影响顶空-气相色谱法测定水中吡啶准确度的关键因素探讨

通过试验,讨论盐析效应、顶空的平衡温度和平衡时间、水样的p H值、色谱条件等对顶空-气相色谱法测定环境水体中吡啶准确度的影响。优化上述条件后,方法在0 mg/L~3.95 mg/L范围内线性良好,检出限可达0.016 mg/L,测定下限为0.064 mg/L。用该方法对地表水和生活污水做3个质量浓度水平的加标回收试验,测定6次结果的RSD为1.7%~5.7%,回收率为93.9%~113%。     

低温空管冷冻浓缩技术-GC-MS-FID法自动监测环境空气中VOCs

环境空气中VOCs的自动监测数据是研究重污染天气成因的一个重要依据。低温空管冷冻浓缩技术-GC-MSFID法,可用于环境空气中多组分VOCs复杂样品的自动监测,性能优于吸附管浓缩法。低温空管冷冻浓缩技术的采样流量、采样时间、冷冻温度等条件对环境空气中VOCs的测定有很大影响。实验结果表明:高采样流量低采样时间条件下,低沸点卤代烃捕集效率偏低;低采样流量长采样时间,-120℃捕集温度可满足各类VOCs的测试。降低采样流量增加采样时间,沸点较高的各类VOCs的捕集效率比较高。相同捕集温度下,降低采样体积,各类VOCs的响应同步降低,可用于高浓度C_5~C_(12)碳氢化合物、卤代烃和醛酮含氧化合物样品的测定。     

In-vivo passive sampling to measure elimination kinetics in bioaccumulation tests

The application of in-tissue passive sampling to quantify chemical kinetics in fish bioconcentration experiments was investigated. A passive sampler consisting of an acupuncture needle covered with a PDMS tube was developed together with a method for its deployment in rainbow trout. The time to steady state for chemical uptake into the passive sampler was >1 d, so it was employed as a kinetically limited sampler with a deployment time of 2 h. The passive sampler was employed in parallel with the established whole tissue extraction method to study the elimination kinetics of 10 diverse chemicals in rainbow trout. 4-n-nonylphenol and 2,4,6-tri-tert-butylphenol were close to or below the limit of quantification in the sampler. For chlorpyrifos, musk xylene, hexachlorobenzene, 2,5-dichlorobiphenyl and p,p′-DDT, the elimination rate constants determined with the passive sampler method and the established method agreed within 18%. Poorer agreement (35%) was observed for 2,3,4-trichloroanisole and p-diisopropylbenzene because fewer data were obtained with the passive sampling method due to its lower sensitivity. The work shows that in-tissue passive sampling can be employed to measure contaminant elimination kinetics in fish. This opens up the possibility of studying contaminant kinetics in individual fish, thereby reducing the fish requirements and analytical costs for the determination of bioconcentration factors.     

临安区域本底站大气甲烷浓度变化特征

通过分析2006年8月～2009年7月临安区域大气本底站Flask瓶采样获得的CH4浓度特征,结合地面风向、后向轨迹、排放清单,研究了CH4浓度变化特征和长三角地区排放源对CH4浓度的影响作用。结果表明,临安区域大气本底站的CH4浓度分布在1 7584×10-9~1 9700×10-9,具有较明显的季节波动变化特征,浓度季节变化幅度为737×10-9;CH4浓度平均年增幅达176×10-9,增速较快。东北风和东南风时,CH4浓度较高;西南风时CH4浓度较低。导致CH4高浓度分布的气团主要来自临安站的东北、偏东方向;导致CH4低浓度分布的气团集中在西南 偏南     

Uncertainty Analysis of Hydrologic and Water Quality Predictions for a Small Watershed Using SWAT2000

Hydrologic and water quality (H/WQ) models are being used with increasing frequency to devise alternative pollution control strategies. It has been recognized that such models may have a large degree of uncertainty associated with their predictions, and that this uncertainty can significantly impact the utility of the model. In this study, ARRAMIS (Advanced Risk & Reliability Assessment Model) software package was used to analyze the uncertainty of the SWAT2000 (Soil and Water Assessment Tool) outputs concerning nutrients and sediment losses from agricultural lands. ARRAMIS applies Monte Carlo simulation technique connected with Latin hypercube sampling (LHS) scheme. This technique is applied to the Warner Creek watershed located in the Piedmont physiographic region of Maryland, and it provides an interval estimate of a range of values with an associated probability instead of a point estimate of a particular pollutant constituent. Uncertainty of model outputs was investigated using LHS scheme with restricted pairing for the model input sampling. Probability distribution functions (pdfs) for each of the 50 model simulations were constructed from these results. Model output distributions of interest in this analysis were stream flow, sediment, organic nitrogen (organic-N), organic phosphorus (organic-P), nitrate, ammonium, and mineral phosphorus (mineral-P) transported with water. Developed probability distribution functions for the model provided information with desirable probability. Results indicate that consideration of input parameter uncertainty produces 64% less mean stream flow along with approximately 8.2% larger sediment loading than obtained using mean input parameters. On the contrary, mean of outputs regarding nutrients such as nitrate, ammonia, organic-N, and organic-P (but not mineral-P) were almost the same as the one using mean input parameters. The uncertainty in predicted stream flow and sediment loading is large, but that for nutrient loadings is the same as that of the corresponding input parameters. This study concluded that using a best possible distribution for the input parameters to reflect the impact of soils and land use diversity in a small watershed on SWAT2000 model outputs may be more accurate than using average values for each input parameter.     

烧结烟气中SO3的测定

建立了烧结烟气中SO3的检测技术,包括SO3的采集装置和测定方法。实验结果表明:质量分数为80%的异丙醇适宜作为吸收液,方法的回收率为95.79%~102.80%,相对标准偏差为0.46%~1.38%。该技术能有效消除烟气中粉尘及SO2对测定的干扰,具有准确、可靠、方便等特点,可应用于烧结烟气脱硫等装置日常运行中SO3含量的测定。     

Passive air monitoring of PCBs and PCNs across East Asia: a comprehensive congener evaluation for source characterization

A comprehensive congener specific evaluation of polychlorinated biphenyls (PCBs) and polychlorinated naphthalenes (PCNs) in the atmosphere was conducted across East Asia in spring 2008, applying polyurethane foam (PUF) disk passive air sampler (PAS) as monitoring device. Mean concentrations derived for Japan, China and Korea were 184 ± 24, 1100 ± 118, and 156 ± 20 pg m⁻³ for ∑₂₀₂ PCBs, and 9.5 ± 1.5, 61 ± 6, and 16 ± 2.4 pg m⁻³ for ∑₆₃ PCNs, respectively. Relative to reported data from 2004, the present results suggest that air PCBs concentrations have not changed much in Japan and Korea, while it has increased by one order of magnitude in China. From principal component analysis, combustion emerged highly culpable in contemporary emissions of both PCBs and PCNs across the East Asian sub-region. Another factor derived as important to air PCBs was re-emissions/volatilization. Signals from PCBs formulations were also picked, but their general importance was virtually consigned to the re-emissions/volatilization tendencies. On the contrary, counterpart PCNs formulations did not appear to contribute much to air PCNs.     

Ozonation of azo dye Acid Red 14 in a microporous tube-in-tube microchannel reactor: decolorization and mechanism

Despite the great success of time-weighted average passive sampling of hydrophobic contaminants, such as PCBs and PAHs, the sampling of polar organic compounds still presents a challenge because the equilibrium between water and most sampling phases is attained in a relatively short time. In this study, we proposed a new time-integrative sampler using in situ solvent extraction (TISIS) for polar organic chemicals. The sampler was composed of a 15 cm poly(dimethylsiloxane) (PDMS) tubing, with an internal diameter of 0.5 mm and wall thickness of 0.5 mm, through which an extraction solvent (acetonitrile) was passed. Four polar organic contaminants, caffeine, atrazine, diuron and 17α-ethynylestradiol, were chosen for the evaluation of the performance of the sampler. Without the use of in situ solvent extraction, the PDMS tubing when exposed to a constant aqueous concentration of the four model compounds was able to linearly accumulate those compounds for less than 12 h and equilibrium between the PDMS tubing and water was attained in 2 d under our laboratory conditions. However, TISIS when exposed to a constant aqueous concentration was able to linearly accumulate all the model compounds without any exposure time limitation. The measured sampling rates at three different extraction flow rates (0.2, 0.5, 1.5 mL min⁻¹) were similar, regardless of the chemicals, indicating that the overall mass transfer from aqueous solution to the extraction solvent was most likely dominated by partitioning to the PDMS tubing and the internal diffusion within PDMS. In addition, a pulsed exposure experiment confirmed that TISIS operated in a time-integrative mode when the environmental concentration was highly fluctuated.     

A Sampler for Measuring Deposited Fine Sediments in Streams1

Turner, Andy W., Jeff J. Hillis, and Charles F. Rabeni, 2012. A Sampler for Measuring Deposited Fine Sediments in Streams. Journal of the American Water Resources Association (JAWRA) 48(2): 366‐378. DOI: 10.1111/j.1752‐1688.2011.00618.x Abstract: Improvements and standardization of methodologies to quickly and accurately quantify deposited sediment in streams will allow advances in our understanding of biological effects of sedimentation. Most methods used to evaluate streambed conditions as part of biological monitoring or assessment programs are selected for ease of use, but can be subjective, inappropriate, and often of unknown accuracy. We developed a portable, light‐weight device to quantify deposited unconsolidated sediment (particles <2 mm) in wadeable streams. This deposited sediment sampler is a hand‐held unit that circumscribes an area of the streambed and through suction creates a force that suspends unconsolidated materials into a collector. Laboratory evaluations determined the efficiency (percent of available deposited sediment recovered) of the sampler to collect different sizes and concentrations of deposited sediment under differing streambed conditions, which allowed appropriate correction factors to be applied to each of four categories of streambed particle size. Field trials comparing our sampler to other methods commonly used by many state and federal agencies showed high comparability. The sampler can be constructed in just a few hours from inexpensive, easily obtained materials.     

Influence of Sampling Frequency on Estimation of Annual Total Phosphorus and Total Suspended Solids Loads1

Abstract: The determination of sediment and nutrient loads is typically based on the collection and analysis of grab samples. The frequency and regularity of traditional sampling may not provide representation of constituent loading, particularly in systems with flashy hydrology. At two sites in the Little Bear River, Utah, continuous, high‐frequency turbidity was used with surrogate relationships to generate estimates of total phosphorus and total suspended solids concentrations, which were paired with discharge to estimate annual loads. The high frequency records were randomly subsampled to represent hourly, daily, weekly, and monthly sampling frequencies and to examine the effects of timing, and resulting annual load estimates were compared to the reference loads. Higher frequency sampling resulted in load estimates that better approximated the reference loads. The degree of bias was greater at the more hydrologically responsive site in the upper watershed, which required a higher sampling frequency than the lower watershed site to achieve the same level of accuracy in estimating the reference load. The hour of day and day of week of sampling impacted load estimation, depending on site and hydrologic conditions. The effects of sampling frequency on the determination of compliance with a water quality criterion were also examined. These techniques can be helpful in determining necessary sampling frequency to meet the objectives of a water quality monitoring program.