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1.
The Peroxy Radical Chemical Amplifier (PERCA) technique is a proven method for measurement of ambient levels of peroxy radicals at ground level, but there are no published instances of the technique being used on an aerial platform. Here we describe deployment of a PERCA on the former UK Meteorological Office C-130 Hercules research aircraft. The instrument uses the established method of chemical amplification and conversion of peroxy radicals to nitrogen dioxide (NO2) by doping the sample air-flow matrix with CO and NO, subsequently measuring the NO2 yield with an improved 'Luminox' LMA-3 NO2 detector. NO2 from the amplification chemistry is distinguished from other sources of NO2 reaching the detector by periodically injecting CO approximately 1 s downstream of the NO injection point (termination mode). Chain lengths (CL's) for the amplification chemistry were typically approximately 260 (ground level) to approximately 200 (7,000 m). This variation with altitude is less than the variation associated with the 'age' of the PFA inlet material where the amplification chemistry occurs; CL's of approximately 200 with old tubing to approximately 300 with new clean tubing were typical (ground level values). The CL determinations were made in-flight using an onboard calibration unit based on the 254 nm photolysis of 7.5 to 10 parts per billion (by volume, ppbv) of CH3I in air, producing CH3O2 in a quantitative manner. The noise-equivalent detection limit for peroxy radicals (HO2 + RO2) is 2 parts per trillion (by volume, pptv) at 3,650 m when the background ambient ozone levels are stable, based on a 5 min average of five 30 s amplification cycles and five 30 s termination cycles. This detection limit is a function of several factors but is most seriously degraded when there is large variability in the ambient ozone concentration. This paper describes the instrument design, considers its performance and proposes design improvements. It concludes that the performance of an airborne PERCA in the free troposphere can be superior to that of ground-based instruments when similar sampling frequencies are compared.  相似文献   

2.
We have examined the sensitivity of sequential two photon laser induced fluorescence (LIF) detection of elemental mercury, Hg(0) in the gas phase. The most sensitive approach involves an initial laser excitation of the 6(3)P1-6(1)S0 transition at 253.7 nm, followed by excitation with a second laser to the 7(1)S0 level. Blue shifted fluorescence is observed on the 6(1)P1-6(1)S0 transition at 184.9 nm. The excitation scheme, involving sequential excitation of two atomic transitions, followed by detection of the emission from a third is extremely specific and precludes detection of anything other than atomic mercury. Using our 10 Hz laser system we have achieved a detection sensitivity of 0.1 ng m(-3) at a sampling rate of 0.1 Hz, i.e. averaging 100 laser shots at a pressure of one atmosphere in air. At low concentrations we sampled simultaneously with an automated mercury analyzer (Tekran 2537A), to ensure accuracy. We have examined the linearity of the technique, generating flows containing mercury concentrations between 1 and 10,000 ng m(-3) using a permeation tube and dynamic dilution, but relying on the concentrations given by the Tekran at low levels and the concentration calculated from dilution at high levels. We find that the detection is linear over the five orders of magnitude that we were able to vary the concentration. Our measured detection limits in He and Ar are much lower as these gases are inefficient fluorescence quenchers.  相似文献   

3.
We present in this paper fifteen years' measurements, from March 1991 to September 2005, of stratospheric NO2 vertical columns measured by a SAOZ zenith-sky visible spectrometer. The instrument spent most of its time at Aberystwyth, Wales, with occasional excursions to other locations. The data have been analysed with the WinDOAS analysis program with low-temperature high-resolution NO2 cross-sections and fitting a slit function to each spectrum. Because of a change in detector in May 1998 there is some uncertainty about the relative changes before and after this date, which are partially constrained by the results of an intercomparison exercise. However, the effect of the Mt Pinatubo aerosol cloud is very evident in the data from 1991-94, with a decrease of 10% in NO2 in the summer of 1992 (the SAOZ was located in Lerwick, Scotland during the winter of 1991-92 and observed very low NO2 values but these cannot be directly compared to the Aberystwyth data). To focus more on interannual and long-term variations in NO2, a seasonal variation comprising an annual and semi-annual component was fitted to the morning and evening twilight separately from 1995 to the present. This fit yielded average NO2 columns of 4.08 x 10(15) cm(-2) and 2.68 x 10(15) cm(-2) for the evening and morning twilight, respectively, with a corresponding annual amplitude of +/-2.08 x 10(15) cm(-2) and +/-1.50 x 10(15) cm(-2). Departures from the fitted curve show a trend of 6% per decade, consistent with that reported elsewhere, for the period 1998-2003, but in the past two years a distinct interannual variation of amplitude of approximately 8% has emerged.  相似文献   

4.
An ion selective electrode (ISE) for the measurement of Cr(VI), using supported liquid membranes (SLMs), containing tricaprylmethyl ammonium chloride (Aliquat336), was investigated in this study. Aliquat336, as a carrier, had a high selectivity for Cr(VI) in the presence of interfering ions, in the order SO4(2-) > CO3(2-) > Cl(-) > NO2(-) > NO3(-) > I(-) > SCN(-). The composition of the SLM for the detection of Cr(VI) was optimized at 0.169 mL Aliquat336 mL(-1) NPOE (o-nitrophenyl octyl ether) 0.5 g Poly (vinyl chloride), for the preparation of a 19.6 cm2 sheet. The Cr(VI) concentrations were measured, using the SLM prepared in the study, in the range 2.023 x 10(-5) to 0.1 M (1.052 to 5200 ppm). It seemed that the Cr(VI) was transported as a negatively charged monovalent ion, as indicated by the slope of the electromotive force (emt) response. The selectivity coefficients and detection limits for the Cr(VI). against the interfering ions, were determined experimentally using the fixed interference (FIM) and the separate solution methods (SSM).  相似文献   

5.
Traffic emission factors of ultrafine particles: effects from ambient air   总被引:1,自引:0,他引:1  
Ultrafine particles have a significant detrimental effect on both human health and climate. In order to abate this problem, it is necessary to identify the sources of ultrafine particles. A parameterisation method is presented for estimating the levels of traffic-emitted ultrafine particles in terms of variables describing the ambient conditions. The method is versatile and could easily be applied to similar datasets in other environments. The data used were collected during a four-week period in February 2005, in Gothenburg, as part of the G?te-2005 campaign. The specific variables tested were temperature (T), relative humidity (RH), carbon monoxide concentration (CO), and the concentration of particles up to 10 μm diameter (PM(10)); all indicators are of importance for aerosol processes such as coagulation and gas-particle partitioning. These variables were selected because of their direct effect on aerosol processes (T and RH) or as proxies for aerosol surface area (CO and PM(10)) and because of their availability in local monitoring programmes, increasing the usability of the parameterization. Emission factors are presented for 10-100 nm particles (ultrafine particles; EF(ufp)), for 10-40 nm particles (EF(10-40)), and for 40-100 nm particles (EF(40-100)). For EF(40-100) no effect of ambient conditions was found. The emission factor equations are calculated based on an emission factor for NO(x) of 1 g km(-1), thus the particle emission factors are easily expressed in units of particles per gram of NO(x) emitted. For 10-100 nm particles the emission factor is EF(ufp) = 1.8×10(15)×(1 - 0.095×CO - 3.2×10(-3)×T) particles km(-1). Alternative equations for the EFs in terms of T and PM(10) concentration are also presented.  相似文献   

6.
We developed a method to analyze atmospheric SO(x) (particulate SO(4)(2-)+ gaseous SO(2)) and NO(x) (NO + NO(2)) simultaneously using a battery-operated portable filter pack sampler. NO(x) determination using a filter pack method is new. SO(x) and NO(x) were collected on a Na(2)CO(3) filter and PTIO (2-phenyl-4,4,5,5-tetramethylimidazoline-3-oxide-1-oxyl) + TEA (triethanolamine) filters (6 piled sheets), respectively. Aqueous solutions were then used to extract pollutants trapped by the filters and the resulting extracts were pre-cleaned (e.g. elimination of PTIO) and analyzed for sulfate and nitrite by ion chromatography. Recoveries of SO(2) and NO(x) from standard pollutant gases and consistency of the field data with those from other instrumental methods were examined to evaluate our method. SO(x) and NO(x) could be analyzed accurately with determination limits of 0.2 ppbv and 1.0 ppbv (as daily average concentrations), respectively. The sampler can determine SO(x) and NO(x) concentrations at mountainous or remote sites without needing an electric power supply.  相似文献   

7.
3, 4-Dihydroxybenzaldehydeisonicotinoylhydrazone was prepared, characterized with spectral analyses and used for developing a new method for the simple, sensitive and rapid spectrophotometric determination of vanadium(V) which gives maximum absorbance at wave length 360 nm. The metal ion gives a yellow colored complex with 3, 4-DHBINH in acetate buffer of pH 5.5 with 1:1 (metal:ligand) composition. The method obeys Beer's law in the range 0.5-5.3 mug mL(-1) of vanadium(V). The molar absorptivity and Sandell's sensitivity were found to be 1.29 x 10(4) L mol(-1) cm(-1) and 0.003949 mug cm(-2) respectively. The correlation co-efficient of the V(V)-3, 4-DHBINH complex was 0.992 which indicated an excellent linearity between the two variables. The repeatability of the method was checked by finding the relative standard deviation (RSD) as 0.424% (n = 5), and its detection limit 0.01677 mug mL(-1) of vanadium(V). The instability constant of the method was calculated by Asmus' method as 4.1666 x 10(-3). The interfering effect of various cations and anions were also studied. The proposed method was successfully applied to the determination of vanadium(V) in environmental samples (water and soil) tobacco leaves and alloy samples. The validity of the method was tested by comparing the results with those obtained using an atomic absorption spectrophotometer.  相似文献   

8.
The purpose of this paper is to review the literature to characterize infiltration rates from landfill liners to support groundwater modeling efforts. The focus of this investigation was on collecting studies that describe the performance of liners 'as installed' or 'as operated'. This document reviews the state of the science and practice on the infiltration rate through compacted clay liner (CCL) for 149 sites and geosynthetic clay liner (GCL) for 1 site. In addition, it reviews the leakage rate through geomembrane (GM) liners and composite liners for 259 sites. For compacted clay liners (CCL), there was limited information on infiltration rates (i.e., only 9 sites reported infiltration rates.), thus, it was difficult to develop a national distribution. The field hydraulic conductivities for natural clay liners range from 1 x 10(-9) cm s(-1) to 1 x 10(-4) cm s(-1), with an average of 6.5 x 10(-8) cm s(-1). There was limited information on geosynthetic clay liner. For composite lined and geomembrane systems, the leak detection system flow rates were utilized. The average monthly flow rate for composite liners ranged from 0-32 lphd for geomembrane and GCL systems to 0 to 1410 lphd for geomembrane and CCL systems. The increased infiltration for the geomembrane and CCL system may be attributed to consolidation water from the clay.  相似文献   

9.
The emission of nitrogen compounds from power plants accounts for a significant proportion of the total emissions of nitrogen to the atmosphere. This study seeks to understand the nature of chemical reactions in the atmosphere involving nitrogen, which is important in undertaking quantitative assessments of the contribution of such reactions to local and regional air pollution. The slant column density (SCD) of power-plant-generated NO(2) was derived using imaging differential optical absorption spectroscopy (I-DOAS) with scattered sunlight as a light source. The vertical structure of NO(2) SCD from power plant stacks was simultaneously probed using a pushbroom sensor. Measured SCDs were converted to mixing ratios in calculating the rate of NO(2) increase at the center of the plume. This study presents quantitative measurements of the rate of NO(2) increase in a rising plume. An understanding of the rate of NO(2) increase is important because SO(2) and NO(x) compete for the same oxidizing radicals, and the amount of NO(x) is related to the rates of SO(2) oxidation and sulfate formation. This study is the first to directly obtain the rate of NO(2) increase in power plant plumes using the I-DOAS technique. NO(2) increase rates of 60 and 70 ppb s(-1) were observed at distances of about 45 m from the two stacks of the Pyeongtaek Power Plant, northwest South Korea.  相似文献   

10.
On-site continuous measurement of nitrate in the River Taw situated in Devon (UK) was performed automatically for two months using a recently developed ion-selective electrode (ISE). A non-submersible electrode support system was developed and a field instrument was constructed comprising the nitrate-ISEs, a reference electrode and a temperature probe connected through a pre-amplifier to a data-logger and battery supply. The nitrate-ISE was constructed using a commercially available electrode body with a membrane incorporated into the tip. This rubbery membrane contained the sensor molecule (N,N,N-triallylleucine betaine chloride, 6.5% m/m) covalently bound to polystyrene-block-polybutadiene-block-polystyrene, SBS, (43.5% m/m), with 2-nitrophenyloctyl ether (2-NPOE) as mediator (40% m/m). The Nernstian slope was -59.1 mV per decade over a linear range of 1400-0.07 mg L(-1) nitrate-N. The limit of detection was 0.007 mg L(-1) nitrate-N with a selectivity coefficient for nitrate against chloride (k(pot)NO3-, Cl-) of 3.4 x 10(-3). The speed of response was less than a minute over the linear Nernstian range. The lifetime in the laboratory exceeded 5 months with no potentiometric drift over the linear Nernstian range. A temperature correction algorithm was also used to accomodate the temperature changes encountered in the river. The river nitrate results obtained with the ISEs at hourly intervals compared very favourably (R2 = 0.9) with those obtained with laboratory automated chemical determinations made on contemporaneous river samples over a concentration range 0.55-2.00 mg L(-1) nitrate-N. The ISEs did not require re-calibration and no deterioration in performance or fouling of the membrane surface was observed during 40 days.  相似文献   

11.
A field campaign on aerosol chemical properties and trace gases measurements was carried out along the Delhi-Hyderabad-Delhi road corridor (spanning about 3,200 km) in India, during February 1-29, 2004. Aerosol particles were collected on quartz and cellulose filters using high volume (PM(10)) sampler at various locations along the route (i.e., urban, semi-urban, rural, and forest areas) and have been characterized for major cations (Na(+), Ca(2+), Mg(2+), K(+), and NH (4) (+)), anions (Cl(-), NO (3)(-), and SO (4)(2-)), and heavy metals (Cu, Cd, Fe, Zn, Mn, and Pb). Simultaneously, we measured NO(2) and SO(2) gases. These species show large spatial and temporal variations. The ambient PM(10) concentration has been observed to be the highest (55 ± 4 μg m(-3)) near semi-urban areas followed by forest areas (48 ± 2 μg m(-3)) and in rural areas (44 ± 22 μg m(-3)). The concentrations of NO( x ) (NO(2)+NO) and SO(2) ranged from 16 to 69 μg m(-3) and 4 to 11 μg m(-3), respectively. Among anions, NO(3)(-) and SO(4) (2-) are the major constituents of PM(10). The urban and semi-urban sites showed enhanced concentrations of Fe, Zn, Mn, Cd, and Pb. This study provide information about atmospheric concentrations of various species in the northern to central India, which may be important for policy makers to better understand the air quality of the region.  相似文献   

12.
研究了在溴代十六烷基吡啶(CPB)、正丁醇、正庚烷、水自制微乳溶液存在下,镍与二溴对甲偶氮羧(DBpMCA)的显色反应,在pH值为9.07的Na2B4O7-HCl缓冲溶液中,镍与试剂形成淡红色配合物,最大吸收峰位于560nm波长处,表观摩尔吸光系数ε为2.8×10^5L/(mol·cm)。优化了试验条件,考察了共存离子的影响,方法在0.002mg/L~0.320mg/L范围内符合比尔定律,检出限为0.0006mg/L,生活垃圾、水、土壤样品测定的RSD为2.1%~5.2%,加标回收率为96.6%~104%。  相似文献   

13.
The Po valley in northern Italy is renowned for its high air pollutant concentrations. Measurements of air pollutants from a background site in Modena, a town of 200 thousand inhabitants within the Po valley, are analysed. These comprise hourly data for CO, NO, NO(2), NO(x), and O(3), and daily gravimetric equivalent data for PM(10) from 1998-2010. The data are analysed in terms of long-term trends, annual, weekly and diurnal cycles, and auto-correlation and cross-correlation functions. CO, NO and NO(2) exhibit a strongly traffic-related pattern, with daily peaks at morning and evening rush hour and lower concentrations over the weekend. Ozone shows an annual cycle with a peak in July due to local production; notwithstanding the diurnal cycle dominated by titration by nitrogen oxide, the decreasing long term trend in NO concentration did not affect the long term trend in O(3), whose mean concentration remained steady over the sampling period. PM(10) shows a strong seasonality with higher concentration in winter and lower concentration in summer and spring. Both PM(10) and ozone show a marked weekly cycle in summer and winter respectively. Regressions of PM(10) upon NO(x) show a consistently greater intercept in winter, representing higher secondary PM(10) in the cooler months of the year. There is a seasonal pattern in primary PM(10) to NO(x) ratios, with lower values in winter and higher values in summer, but the reasons are unclear.  相似文献   

14.
A new simple, rapid selective and highly sensitive chromogenic reagent dibromo-p-methyl-carboxyazo (DBMCA) was synthesized and studied in detail for the spectrophotometric detection of lead. In 0.25 M phosphoric acid medium, which greatly increases the selectivity, Lead reacts with DBMCA to form a 1:2 blue complex having a sensitivity absorption peak at 646 nm. Under optimal conditions, Beer's Law is obeyed over the range from 0.09 to 0.8 microg mL(-1) Pb (II) and the apparent molar absorptivity is 1.03 x 10(5) mL(-1) cm(-1). The detection limit and the variation coefficient were found to be 2.12 microg mL(-1) and 1.0% respectively. It is found that, except for Ca (II) and Ba (II) all foreign ions studied do not interfere with detection. The interference caused by Ca (II) and Ba (II) can be easily eliminated by prior extraction with potassiumiodide-methylisobutylketone. The proposed method has been applied successfully for to the detection of Lead in vegetable leaves with good results.  相似文献   

15.
The use of underwater optical sensors to monitor pollution and climate change processes has led to the development of robust instruments able to be deployed in lakes and seas for months at a time. However, despite this improvement in their durability they are subject to biofouling on their optical ports resulting in erroneous readings. The use of hydrogel coatings containing the cationic surfactant benzalkonium chloride (BAC) has been shown to prevent the development of biofouling for up to 12 weeks in the marine environment. In this study the use of hydrogel coatings in the freshwater environment was less successful with fouling visible at 2 weeks. In both field and laboratory studies a rapid initial loss of BAC from the hydrogel film was observed. The loss is a combination of diffusive and mass flow but the period from 12 to 50 h appeared to fit to diffusion kinetics and a diffusion coefficient of 7.3 x 10(-8) cm2 s(-1) (13 degrees C) was calculated, an order of 10 times greater than that found in seawater. Subsequently the rate of loss of the residual BAC, for which a diffusion coefficient of 5.7 x 10(-10) cm2 s(-1) (15 degrees C) was measured, was too low to prevent the early stages of biofouling.  相似文献   

16.
Emissions of volatile chemicals control the hydroxyl radical (OH), the atmosphere's main cleansing agent, and thus the production of secondary pollutants. Accounting for all of these chemicals can be difficult, especially in environments with mixed urban and forest emissions. The first direct measurements of the atmospheric OH reactivity, the inverse of the OH lifetime, were made as part of the Southern Oxidant Study (SOS) at Cornelia Fort Airpark in Nashville, TN in summer 1999. Measured OH reactivity was typically 11 s(-1). Measured OH reactivity was 1.4 times larger than OH reactivity calculated from the sum of the products of measured chemical concentrations and their OH reaction rate coefficients. This difference is statistically significant at the 1sigma uncertainty level of both the measurements and the calculations but not the 2sigma uncertainty level. Measured OH reactivity was 1.3 times larger than the OH reactivity from a model that uses measured ambient concentrations of volatile organic compounds (VOCs), NO, NO2, SO2, and CO. However, it was within approximately 10% of the OH reactivity from a model that includes hydrocarbon measurements made in a Nashville tunnel and scaled to the ambient CO at Cornelia Fort Airpark. These comparisons indicate that 30% of the OH reactivity in Nashville may come from short-lived highly reactive VOCs that are not usually measured in field intensive studies or by US EPA's Photochemical Assessment Monitoring Stations.  相似文献   

17.
A canister-based 1 week sampling method using a mechanical flow controller and a 6 L fused-silica-lined canister was evaluated for the long-term measurement of 47 VOCs in ambient air at pptv (volume/volume) to ppbv levels by use of a three-stage preconcentation method followed by GC-MS analysis. The GC conditions were initially optimized for complete separations of several pptv-level VOCs (e.g. vinyl chloride, 1,3-butadiene, acrylonitrile, 1,2-dichloroethane and chloroform) in ambient air because the selected ions are easily interfered with by coexisting C4-, C5-hydrocarbons and analytes presented at ppbv levels. Thirty-four VOCs determined by the 1 week and 24 h sampling method in December 16-22 (2002) had concentrations of 6.0-15000 pptv per compound. Concentrations of 28 VOCs (including polar VOCs (e.g. methyl isobutyl ketone and butyl acetate)) obtained by the method were approximately equal to the mean values calculated from 24 h sampling (< +/- 10% deviation). Six VOCs that had low concentrations of 6.0-43 pptv showed more than +/- 10% deviation. Thirteen VOCs were not detected during the entire sampling period. The effect of relative humidity or ozone for the specific VOCs (e.g. MIBK, butyl acetate, vinyl chloride, 1,3-butadiene and styrene) was negligible.  相似文献   

18.
A diffusive gradient in thin films (DGT) technique for measuring methylmercury (MeHg) concentrations in natural waters was developed using 3-mercaptopropyl-functionalized silica gel to preconcentrate the methylmercury. The new resin was characterized and calibrated. Methylmercury is efficiently accumulated at a pH range of 3-9. Basic performance tests of the new DGT device confirmed the applicability of Fick's first law for such DGT measurements. The diffusion coefficient of methylmercury in polyacrylamide gel was 5 x 10(-6) cm(2) s(-1). Methylmercury concentrations determined by DGT deployed for different time periods in the field are statistically not different from results obtained through direct measurements. The DGT technique represents therefore an alternative in situ sampling method for methylmercury. The detection limit of the overall method is 1 pg of MeHg, which correspond to approximately 30 pg L(-1) of MeHg in a water sample, when deploying a typical DGT device for 24 hours. Lower MeHg concentrations are measurable using longer deployment times or thinner diffusive gel layers.  相似文献   

19.
选取汽油车尾气中CO、HC、NO等3种气态污染物,以稳态工况法为基准,与车辆实际行驶时的遥感测试结果比对,从而制定相应的排放控制限值。建议遥感检测法对于CO、HC、NO的限值,2001年10月1日前注册登记的汽油车分别为3.0%、1000×10-6、3500×10-6,2001年10月1日起注册登记的汽油车分别为2.0%、500×10-6、2000×10-6。提出当机动车所有人对检测结果有异议时,可在规定期限内至指定机构按年检方法复检。  相似文献   

20.
A combined NO2-SO2 Radiello radial-type diffusive sampler was validated under controlled laboratory conditions and compared with NO2-SO2 results of 3 other type of samplers in a field comparison at two locations Ghent-Mariakerke and Borgerhout in Flanders. Laboratory exposures at different temperatures (-5, 10 and 30 degrees C) and relative humidities (0, 50 and 80% RH) in combination with varying concentration levels and exposure times were carried out, with a focus on extreme conditions. Concentration level and exposure time were changed together following suppliers linear working range of samplers and assuring absolute amounts of compounds on the sampler corresponding to those of environmental levels. The average uptake rate for NO2 for 24 hour exposures at 10 degrees C and 50% RH and tested concentration levels (+/-73, 146 and 293 ppb NO2) was 0.076 +/- 0.011 ng ppb(-1) min(-1). Uptake rates during all experiments were lower than the uptake rate given in the instruction manual of the sampler. A significant effect of temperature and relative humidity on NO2 uptake rate was observed. The temperature effect from 10 to 30 degrees C corresponds to the temperature effect given by the supplier of the samplers. High relative humidity (70 to 80%) caused a strong non-reproducible decrease of uptake rate for NO2 at 24 hour experiments but this effect was not observed at longer exposures except for the tests at -5 degrees C. At the tested temperature below zero in combination with high relative humidity the sampler showed anomalous behaviour for NO2. The possible effect of concentration level and exposure time for NO2 needs further research. The average uptake rate for SO2 calculated from all exposures is 0.478 +/- 0.075 ng of sulfate ion each ppb min of SO2 and accords to suppliers uptake rate. No clear effects of temperature, relative humidity or concentration level/exposure time on the uptake rate for SO2 were found, partly due to the large scatter of results. Although NO2 accuracy of Radiello samplers was better during field campaigns than during laboratory validation, IVL and OGAWA samplers gave better results for NO2. In the field, IVL samplers showed best agreement with the continuous analyzers for both NO2 and SO2.  相似文献   

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