High resolution profiles of trace metals in pore waters of marine and riverine sediments assessed by DET and DGT

In polluted aquatic systems, toxic metals are often accumulated in bottom sediments. They are, however, not necessarily stored definitively because diagenetic processs can modify redox, pH and even the amount of complexing ligands, releasing the trace metals back into the pore waters and the water column. Especially the labile metal fraction in the pore waters is important since this is the bioavailable fraction determining the bio-toxicity of the sediments. The goal of our study was therefore to assess, with novel sampling techniques, this bioavailable metal fraction in the pore waters as well as the flux towards the overlying water column. High-resolution profiles of trace metals in pore waters of marine and riverine sediments were assessed by DET （diffusive equilibrium in thin films） and DGT （diffusive gradients in thin films） gel techniques. The DET technique uses a diffusive gel layer that equilibrates with the aquatic system and with this technique the concentrations of total dissolved trace metals are obtained directly. The DGT technique uses an acrylamide diffusive gel backed by a resin gel （Chelex） which binds trace metals. With the DGT technique only labile species of selected metals can be captured. According to the redox potential measurements, the marine sediments were suboxic （200 mV to -220 mV versus Ag/AgCl electrode）, while the riverine sediments were completely anoxic （-160 mV to -220 mV versus Ag/AgCl electrode）. This redox potential was apparently controlling the trace metals species in the pore waters： for example a strong correlation between Mn and Co was found in the riverine sediments （for DET and DGT sampling）, while in the marine sediments trace metals presented various behaviors.     

Microwave-assisted extraction of organochlorine pesticides from sediments and determination by gas chromatograph with electron capture detection

A simple and rapid procedure to extract organochlorine pesticides （OCPs） from sediments by means of microwave energy is proposed. Sediment samples were irradiated with microwaves in a closed vessel system while immersed in hexane-acetone （1 ： 1, v/v）. The sample extracts were cleaned up using solid phase extraction with Florisil as adsorbent. Pesticides were eluted with hexane-ethyl acetate （80 ： 20, v/v） and determined by gas chromatographic separation with electron capture detection. Three oven programs were assayed with two different solvent mixtures in order to achieve adequate experimental conditions for the complete extraction of organochlorine pesticides from the matrix. Different variables such as the composition of extraction solvent,     

Improved reliability in the interpretation of geochemical measurements by the quantification of uncertainty from sampling

All geochemical measurements require the taking of field samples, but the uncertainty that this process causes is often ignored when assessing the reliability of the interpretation, of the geochemistry or the health implications. Recently devised methods for the estimation, optimisation and reduction of this uncertainty have been evaluated by their application to the investigation of contaminated land. Uncertainty of measurement caused by primary sampling has been estimated for a range of six different contaminated land site investigations, using an increasingly recognized procedure. These site investigations were selected to reflect a wide range of different sizes, contaminants （organic and metals）, previous land uses （e.g. tin mining, railway sidings and gas works）, intended future use （housing to nature reserves） and routinely applied sampling methods. The results showed that the uncertainty on measurements was substantial, ranging from 25% to 186% of the concentration values at the different sites. Sampling was identified as the dominant source of the uncertainty （〉70% of measurement uncertainty） in most cases. The fitness-for-purpose of the measurements was judged using the optimized contaminated land investigation （OCLI） method. This identifies the optimal level of uncertainty that reduces to overall financial loss caused by the measurement procedures and the misclassification of the contamination, caused by the uncertainty. Generally the uncertainty of the actual measurements made in these different site investigations was found to be sub-optimal, and too large by a factor of approximately two. The uncertainty is usually limited by the sampling, but this can be reduced by increasing the sample mass by a factor of 4 （predicted by sampling theory）. It is concluded that knowing the value of the uncertainty enables the interpretation to be made more reliable, and that sampling is the main factor limiting most investigations. This new approach quantifies this problem for the first time, and allows sampling procedures to be critically evaluated, and modified, to improve the reliability of the geochemical assessment.     

Hydrogeochemical controls on surface and groundwater chemistry in naturally acidic, porphyry-related mineralized areas, southern Rocky Mountains

In southern Rocky Mountains, catchments characterized by acidic, metalliferous waters that are relatively unaffected by human activity usually occur within areas that have active or historical mining activity. The US Geological Survey has utilized these mineralized but unmined catchments to constrain geochemical processes that control the surface- and ground-water chemistry associated with near surface acid weathering as well as to estimate premining conditions. Study areas include the upper Animas River watershed, Lake City, Mt. Emmons, and Montezuma in Colorado and Questa in New Mexico. Although host-rock lithologies range from Precambrian gneisses to Cretaceous sedimentary units to Tertiary volcanic complexes, mineralization is Tertiary in age and associated with intermediate to felsic composition, porphyritic plutons. Pyrite is ubiquitous. Variability of metal concentrations in water is caused by two main factors： mineralogy and hydrology. Parameters that potentially affect water chemistry include： host-rock lithology, intensity of hydrothermal alteration, sulfide mineralogy and chemistry, gangue mineralogy, length of flow path, precipitation, evaporation, and redox conditions. Springs and headwater streams have pH values as low as 2.5, sulfate up to 3700 mg/L and high dissolved metal concentrations （for example： Al up to 170 mg/L; Fe up to 250 mg/L; Cu up to 3.5 mg/L and Zn up to 14 mg/L）. With the exception of evaporative waters, the lowest pH values and highest Fe and Al concentrations occur in water draining the most intense hydrothermally altered areas consisting of the mineral assemblage quartz-sericite-pyrite. Stream beds tend to be coated with iron floc, and some reaches are underlain by ferricrete. When iron-rich ground water interacts with oxygenated waters in the stream or hyporheic zone, ferrous iron is oxidized to ferric iron, which is less soluble, leading to the precipitation of iron oxyhydroxides.     

Quantification of the risk associated with high levels of mercury pollution at Temirtau, Kazakhstan

This research aims to establish the risks of hurnan exposure to modeling approach. The study site was located on the River Nura 1990s, an acetaldehyde production plant located in the industrial high environmental mercury levels, based on a quantitative risk in central Kazakhstan. From the 1950s until its closure in the mid city of Temirtau released mercury-containing wastewater into the river. River sediments are highly contaminated with mercury up to a distance of 25 km and beyond. In addition, a local power station released an estimated 6 million tonnes of fly-ash into the water and the mercury has become quite tightly associated with the ash deposits. River water, fish and agricultural land in the floodplain are also contaminated with mercury, yet the risks posed to the local population have not been evaluated to date. In June and July 2005, we took samples of soil, interior and exterior dust, drinking water, and food from individual households, communal areas and markets. Additionally, water and sediment samples and fish were taken from the river. Interviews were conducted with householders to establish their age and body weight, general living conditions and sources of irrigation and drinking water. A food frequency questionnaire （FFQ） was designed to investigate the frequencies of consumption of several common regional food items, including fish from the fiver and/or local market. Human hair samples were also collected to estimate the mercury bioburden and to enable the validity of the modeling approach to be established. The paper expands on the main pathways of contamination and looks at linkages between exposure pathways and mercury concentrations found in human hair. Uncertainties inherent in risk analysis as well as their influence on the relative importance of different exposure routes are also discussed.     

Total gaseous mercury emissions from mercury-enriched soil in Guizhou, China

Guizhou is located in the Circum-Pacific Global Mercuriferous Belt, and mercury concentrations in soil in this area are enriched. In-situ total gaseous mercury （TGM） exchange fluxes between air and soil surface were intensively measured at four sampling sites in Guiyang from 21 May to 16 June, 2003, and five sites in the Lanmuchang mercury mining area in December 2002 and May 2003, respectively. The in-situ Hg flux measurement was conducted with a dynamic flux chamber （DFC） of quartz. Overall, net emissions were obtained from all sampling sites. Soil mercury concentration and solar radiation have been proved to be the two most important parameters to control mercury emissions from soil. Meanwhile, rain events can enhance mercury emission rate significantly.     

Changes to cadmium associations in canal sediments on drying and oxidation

The mainly 19th Century canal system in the UK, largely managed by British Waterways, has been increasingly brought back into operation over the last few decades, and is now widely used for both leisure, and, increasingly, transport. Both initial and routine dredging of the canal sediment is carried out and these sediments are generally disposed of to land. Because many of the canals were connected with primary industries, their sediments can locally be significantly contaminated with heavy metals, and the behaviour of these metals under differing redox conditions, when introduced into a new environment （i.e., on land） is of importance for environmental risk-assessment purposes. Canal sediments are often rich in sulfidic mineral phases, and we have attempted to quantify the influence of these sulfidic phases on the release and retention of metals in dredged canal sediments, using a combination of traditional chemical techniques （e.g. sequential extraction） and X-ray absorption spectroscopy （XAS）. Sediment samples have been collected from urban fresh-water canals, one in the British Midlands and one in Northern France. It appears from XAS that Cd is largely associated with oxygen in air-dried sediment, and with sulphur in vacuum-dried sediment.     

Study on Kailyard soil amendment by adding compost of sludge

Mixture of municipal sewage sludge and organic garbage, which was alternatively treated by aerobic and anaerobic composting technologies for 60 days. The characteristics of the compost are as follows： the total nitrogen （TN）, total phosphors （TP） and total potassium （TK） are 1.40%, 0.101% and 1908.32 mg/kg on dry weight basis, the contents of Cu, Ni, Cd, Cr, Pb and Zn are 131.23, 21.49, 1.31, 35.49, 72.50 and 616.76 mg/kg on dry weight basis. A basin-scale experiment was carded out by planting watercress with kailyard soil fertilizing with the compost, the results showed that the municipal sewage sludge and organic garbage compost could promote the production of watercress to different degrees, the crop biomass increased from 74.46% to 312.00% with the amount of compost fertilizing on the kaliyard soil while the amount of compost fertilizing on the kaliyard soil below 150 g per 3.75 kg kaliyard soil and decreased from 312.00% to 102.29% while the amount of compost fertilizing on it over 150 g per 3.75 kg kaliyard soil, so the optimal addition of compost in the watercress and soil was 150 g compost per 3.75 kg kailyard soil. Furthermore,     

Influence of humic acid on bioavailability of heavy metals in sediments

The mimetic ocean environment and chemical method were used to research the bioavailability effect of humic acid on five heavy metals in sediment, including Cd, Cu, Zn, Pb and Ni. The sediment was separated into four containers with artificial seawater, and each of them had different concentrations of humic acid. The values of concentrations covered the whole range found in natural sediment （0.1%-10%）. According to the 48 hours LC50 of clam and distribution coefficient, metals were added in artificial seawater, and their speciation was determined at first and then after two days＇ incubation. It was found the bioavailability of heavy metals was reduced in the presence of humic acid. The obvious negative effect on Zn was observed, but the influence on Cd was not remarkable. In addition, the contents of Pb and Ni increased obviously in organic phase, and they are correlative with the concentrations of humic acid.