全自动石墨消解-原子荧光法测定土壤总汞

采用全自动石墨消解-原子荧光光度法对土壤总汞进行测定,确定最佳消解时间为1 h,消解液最佳用量为8.0 m L。方法在总汞质量浓度为0.2~2.0μg/L范围内具有良好的线性,相关系数为0.999 9,当取样量为0.500 0 g时,检出限为0.002 mg/kg;测定不同标准土壤样品总汞的结果均在保证值范围内,精密度为4.0%~7.0%,加标回收率为95.0%~108.5%;对甘肃省实际土壤及沉积物样品测定进一步验证了方法的适用性。该法适合大批量样品分析,对于提高工作效率有重要意义。     

程序控温石墨消解-原子荧光法测定土壤中总砷

采用程序控温石墨全自动消解仪消解土壤样品,原子荧光光谱法测定总砷。通过试验确定原子荧光光度计的最佳工作条件,使得该方法在2.00μg／L ～20.0μg／L 范围内线性良好,检出限为0.025 mg／kg,加标回收率在96.0％～10^5％之间,RSD为1.9％～3.3％。用该方法与国标法同时测定土壤标准样品和实际样品,结果无显著差异。     

Determination of ortho-phthalaldehyde in air and on surfaces

Three sampling and analytical methods have been developed and evaluated for ortho-phthalaldehyde (OPA): (1) an HPLC-UV method for OPA in air, (2) a fluorimetric method for OPA on surfaces, and (3) a colorimetric method for OPA on surfaces. (1) The air sampler contains 350 mg of silica gel coated with 1 mg of acidified 2,4-dinitrophenylhydrazine (DNPH). Air sampling may be conducted at 0.03 to 1.0 L min(-1) for periods up to 8 h. Samples were eluted with ethyl acetate, and the eluents were allowed to stand for 72 h. Analysis was by high performance liquid chromatography (HPLC) with a UV detector set at 369 nm. An unusual phenomenon was the observation that the stability of the sample on a sampler at 3 degrees C tends to decrease as the total quantity of OPA collected on the sampler decreases. Elution of the samples within 24 h of air sampling is required. The detection limit (LOD) is approximately 0.02 microg of OPA per sample. OPA on surfaces may be collected with strips cut from a sheet of polyvinyl alcohol (PVA wipe). (2) In the surface wipe method with analysis by fluorescence measurement, the strips of PVA wipe were placed into dimethyl sulfoxide. An aliquot was treated with aqueous N-acetyl-l-cysteine and ethylenediamine. Analysis was performed with a portable fluorometer (excitation and emission wavelengths = 365 nm and 438 nm, respectively). The LOD is 0.2 microg per sample. (3) In the surface wipe method with visual colorimetric detection, the strips of PVA wipe were placed into 30 : 70 acetonitrile : water. An aliquot was treated with N-(1-naphthyl)ethylenediamine in 0.1 m sulfuric acid. After color development, the LOD is approximately 48 microg per sample. These methods have been field tested in a hospital.     

PT-GC-CAFS联用技术测定污水处理厂外排水中烷基汞残留量

建立了吹扫捕集-气相色谱-冷原子荧光(PT-GC-CAFS)联用技术、多功能自动进样器进样测定污水处理厂外排水中烷基汞残留量的方法。用烷基化试剂直接衍生,吹扫捕集吸附/富集,以PEG20M填充柱为分离柱,用冷原子荧光作为检测器进行测定,整体分析工作在10 min内完成。在所选实验条件下,方法对所测甲基汞、乙基汞的线性相关系数分别为0.999 9、1.000,最低检出限分别为0.002、0.003 ng/L,相对标准偏差为1.4%~10.2%,2.3%~9.7%;在不同质量浓度水平上进行加标回收率实验,甲基汞的回收率为93.7%~101.7%,乙基汞为94.1%~103.6%。该方法用于污水处理厂外排水中烷基汞残留量的分析测定,结果令人满意。     

高通量固定污染源废气颗粒物中总汞的测定

用玻璃纤维滤筒采集固定污染源废气颗粒物,借助硝酸和氢氟酸的作用,使滤筒和废气颗粒物在160℃下消解,再用原子荧光法测定消解液中总汞。用50%热硝酸溶液处理玻璃纤维滤筒,消除滤筒本底值不一对测定结果的干扰,并优化消解过程,使该方法在0.050μg/L~1.00μg/L范围内线性良好。当采样体积为10 L时,方法检出限为4.5×10~(-5)mg/m~3,空白加标样6次测定结果的RSD为7.2%,加标回收率为87.0%~113%。将该方法用于测定某固定污染源废气颗粒物中总汞,测定值在标准排放限值内。     

热分解-冷原子吸收法测定土壤中汞

采用热分解处理土壤样品,用冷原子吸收法测定样品中的汞,通过优化固体测汞仪的分析条件、确定校准曲线的线性范围和样品的称样量,使该方法在0.025 mg/kg~1.50 mg/kg范围内线性良好。当取样量为0.2 g时,方法检出限为0.000 9 mg/kg,有证标准物质的测定结果在保证值范围内,高、低浓度标准物质6次测定结果的RSD分别为4.6%和4.8%。用热分解法与国标法同时处理样品并测定,其测定结果无显著差别。     

Simultaneous determination of malachite green, enrofloxacin and ciprofloxacin in fish farming water and fish feed by liquid chromatography with solid-phase extraction

An effective and sensitive method for simultaneous analysis of malachite green (MG), enrofloxacin (ENFLX) and ciprofloxacin (CPFLX) by liquid chromatography-diode array detection with solid-phase extraction (SPE) is developed. The conditions of SPE and LC were investigated and optimised. The effective separation of these compounds was achieved using a ZY1104 C18 column (250 × 4.6 mm, 5 μm) with 20 mM tetrabutyl ammonium bromide (pH 3.0)-acetonitrile as mobile phase and gradient elution. The diode array detection was used at 278 nm for ENFLX and CPFLX and at 613 nm for MG. Under the optimal conditions, the method LOD values of MG, ENFLX and CPFLX were 0.01, 0.07 and 0.10 μg L(?-1) for fish farming water samples and 1.5, 10.5 and 15 μg kg(?-1) for fish feed samples, respectively. The relative recoveries of the three analytes were achieved to be 76.7-82.3% with the RSDs (n = 5) of 3.2-4.6% for spiked fish farming water samples and 78.8-93.7% with the RSDs (n = 5) of 3.1-4.8% for spiked fish feed samples.     

Linkages of P and Al Export at High Discharge at the Bear Brook Watershed in Maine

Phosphorus chemistry in streams was evaluated at the paired watershed study at the Bear Brook Watershed, Maine. The West Bear catchment has been treated bimonthly since 1989 with 1,800 eq (NH4)2SO4 ha-1 yr-1. East Bear was the untreated reference watershed. During 1993, concentration of total phosphorus (P) in weekly samples from East and West Bear Brook ranged from 0 to 15 g L-1. The median values were 2 and 4 g L-1 for East and West Bear, respectively. During a high discharge event in January of 1995, the concentration of dissolved P remained relatively constant ( 3 g L-1) as pH decreased from 5.63 to 5.08 and from 5.14 to 4.75 in East and West Bear, respectively. The concentration of total P increased to ca. 60 g L-1 during the rising limb of the hydrograph in West Bear, four times the value in East Bear, total P then declined rapidly as discharge remained high followed by an increase. Dissolved Al increased in both streams during the episodic acidification. West Bear, the more acidic, had concentrations of dissolved Al four times those of East Bear (maximum of 1.1 mg L-1 versus 0.25 mg L-1). Acid-soluble particulate Al increased to 0.2 and 4.2 mg L-1 for East and West Bear, respectively, in parallel to total P (but was 102 greater than total P) and then declined in parallel to total P while discharge remained high. Total P, dissolved P, and particulate Al did not relate to pH. Total P and particulate Al and Fe were strongly correlated. Concurrently, base cations remained relatively constant or decreased slightly. Particulate acid-soluble Al exceeded particulate acid-soluble base cations. We hypothesize that the particulate P was occluded in, or adsorbed on, acid-soluble particulate Al(OH)3. This Al(OH)3. This Al(OH)3 precipitates as emerging acidic groundwater degasses CO2 and pH rises. The export of Al and P is greater from the treated watershed because the induced acidification is translocating more Al from soils to the stream. Most of the export of P is related to acid-soluble Al particulate material.     

增压溶样－冷原子荧光法测定煤样中的汞

采用增压溶样器加７：３：５的ＨＮＯ３－Ｈ２ＳＯ４－ＨＣｌＯ４混合酸处理煤样．用冷原子荧光法测定煤样中的总汞含量。该法的加标回收率为９２．７～１１２．５％，结果令人满意。     

Dissolved Oxygen Conditions in Northern Gulf of Mexico Estuaries

Because deficient dissolved oxygen (DO) levels may have severe detrimental effects on estuarine and marine life, DO has been widely used as an indicator of ecological conditions by environmental monitoring programs. The U.S. EPA's Environmental Monitoring and Assessment Program for Estuaries (EMAP-E) monitored DO conditions in the estuaries of the Gulf of Mexico from 1991 to 1994. DO was measured in two ways: 1) instantaneous profiles from the surface to the bottom were taken during the day, and 2) continuous measurements were taken near the bottom at 15 min intervals for at least 12 h. This information was summarized to assess the spatial distribution and severity of DO conditions in these estuaries. Depending on the criteria used to define hypoxia (DO concentrations usually <2 mg L-1 or <5 mg L-1) and the method by which DO is measured, we estimate that between 5.2 and 29.3% of the total estuarine area in the Louisianian Province was affected by low DO conditions.     

微波消解—原子吸收/原子荧光光度法测定活性污泥中的Cd、Pb、Ni、Cu、Zn、Cr、K、As、Hg

通过实验,建立了活性污泥中金属和重金属的测定方法。活性污泥样品经硝酸—氢氟酸或硝酸—高氯酸微波消解处理后,Pb、Ni、Cu、Zn、Cr、K选用火焰原子吸收分光光度法测定,Cd用石墨炉原子吸收分光光度法测定,As、Hg用原子荧光光度法测定。该方法操作简单,结果准确,重现性好。样品加标回收率为93%-108%,相对标准偏差〈5%。     

Synthesis, spectral assignment and application of a recently synthesized macrocyclic ionophore to simultaneous pre-concentration and determination of ultra traces of copper and lead by solid phase extraction-flame atomic absorption spectrometry

Ethyl(2-ethylamino)thiophenol-2,6-pyridinedicarboxylate (ETPD) was synthesized from the reaction of disodium pyridine-2,6-dicarboxylate with 1,2-dibromoethane in methanol, followed by treatment with 2-aminothiophenol. The spectral characterization of ETPD is described in detail. This electron-donating agent was successfully utilized for simultaneous enrichment of ultra trace levels of copper and lead in a wide variety of samples. By passing the aqueous solutions through octadecylsilyl bonded phase membrane disks impregnated with 12 mg of ETPD at flow rates of 45 mL min^?1, Cu and Pb were selectively trapped on the disk surface over the pH range 3.0 to 7.0, whereas most other ions were negligibly retained. Numerous chemical parameters affecting sorption and subsequent elution were also investigated. The target ions were stripped from the disk surfaces by reverse flow, at rates of 12 mL min^?1, and were immediately introduced to the nebulizer of an atomic absorption spectrometer. This inexpensive and off-line method offers enrichment factors of 400 and 300 and detection limits of 2.5 and 0.2 μg L^?1 for copper and lead, respectively. The potential applicability of the method was confirmed by its reliable use in quantification of these elements in some real water samples, industrial effluents, three tea samples and peppers, as well as by comparison with graphite furnace atomic absorption spectrometric determinations.     

原子荧光法测定水中砷含量的不确定度评定

以氢化物-原子荧光法测定水中砷含量为例,应用不确定度理论,从测试过程和计算方法的角度分析了测量不确定度的各种影响因素:标准物质、溶液稀释情况、工作曲线的非线性以及原子荧光光度计的测量性能等,对各测量不确定度分量进行计算和评定。结果表明:原子荧光法测定水中砷含量的测量不确定度的主要影响因素是工作曲线的非线性和原子荧光光度计的测量性能,其次是标准储备液的逐级稀释,当水样稀释倍数非常低时,因水样稀释引入的不确定度可忽略不计。砷含量的扩展不确定度为1.2μg/L,置信水平为95%。     

Speciation of arsenic in plants by HPLC-HG-AFS: extraction optimisation on CRM materials and application to cultivated samples

A recently developed method for the determination of arsenic species (arsenite, arsenate, monomethylarsonate, MMAA, and dimethylarsinate, DMAA) has been applied to the study of arsenic speciation in plants. This method uses ion-exchange liquid chromatography coupled on-line to atomic fluorescence spectrometry through continuous hydride generation. Various extraction procedures have been studied in detail using three plant certified reference materials. None of the procedures tested revealed fully satisfying results with all kinds of plant samples; microwave assisted extraction with 0.3 mol dm-3 orthophosphoric acid was found to be the most convenient for dealing with terrestrial plants. Species stability appears good. This method was applied to real world cultivated plant parts. Arsenate appears to predominate in soils, roots and leaves; unidentified species (probably arsenosugars) play an important role (60%) in rice fruits. Carrot was found to be the most contaminated edible plant part, containing 1 mg kg-1 essentially as arsenate species. MMAA was detected in all soils and some plant parts especially shallots at low levels, whereas DMAA was found only in one soil sample and in hot pepper leaves. Arsenite is a minor component of all soils; it is also present in some plant parts at low levels. However, no evident relationships were found between As speciation in the various plant parts and much more detailed studies will be necessary to elucidate As behaviour in plants.     

On-filter determination of collected wood dust by diffuse reflectance infrared Fourier-transform spectroscopy (DRIFTS)

A new analytical technique based on DRIFTS spectroscopy has been developed for the specific and sensitive determination of size-fractionated wood dust from 37 mm glass fiber filter samples collected with the Respicon sampler. A translational diffuse reflectance apparatus was modified to accept filter samples by incorporating a special filter holder in the sample stage and a clockwork motor to drive the translational stage during infrared scanning, thus providing an average analysis across the filter face. Filter samples were pre-treated with ethyl acetate to uniformly redeposit dust onto the filter and extract potential chemical interferences. Two absorbance maxima (1251 and 1291 cm(-1)), corresponding to the cellulose content of the wood, were suitable for quantitation of wood dust. Analysis of seven species of wood at 1291 cm(-1) showed an equivalent quantitative response for all species except maple. The response at 1251 cm(-1) was more variable across species but more sensitive for the softwoods. There was a statistically significant effect of particle size on the analytical response, so that analytical standards should be matched to the samples in terms of particle size distribution. Analytical limit of detection was approximately 0.08 mg of wood dust per sample with overall precision of about 6%. Comparison of DRIFTS and gravimetric analyses of 51 pure wood dust samples ranging from about 0.2 to 2 mg yielded a slope of 1.08 and r2 equal to 0.9. Other particulate contaminants common in the industrial wood processing industry showed little or no interference with the determination of wood dust by this method.     

超高效液相色谱-电喷雾串联四级杆质谱法快速分析水中微囊藻毒素LR

建立超高效液相色谱-电喷雾串联四极杆质谱快速测定水中微囊藻毒素LR(MC-LR)的方法。水样经0.2μmGHP一次性针头过滤器过滤,应用超高效液相色谱/电喷雾串联四极杆质谱仪多离子反应监测(MRM)法定量检测MC-LR。经方法学验证,该方法对MC-LR的最低检出限LOD为0.08μg/L(进样量10μl),最低定量限LOQ是0.10μg/L。在0.2~20.0μg/L的线性范围中,相关系数r=0.9982,回收率范围91.5%~110.3%。方法灵敏度高,专属性强,操作简便快速,定量准确,测定浓度范围宽,是环境水质样品中MC-LR含量检测的理想方法。     

Evaluation of trace heavy metal levels of some fish species sold at retail in Kayseri, Turkey

Cd, Ni, Cr, Zn, Cu and Pb concentrations of muscle tissue of 61 fish samples belonging to six fish species (Sparus auratus, Pomatomus saltatrix, Sarda sarda, Engraulis encrasicholus, Sander lucioperca, Scomber scombrus) retailed in Kayseri, Turkey were determined by flame atomic absorption spectrometry after wet digestion. Cd concentrations of at least 31 fish samples (50.8%) and Pb concentrations of at least six fish samples (9.8%) exceeded the corresponding Turkish permissible limit of 0.05 and 0.2 mg kg(-1) respectively whereas Zn concentrations of 11 fish samples (18%) exceeded the Turkish Food Codex limits of 50 mg kg(-1) for Zn. Cu concentrations of all fish species analyzed (100%) were below the corresponding Turkish legislations of 20 mg kg(-1). No limits were established concerning Ni and Cr concentrations in fish by the Turkish governmental authorities.     

七虎林河流域上游溶解性有机质光谱特性分析

七虎林河源头区地表腐殖质随着径流的冲刷进入水体,形成了天然有机质(NOM),其中,溶解性有机质(DOM)易对河流水质造成影响。为了研究七虎林河中DOM的时空分布特征及其对水质的影响,开展了6次采样,分析了水体及土壤吸收光谱和荧光光谱特征参数,利用平行因子(PARAFAC)算法解析了水体DOM的特性及来源。结果表明：七虎林河上游水体五日生化需氧量(BOD₅)、高锰酸盐指数(COD_Mn)、化学需氧量(COD)、可溶性有机碳(DOC)的浓度分别为1.4 mg/L±0.2 mg/L、6.1 mg/L±3.0 mg/L、21 mg/L±8 mg/L、7.0 mg/L±3.2 mg/L,BOD₅/COD平均值为0.08,说明流域内水体DOM的可生化性差,对水质影响较小。光谱特征参数紫外吸收系数(SUVA₂₅₄)、荧光指数(FI)、腐殖化指数(HIX)、生物源指数(BIX)分析结果表明,七虎林河上游云山水库库上林区河段DOM的物质组成与水库及库下河段差异显著。库上河段DOM的芳香碳含量更高、分子量更大、自生源组分...     

A simple extraction procedure for determination of total mercury in crude oil

The determination of mercury in crude oil and petroleum products is particularly difficult due to the volatile nature of both mercury and the matrix, which may lead to significant loss of the analyte. A simple extraction method for total mercury has been developed to determine total mercury in crude oil using cold vapor atomic fluorescence spectrometry. The homogenized crude oil sample was diluted to 5, 10, and 20 % (w/w) in toluene. The diluted crude oil samples were spiked with 10 and 40 μg/kg (w/w). The samples were extracted using an oxidant/acid solution, BrCl/HCl. The mercury was extracted into the aqueous phase; the ionic mercury was then reduced to volatile elemental mercury (Hg⁰) by stannous chloride (SnCl₂). The mercury vapor was detected by Merlin cold vapor atomic fluorescence spectrometry at a 253.7-nm wavelength. The average recoveries for mercury in spiked diluted crude oil (10 and 40 μg/kg, w/w) were between 96 and 103 %, respectively, in 5 and 10 % spiked diluted crude oil. Whereas, low recoveries (<50 %) were recorded in 20 % diluted spiked crude oil. The method detection limit was calculated as t _{(0.01)(n ? 1)}?×?SD where t is the student's value for 99 % confidence level and standard deviation estimate with n???1 degrees of freedom. The method detection limit was found to be 0.38 μg/kg based on 5 g of diluted crude oil sample. The method is sensitive enough to determine low levels of mercury in crude oil.     

能量色散X射线荧光光谱法测定土壤和沉积物中稀土元素

建立了偏振能量色散X射线荧光光谱法测定土壤和沉积物中稀土元素的方法,该方法较传统的方法具有前处理简单、测量自动化程度高、灵敏度高和检出限低(检出限范围为0.05~2.80 mg/kg)等优点。对土壤和沉积物标准物质的测定结果表明:测定结果与认定值能较好吻合,相对标准偏差范围为0.2%~9.4%,能满足测试的需求。分别用该方法和电感耦合等离子体质谱法对实际样品进行测定,2种方法的测定结果有较好的一致性,表明该方法测定结果准确可靠,可用于实际样品的测定。