Phytoassessment of Vetiver grass enhanced with EDTA soil amendment grown in single and mixed heavy metal-contaminted soil.

Over the years, ethylene-diamine-tetra-acetate (EDTA) has been widely used for many purposes. However, there are inadequate phytoassessment studies conducted using EDTA in Vetiver grass. Hence, this study evaluates the phytoassessment (growth performance, accumulation trends, and proficiency of metal uptake) of Vetiver grass, Vetiveria zizanioides (Linn.) Nash in both single and mixed heavy metal (Cd, Pb, Cu, and Zn)-disodium EDTA-enhanced contaminated soil. The plant growth, metal accumulation, and overall efficiency of metal uptake by different plant parts (lower root, upper root, lower tiller, and upper tiller) were thoroughly examined. The relative growth performance, metal tolerance, and phytoassessment of heavy metal in roots and tillers of Vetiver grass were examined. Metals in plants were measured using the flame atomic absorption spectrometry (F-AAS) after acid digestion. The root-tiller (R/T) ratio, biological concentration factor (BCF), biological accumulation coefficient (BAC), tolerance index (TI), translocation factor (TF), and metal uptake efficacy were used to estimate the potential of metal accumulation and translocation in Vetiver grass. All accumulation of heavy metals were significantly higher (p < 0.05) in both lower and upper roots and tillers of Vetiver grass for Cd + Pb + Cu + Zn + EDTA treatments as compared with the control. The single Zn + EDTA treatment accumulated the highest overall total amount of Zn (8068 ± 407 mg/kg) while the highest accumulation for Cu (1977 ± 293 mg/kg) and Pb (1096 ± 75 mg/kg) were recorded in the mixed Cd + Pb + Cu + Zn + EDTA treatment, respectively. Generally, the overall heavy metal accumulation trends of Vetiver grass were in the order of Zn >>> Cu > Pb >> Cd for all treatments. Furthermore, both upper roots and tillers of Vetiver grass recorded high tendency of accumulation for appreciably greater amounts of all heavy metals, regardless of single and/or mixed metal treatments. Thus, Vetiver grass can be recommended as a potential phytoextractor for all types of heavy metals, whereby its tillers will act as the sink for heavy metal accumulation in the presence of EDTA for all treatments.

Effects of Different Soil Amendments on Mixed Heavy Metals Contamination in Vetiver Grass.

Three different types of low cost soil amendments, namely, EDTA, elemental S and N-fertilizer, were investigated with Vetiver grass, Vetiveria zizanioides (Linn.) Nash growing under highly mixed Cd-Pb contamination conditions. A significant increase (p < 0.05) in Cd and Pb accumulation were recorded in the shoots of all EDTA and N-fertilizer assisted treatments. The accumulation of Cd in 25 mmol EDTA/kg soil and 300 mmol N/kg soil showed relatively higher translocation factor (1.72 and 2.15) and percentage metal efficacy (63.25 % and 68.22 %), respectively, compared to other treatments. However, it was observed that the increased application of elemental S may inhibit the availability of Pb translocation from soil-to-root and root-to-shoot. The study suggests that viable application of 25 mmol EDTA/kg, 300 mmol N/kg and 20 mmol S/kg soil have the potential to be used for soil amendment with Vetiver grass growing under contaminated mixed Cd-Pb soil conditions.

Heavy metals phyto-assessment in commonly grown vegetables: water spinach (I. aquatica) and okra (A. esculentus).

The growth response, metal tolerance and phytoaccumulation properties of water spinach (Ipomoea aquatica) and okra (Abelmoschus esculentus) were assessed under different contaminated spiked metals: control, 50 mg Pb/kg soil, 50 mg Zn/kg soil and 50 mg Cu/kg soil. The availability of Pb, Zn and Cu metals in both soil and plants were detected using flame atomic absorption spectrometry. The concentration and accumulation of heavy metals from soil to roots and shoots (edible parts) were evaluated in terms of translocation factor, accumulation factor and tolerance index. Okra recorded the highest accumulation of Pb (80.20 mg/kg) in its root followed by Zn in roots (35.70 mg/kg) and shoots (34.80 mg/kg) of water spinach, respectively. Different accumulation trends were observed with, Pb > Zn > Cu in okra and Zn > Pb > Cu in water spinach. Significant differences (p < 0.01) of Pb, Zn and Cu accumulation were found in both water spinach and okra cultivated among tested treatments. However, only the accumulation of Pb metal in the shoots of water spinach and okra exceeded the maximum permissible levels of the national Malaysian Food Act 1983 and Food Regulations 1985 (2006) as well as the international Codex Alimentarius Commission limits. This study has shown that both water spinach and okra have good potential as Pb and Zn phytoremediators.

Distribution and health risk assessment of trace metals in freshwater tilapia from three different aquaculture sites in Jelebu Region (Malaysia).

The trace metal concentrations in edible muscle of red tilapia (Oreochromis spp.) sampled from a former tin mining pool, concrete tank and earthen pond in Jelebu were analysed with microwave assisted digestion-inductively coupled plasma-mass spectrometry. Results were compared with established legal limits and the daily ingestion exposures simulated using the Monte Carlo algorithm for potential health risks. Among the metals investigated, arsenic was found to be the key contaminant, which may have arisen from the use of formulated feeding pellets. Although the risks of toxicity associated with consumption of red tilapia from the sites investigated were found to be within the tolerable range, the preliminary probabilistic estimation of As cancer risk shows that the 95th percentile risk level surpassed the benchmark level of 10(-5). In general, the probabilistic health risks associated with ingestion of red tilapia can be ranked as follows: former tin mining pool > concrete tank > earthen pond.

New macroporous ß-cyclodextrin functionalized ionic liquid polymer as an adsorbent for solid phase extraction with phenols.

Cyclodextrin-ionic liquid polymer (ßCD-BIMOTs-TDI) is a new class of macroporous material and has great potential to be used as an SPE adsorbent material for extraction of phenols in river water samples. Six phenols, as model analytes, were extracted on a ßCD-BIMOTs-TDI SPE cartridge, and then, eluted with 2 mL of methanol containing 1% acetic acid. The optimum experimental condition was 15 mL of sample volume (sample at pH 6) and 2 mL of methanol containing 1% acetic acid as an eluent solvent. The eluent concentration was determined by using Gas Chromatography-Flame Ionization Detector (GC-FID). Under optimized condition, high sensitivity (detection limits 0.23-0.35 µg/L) and good recoveries (87-116%) were achieved with satisfactory relative standard deviation (RSD) (0.1-1.7%). The developed ßCD-BIMOTs-TDI-SPE was then compared with other adsorbents, and the obtained results showed that the ßCD-BIMOTs-TDI exhibited higher extraction recovery due to the unique structure and properties. Finally, the ßCD-BIMOTs-TDI was applied as a solid phase extraction sorbent for phenols determination under optimized condition, in river and tap waters, prior to the GC-FID separation.

Cloud point extraction of parabens using non-ionic surfactant with cylodextrin functionalized ionic liquid as a modifier.

A cloud point extraction (CPE) process using non-ionic surfactant (DC193C) to extract selected paraben compounds from water samples was investigated using reversed phase high performance liquid chromatography (RP-HPLC). The CPE process with the presence of ß-cyclodextrin (ßCD) functionalized ionic liquid as a modifier (CPE-DC193C-ßCD-IL) is a new extraction technique that has been applied on the optimization of parameters, i.e., pH, ßCD-IL concentration and phase volume ratio. This CPE-DC193C-ßCD-IL method is facilitated at 30 °C, showing great losses of water content in the surfactant-rich phase, resulting in a high pre-concentration factor and high distribution coefficient. The developed method CPE-DC193C-ßCD-IL did show enhanced properties compared to the CPE method without the modifier (CPE-DC193C). The developed method of CPE-DC193C-ßCD-IL gives an excellent performance on the detection of parabens from water samples with the limit of detection falling in the range of 0.013-0.038 µg mL-1. Finally, the inclusion complex formation, hydrogen bonding, and π-π interaction between the ßCD-IL, benzyl paraben (ArP), and DC 193C were proven using 1H NMR and 2D NOESY spectroscopy.

Synthesis and characterization of ß-cyclodextrin functionalized ionic liquid polymer as a macroporous material for the removal of phenols and As(V).

ß-Cyclodextrin-ionic liquid polymer (CD-ILP) was first synthesized by functionalized ß-cyclodextrin (CD) with 1-benzylimidazole (BIM) to form monofunctionalized CD (ßCD-BIMOTs) and was further polymerized using a toluene diisocyanate (TDI) linker to form insoluble CD-ILP (ßCD-BIMOTs-TDI). The ßCD-BIMOTs-TDI polymer was characterized using various tools and the results obtained were compared with those derived from the native ß-cyclodextrin polymer (ßCD-TDI). The SEM result shows that the presence of ionic liquid (IL) increases the pore size, while the thermo gravimetric analysis (TGA) result shows that the presence of IL increases the stability of the polymer. Meanwhile, Brunauer-Emmett-Teller (BET) results show that ßCD-BIMOTs-TDI polymer has 1.254 m(2)/g surface areas and the Barret-Joyner-Halenda (BJH) pore size distribution result reveals that the polymer exhibits macropores with a pore size of 77.66 nm. Preliminary sorption experiments were carried out and the ßCD-BIMOTs-TDI polymer shows enhanced sorption capacity and high removal towards phenols and As(V).

Synthesis and evaluation of molecularly imprinted silica gel for 2-hydroxybenzoic Acid in aqueous solution.

A molecularly imprinted silica gel sorbent for selective removal of 2-Hydroxybenzoic acid (2-HA) was prepared by a surface imprinting technique with a sol-gel process. The 2-HA molecularly imprinted silica gel (2-HA-MISG) sorbent was evaluated by various parameters, including the influence of pH, static, kinetic adsorption and selectivity experiments. The optimum adsorption capacity to the 2-HA appeared to be around pH 2 by the polymer. Morevoer, the imprinted sorbent displayed fast uptake kinetics, obtained within 20 min. The adsorption capacity of the 2-HA-MISG (76.2 mg g-1) was higher than that of the non-imprinted silica gel (NISG) (42.58 mg g-1). This indicates that the 2-HA-MISG offers a higher affinity for 2-HA than the NISG. The polymer displays good selectivity and exhibits good reusability. Experimental results show the potential of molecularly imprinted silica sorbent for selective removal of 2-HA.

Ozonation of metoprolol in aqueous solution: ozonation by-products and mechanisms of degradation.

This study investigated the degradation pathway of metoprolol, a widely used ß-blocker, in the ozonation via the identification of generated ozonation by-products (OPs). Structure elucidation of OPs was performed using HPLC coupled with quadrupole time-of-flight high-resolution mass spectrometry. Seven OPs were identified, and four of these have not been reported elsewhere. Identified OPs of metoprolol included aromatic ring breakdown by-products; aliphatic chain degraded by-products and aromatic ring mono-, di-, and tetrahydroxylated derivatives. Based on the detected OPs, metoprolol could be degraded through aromatic ring opening reaction via reaction with ozone (O3) and degradation of aliphatic chain and aromatic ring via reaction with hydroxyl radical (•OH).

A simple and efficient multi-residue method based on QuEChERS for pesticides determination in palm oil by liquid chromatography time-of-flight mass spectrometry.

In this study, a rapid, specific and sensitive multi-residue method based on acetonitrile extraction followed by dispersive solid-phase extraction (d-SPE) clean-up was implemented and validated for multi-class pesticide residues determination in palm oil for the first time. Liquid-liquid extraction followed by low-temperature precipitation procedure was evaluated in order to study the freezing-out clean-up efficiency to obtain high recovery yield and low co-extract fat residue in the final extract. For clean-up step, d-SPE was carried out using a combination of anhydrous magnesium sulphate (MgSO(4)), primary secondary amine, octadecyl (C(18)) and graphitized carbon black. Recovery study was performed at two concentration levels (10 and 100 ng g(-1)), yielding recovery rates between 74.52% and 97.1% with relative standard deviation values below 10% (n = 6) except diuron. Detection and quantification limits were lower than 5 and 9 ng g(-1), respectively. In addition, soft matrix effects (≤±20%) were observed for most of the studied pesticides except malathion that indicated medium (20-50%) matrix effects. The proposed method was successfully applied to the analysis of suspected palm oil samples.

Removal of selected endocrine disrupting chemicals and personal care products in surface waters and secondary wastewater by ozonation.

This study investigated the removal of parabens, N,N-diethyl-m-toluamide (DEET), and phthalates by ozonation. The second-order rate constants for the reaction between selected compounds with ozone at pH 7 were of (2.2 +/-0.2) X 10(6) to (2.9 +/-0.3) X 10(6) M 1/s for parabens, (2.1+/- 0.3) to (3.9 +/-0.5) M-1/s for phthalates, and (5.2 +/-0.3) M-1/s for DEET. The rate constants for the reaction between selected compounds with hydroxyl radical ranged from (2.49 +/-0.06) x 10(9) to (8.5 +/-0.2) x 10(9) M-1/s. Ozonation of selected compounds in secondary wastewater and surface waters revealed that ozone dose of 1 and 3 mg/L yielded greater than 99% depletion of parabens and greater than 92% DEET and phthalates, respectively. In addition, parabens were found to transform almost exclusively through the reaction with ozone, while DEET and phthalates were transformed almost entirely by hydroxyl radicals (.OH).

Speciation of heavy metals by modified BCR sequential extraction procedure in different depths of sediments from Sungai Buloh, Selangor, Malaysia.

The sequential extraction procedure proposed by the European Standard, Measurements and Testing (SM&T) program, formerly the Community Bureau of Reference (BCR), was applied for partitioning of heavy metals (HMs) in river sediments collected along the course of Sungai Buloh and the Straits of Malacca in Selangor, Malaysia. Eight elements (V, Pb, Cd, Cr, Co, Ni, Cu and Zn) from seven stations (S1-S7) and at different depths were analyzed using the modified BCR Sequential Extraction Procedure (SEP) in combination with ICP-MS to obtain the metal distribution patterns in this region. The results showed that heavy metal contaminations at S2 and S3 was more severe than at other sampling sites, especially for Zn, Cu, Ni and Pb. Nevertheless, the element concentrations from top to bottom layers decreased predominantly. The samples from the Straits of Malacca (S4-S7) the highest contamination factors obtained were for Co, Zn and Pb while the lowest were found for V and Cr, similar to Sungai Buloh sediments. The sediments showed a low risk for V, Cr, Cu and Pb with RAC values of less than 10%, but medium risk for Co, Zn (except S3), Cd at S1 and S2 and Ni at S1, S3 and S5. Zn at S3 and Cd at S3-S7 showed high risk to our sediment samples. There is not any element of very high risk conditions in the selected samples.

Low temperature followed by matrix solid-phase dispersion-sonication procedure for the determination of multiclass pesticides in palm oil using LC-TOF-MS.

A simple and effective multiresidue method based on precipitation at low temperature followed by matrix solid-phase dispersion-sonication was developed and validated to determine dimethoate, malathion, carbaryl, simazine, terbuthylazine, atrazine and diuron in palm oil using liquid chromatography time-of-flight mass spectrometry (LC-TOF-MS). Liquid-liquid extraction (LLE) followed by low temperature method were optimized by studying the effect of type and volume of organic solvent (acetonitrile, acetonitrile:n-hexane (3:2 v/v) and acetone) and time of freezing to obtain high recovery yield and low co-extract fat residue in the final extract. The optimal conditions for matrix solid-phase dispersion (MSPD) were obtained using 5 g of palm oil, 2 g of primary secondary amine (PSA) as dispersing sorbent, 1 g of graphitized carbon black (GCB) as clean-up sorbent and 15 mL of acetonitrile as eluting solvent under conditions of 15 min ultrasonication at room temperature. Method validation was performed in order to study sensitivity, linearity, precision, and accuracy. Average recoveries at three concentration levels (25, 50 and 100 µg kg(-1)) were found in the range of 72.6-91.3% with relative standard deviations between 5.3% and 14.2%. Detection and quantification limits ranged from 1.5 to 5 µg kg(-1) and from 2.5 to 9 µg kg(-1), respectively.

Comparison of unmodified and modified BCR sequential extraction schemes for the fractionation of heavy metals in shrimp aquaculture sludge from Selangor, Malaysia.

A study was carried out to investigate the fractionation of Cd, Cr, Cu, Fe, Mn, Pb, and Zn in shrimp aquaculture sludge from Selangor, Malaysia, using original (unmodified) and modified four-steps BCR (European Community Bureau of Reference, now known as the Standards Measurements and Testing Program) sequential extraction scheme. Step 2 of the unmodified BCR procedure (subsequently called Method A) involves treatment with 0.1 M hydroxylammonium chloride at pH 2, whereas 0.5 M hydroxylammonium chloride at pH 1.5 was used in the modified BCR procedure (subsequently called Method B). Metal analyses were carried out by flame atomic absorption spectrometry. A pseudo-total aqua-regia digest of BCR CRM 701 has also been undertaken for quality assurance purposes. The recovery of Method A for all metals studied ranges from 96.14% to 105.26%, while the recovery for Method B ranges from 95.94% to 122.40%. Our results reveal that Method A underestimated the proportion of metals bound to the easily reducible fraction except for copper. Therefore, the potential mobility of these elements is higher than others. Thus, to use this sludge as a fertilizer we have to first find a remediation for reduction of heavy metal contamination.

Removal of parabens from aqueous solution using ß-cyclodextrin cross-linked polymer.

The removal of four parabens, methyl-, ethyl-, propyl-, and benzyl-paraben, by ß-cyclodextrin (ß-CD) polymer from aqueous solution was studied. Different ß-CD polymers were prepared by using two cross-linkers, i.e., hexamethylene diisocyanate (HMDI) and toluene-2,6-diisocyanate (TDI), with various molar ratios of cross-linker. ß-CD-HMDI polymer with molar ratio of 1:7 and ß-CD-TDI polymer with ratio 1:4 gave the highest adsorption of parabens among the ß-CD-HMDI and ß-CD-TDI series, and were subsequently used for further studies. The adsorption capacity of ß-CD-HMDI is 0.0305, 0.0376, 0.1854 and 0.3026 mmol/g for methyl-, ethyl-, propyl-, and benzyl-paraben, respectively. ß-CD-TDI have higher adsorption capacities compared with ß-CD-HMDI, the adsorption capacity are 0.1019, 0.1286, 0.2551, and 0.3699 mmol/g methyl-, ethyl-, propyl-, and benzyl-paraben respectively. The parameters studied were adsorption capacity, water retention, and reusability. Role of both cross-linker in adsorption, hydrophobicity of polymers, and adsorption capacity of different parabens were compared and discussed. All experiments were conducted in batch adsorption technique. These polymers were applied to real samples and showed positive results.

Ozonation of parabens in aqueous solution: kinetics and mechanism of degradation.

This study investigated the reaction kinetics and degradation mechanism of parabens (methylparaben, ethylparaben, propylparaben and butylparaben) during ozonation. Experiments were performed at pH 2, 6 and 12 to determine the rate constants for the reaction of protonated, undissociated and dissociated paraben with ozone. The rate constants for the reaction of ozone with dissociated parabens (3.3 × 10(9)-4.2 × 10(9)M(-1)s(-1)) were found to be 10(4) times higher than the undissociated parabens (2.5 × 10(5)-4.4 × 10(5)M(-1)s(-1)) and 10(7) times higher than with the protonated parabens (1.02 × 10(2)-1.38 × 10(2)M(-1)s(-1)). The second-order rate constants for the reaction between parabens with hydroxyl radicals were found to vary from 6.8 × 10(9) to 9.2 × 10(9)M(-1)s(-1). Characterization of degradation by-products (DBPs) formed during the ozonation of each selected parabens has been carried out using GCMS after silylation. Twenty DBPs formed during ozonation of selected parabens have been identified. Hydroxylation has been found to be the major reaction for the formation of the identified DBPs. Through the hydroxylation reaction, a variety of hydroxylated parabens was formed.

Comparative study on open system digestion and microwave assisted digestion methods for metal determination in shrimp sludge compost.

The aim of this work was to evaluate two different digestion methods for the determination of the total concentration of metals (Zn, Cu, Cr, Ni, Pb and Cd) in shrimp sludge compost. The compost made from shrimp aquaculture sludge co-composted with organic materials (peat, crushed bark and manure) was used as an organic growing medium for crop. Open system digestion and microwave assisted digestion procedures were employed in sample preparation. Various combinations and volumes of hydrofluoric, nitric and hydrochloric acids were evaluated for the efficiency of both methods. A certified reference material (CRM 146) was used in the comparison of these two digestion methods. The results revealed a good agreement between both procedures and the certified valued. The best recoveries were found in the range between 95% and 99% for microwave assisted digestion with a mixture of 2 ml of HF, 6 ml of HNO(3) and 2 ml of HCl. This procedure was recommended as the method for digestion the compost herein based on the recovery analysis and time taken.

Degradation of DEET by ozonation in aqueous solution.

This study was undertaken in order to understand the factors affecting the degradation of an insect repellent, N,N-diethyl-m-toluamide (DEET) by ozonation. Kinetic studies on DEET degradation were carried out under different operating conditions, such as varied ozone doses, pH values of solution, initial concentrations of DEET, and solution temperatures. The degradation of DEET by ozonation follows the pseudo-first-order kinetic model. The rate of DEET degradation increased exponentially with temperature in the range studied (20-50 degrees C) and in proportion with the dosage of ozone applied. The ozonation of DEET under different pH conditions in the presence of phosphate buffer occurred in two stages. During the first stage, the rate constant, k(obs), increased with increasing pH, whereas in the second stage, the rate constant, k(obs2), increased from pH 2.3 up to 9.9, however, it decreased when the pH value exceeded 9.9. In the case where buffers were not employed, the k(obs) were found to increase exponentially with pH from 2.5 to 9.2 and the ozonation was observed to occur in one stage. The rate of degradation decreased exponentially with the initial concentration of DEET. GC/MS analysis of the by-products from DEET degradation were identified to be N,N-diethyl-formamide, N,N-diethyl-4-methylpent-2-enamide, 4-methylhex-2-enedioic acid, N-ethyl-m-toluamide, N,N-diethyl-o-toluamide, N-acetyl-N-ethyl-m-toluamide, N-acetyl-N-ethyl-m-toluamide 2-(diethylamino)-1-m-tolylethanone and 2-(diethylcarbamoyl)-4-methylhex-2-enedioic acid. These by-products resulted from ozonation of the aliphatic chain as well as the aromatic ring of DEET during the degradation process.