Application of seeded batch crystallization methods for reduction of the scaling tendency of seawater – A study of growth kinetics of calcium carbonate in seawater

The objective of this study is to evaluate the applicability of a seeded batch crystallization method as a pre‐treatment stage to the reduction of the the scaling potential of seawater. The crystallization process of calcium carbonate in supersaturated seawater is studied experimentally in a seeded batch crystallizer. Results show that the initial pH value of seawater must be adjusted to be in the range of 8‐9. Calcite seeds will not have the potential to start the growth process in seawater at he the normal pH (7.36) compared to the above mentioned range. The growth kinetic parameters are determined from the measured desupersaturation curves. It is found that the growth process of calcite is controlled by surface integration step. The growth rate of calcite increases with increasing temperature and seeding ratio (up to 1 g/L), while it decreases with increasing the salinity of seawater. Crystals of calcite morphology are found to be growing faster than seeds of aragonite morphology. Stirrer speed has no distinct effect on the growth rate of calcite in seawater. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

在线样品前处理大体积进样离子色谱法直接测定海水中亚硝酸盐、硝酸盐和磷酸盐

采用戴安公司谱睿(Pre)在线样品除氯技术,结合OnGuard Ba柱去除硫酸盐,建立了离子色谱直接测定海水中亚硝酸盐、硝酸盐和磷酸盐的方法。该方法以IonPac AG23为富集柱,高容量IonPac AS23为分离柱,淋洗液自动发生装置在线产生KOH溶液进行梯度淋洗,抑制电导检测。实验结果表明: 样品稀释5～10倍时,直接进样不会干扰目标物测定。当流速为1 mL/min、进样量为500 μL时,海水中NO~2-N、NO~3-N、PO3~4-P的方法检出限分别为0.3、0.4、0.2 μg/L,线性范围分别为10～500 μg/L、14～680 μg/L、3.4～170 μg/L,线性相关系数r均大于0.9990。测得人工海水样品中目标物的加标回收率为92%～106%,相对标准偏差(RSD, n=6)为1.2%～7.7%。该方法一次进样可在13 min内完成分析,具有操作简单快捷、无污染等优点,能满足近海海水中NO~2、NO~3、PO3~4的定量分析要求。     

Solid-phase extraction using a molecularly imprinted polymer for the selective purification and preconcentration of norfloxacin from seawater

Abstract

A highly selective and effective method for the purification and preconcentration of norfloxacin (NFX) in seawater samples was developed based on molecularly imprinted solid-phase extraction (MISPE). The molecularly imprinted polymer was synthesized by precipitation polymerization. Methacrylic acid (MAA) and ethylene glycol dimethacrylate (EGDMA) were used as the functional monomer and crosslinker, respectively. The resulting molecularly imprinted polymer (MIP) showed high adsorption for NFX and was selective for its solid-phase extraction. An offline MISPE method followed by high performance liquid chromatography with diode array detection was established for the determination of NFX in seawater. The recoveries of spiked seawater samples using the MISPE columns were satisfactorily higher than 77.6%. The relative standard deviation was less than 5.60%, and the limit of detection was 0.027?μg L^?1. Four seawater samples obtained from the Bohai Sea were analyzed, and NFX was found only at one location at a concentration of 0.280?μg L^?1.     

Integrating Hydrogeochemical and Geophysical Data for Testing a Finite Volume Based Numerical Model for Saltwater Intrusion

In this paper, hydrogeological and geophysical data are used to validate a numerical model developed to predict seawater intrusion into coastal aquifers. The cell-centered finite volume method is adopted here to solve the set of coupled partial differential equations describing the motion of saltwater and freshwater separated by a sharp interface. These equations are based on the Dupuit approximation and are obtained from integration of 3D flow equations for fresh and salt water zones over the vertical dimension. In order to have flexibility upon complex configurations domain, non structured grid meshing is utilized. To approximate the diffusion fluxes, Green-Gauss type reconstruction, based on diamond-cell and least squares interpolation, is performed. The model is first validated using academic test case studies with known closed form solutions. The mathematical model has been calibrated using hydrogeochemical and geophysical data. The geophysical method applied in this study has been a frequency domain electromagnetic method. In this method the apparent electrical conductivity is measured by induction using two separate hand-held transmitter and receiver coils. During the operation the transmitter coil is energized by a low frequency alternating current that radiates an electromagnetic field and the receiver coil detects the resulting field. Taking into account the relationship between the bulk conductivity of the subsoil and the conductivity of groundwater, EM soundings have been interpreted to provide complementary information to hydrogeochemical data to outline the fresh–saltwater interface. This methodology has been applied to the case of saltwater intrusion into the Llobregat delta aquifer, near Barcelona, Spain.     

Effects of viscosity and chemical relaxation on acoustic pulse propagation in seawater

This paper considers acoustic pulse distortion in seawater due to effects of viscosity and chemical relaxation. The acoustic medium is modelled as a linear, time-invariant, space-invariant filter. The deformation of initially Gaussian-shaped pulses is estimated. The combined effects of the dissipative processes are that as a pulse propagates through the medium, the maximum amplitude is decreased, the pulse is stretched in time and a delayed tail is developed. Input pulses with high-frequency energy contents can undergo a considerable deformation due to these phenomena.     

吹扫捕集-气相色谱分析海水和沉积物中的苯、甲苯、乙苯及二甲苯

单环芳烃苯、甲苯、乙苯和二甲苯（简称BTEX）是石油的重要组分，也是环境中需要重点监测的致癌污染物。本实验建立了动态顶空（吹扫捕集）和光离子化检测器的气相色谱测量海水、沉积物中痕量BTEX的方法。在120—1200ng／L的浓度范围，苯、甲苯、乙苯、间对二甲苯及邻二甲苯标准溶液的检出限分别为6．4、35．2、15．8、12．3、10．7ng／L，相对标准偏差0．9％-6．1％。样品无需预处理，海水中BTEX回收率为93．50％-98．40％。7个渤海表层海水样品中BTEX的浓度均低于140ng／L；海底沉积物中苯、甲苯、乙苯、间对二甲苯及邻二甲苯浓度分别为169—1243、531—1732、1308—5624、237—1136、510—5194ng／L。测量方法和结果对评价环境污染具有重要意义。     

Utilisation of liquid chromatography in aquatic photodegradation studies of pesticides: A comparison between distilled water and seawater

Summary The advantages of liquid chromatography with diode array and mass spectrometric detection are described for the direct characterization of the photodegradation products of Fenitrothion, Atrazine and Diuron in distilled water and artifical seawater samples. The photodegradation (UV >290 nm) of the herbicides Atrazine and Diuron was examined in distilled water and in artificial seawater containing humic acids. Major photodegradation products were hydroxyatrazine and Monuron, respectively. The results showed a faster degradation in seawater as compared to distilled water for Atrazine whereas for Diuron a quenching effect was observed thus retarding photodegradation. The photodegradation of Fenitrothion was also investigated. For this pesticide, hydrolysis predominates in seawater and photolysis is very slow in distilled water, so that acetone was needed as photosensitizer.Presented at the 5th International Symposium on Environmental Pollution and its Impact on Life in the Mediterranean Region, Blanes, Spain, 2–6 October, 1989.     

Influence of clay suspensions on the precipitation of CaCO3 in seawater

The effect of montmorillonite and kaolinite, most common clay in marine water, on nucleation and growth of calcium carbonate in standard sea water was studied. Crystallization was induced by the degasification of the dissolved carbonic gas. It was shown by XRD and SEM analysis that CaCO₃ crystallize under its aragonite polymorph some either the clay concentration or type. It was also found that tested clays inhibited significantly the crystallization of calcium carbonate, especially for concentrations higher than 25 mgL^–1. From the fine analyses of the formed solid, it was suggested that the tested clays have an indirect effect on nucleation and growth of aragonite by increasing the Mg ions concentration, strong inhibitor of CaCO₃ formation, in the neighbourhood of clay particles where supersaturation is the higher and than crystallization can occur. In addition to its indirect role, kaolinite can interact with aragonite by adsorbing on their faces and blocking growth sites (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Electrochemical studies on the corrosion of brass in seawater under anaerobic conditions

This paper reports an electrochemical study on the corrosion of brass in deoxygenated nonbuffered and buffered natural and artificial seawater solutions under anaerobic conditions. Cyclic voltammograms of brass and copper in natural seawater (NSW) and artificial seawater (ASW) were obtained in the passive and transpassive potential regions. The corrosion resistance of brass in natural and artificial seawater was evaluated, and open-circuit potentials were recorded over exposure period of 1 week. Brass samples from 3-month exposures in deoxygenated nonbuffered ASW and NSW, under open-circuit potential, have been imaged by scanning electron microscopy, and the elemental composition of the corrosion products was obtained by energy dispersive spectrometry analysis. It has been concluded that, under anaerobic conditions, the aggressivity of NSW is higher, with brass being less resistant to corrosion than copper, and that buffer contributes to reduce the aggressivity of both media.     

A Novel Scheme for the Classification of Heavy Metal Species in Natural Waters

Abstract

A scheme is proposed which permits the quantitative assay of seven different heavy metal species in natural waters. The concentration of each species is calculated from measurements using anodic stripping voltammetry of labile and total metal in samples which were (a) untreated, (b) u.v. irradiated, (c) passed through a chelating resin column, and (d) u.v. irradiated then passed through a chelating resin column. The scheme was applied to the analysis of Cd, Pb and Cu in seawater.