Determination of Organic Phosphonates in Aqueous Samples Using Liquid Chromatography/Particle-beam Mass Spectrometry

Organic phosphonates are widely used, and in general, they are not easily biodegradable. Therefore, our interest was focussed on the development of an analytical method for the trace-level determination of organic phosphonates in water. Our method combines preconcentration of the analytes by evaporating the water sample with the methylation of the phosphonates using diazomethane. Analysis of the totally methylated phosphonates is done by liquid chromatography coupled with mass Spectrometry by the particle-beam interface. The derivatives could be clearly identified by their electron impact mass spectra as well as their chemical ionisation mass spectra. The totally methylated phosphonates can be separated by liquid chromatography using a 125 mm × 4 mm LiChrospher 100 Diol column and a gradient mobile phase containing n-hexane and isopropyl alcohol. After optimizing preconcentration and derivatization procedures as well as all particle-beam and mass spectra conditions, detection limits in the low ppb range were attained.     

CMBEAR: Python-Based Recharge Estimator Using the Chloride Mass Balance Method in Australia

The chloride mass balance (CMB) method is widely used to estimate long-term rates of groundwater recharge. In regions where surface water runoff is negligible, recharge can be estimated using measurements of chloride concentrations of groundwater and precipitation, and an estimate of long-term average rainfall. This paper presents the Chloride Mass Balance Estimator of Australian Recharge (CMBEAR), a Jupyter (Python) Notebook that is set up to rapidly apply the CMB method using gridded maps of chloride deposition rates across the Australian continent. For an Australian context, the chloride deposition rate and rainfall maps have been provided. Thus, CMBEAR requires only a spreadsheet with the groundwater chloride concentration, the latitude and longitude of the sample location, and some simple user inputs. CMBEAR may be easily applied in other regions, providing that a gridded chloride deposition map is available. Recharge estimates from CMBEAR are compared against published applications of the CMB method. CMBEAR is also applied to a large dataset from the Northern Territory and is used to produce a gridded map of recharge for western Victoria. CMBEAR provides a reproducible and straightforward approach to apply the CMB method to estimate groundwater recharge.     

Problems and Solutions in Pesticide Analysis Using Solid‐phase Extraction (SPE) and Gas Chromatography Ion‐trap Mass Spectrometry Detection (GC‐MS)

In the present study an analytical method was tested for the determination of selected pesticides and metabolites using solid‐phase extraction (SPE) and gas chromatography ion‐trap mass spectrometry (GC‐MS). The extraction efficiency of C18, Isolut ENV+, and Lichrolut EN for SPE was compared for trifluralin, fenitrothion, endosulfan, propargite, 2,4‐D, 3‐methyl‐4‐nitrophenol, 2‐(4‐tert‐butylphenoxy)cyclohexanol, endosulfan sulfate, and 2,4‐dichlorophenol. Isolut ENV+ and C18 showed good results as sorbents and acetone as an elution solvent for SPE for the selected pesticides. Recoveries varied between 36% and 176% with a relative standard deviation of 2...18%. Because of coextracts from the SPE materials, recovery values higher than 100% were obtained for fenitrothion, endosulfan sulfate, and 2,4‐D with C18 as well as for endosulfan sulfate and 3‐methyl‐4‐nitrophenol with Isolut ENV+. A standard addition method was used to verify the occurrence of coextracts in the sample after SPE.     

前门控CT冠脉造影低体质量指数与图像质量相关性研究

目的：在固定球管输出的情况下,观察低体质量指数与图像质量的相关性。方法：研究选取心率≤65bpm、心率变异≤5bpm、体质量指数≤24kg/m2患者40例,平均年龄（53.16±6.53）岁,平均体质量指数（20.12±2.13）kg/m2。所选患者采用前瞻性心电门控技术,管电压120kV,管电流400mA。扫描结束后测量主动脉根部衰减值、噪声值,并计算信噪比。采用Pearson相关分析体质量指数与图像质量的相关性。结果：Pearson相关分析示体质量指数与主动脉衰减值无相关（r=0.163,P=0.314）,体质量指数与噪声值为正相关（r=0.714,P=0.000）,体质量指数与信噪比为负     

Study on the Seismogeny and Occurrence of Earthquakes by Using Pattern Dynamics

The mesoscopic damage dynamics and damage evolution have been applied to probe theevolutional process induced catastrophe in the earthquake activity.It is a new method.In thispaper,a brief introduction of the basic principle about damage dynamics and evolution ismade.At the same time,using the theory of the pattern dynamics we studied all earthquakes(M_L≥5.0)which occurred along Zhangjiakou-Bohai Sea earthquake belt in the capitalregion.The result indicates that the preparation and happening of the real earthquakes andthe theory are consistent.There are two kinds of evolutional model according to the finalstate,namely,global stability model(GS)and evolution induced catastrophe model(EIC).The two models haven’t evident boundary.The transitional zone exhibits the indeterminacyof the seismic process and the effect of the random variation.This research proposed newapproaches for earthquake prediction.     

运用图型动力学观点研究地震的孕育与发生

从细观损伤力学及损伤演化的角度探索地震活动中的演化诱致发震是一种全新的方法.本文简要介绍了细观损伤演化诱致突变理论和图型动力学的基本原理,并对首都圈地区张家口-渤海地震带上ML 5.0以上地震进行分析研究.结果表明,实际震例与图型动力学理论存在较好的一致性,按演化的最终状态可分为两种演化模式,即整体稳定模式(GS模)和演化诱致突变模式(EIC模),两模式间没有明显界限,存在过渡区,过渡区明确给出了地震孕育过程的不确定性和随机影响的作用.此研究为地震预报提供了更为科学的思路和方法.     

Occurrence of an Algal Mass Development in an Acidic (pH 2.5):, Iron and Aluminium‐rich Coal Mining Pond

A bloom of Chlamydomonas botryopara was observed in an extremely acid coal mining pond (pH 2.5) with high concentrations of iron and aluminium (1160...3760 mg L^–1 Fe, 133...387 mg L^–1 Al). Cell density of algae was counted as 6.45 · 10⁶ mL^–1 corresponding to 700 mg L^–1 fresh weight and 2660 μg L^–1 chlorophyll‐a. The nutrient concentrations were 3.5 mg L^–1 soluble reactive phosphorus and 0.15 mg L^–1 dissolved inorganic nitrogen. This observation supports the hypothesis that a low nutrient availability rather than extreme conditions (e.g. high acidity and low pH) limit the development of phytoplankton in many acidified lakes.     

Mass Flux Analysis of Abiotic Tetrachloroethene Dense Nonaqueous Phase Liquid Pool Dissolution in a Heterogeneous Flow Environment

Porous aquifer materials are often characterized by layered heterogeneities that influence groundwater flow and present complexities in contaminant transport modeling. Such flow variations also have the potential to impact the dissolution flux from dense nonaqueous phase liquid (DNAPL) pools. This study examined how these heterogeneous flow conditions affected the dissolution of a tetrachloroethene (PCE) pool in a two-dimensional intermediate-scale flow cell containing coarse sand. A steady-state mass-balance approach was used to calculate the PCE dissolution rate at three different flow rates. As expected, aqueous PCE concentrations increased along the length of the PCE pool and higher flow rates decreased the aqueous PCE concentration in the effluent. Nonreactive tracer studies at two flow rates confirmed the presence of a vertical flow gradient, with the most rapid velocity located at the bottom of the tank. These results suggest that flow focusing occurred near the DNAPL pool. Effluent PCE concentrations and pool dissolution flux rates were compared to model predictions assuming local equilibrium (LE) conditions at the DNAPL pool/aqueous phase interface and a uniform distribution of flow. The LE model did not describe the data well, even over a wide range of PCE solubility and macroscopic transverse dispersivity values. Model predictions assuming nonequilibrium mass-transfer-limited conditions and accounting for vertical flow gradients, however, resulted in a better fit to the data. These results have important implications for evaluating DNAPL pool dissolution in the field where subsurface heterogeneities are likely to be present.     

Rapid Analysis of 1,4‐Dioxane in Groundwater by Frozen Micro‐Extraction with Gas Chromatography/Mass Spectrometry

An innovative micro‐extraction of aqueous samples coupled with gas chromatography/mass spectrometry in selected ion‐monitoring mode (GC/MS‐SIM) was developed to selectively analyze for 1,4‐dioxane with low part‐per‐billion detection sensitivity. Recoveries of 1,4‐dioxane ranged from 93% to 117% for both spiked laboratory reagent water and natural groundwater matrices, the later having elevated organic carbon content (8.34 ± 0.31 mg/L as total organic carbon). We observed that freezing the aqueous sample along with the extraction solvent enhanced the extraction efficiency, minimized physical interferences, and improved sensitivity resulting in a limit of detection for 1,4‐dioxane to approximately 1.6 μg/L. This method substantially reduces the labor, time, reagents and cost, and uses instruments that are commonly found in analytical laboratories. This method requires a relatively small sample volume (200 μL), and can be considered a green analytical method as it minimizes the use of toxic solvents and the associated laboratory wastes.     

Mercury in the ecosystem of Admiralty Bay,King George Island,Antarctica: Occurrence and trophic distribution

Mercury (Hg) can reach the environment through natural and human-related sources, threatening ecosystems all over the planet due to its well known deleterious effects. Therefore, Antarctic trophic webs, despite being relatively isolated, are not exempt of its influence. To evaluate Hg concentrations in an Antarctic ecosystem, different tissues from 2 species of invertebrates, 2 of fish, 8 of birds, 4 of pinnipeds and at least 5 of vegetation were investigated (n = 176). For animals, values ranged from 0.018 to 48.7 μg g^? 1 dw (whole Antarctic krill and Antarctic Fur Seal liver). They were generally correlated to trophic position (assessed by δ¹⁵N and δ¹³C) but also to cephalopods and myctophids consumption. For vegetation, values ranged from 0.014 to 0.227 μg g^? 1 dw (Colobanthus quitensis and an unidentified lichen), with lichens presenting significantly higher values than mosses, likely due to year-round exposure and absorption of animal derived organic matter, as hypothesized by literature.     

Occurrence,shape and movement of daily rainfall in the Huai Basin,China

The upper reaches of the Huai River in Central China are located in the East Asian monsoon region. Strong seasonality, as well as large interannual variability of rainfall, causes floods and an uneven supply of water. In order to conserve the water and mitigate the floods, dams and flood protection structures are constructed. Their design requires information about the rainfall. Daily observations from 1957 to 1986 from 78 rain gauges were used to study shape, orientation, movement and geographical and seasonal occurrence of storms in the 79 000 km² study area. The rainfall characteristics were described using graphical plots, cross‐ and autocorrelation. Storms larger than 50 mm/day were found to occur from February to November, whereas storms exceeding 350 mm/day were confined to the main rainfall season from late June to mid‐August. The southern part of the study area experienced a break in the rainfall season in late July, corresponding to the seasonal northward shift of the rain belt. A weekly periodicity of 7–8 days for rainfall was found during June–July, but not during August–September. During the whole period June–September, the spatial pattern of daily rainfall revealed an elongated shape, more pronounced during June–July than August–September. The rainfall area was orientated approximately from WSW to ENE during the whole period, and showed an anticlockwise rotation of about 16° per day during June–July. The cross‐correlation analysis revealed that the rainfall area moved about 100 km/day eastward. These results and an investigation of meteorological maps indicate that the spatial correlation pattern of daily rainfall is produced by cold fronts on the Mei‐Yu front. Suggestions are made as to how to use the results for the construction of design rainfalls in the study area. Copyright © 1999 John Wiley & Sons, Ltd.     

Toxic Cyanobacteria in Greek Freshwaters, 1987—2000: Occurrence,Toxicity, and Impacts in the Mediterranean Region

In a survey in Greece from 1987 to 2000 hepatotoxic cyanobacterial blooms were observed in 9 out of 33 freshwaters. Microcystins (MCYSTs) were detected by HPLC in 7 of these lakes, and the total MCYST concentration per scum dry weight ranged from 50.3 to 1638 ± 464 μg g^—1. Cyanobacterial genera (Microcystis, Anabaena, Anabaenopsis, Aphanizomenon, Cylindrospermopsis) with known toxin producing taxa were present in 31 freshwaters. From our data and a review of the literature, it would appear that Mediterranean countries are more likely 1) to have toxic cyanobacterial blooms consisting of Microcystis spp. and 2) to have higher intracellular MCYST concentrations. A case study in Lake Kastoria is used to highlight seasonal patterns of cyanobacterial and MCYST‐LR occurrence and to assess cyanotoxin risk. Cyanobacterial biovolume was high (> 11 μL L^—1) throughout the year and was in excess of Guidance Level 2 (10 μL L^—1) proposed by WHO for recreational waters and Alert Level 2 for drinking water. Further, surface water samples from April to November exceeded Guidance Level 3, with the potential for acute cyanobacterial poisoning. Intracellular MCYST‐LR concentrations (max 3186 μg L^—1) exceeded the WHO guideline for drinking water (1 μg L^—1) from September to November with a high risk of adverse health effects. Preliminary evidence indicates that in 3 lakes microcystins are accumulated in some aquatic organisms. Generally, a high risk level can be deduced from the data for the Mediterranean region.     

Terbuthylazine and Deethylterbuthylazine in Rain and Surface Water – Determination by Enzyme Immunoassay and Gas Chromatography/Mass Spectrometry

Rain and surface water samples from Southern Germany were investigated from 1991 to 1995 for terbuthylazine and one of its major metabolites, deethylterbuthylazine. The concentrations observed were compared to the concentrations found for atrazine and deethylatrazine in the same water samples. Concentrations ranged from < 0.02 μg/L to 0.7 μg/L for terbuthylazine and from < 0.02 μg/L to 0.6 μg/L for deethylterbuthylazine, compared to concentrations of < 0.02 μg/L to 3 μg/L and < 0.02 μg/L to 0.5 μg/L for atrazine and deethylatrazine, respectively. The ratios of metabolite concentrations to parent compound concentrations were calculated for deethylterbuthylazine to terbuthylazine (DTR) and deethylatrazine to atrazine (DAR). In rain water, DTR of 0.8…3.0 and DAR of 0.3… 1.9 were determined with mean values of 0.9… 1.7 for DTR and 0.6…0.9 for DAR in the different years. The ratios increased during summer periods. The highest ratios were observed in samples from forest stands, showing that degradation of the herbicide has occurred during transport between the source and the sampling site. The DTR in rain water were about 50… 100% higher than the DAR. This indicates a higher degradation rate of terbuthylazine during atmospheric transport. In surface water, DTR of 0.3… 1.2 with mean values of 0.5…0.8 and DAR of 0.2…2.2 with mean values of 0.2… 1.3 were observed. The ratios increased from June to September.     

Removal of Bromate from Water Using De‐Acidite FF‐IP Resin and Determination by Ultra‐Performance Liquid Chromatography‐Tandem Mass Spectrometry

Contamination of water due to bromate is a severe health hazard. The aim of the present study was to remove bromate from water using a crosslinked polystyrene based strongly basic anion exchange resin De‐Acidite FF‐IP. Batch experiments were performed to study the influence of various experimental parameters such as effect of pH, contact time, temperature, and effect of competing anions on bromate removal by De‐Acidite FF‐IP resin. At optimum parameters, the removal rate of bromate was very fast and 90% removal took place in 5 min and equilibrium was established within 10 min. The presence of competitive anions reduced the bromate adsorption in the order of Cl^? > F^? > CO > SO > NO > PO. The practical utility of this resin has been demonstrated by removing bromate in some of the commercial bottled water from Saudi Arabia. The level of bromate was determined using a very sensitive, precise and rapid method based on ultra‐performance liquid chromatography‐tendem mass spectrometry (UPLC‐MS/MS).