Spectrophotometric analyses of hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) in water

A simple and accurate spectrophotometric method for on-site analysis of royal demolition explosive(RDX) in water samples was developed based on the Berthelot reaction. The sensitivity and accuracy of an existing spectrophotometric method was improved by:replacing toxic chemicals with more stable and safer reagents; optimizing the reagent dose and reaction time; improving color stability; and eliminating the interference from inorganic nitrogen compounds in water samples. Cation and anion exchange resin cartridges were developed and used for sample pretreatment to eliminate the effect of ammonia and nitrate on RDX analyses. The detection limit of the method was determined to be 100 μg/L. The method was used successfully for analysis of RDX in untreated industrial wastewater samples. It can be used for on-site monitoring of RDX in wastewater for early detection of chemical spills and failure of wastewater treatment systems.     

Applying a new method for direct collection,volume quantification and determination of N2 emission from water

The emission of N2 is important to remove excess N from lakes, ponds, and wetlands. To investigate the gas emission from water, Gao et al.(2013) developed a new method using a bubble trap device to collect gas samples from waters. However, the determination accuracy of sampling volume and gas component concentration was still debatable. In this study, the method was optimized for in situ sampling, accurate volume measurement and direct injection to a gas chromatograph for the analysis of N2 and other gases. By the optimized new method, the recovery rate for N2 was 100.28% on average; the mean coefficient of determination(R2) was 0.9997; the limit of detection was 0.02%. We further assessed the effects of the new method, bottle full of water, vs. vacuum bag and vacuum vial methods, on variations of N2 concentration as influenced by sample storage times of 1,2, 3, 5, and 7 days at constant temperature of 15°C, using indices of averaged relative peak area(%) in comparison with the averaged relative peak area of each method at 0 day.The indices of the bottle full of water method were the lowest(99.5%–108.5%) compared to the indices of vacuum bag and vacuum vial methods(119%–217%). Meanwhile, the gas chromatograph determination of other gas components(O2, CH4, and N2O) was also accurate. The new method was an alternative way to investigate N2 released from various kinds of aquatic ecosystems.     

Identification of the bound residue composition derived from 14C-labeled chlorsulfuron in soil by using LC-MS and isotope tracing method

A new method for extracting the bound residue(BR) derived from ^14C-iabeled chlorsulfuron in soils was developed, and the technique of combining LC-MS with isotope tracing method was subsequently applied to identify the composition of the ^14C-BR in a loamy Fluvent derived from manne deposit. The results showed that the ^14C- [ 2- amino-4- methoxyl-6- methyl- 1,3,5 ]-triazine, ^14C- [ 2-amino-4-hydroxyl-6-methyl-1,3,5]-tdazine and ^14C-chlorsulfuron parent compound constituted the main composition of the ^14C-BR denved from ^14C-labeled chlorsulfuron in the soil. The radioactive ratio of three compounds accounted for 39.8 %, 35.4 % and 17.9 % of total recovered radioactivity, respectively. However, a small amount(3.6 % of total recovered radioactivity) of the complex of ^14C- [ 2-amino-4-hydroxyl-6-methyl-1,3,5]-tdazine might have existed in the ^14C-BR in association with an unknown soil substrate. 2-chlorobenzenesulfonamide was also detected to be one of the components of the BR. The results could well explain the mechanism of phytotoxicity caused by the BR derived from chlorsulfuron in soil. In addition, the mechanism of BR formation in soil was also discussed in details.     

Application of comprehensive two-dimensional gas chromatography with mass spectrometric detection for the analysis of selected drug residues in wastewater and surface water

Pharmaceutical residues have become tightly controlled environmental contaminants in recent years, due to their increasing concentration in environmental components. This is mainly caused by their high level of production and everyday consumption. Therefore there is a need to apply new and sufficiently sensitive analytical methods, which can detect the presence of these contaminants even in very low concentrations. This study is focused on the application of a reliable analytical method for the analysis of 10 selected drug residues, mainly from the group of non-steroidal anti-inflammatory drugs (salicylic acid, acetylsalicylic acid, clofibric acid, ibuprofen, acetaminophen, caffeine, naproxen, mefenamic acid, ketoprofen, and dicofenac), in wastewaters and surface waters. This analytical method is based on solid phase extraction, derivatization by N-methyl-N-(trimethylsilyl)trifluoroacetamide (MSTFA) and finally analysis by comprehensive two-dimensional gas chromatography with Time-of-Flight mass spectrometric detection (GC×GC- TOF MS). Detection limits ranged from 0.18 to 5 ng/L depending on the compound and selected matrix. The method was successfully applied for detection of the presence of selected pharmaceuticals in the Svratka River and in wastewater from the wastewater treatment plant in Brno-Modrice, Czech Republic. The concentration of pharmaceuticals varied from one to several hundreds of ng/L in surface water and from one to several tens of μg/L in wastewater.     

Bio-reduction of nitrate from groundwater using a hydrogen-based membrane biofilm reactor

A hydrogen-based membrane biofilm reactor(MBfR) using H2 as electron donor was investigated to remove nitrate from groundwater.When nitrate was first introduced to the MBfR,denitrification took place on the shell side of the membranes immediately,and the effluent concentration of nitrate continuously decreased with 100% removal rate on day 45 under the influent nitrate concentration of 5 mg NO3--N/L,which described the acclimating and enriching process of autohydrogenotrophic denitrification bacteria.A series of short-term experiments were applied to investigate the effects of hydrogen pressures and nitrate loadings on denitrification.The results showed that nitrate reduction rate improved as H2 pressure increasing,and over 97% of total nitrogen removal rate was achieved when the nitrate loading increased from 0.17 to 0.34 g NO3--N/(m2 ·day) without nitrite accumulation.The maximum denitrification rate was 384 g N/(m3 ·day).Partial sulfate reduction,which occurred in parallel to nitrate reduction,was inhibited by denitrififcation due to the competition for H2 .This research showed that MBfR is effective for removing nitrate from the contaminated groundwater.     

Reduction of nitrate from groundwater: powder catalysts and catalytic membrane

The reduction of nitrate contaminant in groundwater has gained renewed and intensive attention due to the environmental problems and health risks. Catalytic denetrification presents one of the most promising approaches for the removal of nitrate from water. Catalytic nitrate reduction from water by powder catalysts and catalytic membrane in a batch reactor was studied. And the effects of the initial concentration, the amounts of catalyst, and the flux H2 on the nitrate reduction were also discussed. The results demonstrated that nitrate reduction activity and the selectivity to nitrogen gas were mainly controlled by diffusion limitations and the mass transfer of the reactants. The selectivity can improved while retaining a high catalytic activity under controlled diffusion condition or the intensification of the mass transfer, and a good reaction condition. The total nitrogen removal efficiency reached above 80%. Moreover, catalytic membrane can create a high effective gas/liquid/solid interface, and show a good selectivity to nitrogen in comparative with the powder catalyst, the selectivity to nitrogen was improved from 73.4 % to 89.4%.     

Assessment of aerobic biodegradation of lower-chlorinated benzenes in contaminated groundwater using field-derived microcosms and compound-specific carbon isotope fractionation

Biodegradation of lower chlorinated benzenes (tri-, di- and monochlorobenzene) was assessed at a coastal aquifer contaminated with multiple chlorinated aromatic hydrocarbons. Field-derived microcosms, established with groundwater from the source zone and amended with a mixture of lower chlorinated benzenes, evidenced biodegradation of monochlorobenzene (MCB) and 1,4-dichlorobenzene (1,4-DCB) in aerobic microcosms, whereas the addition of lactate in anaerobic microcosms did not enhance anaerobic reductive dechlorination. Aerobic microcosms established with groundwater from the plume consumed several doses of MCB and concomitantly degraded the three isomers of dichlorobenzene with no observable inhibitory effect. In the light of these results, we assessed the applicability of compound stable isotope analysis to monitor a potential aerobic remediation treatment of MCB and 1,4-DCB in this site. The carbon isotopic fractionation factors (ε) obtained from field-derived microcosms were -0.7‰ ± 0.1 ‰ and -1.0‰ ± 0.2 ‰ for MCB and 1,4-DCB, respectively. For 1,4-DCB, the carbon isotope fractionation during aerobic biodegradation was reported for the first time. The weak carbon isotope fractionation values for the aerobic pathway would only allow tracing of in situ degradation in aquifer parts with high extent of biodegradation. However, based on the carbon isotope effects measured in this and previous studies, relatively high carbon isotope shifts (i.e., ∆δ¹³C > 4.0 ‰) of MCB or 1,4-DCB in contaminated groundwater would suggest that their biodegradation is controlled by anaerobic reductive dechlorination.     

Halogen-specific total organic halogen analysis: Assessment by recovery of total bromine

Determination of halogen-specific total organic halogen(TOX) is vital for studies of disinfection of waters containing bromide, since total organic bromine(TOBr) is likely to be more problematic than total organic chlorine. Here, we present further halogen-specific TOX method optimisation and validation, focusing on measurement of TOBr. The optimised halogen-specific TOX method was validated based on the recovery of model compounds covering different classes of disinfection by-products(haloacetic acids, haloacetonitriles,halophenols and halogenated benzenes) and the recovery of total bromine(mass balance of TOBr and bromide concentrations) during disinfection of waters containing dissolved organic matter and bromide. The validation of a halogen-specific TOX method based on the mass balance of total bromine has not previously been reported. Very good recoveries of organic halogen from all model compounds were obtained, indicating high or complete conversion of all organic halogen in the model compound solution through to halide in the absorber solution for ion chromatography analysis. The method was also successfully applied to monitor conversion of bromide to TOBr in a groundwater treatment plant. An excellent recovery(101%)of total bromine was observed from the raw water to the post-chlorination stage. Excellent recoveries of total bromine(92%–95%) were also obtained from chlorination of a synthetic water containing dissolved organic matter and bromide, demonstrating the validity of the halogen-specific TOX method for TOBr measurement. The halogen-specific TOX method is an important tool to monitor and better understand the formation of halogenated organic compounds, in particular brominated organic compounds, in drinking water systems.     

Nitric oxide removal by wastewater bacteria in a biotrickling filter

Nitric oxide(NO) is one of the most important air pollutants in atmosphere mainly emitted from combustion source. A biotrickling filter was designed and operated to remove NO from an air stream using bacteria extracted from the sewage sludge of a municipal sewage treatment plant. To obtain the best operation conditions for the biotrickling filter, orthogonal experiments(L9(34)) were designed. Inlet oxygen concentration was found to be the most significant factor of the biotrickling filter and has a significant negative effect on the system. The optimal conditions of the biotrickling filter occurred at a temperature of 40℃, a pH of 8.0 and a chemical oxygen demand of 165 mg/L in the recycled water with no oxygen in the system. The bacteria sample was detected by DNA sequencing technology and showed 93%–98% similarity to Pseudomonas mendocina. Moreover, a full gene sequencing results indicated the bacterium was a brand new strain and named as P. mendocina DLHK. This strain can transfer nitrate to organic nitrogen. The result suggested the assimilation nitrogen process in this system. Through the isotope experimental analysis, two intermediate products(15NO and 15N2O) were found. The results indicated the denitrification function and capability of the biotrickling filter in removing NO.     

Impact of municipal solid waste incineration on heavy metals in the surrounding soils by multivariate analysis and lead isotope analysis

Municipal solid waste(MSW) incineration has become an important anthropogenic source of heavy metals(HMs) to the environment. However, assessing the impact of MSW incineration on HMs in the environment, especially soils, can be a challenging task because of various HM sources. To investigate the effect of MSW incineration on HMs in soils, soil samples collected at different distances from four MSW incinerators in Shanghai, China were analyzed for their contents of eight HMs(antimony, cadmium, chromium, copper,lead, mercury, nickel, and zinc) and lead(Pb) isotope ratios. Source identification and apportionment of HMs were accomplished using principal component analysis and Pb isotope analysis. Results indicated that the relatively high contents of cadmium, lead,antimony, and zinc in the soils at 250 m and 750–1250 m away from the MSW incinerators were related to MSW incineration, while the elevated contents of the other four HMs were associated with other anthropogenic activities. Based on Pb isotope analysis, the contribution ratio of MSW incineration(which had been operated for more than 14 years)to the accumulation of Pb in soil was approximately 10% on average, which was lower than coal combustion only. Incinerator emissions of Pb could have a measurable effect on the soil contamination within a limited area(≤1500 m).     

浐河、涝河河水硝酸盐氮污染来源的氮同位素示踪

通过分析河水和工业污染水体硝酸盐氮同位素组成,对西安市周边主要河流浐河和涝河的硝酸盐污染源进行了初步研究.结果发现,浐河、涝河从上游至下游,河水硝酸盐氮同位素组成δ15N-NO3-值呈逐渐升高的趋势(1.3‰～9.0‰和3.3‰～7.4‰),而沿河流域2个工业排污口废水样的δ15N-NO3-值为:11.5‰和11.1‰.不同来源的硝酸盐氮同位素表现出明显的差别,工业排污可能是该河流硝酸盐氮浓度增高主要原因之一.相对于河水硝酸盐浓度变化,河水中硝酸盐氮同位素能够作为示踪水系硝酸盐氮污染来源和过程的可靠手段.同时,本研究大致区分了浐河和涝河流域主要的氮源输入,为研究硝酸盐污染,营养元素流失提供了重要的信息.     

利用氮氧同位素解析赤水河流域水体硝酸盐来源及其时空变化特征

赤水河流域作为长江上游重要的水源涵养区,其生态环境状况及水环境质量备受关注。为了了解流域河水氮素来源,本次研究利用硝酸盐稳定同位素(~(15)N、~(18)O)示踪技术并结合流域土地利用类型空间分布分析了赤水河流域丰水期与枯水期干流及主要支流河水硝酸盐来源与转化过程。结果表明,流域水体NO_3~-浓度具有明显的时空变化,其中丰水期NO_3~-浓度要高于枯水期,喀斯特区域的NO_3~-浓度要高于非喀斯特区域。流域干、支流水体δ~(15)N-NO_3~-、δ~(18)O-NO_3~-季节性差异明显,丰水期支流δ~(15)N-NO_3~-差异较大,干流差异较小,而枯水期支流δ~(15)N-NO_3~-差异较小,干流差异较大。结合氮氧同位素和土地利用信息发现,丰水期支流NO_3~-受其土地利用方式的影响,其来源具有多样性;干流NO_3~-浓度则主要受支流混合作用影响。枯水期干流NO_3~-受流域人为活动影响较为显著,点源输入造成水体氮同位素分布范围较宽,主要来源表现为生活污水和土壤有机氮;而支流NO_3~-多表现为土壤有机氮来源,部分支流受流域内城镇影响,生活污水对河流NO_3~-贡献较大。流域水体氮污染控制应以农业面源氮流失为主,同时严格控制点源污染的输入。     

九龙江流域大气氮湿沉降研究

通过2004～2005年对位于我国东南沿海的九龙江流域及周边共17个站点的实地观测,运用GIS技术定量揭示了大气氮湿沉降强度和时空分布特征,并利用氮稳定同位素分析雨水硝态氮的主要来源.结果表明,①17个站点雨水总氮平均浓度为(2.20±1.69)～(3.26±1.37) mg·L-1(以N计,下同),铵态氮、硝态氮和有机氮分别占39%、25%和36%;②雨水氮浓度随降雨强度的增大呈降低趋势,旱季浓度明显大于雨季,降水对大气具有清洗作用;③低δ15N值表明雨水硝态氮主要来源于汽车尾气排放、化石燃料燃烧和化肥施用;④九龙江流域大气氮湿沉降量平均9.9 kg·hm-2,春夏2季约占全年的91%,大气氮湿沉降占沉降总量的66%,揭示了该地区1∶2的大气氮干湿沉降结构.大气氮湿沉降时空差异与降雨量和氮的排放直接相关.     

离子交换树脂法高效提取水中硝酸盐研究

硝酸盐是水体中重要的污染物之一,硝酸盐中的稳定氮氧同位素组成可用于有效识别其污染来源,而水体中硝酸盐的高效提取是其氮氧同位素测试的前提和关键步骤。阴离子树脂交换法提取硝酸盐是目前普遍采用的方法,但对于提取效率的影响因素还缺乏深入研究。文章通过室内实验,探讨了国产717型阴离子树脂对硝酸盐的吸附效率,以及不同洗脱剂的洗脱效率,系统研究了水体中硝酸盐高效提取过程影响因素。结果表明:12.56 mL体积的国产717型树脂对NO3-的吸附量高达200 mg以上;40 mL 4 mol/L的KCl溶液对4 cm长的吸附树脂柱(直径2 cm)的洗脱效率可达95%以上;SO42-的对NO3-的吸附和洗脱具有显著的影响。     

芬顿反应强化污泥脱水试验及机理研究

胞外聚合物(EPS)是影响剩余污泥脱水性能的关键因素。脱水试验过程中,将芬顿试剂和剩余污泥混合,控制芬顿试剂和稀硫酸的投加量,测定剩余污泥的毛细吸收时间和比阻,总结出芬顿反应对剩余污泥脱水性能的影响规律。试验表明:Fenton反应的最佳条件是pH为3,H_2O_2投加量为12.4g/L,Fe~(2+)投加量为1.5g/L,反应12min后,对应的毛细吸水时间(CST)和污泥比阻(SRF)分别为21s和0.3×1012m/kg。分析表明:Fenton反应能够破坏剩余污泥中EPS的蛋白质和多糖成分,瓦解EPS锁水结构,改善污泥的脱水性能。     

碳源对生物滞留系统中硝酸盐异化还原成铵的影响研究

通过构建模拟实验,利用~(15)N同位素示踪技术研究在生物滞留系统中碳源对生物滞留系统中硝酸盐异化还原成铵(DNRA)的影响。结果表明:5个处理组(葡萄糖50,100,150,200,250 mg/L)中NO_3~-发生转化的量分别为41.1%、47.9%、50.7%、56.2%和57.6%。以葡萄糖为碳源,初始浓度为100 mg/L时,DNRA作用效果最显著,~(15)N-NH_4~+含量占初始添加~(15)N的24.7%;初始浓度为250 mg/L时,DNRA作用最弱,~(15)N-NH_4~+含量占初始添加~(15)N的13.7%。反硝化和DNRA作用同时进行,系统中~(15)N-NO_3~-含量的减少均伴随着DNRA过程中间产物~(15)N-NO_2~-含量的积累和最终产物~(15)N-NH+4含量的增加。     

农田退水期阿什河氮污染特征及来源解析

利用水质监测技术和稳定同位素示踪技术,对春季农田退水期阿什河河水中ρ(NH₄+-N)、ρ(NO₃--N)和ρ(TN)特征进行研究并对氮污染来源进行解析. 结果表明,ρ(NH₄+-N)、ρ(NO₃--N)和ρ(TN)除在阿什河上游源头区水体中较低外,其余大部分区域均较高. 上游源头区采样点 δ 15N值为3.68‰～6.09‰,主要受大气沉降氮和土壤有机氮的污染;中下游区域中一部分采样点δ15N值为5.32‰～7.72‰,主要受农田退水和农村生活污水影响,另一部分采样点δ15N值为8.45‰～11.86‰,主要受畜禽养殖污水影响较大;下游采样点δ15N值较低(3.25‰～4.15‰),主要受工业来源废水污染. 农田,特别是河流两岸的稻田退水对阿什河水质影响较大;城区对阿什河TN和NH₄+-N影响较大,对NO₃--N影响较小.      

楠溪江硝态氮来源定量识别及其不确定性分析

选择温州市楠溪江流域为研究区,通过水化学分析和硝态氮中氮氧稳定同位素示踪技术,对水体硝态氮时空分布特征、迁移转化过程和污染来源进行识别,结合稳定同位素源解析模型（SIAR）,定量识别不同污染源的贡献率,并在此基础上应用概率统计方法对模拟结果的不确定性进行分析.结果表明：研究区水体氮素赋存形态以硝态氮为主;硝态氮含量呈现明显的时空变化,时间上,丰水期硝态氮浓度高于枯水期,空间上,支流硝态氮浓度高于主河道;硝化作用主导了流域内硝态氮的转化过程,化肥、土壤有机氮和粪便污水是楠溪江水体硝态氮的主要来源;SIAR模型计算显示大气沉降、化肥、土壤有机氮、粪便污水对枯水期水体硝态氮的贡献率分别为3.0%~12.9%,25.5%~32.7%,28.7%~36.2%和24.7%~37.5%,对丰水期水体硝态氮贡献率为2.5%~14.3%,28.5%~40.0%,28.8%~39.7%和18.9%~29.90%.模拟结果的不确定性分析表明SIAR模拟结果存在一定程度的不确定性,不同污染源贡献率的不确定性从大到小排序为：土壤有机氮>化肥>粪便污水>大气沉降.     

九龙江流域河流氮输出对土地利用模式和水文状况的响应

流域土地利用模式与水文状况影响河流氮的来源、迁移转化和输出,关乎流域健康与淡水生态系统服务的供给.本研究基于2010~2017年观测数据,采用流域模型、地理信息技术和数理统计等方法从多时空尺度探究亚热带中尺度近海流域——九龙江流域河流氮输出对流域土地利用模式和水文状况的响应机制.结果表明,NO₃^--N是九龙江流域河流水体主要的无机氮形态;农业和城市流域河流水体的氮浓度、输出负荷及其年际与季节变异性高于自然流域;丰水年各类流域河流水体的氮浓度和输出负荷差异总体上高于枯水年;相比水文状况,土地利用与氮年均浓度和输出负荷的正相关性更显著.总体而言,河流氮输出时空变化特征受流域土地利用模式和水文状况的共同作用.     

九龙江流域地表水中硝酸盐来源辨析

从九龙江流域遴选出2个典型小流域--仙都和五川小流域作为研究区,于2005年春季运用15N同位素示踪法对其地表水中硝酸盐来源进行研究.结果表明,仙都小流域地表水中溶解态总氮、硝氮和氨氮的浓度范围(以N计,下同)分别为1.47～5.31 mg/L、0.83～4.05mg/L和0.21～0.36mg/L,硝酸盐的δ15N值(以样品相对于标准大气N2的15N和14N比值的千分偏差表示)范围在2.5460-7.92%之间;五川小流域地表水中溶解态总氮、硝氮和氨氮的浓度范围分别为1.14～5.56mg/L、0.96～1.46mg/L和0.12～1.28mg/L,硝酸盐的δ15N值范围在-0.19‰～5.89‰之间.对照不同来源的硝酸盐δ15N特征值,结合研究区的农作物种植和施肥状况,得出如下结论:仙都小流域地表水中硝酸盐主要来自无机化肥与土壤有机氮,有机肥有一定的贡献;五川小流域地表水中硝酸盐的来源以无机化肥与土壤有机氮为主,有机肥的贡献很小;2个小流域地表水中硝酸盐的来源随时空变化而有差异,与当地农作物种类及农田时令密切相关.