Applied Geochemistry (v.18, #2)

Pesticides and other micro-organic contaminants in freshwater sedimentary environments—a review by N. Warren; I.J. Allan; J.E. Carter; W.A. House; A. Parker (159-194).
A wide range of issues relating to the presence and fate of pesticides and other micro-organic contaminants (MOCs) in surface freshwater sedimentary environments is reviewed. These issues include the sources, transport and occurrence of MOCs in freshwater environments; their ecological effects; their interaction with sedimentary material; and a range of processes related to their fate, including degradation, diffusion in bed sediments, bioturbation and slow contaminant release. An emphasis is placed on those processes—chemical, physical or biological—in which sediments play a role in determining the fate of micro-organics in freshwater environments. The issues of occurrence, source and transport, and the ecological effects of micro-organics are introduced more briefly, the focus where these aspects are concerned being largely on pesticides. In the concluding section, key points and issues relating to the study of micro-organics in freshwater environments are summarised and areas where initial or further research would be welcome are highlighted. It is hoped that this paper will both form a useful reference for workers in the field of micro-organic contaminants, and also stimulate new work in the freshwater environment and beyond.

Storage of sediment-associated nutrients and contaminants in river channel and floodplain systems by D.E Walling; P.N Owens; J Carter; G.J.L Leeks; S Lewis; A.A Meharg; J Wright (195-220).
Samples of fine-grained channel bed sediment and overbank floodplain deposits were collected along the main channels of the Rivers Aire (and its main tributary, the River Calder) and Swale, in Yorkshire, UK, in order to investigate downstream changes in the storage and deposition of heavy metals (Cr, Cu, Pb, Zn), total P and the sum of selected PCB congeners, and to estimate the total storage of these contaminants within the main channels and floodplains of these river systems. Downstream trends in the contaminant content of the <63 μm fraction of channel bed and floodplain sediment in the study rivers are controlled mainly by the location of the main sources of the contaminants, which varies between rivers. In the Rivers Aire and Calder, the contaminant content of the <63 μm fraction of channel bed and floodplain sediment generally increases in a downstream direction, reflecting the location of the main urban and industrialized areas in the middle and lower parts of the basin. In the River Swale, the concentrations of most of the contaminants examined are approximately constant along the length of the river, due to the relatively unpolluted nature of this river. However, the Pb and Zn content of fine channel bed sediment decreases downstream, due to the location of historic metal mines in the headwaters of this river, and the effect of downstream dilution with uncontaminated sediment. The magnitude and spatial variation of contaminant storage and deposition on channel beds and floodplains are also controlled by the amount of <63 μm sediment stored on the channel bed and deposited on the floodplain during overbank events. Consequently, contaminant deposition and storage are strongly influenced by the surface area of the floodplain and channel bed. Contaminant storage on the channel beds of the study rivers is, therefore, generally greatest in the middle and lower reaches of the rivers, since channel width increases downstream. Comparisons of the estimates of total storage of specific contaminants on the channel beds of the main channel systems of the study rivers with the annual contaminant flux at the catchment outlets indicate that channel storage represents <3% of the outlet flux and is, therefore, of limited importance in regulating that flux. Similar comparisons between the annual deposition flux of specific contaminants to the floodplains of the study rivers and the annual contaminant flux at the catchment outlet, emphasise the potential importance of floodplain deposition as a conveyance loss. In the case of the River Aire the floodplain deposition flux is equivalent to between ca. 2% (PCBs) and 36% (Pb) of the outlet flux. With the exception of PCBs, for which the value is ≌0, the equivalent values for the River Swale range between 18% (P) and 95% (Pb). The study emphasises that knowledge of the fine-grained sediment delivery system operating in a river basin is an essential prerequisite for understanding the transport and storage of sediment-associated contaminants in river systems and that conveyance losses associated with floodplain deposition exert an important control on downstream contaminant fluxes and the fate of such contaminants.

The impact of tailings dam spills and clean-up operations on sediment and water quality in river systems: the Rı́os Agrio–Guadiamar, Aznalcóllar, Spain by Karen A Hudson-Edwards; Mark G Macklin; Heather E Jamieson; Paul A Brewer; Tom J Coulthard; Andy J Howard; Jon N Turner (221-239).
The Aznalcóllar tailings dam at Boliden Apirsa's Aznalcóllar/Los Frailes Ag–Cu–Pb–Zn mine 45 km west of Seville, Spain, was breached on 25 April 1998, flooding approximately 4600 hectares of land along the Rı́os Agrio and Guadiamar with approximately 5.5 million m3 of acidic water and 1.3×106 m3 of heavy metal-bearing tailings. Most of the deposited tailings and approximately 4.7×106 m3 of contaminated soils were removed to the Aznalcóllar open pit during clean-up work undertaken immediately after the spill until January 1999. Detailed geomorphological and geochemical surveys of the post-clean-up channel, floodplain and valley floor, and sediment and water sampling, were carried out in January and May 1999 at 6 reaches representative of the types of river channel and floodplain environments in the Rı́o Guadiamar catchment affected by the spill. The collected data show that the clean-up operations removed enough spill-deposited sediment to achieve pre-spill metal (Ag, As, Cd, Cu, Pb, Sb, Tl, Zn) concentrations in surface sediment. These concentrations, however, are still elevated above pre-mining concentrations, and emphasise that mining continues to contaminate the Agrio-Guadiamar river system. Dilution by relatively uncontaminated sediment appears to reduce metal concentrations downstream but increases in metal and As concentrations occur downstream, presumably as a result of factors such as sewage and agriculture. River water samples collected in May 1999 have significantly greater dissolved concentrations of metals and As than those from January 1999, probably due to greater sulphide oxidation from residual tailings with concomitant release of metals in the warmer early summer months. These concentrations are reduced downstream, probably by a combination of dilution and removal of metals by mineral precipitation. Single chemical extractions (de-ionised water, CaCl2 0.01 mol l−1, CH3COONH4 1 M, CH3COONa 1 M and ammonium oxalate 0.2 M) on alluvial samples from reaches 1 and 6, the tailings, pre-spill alluvium and marl have shown that the order of sediment-borne contaminant mobility is generally Zn>Cd>Cu>Pb>As. Pb and As are relatively immobile except possibly under reducing conditions. Much of the highly contaminated sediment remaining in the floodplain and channel still contains a large proportion of tailings-related sulphide minerals which are potentially reactive and may continue to release contaminants to the Agrio–Guadiamar river system. Our work emphasises the need for pre-mining geomorphological and geochemical data, and an assessment of potential contributions of contaminants to river systems from other, non-mining sources.

The long term fate and environmental significance of contaminant metals released by the January and March 2000 mining tailings dam failures in Maramureş County, upper Tisa Basin, Romania by Mark G. Macklin; Paul A. Brewer; Dan Balteanu; Tom J. Coulthard; Basarab Driga; Andy J. Howard; Sorin Zaharia (241-257).
In January and March 2000 two tailings dam failures in Maramureş County, northwest Romania, resulted in the release of 200,000 m3 of contaminated water and 40,000 tonnes of tailings into tributaries of the Tisa River, a major tributary of the Danube. The high concentrations of cyanide and contaminant metals released by these dam failures resulted in pollution and fish deaths not only in Romania, but also downstream in the Tisa and Danube rivers within Hungary, Serbia and Bulgaria. Following these accidents, a research programme was initiated in northwest Romania to establish metal levels in rivers affected by the tailings dam failures and to compare these to metal values in river systems contaminated by historic mining and industrial activity. In July 2000, 65 surface water, 65 river sediment and 45 floodplain sediment samples were collected from trunk streams and principal tributaries of the Lapuş/Someş rivers (affected by the January 2000 spill) and the Vişeu/Tisa rivers (affected by the March 2000 Novat spill) down to the Hungarian and Ukrainian borders, respectively. Sample analyses for Pb, Zn Cu and Cd show that metal contamination in surface water and river sediment decreases rapidly downstream away from presently active mines and tailings ponds. Concentrations of heavy metals in water and sediment leaving Romania, and entering Hungary and the Ukraine, generally fall below EC imperative and Dutch intervention values, respectively. However, Zn, Cu and Cd concentrations in river sediments approach or exceed intervention values at the Romanian border. The results of this survey are compared with earlier surveys to ascertain the long-term fate and environmental significance of contaminant metals released by mine tailings dam failures in Maramureş County.

Geochemistry and petrography of phosphorus in urban canal bed sediment by J Dodd; D.J Large; N.J Fortey; S Kemp; M Styles; P Wetton; A Milodowski (259-267).
Urban canal sediment provides an opportunity to investigate the processes controlling P geochemistry in a system dominated by anthropogenic input. To achieve this a combined study was undertaken of pore water geochemistry and petrology of the top 25 cm canal bed sediment from two urban canals in the English West Midland conurbation. Processes in the sediment are dominated by the geochemistry of Fe, P and organic matter. Results indicate that sediment re-suspension by boat traffic has a major influence on pore water chemistry. In addition to the sediment water interface an additional interface at 6–7 cm depth was identified and corresponds to the maximum depth of sediment re-suspension by boat traffic. Phosphorus in the sediment occurs predominantly as vivianite. Low PO4 concentrations occur close to the sediment water interface in summer due to frequent re-suspension and Fe oxidation. High PO4 concentrations occur close to the sediment water interface in winter when boat traffic is infrequent. The greatest potential to exchange phosphate between sediment and water column will therefore occur during infrequent boat traffic regimes.

Urban sediments are part of a complex system in which particulates accumulate potentially toxic pollutants, ultimately posing a threat to urban water-bodies and public health. It is therefore important to recognise sources, signatures and pathways of urban particulates. Urban sediment samples were analysed from both inner and outer city road surfaces of Manchester, UK. High metal concentrations, coupled with the largely ferrimagnetic multi-domain (MD) mineral magnetic composition of the particulates, indicate inputs of anthropogenic origin, primarily particulates derived from automobiles, as being the dominant source to the urban sediment system. Iron and Pb concentrations show a clear spatial trend, whereby concentrations are enhanced in the inner city samples. Lead concentrations for inner and outer city samples average 354 and 185 μg g−1, respectively. Iron concentrations for inner and outer city samples average 11302 and 6486 μg g−1, respectively. Sequential extraction analysis shows the metals Mn, Fe, Zn and Pb are largely associated with the reducible fraction, whereas Cu is largely associated with the oxidisable fraction. Zinc is the only metal showing significant association with the exchangeable fraction (up to 33%), suggesting that it may be the most susceptible metal to mobilisation during runoff. Metal fractions identified as showing larger associations with the reducible and oxidisable fractions will continue to be vulnerable to mobilisation as a result of changes in ambient pH and/or redox conditions. Mineral magnetic concentration parameters, such as the saturation isothermal remanent magnetisation (SIRM), together with hysteresis parameters such as the coercive force and interparametric ratios (such as (Bo)cr/Hc and IRM-100mT/SIRM) show that ferrimagnetic MD minerals dominate the Manchester urban sediments. Average results for frequency-dependent susceptibility as a percentage (2%) suggest that the composition of these Manchester sediments is not dominated by soil-derived material, and therefore magnetically coarser, anthropogenically-derived material is dominant. Unlike Pb and Fe concentrations, mineral magnetic characteristics of the Manchester urban sediment samples exhibit no significant spatial variation.

Distinguishing between natural and anthropogenic sources of metals entering the Irish Sea by J Ridgway; N Breward; W.J Langston; R Lister; J.G Rees; S.M Rowlatt (283-309).
International agreements (e.g. OSPAR) on the release of hazardous substances into the marine environment and environmental assessments of shelf seas require that concentrations and bioavailability of metals from anthropogenic sources can be distinguished from those originating as a result of natural geological processes. The development of a methodology for distinguishing between anthropogenic and natural sources of metals entering the Irish Sea through river inputs is described. The geochemistry of stream, river and estuarine sediments has been used to identify background geochemical signatures, related to geology, and modifications to these signatures by anthropogenic activities. The British Geological Survey (BGS) geochemical database, based on stream sediments from 1 to 2 km2 catchments, was used to derive the background signatures. Where mining activity was present, the impact on the signature was estimated by comparison with the geochemistry of sediments from a geologically similar, but mining free, area. River sediment samples taken upstream and downstream of major towns were used respectively to test the validity of using stream sediments to estimate the chemistry of the major river sediment and to provide an indication of the anthropogenic impact related to urban and industrial development. The geochemistry of estuarine sediments from surface samples and cores was then compared with river and offshore sediment chemistry to assess the importance of riverine inputs to the Irish Sea. Studies were undertaken in the Solway, Ribble, Wyre and Mersey estuaries. The results verify that catchment averages of stream sediments and major river samples have comparable chemistry where anthropogenic influences are small. Major urban and industrial (including mining) development causes easily recognised departures from the natural multi-element geochemical signature in river sediment samples downstream of the development and enhanced metal levels are observed in sediments from estuaries with industrial catchments. Stream sediment chemistry coupled with limited river and estuarine sampling provides a cost-effective means of identifying anthropogenic metal inputs to the marine environment. Investigations of field and laboratory protocols to characterise biological impact (bioaccumulation) of metals in sediments of the Irish Sea and its estuaries show that useful assessments can be made by a combination of surveys with bioindicator species such as clams Scrobicularia plana, selective sediment measurements that mimic the ‘biologically available’ fractions, and laboratory (mesocosm) studies.

Reconstructing historical trends in metal input in heavily-disturbed, contaminated estuaries: studies from Bilbao, Southampton Water and Sicily by Andrew B. Cundy; Ian W. Croudace; Alejandro Cearreta; Marı&#x0301;a J. Irabien (311-325).
Estuaries may be important reservoirs for contaminants as they tend to act as sinks for fine, contaminant-reactive sediments, and, historically, they have acted as centres for industrial and urban development. Analysis of dated sediment cores from these areas may allow historical trends in heavy metal input to be reconstructed, and recent and historical inputs of metal contaminants to be compared. Undisturbed saltmarsh settings have been used widely in the reconstruction of historical trends in metal input as saltmarshes provide a stable, vegetated substrate of dominantly fine sediments, and are less prone to erosion and reworking than adjacent mudflat areas. In comparison, much less research on historical pollution trends has been undertaken at estuarine sites which are prone to severe local disturbance, such as intertidal areas which are routinely dredged or where sedimentary processes have been modified by human activities such as shipping, salt working, port activities, land claim etc. This paper assesses the usefulness of 210Pb and 137Cs dating, combined with geochemical studies, in reconstructing historical trends in heavy metal input and sediment accretion in 3 heavily-modified, industrialised estuarine areas in Europe: the Bilbao estuary (Spain), Southampton Water (UK), and the Mulinello estuary (Sicily). Of these sites, only a salt marsh core from the Mulinello estuary provides a high-resolution record of recent heavy metal inputs. In Southampton Water only a partial record of changing metal inputs over time is retained due to land-claim and possible early-diagenetic remobilisation, while at Bilbao the vertical distribution of heavy metals in intertidal flats is mainly controlled by input on reworked sediment particles and variations in sediment composition. Where 137Cs and 210Pb distributions with depth allow a chronology of sediment deposition to be established, and early-diagenetic remobilisation has been minimal, mudflat and saltmarsh cores from even the most heavily-disturbed estuarine sites can provide useful information on variations in historical contaminant input. When the sediments have been vigorously mixed or reworked, large-scale compositional variations are present, or significant early-diagenetic remobilisation has occurred, however, only general information on the scale of contamination can be obtained.

The concept that total organic C (TOC) is the main factor dominating the sorption of PCBs to sediment is over simplified. Numerous discrepancies are found when trying to compare concentrations predicted from laboratory observations to field concentrations. Some studies show a lack of correlation between PCB and TOC or particle size, but state that it is the origin of the organic matter or the clay swelling that is most important in determining the partitioning to sediment. It may also be argued that the discrepancies are merely a reflection of localised inputs of PCBs. An evaluation of the influence of these factors was undertaken at an intertidal site in the Clyde Estuary, previously highlighted as being highly contaminated by PCBs. Analysis of a series of sediment samples failed to show a strong correlation of PCB content with TOC or particle size. Separation into grain-size fractions and subsequent analysis suggested that both variation in organic matter source and mineralogical composition exerts an influence on congener distribution with implications for the mobility of PCBs within intertidal sediments.