A Comparison of Precipitation Sensors Used on the Wet-Only Collectors

The variability in performance of three precipitation sensor types, mounted on three identical wet-only collectors, has been compared for eight months at a single site. The catch efficiencies, determined from the sample volumes, are relatively high for these three apparatuses, since they exceed 89% on average. The recorded data of openings and closings of collector lids reveal that the highest losses of collection efficiency, observed for rainfalls of low intensity and low amount, are largely imputable to design and running characteristics of each sensor. Ionic compositions between the samples of these three collectors are relatively close, although significant differences are especially found for H⁺, Ca²⁺, Mg²⁺ and K⁺, suggesting that these apparatuses are differently exposed to the dry deposition of soil particles. The RS 85 sensor seems to be the most suitable one of the three, since it ensures a high catch efficiency for all rain types and tends to limit the exposures of funnel to the dry deposition.     

X射线荧光光谱法测定土壤样品中铅的不确定度评定

用实例对X射线荧光光谱法测定土壤样品中铅的不确定度进行了评定.测量结果的不确定度由仪器综合稳定性、制样、标准物质、回归工作曲线、重复测量等所引入的不确定度分量组成.在对各个不确定度分量进行量化的基础上,通过合成得到测量结果的标准不确定度,再乘以95%置信概率下的扩展因子2,得到测量结果的扩展不确定度.     

Polycyclic aromatic hydrocarbons in effluents from wastewater treatment plants and receiving streams in Tianjin, China

Surface water, suspended particulate matter, pore water, and sediment samples were collected and analyzed for polycyclic aromatic hydrocarbons (PAHs) in Yongding New River, South Drainage Canal and North Drainage Canal, which receive most of wastewater from industrial city of Tianjin. PAH concentrations in effluent samples of wastewater treatment plants (WTP) discharging into the South Drainage Canal and North Drainage Canal were quantified for the first time. The results showed that the discharge of the WTPs recently only contributed to the PAH contamination in the canals near the outlets of the WTPs. PAH levels in sediments of the streams were greatly higher than those in soils by riverbank probably due to receiving large amounts of untreated wastewater. Unusually high benz[a] anthracene concentration strongly influenced the seasonal and spatial variation of total PAH concentrations in South Drainage Canal. Paired samples t test of ??Nap, Fl, Phe, Fluo and ??Nap, Phe, Fluo, Chry concentrations, which were dominant components in the air samples from non-heating and heating season, respectively, in the suspended particulate matters from the streams showed that PAH source from air deposition was more important for Yongding New River than that for South Drainage Canal and North Drainage Canal. Source apportionment based on PAH profiles indicated that coal combustion was the major PAH contamination source, and coke oven sources and wood combustion also contributed to the PAH contamination of the streams. This was further indicated by organic petrography analysis.     

Energy-dispersive X-ray fluorescence systems as analytical tool for assessment of contaminated soils

To determine the heavy metal content in soil samples at contaminated locations, a static and time consuming procedure is used in most cases. Soil samples are collected and analyzed in the laboratory at high quality and high analytical costs. The demand by government and consultants for a more dynamic approach and by customers requiring performances in which analyses are performed in the field with immediate feedback of the analytical results, is growing. Especially during the follow-up of remediation projects or during the determination of the sampling strategy, field analyses are advisable. For this purpose four types of ED-XRF systems, ranging from portable up to high performance laboratory systems, have been evaluated. The evaluation criteria are based on the performance characteristics for all the ED-XRF systems such as limit of detection, accuracy and the measurement uncertainty on one hand, and also the influence of the sample pretreatment on the obtained results on the other hand. The study proved that the field portable system and the bench top system, placed in a mobile van, can be applied as field techniques, resulting in semi-quantitative analytical results. A limited homogenization of the analyzed sample significantly increases the representativeness of the soil sample. The ED-XRF systems can be differentiated by their limits of detection which are a factor of 10 to 20 higher for the portable system. The accuracy of the results and the measurement uncertainty also improved using the bench top system. Therefore, the selection criteria for applicability of both field systems are based on the required detection level and also the required accuracy of the results.     

Source analysis of particulate matter associated polycyclic aromatic hydrocarbons (PAHs) in an industrial city in northeastern China

Particle-associated polycyclic aromatic hydrocarbon (PAH) concentrations were investigated at eight sampling sites during cold periods where heating is used (heating period) (February to March, 2005) and warm periods where heating is not required (non-heating periods) (August to September 2006) in the urban area of Anshan, an iron and steel city in northeastern China. Eleven PAH species were measured using GC-MS. The total average concentrations of PAHs ranged from 46.14 to 385.60 ng m(-3) in the heating period and from 5.28 to 146.40 ng m(-3) in the non-heating period. The lowest concentration of ∑PAHs was observed at Qianshan, a monitoring site far from the city and industrial area, and the highest concentration occurred in the site located at the factory area of Anshan Iron and Steel Incorporation. Moreover, ambient PAH profiles were studied and high molecular weight PAH (including 4-6 rings) species occurred in the high fractions. Toxic equivalent factors analysis gave the potential carcinogenic risks in Anshan. For the heating sampling period, BaP equivalent concentration is in the range of 41.98 to 220.83 ng m(-3), and 9.23 to 126.00 ng m(-3) for the non-heating sampling period. By diagnostic ratio analysis, traffic emission and combustion (coal or biomass) were potential sources for PAHs in Anshan. Finally, PCA results indicated the major sources were vehicle emission, steel industry emission, and coal combustion for both heating and non-heating seasons, which agreed with the results from the diagnostic ratio analysis.     

The distribution of polynuclear aromatic hydrocarbons in ambient air particulates in Singapore

Ambient air particulates were collected using high volume samplers at seven locations throughout Singapore. The particulates were analyzed for eleven polynuclear aromatic hydrocarbons (PAH) using high performance liquid chromatography (HPLC) with fluorescence detection. Several sample preparation techniques were used to determine which method would yield the most PAHs from the bulk sample matrix. PAH profiles (standardised against the concentration of benzo(a)pyrene) were obtained to characterise the different sampling sites chosen.     

M12半自动净化法与手工净化法应用于飞灰中二噁英类检测比较

研究比较了M12半自动净化法与手工净化法应用于二噁英检测的效果。结果显示,采用高分辨气相色谱-高分辨质谱法(HRGC-HRMS)检测飞灰样品中的二噁英,手工净化法的回收率要优于M12半自动净化法的回收率,但M12半自动净化法除2种单体外,其余单体回收率均满足对二噁英的分析要求,且2种净化方法所得二噁英的总毒性当量结果相近,证明手工净化法与HRGC-HRMS联用检测飞灰中二噁英的效果较好,但M12半自动净化法也能够满足HRGC-HRMS检测二噁英的净化要求。应用酶联免疫法检测飞灰样品中二噁英的总毒性量,当样品中二噁英浓度较高时,M12半自动净化法和手工净化法净化测得结果与基准值一致性较好;当样品中二噁英浓度较低时,手工净化法检测结果与基准值差别较大,表明酶联免疫法更适合用M12半自动净化法进行净化。     

Transport,deposition and biodegradation of particle bound polycyclic aromatic hydrocarbons in a tidal basin of an industrial watershed

Polycylic aromatic hydrocarbons (PAHs) are commoncontaminants in industrial watersheds. Their origin,transport and fate are important to scientists,environmental managers and citizens. The Philadelphia NavalReserve Basin (RB) is a small semi-enclosed embayment nearthe confluence of the Schuylkill and Delaware Rivers inPennsylvania (USA). We conducted a study at this site todetermine the tidal flux of particles and particle-boundcontaminants associated with the RB. Particle traps wereplaced at the mouth and inside the RB and in the Schuylkilland Delaware Rivers. There was net particle deposition intothe RB, which was determined for three seasons. Spring andfall depositions were highest (1740 and 1230 kg ofparticles, respectively) while winter deposition wasinsignificant. PAH concentrations on settling particlesindicated a net deposition of 12.7 g PAH in fall and 2.1 gPAH in spring over one tidal cycle. There was nosignificant PAH deposition in the winter. Biodegradationrates, calculated from ¹⁴C-labeled PAH substratemineralization, could attenuate only about 0.25% of the PAHdeposited during a tidal cycle in fall. However, in thespring, biodegradation could be responsible for degrading50% of the settling PAHs. The RB appears to be a sink forPAHs in this watershed.     

Comparison of polycyclic aromatic hydrocarbon uptake pathways and risk assessment of vegetables from waste-water irrigated areas in northern China

Atmospheric deposition is the dominant pathway for PAH uptake by vegetables grown in peri-urban areas. Different polycyclic aromatic hydrocarbon (PAH) uptake pathways and the associated health risk were investigated in vegetable samples collected from the Beijing-Tianjin city cluster, China, where irrigation with waste or reclaimed water has been practised for many decades. Sampling comprised 23 diverse sites and the roots and shoots of six types of vegetables. Among the different edible vegetable parts, the highest PAH concentrations were found in radish roots and the lowest in cauliflower heads. Bioconcentration factors (BCFs) for individual PAHs showed a weakly decreasing trend with increasing log K(OW). To investigate whether the air-leaf or soil-root-shoot uptake dominates, the measured values were compared with estimations from a generic one-compartment model. The results and related observations are more consistent with an atmospheric uptake pathway than a soil-uptake pathway. The PAH isomeric ratios are consistent with pyrogenic sources (from combustion of fossil fuel and biomass). A health risk assessment on the consumption of the edible parts of vegetables revealed that all studied vegetables, except for 16% of Chinese cabbage samples, are safe for consumption. The results of this study indicate the potential health risk of consuming vegetables from waste-water irrigated areas of this city cluster and provide new insights regarding the transfer of PAHs in vegetables grown in this region.     

6项环境监测分析方法标准中钴、铬、钼、钛的不确定度分析及其在达标判定中的应用

研究依据测定不确定度的基本理论和ISO 21748：2017《采用重复性、再现性和正确度评估测量不确定度的导则》,提出了基于中国环境监测分析方法标准多家实验室验证中已获得的数据计算合成标准不确定度的方法,将方法标准中规定的重复性、再现性等指标与合成标准不确定度进行了衔接。分析了近年发布的6项水质监测分析方法标准中钴、铬、钼、钛等4种金属元素的相对合成标准不确定度,结果表明：被测量的浓度是影响方法标准测量不确定度的重要因素。对于火焰原子吸收分光光度法（FAAS）和石墨炉原子吸收分光光度法（GAAS）,样品浓度为方法标准测定下限3倍左右时,测定结果的相对标准不确定度可保持在15%以下;对于电感耦合等离子体发射光谱法（ICP-AES）,样品浓度为方法标准测定下限3~5倍时,测定结果的相对标准不确定度为12%~17%;对于电感耦合等离子体质谱法（ICP-MS）,钛元素浓度为测定下限3倍左右时,相对标准不确定度在15%以下,而钴、铬、钼的浓度在测定下限40~100倍以上时,相对标准不确定度在15%以下。6项方法标准可分别用于《地表水环境质量标准》（GB 3838—2002）以及22项水污染物排放标准钴、铬、钼、钛的达标监测。     

Apportioning variability of polycyclic aromatic hydrocarbons (PAHs) and chlordanes in indoor and outdoor environments

Measurements of semi-volatile organic compounds (SVOCs) in air are subject to substantial variability and uncertainty. This study apportions total variance of polycyclic aromatic hydrocarbons (PAHs) and chlordanes to variability and uncertainty components. Concentrations of PAHs and chlordanes were measured inside and outside of 116 residences in three large cities in the U.S. during 1999-2000. Total variance was apportioned to between-city, between-tract, between-residence, and seasonal variation, as well as measurement uncertainty using variance component analysis and log-transformed data for frequently detected compounds. Outdoors, seasonal variation was the greatest portion (44-67%) of total variance, and city effects were significant (19-24%). Indoors, seasonality dominated variability of PAH measurements (>50%). Gas-phase PAHs varied more within city than between cities; particulate-phase PAHs varied significantly between cities but were largely homogeneous within cities. Gas-phase chlordanes showed larger intra-urban variation (63%) than seasonal variation (18%). Measurement uncertainty was generally below 10% with a few exceptions occurring at very low concentrations. Results indicate a need to collect multiple-season samples to account for the large temporal variation between seasons. Samples from centrally located monitoring stations could be representative of ambient SVOCs. Variance component analysis is useful to weigh influential factors in SVOC concentrations, identify and apportion sources, evaluate method performance, and design effective monitoring programs.     

Measurements of polycyclic aromatic hydrocarbons at an industrial site in India

Polycyclic Aromatic Hydrocarbon (PAH) concentrations were measured in Total Suspended Particulate Matter (TSPM) from December 2005 to August 2006 at Nunhai, an industrial site in Agra (India). Particulate matter samples were collected on glass fibre filters using High Volume Sampler (HVS-430) and were extracted using dichloromethane with ultrasonication and analyzed by GC. Total PAH concentration varies between 0.04 to 2.5 microg m(-3) accounting only 1.6 x 10(-3)% of TSPM. The mass distribution in air was dominated by high molecular weight DbA, BghiP, BaP, BkF and IP. Combustion PAH (CPAH) except BeP represents 58% of the total PAH mass and IARC classified total carcinogenic PAH accounting 63% of TPAH concentration. Correlation studies between PAH revealed the contribution of low molecular weight PAH was mainly due to primary emission from diesel exhaust while high molecular weight PAH were formed during combustion. The presence of specific tracers and calculation of characteristic molecular diagnostic ratios Fla/(Fla + Pyr), BaP/(BaP + Chy), BaA/(BaA + Chy), IP/(IP + BghiP), BaP/BghiP and IP/BghiP) were used to identify the sources of the emissions of PAHs in the atmospheric samples. Seasonal variation in atmospheric PAH showed four fold increase in winter concentration than summer. The BaP and relative BaP amount calculated from the measurements suggested that photo-oxidation may also be responsible for the variation in PAH concentrations during winter and summer. Seasonal trends in atmospheric PAH concentration in the study area were influenced by fossil fuel usage for domestic heating, boundary height and temperature.     

Assessment of pumped mercury vapour adsorption tubes as passive samplers using a micro-exposure chamber

Mercury vapour adsorption tubes manufactured for pumped sampling and analysis have been evaluated for their performance as passive samplers. This has been done by exposing these tubes in a novel micro-exposure chamber. The uptake rates of these tubes have been found to be low (approximately 0.215 ml min(-1)) as compared to bespoke passive samplers for mercury vapour (typically in excess of 50 ml min(-1)). The measured uptake rates were shown to vary significantly between tubes and this was attributed to the variability in the air-sorbent interface and the proportion of the cross sectional area removed by the crimp in the quartz tubes used to secure the sorbent material. As a result of this variability the uptake rate of each tube must be determined using the micro-exposure chamber prior to deployment. Results have shown that the uptake rate determined in the micro-exposure chamber is invariant of concentration, and therefore these uptakes rates may be determined at a high mercury vapour concentration for many tubes at once in less than one hour. The uptake rate of the adsorption tubes under these conditions may be determined with a precision of 5%. Measurements made on a limited field trial in indoor and outdoor ambient air have shown that these tubes give results in acceptable agreement with more traditional pumped sampling methods, although longer sampling periods are required in order to reduce the uncertainty of the measurement, which is currently approximately 30%.     

Biomonitoring of polycyclic aromatic hydrocarbons in urban and industrial environments of the Western Black Sea Region,Turkey

This research was carried out in the cities of Zonguldak and Eregli, which have been characterized as urban and industrial environments of the Western Black Sea Region, Turkey, in order to assess the contamination of polycyclic aromatic hydrocarbons (PAHs) using mosses as biomonitors. The methodology involved the collection of moss samples (Hypnum cupressiforme), ultrasonic extraction with dichloromethane, cleanup using silica gel and analysis by liquid chromatography with ultraviolet detection. The total PAH concentrations ranged from 78.1 to 1693.5 ng g^?1 in Zonguldak and from 15.2 to 275.1 ng g^?1 in Eregli. The total PAH concentration in Eregli was about six times lower than that in Zonguldak, revealing the importance of switching from coal to natural gas in residential heating. The diagnostic ratios and the correlation analysis have indicated that coal combustion and traffic emissions were the major PAH sources at both sites. The contour maps were constructed for the determination of spatial distributions of total PAHs, and it was shown for Zonguldak as well as for Eregli that the PAH pollution was much more predominant in highly populated regions. Moving away from the city centres, a gradual decrease in PAH pollution rates was observed.     

Atmospheric polycyclic aromatic hydrocarbons in an industrialized city, Kocaeli, Turkey: study of seasonal variations, influence of meteorological parameters and health risk estimation

Ambient gas and particle phase samples were collected during two sampling periods from a residential area of an industrialized city, Kocaeli, Turkey. The sampling occurred during winter months when structures were being heated, and summer months when structures were not being heated. Σ(13)PAH (gas + particle) concentrations ranged between 6.2 ng m(-3) (DahA) and 98.6 ng m(-3) (Phe) in the heating (winter) period and 3.0 ng m(-3) (BaA) and 35.1 ng m(-3) (Phe) in the non-heating (summer) period. Phe, Flt and Pyr were found to be at high concentrations in both sampling periods. Winter time to summer time concentration ratios for individual ambient PAH concentration ratios ranged between 1.2 (DahA) and 17.5 (Flu), indicating the effect of the emissions from residential heating on measured concentrations of PAHs, but great industrial plants and the only incinerator facility of Turkey are other important pollution sources around the city. Temperature dependence of gas phase PAHs was investigated using the Clausius-Clapeyron equation. A high slope obtained (5069.7) indicated the effect of the local sources on measured gas phase PAHs. Correlation of the supercooled vapor pressure (P) with the gas particle partitioning coefficient (K(p)) and particle phase fraction was also evaluated. The relationship between the meteorological parameters and individual PAH (gas + particle) concentrations was investigated further by multiple linear regression analysis. It was found that the temperature had a significant effect on all of the measured PAH concentrations, while the effects of the wind speed and direction were not significant on the individual PAHs. On the other hand, PAH concentrations showed a strong linear relationship with the ventilation coefficient (VC) which showed the influence of local sources on measured PAHs. Benzo[a]pyrene toxic equivalent (BaP(eq.)) concentrations were used for health risk assessment purposes. The winter period risk level (2.92 × 10(-3)) due to the respiratory exposure to PAHs was found to be almost 3 times higher than in the summer period (1.15 × 10(-3)).     

An experimental design for the optimization of the extraction methods of metallic mobile fractions from environmental solid samples

The evaluation of the cadmium and lead mobile forms from environmental solid samples provides information about their mobility and bioavailability. In the present study, the Cd and Pb mobile fractions were obtained by two modified extraction methods applied to industrial and acidic pH soils or to polluted sediments. In order to highlight that the extraction procedure does not significantly influence the quantitative atomic absorption spectrometric determination of cadmium and lead, the robustness of the extraction methods was evaluated and proven applying a Youden and Steiner factorial design. Within this experimental design, the shaking rate, the shaking time, and the solid/liquid extraction ratio were modified. The measurement uncertainty of the whole analytical procedure was assessed, the contribution of the factors involved in the extraction process being insignificant compared to the other uncertainty sources. The importance of the study is related to the fact that it proves the applicability in the routine laboratory practice of the modified extraction methods by increasing the extraction ratio following thorough optimization and robustness studies.     

Spatial and temporal distribution of polycyclic aromatic hydrocarbons (PAHs) in sediments of the Nansi Lake, China

Polycyclic aromatic hydrocarbons (PAHs) were measured in surface sediments and dated core sediments from the Nansi Lake of China to investigate the spatial and temporal distribution characteristics. The concentrations of 16 kinds priority PAH compounds were determined by GC-MS method. And ²¹⁰Pb isotope dating method was used to determine the chronological age of the sediment as well as the deposition rate. The results indicated that the total PAHs concentration ranges in surface and core sediment samples were 160 ~32,600 and 137 ~ 693 ng/g (dry wt.), respectively. The sediment rate and the average mass sedimentation were calculated to be 0.330 cm·year^???1 and 0.237 g·cm^???2·yr^???1 and the sediment time of the collected core sample ranged from 1899 to 2000. The peak of PAH concentrations came at recent years. The source analysis showed PAHs mainly came from the contamination of low temperature pyrogenic processes, such as coal combustion. The PAHs concentrations were lower than ERL and LEL values for most collected samples. However, in several surface sediment samples especially in estuary sites, the PAHs concentrations were not only higher than ERL and LEL values, but also higher than ERM values.     

SI-traceable certification of Cu, Cr, Cd and Pb in sediment and fly ash candidate reference materials

Many fields in environmental analytical chemistry deal with very low limits and thresholds as set by governmental legislations or transnational regulations. The need for the accuracy, comparability and traceability of analytical measurements in environmental analytical chemistry has significantly increased and total uncertainties are even asked for by accreditation bodies of environmental laboratories. This paper addresses achieving these goals to guarantee accuracy, quality control, quality assurance or validation of a method by means of certified reference materials. The assessment of analytical results in certified reference materials must be as accurate as possible and every single step has to be fully evaluated. This paper presents the SI-traceable certification of Cu, Cr, Cd and Pb contents in geological and environmentally relevant matrices (three sediments and one fly ash sample). Certification was achieved using isotope dilution (ID) ICPMS as a primary method of measurement. In order to reduce significantly the number of analytical steps and intermediate samples a multiple spiking approach was developed. The full methodology is documented and total uncertainty budgets are calculated for all certified values. A non-element specific sample digestion process was optimised. All wet chemical digestion methods examined resulted in a more or less pronounced amount of precipitate. It is demonstrated that these precipitates originate mainly from secondary formation of fluorides (essentially CaF2) and that their formation takes place after isotopic equilibration. The contribution to the total uncertainty of the final values resulting from the formation of such precipitates was in general < 0.1% for all investigated elements. Other sources of uncertainty scrutinised included the moisture content determination, procedural blank determination, cross-contamination from the different spike materials, correction for spectral interferences, instrumental background and deadtime effects, as well as the use of either certified values or IUPAC data in the IDMS equation. The average elemental content in the sediment samples was 30-130 micrograms g-1 for Pb, 0.5-3 micrograms g-1 for Cd and 50-70 micrograms g-1 for Cu. Cr was measured in one sample and was about 60 micrograms g-1. The concentrations in the fly ash sample were up to 2 orders of magnitude higher. Expanded uncertainty for the investigated elements was about 3% (coverae factor k = 2) except for Cr, (measured by high resolution ICPMS), for which the expanded uncertainty was about 7% (k = 2).     

Nitrous oxide emissions from waste water

The estimation of nitrous oxide emissions is complicated by the high degree of uncertainty on the emission factors involved and by the limited acquaintance with all significant nitrous oxide sources. A potentially important source for which emission data are lacking is the sewage system transporting waste water from human activities. For this study an experimental measurement campaign has been carried out on waste water sampled at different sewage treatment plants. The nitrous oxide developing from the water samples was monitored by means of gas chromatography. The methodological analysis was based on the concentration/time curves obtained. Our results indicate that the formation of nitrous oxide from the waste water matrices results from microbiological denitrification. We deduced tentative emission factors for the waste water types studied.     

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%。