Accurate quantum yields are crucial for modeling photochemical reactions in natural and engineered treatment systems. Quantum yields are usually determined using a single representative light source such as xenon lamps to mimic sunlight or UVC light for water treatment. However, photodegradation modeling can be improved by understanding the wavelength dependence of quantum yields and the potential errors introduced by the experimental setup.
View Article and Find Full Text PDFChromophoric dissolved organic matter (CDOM) is an important photochemical precursor to reactive intermediates (RIs) (e.g., excited triplet states of chromophoric dissolved organic matter (CDOM), hydroxyl radicals (·OH), and singlet oxygen (O)) in aquatic systems to drive the photodegradation of contaminants.
View Article and Find Full Text PDFEnviron Sci Process Impacts
December 2021
Environmental photodegradation is dependent on the solar irradiance that reaches the Earth's surface, and photodegradation half-lives of contaminants are typically estimated assuming clear sky (, cloudless) conditions. In this work, the effect of cloud cover on solar irradiance was investigated. Data from the National Renewable Energy Laboratory (NREL), which spanned 3 years of observations (10/2017 to 12/2020), were used to train two machine learning models to predict irradiance based on three inputs - day of year, time of day, and percentage of the sky that was cloudy.
View Article and Find Full Text PDFEnviron Sci Process Impacts
August 2021
The steady-state concentration of singlet oxygen within a lake ([O]) is an important parameter that can affect the environmental half-life of pollutants and environmental fate modelling. However, values of [O] are often determined for the near-surface of a lake, and these values typically do not represent the average over the epilimnia of lakes. In this work, the environmental and physical factors that have the largest impact on [O] within lake epilimnia were identified.
View Article and Find Full Text PDFMedetomidine has been authorized in ship hull paints as an antifouling biocide under the biocidal product regulation in Europe since 2016. Its release into marine systems causes concerns over persistence and toxicity. However, the environmental fate of medetomidine has not been fully investigated.
View Article and Find Full Text PDFTriclosan is a high-production volume chemical, which has become widely detected in environmental systems because of its widespread usage. Photodegradation has been identified as a major degradation pathway, but the identified photoproducts are also chemicals of concern. In this study, lower chlorinated derivatives of triclosan were synthesized to investigate the impact the chlorine substituents have on the photodegradation rate and the photoproducts produced.
View Article and Find Full Text PDFEnviron Sci Process Impacts
December 2019
Correction for 'Updated and validated solar irradiance reference spectra for estimating environmental photodegradation rates' by Jennifer N. Apell and Kristopher McNeill, Environ. Sci.
View Article and Find Full Text PDFPhotodegradation can be an important abiotic degradation process to consider for the fate and persistence assessment of chemical substances in the environment. In this work, using a fragrance ingredient (FI, (E)-4-(2,2,3,6-tetramethylcyclohexyl)but-3-en-2-one) as an example, we developed a streamlined workflow to investigate direct photodegradation of chemicals in the aquatic environment, including laboratory investigation of kinetics and transformation products and estimation of its aquatic environmental half-lives. Direct photodegradation was determined to be the dominant photodegradation process for FI with a quantum yield of 0.
View Article and Find Full Text PDFFludioxonil is a pyrrole-containing pesticide whose registration as a plant protection product is currently under review in the United States and Europe. There are concerns over its potential persistence and toxicity in the aquatic environment; however, the pyrrole moiety represents a potential reaction site for indirect photodegradation. In this study, the direct and indirect photodegradation of fludioxonil, along with pyrrole, 3-cyanopyrrole, and 3-phenylpyrrole, were investigated.
View Article and Find Full Text PDFAnticipating, identifying, and prioritizing strategic needs represent essential activities by research organizations. Decided benefits emerge when these pursuits engage globally important environment and health goals, including the United Nations Sustainable Development Goals. To this end, horizon scanning efforts can facilitate identification of specific research needs to address grand challenges.
View Article and Find Full Text PDFEnviron Sci Process Impacts
March 2019
Irradiance reference spectra are used to calculate environmentally relevant photodegradation half-lives, but the currently used spectra were originally published in the 1980s with limited validation. The goal of this work is to provide updated irradiance reference spectra using the Simple Model of the Atmospheric Radiative Transfer of Sunshine (SMARTS). The SMARTS irradiance spectra were validated against measurements from several high-resolution spectroradiometers, and the updated irradiance reference spectra use current measurements for atmospheric species that can affect the irradiance that reaches the Earth's surface.
View Article and Find Full Text PDFPolychlorinated biphenyl (PCB) fluxes from contaminated sediments can be caused by mechanisms including diffusion, bioirrigation, and resuspension, but it is often unclear which mechanisms are important. In the Lower Duwamish Waterway (Seattle, Washington), the presence of abundant benthic macrofauna suggests that porewater bioirrigation may be an important mechanism for PCB transport from the bed into the overlying water column. In this field study, the fluxes of PCBs due to bioirrigation were quantified by using (a) polyethylene (PE) samplers to quantify in situ and ex situ (i.
View Article and Find Full Text PDFThis work presents the results of an international interlaboratory comparison on ex situ passive sampling in sediments. The main objectives were to map the state of the science in passively sampling sediments, identify sources of variability, provide recommendations and practical guidance for standardized passive sampling, and advance the use of passive sampling in regulatory decision making by increasing confidence in the use of the technique. The study was performed by a consortium of 11 laboratories and included experiments with 14 passive sampling formats on 3 sediments for 25 target chemicals (PAHs and PCBs).
View Article and Find Full Text PDFThe industrialized portion of the Houston Ship Channel (HSC) is heavily contaminated with anthropogenic contaminants, most prominent of which are the polychlorinated biphenyls (PCBs). This contamination has driven adaptive evolution in a keystone species for Galveston Bay, the Gulf killifish (Fundulus grandis). We investigated the geographical extent of PCB impacts by sampling 12 sites, ranging from the heavily industrialized upper portion of the HSC to Galveston Island.
View Article and Find Full Text PDFObjective: Firefighters are at an increased risk for many types of cancer. Although most studies on this topic focus on exposures encountered while fighting fires, exposures at the fire station are also cause for concern. This pilot study aimed to describe air quality within a few fire stations in and around Boston, Massachusetts, and to investigate physical and organizational factors that may influence levels of contaminants in stations.
View Article and Find Full Text PDFWaterbodies polluted with polychlorinated biphenyls (PCBs) may cause the air in the surrounding area to become PCB-contaminated. Conversely, when a waterbody is located in or near an urban area, the deposition of atmospheric PCBs may act as a low-level, ongoing source of PCB contamination to that water. Distinguishing these situations is necessary to be protective of human populations and to guide efforts seeking to cleanup such aquatic ecosystems.
View Article and Find Full Text PDFSuperfund sites with sediments contaminated by hydrophobic organic compounds (HOCs) can be difficult to characterize because of the complex nature of sorption to sediments. Porewater concentrations, which are often used to model transport of HOCs from the sediment bed into overlying water, benthic organisms, and the larger food web, are traditionally estimated using sediment concentrations and sorption coefficients estimated using equilibrium partitioning (EqP) theory. However, researchers have begun using polymeric samplers to determine porewater concentrations since this method does not require knowledge of the sediment's sorption properties.
View Article and Find Full Text PDFPolymeric passive samplers have become a common method for estimating freely dissolved concentrations in environmental media. However, this approach has not yet been adopted by investigators conducting remedial investigations of contaminated environmental sites. Successful adoption of this sampling methodology relies on an understanding of how passive samplers accumulate chemical mass as well as developing guidance for the design and deployment of passive samplers.
View Article and Find Full Text PDFUnderstanding the transfer of chemicals between passive samplers and water is essential for their use as monitoring devices of organic contaminants in surface waters. By applying Fick's second law to diffusion through the polymer and an aqueous boundary layer, the authors derived a mathematical model for the uptake of chemicals into a passive sampler from water, in finite and infinite bath conditions. The finite bath model performed well when applied to laboratory observations of sorption into polyethylene (PE) sheets for various chemicals (polycyclic aromatic hydrocarbons, polychlorinated biphenyls [PCBs], and dichlorodiphenyltrichloroethane [DDT]) and at varying turbulence levels.
View Article and Find Full Text PDFHydrophobic organic compounds (HOCs) like polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs) tend to accumulate in sediment beds when they are released into aquatic environments. Due to this buildup of HOCs in the sediment, the highest water concentrations are often in the pore water. Passive samplers can be used in the field (i.
View Article and Find Full Text PDFDissolved organic matter (DOM) and hardness cations are two common constituents of natural waters that substantially impact water treatment processes. Anion exchange treatment, and in particular magnetic ion exchange (MIEX), has been shown to effectively remove DOM from natural waters. An important advantage of the MIEX process is that it is used as a slurry in a completely mixed flow reactor at the beginning of the treatment train.
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