Influence of Salinity on the Partitioning Behavior of Six Commonly Used Pesticides in Fish Eggs.

Salinity has been reported to impact the octanol-water partition coefficient of organic contaminants entering aquatic ecosystems. However, limited data are available on the impacts of salinity on their partitioning from the aqueous phase to adjacent organic compartments. The pesticides bifenthrin, chlorpyrifos, dicloran, myclobutanil, penconazole, and triadimefon were used to investigate the effects of salinity on their partitioning to capelin (Mallotus villosus) eggs in 5 practical salinity units (PSU) versus 25 PSU artificial seawater (ASW). The partitioning coefficient was significantly higher in 25 versus 5 PSU ASW for bifenthrin, chlorpyrifos, dicloran, penconazole, and triadimefon by 31%, 28%, 35%, 28%, and 20%, respectively, while for myclobutanil there was no significant difference. Moreover, pesticide partitioning to store-bought capelin eggs was consistent with the partitioning observed for the standard assay species, inland silversides (Menidia beryllina) eggs, after partitioning between the eggs and exposure solution had reached a state of equilibrium. The present study illustrates the importance of considering the influence of salinity on the environmental partitioning and fate of hydrophobic organic contaminants in aquatic ecosystems. Environ Toxicol Chem 2024;43:299-306. © 2023 SETAC.

Tissue Equivalent Curved Organic X-ray Detectors Utilizing High Atomic Number Polythiophene Analogues.

Organic semiconductors are a promising material candidate for X-ray detection. However, the low atomic number (Z) of organic semiconductors leads to poor X-ray absorption thus restricting their performance. Herein, the authors propose a new strategy for achieving high-sensitivity performance for X-ray detectors based on organic semiconductors modified with high -Z heteroatoms. X-ray detectors are fabricated with p-type organic semiconductors containing selenium heteroatoms (poly(3-hexyl)selenophene (P3HSe)) in blends with an n-type fullerene derivative ([6,6]-Phenyl C71 butyric acid methyl ester (PC70 BM). When characterized under 70, 100, 150, and 220 kVp X-ray radiation, these heteroatom-containing detectors displayed a superior performance in terms of sensitivity up to 600 ± 11 nC Gy-1  cm-2 with respect to the bismuth oxide (Bi2 O3 ) nanoparticle (NP) sensitized organic detectors. Despite the lower Z of selenium compared to the NPs typically used, the authors identify a more efficient generation of electron-hole pairs, better charge transfer, and charge transport characteristics in heteroatom-incorporated detectors that result in this breakthrough detector performance. The authors also demonstrate flexible X-ray detectors that can be curved to a radius as low as 2 mm with low deviation in X-ray response under 100 repeated bending cycles while maintaining an industry-standard ultra-low dark current of 0.03 ± 0.01 pA mm-2 .

Impact of Reactive Oxygen Species Scavenging on the Intermediate Production of Anthracene and Anthraquinone in Fresh versus Saltwater Environments.

While salinity can alter the photodegradation of hydrophobic organic compounds (HOCs), the cause of their altered kinetics in seawater is not well understood. Because HOC intermediate photoproducts are often more toxic than their parent compounds, characterizing the generation of intermediates in saline environments is needed to accurately predict their health effects. The present study investigated the influence of salinity on the generation of anthraquinone through the photolysis of anthracene and the generation of anthrone and 1-hydroxyanthraquinone from the photolysis of anthraquinone as well as their reactivities with hydroxyl radicals. This was conducted by measuring the photolysis rates of anthracene and anthraquinone and characterizing their product formation in buffered deionized water, artificial seawater, individual seawater halides (bromide, chloride, and iodide), dimethyl sulfoxide, furfuryl alcohol, and solutions of hydrogen peroxide. Salinity enhanced the persistence of anthraquinone by a factor >10 and altered its product formation, including the generation of the suspected carcinogen 1-hydroxyanthraquinone. In part, this was attributed to reactive oxygen species (ROS) scavenging by the seawater constituents chloride and bromide. In addition, anthraquinone and its hydroxylated products were found to be moderately to highly reactive with hydroxyl radicals, further illustrating their tendency to react with ROS in aqueous environments. The present study emphasizes the importance of considering the effects of salinity on organic contaminant degradation; it can significantly enhance the persistence of HOCs and alter their intermediate formation, subsequently impacting chemical exposure times and potential toxic effects on estuarine/marine organisms. Environ Toxicol Chem 2023;42:1721-1729. © 2023 SETAC.

Mixed 3D-2D Perovskite Flexible Films for the Direct Detection of 5 MeV Protons.

This study reports on a novel, flexible, proton beam detector based on mixed 3D-2D perovskite films deposited by solution onto thin plastic foils. The 3D-2D mixture allows to obtain micrometer-thick and highly uniform films that constitute the detector's active layer. The devices demonstrate excellent flexibility with stable electric transport properties down to a bending radius of 3.1 mm. The detector is characterized under a 5 MeV proton beam with fluxes in the range [4.5 × 105 - 1.4 × 109 ] H+ cm-2 s-1 , exhibiting a stable response to repetitive irradiation cycles with sensitivity up to (290 ± 40) nC Gy-1 mm-3 and a limit of detection down to (72±2) µGy s-1 . The detector radiation tolerance is also assessed up to a total of 1.7 × 1012 protons impinging on the beam spot area, with a maximum variation of the detector's response of 14%.

Molecular Weight Tuning of Organic Semiconductors for Curved Organic-Inorganic Hybrid X-Ray Detectors.

Curved X-ray detectors have the potential to revolutionize diverse sectors due to benefits such as reduced image distortion and vignetting compared to their planar counterparts. While the use of inorganic semiconductors for curved detectors are restricted by their brittle nature, organic-inorganic hybrid semiconductors which incorporated bismuth oxide nanoparticles in an organic bulk heterojunction consisting of poly(3-hexylthiophene-2,5-diyl) (P3HT) and [6,6]-phenyl C71 butyric acid methyl ester (PC70 BM) are considered to be more promising in this regard. However, the influence of the P3HT molecular weight on the mechanical stability of curved, thick X-ray detectors remains less well understood. Herein, high P3HT molecular weights (>40 kDa) are identified to allow increased intermolecular bonding and chain entanglements, resulting in X-ray detectors that can be curved to a radius as low as 1.3 mm with low deviation in X-ray response under 100 repeated bending cycles while maintaining an industry-standard dark current of <1 pA mm-2 and a sensitivity of ≈ 0.17 µC Gy-1 cm-2 . This study identifies a crucial missing link in the development of curved detectors, namely the importance of the molecular weight of the polymer semiconductors used.

Direct detection of 5-MeV protons by flexible organic thin-film devices.

The direct detection of 5-MeV protons by flexible organic detectors based on thin films is here demonstrated. The organic devices act as a solid-state detector, in which the energy released by the protons within the active layer of the sensor is converted into an electrical current. These sensors can quantitatively and reliably measure the dose of protons impinging on the sensor both in real time and in integration mode. This study shows how to detect and exploit the energy absorbed both by the organic semiconducting layer and by the plastic substrate, allowing to extrapolate information on the present and past irradiation of the detector. The measured sensitivity, S = (5.15 ± 0.13) pC Gy-1, and limit of detection, LOD = (30 ± 6) cGy s-1, of the here proposed detectors assess their efficacy and their potential as proton dosimeters in several fields of application, such as in medical proton therapy.

Designing Ultraflexible Perovskite X-Ray Detectors through Interface Engineering.

X-ray detectors play a pivotal role in development and advancement of humankind, from far-reaching impact in medicine to furthering the ability to observe distant objects in outer space. While other electronics show the ability to adapt to flexible and lightweight formats, state-of-the-art X-ray detectors rely on materials requiring bulky and fragile configurations, severely limiting their applications. Lead halide perovskites is one of the most rapidly advancing novel materials with success in the field of semiconductor devices. Here, an ultraflexible, lightweight, and highly conformable passively operated thin film perovskite X-ray detector with a sensitivity as high as 9.3 ± 0.5 µC Gy-1 cm-2 at 0 V and a remarkably low limit of detection of 0.58 ± 0.05 µGy s-1 is presented. Various electron and hole transporting layers accessing their individual impact on the detector performance are evaluated. Moreover, it is shown that this ultrathin form-factor allows for fabrication of devices detecting X-rays equivalently from front and back side.

Characterization of an organic semiconductor diode for dosimetry in radiotherapy.

PURPOSE: The development of novel detectors for dosimetry in advanced radiotherapy modalities requires materials that have a water equivalent response to ionizing radiation such that characterization of radiation beams can be performed without the need for complex calibration procedures and correction factors. Organic semiconductors are potentially an ideal technology in fabricating devices for dosimetry due to tissue equivalence, mechanical flexibility, and relatively cheap manufacturing cost. The response of a commercial organic photodetector (OPD), coupled to a plastic scintillator, to ionizing radiation from a linear accelerator and orthovoltage x-ray tube has been characterized to assess its potential as a dosimeter for radiotherapy. The radiation hardness of the OPD has also been investigated to demonstrate its longevity for such applications. METHODS: Radiation hardness measurements were achieved by observing the response of the OPD to the visible spectrum and 70 keV x rays after pre-exposure to 40 kGy of ionizing radiation. The response of a preirradiated OPD to 6-MV photons from a linear accelerator in reference conditions was compared to a nonirradiated OPD with respect to direct and indirect (RP400 plastic scintillator) detection mechanisms. Dose rate dependence of the OPD was measured by varying the surface-to-source distance between 90 and 300 cm. Energy dependence was characterized from 29.5 to 129 keV with an x-ray tube. The percentage depth dose (PDD) curves were measured from 0.5 to 20 cm and compared to an ionization chamber. RESULTS: The OPD sensitivity to visible light showed substantial degradation of the broad 450 to 600 nm peak from the donor after irradiation to 40 kGy. After irradiation, the spectral shape has a dominant absorbance peak at 370 nm, as the acceptor better withstood radiation damage. Its response to x rays stabilized to 30% after 35 kGy, with a 0.5% difference between 770 Gy increments. The OPD exhibited reproducible detection of ionizing radiation when coupled with a scintillator. Indirect detection showed a linear response from 25 to 500 cGy and constant response to dose rates from 0.31 Gy/pulse to 3.4 × 10-4  Gy/pulse. However, without the scintillator, response increased by 100% at low dose rates. Energy independence between 100 keV and 1.2 MeV advocates their use as a dosimeter without beam correction factors. A dependence on the scintillator thickness used during a comparison of the PDD to the ionizing chamber was identified. A 1-mm-thick scintillator coupled with the OPD demonstrated the best agreement of ± 3%. CONCLUSIONS: The response of OPDs to ionizing radiation has been characterized, showing promising use as a dosimeter when coupled with a plastic scintillator. The mechanisms of charge transport and trapping within organic materials varies for visible and ionizing radiation, due to differing properties for direct and indirect detection mechanisms and observing a substantial decrease in sensitivity to the visible spectrum after 40 kGy. This study proved that OPDs produce a stable response to 6-MV photons, and with a deeper understanding of the charge transport mechanisms due to exposure to ionizing radiation, they are promising candidates as the first flexible, water equivalent, real-time dosimeter.

Morphology and mobility as tools to control and unprecedentedly enhance X-ray sensitivity in organic thin-films.

Organic semiconductor materials exhibit a great potential for the realization of large-area solution-processed devices able to directly detect high-energy radiation. However, only few works investigated on the mechanism of ionizing radiation detection in this class of materials, so far. In this work we investigate the physical processes behind X-ray photoconversion employing bis-(triisopropylsilylethynyl)-pentacene thin-films deposited by bar-assisted meniscus shearing. The thin film coating speed and the use of bis-(triisopropylsilylethynyl)-pentacene:polystyrene blends are explored as tools to control and enhance the detection capability of the devices, by tuning the thin-film morphology and the carrier mobility. The so-obtained detectors reach a record sensitivity of 1.3 · 104 µC/Gy·cm2, the highest value reported for organic-based direct X-ray detectors and a very low minimum detectable dose rate of 35 µGy/s. Thus, the employment of organic large-area direct detectors for X-ray radiation in real-life applications can be foreseen.

Degradation of Dicloran in Irradiated Water-Sediment Systems.

Shallow water systems are uniquely susceptible to environmental processes such as photolysis and hydrolysis that can influence the dissipation of pesticides into sediments. The fungicide dicloran has previously been shown to undergo photolysis and is reported to dissipate in soils and sediments. The photodegradation and dissipation of dicloran in freshwater and seawater was monitored in a laboratory-simulated shallow water system. While no difference was observed between freshwater and seawater systems in the presence of simulated sunlight, the dissipation of dicloran in dark trial systems differed between salinities; 30% of the applied mass dissipated into the sediment in freshwater vs 22% in seawater, and the photodegradation rate and half-life were also impacted by the presence of sediment. The potential for dicloran to dissipate and photodegrade affects the overall behavior of dicloran between waters. Differences in chemical behavior with sediment presence and potential for photodegradation have the capacity to impact organisms within the ecosystem and suggest that these factors may need to be implemented into chemical exposure assessments dependent upon location.

Space Environment Effects on Flexible, Low-Voltage Organic Thin-Film Transistors.

Organic electronic devices fabricated on flexible substrates are promising candidates for applications in environments where flexible, lightweight, and radiation hard materials are required. In this work, device parameters such as threshold voltage, charge mobility, and trap density of 13-bis(triisopropylsilylethynyl)pentacene (TIPS-pentacene)-based organic thin-film transistors (OTFTs) have been monitored for performing electrical measurements before and after irradiation by high-energy protons. The observed reduction of charge carrier mobility following irradiation can be only partially ascribed to the increased trap density. Indeed, we used other techniques to identify additional effects induced by proton irradiation in such devices. Atomic force microscopy reveals morphological defects occurring in the organic dielectric layer induced by the impinging protons, which, in turn, induce a strain on the TIPS-pentacene crystallites lying above. The effects of this strain are investigated by density functional theory simulations of two model structures, which describe the TIPS-pentacene crystalline films at equilibrium and under strain. The two different density of states distributions in the valence band have been correlated with the photocurrent spectra acquired before and after proton irradiation. We conclude that the degradation of the dielectric layer and the organic semiconductor sensitivity to strain are the two main phenomena responsible for the reduction of OTFT mobility after proton irradiation.

Direct X-ray photoconversion in flexible organic thin film devices operated below 1 V.

The application of organic electronic materials for the detection of ionizing radiations is very appealing thanks to their mechanical flexibility, low-cost and simple processing in comparison to their inorganic counterpart. In this work we investigate the direct X-ray photoconversion process in organic thin film photoconductors. The devices are realized by drop casting solution-processed bis-(triisopropylsilylethynyl)pentacene (TIPS-pentacene) onto flexible plastic substrates patterned with metal electrodes; they exhibit a strong sensitivity to X-rays despite the low X-ray photon absorption typical of low-Z organic materials. We propose a model, based on the accumulation of photogenerated charges and photoconductive gain, able to describe the magnitude as well as the dynamics of the X-ray-induced photocurrent. This finding allows us to fabricate and test a flexible 2 × 2 pixelated X-ray detector operating at 0.2 V, with gain and sensitivity up to 4.7 × 104 and 77,000 nC mGy-1 cm-3, respectively.

Experimental study of clay-hydrocarbon interactions relevant to the biodegradation of the Deepwater Horizon oil from the Gulf of Mexico.

Adding clay to marine oil pollution represents a promising approach to enhance bacterial hydrocarbon degradation in nutrient poor waters. In this study, three types of regionally available clays (Ca-bentonite, Fuller's Earth and kaolin) were tested to stimulate the biodegradation of source and weathered oil collected from the Deepwater Horizon spill. The weathered oil showed little biodegradation prior to experimentation and was extensively degraded by bacteria in the laboratory in a similar way as the alkane-rich source oil. For both oils, the addition of natural clay-flakes showed minor enhancement of oil biodegradation compared to the non-clay bearing control, but the clay-oil films did limit evaporation. Only alkanes of a molecular weight (MW) > 420 showed significant reduction by enhanced biodegradation following natural clay treatment. In contrast, all fertilized clay flakes showed major bacterial degradation of the oil, with a 6-10 times reduction in alkane content, and an up to 8 fold increase in the rate of O2 consumption. Compared to the control, such treatment showed particular reduction of longer chained alkanes (MW > 226). The application of natural and fertilized clay flakes also showed selective reduction of PAHs, mainly in the MW range of 200-300, but without significant change in the toxicity indices measured. These results imply that a large variety of clays may be used to boost oil biodegradation by aiding attachment of fertilizing nutrients to the oil.

Organic semiconducting single crystals as solid-state sensors for ionizing radiation.

So far, organic semiconductors have been mainly proposed as detectors for ionizing radiation in the indirect conversion approach, i.e. as scintillators, which convert ionizing radiation into visible photons, or as photodiodes, which detect visible photons coming from a scintillator and convert them into an electrical signal. The direct conversion of ionizing radiation into an electrical signal within the same device is a more effective process than indirect conversion, since it improves the signal-to-noise ratio and it reduces the device response time. We report here the use of Organic Semiconducting Single Crystals (OSSCs) as intrinsic direct ionizing radiation detectors, thanks to their stability, good transport properties and large interaction volume. Ionizing radiation X-ray detectors, based on low-cost solution-grown OSSCs, are here shown to operate at room temperature, providing a stable linear response with increasing dose rate in the ambient atmosphere and in high radiation environments.

Bioremediating oil spills in nutrient poor ocean waters using fertilized clay mineral flakes: some experimental constraints.

Much oil spill research has focused on fertilizing hydrocarbon oxidising bacteria, but a primary limitation is the rapid dilution of additives in open waters. A new technique is presented for bioremediation by adding nutrient amendments to the oil spill using thin filmed minerals comprised largely of Fullers Earth clay. Together with adsorbed N and P fertilizers, filming additives, and organoclay, clay flakes can be engineered to float on seawater, attach to the oil, and slowly release contained nutrients. Our laboratory experiments of microbial activity on weathered source oil from the Deepwater Horizon spill in the Gulf of Mexico show fertilized clay treatment significantly enhanced bacterial respiration and consumption of alkanes compared to untreated oil-in-water conditions and reacted faster than straight fertilization. Whereas a major portion (up to 98%) of the alkane content was removed during the 1 month period of experimentation by fertilized clay flake interaction; the reduced concentration of polyaromatic hydrocarbons was not significantly different from the non-clay bearing samples. Such clay flake treatment could offer a way to more effectively apply the fertilizer to the spill in open nutrient poor waters and thus significantly reduce the extent and duration of marine oil spills, but this method is not expected to impact hydrocarbon toxicity.

Inkjet printed arrays of pressure sensors based on all-organic field effect transistors.

In this paper we propose totally flexible organic field effect transistors (OFETs) assembled on plastic films as sensors for mechanical variables. First mechanical sensors for pressure and bending detection are presented. A sharp and reversible sensitivity of the output current of the device to an elastic deformation induced by means of a mechanical stimulus on the device channel has been observed and suggested the idea of employing arrays of such sensors for detecting the deformation applied onto a planar surface. Second the possibility of using similar devices for bio- and chemo-detection is described. By exploiting the properties of the basic structure, the device can be combined with any kind of substrate to detect for instance the pressure applied by people walking or standing on a functionalized carpet. This emerging technology seems to be promising for applications in the field of remote and non invasive monitoring of elderly and disabled people.