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.     

Performance evaluation of phycocyanin probes for the monitoring of cyanobacteria

The performance of two field probes (YSI 6600 and TriOS), used for the measurement of in vivo phycocyanin fluorescence, was compared and validated in the laboratory in 2008 and 2009 with cultures of Microcystis aeruginosa and field samples. The background noise of the two probes was low and the detection limits were estimated at 1500 cells mL(-1) for the YSI and 0.69 μg PC L(-1) for the TriOS. The linearity and repeatability of both probes have been excellent. Strong relationships were observed between the in vivo fluorescence and the total cyanobacterial biovolume (R(2) = 0.82 YSI; 0.83 TriOS) or the abundance (R(2) = 0.71 YSI; 0.75 TriOS) of cyanobacteria. However, the difference between cell densities determined by microscopy and measured by the YSI can be very large and has been associated to the variability of cell volume among cyanobacteria. This last observation makes the YSI a qualitative tool if a post-calibration is not done. The analysis of filtrated samples showed that dissolved phycocyanin (extracellular) may represent a significant fluorescence signal. No relationship could be established between the abundance, the total cyanobacterial biovolume or the in vivo fluorescence of phycocyanin and the concentrations of cyanotoxins (R(2) ≤ 0.22).     

Stabilities of 58 volatile organic compounds in fused-silica-lined and SUMMA polished canisters under various humidified conditions

Fused-silica-lined (FSL) canisters and SUMMA polished (SUMMA) canisters were compared for the recoveries and the stabilities of 58 volatile organic compounds (VOCs) at low ppbv (volume/volume) levels under various humidified conditions using a three-stage preconcentration method followed by GC-MS analysis. The target VOCs included non-polar VOCs (e.g. halogenated hydrocarbons and aromatic hydrocarbons) and polar VOCs (e.g. alcohols, ketones, esters, ethers, nitriles and thiols). The three-stage preconcentration method was initially optimized for simultaneous analysis of non-polar and polar VOCs because determination of canister stability is dependent on the accuracy of analytical measurements. The method showed good linearity over the concentration range from 1 to 25 ppbv for all target analytes, and the correlation coefficients were higher than 0.9974. The method detection limits ranged from 0.023 to 0.39 ppbv. The test mixtures loaded in both type of canisters (n = 3) had concentrations of 1.7-2.5 ppbv per compound at ambient pressure under various humidified conditions (%RH = 1.6, 8.0, 27, 39, 53 and >99% with excess water present). All canister samples were initially analyzed on day 0 (after 6-12 h). The effect of competitive adsorption of water vapor and polar VOCs on active sites of interior surface was remarkably observed for SUMMA canisters. Polar VOCs had a greater requirement for water vapor to be present. The RH percentages that ensured good recovery on day 0 were RH > 8% for non-polar VOCs and RH > 27% for polar VOCs (except alcohols under the condition of RH > 99%). All thiols were not recovered from SUMMA canisters under all conditions. FSL canisters showed good recoveries of more than 86% for all VOCs under all conditions on day 0 (except alcohols under the condition of RH > 99%). The recoveries of alcohols in both canisters under the condition of RH > 99% displayed relatively low recoveries in the range 25-76% because of the partitioning effect into condensed water. The canister samples under the conditions of RH 8.0, 27, 53 and > 99% were analyzed for the stability test on days 3, 7, 14 and 28 after loading. All non-polar VOCs were reasonably stable in the FSL canisters under all examined conditions over 28 days. However, several polar VOCs that have relatively lower vapor pressure, e.g. MIBK, butyl acetate and alcohols except ethanol, showed unstable characteristics under relatively dry conditions (RH 8 and 27%) during 28 days. RH > 53% was needed to ensure good stabilities of all analytes except thiols with the recoveries of > 80% over 28 days for both canisters. Although the FSL canister showed good recoveries of more than 86% for thiols on day 0, drastic degradations were observed after day 3 and they were not detected after day 14.     

对美国格林威治湾底栖动物造成危害的潜在胁迫因子的诊断

格林威治湾是纳拉甘西特湾一处受到多种影响因子作用的城市化形成港湾。本研究鉴定了对于格林威治湾底栖动物的重要影响因素。首先利用现存数据与信息来验证水体受损情况。其次确定了影响来源，影响因素和具体影响的存在。继而探究了来源，影响因素和具体影响之间的关系。这使我们能够鉴定出最可能危害水体的影响因素。本研究评估了化学制品、营养物质和悬浮沉积物3类污染物。这种证据权重的方法表明格林威治湾主要受到富营养化相关的影响因素危害。格林威治湾的沉积物富含碳，低溶解氧浓度的情况十分常见，尤其在格林威治湾西部。底栖生物群落出现发育不良的情况，与在氧气不足情况下的预测结果吻合。尽管我们的分析表明环境中的污染物浓度可能导致有害结果的出现，我们并未在结果中检出毒性。这是由于沉积物中存在大量的有机物，这些有机物限制了污染物的生物可利用性。我们的分析还表明悬浮沉积物的影响对于湾区的大部分区域而言几乎不存在。本分析展示了诊断法步骤可以用于组织和评估影响格林威治湾生态健康的潜在影响因素。诊断法步骤对于管理受到多重因素影响的水体非常有用。
精选自Marguerite Pelletier, Kay Ho, Mark Cantwell, Monique Perron, Kenneth Rocha, Robert M. Burgess, Roxanne Johnson, Kenneth Perez, John Cardin, Michael A. Charpentier. Diagnosis of potential stressors adversely affecting benthic invertebrate communities in Greenwich Bay, Rhode Island, USA. Environmental Toxicology and Chemistry: Volume 36, Issue 2, pages 449–462, July 2017. DOI: 10.1002/etc.3562
详情请见http://onlinelibrary.wiley.com/wol1/doi/10.1002/etc.3562/full
     

Photocatalytic degradation of humic acid in saline waters. Part 1. Artificial seawater: influence of TiO2, temperature,pH, and air-flow

We report the first systematic study on the photocatalytic oxidation of humic acid (HA) in artificial seawater (ASW). TiO(2) (Degussa P25) dispersions were used as the catalyst with irradiation from a medium-pressure mercury lamp. The optimum quantity of catalyst was found to be between 2 and 2.5 gl(-1); while the decomposition was fastest at low pH values (pH 4.5 in the range examined), and the optimum air-flow, using an immersion well reactor with a capacity of 400 ml, was 850 ml min(-1). Reactivity increased with air-flow up to this figure, above which foaming prevented operation of the reactor. Using pure oxygen, an optimal flow rate was observed at 300 ml min(-1), above which reactivity remains essentially constant. Following treatment for 1 h, low-salinity water (2700 mg l(-1)) was completely mineralised, whereas ASW (46000 mg l(-1)) had traces of HA remaining. These effects are interpreted and kinetic data presented. To avoid problems of precipitation due to change of ionic strength humic substances were prepared directly in ASW, and the effects of ASW on catalyst suspension and precipitation have been taken into account. The Langmuir-Hinshelwood kinetic model has been shown to be followed only approximately for the catalytic oxidation of HA in ASW. The activation energy for the reaction derived from an Arrhenius treatment was 17 (+/-0.6) kJ mol(-1).