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Evaluation of the measurement uncertainty in automated long-term sampling of PCDD/PCDFs
2013
Vicaretti, M. | D’Emilia, G. | Mosca, S. | Guerriero, E. | Rotatori, M.
Since the publication of the first version of European standard EN-1948 in 1996, long-term sampling equipment has been improved to a high standard for the sampling and analysis of polychlorodibenzo-p-dioxin (PCDD)/polychlorodibenzofuran (PCDF) emissions from industrial sources. The current automated PCDD/PCDF sampling systems enable to extend the measurement time from 6-8 h to 15-30 days in order to have data values better representative of the real pollutant emission of the plant in the long period. EN-1948:2006 is still the European technical reference standard for the determination of PCDD/PCDF from stationary source emissions. In this paper, a methodology to estimate the measurement uncertainty of long-term automated sampling is presented. The methodology has been tested on a set of high concentration sampling data resulting from a specific experience; it is proposed with the intent that it is to be applied on further similar studies and generalized. A comparison between short-term sampling data resulting from manual and automated parallel measurements has been considered also in order to verify the feasibility and usefulness of automated systems and to establish correlations between results of the two methods to use a manual method for calibration of automatic long-term one. The uncertainty components of the manual method are analyzed, following the requirements of EN-1948-3:2006, allowing to have a preliminary evaluation of the corresponding uncertainty components of the automated system. Then, a comparison between experimental data coming from parallel sampling campaigns carried out in short- and long-term sampling periods is realized. Long-term sampling is more reliable to monitor PCDD/PCDF emissions than occasional short-term sampling. Automated sampling systems can assure very useful emission data both in short and long sampling periods. Despite this, due to the different application of the long-term sampling systems, the automated results could not be directly compared with manual results, not even in terms of measurement uncertainty. This investigation focuses on both uncertainty and repeatability of the automated sampling method. The standard 20988, developed by Internarional Organization of Standardization (ISO) can be used to estimate the measurement uncertainty. The results confirm that the uncertainties of manual and automated methods are comparable. At the same time, it is not appropriate to consider the manual method as a reference for the evaluation of the uncertainty of the automated sampling system, due to the high variability of both systems.
Show more [+] Less [-]Strengths and weaknesses of microarray approaches to detect Pseudo-nitzschia species in the field
2013
Barra, Lucia | Ruggiero, Maria Valeria | Sarno, Diana | Montresor, Marina | Kooistra, Wiebe H. C. F.
The planktonic diatom genus Pseudo-nitzschia contains several genetically closely related species. Some of these can produce domoic acid, a potent neurotoxin. Thus, monitoring programs are needed to screen for the presence of these toxic species. Unfortunately, many are impossible to distinguish using light microscopy. Therefore, we assessed the applicability of microarray technology for detection of toxic and non-toxic Pseudo-nitzschia species in the Gulf of Naples (Mediterranean Sea). Here, 11 species have been detected, of which at least 5 are potentially toxic. A total of 49 genus- and species-specific DNA probes were designed in silico against the nuclear LSU and SSU rRNA of 19 species, and spotted on the microarray. The microarray was tested against total RNA of monoclonal cultures of eight species. Only three of the probes designed to be species-specific were indeed so within the limits of our experimental design. To assess the effectiveness of the microarray in detecting Pseudo-nitzschia species in environmental samples, we hybridized total RNA extracted from 11 seasonal plankton samples against microarray slides and compared the observed pattern with plankton counts in light microscopy and with expected hybridization patterns obtained with monoclonal cultures of the observed species. Presence of species in field samples generally resulted in signal patterns on the microarray as observed with RNA extracted from cultures of these species, but many a-specific signals appeared as well. Possible reasons for the numerous cross reactions are discussed. Calibration curves for Pseudo-nitzschia multistriata showed linear relationship between signal strength and cell number.
Show more [+] Less [-]Spatial distribution and ecotoxicological risk assessment of heavy metals in surface sediments of the southern Bohai Bay, China
2013
Hu, Bangqi | Li, Guogang | Li, Jun | Bi, Jianqiang | Zhao, Jingtao | Bu, Ruyuan
The concentrations of heavy metals (Cd, Cr, Cu, Ni, Pb, and Zn) and organic carbon in surface sediments, collected from the southern Bohai Bay, were determined to assess the potential contamination and determine the environmental risks associated with heavy metals. Results showed that heavy metal concentrations in the sediments generally met the China Marine Sediment Quality criteria. Both the ecotoxicological index and the potential ecological risk index suggest that the combined ecological risk of the six studied metals may be low, with the highest ecotoxicological potential zones located in the offshore area. The methods of enrichment factor and geoaccumulation index suggested that elevated concentrations of Cd, Cr, and Ni are presented in the region. Multivariate analysis also indicated that the lithogenic factor dominates the distribution of most part of the considered metals in the study area, whereas Cd and Cr are clearly influenced by anthropogenic inputs. The results of this study are likely to be a useful tool to authorities in charge of sustainable marine management.
Show more [+] Less [-]Immobilization of metal wastes by reaction with H₂S in anoxic basins : Concept and Elaboration
2013
Schuiling, R. D.
Metal wastes are produced in large quantities by a number of industries. Their disposal in isolated waste deposits is certain to cause many subsequent problems, because every material will sooner or later return to the geochemical cycle. The sealing of disposal sites usually starts to leak, often within a short time after the disposal site has been filled. The contained heavy metals are leached from the waste deposit and will contaminate the soil and the groundwater. It is evident that storage as metal sulfides in a permanently anoxic environment is the only safe way to handle metal wastes. The world's largest anoxic basin, the Black Sea, can serve as a georeactor. The metal wastes are sustainably transformed into harmless and immobile solids. These are incorporated in the lifeless bottom muds, where they are stored for millions of years.
Show more [+] Less [-]Development and modeling of a flat plate serpentine reactor for photocatalytic degradation of 17-ethinylestradiol
2013
Wang, Dawei | Li, Yi | Zhang, Wenlong | Wang, Qing | Wang, Peifang | Wang, Chao
A flat plate serpentine reactor modified from ultraviolet disinfection pool in municipal wastewater treatment plants was developed for the removal of 17-ethinylestradiol (EE2) for the first time. The photocatalytic degradation performance of EE2 was investigated in this serpentine reactor under different conditions such as inlet concentrations, loaded catalyst concentrations, incident radiations fluxes, and flow velocities. More than 98 % of EE2 was removed under certain conditions within 120 min. An integrated model including a six-flux adsorption–scattering model and a modified flow diffusion model was established to investigate the effect of radiation field and flow velocities, respectively. A satisfactory agreement was observed between the model simulation and experimental results, showing a potential for design and scale-up of photocatalytic reactor for wastewater treatment.
Show more [+] Less [-]Spatial and temporal trend of Chinese manure nutrient pollution and assimilation capacity of cropland and grassland
2013
Ouyang, Wei | Hao, Fanghua | Wei, Xinfeng | Huang, Moucai
Dynamics of livestock and poultry manure nutrient was analyzed at a provincial scale from 2002 to 2008. The nutrient capacity of 18 kinds of croplands and grasslands to assimilate nutrients was assessed in the same temporal–spatial scale. Manure nitrogen (N) had increased from 5.111 to 6.228 million tons (MT), while manure phosphorus (P) increased from 1.382 to 1.607 MT. Manure N and P share similar spatial patterns of yields, but proportion of specialized livestock husbandry and contribution of leading livestock categories (swine, cattle, cow, sheep, layer chicken, broiler chicken) were different. The nutrients generated from dominant seven provinces took more than about half of total manure N in China. After subtracting the chemical fertilizers, there were some manure nutrient capacities in western part of China. Risk analysis of manure nutrient pollution overload in eastern and southern parts of China was serious, which should restrict livestock's developments. Amount of chemical fertilizers applied should be reduced to make room for manure nutrients. For the sake of greenhouse effects, the emission of methane (CH₄) and nitrous oxide (NO ₓ ) emissions in China is serious for the global change, thus merits further statistics and studies. The spatial and temporal pattern of Chinese manure nutrient pollution from livestock and the assimilation capacity of cropland and grassland can provide useful information for policy development on Chinese soil environment and livestock.
Show more [+] Less [-]Short-chain chlorinated paraffins (SCCPs) in surface soil from a background area in China: occurrence, distribution, and congener profiles
2013
Wang, Xue-Tong | Zhang, Yuan | Miao, Yi | Ma, Ling-Ling | Li, Yuan-Cheng | Chang, Yue-Ya | Wu, Ming-Hong
Short-chain chlorinated paraffins (SCCPs) are extremely complex technical mixtures of polychlorinated n-alkanes with carbon chain lengths from C₁₀to C₁₃and chlorine content between 49 and 70 %. SCCPs are under consideration for inclusion in the Stockholm Convention on persistent organic pollutants. SCCPs have been used extensively in industrial production, but little is known about the pollution level in soil environment in China. In this study, levels and distribution of SCCPs in soil samples from Chongming Island were analyzed. Concentrations of total SCCPs in soil samples ranged from 0.42 to 420 ng g⁻¹, with a median of 9.6 ng g⁻¹. The ubiquitous occurrence of SCCPs in Chongming Island implied that long-range atmospheric transport and soil–air exchange may be the most important pathways for SCCP contamination in the background area. The localized SCCP contamination could be derived from an unidentified source. Hierarchical cluster analysis indicated that C₁₃- and C₁₁-congeners were predominant in most soils and C₁₀- and C₁₂-congeners dominated in the remaining soils. Cl₇- and Cl₈-congeners were on the average the most dominant chlorine congeners in nearly all soils. Principal component analysis suggested that the separation of even and odd carbon chain congeners occurred during long-range atmospheric transport and aging in soil in the study area.
Show more [+] Less [-]Impact of chronic exposure to low doses of chlorpyrifos on the intestinal microbiota in the Simulator of the Human Intestinal Microbial Ecosystem (SHIME®) and in the rat
2013
Joly, Claire | Gay-Quéheillard, Jérôme | Léké, André | Chardon, Karen | Delanaud, Stéphane | Bach, Véronique | Khorsi-Cauet, Hafida
The impact of the insecticide chlorpyrifos (CPF) on the mammalian digestive system has been poorly described. The present study aimed at evaluating the effect of chronic, low-dose exposure to CPF on the composition of the gut microbiota in a Simulator of the Human Intestinal Microbial Ecosystem: the SHIME® and in rats. The SHIME® comprises six reactor vessels (stomach to colon). The colonic segments were inoculated with feces from healthy humans. Then, the simulator was exposed to a daily dose of 1 mg of CPF for 30 days. The changes over time in the populations of bacteria were examined at different time points: prior to pesticide exposure (as a control) and after exposure. In parallel, pregnant rats were gavaged daily with 1 mg/kg of CPF (or vehicle) until the pups were weaned. Next, the rats were gavaged with same dose of CPF until 60 days of age (adulthood). Then, samples of different parts of the digestive tract were collected under sterile conditions for microbiological assessment. Chronic, low-dose exposure to CPF in the SHIME® and in the rat was found to induce dysbiosis in the microbial community with, in particular, proliferation of subpopulations of some strains and a decrease in the numbers of others bacteria. In compliance with European guidelines, the use of the SHIME® in vitro tool would help to (1) elucidate the final health effect of toxic agents and (2) minimize (though not fully replace) animal testing. Indeed, certain parameters would still have to be studied further in vivo.
Show more [+] Less [-]Treatment of industrial wastewater containing Congo Red and Naphthol Green B using low-cost adsorbent
2013
Attallah, M. F. | Ahmed, I. M. | Hamed, Mostafa M.
The present work investigates the potential use of metal hydroxides sludge (MHS) generated from hot dipping galvanizing plant for adsorption of Congo Red and Naphthol Green B dyes from aqueous solutions. Characterization of MHS included infrared and X-ray fluorescence analysis. The effect of shaking time, initial dye concentration, temperature, adsorbent dosage and pH has been investigated. The results of adsorption experiments indicate that the maximum capacity of Congo Red and Naphthol Green B dyes at equilibrium (q ₑ) and percentage of removal at pH 6 are 40 mg/g, 93 %, and 10 mg/g, 52 %, respectively. Some kinetic models were used to illustrate the adsorption process of Congo Red and Naphthol Green B dyes using MHS waste. Thermodynamic parameters such as (ΔG, ΔS, and ΔH) were also determined.
Show more [+] Less [-]Assessment of plant-driven uptake and translocation of clofibric acid by Scirpus validus
2013
Zhang, Dong Qing | Gersberg, Richard M. | Hua, Tao | Zhu, Junfei | Ng, Wun Jern | Tan, Soon Keat
Pharmaceutical compounds are now considered as emerging contaminants of environmental concern. The overall objective of this study was to evaluate the uptake and translocation of clofibric acid (CA) by the macrophyte Scirpus validus growing hydroponically. A set of the three replicates was established for each exposure time and for each CA concentration. Plants were grown in 4 L vessels (four plants per vessel corresponding to the three exposure period studies, i.e., 7, 14, 18, and 21 days) which contained an aerated modified Hoagland nutrient solution that was spiked with CA at concentrations of 0.5, 1.0, and 2.0 mg L⁻¹. At each exposure period, CA concentration was measured in the nutrient solutions. A sea sand disruption method was employed for the extraction of CA from plant tissues. The determination of the pharmaceutical concentration was carried out using solid phase extraction (SPE) followed by chromatographic analysis. The quantification of CA concentrations in both nutrient solutions (after SPE) and plant tissues (after extraction) was conducted by chromatographic analysis. CA concentrations of 5.4–26.8 μg g⁻¹(fresh weight) were detected in the roots and 7.2–34.6 μg g⁻¹(fresh weight) in the shoots after 21 days. Mass balance calculations showed that S. validus uptake alone accounted for a significant contribution (6–13 % for the roots and 22–49 % for the shoots) of the total loss of CA. The bioaccumulation factors (BAFs) based on fresh weight for the roots ranged from 6.6 to 23.2, while values for the shoots ranged from 9.5 to 32.1. All the BAFs for the shoots were greater than those in the roots, implying that CA has greater tendency to be translocated to the shoots, rather than the roots of S. validus. All the shoot-to-root concentration ratios were more than 1, denoting that the shoots of S. validus do preferentially accumulate CA. We demonstrated that CA can be actively taken up, subsequently translocated and accumulated by aboveground tissues of S. validus. Since S. validus could account for the removal of 28–62 % of the total mass loss of CA from the system, such phytoremediation technology has great potential for the removal of pharmaceuticals such as CA from inflowing waters.
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