Influence of nitrogen speciation on Cd-induced toxicity in Landoltia punctata.

Nitrogen (N) plays an important role in plant growth and developmental metabolic processes, research on nitrogen speciation regulating Cd accumulation in duckweed is still limited. In this study, the effects of three nitrogen sources (NH4Cl, Ca(NO3)2 and NH4NO3) on the growth, Cd accumulation, and photosynthetic parameters of Landoltia punctata (L. punctata) were analyzed. The results showed that Cd enrichment in L. punctata was significantly reduced (p < 0.05) with different nitrogen treatments compared to the control (CK). Ammonium nitrogen (NH4-N) is more conducive to the accumulation of Cd in L. punctata than nitrate nitrogen (NO3-N). The sum of the cell wall components and soluble components of Cd in the NH4-N treatment group was greater than that in the NO3-N treatment group. The proportion of FNaCl extracts in the NH4-N treatment group was greater than in the NO3-N treatment group. NO3-N led to a greater reduction in photosynthetic pigment content than NH4-N. Overall, applying different forms of nitrogen can alleviate Cd toxicity in L. punctata, and the detoxification effect of the NH4-N treatment is stronger than that of NO3-N treatment. This study will provide theoretical and practical support for the application of duckweed in Cd phytoremediation even in eutrophic aquatic environments.

Cd pollution has become a major global public environmental issue. Duckweed is an ideal species to restore Cd-polluted waters due to its fast growth, easy harvesting and hyperaccumulation Cd. Currently, no definite conclusion has been given on the detoxification effect of nitrogen morphology regulating the accumulation of Cd in plant. In this study, the influence of different nitrogen forms on Cd-induced toxicity in Landoltia punctata were revealed through the changes in biomass, Cd subcellular distribution, Cd chemical morphology and photosynthetic pigment. These findings can provide a new way of analyzing the mechanism of Cd enrichment in plants, and also provide theoretical and technical support for the remediation of Cd pollution by using duckweed resources. The Cd-accumulation duckweed can be pyrolyzed to produce biochar, which can not only control the second pollution by decomposed plant bodies but also realizes the efficient use of waste.

Determination of fecal sterols by gas chromatography-mass spectrometry with solid-phase extraction and injection-port derivatization.

Injection-port derivatization combined with solid-phase extraction (SPE) was developed and applied for the first time to determine five types of fecal sterols (coprostanol, cholestanol, epicholestanol, epicoprostanol and cholesterol) with gas chromatography-mass spectrometry (GC-MS). In this method, silylation of fecal sterols was performed with N,O-bis(trimethylsilyl)trifluoroacetamide (BSTFA) at GC injection-port. The factors influential to this technique such as injection-port temperature, purge-off time, derivatization reagent (BSTFA) volume, and the type of organic solvent were investigated. In addition, the conditions of SPE (including the type of SPE cartridge, the type of elution organic solvent) were also studied. After SPE followed by injection-port silylation by GC-MS, good linearity of analytes was achieved in the range of 0.02-10ng/mL with coefficients of determination, R(2)>0.995. Good reproducibility was obtained with relative standard deviation less than 19.6%. The limits of detection ranged from 1.3ng/mL to 15ng/mL (S/N=3) in environmental water samples. Compared with traditional off-line silylation of fecal sterols performed with water bath (60 degrees C, 30min), this injection-port silylation method is much simpler and convenient. The developed method has been successfully applied for the analysis of fecal sterols from real environmental water samples.

Picogram determination of estrogens in water using large volume injection gas chromatography-mass spectrometry.

In this study, a simple and efficient large volume injection gas chromatography-mass spectrometry (GC-MS) method, via a programmable-temperature vaporizer (PTV) inlet, has been developed and applied in the determination of estrogens in environmental water samples without a prior derivatization process. Three commonly used estrogens estrone, 17 beta-estradiol and 17 alpha-ethynylestradiol were selected as target compounds for this study. It has been demonstrated that the type of gas chromatograph liner and the initial inlet temperature can greatly affect the response intensity of estrogens. Three different types of PTV liners have been studied; the multibaffle liner generated the strongest response intensities towards the estrogen analytes. The results showed that the response intensities of estrogens reduced sharply while the initial inlet temperature increased. Various instrument conditions and sample preparation methods were studied in detail. The optimized method has been validated with good linearity, precision and accuracy. The method detection limit of each estrogen was found to be 0.041 ng/L for estrone, 0.046 ng/L for 17 beta-estradiol and 0.031 ng/L for 17 alpha-ethynylestradiol. To the best of our knowledge, these results represent the best sensitivities achieved for estrogens analyzed in water samples via traditional GC-MS method without a derivatization process. This method has been successfully applied in the analyses of different water samples.

Picogram determination of N-nitrosodimethylamine in water.

N-nitrosodimethylamine (NDMA) persistence within surface waters is a major concern for downstream communities exploiting these waters as drinking water supplies. The objective of this study is to develop a novel and efficient analytical method for NDMA via different technologies: pulsed splitless gas chromatography-nitrogen phosphorus detector (GC-NPD), large volume injection (LVI) gas chromatography-mass spectrometry (GC/MS) via programmable temperature vaporizer (PTV) inlet or PTV-gas chromatography-triple quadruple mass spectrometry (GC-MS/MS) and continuous liquid-liquid extraction. It was found that the sensitivity required for NDMA analysis by GC-NPD can only be achieved when the NPD bead is extremely clean. LVI via PTV can greatly improve GC-MS system sensitivity for analyzing NDMA. With the help of DB-624 (25 m x 200 microm x 1.12 microm) connected with DB-5MS (30 m x 250 microm x 0.25 microm) in series, PTV-GC/MS could overcome the matrix interference for the trace analysis of NDMA. Variable instrument conditions were studied in detail, with the optimized process being validated via precision and accuracy studies. PTV- triple quadruple GC-MS/MS system could efficiently remove the interference on a single DB-5MS (30 m x 250 microm x 0.25 microm) column with good sensitivity and selectivity. The developed methods have been successfully applied to test NDMA in different types of water samples with satisfactory results.

Investigation of ozonation kinetics and transformation products of sucralose.

Sucralose is one of widely used artificial sweeteners, which has been ubiquitously detected in various water sources, such as wastewater and randomly in reservoir water. It is also reported to be persistent to various water treatment techniques. Although there are some studies on removal of sucralose by advanced oxidation process, limited information, in terms of reaction kinetics, transformation products and degradation pathway etc., was reported in its ozonation process. In this study, the reaction kinetics, removal efficiency, influence of pH, humic acid and carbonate on sucralose degradation by ozone, have been studied systematically. The results demonstrated that ozonation of sucralose was initiated by the formation of OH radical. Sucralose could be completely removed with excess O3 at neutral and basic conditions in ultrapure water. The rate of degradation decreased significantly in acidic condition and in the presence of carbonate and OH radical scavenger (e.g. tert-butanol). The acidity was the key factor affecting the degradation of sucralose. The rate constant was about 500 times higher at pH7 than that at pH4. Transformation products study indicated that the ozonation of sucralose were more complex than that in photolysis reaction. Although ozonation of sucralose was initiated by OH radical, both OH radical and O3 might be involved in the formation of transformation products and total organic carbon (TOC) removal. Various transformation products, such as aldehydes, carboxylic acids and probable chloride containing products, were identified and characterized in details. An ozonation degradation pathway of sucralose was proposed as well.

Routine analysis of off-flavor compounds in water at sub-part-per-trillion level by large-volume injection GC/MS with programmable temperature vaporizing inlet.

"Earthy-musty" off-flavor problem in water samples are due to organic compounds present at the sub-part-per-trillion level. Most of the developments in the analysis of tastes and odorous compounds focus on the extraction pre-concentration technique, with detection at picogram per liter level of the earthy-musty off-flavor compounds difficult to be achieved. The objective of this study is to develop a new method involving the large-volume injection (LVI) GC/MS via programmable temperature vaporizing (PTV) inlet and continuous liquid-liquid extraction, to attain analytical sensitivity equal to or better than olfactory sensitivity. Six "earthy-musty" organic compounds, 2-methylisoborneol (MIB), geosmin, 2,4,6-trichloroanisole, 2,3,6-trichloroanisole, 2,3,4-trichloroanisole and 2,4,6-tribromoanisole, were used as probes for this study. It was found that LVI via PTV could greatly improve system sensitivity towards off-flavor compound detection. Variable instrument conditions and sample preparation conditions were studied in detail. This reliable and efficient method has been optimized and validated. The method detection limit were found to be from 35 to 70 pg/L for haloanisoles, 50 pg/L for geosmin and 0.34 ng/L for MIB, with relative standard deviation of calibration curve ranging from 4.7% to 15.1% and recovery ranging from 58% to 96%. This method has been successfully applied to test off-flavor compounds in different types of water samples with satisfactory results.

Study on the kinetics and transformation products of salicylic acid in water via ozonation.

As salicylic acid is one of widely used pharmaceuticals, its residue has been found in various environmental water systems e.g. wastewater, surface water, treated water and drinking water. It has been reported that salicylic acid can be efficiently removed by advanced oxidation processes, but there are few studies on its transformation products and ozonation mechanisms during ozonation process. The objective of this study is to characterize the transformation products, investigate the degradation mechanisms at different pH, and propose the ozonation pathways of salicylic acid. The results showed that the rate of degradation was about 10 times higher at acidic condition than that at alkaline condition in the first 1 min when 1 mg L(-1) of ozone solution was added into 1 mg L(-1) of salicylic acid solution. It was proposed that ozone direct oxidation mechanism dominates at acidic condition, while indirect OH radical mechanism dominates at alkaline condition. A two stages pseudo-first order reaction was proposed at different pH conditions. Various hydroxylation products, carbonyl compounds and carboxylic acids, such as 2,5-dihydroxylbenzoic acid, 2,3-dihydroxylbenzoic acid, catechol, formaldehyde, glyoxal, acetaldehyde, maleic acid, acetic acid and oxalic acid etc. were identified as ozonation transformation products. In addition, acrylic acid was identified, for the first time, as ozonation transformation products through high resolution liquid chromatography-time of flight mass spectrometer. The information demonstrated in this study will help us to better understand the possible effects of ozonation products on the water quality. The degradation pathways of salicylic acid by ozonation in water sample were proposed. As both O3 and OH radical were important in the reactions, the degradation pathways of salicylic acid by ozonation in water sample were proposed at acidic and basic conditions. To our knowledge, there was no integrated study reported on the ozonation of salicylic acid in water, in terms of transformation products, kinetic, mechanism, as well as degradation pathways.

Simultaneous picogram determination of "earthy-musty" odorous compounds in water using solid-phase microextraction and gas chromatography-mass spectrometry coupled with initial cool programmable temperature vaporizer inlet.

"Earthy-musty" off-flavor problem in water samples are due to organic compounds present at the sub-part-per-trillion level. Most of the developments in the analysis of tastes and odorous compounds focus on the extraction pre-concentration technique, with detection at picogram per liter level of the earthy-musty off-flavor compounds difficult to be achieved. In this study, a simple, efficient and sensitive method for the analysis of odorous compounds has been developed by the application of solid-phase microextraction (SPME) and gas chromatography-mass spectrometry (GC-MS) with initial cool programmable temperature vaporizer (PTV) inlet for the first time. Compared with initial hot PTV inlet, the initial cool inlet could greatly improve the system sensitivity, especially for the compounds with good volatility, e.g. 2-methylisoborneol (MIB). StableFlex divinylbenzene/Carboxen/polydimethylsiloxane (DVB/CAR/PDMS) fiber was found to possess the best extraction efficiency towards these odorous compounds in water. Various SPME and PTV conditions have been studied and optimized in detail. The optimized method has been validated with good linearity, precision and accuracy. The method detection limits (MDL) of the targeted odorous compounds were found to be 0.32ng/L for 2,4,6-trichloroanisole (2,4,6-TCA), 0.14ng/L for 2,3,6-trichloroanisole (2,3,6-TCA), 0.16ng/L for 2,3,4-trichloroanisole (2,3,4-TCA), 0.38ng/L for 2,4,6-tribromoanisole (2,4,6-TBA), 0.16ng/L for gesomin and 0.15ng/L for MIB. To the best of our knowledge, this represents the best sensitivity achieved for analysis of gesomin and MIB in water via the simple and efficient SPME method. The current method has been successfully applied in the analyses of different water samples.

Trace analysis of acidic pharmaceutical residues in waters with isotope dilution gas chromatography-mass spectrometry via methylation derivatization.

Acidic pharmaceutical residues are pollutants of emerging concern and are generally monitored by HPLC-MS/MS. However, due to the limited separation efficiency of HPLC column and lack of suitable mass transition for confirmation analysis, some interference may not be separated completely and differentiated from ibuprofen, which may cause the results with interference, especially in sample with complex matrix. The objective of this study is to develop a sensitive and reliable method for the determination of acidic pharmaceutical residues in water samples by GC-MS with better resolution by using methylation derivatization and isotope dilution techniques. TMSDM, a mild reagent, was used as the derivatization reagent coupling with the isotope dilution technique, for the first time, to improve the precision and accuracy of the analytical method to determine the pharmaceutical residues in water. The MDLs for the five acidic organic compounds: ibuprofen, gemfibrozil, naproxen, ketoprofen and diclofenac were from 0.7 to 1.1 ng/L, with recoveries ranging from 93 to 110%. Alternative to the HPLC-MS/MS method, the developed GC-MS protocols provides an additional option for the analysis of acidic pharmaceutical residues in water, with better separation efficiency in reducing interferences from complicated sample matrix, for determination of ibuprofen residues.