversion of sewage sludge into biochar could be a sustainable management option for Mediterranean agricultural soils. The aim of this work is to evaluate the effects of biochar from sewage sludge pyrolysis on soil properties; heavy metals solubility and bioavailability in a Mediterranean agricultural soil and compared with those of raw sewage sludge. Biochar (B) was prepared by pyrolysis of selected sewage sludge (SL) at 500 °C. The pyrolysis process decreased the plant-available of Cu, Ni, Zn and Pb, the mobile forms of Cu, Ni, Zn, Cd and Pb and also the risk of leaching of Cu, Ni, Zn and Cd. A selected Mediterranean soil was amended with SL and B at two different rates in mass: 4% and 8%. The incubation experiment (200 d) was conducted in order to study carbon mineralization and trace metal solubility and bioavailability of these treatments. Both types of amendments increased soil respiration with respect to the control soil. The increase was lower in the case of B than when SL was directly added. Metals mobility was studied in soil after the incubation and it can be established that the risk of leaching of Cu, Ni and Zn were lower in the soil treated with biochar that in sewage sludge treatment. Biochar amended samples also reduced plant availability of Ni, Zn, Cd and Pb when compared to sewage sludge amended samples.     

Trace metal uptake by tropical vegetables grown on soil amended with urban sewage sludge

Trace metal uptake was measured for tropical and temperate leafy vegetables grown on soil from an urban sewage disposal farm in the UK. Twenty-four leafy vegetables from East Africa and the UK were assessed and the five vegetable types that showed the greatest Cd concentrations were grown on eight soils differing in the severity of contamination, pH and other physico-chemical properties. The range of Cd concentrations in the edible shoots was greater for tropical vegetables than for temperate types. Metal uptake was modelled as a function of (i) total soil metal concentration, (ii) CaCl₂-soluble metal, (iii) soil solution concentration and (iv) the activity of metal ions in soil pore water. Tropical vegetables were not satisfactorily modelled as a single generic ‘green vegetable’, suggesting that more sophisticated approaches to risk assessment may be required to assess hazard from peri-urban agriculture in developing countries.     

有机微污染物在污水处理过程中的变化研究

多环芳烃等有毒有机微污染物对污水处理综合指标BOD、COD和TOC等的贡献极小,但危害却很大.采用固相萃取的前处理方法和GC/MS、GC/μECD的分析方法,针对北京市某污水处理厂的总泵进水、二沉出水以及混凝沉淀出水中有机氯农药、多环芳烃和酚类的浓度进行分析.研究结果表明,在不同处理工艺段中,有机氯农药、多环芳烃和酚类的质量浓度分别为nd～10、nd～835、nd～3 248 μg/L.所有检出化合物均未超出中国污水与地表水相应标准限值,其中多环芳烃和酚残留水平较高,应为重点监测对象.这些污染物多数能够在二级处理过程中得到有效去除,但混凝沉淀并没有显著地进一步去除效果.     

Effects of sewage sludge amendment on heavy metal accumulation and consequent responses of Beta vulgaris plants

Use of sewage sludge, a biological residue produced from sewage treatment processes in agriculture is an alternative disposal technique of waste. To study the usefulness of sewage sludge amendment for palak (Beta vulgaris var. Allgreen H-1), a leafy vegetable and consequent heavy metal contamination, a pot experiment was conducted by mixing sewage sludge at 20% and 40% (w/w) amendment ratios to the agricultural soil. Soil pH decreased whereas electrical conductance, organic carbon, total N, available P and exchangeable Na, K and Ca increased in soil amended with sewage sludge in comparison to unamended soil. Sewage sludge amendment led to significant increase in Pb, Cr, Cd, Cu, Zn and Ni concentrations of soil. Cd concentration in soil was found above the Indian permissible limit in soil at both the amendment ratios.

The increased concentration of heavy metals in soil due to sewage sludge amendment led to increases in heavy metal uptake and shoot and root concentrations of Ni, Cd, Cu, Cr, Pb and Zn in plants as compared to those grown on unamended soil. Accumulation was more in roots than shoots for most of the heavy metals. Concentrations of Cd, Ni and Zn were more than the permissible limits of Indian standard in the edible portion of palak grown on different sewage sludge amendments ratios. Sewage sludge amendment in soil decreased root length, leaf area and root biomass of palak at both the amendment ratios, whereas shoot biomass and yield decreased significantly at 40% sludge amendment. Rate of photosynthesis, stomatal conductance and chlorophyll content decreased whereas lipid peroxidation, peroxidase activity and protein and proline contents, increased in plants grown in sewage sludge-amended soil as compared to those grown in unamended soil.

The study clearly shows that increase in heavy metal concentration in foliage of plants grown in sewage sludge-amended soil caused unfavorable changes in physiological and biochemical characteristics of plants leading to reductions in morphological characteristics, biomass accumulation and yield. The study concludes that sewage sludge amendment in soil for growing palak may not be a good option due to risk of contamination of Cd, Ni and Zn and also due to lowering of yield at higher mixing ratio.