Geogenic Pollution of Groundwater Quality in Gampaha District, Sri Lanka: A Case Study of Groundwater Acidification from Rathupaswala

Over recent decades, Gampaha district, Sri Lanka, has experienced significant urbanisation and industrial growth, increasing groundwater demand due to limited and polluted surface water resources. In 2013, a community uprising in Rathupaswala, a village in Gampaha district, accused a latex glove manufacturing factory of causing groundwater acidity (pH < 4). This study evaluates the spatial and temporal changes in geochemical parameters across three transects in the southern part of Gampaha district to 1) assess the impact of geological formations on groundwater;2) compare temporal variations in groundwater;and 3) explain acidification via a geochemical model. Seventy-two sample locations were tested for pH, electrical conductivity (EC), and anion concentrations (sulphate, nitrate, chloride and fluoride). Depth to the water table and distance from the sea were measured to study variations across sandy, peaty, lateritic, and crystalline aquifers. Results showed pH readings around 7 for sandy and crystalline aquifers, below 7 for peaty aquifers, and below 5 for lateritic aquifers, with significant water table fluctuations near Rathupaswala area. Principal component analysis revealed three principal components (PCs) explaining 86.0% of the variance. PC1 (40.6%) correlated with pH, EC, and sulphate (saltwater intrusion), while PC2 (32.0%) correlated with nitrates and depth to the water table (anthropogenic nutrient pollution). A geochemical transport model indicated a cone of depression recharged by acidic groundwater from peat-soil aquifers, leading to acidic groundwater in Rathupaswala area. Previous attributions of acidic pH to the over-exploitation of groundwater by the latex factory have been reevaluated;the results suggest natural acidification from prolonged water-rock interactions with iron-rich lateritic aquifers. Groundwater pH is influenced by local climate, geology, topography, and drainage systems. It is recommended that similar water-rock interaction conditions may be present throughout the wet zone of Sri Lanka, warranting detailed studies to confirm this hypothesis.

Volatile Compounds Fingerprints for White Duck down and White Goose down Determined by Gas Chromatography-Ion Mobility Spectrometry

This work first describes a simple approach for the untargeted profiling of volatile compounds for distinguishing between white duck down (WDD) and white goose down (WGD) based on resolution-optimized GC-IMS combined with optimized chemometric techniques, namely PCA. The detection method for down samples was established by using GC-IMS. Meanwhile, the reason of unpleasant odors caused by WDD was explained on the basis of the characteristic volatile compounds identification. GC-IMS fingerprinting can be considered a revolutionary approach for a truly fully automatable, cost-efficient, and in particular highly sensitive method. A total of 22 compounds were successfully separated and identified through GC-IMS method, and the significant differences in volatile compounds were observed in three parts of WDD and WGD samples. The most characteristic volatile compounds of WGD belong to aldehydes, whereas carboxylic acids from WDD were detected generated by autoxidation reaction. Meanwhile, the main reason of unpleasant odor generation was possibly attributed to the high concentration of volatile carboxylic acids of WDD. Therefore, the constructed model presents a simple and efficient method of analysis and serves as a basis for down processing and quality control.

Analysis of Sugar Components of Fermented Rice Wine by Ion Chromatography

[Objective] The aim was to analyze sugar components in fermented rice wine by ion chromatography. [Method] The optimal condition for chromatography system of sugar analysis was selected by measuring sugars in fermented rice wine with ion chromatography and pulsed amperometric detection. [Result] The optimal measurement conditions were as follows： Leacheate （Leachate）, consisting of NaOH and CH3COONa, was eluted by gradient concentrations, with column temperature at 35 ℃ and flow rate at 0.4 ml/min. In the condition, sugars in rice wine were ana- lyzed and the results showed that the method is featured by low detection limit, good repetition and high recovery rate. [Conclusion] The research establishes and determines the approaches and optimum conditions for sugar analysis in rice wine by ion chromatography and pulsed amperometric detection, providing references for advancement of research on quality improvement of fermented rice wine.

Determination of Chlorine and Bromine in Plant Materials by Ion Chromatography

A method was developed for determination of chlorine and bromine in plant materials by ion chromatography using temperature programing-semi molten for sample preparation. Values of detection limits of the method found were 1.0×10^-5 for CI and 1.3×10^-6 for Br. The measuring range of the method found were 0.3-20.0 mg/L for CI and 4,0-120,0 μg/L for Br. The results obtained agreed quite well with those reference values.

Application of ion chromatography to the determination of water-soluble inorganic and organic ions in atmospheric aerosols

A simple, sensitive and convenient ion chromatography(IC) method was established for the simultaneous determination of twelve water-soluble inorganic anions(F -, Cl -, NO - 2, NO - 3, SO 2- 3, SO 2- 4, PO 3- 4), and fifteen water-soluble organic ions(formate, acetate, MSA, oxalate, malonate, succinate, phthalates, etc.) in atmospheric aerosols. The linear concentrations ranged from 0.005 μg/m 3 to 500 μg/m 3(r = 0.999—0.9999). The relative standard deviation(RSD) were 0.43%—2.00% and the detection limits were from 2.7 ng/m 3 to 88 ng/m 3. The proposed method was successfully applied to the simultaneous determination of those inorganic ions and organic ions in PM 2.5 of Beijing.

Liquid chromatography coupled with time-of-flight and ion trap mass spectrometry for qualitative analysis of herbal medicines

With the expansion of herbal medicine （HM） market, the issue on how to apply up-to- date analytical tools on qualitative analysis of HMs to assure their quality, safety and efficacy has been arousing great attention. Due to its inherent characteristics of accurate mass measurements and multiple stages analysis, the integrated strategy of liquid chromatography （LC） coupled with time-of-flight mass spectrometry （TOF-MS） and ion trap mass spectrometry （IT-MS） is well-suited to be performed as qualitative analysis tool in this field. The purpose of this review is to provide an overview on the potential of this integrated strategy, including the review of general features of LC-IT-MS and LC-TOF-MS, the advantages of their combination, the common procedures for structure elucidation, the potential of LC-hybrid-IT-TOF/MS and also the summary and discussion of the applications of the integrated strategy for HM qualitative analysis （2006-2011）. The advantages and future developments of LC coupled with IT and TOF-MS are highlighted.

Simultaneous determination of fluorine and iodine in urine by ion chromatography with electrochemical pretreatment

A new method for the simultaneous determination of fluorine and iodine in urine by ion chromatography （IC） with electrochemical pretreatment has been developed. The pretreatment was performed in a novel electrochemical oxidationneutralization device （EOND）, in which iodide of the sample was oxidized to iodate and the alkaline digestion sample solution was neutralized. Under the optimized conditions, the limits of detection （LOD, S/N = 3） were 2.5 μg/L for fluoride and 20 μg/L for iodate, respectively. The recoveries were in the range of 93-102% for fluoride and 86-98% for iodate.

Science Letters:Simultaneous determination of fluoride, chloride, sulfate, phosphate, monofluorophosphate, glycerophosphate, sorbate, and saccharin in gargles by ion chromatography

Simple, reliable and sensitive analytical methods to determine anticariogenic agents, preservatives, and artificial sweeteners contained in commercial gargles are necessary for evaluating their effectiveness, safety, and quality. An ion chroma-tography (IC) method has been described to analyze simultaneously eight anions including fluoride, chloride, sulfate, phosphate, monofluorophosphate, glycerophosphate (anticariogenic agents), sorbate (a preservative), and saccharin (an artificial sweetener) in gargles. In this IC system, we applied a mobile phased gradient elution with KOH, separation by IonPac AS18 columns, and suppressed conductivity detection. Optimized analytical conditions were further evaluated for accuracy. The relative standard deviations (RSDs) of the inter-day's retention time and peak area of all species were less than 0.938% and 8.731%, respectively, while RSDs of 5-day retention time and peak area were less than 1.265% and 8.934%, respectively. The correlation coefficients for targeted analytes ranged from 0.999 7 to 1.000 0. The spiked recoveries for the anions were 90%~102.5%. We concluded that the method can be applied for comprehensive evaluation of commercial gargles.

A novel protein refolding method integrating ion exchange chromatography with artificial molecular chaperone

Artificial molecular chaperone （AMC） and ion exchange chromatography （IEC） were integrated, thus a new refolding method, artificial molecular chaperone-ion exchange chromatography （AMC-IEC） was developed. Compared with AMC and IEC, the activity recovery of lysozyme obtained by AMC-IEC was much higher in the investigated range of initial protein concentrations, and the results show that AMC-IEC is very efficient for protein refolding at high concentrations. When the initial concentration of lysozyme is 180 mg/mL, its activity recovery obtained by AMC-IEC is still as high as 76.6%, while the activity recoveries obtained by AMC and IEC are 45.6% and 42.4%, respectively.

Offline two-dimensional liquid chromatography coupled with ion mobility-quadrupole time-of-flight mass spectrometry enabling fourdimensional separation and characterization of the multicomponents from white ginseng and red ginseng

Inherent complexity of plant metabolites necessitates the use of multi-dimensional information to accomplish comprehensive profiling and confirmative identification.A dimension-enhanced strategy,by offline two-dimensional liquid chromatography/ion mobility-quadrupole time-of-flight mass spectrometry(2 D-LC/IM-QTOF-MS)enabling four-dimensional separations(2 D-LC,IM,and MS),is proposed.In combination with in-house database-driven automated peak annotation,this strategy was utilized to characterize ginsenosides simultaneously from white ginseng(WG)and red ginseng(RG).An offline 2 DLC system configuring an Xbridge Amide column and an HSS T3 column showed orthogonality 0.76 in the resolution of ginsenosides.Ginsenoside analysis was performed by data-independent high-definition MSE(HDMSE)in the negative ESI mode on a Vion?IMS-QTOF hybrid high-resolution mass spectrometer,which could better resolve ginsenosides than MSEand directly give the CCS information.An in-house ginsenoside database recording 504 known ginsenosides and 58 reference compounds,was established to assist the identification of ginsenosides.Streamlined workflows,by applying UNIFI?to automatedly annotate the HDMSEdata,were proposed.We could separate and characterize 323 ginsenosides(including 286 from WG and 306 from RG),and 125 thereof may have not been isolated from the Panax genus.The established 2 D-LC/IM-QTOF-HDMSEapproach could also act as a magnifier to probe differentiated components between WG and RG.Compared with conventional approaches,this dimensionenhanced strategy could better resolve coeluting herbal components and more efficiently,more reliably identify the multicomponents,which,we believe,offers more possibilities for the systematic exposure and confirmative identification of plant metabolites.

Determination of fluorinated quinolone antibacterials by ion chromatography with fluorescence detection

For preparing fluorinated quinolone antibiotic medicine locally used in stomatology, simultaneous determination of norfloxacin, ciprofloxacin, and enoxacin was carried out by multiphase ion chromatography with fluorescence detection. Quinolone antibiotics were separated by Dionex OmniPac PAX-500 column with an eluent of 15 mmol/L H2SO4 and 35% methanol （v/v） at a flow-rate of 1.0 ml/min and detected with fluorescence with excitation and emission wave lengths of 347 ran and 420 ran respectively. The detection limits （S/N=3） of norfloxacin, ciprofloxacin and enoxacin were 50, 105 and 80 ng/ml respectively. The relative standard deviations of retention time, peak area and peak height were less than 1.1% and good linear relationship resulted. The developed method was applied to pharmaceutical formulations and biological fluids.

Determination of sulfur anions by ion chromatography-postcolumn derivation and UV detection

A novel method for determination of formaldehyde sulfoxylate, sulfite, thiocyanate, and thiosulfate in foodstuffs by ion chromatography separation with postcolumn derivation and UV detection has been developed. All species are separated at Dionex IonPac AG22A and AS22A with mobile phase of a mixture of 4.5 mmol/L sodium carbonate and 0.8 mmol/L sodium bicarbonate at a flow-rate of 1.0 mL/min. The postcolunm derivation solution was 0.24% iodine in 0.2% phosphate acid and the detection wavelength was set at 288 nm. The detection limits （LOD, signal-to-noise ratio of 3） of formaldehyde sulfoxylate, sulfite, thiocyanate, and thiosulfate were 0.004, 0.006, 0.006, and 0.007 mg/L, respectively. Within-day relative standard deviations （RSD, n = 10） of formaldehyde sulfoxylate, sulflte, thiocyanate, and thiosulfate were 3.24%, 3.76%, 2.68%, and 2.07%, respectively. The recoveries of the four anions were in the range of 67.2-116.5%.

Determination of haloacetic acids in hospital effuent after chlorination by ion chromatography

The ion chromatography combined solid phase extraction （SPE） method was developed for the analysis of low concentration haloacetic acids （HAAs）, a class of disinfection by-products formed from chlorination of hospital wastewater. The monitored HAAs included monochloroacetic acid, monobromoacetic acid, dichloroacetic acid, dibromoacetic acid and trichloroacetic acid. The method employed a sodium hydroxide eluent at a flow rate of 0.8 ml/min, electrolytically generated gradients, and suppressed conductivity detection. To analyze the HAAs in real hospital wastewater samples, C18 pretreatment cartridge was utilized to reduce samples＇ turbidity. Preconcentration with SPE and matrix elimination with treatment cartridges were investigated and found to be able to obtain acceptable detection limits. Linearity, repeatability and detection limits of the above method were evaluated. The detection limits of monobromoacetic acid and dibromoacetic acid were 2.61 μg/L and 1.30 μg/L, respectively, and the other three acids are ranging from 0.48 to 0.82μg/L under 25-fold preconcentration. When the above optimization procedure was applied to three hospital wastewater samples with different treatment processes in Tianjin, it was found that the dichloroacetic acid was the major compound, and the growth ratios of the HAAs after disinfection by sodium hypochlorite were 91.28%, 63.61% and 79.50%, respectively.

Measurement of trace nitrate concentrations in seawater by ion chromatography with valve switching

An ion chromatographic method with a valve switching facility was developed to determine trace nitrate concentrations in seawater using two pumps, two different suppressors, and two columns. A carbohydrate membrane desalter was used to reduce the high concentrations of sodium salts in samples. In this method, trace nitrate was eluted from the concentrator column to the analytical columns, while the matrix fl owed to waste. Neither chemical pre-treatment nor sample dilution was required. In the optimized separation conditions, the method showed good linearity( R >0.99) in the 0.05 and 50 mg/L concentration range, and satisfactory repeatability(RSD<5%, n =6). The limit of detection for nitrate was 0.02 mg/L. Results showed that the valve switching system was suitable and practical for the determination of trace nitrate in seawater.

Detection of Cyanide in Pollution-free Livestock Product Breeding Water by Ion Chromatography

In order to verify the accuracy of ion chromatography for cyanide detection,optimization conditions were studied,and comparison was made for the detection results of cyanide between titration and isonicotinic acid pyrazolone spectrophotometry. The results showed that ion chromatography has good linearity and reproducibility,with the recovery rate of 95%-105% and the limit of detection of 0. 001 mg/L. This method is simple,rapid,safe,selective,and suitable for the determination of cyanide in pollution-free livestock product breeding water.

Arsenic Speciation Analysis by Ion Chromatography - A Critical Review of Principles and Applications

Multiple acute and chronic toxicity of arsenic species and its mobilisation from geological deposits into ground and drinking water resources is one of the greatest threats to human health. Arsenic speciation analy-sis, mostly done by liquid chromatography, is a challenging task which requires an intense high quality work with respect to extraction, preservation, separation, detection and validation. A growing number of As-spe-cies and low regulatory limits (10 μg/L) may require more than one speciation method preferably performed by species specific procedures and detectors. Beside As-fractionation for special application there are many selective speciation methods based on high performance separation techniques like capillary electrophoreses, gas and liquid chromatography. Both, fractionation and speciation methods are reviewed. However, the focus is on scopes and limits of ion chromatographic separations, the most frequently used methods. Based on IC-principles the methods applied are critically discussed and recommendations given which should result in more robust and reliable As-speciation.

Separation Behavior of U(VI) and Th(IV) on a Mixed Ion Exchange Column Using 2,6-Pyridine Dicarboxylic Acid as a Complexing Agent and Determination of Trace Level Thorium in Uranium Matrix Employing High Performance Ion Chromatography

Retention behavior of U(VI) and Th(IV) as their 2, 6-pyridine dicarboxylic acid (PDCA) complexes on reversed phase and ion exchange (cation, anion and mixed ion exchange) columns was studied and based on the results, a simple ion chromatography method for the determination of trace level thorium in uranium oxide using 0.075mM 2, 6-pyridine dicarboxylic acid (PDCA) and 1M KNO3 in 1.2M HNO3 as eluent (flow rate 1 mL/min)was proposed. The advantage of the developed method is that the separation of uranium matrix is not required prior to the ion chromatographic determination of trace Th. Separation was carried out on a mixed ion exchange stationary phase and a 10?4 M arsenazo (III) solution was used as post column reagent for detecting the separated metal ions. The separation of Th from uranium using PDCA in the present investigation is attributed through cation exchange mechanism. A calibration plot was constructed by following the standard addition method over the concentration range of 0.25 to 10 ppm of Th in the presence of uranium matrix, which resulted in a linear regression coefficient of 0.9978. The precision of the method was better than 5% and the LOD for Th was found to be 0.1ppm (S/N=3). The method has been validated by comparing the results with the results obtained from ICP-MS analysis where the This separated from the uranium matrix. The proposed method is simple, rapid, accurate and cost effective compared to techniques like ICP-MS or ICP-AES and is suitable for the routine kind of analysis.

Organic acids and inorganic anions in Bayer liquors by ion chromatography after solid-phase extraction

A method for the simultaneous separation and determination of organic acids and inorganic anions in Bayer liquors was developed by gradient ion chromatography with suppressed conductivity detection. Formate, acetate, propionate, oxalate, succinate, glutarate, fluoride, chloride and sulfate were separated and determined in 33 min. The samples were pretreated with solid-phase extraction, which has high selectivity for removing a large number of metallic ions in the Bayer liquors, and filtered with a 0.45 μm filter membrane before being injected into the ion chromatographic system. The separation of six organic acids and three inorganic anions was achieved on an IonPac AS11-HC column with KOH as the eluent, and the detection was performed by a conductivity detection mode. No interference is found in the presence of fluorate, chlorate and sulphate when organic acids are determined. The calibration graphs of peak area for all the analytes are linear over a wide range. The relative standard derivation of the peak area of analytes is less than 2.14%. Under optimum conditions the detection ranges from 0.2 to 100.0 mg/L. The average recoveries of the added standards are between 94.3% and 102.8%.

Speciation Analysis of Arsenic Compounds in Seafood by Ion Chromatography-Atomic Fluorescence Spectrometry

Ion chromatography-ultra violet-hydride generation-Atomic Florescence Spectrometry was applied to detect 5 arsenic species in seafoods. The arsenic species studied include arsenobetaine(As B), arsenite(As(III)), dimethylarsinic acid(DMA), monomethylarsonic acid(MMA), and arsenate(As(V)), which were extracted from samples using 2% formic acid. Gradient elution using 33 mmol L^(-1) CH_3COONH_4 and 15 mmol L^(-1) Na_2CO_3 with 10 mL CH_3CH_2OH at pH 8.4 allowed the chromatographic separation of all the species on a Hamilton PRP-X100 anion-exchange column in less than 8 min. In this study, an ultrasound extraction method was used to extract arsenic species from seafood. The extraction efficiency was good and the recoveries from spiked samples were in the range of 72.6%–109%; the precision between sample replicates was higher than 3.6% for all determinations. The detection limits were 3.543 μg L^(-1) for As B, 0.4261 μg L^(-1) for As(III), 0.216 μg L^(-1) for DMA, 0.211 μg L^(-1) for MMA, and 0.709 μg L^(-1) for As(V), and the linear coefficients were greater than 0.999. We also developed an application of this method for the determination of arsenic species in bonito, Euphausia superba, and Enteromorpha with satisfactory results. Therefore, it was confirmed that this method was appropriate for the detection of arsenic species in seafood.

Determination of inorganic anions in ethyl acetate by in-line hollow fiber membrane extraction with ion chromatography

In this work, a novel hollow fiber membrane extractor was set up to extract inorganic anions from ethyl acetate using deionized water. Inorganic anions in slightly soluble organic solvents can be determined by the in-line hollow fiber membrane extractor coupled with ion chromatography at first time. Different aspects of the extraction procedure such as magnetic stirring speed, extraction flow rate and extraction time were optimized to achieve high extraction efficiency and good separation results. Satisfactory linear range, limits of detection and good repeatability were obtained. The procedure was applied to analyze inorganic anions in two commercial ethyl acetate samples.