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Showing papers in "Environmental Chemistry Letters in 2007"


Journal ArticleDOI
TL;DR: Emphasis will be placed on the use of bioaccumulation and biomarker responses in air, soil, water and food, as monitoring tools for the assessment of the risks and hazards of PAH concentrations for the ecosystem, as well as on its limitations.
Abstract: Polycyclic aromatic hydrocarbons (PAHs) are a large group of organic compounds with two or more fused aromatic rings. They have a relatively low solubility in water, but are highly lipophilic. Most of the PAHs with low vapour pressure in the air are adsorbed on particles. When dissolved in water or adsorbed on particulate matter, PAHs can undergo photodecomposition when exposed to ultraviolet light from solar radiation. In the atmosphere, PAHs can react with pollutants such as ozone, nitrogen oxides and sulfur dioxide, yielding diones, nitro- and dinitro-PAHs, and sulfonic acids, respectively. PAHs may also be degraded by some microorganisms in the soil. PAHs are widespread environmental contaminants resulting from incomplete combustion of organic materials. The occurrence is largely a result of anthropogenic emissions such as fossil fuel-burning, motor vehicle, waste incinerator, oil refining, coke and asphalt production, and aluminum production, etc. PAHs have received increased attention in recent years in air pollution studies because some of these compounds are highly carcinogenic or mutagenic. Eight PAHs (Car-PAHs) typically considered as possible carcinogens are: benzo(a)anthracene, chrysene, benzo(b)fluoranthene, benzo(k)fluoranthene, benzo(a)pyrene (B(a)P), dibenzo(a,h)anthracene, indeno(1,2,3-cd)pyrene and benzo(g,h,i)perylene. In particular, benzo(a)pyrene has been identified as being highly carcinogenic. The US Environmental Protection Agency (EPA) has promulgated 16 unsubstituted PAHs (EPA-PAH) as priority pollutants. Thus, exposure assessments of PAHs in the developing world are important. The scope of this review will be to give an overview of PAH concentrations in various environmental samples and to discuss the advantages and limitations of applying these parameters in the assessment of environmental risks in ecosystems and human health. As it well known, there is an increasing trend to use the behavior of pollutants (i.e. bioaccumulation) as well as pollution-induced biological and biochemical effects on human organisms to evaluate or predict the impact of chemicals on ecosystems. Emphasis in this review will, therefore, be placed on the use of bioaccumulation and biomarker responses in air, soil, water and food, as monitoring tools for the assessment of the risks and hazards of PAH concentrations for the ecosystem, as well as on its limitations.

798 citations


Journal ArticleDOI
TL;DR: In this article, a non-toxic, biodegradable, and recyclable liquid manufactured from renewable sources, has a high potential to serve as alternative green solvent for organic reactions.
Abstract: Organic synthesis is usually performed in solution to dissolve both reactants and catalysts and to deliver heat. Here, we show that glycerol, which is a non-toxic, biodegradable, and recyclable liquid manufactured from renewable sources, has a high potential to serve as alternative green solvent for organic reactions. Several catalytic and non-catalytic reactions were successfully performed in glycerol. High products yields and selectivities were achieved. Besides solubility of the reactants and the catalysts and easy separation of the product, glycerol offers several other benefits such as catalyst recycling, microwave assisting reaction, and biphasic and emulsion modes.

209 citations


Journal ArticleDOI
TL;DR: In this paper, the first time that carbonate was quantified in soil samples by FT-IR spectroscopy was performed with the results obtained from the spectral bands at 875 and 2506 cm−1.
Abstract: Measurements of calcium carbonate contents in soils were performed with FT-IR (Fourier transform infrared) spectroscopy and with the gas volumetric Scheibler method. To the authors’ knowledge it is the first time that carbonate was quantified in soil samples by FT-IR spectroscopy. The carbonate contents of the test soils ranged from 11.3 to 13.1%. Both methods gave similar results, however, results obtained from FT-IR spectra depend on the spectral band used for the carbonate determination. In our investigation we used the bands at 875 and 2506 cm−1. In case of the band at 2506 cm−1 the difference between FT-IR and Scheibler method was a factor of 1.56, in case of 875 cm−1 the respective factor was 1.16. It can be concluded that FT-IR with both bands has a potential to be used in practice as substitution of the Scheibler method. The advantages of the FT-IR method are better reproducibility and the simultaneous characterization of soil organic matter in bulk samples. The disadvantage is its higher cost.

169 citations


Journal ArticleDOI
TL;DR: In this paper, the effects of pH, electrolyte concentration and temperature on the adsorption equilibrium were examined and the data correlated with a dual site adaption model and the enthalpy and entropy were found to be approximately −16 and −25 J/mol, respectively.
Abstract: The adsorption of antibiotic tetracycline onto silica particles was investigated. The effects of pH, electrolyte concentration and temperature on the adsorption equilibrium were examined and the data correlated with a dual site adsorption model. Adsorption of tetracycline onto approximately 9% of the adsorption sites was found to be irreversible, whereas the rest exhibited Langmuir behaviour. Increasing pH of the solution had a strong negative effect on the adsorbed amounts. Adsorption decreased also with increasing ionic strength and temperature. The enthalpy and entropy of adsorption were found to be approximately −16 and −25 J/mol, respectively.

145 citations


Journal ArticleDOI
TL;DR: In this article, an environmentally friendly electrochemical treatment, electro-Fenton process, was applied to the depollution of a synthetic dismissal composed of three dyes, yellow drimaren, congo red and methylene blue, frequently used in textile and dyehouses.
Abstract: An environmentally friendly electrochemical treatment, electro-Fenton process, was applied to the depollution of a synthetic dismissal composed of three dyes, yellow drimaren, congo red and methylene blue, frequently used in textile and dyehouses. Here, we show that those dyes and their mixture are quickly degraded under current controlled electrolysis conditions, leading to an almost complete mineralization. The results show the efficiency of electro-Fenton process to quickly degrade aqueous effluents polluted by synthetic organic dyes.

111 citations


Journal ArticleDOI
TL;DR: A review of applications of stable isotopes to a variety of environmental problems can be found in this article, where the authors provide a comprehensive overview of areas where isotopes have been used and potential applications for the future.
Abstract: In the past decade, environmental forensics has emerged as a discipline directed toward determining parties liable for causing spills of contaminants into the environment. Such investigations, while geared toward determining the guilty parties in order to recover costs of the cleanup and remediation, require various questions to be addressed. These include determination of the nature of the product; Where did it come from?; Extent of weathering, if any; How long has it been there?; and Is it degrading naturally? Traditionally, these studies have been addressed through utilization of techniques such as gas chromatography (GC) and gas chromatography–mass spectrometry (GCMS). However, in recent years, stable isotopes, primarily determined through the use of combined gas chromatography–isotope ratio mass spectrometry (GCIRMS), have emerged as an equally important tool in environmental forensics. For relatively low molecular, volatile compounds such as MTBE, BTEX, or chlorinated solvents, the isotopes, primarily carbon and hydrogen, have been used extensively for evaluating the onset of natural attenuation. For larger molecules such as PCBs or PAHs, in which the effects of biodegradation on the isotope composition of these molecules is minimal, the isotopic fingerprints of the individual compounds can be used for correlation purposes. In this paper, a brief introduction to isotope geochemistry will be given, followed by a review of applications of stable isotopes to a variety of environmental problems. While the review may not necessarily be exhaustive, it will provide a comprehensive overview of areas where isotopes have been used and potential applications for the future. Most of the review is concerned with carbon and hydrogen isotopes, although a brief overview of the emerging area of chlorine isotopes will also be discussed.

109 citations


Journal ArticleDOI
TL;DR: In this paper, cross-linked nanoporous polymers that have been copoly-merized with previously functionalized carbon nanotubes were used to remove organic contaminants from water.
Abstract: Some organic compounds are major water pol- lutants. They can be toxic or carcinogenic even at low con- centrations. Current technologies, however, fail to remove these contaminants to parts per billion (ppb) levels. Here we report on the removal of organic pollutants from water using cross-linked nanoporous polymers that have been copoly- merized with previously functionalized carbon nanotubes. These novel polymers can remove model organic species such as p-nitrophenol by as much as 99% from a 10 mg/L spiked water sample compared to granular activated carbon and native cyclodextrin polymer that removed only 47 and 58%, respectively. These polymers have also demonstrated the ability to remove trichloroethylene (10 mg/L spiked sam- ple) to non-detectable levels (detection limit <0.01 ppb) compared to 55 and 70% for activated carbon and native cyclodextrin polymers, respectively.

105 citations


Journal ArticleDOI
TL;DR: In this article, the retention capacity of organic matter and minerals from soils was studied in a long-term field experiment in which the organic carbon content had been altered, but the mineral phase had remained constant over time.
Abstract: Sorption of heavy metals to organic matter and mineral soil constituents can hardly be separated experimentally. Here we studied the retention capacity of organic matter and minerals from soils in a long-term field experiment in which the organic carbon content had been altered, but the mineral phase had remained constant over time. The sorption of Cu, Cd and Zn showed a non-additive contribution of soil organic matter and minerals to the sorption capacity of soil. Sorption on organic matter exceeded mineral sorption from 6 to 13 times. This is the first time that sorption to soil organic matter is quantified in bulk soils.

95 citations


Journal ArticleDOI
TL;DR: In this article, the synthesis of several insoluble monosubstituted cyclodextrin polymers or "nanosponges" was reported, which showed that these polymers have improved abilities in the absorption of p-nitrophenol and pentachlorophenol from aqueous solutions.
Abstract: Water is an important resource for domestic, industrial, agricultural and recreational purposes. The quality of water is however significantly deteriorating due to the accumulation of organic pollutants in aqueous systems. Conventional water treatment technologies fail to remove these contaminants to desirable levels. Recent studies have revealed that cyclodextrin nanoporous polymers are capable of absorbing pollutants from water to parts per billion levels. We have demonstrated that functionalised cyclodextrin polymers have enhanced absorption capacities for some organic pollutants. Here we report the synthesis of several insoluble monosubstituted cyclodextrin polymers or “nanosponges”. We show that these polymers have improved abilities in the absorption of p-nitrophenol and pentachlorophenol from aqueous solutions.

77 citations


Journal ArticleDOI
TL;DR: In this paper, the results obtained in several projects on atmospheric aerosol pollution developed during the last years in the Western Mediterranean are synthesized and the strategies for suitable monitoring in ambient air are discussed.
Abstract: This article synthesises the results obtained in several projects on atmospheric aerosol (particulate matter – PM) pollution developed during the last years in the Western Mediterranean. It focuses on particulate matter sources and the strategies for suitable monitoring in ambient air. The article has been structured in several sections that give response to the main questions that prompted these studies. After analysing the main PM features in the Mediterranean, a brief review of the main factors differentiating the particulate matter composition with respect to Central Europe is presented. Finally, the suitability of the different metrics or parameters for monitoring ambient air PM levels in different types of environments is discussed.

57 citations


Journal ArticleDOI
TL;DR: In this article, the authors studied the mobility and transport of heavy metals such as Cu, Zn, As, Cd, Cr, Ni, and Pb, from soil and soil amended with sewage sludge to sorghum plants.
Abstract: We studied the mobility and transport of heavy metals such as Cu, Zn, As, Cd, Cr, Ni, and Pb, from soil and soil amended with sewage sludge to sorghum plants. The total and ethylenediaminetetraacetic acid (EDTA) extractable heavy metals in agricultural soil and untreated domestic sewage sludge (DWS) samples were determined. The correlation between the total and extractable metals in soil and sewage sludge was investigated. The total and extractable heavy metals in soil, sewage sludge and sorghum grain were analysed by flame and electro thermal atomic absorption spectrometer (FAAS/ETAAS), after digestion in microwave oven. Statistically good correlations were obtained between the total contents of all heavy metals and their respective extractable fractions in soil and domestic wastewater sludge. Transfer factors of all heavy metals from domestic sewage sludge to sorghum grains were determined.

Journal ArticleDOI
TL;DR: In this paper, the analysis of trace amounts of neonicotinoid insecticides by liquid chromatography coupled with a thermal lens spectrometric detector (TLS) was studied.
Abstract: We studied the analysis of trace amounts of neonicotinoid insecticides by liquid chromatography coupled with a thermal lens spectrometric detector (TLS). This multi-residue analysis method is based on the reversed phase separation on C18 column, isocratic elution and collinear dual beam TLS detection. The insecticides thiamethoxam, imidacloprid, acetamiprid and thiacloprid were detected with retention times of 4.4, 5.7, 6.5 and 8.5 min and limits of quantifications of 50, 89, 10, and 25 μg/L, respectively. The retention times agreed well with those obtained by the same chromatographic method but using a diode-array detector (DAD). The limits of quantifications for imidacloprid were identical in both techniques. However, the limits of quantifications for thiamethoxam, acetamiprid and thiacloprid were up to 8.5 times lower using the TLS detector compared to the diode-array detector. The applicability of the developed procedure was tested on spiked river water and potato samples.

Journal ArticleDOI
TL;DR: In this article, the effect of contact time, pH, and Fe content on the adsorption of both arsenite and arsenate species on the new material was investigated, which can be explained on the basis of electrostatic interactions between ionic species in solution and the ≡FeOH surface groups.
Abstract: We loaded a lignocellulosic substrate extracted from wheat bran with ferric ions. This new low-cost adsorbent was prepared for the adsorption and removal of arsenate and arsenite ions from aqueous systems. The loading process of Fe in this biomaterial was done by hydrolization of a ferric salt while an alkaline solution was added dropwise. The new material obtained has a high sensivity to arsenite and arsenate species. Here, we investigated the effect of contact time, pH, and Fe content on the adsorption of both arsenic ions on the new material. This adsorption was found to be highly pH-dependent, which can be explained on the basis of electrostatic interactions between ionic species in solution and the ≡FeOH surface groups. The maximum adsorption capacity of arsenite and arsenate species vary linearly with the amount of Fe loaded on the lignocellulosic substrate.

Journal ArticleDOI
TL;DR: In this paper, the photodegradation of the herbicides atrazine and ametryn with visible light in aerated neutral aqueous solutions and 5, 10, 15, 20, 20-tetrakis (2,6-dichloro-3-sulfophenyl) porphyrin or 5.
Abstract: The photodegradation of the herbicides atrazine and ametryn with visible light in aerated neutral aqueous solutions and 5, 10, 15, 20-tetrakis (2,6-dichloro-3-sulfophenyl) porphyrin or 5, 10, 15, 20-tetrakis (4-sulfophenyl) porphyrin as sensitizers are reported for the first time. Our findings show that the degradation percentage reached 30% for atrazine and 63% for ametryn. The final photoproducts were characterized as dealkylated s-triazines. Photolysis of the pesticides in the presence of a singlet oxygen quencher showed only a minor contribution of this type of mechanism, while a bimolecular quenching reaction between the triplet state of the sensitizer and the pesticides is excluded by flash photolysis studies. It is proposed that the mechanism may involve the formation of a superoxide radical anion from the triplet state of the sensitizer and molecular oxygen, followed by a radical decomposition pathway.

Journal ArticleDOI
TL;DR: In this article, water samples from 56 lakes of Missouri, USA, were analyzed for their fluorescence excitation/emission matrix (EEM) spectroscopy and the formation potentials of total trihalomethanes (TTHM) and N-nitrosodimethylamine (NDMA).
Abstract: Water samples from 56 lakes of Missouri, USA, were analysed for their fluorescence excitation/emission matrix (EEM) spectroscopy and the formation potentials of total trihalomethanes (TTHM) and N-nitrosodimethylamine (NDMA). Comparing the excitation/emission matrix fingerprints with trihalomethanes formation revealed that water with higher fluorescence intensity generally exhibited higher trihalomethanes formation potential. Moreover, waters with fluorescence centre at excitation: 290–310 nm/emission: 330–350 nm were related to high N-nitrosodimethylamine and trihalomethanes formation potentials. The results suggest that excitation/emission matrix fingerprints could be used as surrogate parameters for monitoring trihalomethanes and N-nitrosodimethylamine formation potentials.

Journal ArticleDOI
TL;DR: In this paper, the thermal behavior of Miscanthus × Giganteus (M×G) is studied by thermogravimetric analysis and it is found that the global pyrolysis of M×G can be satisfactorily described using a six steps-kinetic scheme.
Abstract: In this paper the thermal behaviour of Miscanthus × Giganteus (M×G) is studied by thermogravimetric analysis. In order to characterise the thermal behaviour of its cellulose, hemicellulose and lignin, the raw M×G material was treated sequentially by water, H2SO4 and KOH. The global kinetic parameters for each component were determined by subsequent modelling of the TG data with the Ozawa-Flynn-Wall method and multivariate non-linear regression. It is found that the global pyrolysis of M×G can be satisfactorily described using a six steps-kinetic scheme. The analytical method proposed here could be extended to other biomass products.

Journal ArticleDOI
TL;DR: A cost-effective and sensitive spectrophotometric method for the determination of arsenic at trace level using a new reagent, leuco malachite green was developed in this article.
Abstract: We developed a cost-effective and sensitive spectrophotometric method for the determination of arsenic at trace level using a new reagent, leuco malachite green Here we show that, arsenic reacts with potassium iodate in acidic conditions to liberate iodine, and the liberated iodine selectively oxidizes leuco malachite green to malachite green dye We studied the Beer’s law at 617 nm, which showed linearity over the concentration range 009–09 μg ml−1 of arsenic We show that the molar absorptivity, Sandell’s sensitivity and detection limit of the method are 61 × 104 l mol−1 cm−1, 00012 μg cm−2 and 0025 μg ml−1, respectively We applied the developed method for the determination of arsenic in environmental samples

Journal ArticleDOI
TL;DR: In this paper, the authors report early success for sequestering {sup 129}I. Sorption coefficients (K{sub d}) for I{sup -} and IO{sub 3}{sup -] onto delafossites, spinels and layered metal hydroxides were measured in order to compare their applicability for extracting I.
Abstract: The objective of this document is to report on early success for sequestering {sup 129}I. Sorption coefficients (K{sub d}) for I{sup -} and IO{sub 3}{sup -} onto delafossites, spinels and layered metal hydroxides were measured in order to compare their applicability for sequestering {sup 129}I. The studies were performed using a dilute fluid composition representative of groundwater indigenous to the Yucca mountain area. Delafossites generally exhibited relatively poor sorption coefficients (< 10{sup 1.7} mL/g). In contrast, the composition of the layered hydroxides significantly affects their ability to sorb I. Cu/Al and Cu/Cr layered hydroxide samples exhibit K{sub d}'s greater than 10{sup 3} mL/g for both I{sup -} and IO{sub 3}{sup -}.

Journal ArticleDOI
TL;DR: In this article, the aliphatic fractions of 25 soil samples from a former coking plant site by microscopy and gas chromatography-mass spectrometry (GC-MS) were analyzed and considered as reference materials.
Abstract: Polluted soils of former coking plants are characterized by multiple organic contributions, e.g. coal tar, coal, coke, soot, and natural organic matter, that can either be sources of polycyclic aromatic hydrocarbons (PAHs) or act as sorption surfaces for pollutants. The contamination level is usually based on the quantification of 16 PAHs but it does not provide any information on PAH sources. We studied the aliphatic fractions of 25 soil samples from a former coking plant site by microscopy and gas chromatography-mass spectrometry (GC-MS). The microscopic investigation allowed to identify four main organic contributions: coal tar, coal, coke, and natural organic matter. These isolated sources were analyzed and considered as reference materials. Although the PAH distributions were very similar in the 25 contaminated soils, alkanes and hopanes distributions were representative from various contributions characterizing the relative enrichment in coal, coal tars, or natural organic matter. Two principal component analyses based on n-alkanes and hopanes showed that three molecular indices, the carbon preference index, the low molecular weight/high molecular weight n-alkanes ratio, and the 18α(H)-22,29,30-trisnorhopane/(18α(H)-22,29,30-trisnorhopane+17α(H)-22,29,30-trisnorhopane) ratio allow to classify polluted soils according to various organic contributions.

Journal ArticleDOI
TL;DR: In this paper, the feasibility of using biological granular activated carbon-packed column in treating methylene blue-containing wastewater was studied and it was observed that the colour and chemical oxygen demand removal efficiencies were 99 and 78%, respectively.
Abstract: We studied the feasibility of using biological granular activated carbon-packed column in treating methylene blue-containing wastewater. The granular activated carbon with immobilized microbes was packed into a column and fed with 3 liter methylene blue-containing wastewater daily. With initial 1350 mg/l of methylene blue and 1550 mg/l of chemical oxygen demand, it was observed that the colour and chemical oxygen demand removal efficiencies were 99 and 78%, respectively. The high treatment performance of the system could be due to the simultaneous adsorption and biodegradation processes and advantages of immobilized microbes compare to suspended cell system.

Journal ArticleDOI
TL;DR: In this article, the authors analyzed concentration levels of pollutants collected in 2004 and 2005 in air samples from the city of Kragujevac, Serbia, following the war accident of 1999.
Abstract: For the duration of the war accident in former Yugoslavia, several industrial and military targets were burnt and damaged, resulting in a significant release of persistent organic pollutants. Locations heavily targeted in the attacks were later defined by UNEP as four “hot spots”: Kragujevac, Novi Sad, Pancevo and Bor. We analyzed concentration levels of pollutants collected in 2004 and 2005 in air samples from the city of Kragujevac, Serbia, following the war accident of 1999. Pollutants included polycyclic aromatic hydrocarbons (PAHs), hexachlorocyclohexane (HCH), dichloro-diphenyl-trichloroethane (DDT), dichloro-diphenyl-dichloroethylene (DDE), dichloro-diphenyl-dichloroethane (DDD) and polychlorinated biphenyls (PCBs). We present results obtained during air sampling campaign conducted in July 2004 by the active sampling method; and during September 2004–June 2005 by the passive sampling method. Our findings show the occurrence of residual quantities of DDT, HCH, PCBs and PAHs in air samples. High levels of PCBs are probably due to the destruction of transformers during the war accident.

Journal ArticleDOI
TL;DR: In this article, the potential of the photocatalytic oxidation to selectively oxidise steroid estrogens, β-estradiol and 17α-ethynylstradiol, in the presence of saccharose and ethanol as co-pollutants was clearly demonstrated.
Abstract: The potential of the photocatalytic oxidation to selectively oxidise steroid estrogens, β-estradiol and 17α-ethynylestradiol, in the presence of saccharose and ethanol as co-pollutants was clearly demonstrated. The alkaline media conditions remained the most beneficial for the PCO regardless the presence of co-pollutants under consideration. Saccharose appeared to be the more powerful competitor than ethanol. The influence of the co-pollutants is explained by their competition for the adsorption sites and also scavenging of the OH-radicals.

Journal ArticleDOI
A. Cafissi1, S. Beduschi, V. Balacco, B. Sacchi1, Stefano P. Trasatti1 
TL;DR: In this paper, the chemical dechlorination of polychlorinated biphenyls (PCBs) in some dielectric oils via nucleophilic substitution of the chloro atoms by polyethylene alkoxide was investigated.
Abstract: We studied the chemical dechlorination of the polychlorinated biphenyls (PCBs) in some dielectric oils via nucleophilic substitution of the chloro atoms by polyethylene alkoxide. The influence of temperature, ultrasounds, polyethylene glycol (PEG) and base type was investigated. Our findings show that dechlorination of PCBs by chemical treatment is effective at moderate temperature (90–100°C) and is strongly dependent on the nature of matrix oil. Stirring affects the process yield by influencing the homogeneity of the oil/glycol two-phase system. Ultrasounds can improve the process efficiency by making operating conditions less severe.

Journal ArticleDOI
TL;DR: The effect of organic arsenic compounds and inorganic As(V) and As(III) on Vibrio fischeri luminescence and butyrylcholinesterase activity were evaluated using Microtox and microcalorimetric analysis as mentioned in this paper.
Abstract: The effect of organic arsenic compounds and inorganic As(V) and As(III) on Vibrio fischeri luminescence and butyrylcholinesterase activity were evaluated using Microtox and microcalorimetric analysis. Organic arsenic compounds were arsenocholine (AsC), arsenobetaine (AsB), dimethylarsinic acid (DMA), monomethylarsonic acid (MMA) and the antibiotic 4-hydroxy-3-nitrobenzene arsonic acid (HNAA, Roxarsone(R)). HNAA, As(III) and As(V) were found to inhibit Vibrio fischeri light emission whereas MMA, DMA, AsC and AsB produced only a slight effect. By contrast, only AsC, AsB and As(III) were found to inhibit butyrylcholinesterase activity.

Journal ArticleDOI
TL;DR: In this paper, acid hydrolysis of estuarine water samples for the determination of amino acids (AAs) was tested and found to be effective at high (250μm) nitrate concentrations when the anti-oxidant, ascorbic acid, was added to the samples.
Abstract: Acid hydrolysis of estuarine water samples for the determination of amino acids (AAs) was tested and found to be effective at high (250 μM) nitrate concentrations when the anti-oxidant, ascorbic acid, was added to the samples. Hydrolysable AA concentrations were then determined in surface sediments collected from low and high salinity regions of the Tamar Estuary (UK) during winter 2003 and 2004, and in overlying water when simulated resuspension of sediment particles was performed. Concentrations of AAs in sediment samples comprised <50% of particulate nitrogen, fitting the paradigm that most sedimentary nitrogen is preserved within an organic matrix. When sediment samples were resuspended in overlying water (salinity 17.5), the rapid, measured increase in dissolved AA concentrations almost equalled the reported nitrate concentration in the lower estuary, with the subsequent decrease in the total dissolved AA levels suggested that bacterial uptake was occurring. Our data concur with previous studies on nitrogen desorption from sediments and suggest that an understanding of organic nitrogen cycling will be an important aspect of future effective estuarine management.

Journal ArticleDOI
TL;DR: In this paper, the authors demonstrate the successful use of an improved activated carbon technique using dichloromethane instead of chloroform, and slower leaching rate of 15 mL/min to quantify DDT and its metabolites in surface water.
Abstract: Currently, South Africa is designing a strategy for surface water protection involving organic contaminants such as dichlorodiphenyltrichloroethane (DDT), which is currently used for malaria control in mosquito-infested ar- eas. Here, we demonstrate the successful use of an improved activated carbon technique using dichloromethane instead of chloroform, and slower leaching rate of 15 mL/min to quantify DDT and its metabolites in surface water. The re- covery tests for 2,4 � DDT, 2,4 � DDD, 2,4 � DDE, and 4,4 � DDT, 4,4 � DDD, 4,4 � DDE ranged from 75 to 84% and 87 to 96%, re- spectively (DDE: dichlorodiphenyldichloroethylene, DDD: dichlorodiphenyldichloroethane). The main advantages of this technique over conventional liquid-liquid extractions are reduced amount of organic solvent, little sample preparation, and larger sample throughput. Because activated charcoal is fairly cheap, the technique can be routinely used to quan- tify and monitor DDT and its metabolites in surface water samples.

Journal ArticleDOI
TL;DR: Titanium dioxide photocatalysis, using 200 mgl(-1) of TiO2, and photo-Fenton, using 20 mg l(- 1) of iron, were applied to the treatment of dimethoate dissolved in water at 50 mg l(1) as discussed by the authors.
Abstract: Titanium dioxide photocatalysis, using 200 mgl(-1) of TiO2, and photo-Fenton, using 20 mg l(-1) of iron, were applied to the treatment of dimethoate dissolved in water at 50 mg l(-1). A heterogeneous photocatalysis test was performed in a 35-1 solar pilot plant with Compound Parabolic Collectors (CPCs) under natural illumination. A homogeneous photocatalysis test was performed in a different solar pilot plant with four CPC units and a total volume of 75 1. In this work total disappearance of dimethoate and 90% of mineralization were attained in both solar treatments. Treatment time, hydrogen peroxide consumption and ferric phosphate precipitation during photo-Fenton treatment were discussed.

Journal ArticleDOI
TL;DR: In this paper, the lowest excited state (3MLCT) of Ru(bpy)ForgeModLoader 3� 2+¯¯¯¯ 2+>>\s is used to break down chlorophenol pollutant molecules to harmless products, which has the advantage of using visible light and a shortlived catalytically active species.
Abstract: Advanced oxidation processes, such as photocatalysed oxidation, provide an important route for degradation of wastes. In this study, the lowest excited state (3MLCT) of Ru(bpy) 3 2+ is used to break down chlorophenol pollutant molecules to harmless products. This has the advantage of using visible light and a short-lived catalytically active species. Photolysis of deaerated aqueous solutions of a variety of mono- and poly-substituted chlorophenols has been followed in the presence of Ru(bpy) 3 2+ /S2O 8 2− with near visible light (λ > 350 nm) by UV/visible absorption spectroscopy, luminescence, potentiometry, NMR and HPLC techniques. Upon irradiation, a decrease is observed in the chlorophenol concentration, accompanied by the formation of Cl−, H+ and SO 4 2− ions as the main inorganic products. Benzoquinone, phenol, dihydroxybenzenes and chlorinated compounds were the dominant organic products. As the ruthenium(II) complex is regenerated in the reaction, the scheme corresponds to an overall catalytic process. The kinetics of the rapid chlorophenol photodechlorination has been studied, and are described quite well by pseudo-first order behaviour. Further studies on this were made by following Cl− release with respect to the initial Ru(bpy) 3 2+ and S2O 8 2− concentrations. A comparison is presented of the photodechlorination reactivity of the mono and polychlorophenols studied at acidic and alkaline pH.

Journal ArticleDOI
TL;DR: In this paper, a dynamic dilution system was used for the study of the influence of ozone on the sampling and storage of volatile organic compounds (VOCs) at 0, 4, 7 and 14 days in TO-Can canisters at two ozone concentrations, 60 and 150 ppbv.
Abstract: A dynamic dilution system was used for the study of the influence of ozone on the sampling and storage of volatile organic compounds (VOCs) at 0, 4, 7 and 14 days in “TO-Can” canisters at two ozone concentrations, 60 and 150 ppbv. Among the 31 ozone precursors VOCs, a representative mixture containing five alkenes, five aromatics, acetylene and 1,3 butadiene was selected using the Clausius–Clapeyron equation. Here, we demonstrate that the presence of ozone have no influence on the concentrations of VOCs after 14 days storage period and consequently no problem of representativity of the sampling appears after 14 days of storage. The main explanation is the degradation of ozone in contact with deactivated walls of canisters.

Journal ArticleDOI
TL;DR: In this article, a method for the determination of inorganic arsenic in natural waters using differential pulse cathodic stripping voltammetry was presented, which was applied to water samples collected in an arsenic-contaminated region of Brazil, in particular, to verify the efficiency of the solar oxidation and removal of arsenic process applied to these waters.
Abstract: Here, we show a fast and sensitive method for the determination of inorganic arsenic in natural waters using differential pulse cathodic stripping voltammetry. All the arsenite determinations were done in 2.0 mol L−1 HCl + 3.15 × 10−4 mol L−1 Cu(II) supporting electrolyte. 1 × 10−3 mol L−1 sodium thiosulphate was used as As(V) reducing agent. The detection limit was 0.5 μg L−1 for both species. The method has been applied to water samples collected in an arsenic-contaminated region of Brazil, in particular, to verify the efficiency of the solar oxidation and removal of arsenic process applied to these waters.