Showing papers in "Environmental Science: Processes & Impacts in 2021"

The fate of plastic in the ocean environment – a minireview

Abstract: The presence of plastics in the marine environment poses a threat to ocean life and has received much scientific and public attention in recent years. Plastics were introduced to the market in the 1950s and since then, global production figures and ocean plastic littering have increased exponentially. Of the 359 million tonnes (Mt) produced in 2018, an estimated 14.5 Mt has entered the ocean. In particular smaller plastic particles can be ingested by marine biota causing hazardous effects. Plastic marine debris (PMD) is exposed to physical, chemical and biological stressors. These cause macro and microplastic to break down into smaller fragments, including sub micrometre sized nanoplastic particles, which may account for an important but so far unevaluated fraction of the ocean plastic budget. Physicochemical and biological deterioration of PMD also leads to the release of more volatile compounds and the terminal oxidation of PMD, which most likely accounts for an important but also unevaluated fraction in the ocean plastic budget. This minireview provides an overview on (1) the quantity of plastic production and waste, pathways for plastics to enter the marine realm, the inventory of PMD and the negative effects of PMD to ocean life. (2) We discuss plastic degradation mechanisms in the ocean, expanding on the processes of photodegradation and biodegradation. (3) This review also highlights the emerging topic of nanoplastics in the sea and provides an overview on their specific physical and chemical properties, potential harm to ocean life, and nanoplastic detection techniques.

Recent advances in the applications of nano-agrochemicals for sustainable agricultural development

Abstract: Modern agricultural practices have triggered the process of agricultural pollution. This process can cause the degradation of eco-systems, land, and environment owing to the modern-day by-products of agriculture. The substantial use of chemical fertilizers, pesticides, and, contaminated water for irrigation cause further damage to agriculture. The current scenario of the agriculture and food sector has therefore become unsustainable. Nanotechnology has provided innovative and resourceful frontiers to the agriculture sector by contributing practical applications in conventional agricultural ways and practices. There is a large possibility that agri-nanotechnology can have a significant impact on the sustainable agriculture and crop growth. Recent research has shown the potential of nanotechnology in improving the agriculture sector by enhancing the efficiency of agricultural inputs and providing solutions to agricultural problems for improving food productivity and security. The prospective use of nanoscale agrochemicals such as nanofertilizers, nanopesticides, nanosensors, and nanoformulations in agriculture has transformed traditional agro-practices, making them more sustainable and efficient. However, the application of these nano-products in real field situations raises concern about nanomaterial safety, exposure levels, and toxicological repercussions to the environment and human health. The present review gives an insight into recent advancements in nanotechnology-based agrochemicals that have revolutionized the agriculture sector. Further, the implementation barriers related to the nanomaterial use in agriculture, their commercialization potential, and the need for policy regulations to assess possible nano-agricultural risks are also discussed.

Plastic particles in soil: state of the knowledge on sources, occurrence and distribution, analytical methods and ecological impacts.

Abstract: Increased production and use of plastics has resulted in growth in the amount of plastic debris accumulating in the environment, potentially fragmenting into smaller pieces. Fragments <5 mm are typically defined as microplastics, while fragments <0.1 μm are defined as nanoplastics. Over the past decade, an increasing number of studies have reported the occurrence and potential hazards of plastic particles in the aquatic environment. However, less is understood about plastic particles in the terrestrial environment and specifically how much plastic accumulates in soils, the possible sources, potential ecological impacts, interaction of plastic particles with the soil environment, and appropriate extraction and analytical techniques for assessing the above. In this review, a comprehensive overview and a critical perspective on the current state of knowledge on plastic pollution in the soil environment is provided: detailing known sources, occurrence and distribution, analytical techniques used for identification and quantification and the ecological impacts of particles on soil. In addition, knowledge gaps are identified along with suggestions for future research.

Absorption, distribution, and toxicity of per- and polyfluoroalkyl substances (PFAS) in the brain: a review.

Abstract: Per- and polyfluoroalkyl substances (PFAS) are a class of synthetic chemicals colloquially known as “forever chemicals” because of their high persistence. PFAS have been detected in the blood, liver, kidney, heart, muscle and brain of various species. Although brain is not a dominant tissue for PFAS accumulation compared to blood and liver, adverse effects of PFAS on brain functions have been identified. Here, we review studies related to the absorption, accumulation, distribution and toxicity of PFAS in the brain. We summarize evidence on two potential mechanisms of PFAS entering the brain: initiating blood–brain barrier (BBB) disassembly through disrupting tight junctions and relying on transporters located at the BBB. PFAS with diverse structures and properties enter and accumulate in the brain with varying efficiencies. Compared to long-chain PFAS, short-chain PFAS may not cross cerebral barriers effectively. According to biomonitoring studies and PFAS exposure experiments, PFAS can accumulate in the brain of humans and wildlife species. With respect to the distribution of PFAS in specific brain regions, the brain stem, hippocampus, hypothalamus, pons/medulla and thalamus are dominant for PFAS accumulation. The accumulation and distribution of PFAS in the brain may lead to toxic effects in the central nervous system (CNS), including PFAS-induced behavioral and cognitive disorders. The specific mechanisms underlying such PFAS-induced neurotoxicity remain to be explored, but two major potential mechanisms based on current understanding are PFAS effects on calcium homeostasis and neurotransmitter alterations in neurons. Based on the information available about PFAS uptake, accumulation, distribution and impacts on the brain, PFAS have the potential to enter and accumulate in the brain at varying levels. The balance of existing studies shows there is some indication of risk in animals, while the human evidence is mixed and warrants further scrutiny.

Occurrence, human exposure, and risk of microplastics in the indoor environment

Abstract: Microplastics (MPs) are a group of emerging contaminants that have attracted increasing scientific and societal attention over the past decade due to their ubiquitous detection in all environmental compartments. So far, most studies on MPs focus on characterizing their occurrence, fate, and impact in the aquatic environment. Therefore, very little is known about the magnitude, patterns, and associated risks of human exposure to MPs, particularly indoors. This is a significant research gap given that people spend most of their time (up to 90%) indoors, which is exacerbated over the past year by COVID-19 lockdown measures. Critical evaluation of the existing literature revealed the presence of MPs at higher concentrations in indoor air and dust (from homes and offices) compared to outdoors. This was attributed to several factors including: indoor MPs sources (e.g. furniture, textiles), increased deposition of atmospheric MPs indoors, and less atmospheric mixing and dilution compared to outdoor air. Current understanding is that indoor human exposure to MPs occurs via a combination of inhalation, ingestion, and dermal contact. Dietary intake was considered the major pathway of human exposure to MPs until recent studies revealed potential high exposure via inhalation. Moreover, exposure via inadvertent dust ingestion and dermal contact cannot be neglected, particularly for young children. This is alarming due to the potential toxic implications of MPs exposure. Early toxicological evidence indicates that small MPs (<20 microm) can cause oxidative stress and inflammation, while particles <5 microm can be engulfed by cells and translocated to accumulate in different organs. Also, there is increasing concern over potential leaching of toxic chemicals used as plastic additives (e.g. plasticizers and flame retardants) upon exposure to MPs due to their large surface area. However, MPs exposure and risk assessment in humans is still in its infancy and more research is necessary to provide the knowledge base required for regulations to protect human health and environment against MPs.

Chlorpyrifos in environment and food: a critical review of detection methods and degradation pathways

Abstract: Chlorpyrifos (CP) is a class of organophosphorus (OP) pesticides, which find extensive applications as acaricide, insecticide and termiticide. The use of CP has been indicated in environmental contamination and disturbance in the biogeochemical cycles. CP has been reported to be neurotoxic and has a detrimental effect on immunological and psychological health. Therefore, it is necessary to design and develop effective degradation methods for the removal of CP from the environment. In the past few years, physicochemical (advanced oxidation process) and biological treatment approaches have been widely employed for the pesticide removal. However, the byproducts of this process are more toxic than the parent compound and along with an incomplete degradation of CP. This review focuses on the toxicity of CP, the sources of contamination, degradation pathways, physicochemical, biological, and nano-technology based methods employed for the degradation of CP. In addition, consolidated information on various detection methods and materials used for the detection have been provided in this review.

Phthalate pollution: environmental fate and cumulative human exposure index using the multivariate analysis approach.

Abstract: A comprehensive review was performed on the environmental fate, environmental occurrence, toxicity, physical–chemical properties, abiotic and biotic removal and degradation of phthalate esters (PAEs) to compute the overall phthalate exposure and their impact on human beings. The removal and degradation of these wide spread pollutants by abiotic processes such as hydrolysis and photodecomposition are very slow and insignificant. On the other hand, the breakdown of PAEs by microorganisms is considered to be one of the major routes of environmental degradation for these widespread pollutants. Numerous microbial strains have been reported to degrade these compounds under aerobic, anaerobic and facultative conditions. Concurrently, the environmental fate, transport and transformation/degradation of these compounds under natural conditions are highly dependent on their physical and chemical properties. In order to understand the relationship between the concentrations of PAEs of different environmental compartments and human exposure prospects, a novel average phthalate pollution index (PPI) and cumulative phthalate exposure index (PEI) were proposed using the multivariate analysis approach. These indices were computed on the basis of relative importance, environmental occurrence, toxicity, physical–chemical properties, abiotic and biotic removal and degradation of dimethyl phthalate (DMP), diethyl phthalate (DEP), dibutyl phthalate (DBP), butyl benzyl phthalate (BBP) and diethyl-hexyl phthalate (DEHP). At present, the average PPI and cumulative PEI of 29 countries were evaluated using the concentrations of PAEs reported in the literature. These indices signify the overall phthalate pollution, human exposure and their interrelation. According to the index, Slovakia, Canada, Taiwan, Sweden and South Africa are among the top five countries in terms of cumulative phthalate exposure as per the existing data. The exposure percentage of total PAEs significantly varies between 23 and 44% since many environmental compartments are not directly exposed to human beings and they are degraded under natural conditions.

PFAS soil and groundwater contamination via industrial airborne emission and land deposition in SW Vermont and Eastern New York State, USA.

Abstract: In order to understand the extent to which airborne PFAS emission can impact soil and groundwater, we conducted a sampling campaign in areas of conserved forest lands near Bennington, VT/Hoosick Falls, NY. This has been home to sources of PFAS air-emissions from Teflon-coating operations for over 50 years. Since 2015, the Vermont and New York Departments of Environmental Conservation have documented ∼1200 residential wells and two municipal water systems across a 200 km2 area contaminated with perfluorooctanoic acid (PFOA). Given the large areal extent of the plume, and the fact that much of the contaminated area lies up-gradient and across rivers from manufactures, we seek to determine if groundwater contamination could have resulted primarily from air-emission, land deposition, and subsequent leaching to infiltrating groundwater. Sampling of soils and groundwater in the Green Mountain National Forest (GMNF) downwind of factories shows that both soil and groundwater PFOA contamination extend uninterrupted from inhabited areas into conserved forest lands. Groundwater springs and seeps in the GMNF located 8 km downwind, but >300 meters vertically above factories, contain up to 100 ppt PFOA. Our results indicate that air-emitted PFAS can contaminate groundwater and soil in areas outside of those normally considered down-gradient of a source with respect to regional groundwater flow.

Frequency of use of household products containing VOCs and indoor atmospheric concentrations in homes

Abstract: Volatile organic compounds (VOCs) are a key class of atmospheric emission released from highly complex petrochemical, transport and solvent sources both outdoors and indoors. This study established the concentrations and speciation of VOCs in 60 homes (204 individuals, 360 × 72 h samples, 40 species) in summer and winter, along with outdoor controls. Self-reported daily statistics were collected in each home on the use of cleaning, household and personal care products, all of which are known to release VOCs. Frequency of product use varied widely: deodorants: 2.9 uses home per day; sealant-mastics 0.02 uses home per day. The total concentration of VOCs indoors (range C2-C10) was highly variable between homes e.g. range 16.6-8150 μg m-3 in winter. Indoor concentrations of VOCs exceeded outdoor for 84% of households studied in summer and 100% of homes in winter. The most abundant VOCs found indoors in this study were n-butane (wintertime range: 1.5-4630 μg m-3), likely released as aerosol propellant, ethanol, acetone and propane. The cumulative use VOC-containing products over multiday timescales by occupants provided little predictive power to infer 72 hour averaged indoor concentrations. However, there was weak covariance between the cumulative usage of certain products and individual VOCs. From a domestic emissions perspective, reducing the use of hydrocarbon-based aerosol propellants indoors would likely have the largest impact.

Advances in research on petroleum biodegradability in soil

Abstract: With the increased demand for petroleum and petroleum products from all parts of the society, environmental pollution caused by petroleum development and production processes is becoming increasingly serious. Soil pollution caused by petroleum seriously affects environmental quality in addition to human lives and productivity. At present, petroleum in soil is mainly degraded by biological methods. In their natural state, native bacteria in the soil spontaneously degrade petroleum pollutants that enter the soil; however, when the pollution levels increase, the degradation rates decrease, and it is necessary to add nutrients, dissolved oxygen, biosurfactants and other additives to improve the degradation ability of the native bacteria in the soil. The degradation process can also be enhanced by adding exogenous petroleum-degrading bacteria, microbial immobilization technologies, and microbial fuel cell technologies.

Distribution and fate of per- and polyfluoroalkyl substances (PFAS) in wastewater treatment facilities.

Abstract: Anthropogenic compounds known as per- and polyfluoroalkyl substances (PFAS) represent a major class of contaminants of emerging concern composed of nearly 5000 chemicals. Many PFAS are persistent, bioaccumulative and toxic, and their widespread use makes their environmental distribution a growing concern. Wastewater treatment facilities (WWTFs) are a conduit of PFAS to the environment, integrating common household products from municipal sewage, industrial wastewater sources, septic materials, and firefighting wastewaters in effluent and sludge. This study investigated the distribution and fate of twenty-four PFAS within six New Hampshire municipal WWTFs applying a range of biological and disinfection unit processes. PFAS quantification was conducted using two approaches: (1) liquid chromatography with tandem mass spectrometry (LC-MS/MS) of 24 known compounds and (2) a total oxidizable precursor assay (TOP assay) followed by LC-MS/MS to determine the total oxidizable PFAS concentration. Of the 24 PFAS analyzed, up to 7 and 12 constituents were detected in influent and effluent of WWTFs, respectively, with concentrations ranging from 30 to 128 ng L-1 in March. Effluent ΣPFAS concentration increased during July, with concentrations between 70 and 198 ng L-1 for the same detected constituents. Short-chain PFAS were dominant in both influent and effluent, while long-chain compounds dominated in WWTF sludge. The increase in terminal end-products after oxidation by the TOP assay indicates the presence of unquantified PFAS precursors in both influent and effluent. A significantly lower proportion of oxidizable PFAS precursors were detected in July influent and effluent relative to March, indicating a possible role of season or temperature on microbial transformation of these compounds prior to reaching WWTFs and during treatment. These results provide new insight into PFAS distribution and fate during two seasons in New England municipal WWTFs.

Assessment of emerging polar organic pollutants linked to contaminant pathways within an urban estuary using non-targeted analysis

Abstract: A comprehensive, non-targeted analysis of polar organic pollutants using high resolution/accurate mass (HR/AM) mass spectrometry approaches has been applied to water samples from San Francisco (SF) Bay, a major urban estuary on the western coast of the United States, to assess occurrence of emerging contaminants and inform future monitoring and management activities. Polar Organic Chemical Integrative Samplers (POCIS) were deployed selectively to evaluate the influence of three contaminant pathways: urban stormwater runoff (San Leandro Bay), wastewater effluent (Coyote Creek, Lower South Bay), and agricultural runoff (Napa River). Grab samples were collected before and after deployment of the passive samplers to provide a quantitative snapshot of contaminants for comparison. Composite samples of wastewater effluent (24 hours) were also collected from several wastewater dischargers. Samples were analyzed using liquid-chromatography coupled to high resolution mass spectrometry. Resulting data were analyzed using a customized workflow designed for high-fidelity detection, prioritization, identification, and semi-quantitation of detected molecular features. Approximately 6350 compounds were detected in the combined data set, with 424 of those compounds tentatively identified through high quality spectral library match scores. Compounds identified included ethoxylated surfactants, pesticide and pharmaceutical transformation products, polymer additives, and rubber vulcanization agents. Compounds identified in samples were reflective of the apparent sources and pathways of organic pollutant inputs, with stormwater-influenced samples dominated by additive chemicals likely derived from plastics and vehicle tires, as well as ethoxylated surfactants.

Insufficient evidence for the existence of natural trifluoroacetic acid

Abstract: Trifluoroacetic acid (TFA) is a persistent and mobile pollutant that is present ubiquitously in the environment. As a result of a few studies reporting its presence in pre-industrial samples and a purported unaccounted source, TFA is often claimed to exist naturally. Here, we examine the evidence for natural TFA by: (i) critically evaluating measurements of TFA in pre-industrial samples; (ii) examining the likelihood of TFA formation by hypothesized mechanisms; (iii) exploring other potential TFA sources to the deep ocean; and (iv) examining global budgets of TFA. We conclude that the presence of TFA in the deep ocean and lack of closed TFA budget is not sufficient evidence that TFA occurs naturally, especially without a reasonable mechanism of formation. We argue the paradigm of natural TFA should no longer be carried forward.

Distribution and ecological risk assessment of typical antibiotics in the surface waters of seven major rivers, China

Abstract: The consumption and production of antibiotics in China rank highest in the world. As such, the occurrence of antibiotics in environmental media of China has raised significant concerns. Rivers play an important role in the sustainable development of China's economy and society, possibly causing high levels and detection frequencies of antibiotics in the aquatic environment of rivers in China. Therefore, it is necessary to understand the distribution and risk level of antibiotics in rivers. From south to north, China has seven major rivers vertically and horizontally. They are Yangtze River, Yellow River, Hai River, Liao River, Huai River, Songhua River and Pearl River. In this review, we made an extensive literature survey and published all studies on antibiotic concentrations in seven river systems of China from 2010 to 2020 were sorted out to provide a clear draw of the distribution characteristics of antibiotics. We found that 70 antibiotics have been detected in the seven major river systems. 13 typical antibiotics in surface waters of seven river systems were systematically reviewed and ecological risk assessment was conducted. The occurrence frequencies of high-risk antibiotics in surface waters followed the rank order: ETM–H2O > CIP > OFX > SMX > NOR. The RQs values of seven rivers decreased in the order of Hai River (1.58–18 094.3) > Liao River (1.14–290.23) > Pearl River (2.11–118.25) > Yangtze River (0.3–64.78) > Yellow River (7.56–35.45) > Songhua River (0.03–22.26) > Huai River (1.87–20.83).

Fates and spatial variations of accumulation mode particles in a multi-zone indoor environment during the HOMEChem campaign.

Abstract: Studying the indoor dynamics that impact particles is crucial in order to understand indoor air chemistry and assess overall human exposure to particles. This work investigates spatial gradients in particle concentration, caused by indoor transport and loss mechanisms. We conducted a variety of cooking experiments during the House Observations of Microbial and Environmental Chemistry (HOMEChem) campaign in June 2018 that allowed us to probe these mechanisms. We measured size-resolved (0.06–1 μm and 0.13–3 μm) particle number concentrations from cooking experiments using optical instruments at four locations throughout the house simultaneously. The particle number concentration in the kitchen was 40 ± 10% and 70 ± 10% higher than the concentrations in the living room and the bedroom, respectively. There was a minor size dependence, with larger differences in the smaller sizes of the accumulation mode (0.1–2.5 μm) than the larger end of the range. Dilution accounts for the majority of these concentration differences. Surface deposition was the dominant fate of particles within a zone, with observed deposition velocities ranging from 0.1 to 0.6 m h−1.

COVID-19 lockdowns induced land surface temperature variability in mega urban agglomerations in India.

Abstract: The COVID-19 pandemic forced a nationwide lockdown in India for months when close to 1.3 billion people were confined to their homes. An abrupt halt in the majority of the urban activities reduced the generation of anthropogenic heat which often exacerbates the Urban Heat Island (UHI) effect in the urban pockets of the country. We studied the lockdown impact on seven highly populated and polluted mega urban agglomerations across India, namely Delhi, Ahmedabad, Hyderabad, Kolkata, Mumbai, Bengaluru and Chennai, using near-anniversary Landsat 8 data. The results revealed that the lockdowns have improved the air quality and reduced the Land Surface Temperature (LST) and hence the UHI effect over these cities. Each of the cities experienced an improved Air Quality Index (AQI) ranging from 18 to 151 units except Chennai (with a marginal 8 units increase in AQI), a decrease in mean LST in the range of 0.27 °C to 7.06 °C except Kolkata which showed an increment by ∼4 °C, and a reduction in daily averaged air temperature ranging from 0.3 °C to 10.88 °C except Hyderabad which witnessed an increase of 0.09 °C during the lockdown (April 2020) compared to the previous years (April 2019 and 2018). Delhi exhibited the maximum positive impact of the lockdown in all aspects with two-fold improved air quality, and Ahmedabad showed the least improvement. In addition to the variations in regional land use and land cover and proportion of essential industries that remained operational throughout the lockdown, the geographic location, topography, local meteorology and climate were some of the other factors also responsible for either aiding or overcompensating the large scale LST variabilities observed in these cities. These results hint at an unprecedented opportunity to evaluate the effectiveness of periodic planned lockdowns as a possible mitigating measure to reduce LST spikes and degraded air quality in urban areas in the future.

Risk assessment of soil heavy metal contamination at the census tract level in the city of Santa Ana, CA: implications for health and environmental justice.

Abstract: (1) Background: exposure to heavy metals is associated with adverse health effects and disproportionately impacts low-income communities and communities of color. We carried out a community-based participatory research study to examine the distribution of heavy metal concentrations in the soil and social vulnerabilities to soil heavy metal exposures across Census tracts in Santa Ana, CA. (2) Methods: soil samples (n = 1528) of eight heavy metals including lead (Pb), arsenic (As), manganese (Mn), chromium (Cr), nickel (Ni), copper (Cu), cadmium (Cd), and zinc (Zn) were collected in 2018 across Santa Ana, CA, at a high spatial resolution and analyzed using XRF analysis. Metal concentrations were mapped out and American Community Survey data was utilized to assess metals throughout Census tracts in terms of social and economic variables. Risk assessment was conducted to evaluate carcinogenic and non-carcinogenic risk. (3) Results: concentrations of soil metals varied according to landuse type and socioeconomic factors. Census tracts where the median household income was under $50 000 had 390%, 92.9%, 56.6%, and 54.3% higher Pb, Zn, Cd, and As concentrations compared to high-income counterparts. All Census tracts in Santa Ana showed hazard index >1, implying the potential for non-carcinogenic health effects, and nearly all Census tracts showed a cancer risk above 10−4, implying a greater than acceptable risk. Risk was predominantly driven by childhood exposure. (4) Conclusions: findings inform initiatives related to environmental justice and highlight subpopulations at elevated risk of heavy metal exposure, in turn underscoring the need for community-driven recommendations for policies and other actions to remediate soil contamination and protect the health of residents.

Metals in microplastics: determining which are additive, adsorbed, and bioavailable

Abstract: Microplastics from the North Atlantic Gyre deposited on Guadeloupe beaches were sampled and characterized. A new method is developed to identify which elements were present as additives in these microplastics. The method used both acidic leaching and acidic digestion. Several elements (Al, Zn, Ba, Cu, Pb, Cd, Mn, Cr) were identified as pigments. Furthermore, some elements used as additives to plastics (especially the non-essential elements) seem to contribute to most of the acidic leaching, suggesting that these additives can leach and adsorb onto the surface microplastics, becoming bioavailable. Based on the acidic leaching element content, only Cd should represent a danger for fish when ingested. However, further studies are needed to determine the potential synergetic effect on health caused by the ingestion of several elements and microplastics.

Macroplastics in rivers: present knowledge, issues and challenges

Abstract: Macroplastics are the primary contributor to riverine plastic pollution by mass, posing a wide range of serious threats for riverine systems, from adversely affecting various life forms within the riverine system, to potentially increasing flood risk, and generally resulting in adverse effects on any livelihoods. Compared to other river-related research disciplines, research into riverine macroplastics and their effects has not yet featured prominently. Various quantification methods are presently used to assess the presence of macroplastics at different locations within river systems; however, overcoming limitations and unifying methods remain an essential need. Macroplastic dynamics in rivers are subject to various factors, including both material and river characteristics. We review the diverse factors that potentially influence macroplastic dynamics in rivers, and highlight our knowledge limits. We advocate for future research that enables synergies between improved field quantification techniques, use of global protocols and data sharing, and laboratory experiments. This is needed to obtain a riverine macroplastic budget model, required for the implementation of targeted management practices. Finally, a multilayer potential management strategy is presented: (i) reducing the macroplastic supply into rivers; (ii) removing effectively and safely macroplastics from within rivers; and (iii) treating macroplastics once removed from the riverine system.

PFOS dominates PFAS composition in ambient fine particulate matter (PM2.5) collected across North Carolina nearly 20 years after the end of its US production

Abstract: Contamination of drinking water by per- and polyfluoroalkyl substances (PFASs) emitted from manufacturing plants, fire-fighting foams, and urban waste streams has received considerable attention due to concerns over toxicity and environmental persistence; however, PFASs in ambient air remain poorly understood, especially in the United States (US). We measured PFAS concentrations in ambient fine particulate matter (PM2.5) at 5 locations across North Carolina over a 1 year period in 2019. Thirty-four PFASs, including perfluoroalkyl carboxylic, perfluoroalkane sulfonic, perfluoroalkyl ether carboxylic and sulfonic acids were analyzed by UHPLC/ESI-MS/MS. Quarterly averaged concentrations ranged from <0.004-14.1 pg m-3. Perfluorooctanoic acid (PFOA) and perfluorooctane sulfonic acid (PFOS) ranged from <0.18 to 14.1 pg m-3, comparable to previous PM2.5 measurements from Canada and Europe (<0.02-3.5 pg m-3). Concentrations above 1 pg m-3 were observed in July-September at Charlotte (14.1 pg m-3, PFOA), Wilmington (4.75 pg m-3, PFOS), and Research Triangle Park (1.37 pg m-3, PFOS). Notably, PM2.5 has a short atmospheric lifetime (<2 weeks), and thus, the presence of PFOS in these samples raises questions about their sources, since PFOS production was phased out in the US ∼20 years ago. This is the first US study to provide insights into ambient PFAS concentrations in PM2.5.

Why analysing microplastics in floodplains matters: application in a sedimentary context

Abstract: Microplastics in the environment are a relatively new form of anthropogenic contamination. Right now, the research focus is on the detection of microplastic accumulation in different environmental compartments and understanding the processes that have led to its transport. Detailed information on microplastics in floodplain areas and their distribution in depth are still missing to better understand accumulation points. Therefore, this study presents on the one hand microplastic detection in fluvial sediments from nine sampling sites along a river course. Polymers were determined with infrared spectroscopy and additional sedimentary analysis of the grain size and heavy metal concentration was performed. In total, there was less microplastic in the upper than in the lower river course and slip-off slopes were identified as accumulation hotspots also in deeper sediment layers. Mostly, microplastic particles were detected in fine sediment and heavy metal concentrations along the river were similar to those of microplastics. On the other hand, besides the spatial distribution of microplastics and accumulation in floodplain areas, microplastic analysis offered information in a sedimentary context. Sedimentation rates (0.29-4.00 cm a-1) and patterns between temporal deposition and microplastic polymers were identified. The basis for the development of a dating method by detection of MPs in sediments was thus established. Microplastics as a contaminant provide, in addition to the identification of deposition areas, further data in a temporal and sedimentary perspective.

Ionization selectivity of electrospray and atmospheric pressure photoionization FT-ICR MS for petroleum refinery wastewater dissolved organic matter.

Abstract: Dissolved organic matter (DOM) in petroleum refinery wastewater is an extremely complex mixture. A better understanding of chemical compositions of DOM at the molecular level is necessary for the design and optimization of wastewater treatment processes. In this study, two largely different DOM samples, one from a petroleum refinery wastewater and the other from the Suwannee river water, were characterized by Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) coupled with positive-/negative-ion electrospray ionization (ESI), and positive-ion atmospheric pressure photoionization (APPI). For wastewater DOM, a total of 6226 molecular formulae were assigned in the three ionization modes. However, only 1182 molecular formulae were common in all three mass spectra, indicating that the techniques were highly complementary in the types of molecules they ionize. Acid Ox (x = 1–9) and basic N1Ox (x = 0–2) classes were dominant in the wastewater DOM detected in negative-ion and positive-ion ESI mode, respectively. And the wastewater DOM contains considerable amounts of polycyclic aromatic hydrocarbons that did not respond to ESI but can be ionized selectively by APPI. Compared with riverine DOM, the refinery wastewater DOM has a higher molecular complexity and is more enriched in hydrocarbon, and nitrogen- and sulfur-containing compounds. The results show that the major components of refinery wastewater DOM were distinctive from those of the natural organic matter. Though not quantitative, the results obtained by various ionization techniques were found to be complementary, and are helpful to our understanding of the selectivity of different ionization techniques as well as the molecular compositions of DOM.

Polyvinyl chloride in consumer and environmental plastics, with a particular focus on metal-based additives

Abstract: Polyvinyl chloride (PVC) is one of the most widely used thermoplastics but is also a material of concern because of the generation and release of harmful chemicals during its life cycle. Amongst the chemicals added to PVC are metal-based stabilisers and Sb-based halogenated flame retardant synergists. However, very little quantitative information exists on these additives, and in particular in PVC lost to the environment. In this study, the distribution of PVC amongst consumer plastics in societal circulation and plastics retrieved from marine and lacustrine beaches and agricultural soils are compared, along with the presence and concentrations of Ba, Cd, Pb, Sb, Sn and Zn as proxies for common metal-based additives and determined by X-ray fluorescence spectrometry. About 10% of consumer plastics and 2% of environmental plastics were constructed of PVC, with the discrepancy attributed to the long service lives and managed disposal of PVC used in the construction sector and the propensity of the plastic to sink in aquatic systems and evade detection. Metal-based additives, defined as having a metal concentration >1000 mg kg−1, were present in about 75% of consumer and environmental PVC, with Ba and Pb most abundant and Cd and Zn least abundant in both types of sample, and median concentrations statistically different only for Ba. Metals also appeared to be present as contaminants (defined as concentrations <1000 mg kg−1) arising from manufacturing or recycling. Metals in PVC are believed to pose little risk when the material is in use, but experimental evidence in the literature suggests that significant mobilisation and exposure may occur from PVC microplastics when ingested by wildlife.

Ammonia fluxes and emission factors under an intensively managed wetland rice ecosystem.

Abstract: Nitrogen (N) loss from rice production systems in the form of ammonia (NH3) can be a significant N loss pathway causing significant economic and environmental costs. Yet, data on NH3 fluxes in wetland rice ecosystems are still very scarce which limits the accuracy of national and global NH3 budgets. We measured the NH3 fluxes in situ in a wetland rice field and estimated emission factors (EF) under two soil management systems (i.e. conventional tillage, CT and strip tillage, ST); two residue retention levels (i.e. 15%, LR and 40% crop residue by height, HR); and three N fertilization rates (i.e. 108, 144 and 180 kg N ha−1) in two consecutive years (2019 and 2020). The highest NH3 peaks were observed within the first 3 days after urea application. The mean and cumulative NH3 fluxes significantly increased with the increases in N fertilization rates and were 18.5% and 18.6% higher in ST than in CT in 2020 but not in 2019. Overall, the highest mean NH3 fluxes were in 180 kg N ha−1 coupled with either HR or LR and ST or CT. In 2019, the NH3 EF was unchanged by any treatments. In 2020, the lower EF was in CT coupled with LR (15%) than all other treatment combinations, where ST with HR showed the highest EF (20%). Likewise, the lowest N rate (108 kg N ha−1) in ST had the highest NH3 EF (20%) that was similar to higher N rates (144 and 180 kg N ha−1) in the same tillage treatment and to 180 kg N ha−1 in CT. Our results highlight that NH3 fluxes in rice field particularly the effects of ST correlated with higher soil pH and NH4+ content and lower redox potential. Our results highlight that NH3 fluxes are a potentially large N loss pathway in wetland rice under conventional and decreased soil disturbance regimes.

Recent progress in research on PM2.5 in subways.

Abstract: Nowadays, PM2.5 concentrations greatly influence indoor air quality in subways and threaten passenger and staff health because PM2.5 not only contains heavy metal elements, but can also carry toxic and harmful substances due to its small size and large specific surface area. Exploring the physicochemical and distribution characteristics of PM2.5 in subways is necessary to limit its concentration and remove it. At present, there are numerous studies on PM2.5 in subways around the world, yet, there is no comprehensive and well-organized review available on this topic. This paper reviews the nearly twenty years of research and over 130 published studies on PM2.5 in subway stations, including aspects such as concentration levels and their influencing factors, physicochemical properties, sources, impacts on health, and mitigation measures. Although many determinants of station PM2.5 concentration have been reported in current studies, e.g., the season, outdoor environment, and station depth, their relative influence is uncertain. The sources of subway PM2.5 include those from the exterior (e.g., road traffic and fuel oil) and the interior (e.g., steel wheels and rails and metallic brake pads), but the proportion of these sources is also unknown. Control strategies of PM mainly include adequate ventilation and filtration, but these measures are often inefficient in removing PM2.5. The impacts of PM2.5 from subways on human health are still poorly understood. Further research should focus on long-term data collection, influencing factors, the mechanism of health impacts, and PM2.5 standards or regulations.

Concentrations and properties of ice nucleating substances in exudates from Antarctic sea-ice diatoms

Abstract: The ocean contains ice nucleating substances (INSs), some of which can be emitted to the atmosphere where they can influence the formation and properties of clouds. A possible source of INSs in the ocean is exudates from sea-ice diatoms. Here we examine the concentrations and properties of INSs in supernatant samples from dense sea-ice diatom communities collected from Ross Sea and McMurdo Sound in the Antarctic. The median freezing temperatures of the samples ranged from approximately -17 to -22 °C. Based on our results and a comparison with results reported in the literature, the ice nucleating ability of exudates from sea-ice diatoms is likely not drastically different from the ice nucleating ability of exudates from temperate diatoms. The number of INSs per mass of DOC for the supernatant samples were lower than those reported previously for the sea surface microlayer and bulk sea water collected in the Arctic and Atlantic. The INSs in the supernatant sample collected from Ross Sea were not sensitive to temperatures up to 100 °C, were larger than 300 kDa, and were different from ice shaping and recrystallization inhibiting molecules present in the same sample. Possible candidates for these INSs include polysaccharide containing nanogels. The INSs in the supernatant sample collected from McMurdo Sound were sensitive to temperatures of 80 and 100 °C and were larger than 1000 kDa. Possible candidates for these INSs include protein containing nanogels.

The fate of poly- and perfluoroalkyl substances in a marine food web influenced by land-based sources in the Norwegian Arctic

Abstract: Although poly- and perfluorinated alkyl substances (PFAS) are ubiquitous in the Arctic, their sources and fate in Arctic marine environments remain unclear. Herein, abiotic media (water, snow, and sediment) and biotic media (plankton, benthic organisms, fish, crab, and glaucous gull) were sampled to study PFAS uptake and fate in the marine food web of an Arctic Fjord in the vicinity of Longyearbyen (Svalbard, Norwegian Arctic). Samples were collected from locations impacted by a firefighting training site (FFTS) and a landfill as well as from a reference site. Mean concentration in the landfill leachate was 643 ± 84 ng L-1, while it was 365 ± 8.0 ng L-1 in a freshwater pond and 57 ± 4.0 ng L-1 in a creek in the vicinity of the FFTS. These levels were an order of magnitude higher than in coastal seawater of the nearby fjord (maximum level , at the FFTS impacted site). PFOS was the most predominant compound in all seawater samples and in freshly fallen snow (63-93% of ). In freshwater samples from the Longyear river and the reference site, PFCA ≤ C9 were the predominant PFAS (37-59%), indicating that both local point sources and diffuse sources contributed to the exposure of the marine food web in the fjord. concentrations increased from zooplankton (1.1 ± 0.32 μg kg-1 ww) to polychaete (2.8 ± 0.80 μg kg-1 ww), crab (2.9 ± 0.70 μg kg-1 ww whole-body), fish liver (5.4 ± 0.87 μg kg-1 ww), and gull liver (62.2 ± 11.2 μg kg-1). PFAS profiles changed with increasing trophic level from a large contribution of 6:2 FTS, FOSA and long-chained PFCA in zooplankton and polychaetes to being dominated by linear PFOS in fish and gull liver. The PFOS isomer profile (branched versus linear) in the active FFTS and landfill was similar to historical ECF PFOS. A similar isomer profile was observed in seawater, indicating major contribution from local sources. However, a PFOS isomer profile enriched by the linear isomer was observed in other media (sediment and biota). Substitutes for PFOS, namely 6:2 FTS and PFBS, showed bioaccumulation potential in marine invertebrates. However, these compounds were not found in organisms at higher trophic levels.

Surface-water/groundwater boundaries affect seasonal PFAS concentrations and PFAA precursor transformations.

Abstract: Elevated concentrations of per- and polyfluoroalkyl substances (PFAS) in drinking-water supplies are a major concern for human health. It is therefore essential to understand factors that affect PFAS concentrations in surface water and groundwater and the transformation of perfluoroalkyl acid (PFAA) precursors that degrade into terminal compounds. Surface-water/groundwater exchange can occur along the flow path downgradient from PFAS point sources and biogeochemical conditions can change rapidly at these exchange boundaries. Here, we investigate the influence of surface-water/groundwater boundaries on PFAS transport and transformation. To do this, we conducted an extensive field-based analysis of PFAS concentrations in water and sediment from a flow-through lake fed by contaminated groundwater and its downgradient surface-water/groundwater boundary (defined as ≤100 cm below the lake bottom). PFAA precursors comprised 45 ± 4.6% of PFAS (PFAA precursors + 18 targeted PFAA) in the predominantly oxic lake impacted by a former fire-training area and historical wastewater discharges. In shallow porewater downgradient from the lake, this percentage decreased significantly to 25 ± 11%. PFAA precursor concentrations decreased by 85% between the lake and 84–100 cm below the lake bottom. PFAA concentrations increased significantly within the surface-water/groundwater boundary and in downgradient groundwater during the winter months despite lower stable concentrations in the lake water source. These results suggest that natural biogeochemical fluctuations associated with surface-water/groundwater boundaries may lead to PFAA precursor loss and seasonal variations in PFAA concentrations. Results of this work highlight the importance of dynamic biogeochemical conditions along the hydrological flow path from PFAS point sources to potentially affected drinking water supplies.

Emerging investigator series: municipal wastewater as a year-round point source of neonicotinoid insecticides that persist in an effluent-dominated stream

Abstract: Neonicotinoids in aquatic systems have been predominantly associated with agriculture, but some are increasingly being linked to municipal wastewater. Thus, the aim of this work was to understand the municipal wastewater contribution to neonicotinoids in a representative, characterized effluent-dominated temperate-region stream. Our approach was to quantify the spatiotemporal concentrations of imidacloprid, clothianidin, thiamethoxam, and transformation product imidacloprid urea: 0.1 km upstream, the municipal wastewater effluent, and 0.1 and 5.1 km downstream from the wastewater outfall (collected twice-monthly for one year under baseflow conditions). Quantified results demonstrated that wastewater effluent was a point-source of imidacloprid (consistently) and clothianidin (episodically), where chronic invertebrate exposure benchmarks were exceeded for imidacloprid (36/52 samples; 3/52 > acute exposure benchmark) and clothianidin (8/52 samples). Neonicotinoids persisted downstream where mass loads were not significantly different than those in the effluent. The combined analysis of neonicotinoid effluent concentrations, instream seasonality, and registered uses in Iowa all indicate imidacloprid, and seasonally clothianidin, were driven by wastewater effluent, whereas thiamethoxam and imidacloprid urea were primarily from upstream non-point sources (or potential in-stream transformation for imidacloprid urea). This is the first study to quantify neonicotinoid persistence in an effluent-dominated stream throughout the year-implicating wastewater effluent as a point-source for imidacloprid (year-round) and clothianidin (seasonal). These findings suggest possible overlooked neonicotinoid indoor human exposure routes with subsequent implications for instream ecotoxicological exposure.

Reactivity-directed analysis – a novel approach for the identification of toxic organic electrophiles in drinking water

Abstract: Drinking water consumption results in exposure to complex mixtures of organic chemicals, including natural and anthropogenic chemicals and compounds formed during drinking water treatment such as disinfection by-products. The complexity of drinking water contaminant mixtures has hindered efforts to assess associated health impacts. Existing approaches focus primarily on individual chemicals and/or the evaluation of mixtures, without providing information about the chemicals causing the toxic effect. Thus, there is a need for the development of novel strategies to evaluate chemical mixtures and provide insights into the species responsible for the observed toxic effects. This critical review introduces the application of a novel approach called Reactivity-Directed Analysis (RDA) to assess and identify organic electrophiles, the largest group of known environmental toxicants. In contrast to existing in vivo and in vitro approaches, RDA utilizes in chemico methodologies that investigate the reaction of organic electrophiles with nucleophilic biomolecules, including proteins and DNA. This review summarizes the existing knowledge about the presence of electrophiles in drinking water, with a particular focus on their formation in oxidative treatment systems with ozone, advanced oxidation processes, and UV light, as well as disinfectants such as chlorine, chloramines and chlorine dioxide. This summary is followed by an overview of existing RDA approaches and their application for the assessment of aqueous environmental matrices, with an emphasis on drinking water. RDA can be applied beyond drinking water, however, to evaluate source waters and wastewater for human and environmental health risks. Finally, future research demands for the detection and identification of electrophiles in drinking water via RDA are outlined.