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Ott, R. F. ; Gallen, S. F. ; Caves Rugenstein, J. K. ; Ivy-Ochs, S. ; Helman, D. ; Fassoulas, C. ; Vockenhuber, C. ; Christl, M. ; Willett, S. D. Chemical Versus Mechanical Denudation in Meta-Clastic and Carbonate Bedrock Catchments on Crete, Greece, and Mechanisms for Steep and High Carbonate Topography. Journal of Geophysical Research: Earth Surface 2019, 124. Publisher's VersionAbstract
Abstract On Crete—as is common elsewhere in the Mediterranean—carbonate massifs form high mountain ranges whereas topography is lower in areas with meta-clastic rocks. This observation suggests that differences in denudational processes between carbonate-rich rocks and quartzofeldspathic units impart a fundamental control on landscape evolution. Here we present new cosmogenic basin-average denudation rate measurements from both 10Be and 36Cl in meta-clastic and carbonate bedrock catchments, respectively, to assess relationships between denudation rates, processes, and topographic form. We compare total denudation rates to dissolution rates calculated from 49 new and previously published water samples. Basin-average denudation rates of meta-clastic and carbonate catchments are similar, with mean values of  0.10 mm/a and  0.13 mm/a, respectively. The contribution of dissolution to total denudation rate was <10% in the one measured meta-clastic catchment, and  40% for carbonate catchments ( 0.05 mm/a), suggesting the dominance of physical over chemical weathering at the catchment scale in both rock types. Water mass-balance calculations for three carbonate catchments suggests 40–90% of surface runoff is lost to groundwater. To explore the impact of dissolution and infiltration to groundwater on relief, we develop a numerical model for carbonate denudation. We find that dissolution modifies the river profile channel steepness, and infiltration changes the fluvial response time to external forcing. Furthermore, we show that infiltration of surface runoff to groundwater in karst regions is an efficient way to steepen topography and generate the dramatic relief in carbonates observed throughout Crete and the Mediterranean.
Brienza, M. ; Nir, S. ; Plantard, G. ; Goetz, V. ; Chiron, S. Combining micelle-clay sorption to solar photo-Fenton processes for domestic wastewater treatment. Environmental Science and Pollution Research 2019, 26, 18971-18978. Publisher's VersionAbstract
A tertiary treatment of effluent from a biological domestic wastewater treatment plant was tested by combining filtration and solar photocatalysis. Adsorption was carried out by a sequence of two column filters, the first one filled with granular activated carbon (GAC) and the second one with granulated nano-composite of micelle-montmorillonite mixed with sand (20:100, w/w). The applied solar advanced oxidation process was homogeneous photo-Fenton photocatalysis using peroxymonosulfate (PMS) as oxidant agent. This combination of simple, robust, and low-cost technologies aimed to ensure water disinfection and emerging contaminants (ECs, mainly pharmaceuticals) removal. The filtration step showed good performances in removing dissolved organic matter and practically removing all bacteria such as Escherichia coli and Enterococcus faecalis from the secondary treated water. Solar advanced oxidation processes were efficient in elimination of trace levels of ECs. The final effluent presented an improved sanitary level with acceptable chemical and biological characteristics for irrigation. © 2018, Springer-Verlag GmbH Germany, part of Springer Nature.
Olk, D. C. ; Bloom, P. R. ; Perdue, E. M. ; McKnight, D. M. ; Chen, Y. ; Farenhorst, A. ; Senesi, N. ; Chin, Y. - P. ; Schmitt-Kopplin, P. ; Hertkorn, N. ; et al. Environmental and agricultural relevance of humic fractions extracted by alkali from soils and natural waters. Journal of Environmental Quality 2019, 48, 217-232. Publisher's VersionAbstract
To study the structure and function of soil organic matter, soil scientists have performed alkali extractions for soil humic acid (HA) and fulvic acid (FA) fractions for more than 200 years. Over the last few decades aquatic scientists have used similar fractions of dissolved organic matter, extracted by resin adsorption followed by alkali desorption. Critics have claimed that alkali-extractable fractions are laboratory artifacts, hence unsuitable for studying natural organic matter structure and function in field conditions. In response, this review first addresses specific conceptual concerns about humic fractions. Then we discuss several case studies in which HA and FA were extracted from soils, waters, and organic materials to address meaningful problems across diverse research settings. Specifically, one case study demonstrated the importance of humic substances for understanding transport and bioavailability of persistent organic pollutants. An understanding of metal binding sites in FA and HA proved essential to accurately model metal ion behavior in soil and water. In landscape-based studies, pesticides were preferentially bound to HA, reducing their mobility. Compost maturity and acceptability of other organic waste for land application were well evaluated by properties of HA extracted from these materials. A young humic fraction helped understand N cycling in paddy rice (Oryza sativa L.) soils, leading to improved rice management. The HA and FA fractions accurately represent natural organic matter across multiple environments, source materials, and research objectives. Studying them can help resolve important scientific and practical issues. Copyright © American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America.
Ashkenazi, E. ; Chen, Y. ; Avni, Y. Olive tree survival and adaptation to the harsh growing conditions in the arid desert environment of the Negev Highlands, Southern Israel. Israel Journal of Plant Sciences 2019, 65, 147-152. Publisher's VersionAbstract
Twenty-three olive trees were found to grow in traditional orchard sites in the Negev Highlands desert, southern Israel. Their location was marked on maps, and their growth, morphology, biology, preservation and survival was monitored. Some of them are presently maintained by the Bedouin population of the Negev, whereas others seemed to have survived from earlier periods. The average annual rainfall in this region is 90-130 mm. Most of the orchards were deliberately planted in preexisting agricultural plots, built during the Byzantine and Early Muslim era (3rd-8th centuries CE). They were irrigated by harvesting runoff water. The Byzantine era was the most populated period in the Negev Highlands, when wine and olive oil were the main horticultural products. A variety of domesticated fruit trees are found in the present abandoned orchards: olive, fig, grapevine, pomegranate, almond, date palm, carob, pistachio and bitter orange. The trees have not been artificially irrigated for at least seven decades. Nevertheless, most of them continue to flourish and bear fruit. We focused on understanding the abandoned olive trees' survival and adaptation mechanisms. Olive trees growing was a favorite crop to Byzantine farmers due to the significant economic value of olive oil and good adaptation to the environmental conditions in the Negev Highlands. © Koninklijke Brill NV, Leiden, 2018.
Olk, D. C. ; Bloom, P. R. ; De Nobili, M. ; Chen, Y. ; McKnight, D. M. ; Wells, M. J. M. ; Weber, J. Using humic fractions to understand natural organic matter processes in soil and water: Selected studies and applications. Journal of Environmental Quality 2019, 48, 1633-1643. Publisher's VersionAbstract
Natural organic matter (NOM) plays key environmental roles in both aquatic and soil systems. A long-standing approach for evaluating NOM composition and activity is to extract soils with alkali solutions to obtain humic substances, namely humic acids (HA), and fulvic acids (FA), or to briefly expose isolated fractions of dissolved organic matter to alkali. Critics have claimed these methods create laboratory artifacts and are thus unsuitable for studying NOM behavior in field conditions. In response, we describe case studies in which humic fractions were analyzed to identify significant processes in environmental or agricultural issues. Specifically, humic fractions played a key role in maintaining toxic levels of arsenic (As) in drinking water supplies in South and Southeast Asia. Elsewhere, binding reactions of FA and HA with prions were shown to provide a plausible mechanism for variable persistence of prion infectivity across soil types. Humic substances were also shown to enhance iron (Fe) uptake by plants in solution culture and field conditions. Their specific binding sites for mercury (Hg) as determined in laboratory conditions enabled accurate modeling of soil Hg binding under varying conditions. A young HA fraction reproduced in controlled conditions the capacity of animal manure to maintain potassium (K) availability in strongly K-fixing field soils, leading to development of a commercially successful humic-K fertilizer. Humic fractions accurately represented NOM across multiple settings and research objectives while providing novel opportunities for advanced analyses. The study of humic fractions has helped resolve scientific and practical issues in aquatic and soil systems. © 2019 The Author(s).
Ashkenazi, E. ; Avni, Y. ; Chen, Y. The vitality of fruit trees in ancient Bedouin orchards in the Arid Negev Highlands (Israel): Implications of climatic change and environmental stability. Quaternary International 2019. Publisher's VersionAbstract
Thirty-seven sites with fruit tree orchards were found in the arid Negev Highlands of southern Israel. A variety of domesticated fruit trees were planted in these orchards, including date palm, fig, olive, pomegranate, almond, carob, pistachio, grapevine and bitter orange. The orchards were irrigated only by runoff water accumulating in runoff-harvesting systems built during the Byzantine and Early Muslim eras, some 1000–1500 years ago, which, despite their antiquity, are still vivid and occasionally fruit bearing today. The oldest olive trees seem to be direct descendants of trees planted during Byzantine times, whereas the youngest trees were planted by the Bedouin population of the Negev Highlands in the last few decades. The fact that the Bedouin population, with very little experience in agriculture, has succeeded to cultivate a large variety of fruit trees in the present harsh arid climate utilizing the historical agricultural installations has important environmental implications. It indicates that the original builders of the desert agriculture systems were highly sophisticated in transforming desert soil into arable land. However, this was achieved through hard labor, involving the construction of a vast number of stone dams and agricultural terraces to divert channels, and the clearing of rocky surfaces. This huge effort indicates that the climate and environment prevailing during the Byzantine–Early Muslim eras was equally harsh and arid; otherwise, the invested labor would not have been justified. We conclude that the Byzantine farmers, with their greater agricultural experience and long heritage in dry land agriculture, have achieved greater success than today Bedouin population, at cultivating of fruit trees under the harsh conditions of the Negev Highlands. Therefore we deduce that the ancient desert agriculture was not the outcome of better climate; rather, the climate prevailing during the relevant historical times was probably dry and harsh, much like today. The fact that the Bedouin population in that geograghical area is cultivating orchards utilizing the same constructions, and technologies indicates that the present environmental and climatic conditions were are suitable for practicing desert agriculture and have hardly changed since the Byzantine era. © 2019 Elsevier Ltd and INQUA
Dalal, A. ; Bourstein, R. ; Haish, N. ; Shenhar, I. ; Wallach, R. ; Moshelion, M. Dynamic physiological phenotyping of drought-stressed pepper plants treated with “productivity-enhancing” and “survivability-enhancing” biostimulants. Frontiers in Plant Science 2019, 10. Publisher's VersionAbstract
The improvement of crop productivity under abiotic stress is one of the biggest challenges faced by the agricultural scientific community. Despite extensive research, the research-to-commercial transfer rate of abiotic stress-resistant crops remains very low. This is mainly due to the complexity of genotype × environment interactions and in particular, the ability to quantify the dynamic plant physiological response profile to a dynamic environment. Most existing phenotyping facilities collect information using robotics and automated image acquisition and analysis. However, their ability to directly measure the physiological properties of the whole plant is limited. We demonstrate a high-throughput functional phenotyping system (HFPS) that enables comparing plants’ dynamic responses to different ambient conditions in dynamic environments due to its direct and simultaneous measurement of yield-related physiological traits of plants under several treatments. The system is designed as one-to-one (1:1) plant–[sensors+controller] units, i.e., each individual plant has its own personalized sensor, controller and irrigation valves that enable (i) monitoring water-relation kinetics of each plant–environment response throughout the plant’s life cycle with high spatiotemporal resolution, (ii) a truly randomized experimental design due to multiple independent treatment scenarios for every plant, and (iii) reduction of artificial ambient perturbations due to the immobility of the plants or other objects. In addition, we propose two new resilience-quantifying-related traits that can also be phenotyped using the HFPS: transpiration recovery rate and night water reabsorption. We use the HFPS to screen the effects of two commercial biostimulants (a seaweed extract –ICL-SW, and a metabolite formula – ICL-NewFo1) on Capsicum annuum under different irrigation regimes. Biostimulants are considered an alternative approach to improving crop productivity. However, their complex mode of action necessitates cost-effective pre-field phenotyping. The combination of two types of treatment (biostimulants and drought) enabled us to evaluate the precision and resolution of the system in investigating the effect of biostimulants on drought tolerance. We analyze and discuss plant behavior at different stages, and assess the penalty and trade-off between productivity and resilience. In this test case, we suggest a protocol for the screening of biostimulants’ physiological mechanisms of action. © 2019 Dalal, Bourstein, Haish, Shenhar, Wallach and Moshelion.
Kessouri, P. ; Furman, A. ; Huisman, J. A. ; Martin, T. ; Mellage, A. ; Ntarlagiannis, D. ; Bücker, M. ; Ehosioke, S. ; Fernandez, P. ; Flores-Orozco, A. ; et al. Induced polarization applied to biogeophysics: recent advances and future prospects. Near Surface Geophysics 2019, 17, 595-621. Publisher's VersionAbstract
This paper provides an update on the fast-evolving field of the induced polarization method applied to biogeophysics. It emphasizes recent advances in the understanding of the induced polarization signals stemming from biological materials and their activity, points out new developments and applications, and identifies existing knowledge gaps. The focus of this review is on the application of induced polarization to study living organisms: soil microorganisms and plants (both roots and stems). We first discuss observed links between the induced polarization signal and microbial cell structure, activity and biofilm formation. We provide an up-to-date conceptual model of the electrical behaviour of the microbial cells and biofilms under the influence of an external electrical field. We also review the latest biogeophysical studies, including work on hydrocarbon biodegradation, contaminant sequestration, soil strengthening and peatland characterization. We then elaborate on the induced polarization signature of the plant-root zone, relying on a conceptual model for the generation of biogeophysical signals from a plant-root cell. First laboratory experiments show that single roots and root system are highly polarizable. They also present encouraging results for imaging root systems embedded in a medium, and gaining information on the mass density distribution, the structure or the physiological characteristics of root systems. In addition, we highlight the application of induced polarization to characterize wood and tree structures through tomography of the stem. Finally, we discuss up- and down-scaling between laboratory and field studies, as well as joint interpretation of induced polarization and other environmental data. We emphasize the need for intermediate-scale studies and the benefits of using induced polarization as a time-lapse monitoring method. We conclude with the promising integration of induced polarization in interdisciplinary mechanistic models to better understand and quantify subsurface biogeochemical processes. © 2019 European Association of Geoscientists & Engineers
Kuzma, T. ; Schwartz, N. ; Smith, R. H. Spectral induced polarization of roots in hydroponic solution and soil. In 2018 SEG International Exposition and Annual Meeting, SEG 2018; 2018 SEG International Exposition and Annual Meeting, SEG 2018; 2019; pp. 2566-2570. Publisher's VersionAbstract
Monitoring plant root within the subsurface is important but challenging, due to the opacity of the soil. Recently, it was demonstrated that the spectral induced polarization (SIP) method has the potential to image roots, but the mechanisms governing the SIP signal of roots remain poorly understood. Here, we present a numerical model and experimental setup that was designed to establish relationships between root properties and the SIP response and to enhance our understanding of the polarization mechanisms of roots. Our preliminary results show a positive correlation between root mass and quadrature conductivity in nutrient solution. Surprisingly, a negative relation was found in soil. Overall, the results from this study further demonstrate the potential of the SIP method to monitor roots. © 2018 SEG.
Levy, L. ; Izbitski, A. ; Mishael, Y. G. Enhanced gemfibrozil removal from treated wastewater by designed “loopy” clay-polycation sorbents: Effect of diclofenac and effluent organic matter. Applied Clay Science 2019, 182. Publisher's VersionAbstract
Novel clay-polymer nano composites (CPN) were designed for the removal of gemfibrozil (GFZ) from treated wastewater (TWW). The pyridine groups of poly-4-vinylpyridine (PVP) were 100% or 50% (randomly) substituted with bromo-ethanol to synthesize OH100PVP and OH50PVP, respectively. The effect of polymer charge density and loading on the structures of the CPNs, were investigated. At high polymer loadings OH100PVP adsorbed mainly in a flat configuration, as trains, while OH50PVP adsorbed in a more extended configuration, as loops and tails. The affinity and capacity of GFZ towards the OH50PVP CPN was significantly higher than to the OH100PVP, despite the latter's higher charge density, this high affinity of GFZ was explained in terms of more accessible adsorption sites due to the extended configuration of OH50PVP. The kinetics of GFZ removal from TWW by the CPN and by granulated activated carbon (GAC) was measured and modeled by the time dependent Langmuir equation. The effect of effluent organic matter (EfOM) and of a competing anionic pharmaceutical, diclofenac (DCF), on the kinetics of GFZ removal was thoroughly explored. Finally, the overall removal of the studied anionic pharmaceuticals was four-fold higher than by GAC at realistic contact times. © 2019 Elsevier B.V.
Helman, D. ; Lensky, I. M. ; Bonfil, D. J. Early prediction of wheat grain yield production from root-zone soil water content at heading using Crop RS-Met. Field Crops Research 2019, 232, 11 - 23. Publisher's VersionAbstract
Wheat production in drylands is determined greatly by the available water at the critical growth stages. In dry years, farmers usually face the dilemma of whether to harvest at an early stage for hay or silage, with reduced profit, or leave the crop for grain production with the risk of a major economic loss. Thus, an early prediction of potential wheat grain yield production is essential for agricultural decision making, particularly in water-limited areas. Here, we test whether using a proximal-based biophysical model of actual evapotranspiration (water use) and root-zone soil water content (SWC) – Crop RS-Met – may assist in providing early grain yield predictions in dryland wheat fields. Crop RS-Met was examined in eight experimental fields comprising a variety of spring wheat (Triticum aestivum L.) cultivars exposed to different treatments and amounts of water supply (185 mm - 450 mm). Crop RS-Met was first validated against SWC measurements at the root-zone profile. Then, modeled SWC at heading (SWCHeading) was regressed against end-of-season grain yields (GYEOS), which ranged from 1.30 tons ha−1 to 7.12 tons ha−1, for a total of 56 treatment blocks in 4 seasonal years (2014–2017). Results show that Crop RS-Met accurately reproduce seasonal changes in SWC with an average R2 of 0.89 ± 0.05 and RMSE and bias of 0.014 ± 0.004 m3 m−3 and -0.002 ± 0.004 m3 m−3, respectively. Modeled SWCHeading showed high and significant positive linear relationship with GYEOS (GYEOS[tons ha-1] = 0.080×SWCHeading[mm] - 5.387; R2 = 0.90; P < 0.001; N=56). Moreover, Crop RS-Met showed to be capable of accurately predicting GYEOS even in cases where water supply and grain yield had adverse relationships. Aggregating results to the field-scale level and classifying fields per water supply conditions resulted in an even stronger linear relationship (R2 = 0.94; P < 0.001; N=9). We conclude that Crop RS-Met may be used to predict GYEOS at heading in dryland fields for possible use by farmers in decision making at critical wheat growth stages.
Helman, D. ; Bonfil, D. J. ; Lensky, I. M. Crop RS-Met: A biophysical evapotranspiration and root-zone soil water content model for crops based on proximal sensing and meteorological data. Agricultural Water Management 2019, 211, 210 - 219. Publisher's VersionAbstract
Assessing crops water use is essential for agricultural water management and planning, particularly in water-limited regions. Here, we present a biophysical model to estimate crop actual evapotranspiration and root-zone soil water content using proximal sensing and meteorological data (Crop RS-Met). The model, which is based on the dual FAO56 formulation, uses a water deficit factor calculated from rainfall and atmospheric demand information to constrain actual evapotranspiration and soil water content in crops growing under dry conditions. We tested the Crop RS-Met model in a dryland experimental field comprising a variety of wheat (Triticum aestivum L. and T. durum) cultivars with diverse phenology. Crop RS-Met was shown to accurately capture seasonal changes in wheat water use during the growing season. The average R2 of modeled vs. observed soil water content for all cultivars (N = 11) was 0.92 ± 0.02 with average relative RMSE and bias of 9.29 ± 1.30% and 0.13 ± 0.03%, respectively. We found that changing the integration time period of the water deficit factor in Crop RS-Met affects the accuracy of the model implying that this factor has a vital role in modeling crop water use under dry conditions. Currently, Crop RS-Met has a simple representation of surface runoff and does not take into consideration heterogeneity in the soil profile. Thus, efforts to combine numerical models that simulate soil water dynamics with a Crop RS-Met model driven by high-resolution remote sensing data may be needed for a spatially continuous assessment of crop water use in fields with more complex edaphic characteristics.
Miller, O. ; Helman, D. ; Svoray, T. ; Morin, E. ; Bonfil, D. J. Explicit wheat production model adjusted for semi-arid environments. Field Crops Research 2019, 231, 93 - 104. Publisher's VersionAbstract
Current literature suggests that wheat production models are limited either to wide-scale or plot-based predictions ignoring pattern of habitat conditions and surficial hydrological processes. We present here a high-spatial resolution (50 m) non-calibrated GIS-based wheat production model for predictions of aboveground wheat biomass (AGB) and grain yield (GY). The model is an integration of three sub-models, each simulating elemental processes relevant for wheat growth dynamics in water-limited environments: (1) HYDRUS-1D, a finite element model that simulates one-dimensional movement of water in the soil profile; (2) a two-dimensional GIS-based surface runoff model; and (3) a one-dimensional process-driven mechanistic wheat growth model. By integrating the three sub-models, we aimed to achieve a more accurate spatially continuous water balance simulation with a better representation of root zone soil water content (SWC) impacts on plant development. High-resolution grid-based rainfall data from a meteorological radar system were used as input to HYDRUS-1D. Twenty-two commercial wheat fields in Israel were used to validate the model in two seasons (2010/11 and 2011/12). Results show that root zone SWC was accurately simulated by HYDRUS-1D in both seasons, particularly at the top 10-cm soil layer. Observed vs simulated AGB and GY were highly correlated with R2 = 0.93 and 0.72 (RMSE = 171 g m−2 and 70 g m−2) having low biases of -41 g m−2 (8%) and 52 g m−2 (10%), respectively. Model sensitivity test showed that HYDRUS-1D was mainly driven by spatial variability in the input soil characteristics while the integrated wheat production model was mostly affected by rainfall spatial variability indicating the importance of using accurate high-resolution rainfall data as model input. Using the integrated model, we predict decreases in AGB and GY of c. 10.5% and c. 12%, respectively, for 1 °C of warming and c. 7.7% and c. 7.3% for 5% reduction in rainfall amount in our study sites. The suggested model could be used by scientists to better understand the causes of spatial and temporal variability in wheat production and the consequences of future scenarios such as climate change.
Engel, M. ; Chefetz, B. The missing link between carbon nanotubes, dissolved organic matter and organic pollutants. Advances in Colloid and Interface Science 2019, 271. Publisher's VersionAbstract
Ternary interactions between carbon nanotubes (CNTs), dissolved organic matter (DOM) and small organic molecules (namely low molecular mass organic pollutants) are of great importance since they can affect the reactivity and fate of all involved compartments in the environment. This review thoroughly assesses existing knowledge on the adsorption of DOM and small organic molecules by CNTs, while giving special attention to (i) the complex nature of DOM, (ii) the ternary rather than binary interactions between CNTs, DOM and the small organic molecules and (iii) the DOM-organic molecule interactions. We discuss in detail the main factors influencing DOM adsorption by CNTs and attempt to differentiate between the role of DOM composition and conformation. We then outline how the presence of DOM influences the adsorption of small organic molecules by CNTs, considering the introduction stage of DOM and the impact of the organic molecule's properties. DOM adsorption by CNTs is highly dependent on its composition and is governed by the size, hydrophobicity and aromaticity of DOM. DOM adsorption was found to alter the assembly of the CNTs, resulting in changes in the distribution of adsorption sites. Small organic molecules may adsorb to residual surface area on the CNTs, to DOM-coating the CNTs or remain in solution, possibly complexed with DOM. This results in their suppressed or enhanced adsorption in comparison to DOM-free media. The physicochemical properties of the organic molecules (hydrophobicity, size, structure and charge) also play a major role in this process. We present knowledge gaps that need clarification such as the extent of DOM desorption from CNTs, the amount of co-adsorbed DOM during competition with small organic molecules for adsorption sites on the CNTs and the behavior of CNTs under realistic conditions. More data generated from experiments using natural DOM rather than dissolved humic substances are required to improve our understanding of the interactions between CNTs and small organic molecules in realistic environmental scenarios. This review provides conclusions and research directions needed to evaluate the nature of interactions between CNTs, DOM and organic pollutants in aquatic systems affected by anthropogenic activities. © 2019 Elsevier B.V.
Wang, Y. ; Yang, K. ; Chefetz, B. ; Xing, B. ; Lin, D. The pH and concentration dependent interfacial interaction and heteroaggregation between nanoparticulate zero-valent iron and clay mineral particles. Environmental Science: Nano 2019, 6 2129-2140. Publisher's VersionAbstract
Heteroaggregation with clay mineral particles (CMPs) is significant to the environmental application and fate of increasingly produced nanoparticulate zero-valent iron (nZVI). Co-settling, kinetic aggregation, calculation of the classical Derjaguin-Landau-Verwey-Overbeek interaction energy, and electron microscopic observation were carried out to investigate the interaction between nZVIs (three naked nZVIs of different sizes and one carboxymethyl cellulose (CMC) coated nZVI) and CMPs (kaolinite and montmorillonite). Under pH 6.5 and 9.5 conditions, Lewis acid-base interaction contributed to the attachment between nZVIs and CMPs, while electrostatic attraction was involved in nZVI-CMP attachment under pH 3.5. Compared with the heteroaggregates formed by nZVIs attaching to CMP edges and faces under pH 6.5 and 3.5 conditions, the heteroaggregates were smaller with nZVIs mainly connecting to CMP edges under pH 9.5. Small nZVI homoaggregates were bound to CMP edges at low nZVI concentrations (nZVI/CMP mass ratio at 0.015) with CMP concentrations of 330 mg L-1 and large nZVI-CMP heteroaggregates formed by nZVI bridging with increasing nZVI concentrations. The smallest nZVI exhibited the strongest heteroaggregation with CMPs; the CMC coating inhibited the interfacial interaction and heteroaggregation between nZVIs and CMPs; kaolinite had higher potential to interact with nZVIs under neutral conditions. These findings are helpful for understanding the interaction between nZVIs and minerals and of significance to environmental remediation using nZVIs. © 2019 The Royal Society of Chemistry.
Fu, Q. ; Malchi, T. ; Carter, L. J. ; Li, H. ; Gan, J. ; Chefetz, B. Pharmaceutical and Personal Care Products: From Wastewater Treatment into Agro-Food Systems. Environmental Science and Technology 2019. Publisher's VersionAbstract
Irrigation with treated wastewater (TWW) and application of biosolids introduce numerous pharmaceutical and personal care products (PPCPs) into agro-food systems. While the use of TWW and biosolids has many societal benefits, introduction of PPCPs in production agriculture poses potential food safety and human health risks. A comprehensive risk assessment and management scheme of PPCPs in agro-food systems is limited by multiple factors, not least the sheer number of investigated compounds and their diverse structures. Here we follow the fate of PPCPs in the water-soil-produce continuum by considering processes and variables that influence PPCP transfer and accumulation. By analyzing the steps in the soil-plant-human diet nexus, we propose a tiered framework as a path forward to prioritize PPCPs that could have a high potential for plant accumulation and thus pose greatest risk. This article examines research progress to date and current research challenges, highlighting the potential value of leveraging existing knowledge from decades of research on other chemicals such as pesticides. A process-driven scheme is outlined to derive a short list that may be used to refocus our future research efforts on PPCPs and other analogous emerging contaminants in agro-food systems. © 2019 American Chemical Society.
Kohl, A. ; Golan, N. ; Cinnamon, Y. ; Genin, O. ; Chefetz, B. ; Sela-Donenfeld, D. A proof of concept study demonstrating that environmental levels of carbamazepine impair early stages of chick embryonic development. Environment International 2019, 129, 583-594. Publisher's VersionAbstract
Carbamazepine (CBZ)is an anticonvulsant drug used for epilepsy and other disorders. Prescription of CBZ during pregnancy increases the risk for congenital malformations. CBZ is ubiquitous in effluents and persistent during wastewater treatment. Thus, it is re-introduced into agricultural ecosystems upon irrigation with reclaimed wastewater. People consuming produce irrigated with reclaimed wastewater were found to be exposed to CBZ. However, environmental concentrations of CBZ (μg L−1)are magnitudes lower than its therapeutic levels (μg ml−1), raising the question of whether and how environmental levels of CBZ affect embryonic development. The chick embryo is a powerful and highly sensitive amniotic model system that enables to assess environmental contaminants in the living organism. Since the chick embryonic development is highly similar to mammalians, yet, it develops in an egg, toxic effects can be directly analyzed in a well-controlled system without maternal influences. This research utilized the chick embryo to test whether CBZ is embryo-toxic by using morphological, cellular, molecular and imaging strategies. Three key embryonic stages were monitored: after blastulation (st.1HH), gastrulation/neurulation (st.8HH)and organogenesis (st.15HH). Here we demonstrate that environmental relevant concentrations of CBZ impair morphogenesis in a dose- and stage- dependent manner. Effects on gastrulation, neural tube closure, differentiation and proliferation were exhibited in early stages by exposing embryos to CBZ dose as low as 0.1 μg L−1. Quantification of developmental progression revealed a significant difference in the total score obtained by CBZ-treated embryos compared to controls (up to 5-fold difference, p < 0.05). Yet, defects were unnoticed as embryos passed gastrulation/neurulation. This study provides the first evidence for teratogenic effect of environmental-relevant concentrations of CBZ in amniotic embryos that impair early but not late stages of development. These findings call for in-depth risk analysis to ensure that the environmental presence of CBZ and other drugs is not causing irreversible ecological and public-health damages. © 2019
Guo, H. ; Ma, C. ; Thistle, L. ; Huynh, M. ; Yu, C. ; Clasby, D. ; Chefetz, B. ; Polubesova, T. ; White, J. C. ; He, L. ; et al. Transformation of Ag ions into Ag nanoparticle-loaded AgCl microcubes in the plant root zone. Environmental Science: Nano 2019, 6 1099-1110. Publisher's VersionAbstract
Natural formation of metal nanoparticles is an important pathway that will modify the fate, behavior, and biological availability of heavy metal ions in the environment. Most work has focused on the ability of natural organic matter (NOM) and extracellular polymeric substances (EPS) to convert metal ions into nanoparticles. However, plant roots, ubiquitous in soil and aquatic environments, may have a significant role in the formation of naturally occurring metal nanoparticles. This work demonstrates the importance of plant roots and associated exudates in mediating the transformation of Ag+ in the presence of sunlight. Using Ag+ as the starting material, transformation took place in three steps: 1) formation of AgCl microcubes (μAgCl) through complexation of Ag+ by plant-released chloride ions in root exudates; 2) stabilization of μAgCl by biomolecules in root exudates; 3) partial photoreduction of μAgCl to Ag(0) nanoparticles (nAg) facilitated by exudate biomolecules. Morphological and compositional changes were observed by scanning electron microscopy with energy dispersive X-ray spectroscopy (SEM-EDS) on the particles from 0-24 h: Cubic AgCl microcrystals were converted into cauliflower-shaped core-shell structures with nAg clusters as the shell and μAgCl as the core. The quantification of Ag+, μAgCl and nAg species over time demonstrates that the transformation kinetics fit (R2 = 0.99) a second-order reaction (k = 1.11 mM-1 h-1). The discovery of plant root exudate-mediated phototransformation of Ag+ adds new knowledge to our understanding of Ag transformation in the plant root zone and will guide the assessment of both exposure and risk in the environment. © 2019 The Royal Society of Chemistry.
Chefetz, B. ; Marom, R. ; Salton, O. ; Oliferovsky, M. ; Mordehay, V. ; Ben-Ari, J. ; Hadar, Y. Transformation of lamotrigine by white-rot fungus Pleurotus ostreatus. Environmental Pollution 2019, 250, 546-553. Publisher's VersionAbstract
One of the most persistent pharmaceutical compounds commonly found in treated wastewater is lamotrigine (LTG). It has also been detected in soils and crops irrigated with treated wastewater. Here we focused on the ability of the white-rot edible mushroom Pleurotus ostreatus to remove and transform LTG in liquid cultures. At concentrations of environmental relevance (1 and 10 μg L−1) LTG was almost completely removed from the culture medium within 20 days. To elucidate the mechanism of LTG removal and transformation, we applied a physiological-based approach using inhibitors and a competing agent. These experiments were conducted at a higher concentration for metabolites detection. Based on identification of sulfur-containing metabolites and LTG N2-oxide and the effect of specific inhibitors, cytochrome P450 oxidation is suggested as one of the reaction mechanisms leading to LTG transformation. The variety and number of transformation products (i.e., conjugates) found in the current study were larger than reported in mammals. Moreover, known conjugates with glucuronide, glutathione, or cysteine/glycine, were not found in our system. Since the majority of the identified transformation products were conjugates of LTG, this study highlights the persistence of LTG as an organic pollutant in ecosystems exposed to wastewater. © 2019 Elsevier Ltd
Bhaduri, B. ; Polubesova, T. ; Chefetz, B. Interactions of organic dye with Ag- and Ce-nano-assemblies: Influence of dissolved organic matter. Colloids and Surfaces A: Physicochemical and Engineering Aspects 2019, 577, 683 - 694. Publisher's VersionAbstract
Rapid industrialization leads to the introduction of dyes and nanoparticles (NPs) into the environment posing threats to water quality and aquatic organisms. The highly reactive NPs are known to interact with dyes to form stable NPs-dye complexes. Herein, we report the adsorptive interactions of two inorganic NPs, Ag-Ag2S and CeO2 with cationic methylene blue. Experiments were also performed with NPs coated with 2 types of dissolved organic matter. The maximal adsorption capacities for methylene blue with Ag-Ag2S and CeO2 were calculated to be 16.64 and 5.35 mg g−1, respectively. The obtained adsorption capacities are attributed to electrostatic interactions (attractive/repulsive) between the NPs and the dyes and also the van der Waals force of interaction between the dye molecules. DOM coatings on the NPs significantly reduced the adsorption of dyes (maximum adsorption capacities for methylene blue with DOM coated Ag-Ag2S and CeO2 were reduced by ˜40% and ˜61%, respectively; the more hydrophobic DOM coating on the NPs resulted in reduction of adsorption capacity by ˜54 and ˜70%, respectively). Our results suggest that the DOM coatings alter the arrangements of the NPs in the dye solution, creating the active surface sites less accessible for adsorption. Furthermore, the reduction of the adsorption efficiency for the NPs toward dyes with simultaneously addition of DOM is probably due to blockage of the active surface sites by the DOM molecules and the competition between the dye and the DOM.