Partitioning between soluble and insoluble fractions of major and trace elements in size-classified airborne particulate matter collected in Tokyo

Airborne particulate matter (APM) is a major air pollutant, and the effect on human health of fine APM (PM2.5) deposited deep inside the lungs has recently become a serious concern. Moreover, soluble constituents may leach from APM, and intensify some health disorders. To identify the soluble chemical constituents of APM, size-classified APM was sampled in central Tokyo, and the elemental compositions of the water-soluble, acid-soluble and insoluble fractions were investigated. The extraction procedure was validated by calculating the mass balance of soluble and insoluble fractions of a standard APM reference material (NIST SRM 1648). Among the major elements, Fe and Ti in APM of all size classes and K in coarse APM were distributed primarily in the insoluble fraction and were inferred to be present as oxides or silicates, whereas Na and Mg in all size classes and K in fine APM were primarily in the water-soluble fraction and were inferred to be have originated mainly from sea salt. Among the trace elements, Zn and Cd in the fine APM (d < 2 microm) had large enrichment factors, indicating an anthropogenic origin, and were distributed primarily in the water-soluble fraction. When fine anthropogenic APM enters into the lungs, leached toxic elements, such as Cd, may adversely affect health. The higher the bonding energy of the monoxide molecule of the element was, the higher its distribution ratio was in the water-soluble fraction. Therefore, many metallic elements in APM were inferred to be present as oxygen-bonded compounds.     

Interlaboratory evaluation of trace element determination in workplace air filter samples by inductively coupled plasma mass spectrometry

Inductively coupled plasma mass spectrometry (ICP-MS) is becoming more widely used for trace elemental analysis in the occupational hygiene field, and consequently new ICP-MS international standard procedures have been promulgated by ASTM International and ISO. However, there is a dearth of interlaboratory performance data for this analytical methodology. In an effort to fill this data void, an interlaboratory evaluation of ICP-MS for determining trace elements in workplace air samples was conducted, towards fulfillment of method validation requirements for international voluntary consensus standard test methods. The study was performed in accordance with applicable statistical procedures for investigating interlaboratory precision. The evaluation was carried out using certified 37-mm diameter mixed-cellulose ester (MCE) filters that were fortified with 21 elements of concern in occupational hygiene. Elements were spiked at levels ranging from 0.025 to 10 μg filter(-1), with three different filter loadings denoted "Low", "Medium" and "High". Participating laboratories were recruited from a pool of over fifty invitees; ultimately twenty laboratories from Europe, North America and Asia submitted results. Triplicates of each certified filter with elemental contents at three different levels, plus media blanks spiked with reagent, were conveyed to each volunteer laboratory. Each participant was also provided a copy of the test method which each participant was asked to follow; spiking levels were unknown to the participants. The laboratories were requested to prepare the filters by one of three sample preparation procedures, i.e., hotplate digestion, microwave digestion or hot block extraction, which were described in the test method. Participants were then asked to analyze aliquots of the prepared samples by ICP-MS, and to report their data in units of μg filter(-1). Most interlaboratory precision estimates were acceptable for medium- and high-level spikes (RSD <25%), but generally yielded greater uncertainties than were anticipated at the outset of the study.     

大气预浓缩仪-GC/FPD测定环境空气中的痕量硫化物

采用大气预浓缩仪-GC/FPD建立了环境空气中7种含硫化合物的测定方法。结果表明,经惰性化改造后的大气预浓缩仪-GC/FPD测定系统的基线低,对硫化物无残留。7种化合物的线性回归方程的相关系数均在0.995以上,高、中、低3种浓度的空白加标回收率分别为98.6%~105.3%、99.1%~103.7%、85.7%~99.7%,除硫化氢的相对标准偏差为10.9%外,其余6种含硫化合物的相对标准偏差可控制在6.9%以内。当进样体积为400 m L时,方法的检出限在0.10~1.1 ng/m3。CO2、H2O对实际样品的测定无干扰。因此,该方法能够满足目前监测工作的要求,更加适用于环境空气中痕量含硫化合物的测定。     

废水中有机污染指标监测方法的选择

综合考察了废水中各种有机污染物综合指标的测试对象、干扰、准确度、精确度及其分析测试技术等各种因素 ,对实现其自动化连续测量的影响。针对某些监测技术产生的严重二次污染问题 ,提出了绿色 (清洁 )监测技术的概念。文章认为在重点废水污染源安装在线监测系统实行总量控制的过程中 ,应避免使用造成严重二次污染的 CODCr在线监测仪 ,而应当采用臭氧氧化法在线监测仪 ,或其他综合指标 ,如 TOC     

Characterisation of trace elements and methylmercury in an estuarine sediment reference material, IAEA-405

An estuarine sediment sample, IAEA-405, was recently characterised for trace elements and methylmercury (MeHg) for ultimate use as a marine reference material. The reference values were calculated using data sets from 120 laboratories that participated in a world-wide intercomparison exercise. The data evaluation is highlighted, and includes comparisons of different analytical methods, as well as the distribution of data. Overall laboratory performance for this exercise was encouraging: 86 laboratories (72%) reported data with <25% outliers. There was sufficient acceptable data to establish recommended values for 17 elements and information values for a further 15 elements. In addition, a recommended value was established for methylmercury. The estuarine sediment sample, IAEA-405, can be used as a reference material for quality control in the determination of trace elements and methylmercury in moderately polluted sediments.     

Risk assessment of trace metals in an extreme environment sediment: shallow,hypersaline, alkaline,and industrial Lake Acıgöl,Denizli, Turkey

The major and trace element component of 48 recent sediment samples in three distinct intervals (0–10, 10–20, and 20–30 cm) from Lake Ac?göl is described to present the current contamination levels and grift structure of detrital and evaporate mineral patterns of these sediments in this extreme saline environment. The spatial and vertical concentrations of major oxides were not uniform in the each subsurface interval. However, similar spatial distribution patterns were observed for some major element couples, due mainly to the detrital and evaporate origin of these elements. A sequential extraction procedure including five distinct steps was also performed to determine the different bonds of trace elements in the <?60-μ particulate size of recent sediments. Eleven trace elements (Ni, Fe, Cd, Pb, Cu, Zn, As, Co, Cr, Al and Mn) in nine surface and subsurface sediment samples were analyzed with chemical partitioning procedures to determine the trace element percentage loads in these different sequential extraction phases. The obtained accuracy values via comparison of the bulk trace metal loads with the total loads of five extraction steps were satisfying for the Ni, Fe, Cd, Zn, and Co. While, bulk analysis results of the Cu, Ni, and V elements have good correlation with total organic matter, organic fraction of sequential extraction characterized by Cu, As, Cd, and Pb. Shallow Lake Ac?göl sediment is characteristic with two different redox layer a) oxic upper level sediments, where trace metals are mobilized, b) reduced subsurface level, where the trace metals are precipitated.     

Distribution and partitioning of trace metals in sediments of the lower reaches of the New Calabar River,Port Harcourt,Nigeria

The distribution of trace metals in sediments of the lower reaches of the New Calabar River, Nigeria was evaluated togetherwith the partitioning of their chemical species between fivegeochemical phases. Samplings were made in five zones at the lower reaches of the New Calaber River. All the trace metals were determined by AAS after selective chemical extractions andconcentrations given in g gm^-1 (dry weight basis). The average totalconcentrations found for trace metals in the sediment were (mean ± rsd.) Pb: 41.6 ± 0.29, Zn: 31.60 ± 0.42, Cd: 12.80 ± 0.92, Co: 92 ± 0.25, Cu: 25.5 ± 0.65 and Ni: 3.2 ± 0.25. Maxima and minima concentrations are inconsistent with previous studies in other rivers of this region. Spatial distribution revealed that the sources of trace metals into theriver appeared to be of non-point. Five contamination indices were applied in studying the partitioning of the trace metals inthe sediment. These indices provided bases for ascertaining the potential environmental risk of trace metals in the river system.The results denote high partition levels in the more mobile andmore dangerous phases.     

基于CFSv2的延伸期空气质量数值预报技术及效果评估

介绍了基于CFSv2产品开展空气质量数值模拟的技术方法以及基于该技术的成都市延伸期空气质量预报系统,评价了2019年9月25日至12月25日的预报结果,以2019年12月为例分析了系统对具体污染过程的预报能力。结果表明,系统AQI预报准确率为36.67%,等级预报准确率为68.93%,"时段1"的预报效果优于其余时段,但"时段2"和"时段3"在污染物浓度水平上仍然具有较高的参考价值。系统在PM2.5浓度、气温和气压的变化趋势上提供21 d左右的参考。后续工作中,将针对CFSv2产品开展气象模型参数方案优选,并尝试结合基于GFS产品驱动的常规业务数值预报产品为延伸期空气质量预报提供污染物浓度初始场,减少误差传递,从而提高延伸期空气质量预报产品的准确性和可用性。     

广东省空气质量等级预报准确性评估

对广东省空气质量等级预报准确性评估进行了探讨,结果表明,在不区分污染等级的情况下,2016年夏季广东各市的预报准确性差异较大,中山预报准确性达92%,是全省唯一一个准确性超过90%的城市,云浮最低,为53%。在区分污染等级时,实测为轻度及以上污染级别的情况下,各市的准确性普遍较低,仅佛山、东莞与广州的准确性达50%以上,而有11个城市的准确性为0。综合考虑不同污染级别的准确性得分后,佛山市排名第1,较不区分污染等级时的排名提前9名。指出,采用区分污染等级的预报效果评估办法更加适合广东空气污染较轻的区域。在首要污染物为臭氧的情况下,广东省平均的等级预报准确性低于首要污染物为其他物种的情况。     

Chemical Constituents of Fugitive Dust

Wind erosion selectively winnows the fine, most chemically concentrated portions of surface soils and results in the inter-regional transport of fugitive dust containing plant nutrients, trace elements and other soil-borne contaminants. We sampled and analyzed surface soils, sediments in transport over eroding fields, and attic dust from a small area of the Southern High Plains of Texas to characterize the physical nature and chemical constituents of these materials and to investigate techniques that would allow relatively rapid, low cost techniques for estimating the chemical constituents of fugitive dust from an eroding field. From chemical analyses of actively eroding sediments, it would appear that Ca is the only chemical species that is enriched more than others during the process of fugitive dust production. We found surface soil sieved to produce a sub-sample with particle diameters in the range of 53–74 μm to be a reasonably good surrogate for fugitive dust very near the source field, that sieved sub-samples with particle diameters <10 μm have a crustal enrichment factor of approximately 6, and that this factor, multiplied by the chemical contents of source soils, may be a reasonable estimator of fugitive PM₁₀ chemistry from the soils of interest. We also found that dust from tractor air cleaners provided a good surrogate for dust entrained by tillage and harvesting operations if the chemical species resulting from engine wear and exhaust were removed from the data set or scaled back to the average of enrichment factors noted for chemical species with no known anthropogenic sources. Chemical analyses of dust samples collected from attics approximately 4 km from the nearest source fields indicated that anthropogenic sources of several environmentally important nutrient and trace element species are much larger contributors, by up to nearly two orders of magnitude, to atmospheric loading and subsequent deposition than fugitive dust from eroding soils.     

Evaluating performance of stormwater sampling approaches using a dynamic watershed model

Accurate quantification of stormwater pollutant levels is essential for estimating overall contaminant discharge to receiving waters. Numerous sampling approaches exist that attempt to balance accuracy against the costs associated with the sampling method. This study employs a novel and practical approach of evaluating the accuracy of different stormwater monitoring methodologies using stormflows and constituent concentrations produced by a fully validated continuous simulation watershed model. A major advantage of using a watershed model to simulate pollutant concentrations is that a large number of storms representing a broad range of conditions can be applied in testing the various sampling approaches. Seventy-eight distinct methodologies were evaluated by "virtual samplings" of 166 simulated storms of varying size, intensity and duration, representing 14 years of storms in Ballona Creek near Los Angeles, California. The 78 methods can be grouped into four general strategies: volume-paced compositing, time-paced compositing, pollutograph sampling, and microsampling. The performances of each sampling strategy was evaluated by comparing the (1) median relative error between the virtually sampled and the true modeled event mean concentration (EMC) of each storm (accuracy), (2) median absolute deviation about the median or "MAD" of the relative error or (precision), and (3) the percentage of storms where sampling methods were within 10% of the true EMC (combined measures of accuracy and precision). Finally, costs associated with site setup, sampling, and laboratory analysis were estimated for each method. Pollutograph sampling consistently outperformed the other three methods both in terms of accuracy and precision, but was the most costly method evaluated. Time-paced sampling consistently underestimated while volume-paced sampling over estimated the storm EMCs. Microsampling performance approached that of pollutograph sampling at a substantial cost savings. The most efficient method for routine stormwater monitoring in terms of a balance between performance and cost was volume-paced microsampling, with variable sample pacing to ensure that the entirety of the storm was captured. Pollutograph sampling is recommended if the data are to be used for detailed analysis of runoff dynamics.     

Ensuring quality in long term environmental monitoring for chemical speciation

The awareness regarding quality assurance (QA) and quality control (QC) for environmental monitoring has considerably increased in the past few years, especially with respect to the determination of chemical species, since errors occurring at various levels may considerably affect the interpretation of results (e.g. studies of toxic impact, geochemical pathways, etc.). QA for environmental analysis covers a broad range of activities from sample collection to laboratory work and the approach for ensuring quality data should be considered in a global context. However, whereas great emphasis has been placed on QA within the laboratory, there have been few systematic attempts to evaluate risks of discrepancies related, for example, to field manipulations. The situation is even worse when monitoring is applied to relatively new fields such as chemical speciation. This paper outlines some of the main aspects of quality control of environmental analysis, including the validation of methods, sampling and sample handling, storage, etc., with special emphasis on the monitoring of chemical forms of elements (e.g. species of tin, mercury, lead and selenium).     

Comparison of ozone levels between working days and weekends in Athens,Greece

Athens has a major problem of ozone air pollution due to its climate which is dominated by hot and dry summers with intensesunshine. As a result there is a high violation of the air quality limits of ozone. By comparing ozone air pollution betweenweekdays and weekends it is possible to estimate the effect of the reduction of primary pollutants causing the formation ofozone on the levels of this pollutant. Thus it was estimated thatwhile during the weekends the concentrations of the ozone precursors (nitrogen oxides and volatile organic compounds) werereduced by the order of 10–20%, the effect on ozone levels was lower.     

环境空气VOCs在线监测中标准气体的比对研究

环境空气中挥发性有机物(VOCs)的在线监测技术近年来受到普遍关注.相对于传统的离线手工监测,在线监测能够解决监测数据时空代表性不足的问题,同时更好地满足环境质量连续监测和研究的需要.现有环境空气常规气体在线监测技术规范对量值溯源有较高的要求,其中标准气体的溯源和比对是质量控制和质量保证的根本.通过构建上海市环境空气V...     

Comparison of Streambed Sediment and Aquatic Biota as Media for Characterizing Trace Elements and Organochlorine Compounds in the Willamette Basin, Oregon

During 1992–93, 27 organochlorine compounds (pesticides plus total PCB) and 17 trace elements were analyzed in bed sediment and aquatic biota from 20 stream sites in the Willamette Basin as part of the U.S. Geological Survey's National Water-Quality Assessment Program. Data from each medium were compared to evaluate their relative effectiveness for assessing occurrence (broadly defined as documentation of important concentrations) of these constituents. Except for Cd, Hg, Se, and Ag, trace element concentrations generally were higher in bed sediment than in biota. Conversely, although frequencies of detection for organochlorine compounds in biota were only slightly greater than in bed sediment, actual concentrations in biota (normalized to lipid) were as much as 19 times those in sediment (normalized to organic carbon). Sculpin (Cottus spp.) and Asiatic clams (Corbicula fluminea), found at 14 and 7 sites, respectively, were the most widespread taxa collected during the study. Concentrations of trace elements, particularly As and Cu, were typically greater in Asiatic clams than in sculpin. In contrast, almost half of the organochlorine compounds analyzed were found in sculpin, but only DDT and its degradation products were detected in Asiatic clams; this may be related to the lipid content of sculpin, which was about three times higher than for clams. Thus, the medium of choice for assessing occurrence depends largely on the constituent(s) of interest.     

基于便携式氢火焰离子化检测器法测定固定污染源废气中非甲烷总烃的研究

通过实验室和固定污染源废气现场比对测试,对便携式氢火焰离子化检测器法(催化氧化法和气相色谱法)测定非甲烷总烃的检出限、转化效率、精密度和准确度等性能指标开展研究。实验室测试结果表明,便携式氢火焰离子化检测器法测定非甲烷总烃的检出下限(0. 3 mg/m³)、转化效率(98. 2%)、精密度(3. 49%)、准确度(-2. 38%)基本满足方法技术指标的要求,但是对于催化氧化法还需重点关注其转化效率。固定污染源废气现场比对测试结果表明,便携式氢火焰离子化检测器法与实验室方法测试结果的相对准确度(33. 2%)、相对误差(-9. 27%～23. 7%)基本能满足测试方法的测试要求,趋势性也保持一致,适用于现场测试。     

污染源自动监控相关问题探讨

简述了污染源自动监控现状,指出了目前自动监测数据的准确性难以保证,部分自动监测数据的合法性,排污企业直接付费方式及现场端建设规范、管理等方面存在的问题,提出应严格在线监测设备社会运营企业的经营许可与监督检查,采取必要的激励与处罚措施,安装监控设备"对症下药",积极制定地方法规、标准,为自动监测数据的应用清除障碍,改变运...     

Concentrations, enrichment and predominant sources of Sb and other trace elements in size classified airborne particulate matter collected in Tokyo from 1995 to 2004

APM was collected and trace elements existing in the particles were monitored since May 1995 in this study. APM sample was collected separately by size (d < 2 microm, 2-11 microm and >11 microm) on the roof of the university building (45 m above ground) in the campus of Faculty of Science and Engineering, Chuo University, Tokyo, Japan, using an Anderson low volume air sampler. The collected sample was digested by HNO3, H2O2 and HF using a microwave oven, and major elements (Na, Mg, Al, K, Ca and Fe) were measured by ICP-AES, and trace elements (Li, Be, Ti, V, Cr, Mn, Co, Ni, Cu, Zn, As, Se, Mo, Cd, Sb, Ba and Pb) were measured by ICP-MS. It was observed that the APM concentration was higher between the winter and the spring, compared to during the summer. The enrichment factor was calculated for each element in each set of APM (d < 2 microm, 2-11 microm and >11 microm). Seasonal trends of enrichment factors were examined, and the elements were classified into 3 groups according to the common seasonal behavior. It is likely that the elements in the same group have common origins. Toxic pollutant elements (Sb, Se, Cd, Pb and As) were found in small particles with d of <2 microm in concentrated levels. Antimony (Sb) had the highest enrichment factor, and the results suggested that Sb level in APM was extremely high. The origins of Sb were sought, and wastes from plastic incineration and brake pad wears of automobiles were suspected. Each set of APM (d < 2 microm, 2-11 microm and >11 microm) was classified by the shape, and the shape-dependent constituents of a single APM particle were quantitatively measured by SEM-EDX. High concentration of Sb was found in APM <2 microm and square particles. Particles less than 2 microm and square shaped particles were major particles produced by actual car braking experiments. From these experimental results it was concluded that the source of Sb in squared APM <2 microm is considered to be from brake pad wear.     

Environmental Monitoring of Heavy Metals in Bulgarian Black Sea Green Algae

Fe, Mn, Cu, Pb and Cd concentration distribution in six green macroalgae species from the Bulgarian Black Sea coast were determined. The measurement of these metals was carried out during six seasons from 1996 to 2002 using atomic absorption spectrometry (AAS). Samples were collected from eight different sites–Shabla, Kaliakra, Tuzlata, Ravda, Ahtopol and Sinemoretz. The obtained heavy metal (HM) data (mean values g/g) for all algae are: 650 ± 100 for Fe, 184 ± 15 for Mn, 5.6 ± 0.5 for Cu, 3.3 ± 0.3 for Pb and 1.1 ± 0.2 for Cd. The obtained HM contents indicate that different species demonstrate various degree of metal accumulation and the obtained higher values in the northern sector of the studied zone can be attributed to the discharge influence of the big rivers, entering the Black Sea–Danube, Dnyepr, Dnester and local pollutant emissions. All data show that there is no serious contamination in green macroalgae with heavy and toxic metals along the whole Bulgarian Black Sea coast.     

沈阳市冬季环境空气质量统计预报模型建立及应用

利用沈阳市2013年1—2月大气自动监测数据和同期气象资料,选取19项预报因子,采用逐步回归方法建立了沈阳市冬季环境空气质量统计预报模型,预报项目包括细颗粒物(PM2.5)、可吸入颗粒物(PM10)、二氧化硫(SO2)、二氧化氮(NO2)、一氧化碳(CO)日均浓度及臭氧(O3)日最大8 h平均浓度。2013年11月至2014年1月,应用该模型并结合人为经验修订,开展了沈阳市环境空气质量预报工作,预报结果与实测结果的对比验证结果表明,环境空气预测结果级别准确率达到79.1%,首要污染物准确率为73.6%。