The deployment of γ-irradiation for reducing polycyclic aromatic hydrocarbons and microbial load in wheat kernels

Food contamination may contribute to serious human health problems. In this work, the effect of γ-irradiation 0, 5, 10, and 15 kGy doses on the removal of polycyclic aromatic hydrocarbons from wheat kernels was investigated. Additionally, variations in the contents of 16 congeners on bacterial load and other chemical parameters were studied. Polycyclic aromatic hydrocarbons concentrations were determined by high-performance liquid chromatography followed by fluorescence detection. The effects of γ-irradiation on the concentrations varied for each congener, with the highest irradiation dose being the most effective. Benzo[a]pyrene was reduced by ～50%, and the total concentration of all congeners decreased dramatically from 154 to 21 µg.kg^?1 upon 15 kGy irradiation at a dose rate of 8.49 kGy h^?1. The total bacterial load was reduced from 2.4 to < 1 log₁₀ cfu g^?1, while wheat chemical properties were not affected.     

Continuous monitoring of ambient polycyclic aromatic hydrocarbons near open‐air burning of metal scraps

Airborne concentrations of PAH in the vicinity of the source region with open‐air burning of metal scraps were measured between February, 1992 and November, 1993. The activity of open‐air burning decreased significantly since 1993 due to prohibition regulation. Both gaseous phase and particle‐bound PAH were measured at five sampling sites, which included one reference sampling site far away from the source region. Both values of gaseous and particle‐bound PAH concentrations, which were measured in the vicinity of source region, decreased clearly during the two years monitoring period. It shows that the uncontrolled open‐air burning of metal scraps was a significant emission source of airborne PAH in the study area. The profiles of various species of PAH were also compared. A large decrease in benzo(a)pyrene was observed in the source region.     

Aliphatic and polycyclic aromatic hydrocarbons in the bottom sediments from Klaipėda Harbour,Lithuania (Baltic Sea)

A total of 22 bottom surface sediment samples were collected from Klaip?da Harbour, Lithuania (Baltic Sea). Sediment parameters, such as grain size and concentrations of total organic carbon, aliphatic hydrocarbons (ALHs) and polycyclic aromatic hydrocarbons (PAHs), were determined. Hydrocarbon contamination levels in the sediments were estimated based on classifications provided in the literature, and potential biological effects were assessed based on the effects range low–effects range median values of the Sediment Quality Guidelines and on the total toxic benzo(a)pyrene equivalent. The results demonstrated that concentrations of PAHs and total aliphatic hydrocarbons in the sediments varied between 1.6 and 5456?ng?g^?1 d.w. and 6.9 and 727?μg?g^?1 d.w., respectively. In most cases, the concentrations of ALHs and PAHs in the sediments indicated low to moderate levels of pollution and were not observed to have any significant adverse effects on living biota. To determine possible sources of hydrocarbons, hydrocarbon compositions were analysed, and ALHs’ and PAHs’ specific diagnostic ratios were calculated. According to the results, the Klaip?da Harbour bottom sediments were dominated by PAHs of pyrogenic origin, whereas the origin of ALHs was mixed, that is, anthropogenic with a biogenic (aquatic and terrestrial) input.     

Biogeochemistry of aromatic hydrocarbons in the benthos of microcosms†

Investigations into the fate of petroleum compounds in the marine environment were carried out using experimental microcosms of two sizes and designs. Aromatic hydrocarbons or No. 2 fuel oil were spiked to the water of a 13 m³ continuous flow system and to a 2281 recycled flow system. The transport and alteration of this oil was traced in the sediment and benthic organisms (Glycera americana, Crepidula sp., and Nephtys incisa) of these microcosms. Measurable contamination was found in both sample types. The aromatic hydrocarbon distribution, including relative isomeric distribution (e.g., C₂‐phenanthrenes) was found to be different in sediment and in organisms from that which was originally introduced to the experimental microcosm. Differences in isomer distribution between Glycera and Crepidula were also detected. Based on the experimental data: molecular weight and specific isomeric form, biochemical processes, solubility, and particle adsorption/desorption influence the fate of petroleum compounds in benthic ecosystems.     

Bioaccumulation and adverse effects of trace metals and polycyclic aromatic hydrocarbons in the common onion Allium cepa as a model in ecotoxicological bioassays

The common onion Allium cepa can be easily used in ecotoxicological bioassays to evaluate the bioavailability and adverse effects of pollutants and complex mixtures like waste, industrial effluent or coal-mining drainage that contain elevated levels of trace metals and polycyclic aromatic hydrocarbons (PAHs). In this study, onions were exposed for 7 days to individual metals (1?µg?mL^?1), i.e., aluminium, copper, iron and manganese, or PAHs (1.5?ng?mL^?1), i.e., benzo[a]antracene and benzo[a]pirene. Biological effects, measured as growth inhibition of roots and leaves, were integrated with analysis of bioaccumulation in roots, bulbs and leaves. Copper, iron and benzo[a]pirene caused a significant inhibition in root development of newly formed tissues, whereas only slight variations were caused by other chemicals; the number of new root filaments and the length of the leaves did not show significant variations, thus not representing sensitive parameters to evaluate adverse effects of pollutants in A. cepa. Chemicals bioaccumulation was always significant in roots, whereas levels in bulbs and leaves exhibited increased levels only for manganese, and a decrease for aluminium. The overall results confirmed the sensitivity of the bioassays with A. cepa, suggesting their utility for future applications to evaluate the adverse effects of complex mixtures containing metals or PAHs.     

An investigation into the occurrence and distribution of polycyclic aromatic hydrocarbons in two soil size fractions at a former industrial site in NE England,UK using in situ PFE–GC–MS

Polycyclic aromatic hydrocarbon (PAH) concentrations were determined in 16 topsoils (0–10 cm) collected across the site of a former tar works in NE England. The soils were prepared in the laboratory to two different particle size fractions: <250 μm (fraction A) and >250 μm to <2 mm (fraction B). Sixteen priority PAHs were analysed in the soils using in situ pressurised fluid extraction (PFE) followed by gas chromatography—mass spectrometry (GC–MS). The average total PAH concentration in the soils ranged from 9.0 to 1,404 mg/kg (soil fraction A) and from 6.6 to 872 mg/kg (soil fraction B). These concentrations are high compared with other industrially contaminated soils reported in the international literature, indicating that the tar works warrants further investigation/remediation. A predominance of higher-molecular-weight compounds was determined in the samples, suggesting that the PAHs were of pyrogenic (anthropogenic) origin. Statistical comparison (t-test) of the mean total PAH concentrations in soil fractions A and B indicated that there was a significant difference (95% confidence interval) between the fractions in all but two of the soil samples. Additionally, comparisons of the distributions of individual PAHs (i.e. 16 PAHs × 16 soil samples) in soil fractions A and B demonstrated generally higher PAH concentrations in fraction A (i.e. 65.8% of all individual PAH concentrations were higher in soil fraction A). This is important because fraction A corresponds to the particle size thought to be most important in terms of human contact with soils and potential threats to human health.     

Spatiotemporal multimedia emission inventory for polycyclic aromatic hydrocarbons near petroleum production plants in China based on a 10′ × 10′ grid

A spatiotemporal model was developed to investigate emissions of polycyclic aromatic hydrocarbons (PAHs) in Daqing, a Chinese city with large petroleum industry plants. The model was based on land-use types determined on a 10′?×?10′ grid. A geographic information system and regression analyses were used to characterise spatial and temporal variations in PAH emissions into multiple environmental media. The simulated results were validated using previously published experimental data, and the model was found to function well. PAH emissions to the atmosphere, soil, and surface water between 1998 and 2013 were estimated. The results indicated that PAH emissions to the atmosphere increased but PAH emissions to the soil and surface water decreased over the study period. PAH emissions to the atmosphere were markedly higher in winter than in summer. PAH emissions were concentrated in urban areas and areas near petroleum production plants, indicating that PAH emissions were closely related to industrial activities. The results will support research into the migration and transformation of PAHs and human health and ecological risk assessments. The results may also be useful for developing policies for controlling PAH pollution and managing risks associated with PAHs.     

Modeling toxic endpoints for improving human health risk assessment of polycyclic aromatic hydrocarbons – parent compounds and simple mixtures

Risk assessments for mixtures of polycyclic aromatic hydrocarbons (PAH) are problematic due to the lack of available potency and toxicity data on individual compounds and mixtures. This article examines the toxicity of parent compounds and designed mixtures of PAH in order to bridge the gap between component assessment and mixture assessment for this class of ubiquitous compounds. The objective for this study was to test seven parent PAH compounds and four PAH mixtures in a set of three bioassays to evaluate the toxicity of parent compound PAH and binary mixtures of PAH. PAH and mixtures were examined in the Salmonella/microsome mutagenicity assay, a Gap Junction Intercellular Communication assay, and the 7-ethoxyresorufin-O-deethylase assay. These assays were chosen for their ability to measure specific toxic endpoints related to the carcinogenic process (i.e. initiation, promotion, and progression). Two compounds similar in structure, benzo(a) pyrene (BAP) and benzanthracene, consistently produced positive results in all three bioassays. Conversely, a linear PAH, anthracene, produced negative results in all three bioassays. An antagonistic response was observed for the mixtures in all three bioassays. Chemical structure was important in explaining the observed responses. Using chemical structure–activity relationships with the steps of the carcinogenic process may be used to improve estimates of toxicity for compounds and mixtures for human health risk assessments.     

Air pollution from aluminum smelting plants. II. the contribution from an aluminum smelting plant using the söderberg process to polycyclic aromatic hydrocarbons and mutagens in ambient air

Extracts of airborne particles collected in the surroundings of an aluminum smelting plant have been analyzed for polycyclic aromatic hydrocarbons (PAH) and tested for mutagenic activity. The results were discussed in relation to the meteorological conditions during sampling and showed that the ambient concentrations of these parameters are significantly influenced by the emissions from the smelting plant in the summer, but not in the winter. The results from the mutagenicity testing showed that the mutagenic activity of particle extracts from this area was equal to or lower than what has been reported from other urban areas in Scandinavia.

The contribution of PAH and mutagens to the concentrations of these compounds in ambient air was estimated based on parallel measurements of fluoride and from emission values of fluoride, PAH and mutagens. It was concluded that whereas the smelter emissions could account for more than 50% of the yearly average of ambient PAH, the contribution of mutagens was significantly less.     

Microbiological degradation of polycyclic aromatic hydrocarbons: Anthracene,benzo(K)fluoranthene,dibenzothiophene, benzo(H) quinoline and 2‐nitronaphthalene

Biodegradation experiments of various polycyclic aromatic hydrocarbons were studied with mixed bacteria culture under aerobic conditions. An easy‐to‐handle clean‐up procedure was developed for PAH and their metabolites simultaneously as well as a gc‐ms‐method to identify and quantify these compounds.

Anthracene and dibenzothiophene are completely degradable in an aqeous system, whereas biodegradation of benzo(k)fluoranthene and benzo(h)quinoline is possible only in an oil‐in‐water‐system with dodecane as cosubstrate. No degradation of nitronaphthalene was observed in aqueous systems. New metabolites are 2,3‐dihydroxybenzothiophene, hydroxybenzothiophenecarbonic acid and benzothiophenequinone for dibenzothiophene and hydroxyfluoranthenic acid for benzo(k)flouranthene. Whereas the former metabolites are degradable under the experimental conditions, the latter accumulates during the degradation experiment.

The results are important for microbiological wastewater treatment, since knowledge of biodegradation processes is indespensable for the successful treatment of PAH‐containing wastewater.     

A novel polyacrylonitrile–zeolite nanocomposite to clean Cs and Sr from radioactive waste

Radioactive wastes containing Cs⁺ and Sr²⁺ are among the most dangerous environmental pollutants. Therefore, removing Cs⁺ and Sr²⁺ from environmental media is needed. Removal can be done by nanocrystalline ion exchangers. Nanocrystalline ion exchangers are studied in depth for the treatment of nuclear wastes because these exchangers have high exchange capacity and fast kinetics. However, operating the columns of these exchangers is very difficult. This issue may be overcome by the preparation and use of nanocomposites. Here, we prepared a novel polyacrylonitrile–zeolite nanocomposite for the removal of Cs⁺ and Sr²⁺ in a fixed-bed column operation. We studied the effect of influent flow rate, nanocomposite bed height and initial concentrations. Experimental data were analysed using the Thomas model and the bed-depth service time model. The results reveal that total adsorbed ion and bed capacity increased with increasing initial ions concentration and bed height; and decreased with increasing influent flow rate. The maximum bed capacity was 0.085 meq/g for Cs⁺ and 0.128 meq/g for Sr²⁺. The critical bed height (Z ₀) was 4.35 cm for Cs⁺ and 2.89 cm for Sr²⁺. These findings demonstrate that the new nanocomposite is suitable for removal of Cs⁺ and Sr²⁺.     

Dispersive liquid–liquid microextraction of cadmium(II) for preconcentration prior to flame atomic absorption spectrometric detection in water

A dispersive liquid–liquid microextraction procedure for cadmium(II) as its 2-(5-bromo-2-pyridylazo)-5-diethylamino-phenol chelate is presented. Carbon tetrachloride and methanol were used as extraction and dispersive solvents, respectively. After phase separation, the preconcentrated-separated cadmium(II) is determined by flame atomic absorption spectrometry with a microinjection technique. The factors which affected the extraction efficiency, i.e. the pH of the sample solution and the volumes of reagent and sample were investigated. The effects of some alkali, alkali earth, and transition metal ions, and of some anions on the recovery of cadmium were also studied. A preconcentration factor of 250 was obtained for a sample volume of 50?mL under optimum conditions. The method was validated by analysis of certified reference materials and applied to some water samples from Turkey.     

Potentiometric techniques applied to the modelling of actinide migration in natural water systems†

The utility of potentiometric techniques applied to environmental problems is discussed. The applicability of this technique to the estimation of thermodynamic quantities important for the modelling of uranium migration in natural waters is demonstrated. An experimental methodology for the determination of the UO₂(s) solubility product and the UO²⁺/U⁴⁺ redox potentials is proposed.     

Occupational exposure to airborne aromatic amines in rubber manufacturing: Determination by gas chromatography‐mass spectrometry

Aromatic amines (AAs) are used in a variety of chemical industries and consequently they are the object of great attention in occupational hygiene owing to the carcinogenic effects that many of them have shown. This work outlines a procedure for the determination of occupational exposure to airborne AAs in the rubber industry and the application of this method in a tyre manufacturing plant using p‐phenylenediamines as antiozonants. Samples were collected on a glass fibre filter followed by a silica gel tube and analyzed by GC‐MS/SIM using a capillary column coated with methyl silicone. p‐Phenylendiamines and other AAs probably formed as thermodegradation products were found in concentrations of up to 10 μg/m³ during rubber vulcanization.     

Efficient synthesis of α,β-unsaturated ketones with trans-selective Horner–Wadsworth–Emmons reaction in water

Organic reactions in aqueous media are being developed because water is environmentally benign. The Horner–Wadsworth–Emmons reaction is a modified Wittig reaction for the synthesis of α,β-unsaturated ketones and other conjugated compounds. Here we prepared high molecular weight ketones by the Horner–Wadsworth–Emmons reaction of dimethyl-2-oxopropylphosphonate and various aldehydes in water at room temperature. The product was precipitated during the reaction process and was separated readily by a simple filtration in 90–99 % yield.     

Turbulent air–water flows in hydraulic structures: dynamic similarity and scale effects

In hydraulic structures, free-surface aeration is commonly observed: i.e., the white waters. The air bubble entrainment may be localised (hydraulic jumps, plunging jets) or continuous along an interface (water jets, chutes). Despite recent advances, there are some basic concerns about the extrapolation of laboratory results to large size prototype structures. Herein the basic air bubble entrainment processes are reviewed and the relevant dynamic similarities are discussed. Traditionally, physical studies are conducted using a Froude similitude which implies drastically smaller laboratory Reynolds numbers than in the corresponding prototype flows. Basic dimensional analyses are developed for both singular and interfacial aeration processes. The results are discussed in the light of systematic investigations and they show that the notion of scale effects is closely linked with the selection of relevant characteristic air–water flow properties. Recent studies of local air–water flow properties highlight that turbulence levels, entrained bubble sizes and interfacial areas are improperly scaled based upon a Froude similitude even in large-size models operating with the so defined Reynolds numbers ρ _w × q _w/μ _w up to 5 E+5. In laboratory models, the dimensionless turbulence levels, air–water interfacial areas and mass transfer rates are drastically underestimated.     

Total phosphorus concentrations in surface water of typical agro- and forest ecosystems in China, 2004–2010

The concentrations of total phosphorus （TP） from 83 surface water sampling sites in 29 of the Chinese Ecosystem Research Network （CERN） monitored ecosystems, representing typical agro- and forest ecosystems, were assessed using monitoring data collected between 2004 and 2010 from still and flowing surface water. Results showed that, TP concentrations were significantly higher in agro-ecosystems than those in forest ecosystems both for still and flowing surface water. For agro- ecosystems, TP concentrations in the southern area were significantly higher than those in the northern and north- western areas for both still and flowing surface water, however no distinct spatial pattern was observed for forest ecosystems. In general, the median values of TP within agro- and forest ecosystems did not exceed the Class V guideline for still （0.2mg.L-1） or flowing （0.4mg.L-1） surface water, however, surface water at some agro- ecosystem sampling sites was frequently polluted by TE Elevated concentrations were mainly found in still surface water at the Changshu, Fukang, Linze and Naiman monitored ecosystems, where exceedance （〉 0.2 mg.L-1） frequencies varied from 43% to 78%. For flowing water, elevated TP concentrations were found at the Hailun, Changshu and Shapotou monitored ecosystems, where exceedance （〉 0.4 mg. L-1） frequencies varied from 29% to 100%. Irrational fertilization, frequent irrigation and livestock manure input might be the main contributors of high TP concentrations in these areas, and reduced fertilizer applications, improvements in irrigation practices and centralized treatment of animal waste are necessary to control P loss in these TP vulnerable zones.     

Compositional data analysis and geochemical modeling of CO2–water–rock interactions in three provinces of Korea

Environmental Geochemistry and Health - The CO2-rich spring water (CSW) occurring naturally in three provinces, Kangwon (KW), Chungbuk (CB), and Gyeongbuk (GB) of South Korea was classified based...     

National water footprint in an input–output framework—A case study of China 2002

Water footprint is an indicator showing the consumption impact on environment with water equivalent, which allows a detailed quantification of water use directly and indirectly in sectors for the domestic and abroad final consumption. This paper presents a framework of calculating national water footprint (NWF) with input–output method on China 2002. The results indicated that the NWF of China was 381 m³/cap yr in 2002. A new indicator termed as national water footprint intensity (NWFI) is also derived from NWF to evaluate the water consumption intensities of different sectors. Then the evaluation of virtual water trade in sectors is followed, the results of which give a detailed quantification of net virtual water import of sectors, verifying that China is a net virtual water exporter concerning the whole national sectors, which is different from the previous studies. Finally, it is suggested that the sectors with high NWFI and volume of net virtual water export should be regarded as the priority of Chinese water-saving strategy.     

Variations in heavy metal contamination of stream water and groundwater affected by an abandoned lead–zinc mine in Korea

This study evaluated variations in heavy metal contamination of stream waters and groundwaters affected by an abandoned lead–zinc mine, where a rockfill dam for water storage will be built 11 km downstream. For these purposes, a total of 10 rounds of stream and groundwater samplings and subsequent chemical analyses were performed during 2002–2003. Results of an exploratory investigation of stream waters in 2000 indicated substantial contamination with heavy metals including zinc (Zn), iron (Fe) and arsenic (As) for at least 6 km downstream from the mine. Stream waters near the mine showed metal contamination as high as arsenic (As) 8,923 μg L⁻¹, copper (Cu) 616 μg L⁻¹, cadmium (Cd) 223 μg L⁻¹ and lead (Pb) 10,590 μg L⁻¹, which greatly exceeded the Korean stream water guidelines. Remediation focused on the mine tailing piles largely improved the stream water qualities. However, there have still been quality problems for the waters containing relatively high concentrations of As (6–174 μg L⁻¹), Cd (1–46 μg L⁻¹) and Pb (2–26 μg L⁻¹). Rainfall infiltration into the mine tailing piles resulted in an increase of heavy metals in the stream waters due to direct discharge of waste effluent, while dilution of the contaminated stream waters improved the water quality due to mixing with metal free rain waters. Levels of As, Cu and chromium (Cr) largely decreased after heavy rain but that of Pb was rather elevated. The stream waters were characterized by high concentrations of calcium (Ca) and sulfate (SO₄), which were derived from dissolution and leaching of carbonate and sulfide minerals. It was observed that the proportions of Ca and SO₄ increased while those of bicarbonate (HCO₃) and sodium and potassium (Na+K) decreased after a light rainfall event. Most interestingly, the reverse was generally detected for the groundwaters. The zinc, being the metal mined, was the most dominant heavy metal in the groundwaters (1758–10,550 μg L⁻¹) near the mine, which far exceeded the Korean standard of 1000 μg L⁻¹ for drinking water. The decreases in the heavy metals contents in the groundwaters associated with reduced rainfall were quite different from the increases observed for the stream waters, which is not clearly understood at this time and warrants further investigation.