Mobilization of aluminium and deposition on fish gills during sea salt episodes--catchment liming as countermeasure

Episodic events may be critical with respect to aluminium (Al) toxicity in moderately acidified salmon rivers. The present work demonstrates that sea salt episodes enhance the toxicity of Al in acidic rivers. The documented sea salt episode (300 [micro sign]M Cl) mobilized positively charged Al species (0.4 to 1.1 [micro sign]M Al(i)), enhanced the Al accumulation on fish gills (0.9 to 10 [micro sign]mol g(-1) dw) and caused increased stress responses (6 to15 mM blood glucose) in fish. Accumulated Al on gills remained high several days after the episode. The presented results are based on a six-week field study in two tributary rivers on the west coast of Norway. Changes in the river water qualities and Al speciation were followed using in situ fractionation techniques. Al accumulation on gills and stress responses were followed for Atlantic salmon (Salmo salar) kept in tanks continually exposed to the changing water quality. The potential mobilization of Al from the two catchments was studied by extracting soils with diluted seawater (salinity of 3). To counteract Al toxicity, one of the tributary catchments has been limed. The potential mobility of Al by sea salt was lower in limed soils compared to acid soils, and the Al deposition on fish gills (<3.5 [micro sign]mol g(-1) dw) and associated stress responses stayed low during the sea salt episode in the river draining the limed catchment. Thus, for acid river systems in coastal areas, catchment liming should be considered as a useful countermeasure for Al toxicity.     

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.     

PM10 Concentration Measurements in Dublin City

Mass Concentration of ambient particulate matter with an aerodynamic diameter less than 10µm (PM10) are reported for the first time for a range of sites in Dublin City over a 6 month period from January 1st 1996 to June 30th 1996. PM10 gravimetric mass concentration measurements are made with low flow Partisol 2000 air samplers using an impaction type PM10 inlet and 47mm diameter glass fibre filters. In addition, much finer time resolution measurements (minimum sampling frequency of 30 minutes) are made using a tapered element oscillating microbalance (TEOM) PM10 mass monitor. These PM10 mass concentrations methods are also compared with mass concentration inferred using the standard black smoke method. Analysis of the ambient mass concentration data with reference to traffic density and meteorological influences are presented. Results for the first six months of 1996 show that the average PM10 values range from a high of 49 µg m-3 at the Dublin city centre site to 14 µg m-3 at one of the suburban sites. Intercomparison between PM10 and black smoke mass concentrations show that the relationship is site specific. Statistical analysis between PM10 levels and car traffic number show a positive correlation while a weak negative correlation is found between PM10 levels and rainfall amount, wind speed and air temperature.     

石墨炉原子吸收光谱法测定环境空气中钴

采用超细玻璃纤维滤膜采集环境空气中钴,硝酸-过氧化氢-氢氟酸混合进行消解,采用硝酸镁和硝酸混合液作为基体改进剂,石墨炉原子吸收光谱法测定环境空气中钴。此方法对测定环境空气中钴的灵敏度、准确度都有很大的提高,方法的最低检出浓度为0.25μg/L,当采样体积为100 L,钴最低检出质量浓度为0.000 1 mg/m3。对实际样品进行分析,钴的加标回收率为91.0%~106.5%。     

Long-term measurement of volatile organic compounds in ambient air by canister-based one-week sampling method

A canister-based 1 week sampling method using a mechanical flow controller and a 6 L fused-silica-lined canister was evaluated for the long-term measurement of 47 VOCs in ambient air at pptv (volume/volume) to ppbv levels by use of a three-stage preconcentation method followed by GC-MS analysis. The GC conditions were initially optimized for complete separations of several pptv-level VOCs (e.g. vinyl chloride, 1,3-butadiene, acrylonitrile, 1,2-dichloroethane and chloroform) in ambient air because the selected ions are easily interfered with by coexisting C4-, C5-hydrocarbons and analytes presented at ppbv levels. Thirty-four VOCs determined by the 1 week and 24 h sampling method in December 16-22 (2002) had concentrations of 6.0-15000 pptv per compound. Concentrations of 28 VOCs (including polar VOCs (e.g. methyl isobutyl ketone and butyl acetate)) obtained by the method were approximately equal to the mean values calculated from 24 h sampling (< +/- 10% deviation). Six VOCs that had low concentrations of 6.0-43 pptv showed more than +/- 10% deviation. Thirteen VOCs were not detected during the entire sampling period. The effect of relative humidity or ozone for the specific VOCs (e.g. MIBK, butyl acetate, vinyl chloride, 1,3-butadiene and styrene) was negligible.     

Determination of metal partitioning in porewater extracted from the Seine River Estuary sediment (France)

Total dissolved trace and major metals and their partitioning in porewater sediment have been investigated at two sites in the Seine River estuary (France). For this purpose, solid phase extraction (SPE) has been employed using specific chelating resins for the separation and preconcentration of organic and inorganic forms of studied metals under controlled (N2) inert atmosphere. In fact, the study is focused on the development of a method for sample collection and handling under inert atmosphere in order to avoid some potential artefacts of the extracted porewater, to preserve the samples from possible chemical oxidation changes and to determine metals partitioning between organic and inorganic forms. For this point, a separation and preconcentration method using two columns in series (chelamine and C18 columns) was used. The trace and major metals fixed on the two resins for all determinations were stripped by nitric acid (2 M) and analyzed by Inductively Coupled Plasma Atomic Emission Spectroscopy (ICP-AES) and Zeeman Graphite Furnace Atomic Absorption Spectroscopy (ZGF-AAS). The relationship between the distribution of metals and physico-chemical parameters such as pH and Eh (redox potential) as a function of depth was discussed. Some tendency in the distributions and seasonal variability of these traces and major metals are improved. The concentrations for all studied metals decreased as a function of depth where iron and manganese were found at mg L(-1) levels and other metals were found at [micro sign]g L(-1) levels, as well as there were significant fractions of all metals (except of manganese) which were complexed by organic matter. The comparison of data for the major elements (Fe and Mn), obtained by direct determination (without preconcentration) and preconcentration, show a very good recovery.     

A comparison of sampling and analysis methods for low-ppbC levels of volatile organic compounds in ambient air

A carefully designed study was conducted during the summer of 1998 to collect samples of ambient air by canisters and compare the analysis results to direct sorbent preconcentration results taken at the time of sample collection. Thirty-two 1 h sample sets were taken, each composed of a "near-real-time" sample analyzed by an autoGC-MS XonTech 930/Varian Saturn 2000 system, and Summa and Silco canisters. Hourly total non-methane organic carbon (TNMOC), ozone, and meteorological measurements were also made. Each canister was analyzed on the autoGC-MS system for a target list of 108 volatile organic compounds (VOCs) and on a manual cryosampling GC-FID system. Comparisons were made between the collection and analysis methods. Because of the low sample loading (150-250 ppbC TNMOC), these comparisons were a stringent test of sample collection and analysis capabilities. The following specific conclusions may be drawn from this study. Reasonable precision (within 15% mean difference of duplicate analyses from the same canister) can be obtained for analyses of target VOCs at low-ppbC concentrations. Relative accuracy between the GC-MS and GC-FID analysis methods is excellent, as demonstrated by comparisons of analyses of the same canisters, if measurements are sufficiently above the detection limits. This is especially significant as the GC-MS and GC-FID were independently calibrated. While statistically significant differences may be observed between the results from canister and near-real-time samples, the differences were generally small and there were clear correlations between the canister results and the near-real-time results. Canister cleanliness limits detection below the EPA Method TO-14 acceptance standard of 0.2 ppbv (0.2-2 ppbC for target analytes).     

A passive sampling method to determine ammonia in ambient air

Ambient ammonia concentrations, mainly originating from agricultural activities, have increased in the last few decades in Europe. As a consequence, critical loads on oligotrophic ecosystems such as forests and mires are greatly exceeded. Monitoring of ambient ammonia concentrations is necessary in order to investigate source-receptor relationships. Measuring ambient ammonia concentrations continuously with high time resolution is very expensive and cost-efficient systems are required. Where time resolution is of minor importance, several cost-effective systems, mainly dry denuder and passive samplers, can be applied. In this paper the Zürcher passive sampler, a diffusive sampling system, is presented. It is a Palmes type sampler with an acidic solution as absorbent and is easy to handle. It was tested at 46 sites in Switzerland over one year. The average concentration in ambient air was 2.5 microg m(-3) +/- 0.4 microg m(-3). The average of the blank values were 0.21 microg m(-3). The detection limit (double the standard deviation of the blank values) was 0.36 microg m(-3). Three passive samplers were exposed at each site and each period. The mean standard deviation of these triplicate measurements was 9.5%. Compared with a discontinuous tubular denuder system and a continuous annular denuder system, the deviation was less than 10%. The Zürcher passive sampler is a useful and cost-efficient tool to determine long-term average ammonia concentrations (one- to four-week periods) in ambient air for mean concentrations above 1 microg m(-3).     

Performance evaluation of a sorbent tube sampling method using short path thermal desorption for volatile organic compounds

Air sampling, using sorbents, thermal desorption and gas chromatography, is a versatile method for identifying and quantifying trace levels of volatile organic compounds (VOCs). Thermal desorption can provide high sensitivity, appropropriate choices of sorbents and method parameters can accommodate a wide range of compounds and high humidity, and automated short-path systems can minimize artifacts, losses and carry-over effects. This study evaluates the performance of a short-path thermal desorption method for 77 VOCs using laboratory and field tests and a dual sorbent system (Tenax GR, Carbosieve SIII). Laboratory tests showed that the method requirements for ambient air sampling were easily achieved for most compounds, e.g., using the average and standard deviation across target compounds, blank emissions were < or = 0.3 ng per sorbent tube for all target compounds except benzene, toluene and phenol; the method detection limit was 0.05 +/- 0.08 ppb, reproducibility was 12 +/- 6%, linearity, as the relative standard deviation of relative response factors, was 16 +/- 9%, desorption efficiency was 99 +/- 28%, samples stored for 1-6 weeks had recoveries of 87 +/- 9%, and high humidity samples had recoveries of 102 +/- 12%. Due to sorbent, column and detector characteristics, performance was somewhat poorer for phenol groups, ketones, and nitrogen containing compounds. The laboratory results were confirmed in an analysis of replicate samples collected in two field studies that sampled ambient air along roadways and indoor air in a large office building. Replicates collected under field conditions demonstrated good agreement except for very low concentrations or large (> 41 volume) samples of high humidity air. Overall, the method provides excellent performance and satisfactory throughput for many applications.     

加速溶剂萃取-高效液相色谱法测定环境空气中的苯并(a)芘

采用加速溶剂萃取一高效液相色谱法荧光检测器测定环境空气中的苯并（a）芘，以乙腈／水为流动相，检测器激发波长为290nm，发射波长为430nm。方法线性良好，检出限为0．08μg／L，当采样体积为1080m。时，最低检测质量浓度为3×10^-7μg／m^3（标准状态下），实际样品加标回收率为87．2％～109％。与超声波萃取法相比，两种方法回收率相近，而加速溶剂萃取法乙腈用量更少。     

Low-flow active and passive sampling of VOCs using thermal desorption tubes: theory and application at an offset printing facility

While air sampling techniques using adsorbent-based collection, thermal desorption and chromatographic analysis have found a niche in ambient air sampling, occupational applications have been more limited. This paper evaluates the use of thermal desorption techniques for low flow active and passive sampling configurations which allow conveniently long duration sampling in occupational settings and other high concentration environments. The use of an orifice enables flows as low as 0.5 ml min(-1) and sampling periods up to several days without significant biases. A model is used to predict sampling rates of a passive sampler encompassing an orifice, a void space, glass wool, and the adsorbent. Laboratory and field tests conducted at a commercial offset printing facility, which contained a variety of volatile organic compounds (primarily aromatic but also a few chlorinated and terpene compounds at levels from 1 to 67,000 microg m(-3)), are used to evaluate the approach. Tenax GR and Carbosieve SIII, both singly and together, were employed as adsorbents. Side-by-side tests comparing high flow, low flow and passive samplers show excellent agreement and high linearity (r = 0.95) for concentrations spanning nearly five orders of magnitude. Active samplers were tested at flows as low as 0.5 ml min(-1), compared to typical flows up to 40 ml min(-1). Passive samplers demonstrated a linear range and agreement with predictions for adsorbate loadings from approximately 1 ng to nearly 10 microg. Using a chemical mass balance receptor model, concentrations in the facility were apportioned to solvents, inks and other indoor and outdoor sources. Overall, the use of low flow active and passive sampling approaches employing thermal desorption techniques provides good performance and tremendous flexibility that facilitates use in many applications, including workplace settings.     

Large particles are responsible for elevated bacterial marker levels in school air upon occupation

Muramic acid (Mur) is found in bacterial peptidoglycan (PG) whereas 3-hydroxy fatty acids (3-OH FAs) are found in Gram-negative bacterial lipopolysaccharide (LPS). Thus Mur and 3-OH FAs serve as markers to assess bacterial levels in indoor air. An initial survey, in a school, demonstrated that the levels of dust, PG and LPS (pmol m(-3)) were each much higher in occupied rooms than in the same rooms when unoccupied. In each instance, the Mur content of dust was increased and the hydroxy fatty acid distribution changed similarly suggesting an alteration in the bacterial population. Here, findings are compared with results from two additional schools. Follow-up aerosol monitoring by particle size was also performed for the first time for all 3 schools. The particle size distribution was shown to be quite different in occupied versus unoccupied schoolrooms. Within individual classrooms, concentrations of airborne particles [greater-than-or-equal]0.8 [micro sign]m in diameter, and CO(2) were correlated. This suggests that the increased levels of larger particles are responsible for elevation of bacterial markers during occupation. Release of culturable and non-culturable bacteria or bacterial aggregates from children (e.g. from flaking skin) might explain this phenomenon.     

Determination of isocyanates, aminoisocyanates and amines in air formed during the thermal degradation of polyurethane

An air sampling method for the determination of isocyanates, aminoisocyanates and amines formed during the thermal degradation of polyurethane (PUR) is presented. The method is based on the collection of air samples using impinger flasks containing di-n-butylamine (DBA) in toluene with a glass fibre filter in series. Isocyanates are derivatized with DBA to urea derivatives, and amines are derivatized in a subsequent work-up procedure with ethyl chloroformate (ET) to carbamate esters. Amine, aminoisocyanate and isocyanate derivatives were characterized using liquid chromatography-time of flight mass spectrometry (LC-TOFMS) and liquid chromatography-chemiluminescent nitrogen detection (LC-CLND). Quantification was performed by LC-MS, monitoring molecular ions [MH]+ in the electrospray mode. The instrumental detection limits for amines, aminoisocyanates and isocyanates were in the ranges 30-40, 2-3 and 3-70 fmol, respectively. Thermal degradation products of PUR were observed in high concentrations during welding in district heating pipes and PUR-coated metal sheets. Eleven isocyanates, three amines and five aminoisocyanates were identified. The concentrations of isocyanates, aminoisocyanates and amines in samples collected in the smoke close to the welding spot were in the ranges 150-650, 4-290 and 1-70 ppb, respectively. In samples collected in the breathing zone, isocyanates and aminoisocyanates were observed in the ranges 9-120 and 4-19 ppb, respectively. The compounds were present in both gas and particle phases. Volatile compounds dominated in the gas phase, whereas less volatile compounds dominated in the particle phase. The method presented makes it possible to sample and determine amines and aminoisocyanates, in addition to isocyanates. The need to monitor these compounds is clearly illustrated by the high concentrations found during the thermal degradation of PUR.     

环境空气中二甲胺的测定

利用二甲胺与氯化铜及二硫化碳作用生成黄棕色二甲氨基二硫代甲酸铜的反应，分析测试环境空气中二甲胺的含量。确定了环境空气中二甲胺分析测试的显色温度和时间，采用2cm比色皿，以水为参比，在430nm处比色测定。结果表明，当采样流量为0．5L／min、采样时间为60min时，本方法检出限为0．007mg／m^3。该方法操作方便，精密度较好，能够满足环境空气中二甲胺的分析测试要求。     

Continuous and filter-based measurements of PM2.5 nitrate and sulfate at the Fresno Supersite

PM(2.5) nitrate [Formula: see text] and sulfate ([Formula: see text]) were measured continuously with R&P8400N and R&P8400S instruments, respectively, and compared with filter-based measurements at the Fresno Supersite from October, 2000 through December, 2005. [Formula: see text] concentrations were higher in winter than summer with a long-term decreasing trend. Correlations between 24-h average continuous and filter-based [Formula: see text] were greater than 0.96 in 4 out of 5 years. Continuous [Formula: see text] was generally lower than filter-based [Formula: see text] although the difference decreased over time, from -52% in 2001 to +13% in 2005. These differences were similar in winter (-23%) and summer (-19%) while the corresponding differences between ambient and instrument temperature were -12 and 0.7 degrees C, respectively. Neither seasonal nor long-term trends in [Formula: see text] can be explained by variations in ambient temperature, the difference between ambient and instrument temperature, or changes in aerosol chemical composition. There were no seasonal or long-term trends in [Formula: see text] concentrations, partially due to low concentrations observed in Fresno. Long-term variability in the performance of R&P8400 [Formula: see text] and [Formula: see text] instruments suggest that collocation with filter measurements is needed for long-term measurements.     

Arsenic compounds in the haemolymph of the Dungeness crab, Cancer magister, as determined by using HPLC on-line with inductively coupled plasma mass spectrometry

Arsenobetaine, two arsenosugars, dimethylarsinate and several unidentified arsenic species were detected in extracts of the haemolymph of the Dungeness crab, Cancer magister, by using HPLC-ICP-MS. This is the first report of the presence of arsenosugars in the haemolymph/blood of marine animals. Total, extractable and residual arsenic concentrations were determined by ICP-MS. The concentration of total arsenic was in the range of 1.4-3.8 [micro sign]g ml(-1). Nearly all (98%) the arsenic was found to be extractable, and accounted for primarily by arsenobetaine, two arsenosugars and dimethylarsinate. The results demonstrate that arsenic compounds present in the diet of crabs are not fully metabolized in the gut. They are, at least partly, taken up into the haemolymph. The concurrence of arsenobetaine and arsenosugars suggests that the use of repeated haemolymph sampling in crustaceans could facilitate investigations into the kinetics of the biotransformation pathways of arsenic compounds. Finally, the present study clearly demonstrates the unique capabilities of HPLC-ICP-MS for the detection and identification of minor arsenic components amongst the predominant arsenobetaine.     

Flow-injection analysis with fluorescence detection for the determination of trace levels of ammonium in seawater

A method using flow-injection, gas-diffusion, derivatisation and then fluorescent detection has been established for ammonium ion determination in seawater. The fluorescent derivative formed by reacting ortho-phthaldialdehyde (OPA) and sulfite with ammonia gives high sensitivity while removing potential interferences. This is required to measure the low concentrations of ammonium often seen in the open ocean. The experimental conditions (flow-rate, reagent concentrations, membrane configurations, etc.) were manipulated to improve performance. For a sample throughput of 30 samples h(-1), the limit of detection was 7 nM, the coefficient of variation was 5.7% at 800 nM, and the calibration curve was linear to at least 4 micromol L(-1). Interferences were minimised by a gaseous diffusion step. Volatile small molecular-weight amines as interferents were discriminated against by this method. They neither passed through the membrane as efficiently as ammonia, nor reacted as readily with OPA when sulfite was the reductant. Contamination by ammonia from laboratory and shipboard sources complicates application of the method to natural waters, especially measurement of low concentrations (<100 nM) in open-ocean waters. Steps to overcome contamination are described in detail. Some results are presented for ammonium determination in Southern Ocean and Huon Estuary (Tasmania) waters.     

广东省南海市主干道气溶胶中多环芳烃(PAHs)的研究

气溶胶采样点位于广东省南海市桂江路边缘及两侧 ,采集时间为 2 4 h,连续采集三天。使用仪器为国产大体积采样器。同时在公园内设点采样 ,以作背景研究。样品经超声波抽提和层析柱分离得到正构烷烃、芳烃 (AHs)和极性组分等三种有机组分。对 PAHs进行 GC MS分析 ,气溶胶中具有较高含量的芴、菲、蒽、荧蒽、芘、苯并 [a]蒽、、苯并 [b]荧蒽、苯并 [k]荧蒽、苯并 [a]芘、茚并 [1 ,2 ,3-cd]芘、二苯并 [a,h]蒽、苯并 [g,h,i]等。通过 TSP研究认为 ,主干道的机动车排放和扬尘是气溶胶的主要来源 ,气候改变也是 TSP变化的另一重要因素。     

Assessment of PAH pollution in the southern Baltic Sea through the analysis of sediment, mussels and fish bile

The concentrations of fifteen PAH compounds in samples of sediment and blue mussel tissue (Mytilus trossulus) were measured. In addition, the biliary polycyclic aromatic hydrocarbon metabolites present in flounder (Platichthys flesus) were analysed. Two methods were used in the analysis of PAH metabolites; high performance liquid chromatography (HPLC) and fixed wavelength fluorescence (FF). The major PAH metabolite which could be measured using the HPLC method was 1-OH pyrene. It was possible to detect 1-OH Phe and 3-OH B[a]P in 70 and 24 samples respectively, of the 87 samples analysed. However, the concentrations of 1-OH Phe and 3-OH B[a]P were below or near to the LOQ (0.002 μg ml(-1) bile). The bile of flounder samples from the Gulf of Gdańsk had 1-OH Pyr concentrations which ranged from 0.019 to 0.066 μg ml(-1) bile. The high linear correlation observed between the quantity of 1-OH pyrene determined by the HPLC-F method and the content of the sum of pyrene-type PAHs obtained by the FF method indicated the FF method of determination of pyrene-type PAH metabolites can be used as a screening method. The content of ∑(15)PAHs in sediments collected in the Gulf of Gdansk, in 2008, ranged from 29.3 to 103 μg kg(-1) dw. In mussel tissue ∑(15)PAHs concentrations were between 173.2 μg kg(-1) dw and 237.7 μg kg(-1) dw. All concentrations measured in the current study, in mussel tissue, were below the OSPAR toxicity threshold values.     

Characterization of ambient air quality during a rice straw burning episode

Spatiotemporal characteristics and impact of ambient air-quality attributed to open burning of rice straw were analyzed and estimated with measured data. Two multivariate analytic methods, factor analysis and cluster analysis, were adopted to analyze the temporal and spatial impact on ambient air-quality during the rice straw burning episode. Temporal features of three scenarios were cited to compare the concentrations for ambient air-quality between the rice straw burning episode and non-episodes over two typical stations by factor analysis. Factor analysis demonstrated that the first rotational component, identified as being highly correlated to the open burning of rice straw, accounts for about 40% of the concentration variance for ambient air-quality. In typical air-quality stations, the average hourly incremental concentrations between the episode and non-episodes were greater than 300 μg m(-3) for PM(10), 1.0 ppm for CO and 35 ppb for NO(2) during the impact of rice straw burning. Factor analysis presented that the first rotated component was highly correlated with several primary pollutants (NO(2), NMHC, PM(10) and CO) during the rice straw burning episode, while every component was only highly correlated with a unique air pollutant during non-episodes. The delineation isopleths indicated that factor analysis could serve as a better method than cluster analysis and provides cross-county cooperation for local governments located in the same separated district during the rice straw burning season. The results of factor analysis revealed that CO is the best index to demonstrate the impact of rice straw burning than the other six air pollutants measured during the episode. Backward trajectory analysis supplied a cause-effect relationship between measured stations and specific rice planted regions during the rice straw burning episode.