Simultaneous determination of seven anticoagulant rodenticides in agricultural products by gel permeation chromatography and liquid chromatography–tandem mass spectrometry

A sensitive and reliable method for the simultaneous determination of hydroxycoumarin-type (brodifacoum, bromadiolone, coumatetralyl, and warfarin) and indandione-type (chlorophacinone, diphacinone, and pindone) rodenticides in agricultural products by gel permeation chromatography (GPC) and liquid chromatography–tandem mass spectrometry (LC–MS/MS) was developed. The procedure involved extraction of the rodenticides from samples with acetone, followed by liquid–liquid partitioning with hexane/ethyl acetate (1:1, v/v) and 10% sodium chloride aqueous solution, then cleanup using GPC, and finally, analysis using LC–MS/MS. High recoveries from the GPC column were obtained for all rodenticides tested using a mobile phase of acetone/cyclohexane/triethylamine (400:1600:1, v/v/v). An ODS column, which contains low levels of metal impurities, gave satisfactory peak shapes for both hydroxycoumarin- and indandione-type rodenticides in the LC–MS/MS separation. The average recoveries of rodenticides from eight agricultural foods (apple, eggplant, cabbage, orange, potato, tomato, brown rice, and soybean) fortified at 0.0005–0.001 mg/kg ranged from 76 to 116%, except for bromadiolone in orange (53%) and diphacinone in soybean (54%), and the relative standard deviations ranged from 1 to 16%. The proposed method effectively removed interfering components, such as pigments and lipids, and showed high selectivity. In addition, the matrix effects were negligible for most of the rodenticide/food combinations. The results suggest that the proposed method is reliable and suitable for determining hydroxycoumarin- and indandione-type rodenticides in agricultural products.     

Taking the bait: species taking oral rabies vaccine baits intended for raccoons

Raccoon rabies in eastern USA is managed by strategically distributing oral rabies vaccine (ORV) baits. The attractiveness, palativity, density, and non-target species bait take affect ORV effectiveness. We examined raccoon and non-target species differences in investigating/removing fish-meal polymer and coated sachet baits applied to simulate two aerial bait distribution densities. Bait densities of 150 baits/km² and 75 baits/km² were evaluated, respectively, in zones expected to have high and low raccoon densities. Three primary non-target species visited baits: coyotes, white-tailed deer, and feral swine. The proportion of bait stations visited by raccoons during 1 week observation periods ranged from 50 to 70%, exceeding non-target species visitation. Raccoon take rates for visited baits averaged from 59 to 100%. Raccoon visitation was similar for both bait densities, indicating a proportionally greater quantity of baits were taken in the higher bait density zone. Coyote visitation rates ranged from 16 to 26%, with take rates for visited baits between 46 and 100%. Coyotes were expected to take baits intended for raccoons, because similar baits are applied to vaccinate coyotes. Deer regularly investigated but rarely took baits. Feral swine were in low abundance in the high bait density zone (higher human density) and visited ≤?1% of baits there but visited baits at frequencies similar to coyotes and deer in the low-density zone and were likely to take encountered baits (63–100%). Non-target bait consumption could be a concern in some circumstances for achieving sufficient raccoon sero-conversion rates.

     

Longevity of rodenticide bait pellets in a tropical environment following a rat eradication program

Invasive rodents (primarily Rattus spp.) are responsible for loss of biodiversity in island ecosystems worldwide. Large-scale rodenticide applications are typically used to eradicate rats and restore ecological communities. In tropical ecosystems, environmental conditions rapidly degrade baits and competition for baits by non-target animals can result in eradication failure. Our objective was to evaluate persistence of rodenticide baits during a rat eradication program on Palmyra Atoll; a remote tropical atoll with intense competition for resources by land crabs. Following aerial application, bait condition was monitored in four terrestrial environments and in the canopy foliage of coconut palms. Ten circular PVC hoops were fixed in place in each of Palmyra’s four primary terrestrial habitats and five rodenticide pellets were placed in each hoop. Five coconut palms were selected in three distinct regions of the atoll. One rodenticide pellet was placed on each of five palm fronds in each coconut palm. Fresh baits were placed in all monitoring locations after each broadcast bait application. Bait condition and survival was monitored for 7 days after the first bait application and 6 days after second application. Bait survival curves differed between applications at most monitoring sites, suggesting a decrease in overall rat activity as a result of rodenticide treatment. One terrestrial site showed near 100 % bait survival after both applications, likely due to low localized rat and crab densities. Median days to pellet disappearance were one and two days for the first and second application, respectively. Differences in survival curves were not detected in canopy sites between bait applications. Median days to pellet disappearance in canopy sites were 2 and 4 days for the first and second application, respectively. Frequent rainfall likely contributed to rapid degradation of bait pellets in coconut palm fronds.     

Assessing spatial variation and overall density of aerially broadcast toxic bait during a rat eradication on Palmyra Atoll

Baits containing brodifacoum rodenticide were aerially applied to eradicate invasive black rats from Palmyra Atoll, an important biodiversity center. Bait application must be sufficient to be effective, while minimizing environmental hazards by not exceeding designated label rates, prompting our bait density assessments for two aerial drops. With few physical or human resources on this remote, uninhabited atoll, assessments were particularly challenging, requiring observations within 30 min of aerial application to avoid bait loss to rats, crabs, or elements. We estimated bait density using quadrat sampling within 13 terrestrial sampling areas. We also sampled 10 tidal flat areas to assess inadvertent bait scatter into marine aquatic environments. Of particular value for challenging sampling circumstances, our quadrats had to be lightweight and durable, which we addressed by using widely available PVC hoops (“Hula Hoops”), the size of which was ideal for sampling purposes. At 77.5 and 78.7 kg/ha, overall bait densities were very near to the target densities of 80 and 75 kg/ha, respectively. However, considerable variability in bait densities existed among sampled areas, 8.6–178.2 and 31.4–129.5 kg/ha for the respective drops, respectively. Environmental, human, and equipment factors likely accounted for this variability. Tidal flat sampling revealed variable bait scatter into aquatic environments, from 0–46.3 kg/ha across the two drops. No differences were found in average bait densities among 1-, 4-, and 7-m distances from high tide lines. Our methods might broadly assist bait density (and other) surveys under challenging circumstances.     

Mercury species accumulation and trophic transfer in biological systems using the Almadén mining district (Ciudad Real,Spain) as a case of study

The impact of mercury (Hg) pollution in the terrestrial environments and the terrestrial food chains including the impact on human food consumption is still greatly under-investigated. In particular, studies including Hg speciation and detoxification strategies in terrestrial animals are almost non-existing, but these are key information with important implications for human beings. Therefore, in this work, we report on Hg species (inorganic mercury, iHg, and monomethylmercury, MeHg) distribution among terrestrial animal tissues obtained from a real-world Hg exposure scenario (Almadén mining district, Spain). Thus, we studied Hg species (iHg and MeHg) and total selenium (Se) content in liver and kidney of red deer (Cervus elaphus; n?=?41) and wild boar (Sus scrofa; n?=?16). Similar mercury species distribution was found for both red deer and wild boar. Major differences were found between tissues; thus, in kidney, iHg was clearly the predominant species (more than 81 %), while in liver, the species distribution was less homogeneous with a percentage of MeHg up to 46 % in some cases. Therefore, Hg accumulation and MeHg transfer were evident in terrestrial ecosystems. The interaction between total Se and Hg species has been evaluated by tissue and by animal species. Similar relationships were found in kidney for both Hg species in red deer and wild boar. However, in liver, there were differences between animals. The possible underlying mechanisms are discussed.     

Effects of sodium arsenate exposure on liver fatty acid profiles and oxidative stress in rats

The present study aimed to evaluate the effect of arsenic on liver fatty acids (FA) composition, hepatotoxicity and oxidative status markers in rats. Male rats were randomly devised to six groups (n?=?10 per group) and exposed to sodium arsenate at a dose of 1 and 10 mg/l for 45 and 90 days. Arsenate exposure is associated with significant changes in the FA composition in liver. A significant increase of saturated fatty acids (SFA) in all treated groups (p?<?0.01) and trans unsaturated fatty acids (trans UFA) in rats exposed both for short term for 10 mg/l (p?<?0.05) and long term for 1 and 10 mg/l (p?<?0.001) was observed. However, the cis UFA were significantly decreased in these groups (p?<?0.05). A markedly increase of indicator in cell membrane viscosity expressed as SFA/UFA was reported in the treated groups (p?<?0.001). A significant increase in the level of malondialdehyde by 38.3 % after 90 days of exposure at 10 mg/l was observed. Compared to control rats, significant liver damage was observed at 10 mg/l of arsenate by increasing plasma marker enzymes after 90 days. It is through the histological investigations in hepatic tissues of exposed rats that these damage effects of arsenate were confirmed. The antioxidant perturbations were observed to be more important at groups treated by the high dose (p?<?0.05). An increase in the level of protein carbonyls was observed in all treated groups (p?<?0.05). The present study provides evidence for a direct effect of arsenite on FA composition disturbance causing an increase of SFA and TFAs isomers, liver dysfunction and oxidative stress. Therefore, arsenate can lead to hepatic damage and propensity towards liver cancer.     

Sodium arsenate induce changes in fatty acids profiles and oxidative damage in kidney of rats

Six groups of rats (n?=?10 per group) were exposed to 1 and 10 mg/l of sodium arsenate for 45 and 90 days. Kidneys from treated groups exposed to arsenic showed higher levels of trans isomers of oleic and linoleic acids as trans C181n-9, trans C18:1n-11, and trans C18:2n-6 isomers. However, a significant decrease in eicosenoic (C20:1n-9) and arachidonic (C20:4n-6) acids were observed in treated rats. Moreover, the “Δ5 desaturase index” and the saturated/polyunsaturated fatty acids ratio were increased. There was a significant increase in the level of malondialdehyde at 10 mg/l of treatment and in the amount of conjugated dienes after 90 days (p?p?p?p?n-6 polyunsaturated fatty acids and leads to an increase in the trans FAs isomers. Therefore, FA-induced arsenate kidney damage could contribute to trigger kidney cancer.     

Rodenticides in British barn owls

Out of 145 Barn Owls found dead through accidents (66%), starvation (32%), shooting (2%) and poisoning (<1%), 10% contained residues of rodenticides, difenacoum or brodifacoum, in their livers. Difenacoum was in the range 0.005-0.106 microg g(-1) fresh weight, and brodifacoum was in the range 0.019-0.515 microg g(-1). Minimum levels of detection were about 0.005 microg g(-1) for both chemicals. Mice fed for 1 day on food containing difenacoum and brodifacoum died after 2-11 days. Within these mice residues were present at greater concentration in the liver than in the rest of the carcass. The mean mass of residue in a whole 35g mouse was estimated at 10.17 microg (range 4.73-20.65 microg) for difenacoum and 15.36 microg (range 8.07-26.55) for brodifacoum. Such poisoned mice were fed to Barn Owls for successive periods of 1, 3 and 6 days. All six owls fed on difenacoum-dosed mice survived all three treatments, in which up to an estimated 101.7 microg of difenacoum was consumed, and the coagulation times of their blood returned to near normal in less than 5-23 days. Four of the six owls fed on brodifacoum-dosed mice died 6-17 days after the 1-day treatment, but the survivors also survived the 3-day and 6-day treatments. Those that died had each eaten 3 mice, with a combined weight of about 105g and a total brodifacoum content of about 46.07 microg, which was equivalent to a dose of 0.150-0.182 mg kg(-1) of owl body weight. After death these owls had 0.63-1.25 micro g(-1) of brodifacoum in their livers. Blood from the survivors would not coagulate at 9 days post-treatment, but did so at 16 days in one bird and between 38 and 78 days in the other. It is concluded that: (1) Barn Owls in Britain are now widely exposed to second-generation rodenticides; (2) not all owls exposed to these chemicals are likely to receive a lethal dose; (3) brodifacoum is more toxic to owls than difenacoum; and (4) while there is yet no evidence that rodenticides have had any appreciable effect on Barn Owl populations in Britain, further monitoring of residue levels and population trends in desirable.     

Biosorption of arsenic in drinking water by submerged plant: Hydrilla verticilata

To evaluate the biosorption efficacy of submerged aquatic plant Hydrilla verticilata for arsenic uptake from drinking water. H. verticillata, a submerged aquatic plant was utilized successfully for arsenic uptake from aqueous solution. Batch studies with various parameters viz. pH, sorbent dose, contact time, initial metal ion concentration, and temperature were carried out. Data were utilized to plot Lagergren graph along with pseudo-second-order graphs for kinetic studies to estimate the removal efficacy and to determine the nature of reaction. Scanning electron microscopy (SEM) and Fourier transform infrared spectroscopy (FTIR) have been performed for characterization of metals on biomass. The study showed 96.35 % maximum absorption of arsenic by H. verticilata at initial concentration of 100 ppb with 0.5 g of biomass/100 ml for 5 h contact time at pH?6.0 with 150 rpm agitation rate. Data followed Langmuir isotherm showing sorption to be monolayer on homogeneous surface of biosorbent. The negative values of ΔG° indicated spontaneous nature; whereas ΔH° indicates exothermic nature of system and negative value of ?S° entropy change correspond to a decrease in the degree of freedom to the adsorbed species followed by pseudo-second-order adsorption kinetics. FTIR and SEM results showed apparent changes in functional group regions after metal chelation and the changes in surface morphology of biosorbent. This is a comparatively more effective, economic, easily available, and environmentally safe source for arsenic uptake from solution due to its high biosorption efficacy than other biosorbents already used.     

Isolation and characterization of novel phorate-degrading bacterial species from agricultural soil

Based upon 16S rDNA sequence homology, 15 phorate-degrading bacteria isolated from sugarcane field soils by selective enrichment were identified to be different species of Bacillus, Pseudomonas, Brevibacterium, and Staphylococcus. Relative phorate degradation in a mineral salt medium containing phorate (50 μg ml^?1) as sole carbon source established that all the bacterial species could actively degrade more than 97 % phorate during 21 days. Three of these species viz. Bacillus aerophilus strain IMBL 4.1, Brevibacterium frigoritolerans strain IMBL 2.1, and Pseudomonas fulva strain IMBL 5.1 were found to be most active phorate metabolizers, degrading more than 96 % phorate during 2 days and 100 % phorate during 13 days. Qualitative analysis of phorate residues by gas liquid chromatography revealed complete metabolization of phorate without detectable accumulation of any known phorate metabolites. Phorate degradation by these bacterial species did not follow the first-order kinetics except the P. fulva strain IMBL 5.1 with half-life period (t½) ranging between 0.40 and 5.47 days.     

Integrated Bacillus sp. immobilized cell reactor and Synechocystis sp. algal reactor for the treatment of tannery wastewater

The wastewater discharged from leather industries lack biodegradability due to the presence of xenobiotic compounds. The primary clarification and aerobic treatment in Bacillus sp. immobilized Chemo Autotrophic Activated Carbon Oxidation (CAACO) reactor removed considerable amount of pollution parameters. The residual untreated organics in the wastewater was further treated in algal batch reactor inoculated with Synechocystis sp. Sodium nitrate, K₂HPO₄, MgSO₄.7H₂O, NH₄Cl, CaCl₂·2H₂O, FeCl₃ (anhydrous), and thiamine hydrochloride, rice husk based activated carbon (RHAC), immobilization of Bacillus sp. in mesoporous activated carbon, sand filter of dimensions diameter, 6 cm and height, 30 cm; and the CAACO reactor of dimensions diameter, 5.5 cm and height, 30 cm with total volume 720 ml, and working volume of 356 ml. In the present investigation, the CAACO treated tannery wastewater was applied to Synechocystis sp. inoculated algal batch reactor of hydraulic residence time 24 h. The BOD₅, COD, and TOC of treated wastewater from algal batch reactor were 20?±?7, 167?±?29, and 78?±?16 mg/l respectively. The integrated CAACO system and Algal batch reactor was operated for 30 days and they accomplished a cumulative removal of BOD₅,COD, TOC, VFA and sulphide as 98 %, 95 %, 93 %, 86 %, and 100 %, respectively. The biokinetic constants for the growth of algae in the batch reactor were specific growth rate, 0.095(day^?1) and yield coefficient, 3.15 mg of algal biomass/mg of COD destructed. The degradation of xenobiotic compounds in the algal batch reactor was confirmed through HPLC and FT-IR techniques. The integrated CAACO–Algal reactor system established a credible reduction in pollution parameters in the tannery wastewater. The removal mechanism is mainly due to co-metabolism between algae and bacterial species and the organics were completely metabolized rather than by adsorption.     

PFAS profiles in three North Sea top predators: metabolic differences among species?

Profiles of seven compounds of perfluoro-alkyl substances (PFASs) were compared among three species of top predators from the Danish North Sea: the white-beaked dolphin (Lagenorhynchus albirostris), the harbor porpoise (Phocoena phocoena), and the harbor seal (Phoca vitulina). The seals had higher total burdens (757.8 ng g^?1 ww) than the dolphins (439.9 ng g^?1 ww) and the porpoises (355.8 ng g^?1 ww), probably a reflection of feeding closer to the shore and thus contamination sources. The most striking difference among the species was the relative contribution of perfluorooctanesulfonamide (PFOSA) to the profiles; the seals (0.1 %) had much lower levels than porpoises (8.3 %) and dolphins (26.0 %). In combination with the values obtained from the literature, this result indicates that Carnivora species including Pinnipedia have a much higher capacity of transforming PFOSA to perfluorooctane sulfonic acid (PFOS) than cetacean species. Another notable difference among the species was that the two smaller species (seals and porpoises) with supposedly higher metabolic rates had lower concentrations of the perfluorinated carboxylic acids, which are generally more easily excreted than perfluorinated sulfonamides. Species-specific characteristics should be recognized when PFAS contamination in marine mammals is investigated, for example, several previous studies of PFASs in cetaceans have not quantified PFOSA.     

Low doses of chlorpyrifos interfere with spermatogenesis of rats through reduction of sex hormones

Use of pesticides results in indirect effects on human health. We aimed to evaluate implications of toxicological effects of subchronic chlorpyrifos exposure on reproductive function in male rats. A total of 48 adult Wistar male rats were separated into four groups (n = 12). Animals were gavaged with 2.5 mg/kg (T1), 5 mg/kg (T2), or 10 mg/kg (T3) body weight of chlorpyrifos (CPF) or distilled water (control) daily for 30 days. Organ weights, epididymal sperm parameters, DNA integrity, sex hormonal (FHS and LH) levels, and alanine aminotransferase (ALT), aspartate aminotransferase (AST), gamma-glutamyl transferase (GGT), and creatinine concentrations were determined on day 31. Another two sets of (four groups/set; n = 10) animals were orally treated with the same doses of CPF, control animal groups were treated with distilled water only for 30 days, and fertility indices and blood plasma acetylcholine esterase (AchE) were determined on day 31. Exposure to CPF resulted in a significant (p < 0.05) decrease in weights of testis and epididymis. An increase in liver weight resulted in reduced sperm counts and sperm motility and an increase in sperm abnormalities. Significant reduction in serum testosterone (p < 0.01), luteinizing hormone (p < 0.05), and follicular stimulating hormone (p < 0.05) levels was evident in animals treated with the highest dose. A significant decrease in the number of viable implantation sites and pups was observed in female rats mated with the T3 (p < 0.01) and T2 (p < 0.05) males. The ALT, AST, GGT, and creatinine contents were significantly increased (p < 0.05 and p < 0.01, respectively) on CPF exposure. A significant (p < 0.01) reduction in blood plasma AchE enzyme was observed with the highest dose. Our results demonstrated that prolonged exposure of CPF induces spermatogenesis damage, possibly through interference with sex hormones and AchE enzyme resulting in reduction of fertility. Therefore, awareness programs on handling CPF (pesticides) to enhance safety warrant minimization of its hazards.     

Seasonal and annual dynamics of harmful algae and algal toxins revealed through weekly monitoring at two coastal ocean sites off southern California, USA

Reports of toxic harmful algal blooms (HABs) attributed to the diatom Pseudo-nitzschia spp. have been increasing in California during the last several decades. Whether this increase can be attributed to enhanced awareness and monitoring or to a dramatic upswing in the development of HAB events remains unresolved. Given these uncertainties, the ability to accurately and rapidly identify an emerging HAB event is of high importance. Monitoring of HAB species and other pertinent chemical/physical parameters at two piers in southern California, Newport and Redondo Beach, was used to investigate the development of a site-specific bloom definition for identifying emerging domoic acid (DA) events. Emphasis was given to abundances of the Pseudo-nitzschia seriata size category of Pseudo-nitzschia due to the prevalence of this size class in the region. P. seriata bloom thresholds were established for each location based on deviations from their respective long-term mean abundances, allowing the identification of major and minor blooms. Sixty-five percent of blooms identified at Newport Beach coincided with measurable DA concentrations, while 36 % of blooms at Redondo Beach coincided with measurable DA. Bloom definitions allowed for increased specificity in multiple regression analysis of environmental forcing factors significant to the presence of DA and P. seriata. The strongest relationship identified was between P. seriata abundances 2 weeks following upwelling events at Newport Beach.     

Short-time exposure to mono-n-butyl phthalate (MBP)-induced oxidative stress associated with DNA damage and the atrophy of the testis in pubertal rats

Phthalates are widely used as plasticizer in various consumer domestic products and are known to disturb the male reproductive function in rodents. This study investigated the involvement of oxidative stress and the atrophy of the testes in pubertal rats exposed to mono-n-butyl phthalate (MBP). Four-week-old pubertal male rats were separated into three groups. In group I, 21 rats were fed rat chow containing 2 % MBP for 3 days. In group II, 21 rats were fed rat chow containing 2 % MBP for 3 days and antioxidant vitamins C (250 mg/kg/day) and E (50 mg/kg/day) were injected daily. In group III, 21 rats were fed standard rat chow and used as controls. After 3 days, each testis was weighed and the germ cell development was evaluated using the Johnsen score. The urinary 8-hydroxy-2′-deoxyguanosine (8-OHdG) levels were measured as a biological marker of oxidative DNA damage. The mean testis weight was significantly lower for group I than groups II or III (p?<?0.05). The mean Johnsen score was significantly lower for group I than for groups II or III (p?<?0.05). Urinary 8-OHdG concentrations were higher in group I than in groups II or III. Short-time exposure to MBP may therefore induce oxidative DNA damage in rat testes, while antioxidant vitamins administered during exposure may protect against this stress.     

The impact of angler groundbait on benthic invertebrates and sediment respiration in a shallow eutrophic reservoir

In an experiment to determine the impact of angler baits, cereal or maggots were added to areas of sediment in a eutrophic reservoir at realistic rates, over a 12-week period. The densities of benthic invertebrate taxa were estimated before treatment, immediately after treatment, and, finally, after a 4-month recovery period. All taxa except the tubificid Limnodrilus hoffmeisteri were reduced in density by cereal baiting, the most sensitive being naidid worms and cladocerans. Recovery of the benthic community was not apparent after 4 months, although cyclopoid copepods were significantly more abundant in treated areas. Baiting with maggots had a qualitatively similar effect. Laboratory experiments to determine the rate of oxygen consumption by sediments treated with cereal bait suggest that demand for oxygen can be increased 100-fold by a single application of bait. It is suggested that this demand for oxygen could result in local deoxygenation under warm, calm conditions, and that this is the probable mechanism of the impact of cereal bait on benthic invertebrates.     

Determination of phenols and pharmaceuticals in municipal wastewaters from Polish treatment plants by ultrasound-assisted emulsification–microextraction followed by GC–MS

A method combining ultrasound-assisted emulsification–microextraction (USAEME) with gas chromatography–mass spectrometry (GC–MS) was developed for simultaneous determination of four acidic pharmaceuticals, ibuprofen, naproxen, ketoprofen, and diclofenac, as well as four phenols, 4-octylphenol, 4-n-nonylphenol, bisphenol A, and triclosan in municipal wastewaters. Conditions of extraction and simultaneous derivatization were optimized with respect to such aspects as type and volume of extraction solvent, volume of derivatization reagent, kind and amount of buffering salt, location of the test tube in the ultrasonic bath, and extraction time. The average correlation coefficient of the calibration curves was 0.9946. The LOD/(LOQ) values in influent and effluent wastewater were in the range of 0.002–0.121/(0.005–0.403) μg L^?1 and 0.002–0.828/(0.006–2.758) μg L^?1, respectively. Quantitative recoveries (≥94 %) and satisfactory precision (average RSD 8.2 %) were obtained. The optimized USAEME/GC–MS method was applied for determination of the considered pharmaceuticals and phenols in influents and treated effluents from nine Polish municipal wastewater treatment plants. The average concentration of acidic pharmaceuticals in influent and effluent wastewater were in the range of 0.06–551.96 μg L^?1 and 0.01–22.61 μg L^?1, respectively, while for phenols were in the range of 0.03–102.54 μg L^?1 and 0.02–10.84 μg L^?1, respectively. The removal efficiencies of the target compounds during purification process were between 84 and 99 %.     

Removal of arsenic species from water by batch and column operations on bagasse fly ash

Bagasse fly ash (BFA, a sugar industrial waste) was used as low-cost adsorbent for the uptake of arsenate and arsenite species from water. The optimum conditions for the removal of both species of arsenic were as follows: pH 7.0, concentration 50.0 μg/L, contact time 50.0 min, adsorbent dose 3.0 g/L, and temperature 20.0 °C, with 95.0 and 89.5 % removal of arsenate and arsenite, respectively. The Langmuir, Freundlich, Temkin, and Dubinin–Radushkevich adsorption isotherms were used to analyze the results. The results of these models indicated single-layer uniform adsorption on heterogeneous surface. Thermodynamic parameters, i.e., ΔG°, ΔH°, and ΔS°, were also calculated. At 20.0 to 30.0 °C, the values of ΔG° lie in the range of ?4,722.75 to ?4,878.82 and ?4,308.80 to ?4,451.73 while the values of ΔH° and ΔS° were ?149.90 and ?121.07, and 15.61 and 14.29 for arsenate and arsenite, respectively, indicating that adsorption is spontaneous and exothermic. Pseudo-first-order kinetics was followed. In column experiments, the adsorption decreased as the flow rate increased with the maximum removal of 98.9 and 95.6 % for arsenate and arsenite, respectively. The bed depth service time and Yoon and Nelson models were used to analyze the experimental data. The adsorption capacity (N _o) of BFA on column was 3.65 and 2.98 mg/cm³ for arsenate and arsenite, respectively. The developed system for the removal of arsenate and arsenite species is economic, rapid, and capable of working under natural conditions. It may be used for the removal of arsenic species from any contaminated water resources.     

Assessment of sewage sludge bioremediation at different hydraulic retention times using mixed fungal inoculation by liquid-state bioconversion

Sustainable, environmental friendly, and safe disposal of sewage treatment plant (STP) sludge is a global expectation. Bioremediation performance was examined at different hydraulic retention times (HRT) in 3–10 days and organic loading rates (OLR) at 0.66–7.81 g chemical oxygen demand (COD) per liter per day, with mixed filamentous fungal (Aspergillus niger and Penicillium corylophilum) inoculation by liquid-state bioconversion (LSB) technique as a continuous process in large-scale bioreactor. Encouraging results were monitored in treated sludge by LSB continuous process. The highest removal of total suspended solid (TSS), turbidity, and COD were achieved at 98, 99, and 93 %, respectively, at 10 days HRT compared to control. The minimum volatile suspended solid/suspended solid implies the quality of water, which was recorded 0.59 at 10 days and 0.72 at 3 days of HRT. In treated supernatant with 88 % protein removal at 10 days of HRT indicates a higher magnitude of purification of treated sludge. The specific resistance to filtration (SRF) quantifies the performance of dewaterability; it was recorded minimum 0.049 × 10¹² m kg^?1 at 10 days of HRT, which was equivalent to 97 % decrease of SRF. The lower OLR and higher HRT directly influenced the bioremediation and dewaterability of STP sludge in LSB process. The obtained findings imply encouraging message in continuing treatment of STP sludge, i.e., bioremediation of wastewater for environmental friendly disposal in near future.     

Temporal variation of volatile organic compounds and their major emission sources in Seoul, Korea

This study examines the characteristics of volatile organic compounds (VOCs) and their major emission sources at the Bulgwang site in Seoul, Korea. The annual levels of VOCs (96.2–121.1 ppb C) have shown a decreasing trend from 2004 to 2008. The most abundant component in Seoul was toluene, which accounted for over 23.5 % of the total VOCs on the parts per billion on a carbon basis, and the portions of alkanes with two to six carbons constituted the largest major lumped group, ranging from 40.1 to 48.4 % (45.3?±?3.7 %) of the total VOCs. Major components of the solvent (toluene, m/p-xylene, o-xylene, and ethylbenzene) showed high in daytime and summer and low in nighttime and winter due mainly to the variation of the ambient temperature. The species mostly emitted from gasoline vapor (i/n-butane, i/n-pentane, n-hexane, and 2-methylpentane) and vehicular exhaust (ethylene, acetylene, and benzene) showed bimodal peaks in the diurnal variation around the commuting hours because of the high traffic volume. For the 14 out of 15 highest concentration species, the weekend effect was only evident on Sundays because of the stepwise implementation of the 5-day work-week system. Principal components analysis (PCA) was applied in order to identify the sources of the 15 highest concentration VOCs and, as a result, three principal components such as gasoline vapor (48.9 %), vehicular exhaust (17.9 %), and evaporation of solvents (9.8 %) were obtained to explain a total of 76.6 % of the data variance. Most influential contributing sources at the sampling site were traffic-related ones although the use of solvent was the dominant emission source based on the official emission inventory.