污水处理厂还原硫化物和臭气浓度的电子鼻监测技术探究

用电子鼻监测技术探究污水处理厂还原硫化物质量浓度和臭气质量浓度预测方法。结果表明,使用响应面分析法(RSM)建立还原硫化物质量浓度与电子鼻响应值关系,构建还原硫化物质量浓度预测模型,准确率可达95%。使用偏最小二乘法(PLS)建立不同质量浓度还原硫化物的传感器响应值与对应臭气质量浓度之间的关系,构建臭气浓度预测模型,并用实际样品验证。     

水和废水中总氮的现场快速分析方法研究

在现行水中总氮分析方法的基础上,利用便携式分光光度计和密封消解管,实验了过硫酸钾氧化、硫酸联氨还原、重氮－偶联反应的最佳条件,讨论了碱性过硫酸钾溶液用量及硫酸联氨溶液用量对分析结果的影响,从而建立了水体总氮的碱性过硫酸盐消解－分光光度分析方法,该方法可在现场简便快速地测定水和废水中的总氮。     

Atmospheric aerosol concentration level and chemical characteristics of water-soluble ionic species in wintertime in Beijing,China

Total suspended particulate (TSP) samples were collected during wintertime from November 24, 1998 to February 12, 1999 in Beijing. Ionic species including Cl-, NO3(-), SO4(2-), Na+, NH4(+), K+, Mg2+ and Ca2+ were determined by Ion Chromatography (IC). The sum average concentration of all the determined ions accounted for 18.9% of the TSP concentration, and SO4(2-) appeared the dominant ion with an average concentration of 30.84 microg m(-3); the sum mass concentration of SO4(2-), NO3(-), Ca2+ and NH4(+) accounted for about 83.2% of all the eight ions measured. The study indicated that the chemical form of sulfate and ammonium varies with TSP concentration levels. During heavy pollution periods, the average TSP concentration was 0.66 mg m(-3), and the NH4(+)/SO4(2-) molar ratio was low (0.58). It indicated that sulfate may present as CaSO4 and (NH4)2SO4 x CaSO4 x 2H2O. When TSP concentration (average 0.186 mg m(-3)) was relatively low, the NH4(+)/SO4(2-) molar ratio was 1.94, close to the theoretical ratio of 2 of (NH4)2SO4. Under this condition (NH4)2SO4 is expected to exist as the major form of sulfate. When the TSP concentration level was medium (average 0.35 mg m(-3)), the NH4+/SO4(2-) molar ratio appeared an average value (1.27), (NH4)2SO4, (NH4)2SO4 x CaSO4 x 2H2O and CaSO4 are expected to be present in those aerosol particles. Meteorological conditions including wind speed and wind direction were related to the TSP concentration level.     

大气痕量有机硫化物的光电离色谱法测定及硫酸铵在湿浸土壤中释放有机硫化物的研究

采用国产光电离色谱仪(GC-PID)对有机硫化物:乙基硫醇,二甲基硫,二甲基二硫进行了分离分析,其最小检知量在亚微克/升级,并对北京郊区的某些天然源环境样品进行了有机硫化物浓度的测定,实验数据证实,在鸡场,猪场,水稻田与塑料蔬菜大棚等环境大气中含有机硫化物。研究了硫酸铵作为氮肥加入到水浸土壤中后,由于缺氧而生成有机硫化物的现象,观察了其对有机硫化物的释放规律及硫酸铵与葡萄糖分别作为硫源与碳源对有机硫化物生成的影响,实验结果认为:硫酸铵在五种不同类型的水浸土壤中(环境温度25℃),均可解离释放出有机硫化物,随其在土壤中加入量的增多,释放气中的有机硫浓度增加,二甲基硫的释放量最大。     

Cross-sensitivities of electrochemical detectors used to monitor worker exposures to airborne contaminants: false positive responses in the absence of target analytes

Ideally, the response of electrochemical detectors is proportional to the concentration of targeted airborne chemicals and is not be affected by concomitantly present substances. Manufacturers provide a limited list of cross-sensitivities but end-users have anecdotally reported unexpected interferences by other substances. Electrochemical detectors designed to measure airborne levels of CO, H(2)S, NO, NO(2), or SO(2), were challenged with potentially interfering substances in the absence of target analytes. Cross-sensitivities undocumented by the manufacturers were observed and were found to vary between different models of instruments for the same challenge chemical.     

A Comparison of Aerial and Ground Level Measurements of 137Cs in the Marshall Islands

The purpose of this paper is to present and compare two independent sets of environmental gamma spectrometry measurements of¹³⁷ Cs collected nearly 14 years apart. One set of data was collected in 1978 by a contractor of the U.S. Department of Energy during an aerial radiological survey of the northern atolls of the Marshall Islands. That program used helicopter mounted sodium-iodide scintillation detectors; measurements were made from an altitude of 38 m. The second measurement program was conducted from early 1990 through late 1994 by the Republic of the Marshall Islands Government in a survey of the entire nation. This latter program used ground level in situ gamma spectrometry with high-purity germanium detectors. In this comparison, we highlight differences between the findings of the two studies and probable reasons for those differences, though we also discuss the effectiveness of the two techniques for monitoring the ionizing radiation environment. In the comparison of exposure rates from ¹³⁷Cs, fair agreement was noted after accounting for radioactive decay during the intervening years. Though the distributions were statistically different over their entire range, they were nearly identical above 1 R h^-1. There was considerable difference in the estimates of¹³⁷ Cs inventory; the difference was greater at low activity levels with the NaI measurements consistently larger than the in situ measurements. Reasons for this difference is attributed to three factors which differed between the two studies: (1) the assumed penetration of the cesium into the soil column, (2) the assumption of soil density, and (3) differences in the ability of the two different detector systems to reject interfering spectral contributions. Precise measurement of the lowest levels has implications for determining those atolls that exceeded the deposition of ¹³⁷Cs from global fallout. This issue is discussed in addition to a comparison of the findings from the two measurement programs.     

Investigation of Building - Influenced Atmospheric Dispersion Using a Dual Source Technique

Dispersion of atmospheric contaminants in the vicinity of an isolated cubical model building was investigated in the field. A dual source/receptor technique was used in the experiments, which was proved to be very useful for the investigation of pollution dispersion. This experimental technique involved the simultaneous release of two different tracer gases from two different point sources, and the deployment of a FID (Flame Ionization Detector) co-located with a UVIC®(Ultra-Violet Ion Collector) detector. Both mean concentrations and concentration fluctuation statistics were examined. In this paper concentration fluctuation statistics are presented. The effect of the upwind source location on intermittency values and on the cumulative density function (cdf) is examined. The exact location of a source placed upwind of an obstacle has a very significant and complex effect on both mean concentrations and concentration fluctuations. As the lateral or vertical displacement between the two sources is increased, cross-correlation values between data taken simultaneously by two co-located detectors decrease rapidly.     

Reduced sulfur compounds in ambient air surrounding an industrial region in Korea

The atmospheric concentrations of several reduced sulfur compounds (RSCs) including H(2)S, CH(3)SH, DMS, CS(2), and DMDS were measured concurrently from a series of field campaigns covering multiple locations in the surroundings of a large industrial region (August 2004 to September 2005). These field studies have been designed and undertaken to inspect the concentrations of RSCs in ambient air. The RSC concentrations were found to occur in a highly variable range. H(2)S (1.06 +/- 2.07 ppb) was found to be the most abundant RSC followed by CS(2) (0.84 +/- 0.54 ppb), DMDS (0.36 +/- 1.21 ppb), DMS (0.24 +/- 0.83 ppb), and CH(3)SH (0.11 +/- 0.23 ppb). The RSC levels measured at the study area were comparable to those observed previously from other polluted environmental settings. When these RSC data were examined further in terms of spatial (industrial vs. non-industrial sites) and seasonal (summer vs. winter seasons) grouping schemes, differences in their concentration levels were statistically insignificant in most cases. In contrast, there were fairly strong variations in temporal patterns over a diurnal cycle. If these RSC concentration data were converted to diagnose the malodor strengths, their effects were in most cases insignificant with minor contribution towards odor nuisances.     

乌鲁木齐市米东区恶臭气体NH3和H2S污染特征分析

为了了解和评价乌鲁木齐市米东区恶臭气体污染现状,2007年冬季对该地区NH3和H2S网格布点采样,用气相色谱法分析,并运用GIS等工具对NH3和H2S污染物来源及其影响因素进行综合分析评价。结果表明,该地区NH3和H2S污染严重,其浓度分别为其他地区的5倍和1．6倍,且污染物扩散能力较弱。     

Characterization and optimization of an online system for the simultaneous measurement of atmospheric water-soluble constituents in the gas and particle phases

In this work we present the results of extensive characterization and optimization of the Ambient Ion Monitor-Ion Chromatograph (AIM-IC) system, an instrument developed by URG Corp. and Dionex Inc. for simultaneous hourly measurements of the water-soluble chemical composition of atmospheric fine particulate matter (PM(2.5)) and associated precursor gases. The sampling assembly of the AIM-IC consists of an inertial particle size-selection assembly, a parallel-plate wet denuder (PPWD) for the collection of soluble gases, and a particle supersaturation chamber (PSSC) for collection of particles, in series. The analytical assembly of the AIM-IC consists of anion and cation IC units. The system detection limits were determined to be 41 ppt, 5 ppt, and 65 ppt for gas phase NH(3(g)), SO(2(g)), and HNO(3(g)) and 29 ng m(-3), 3 ng m(-3), and 45 ng m(-3) for particle phase NH(4)(+), SO(4)(2-), and NO(3)(-) respectively. From external trace gas calibrations with permeation sources, we determined that the AIM-IC is biased low for NH(3(g)) (11%), SO(2(g)) (19%), and HNO(3(g)) (12%). The collection efficiency of SO(2(g)) was found to strongly depend on the composition of the denuder solution and was found to be the most quantitative with 5 mM H(2)O(2) solution for mixing ratios as high as 107 ppb. Using a cellulose membrane in the PPWD, the system responded to changes in SO(2(g)) and HNO(3(g)) within an hour, however for NH(3(g)), the timescale can be closer to 20 h. With a nylon membrane, the instrument response time for NH(3(g)) was significantly improved, becoming comparable to the responses for SO(2(g)) and HNO(3(g)). Performance of the AIM-IC for collection and analysis of PM(2.5) was evaluated by generating known number concentrations of ammonium sulfate and ammonium nitrate particles (with an aerodynamic diameter of 300 nm) under laboratory conditions and by comparing AIM-IC measurements to measurements from a collocated Aerosol Mass Spectrometer (AMS) during a field-sampling campaign. On average, the AIM-IC and AMS measurements agreed well and captured rapid ambient concentration changes at the same time. In this work we also present a novel inlet configuration and plumbing for the AIM-IC which minimizes sampling inlet losses, reduces peak smearing due to sample carryover, and allows for tower-height sampling from the base of a research tower.     

吹扫捕集-气相色谱联用同时测定水中致嗅挥发性有机硫化物

建立了一种利用吹扫捕集(PT)-气相色谱(GC)/火焰光度检测器(FPD)同时测定水中16种致嗅类有机硫化物的分析方法。研究并优化了捕集阱类型、吹扫温度、吹扫时间,解吸温度以及解吸时间对PT的影响。实验表明:大部分硫醚类和硫醇类化合物分别在1~100 ng/L和3~300 ng/L范围内线性良好,线性相关系数大于0.99;相对标准偏差小于9.47%(n=6);加标回收率为81.68%~115.18%。定量下限(10倍信噪比)范围从0.19 ng/L(二乙基二硫醚)到2.67 ng/L(2-甲基-1-丙硫醇)。采用此方法对北京市3条河流水样进行了检测,除1-丙基二硫醚和2-甲基-2-丙硫醇外,其他14种有机硫化物都有检出,质量浓度为1.95~1 282.35 ng/L。     

Short-term Distributions of Reduced Sulfur Compounds in the Ambient Air Surrounding a Large Landfill Facility

In order to explore the environmental behavior of reduced sulfur compounds (RSC) as malodorous components emitted from diverse source processes, the distribution characteristics of four sulfur (S) compounds - hydrogen sulfide (H₂S), methyl mercaptan (CH₃SH), dimethyl sulfide (DMS: (CH₃)₂S), and dimethyl disulfide (DMDS: (CH₃)₂S₂) – were investigated in a municipal landfill area. In the course of this study, their ambient concentration levels were measured during two time periods from 13 individual spots selected as a function of distance from the center of the landfill site. The results generally indicated the absolute dominance of H₂S over the other S compounds investigated (up to 5 km radius) such that their mean values were found as 1415 (H₂S), 148 (DMS), 20.6 (CH₃SH), and 14.4 ppt (DMDS). When our data were compared in terms of either varying distance from the source or relationship with meteorological conditions, the H₂S data sets were most evident to reflect the potential effects of strong source processes in the landfill environment, relative to other S gases (or to volatile organic compounds measured concurrently). The results of this study further indicated the relatively good correspondence between the measured H₂S concentration level and humans' intuitive sensory of odor and nuisance.     

Sample damage during X-ray fluorescence analysis--case study on ammonium salts in atmospheric aerosols

Atmospheric aerosols can consist of, amongst others, compounds like NH(4)NO(3) or (NH(4))(2)SO(4). Such components can suffer radiation damage and/or evaporate during EDXRF measurements, providing errors on successively applied analysis. The aim of this work is to investigate the influence of measurements using conventional EDXRF on the volatile compounds and to compare it with the influence of polarized beam EDXRF using secondary targets (and hence indirect irradiation). The effect of different parameters (acquisition time, accelerating voltage, current and medium) on the concentration loss was studied. The measurements performed in vacuum during a long period lead to the highest losses of volatile compounds. The influence of direct irradiation was proved to be larger than the indirect variant.     

Ammonia Monitoring in Switzerland with Passive Samplers: Patterns, Determinants and Comparison with Modelled Concentrations

Gaseous ammonia (NH3) is an important form of N deposition to ecosystems, but it is not being routinely monitored in Switzerland. Therefore, a study was conducted to estimate annual means and seasonal patterns of NH3 concentrations for different site types in Switzerland, and to compare annual measured and modelled NH3 concentrations. NH3 concentrations were measured using the 'Zürcher' passive sampler, a Palmes type sampler with an acidic solution as absorbent. Twenty-four sampling sites were run for one year, and 17 for two years. The samplers were changed fortnightly or monthly. Spatial emission patterns were mapped by combining information on (1) the location of emission sources, (2) national statistics on NH3-emitting activities and (3) activity-specific emission factors. The spatial resolution was one hectare. The mean annual NH3 concentration in the ambient air of the 41 sites was 2.5+/-0.3 microg m(-3) (mean+/-standard error). It ranged from 0.4 to 7.5 microg m(-3). The site type and the season were the most important factors explaining the variation in the seasonal mean concentration. NH3 concentrations were highest in intensively used agricultural areas and in cities, and lowest in Alpine sites remote from emission sources. At 39 out of 41 sites, the NH3 concentrations were higher in summer (3.1+/-0.3 microg m(-3)) than in winter (2.0+/-0.3 microg m(-3)). Modelled NH3 concentrations did not systematically deviate from measured concentrations (r2 = 0.69). With the combined monitoring and modelling approach, it is now possible to obtain a reasonable and consolidated picture of the overall NH3 situation in Switzerland.     

Triethoxysilyl-substituted aminoethanethiol ligands for zinc and cadmium complexes and aminoethanethiol-modified silica gel. Evaluation of the corresponding supported molecular trap for metallic pollutant uptake (Cd2+, Hg2+ and Pb2+)

The reaction of 2-[3-(triethoxysilyl)propylamino]ethanethiol (LH, a) and 1-methyl-2-[3-(triethoxysilyl)propylamino]ethanethiol (LH, b) with ZnX2 and CdX2 (X = Cl, Br, I, NO3) in tetrahydrofuran (THF) or CH2Cl2 gives several complexes depending on the experimental conditions. Elemental analyses, IR, Raman, 13C[1H], 1H NMR and mass spectroscopies indicated the formation of mononuclear and dinuclear complexes. In the absence of NEt3 as proton quencher, the protonated ligands react in their zwitterionic form giving dinuclear [M(LH)X2]2 [M = Zn (1), Cd (2); LH = a, b; X = Cl, Br, I] or mononuclear M(NO3)2(LH)2 [M = Zn (5), Cd (6); LH = a] complexes. In both cases, coordination occurs through the S atoms, the ligands acting as terminal and bridging species. With NEt3, the deprotonated ligands are chelated through their N and S atoms and bridging occurs through the S atoms in [MLX]2 [M = Zn (3), Cd (4); LH = a; X = Cl, Br] complexes. The LH ligand is chemically grafted onto silica, the procedure optimized and the resulting material characterized by 13C and 29Si cross-polarization, magic-angle spinning (CP-MAS) NMR and DRIFT. This material is evaluated as a supported molecular trap for binding heavy metals (Cd2+, Hg2+, Pb2+) in aqueous solution. In both batch and column processes, it appears that Hg2+ and Pb2+ are trapped more than Cd2+, but in all cases values lower than those allowed were obtained.     

Determination of CH4, CO2 and N2O in air samples and soil atmosphere by gas chromatography mass spectrometry, GC-MS

A method for determination of the climate gases CH4, CO2 and N2O in air samples and soil atmosphere was developed using GC-MS. The method uses straightforward gas chromatography (separation of the gases) with a mass spectrometric detector in single ion mode (specific determination). The gases were determined with high sensitivity and high sample throughput (18 samples h(-1)). The LOD (3sigma) for the gases were 0.10 micro L L(-1) for CH4, 20 microL L(-1) for CO2 and 0.02 microL L(-1) for N2O. The linear range (R2 = 0.999) was up to 500 microL L(-1) for CH4, 4000 microL L(-1) for CO2 and 80 microL L(-1) for N2O. The samples were collected in 10 mL vials and a 5 microL aliquot was injected on column. The method was tested against certified gas references, the analytical data gave an accuracy within +/-5% and a precision of +/-3%. The presence of < or = 10% by volume of C2H2 (often used experimentally to prevent N2 formation from N2O) did not interfere with detection for the targeted trace gases.     

Quality control and quality assurance for particle size distribution measurements at an urban monitoring station in Augsburg, Germany

Long-term observations of atmospheric constituents such as aerosol particles are increasingly needed to assess their impact on climate and human health. In contrast to particle mass concentration (MC), there are currently no standardized quality control (QC) and quality assurance (QA) procedures for the measurement of particle size distribution (PSD). This study describes some fundamental QC and QA procedures associated with the collection and evaluation of a 2 year dataset between 2005 and 2006 at an urban background monitoring site in Augsburg, Germany. The considered parametres include ambient PSD between 3 nm and 10 microm (merged from a twin differential mobility and an aerodynamic particle sizer, TDMPS and APS, respectively) as well as total particle number (TNC), length (LC) and MC determined by independent instruments. The hourly 1st and 0th moment of PSD showed good correlations with the independently measured LC (R(2) = 0.86) and TNC (R(2) = 0.79), respectively, the deviation for LC with 4% and for TNC with 22% being rather small. The volume concentration (3rd moment) of hourly measured PSD and the resultant MC (when assuming a realistic apparent density of 1.5 g cm(-3)) correlated well with the independently measured MC of PM(2.5) or PM(10) (R(2) > 0.86) and showed only small deviation from PM(2.5) (1%) or PM(10) (5%), respectively. The study demonstrates that the described QC and QA measures define both a high accuracy of the PSD measurements and their long-term comparability against data obtained in similar measurement programmes.     

Estimating the radon concentration in water and indoor air

The paper presents the results of radon concentration measurements in the vicinity of water, indoor air and in contact to building walls. The investigations were carried out using CR-39 track detectors. Samples of ground water flowing out of many springs mostly in Arabian Gulf area except one from Germany have been studied. The results are compared with international recommendations and the values are found to be lower than the recommended value. Measuring the mean indoor radon concentrations in air and in contact to building walls in the dwellings of Kuwait University Campus were found 24.2 +/- 7.7, and 462 +/- 422 Bq m(-3) respectively. These values lead to average effective dose equivalent rates of 1.3 +/- 0.4 and 23 +/- 21 mSv year(-1), respectively.     

Development of a simple extraction cell with bi-directional continuous flow coupled on-line to ICP-MS for assessment of elemental associations in solid samples

A continuous-flow system comprising a novel, custom-built extraction module and hyphenated with inductively coupled plasma-mass spectrometric (ICP-MS) detection is proposed for assessing metal mobilities and geochemical associations in soil compartments as based on using the three step BCR (now the Measurements and Testing Programme of the European Commission) sequential extraction scheme. Employing a peristaltic pump as liquid driver, alternate directional flows of the extractants are used to overcome compression of the solid particles within the extraction unit to ensure a steady partitioning flow rate and thus to maintain constant operationally defined extraction conditions. The proposed flow set-up is proven to allow for trouble-free handling of soil samples up to 1 g and flow rates < or =10 mL min(-1). The miniaturized extraction system was coupled to ICP-MS through a flow injection interface in order to discretely introduce appropriate extract volumes to the detector at a given time and with a given dilution factor. The proposed hyphenated method demonstrates excellent performance for on-line monitoring of major and trace elements (Ca, Mn, Fe, Ni, Pb, Zn and Cd) released when applying the various extracting reagents as addressed in the BCR scheme, that is, 0.11 M CH(3)COOH, 0.1 NH(2)OH.HCl and 30% H(2)O(2), even when a well recognized matrix-sensitive detector, such as ICP-MS, is used. As a result of the enhanced temporal resolution of the ongoing extraction, insights into the breaking down of phases and into the kinetics of the metal release are obtained. With the simultaneous multielement detection capability of ICP-MS, the dynamic fractionation system presents itself as an efficient front-end for evaluation of actual elemental association by interelement comparison of metals leached concurrently during the extraction time. Thus, the intimate elemental association between Cd and Zn in contaminated soils could be assessed.     

Passive ammonia monitoring in the United States: comparing three different sampling devices

The need for ambient gaseous ammonia (NH(3)) measurements has increased in the last decade as reactive NH(3) concentrations and deposition fluxes show little change even with tightening standards on nitrogen oxides (NO(x)) emissions. Currently, there are several networks developing methods for adding NH(3) measurements in the U.S. Gaseous NH(3) measurements will provide scientists and policymakers data which can be used to estimate ecosystem inputs, validate air quality models including trends and regional variability, and evaluate changes to the environment based on additional emission reduction requirements and estimates of critical nitrogen load exceedances. The passive samplers described in this paper were deployed in duplicate or triplicate and collocated with annular denuders or continuous instruments to determine their accuracy. The samplers assessed included the Adapted Low-Cost Passive High Absorption (ALPHA), Radiello(?), and Ogawa passive samplers. The median relative percent differences (MRPD) between the reference method and passive samplers for the ALPHA, Radiello(?) and Ogawa were -2.4%, -37% and -44%, respectively. The precision between duplicate samplers for the ALPHA and Ogawa samplers, was 7% and 6%, respectively. Triplicate Radiello(?) precision was assessed using the coefficient of variation (CV). The CV for the Radiello(?) samplers was 10%. This article discusses the statistical results from these studies.