Chemometric tools applied to optimize a fast solid-phase microextraction method for analysis of polycyclic aromatic hydrocarbons in produced water

Environmental Science and Pollution Research - Chemometric tools are powerful strategies to efficiently optimize many processes. These tools were employed to optimize a fast-solid phase...     

Photolysis of polycyclic aromatic hydrocarbons in water

We have studied the photochemical reactions of eight polycyclic aromatics and heteroatom analogs (PAHs). Quantum yields and rate constants in sunlight and at single wavelengths were measured and half-lives of the PAHs as a function of the time of year were calculated. Product studies and the effect of humic acid and oxygen on rates are reported.     

固相萃取-气相色谱/质谱法测定水中多环芳烃

建立了固相萃取-气相色谱／质谱联用测定水中多环芳烃(PAHs)的分析方法．优化了固相萃取条件。结果表明,固相萃取效率高、萃取时间短,采用MS的选择离子检测方式对实际水样中PAHs进行定性定量分析,平均回收率在80．4％～115％之间,相对标准偏差为7．03％～18．5％,方法的检出限在0．010～0．020μg／L之间。通过实际样品中PAHs的分析表明,该法快速,溶剂用量少,能满足痕量分析的要求。     

Determination of polycyclic aromatic hydrocarbons in roasted coffee

Polycyclic aromatic hydrocarbons (PAHs) are suspected to be carcinogenic and mutagenic. This study describes the presence of PAHs in light, medium and dark roasted coffee including instant and decaffeinated brands. Total PAHs concentration was related to the degree of roasting with light roasted coffee showing the least and dark roasted coffee showing the highest level. Both instant and decaffeinated coffee brand showed lower levels of PAHs. Naphthalene, acenaphthylene, pyrene and chrysene were the most abundant individual isomers. The concentrations ranged from 0 to 561 ng g^?1 for naphthalene, 0 to 512 ng g^?1 for acenaphthylene, 60 to 459 ng g^?1 for pyrene and 56 to 371 ng g^?1 for chrysene. Thus, roasting conditions should be controlled to avoid the formation of PAHs due to their suspected carcinogenic and mutagenic properties.     

Determination of polycyclic aromatic hydrocarbons in dry tea

Twenty-eight different tea samples sold in the United States were evaluated using high-performance liquid chromatography (HPLC) with fluorescence detection (FLD) for their contamination with polycyclic aromatic hydrocarbons (PAHs). Many PAHs exhibit carcinogenic, mutagenic, and teratogenic properties and have been related to several kinds of cancer in man and experimental animals. The presence of PAHs in environmental samples such as water, sediments, and particulate air has been extensively studied, but food samples have received little attention. Eighteen PAHs congeners were analyzed, with percentage recovery higher than 85%. Contamination expressed as the sum of the 18 analyzed PAHs was between 101 and 1337 μg/kg on dry mass and the average contents in all of the 28 examined samples was 300 μg/kg on dry mass. Seven of the congeners were found in all samples with wide ranges of concentrations as follows: fluorene (7–48 μg/kg), anthracene (1–31 μg/kg), pyrene (1–970 μg/kg), benzo(a)anthracene (1–18 μg/kg) chrysene (17–365 μg/kg), benzo(a)pyrene (1–29 μg/kg), and indeno(1,2,3-cd)pyrene (4–119 μg/kg). The two most toxic congeners benzo(a)pyrene and dibenzo(a,h)anthracene were found at high concentrations only in Earl Grey Twinnings, Earl Grey Harney& Sons Fine Teas, and Chai Ultra Spice Black Tea Twinnings. Six PAH congeners are considered as suspected carcinogens (U.S.EPA), formed the basis of the estimation of the toxic equivalent (TEQ), Chai Ultra-Spice Black Tea Twinnings had the highest TEQ (110.9) followed by two grey tea samples, Earl Grey Harney & Sons Fine Tea (57.7) and Earl Grey Twinnings (54.5). Decaffeinated grey teas had the lowest TEQs, decaffeinated Earl Grey Bigelow (9.4) and Green Tea Honey Lemon Decaffeinated Lipton (9.6).     

固相萃取与气相色谱-质谱联用测定水中痕量多环芳烃

采用固相萃取与气相色谱-质谱联用测定水中痕量多环芳烃(PAHs)。通过正交试验,得到最佳固相萃取条件为:上样流速为5mL/min、采用二氯甲烷洗脱、洗脱剂用量为3mL、洗脱流速为2mL/min。测定结果显示,固相萃取与气相色谱—质谱联用技术对萘、菲、荧蒽3种PAHs的检出限为0.03～0.07μg/L,加标回收率为70%～100%,相对标准偏差为3.90%～9.58%。该方法精密度高、准确度好,能满足实际水样中痕量PAHs的测定要求。     

Biodegradation of polycyclic aromatic hydrocarbons by a mixed culture

We investigated the potential biodegradation of polycyclic aromatic hydrocarbons (PAHs) by an aerobic mixed culture utilizing phenanthrene as its carbon source. Following a 3-5 h post-treatment lag phase, complete degradation of 5 mg/l phenanthrene occurred within 28 h (optimal conditions determined as 30 degrees C and pH 7.0). Phenanthrene degradation was enhanced by the individual addition of yeast extract, acetate, glucose or pyruvate. Results show that the higher the phenanthrene concentration, the slower the degradation rate. While the mixed culture was also capable of efficiently degrading pyrene and acenaphthene, it failed to degrade anthracene and fluorene. In samples containing a mixture of the five PAHs, treatment with the aerobic culture increased degradation rates for fluorene and anthracene and decreased degradation rates for acenaphthene, phenanthrene and pyrene. Finally, it was observed that when nonionic surfactants were present at levels above critical micelle concentrations (CMCs), phenanthrene degradation was completely inhibited by the addition of Brij 30 and Brij 35, and delayed by the addition of Triton X100 and Triton N101.     

Temperature dependence of the infinite dilution activity coefficient and Henry's law constant of polycyclic aromatic hydrocarbons in water

The water solubility of 9,10-dihydroanthracene was experimentally determined between 278.12 and 313.17 K. Determinations were carried out by an experimental procedure developed in our laboratory, which is a modification of the dynamic coupled column liquid chromatographic technique. The uncertainty of the experimental determinations ranged from +/- 0.50% to +/- 3.10%. These data, as well as the water solubility data of other five polycyclic aromatic hydrocarbons (PAHs) previously studied, were used to calculate the temperature dependence of the infinite dilution activity coefficient of 9,10-dihydroanthracene, anthracene, pyrene, 9,10-dihydrophenanthrene, m-terphenyl, and guaiazulene in water. Molar excess enthalpies and entropies at infinite dilution, at 298.15 K, were also derived. The temperature dependence of the infinite dilution activity coefficients was used, together with literature values of the vapor pressures of supercooled liquid PAHs (p(B)(sc)), to estimate their Henry's law constants (HLC). Only HLC for anthracene, pyrene, and 9,10-dihydrophenanthrene were calculated, since no p(B)(sc) data were available in the literature for 9,10-dihydroanthracene, m-terphenyl, and guaiazulene. From the observed temperature dependence of the Henry's law constants the enthalpy and entropy of the phase change from the dissolved phase to the gas phase were also derived for anthracene, pyrene, and 9,10-dihydrophenanthrene.     

Desorption of polycyclic aromatic hydrocarbons from carbon nanomaterials in water

Desorption behavior of pyrene, phenanthrene and naphthalene from fullerene, single-walled carbon nanotubes (SWCNTs) and multi-walled carbon nanotubes (MWCNTs) was examined. Available adsorption space of carbon nanotubes (CNTs) was found to be the cylindrical external surface, neither the inner cavities nor inter-wall spaces due to impurities in the CNTs and restricted spaces (0.335nm) of the MWCNTs, respectively. Desorption hysteresis was observed for fullerene but not for CNTs. Deformation-rearrangement was proposed to explain the hysteresis of polycyclic aromatic hydrocarbons (PAHs) for fullerene, due to the formation of closed interstitial spaces in spherical fullerene aggregates. However, long, cylindrical carbon nanotubes could not form such closed interstitial spaces in their aggregates due to their length, thus showing no significant hysteresis. High adsorption capacity and reversible adsorption of PAHs on CNTs imply the potential release of PAHs if PAH-adsorbed CNTs are inhaled by animals and humans, leading to a high environmental and public health risk.     

含油污泥及其污染水体中多环芳烃及其急性生物毒性测定

为了更好地控制含油污泥的环境污染,通过实验分析了五种不同来源的含油污泥中多环芳烃（PAHs）的含量、来源以及总毒性当量浓度（TEQ）,测定了不同有机溶剂浸提液的急性生物毒性,并对油泥污染水样的PAHs和急性生物毒性进行了分析。研究发现,不同含油污泥中PAHs含量为496.10~4 233.25 μg·g-1,PAHs总毒性当量（TEQ）为8.41~231.56 μg·g-1,炼化厂含油污泥中的PAHs主要来源于石油及其精炼产品的热转化,其他含油污泥中的PAHs主要来源于原油本身。正己烷是3种受试有机溶剂中最适合测量含油污泥急性生物毒性的溶剂。被污染水样中PAHs含量为9.68~385.16 ng·mL-1,除被清罐油泥污染的水样外,其他油泥污染水样中苯并（a）芘（BaP）未超标,但所有测试水样都具有较高的急性生物毒性,相对发光抑制率最高达到87.46%,大大超过了毒性参照物100 mg·L-1的Zn2+的抑制率。     

Formation of polycyclic aromatic hydrocarbons by ionizing radiations

Gaseous o-terphenyl, 1-phenylnaphthalene, and 9-phenylanthracene were submitted to gamma rays. The yields of cyclization products, polycyclic aromatic hydrocarbons, show that at least one twentieth of the intermediates formed undergo intramolecular reaction.     

Uptake of polycyclic aromatic hydrocarbons by maize plants

Roots and above-ground parts (tops) of maize plants, comprising cuticles, leaves and stems, have been exposed separately to polycyclic aromatic hydrocarbons (PAHs) by means of air-tight bicameral exposure devices. Maize roots and tops of plants directly accumulate PAHs from aqueous solutions and from air in proportion to exposure levels. Root and leaf concentration factors (log RCF and log LCF) are log-linear functions of log-based octanol-water partition coefficient (log Kow) and log-based octanol-air partition coefficient (log Koa). The PAHs' concentrations among cuticles, leaves and stems display good correlations with each other. PAH concentrations in each part of the plant tested correlated positively with atmospheric PAHs' concentrations. Comparisons between PAHs' concentrations of root epidermis and root tissue showed similar correlations. Bulk concentrations of contaminants in various plant tissues differed greatly, but these differences disappeared after normalization to lipid contents suggesting lipid-based partitioning of PAHs among maize tissues.     

GC/MS法测定润滑油基础油中多环芳烃

对润滑油基础油中多环芳烃的气相色谱/质谱(GC/MS)测定方法进行了研究,探讨了样品的提取,固相萃取柱净化等前处理方法,同时也对仪器测定条件进行了优化.结果表明,在检测润滑油基础油中多环芳烃时,经优化的GC/MS法的加标回收率和精密度均达到较满意的水平.     

Characterizing the interactions between polycyclic aromatic hydrocarbons and fulvic acids in water

Polycyclic aromatic hydrocarbons (PAHs) are persistent, bioaccumulative, and toxic chemicals and are listed as priority pollutants by the US EPA. Although they are sparsely soluble in water, their solubility can be increased by binding to dissolved organic matter in natural waters, which will further increase their environmental risk as toxic pollutants. In this study, the interaction between PAHs, exemplified by fluorene and anthracene, and fulvic acid (FA) was studied using fluorescence quenching titration method with fluorescence emission spectra, respectively. The association of FA with the mixture of fluorene and anthracene was also evaluated by excitation–emission matrix (EEM) fluorescence spectrometry combined with parallel factor (PARAFAC) analysis. Results demonstrate that EEM fluorescence spectrometry with PARAFAC analysis was sensitive and reliable to determine the binding properties of PAHs with FA in a mixed aqueous solution. The conditional stability constants and binding capacities show that both PAHs bind to FA tightly.     

Oxidation of polycyclic aromatic hydrocarbons by horseradish peroxidase in water containing an organic cosolvent

Polycyclic aromatic hydrocarbons (PAHs) are environmental contaminants that are toxic, mutagenic, and carcinogenic. We investigated the horseradish peroxidase (HRP)-catalyzed oxidation of PAHs in water containing N,N-dimethylformamide. Four PAHs (anthracene, phenanthrene, pyrene, and fluoranthene) were investigated using single-PAH and mixed-PAH systems. The results provide useful information regarding the preferential oxidation of anthracene over other PAHs regardless of the reaction time, enzyme dosage, and hydrogen peroxide concentration. The removal of PAHs was found to be very strongly correlated with the ionization potential (IP), and much greater PAH oxidation was observed at a lower IP. The oxidation of anthracene was specifically pH- and temperature-dependent, with the optimal pH and temperature being 8.0 and 40 °C, respectively. The redox mediators 1-hydroxybenzotriazole and veratryl alcohol promoted the transformation of anthracene by HRP; 9,10-anthraquinone was the main product detected from the anthracene oxidation system. The results of this study not only provide a better understanding of the oxidation of PAHs by utilizing a plant biocatalyst, but also provide a theoretical basis for establishing the HRP-catalyzed treatment of PAH-contaminated wastewater.     

Reductive hydrogenation of polycyclic aromatic hydrocarbons catalyzed by metalloporphyrins

The hydrogenation of polycyclic aromatic hydrocarbons (PAHs) (naphthalene, anthracene, and phenanthrene) catalyzed by metalloporphyrins based on cobalt, nickel or iron was studied in aqueous solutions at room temperature and ambient pressure. Nickel porphyrin (P1) activated by nanosized zero-valent iron (nano-ZVI) and cobalt porphyrins (P2) and (P4) activated by titanium(III) citrate as the electron donor were demonstrated to be promising catalysts for the reductive hydrogenation of PAHs. In particular, partially saturated di-, tetra-, and octahydrogenated products were obtained for anthracene or phenanthrene using a nickel porphyrin activated by nano-ZVI, while naphthalene was transformed to tetralin. Systems containing cobalt porphyrins activated by titanium(III) citrate exhibited a high selectivity and activity toward hydrogenation of anthracene, producing 9,10-dihydroanthracene. However, no formation of hydrogenated hydrocarbons was observed from naphthalene or phenanthrene using cobalt porphyrins.     

Different behaviours in the solubilization of polycyclic aromatic hydrocarbons in water induced by mixed surfactant solutions

Water solubility of polycyclic aromatic hydrocarbons (PAHs), viz, naphthalene and phenanthrene, in micellar solutions at 25 °C was investigated, using two series of different binary mixtures of anionic and nonionic surfactants. Tween 80 and Brij-35 were used as nonionic surfactants whereas fatty acids or amphiphilic cyclodextrins (Mod-β-CD) synthesized in our laboratory were used as anionic ones. Solubilization capacity has been quantified in terms of the molar solubilization ratio and the micelle-water partition coefficient, using UV-visible spectrophotometry. Anionic surfactants exhibited less solubilization capacity than nonionics. The mixtures between Tween 80 and Mod-β-CD did not show synergism to increase the solubilization of PAHs. On the other hand, the mixtures formed by Tween 80 and fatty acids at all mole fractions studied produced higher enhancements of the solubility of naphthalene than the individual surfactants. The critical micellar concentration of the mixtures of Tween 80/sodium laurate was determined by surface tension measurements and spectrofluorimetry using pyrene as probe. The system is characterized by a negative interaction parameter (β) indicating attractive interactions between both surfactants in the range of the compositions studied.     

Lability of polycyclic aromatic hydrocarbons in the rhizosphere

Remediation of soils containing high concentrations of polycyclic aromatic hydrocarbons (PAHs) seldom results in complete removal of contaminants, but residual toxicity often is reduced. In this study, soil from a former manufactured gas plant site was treated for 12 months by phytoremediation and then tested for total PAHs, Tenax-TA extractable ("labile") PAHs, aqueous soluble PAHs (PAH(wp)) , and biotoxicity assessed by earthworms survival, nematode mortality, emergence of lettuce seedlings, and microbial respiration. Prior to phytoremediation, the soil had toxic impacts on all bioassays (except the nematodes), and 12 months of remediation decreased this response. Change in labile PAHs was a predictor for change in total PAH for 3- and 4-ring compounds but not for the 5- and 6-ring. Decreases in labile PAHs were correlated (r(2)>or=0.80) with toxicity in the bioassays except microbial respiration. PAH(wp) was correlated only with nematode toxicity prior to remediation but with none of the tests after remediation. Total PAHs were not correlated with any of the bioassay tests. Tenax-TA appears to have potential for predicting residual toxicity in remediated soils and is superior to total concentrations for that application.     

Solubilization properties of polycyclic aromatic hydrocarbons by saponin, a plant-derived biosurfactant

The enhanced solubilization of polycyclic aromatic hydrocarbons (PAHs) by saponin, a plant-derived non-ionic biosurfactant, was investigated. The results indicated that the solubilization capabilities of saponin for PAHs were greater than some representative synthetic non-ionic surfactants and showed strong dependence on solution pH and ionic strength. The molar solubilization ratio (MSR) of saponin for phenanthrene was about 3-6 times of those of the synthetic non-ionic surfactants, and decreased by about 70% with the increase of solution pH from 4.0 to 8.0, but increased by approximately 1 times with NaCl concentration increased from 0.01 to 1.0 M. Heavy metal ions can enhance saponin solubilization for phenanthrene and the corresponding MSR values increased by about 25% with the presence of 0.01 M of Cd²⁺ or Zn²⁺. Saponin is more effective in enhancing PAHs solubilization than synthetic non-ionic surfactants and has potential application in removing organic pollutants from contaminated soils.