Biosorption of Pb, Cd, Cu and Zn from the wastewater by treated Azolla filiculoides with H2O2/MgCl2

The adsorption of heavy metals onto treated Azolla filiculoides by H₂O₂/MgCl₂, as a cosmopolitan free-floating waterfern, was investigated from aqueous solutions in the batch biosorption experiments. The maximum uptake capacities of the collected Azolla from rice field at the optimal conditions for Pb, Cd, Cu and Zn ions were approximately 228, 86, 62 and 48 mg/g (dry Azolla), respectively. On the other hand, the maximum uptake capacities of the collected Azolla from the Anzali International Wetland in the north part of Iran at the same conditions for these heavy metals were about 124, 58, 33 and 34 mg/g (dry Azolla), respectively. Such decrease of uptakes is due to the pollution of Anzali International Wetland, which reduces the capacity uptake of metals. The recovery of biosorbed heavy metals from the rice field Azolla was carried out by HCl and NaCl desorbents that the recovery of 64–86% and 51–72% was occurred, respectively.     

Influences of the basin brines on extractable bitumen of Kupferschiefer from southwestern Poland

A study of the influences of the basin brines on hydrocarbon generation of the Kupferschiefer in southwestern Poland has been carried out.The samples from the Konrad and Polkowics mines were analyzed by orgainc geochemical,microscopic and FTIR methods.The results indicate that organic matter of Kupferschiefer tends to decrease with the ascending,oxidizing brines,In the Konrad profile,the Kupferschiefer was strongly oxidized.The extract yields were depleted up to 50mg Ext/g Corg.Gas chromatography(GC) and gas chromatography-mass spctrometry(GC/MS) data indicate that the depletion occureed predominantly in saturated hydrocarbon compounds.The identified n-alkanes in smpale KD1 were depleted at least to 5000μg/g Corg.The aromatic compounds show a fidderent trend of variation.The concentrations of phenanthrene alkylphenanthrenes(Ph-PAH) and naphthalene alkylnaphthalenes(Na-PAH) show a decrease,whereas sulfur polyaromatic hydrocarbons(S-PAH)and oxygen polyaromatic hydrocarbons(O-PAH) show an incrase under the influences of oxidizing brines,In the Polkowice profile,organic matter under the influences of oxidizing fluids shows a simlar trend of varation as in the Konrad mine.Analyses of polar compounds shed light on the oxidation processes at the molecule level.The dominant products of oxidation are aliphatic acid.alcohol and ester.FTIR results indicate that the oxidation of organic matter led to a decrease in aliphatic CH3 and an increase in C-O,C=O bands.     

Pollution characteristics of polycyclic aromatic hydrocarbons （PAHs） in oily sludge from the Zhongyuan Oilfield and its peripheral soils

The purpose of this study is to determine the degree of contamination caused by polycyclic aromatic hydrocarbons (PAHs) in oily sludge and soils around it in the Zhongyuan Oilfield. The contents of polycyclic aromatic hydrocarbons in oily sludge samples were determined with HPLC. The contents of PAHs of oily sludge from three different oil production plants vary from high to low in the order of the Wenming oily sludge dumping site of No. 3 Oil Production Plant (3W)>the Mazhai oily sludge dumping site of No. 3 Oil Production Plant (3M)>the Wen’er oily sludge dumping site of No. 4 Oil Production Plant (4W). Naphthalene, acenaphthylene, acenaphthene, fluorine and phenanthrene are the major pollutants of PAHs in oily sludge. The contents of PAHs in soil samples around the oily sludge dumping sites vary widely from 434.49 to 2408.8 ng/g. Naphthalene, acenaphthene, fluorine, phenanthrene and pyrene are the characteristic factors of PAHs in soil samples of 3M and 3W, and naphthalene, acenaphthene, fluorine and phenanthrene are the characteristic factors of PAHs in soil samples of 4W. According to these data and the ratios of Fl/Py, PAHs in oily sludge samples come mainly from petrogenic sources, and soil samples are divided into petrogenic soil samples and mixed-source soil samples, and both petrogenic and pyrogenic soil samples in terms of the sources of PAHs. The classification by Nemero index P indicates that soils around the oily sludge dumping sites have been seriously polluted.     

Organic geochemistry and petrography of Tertiary coals and carbonaceous shales from Argentina

A series of eight Tertiary coal and carbonaceous shale samples with vitrinite reflectance values between 0.50 and 0.58% were extracted, fractionated and the saturated and aromatic hydrocarbons analysed for characteristic components by GC and GC-MS. Additionally, a microscopical study was undertaken in order to obtain a more precise picture of the samples under investigation.The saturated hydrocarbon fractions displayed the typical n-alkane distribution for coals of this rank, with CPI values between 2.0 and 3.1. Among the branched/cyclic compounds, pristane and α, β-homohopane were recognised as relevant components pointing to an oxic depositional environment. Detection of benzohopanes (C₃₂–C₃₅) in the aromatic hydrocarbon fractions suggests that bacteriohopanetetrol was a significant constituent of the coal biomass. Taking into consideration the Pr/Ph ratios, ash contents and microscopical characteristics of the samples, aspects of the possible degradation of hopanetetrol to homohopane are discussed. Resin-derived diterpenoids with the phyllocladane and kaurane skeleton were tentatively identified and, although minor compounds, they are interpreted to be a sign of the contribution of Podocarpaceae and Araucareaceae to the coal swamp.Aromatic compounds were dominated by alkylnaphthalene derivatives, presumably formed by C-ring cleavage and aromatisation of higher plant-derived pentacyclic triterpenois, which were main components in the high-boiling range of the fractions investigated. Angiosperms (especially Fagaceae) are postulated as source for these polycyclic compounds and, hence, for some of the polyalkylated aromatic bicyclics detected.     

Accumulation and risk assessment of polycyclic aromatic hydrocarbons (PAHs) in soils around oil sludge in Zhongyuan oil field, China

In this paper, the contents of polycyclic aromatic hydrocarbons (PAHs) in soil samples around three different oily sludge plants in winter were analyzed by high performance liquid chromatography (HPLC) and the pollution degree with PAHs in soil samples was determined. Soil samples were collected from the agricultural soil around three different oily sludge plants (the Third Wenming Plant, the Third Mazhai Plant, and the Fourth Wener Plant) along with the leeway in Zhongyuan oil field. The distances from collected sample sites to oily sludge plants are 10, 20, 50, 100, 200, and 500 m, respectively. The results show that the contents of PAHs in soil samples decrease dramatically with the increase of the distance from the oily sludge, and that the PAHs with 2–4 rings are major pollutants in the oily sludge and soil samples. The main factors, which influenced the distribution of PAHs are discussed. Based on Nemero Index P, the classification evaluation shows that the soils around the oily sludge are heavily polluted in winter. The health risk assessment and ecological risk assessment of the soils around the oily sludge in Zhongyuan oil field in winter are analyzed.     

Dissipation of polycyclic aromatic hydrocarbons in crop soils amended with oily sludge

Oil fields present a potential ecological risk to nearby farmland soil. Here we present a new method designed to evaluate the ability of winter wheat (Triticum aestivum) to contribute to the dissipation of polycyclic aromatic hydrocarbons (PAHs), which are priority pollutants in soils contaminated by oily sludge. The influence of different doses of oily sludge on the dissipation of PAHs was studied along with individual PAH profiles in soils after different periods of plant growth. Five soil samples were artificially contaminated with different percentages of oily sludge (0 %, 5 %, 10 %, 15 % and 20 %). Winter wheat grew in the oily sludge–amended soils for 265 days. PAH content in the soils was monitored over the course of the study. The rate of PAH dissipation is related to the properties of different PAHs, period of winter wheat growth, and oily sludge application dose. Analysis for treated soils indicates that the dissipation of PAHs increased significantly over the first 212 days, followed by minimal changes over the final 53 days of treatment. In contrast, PAH dissipation slowed with increasing oily sludge application. For each PAH, the experimental results showed a significant compound-dependent trend. Winter wheat in the present study significantly enhanced the dissipation of PAHs in oily sludge–contaminated soil.     

Aquathermolysis of humic and fulvic acids: Simulation of organic matter maturation in hot thermal waters

Dissolved aromatic compounds in Hungarian thermal waters were first reported more than 10 years ago. Among the identified compounds were alkylbenzene, polyaromatic hydrocarbon and heteroaromatic homologue series. The appearance of dissolved organic compounds has been bound to a threshold temperature of ∼80 °C, and their distribution is controlled by the water temperature. Relative demethylation and aromatisation were observed with increasing temperature. The origin of these compounds is not proved. Among precursor candidates are humic substances.Simulation experiments were carried out on humic and fulvic acid and on their mixture to gain information on aromatic compounds formed. The samples were heated and products were measured with GC-MS.In the presence of oxygen, increasing concentration of benzene can be observed as a function of temperature. Toluene and thiophene can be identified, other alkylbenzenes are missing. Under reductive conditions the concentration of benzene, toluene and the ratio of short to long chained aromatics generally increases in every sample as a function of temperature. Main compounds are toluene and benzene. The amount of heteroaromatic compounds increases with temperature, but their relative concentration compared to aromatic hydrocarbons decreases. At higher temperatures the proportion of pyrroles drops and S and O containing ones become dominant.The different processes (formation, aromatisation, polycondensation, relative demethylation, decomposition) occur in parallel but their relative intensities vary as a function of temperature. The effects of duration and increasing temperature are similar but not equal: both demethylation and aromatisation can be observed.     

Influence of water quality change in Fu River on Wetland Baiyangdian

Fu River is the only river that has perennial flow into Wetland Baiyangdian and is mainly composed of living sewage and industrial wastewater from Baoding city. Pollutant concentrations were monitored at three sections in the upstream, midstream, and downstream of Fu River and water quality in Wetland Baiyangdian was monitored at seven monitoring sites from 2001 to 2005. Results show that pollutant concentrations in Fu River and pollution load entering Wetland Baiyangdian generally increased during 2001–2005. On average, the concentrations of COD_Mn and BOD₅ increased by 46.5% and 50% from 2001 to 2005 in Fu River and COD_Mn increased by 17% in Wetland Baiyangdian. The total amount of COD_Mn and BOD₅ entering Wetland Baiyangdian increased from 1630 and 997 t/a to 2243 and 1583 t/a from 2001 to 2005, respectively. Total amount of water within the wetland and non-point source pollution input from surrounding areas also influenced the water quality in the wetland.     

Uptake, accumulation and translocation of polycyclic aromatic hydrocarbons by winter wheat cultured on oily sludge-amended soil

The purpose of this study is to comparatively investigate the plant uptake, accumulation and translocation behaviors of polycyclic aromatic hydrocarbons (PAHs) as priority pollutants in soil contaminated with oily sludge. The influence of different oily sludge application doses on the uptake of contaminants was studied together with the profile of individual PAH in roots, straws and leaves of winter wheat. Pot experiments were conducted using oily sludge application doses of 0, 5, 10, 15 and 20 percent, respectively. The total PAHs contents of control soil and oily sludge were 16.96 and 3504.66 μg/g, respectively. Analysis for the contents of the 16 PAHs was carried out with a HPLC-UV using plant tissue samples obtained at the 265th day of growth. The total PAHs contents in treated winter wheat were 9.02-334.81 ng/g for roots, 8.45-336.52 ng/g for straws and 10.70-406.32 ng/g for leaves. In addition to 5% of oily sludge dose, the total PAHs content in leaves was always highest under other doses of oily sludge application. With respect to individual PAH, the content did not show a significant plant tissue related trend. However, both the total content and individual content of PAHs in treated winter wheat tissues did increase with increasing oily sludge application dose. Another analysis for the control soil indicates that the degradation rate of PAHs was significantly enhanced by winter wheat after 265 days of growth based on the residual concentrations of PAHs in planted and unplanted soils.     

Méthodologie de l'extraction des hydrocarbures aromatiques polycycliques. Application à des sédiments de la lagune de Bizerte (Tunisie)Methodology of extraction of polycyclic aromatic hydrocarbons. Application to sediment from the Bizerte Lagoon (Tunisia)

The marine environment is very complex, with several important chemical, biological, and sedimentological interactions. Sediments constitute a reservoir for numerous pollutants, including polycyclic aromatic hydrocarbons (PAHs). PAHs are known by their mutagenic and/or carcinogenic effect. This study evaluates contamination levels in Bizerte Lagoon with respect to PAHs. The extraction efficiency of PAHs from sediment has been evaluated using Soxhlet or ultrasonic procedures, based on the recovery of an internal standard (9,10-dihydroanthracene). Several PAHs were found, including sixteen that are reported in the priority list of pollutants of the US Environmental Protection Agency (EPA). PAHs analysis was carried out by GC–FID and GC–MS for 16 samples sampled in two seasons: summer and winter. Results permit an assessment of PAHs pollution in the Bizerte Lagoon. To cite this article: N. Mzoughi et al., C. R. Geoscience 334 (2002) 893–901.     

Novel aryl polycyclic aromatic hydrocarbons: Phenylphenanthrene and phenylanthracene identification, occurrence and distribution in sedimentary rocks

Numerous reports have recognised the presence of compounds with molecular weight 254 a.m.u. in aromatic fractions. However, their unequivocal identification has not been achieved due to a lack of reference substances. In geological samples, such m/z 254 compounds could potentially be represented by a number of structural isomers of binaphthyl, phenylphenanthrene, phenylanthracene and indenofluorene with each compound type possessing several positional isomers. In this work, all these m/z 254 compounds, with the exception of the tentatively recognised indenofluorenes, have been unequivocally identified in sedimentary rocks for the first time. Comparison of the mass spectra and the gas chromatography (GC) retention times of synthesised standards with the natural compounds in rocks shows that the major components of aromatic fractions are phenylphenanthrene isomers and, to a lesser extent, binaphthyls and 9-phenylanthracene. The elution sequence expressed as standard retention indices of all these m/z 254 isomers were determined by using high resolution capillary GC with three stationary phases: 5%, 35% and 50% (mole fraction) phenyl substituted methylpolysiloxane on HP-5MS, DB-35MS and DB-17MS columns, respectively. A survey of more than 350 sedimentary rock samples of varying origins and maturity (R_r 0.3–1.4%) reveals that relative abundances of the m/z 254 isomers depend on the maturity of the organic matter. The isomers initially appear at the onset of oil generation (R_r > 0.5%) exclusively in diagenetically/catagenetically oxidised samples containing varying proportions of Types II and III kerogen. Interestingly, all five possible positional phenylphenanthrene isomers (including the most sterically hindered isomer 4-phenylphenanthrene) are present from the beginning of the oil generation window. Such a distribution suggests that low-regioselectivity reactions are likely to be involved in the formation. Interaction, during maturation, of phenyl radicals from primary cracking with aromatic moieties of more resistant terrigenic components of kerogen in an oxidising diagenetic realm is postulated to be responsible for the neoformation of phenylated aromatics in geological samples. Up to the final stages of oil generation, the evolution of the phenyl PAH distributions presumably involve 1,2-phenyl shift reactions and cyclisation, if allowed by the molecular geometry. A near thermodynamically-controlled distribution, with only 3- and 2-phenylphenanthrene and minor 2,2′-binaphthyl remaining, is approached when vitrinite reflectance reaches 1.2% (R_r). The three compounds seem to be persistent beyond the oil window as is suggested by their presence in hydrothermal oil formed at T > 300 °C.     

Evidence for in situ methanogenic oil degradation in the Dagang oil field

In situ biotransformation of oil to methane was investigated in a reservoir in Dagang, China using chemical fingerprinting, isotopic analyzes and molecular and biological methods. The reservoir is highly methanogenic despite chemical indications of advanced oil degradation, such as depletion of n-alkanes, alkylbenzenes and light polycyclic aromatic hydrocarbon (PAH) fractions or changes in the distribution of several alkylated polycyclic aromatic hydrocarbons. The degree of degradation strongly varied between different parts of the reservoir, ranging from severely degraded to nearly undegraded oil compositions. Geochemical data from oil, water and gas samples taken from the reservoir are consistent with in situ biogenic methane production linked to aliphatic and aromatic hydrocarbon degradation. Microcosms were inoculated with production and injection waters in order to characterize these processes in vitro. Subsequent degradation experiments revealed that autochthonous microbiota are capable of producing methane from ¹³C labelled n-hexadecane or 2-methylnaphthalene and suggest that further methanogenesis may occur from the aromatic and polyaromatic fractions of Dagang reservoir fluids. The microbial communities from produced oil–water samples were composed of high numbers of microorganisms (on the order to 10⁷), including methane producing Archaea within the same order of magnitude. In summary, the investigated sections of the Dagang reservoir may have significant potential for testing the viability of in situ conversion of oil to methane as an enhanced recovery method and biodegradation of the aromatic fractions of the oil may be an important methane source.     

Treatment of oily sludge by advanced oxidation process

For treating oily sludge, wet peroxide oxidation (WPO) and catalytic wet oxidation (CWO) were investigated. The CWO experiment was carried out in a 0.5?L batch reactor using FeCl₃ as catalyst. By using WPO, the effects of reaction parameters such as residence time, temperature, H₂O₂ excess, and initial COD were investigated. The results demonstrated that >80?% chemical oxygen demand (COD) was removed by CWO and >90?% COD was removed by WPO. Significantly, more of COD could be removed from the oily sludge by adding H₂O₂ in small doses. In conclusion, WPO was much more effective in the removal of organic compounds from oily sludge.     

CHARACTERISTICS OF AROMATIC HYDROCARBONS IN CRUDE OILS

Crude oils from different basins in China ,Australia and New Zealand were analyzed to character-ize aromatic hydrocarbons produced in different environments by means of GC/MS .The distributions of some common compounds such as naphthalene, phenanthrene, chrysene,pyrene, fluoranthene, fluorine,dibenzothiophene and dibenzofuran were found to be related to sedimentary environments.Especially the relative contents of fluorenes ,dibenzofurans and dibenzothiophenes can be used to di-vide the oils into three types(1) saline or marine carbonate environment;(2) fresh-brackish water lake;(3) swamp and coal-bearing sequence.A romatic biomarkers (e.g.retene, nor-abietene,derivatives of lupeol and β-amyrin)represent higher plant inpults with respect to the precursors of crude oils. High contents of sulphur-containing compounds like benzothiophene and dibenzothiophene series indicate a reducing sulphur-abundant diagenetic condition .The benzohopane series (C32-C35) was identified both in hypersaline and coal-bearing basins, and it is postulated to be the result of strong bacteria activity.In all the sam-ples, a complete series of alkyl benzenes was analyzed .The similarity of its carbon-number distrbu-tion with that of n-alkanes probably suggests their genetic relationship. The distribution of the methylphenanthrene series reflects the evolution degree of crude oils,MPI holding a positive correlation with C29-sterane 20S/(20S 20R).     

Volatile organic compounds in open ocean and coastal surface waters

Volatile organic compounds with volatilities ranging between those of n-hexane and n-pentadecane were identified in open ocean and coastal marine surface water samples taken in the north central part of the Gulf of Mexico. Approximately 40 organic compounds were found. The types and concentrations of the compounds found depended upon the extent of anthropogenic and terrestrial influences. Open ocean samples consisted mostly of aromatic hydrocarbons, whereas coastal samples included alkanes, cycloalkanes, cycloalkenes, aromatic hydrocarbons, aldehydes and chlorinated hydrocarbons. Unpolluted open ocean and coastal water samples had individual concentrations rarely exceeding 5 ng/kg; some aromatic hydrocarbons approached 15 ng/kg. n-Pentadecane dominated the hydrocarbons in these samples (50–100 ng/kg). The most polluted coastal water samples had individual volatile organic concentrations as great as 150 ng/kg with total concentrations approaching 1000 ng/kg. The terpene, limonene, was found extensively in the coastal samples (up to 40 ng/kg). Photooxidization of hydrocarbons in industrial/urban atmospheres was considered as a possible source of aldehydes present in coastal water. The dynamic headspace stripping/Tenax-GC adsorption method coupled with packed column gas chromatography, and gas chromatography-mass spectrometry were used for volatile organic analysis.     

Pollution of organic compounds and heavy metals in a coal gangue dump of the Gequan Coal Mine, China

Samples around a coal gangue dump of the Gequan Coal Mine were collected in April 2009. GC (gas chromatography) and GC/MS (gas chromatography/mass spectrometry) were employed to analyze the composition of organic matter in the samples. ICP-MS (inductively coupled plasma mass spectrometry) was used to determine the concentrations of heavy metals. The contents of organic extracts are within the range of 140-750 mg/kg. Alkand aro-ratios are relatively high. Compared to those of the background sample (GQ13 ), the contents of saturated hydrocarbon compounds in all the samples are relatively high. The contents of polycyclic aromatic hydrocarbons (PAHs) are relatively high with the distance getting closer to the coal gangue dump. These indicate that organic matter in the samples is from coal particles of the coal gangue dump. The distributions of heavy metals are very similar: the contents decrease with distance from the dump, which indicates that the harmful heavy metals from the coal gangue dump have polluted as thick as at least 500 m.     

Characterization of aromatic steroids and hopanoids in marine and lacustrine crude oils using comprehensive two dimensional gas chromatography coupled to time-of-flight mass spectrometry (GCxGC-TOFMS)

The distribution of the aromatic steroids and hopanoids in six crude oils was determined using comprehensive two dimensional gas chromatography time-of-flight mass spectrometry (GCxGC-TOFMS) in order to improve their identification and application in geochemical studies. Co-elution between monoaromatic and triaromatic steroids and benzohopanes and their methylated homologues, which are commonly observed in ¹D conventional GC, were resolved, with GCxGC facilitating recognition of the compounds. One important feature was that, despite the oils showing mid-oil window maturity characteristics, the distribution of long chain aromatic steroids decreased in lacustrine samples vs. marine samples. This difference in the distribution of long chain and short chain aromatic steroids may reflect the different origins of these oils although this aspect needs further evaluation.     

Polar non-hydrocarbon contaminants in reservoir core extracts

A geochemical investigation of oils in sandstone core plugs and drill stem test oils was carried out on samples from a North Sea reservoir. A sample of diesel used as a constituent of the drilling fluids was also analysed. The aliphatic and aromatic hydrocarbons and polar non-hydrocarbons were isolated using solid phase extraction methods. GC analysis of the hydrocarbon fraction of the core extract indicated that contamination may be diesel derived. From analysis of diesel some compound classes are less likely to be affected by contamination from diesel itself including: steranes, hopanes, aromatic steroid hydrocarbons, benzocarbazoles and C₀–C₃-alkylphenols.     

Photocatalytic activity evaluation of TiO<Subscript>2</Subscript> nanoparticles based on COD analyses for water treatment applications: a standardization attempt

Evaluation of the photocatalytic activities of TiO₂ nanomaterials based on the chemical oxygen demand (COD) analyses under identical experimental conditions was not previously reported. In this work, COD has been selected as an adequate industrial water quality measure toward the establishment of a representative standard test method. The initial COD values of six organic pollutants representing dye, surfactants, phenols and alcohol were set at 30 ± 2 mg/L. Ten of different commercial and synthesized TiO₂ samples representing anatase, rutile and mixed phases were used and characterized. The data of photocatalytic processes were compared to that obtained using the commonly widespread Degussa-P25 TiO₂ (TD). The COD of all pollutants was completely removed by TD at UV exposure dose ≤9.36 mWh/cm². Consequently, the maximum irradiation dose was set at this value in all experiments. The percentages of COD removal as well as the values of the accumulated UV doses required for complete removal of pollutants were measured using the different TiO₂ samples. TiO₂ samples show different performance abilities toward the various pollutants compared to TD. Based on the obtained data, TiO₂ photocatalysts were divided into two categories according to the hydroxyl radical formation rates. Comparison with previous studies reveals that the photocatalytic efficiency evaluation depends on the method of measurement. COD is recommended to be used as an adequate technique of analysis that meets the purpose of water treatment applications.     

Off-line solid-phase extraction procedure for the determination of polycyclic aromatic hydrocarbons from aqueous matrices

An off-line solid-phase extraction procedure followed by high-performance liquid chromatography with ultraviolet detection for the determination of 16 priority polycyclic aromatic hydrocarbon pollutants in aqueous matrices was described. Diverse aspects determining extraction efficiency such as packing type (disk or cartridge), elution solvents and addition of organic modifiers to the sample were evaluated. Elution with acetonitrile yields the highest recoveries. Rinsing the sample bottle with acetonitrile and combining the rinse with the sample extract avoids the adsorption of polycyclic aromatic hydrocarbons on the walls of the water containers. The use of isopropanol or methanol 10 % (V/V) was the most appropriate amount for the enrichment of 2- to 6-ring aromatic compounds only on C18 cartridge. The recoveries for all studied polycyclic aromatic hydrocarbons are ranged from 71.4 to 95.2 % for a treated water samples of 500 mL. The proposed method gives very low detection limits (subnanograms per liter) and it has been applied to drinking water, surface water and industrial effluent (oil refinery) samples with good results.