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1.
Environ Toxicol Chem ; 2024 Jun 19.
Article in English | MEDLINE | ID: mdl-38896102

ABSTRACT

Exposure to per- and polyfluoroalkyl substances (PFAS) has been associated with toxicity in wildlife and negative health effects in humans. Decades of fire training activity at Joint Base Cape Cod (MA, USA) incorporated the use of aqueous film-forming foam (AFFF), which resulted in long-term PFAS contamination of sediments, groundwater, and hydrologically connected surface waters. To explore the bioconcentration potential of PFAS in complex environmental mixtures, a mobile laboratory was established to evaluate the bioconcentration of PFAS from AFFF-impacted groundwater by flow-through design. Fathead minnows (n = 24) were exposed to PFAS in groundwater over a 21-day period and tissue-specific PFAS burdens in liver, kidney, and gonad were derived at three different time points. The ∑PFAS concentrations in groundwater increased from approximately 10,000 ng/L at day 1 to 36,000 ng/L at day 21. The relative abundance of PFAS in liver, kidney, and gonad shifted temporally from majority perfluoroalkyl sulfonamides (FASAs) to perfluoroalkyl sulfonates (PFSAs). By day 21, mean ∑PFAS concentrations in tissues displayed a predominance in the order of liver > kidney > gonad. Generally, bioconcentration factors (BCFs) for FASAs, perfluoroalkyl carboxylates (PFCAs), and fluorotelomer sulfonates (FTS) increased with degree of fluorinated carbon chain length, but this was not evident for PFSAs. Perfluorooctane sulfonamide (FOSA) displayed the highest mean BCF (8700 L/kg) in day 21 kidney. Suspect screening results revealed the presence of several perfluoroalkyl sulfinate and FASA compounds present in groundwater and in liver for which pseudo-bioconcentration factors are also reported. The bioconcentration observed for precursor compounds and PFSA derivatives detected suggests alternative pathways for terminal PFAS exposure in aquatic wildlife and humans. Environ Toxicol Chem 2024;00:1-12. © 2024 The Author(s). Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC.

2.
Innovation (Camb) ; 5(4): 100612, 2024 Jul 01.
Article in English | MEDLINE | ID: mdl-38756954

ABSTRACT

Environmental pollution is escalating due to rapid global development that often prioritizes human needs over planetary health. Despite global efforts to mitigate legacy pollutants, the continuous introduction of new substances remains a major threat to both people and the planet. In response, global initiatives are focusing on risk assessment and regulation of emerging contaminants, as demonstrated by the ongoing efforts to establish the UN's Intergovernmental Science-Policy Panel on Chemicals, Waste, and Pollution Prevention. This review identifies the sources and impacts of emerging contaminants on planetary health, emphasizing the importance of adopting a One Health approach. Strategies for monitoring and addressing these pollutants are discussed, underscoring the need for robust and socially equitable environmental policies at both regional and international levels. Urgent actions are needed to transition toward sustainable pollution management practices to safeguard our planet for future generations.

3.
Article in English | MEDLINE | ID: mdl-38752651

ABSTRACT

Federal, state, tribal, or local entities in the United States issue fish consumption advisories (FCAs) as guidance for safer consumption of locally caught fish containing contaminants. Fish consumption advisories have been developed for commonly detected compounds such as mercury and polychlorinated biphenyls. The existing national guidance does not specifically address the unique challenges associated with bioaccumulation and consumption risk related to per- and polyfluoroalkyl substances (PFAS). As a result, several states have derived their own PFAS-related consumption guidelines, many of which focus on one frequently detected PFAS, known as perfluorooctane sulfonic acid (PFOS). However, there can be significant variation between tissue concentrations or trigger concentrations (TCs) of PFOS that support the individual state-issued FCAs. This variation in TCs can create challenges for risk assessors and risk communicators in their efforts to protect public health. The objective of this article is to review existing challenges, knowledge gaps, and needs related to issuing PFAS-related FCAs and to provide key considerations for the development of protective fish consumption guidance. The current state of the science and variability in FCA derivation, considerations for sampling and analytical methodologies, risk management, risk communication, and policy challenges are discussed. How to best address PFAS mixtures in the development of FCAs, in risk assessment, and establishment of effect thresholds remains a major challenge, as well as a source of uncertainty and scrutiny. This includes developments better elucidating toxicity factors, exposures to PFAS mixtures, community fish consumption behaviors, and evolving technology and analytical instrumentation, methods, and the associated detection limits. Given the evolving science and public interests informing PFAS-related FCAs, continued review and revision of FCA approaches and best practices are vital. Nonetheless, consistent, widely applicable, PFAS-specific approaches informing methods, critical concentration thresholds, and priority compounds may assist practitioners in PFAS-related FCA development and possibly reduce variability between states and jurisdictions. Integr Environ Assess Manag 2024;00:1-20. © 2024 SETAC.

4.
Environ Sci Technol ; 58(15): 6772-6780, 2024 Apr 16.
Article in English | MEDLINE | ID: mdl-38577774

ABSTRACT

The quality of chemical analysis is an important aspect of passive sampling-based environmental assessments. The present study reports on a proficiency testing program for the chemical analysis of hydrophobic organic compounds in silicone and low-density polyethylene (LDPE) passive samplers and hydrophilic compounds in polar organic chemical integrative samplers. The median between-laboratory coefficients of variation (CVs) of hydrophobic compound concentrations in the polymer phase were 33% (silicone) and 38% (LDPE), similar to the CVs obtained in four earlier rounds of this program. The median CV over all rounds was 32%. Much higher variabilities were observed for hydrophilic compound concentrations in the sorbent: 50% for the untransformed data and a factor of 1.6 after log transformation. Limiting the data to the best performing laboratories did not result in less variability. Data quality for hydrophilic compounds was only weakly related to the use of structurally identical internal standards and was unrelated to the choice of extraction solvent and extraction time. Standard deviations of the aqueous concentration estimates for hydrophobic compound sampling by the best performing laboratories were 0.21 log units for silicone and 0.27 log units for LDPE (factors of 1.6 to 1.9). The implications are that proficiency testing programs may give more realistic estimates of uncertainties in chemical analysis than within-laboratory quality control programs and that these high uncertainties should be taken into account in environmental assessments.


Subject(s)
Polyethylene , Water Pollutants, Chemical , Polyethylene/analysis , Water Pollutants, Chemical/analysis , Environmental Monitoring/methods , Organic Chemicals , Silicones
5.
Environ Sci Technol Lett ; 11(2): 166-171, 2024 Feb 13.
Article in English | MEDLINE | ID: mdl-38405271

ABSTRACT

Per- and polyfluorinated alkyl substances (PFAS) are a family of pollutants of high concern due to their ubiquity and negative human health impacts. The long-range marine transport of PFAS was observed during year-long deployments of passive tube samplers in the Fram Strait across three depth transects. Time weighted average concentrations ranged from 2.4-360 pg L-1, and 10 different PFAS were regularly observed. PFAS profiles and concentrations were generally similar to those previously characterized for polycyclic aromatic hydrocarbons (PAHs) at these sites. The detection of several anionic PFAS in "old" water demonstrated that they are not perfect water mass tracers, but are also transported to depth via settling particles. Mass flows of PFAS through the Fram Strait in and out of the Arctic Ocean were basically similar (112 ±82 Mg year-1 northward flow, 100 ±54 Mg year-1 southward flow). For FOSA, export from the Arctic Ocean via the Fram Strait exceeded import by Atlantic Water, likely due to preferential transport and deposition in the Arctic Ocean. These observations suggest PFAS in the Arctic are governed by the feedback loop previously described for PAHs in the region - with additional atmospheric transport delivering volatile PFAS to the Arctic, which then get exported further.

6.
ACS ES T Water ; 4(1): 114-124, 2024 Jan 12.
Article in English | MEDLINE | ID: mdl-38222965

ABSTRACT

Despite concerns over the ubiquity of per- and polyfluoroalkyl substances (PFAS), little is known about the diversity of input sources to surface waters and their seasonal dynamics. Frequent use of PFAS in textiles means both active and closed textile mills require evaluation as PFAS sources. We deployed passive samplers at seven sites in an urban river and estuary adjacent to textile mills in Southern Rhode Island (USA) over 12 months. We estimated monthly mass flows (g month-1) of perfluorohexanoic acid (PFHxA: 45±56), and perfluorooctanoic acid (PFOA: 30±45) from the upstream river influenced by an active mill. Average mass flows were 73-155% higher downstream, where historical textile waste lagoons contributed long chain perfluoroalkyl acids (PFAA). Mass flows of PFNA increased from 7.5 to 21 g month-1 between the upstream and downstream portions of the rivers. Distinct grouping of the two main PFAS sources, active textile mills and historical waste lagoons, were identified using principal components analysis. Neither suspect screening nor extractable organofluorine analysis revealed measurable PFAS were missing beyond the targeted compounds. This research demonstrates that both closed and active textile mills are important ongoing PFAS sources to freshwater and marine regions and should be further evaluated as a source category.

7.
Mar Pollut Bull ; 197: 115768, 2023 Dec.
Article in English | MEDLINE | ID: mdl-37956493

ABSTRACT

Hydrophobic organic contaminants (HOCs) are tracers of anthropogenic impacts, which can negatively affect water quality. The relative importance of new emissions versus the remobilization of HOCs from legacy reservoirs is not well constrained. Polyethylene passive samplers were deployed in vertical profiles at four sites to determine the concentrations and gradients of atmospheric and freely dissolved polycyclic aromatic hydrocarbons (PAHs) and freely dissolved organochlorinated pesticides (OCPs) in Narragansett Bay, an urban estuary. The concentrations of the sum of 20 PAHs ranged from 4.3 to 240 ng/m3 in the air and 3.2-21 ng/L in the water column, dominated by phenanthrene and pyrene. OCP concentrations varied from below the detection limit to 150 ng/L in the water column. Common OCPs included α-hexachlorocyclohexane, hexachlorobenzene, and aldrin. Gradients displayed net deposition for PAHs, but equilibrium through the water column. Results from this study provided evidence that key OCPs displayed mostly similar concentrations (at or near equilibrium) in the water at both Conimicut Point and Block Island.


Subject(s)
Hydrocarbons, Chlorinated , Pesticides , Polycyclic Aromatic Hydrocarbons , Water Pollutants, Chemical , Polycyclic Aromatic Hydrocarbons/analysis , Environmental Monitoring/methods , Estuaries , Hydrocarbons, Chlorinated/analysis , Pesticides/analysis , Water Pollutants, Chemical/analysis
8.
Environ Sci Technol ; 57(48): 19066-19077, 2023 Dec 05.
Article in English | MEDLINE | ID: mdl-37943968

ABSTRACT

Pollution by chemicals and waste impacts human and ecosystem health on regional, national, and global scales, resulting, together with climate change and biodiversity loss, in a triple planetary crisis. Consequently, in 2022, countries agreed to establish an intergovernmental science-policy panel (SPP) on chemicals, waste, and pollution prevention, complementary to the existing intergovernmental science-policy bodies on climate change and biodiversity. To ensure the SPP's success, it is imperative to protect it from conflicts of interest (COI). Here, we (i) define and review the implications of COI, and its relevance for the management of chemicals, waste, and pollution; (ii) summarize established tactics to manufacture doubt in favor of vested interests, i.e., to counter scientific evidence and/or to promote misleading narratives favorable to financial interests; and (iii) illustrate these with selected examples. This analysis leads to a review of arguments for and against chemical industry representation in the SPP's work. We further (iv) rebut an assertion voiced by some that the chemical industry should be directly involved in the panel's work because it possesses data on chemicals essential for the panel's activities. Finally, (v) we present steps that should be taken to prevent the detrimental impacts of COI in the work of the SPP. In particular, we propose to include an independent auditor's role in the SPP to ensure that participation and processes follow clear COI rules. Among others, the auditor should evaluate the content of the assessments produced to ensure unbiased representation of information that underpins the SPP's activities.


Subject(s)
Conflict of Interest , Ecosystem , Humans , Environmental Pollution , Biodiversity
9.
Environ Sci Technol ; 57(25): 9342-9352, 2023 06 27.
Article in English | MEDLINE | ID: mdl-37294896

ABSTRACT

Persistent organic pollutants (POPs) are recognized as pollutants of global concern, but so far, information on the trends of legacy POPs in the waters of the world has been missing due to logistical, analytical, and financial reasons. Passive samplers have emerged as an attractive alternative to active water sampling methods as they accumulate POPs, represent time-weighted average concentrations, and can easily be shipped and deployed. As part of the AQUA-GAPS/MONET, passive samplers were deployed at 40 globally distributed sites between 2016 and 2020, for a total of 21 freshwater and 40 marine deployments. Results from silicone passive samplers showed α-hexachlorocyclohexane (HCH) and γ-HCH displaying the greatest concentrations in the northern latitudes/Arctic Ocean, in stark contrast to the more persistent penta (PeCB)- and hexachlorobenzene (HCB), which approached equilibrium across sampling sites. Geospatial patterns of polychlorinated biphenyl (PCB) aqueous concentrations closely matched original estimates of production and use, implying limited global transport. Positive correlations between log-transformed concentrations of Σ7PCB, ΣDDTs, Σendosulfan, and Σchlordane, but not ΣHCH, and the log of population density (p < 0.05) within 5 and 10 km of the sampling sites also supported limited transport from used sites. These results help to understand the extent of global distribution, and eventually time-trends, of organic pollutants in aquatic systems, such as across freshwaters and oceans. Future deployments will aim to establish time-trends at selected sites while adding to the geographical coverage.


Subject(s)
Air Pollutants , Environmental Pollutants , Hydrocarbons, Chlorinated , Pesticides , Polychlorinated Biphenyls , Polychlorinated Biphenyls/analysis , Environmental Monitoring/methods , Hexachlorobenzene/analysis , Fresh Water , Air Pollutants/analysis , Pesticides/analysis , Hydrocarbons, Chlorinated/analysis
10.
Lancet Planet Health ; 7(5): e435-e440, 2023 05.
Article in English | MEDLINE | ID: mdl-37164519

ABSTRACT

Global production and emission of chemicals exceeds societal capacities for assessment and monitoring. This situation calls for improved chemical regulatory policy frameworks and increased support for expedited decision making within existing frameworks. The polar regions of the Earth represent unique sentinel areas for the study of global chemical behaviour, and data arising from these areas can strengthen existing policy frameworks. However, chemical pollution research and monitoring in the Antarctic is underdeveloped, with geopolitical complexities and the absence of legal recognition of international chemical policy serving to neutralise progress made in other global regions. This Personal View represents a horizon scan by the action group Input Pathways of Persistent Organic Pollutants to Antarctica, of the Scientific Committee for Antarctic Research. Four priority research and research facilitation gaps are outlined, with recommendations for Antarctica Treaty parties for strategic action against these priorities.


Subject(s)
Environmental Monitoring , Environmental Pollution , Antarctic Regions , Environmental Pollution/prevention & control , Organic Chemicals , Public Policy
11.
Article in English | MEDLINE | ID: mdl-37009204

ABSTRACT

Per- and polyfluoroalkyl substances (PFAS) are a diverse group of surface treatment chemicals falling under non-polymeric and polymeric categories. Polymeric PFAS are comprised of fluoropolymers, perfluoropolyethers and side-chain fluorinated polymers (SCFPs). Fluorinated polymers and polymeric substances have gained a significant market due to their chemical stability. To date, research and regulatory concern has primarily focused on the environmental occurrence and health effects of non-polymeric PFAS, particularly perfluoroalkyl acids and precursors. Industries consider most fluoropolymers as being "polymers of low concern", although there is already a considerable environmental burden and widespread contamination resulting from their production, manufacturing and use. For example, SCFPs are widely used, and known to release their perfluorinated side chains. Concerted action is needed to address the dearth of environment-associated information and understanding on polymeric PFAS.

12.
ACS ES T Water ; 3(2): 332-341, 2023 Feb 10.
Article in English | MEDLINE | ID: mdl-37006340

ABSTRACT

Per- and polyfluoroalkyl substances (PFAS) are a group of 4000+ man-made compounds of great concern due to their environmental ubiquity and adverse effects. Despite a general interest, few reliable detection tools for integrative passive sampling of PFAS in water are available. A microporous polyethylene tube with a hydrophilic-lipophilic balance sorbent could serve as a flow-resistant passive sampler for PFAS. The tube's sampling rate, Rs, was predicted based on either partitioning and diffusion, or solely diffusion. At 15 °C, the laboratory measured Rs for perfluorohexanoic acid of 100+/-81 mL day-1 were better predicted by a partitioning and diffusion model (48+/-1.8 mL day-1) across 10-60 cm s-1 water flow speeds (15+/-4.2 mL day-1 diffusion only). For perfluorohexane sulfonate, Rs at 15°C were similarly different (110+/-60 mL day-1 measured, 120+/- 63 versus 12+/-3.4 mL day-1 in respective models). Rs values from field deployments were in-between these estimates (46 +/-40 mL day-1 for perfluorohexanoic acid). PFAS uptake was not different for previously biofouled membranes in the laboratory, suggesting the general applicability of the sampler in environmental conditions. This research demonstrates that the polyethylene tube's sampling rates are sensitive to the parameterization of the models used here and partitioning-derived values should be used.

13.
Mar Pollut Bull ; 191: 114982, 2023 Jun.
Article in English | MEDLINE | ID: mdl-37121185

ABSTRACT

The seasonal monsoon variations have significant impact on the atmospheric transport of semi-volatile organic pollutants over the South China Sea (SCS). We analyzed polycyclic aromatic hydrocarbons (PAHs) over the basin and island areas (Yongxing Island and Yongshu Island) in 2017. Gaseous PAHs (0.17-1.4 ng m-3) showed spatio-temporal distinctions in their composition and sources among the basin and island areas. Mixed combustion sources of PAHs were identified over the SCS, including a petroleum source near the island areas. The transport routes of PAHs were inferred by the air mass back trajectories and potential source contribution factor analysis, identifying strong biomass burning signals from the Indochina Peninsula and other Southeast Asian countries. Emissions from approximately 90 % of the combustion sources were transported to basin areas by monsoons, whereas the island areas were dominated by local emissions. This study emphasizes the main potential terrestrial source of PAHs over the SCS under monsoon influences.


Subject(s)
Air Pollutants , Polycyclic Aromatic Hydrocarbons , Air Pollutants/analysis , Gases , Polycyclic Aromatic Hydrocarbons/analysis , China , Biomass , Seasons , Environmental Monitoring
14.
Chemosphere ; 327: 138530, 2023 Jun.
Article in English | MEDLINE | ID: mdl-37001758

ABSTRACT

Polar regions should be given greater consideration with respect to the monitoring, risk assessment, and management of potentially harmful chemicals, consistent with requirements of the precautionary principle. Protecting the vulnerable polar environments requires (i) raising political and public awareness and (ii) restricting and preventing global emissions of harmful chemicals at their sources. The Berlin Statement is the outcome of an international workshop with representatives of the European Commission, the Arctic Council, the Antarctic Treaty Consultative Meeting, the Stockholm Convention on Persistent Organic Pollutants (POPs), environmental specimen banks, and data centers, as well as scientists from various international research institutions. The statement addresses urgent chemical pollution issues in the polar regions and provides recommendations for improving screening, monitoring, risk assessment, research cooperation, and open data sharing to provide environmental policy makers and chemicals management decision-makers with relevant and reliable contaminant data to better protect the polar environments. The consensus reached at the workshop can be summarized in just two words: "Act now!" Specifically, "Act now!" to reduce the presence and impact of anthropogenic chemical pollution in polar regions by. •Establishing participatory co-development frameworks in a permanent multi-disciplinary platform for Arctic-Antarctic collaborations and establishing exchanges between the Arctic Monitoring and Assessment Program (AMAP) of the Arctic Council and the Antarctic Monitoring and Assessment Program (AnMAP) of the Scientific Committee on Antarctic Research (SCAR) to increase the visibility and exchange of contaminant data and to support the development of harmonized monitoring programs. •Integrating environmental specimen banking, innovative screening approaches and archiving systems, to provide opportunities for improved assessment of contaminants to protect polar regions.


Subject(s)
Environmental Monitoring , Environmental Pollutants , Antarctic Regions , Arctic Regions , Cold Climate , Environmental Pollutants/analysis , Environmental Pollution/prevention & control , Risk Assessment
15.
Environ Sci Technol ; 57(14): 5544-5557, 2023 04 11.
Article in English | MEDLINE | ID: mdl-36972291

ABSTRACT

Aqueous film-forming foams historically were used during fire training activities on Joint Base Cape Cod, Massachusetts, and created an extensive per- and polyfluoroalkyl substances (PFAS) groundwater contamination plume. The potential for PFAS bioconcentration from exposure to the contaminated groundwater, which discharges to surface water bodies, was assessed with mobile-laboratory experiments using groundwater from the contamination plume and a nearby reference location. The on-site continuous-flow 21-day exposures used male and female fathead minnows, freshwater mussels, polar organic chemical integrative samplers (POCIS), and polyethylene tube samplers (PETS) to evaluate biotic and abiotic uptake. The composition of the PFAS-contaminated groundwater was complex and 9 PFAS were detected in the reference groundwater and 17 PFAS were detected in the contaminated groundwater. The summed PFAS concentrations ranged from 120 to 140 ng L-1 in reference groundwater and 6100 to 15,000 ng L-1 in contaminated groundwater. Biotic concentration factors (CFb) for individual PFAS were species, sex, source, and compound-specific and ranged from 2.9 to 1000 L kg-1 in whole-body male fish exposed to contaminated groundwater for 21 days. The fish and mussel CFb generally increased with increasing fluorocarbon chain length and were greater for sulfonates than for carboxylates. The exception was perfluorohexane sulfonate, which deviated from the linear trend and had a 10-fold difference in CFb between sites, possibly because of biotransformation of precursors such as perfluorohexane sulfonamide. Uptake for most PFAS in male fish was linear over time, whereas female fish had bilinear uptake indicated by an initial increase in tissue concentrations followed by a decrease. Uptake of PFAS was less for mussels (maximum CFb = 200) than for fish, and mussel uptake of most PFAS also was bilinear. Although abiotic concentration factors were greater than CFb, and values for POCIS were greater than for PETS, passive samplers were useful for assessing PFAS that potentially bioconcentrate in fish but are present at concentrations below method quantitation limits in water. Passive samplers also accumulate short-chain PFAS that are not bioconcentrated.


Subject(s)
Fluorocarbons , Groundwater , Water Pollutants, Chemical , Animals , Male , Female , Water Pollutants, Chemical/analysis , Fishes , Water , Fluorocarbons/analysis , Alkanesulfonates , Massachusetts , Polyethylene
16.
Environ Sci Technol ; 57(14): 5592-5602, 2023 04 11.
Article in English | MEDLINE | ID: mdl-36972708

ABSTRACT

Drinking water supplies across the United States have been contaminated by firefighting and fire-training activities that use aqueous film-forming foams (AFFF) containing per- and polyfluoroalkyl substances (PFAS). Much of the AFFF is manufactured using electrochemical fluorination by 3M. Precursors with six perfluorinated carbons (C6) and non-fluorinated amine substituents make up approximately one-third of the PFAS in 3M AFFF. C6 precursors can be transformed through nitrification (microbial oxidation) of amine moieties into perfluorohexane sulfonate (PFHxS), a compound of regulatory concern. Here, we report biotransformation of the most abundant C6 sulfonamido precursors in 3M AFFF with available commercial standards (FHxSA, PFHxSAm, and PFHxSAmS) in microcosms representative of the groundwater/surface water boundary. Results show rapid (<1 day) biosorption to living cells by precursors but slow biotransformation into PFHxS (1-100 pM day-1). The transformation pathway includes one or two nitrification steps and is supported by the detection of key intermediates using high-resolution mass spectrometry. Increasing nitrate concentrations and total abundance of nitrifying taxa occur in parallel with precursor biotransformation. Together, these data provide multiple lines of evidence supporting microbially limited biotransformation of C6 sulfonamido precursors involving ammonia-oxidizing archaea (Nitrososphaeria) and nitrite-oxidizing bacteria (Nitrospina). Further elucidation of interrelationships between precursor biotransformation and nitrogen cycling in ecosystems would help inform site remediation efforts.


Subject(s)
Fluorocarbons , Groundwater , Water Pollutants, Chemical , Ecosystem , Water Pollutants, Chemical/analysis , Groundwater/chemistry , Biotransformation , Fluorocarbons/analysis , Alkanesulfonates
18.
Environ Sci Process Impacts ; 25(3): 531-541, 2023 Mar 22.
Article in English | MEDLINE | ID: mdl-36661269

ABSTRACT

This study presents first-hand information on the occurrence of persistent organic pollutants (POPs) in the ambient air and surface soil along the Indus flood-plain, Pakistan. The sampling campaign was conducted at 15 site locations during 2014-15, along the Indus River (approximately 1300 km). Composite surface soil samples (N = 15) and passive air samples (N = 15) were collected for the estimation of gaseous POPs as well as air-soil exchange to evaluate the POP emission and distribution or dispersion patterns, source tracking, and contribution of the local and regional sources towards POP accumulation in the Indus River system. Among the studied POPs, levels of DDTs and PCBs were noticeably higher in ambient air (50-560 and 10-1100 pg m-3) and in soil (0.20-350 and 1.40-20 ng g-1), respectively. Regarding the spatial patterns, higher DDT concentrations (ng g-1) were detected in the air and soil samples collected from the wet mountain zone (WMZ) (p < 0.05), followed by the alluvial riverine zone (ARZ), low-lying mountain zone (LLZ), and frozen mountain zone (FMZ). The PCB data did not exhibit significant differences (p > 0.05) for the air samples, while PCB concentrations were significantly higher (p < 0.05) in soil from the LLZ, which may be associated with rapid urbanization and industrial activities in this area. The air-soil exchange of DDTs and PCBs showed net volatilization at most of the studied sites except for a few samples from the FMZ and WMZ. Results of this study about air-soil exchange gradients indicate the long range regional atmospheric transport (LRAT) of POPs to the colder areas (FMZ) of Pakistan, where these act as a secondary source of POPs in these areas.


Subject(s)
Air Pollutants , Environmental Pollutants , Hydrocarbons, Chlorinated , Pesticides , Polychlorinated Biphenyls , Soil Pollutants , Polychlorinated Biphenyls/analysis , Soil , Pakistan , Rivers , Gases , Environmental Monitoring/methods , Air Pollutants/analysis , Soil Pollutants/analysis , Hydrocarbons, Chlorinated/analysis , Pesticides/analysis
19.
Mar Chem ; 257: 1-11, 2023 Nov 20.
Article in English | MEDLINE | ID: mdl-38274497

ABSTRACT

Black carbon (BC) is ubiquitous in pelagic sediments and presumed to have an older radiocarbon age due to long ocean residence times and pre-aging in terrestrial soils. Here, we analyzed sediments from five regions in the subtropical Atlantic Ocean to quantify the black carbon fraction of the total organic carbon pool. Black carbon, derived from the chemothermal oxidation method, comprised between 17±6% of the sedimentary organic carbon in the Northwest Argentina Basin and 65±18% in the Amazon Delta. Black carbon sediment accumulation rates were six times greater in the Sierra Leone Rise (8.4±4.1 mg cm-2 kyr-1) compared to the remote Northwest Argentina Basin (1.3±0.4 mg cm-2 kyr-1), possibly due to enhanced regional atmospheric deposition from annual African grassland fires. The radiocarbon age for BC from subtropical Atlantic sediments were more modern compared to the bulk total organic carbon, and BC source was apportioned as biomass burning byproducts from their stable carbon isotopic signatures and characteristic ratios of polycyclic aromatic hydrocarbons. This study demonstrated that subtropical Atlantic Ocean sediments serve as an important sink for young BC.

20.
ACS ES T Water ; 3(8): 2355-2362, 2023 Aug 11.
Article in English | MEDLINE | ID: mdl-38370143

ABSTRACT

Characterizing sorbent affinity for a target compound (described by sorbent-water distribution coefficient, Ksw) is a necessary step in the sorbent selection and performance-testing process in the process of capturing aquatic contaminants. However, no standardized procedure exists to measure Ksw, and studies display significant variations in set-up and performance. For per- and polyfluoroalkyl substances (PFAS), most Ksw determinations employ batch experiments with small-scale water-sorbent mixtures, methanol-based spike of target compound(s), and analysis after assumed equilibrium, but methodological details of the above procedure differ and might cause artifacts in the determination of Ksw. We conducted several batch experiments systematically varying a general procedure to characterize effects of sub-optimal experimental design. Using a selection of PFAS (6-carbon fluorinated chain length with differing functional groups) and two sorbents, we tested variations of solution:sorbent ratio, methanol content, and PFAS initial concentration, and compared derived Ksw values. Each methodological component affected log(Ksw), usually by suppressing the value (by 0-48%) when compared with a "best design" procedure. Thus, we suggest (1) a reference procedure for PFAS and sorbents used here, and (2) general guidelines for batch experiment design with different compounds and sorbents. Additionally, we report well-constrained Ksw values for 23 PFAS and two sorbents.

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