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The influence of long-term fertilization on cadmium (Cd) accumulation in soil and its uptake by crops Full text
2014
Wang, Qingyun | Zhang, Jiabao | Zhao, Bingzi | Xin, Xiuli | Zhang, Congzhi | Zhang, Hailin
Continuous application of organic and inorganic fertilizers can affect soil and food quality with respect to heavy metal concentrations. The risk of cadmium (Cd) contamination in a long-term (over 20 years) experimental field in North China with an annual crop rotation of winter wheat and summer maize was investigated. The long-term experiment had a complete randomized block design with seven fertilizer treatments and four replications. The seven fertilizer treatments were (1) organic compost (OM), (2) half organic compost plus half chemical fertilizer (OM + NPK), (3) NPK fertilizer (NPK), (4–6) chemical fertilizers without one of the major nutrients (NP, PK, and NK), and (7) an unamended control (CK). Soil samples from 0 to 20 cm were collected in 1989, 1999, and 2009 to characterize Cd and other soil properties. During the past 20 years, various extents of Cd accumulation were observed in the soil, and the accumulation was mainly affected by atmospheric dry and wet deposition and fertilization. In 2009, the average Cd concentration in the soil was 148 ± 15 μg kg⁻¹and decreased in the order of NPK ≈ OM + NKP ≈ PK > NP ≈ NK > OM ≈ CK. Sequential extraction of Cd showed that the acid-soluble fraction (F1, 32 ± 7 %) and the residual fraction (F4, 31 ± 5 %) were the dominant fractions of Cd in the soil, followed by the reducible fraction (F2, 22 ± 5 %) and oxidizable fraction (F3, 15 ± 6 %). The acid-soluble Cd fraction in the soil and Cd accumulation in the crops increased with soil plant available K. Fraction F3 was increased by soil organic C (SOC) and crop yields, but SOC reduced the uptake of soil Cd by crops. The long-term P fertilization resulted in more Cd buildup in the soil than other treatments, but the uptake of Cd by crops was inhibited by the precipitation of Cd with phosphate in the soil. Although soil Cd was slightly increased over the 20 years of intensive crop production, both soil and grain/kernel Cd concentrations were still below the national standards for environmental and food safety.
Show more [+] Less [-]Effect of organic amendments on the mobility of trace elements in phytoremediated techno-soils: role of the humic substances Full text
2014
Hattab, N. | Soubrand, M. | Guégan, R. | Motelica-Heino, M. | Bourrat, X. | Faure, O. | Bouchardon, J. L.
The efficiency of aided phytostabilization using organic amendments such as ramial chipped wood (RCW) and composted sewage sludge (CSS) was studied on contaminated techno-soils, on nine experimental plots. The objective was to characterize the role of fulvic (FA) and humic acids (HA) on the mobilization of trace elements, specifically As, Cu, Mo, Pb and Zn. Results showed that the addition of CSS increased the total organic carbon and nitrogen content more than with RCW and as a result, the C/N ratio in the CSS soil was higher than in the RCW and non-amended (NE) soil, reflecting the high decomposition of soil organic matter in the CSS soil compared with the other soils. The RCW and CSS amendments increased the hydrogen index (HI) values and the oxygen index (OI) values compared with the NE soil, especially for the soil treated with CSS which contained more aliphatic than aromatic compounds. The addition of CSS to the techno-soil significantly increased the percentage of C ₒᵣg associated with the HA fractions compared with the RCW and NE soils. The soil amended with CSS showed the highest E ₄/E ₆ ratio and the lowest E ₂/E ₃ ratio of FA. Zn and As were more abundant in the FA fraction than in the HA fraction, whereas Pb, Cu and Mo were more associated to HA than to FA in the treated and untreated soils, which may explain the difference in their mobility and availability.
Show more [+] Less [-]Non-steroidal anti-inflammatory drugs in Indian rivers Full text
2014
Shanmugam, Govindaraj | Sampath, Srimurali | Selvaraj, Krishna Kumar | Larsson, D. G Joakim | Ramaswamy, Babu Rajendran
Pharmaceutical concentration data for Indian surface waters are currently scarce. Sewage often enters Indian rivers without prior treatment, and so previously reported environmental concentrations from regions with routinely implemented sewage treatment cannot simply be used to predict concentrations in Indian surface water. Improved knowledge of pharmaceutical concentrations in Indian waters would enable determination of potential risks posed to aquatic wildlife and human health in this region. The concentrations of five common non-steroidal anti-inflammatory drugs (NSAIDs; diclofenac, ketoprofen, naproxen, ibuprofen, and acetylsalicylic acid) were determined in surface waters from 27 locations of the Kaveri, Vellar, and Tamiraparani Rivers in southern India. The samples were extracted by solid-phase extraction and analyzed by GC-MS. The measured concentrations of four of the five drugs in this reconnaissance were relatively similar to those reported elsewhere (ND–200 ng/l); however, acetylsalicylic acid, the most readily degradable of the investigated drugs, was found at all sites and at considerably higher concentrations (up to 660 ng/l) than reported in European surface waters. This is the first report on the occurrence of NSAIDs in Indian rivers. The finding of elevated concentrations of acetylsalicylic acid is most likely a result of direct discharges of untreated sewage. Therefore, readily degradable pharmaceuticals may present larger concern in regions without consistent sewage treatment. Based on measured environmental concentrations, the risks of direct toxicity to aquatic wildlife and of humans consuming the water are discussed.
Show more [+] Less [-]NAPL migration and ecotoxicity of conventional and renewable fuels in accidental spill scenarios Full text
2014
Malk, Vuokko | Barreto Tejera, Eduardo | Simpanen, Suvi | Dahl, Mari | Mäkelä, Riikka | Häkkinen, Jani | Kiiski, Anna | Penttinen, Olli-Pekka
Fuels derived from non-petroleum renewable resources have raised interest due to their potential in replacing petroleum-based fuels, but information on their fate and effects in the terrestrial and aquatic environments in accidental spill scenario is limited. In this study, migration of four fuels (conventional diesel, conventional gasoline, renewable diesel NExBTL, and ethanol-blended gasoline RE85 containing maximum 85 % ethanol) as non-aqueous phase liquids (NAPL) in soil was demonstrated in a laboratory-scale experiment. Ecotoxicity data was produced for the same fuels. There was no significant difference in migration of conventional and renewable diesel, but gasoline migrated 1.5 times deeper and 7–9 times faster in sand than diesel. RE85 spread horizontally wider but not as deep (p < 0.05) as conventional gasoline. Conventional gasoline was the most toxic (lethal concentration [LC50] 20 mg/kg total hydrocarbon content [THC]) among the studied fuels in soil toxicity test with earthworm Eisenia fetida followed by ethanol-blended gasoline (LC50 1,643 mg/kg THC) and conventional diesel (LC50 2,432 mg/kg THC), although gasoline evaporated fast from soil. For comparison, the toxicity of the water-accommodated fractions (WAF) of the fuels was tested with water flea Daphnia magna and Vibrio fischeri, also demonstrating groundwater toxicity. The WAF of conventional gasoline and RE85 showed almost similar toxicity to both the aquatic test species. EC50 values of 1:10 (by volume) WAF were 9.9 %WAF (gasoline) and 9.3 %WAF (RE85) to D. magna and 9.3 %WAF (gasoline) and 12.3 %WAF (RE85) to V. fischeri. Low solubility decreased toxicity potential of conventional diesel in aquatic environment, but direct physical effects of oil phase pose a threat to organisms in nature. Renewable diesel NExBTL did not show clear toxicity to any test species.
Show more [+] Less [-]Electrochemical removal of synthetic textile dyes from aqueous solutions using Ti/Pt anode: role of dye structure Full text
2014
Araújo, Cynthia K. C. | Oliveira, Gustavo R. | Fernandes, Nedja S. | Zanta, Carmem L. P. S. | Castro, Suely Souza Leal | da Silva, Djalma R. | Martínez-Huitle, Carlos A.
In this work, the efficiency of electrochemical oxidation (EO) was investigated for removing a dye mixture containing Novacron Yellow (NY) and Remazol Red (RR) in aqueous solutions using platinum supported on titanium (Ti/Pt) as anode. Different current densities (20, 40 and 60 mA cm⁻²) and temperatures (25, 40 and 60 °C) were studied during electrochemical treatment. After that, the EO of each of these dyes was separately investigated. The EO of each of these dyes was performed, varying only the current density and keeping the same temperature (25 °C). The elimination of colour was monitored by UV-visible spectroscopy, and the degradation of organic compounds was analysed by means of chemical oxygen demand (COD). Data obtained from the analysis of the dye mixture showed that the EO process was effective in colour removal, in which more than 90 % was removed. In the case of COD removal, the application of a current density greater than 40 mA cm⁻²favoured the oxygen evolution reaction, and no complete oxidation was achieved. Regarding the analysis of individual anodic oxidation dyes, it was appreciated that the data for the NY were very close to the results obtained for the oxidation of the dye mixture while the RR dye achieved higher colour removal but lower COD elimination. These results suggest that the oxidation efficiency is dependent on the nature of the organic molecule, and it was confirmed by the intermediates identified.
Show more [+] Less [-]Low-cost adsorbent prepared from sewage sludge and corn stalk for the removal of COD in leachate Full text
2014
He, Ying | Liao, Xiaofeng | Liao, Li | Shu, Wei
Sewage sludge (SS) with corn stalk (CS) was used to prepare SS-based activated carbon (SAC) by pyrolysis with ZnCl₂. The effects of mixing ratio on surface area and pore size distribution, elemental composition, surface chemistry, and morphology were investigated. The results demonstrated that the addition of CS into SS samples improved the surface area (from 92 to 902 m²/g) and the microporosity (from 1.2 to 4.1 %) of the adsorbents and, therefore, enhancing the adsorption performance. The removal of leachate chemical oxygen demand (COD) was also determined. It was found that the COD removal rate reached 85 % at pH 4 with the SAC (90 wt% CS) dosage of 2 % (g/mL) and an adsorption time of 40 min. The adsorption experimental data were fitted by both Langmuir and Freundlich adsorption isotherms. Long-chain alkanes and refractory organics were found in raw leachate, but could be removed by SAC largely.
Show more [+] Less [-]Concentrations, atmospheric partitioning, and air–water/soil surface exchange of polychlorinated dibenzo-p-dioxin and dibenzofuran along the upper reaches of the Haihe River basin, North China Full text
2014
Nie, Zhiqiang | Die, Qingqi | Yang, Yufei | Tang, Zhenwu | Wang, Qi | Huang, Qifei
Polychlorinated dibenzo-p-dioxin and dibenzofuran (PCDD/PCDF) were overall measured and compared in ambient air, water, soils, and sediments along the upper reaches of the Haihe River of North China, so as to evaluate their concentrations, profiles, and to understand the processes of gas–particle partitioning and air–water/soil exchange. The following results were obtained: (1) The average concentrations (toxic equivalents, TEQs) of 2,3,7,8-PCDD/PCDF in air, water, sediment, and soil samples were 4,855 fg/m³, 9.5 pg/L, 99.2 pg/g dry weight (dw), and 56.4 pg/g (203 fg TEQ/m³, 0.46 pg TEQ/L, 2.2 pg TEQ/g dw, and 1.3 pg TEQ/g, respectively), respectively. (2) Although OCDF, 1,2,3,4,6,7,8-HpCDF, OCDD, and 1,2,3,4,6,7,8-HpCDD were the dominant congeners among four environmental sinks, obvious discrepancies of these congener and homologue patterns of PCDD/PCDF were observed still. (3) Significant linear correlations for PCDD/PCDF were observed between the gas–particle partition coefficient (Kₚ) and the subcooled liquid vapor pressure (PL⁰) and octanol–air partition coefficient (Kₒₐ). (4) Fugacity fraction values of air–water exchange indicated that most of PCDD/PCDF homologues were dominated by net volatilization from water into air. The low-chlorinated PCDD/PCDF (tetra- to hexa-) presented a strong net volatilization from the soil into air, while high-chlorinated PCDD/PCDF (hepta- to octa-) were mainly close to equilibrium for air–soil exchange.
Show more [+] Less [-]Sensitivity of hypogean and epigean freshwater copepods to agricultural pollutants Full text
2014
Di Lorenzo, T. | Di Marzio, W. D. | Sáenz, M. E. | Baratti, M. | Dedonno, A. A. | Iannucci, A. | Cannicci, S. | Messana, G. | Galassi, D. M. P.
Widespread pollution from agriculture is one of the major causes of the poor freshwater quality currently observed across Europe. Several studies have addressed the direct impact of agricultural pollutants on freshwater biota by means of laboratory bioassays; however, as far as copepod crustaceans are concerned, the ecotoxicological research is scarce for freshwater species and almost nonexistent for the hypogean ones. In this study, we conducted a comparative analysis of the available literature data on the sensitivity of freshwater copepods to agricultural pollutants. We also assessed the acute and chronic sensitivity of a hypogean and an epigean species, both belonging to the Crustacea Copepoda Cyclopoida Cyclopidae, to two N-fertilizers (urea and ammonium nitrate) and two herbicides (ARIANEᵀᴹII from Dow AgroSciences LLC, and Imazamox), widely used for cereal agriculture in Europe. According to the literature review, freshwater copepods are sensitive to a range of pesticides and N-fertilizers. Ecotoxicological studies on hypogean species of copepods account only one study. There are no standardized protocols available for acute and chronic toxicity tests for freshwater copepods, making comparisons about sensitivity difficult. From our experiments, ionized ammonia proved to be more toxic than the herbicide Imazamox, in both short and chronic bioassays. Urea was the less toxic chemical for both species. The hypogean species was more sensitive than the epigean one to all chemicals. For both species and for all tested chemicals, acute lethality and chronic lethality were induced at concentrations higher than the law limits of good water body quality in Europe, except for ionized ammonia, which provoked the chronic lethality of the hypogean species at a lower concentration. The hazardous concentration (HC) of un-ionized ammonia for 5 % of freshwater copepods, obtained by a species sensitivity distribution, was 92 μg l⁻¹, significantly lower than the HC computed for traditional test species from freshwater environments.
Show more [+] Less [-]High throughput and miniaturised systems for biodegradability assessments Full text
2014
Cregut, Mickael | Jouanneau, Sulivan | Brillet, François | Durand, Marie-José | Sweetlove, Cyril | Chenèble, Jean-Charles | L’Haridon, Jacques | Thouand, Gérald
The society demands safer products with a better ecological profile. Regulatory criteria have been developed to prevent risks for human health and the environment, for example, within the framework of the European regulation REACH (Regulation (EC) No 1907, 2006). This has driven industry to consider the development of high throughput screening methodologies for assessing chemical biodegradability. These new screening methodologies must be scalable for miniaturisation, reproducible and as reliable as existing procedures for enhanced biodegradability assessment. Here, we evaluate two alternative systems that can be scaled for high throughput screening and conveniently miniaturised to limit costs in comparison with traditional testing. These systems are based on two dyes as follows: an invasive fluorescent dyes that serves as a cellular activity marker (a resazurin-like dye reagent) and a noninvasive fluorescent oxygen optosensor dye (an optical sensor). The advantages and limitations of these platforms for biodegradability assessment are presented. Our results confirm the feasibility of these systems for evaluating and screening chemicals for ready biodegradability. The optosensor is a miniaturised version of a component already used in traditional ready biodegradability testing, whereas the resazurin dye offers an interesting new screening mechanism for chemical concentrations greater than 10 mg/l that are not amenable to traditional closed bottle tests. The use of these approaches allows generalisation of high throughput screening methodologies to meet the need of developing new compounds with a favourable ecological profile and also assessment for regulatory purpose.
Show more [+] Less [-]Biodegradation potential of cyano-based ionic liquid anions in a culture of Cupriavidus spp. and their in vitro enzymatic hydrolysis by nitrile hydratase Full text
2014
Neumann, Jennifer | Pawlik, Magdalena | Bryniok, Dieter | Thöming, Jorg | Stolte, Stefan
Biodegradation tests with bacteria from activated sludge revealed the probable persistence of cyano-based ionic liquid anions when these leave waste water treatment plants. A possible biological treatment using bacteria capable of biodegrading similar compounds, namely cyanide and cyano-complexes, was therefore examined. With these bacteria from the genera Cupriavidus, the ionic liquid anions B(CN)₄⁻, C(CN)₃⁻, N(CN)₂⁻combined with alkaline cations were tested in different growth media using ion chromatography for the examination of their primary biodegradability. However, no enhanced biodegradability of the tested cyano-based ionic liquids was observed. Therefore, an in vitro enzymatic hydrolysis test was additionally run showing that all tested ionic liquid (IL) anions can be hydrolysed to their corresponding amides by nitrile hydratase, but not by nitrilase under the experimental conditions. The biological stability of the cyano-based anions is an advantage in technological application, but the occurrence of enzymes that are able to hydrolyse the parent compound gives a new perspective on future cyano-based IL anion treatment.
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