提高碘量法测定天然气中硫化氢效率的方法

碘量法是测定管道输送天然气中硫化氢的一种经典方法,而管道输送天然气中硫化氢含量较低,按照GB/T11060.1–2010方法测定,取样量较大,取样时间长,影响工作效率。针对此问题,从两方面对碘量法进行改进:减小天然气取样量进行试验,并与国标规定取样量时的实验结果进行比对,确定最佳取样量;增大取样流量进行试验,并与国标规定取样流量时的实验结果进行比对,确定最佳取样流量。对硫化氢质量浓度为7.2~14.3,14.3~28.7 mg/m~3的天然气样品进行试验测定,结果表明,将天然气取样量减少为20 L,取样时间分别由200,100 min缩短为40 min;将天然气取样流量设定为750 m L/min,取样时间分别由200,100 min缩短为133,67 min。减少取样量或者提高取样流量,均能缩短管输天然气的取样时间,提高检测效率。     

固体分层取样方案的最优化设计

本文首次从理论上探讨了取得量对分层取样误差的影响,提出了总取样量一定时各层的最佳取样量和最小取样方差的计算公式,从而为分层取样的最佳取样方案设计提供了理论依据。     

Grab vs. composite sampling of particulate materials with significant spatial heterogeneity—A simulation study of “correct sampling errors”

Sampling errors can be divided into two classes, incorrect sampling and correct sampling errors. Incorrect sampling errors arise from incorrectly designed sampling equipment or procedures. Correct sampling errors are due to the heterogeneity of the material in sampling targets. Excluding the incorrect sampling errors, which can all be eliminated in practice although informed and diligent work is often needed, five factors dominate sampling variance: two factors related to material heterogeneity (analyte concentration; distributional heterogeneity) and three factors related to the sampling process itself (sample type, sample size, sampling modus). Due to highly significant interactions, a comprehensive appreciation of their combined effects is far from trivial and has in fact never been illustrated in detail. Heterogeneous materials can be well characterized by the two first factors, while all essential sampling process characteristics can be summarized by combinations of the latter three. We here present simulations based on an experimental design that varies all five factors. Within the framework of the Theory of Sampling, the empirical Total Sampling Error is a function of the fundamental sampling error and the grouping and segregation error interacting with a specific sampling process. We here illustrate absolute and relative sampling variance levels resulting from a wide array of simulated repeated samplings and express the effects by pertinent lot mean estimates and associated Root Mean Squared Errors/sampling variances, covering specific combinations of materials’ heterogeneity and typical sampling procedures as used in current science, technology and industry. Factors, levels and interactions are varied within limits selected to match realistic materials and sampling situations that mimic, e.g., sampling for genetically modified organisms; sampling of geological drill cores; sampling during off-loading 3-dimensional lots (shiploads, railroad cars, truckloads etc.) and scenarios representing a range of industrial manufacturing and production processes. A new simulation facility “SIMSAMP” is presented with selected results designed to show also the wider applicability potential. This contribution furthers a general exposé of all essential effects in the regimen covered by “correct sampling errors”, valid for all types of materials in which non-bias sampling can be achieved.     

Field sampling demonstration of portable thermal desorption collection and analysis instrumentation

The HAPSITE® (Hazardous Air Pollutants on Site) is a portable gas chromatography-mass spectrometry (GC–MS) unit designed to aid air sampling technicians by identifying and quantifying volatile organic compounds from occupational and environmental sampling. The main goal of the present study was to extend prior laboratory-based work with the portable HAPSITE® ER (extended range model) thermal desorption (TD) capability to real-world field samples from both indoor and outdoor environments using different types of active and passive sampling mechanisms. Understanding the performance of the HAPSITE® ER in a realistic field setting will allow air quality sampling technicians to make improved decisions related to sampling and analysis methods in the field. An important finding was that certain charcoal-based TD sorbents were contraindicated for the HAPSITE® ER because of a substantial hydrocarbon bleed which degraded system performance. A novel time series TD sampler (Logistically Enabled Sampling System-Portable [LESS-P]) was validated using Tenax TA TD tubes against standard active sampling across multiple field sampling sites, and the qualitative analytical trends and compound identities were similar between LESS-P replicates analysed via benchtop GC–MS and HAPSITE® ER. Once validated, the LESS-P was used to determine the reference concentrations for passive sampling calculations. The results confirmed the passive sampling methodology within the benchtop system, but highlighted some systemic sensitivity limitations that must be addressed in order for the HAPSITE® to be accurately applied to passive sampling. We propose that the LESS-P time-series sampler may help to alleviate the requirement for sampling technicians to be on-site during active sampling, allowing for automated sampling throughout the duration of a sampling event.     

探讨二元颗粒混合物取样误差的新的数学模型

采用新的数学模型研究二元颗粒混合物的取样误差,首次提出了取样的逻辑质量单元的理论,探讨了逻辑质量单元的物理意义,建立了按质量取样的标准偏差的计算公式.应用颗粒药品二元混合物的取样实验,证实了该公式的正确性.     

二元颗粒混合物按质量取样的误差研究

二元颗粒混合物的随机取样方式有两种：一是按颗粒数目取样,二是按质量取样本文对二元颗粒混合物按质量取样的误差进行了深入研究,详细分析了混合物的各种参对被测组分含量取样误差的影响,应用Ｍｏｎｔｅ Ｃａｒｌｏ技术对取样进行了模拟。以颗粒药品的二元混合物为例对按颗粒数目取样和按质量取样的误差进行了比较。此项研究对于分析取样理论和应用具有重要的价值。     

Solid-phase microextraction under controlled agitation conditions for rapid on-site sampling of organic pollutants in water

An electric drill coupled with a solid-phase microextraction (SPME) polydimethylsiloxane (PDMS) fiber or a PDMS thin film was used for rapid sampling of polycyclic aromatic hydrocarbons (PAHs) in aqueous samples. Laboratory experiments demonstrated that the sampling rates of SPME fiber and thin film can be predicted theoretically. Compared with the SPME fiber, the PDMS thin film active sampler exhibited a higher sampling rate and much better sensitivity due to its higher surface-to-volume ratio and its larger extraction phase volume. The amount of the analytes extracted by the thin film was around 100 times higher than those obtained by fiber, for both 5 min rapid sampling and equilibrium extraction. A new thin film active sampler was then developed for rapid on-site water sampling. The sampling kit included a portable electric drill, a copper mesh pocket, a piece of thin film, and a liner. Laboratory experiments indicated that the sampling remained in the linear uptake phase with this sampler to 8 min for the PAHs. Field test illustrated that this novel sampler was excellent for rapid on-site water sampling due to its short sampling period, high sampling efficiency and durability The thin film sampling kit facilitates on-site sampling, sample preparation, storage and transport. This new sampler is more user-friendly and easier to commercialize than previous samplers.     

Quantitative Sampling of Trace Organic Vapours by Gas Syringe and Porous Polymer Adsorbent Methods. A Comparative Study Using Naphthalene as a Reference Substance

Abstract

Two methods of sampling high molecular weight vapours, gas syringe sampling and porous polymer adsorbent sampling were studied. The methods were compared using a saturated naphthalene reference vapour of known concentration. The results showed that the porous polymer adsorbent method was more accurate than the gas syringe method. The accuracies of both methods were dependent on details in their respective techniques. For porous polymer adsorbents it was shown that the technique should be such that passive sampling did not occur. Sample volume, sampling rate, the number of fills before injecting and cleaning the syringe before sampling all influenced the accuracy of the gas syringe sampling method.     

在线采样技术在中国的发展

在线采样技术能实时采样,满足在线监测的采样要求。按照采样进样介质的不同分为气体、液体、固体三类。对气体中有毒气体、大气颗粒物、VOCs,液体中水样、原油,固体中煤的机械化采样技术进行了概述,旨在帮助了解在线采样技术在国内矿业、环境行业的发展和应用。随着5G时代的到来,在线采样技术一定会发挥越来越重要的作用。     

Sampling and sampling strategies for environmental analysis

Sampling errors are generally believed to dominate the errors of analytical measurement during the entire environmental data acquisition process. Unfortunately, environmental sampling errors are hardly quantified and documented even though analytical errors are frequently yet improperly reported to the third decimal point in environmental analysis. There is a significant discrepancy in directly applying traditional sampling theories (such as those developed for the binary particle systems) to trace levels of contaminants in complex environmental matrices with various spatial and temporal heterogeneities. The purpose of this critical review is to address several key issues in the development of an optimal sampling strategy with a primary goal of sample representativeness while minimizing the total number of samples and sampling frequencies, hence the cost for sampling and analysis. Several biased and statistically based sampling approaches commonly employed in environmental sampling (e.g. judgmental sampling and haphazard sampling vs. statistically based approaches such as simple random, systematic random, and stratified random sampling) are examined with respect to their pros and cons for the acquisition of scientifically reliable and legally defensible data. The effects of sample size, sample frequency and the use of compositing are addressed to illustrate the strategies for a cost reduction as well as an improved representativeness of sampling from spatially and temporally varied environmental systems. The discussions are accompanied with some recent advances and examples in the formulation of sampling strategies for the chemical or biological analysis of air, surface water, drinking water, groundwater, soil, and hazardous waste sites.     

Evaluation of needle trap micro-extraction and automatic alveolar sampling for point-of-care breath analysis

Needle trap devices (NTDs) have shown many advantages such as improved detection limits, reduced sampling time and volume, improved stability, and reproducibility if compared with other techniques used in breath analysis such as solid-phase extraction and solid-phase micro-extraction. Effects of sampling flow (2–30 ml/min) and volume (10–100 ml) were investigated in dry gas standards containing hydrocarbons, aldehydes, and aromatic compounds and in humid breath samples. NTDs contained (single-bed) polymer packing and (triple-bed) combinations of divinylbenzene/Carbopack X/Carboxen 1000. Substances were desorbed from the NTDs by means of thermal expansion and analyzed by gas chromatography-mass spectrometry. An automated CO₂-controlled sampling device for direct alveolar sampling at the point-of-care was developed and tested in pilot experiments. Adsorption efficiency for small volatile organic compounds decreased and breakthrough increased when sampling was done with polymer needles from a water-saturated matrix (breath) instead from dry gas. Humidity did not affect analysis with triple-bed NTDs. These NTDs showed only small dependencies on sampling flow and low breakthrough from 1–5 %. The new sampling device was able to control crucial parameters such as sampling flow and volume. With triple-bed NTDs, substance amounts increased linearly with increasing sample volume when alveolar breath was pre-concentrated automatically. When compared with manual sampling, automatic sampling showed comparable or better results. Thorough control of sampling and adequate choice of adsorption material is mandatory for application of needle trap micro-extraction in vivo. The new CO₂-controlled sampling device allows direct alveolar sampling at the point-of-care without the need of any additional sampling, storage, or pre-concentration steps.     

粒状物质的微观均匀度及其对取样误差的影响分析

研究物质的取样属性与以取样误差之间的关系是分析化学取样学的重要内容。从微观角度探讨了物质的理论性质及其对取样误差的影响。以碳化硅为例,考察了粒度分布、组分随粒度的变化以及均匀度因子等,分析了取样误差的来源。首次通过粒度分级成功地对碳化硅进行了分层,并对分层取样和随机取样的误差进行了分析和讨论,为制定合理的取样方案提供了有利的依据。本文的研究方法可适用于所有粒状物质的取样,同时也为分析化学取样学的深     

A divide-and-conquer strategy to improve diffusion sampling in generalized ensemble simulations

Generalized ensemble simulations generally suffer from the associated diffusion-sampling problem; the increased entropic barrier can greatly abolish sampling efficiency, in particular, with the increase of number of degrees of freedom in the target conformational space. Taking advantage of the recent simulated scaling method, we formulate a divide-and-conquer sampling strategy to solve this problem so as to robustly improve the sampling efficiency in generalized ensemble simulations. In the present method, the target conformational space sampling enhancement is decomposed to the sampling enhancements of several subconformational regions, and multiple independent SS simulations are performed to establish the individual sampling enhancement for each of the subconformational regions; in order to realize the global importance sampling, structure exchanges among these replicas are performed based on the Monte Carlo acceptance/rejection procedure. As demonstrated in our studies, the present divide-and-conquer sampling algorithm, named by us as "simulated scaling based variant Hamiltonian replica exchange method," has superior sampling capability so as to possibly play an essential role in dealing with the present bottleneck of generalized ensemble method developments: the system size limitations.     

Uncertainty of sampling in chemical analysis

 Uncertainty of sampling is the contribution from sampling errors to the combined uncertainty associated with an analytical measurement when the measurand is the concentration of the analyte in the 'target', the total bulk of material that the sample is meant to represent. Of the errors considered to contribute to uncertainty, random errors of sampling, characterised by precision, are much more accessible to investigation than those due to bias. Where an approximation to random sampling can be achieved, realistic precisions can normally be estimated. In some instances reproducibility precision is significantly greater than repeatability precision, and the contribution of between-sampler variations to sampling uncertainty must be acknowledged. However, the collaborative trial of a sampling method is an expensive and difficult exercise to execute. A system of internal quality control for routine sampling can be introduced. Fitness for purpose has been defined in terms of the required combined uncertainty of sampling and analysis. Received: 4 November 1997 · Accepted: 26 November 1997     

Modifying uncertainty from sampling to achieve fitness for purpose: a case study on nitrate in lettuce

Existing methods have been applied to estimate the uncertainty of measurement, caused by both sampling and analysis, and fitness-for-purpose of these measurements. A new approach has been taken to modify the measurement uncertainty by changing the contribution made by the sampling process. A case study on nitrate in lettuce has been used to demonstrate the applicability of this new generic approach. The sampling theory of Gy was used to predict the alterations in the sampling protocol required to achieve the necessary change in sampling uncertainty. An experimental application of this altered sampling protocol demonstrated that the predicted change in sampling uncertainty was achieved in practice. For the lettuce case study, this approach showed that composite samples containing 40 heads, rather than the usual ten heads, produced measurements of nitrate that where more fit-for-purpose.     

How does the molecular velocity distribution affect kinetics measurements by time‐resolved mass spectrometry?

The equations governing the time fidelity in molecular‐beam mass sampling are derived for supersonic‐beam sampling, where the velocity distribution is well‐fitted by a displaced Maxwell–Boltzmann distribution. Supersonic sampling is shown to offer much higher fidelity than the corresponding effusive‐beam sampling, and rules of thumb are derived for the validity of kinetic measurements for supersonic‐beam sampling. © 2007 Wiley Periodicals, Inc. Int J Chem Kinet 39: 565–570, 2007     

Efficient sampling algorithms for Monte Carlo based treatment planning

Efficient sampling algorithms are necessary for producing a fast Monte Carlo based treatment planning code. This study evaluates several aspects of a photon-based tracking scheme and the effect of optimal sampling algorithms on the efficiency of the code. Four areas were tested: pseudo-random number generation, generalized sampling of a discrete distribution, sampling from the exponential distribution, and delta scattering as applied to photon transport through a heterogeneous simulation geometry. Generalized sampling of a discrete distribution using the cutpoint method can produce speedup gains of one order of magnitude versus conventional sequential sampling. Photon transport modifications based upon the delta scattering method were implemented and compared with a conventional boundary and collision checking algorithm. The delta scattering algorithm is faster by a factor of six versus the conventional algorithm for a boundary size of 5 mm within a heterogeneous geometry. A comparison of portable pseudo-random number algorithms and exponential sampling techniques is also discussed.     

Sampling for microanalysis: Theories and strategies

Summary Analysts should consider more than simply the determination of the composition of the test portion provided; they should also assess the degree to which the test portion represents the population under evaluation. To do this requires an understanding of both sampling theory and of practical sampling strategies. An acceptable sampling program should include an adequate statistical design, proper sample collection and transport to the analytical laboratory, and proper training of those performing the sampling. Statistical theories and relations that can serve as aids for more efficient sampling include those of Ingamells and Switzer, Gy, Benedetti-Pichler, and others; most of these apply to particulate mixtures and are based on Gaussian distributions. Other treatments of sampling include geostatistical procedures such as kreiging, and the use of fractals. Many environmental and industrial monitoring and quality control operations now in use are based on sampling protocols arrived at by ad hoc procedures. The quality of trace analytical data can be improved and costs of analyses decreased by developing better sampling plans.     

Improvements to the distance geometry algorithm for conformational sampling of cyclic structures

Modifications to the distance geometry algorithm as embodied in the program DGEOM have been made to improve sampling capabilities. Specifically, torsion angle sampling replaces distance sampling for 1,4 atomic relationships and correlated distance sampling is disabled. The effects of these modifications are illustrated by comparing the different sets of conformations produced for butane. In addition, these changes are shown to increase the conformational sampling of two medium-sized rings, cycloheptadecane and caprylolactam. The current results for these molecules are compared to those of other conformational searching methods.