"Old" and "new" contaminants and their management: learning from the past, looking to the future.

Within the 50 year lifetime of the Society for Environmental Geochemistry and Health (SEGH), we have seen a number of contaminants transfer from being the wonder chemical of their day through to becoming current contaminants of concern. This is also true for a variety of emerging contaminants such as plastic microbeads, pharmaceutical residues, and fire retardant chemicals, amongst others. This thought piece discusses the risk associated with a range of these emerging contaminants, their global nature, how existing models and frameworks can be applied to deal with their impacts, and research and management gaps and challenges.

Developing field-scale, gentle remediation options for nuclear sites contaminated with 137Cs and 90Sr: The role of Nature-Based Solutions.

The remediation of contaminated land using plants, bacteria and fungi has been widely examined, especially in laboratory or greenhouse systems where conditions are precisely controlled. However, in real systems at the field scale conditions are much more variable and often produce different outcomes, which must be fully examined if 'gentle remediation options', or GROs, are to be more widely implemented, and their associated benefits (beyond risk-management) realized. These secondary benefits can be significant if GROs are applied correctly, and can include significant biodiversity enhancements. Here, we assess recent developments in the field-scale application of GROs for the remediation of two model contaminants for nuclear site remediation (90Sr and 137Cs), their risk management efficiency, directions for future application and research, and barriers to their further implementation at scale. We also discuss how wider benefits, such as biodiversity enhancements, water filtration etc. can be maximized at the field-scale by intelligent application of these approaches.

Novel DGT Configurations for the Assessment of Bioavailable Plutonium, Americium, and Uranium in Marine and Freshwater Environments.

Plutonium, americium, and uranium contribute to the radioactive contamination of the environment and are risk factors for elevated radiation exposure via ingestion through food or water. Due to the significant environmental inventory of these radioelements, a sampling method to accurately monitor their bioavailable concentrations in natural waters is necessary, especially since physicochemical factors can cause significant temporal fluctuations in their waterborne concentrations. To this end, we engineered novel diffusive gradients in thin-film (DGT) configurations using resin gels, which are selective for UO22+, Pu(IV + V), and Am(III) among an excess of extraneous cations. In this work, we also report an improved synthesis of our in-house ion-imprinted polymer resin, which we used to manufacture a resin gel to capture Am(III). The effective diffusion coefficients of Pu, Am, and U in agarose cross-linked polyacrylamide were determined in freshwater and seawater simulants and in natural seawater, to calibrate these configurations for environmental deployments.

Systematic and bibliographic review of sustainability indicators for contaminated site remediation: Comparison between China and western nations.

Sustainable remediation, which promotes the use of more sustainable practices during environmental clean-up activities, is an area of intense international development. While numerous indicators related to sustainable remediation assessment have been utilized and published in related academic literature, they are difficult to unify and vary in emphasis between countries. Following literature retrieval from CNKI, Springer, ScienceDirect, and Wiley Online databases, we present a systematic and bibliometric analysis of relevant national and international literature to define the most frequently considered indicators of sustainability, which play important roles in selecting remediation technologies or site management methods from a sustainability perspective. Following the application of co-occurrence analysis and social network analysis, the results indicate that 1) environmental criteria are most commonly used in evaluating remediation technologies, with significantly less emphasis on social criteria in Chinese publications in particular; 2) with an increasing number of publications in the last 20 years, sustainable remediation has gone through an initial stage, rising stage, and burst or wider adoption stage, characterized by a transformation of the research theme from a predominantly risk-based management approach to a sustainability-based one, with risk management as an underpinning principle; 3) health, resource, cost, and time are the most widely used indicators in terms of social, environmental, economic, and technical criteria, respectively; 4) clear differences exist between China and other nations, particularly in the frequency of usage of each indicator, the application of social criteria, and preferred stakeholders. Nevertheless, China has made significant progress and now makes increasing contributions to sustainable remediation at an international level.

Analysis of influencing factors on public perception in contaminated site management: Simulation by structural equation modeling at four sites in China.

Public perception towards contaminated site management, a not readily quantifiable latent parameter, was linked through structural equation modeling in this paper to 22 measurable/observable manifest variables associated with the extent of information dissemination and public knowledge of soil pollution, attitude towards remediation policies, and participation in risk mitigation processes. Data obtained through a survey of 412 community residents at four remediation sites in China were employed in the model validation. The outcomes showed that public perception towards contaminated site management might be explained through selected measurable parameters in five categories, namely information disclosure, knowledge of soil pollution, expectations of remediation and redevelopment outcomes, public participation, and site policy, along with their interactions. Among these, information dissemination and attitude towards management policies exhibited significant influence in promoting positive public perception. Based on these examples, responsible agencies therefore should focus on public accessibility to reliable information, and encourage public inputs into policies for contaminated site management, in order to gain public confidence during remediation and regeneration projects.

The Fate of Contaminants and Stable Pb Isotopes in a Changing Estuarine Environment: 20 Years On.

Estuarine sediments provide an important sink for contaminants discharged into fluvial, estuarine, and nearshore settings, and numerous authors have utilized this trapping function to assess historical contaminant loadings and contaminant breakdown/transformation processes. This Article examines the retention of elemental and isotopic sedimentary signatures in an industrialized estuarine system subject to a strongly upward sea-level trend, over a 20 year period. Two contrasting saltmarsh sites (at Hythe and Hamble, part of the wider Southampton Water estuarine system, UK) were examined, which had been previously cored and analyzed in the early 1990s. Much of the geochemical record of recent anthropogenic activity has been eroded and lost at the Hamble site. In contrast, radiometric, isotopic and elemental records of anthropogenic activity have been retained in the Hythe marsh, with 137Cs and Cu depth profiles showing retention of input maxima related to fallout and local industrial discharges, respectively. Stable Pb isotope data show a broad degree of correspondence in cores analyzed in 1994 and 2014 when plotted against sediment (radiometric) age, indicating the usefulness of isotopic data in retaining information on Pb sources and in disentangling Pb input histories. New ultrahigh precision, double-spike mass spectrometry stable Pb isotope data allow clearer discrimination of historical Pb input phases, and highlight within-estuary mixing and supply of reworked, secondary contamination from erosion of anthropogenically labeled sediments elsewhere in the estuary.

Remediation of hexavalent chromium contamination in chromite ore processing residue by sodium dithionite and sodium phosphate addition and its mechanism.

Large amounts of chromite ore processing residue (COPR) wastes have been deposited in many countries worldwide, generating significant contamination issues from the highly mobile and toxic hexavalent chromium species (Cr(VI)). In this study, sodium dithionite (Na2S2O4) was used to reduce Cr(VI) to Cr(III) in COPR containing high available Fe, and then sodium phosphate (Na3PO4) was utilized to further immobilize Cr(III), via a two-step procedure (TSP). Remediation and immobilization processes and mechanisms were systematically investigated using batch experiments, sequential extraction studies, X-ray diffraction (XRD) and X-ray Photoelectron Spectroscopy (XPS). Results showed that Na2S2O4 effectively reduced Cr(VI) to Cr(III), catalyzed by Fe(III). The subsequent addition of Na3PO4 further immobilized Cr(III) by the formation of crystalline CrPO4·6H2O. However, addition of Na3PO4 simultaneously with Na2S2O4 (via a one-step procedure, OSP) impeded Cr(VI) reduction due to the competitive reaction of Na3PO4 and Na2S2O4 with Fe(III). Thus, the remediation efficiency of the TSP was much higher than the corresponding OSP. Using an optimal dosage in the two-step procedure (Na2S2O4 at a dosage of 12× the stoichiometric requirement for 15 days, and then Na3PO4 in a molar ratio (i.e. Na3PO4: initial Cr(VI)) of 4:1 for another 15 days), the total dissolved Cr in the leachate determined via Toxicity Characteristic Leaching Procedure (TCLP Cr) testing of our samples was reduced to 3.8 mg/L (from an initial TCLP Cr of 112.2 mg/L, i.e. at >96% efficiency).

Carbon-cryogel hierarchical composites as effective and scalable filters for removal of trace organic pollutants from water.

Effective technologies are required to remove organic micropollutants from large fluid volumes to overcome present and future challenges in water and effluent treatment. A novel hierarchical composite filter material for rapid and effective removal of polar organic contaminants from water was developed. The composite is fabricated from phenolic resin-derived carbon microbeads with controllable porous structure and specific surface area embedded in a monolithic, flow permeable, poly(vinyl alcohol) cryogel. The bead-embedded monolithic composite filter retains the bulk of the high adsorptive capacity of the carbon microbeads while improving pore diffusion rates of organic pollutants. Water spiked with organic contaminants, both at environmentally relevant concentrations and at high levels of contamination, was used to determine the purification limits of the filter. Flow through tests using water spiked with the pesticides atrazine (32 mg/L) and malathion (16 mg/L) indicated maximum adsorptive capacities of 641 and 591 mg pollutant/g carbon, respectively. Over 400 bed volumes of water contaminated with 32 mg atrazine/L, and over 27,400 bed volumes of water contaminated with 2 µg atrazine/L, were treated before pesticide guideline values of 0.1 µg/L were exceeded. High adsorptive capacity was maintained when using water with high total organic carbon (TOC) levels and high salinity. The toxicity of water filtrates was tested in vitro with human epithelial cells with no evidence of cytotoxicity after initial washing.

Biochar and compost amendments enhance copper immobilisation and support plant growth in contaminated soils.

Contamination of soil with trace elements, such as Cu, is an important risk management issue. A pot experiment was conducted to determine the effects of three biochars and compost on plant growth and the immobilisation of Cu in a contaminated soil from a site formerly used for wood preservation. To assess Cu mobility, amended soils were analysed using leaching tests pre- and post-incubation, and post-growth. Amended and unamended soils were planted with sunflower, and the resulting plant material was assessed for yield and Cu concentration. All amendments significantly reduced leachable Cu compared to the unamended soil, however, the greatest reductions in leachable Cu were associated with the higher biochar application rate. The greatest improvements in plant yields were obtained with the higher application rate of biochar in combination with compost. The results suggest joint biochar and compost amendment reduces Cu mobility and can support biomass production on Cu-contaminated soils.

Spatio-temporal trends in microplastic presence in the sediments of the River Thames catchment (UK).

This study investigated the spatio-temporal variability of microplastics (MPs) in the sediments of the River Thames (UK) catchment over 30 months (July 2019 - Dec 2021). The average MP concentration was 61 items kg-1 d.w., with fragments <1 mm being dominant and polyethylene (PE) the most common polymer. Adjacent land use influenced MP concentrations and types, with industrial sites showing particularly high levels and a prevalence of small beads and industrial polymers. MP concentrations generally decreased after higher winter flows, likely due to sediment rearrangement or winnowing. This study describes the seasonal concentrations and characteristics of MPs present in sediment from the River Thames catchment, and attempts to identify their likely origin. Further, the study provides new insights into the mobility and fate of MPs in riverine settings under varying flow conditions, which is vital given the predicted increases in flooding under various global heating scenarios.

Dilute concentrations of maritime fuel can modify sediment reworking activity of high-latitude marine invertebrates.

Multiple expressions of climate change, in particular warming-induced reductions in the type, extent and thickness of sea ice, are opening access and providing new viable development opportunities in high-latitude regions. Coastal margins are facing these challenges, but the vulnerability of species and ecosystems to the effects of fuel contamination associated with increased maritime traffic is largely unknown. Here, we show that low concentrations of the water-accommodated fraction of marine fuel oil, representative of a dilute fuel oil spill, can alter functionally important aspects of the behaviour of sediment-dwelling invertebrates. We find that the response to contamination is species specific, but that the range in response among individuals is modified by increasing fuel concentrations. Our study provides evidence that species responses to novel and/or unprecedented levels of anthropogenic activity associated with the opening up of high-latitude regions can have substantive ecological effects, even when human impacts are at, or below, commonly accepted safe thresholds. These secondary responses are often overlooked in broad-scale environmental assessments and marine planning yet, critically, they may act as an early warning signal for impending and more pronounced ecological transitions.

Synthesis and application of hydride silica composites for rapid and facile removal of aqueous mercury.

The adsorption of ionic mercury(II) from aqueous solution on functionalized hydride silicon materials was investigated. The adsorbents were prepared by modification of mesoporous silica C-120 with triethoxysilane or by converting alkoxysilane into siloxanes by reaction with acetic acid. Mercury adsorption isotherms at 208C are reported, and maximum mercury loadings were determined by Langmuir fitting. Adsorbents exhibited efficient and rapid removal of ionic mercury from aqueous solution, with a maximum mercury loading of approximately 0.22 and 0.43 mmol of Hg g1 of silica C-120 and polyhedraloligomeric silsesquioxane (POSS) xerogel, respectively. Adsorption efficiency remained almost constant from pH 2.7 to 7. These inexpensive adsorbents exhibiting rapid assembly, low pH sensitivity, and high reactivity and capacity, are potential candidates as effective materials for mercury decontamination in natural waters and industrial effluents.

Current and emerging technologies for the remediation of difficult-to-measure radionuclides at nuclear sites.

Difficult-to-measure radionuclides (DTMRs), defined by an absence of high energy gamma emissions during decay, are problematic in groundwaters at nuclear sites. DTMRs are common contaminants at many nuclear facilities, with (often) long half-lives and high radiotoxicities within the human body. Effective remediation is, therefore, essential if nuclear site end-state targets are to be met. However, due to a lack of techniques for in situ DTMR detection, technologies designed to remediate these nuclides are underdeveloped and tend to be environmentally invasive. With a growing agenda for sustainable remediation and reduction in nuclear decommissioning costs, there is renewed international focus on the development of less invasive technologies for DTMR clean-up. Here, we review recent developments for remediation of selected problem DTMRs (129I, 99Tc, 90Sr and 3H), with a focus on industrial and site-scale applications. We find that pump and treat (P&T) is the most used technique despite efficacy issues for 129I and 3H. Permeable reactive barriers (PRBs) are a less invasive alternative but have only been demonstrated for removal of 99Tc and 90Sr at scale. Phytoremediation shows promise for site-scale removal of 3H but is unsuitable for 129I and 99Tc due to biotoxicity and bioavailability hazards, respectively. No single technique can remediate all DTMRs of focus. Likewise, there has been no successful site-applied technology with high removal efficiencies for iodine species typically present in groundwaters (iodide/I-, iodate/IO3- and organoiodine). Further work is needed to adapt and improve current techniques to field scales, as well as further research into targeted application of emerging technologies.

Microplastic accumulation in Halophila ovalis beds in the Swan-Canning Estuary, Western Australia.

Small ephemeral seagrass (Halophila ovalis) beds in the Swan-Canning Estuary, Western Australia, were sampled to determine if microplastics attach to seagrass blades and accumulate in higher concentrations in seagrass sediment compared to bare sediment. Three microplastics were observed attached to sampled seagrass blades (n = 108). Microplastics had a mean concentration in seagrass sediments of 1000 ± 100.37se particles kg-1 and in bare sediment of 972 ± 92.19se particles kg-1. ATR FTIR further verified 64.2 % of subsample particles as plastic (n = 28). This is the first known study to identify microplastics within the leaf canopy of H. ovalis however we could not support our hypothesis that this seagrass species acts as a sink for microplastic particles in sediments, as seen in studies on other seagrass species. The ability for seagrass habitats to trap and accumulate microplastics in sediments is likely influenced by species morphology, seagrass canopy density and life history.

The distribution and enrichment of trace elements in surface and core sediments from the Changjiang River Estuary, China: Evidence for anthropogenic inputs and enhanced availability of rare earth elements (REE).

Huge amount of trace metals emitted through manmade activities are carried by the Changjiang River into the East China Sea. Most of them deposit in the Changjiang River Estuary and threaten the regional aquatic environment. In this study, major and trace elements of 34 archive surface sediments and two cores are examined. Sequential extraction procedures were also performed on surface sediments from 12 sites. We found that Tl, Tm, Er show distinct accumulation in surface sediments in the order of Tm > Tl > Er. Particularly, abnormally elevated HREE are observed mainly in those sites near the mouth of the estuary. Most elements exhibit an obvious reduction in the upper 30 cm of core B8, reflecting a decrease of sediment discharge from Changjiang River runoff. The increase of some trace elements recorded in the upper 20 cm of core C3 demonstrates a distinct local anthropogenic input in recent years.

The Searsville Lake Site (California, USA) as a candidate Global boundary Stratotype Section and Point for the Anthropocene series.

Cores from Searsville Lake within Stanford University's Jasper Ridge Biological Preserve, California, USA, are examined to identify a potential GSSP for the Anthropocene: core JRBP2018-VC01B (944.5 cm-long) and tightly correlated JRBP2018-VC01A (852.5 cm-long). Spanning from 1900 CE ± 3 years to 2018 CE, a secure chronology resolved to the sub-annual level allows detailed exploration of the Holocene-Anthropocene transition. We identify the primary GSSP marker as first appearance of 239,240Pu (372-374 cm) in JRBP2018-VC01B and designate the GSSP depth as the distinct boundary between wet and dry season at 366 cm (6 cm above the first sample containing 239,240Pu) and corresponding to October-December 1948 CE. This is consistent with a lag of 1-2 years between ejection of 239,240Pu into the atmosphere and deposition. Auxiliary markers include: first appearance of 137Cs in 1958; late 20th-century decreases in δ15N; late 20th-century elevation in SCPs, Hg, Pb, and other heavy metals; and changes in abundance and presence of ostracod, algae, rotifer and protozoan microfossils. Fossil pollen document anthropogenic landscape changes related to logging and agriculture. As part of a major university, the Searsville site has long been used for research and education, serves users locally to internationally, and is protected yet accessible for future studies and communication about the Anthropocene. Plain Word Summary: The Global boundary Stratotype Section and Point (GSSP) for the proposed Anthropocene Series/Epoch is suggested to lie in sediments accumulated over the last ~120 years in Searsville Lake, Woodside, California, USA. The site fulfills all of the ideal criteria for defining and placing a GSSP. In addition, the Searsville site is particularly appropriate to mark the onset of the Anthropocene, because it was anthropogenic activities-the damming of a watershed-that created a geologic record that now preserves the very signals that can be used to recognize the Anthropocene worldwide.

Hyperstoichiometric interaction between silver and mercury at the nanoscale.

Breaking through the stoichiometry barrier: as the diameter of silver particles is decreased below a critical size of 32 nm, the molar ratio of aqueous Hg(II) to Ag(0) drastically increases beyond the conventional Hg/Ag ratio of 0.5:1, leading to hyperstoichiometry with a maximum ratio of 1.125:1. Therein, around 99% of the initial silver is retained to rapidly form a solid amalgam with reduced mercury.

Environmental risk of trace metals and metalloids in estuarine sediments: An example from Southampton Water, U.K.

Industrial and commercial port activities are widely recognized worldwide as an important source of pollution to proximal estuaries. In this study, we analysed geochemical and sedimentological parameters including major and trace elements, organic matter and sediment texture in surface sediments from the estuarine environment of Southampton Water, U.K. Using these data, and multivariate statistical tools [correlation, factor and cluster analysis and pollution indices such as Enrichment Factor (EF), Pollution Load Index (PLI) and the Adverse Effect Index (AEI)], we examine sedimentary trace metal and metalloid contamination, contamination sources, and potential biological impacts of the contamination present. The geochemical data, multivariate statistical analysis and pollution indices indicate that the spatial distribution of trace metals and metalloids is influenced by both sediment composition (and mixing) and anthropogenic activities. Most trace metal and metalloid concentrations are close to local geological background levels, except for Cu, Zn and Pb. The spatial distribution of these elements indicates that the Exxon oil refinery, Southampton port, local marinas and runoff from domestic and industrial activities act effectively as point sources of these elements. Pollution indices calculations highlight a degraded environment as a result of these pollutants, and further work is needed to assess the current impact of trace metals and metalloids on local ecology.

Role of saltmarsh systems in estuarine trapping of microplastics.

Saltmarshes are important natural ecosystems along many temperate (and other) coastlines. They stabilize sediments and act as biofilters for a range of industrial pollutants and, potentially, microplastics. Accumulation of microplastics along estuarine coastlines may be enhanced by the presence of saltmarsh species, as they offer better particle trapping efficiency than adjacent intertidal mudflats under prevailing flood and ebb tidal currents. However, the trapping efficiency of entire saltmarsh systems under varying flow conditions has not been widely assessed. While the effects of saltmarsh systems on water flow, and on sediment transport and trapping, have been relatively well studied, little is known about the contributions of saltmarsh halophytes, resident organisms and the associated saltmarsh sediments to the trapping of microplastics. To address this, a series of flume experiments were undertaken to examine transport and accumulation of Bakelite particles (~ 500 µm) and PVC nurdles (~ 5 mm) as model plastics in sub-sampled saltmarsh and intertidal mudflat monoliths. The results showed that saltmarsh systems influenced the hydrodynamics within and above the canopy, enhancing turbulence and shear stresses. With increasing flow velocities (≤ 0.51 m s-1), negligible quantities (2 [Formula: see text] 10-4 mg L-1) of sediments and Bakelite particles were eroded and resuspended. The algal biogenic roughness from the mudflat, and the vegetative roughness from the Spartina plants on the saltmarsh, inhibited the transportation of the microplastics within the tested systems. Resident burrowing crabs (Carcinus maenas) promoted the burial, release and transport of microplastics. The results of this study provide evidence of the contributory roles of saltmarsh systems in the sequestration of microplastics and sediment stabilization. Estuarine saltmarsh systems can act as sinks for microplastics with enhanced burial from burrowing crabs under favourable flow conditions.

Time-Integrated Bioavailability Proxy for Actinides in a Contaminated Estuary.

Actinides accumulate within aquatic biota in concentrations several orders of magnitude higher than in the seawater [the concentration factor (CF)], presenting an elevated radiological and biotoxicological risk to human consumers. CFs currently vary widely for the same radionuclide and species, which limits the accuracy of the modeled radiation dose to the public through seafood consumption. We propose that CFs will show less dispersion if calculated using a time-integrated measure of the labile (bioavailable) fraction instead of a specific spot sample of bulk water. Herein, we assess recently developed configurations of the diffusive gradients in thin films (DGT) sampling technique to provide a more accurate predictor for the bioaccumulation of uranium, plutonium, and americium within the biota of the Sellafield-impacted Esk Estuary (UK). We complement DGT data with the cross-flow ultrafiltration of bulk seawater to assess the DGT-labile fraction versus the bulk concentration. Sequential elution of Fucus vesiculosis reveals preferential internalization and strong intracellular binding of less particle-reactive uranium. We find significant variations between CF values in biota calculated using a spot sample versus using DGT, which suggest an underestimation of the CF by spot sampling in some cases. We therefore recommend a revision of CF values using time-integrated bioavailability proxies.