Kate L. Spencer

Use of principal components analysis (PCA) on estuarine sediment datasets: the effect of data pre-treatment.

Principal components analysis (PCA) is a multivariate statistical technique capable of discerning patterns in large environmental datasets. Although widely used, there is disparity in the literature with respect to data pre-treatment prior to PCA. This research examines the influence of commonly reported data pre-treatment methods on PCA outputs, and hence data interpretation, using a typical environmental dataset comprising sediment geochemical data from an estuary in SE England. This study demonstrated that applying the routinely used log (x + 1) transformation skewed the data and masked important trends. Removing outlying samples and correcting for the influence of grain size had the most significant effect on PCA outputs and data interpretation. Reducing the influence of grain size using granulometric normalisation meant that other factors affecting metal variability, including mineralogy, anthropogenic sources and distance along the salinity transect could be identified and interpreted more clearly.

Heavy metal distribution and early-diagenesis in salt marsh sediments from the Medway Estuary, Kent, UK

Salt marsh cores are increasingly being used to study metal pollution chronologies. Salt marshes in macro-tidal estuaries, however, tend to retain a time-integrated or ‘smoothed’ signal rather than a record of discrete pollutant inputs, due to extensive sediment reworking. More generally, an accurate chronology of metal input to salt marsh sediments can be difficult to assess because of the potential early-diagenetic mobility of both the radionuclides used for dating and the contaminants of interest. A dated salt marsh core from the macro-tidal Medway Estuary, southeast England, was assessed using both total sediment metal data and partitioning data. These data indicate that both Mn and Fe have been significantly remobilised and that these diagenetic processes have slightly modified the vertical distributions of Cu, Pb and Zn. Zinc is the most diagenetically reactive followed by Cu and then Pb. However, general trends in pollutant loading can still be identified with maximum inputs occurring between ca. 1900 and 1950, decreasing towards the present day.

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.

Metal fate and effects in estuaries: A review and conceptual model for better understanding of toxicity.

Metal pollution is a global problem in estuaries due to the legacy of historic contamination and currently increasing metal emissions. However, the establishment of water and sediment standards or management actions in brackish systems has been difficult because of the inherent transdisciplinary nature of estuarine processes. According to the European Commission, integrative comprehension of fate and effects of contaminants in different compartments of these transitional environments (estuarine sediment, water, biota) is still required to better establish, assess and monitor the good ecological status targeted by the Water Framework Directive. Thus, the present study proposes a holistic overview and conceptual model for the environmental fate of metals and their toxicity effects on aquatic organisms in estuaries. This includes the analysis and integration of biogeochemical processes and parameters, metal chemistry and organism physiology. Sources of particulate and dissolved metal, hydrodynamics, water chemistry, and mechanisms of toxicity are discussed jointly in a multidisciplinary manner. It is also hypothesized how these different drivers of metal behaviour might interact and affect metal concentrations in diverse media, and the knowledge gaps and remaining research challenges are pointed. Ultimately,estuarine physicochemical gradients, biogeochemical processes, and organism physiology are jointly coordinating the fate and potential effects of metals in estuaries, and both realistic model approaches and attempts.

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.

Sediment transfer and accumulation in two contrasting salt marsh/mudflat systems: the Seine estuary (France) and the Medway estuary (UK)

Understanding the dynamics of fine sediment transport across the upper intertidal zone is critical in managing the erosion and accretion of intertidal areas, and in managed realignment/estuarine habitat recreation strategies. This paper examines the transfer of sediments between salt marsh and mudflat environments in two contrasting macrotidal estuaries: the Seine (France) and the Medway (UK), using data collected during two joint field seasons undertaken by the Anglo-French RIMEW project (Rives-Manche Estuary Watch). High-resolution ADCP, Altimeter, OBS and ASM measurements from mudflat and marsh surface environments have been combined with sediment trap data to examine short-term sediment transport processes under spring tide and storm flow conditions. In addition, the longer-term accumulation of sediment in each salt marsh system has been examined via radiometric dating of sediment cores. In the Seine, rapid sediment accumulation and expansion of salt marsh areas, and subsequent loss of open intertidal mudflats, is a major problem, and the data collected here indicate a distinct net landward flux of sediments into the marsh interior. Suspended sediment fluxes are much higher than in the Medway estuary (averaging 0.09 g/m3/s), and vertical accumulation rates at the salt marsh/mudflat boundary exceed 3 cm/y. Suspended sediment data collected during storm surge conditions indicate that significant in-wash of fine sediments into the marsh interior can occur during (and following) these high-magnitude events. In contrast to the Seine, the Medway is undergoing erosion and general loss of salt marsh areas. Suspended sediment fluxes are of the order of 0.03 g/m3/s, and the marsh system here has much lower rates of vertical accretion (sediment accumulation rates are ca. 4 mm/y). Current velocity data for the Medway site indicate higher velocities on the ebb tide than occur on the flood tide, which may be sufficient to remobilise sediments deposited on the previous tide and so force net removal of material from the marsh.

Sorption of lanthanum onto clay minerals: a potential tracer for fine sediment transport in the coastal marine environment?

Abstract In order to improve predictions of coastal morphological response to sea-level rise and sustainably manage dredged sediment there is an urgent need to develop a field methodology that can measure accurately transport pathways of the <63 µm sediment fraction in coastal and estuarine environments. Techniques such as sediment trend analysis and sediment tracing using fluorescent sands are well established for the silt and sand fraction but are unsuitable for clay sediments due to their cohesive nature. Geochemically labelled clays have been used as fine sediment tracers in freshwater environments with some success, although little is known about their chemical or physical behaviour once released in saline environments. A number of pure clays and natural estuarine sediments were labelled with La following agitation in a 0.01 M solution of La Cl3. In order to examine the retention of La on the clay mineral surface the labelled sediment was washed sequentially four times using both de-ionised water and artificial seawater. A labelled bentonite retained 43000 µg g-1 La and this was only reduced to 36000 µg g-1 La after washing in seawater. This suggests that retention of La is good even in saline conditions and concentrations of La are high enough to enable detection after considerable signal dilution. Sorption of La is dependent predominantly upon the cation exchange capacity of the sediment.

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 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.