NPnEO在中国北方四城市污水处理厂的污染研究

测定了中国北方4个城市污水处理厂进、出水中壬基酚聚氧乙烯醚(NPnEO,n为聚合度)及其代谢产物的浓度及分布,同时测定了其中2个污水处理厂污泥中上述物质的浓度和分布,初步探讨了NPnEO在城市污水处理过程中的迁移转化行为.结果表明:在4个城市污水处理厂的进、出水及其中2个厂的污泥中均检测到了浓度不等的NPnEO及其代谢产物;NPnEO在各城市污水处理厂都得到了一定程度的降解去除,去除率为23.38%～77.11%,平均为52.86%;NPnEO大分子组分降解成了小分子组分,但并未完全矿化;出水中以壬基酚(NP)、壬基酚一乙氧基醚(NP1EO)和壬基酚二乙氧基醚(NP2EO)小分子组分的浓度高.这些小分子产物都具有比母体化合物更高的毒性,并具有环境内分泌干扰性质,因此污水处理过程不但没有降低反而增加了生态风险,是环境中小分子NPnEO的主要来源;污泥对NPnEO,特别是小分子代谢产物有良好的吸附性能,其在污泥中的浓度水平较高,合理处置污泥避免二次污染值得进一步研究探讨.      

壬基酚聚氧乙烯醚在污水处理过程中的迁移转化行为

用正相色谱－质谱联用法（NPLC－MS）分离分析高聚合度的NPnEO(n＞2）,用气相色谱－质谱联用方法（GC－MS）测定其中的NP,NP1EO和NP2EO浓度,对NPnEO在城市污水处理厂的迁移转化行为进行了研究。在污水处理厂的进水中,检测出NP和NPnEO(n=1-23）,总浓度为174nmol/L,其中NP2EO的浓度最高,为89．6nmol/L;其次分别为NP（42．2nmol/L）和NP1EO（12．2nmol/L）;出水中同样检测出NP和NPnEO(n=1-18),其中NP2EO的浓度最高,为37．2nmol/L;其次分别为NP（6．64nmol/L）和NP1EO（0．135nmol/L)。在城市污水处理过程中,NPnEO从高聚合度降妥成低聚合度,NP和NPnEO的总去降率为71％。另外,NP和NPnEO在污泥及污泥过滤水中的分配表明污泥对NPnEO有明显的吸附作用,并近似符合Dubinin-Astakhov等温吸附。     

Sorption of biodegradation end products of nonylphenol polyethoxylates onto activated sludge

IntroductionRecently ,nonylphenolpolyethoxylates (NPnEO (n :numberofethoxyunits(EOs) )havebecomeaproblematicissueforthereasonthatthesecompounds,animportantgroupofnonionicsurfactants ,havebeenusedwidelyinvariousindustriesasflocculants,dispersants,emulsifie…     

Vertical distribution of nonylphenol and nonylphenol ethoxylates in sedimentary core from the Beipaiming Channel, North China

The vertical profiles of nonylphenol （NP） and nonylphenol ethoxylates （NPEOs） were investigated in a sediment core from the Beipaiming Channel, North China using high sensitive LC-MS and GC-MS metthods In this core, relatively high concentrations of NP and NPEOs occurred in the surface sediment （≤40 cm）, with the maximum value of NP and NPEOs reaching 3539 and 12735 mg/g, respectively, whereas, no NP or NPEOs were detected in deeper sediments （〉40 cm）. The high concentrations of NP and NPEOs in the surface layers suggested recent inputs in this area. NPEOs with short ethoxy chains （NPnEO, n=0-3） were dominant in the NPEO mixture with percentages from 54% to 78%, which were similar to the distribution of homolog NPEO in effluents from nearby sewage treatment plants （STPs）, indicating that the channel received the effluents from these STPs. The sewage treatment ratio was quite similar to that found in North America before the 1980s. Finally, the concentrations of NP and NPEOs were related to the total organic carbon （TOC） （p〈0.001）, suggesting that TOC was an important factor for vertical distribution of NPEOs and NP from the Beipaiming Channel.     

Fate and degradation of nonylphenolic compounds during wastewater treatment process

In order to explore the biodegradation behavior of nonylphenolic compounds during wastewater treatment processing, two full-scale wastewater treatment plants were investigated and batch biodegradation experiments were conducted. The biodegradation pathways under the various operational conditions were identified from batch experiments: shortening of ethoxy-chains dominated under the anaerobic condition, whereas oxidizing of the terminal alcoholic group prevailed over the other routes under the aerobic condition. Results showed that the anoxic condition could accelerate the biodegradation rates of nonylphenolic compounds, but had no influence on the biodegradation pathway. The biodegradation rates of nonylphenol (NP) and short-chain nonylphenol polyethoxylates (NPnEOs, n: number of ethoxy units) increased from the anaerobic condition, then the anoxic, finally to the aerobic condition, while those of long-chain NPnEOs and nonylphenoxy carboxylates (NPECs) seemed similar under the various conditions. Under every operational condition, long-chain NPnEOs showed the highest biodegradation activity, followed by NPECs and short-chain NPnEOs, whereas NP showed relatively recalcitrant characteristics especially under the anaerobic condition. In addition, introducing sulfate and nitrate to the anaerobic condition could enhance the biodegradation of NP and short-chain NPnEOs by supplying more positive redox potentials.     

Spatial-temporal distribution and potential ecological risk assessment of nonylphenol and octylphenol in riverine outlets of Pearl River Delta, China

The aquatic environments of the Pearl River Delta in Southern China are subjected to contamination with various industrial chemicals from local industries. In this paper, the occurrence, seasonal variation and spatial distribution of alkylphenol octylphenol （OP） and nonylphenol （NP） in fiver surface water and sediments in the runoff outlets of the Pearl River Delta were investigated. NP and OP were detected in all water and sediment samples and their mean concentrations in surface water during the dry season ranged from 810 to 3366 ng/L and 85.5 to 581 ng/L, respectively, and those in sediments ranged from 14.2 to 95.2 ng/g dw and 0.4 to 3.0 ng/g dw, respectively. In surface water, much higher concentrations were detected in the dry season than those in the wet season. In sediments, the concentrations in the dry season were also mostly higher. High concentrations of NP and OP were found in Humen outlet, likely due to high levels of domestic and industrial wastewater discharges. An ecological risk assessment with the use of hazard quotient （HQ） was also carried out and the HQvalues ranged from 3.6 × 10^-5 to 35 and 64% of samples gave a HQ 〉 1, indicating that the current levels of NP and OP pose a significant risk to the relevant aquatic organisms in the region.     

Pollution of NPEOs in four municipal sewage treatment plants in the north of China

The concentration and distribution of nonylphenol polyethoxylates (NPEOs represents the mixture, and NPnEO represents the monomer) and its metabolites in the influent and effluent of four municipal sewage treatment plants (STPs) in the north of China were measured. Moreover, the concentration and distribution of the above chemicals in the sludge of two STPs were also determined, and the transfer and fate of NPEOs in the sewage treatment process were discussed primarily by analyzing the distribution of the products in the effluent and the sludge. The results showed that NPEOs and its metabolites existed in all the samples of the influent, effluent, and sludge. NPEOs were degraded in the sewage treatment process with the removal efficiency in the range of 23.38%–77.11%, or an average of 52.86%. However, the large analogs of NPnEO were only degraded to small ones, whose degradation rate was rather slow, and consequently the degradation was not complete. Hence, the concentrations of some small metabolites, such as nonylphenol (NP), nonylphenol monoethoxylate (NP1EO), and nonylphenol diethoxylate (NP2EO) were elevated in the effluent. These small metabolites are more toxic than the large NPnEO analogs, and some of them were reported to exhibit environmental endocrine disrupting activity. From this point of view, the process of sewage treatment does not reduce but elevate the risk of NPEOs, which becomes the main source of these small NPnEO in the environment. The sludge exhibited good adsorption ability for NPEOs, especially for the small analogs, which led to the high level of NPEOs in the sludge. Hence, reasonable disposal of the surplus sludge to avoid re-pollution is very important. Translated from Research of Environmental Sciences, 2006, 19(3): 61–66 [译自: 环境科学研究]     

夏季海河与渤海湾中壬基酚和辛基酚污染的状况

对夏季海河与渤海湾表层水中溶解态的壬基酚(NP)和辛基酚(OP)的污染状况进行了调查.结果表明,海河中NP和OP的浓度分别为160～429ng/L和18～56ng/L;渤海湾中NP和OP的浓度分别为33～132ng/L和n.d.～14ng/L.污水排放是海河中NP和OP的重要来源.渤海湾中NP和OP的浓度要远远低于海河,但是海水稀释不是造成其浓度降低的唯一原因.研究还发现该地区NP和OP与COD_Mn和TP具有显著的正相关.与珠江三角洲相比,该地区NP和OP污染情况较为严重,与国外其他类似区域相比则处于中等或较低水平.     

珠三角城市污泥中壬基酚及重金属特征分析

对珠三角地区典型城市的13家污水处理厂剩余污泥中壬基酚(Nonylphenol,NP)、部分重金属及养分含量进行了检测和分析.结果表明,珠三角地区典型城市13家污水处理厂污泥中NP范围在0.45~65.17 mg·kg~(-1)(以干重计,下同)之间,平均值为10.87 mg·kg~(-1),工业废水是影响污水处理厂污泥中NP含量的一个重要因素,该地区污泥中NP含量相比于世界其他地区较低,但其中有2家污水处理厂污泥中NP含量超过或接近2000年欧盟污泥指令文件对污泥中NP、NP1EO、NP2EO(NPE)总量限制值(50 mg·kg~(-1)).13家污水处理厂污泥样中Cu、Pb、Cd及Zn含量的几何平均值分别为435.43、78.88、2.72、1088.01 mg·kg~(-1),与《城镇污水处理厂污染物排放标准》(GB18918—2002)中施用土壤(p H6.5)限值进行比较,仍有部分污水处理厂污泥中Cu、Cd、Zn含量超标.13家污水处理厂污泥样中有机质、总氮、总磷及总钾的算术平均值分别为294.40、12.92、39.63、9.12 g·kg~(-1),与过去的研究相比,污泥中有机质与养分含量总体呈上升趋势.相关性分析的结果表明,13家污水处理厂污泥样中NP含量与污泥中总Cu的含量具有显著的正相关关系.     

太湖流域宜溧河酚类内分泌干扰物的空间分布及风险评价

以NP(nonylphenol,壬基酚)、4-t-OP(4-t-octylphenol,辛基酚)和BPA(bisphenol A,双酚A)为目标物质,研究酚类EDCs(内分泌干扰物)在太湖流域宜溧河地表水体和悬浮物中的空间分布特征及风险评价. 结果表明,太湖流域宜溧河地表水体中ρ(NP)、ρ(4-t-OP)和ρ(BPA)分别为156.2～434.0、11.8～19.4和89.8～353.8 ng/L,悬浮物中w(NP)、w(4-t-OP)和w(BPA)分别为520.0～9 818.2、52.0～454.5和39.0～2 454.5 ng/g. 流域内生活及工业污水排放可能是宜溧河流域水体中酚类EDCs的主要来源,ρ(NP)与ρ(NO₃-)呈显著正相关(R=0.860,P<0.01). 宜溧河水系中酚类EDCs在水相-悬浮物相的有机碳标准分配系数为4.14～6.41,表明悬浮颗粒物的吸附是水体中EDCs迁移的一个重要途径. 研究区域中NP、4-t-OP和BPA的入湖量分别为506、57.9和297 kg/a. 风险评价结果表明,该地区部分河段ρ(EDCs)具有潜在的生态风险.      

Metals and metalloid bioconcentrations in the tissues of Typha latifolia grown in the four interconnected ponds of a domestic landfill site

The uptake of metals in roots and their transfer to rhizomes and above-ground plant parts (stems, leaves) of cattails (Typha latifolia L.) were studied in leachates from a domestic landfill site (Etueffont, France) and treated in a natural lagooning system. Plant parts and corresponding water and sediment samples were taken at the inflow and outflow points of the four ponds at the beginning and at the end of the growing season. Concentrations of As, Cd, Cr, Cu, Fe, Mn, Ni and Zn in the different compartments were estimated and their removal efficiency assessed, reaching more than 90% for Fe, Mn and Ni in spring and fall as well in the water compartment. The above- and below-ground cattail biomass varied from 0.21 to 0.85, and 0.34 to 1.24 kg dry weight/m², respectively, the highest values being recorded in the fourth pond in spring 2011. The root system was the first site of accumulation before the rhizome, stem and leaves. The highest metal concentration was observed in roots from cattails growing at the inflow of the system''s first pond. The trend in the average trace element concentrations in the cattail plant organs can generally be expressed as: Fe > Mn > As > Zn > Cr > Cu > Ni > Cd for both spring and fall. While T. latifolia removes trace elements efficiently from landfill leachates, attention should also be paid to the negative effects of these elements on plant growth.     

Distribution patterns of octylphenol and nonylphenol in the aquatic system at Mai Po Marshes Nature Reserve, a subtropical estuarine wetland in Hong Kong

Spatial and temporal distribution of octylphenol （OP） and nonylphenol （NP） in Mai Po Marshes, a subtropical estuarine wetland in Hong Kong, were investigated. Surface water samples were collected every month from 11 sites during the period of September- December 2004. Concentrations of OP and NP ranged from 11.3 to 348 ng/L and from 29 to 2591 ng/L, respectively. The high levels of NP and OP were found in November and December than in September and October. The levels of OP and NP have no significant spatial differences except September. Total organic matter in the sediments appeared to be an important factor in controlling the fate of these compounds in the aquatic environment.     

Chemical characterization of size-resolved aerosols in four seasons and hazy days in the megacity Beijing of China

Size-resolved aerosol samples were collected by MOUDI in four seasons in 2007 in Beijing. The PM₁₀ and PM_1.8 mass concentrations were 166.0 ± 120.5 and 91.6 ± 69.7 μg/m³, respectively, throughout the measurement, with seasonal variation: nearly two times higher in autumn than in summer and spring. Serious fine particle pollution occurred in winter with the PM_1.8/PM₁₀ ratio of 0.63, which was higher than other seasons. The size distribution of PM showed obvious seasonal and diurnal variation, with a smaller fine mode peak in spring and in the daytime. OM (organic matter = 1.6 × OC (organic carbon)) and SIA (secondary inorganic aerosol) were major components of fine particles, while OM, SIA and Ca^2 + were major components in coarse particles. Moreover, secondary components, mainly SOA (secondary organic aerosol) and SIA, accounted for 46%–96% of each size bin in fine particles, which meant that secondary pollution existed all year. Sulfates and nitrates, primarily in the form of (NH₄)₂SO₄, NH₄NO₃, CaSO₄, Na₂SO₄ and K₂SO₄, calculated by the model ISORROPIA II, were major components of the solid phase in fine particles. The PM concentration and size distribution were similar in the four seasons on non-haze days, while large differences occurred on haze days, which indicated seasonal variation of PM concentration and size distribution were dominated by haze days. The SIA concentrations and fractions of nearly all size bins were higher on haze days than on non-haze days, which was attributed to heterogeneous aqueous reactions on haze days in the four seasons.     

A SPE-HPLC-MS/MS method for the simultaneous determination of prioritised pharmaceuticals and EDCs with high environmental risk potential in freshwater

This work describes the development, optimisation and validation of an analytical method for the rapid determination of 17 priority pharmaceutical compounds and endocrine disrupting chemicals (EDCs). Rather than studying compounds from the same therapeutic class, the analyses aimed to determine target compounds with the highest risk potential (with particular regard to Scotland), providing a tool for further monitoring in different water matrices. Prioritisation was based on a systematic environmental risk assessment approach, using consumption data; wastewater treatment removal efficiency; environmental occurrence; toxicological effects; and pre-existing regulatory indicators. This process highlighted 17 compounds across various therapeutic classes, which were then quantified, at environmentally relevant concentrations, by a single analytical methodology. Analytical determination was achieved using a single-step solid phase extraction (SPE) procedure followed by high-performance liquid chromatography with tandem mass spectrometry (HPLC-MS/MS). The fully optimised method performed well for the majority of target compounds, with recoveries >71% for 15 of 17 analytes. The limits of quantification for most target analytes (14 of 17) ranged from 0.07 ng/L to 1.88 ng/L in river waters. The utility of this method was then demonstrated using real water samples associated with a rural hospital/setting. Eight compounds were targeted and detected, with the highest levels found for the analgesic, paracetamol (at up to 105,910 ng/L in the hospital discharge). This method offers a robust tool to monitor high priority pharmaceutical and EDC levels in various aqueous sample matrices.     

Alternative cropping systems for sustainable water and nitrogen use in the North China Plain

Serious water deficits and excessive nitrogen (N) applications are threatening the sustainability of intensive agriculture in the North China Plain (NCP). This study examined the possibility of replacing the conventional system (Con.W/M) of winter wheat (Triticum aestivum L.) and summer maize (Zea mays L.), with an optimized double cropping system (Opt.W/M), a 2-year system (winter wheat/summer maize-spring maize, W/M-M), and a monoculture system (spring maize, M) based on optimal water and N management strategies. From 2004 to 2010, a long-term field experiment conducted in the NCP showed that although >70 mm of irrigation water can be saved with Opt.W/M compared with Con.W/M, annual net groundwater use under Opt.W/M was still 250 mm, 65-90% of which was consumed during the winter wheat season. When wheat production was decreased, 35% and 61% of irrigation water could be reduced in W/M-M and M compared to Con.W/M, respectively. As a result, annual groundwater use was decreased to 190 mm in W/M-M and 94 mm in M. Meanwhile, the N fertilizer rate was reduced 59% and 72% in W/M-M and M compared to Con.W/M, respectively. There were no significant differences in net economic returns between Con.W/M and W/M-M across the 6-year period. In the 6 years, no significant economic loss was observed between Con.W/M and M except in the 2008-2010 rotation. The W/M-M and M systems showed great potential to reduce water and N application and achieve groundwater use balance, and thus should be considered for economic and sustainable agricultural development in the NCP.     

膜生物反应器法处理模拟印染废水

针对人工模拟的印染废水,设计了缺氧/好氧膜生物反应器相结合的处理装置。系统经过165 d的运+行,结果表明:系统对COD和氨氮一直有很好的去除效果,稳定期COD的去除率可以达到95.0%,NH4+-N平均去除率为96.5%,TP的平均去除率低于50%,TN的去除率处在60%⁸0%之间,活性艳红染料X-3B的去除率在60%80%之间,活性艳红染料X-3B的去除率在60%⁷3%之间,出水含有少量色度。水样中长链的壬基酚聚氧乙烯醚NP10EO的去除率可以达到99%,出水仅含有少量的NP1EO,NP2EO和NP。     

Biotransformation of nonylphenol ethoxylates during sewage treatment under anaerobic and aerobic conditions

Biotransformation of nonylphenol ethoxylates (NPEOs) during continuous anaerobic sewage treatment was compared with the aerobic treatment of sewage spiked with 23 μmol/L technical NPEOs over a period of 90 d. Immediate degradation of NPEOs was observed under both anaerobic and aerobic conditions, indicating that the enzymes and bacteria required for NPEO degradation existed abundantly in both aerobic and anaerobic sludge. Both treatments achieved high removal (＞92%) of the spiked NPEO9 mixture.Liquid chromatography-mass spectrometry (LC-MS) analysis showed that short-chain NPEOs (NPEO1-NPEO3) accumulated in anaerobic (2.01-2.56 μmol/L) and aerobic (1.62-2.03 μmol/L) effluents, with nonylphenol (NP) (0.24-0.31 μmol/L) as another group of metabolites in the anaerobic effluent, and nonylphenoxy carboxylates (NPECs) (2.79-3.30 μmol/L) in the aerobic effluent. Significant accumulation of NP in the anaerobic sludge and NPEO1-3 in the sludge of two reactors was observed. These results indicated that it was difficult to control these harmful metabolites in the conventional treatment processes. Denaturing gradient gel electrophoresis profiles of sludge samples support the speculation that the NPEO degradation bacteria might be the dominant indigenous species.     

渤海中部海域颗粒有机碳季节性变化及碳库估算

依据不同季节的调查,对渤海水体中颗粒有机碳（POC）的时空变化特征、碳库及影响因素进行对比研究.结果表明：春、夏、秋和冬季渤海调查海域颗粒有机碳的平均浓度分别为（338±146）μg/L、（491±136）μg/L、（358±228）μg/L和（2534±2601）μg/L,其中冬季渤海水体中POC浓度最高约是春季的7倍.不同季节渤海调查海域POC分布具有相似的规律,即由近岸浅水区向远岸逐渐降低,高值区多集中在调查海域北侧近岸、黄河入海口以及渤海湾等处.不同季节影响POC分布的因素不同,春、夏和秋季影响渤海调查海域POC分布的因素主要是陆源输入和浮游植物的生长繁殖,沉积物再悬浮是影响冬季渤海调查海域POC分布的主要因素.通过C/N比值探究不同季节渤海水体中POC来源发现,春季有45.3%、52.8%样品的C/N比值分别介于2.6~4.3和4~10之间,夏季有38.7%、32.3%样品的C/N比值分别介于2.6~4.3和4~10之间;秋季有84.4%样品的C/N比值介于4~10;而冬季有72.2%样品的C/N比值大于12,可见渤海水体中POC来源具有季节性差异,春季和夏季渤海调查海域POC主要来源于海洋生物的代谢活动,秋季渤海水体中POC的主要来源是浮游植物,冬季渤海POC的主要来源是再悬浮物作用下沉积物中保留下来的有机物.渤海POC碳库呈季节性变化,春、夏和秋季渤海调查海域POC碳库在6×10⁵~7×10⁵t范围内,冬季碳库最高,为2.5×10⁶t.     

Profile and removal of endocrine disrupting chemicals by using an ER/AR competitive ligand binding assay and chemical analyses

An estrogen receptor (ER)/androgen receptor (AR) ligand competitive binding assay (ER/AR-binding assay) and chemical analyses were used to evaluate the endocrine disrupting chemicals (EDCs) behavior of two municipal wastewater treatment plants (WWTPs) (K and S). In the influents, estrone (E1), androsterone (A), androstenedione (AD), BPA (bisphenol A), NP (nonylphenol) and daidzein (DZ) were detected in high amounts with subsequent 24 h-average concentrations of 350, 1000, 29, 1300, 3900, and 5700 ng/L in K-WWTP and of 310, 620, 59, 1600, 2600, and 8400 ng/L in S-WWTP. The estrogenic (androgenic) activity as 17 -estradiol (E2) equivalents (EEQ) or testosterone (Te) equivalents (TEQ) was consequently 620 ng E2/L (570 ng Te/L) and 580 ng E2/L (800 ng Te/L) for the two WWTPs. The removal e ciencies of the above mentioned sole target chemicals were 51%–100% for K-WWTP and 55.6%–100% for S-WWTP. The removal e ciencies of EEQ were about 73% for both WWTPs, while the removal e ciencies of TEQ were 62.1% for K-WWTP and 98.4% for S-WWTP. In addition, chemical-derived EEQ were about 1.2%–52.4% of those by ER-binding assay for K-WWTP and the corresponding ratios were 1.3%–83.3% for S-WWTP, while chemical derived TEQ were less than 3% of values measured by the AR-binding assay for both WWTPs.     

Comparative cytotoxicity of nanoparticles and ions to Escherichia coli in binary mixtures

The objective of this study was to understand toxicity of mixture of nanoparticles (NPs) (ZnO and TiO₂) and their ions to Escherichia coli. Results indicated the decrease in percentage growth of E. coli with the increase in concentration of NPs both in single and mixture setups. Even a small concentration of 1 mg/L was observed to be significantly toxic to E. coli in binary mixture setup (exposure concentration: 1 mg/L ZnO and 1 mg/L TiO₂; 21.15% decrease in plate count concentration with respect to control). Exposure of E. coli to mixture of NPs at 1000 mg/L (i.e., 1000 mg/L ZnO and 1000 mg/L TiO₂) resulted in 99.63% decrease in plate count concentration with respect to control. Toxic effects of ions to E. coli were found to be lesser than their corresponding NPs. The percentage growth reduction was found to be 36% for binary mixture of zinc and titanium ions at the highest concentration (i.e., 803.0 mg/L Zn and 593.3 mg/L Ti where ion concentrations are equal to the Zn ions present in 1000 mg/L ZnO NP solution and Ti^+ 4 ions present in 1000 mg/L TiO₂ NP solution). Nature of mixture toxicity of the two NPs to E. coli was found to be antagonistic. The alkaline phosphatase (Alp) assay indicated that the maximum damage was observed when E. coli was exposed to 1000 mg/L of mixture of NPs. This study tries to fill the knowledge gap on information of toxicity of mixture of NPs to bacteria which has not been reported earlier.