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Characterization of the reactivity and chlorinated products of carbazole during aqueous chlorination
2017
Xu, Xiong | Wang, Donghong | Li, Chunmei | Feng, Hongru | Wang, Zijian
Carbazole in source water is a potential precursor for toxic chlorocarbazoles in drinking water when chlorine is used as a disinfection agent in drinking water treatment plants. However, the reactivity of carbazole and the specific structures and predominant analogues of chlorocarbazoles produced during aqueous chlorination remain unknown. In this study, the aqueous chlorination of carbazole was performed to characterize its reactivity and the chlorinated products. Chlorocarbazoles generated from carbazole were identified by a comprehensive two-dimensional gas chromatography-mass spectrometry method, and their molecular structures were predicted by the Fukui index of electrophilic attack, f−1(r). As a result, the comprehensive chlorination pathway of carbazole was extrapolated with a total of nine chlorocarbazoles identified, including two monochlorocarbazoles (3-chlorocarbazole and 1-chlorocarbazole), four dichlorocarbazoles (3,6-dichlorocarbazole, 1,6-dichlorocarbazole, 1,3-dichlorocarbazole and 1,8-dichlorocarbazole), two trichlorocarbazoles (1,3,6-trichlorocarbazole and 1,3,8-trichlorocarbazole) and one tetrachlorocarbazole (1,3,6,8-tetrachlorocarbazole). The f−1(r) value indicates that the C1, C3, C6 and C8 atoms of carbazole were the favored positions for electrophilic attack, with the C3 and C6 atoms being the predominant sites for chlorine substitution. 3-Chlorocarbazole, 3,6-dichlorocarbazole, 1,3,6-trichlorocarbazole and 1,3,6,8-tetrachlorocarbazole were the major analogues of each chlorocarbazole group; however, the production of minor analogues such as 1-chlorocarbazole and 1,6-dichlorocarbazole should not be overlooked. The chlorination of carbazole was a pseudo first order reaction with a reaction rate of 0.1836 nmol/(L· h) and half-life of 3.77 h (pH = 6.4, Cl2 = 4.7 mg/L), and the chlorination rate of carbazole was approximately 5 times faster than that of an known chlorination precursor pyrene. These results showed that Fukui index was efficacious to predict the chlorination sites of aromatic compounds, and that carbazole is readily transformed into toxic chlorocarbazoles in drinking water treatment plants that use chlorine as a disinfection agent.
Show more [+] Less [-]Mechanisms of cadmium accumulation (adsorption and absorption) by the freshwater bivalve Corbicula fluminea under hydrodynamic conditions
2016
Nan, Geng | Peifang, Wang | Zhao, Wang | Jun, Hou | Jin, Qian | Lingzhan, Miao
Many heavy metals in sediments and water have potential adverse effects on aquatic organisms such as Corbicula fluminea (O.F. Müller, 1774), a bivalve species frequently used as a biomonitor for metal pollution. Studies over the past decades examining the heavy metal uptake by C. fluminea, very few has investigated the effect of hydrodynamic conditions on accumulation of heavy metal by C. fluminea. Therefore, in this study, to investigate the mechanism of intracellular and extracellular accumulation of metal, individuals of C. fluminea were exposed to cadmium (Cd)-treated water under three different hydrodynamic conditions. These included exposures in two set ups: three rates of rotation (500, 350, 200 r/min) in beakers for 10 days, and then exposure to Cd-treated sediment under two naturally turbulent water conditions (14 cm/s and 3.2 cm/s) in experimental flumes for 23 days. Hydrodynamic force increased the burrowing rate but decreased the activity of C. fluminea. After 10 days of exposure, the extracellular concentrations of Cd in the tissues of C. fluminea in the sand group were significantly higher than that in the gravel groups. The intracellular and extracellular concentrations of Cd in the tissues of C. fluminea dramatically increased in the Cd-treated sediment test. Moreover, the concentration of the extracellular Cd adsorbed on the tissues of C. fluminea in the 14 cm/s and 3.2 cm/s groups was significantly higher than that in the control group, whereas the effect of hydrodynamic force on absorption of Cd by C. fluminea was not obvious. These results suggest that hydrodynamic condition plays an important role in extracellular accumulation of Cd by C. fluminea. In future study, when using C. fluminea to assess Cd pollution in aquatic environment, extracellular Cd adsorbed on the tissue should be removed to avoid the influence of hydrodynamics.
Show more [+] Less [-]Artificial light at night promotes bottom-up changes in a woodland food chain
2022
Lockett, Martin T. | Rasmussen, Rebecca | Arndt, Stefan K. | Hopkins, Gareth R. | Jones, Therésa M.
Artificial light at night (ALAN) is a recognised disruptor of biological function and ecological communities. Despite increasing research effort, we know little regarding the effect of ALAN on woody plants, including trees, or its indirect effects on their colonising invertebrates. These effects have the potential to disrupt woodland food webs by decreasing the productivity of invertebrates and their secretions, including honeydew and lerps, with cascading effects on other fauna. Here, we cultivated juvenile river red gums (Eucalyptus camaldulensis) for 40 weeks under experimentally manipulated light (ALAN) or naturally dark (control) conditions. To assess direct impacts on tree growth, we took multiple measures of growth at four time periods, and also measured physiological function, biomass and investment in semi-mature trees. To assess experimentally the direct and indirect (tree-mediated) impacts of ALAN on invertebrates, from 19 weeks onwards, we matched and mismatched trees with their original ALAN environments. We colonised trees with a common herbivore of E. camaldulensis, the red gum lerp psyllid (Glycaspis nr. brimblecombei) and then measured the effects of current and historic tree lighting treatment on the psyllid life cycle. Our data revealed direct effects of ALAN on tree morphology: E. camaldulensis trees exposed to ALAN shifted biomass allocation away from roots and into leaves and increased specific leaf area. However, while the intensity of ALAN was sufficient to promote photosynthesis (net carbon gain) at night, this did not translate into variation in tree water status or photosystem adaptation to dim night-time light for ALAN-exposed trees. We found some evidence that ALAN had broad-scale community effects—psyllid nymphs colonising ALAN trees produced more lerps—but we found no other direct or indirect impacts of ALAN on the psyllid life cycle. Our results suggest that trees exposed to ALAN may share morphological responses with trees under dim daylight conditions. Further, ALAN may have significant ‘bottom-up’ effects on Eucalyptus woodland food webs through both trees and herbivores, which may impact higher trophic levels including woodland birds, mammals and invertebrates.
Show more [+] Less [-]Direct and indirect impact of sewage sludge compost spreading on Quercus coccifera monoterpene emissions in a Mediterranean shrubland
2011
Olivier, Romain | Staudt, Michael | Lavoir, Anne-Violette | Ormeño, Elena | Rizvi, Syed Hussain | Baldy, Virginie | Rivoal, Annabelle | Greff, Stephane | Lecareux, Caroline | Fernandez, Catherine
Monoterpene emissions of Quercus coccifera L. were repeatedly measured during the two years following the spreading of a sewage sludge compost at rates of 50Mgha⁻¹ and 100Mgha⁻¹, in a twelve-year-old post-fire Mediterranean shrubland. We also monitored the patterns of change in soil and leaf nutrient content, plant water potential, chlorophyll fluorescence, and plant growth. Compost spreading resulted in weak changes in leaf nutrient content and plant water status, and therefore no significant effect on monoterpene emissions at leaf scale, except during one summer sampling, probably related to advanced leaf maturity with the highest compost rate. However, compost increased plant growth, particularly the leaf biomass. The results suggest that compost spreading in Mediterranean shrublands has no strong short-term effect on Q. coccifera monoterpene emissions at leaf level, but may indirectly increase volatile organic compound fluxes at the stand scale, which may contribute to regional ozone pollution.
Show more [+] Less [-]Physiology, morphology, and ozone uptake of leaves of black cherry seedlings, saplings, and canopy trees
1995
Fredericksen, T.S. | Joyce, B.J. | Skelly, J.M. | Steiner, K.C. | Kolb, T.E. | Kouterick, K.B. | Savage, J.E. | Snyder, K.R. (Environmental Resources Research Institute, 220 Forest Resource Laboratory, Pennsylvania State University, University Park, Pennsylvania 16802 (USA))
Ecophysiological Responses of Copaifera langsdorffii Grown in Mining Tailings Under Lower Water Availability
2021
de Pádua, Maxwell Pereira | Caetano, Alessander Lopes | Polo, Marcelo | Pasqual, Moacir | Pereira, Fabricio José
The objective of this work was to test the effect of water limitation on Copaifera langsdorffii Desf. cultivated in mining tailings from the dam rupture in Mariana City, Brazil. Plants were grown in the mining tailing and under two conditions: field capacity (FC) and 50% FC for 60 days. The effects of water restriction on growth, gas exchange, water potential, and leaf anatomy of C. langsdorffii were evaluated. The experimental design was completely randomized with two treatments and 15 replicates, and data was submitted to one-way ANOVA to p < 0.05. Mining tailings showed adequate nutrient levels and the presence of Al, Cd, Pb, and Cr as well as very small particles of 1.19 μm in diameter. The reduction in water availability promoted no changes in the shoot fresh weight, however, increased this parameter for the roots. In addition, water limitation increased plant investment in the root system while reduced biomass allocation to shoots. Lower water levels also increased the root length, number of leaves, and leaf area. However, both water potential and content were not changed by reduced water availability. Lower water levels also increased gas exchange parameters and chlorophyll content. In addition, 50% FC increased the stomatal length/width ratio and their size though no effect in stomatal density was found. Thus, Copaifera langsdorffii grows and thrives in mining tailings even under reduced water availability up to 50% FC showing potential for reforestation systems.
Show more [+] Less [-]Structural and Functional Determinants of Physiological Pliability in Kyllinga brevifolia Rottb. for Survival in Hyper-Saline Saltmarshes
2021
Mumtaz, Sahar | Hameed, Mansoor | Ahmad, Farooq | Ahmad, M. S. A. (Muhammad Sajid Aqeel) | Ahmad, Iftikhar | Ashraf, Muhammad | Saleem, Muhammad Hamzah
The role of morpho-anatomical adaptations of six Kyllinga brevifolia populations in successfully invading hyper-saline environments was investigated. Physiological and anatomical characteristics showed a high degree of plasticity indicating its adaptability potential to a variety of environmental conditions. The population from hyper-saline saltmarsh Sahianwala was exposed to physiological drought for a long time and its survival relied on the prevention of water loss attained by decreased stomatal density and area, lignin deposition in the inner and outer cortical region, especially outside vascular tissue. Larger cells of cortical storage parenchyma aided in water storage and wide metaxylem vessels in better conduction of solutes. Higher accumulation of shoot Ca²⁺ in this habitat protected neutralized the impact of the enhanced shoot and root Na⁺ ion uptake. Organic osmoprotectants like total free amino acid, proline, soluble proteins, and sugars accumulated in a higher quantity that contributed towards an osmotic adjustment in Sahianwala population. Population from seasonal inundation (Treemu Headworks) showed larger root aerenchyma to supply sufficient oxygen for respiration, broader xylem vessels for better water and nutrient conduction, and greater density of leaf stomata for better transpiration. Maximum shoot and root length, total leaf area, and water potential were observed in the least saline Chinyot population indicating its best growth potential in a slightly saline aquatic environment. Each population showed specific physiological and anatomical modifications to colonize their respective habitats.
Show more [+] Less [-]Long-Term Effects of Copper Mine Tailings on Surrounding Soils and Sclerophyllous Vegetation in Central Chile
2022
Espinoza, Sergio E. | Quiroz, Iván A. | Magni, Carlos R. | Yáñez, Marco A. | Martínez, Eduardo E.
This study analyzed the nutrients and metals concentrations of the surrounding soils and sclerophyllous vegetation of a tailing at the CODELCO–El Teniente copper mine in Central Chile. The content of metal, macro-, and micronutrients were analyzed in the soils outward from the tailing till 60-m distance at depths of 30, 60, and 90 cm, and in the foliage and stems of the native vegetation associated to the tailing. At plant level, we measured height, diameter, level of damage, and physiological attributes. Cu, Ni, Cr, and As were higher in the tailing, whereas soil Mn and Fe were higher at 60 m from the tailing. Soil K was higher at 30-cm depth, whereas Na was higher at 90-cm depth. Foliar Cu was higher in Acacia caven (40.5 mg kg⁻¹), whereas the levels of Cu and Zn in stems were higher in Quillaja saponaria (6.5 mg kg⁻¹ for Cu and 13.1 mg kg⁻¹ for Zn). As the values of water potential and quantum efficiency of the photosystem II averaged − 1.1 MPa and 0.73, respectively, these two species exhibited no physiological stress. Only Q. saponaria tended to increase the level of damage at higher distances from the tailing. A. caven and Q. saponaria exhibited foliar contents of Cu and Fe considered toxic (Cu from 18.5 to 40.5 and Fe from 298 to 407 mg kg⁻¹); however, both species were able to prosper at the limit of the tailing.
Show more [+] Less [-]Integrated Geophysical and Geochemical Assessment for the Comprehensive Study of the Groundwater
2016
Kotra, Krishna Kumar | Yedluri, Israel | Prasad, Surendra | Pasupureddi, Sowjanya
Groundwater studies often involve using any one of geophysical, geological, geochemical, or chemical data in the assessment of its characteristics. An integrated method in using all the above had been carried out for more comprehensive and confirmative assessments along the Thandava River basin, India. The geophysical data included the recording of the vertical electrical soundings by Schlumberger array configuration in 50 stations along the basin. Thirty soil samples and rainfall data of 5 years included the geological data. Chemical characterizations for 117 groundwater water samples were carried for two seasons. This study proposes the advantages besides delineating the approach in carrying integrated rather than mere single parameter-based speculative study. This correlative and computer modeling aided study led to an in-depth along with confirmative assessments on various geological, geophysical, and chemical characteristics of the groundwater along with the pollution status. Comprehensive details of groundwater like geomorphology, potential water zones, flow pattern, soil types, geochemical evolution of ions, chemical status, and suitability can be accessed by applying this type of integrated study. Graphical Abstract ᅟ
Show more [+] Less [-]Long-Term Annual and Seasonal Patterns of Acidic Deposition and Stream Water Quality in a Great Smoky Mountains High-Elevation Watershed
2011
Cai, Meijun | Schwartz, John S. | Robinson, R Bruce | Moore, Stephen E. | Kulp, Matt A.
The recovery potential of stream acidification from years of acidic deposition is dependent on biogeochemical processes and varies among different acid-sensitive regions. Studies that investigate long-term trends and seasonal variability of stream chemistry in the context of atmospheric deposition and watershed setting provide crucial assessments on governing biogeochemical processes. In this study, water chemistries were investigated in Noland Divide watershed (NDW), a high-elevation watershed in the Great Smoky Mountains National Park (GRSM) of the southern Appalachian region. Monitoring data from 1991 to 2007 for deposition and stream water chemistries were statistically analyzed for long-term trends and seasonal patterns by using Seasonal Kendall Tau tests. Precipitation declined over this study period, where throughfall (TF) declined significantly by 5.76 cm year−1. Precipitation patterns play a key role in the fate and transport of acid pollutants. On a monthly volume-weighted basis, pH of TF and wet deposition, and stream water did not significantly change over time remaining around 4.3, 4.7, and 5.8, respectively. Per NDW area, TF SO4 2- flux declined 356.16 eq year−1 and SO4 2- concentrations did not change significantly over time. Stream SO4 2- remained about 30 μeq L−1 exhibiting no long-term trends or seasonal patterns. SO4 2- retention was generally greater during drier months. TF monthly volume-weighted NH4 + and NO3 - concentrations significantly increased by 0.80 μeq L−1 year−1 and 1.24 μeq L−1 year−1, respectively. TF NH4 + fluxes increased by 95.76 eq year−1. Most of NH4 + was retained in the watershed, and NO3 - retention was much lower than NH4 +. Stream monthly volume-weighted NO3 - concentrations and fluxes significantly declined by 0.56 μeq L−1 year−1 and 139.56 eq year−1, respectively. Overall, in NDW, inorganic nitrogen was exported before 1999 and retained since then, presumably from forest regrowth after Frazer fir die-off in the 1970s from balsam wooly adelgid infestation. Stream export of NO3 - was greater during winter than summer months. During the period from 1999 to 2007, stream base cations did not exhibit significant changes, apparently regulated by soil supply. Statistical models predicting stream pH, ANC, SO4 2-, and NO3 - concentrations were largely correlated with stream discharge and number of dry days between precipitation events and SO4 2- deposition. Dependent on precipitation, governing biogeochemical processes in NDW appear to be SO4 2- adsorption, nitrification, and NO3 - forest uptake. This study provided essential information to aid the GRSM management for developing predictive models of the future water quality and potential impacts from climate change.
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