Showing papers in "Environmental Science: Processes & Impacts in 2020"

An overview of the uses of per- and polyfluoroalkyl substances (PFAS)

Abstract: Per- and polyfluoroalkyl substances (PFAS) are of concern because of their high persistence (or that of their degradation products) and their impacts on human and environmental health that are known or can be deduced from some well-studied PFAS. Currently, many different PFAS (on the order of several thousands) are used in a wide range of applications, and there is no comprehensive source of information on the many individual substances and their functions in different applications. Here we provide a broad overview of many use categories where PFAS have been employed and for which function; we also specify which PFAS have been used and discuss the magnitude of the uses. Despite being non-exhaustive, our study clearly demonstrates that PFAS are used in almost all industry branches and many consumer products. In total, more than 200 use categories and subcategories are identified for more than 1400 individual PFAS. In addition to well-known categories such as textile impregnation, fire-fighting foam, and electroplating, the identified use categories also include many categories not described in the scientific literature, including PFAS in ammunition, climbing ropes, guitar strings, artificial turf, and soil remediation. We further discuss several use categories that may be prioritised for finding PFAS-free alternatives. Besides the detailed description of use categories, the present study also provides a list of the identified PFAS per use category, including their exact masses for future analytical studies aiming to identify additional PFAS.

A critical review on the potential impacts of neonicotinoid insecticide use: Current knowledge of environmental fate, toxicity, and implications for human health

Abstract: Neonicotinoid insecticides are widely used in both urban and agricultural settings around the world. Historically, neonicotinoid insecticides have been viewed as ideal replacements for more toxic compounds, like organophosphates, due in part to their perceived limited potential to affect the environment and human health. This critical review investigates the environmental fate and toxicity of neonicotinoids and their metabolites and the potential risks associated with exposure. Neonicotinoids are found to be ubiquitous in the environment, drinking water, and food, with low-level exposure commonly documented below acceptable daily intake standards. Available toxicological data from animal studies indicate possible genotoxicity, cytotoxicity, impaired immune function, and reduced growth and reproductive success at low concentrations, while limited data from ecological or cross-sectional epidemiological studies have identified acute and chronic health effects ranging from acute respiratory, cardiovascular, and neurological symptoms to oxidative genetic damage and birth defects. Due to the heavy use of neonicotinoids and potential for cumulative chronic exposure, these insecticides represent novel risks and necessitate further study to fully understand their risks to humans.

Strategies for grouping per- and polyfluoroalkyl substances (PFAS) to protect human and environmental health

Abstract: Grouping strategies are needed for per- and polyfluoroalkyl substances (PFAS), in part, because it would be time and resource intensive to test and evaluate the more than 4700 PFAS on the global market on a chemical-by-chemical basis. In this paper we review various grouping strategies that could be used to inform actions on these chemicals and outline the motivations, advantages and disadvantages for each. Grouping strategies are subdivided into (1) those based on the intrinsic properties of the PFAS (e.g. persistence, bioaccumulation potential, toxicity, mobility, molecular size) and (2) those that inform risk assessment through estimation of cumulative exposure and/or effects. The most precautionary grouping approach of those reviewed within this article suggests phasing out PFAS based on their high persistence alone (the so-called "P-sufficient" approach). The least precautionary grouping approach reviewed advocates only grouping PFAS for risk assessment that have the same toxicological effects, modes and mechanisms of action, and elimination kinetics, which would need to be well documented across different PFAS. It is recognised that, given jurisdictional differences in chemical assessment philosophies and methodologies, no one strategy will be generally acceptable. The guiding question we apply to the reviewed grouping strategies is: grouping for what purpose? The motivation behind the grouping (e.g. determining use in products vs. setting guideline levels for contaminated environments) may lead to different grouping decisions. This assessment provides the necessary context for grouping strategies such that they can be adopted as they are, or built on further, to protect human and environmental health from potential PFAS-related effects.

The high persistence of PFAS is sufficient for their management as a chemical class

Abstract: Per- and polyfluoroalkyl substances (PFAS) are a class of synthetic organic substances with diverse structures, properties, uses, bioaccumulation potentials and toxicities. Despite this high diversity, all PFAS are alike in that they contain perfluoroalkyl moieties that are extremely resistant to environmental and metabolic degradation. The vast majority of PFAS are therefore either non-degradable or transform ultimately into stable terminal transformation products (which are still PFAS). Under the European chemicals regulation this classifies PFAS as very persistent substances (vP). We argue that this high persistence is sufficient concern for their management as a chemical class, and for all “non-essential” uses of PFAS to be phased out. The continual release of highly persistent PFAS will result in increasing concentrations and increasing probabilities of the occurrence of known and unknown effects. Once adverse effects are identified, the exposure and associated effects will not be easily reversible. Reversing PFAS contamination will be technically challenging, energy intensive, and costly for society, as is evident in the efforts to remove PFAS from contaminated land and drinking water sources.

The atmospheric chemistry of indoor environments

Abstract: Through air inhalation, dust ingestion and dermal exposure, the indoor environment plays an important role in controlling human chemical exposure. Indoor emissions and chemistry can also have direct impacts on the quality of outdoor air. And so, it is important to have a strong fundamental knowledge of the chemical processes that occur in indoor environments. This review article summarizes our understanding of the indoor chemistry field. Using a molecular perspective, it addresses primarily the new advances that have occurred in the past decade or so and upon developments in our understanding of multiphase partitioning and reactions. A primary goal of the article is to contrast indoor chemistry to that which occurs outdoors, which we know to be a strongly gas-phase, oxidant-driven system in which substantial oxidative aging of gases and aerosol particles occurs. By contrast, indoor environments are dark, gas-phase oxidant concentrations are relatively low, and due to air exchange, only short times are available for reactive processing of gaseous and particle constituents. However, important gas–surface partitioning and reactive multiphase chemistry occur in the large surface reservoirs that prevail in all indoor environments. These interactions not only play a crucial role in controlling the composition of indoor surfaces but also the surrounding gases and aerosol particles, thus affecting human chemical exposure. There are rich research opportunities available if the advanced measurement and modeling tools of the outdoor atmospheric chemistry community continue to be brought indoors.

A review of aerosol chemistry in Asia: insights from aerosol mass spectrometer measurements

Abstract: Anthropogenic emissions in Asia have significantly increased during the last two decades; as a result, the induced air pollution and its influences on radiative forcing and public health are becoming increasingly prominent The Aerodyne Aerosol Mass Spectrometer (AMS) has been widely deployed in Asia for real-time characterization of aerosol chemistry In this paper, we review the AMS measurements in Asia, mainly in China, Korea, Japan, and India since 2001 and summarize the key results and findings The mass concentrations of non-refractory submicron aerosol species (NR-PM1) showed large spatial distributions with high mass loadings occurring in India and north and northwest China (602-813 μg m-3), whereas much lower values were observed in Korea, Japan, Singapore and regional background sites (75-151 μg m-3) Aerosol composition varied largely in different regions, but was overall dominated by organic aerosols (OA, 32-75%), especially in south and southeast Asia due to the impact of biomass burning While sulfate and nitrate showed comparable contributions in urban and suburban regions in north China, sulfate dominated inorganic aerosols in south China, Japan and regional background sites Positive matrix factorization analysis identified multiple OA factors from different sources and processes in different atmospheric environments, eg, biomass burning OA in south and southeast Asia and agricultural seasons in China, cooking OA in urban areas, and coal combustion in north China However, secondary OA (SOA) was a ubiquitous and dominant aerosol component in all regions, accounting for 43-78% of OA The formation of different SOA subtypes associated with photochemical production or aqueous-phase/fog processing was widely investigated The roles of primary emissions, secondary production, regional transport, and meteorology on severe haze episodes, and different chemical responses of primary and secondary aerosol species to source emission changes and meteorology were also demonstrated Finally, future prospects of AMS studies on long-term and aircraft measurements, water-soluble OA, the link of OA volatility, oxidation levels, and phase state were discussed

Temporal trends of suspect- and target-per/polyfluoroalkyl substances (PFAS), extractable organic fluorine (EOF) and total fluorine (TF) in pooled serum from first-time mothers in Uppsala, Sweden, 1996-2017

Abstract: A combined method for quantitative analysis, along with suspect and non-target screening of per- and polyfluoroalkyl substances (PFAS) was developed using ultra-high pressure liquid chromatography-ultra-high resolution (Orbitrap) mass spectrometry. The method was applied together with measurements of total- and extractable organofluorine (TF and EOF, respectively), to pooled serum samples from 1996–2017 from first-time mothers living in the county of Uppsala, Sweden, some of which (i.e. 148 of 472 women sampled 1996–2012) were exposed to drinking water contaminated with perfluorohexane sulfonate (PFHxS) and other PFAS until mid-2012. Declining trends were observed for all target PFAS as well as TF, with homologue-dependent differences in year of onset of decline. Only 33% of samples displayed detectable EOF, and amongst these samples the percentage of EOF explained by target PFAS declined significantly (−3.5% per year) over the entire study period. This finding corroborates prior observations in Germany after the year 2000, and may reflect increasing exposure to novel PFAS which have not yet been identified. Suspect screening revealed the presence of perfluoro-4-ethylcyclohexanesulfonate (PFECHS), which displayed declining trends since the year 2000. Non-target time trend screening revealed 3 unidentified features with time trends matching PFHxS. These features require further investigation, but may represent contaminants which co-occurred with PFHxS in the contaminated drinking water.

Effects of soil particle size on the adsorption, distribution, and migration behaviors of heavy metal(loid)s in soil: a review

Abstract: In recent years, toxic pollution from heavy metal(loid)s in soil has become a severe environmental problem worldwide. The migration and transformation of heavy metal(loid)s in soil have become hot topics in the field of environmental research. Soil particle size plays an important role in influencing the environmental behavior of heavy metal(loid)s in soil. This review collates and synthesizes the research on the adsorption, distribution, and migration of heavy metal(loid)s in soil particles. There is no unified method for soil particle separation, since the purposes of different studies are different. Regardless of adsorption or distribution characteristics, fine soil particles generally exhibit a higher capacity to combine heavy metal(loid)s; however, certain studies have also observed a contrary phenomenon, according to which heavy metal(loid)s were more enriched in coarser particles. The adsorption and distribution of heavy metal(loid)s in soil particles were essentially determined by the physicochemical properties of the soil particles. Land use obviously affected the distribution of heavy metal(loid)s in the soil particles. Organic matter had an important influence on the distribution and availability of heavy metal(loid)s in agricultural and forest soils, while for urban soils and sediments, clay minerals or metal (hydr)oxides may play the dominant role. Preferential surface migration of fine particles during erosion processes did not always lead to the enrichment of heavy metal(loid)s in the lost soil. Further research should be conducted to explore the relationships among the soil aggregates, organic matter, heavy metal(loid)s, and soil microorganisms; the association between the distribution and availability of heavy metal(loid)s and the properties of soil particles; and the migration patterns of heavy metal(loid)s in soil particles at different scales.

Characterizing microplastic size and morphology of photodegraded polymers placed in simulated moving water conditions.

Abstract: Aquatic plastic debris experiences environmental stressors that lead to breakdown into smaller micro-sized plastic particles. This work quantified microplastic formation with the environmental stressors of UV irradiation followed by mechanical strain induced by movement of water with an emphasis on connecting our results to changes in the materials chemical/physical properties. Polypropylene, polyethylene, and polyethylene terephthalate thin films and polypropylene injection-molded sheets were irradiated with 254 nm UV light, placed into aquatic microcosms, collected through sieving, and counted under a microscope. Results showed increasingly more particles in smaller size classes, the smallest being 74–177 μm. Mechanical strain from the turbulent water caused 2.3–3× more microplastics to be formed for the thinnest (∼25 μm) film and 1.4–2× more for thicker films and sheets. The most common morphology of microplastics was fibers, particularly in thicker polypropylene samples, which was attributed to absorbance of the photons and the changes observed in the crystallinity and glass transition as measured with differential scanning calorimetry (DSC). When irradiated for 24, 48, or 72 h, longer irradiation resulted in more microplastics formed by polypropylene films, which correlated with changes in the glass transition temperature as measured by DSC and the extent of oxidation as measured with FTIR. Irradiation at 300 nm produced fewer microplastics due to slower kinetics of phototransformations. Overall, this work evaluates the impact of combined photodegradation and water motion toward microplastic particles formed. It provides quantitative evidence that mechanical strain of water movement exacerbates photo-induced formation of microplastics and shows that the existence of fibers in natural systems can be the result of photodegradation.

Passive air sampling for semi-volatile organic chemicals

Abstract: During passive air sampling, the amount of a chemical taken up in a sorbent from the air without the help of a pump is quantified and converted into an air concentration. In an equilibrium sampler, this conversion requires a thermodynamic parameter, the equilibrium sorption coefficient between gas-phase and sorbent. In a kinetic sampler, a time-averaged air concentration is obtained using a sampling rate, which is a kinetic parameter. Design requirements for kinetic and equilibrium sampling conflict with each other. The volatility of semi-volatile organic compounds (SVOCs) varies over five orders of magnitude, which implies that passive air samplers are inevitably kinetic samplers for less volatile SVOCs and equilibrium samplers for more volatile SVOCs. Therefore, most currently used passive sampler designs for SVOCs are a compromise that requires the consideration of both a thermodynamic and a kinetic parameter. Their quantitative interpretation depends on assumptions that are rarely fulfilled, and on input parameters, that are often only known with high uncertainty. Kinetic passive air sampling for SVOCs is also challenging because their typically very low atmospheric concentrations necessitate relatively high sampling rates that can only be achieved without the use of diffusive barriers. This in turn renders sampling rates dependent on wind conditions and therefore highly variable. Despite the overall high uncertainty arising from these challenges, passive air samplers for SVOCs have valuable roles to play in recording (i) spatial concentration variability at scales ranging from a few centimeters to tens of thousands of kilometers, (ii) long-term trends, (iii) air contamination in remote and inaccessible locations and (iv) indoor inhalation exposure. Going forward, thermal desorption of sorbents may lower the detection limits for some SVOCs to an extent that the use of diffusive barriers in the kinetic sampling of SVOCs becomes feasible, which is a prerequisite to decreasing the uncertainty of sampling rates. If the thermally stable sorbent additionally has a high sorptive capacity, it may be possible to design true kinetic samplers for most SVOCs. In the meantime, the passive air sampling community would benefit from being more transparent by rigorously quantifying and explicitly reporting uncertainty.

Quantifying the efficiency and selectivity of organohalide dechlorination by zerovalent iron

Abstract: The efficiency and selectivity of zerovalent iron-based treatments for organohalide contaminated groundwater can be quantified by accounting for redistribution of electrons derived from oxidation of Fe0. Several types of efficiency are reviewed, including (i) the efficiency of Fe(0) utilization, eFe(0), (ii) the electron efficiency of target contaminant reduction, ee, and (iii) the electron efficiency of natural reductant demand (NRD) involving H2O, O2, and co-contaminants such as nitrate, eNRD. Selectivity can then be calculated by using ee/eNRD. Of particular interest is ee and the key to its determination is measuring the total quantity of electrons provided by Fe0 oxidation, which can be based on either the loss of Fe(0), the formation of Fe(ii)/Fe(iii), or the composition of the total reaction products. Recently, many data have accumulated on ee for the treatment of various chlorinated solvents (esp. trichloroethylene, TCE) by zerovalent iron (ZVI), and analysis of these data shows that ZVI particle properties (e.g., stabilization with polymers, bimetallic modification, sulfidation, etc.) and other operational factors have variable effects on ee. Of particular interest is that pre-exposure of ZVI to reduced sulfur species (i.e., sulfidation) consistently improves the ee of contaminant reduction, mainly by suppressing the reduction of water.

Emerging per- and polyfluoroalkyl substances (PFAS) in human milk from Sweden and China

Abstract: Twenty per- and polyfluoroalkyl substances (PFAS) were determined in human milk from residents of three Chinese cities (Shanghai, Jiaxing, and Shaoxing; [n = 10 individuals per city]), sampled between 2010 and 2016. These data were compared to a combination of new and previously reported PFAS concentrations in human milk from Stockholm, Sweden, collected in 2016 (n = 10 individuals). Across the three Chinese cities, perfluorooctanoate (PFOA; sum isomers), 9-chlorohexadecafluoro-3-oxanone-1-sulfonic acid (9Cl-PF3ONS; also known as 6:2 Cl-PFESA or by its trade name "F53-B"), and perfluorooctane sulfonate (PFOS; sum isomers) occurred at the highest concentrations among all PFAS (up to 411, 976, and 321 pg mL-1, respectively), while in Stockholm, PFOA and PFOS were dominant (up to 89 and 72 pg mL-1, respectively). 3H-Perfluoro-3-[(3-methoxy-propoxy)propanoic acid] (ADONA) was intermittently detected but at concentrations below the method quantification limit (i.e. <10 pg mL-1) in Chinese samples, and was non-detectable in Swedish milk. The extremely high concentrations of F53-B in Chinese milk suggest that human exposure assessments focused only on legacy substances may severely underestimate overall PFAS exposure in breastfeeding infants.

Perspectives of genetically engineered microbes for groundwater bioremediation.

Abstract: Biodegradation is the main process for the removal of organic compounds from the environment, but proceeds slowly for many synthetic chemicals of environmental concern. Research on microbial biodegradation pathways revealed that recalcitrance is - among other factors - caused by biochemical blockages resulting in dysfunctional catabolic routes. This has raised interest in the possibility to construct microorganisms with improved catabolic activities by genetic engineering. Although this goal has been pursued for decades, no full-scale applications have emerged. This perspective explores the lagging implementation of genetically engineered microorganisms in practical bioremediation. The major technical and scientific issues are illustrated by comparing two examples, that of 1,2-dichloroethane where successful full-scale application of pump-and-treat biotreatment processes has been achieved, and 1,2,3-trichloropropane, for which protein and genetic engineering yielded effective bacterial cultures that still await application.

Comprehensive screening of quaternary ammonium surfactants and ionic liquids in wastewater effluents and lake sediments

Abstract: Quaternary ammonium compounds (QACs) are widely applied as surfactants and biocides in cleaning and personal-care products. Because of incomplete removal during wastewater treatment, QACs are present in wastewater effluents, with which they are discharged into natural waters, where they accumulate in sediments. To assess the levels of QACs in aquatic environments, a liquid chromatography high-resolution mass spectrometry method using both target and suspect screening was developed. The water and sediment sample preparation, measurement, and data analysis workflow were optimized for 22 target compounds with a wide range of hydrophobicity, including ionic liquids that have potential use as solvents and QACs common in personal-care and sanitizing products. In wastewater effluents, average concentrations of all target and suspect QACs combined ranged from 0.4 μg L-1 to 6.6 μg L-1. Various homologs of benzylalkyldimethylammonium (BAC) and dialkyldimethylammonium (DADMAC) as well as the ionic liquid butylpyridinium and 15 suspect QACs were detected in at least one wastewater effluent sample. A spatial profile of sediment samples in a lake demonstrated potential inputs from both municipal wastewater effluent and agricultural sources for BACs. In sediment cores, two distinct trends of temporal QAC accumulation were observed. In lakes with large watersheds and mixed domestic and industrial wastewater sources (Lake Pepin and Duluth Harbor), peak concentrations of QACs were found at depths corresponding to deposition in the 1980s and decreases after this time are attributed to improved wastewater treatment and source control. In a smaller lake with predominantly domestic wastewater inputs (Lake Winona), concentrations of QACs increased slowly over time until today.

Emerging investigator series: use of behavioural endpoints in the regulation of chemicals

Abstract: Interest in behavioural ecotoxicology is growing, partly due to technological and computational advances in recording behaviours but also because of improvements of detection capacity facilitating reporting effects at environmentally relevant concentrations. The peer-reviewed literature now contains studies investigating the effects of chemicals, including pesticides and pharmaceuticals, on migration, dispersal, aggression, sociability, reproduction, feeding and anti-predator behaviours in vertebrates and invertebrates. To understand how behavioural studies could be used in regulatory decision-making we: (1) assessed the legal obstacles to using behavioural endpoints in EU chemicals regulation; (2) analysed the known cases of use of behavioural endpoints in EU chemicals regulation; and (3) provided examples of behavioural endpoints of relevance for population level effects. We conclude that the only legal obstacle to the use of behavioural endpoints in EU chemicals regulation is whether an endpoint is considered to be relevant at the population level or not. We also conclude that ecotoxicity studies investigating behavioural endpoints are occasionally used in the EU chemicals regulation, and underscore that behavioural endpoints can be relevant at the population level. To improve the current use of behavioural studies in regulatory decision-making contribution from all relevant stakeholders is required. We have the following recommendations: (1) researchers should conduct robust, well-designed and transparent studies that emphasize the relevance of the study for regulation of chemicals; (2) editors and scientific journals should promote detailed, reliable and clearly reported studies; (3) regulatory agencies and the chemical industry need to embrace new behavioural endpoints of relevance at the population level.

Distribution of pesticides in agricultural and urban soils of Brazil: a critical review

Abstract: The extensive use of pesticides leads to soil contamination and is harmful to environmental health. Brazil is considered the world's largest consumer of pesticides; however, there is no published review of the distribution and concentration of pesticides in the Brazilian soils. Thus, the objective of this study was to analyze the occurrence of pesticide residues in Brazilian soils through a systematic review of the data obtained from the official records of government agencies and scientific literature. Further, this review aims to estimate the risk quotient using the data extracted from these studies and compare it with the values from current legislation. The studies on pesticides were selected and screened, out of which 21 scientific articles were included in this review. The studies highlighted that 55 pesticides were detected in the soils in Brazil. Of these, 58% belonged to the chemical class of organochlorines and their concentration ranged from 0.0002-1243.68 mg kg-1. DDT (0.00002-1243.68 mg kg-1), HCH (0.00007-962.00 mg kg-1) and diuron (0.0031-4.16 mg kg-1) contributed to highest pesticide concentrations in soil. Residential soils had higher pesticide concentrations and greater risk factors than the agricultural soils. Moreover, 20% of the studies detected mixtures containing more than 10 types of pesticides. This study concluded that the specific scenarios evaluated by the reviewed studies do not reflect the current pesticide use and contamination in Brazil and there is a need for more information related to pesticide contamination in soils.

Positive matrix factorization on source apportionment for typical pollutants in different environmental media: a review

Abstract: A bibliometric analysis of published papers with the key words "positive matrix factorization" and "source apportionment" in 'Web of Science', reveals that more than 1000 papers are associated with this research and that approximately 50% of these were produced in Asia. As a receptor-based model, positive matrix factorization (PMF) has been widely used for source apportionment of various environmental pollutants, such as persistent organic pollutants (POPs), heavy metals, volatile organic compounds (VOCs) as well as inorganic cations and anions in the last decade. In this review, based on the papers mainly from 2008 to 2018 that focused on source apportionment of pollutants in different environmental media, we provide a comparison and summary of the source categories of typical environmental pollutants, with a special focus on polycyclic aromatic hydrocarbons (PAHs), apportioned using PMF. Based on the statistical average, coal combustion and vehicular emission, are shown to be the two most common sources of PAHs, and contribute much more to emissions than other sources, such as biomass burning, biogenic sources and waste incineration. Heavy metals were mainly from agricultural activities, industrial and vehicular emissions and mining activities. Quantitative source apportionment on pollutants such as VOCs and particulate matter were also apportioned, showing a prominent contribution from fossil-fuel combustion. We conclude that, aside from natural sources, abatement strategies should be focused on changes in energy structure and industrial activities, especially in China. Source apportionment of typical POPs including polychlorinated dibenzo-p-dioxins/dibenzofurans (PCDD/Fs), polychlorinated biphenyls (PCBs), halogenated flame retardants (HFRs) and perfluorinated compounds (PFCs) is less comprehensive and further study is required.

How the 2010 Deepwater Horizon spill reshaped our understanding of crude oil photochemical weathering at sea: a past, present, and future perspective

Abstract: The weathering of crude oil at sea has been researched for nearly half a century. However, there have been relatively few opportunities to validate laboratory-based predictions about the rates, relative importance, and controls of oil weathering processes (e.g., evaporation, photo-oxidation, and emulsification) under natural field conditions. The 2010 Deepwater Horizon (DWH) spill in the Gulf of Mexico provided the oil spill science community with a unique opportunity to evaluate our laboratory-based predictions in nature. With a focus on photochemical weathering, we review what we knew prior to the DWH spill, what we learned from the DWH spill, and what priority gaps in knowledge remain. Three key findings from the DWH spill are discussed. First, the rate and extent of photochemical weathering was much greater for the floating surface oil than expected based on early conceptual models of oil weathering. Second, indirect photochemical processes played a major role in the partial oxidation of the floating surface oil. Third, the extensive and rapid changes to the physical and chemical properties of oil by sunlight may influence oil fate, transport, and the selection of response tools. This review also highlights findings and predictions about photochemical weathering of oil from several decades ago that appear to have escaped the broader scientific narrative and ultimately proved true for the DWH spill. By focusing on these early predictions and synthesizing the numerous findings from the DWH spill, we expect this review will better prepare the oil spill science community to respond to the next big spill in the ocean.

Photochemistry of iron in aquatic environments

Abstract: Light energy is a driver for many biogeochemical element cycles in aquatic systems. The sunlight-induced photochemical reduction of ferric iron (Fe(iii) photoreduction) to ferrous iron (Fe(ii)) by either direct ligand-to-metal charge transfer or by photochemically produced radicals can be an important source of dissolved Feaq2+ in aqueous and sedimentary environments. Reactive oxygen species (ROS) are formed by a variety of light-dependent reactions. Those ROS can oxidize Fe(ii) or reduce Fe(iii), and due to their high reactivity they are key oxidants in aquatic systems where they influence many other biogeochemical cycles. In oxic waters with circumneutral pH, the produced Fe(ii) reaches nanomolar concentrations and serves as a nutrient, whereas in acidic waters, freshwater and marine sediments, which are rich in Fe(ii), the photochemically formed Fe(ii) can reach concentrations of up to 100 micromolar and be used as additional electron donor for acidophilic aerobic, microaerophilic, phototrophic and, if nitrate is present, for nitrate-reducing Fe(ii)-oxidizing bacteria. Therefore, Fe(iii) photoreduction may not only control the primary productivity in the oceans but has a tremendous impact on Fe cycling in the littoral zone of freshwater and marine environments. In this review, we summarize photochemical reactions involving Fe, discuss the role of ROS in Fe cycling, and highlight the importance of photoreductive processes in the environment.

Effects of aging and weathering on immobilization of trace metals/metalloids in soils amended with biochar

Abstract: Biochar is an effective amendment for trace metal/metalloid (TMs) immobilization in soils. The capacity of biochar to immobilize TMs in soil can be positively or negatively altered due to the changes in the surface and structural chemistry of biochar after soil application. Biochar surfaces are oxidized in soils and induce structural changes through physical and biochemical weathering processes. These changes in the biochar surface and structural chemistry generally increase its ability to immobilize TMs, although the generation of dissolved black carbon during weathering may increase TM mobility. Moreover, biochar modification can improve its capacity to immobilize TMs in soils. Over the short-term, engineered/modified biochar exhibited increased TM immobilization capacity compared with unmodified biochar. In the long-term, no large distinctions in such capacities were seen between modified and unmodified biochars due to weathering. In addition, artificial weathering at laboratories also revealed increased TM immobilization in soils. Continued collection of mechanistic evidence will help evaluate the effect of natural and artificial weathering, and biochar modification on the long-term TM immobilization capacity of biochar with respect to feedstock and synthesis conditions in contaminated soils.

Insights into origins and function of the unexplored majority of the reductive dehalogenase gene family as a result of genome assembly and ortholog group classification

Abstract: Organohalide respiring bacteria (OHRB) express reductive dehalogenases for energy conservation and growth. Some of these enzymes catalyze the reductive dehalogenation of chlorinated and brominated pollutants in anaerobic subsurface environments, providing a valuable ecosystem service. Dehalococcoides mccartyi strains have been most extensively studied owing to their ability to dechlorinate all chlorinated ethenes – most notably carcinogenic vinyl chloride – to ethene. The genomes of OHRB, particularly obligate OHRB, often harbour multiple putative reductive dehalogenase genes (rdhA), most of which have yet to be characterized. We recently sequenced and closed the genomes of eight new strains, increasing the number of available D. mccartyi genomes in NCBI from 16 to 24. From all available OHRB genomes, we classified predicted translations of reductive dehalogenase genes using a previously established 90% amino acid pairwise identity cut-off to identify Ortholog Groups (OGs). Interestingly, the majority of D. mccartyi dehalogenase gene sequences, once classified into OGs, exhibited a remarkable degree of synteny (gene order) in all genomes sequenced to date. This organization was not apparent without the classification. A high degree of synteny indicates that differences arose from rdhA gene loss rather than recombination. Phylogenetic analysis suggests that most rdhA genes have a long evolutionary history in the Dehalococcoidia with origin prior to speciation of Dehalococcoides and Dehalogenimonas. We also looked for evidence of synteny in the genomes of other species of OHRB. Unfortunately, there are too few closed Dehalogenimonas genomes to compare at this time. There is some partial evidence for synteny in the Dehalobacter restrictus genomes, but here too more closed genomes are needed for confirmation. Interestingly, we found that the rdhA genes that encode enzymes that catalyze dehalogenation of industrial pollutants are the only rdhA genes with strong evidence of recent lateral transfer – at least in the genomes examined herein. Given the utility of the RdhA sequence classification to comparative analyses, we are building a public web server (http://RDaseDB.biozone.utoronto.ca) for the community to use, which allows users to add and classify new sequences, and download the entire curated database of reductive dehalogenases.

High-throughput wastewater analysis for substance use assessment in central New York during the COVID-19 pandemic.

Abstract: Wastewater entering sewer networks represents a unique source of pooled epidemiological information. In this study, we coupled online solid-phase extraction with liquid chromatography-high resolution mass spectrometry to achieve high-throughput analysis of health and lifestyle-related substances in untreated municipal wastewater during the coronavirus disease 2019 (COVID-19) pandemic. Twenty-six substances were identified and quantified in influent samples collected from six wastewater treatment plants during the COVID-19 pandemic in central New York. Over a 12 week sampling period, the mean summed consumption rate of six major substance groups (i.e., antidepressants, antiepileptics, antihistamines, antihypertensives, synthetic opioids, and central nervous system stimulants) correlated with disparities in household income, marital status, and age of the contributing populations as well as the detection frequency of severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) RNA in wastewater and the COVID-19 test positivity in the studied sewersheds. Nontarget screening revealed the covariation of piperine, a nontarget substance, with SARS-CoV-2 RNA in wastewater collected from one of the sewersheds. Overall, this proof-of-the-concept study demonstrated the utility of high-throughput wastewater analysis for assessing the population-level substance use patterns during a public health crisis such as COVID-19.

A global atmospheric chemistry model for the fate and transport of PFCAs and their precursors

Abstract: Perfluorocarboxylic acids (PFCAs) are environmental contaminants that are highly persistent, and many are bio-accumulative and have been detected along with their atmospheric precursors far from emission sources. The overall importance of precursor emissions as an indirect source of PFCAs to the environment is uncertain. Previous studies have estimated the atmospheric source of PFCAs using models and degradation pathways of differing complexities, leading to quantitatively different results. We present results from simulations of atmospheric PFCA formation and fate using the chemical transport model GEOS-Chem. We simulate the most up-to-date chemistry available to our knowledge for the degradation of the precursors fluorotelomer alcohol (FTOH), fluorotelomer olefin (FTO), and fluorotelomer iodide (FTI), as well as the deposition and transport of the precursors, intermediates and end-products of the formation chemistry. We calculate yields of C3–C13 PFCAs formed from 4 : 2 to 12 : 2 fluorotelomer precursors and their deposition to the surface. We find that the ratio of long-chain to short-chain PFCAs increases strongly with distance from source regions. We compare our model results to remote deposition measurements and mid-latitude rainwater measurements. The model captures the observed relationship between rainwater abundance and PFCA chain length, as well as the average deposition rates at mid-latitude and Arctic sites, but underestimates the deposition of PFDoA, PFDA, and TFA at mid-latitudes and PFNA at the Devon Ice Cap. We provide estimates of cumulative PFCA deposition globally. We find that given the most recent emission inventory, the atmospheric source of PFCAs is 6–185 tonnes per year globally and 0.1–2.1 tonnes per year to the Arctic.

Interactions of ferrous iron with clay mineral surfaces during sorption and subsequent oxidation

Abstract: In submerged soils and sediments, clay minerals are often exposed to anoxic waters containing ferrous iron (Fe2+). Here, we investigated the sorption of Fe2+ onto a synthetic montmorillonite (Syn-1) low in structural Fe (<0.05 mmol Fe per kg) under anoxic conditions and the effects of subsequent oxidation. Samples were prepared at two Fe-loadings (0.05 and 0.5 mol Fe added per kg clay) and equilibrated for 1 and 30 days under anoxic conditions (O2 < 0.1 ppm), followed by exposure to ambient air. Iron solid-phase speciation and mineral identity was analysed by 57Fe Mossbauer spectroscopy and synchrotron X-ray absorption spectroscopy (XAS). Mossbauer analyses showed that Fe(II) was partially oxidized (14–100% of total added Fe2+) upon sorption to Syn-1 under anoxic conditions. XAS results revealed that the added Fe2+ mainly formed precipitates (layered Fe minerals, Fe(III)-bearing clay minerals, ferrihydrite, and lepidocrocite) in different quantities depending on the Fe-loading. Exposing the suspensions to ambient air resulted in rapid and complete oxidation of sorbed Fe(II) and the formation of Fe(III)-phases (Fe(III)-bearing clay minerals, ferrihydrite, and lepidocrocite), demonstrating that the clay minerals were unable to protect ferrous Fe from oxidation, even when equilibrated 30 days under anoxic conditions prior to oxidation. Our findings clarify the role of clay minerals in the formation and stability of Fe-bearing solid phases during redox cycles in periodically anoxic environments.

Potential risks of antibiotic resistant bacteria and genes in bioremediation of petroleum hydrocarbon contaminated soils

Abstract: Bioremediation represents a sustainable approach to remediating petroleum hydrocarbon contaminated soils. One aspect of sustainability includes the sourcing of nutrients used to stimulate hydrocarbon-degrading microbial populations. Organic nutrients such as animal manure and sewage sludge may be perceived as more sustainable than conventional inorganic fertilizers. However, organic nutrients often contain antibiotic residues and resistant bacteria (along with resistance genes and mobile genetic elements). This is further exacerbated since antibiotic resistant bacteria may become more abundant in contaminated soils due to co-selection pressures from pollutants such as metals and hydrocarbons. We review the issues surrounding bioremediation of petroleum-hydrocarbon contaminated soils, as an example, and consider the potential human-health risks from antibiotic resistant bacteria. While awareness is coming to light, the relationship between contaminated land and antibiotic resistance remains largely under-explored. The risk of horizontal gene transfer between soil microorganisms, commensal bacteria and/or human pathogens needs to be further elucidated, and the environmental triggers for gene transfer need to be better understood. Findings of antibiotic resistance from animal manures are emerging, but even fewer bioremediation studies using sewage sludge have made any reference to antibiotic resistance. Resistance mechanisms, including those to antibiotics, have been considered by some authors to be a positive trait associated with resilience in strains intended for bioremediation. Nevertheless, recognition of the potential risks associated with antibiotic resistant bacteria and genes in contaminated soils appears to be increasing and requires further investigation. Careful selection of bacterial candidates for bioremediation possessing minimal antibiotic resistance as well as pre-treatment of organic wastes to reduce selective pressures (e.g., antibiotic residues) are suggested to prevent environmental contamination with antibiotic-resistant bacteria and genes.

Emerging investigator series: critical review of photophysical models for the optical and photochemical properties of dissolved organic matter

Abstract: Optical measurements (absorbance and fluorescence) are widely used to track dissolved organic matter (DOM) quantity and quality in natural and engineered systems. Despite many decades of research on the optical properties of DOM, there is a lack of understanding with regards to the underlying photophysical model that is the basis for these optical properties. This review both summarizes advances to date on the photophysical properties of DOM and seeks to critically evaluate the photophysical models for DOM optical properties. Recent studies have refined the quantitative understanding of DOM photophysical properties such as excited state lifetimes and energies, rates of different photophysical processes, and quantum yields. Considering fundamental models, more clarity is needed on whether DOM photophysical processes are due to a superposition of non-interacting components (superposition model), or whether a portion of optical signals can be ascribed to electronically interacting moieties, for example in the form of electron donor–acceptor complexes (charge transfer model). Multiple studies over more than two decades have provided evidence for the charge transfer model. Questions have been raised, however, about the broad applicability of the charge transfer model. The charge transfer and superposition model are critically reviewed in light of this current research. Recommendations are given for future studies to help clarify the accuracy of these competing photophysical models.

Integrated experimental and theoretical approach to probe the synergistic effect of ammonia in methanesulfonic acid reactions with small alkylamines

Abstract: While new particle formation events have been observed worldwide, our fundamental understanding of the precursors remains uncertain. It has been previously shown that small alkylamines and ammonia (NH3) are key actors in sub-3 nm particle formation through reactions with acids such as sulfuric acid (H2SO4) and methanesulfonic acid (CH3S(O)(O)OH, MSA), and that water also plays a role. Because NH3 and amines co-exist in air, we carried out combined experimental and theoretical studies examining the influence of the addition of NH3 on particle formation from the reactions of MSA with methylamine (MA) and trimethylamine (TMA). Experiments were performed in a 1 m flow reactor at 1 atm and 296 K. Measurements using an ultrafine condensation particle counter (CPC) and a scanning mobility particle sizer (SMPS) show that new particle formation was systematically enhanced upon simultaneous addition of NH3 to the MSA + amine binary system, with the magnitude depending on the amine investigated. For the MSA + TMA reaction system, the addition of NH3 at ppb concentrations produced a much greater effect (i.e. order of magnitude more particles) than the addition of ∼12 000 ppm water (corresponding to ∼45–50% relative humidity). The effect of NH3 on the MSA + MA system, which is already very efficient in forming particles on its own, was present but modest. Calculations of energies, partial charges and structures of small cluster models of the multi-component particles likewise suggest synergistic effects due to NH3 in the presence of MSA and amine. The local minimum structures and the interactions involved suggest mechanisms for this effect.

Compound health risk assessment of cumulative heavy metal exposure: a case study of a village near a battery factory in Henan Province, China

Abstract: The concentrations of the heavy metals Hg, As, Ni, Pb, Cd, Cr, Cu and Zn in soil, groundwater, air, and locally produced grain (wheat and corn) and vegetables were determined in a village near a battery factory in Xinxiang, Henan Province, China. A multimedia, multipathway health risk assessment of heavy metal exposure was carried out using the health risk model recommended by the United States Environmental Protection Agency (US EPA). The results showed that the concentrations of Cd in soil, Cd and Pb in wheat, Hg in corn, Cd, Hg, and Pb in vegetables, and Cd and As in PM2.5, PM10, and TSP were all higher than the corresponding limits for heavy metals in China. The non-carcinogenic risks (HIs) for all environmental media were higher in children than in adults, and the carcinogenic risks (TCRs) of heavy metal exposure in other media except for soil were higher in adults than in children. The total HI and TCR in adults and children were higher than the standard limit values because of heavy metal exposure through soil, groundwater, PM10, grain and vegetables. Cd was the most significant heavy metal in terms of HI and TCR factors; among the evaluated pathways, the contribution of diet was the largest. The HI and TCR caused by dietary crops account for 96.7% and 98.9% of the total in adults and 90.2% and 96.2% of the total in children, respectively. To maintain the health of the residents in the study area, it is strongly recommended to stop planting edible agricultural products immediately, start buying grain and vegetables from outside the study area, and strictly strengthen the control of heavy metal pollution in the study area. The source apportionment results show that Cd, Ni and As were mainly from industrial sources, which was related to sewage irrigation and battery plant deposition, and Pb and Cr were mainly from agricultural activities.

Trichloroethylene, a ubiquitous environmental contaminant in the risk for Parkinson's disease

Abstract: Organic solvents are common chemicals used in industry throughout the world, however, there is evidence for adverse health effects from exposure to these compounds. Trichloroethylene (TCE) is a halogenated solvent that has been used as a degreasing agent since the early 20th century. Due to its widespread use, TCE remains one of the most significant environmental contaminants in the US, and extensive research suggests TCE is a causative factor in a number of diseases, including cancer, fetal cardiac development, and neurotoxicity. TCE has also been implicated as a possible risk factor in the development of the most common neurodegenerative movement disorder, Parkinson's disease (PD). However, there is variable concordance across multiple occupational epidemiological studies assessing TCE (or solvent) exposure and risk for PD. In addition, there remains a degree of uncertainty about how TCE elicits toxicity to the dopaminergic system. To this end, we review the specific neurotoxic mechanisms of TCE in the context of selective vulnerability of dopaminergic neurons. In addition, we consider the complexity of combined risk factors that ultimately contribute to neurodegeneration and discuss the limitations of single-factor exposure assessments.

Effects of antibiotics on microbial community structure and microbial functions in constructed wetlands treated with artificial root exudates

Abstract: In the rhizosphere, plant root exudates can mediate the toxicity of antibiotics on microorganisms, yet the mechanisms are poorly understood. To simulate the antibiotic contamination of global rivers and lakes, the current study investigated the effects of two antibiotics (ofloxacin at 8.69 × 104 ng L−1 and tetracycline at 8.62 × 104 ng L−1) and their binary combination (8.24 × 104 ng L−1 ofloxacin and 7.11 × 104 ng L−1 tetracycline) on bacterial communities in micro-polluted constructed wetlands with and without artificial root exudates. The two antibiotics had no significant effects on the removal of excess carbon and nitrogen from the microcosms treated with and without exudates. Furthermore, with regard to bacterial community structure, antibiotic exposure increased the bacterial richness of bulk and exudate treated microcosms (P < 0.05). However, a significant increase (P < 0.05) in bacterial diversity elicited by ofloxacin and antibiotic mixture exposure was only observed in microcosms with exudates. In exudate treated microcosms, ofloxacin promoted the relative abundance of Arthrobacter spp., which are ofloxacin-resistant bacterial species, which significantly varied from what was observed in microcosms free of exudates. Moreover, tetracycline, ofloxacin and their combination all significantly increased the relative abundance of nitrogen cycling bacteria Rhizobacter spp. and Rhizobium spp., and decreased the relative abundance of antibiotic-resistant bacteria Pseudomonas spp. Simultaneously, with regard to bacterial community functions, the functional profiles (Kyoto Encyclopedia of Genes and Genomes) showed that the pathways of amino acid and carbohydrate metabolism were enhanced by antibiotics in microcosms with exudates. The findings illustrate that antibiotics not only alter the bacterial structure and composition but also change their functional properties in constructed wetlands, and these interruption effects could be affected by root exudates of plants, which may further reveal the ecological implication of plants in constructed wetlands.