北京城市污水处理厂污泥中重金属污染状况及潜在生态风险分析

2011—2017年对北京城市中心区8家污水处理厂污泥中8种重金属(Cd、Cr、Cu、Zn、Pb、As、Hg、Ni)开展了持续监测,分析其重金属污染状况、年际及季节变化特征,并应用内梅罗指数法评估污泥在土地利用过程中重金属的潜在生态风险。结果表明:污泥重金属含量为ZnCuCrPbAsNiHgCd,除Hg外,其他重金属含量均低于全国平均水平;四季重金属总量中位值较接近,夏季稍高;Ni、Cd、Hg各年年均值变异系数最大,分别为43%、36%、23%,其他金属变异系数为5%～13%;56%的Hg检测结果超过了《城镇污水处理厂污泥处置农用泥质》(CJ/T 309—2009)中A级污泥限值,且8家污水处理厂均有超标记录;内梅罗指数显示Hg、Zn、Cd、Cu达到重度污染级别,污泥施用于土壤存在较严重的潜在生态风险。因此,污泥用于土壤环境前,需降低其重金属含量。     

洛阳城市污水处理厂污泥中重金属形态及潜在生态风险评价

分析了洛阳市3个污水处理厂脱水污泥中Cu、Zn、Ni、Cr和Pb的含量,采用BCR法研究了污泥中重金属的形态分布特征,并利用地累积指数法(Igeo)和潜在生态危害指数法(RI)评价污泥在农用过程中重金属的潜在生态风险。结果表明,涧西污泥中Cu、Zn和Ni含量超过了农用泥质A级标准的限值(CJ/T309-2009),而新区污泥和瀍东污泥显示出良好的农用性质。污泥中Cu和Cr主要以可氧化态存在,Zn主要以酸溶态和可还原态存在,迁移性强,Ni含量分布相对比较均匀,Pb主要以残渣态存在。Igeo表明,污泥中Cu、Zn是潜在的污染元素。RI表明,Cu表现出高潜在生态风险;Zn的总含量虽高,但Zn的生物毒性响应因子低,对污泥的潜在风险贡献较低。     

濮阳市城市污泥成分及资源化利用生态风险评价

从濮阳市9座规模较大且运行稳定的污水处理厂采集城市污泥,对城市污泥的理化性质和重金属浓度、形态分布进行分析,并对其资源化利用的生态风险进行评价。结果表明,城市污泥呈现高有机质、高氮、高磷的特点,且重金属浓度均低于《城镇污水处理厂污染物排放标准》(GB 18918—2002)中的标准限值,具有较高的资源化利用价值。城市污泥中Cu、Pb、Cd、Ni、Cr、As、Hg主要以可氧化态和残渣态存在,在自然环境下较为稳定;Zn主要以酸可交换态和易还原态存在,具有较强的生物活性和迁移性。城市污泥中重金属的潜在生态风险总体较低,Cu、Zn、Cd、Hg为风险元素,其中Zn的污染程度最高,在城市污泥资源化利用时应制定相应防范措施。     

焦化废水处理过程外排污泥中重金属形态特征及其潜在环境风险

焦化废水处理过程所排放污泥中重金属的含量及化学形态是否构成环境风险将直接影响污泥处置方法的选择,为此,实验采用BCR顺序提取法分析了焦化废水处理站外排污泥中重金属(Cd、Hg、Pb、Cr、As、Ni、Zn、Cu和Mn)的形态特征,并采用地累积指数(Igeo)和潜在生态危害指数(RI)评价了重金属对土壤的潜在环境风险。研究结果表明:除Ni主要以可氧化态存在外,焦化废水外排污泥中其他几种重金属元素主要存在于残渣态,重金属元素的含量低于《城镇污水处理厂污染物排放标准(GB18918—2002)》中的控制限值;与城市污泥相比,焦化废水外排污泥具有低Pb、Cr、Zn、Cu含量,而高Cd、Hg、Mn含量的特点;基于Igeo和RI的评价结果,Cd和Hg是外排污泥中具有一定环境风险的元素,需要考虑其下游去向。焦化废水处理外排污泥中主要存在残渣态重金属成分,不表现为很高的环境风险,其处置应重点考虑其中有机污染物特别是POPs。     

山东省城市污水处理厂污泥重金属污染特征及风险评价

采用电感耦合等离子体质谱仪(ICP-MS)和原子吸收光谱仪重点研究了山东省城市污水处理厂污泥中重金属Cu、Cd、Ni、Pb、Mn、Zn和Cr的污染特征,并对其做了潜在生态风险评价。结果表明:(1)山东省城市污水处理厂污泥呈现高有机质、高氮、高磷和高钾的特点,具有较好的利用价值。(2)污泥中的Mn占重金属总量的质量分数最高,Zn、Cu和Cr占重金属总量的质量分数较高,Cd占重金属总量的质量分数最低。不同城市的重金属浓度大体表现为淄博市济南市枣庄市青岛市烟台市。(3)污泥中生态危害指数最高的重金属为Cu、Cd和Ni;污泥中重金属的复合生态危害指数表现为淄博市济南市枣庄市青岛市烟台市,淄博市和枣庄市城市污水处理厂污泥的重金属潜在生态风险均为中等,其余城市的重金属潜在生态风险均为轻微。Cu和Cd是污泥重金属潜在生态风险的主要贡献因子。(4)对重金属进行主成分分析,第1主成分主要反映了Cu、Ni和Cd的富集程度;第2主成分主要反映了Pb的富集程度;第3主成分主要反映了Zn和Mn的富集程度。     

污泥焚烧底灰中重金属残留特性的实验研究

利用原子吸收分光光度计和程序控制温升炉研究了沈阳市污水处理厂污泥在不同焚烧工况下重金属Cu、Cr、Cd、Zn、Ni和Pb在焚烧底灰中的残留特性。考察了升温速率、焚烧温度、含水率以及停留时间等因素对重金属在污泥底灰中的残留特性的影响。实验表明 ,Pb、Cd和Cu在灰渣中的残留率随着温度和停留时间的增加而降低。大部分的重金属元素Zn、Cu和Cr残留在灰渣中 ,Cd、Pb和Ni部分残留在灰渣中     

北京市PM2.5污染特征 、来源分析及其重金属健康风险评价

分析了2016年北京市的PM_(2.5)及其中的Zn、Pb、Mn、Cu、Cr、As、Ni、Cd、Sb、Co、V、Ba、Al、Fe、Mg、Ti、Ca、S 18种元素含量,并对重金属As、Cr、Pb、Cd、Ni、Mn、Cu和Zn进行了相应的健康风险评价。结果表明:PM_(2.5)质量浓度为14.63～206.35μg/m~3,年平均值为74.00μg/m~3,超过《环境空气质量标准》(GB 3095—2012)二级标准(35μg/m~3)1倍多;PM_(2.5)中S、Zn、Sb、Pb和Cd的富集程度较高,主要来源于机动车尾气排放、燃煤和工业活动;Mn、Pb、Cr、Zn、Cu、As、Cd、Ni 8种重金属对儿童、成人女性、成人男性的非致癌总风险均小于1,不存在非致癌风险;As、Cd、Cr和Ni 4种重金属的致癌风险为1.94×10~(-7)～6.04×10~(-5),均小于10~(-4),部分重金属可能存在潜在致癌风险,主要是As和Cr存在潜在致癌风险。     

污泥焚烧底灰中重金属残留特性的实验研究

利用原子吸收分光光度计和程序控制温升炉研究了沈阳市污水处理厂污泥在不同焚烧工况下重金属Cu,Cr,Cd,Zn,Ni和Pd在焚烧底灰中的残留特性，考察了升温速率，焚烧温度，含水率以及停留时间等因素对重金属在污泥底灰中的残留特性的影响，实验表明，Pd,Cd和Cu在灰渣中的残留率随着渐度和停留时间的增加而降低，大部分的重金属元素Zn,Cr和Cu残留在灰渣中，Cd,Pb和Ni部分残留在灰渣中。     

调理剂对堆肥产品重金属生物有效性的影响

城市污泥中重金属含量及其生物有效性是限制污泥农用的主要因素,因此,研究污泥堆肥化处理过程中重金属生物有效性,对污泥的农用具有重要意义。实验以城市污泥为原料,以菌菇渣和秸秆为调理剂,设置4个处理:A(污泥∶菌菇渣∶秸秆=1∶0.4∶0.025)、B(污泥∶菌菇渣∶秸秆=1∶0.3∶0.025)、C(污泥∶秸秆=1∶0.12)和D(污泥∶秸秆=1∶0.09),进行好氧堆肥实验,采用BCR顺序提取法测定各种形态的重金属,研究堆肥前后重金属形态的变化规律。结果表明,城市污泥中Cu、Ni、Pb和Cr主要以可氧化态及残渣态存在,生物有效性较低,而Zn和Cd主要以酸溶态和可还原态存在,生物有效性较高;堆肥过程显著降低了Cu、Zn、Ni和Pb的生物有效性,并改变了Cu、Zn、Ni、Pb、Cr和Cd的形态分布,使污泥中的Cu、Zn、Ni、Pb和Cd向着更稳定的可氧化态或残渣态转变;污泥经过堆肥处理后,Cu、Zn和Ni 3种重金属生物有效性关系为:ABCD,与其他处理相比,处理A残渣态的Pb和Cr增加比例较多,综合来看,处理A对重金属生物有效性的降低最为明显,重金属钝化效果最佳。     

生物淋滤技术对城市污泥中高浓度重金属的去除

实验以单质硫粉作为能源基质,考查了生物淋滤技术针对城市污泥中高浓度重金属的去除效果,探讨了生物淋滤处置前后污泥中重金属的形态变化规律。结果表明,生物淋滤技术能够有效去除污泥中的高浓度重金属。在硫粉投加量为4 g·L~(-1)、HRT为5 d、污泥回流比为50%、污泥浓度为4%、温度为30℃的条件下,生物淋滤系统pH值可降低至1.5左右,污泥中残留重金属Zn、Cu、Cr、Ni分别可降低至400、400、900和200 mg·kg~(-1)左右,达到了《城镇污水处理厂污泥处置林地用泥质》(CJ/T 362~(-2)011)标准重金属限值。生物淋滤处置后,污泥中残留重金属Zn、Cu、Cr、Ni均主要以稳定形态存在,环境风险较低,为进行土地利用奠定了物质基础。     

Evaluation of trichloroethene recovery processes in heterogeneous aquifer cells flushed with biodegradable surfactants

The ability of two biodegradable surfactants, polyoxyethylene (20) sorbitan monooleate (Tween 80) and sodium dihexyl sulfosuccinate (Aerosol MA), to recover a representative dense non-aqueous-phase liquid (DNAPL), trichloroethene (TCE), from heterogeneous porous media was evaluated through a combination of batch and aquifer cell experiments. An aqueous solution containing 3.3% Aerosol MA, 8% 2-propanol and 6 g/l CaCl(2) yielded a weight solubilization ratio (WSR) of 1.21 g TCE/g surfactant, with a corresponding liquid-liquid interfacial tension (IFT) of 0.19 dyn/cm. Flushing of aquifer cells containing a TCE-DNAPL source zone with approximately two pore volumes of the AMA formulation resulted in substantial (>30%) mobilization of TCE-DNAPL. However, a TCE mass recovery of 81% was achieved when the aqueous-phase flow rate was sufficient to displace the mobile TCE-DNAPL toward the effluent well. Aqueous solutions of Tween 80 exhibited a greater capacity to solubilize TCE (WSR=1.74 g TCE/g surfactant) and exerted markedly less reduction in IFT (10.4 dyn/cm). These data contradict an accepted empirical correlation used to estimate IFT values from solubilization capacity, and indicate a unique capacity of T80 to form concentrated TCE emulsions. Flushing of aquifer cells with less than 2.5 pore volumes of a 4% T80 solution achieved TCE mass recoveries ranging from 66 to 85%, with only slight TCE-DNAPL mobilization (<5%) occurring when the total trapping number exceeded 2 x 10(-5). These findings demonstrate the ability of Tween 80 and Aerosol MA solutions to efficiently recover TCE from a heterogeneous DNAPL source zone, and the utility of the total trapping number as a design parameter for a priori prediction of DNAPL mobilization and bank angle formation when flushing with low-IFT solutions. Given their potential to stimulate microbial reductive dechlorination at low concentrations, these surfactants are well-suited for remedial action plans that couple aggressive mass removal followed by enhanced bioremediation to treat chlorinated solvent source zones.     

The variation of street air levels of PAH and other mutagenic PAC in relation to regulations of traffic emissions and the impact of atmospheric processes

The occurrence of particle associated PAH and other mutagenic PAC was determined in 1996 in the street air of Copenhagen. In addition, particle extracts were tested for mutagenicity. The measurements were compared with previous measurements in 1992/1993. The levels had decreased in this period. The decrease was caused by an implementation of light diesel fuels for buses and the exchange of older petrol-driven passenger cars with catalystequipped new ones. About 65% of the reduction was caused by the application of the light diesel fuels. Under special conditions, chemical processes in the atmosphere produced many more mutagens than the direct emissions. The concentrations of S-PAC and N-PAC were 10 times lower than those of PAH, while the levels of oxy-PAH were in the same order of magnitude as those of PAH. Benzanthrone, an oxy-PAH, is proposed to be formed in the atmosphere in addition to direct emissions. Benzo(a)pyrene, often applied as an air quality criteria indicator, was photochemically degraded in the atmosphere. A strong increase in the mutagenic activities was observed to coincide with a depletion of benzo(a)pyrene.     

Chloroaromatic pollutants in mussels incubated in two finnish watercourses polluted by industry

Concentrations of different chlorinated compounds were measured in mussels incubated in two polluted watercourses, a river (the River Kymijoki) and a lake (Lake Vanaja) for four weeks in summer 1995. The sum concentrations of polychlorinated phenols (PCP) and biphenyls (PCB) were both about 1 μg/g lipid weight (lw) in Lake Vanaja mussels, while in the River Kymijoki mussels PCPs were non-detectable and PCBs were measured 120 ng/g lIw. The concentrations of toxic polychlorinated dibenzo-p-dioxin (PCDD) and dibenzofuran (PCDF) congeners ranged between <17 and 370 pg/g Iw in Lake Vanaja mussels and between <38 and 11,000 pg/g lw in the River Kymijoki mussels. Polychlorinated diphenyl ethers (PCDE) were detected in the mussels incubated in the River Kymijoki (0.4–1.1 ng/g Iw), but not in those incubated in Lake Vanaja. Polychlorinated phenoxyanisoles (PCPA) were measured 33 ng/g lw and polychlorinated phenoxyphenols (PCPP) 300 ng/g lw in the mussels incubated in the River Kymijoki. PCPAs were also detected in reference samples, which were sediment and pike from the River Kymijoki and Baltic salmon, seal and white-tailed sea eagle.     

Teratological effects of pesticides in vertebrates: a review

Abstract

In the last decades, the use and misuse of pesticides in the agriculture have increased, having a severe impact on ecosystems and their fauna. Although the various effects of pesticides on biodiversity have been already documented in several studies, to our knowledge no consistent overview of the impact of pesticides in vertebrates, both terrestrial and aquatic, is available. In this review, we try to present a concise compilation of the teratogenic effects of pesticides on the different classes of vertebrates – mammals, birds, reptiles, amphibians and fish.     

Book review

The Pesticide Manual ‐ A World Compendium, 8th Edition, C.R. Worthing, Editor and S.B. Walker, Assistant Editor, British Crop Protection Council, BCPC Publications Sales, Bear Farm, Binfield, Bracknell, Berkshire RG12 5QE, England. 1987, 1100 pp., UK £50; Overseas £56. ISBN 0–948404–01–9.     

Patterns of volatile metabolites and nonvolatile trichothecenes produced by isolates of <Emphasis Type="Italic">Stachybotrys,Fusarium, Trichoderma,Trichothecium</Emphasis> and <Emphasis Type="Italic">Memnoniella</Emphasis>

We reported previously that trichodiene, a volatile trichothecene derivative, was produced by a Stachybotrys isolate, also known to produce highly cytotoxic, non-volatile, macrocyclic trichothecenes (satrotoxins). We investigated the relationship between the production of trichodiene and various non-volatile trichothecenes for several molds. Volatile metabolites were concentrated by adsorption on Tenax TA and analyzed by GC/MS, while non-volatile metabolites were separated by HPLC, derivatized and analyzed by GC/MS. Stachybotrys chartarum isolates producing macrocyclic trichothecenes secreted significantly larger amounts of trichodiene and other sesquiterpenes than isolates which only produced simple trichothecenes. The amounts of secreted trichodiene were relatively small in all cases. With the exception of Memnoniella, which excreted small amounts of sesquiterpenes, the other isolates produced varying amounts of sesquiterpenes, including trichodiene, as well as simple tricothecenes, no detectable trichodiene, but large amounts of griseofulvin derivatives. In Stachybotrys there is apparently a correlation between trichodiene and macrocyclic trichothecene production. In the remaining isolates, there was no simple relationship between trichodiene and non-volatile trichothecene synthesis. Trichodiene is produced in larger amounts by Stachybotrys isolates, which also produce satratoxins, but it will be difficult to utilize this metabolite to detect toxic isolates in buildings due to the relatively small amounts excreted.     

Observations on the influence of water and soil pH on the persistence of insecticides

Abstract

The pH‐disappearance rate profiles were determined at ca. 25°C for 24 insecticides at 4 or 5 pH values over the range 4.5 to 8.0 in sterile phosphate buffers prepared in water‐ethanol (99: 1 v/v). Half‐lives measured at pH 8 were generally smaller than at lower pH values. Changes in half lives between pH 8.0 and 4.5 were largest (>1000x) for the aryl carbamates, carbofuran and carbaryl, the oxime carbamate, oxamyl, and the organophosphorus insecticide, trichlorfon. In contrast, half lives of phorate, terbufos, heptachlor, fensulfothion and aldicarb were affected only slightly by pH changes. Under the experimental conditions described half lives at pH8 varied from 1–2 days for trichlorfon and oxamyl to >1 year for fensulfothion and cyper‐methrin. Insecticide persistence on alumina (acid, neutral and basic), mineral soils amended with aluminum sulfate or calcium hydroxide to different pH values and four natural soils of different pH was examined. No correlation was observed between the measured pH of these solids and the rate of disappearance of selected insecticides applied to them. These observations demonstrate the difficulty of extrapolating the pH dependent disappearance behaviour observed in homogeneous solution to partially solid heterogeneous systems such as soil.     

Knowledge transfer initiative between molecular biologists and environmental researchers and regulators

A Natural Environment Research Council (NERC) funded Knowledge Transfer (KT) workshop was held in the United Kingdom (UK) to identify the needs and opportunities in the application of molecular biology and ‘omics’ techniques to environmental monitoring and risk assessment. Attendees highlighted a lack of effective communication between end-users and researchers as well as difficulties with data interpretation as reasons behind the slow uptake of molecular biology and omics techniques. A number of promising areas in which new techniques could be implemented at a practical level in the very near future were identified, thereby raising the profile of these recent technologies and providing vital proof of concept work. Molecular taxonomy, bacterial source tracking and pre-screening of chemicals for potential toxicities were all viewed as areas in which omics and molecular techniques could have immediate value, with the aim of reducing cost, increasing efficiency and providing more comprehensive data of improved quality.     

Sorption and predicted mobility of herbicides in Baltic soils

This study was undertaken to determine sorption coefficients of eight herbicides (alachlor, amitrole, atrazine, simazine, dicamba, imazamox, imazethapyr, and pendimethalin) to seven agricultural soils from sites throughout Lithuania. The measured sorption coefficients were used to predict the susceptibility of these herbicides to leach to groundwater. Soil-water partitioning coefficients were measured in batch equilibrium studies using radiolabeled herbicides. In most soils, sorption followed the general trend pendimethalin > alachlor > atrazine～ amitrole～ simazine > imazethapyr > imazamox > dicamba, consistent with the trends in hydrophobicity (log K_ow) except in the case of amitrole. For several herbicides, sorption coefficients and calculated retardation factors were lowest (predicted to be most susceptible to leaching) in a soil of intermediate organic carbon content and sand content. Calculated herbicide retardation factors were high for soils with high organic carbon contents. Estimated leaching times under saturated conditions, assuming no herbicide degradation and no preferential water flow, were more strongly affected by soil textural effects on predicted water flow than by herbicide sorption effects. All herbicides were predicted to be slowest to leach in soils with high clay and low sand contents, and fastest to leach in soils with high sand content and low organic matter content. Herbicide management is important to the continued increase in agricultural production and profitability in the Baltic region, and these results will be useful in identifying critical areas requiring improved management practices to reduce water contamination by pesticides.     

The chemical stability of formulations of some hydrolyzable insecticides in aqueous mixtures with hydrolysis catalysts

Abstract

The active ingredients in commercial formulations of malathion, oxamyl, carbaryl, diazinon, and chlorpyrifos diluted to “spray tank”; concentrations with buffered distilled or natural water of pH 4–9 were stable for at least 24 hr. Formulations of trichlorfon were not stable at pH 7 or above but disappearance rates were slower than for the pure chemical in homogeneous solution. Cupric ion was observed to be an effective catalyst for the hydrolysis of a variety of pure organophosphorus insecticides but did not catalyze hydrolysis of the active ingredients of the formulations examined. Increasing the dilution of the formulation increased the susceptibility of malathion, oxamyl, and carbaryl to hydrolysis.