Occurrence and removal characteristics of phthalate esters from bottled drinking water using silver modified roasted date pits.

BACKGROUND: This paper aims to investigate the occurrence and removal characteristics of phthalate esters from bottled drinking water using silver modified roasted date pits. Three adsorbents, namely roasted date pits (RODP), silver-modified roasted date pits (S-RODP), and activated carbon (AC) were used to investigate their adsorption characterizations in removing dimethyl phthalate (DMP), diethyl phthalate (DEP), dibutyl phthalate (DBP), butyl benzyl phthalate (BBP), di-2-ethylhexyl phthalate (DEHP), and di-n-octyl phthalate (DNOP) from the collected bottle water samples. METHODS: The occurrences of the phthalate esters in the collected bottled water samples were carried out at different temperatures (30, 50, and 60 °C), and analyzed using gas chromatography-mass spectrometry analysis - selected ion monitoring. Batch adsorption isotherms were used to study and establish the efficiency of such adsorbents in removing phthalate esters, in which they describe the adsorbent-adsorbate interaction systems. Adsorption efficiency of the various adsorbents was investigated by using different adsorbent masses (0.05 g, 0.10 g, and 0.15 g) and temperature (30 °C, 50 °C, and 60 °C). Different physical and chemical characterizations were studied using scanning electron microscopy (SEM), Fourier transform infrared (FTIR), Brunauer-Emmett-Teller (BET) surface area, pore radius, and pore volume. RESULTS: The results indicated that the most abundant phthalate esters were DMP followed by DEP under 30 °C; however, DNOP was not detected in any of the tested water samples, except for one sample under 30 °C with a concentration of 0.031 µg/mL. The obtained results showed that phthalate esters leaching to the bottled drinking water were affected by storage temperature. The phthalate esters levels were increased with increasing the temperature to 60 °C. It was concluded that the ability of S-RODP for the adsorption of phthalate esters was better than the removal percentage obtained by AC and RODP. The removal percentage was increased from 90 to 99% by increasing the temperature from 30 to 50 °C and then decreased to 92.3% at 60 °C. CONCLUSION: RODP was successfully used as an effective adsorbent for phthalate esters removal from drinking water. However, S-RODP has the highest removal abilities than other adsorbents due to the newly formed functional groups on its surface.

Analytical strategy for the detection of ecdysterone and its metabolites in vivo in uPA(+/+)-SCID mice with humanized liver, human urine samples, and estimation of prevalence of its use in anti-doping samples.

Ecdysteroids are of interest as potential sport performance enhancers, due to their anabolic effects. The current study aimed to analyze levels of the most abundant ecdysteroid, ecdysterone (20-hydroxyecdysone, 20-OHE) in easily available dietary supplements, and, outline an analytical strategy for its detection, and that, of its metabolites, (1) following administration of pure 20-OHE to uPA(+/+)-SCID mice with humanized liver, (2) in a human volunteer after ingestion of two supplements, one with a relatively low, and the other a high, concentration of 20-OHE, and, (3) to estimate the prevalence of use of 20-OHE in elite athletes (n = 1000). Of the 16 supplements tested, only five showed detectable levels of 20-OHE, with concentrations ranging from undetectable up to 2.3 mg per capsule. Urine of uPA(+/+)-SCID urine showed the presence of 20-OHE and its metabolite, 14 deoxy ecdysterone, within 24 hours (hr) of ingestion. In humans, both the parent and the metabolite were detectable within 2 to 5 hr of ingestion, with the metabolite being detectable for longer than the parent. After ingestion of a low dose supplement, the parent and metabolite were detectable for 70 and 48 hr, while following the higher dose it was 96 and 48 hr, respectively. Analysis of urines from athletes (n = 1000) confirmed four positives for 20-OHE, suggesting a prevalence of use of 0.4%. Prevalence of its use by elite athletes was relatively low, however, this needs to be confirmed in other populations, and with other related ecdysteroids.

Indoor phthalates from household dust in Qatar: implications for non-dietary human exposure.

Phthalates are ubiquitous semi-volatile organic compounds in the indoor environment present in various consumer products such as cosmetics, polyvinylchloride (PVC) flooring, food packing, and many others. Indoor phthalate concentrations were investigated in 15 buildings including 11 homes, 3 laboratories, and 1 from a hospital in Qatar. Dust samples were collected from vacuum cleaning bags usually used for cleaning homes, labs, and hospitals. The main objectives of this study was to determine the occurrence and concentration of phthalates in dust in Qatar and consequently to estimate the non-dietary human exposure. Eleven phthalates was analyzed. The major identified phthalate compounds at homes in Qatar were bis(2-ethylhexyl) phthalate unlabeled (DEHP) and diisononyl phthalate (DINP) at a geometric mean of 288 µg/g (median 395 µg/g) and 106 µg/g (median 101 µg/g) accounting for 57% and 23% of the total measured phthalates, respectively. The major phthalate compounds found in the first lab building were DEHP and DINP with a median of 4861 µg/g and 943 µg/g, respectively, accounting for 82% and 16% of the total phthalates. For the second lab building, the major phthalates were DEHP with a median of 466 µg/g, accounting for 20% of the total phthalates measured, and DINP median of 1725 µg/g, accounting for 71% of the total measured phthalates. The dust sample tested from hospital building had DEHP as the major phthalate compound with a median of 793 µg/g, accounting for 4.0% of the total measured phthalates, and DINP with a median of 19,626 µg/g, accounting for 94%. The estimated human non-dietary exposure for children, adults, and toddlers was based on phthalate concentrations (median) and found to be 225 ng/kg bw/day for children, 2328 ng/kg bw/day for adults, and 2099 ng/kg bw/day for toddlers.

Development of QuEChERS Method for the Determination of Polycyclic Aromatic Hydrocarbons in Smoked Meat Products Using GC-MS from Qatar.

A simple and fast method for the determination of PAHs in smoked meat samples was described. The QuEChERS (Z-Sep) procedure was used for sample preparation. Gas chromatograph-mass spectrometer with electron ionization (EI) was used to separate and detect the PAHs. All 16 common PAHs were analyzed successfully. Matrix-matched calibration was applied. Spiked samples were performed at 1 ng/g (n=10) and 10 ng/g (n=10) for two days. Overall recoveries of PAHs were within 74 to 117%, with RSDs within 1.15 to 37.57% and 1 and 10 ng/g wet weight for first and second day, respectively. In most of the analyzed smoked meat samples, there were no exceeded levels compared to the maximum levels declared by Commission Regulation (EU) number 835/2011. The method can be recommended for routine analysis for laboratories having a large number of samples.

Association of polybrominated diphenyl ethers in two fat compartments with increased risk of insulin resistance in obese individuals.

BACKGROUND: Polybrominated diphenyl ethers (PBDEs), a widely utilized class of flame retardants in various commercial products, represent a prominent source of environmental contaminants. PBDEs tend to accumulate in adipose tissue, potentially altering the function of this endocrine organ and increasing risk of insulin resistance. The aim of this study was to compare levels of PBDEs in adipose tissues from two metabolically distinct obese groups; the insulin sensitive (IS) and the insulin resistant (IR). METHODS: Levels of 28 PBDE congeners were assessed in subcutaneous and omental adipose tissues from 34 obese Qatari individuals (11 IS and 23 IR) using gas chromatography (Trace GC Ultra) coupled to a TSQ Quantum triple Quadrupole mass spectrometer. Correlations of identified PBDEs and mediators of metabolic disease were established and effects of PBDEs treatment on insulin signaling in primary omental preadipocytes were determined. RESULTS: Out of 22 detectable PBDEs in subcutaneous and omental adipose tissues, PBDEs 28, 47, 99 and 153 were predominant in omental adipose tissues from obese Qatari subjects. PBDEs 99, 28, and 47 were significantly higher in IR individuals compared to their IS counterparts. Significant positive correlations were identified between PBDEs 28 and 99 in the omental tissues and with fasting insulin levels. When considering PBDEs congeners, penta congeners were also higher in IR compared to IS individuals, while no significant differences were detected in mono, tri, tertra, hexa, hepta and octa congeners between the two studied groups. Treatment of human omental preadipocytes from insulin sensitive individuals with PBDE28 caused inhibition of phosphorylation of GSK3 α/ß (Ser21/Ser9), mTOR (Ser2448), p70 S6 kinase (Thr389) and S6 ribosomal protein (Ser235/Ser236) and activation of PTEN (Ser380) phosphorylation, suggesting inhibition of insulin signaling. CONCLUSION: This pilot data suggests that accumulation of specific PBDEs in human adipose tissues is associated with insulin resistance in obese individuals. Further investigation of the functional role of PBDEs in the pathology of insulin resistance should help developing therapeutic strategies targeting obese individuals at higher risk.

Simultaneous analysis of organochlorinated pesticides (OCPs) and polychlorinated biphenyls (PCBs) from marine samples using automated pressurized liquid extraction (PLE) and Power Prep™ clean-up.

An automated pressurized liquid extraction (PLE) method followed by Power Prep™ clean-up was developed for organochlorinated pesticide (OCP) and polychlorinated biphenyl (PCB) analysis in environmental marine samples of fish, squid, bivalves, shells, octopus and shrimp. OCPs and PCBs were simultaneously determined in a single chromatographic run using gas chromatography-mass spectrometry-negative chemical ionization (GC-MS-NCI). About 5 g of each biological marine sample was mixed with anhydrous sodium sulphate and placed in the extraction cell of the PLE system. PLE is controlled by means of a PC using DMS 6000 software. Purification of the extract was accomplished using automated Power Prep™ clean-up with a pre-packed disposable silica column (6 g) supplied by Fluid Management Systems (FMS). All OCPs and PCBs were eluted from the silica column using two types of solvent: 80 mL of hexane and a 50 mL mixture of hexane and dichloromethane (1:1). A wide variety of fish and shellfish were collected from the fish market and analyzed using this method. The total PCB concentrations were 2.53, 0.25, 0.24, 0.24, 0.17 and 1.38 ng g(-1) (w/w) for fish, squid, bivalves, shells, octopus and shrimp, respectively, and the corresponding total OCP concentrations were 30.47, 2.86, 0.92, 10.72, 5.13 and 18.39 ng g(-1) (w/w). Lipids were removed using an SX-3 Bio-Beads gel permeation chromatography (GPC) column. Analytical criteria such as recovery, reproducibility and repeatability were evaluated through a range of biological matrices.

Determination of the levels of polycyclic aromatic hydrocarbons in toasted bread using gas chromatography mass spectrometry.

Concentration of 16 polycyclic aromatic hydrocarbons (PAHs) in eighteen baked bread samples using gas oven toasting were evaluated in this study. Samples were classified into the following categories: (1) bread baked from white wheat flour, (2) bread baked from brown wheat flour, and (3) sandwich bread baked from white wheat flour. Analysis was performed by GC-MS after Soxhlet extraction of the sample and clean up of the extract. The levels of B[a]P was not detected in ten of eighteen samples. In the rest of the samples, B[a]P are varied from 2.83 to 16.54 µg/kg. B[a]A, CHR, B[b]FA, B[k] FA, IP, DB[a,h]A, and B[ghi]P concentrations were found to be less than 10.0 µg/kg. However, B[a]P are not detected in original white and brown wheat flour. The total PAHs were varied in the range 1.06-44.24 µg/kg and 3.08-278.66 µg/kg for H-PAH and L-PAH, respectively. Reproducibility and repeatability of the proposed method was calculated and presented in terms of recovery and relative standard deviations (RSD, %). Recoveries were varied from 72.46% to 99.06% with RSD ± 0.28-15.01% and from 82.39% to 95.01% with RSD ±1.91-13.01% for repeatability and reproducibility, respectively. Different commercialized samples of toasted bread were collected and analyzed.

Occurrence and concentrations of polybrominated diphenyl ethers in sewage sludge from three wastewater treatment plants in Kuwait.

Polybrominated diphenyl ether (PBDE) concentrations were measured in sewage sludge samples collected from three wastewater treatment plants in Kuwait over a six month period. PBDEs were detected in all samples analyzed and there were significant differences between the three wastewater treatment plants. The mean (and range) of summation PBDEs concentrations measured are as follows: Jahra 52.5 ng g(-1) (5.7-169.5 ng g(-1)); Reqqa, 144 ng g(-1) (32-296 ng g(-1)); Umm Haylaman, 377 ng g(-1) (23-1599 ng g(-1)). The differences in concentrations of the sum of penta congeners were consistently different at the three treatment plants with values increasing in the order: Jahra

Polycyclic aromatic hydrocarbons in indoor air and dust in Kuwait: implications for sources and nondietary human exposure.

This study reports concentration of polycyclic aromatic hydrocarbons (PAHs) in indoor air and dust samples collected from 24 homes in Kuwait. Mean SigmaPAHs in indoor air ranged from 1.3 to 16 ng/m(3) with a geometric mean of 5.6 ng/m(3), whereas the dust concentrations varied over three orders of magnitude, from 3 to 2920 ng/g, with a geometric mean of 165 ng/g. The low-molecular-weight tricyclic and tetracyclic PAHs dominated the air profile constituting approximately 70-90 % of the measured compounds, with phenanthrene (51%), fluorene (13 %), fluoranthere (8 %), and pyrene (7 %) being the major contributors. The PAH profile in dust was dominated by the high-molecular-weight PAHs, with three compounds (benzo[a]pyrene, benzo[k]fluoranthene, and benzo[b]fluoranthene) contributing approximately 60% of the average SigmaPAHs measured in the samples. Indoor-to-outdoor (I/O) ratios for individual compounds were <1 for the majority of compounds, suggesting that there were no significant indoor sources for these compounds in these homes. Using the measured concentrations in air and dust, together with estimates of inhalation and inadvertent dust ingestion rates for children and adults, estimated human nondietary exposure on a BaP(equiv) basis were 547 pg/kg body weight/day and 205 pg/kg body weight/day for children and adults, respectively. Exposure from dust ingestion contributes about 42% of nondietary intake of SigmaPAHs in children, but only 11% for adults. The threefold difference in exposure estimates between children and adults in this study supports previous reports that children are at greater risk from pollutants that accumulate indoors.

Passive sampler-derived air concentrations for polybrominated diphenyl ethers and polycyclic aromatic hydrocarbons in Kuwait.

The present study presents, to our knowledge, the first ambient air data for a range of polybrominated diphenyl ethers (PBDEs) and polycyclic aromatic hydrocarbons (PAHs) in Kuwait. This was achieved by concurrently deploying polyurethane foam-disk passive samplers at 14 sites over a six-week period. Calculated mean sigma5PBDE concentrations (sum of brominated diphenyl ethers [BDEs] 47, 99, 100, 153, and 154) ranged from 2.5 to 32 pg/m3 of air, with BDE 47 contributing between 39 and 65% of the sigmaPBDEs detected. Differences in relative concentrations were observed between sites, with higher concentrations measured close to suspected sources. Calculated sigmaPAH concentrations ranged from 5 to 13 ng/m3 (mean, 8.3 ng/m3). The compound distribution was dominated by three- and four-ring compounds, which constituted approximately 90% of the sigmaPAHs, with phenanthrene contributing approximately 35%. However, the proportion of five- and six-ring PAHs increased around the "oil lakes," which were formed by the torching of oil wells during the 1991 Gulf War. The oil lakes are a reservoir of PAHs that will continue feeding the atmosphere as long as they remain untreated.

Vacancy ion-exclusion chromatography of inorganic acids on a weakly acidic cation-exchange resin column.

Vacancy ion-exclusion chromatography (VIEC) for inorganic acids such as H(2)SO(4), HCl, H(3)PO(4), HNO(3), HI and HF is tested on a polymethacrylate-based weakly acidic cation-exchange resin column in the H(+)-form. That is, mixture of inorganic acids in the mobile phase is adsorbed to the resin phase passing through the separation column, and each vacant peak induced by injecting water is determined. Retention times are dependent on the degrees of retention for each analyte in the resin phase. In VIEC, well-shaped peaks of inorganic acids are produced, leading to efficient separations. However, retention behaviors of inorganic acids were strongly affected by the concentrations of the acids in the mobile phase. Sulfosalicylic acid was mixed with inorganic acids in the mobile phase prior to the introduction of a separation column in order to obtain the well-resolutions in the lower concentrations of the acids. By using this method, the separations of inorganic acids could be achieved in the range of 0.01-1 mM, and the linear ranges could be extended over two-orders of magnitude. This is considered since the protonated carboxylic groups fixed on the resin phase were increased with increasing the acid concentrations in the mobile phase, and the penetration effects for the acids to the resin phase were thus enhanced. The detection limits (S/N=3) were below 1.0 microM for all analyte acids. Precision values for retention times were below 0.32% and for peak area were below 0.91%.

House dust as a source of human exposure to polybrominated diphenyl ethers in Kuwait.

This study reports concentrations of polybrominated diphenyl ethers (PBDEs) in dust samples collected from 17 homes in Kuwait. PBDEs were measured in all homes investigated with mean summation operatorPBDEs concentration ranging from 1 to 393 ng g(-1), with a geometric mean of 76 ng g(-1). The dominant congener in all samples was BDE 209 constituting ca. 85% of the summationPBDEs followed by BDE 99 (5%), BDE 47 (4.5%), and BDE 183 (2%). The congener mixture in dust is dominated by those in deca and penta formulations. Using the measured concentrations and estimates of dust ingestion rates for children and adults, estimated human non-dietary exposure based on mean PBDE levels were 14.8 and 1.5 ng day(-1) for children and adults, respectively. The 10-fold difference in exposure estimates between children and adults in this study supports previous reports that children are at greater risk from pollutants that accumulate indoors. The ubiquitous distribution of these chemicals as noted in this study highlights the fact that we are continuously exposed to low doses of chemicals in the indoor environment.

Spatial distribution of polybrominated diphenyl ethers in coastal marine sediments receiving industrial and municipal effluents in Kuwait.

Polybrominated diphenyl ether (PBDE) concentrations were measured in surficial sediments from coastal sediments receiving industrial and municipal effluents in Kuwait. The summation PBDE concentrations varied by two orders of magnitude ranging from 80 to 3800 pg g(-1)dw. The congener distribution was dominated by BDE 183, with minor contributions from BDEs 154 and 153. The similarity between the congener profile to that of the technical octa formulation (Bromkal 79-8DE) suggests a source of this product in Kuwait. The observed gradient in concentration distribution, with high summation PBDE concentrations near the shore and an exponential decrease seaward, indicates that wastewater discharge from industrial activities in the study area is the primary source of these compounds in the sediments.

Spatial distribution of polychlorinated biphenyls in coastal marine sediments receiving industrial effluents in Kuwait.

The concentrations of polychlorinated biphenyls (PCBs) were measured in surficial sediments receiving industrial and municipal effluents in Kuwait. The SigmaPCB concentrations varied by two orders of magnitude ranging from 0.4 to 84 microg kg(-1) dw. The homologue distribution in the study favored the more chlorinated congeners and generally followed the order: penta-PCBs > hexa-PCBs > tetra-PCBs approximately hepta-PCBs, with the dominant congeners being 138, 101, 110, 180, 153, 132, 149, and 118. The spatial distribution revealed significant intersite difference in concentration, with high levels encountered close to a harbor and several wastewater outlets suggesting that point source input is the primary delivery mechanism of PCBs to the sediment. This study suggests that atmospheric deposition of PCBs may not be a significant delivery mechanism to sediments in Kuwait possibly due to low annual precipitation and high annual temperatures that are experienced in the Arabian Gulf. The implication of this observation is that PCBs in air are likely to remain in the gas phase long enough to be subject to long-range atmospheric transport to other regions.

High-speed ion-exclusion chromatography of dissolved carbon dioxide on a small weakly acidic cation-exchange resin column with ion-exchange enhancement columns of conductivity detection.

The high-speed ion-exclusion chromatographic determination of dissolved carbon dioxide, i.e., carbonic acid, hydrogencarbonate or carbonate, with conductivity detection was obtained using a small column packed with a weakly acidic cation-exchange resin in the H+-form (40 mm long x 4.6 mm i.d., 3 microm-particle and 0.1 meq./ml-capacity). Two different ion-exchange resin columns, which were a strongly acidic cation-exchange resin in the K+-form and a strongly basic anion-exchange resin in the OH- -form, were connected after the separation column. The sequence of columns could convert dissolved carbon dioxide to KOH having high conductivity response. The enhancement effect for dissolved carbon dioxide could retain even on the vast chromatographic runs, by using the enhancement columns with high ion-exchange capacity above 1.0 meq./ml. The retention time was in 60 s at flow-rate of 1.2 ml/min. The calibration graph of dissolved carbon dioxide estimated as H2CO3- was linear in the range of 0.005-10 mM. The detection limit at signal to noise of 3 was 0.15 microM as H2CO3-. This method was applicable to several rainwater and tap water samples.

Validation of various extraction techniques for the quantitative analysis of polycyclic aromatic hydrocarbons in sewage sludges using gas chromatography-ion trap mass spectrometry.

A new GC-ion trap MS method has been developed for the determination of polycyclic aromatic hydrocarbons (PAHs) in sewage sludge samples. The sludge samples were extracted with Soxhlet, Soxtec, and pressurized liquid extraction (PLE) using 1:1 (v/v) dichloromethane (DCM):n-hexane solvent mixture. A multi-layer clean-up (silica/Al2O3) column were used, followed by gel permeation chromatography (GPC) to eliminate the interfering organic compound as well as the lipids. The extracts were quantified with GC-EI-SIS and GC-EI-MS-MS. The method was successfully applied to determine the concentration of PAHs present in sewage sludge samples collected from four waste water treatment plants (WWTPs). The method recovery values varied from 61.5 to 90.5%, 65.0 to 91.8% and 60.0 to 93.4% for Soxtec extraction, Soxhlet extraction and PLE extraction, respectively. The total concentrations of the 16 PAHs in the sewage sludge samples were found to vary from 1.56 to 6.18 mg/kg. The concentration of PAHs in WWTPs did not significantly vary.

Vacancy ion-exclusion/adsorption chromatography of aliphatic amines on a polymethacrylate-based weakly basic anion-exchange column.

Vacancy ion-exclusion/adsorption chromatography has been applied to investigate the separation behavior of five aliphatic amines (ethylamine, propylamine, butylamine, pentylamine and hexylamine) on a polymethacrylate-based weakly basic anion-exchange column (Tosoh TSKgel DEAE-5PW). This system is consisted of analytes as a mobile phase and water as an injected sample. In the vacancy ion-exclusion/adsorption chromatography, the elution order was as follows: ethylamine < propylamine < butylamine < pentylamine < hexylamine, depending on their hydrophobicity. The retention times of the amines were decreased with decreasing their concentrations in the mobile phase. The retention times and resolutions of the amines were increased by adding a basic compound (e.g., lithium hydroxide or heptylamine) and by increasing the pH of mobile phase (pH > 11). This was because the dissociations of amine samples in the mobile phase were suppressed and thus the hydrophobic adsorption effects were enhanced. The linearity of calibration graphs could be obtained from the peak areas of the amine samples injected to the 0.05, 0.5 and 5 mM of amine mobile phase at pH 11 by heptylamine. The detection limits of aliphatic amines as injected samples were around 1 microM for five aliphatic amines at three different amine mobile phases. From these results, the retention behaviors of aliphatic amines on vacancy ion-exclusion/adsorption chromatography were concluded to be governed by the hydrophobic adsorption effect.

Ion-exclusion chromatography with conductimetric detection of aliphatic carboxylic acids on a weakly acidic cation-exchange resin by elution with benzoic acid-beta-cyclodextrin.

In this study, an aqueous solution consisting of benzoic acid with low background conductivity and beta-cyclodextrin (beta-CD) of hydrophilic nature and the inclusion effect to benzoic acid were used as eluent for the ion-exclusion chromatographic separation of aliphatic carboxylic acids with different pKa values and hydrophobicity on a polymethacrylate-based weakly acidic cation-exchange resin in the H+ form. With increasing concentration of beta-cyclodextrin in the eluent, the retention times of the carboxylic acids decreased due to the increased hydrophilicity of the polymethacrylate-based cation-exchange resin surface from the adsorption of OH groups of beta-cyclodextrin. Moreover, the eluent background conductivity decreased with increasing concentration of beta-cyclodextrin in 1 mM benzoic acid, which could result in higher sensitivity for conductimetric detection. The ion-exclusion chromatographic separation of carboxylic acids with high resolution and sensitivity was accomplished successfully by elution with a 1 mM benzoic acid-10 mM cyclodextrin solution without chemical suppression.

Vacancy ion-exclusion chromatography of haloacetic acids on a weakly acidic cation-exchange resin.

A new and simple approach is described for the determination of the haloacetic acids (such as mono-, di- and trichloroacetic acids) usually found in drinking water as chlorination by-products after disinfection processes and acetic acid. The new approach, termed vacancy ion-exclusion chromatography, is based on an ion-exclusion mechanism but using the sample solution as the mobile phase, pure water as the injected sample, and a weakly acidic cation-exchange resin column (TSKgel OApak-A) as the stationary phase. The addition of sulfuric acid to the mobile phase results in highly sensitive conductivity detection with sharp and well-shaped peaks, leading to excellent and efficient separations. The elution order was sulfuric acid, dichloroacetic acid, monochloroacetic acid, trichloroacetic acid, and acetic acid. The separation of these acids depends on their pKa values. Acids with lower pKa values were eluted earlier than those with higher pKa, except for trichloroacetic acid due to a hydrophobic-adsorption effect occurring as a side-effect of vacancy ion-exclusion chromatography. The detection limits of these acids in the present study with conductivity detection were 3.4 microM for monochloroacetic acid, 0.86 microM for dichloroacetic acid and 0.15 microM for trichloroacetic acid.

Vacancy ion-exclusion chromatography of aromatic carboxylic acids on a weakly acidic cation-exchange resin.

Determination of aromatic carboxylic acids by conventional ion-exclusion chromatography is relatively difficult and methods generally rely on hydrophobic interaction between the solute and the resin. To overcome the difficulties in determining aromatic carboxylic acids a new approach is presented, termed vacancy ion-exclusion chromatography, which is based on use of the sample as mobile phase and an injection of aqueous 10% methanol onto a weakly acidic cation-exchange column (TSKgel OApak-A). Highly sensitive conductivity detection occurred with sharp and well-shaped peaks, leading to very efficient separations. The effects of sulfuric acid concentration added to the mobile phase, flow-rate, and column temperature on the retention volume of tested aromatic carboxylic acids was investigated. Retention times were found to be affected by the concentration of the analytes in the mobile phase and to some extent also by the addition of an organic modifier such as methanol to the injected water sample. Separation of sulfuric acid (SA), naphthalenetetracarboxylic acid (NTCA), phthalic acid (PA) and benzoic acid (BA) was satisfactory using this new approach. Detection limits were 0.66, 0.67, 0.42 and 0.86 microM and detector responses were linear in the range 1-100, 1-80, 2.5-100 and 10-40 microM, for SA, NTCA, PA and BA, respectively. Precision for retention times was 0.36% and for peak areas was 1.5%.