郑州市PM2.5组分季节性特征及来源研究

为了探究郑州市大气PM_(2.5)组分的季节性特征及来源,于2017年12月至2018年11月对郑州市5个点位进行采样,共采集有效环境受体样本1 166个。通过研究受体样本PM_(2.5)中的碳组分、水溶性离子和无机元素信息,获取各组分的季节特征,并结合正定矩阵因子分解(PMF)模型进行来源解析。结果表明,采样期间,郑州市PM_(2.5)平均浓度为69.6μg/m~3,占比较高的化学组分为NO_3~-、有机碳(OC)、SO_4~(2-)和NH_4~+,占比之和为86.7%。其中,NO_3~-、OC和NH_4~+呈现冬季高、夏季低的季节性浓度分布规律,SO_4~(2-)则是秋冬季稍高于春夏季。此外,Al、Si、Fe和Ca的浓度在春秋季略高于冬夏季。PMF模型解析结果显示,二次源为郑州市PM_(2.5)首要污染源,分担率为50.9%,其次是移动源(分担率12.0%)、燃煤源(分担率11.4%)和扬尘源(分担率10.2%)。其中,燃煤源在冬季较高、夏季较低,移动源在夏季最高,扬尘源在春季和秋季较高。     

Assessing Spatial, Temporal, and Analytical Variation of Groundwater Chemistry in a Large Nuclear Complex, USA

Statistical analyses were applied at the Hanford Site, USA, to assess groundwater contamination problems that included (1) determining local backgrounds to ascertain whether a facility is affecting the groundwater quality and (2) determining a ‘pre-Hanford' groundwater background to allow formulation of background-based cleanup standards. The primary purpose of this paper is to extend the random effects models for (1) assessing the spatial, temporal, and analytical variability of groundwater background measurements; (2) demonstrating that the usual variance estimate s ², which ignores the variance components, is a biased estimator; (3) providing formulas for calculating the amount of bias; and (4) recommending monitoring strategies to reduce the uncertainty in estimating the average background concentrations. A case study is provided. Results indicate that (1) without considering spatial and temporal variability, there is a high probability of false positives, resulting in unnecessary remediation and/or monitoring expenses; (2) the most effective way to reduce the uncertainty in estimating the average background, and enhance the power of the statistical tests in general, is to increase the number of background wells; and (3) background for a specific constituent should be considered as a statistical distribution, not as a single value or threshold. The methods and the related analysis of variance tables discussed in this paper can be used as diagnostic tools in documenting the extent of inherent spatial and/or temporal variation and to help select an appropriate statistical method for testing purposes.     

Numerical analysis of water and solute transport in variably-saturated fractured clayey till

This study numerically investigates the influence of initial water content and rain intensities on the preferential migration of two fluorescent tracers, Acid Yellow 7 (AY7) and Sulforhodamine B (SB), through variably-saturated fractured clayey till. The simulations are based on the numerical model HydroGeoSphere, which solves 3D variably-saturated flow and solute transport in discretely-fractured porous media. Using detailed knowledge of the matrix, fracture, and biopore properties, the numerical model is calibrated and validated against experimental high-resolution tracer images/data collected under dry and wet soil conditions and for three different rain events. The model could reproduce reasonably well the observed preferential migration of AY7 and SB through the fractured till, although it did not capture the exact depth of migration and the negligible impact of the dead-end biopores in a near-saturated matrix. A sensitivity analysis suggests fast flow mechanisms and dynamic surface coating in the biopores, and the presence of a plough pan in the till.     

Incorporating layer- and local-scale heterogeneities in numerical simulation of unsaturated flow and tracer transport

This study characterizes layer- and local-scale heterogeneities in hydraulic parameters (i.e., matrix permeability and porosity) and investigates the relative effect of layer- and local-scale heterogeneities on the uncertainty assessment of unsaturated flow and tracer transport in the unsaturated zone of Yucca Mountain, USA. The layer-scale heterogeneity is specific to hydrogeologic layers with layerwise properties, while the local-scale heterogeneity refers to the spatial variation of hydraulic properties within a layer. A Monte Carlo method is used to estimate mean, variance, and 5th, and 95th percentiles for the quantities of interest (e.g., matrix saturation and normalized cumulative mass arrival). Model simulations of unsaturated flow are evaluated by comparing the simulated and observed matrix saturations. Local-scale heterogeneity is examined by comparing the results of this study with those of the previous study that only considers layer-scale heterogeneity. We find that local-scale heterogeneity significantly increases predictive uncertainty in the percolation fluxes and tracer plumes, whereas the mean predictions are only slightly affected by the local-scale heterogeneity. The mean travel time of the conservative and reactive tracers to the water table in the early stage increases significantly due to the local-scale heterogeneity, while the influence of local-scale heterogeneity on travel time gradually decreases over time. Layer-scale heterogeneity is more important than local-scale heterogeneity for simulating overall tracer travel time, suggesting that it would be more cost-effective to reduce the layer-scale parameter uncertainty in order to reduce predictive uncertainty in tracer transport.     

A method for the determination of rhodamine b and brilliant sulfaflavine on cotton string collectors and in a spray tank solution mixture

Abstract

A fluorescent method for the determination of rhodamine B (RhB) and brilliant sulfaflavine (BSF) dual tracers on cotton string collectors and in spray tank solutions was developed for the evaluation of the effects of adjuvants on the atmospheric drift of agricultural sprays. Both tracers on collectors were extracted with deionized water simultaneously and measured directly with a Fluorescent Specrometer by switching the maximum excitation and emission wavelengths. The linear ranges of the RhB and BSF standard curves were 0–50 and 0–10 ppb respectively. Recoveries of tracers on cotton strings ranged from 92.9% ± 1.1% to 95.1% ± 1.0% for RhB and 91.9% ± 2.8% to 103% ± 0.6% for BSF when spiked levels ranged from 0.25 to 2.5 μg per collector. The detection limit of the instrument was approximately 0.1 ppb for both tracers. The detection limits of the analytical method were approximately 0.1 ppb for RhB and 0.3 ppb for BSF when the background levels of cotton strings were subtracted. The presence of one tracer in the solution did not significantly interfere with the detection of the other tracer in the same solution. The presence of adjuvants added to the spray tank solutions did not interfere with the detection of both tracers when the adjuvants were applied at the manufacturer's maximum recommendation rates.     

Mathematical Modeling of Column and Field Dense Nonaqueous Phase Liquid Tracer Tests

Mathematical models for the simulation of dense nonaqueous phase liquid tracer tests (DTTs) in laboratory columns and in the field are developed and examined. The DTT technique is a means of estimating the quantity of dense nonaqueous phase liquid (DNAPL) in a domain of interest in an aquifer. The two-dimensional field DTT model uses the Method of Principal Directions and an asymmetrical upwind algorithm for describing advective transport. Both models include diffusion transport of tracer into and from low-permeability porous structures such as clay lenses, as well as the mass transport kinetics of partitioning tracer to and from the DNAPL droplets. The dependence of the effluent tracer concentration curves on the parameters of the models is explored, and conclusions are drawn regarding the applicability of, and several possible problems with, the DTT technique. Model results indicate that the DTT performs well at locating distributed droplets of DNAPL, but is unlikely to be useful in the assessment of pooled DNAPL.     

Effect of tracer dyes on initial deposits and persistence of bacillus thuringiensis subsp. kurstaki toxin after application of two commercial formulations onto spruce trees

Abstract

The effect of two tracer dyes [Erio Acid Red (EAR) and Acid Black 48 (AB‐48)] on initial deposits and persistence of Bacillus thuringiensis subsp. kurstaki (Btk) toxin (delta‐endotoxin) was studied after spraying two commercial formulations, Foray® 48B and Foray® 76B, over potted white spruce [Picea glauca (Moench) Voss] seedlings, at a dosage rate of 30 billion international units (BIU) per ha. Spray was applied using a spinning disc atomizer calibrated to deliver droplet sizes similar to those utilized in ultra‐low‐volume (ULV) treatments in operational insect control programs. The sprayed seedlings were left outdoors at the Sault Ste. Marie laboratory for 18 days under natural conditions of sunlight, wind and rainfall. Initial deposits and persistence of delta‐endotoxin protein in spruce foliage were determined by immunoassay [enzyme linked immunosorbent assay (ELISA)] quantification of the delta‐endotoxin. The total protein (inactive plus active) and delta‐endotoxin (active protein) concentrations in the two formulations were determined by a gravimetric procedure and by ELISA respectively.

The initial deposit levels of the toxin on foliage were not markedly affected by the addition of either of the two tracer dyes, and showed only a narrow range of 1521 to 1625 ng/g foliage (fresh weight) for Foray 48B, and 1789 to 2056 ng/g for Foray 76B. However, the persistence of the toxin was significantly influenced by the presence of the dyes. The toxin persisted in foliage only for 7 d post‐spray When the EAR dye was added to Foray 48B, compared to 10 d when no dye was added. The average half‐life (DT₅₀) of disappearance was 17.4 h for Foray 48B with EAR, and 20.9 h when no dye was present. In contrast, the situation was reversed in Foray 76B, since the duration of persistence was 10 d when EAR was added to Foray 76B, compared to 7 d when no dye was added. The average DT₅₀ was 27.9 h for Foray 76B with EAR, and 22.2 h without the dye. Persistence was the longest (14 d) when the AB‐48 dye was added to Foray 76B, and the DT₅₀ was 44.9 h.     

ASSESSING FLUSHING-FLOW REQUIREMENTS FOR BROWN TROUT SPAWNING GRAVELS IN STEEP STREAMS1

Flushing flows are re1eses from dams designed to remove fine sediment from downstream spawning habitat. We evaluated flushing flows on reaches proposed for hydroelectric diversions on seven streams in the eastern Sierra Nevada, California, with wild populations of brown trout (Salmo trutta). The stream reaches are steep (average map slopes range from 7 to 17 percent), are dominated by boulder cascades, and afford few opportunities for gravel deposition. Methods for estimating flushing flows from flow records, developed from studies in other localities, produced widely differing results when applied to the study streams, probably reflecting differences in the hydrologic and geomorphic characteristics of the streams on which the methods were developed. Tracer gravel experiments demonstrated that all sampled gravels were washed out by the flows of 1986, a wet year. Size analyses of gravel samples and hydraulic data from field surveys were used in tractive-force calculations in an attempt to specify the flow required to flush the gravels. However, these calculations produced some unrealistic results because the flows were nonuniform in the study reaches. This suggests that the tractive-force approach may not be generally applicable to small, steep streams where nonuniform flow conditions prevail.     

Results from Three Field Tracer Experiments on the Neighbourhood Scale in the City of Birmingham UK

The physical processes governing flow and pollutantdispersion at the neighbourhood scale, a spatial scaleintermediate between the street scale and the city scale, is notwell understood. Furthermore, it is not clear whether a traditional approach using averaged characteristics such as theaerodynamic roughness length is sufficient to predict the concentration field at this scale. To investigate pollutant dispersion in a real urban area, three field experiments were designed within the UK-URGENT programme sponsored by NERC. Theexperiments were performed in the City of Birmingham using a finite duration release of inert, non-toxic and non-depositingtracers, vis. perfluoromethylcyclohexane (PMCH) and perfluoromethylcyclopentane (PMCP). Measurements were taken using air bag samplers placedin an arc at 3.5 km (first experiment) and 1 km (second andthird experiments) from the source; some trap samplers wereplaced outside the main arc in the outskirts of the city. Measurements were analysed in the laboratory using anovel gas-chromatography technique. Data so obtained werecompared with predictions from a simple steady-state modeland a time-dependent model. The concentration-time serieswere very asymmetrical with a sharp rise, a plateau followedby a relatively slow decrease and finally a long-livedplateau above (or possibly very slow decrease to) thebackground level.     

Radiocesium in North San Francisco Bay and Baja California coastal surface waters

Radiocesium, 137Cs, and rare earth elements (REEs) were determined in suspended material and dissolved fractions of waters across the salinity gradient in North San Francisco Bay (estuary). We describe the variation of this conservative isotope tracer with salinity and sediment load. REE data are used to differentiate marine and terrigenous source terrains for suspended material and dissolved fractions. We estimate that about 1-4 x 10(10) Bq of 137Cs migrates annually on suspended material through the North Bay. In addition, 137Cs concentrations were measured in surface waters off Baja California. Combined in situ water density (sigma(t)) and 137Cs data distinguish between California Current and Gulf of California water, and delineate areas of upwelling, where nutrient-rich, deep Pacific Intermediate water, with little or no 137Cs, is brought to the surface off promontories along Baja California.