Reactive uptake of NO2 on volcanic particles: A possible source of HONO in the atmosphere

The heterogeneous degradation of nitrogen dioxide (NO₂) on five samples of natural Icelandic volcanic particles has been investigated. Laboratory experiments were carried out under simulated atmospheric conditions using a coated wall flow tube (CWFT). The CWFT reactor was coupled to a blue light nitrogen oxides analyzer (NO_x analyzer), and a long path absorption photometer (LOPAP) to monitor in real time the concentrations of NO₂, NO and HONO, respectively. Under dark and ambient relative humidity conditions, the steady state uptake coefficients of NO₂ varied significantly between the volcanic samples probably due to differences in magma composition and morphological variation related with the density of surface OH groups. The irradiation of the surface with simulated sunlight enhanced the uptake coefficients by a factor of three indicating that photo-induced processes on the surface of the dust occur. Furthermore, the product yields of NO and HONO were determined under both dark and simulated sunlight conditions. The relative humidity was found to influence the distribution of gaseous products, promoting the formation of gaseous HONO. A detailed reaction mechanism is proposed that supports our experimental observations. Regarding the atmospheric implications, our results suggest that the NO₂ degradation on volcanic particles and the corresponding formation of HONO is expected to be significant during volcanic dust storms or after a volcanic eruption.     

短期干旱胁迫对马尾松排放挥发性有机物的影响

为探究干旱环境对BVOCs排放的影响,应用动态封闭式采样系统和热脱附-气相色谱-飞行质谱仪,对短期干旱胁迫作用下马尾松的BVOCs排放进行了实验室测量,定量分析BVOCs排放速率和排放组成的变化.结果表明,干旱胁迫时异戊二烯的排放受到抑制,排放速率降低约50%;单萜烯和倍半萜烯的排放水平增强,排放速率分别为137.85和0.98μg/（m²·h）,是未受胁迫时的2.9和2.0倍.除反式-α-香柠檬烯外,干旱胁迫促进各单萜烯和倍半萜烯化合物的排放,是未受胁迫时的1.3~42.4倍,其中3-蒈烯排放的响应最敏感,α-葑烯、α-水芹烯和石竹烯的响应最弱.干旱胁迫时单萜烯和倍半萜烯的排放组成有所变化,但主导的化合物种类不变,单萜烯以α-蒎烯、香桧烯和β-蒎烯为主,占比分别为48%、17%和17%;倍半萜烯以石竹烯和长叶烯为主,占比分别为57%和34%.     

Mercury levels in human population from a mining district in Western Colombia

A biomonitoring study was carried out to examine the adverse impacts of total mercury in the blood(HgB), urine(Hg U) and human scalp hair(HgH) on the residents of a mining district in Colombia. Representative biological samples(scalp hair, urine and blood) were collected from volunteered participants(n = 63) to estimate the exposure levels of THg using a Direct mercury analyzer. The geometric mean of THg concentrations in the hair,urine and blood of males were 15.98 μg/g, 23.89 μg/L and 11.29 μg/L respectively, whereas the females presented values of 8.55 μg/g, 5.37 μg/L and 8.80 μg/L. Chronic urinary Hg(HgU)levels observed in male workers(32.53 μg/L) are attributed to their long termed exposures to inorganic and metallic mercury from gold panning activities. On an average, the levels of THg are increasing from blood(10.05 μg/L) to hair(12.27 μg/g) to urine(14.63 μg/L).Significant positive correlation was found between hair and blood urinary levels in both male and female individuals. Thus the present biomonitoring investigation to evaluate the Hg levels and associated health issues would positively form a framework for further developmental plans and policies in building an ecofriendly ecosystem.     

Assessment of uncertainty of NO2 measurements by the chemiluminescence method and discussion of the quality objective of the NO2 European Directive

Hereafter, an assessment of the ability of the chemiluminescence method to measure ambient NO2 with an accuracy within 15%, as requested by the data quality objective of European directive 1999/30/CE, is presented. In general, uncertainty is evaluated using the response to reference materials or by means of inter-comparisons used to determine some statistics like repeatability, reproducibility and calibration bias. These are incomplete approaches and the method of the Guide to the Expression of Uncertainty in Measurement, advised by the Directive, should be preferred. In fact, even if it requires a large data set, it allows the relative influence of all possible sources of uncertainty to be studied. The extent of NO2 uncertainty is mainly dependent on the level of NO. It is decreased by NOx and the correlation between NOx and NO. Furthermore, the uncertainty budget reveals that the contribution of accuracy of calibration standard, linearity, converter efficiency and drift of the analyser between calibration checks to the overall uncertainty is less important than the contribution of interference, mainly humidity and PAN in rural areas. The relative expanded uncertainty of the NO2 hourly average exceeds 30% for NO2 concentrations lower than 40 microg m(-3). Nevertheless, the data quality objective of 15% is reached for 200 microg m(-3), the hourly limit value of the European directive. On the contrary, at the limit value on the annual average, 40 microg m(-3), the data quality objective is not met if NO is higher than 100 microg m(-3). However, the data quality objective could be reached by correcting the measurements with the bias due to interference.     

Arsenic speciation in human hair: a new perspective for epidemiological assessment in chronic arsenicism

The analysis for arsenic in hair is commonly used in epidemiological studies to assess exposure to this toxic element. However, poor correlation between total arsenic concentration in hair and water sources have been found in previous studies. Exclusive determination of endogenous arsenic in the hair, excluding external contamination has become an analytical challenge. Arsenic speciation in hair appears as a new possibility for analytical assessing in As-exposure studies. This study applied a relative simple method for arsenic speciation in human hair based on water extraction and HPLC-HG-ICP-MS. The concentration of arsenic species in human hair was assessed in chronically As(V)-exposed populations from two villages (Esqui?a and Illapata) of the Atacama Desert, Chile. The arsenic concentrations in drinking water are 0.075 and 1.25 mg L(-1), respectively, where As(V) represented between 92 and 99.5% of the total arsenic of the consumed waters. On average, the total arsenic concentrations in hair from individuals of Esqui?a and Illapata were 0.7 and 6.1 microg g(-1), respectively. Four arsenic species, As(III), DMA(V), MMA(V) and As(V), were detected and quantified in the hair extracts. Assuming the found species in extracts represent the species in hair, more than 98% of the total arsenic in hair corresponded to inorganic As. On average, As(III) concentrations in hair were 0.25 and 3.75 microg g(-1) in Esqui?a and Illapata, respectively; while, the As(V) average concentrations were 0.15 and 0.45 microg g(-1) in Esqui?a and Illapata, respectively. Methylated species represent less than 2% of the extracted As (DMA(V)+ MMA(V)) in both populations. As(III) in hair shows the best correlation with chronic exposure to As(V) in comparison to other species and total arsenic. In fact, concentrations of As(total), As(III) and As(V) in hair samples are correlated with the age of the exposed individuals from Illapata (R= 0.65, 0.69, 0.57, respectively) and with the time of residence in this village (R= 0.54, 0.71 and 0.58, respectively).     

Multivariate analysis of the bioaccumulation of polychlorinated biphenyls (PCBs) in the marine pelagic food web from the southern part of the Baltic Sea,Poland

The concentration, pattern, bioaccumulation and biomagnification features of many chlorobiphenyl congeners including non- and mono-ortho chlorine substituted members have been determined in a pelagic food chain including mixed phyto- and zooplankton, herring (Clupea harengus), harbour porpoise (Phocoena phocoena) and black cormorants (Phalacrocorax carbo sinensis) collected from the southern part of the Baltic Proper. TCDD (tetrachlorodibenzo-p-dioxin) toxic equivalents (TEQs) in plankton, herring, harbour porpoise and cormorants were 0.42, 5.3, 79 and 2,700 pg g(-1) lipid weight, respectively. Concentrations of total polychlorinated biphenyls (PCBs) in plankton, herring, harbour porpoise and cormorants were 1.9, 120, 8700 and 2,100 ng g(-1) wet weight (210, 1,300, 10,000 and 42,000 ng g(-1) lipid weight) respectively. Herring, harbour porpoise and black cormorant apparently bioaccumulate many PCBs found in their food, and the values of the bioaccumulation factors (BAFs) for PCBs were approximately 10 in herring, 35 in harbour porpoise and up to 300 in breast muscle of cormorants. Harbour porpoise clearly is able to metabolize the most toxic non-ortho PCBs (no. 77, 126 and 169) and a few mono-ortho PCBs (no. 114, 123 and 156), while all non- and mono-ortho PCBs are bioaccumulated by herring. Penta-, hexa- and hepta-CBs were the dominatant homologue classes both in the muscle tissue and liver. PCB congeners nos. 201, 209, 172/192, 194 and 195 were characterized by the largest BAFs (between 100 and 300). Principal component analysis has been used to analyse the interdependences and differences in the CB congener accumulation patterns between the components of the investigated pelagic food web.     

用广义λ—分布拟合空气污染数据

广义λ-分布是一个四参数可变通的概率模型,包括多种单变量分布,这一模型可用于表示空气污染浓度的频率分布。本文采用土耳其安卡拉每日的烟和SO_2监测数据,来证明广义λ-分布具有良好的拟合性质。这里还讨论了与分位数估计和拟合优度有关的一些结果,并与经典对数正态分布进行了比较。     

Suggested protocol for collecting, handling and preparing peat cores and peat samples for physical, chemical, mineralogical and isotopic analyses

For detailed reconstructions of atmospheric metal deposition using peat cores from bogs, a comprehensive protocol for working with peat cores is proposed. The first step is to locate and determine suitable sampling sites in accordance with the principal goal of the study, the period of time of interest and the precision required. Using the state of the art procedures and field equipment, peat cores are collected in such a way as to provide high quality records for paleoenvironmental study. Pertinent field observations gathered during the fieldwork are recorded in a field report. Cores are kept frozen at -18 degree C until they can be prepared in the laboratory. Frozen peat cores are precisely cut into 1 cm slices using a stainless steel band saw with stainless steel blades. The outside edges of each slice are removed using a titanium knife to avoid any possible contamination which might have occurred during the sampling and handling stage. Each slice is split, with one-half kept frozen for future studies (archived), and the other half further subdivided for physical, chemical, and mineralogical analyses. Physical parameters such as ash and water contents, the bulk density and the degree of decomposition of the peat are determined using established methods. A subsample is dried overnight at 105 degree C in a drying oven and milled in a centrifugal mill with titanium sieve. Prior to any expensive and time consuming chemical procedures and analyses, the resulting powdered samples, after manual homogenisation, are measured for more than twenty-two major and trace elements using non-destructive X-Ray fluorescence (XRF) methods. This approach provides lots of valuable geochemical data which documents the natural geochemical processes which occur in the peat profiles and their possible effect on the trace metal profiles. The development, evaluation and use of peat cores from bogs as archives of high-resolution records of atmospheric deposition of mineral dust and trace elements have led to the development of many analytical procedures which now permit the measurement of a wide range of elements in peat samples such as lead and lead isotope ratios, mercury, arsenic, antimony, silver, molybdenum, thorium, uranium, rare earth elements. Radiometric methods (the carbon bomb pulse of (14)C, (210)Pb and conventional (14)C dating) are combined to allow reliable age-depth models to be reconstructed for each peat profile.     

Development of an ombrotrophic peat bog (low ash) reference material for the determination of elemental concentrations

Given the increasing interest in using peat bogs as archives of atmospheric metal deposition, the lack of validated sample preparation methods and suitable certified reference materials has hindered not only the quality assurance of the generated analytical data but also the interpretation and comparison of peat core metal profiles from different laboratories in the international community. Reference materials play an important role in the evaluation of the accuracy of analytical results and are essential parts of good laboratory practice. An ombrotrophic peat bog reference material has been developed by 14 laboratories from nine countries in an inter-laboratory comparison between February and October 2002. The material has been characterised for both acid-extractable and total concentrations of a range of elements, including Al, As, Ca, Cd, Cr, Cu, Fe, Hg, Mg, Mn, Na, Ni, P, Pb, Ti, V and Zn. The steps involved in the production of the reference material (i.e. collection and preparation, homogeneity and stability studies, and certification) are described in detail.     

Natural mercury enrichment in a minerogenic fen--evaluation of sources and processes

Mercury (Hg) records in natural archives such as peat bogs are often used to evaluate anthropogenic or climatic influences on atmospheric Hg deposition. In this context, there is an ongoing discussion about natural sources or processes of Hg enrichment in natural archives. In the present study we estimated Hg fluxes from rock weathering, direct atmospheric deposition and from indirect atmospheric deposition in the catchment of a pristine minerogenic fen (GC2) located in the Magellanic Moorlands, southernmost Chile. The Hg record in the bog covers 11 174 cal. (14)C years and shows Hg concentrations of up to 570 [micro sign]g kg(-1) with an average of 268 [micro sign]g kg(-1). Hg was found to be enriched in the peat by a factor of 81 if compared to the mean Hg concentrations in the rocks of the catchment (3.2 [micro sign]g kg(-1)). Hg and also Pb, Fe, and As were found to be enriched predominately in goethite layers indicating high retention of these elements in the bog by iron oxyhydrates. It could also be demonstrated that the high peat decomposition rates in minerogenic bogs can increase the Hg concentrations in the minerogenic peat by a factor of approximately 2 at the same atmospheric Hg deposition rate if compared to ombrotrophic sites. This study has shown that Hg in minerogenic peat can be naturally enriched especially through the retention by autochthonous formed goethite and can be a solely internal process which does not require increased external Hg fluxes.