电感耦合等离子体发射光谱法测定腐殖酸中的硼

用NHO3和HCl的混合酸分解腐殖酸样品，选用波长208.96nm于ICP测定。分析结果与比色法、容量法吻合。相对标准偏差为1.05%，回收率为97.87%－104.45%。     

微波消解-ICP/MS法同时测定水产品中13种元素

用硝酸-双氧水体系微波消解，以In、Sc为内标，采用电感耦合等离子体质谱法（ICP／MS）同时测定水产品中V、Cr、C0、Ni、Cu、Zn、As、Se、Cd、Sb、Ba、T1、Pb等13种元素。各元素的检出限在0．05ng／g～0．064μg／g之间，样品平行测定4次的RSD〈5％，鲢鱼样品的加标回收率在81％～117％之间。     

Characterisation of gaseous and particulate atmospheric pollutants in the East Mediterranean by diffusion denuder sampling lines

A field study aimed to characterize atmospheric pollutants in the gaseous and the particulate phases was conducted during the fall-winter of 2004 and the summer of 2005 in the Ashdod area, Israel. The site is influenced by both anthropogenic sources (power plants, refineries, chemical and metal industries, a cargo port, road traffic) and natural sources (sea-spray and desert dust). The use of diffusion lines--a series of annular diffusion denuders for sampling gaseous compounds followed by a cyclone and a filter pack for determining PM(2.5) composition--allowed a good daily characterization of the main inorganic compounds in both the gaseous (HCl, HNO(3), SO(2), NH(3)) and the particulate phase (Cl(-), NO(3)(-), SO(4)(=), NH(4)(+), and base cations). During the summer campaign two other activities were added: an intensive 3-h sampling period and the determination of PM(2.5) bulk composition. The results were interpreted on the basis of meteorological condition, especially the mixing properties of the lower atmosphere as determined by monitoring the natural radioactivity due to Radon progeny, a good proxy of the atmospheric ability to dilute pollutants. Several pollution episodes were identified and the predominance of different sources was highlighted (sea-spray, desert dust, secondary photochemical pollutants). During the summer period a considerable increase of nitric acid and particulate sulphate was observed. Secondary inorganic pollutants (nitrate, sulphate and ammonium) constituted, on the average, 57% of the fine particle fraction, organic compounds 20%, primary anthropogenic compounds 14%, natural components (sea-spray and crustal elements) 9%. The advantages of the diffusion lines in determining gaseous and particulate N- and S- inorganic compounds are discussed.     

Preservation of sulfidic waters containing dissolved As(III)

Solutions containing variable concentrations of sulfide (0 to 31 ppm) and arsenite (0.35 to 10 ppm) were subjected to several different preservation treatments. As predicted by equilibrium thermodynamics, at near-neutral pH the experimental solutions were undersaturated with respect to orpiment (As2S3). However, upon acidification to pH 2 with HCl or HNO3, instantaneous precipitation of poorly crystalline As2S3 occurred in sulfidic solutions which resulted in the loss of dissolved arsenite. These results have implications concerning the practice of acidifying water samples containing hydrogen sulfide with HCl or HNO3 for the purpose of preserving total arsenic values. If a near-neutral water sample contains 1 ppm arsenite and as little as 0.4 ppm sulfide, loss of dissolved arsenic will occur upon acidification. An alternative three-step preservation method involving base addition, oxidation, and acidification is proposed and investigated as an appropriate technique for preserving sulfide-bearing aqueous samples for total arsenic.     

Solid phase extraction of gold(III) on silica gel modified with benzoylthiourea prior to its determination by flame atomic absorption spectrometry

A new method has been developed for the determination of gold based on separation and preconcentration using silica gel modified with benzoylthiourea. The optimum experimental parameters for preconcentration of gold, such as acid concentration, sample flow rate, eluent and matrix ions, have been investigated. Gold could be quantitatively retained in the 0.25-2.0 mol L(-1) HCl and HNO(3) concentrations, and then eluted completely with 0.5 mol L(-1) thiourea in 1.0 mol L(-1) HCl. The sorption capacity of gold(III) is 0.92 +/- 0.04 mmol g(-1) with a high enrichment factor of 267. The relative standard deviation of the method, RSD%, was found as 1.2% for 0.1 microg mL(-1). The detection limit for gold was 1.4 microg L(-1). The validation of the proposed method was checked by the analysis of certified reference soil materials. The presented procedure was applied to the determination of gold in some environmental samples.     

Utilization of the solid sorbent media in monitoring of airborne cyclophosphamide concentrations and the implications for occupational hygiene

The main objective of the study was to evaluate the applicability of two solid sorbent media (Anasorb 708 and Strata X), the impinger filled with distilled water and PTFE filters for determination of airborne cyclophosphamide (CP) in the hospital working environment. For this purpose, air contamination of Masaryk Memorial Cancer Institute (Czech Republic) was monitored using the sampling apparatus containing the samplers described above. In addition, the surface contamination was also determined using the wipe sampling technique. During the monitoring, contamination of three different workplaces (storage room, preparation room and outpatient clinic) was studied. Using Strata X solid sorbent tubes, airborne CP was determined in all (n = 5) samples collected at the outpatient clinic over a 5 day monitoring period (concentration range: 0.3-4.3 ng m(-3)). Other samplers (including PTFE filters) did not collect any detectable amount of CP (the limit of detection, LOD ≤ 0.1 ng m(-3)). Negative results detected at filter samples indicate that CP determined at Strata X samples was most probably of gaseous origin. Surface contamination ranged from <2 to 19, <8 to 418 and 133-15,500 pg cm(-2) at the storage room, preparation room and outpatient clinic, respectively. The study showed that evaporation of antineoplastic drugs should not be neglected, albeit the concentrations determined in our study are relatively low. Therefore, proper monitoring of airborne contamination should involve simultaneous sampling of both particle-bonded and gaseous phases. In this way, Strata X sorbent tubes seem to be an effective tool for the sampling of gaseous CP in the indoor air.     

ICP-AES法和分光光度法测定工业废水中总磷的方法比较

用ICP-AES法和分光光度法同时测定4种不同工业废水中的总磷含量,将2种方法的测定结果作比对。试验表明,ICP-AES法对国家标准样品的测定结果具有较高的准确度和精密度,4种废水样品测定结果的加标回收率为94.0%~110%,RSD在0.9%~3.2%之间。分光光度法适用于低浓度、低干扰样品的测定,对于高浓度含磷废水,取样体积和样品稀释倍数均会对其测定结果产生显著影响。消解样品经浊度-色度补偿后,分光光度法的测定结果精密度较低。     

影响非甲烷总烃监测结果准确性的因素研究及控制

结合非甲烷总烃监测工作实际情况,对样品采集、保存与运输、分析测试与数据处理、采样容器清洗与保存等过程详细研究后发现,采样容器从样品中吸附吸收的难挥发性与高化学活性组分和其自身的本底干扰对监测结果准确性的影响最严重,且其中残留的污染物使用传统方法难以消除。为此,通过改进采样容器清洗方法、完善相关质控措施和制定采样容器合格清洗与分类管理的判断依据,以降低各影响因素对非甲烷总烃监测结果准确性的影响。     

The use of isotopes to identify landfill gas effects on groundwater

An evaluation of the source of volatile organic compounds in groundwater samples was performed at a landfill in southern California. The 3H (tritium) content of the water in leachate and water from the gas-collection system (condensed water and entrained water droplets) and the delta 13C and 14C content of the inorganic carbon in landfill gas CO2, leachate, and gas-collection system water were used to characterize the dissolved inorganic carbon (DIC) inside the landfill, while the same parameters were monitored in groundwater samples from affected monitoring wells and an unaffected well. Tritium levels from leachate and gas-collection system condensate ranged from approximately 2000 TU to over 4000 TU, orders of magnitude higher than unaffected groundwater. The average 14C content of DIC in the landfill pore-water samples was 121 pMC and the 14C content of unaffected groundwater DIC was 93 pMC, while the 14C content of the dissolved inorganic carbon in groundwater with VOC detections ranged from 105 to 119 pMC. The delta 13C of DIC in pore water was consistently above 0 per thousand and the delta 13C of unaffected groundwater DIC was -20.3 per thousand, while the delta 13C of DIC in affected groundwater samples was increased from -17.3 to -13.2 per thousand. The increases in both delta 13C and 14C in landfill gas-impacted groundwater DIC generally correlated with the number of volatile organic compounds detected and their concentrations. Based on the tritium and DIC 14C levels in leachate and water from the gas-collection system compared to those of unaffected water, significant increases in the tritium content of the water would be expected to accompany VOC detections and increases in delta 13C and 14C caused by landfill water. The results rule out landfill water as the VOC source, leaving landfill gas as the source. The identities and concentrations of the specific VOCs in affected groundwater samples varied among wells as well as between two leachate samples, ruling out the use of a VOC "fingerprint" for leachate or landfill gas to be compared to groundwater VOC concentrations.     

空气-乙炔火焰原子吸收法测铬时的干扰及消除

对空气-乙炔火焰原子吸收法测铬(Cr)时共存元素对其测定结果的干扰进行研究。结果表明,当ρ(共存元素)/ρ(Cr)100时,Mg、Co、Al、V、Ni、Fe、Na、Ca对Cr测定有影响,而K、Mn、Zn、Mo、Pb、Si、Cu均不影响Cr的测定;当ρ(共存元素)/ρ(Cr)为10和30时,加入1%HNO_3和2%NH_4Cl可消除干扰;当ρ(共存元素)/ρ(Cr)30时,加入5%HCl和超过1%的NH_4Cl可消除干扰;5%HCl作为介质消除Cr测定干扰的效果要优于1%HNO_3介质。     

顶空-气相色谱-质谱法测定水中痕量丁基黄原酸

建立了顶空-气相色谱-质谱联用测定水中丁基黄原酸的方法。丁基黄原酸在酸性条件下分解成易挥发的二硫化碳,可用顶空-气相色谱分离、质谱定量测定。与传统的分光光度法相比,该法简便、快捷,在0.010～1.00 mg/L范围内线性良好,准确度高,加标回收率为95.1%～100.6%,精密度好,相对标准偏差为3.1%～6.5%,方法检出限为0.002 mg/L,适用于水中丁基黄原酸的监测。     

Diffusive uptake in passive and active adsorbent sampling using thermal desorption tubes

Low flow active sampling techniques collecting vapors and gases using thermally desorbable adsorbents are now feasible and desirable in many applications as they permit long integration times, the potential for miniaturized sampling configurations, and other advantages. At very low air flow rates (< 1 ml min(-1)), diffusive uptake on adsorbents in conventional sorbent tubes may equal or exceed the active (pumped) uptake rate, and even at low flow rates (1-4 ml min(-1)), diffusive uptake may significantly bias measurements. Thus, corrections to account for the diffusive flux or means to limit the diffusive uptake are needed in low flow applications. This paper presents (1) a theoretical analysis of the role of diffusive and advective uptake for several sampling geometries of tube-type samplers; (2) experimental confirmation using both laboratory and field studies; (3) estimates of the tortuosity and porosity of the glass wool packing used to retain the adsorbent, parameters needed to estimate diffusive fluxes in passive and active sampling; (4) a demonstration that orifice-equipped low flow active samplers can reduce diffusive uptake and improve precision, and (5) a model predicting the saturated adsorbent layer that helps to account for the gradual decline in uptake rates seen in passive sampling. Diffusive uptake will depend on the tube configuration and diffusion coefficient of the substance of interest, but for conventional sampling tubes (0.4-0.5 cm id, 1.5 cm air gap), sample flow rates should be maintained above 1 to 4 ml min(-1) to keep errors below 5%. Laboratory experiments showed close agreement with theoretical calculations, and the field study using 1 to 4 d sampling periods and 0.3 ml min(-1) flows demonstrated that the orifice-equipped samplers essentially eliminated diffusive uptake. No significant practical difficulties are encountered using orifices, e.g., pressure drop is minimal. Experimental estimates of tortuosity (0.79 +/- 0.02) and porosity (0.92 +/- 0.10) of the glass wool packing (0.3 cm length) represent relatively little resistance to diffusion; however, variation in the packing and adsorbent placement can degrade the precision achievable by passive samplers. Diffusion barriers, consisting most simply of an orifice, may be used to lower the diffusive uptake. A needle-type orifice permits flows below 0.1 ml min(-1) and is suitable for sampling periods as long as several weeks, and it provided greater precision than conventional open-ended sampling tubes (8% compared to 13%). Finally, the gradual decrease in diffusive fluxes often seen in passive sampling is attributed to additional resistance posed by a saturated adsorbent layer, in agreement with a simple model based on total VOCs and specific adsorptivity of the adsorbent.     

Investigation into antimony mobility in sewage sludge fermentation

Antimony is distributed in the environment in inorganic and organic species with different solubility and mobility characters. Here we investigate the transformation of antimony in view of biomethylation during sewage sludge fermentation as a case study for an anaerobic environment. Our approach was to identify if antimony methylation follows the Challenger pathway by using isotopically enriched antimonite (123Sb(v)). The antimony source was subjected to methylation in sewage sludge, an anaerobic dominant methanogenic Archaea community. The antimony species were determined in the gas phase using cryotrapping (CT)-GC-ICP-MS, and in the medium (sewage slude) by hydride generation (HG) prior CT-GC-ICP-MS. The determined 123/121Sb isotope ratios in the volatile trimethylstibine and non-volatile methylantimony species indicated that the methylation follows the proposed methylation pathway. With this approach we were able to quantify 123Sb incorporation into monomethyl-, dimethyl- and trimethylantimony, respectively. The incorporation decreased with further methylation from 91% to 82% and 73%. Volatilisation as trimethystibine was generally lower than 0.1%, however, up to 0.8% of added antimony was found methylated to methylantimony species and mainly accumulated in the cell. Moreover, antimony biomethylation was enhanced by stimulation of the anaerobic communities of methanogenic Archaea and sulfate reducing bacteria (SRB), with the methanogens showing a higher activity.     

Volatile Organic Compounds: Sampling Methods and Their Worldwide Profile in Ambient Air

The atmosphere is a particularly difficult analytical system because of the very low levels of substances to be analysed, sharp variations in pollutant levels with time and location, differences in wind, temperature and humidity. This makes the selection of an efficient sampling technique for air analysis a key step to reliable results. Generally, methods for volatile organic compounds sampling include collection of the whole air or preconcentration of samples on adsorbents. All the methods vary from each other according to the sampling technique, type of sorbent, method of extraction and identification technique. In this review paper we discuss various important aspects for sampling of volatile organic compounds by the widely used and advanced sampling methods. Characteristics of various adsorbents used for VOCs sampling are also described. Furthermore, this paper makes an effort to comprehensively review the concentration levels of volatile organic compounds along with the methodology used for analysis, in major cities of the world.     

Sequential extractions of selenium soils from Stewart Lake: total selenium and speciation measurements with ICP-MS detection

Different techniques have been employed in order to evaluate the most efficient procedure for the extraction of selenium from soil as required for speciation. Selenium contaminated sediments from Stewart Lake Wetland, California were used. A strong acid mineralization of the samples gives quantitative total selenium, which is then used to estimate recoveries for the milder extraction methods. The different extraction methodologies involve the sequential use of water, buffer (phosphate, pH 7) and either acid solution (e.g. HNO3 or HCl) or basic solutions (e.g. ammonium acetate, NaOH or TMAH). Pyrophosphate extraction was also evaluated and showed that selenium was not associated with humic acids. The extractants were subsequently analyzed by size exclusion chromatography (SEC) with UV (254 and 400 nm) and on-line ICP-MS detection; anion exchange chromatography, and ion-pair reversed phase chromatography with ICP-MS detection. For sequential extractions the extraction efficiencies showed that the basic extractions were more efficient than the acidic. The difference between the acidic and the basic extraction efficiency is carried to the sulfite extraction, suggesting that whatever is not extracted by the acid is subsequently extracted by the sulfite. The species identified with the different chromatographies were selenate, selenite, elemental selenium and some organic selenium.     

Comparison of 24 h averaged VOC monitoring results for residential indoor and outdoor air using Carbopack X-filled diffusive samplers and active sampling--a pilot study

Analytical results obtained by thermal desorption GC/MS for 24 h diffusive sampling of 11 volatile organic compounds (VOCs) are compared with results of time-averaged active sampling at a known constant flow rate. Air samples were collected with co-located duplicate diffusive sampling tubes and one passivated canister. A total of eight multiple-component sampling events took place at fixed positions inside and outside three private homes. Subsequently, a known amount of sample air was transferred from the canister to an adsorbent tube for analysis by thermal desorption GC/MS. Results for the 11 most prevalent compounds--Freon 11, 1,3-butadiene, benzene, toluene, tetrachloroethene, ethylbenzene, m,p-xylene, o-xylene, 4-ethyltoluene, 1,3,5-trimethylbenzene, and p-dichlorobenzene--show that the ratio of average study values (diffusive sampling to active sampling) is 0.92 with 0.70 and 1.14 extreme ratios. Absolute percent difference for duplicate samples using diffusive sampling was <10% for the four most prevalent compounds. Agreement between the two sampling approaches indicates that the prediction of approximately constant diffusive sampling rates based on previous laboratory studies is valid under the field conditions.     

Soil sampling and analysis for volatile organic compounds

Concerns over data quality have raised many questions related to sampling soils for volatile organic compounds (VOCs). This paper was prepared in response to some of these questions and concerns expressed by Remedial Project Managers (RPMs) and On-Scene Coordinators (OSCs). The following questions are frequently asked:

1. Is there a specific device suggested for sampling soils for VOCs?
2. Are there significant losses of VOCs when transferring a soil sample from a sampling device (e.g., split spoon) into the sample container?
3. What is the best method for getting the sample from the split spoon (or other device) into the sample container?
4. Are there smaller devices such as subcore samplers available for collecting aliquots from the larger core and efficiently transferring the sample into the sample container?
5. Are certain containers better than others for shipping and storing soil samples for VOC analysis?
6. Are there any reliable preservation procedures for reducing VOC losses from soil samples and for extending holding times?

Guidance is provided for selecting the most effective sampling device for collecting samples from soil matrices. The techniques for sample collection, sample handling, containerizing, shipment, and storage described in this paper reduce VOC losses and generally provide more representative samples for volatile organic analyses (VOA) than techniques in current use. For a discussion on the proper use of sampling equipment the reader should refer to other sources (Acker, 1974; U.S. EPA, 1983; U.S. EPA, 1986a). Soil, as referred to in this report, encompasses the mass (surface and subsurface) of unconsolidated mantle of weathered rock and loose material lying above solid rock. Further, a distinction must be made as to what fraction of the unconsolidated material is soil and what fraction is not. The soil component here is defined as all mineral and naturally occurring organic material that is 2 mm or less in size. This is the size normally used to differentiate between soils (consisting of sands, silts, and clays) and gravels. Although numerous sampling situations may be encountered, this paper focuses on three broad categories of sites that might be sampled for VOCs:

1. Open test pit or trench.
2. Surface soils (<5 ft in depth).
3. Subsurface soils (>5 ft in depth).

     

On-site Comparison of Canister and Solid-Sorbent Trap Collection of Highly Volatile Hydrocarbons in Ambient Atmospheres

A field experiment for the comparison of the efficiency of canisters and adsorption multibed tubes for sampling atmospheric highly volatile hydrocarbons at ppbv levels is described. The canister was passivated by the Summa process and the adsorption tubes were filled with Carbotrap C, Carbotrap B and Carbosieve S-III. The sampling with the adsorption tubes was performed at ambient temperature and at -10°C. The highest concentrations were generally obtained with canisters but these results are very similar to those obtained with refrigerated multibed adsorption tubes. Both methods appear to be equivalent for most of the highly volatile hydrocarbons encountered in moderately polluted urban areas. In contrast, sampling with ambient temperature tubes provides lower concentrations. This study has also shown that K2CO3 drying efficiently removes humidity from air samples allowing the obtention of reliable concentration data on highly volatile hydrocarbons at ppbv levels. These drying tubes can easily be re-conditioned and tested for blanks and memory effects, which greatly facilitates the control of external contamination and sample cross-contamination.     

An evaluation of a fast sampling procedure for the trace analysis of volatile organic compounds in ambient air

This study deals with the evaluation of a fast method for sampling of volatile organic compounds in ambient air. Special bags made of an inert material are used together with a large handpump which allows a sampling of one liter per second. After the sampling, the pollutants are concentrated by adsorption on Tenax and transfered by heat desorption, to a small capillary precolumn cooled with liquid nitrogen, or directly trapped on the precolumn. The suitability of this technique was evaluated by sampling complex synthetic mixtures of known concentration and composition, after which the samples were submitted to a series of operations such as transport, aging, changing of the humidity, heating and cooling, irradiation, etc. Changes in the original mixtures, caused by adsorption, diffusion, chemical or photochemical reactions were investigated by GC-MS analysis. The results of the study show that under certain conditions the samples can be preserved for a rather long period of time without noticeable changes in composition. However for certain compounds, severe quantitative losses occur after one day storage. Finally a practical application of this method is described in a recent case of strong odour annoyance by a chemical plant in the north of Belgium.     

Performance optimisation of a passive sampler for monitoring hydrophobic organic pollutants in water

The performance of an integrative passive sampler that consists of a C18 Empore disk sorbent receiving phase fitted with low density polyethylene membrane was optimised for the measurement of time-weighted average concentrations of hydrophobic micropollutants in water. A substantial improvement of sampling characteristics including the rate of sampling and the sampling precision was achieved by decreasing the internal sampler resistance to mass transfer of hydrophobic organic chemicals. This was achieved by adding a small volume of n-octanol, a solvent with high permeability (solubility [times] diffusivity) for target analytes, to the interstial space between the receiving sorbent phase and the polyethylene diffusion-limiting membrane.