Flocculation with heterogeneous composition in water environments: A review.

Flocculation is a key process for controlling the fate and transport of suspended particulate matter (SPM) in water environments and has received considerable attention in the field of water science (e.g., oceanography, limnology, and hydrology), remaining an active area of research. The research on flocculation has been conducted to elucidate the SPM dynamics and to diagnose various environmental issues. The flocculation, sedimentation, and transportation of SPM are closely linked to the compositional and structural properties of flocs. In fact, flocs are highly heterogeneous in terms of composition. However, the lack of comprehensive research on floc composition and structure has led to misconceptions regarding the temporal and spatial dynamics of SPM. This review summarizes the current understanding of the heterogeneous composition of flocs (e.g., minerals, organic matter, metals, microplastic, engineered nanoparticles) and its effect on their structure and on their fate and transport within aquatic environments. Furthermore, the effects of human activities (e.g., pollutant discharge, construction) on floc composition are discussed.

A structure-function based approach to floc hierarchy and evidence for the non-fractal nature of natural sediment flocs.

Natural sediment flocs are fragile, highly irregular, loosely bound aggregates comprising minerogenic and organic material. They contribute a major component of suspended sediment load and are critical for the fate and flux of sediment, carbon and pollutants in aquatic environments. Understanding their behaviour is essential to the sustainable management of waterways, fisheries and marine industries. For several decades, modelling approaches have utilised fractal mathematics and observations of two dimensional (2D) floc size distributions to infer levels of aggregation and predict their behaviour. Whilst this is a computationally simple solution, it is highly unlikely to reflect the complexity of natural sediment flocs and current models predicting fine sediment hydrodynamics are not efficient. Here, we show how new observations of fragile floc structures in three dimensions (3D) demonstrate unequivocally that natural flocs are non-fractal. We propose that floc hierarchy is based on observations of 3D structure and function rather than 2D size distribution. In contrast to fractal theory, our data indicate that flocs possess characteristics of emergent systems including non-linearity and scale-dependent feedbacks. These concepts and new data to quantify floc structures offer the opportunity to explore new emergence-based floc frameworks which better represent natural floc behaviour and could advance our predictive capacity.

Accumulation of trace metals in freshwater macroinvertebrates across metal contamination gradients.

Historical mining activities cause widespread, long-term trace metal contamination of freshwater ecosystems. However, measuring trace metal bioavailability has proven difficult, because it depends on many factors, not least concentrations in water, sediment and habitat. Simple tools are needed to assess bioavailabilities. The use of biomonitors has been widely advocated to provide a realistic measure. To date there have been few attempts to identify ubiquitous patterns of trace metal accumulation within and between freshwater biomonitors at geographical scales relevant to trace metal contamination. Here we address this through a nationwide collection of freshwater biomonitors (species of Gammarus, Leuctra, Baetis, Rhyacophila, Hydropsyche) from 99 English and Welsh stream sites spanning a gradient of high to low trace metal loading. The study tested for inter-biomonitor variation in trace metal body burden, and for congruence amongst accumulations of trace metals within taxa and between taxa across the gradient. In general, significant differences in trace metal body burden occurred between taxa: Gammarus sp. was the most different compared with insect biomonitors. Bivariate relationships between trace metals within biomonitors reflected trace metal profiles in the environment. Strong correlations between some trace metals suggested accumulation was also influenced by physiological pathways. Bivariate relationships between insect biomonitors for body burdens of As, Cu, Mn and Pb were highly consistent. Our data show that irrespective of taxonomic or ecological differences, there is a commonality of response amongst insect taxa, indicating one or more could provide consistent measures of trace metal bioavailability.

Systematic Analysis of the Relative Abundance of Polymers Occurring as Microplastics in Freshwaters and Estuaries.

Despite growing interest in the environmental impact of microplastics, a standardized characterization method is not available. We carried out a systematic analysis of reliable global data detailing the relative abundance of polymers in freshwaters and estuaries. The polymers were identified according to seven main categories: polyethylene terephthalate, polyethylene, polyvinyl chloride, polypropylene, polystyrene, polyurethane and a final category of miscellaneous plastic. The results show that microplastics comprised of polyvinyl chloride and polyurethane are significantly less abundant than would be expected based on global production, possibly due to their use. This has implications for models of microplastic release into the environment based on production and fate. When analysed by matrix (water, sediment or biota) distinct profiles were obtained for each category. Polyethylene, polypropylene and polystyrene were more abundant in sediment than in biota, while miscellaneous plastics was more frequent in biota. The data suggest that environmental sorting of microplastic particles, influenced by physical, chemical and biological processes, may play a key role in environmental impact, although partitioning among matrices based on density was not realized. The distinct profile of microplastics in biota raises an important question regarding potential selectivity in uptake by organisms, highlighting the priority for more and better-informed laboratory exposure studies.

Will flooding or erosion of historic landfills result in a significant release of soluble contaminants to the coastal zone?

Historically, solid wastes were commonly landfilled in the coastal zone in sites with limited engineering to isolate waste from adjacent coastal environments. Climate change is increasing the likelihood that these historic coastal landfills will be inundated or eroded resulting in the release of soluble contaminants to the coastal zone. Previously research has focussed on the environmental impacts of leaching from landfills in freshwater environments with little or no consideration being given to saline environments. This research investigated the magnitude, variability and potential environmental consequences of soluble metal release from solid wastes when historic coastal landfills are inundated, or wastes are eroded and released into fresh or saline waters. The proportions of the sites' total metal contents released to solution varied by up to an order of magnitude between different landfills due to the different physical and chemical characteristics of the solid wastes, but the proportions released were typically ≪1% in freshwater. Inundation by saline water significantly increases the proportions of the total metal contents released to solution, e.g. 5450% more Pb in one study site (median value), but again the proportions were typically ≪1%. The exception was Cd, where up to 9% of the total Cd load of one site was released in saline water. This puts into question the suitability of current landfill regulatory tests, e.g. the EU Waste Acceptance Criteria, and many risk assessment methods, which only consider freshwater inundation and leaching. However, the very low proportions of metals mobilised from the solid waste and the high dilution ratios in coastal waters, mean EQSs for the Protection of Surface Water are unlikely to be exceeded, and the release of solid wastes through coastal erosion poses a greater threat to coastal ecological health than leaching of soluble metals from contained solid wastes.

The Impact of Metal-Rich Sediments Derived from Mining on Freshwater Stream Life.

Metal-rich sediments have the potential to impair life in freshwater streams and rivers and, thereby, to inhibit recovery of ecological conditions after any remediation of mine water discharges. Sediments remain metal-rich over long time periods and have long-term potential ecotoxicological interactions with local biota, unless the sediments themselves are physically removed or replaced by less metal-rich sediment. Laboratory-derived environmental quality standards are difficult to apply to the field situation, as many complicating factors exist in the real world. Therefore, there is a strong case to consider other, field-relevant, measures of toxic effects as alternatives to laboratory-derived standards and to seek better biological tools to detect, diagnose and ideally predict community-level ecotoxicological impairment. Hence, this review concentrated on field measures of toxic effects of metal-rich sediment in freshwater streams, with less emphasis on laboratory-based toxicity testing approaches. To this end, this review provides an overview of the impact of metal-rich sediments on freshwater stream life, focusing on biological impacts linked to metal contamination.

Potential contamination of the coastal zone by eroding historic landfills.

Historically solid waste was commonly landfilled in the coastal zone in sites with limited engineering to isolate waste from adjacent coastal environments. Climate change is increasing the likelihood that these historic coastal landfills will erode releasing solid waste to the coastal zone. Historic coastal landfills are frequently located near designated ecological sites; yet, there is little understanding of the environmental risk posed by released waste. This research investigated inorganic and organic contaminant concentrations in a range of solid waste materials excavated from two historic coastal landfills, and the potential ecological impact should eroded waste be released to the coastal environment. Contaminant concentrations in the analysed waste materials exceeded sediment quality guidelines, indicating erosion of historic coastal landfills may pose a significant environmental threat. Paper and textile wastes were found to make a significant contribution to the total contaminant load, suggesting risk assessments should consider a wide range of solid waste materials.

Sediment structure and physicochemical changes following tidal inundation at a large open coast managed realignment site.

Managed realignment (MR) schemes are being implemented to compensate for the loss of intertidal saltmarsh habitats by breaching flood defences and inundating the formerly defended coastal hinterland. However, studies have shown that MR sites have lower biodiversity than anticipated, which has been linked with anoxia and poor drainage resulting from compaction and the collapse of sediment pore space caused by the site's former terrestrial land use. Despite this proposed link between biodiversity and soil structure, the evolution of the sediment sub-surface following site inundation has rarely been examined, particularly over the early stages of the terrestrial to marine or estuarine transition. This paper presents a novel combination of broad- and intensive-scale analysis of the sub-surface evolution of the Medmerry Managed Realignment Site (West Sussex, UK) in the three years following site inundation. Repeated broad-scale sediment physiochemical datasets are analysed to assess the early changes in the sediment subsurface and the preservation of the former terrestrial surface, comparing four locations of different former land uses. Additionally, for two of these locations, high-intensity 3D-computed X-ray microtomography and Itrax micro-X-ray fluorescence spectrometry analyses are presented. Results provide new data on differences in sediment properties and structure related to the former land use, indicating that increased agricultural activity leads to increased compaction and reduced porosity. The presence of anoxic conditions, indicative of poor hydrological connectivity between the terrestrial and post-inundation intertidal sediment facies, was only detected at one site. This site has experienced the highest rate of accretion over the terrestrial surface (ca. 7 cm over 36 months), suggesting that poor drainage is caused by the interaction (or lack of) between sediment facies rather than the former land use. This has significant implications for the design of future MR sites in terms of preparing sites, their anticipated evolution, and the delivery of ecosystem services.

The contaminant legacy from historic coastal landfills and their potential as sources of diffuse pollution.

Prior to modern environmental regulation landfills in low-lying coastal environments were frequently constructed without leachate control, relying on natural attenuation within inter-tidal sediments to dilute and disperse contaminants reducing environmental impact. With sea level rise and coastal erosion these sites may now pose a pollution risk, yet have received little investigation. This work examines the extent of metal contamination in saltmarsh sediments surrounding a historic landfill in the UK. Patterns of sediment metal data suggest typical anthropogenic pollution chronologies for saltmarsh sediments in industrialised nations. However, many metals were also enriched at depth in close proximity to the landfill boundary and are indicative of a historical leachate plume. Though this total metal load is low, e.g., c. 1200 and 1650kg Pb and Zn respectively, with >1000 historic landfills on flood risk or eroding coastlines in the UK this could represent a significant, yet under-investigated, source of diffuse pollution.

Unravelling metal mobility under complex contaminant signatures.

Metals are concerning pollutants in estuaries, where contamination can undergo significant remobilisation driven by physico-chemical forcing. Environmental concentrations of metals in estuarine sediments are often higher than natural backgrounds, but show no contiguity to potential sources. Thus, better understanding the metal mobility in estuaries is essential to improve identification of pollution sources and their accountability for environmental effects. This study aims to identify the key biogeochemical drivers of metal mobilisation on contaminated estuarine sediments through (1) evaluation of the potential mobilisation under controlled conditions, and (2) investigation of the relevance of metal mobilisation for in situ pollution levels in an area with multiple contaminant sources. Sediments from a saltmarsh adjacent to a coastal landfill, a marina, and a shipyard on the Thames Estuary (Essex, UK) were exposed in the laboratory (24h, N=96, 20°C) to water under various salinity, pH, and redox potential. Major cations, Fe(II), and trace metal concentrations were analysed in the leachate and sediment. Salinity, pH and redox had a significant effect on metal mobilisation (p<0.001), e.g. under certain conditions Fe(II) leaching was increased ~1000-fold. Measurements in situ of surface and subsurface sediment cores revealed that landfill proximity poorly explained metal spatial distribution. However, physicochemical parameters explained up to 97% of geochemically normalized metal concentrations in sediments. Organic matter and pH were dominant factors for most of the metal concentrations at the sediment surface. At subsurface, major cations (Ca, Na, Mg and K) were determinant predictors of metal concentrations. Applying the empirical model obtained in the laboratory to geochemical conditions of the studied saltmarsh it was possible to demonstrate that Fe mobilisation regulates the fate of this (and other) metal in that area. Thus, present results highlight the importance of metal mobility to control sediment pollution and estuarine fate of metals.

Quantifying the Structure and Composition of Flocculated Suspended Particulate Matter Using Focused Ion Beam Nanotomography.

Suspended particulate matter (SPM) is present in the natural aquatic environment as loosely bound aggregates or "flocs" and is responsible for the transport and fate of sediment, carbon, nutrients, pollutants, pathogens and manufactured nanoparticles from catchment to coast. Accurate prediction of SPM hydrodynamics requires the quantification of 3D floc properties (size, shape, density and porosity) that span several spatial scales. Yet, current techniques (video camera systems, optical microscopy and transmission electron microscopy, TEM) can only provide 2D simplifications of size and shape with a spatial resolution gap between the "gross" (>100s µm) and nanoscale (<1 µm). Here, we translate 3D-microscopy techniques (focused ion beam nanotomography, FIB-nt) typically used in the biomedical sciences to the study of natural flocculated SPM filling both this spatial and dimensional gap. Fragile 3D floc samples were successfully captured and stabilized, identifying five basic organic and inorganic floc components and quantifying porosity and bacteria numbers. This provides new 3D floc geometric data sets at the nanoscale that will be critical in the development of cohesive sediment transport models. Detailed compositional and structural information could provide novel insights into the association of pathogens and pollutants with SPM and their impact on aquatic life.

The impact of pre-restoration land-use and disturbance on sediment structure, hydrology and the sediment geochemical environment in restored saltmarshes.

Saltmarshes are being lost or degraded as a result of human activity resulting in loss of critical ecosystem services including the provision of wild species diversity, water quality regulation and flood regulation. To compensate, saltmarshes are being restored or re-created, usually driven by legislative requirements for increased habitat diversity, flood regulation and sustainable coastal defense. Yet, there is increasing evidence that restoration may not deliver anticipated ecosystem services; this is frequently attributed to poor drainage and sediment anoxia. However, physical sediment characteristics, hydrology and the sediment geochemical environment are rarely examined in restoration schemes, despite such factors being critical for plant succession. This study presents the novel integration of 3D-computed X-ray microtomography to quantify sediment structure and porosity, with water level and geochemical data to understand the impact of pre-restoration land use and disturbance on the structure and functioning of restored saltmarshes. The study combines a broad-scale investigation of physical sediment characteristics in nine de-embanked saltmarshes across SE England, with an intensive study at one site examining water levels, sediment structure and the sediment geochemical environment. De-embankment does not restore the hydrological regime, or the physical/chemical framework in the saltmarshes and evidence of disturbance includes a reduction in microporosity, pore connectivity and water storage capacity, a lack of connectivity between the sub-surface environment and overlying floodwaters, and impeded sub-surface water flow and drainage. This has significant consequences for the sediment geochemical environment. This disturbance is evident for at least two decades following restoration and is likely to be irreversible. It has important implications for plant establishment in particular, ecosystem services including flood regulation, nutrient cycling and wild species diversity and for future restoration design.

The effects of sulfur amendments on the geochemistry of sulfur, phosphorus and iron in the mangrove plant (Kandelia obovata (S. L.)) rhizosphere.

P (phosphorus) and Fe (iron) are limiting elements and S (sulfur) is an important element of the biogeochemical cycle in the mangrove environment. To assess the effects of sulfur on the geochemical cycling of Fe and P at the sediment-plant interface, the speciation distributions of Fe, P and S in sediments were examined. The data showed that higher proportions of amorphous Fe, Fe-bound phosphate, chromium reducible sulfur and elemental sulfur were found in the rhizosphere, while more crystalline Fe, exchangeable phosphate and acid-volatile sulfide were determined in the non-rhizosphere. Sulfate application induced an increase in the Ex-P concentration, high P accumulation and high iron plaque deposition in the roots. In conclusion, sulfate applications had a significant influence on the geochemical cycling of Fe and P in the sediments. It significantly curtailed the Fe and P limit to plant growth and enhanced plant resistance to the rugged surroundings in mangrove.

The distribution of acid-volatile sulfide and simultaneously extracted metals in sediments from a mangrove forest and adjacent mudflat in Zhangjiang Estuary, China.

The distribution of acid-volatile sulfide (AVS) and simultaneously extracted metals (SEM) were studied in sediments collected from mangrove forest, forest fringe and adjacent mudflat in the Zhangjiang Estuary, China. The aim was to examine the spatial distribution of AVS and SEM in sediments of the Estuary and determine the influence of mangrove trees on AVS and SEM concentrations in the sediments. The results indicated that AVS concentrations in forest sediments were significantly lower than those in mudflat sediments. There was a significant positive correlation between AVS values and moisture contents in forest sediments, while LOI played an important role in AVS concentrations of mudflat sediments. In the forest sediment core, the peak value of AVS appeared deeper in the sediment profile compared to it appeared in the mudflat core. The distribution of SEM showed different trends from that of AVS, and potential toxicity existed in the upriver forest sediments.

Spatial variability of metals in the inter-tidal sediments of the Medway Estuary, Kent, UK.

Concentrations of major and trace metals were determined in eight sediment cores collected from the inter-tidal zone of the Medway Estuary, Kent, UK. Metal associations and potential sources have been investigated using principal component analysis. These data provide the first detailed geochemical survey of recent sediments in the Medway Estuary. Metal concentrations in surface sediments lie in the mid to lower range for UK estuarine sediments indicating that the Medway receives low but appreciable contaminant inputs. Vertical metal distributions reveal variable redox zonation across the estuary and historically elevated anthropogenic inputs. Peak concentrations of Cu, Pb and Zn can be traced laterally across the estuary and their positions indicate periods of past erosion and/or non-deposition. However, low rates of sediment accumulation do not allow these sub surface maxima to be used as accurate geochemical marker horizons. The salt marshes and inter-tidal mud flats in the Medway Estuary are experiencing erosion, however the erosion of historically contaminated sediments is unlikely to re-release significant amounts of heavy metals to the estuarine system.