Assessing potential bioavailability of metals in sediments: A proposed approach

Due to anthropogenic inputs, elevated concentrations of metals frequently occur in aquatic sediments. In order to make defensible estimates of the potential risk of metals in sediments and/or develop sediment quality criteria for metals, it is essential to identify that fraction of the total metal in the sediments that is bioavailable. Studies with a variety of benthic invertebrates indicate that interstitial (pore) water concentrations of metals correspond very well with the bioavailability of metals in test sediments. Many factors may influence pore water concentrations of metals; however, in anaerobic sediments a key phase controlling partitioning of several cationic metals (cadmium, nickel, lead, zinc, copper) into pore water is acid volatile sulfide (AVS). In this paper, we present an overview of the technical basis for predicting bioavailability of cationic metals to benthic organisms based on pore water metal concentrations and metal-AVS relationships. Included are discussions of the advantages and limitations of metal bioavailability predictions based on these parameters, relative both to site-specific assessments and the development of sediment quality criteria.     

The role of humic non-exchangeable binding in the promotion of metal ion transport in groundwaters in the environment

Metal ions form strong complexes with humic substances. When the metal ion is first complexed by humic material, it is bound in an 'exchangeable' mode. The metal ion in this fraction is strongly bound, however, if the metal-humic complex encounters a stronger binding site on a surface, then the metal ion may dissociate from the humic substance and be immobilised. However, over time, exchangeably-bound metal may transfer to a 'non-exchangeable' mode. Transfer into this mode and dissociation from it are slow, regardless of the strength of the competing sink, and so immobilisation may be hindered. A series of coupled chemical transport calculations has been performed to investigate the likely effects of non-exchangeable binding upon the transport of metal ions in the environment. The calculations show that metal in the non-exchangeable mode will have a significantly higher mobility than that in the exchangeable mode. The critical factor is the ratio of the non-exchangeable first-order dissociation rate constant and the residence time in the groundwater column, metal ion mobility increasing with decreasing rate constant. A second series of calculations has investigated the effect of the sorption to surfaces of humic/metal complexes on the transport of the non-exchangeably bound metal. It was found that such sorption may reduce mobility, depending upon the humic fraction to which the metal ion is bound. For the more weakly sorbing humic fractions, under ambient conditions (humic concentration etc.) the non-exchangeable fraction may still transport significantly. However, for the more strongly sorbed fractions, the non-exchangeable fraction has little effect upon mobility. In addition to direct retardation, sorption also increases the residence time of the non-exchangeable fraction, giving more time for dissociation and immobilisation. The non-exchangeable dissociation reaction, and the sorption reaction have been classified in terms of two Damkohler numbers, which can be used to determine the importance of chemical kinetics during transport calculations. These numbers have been used to develop a set of rules that determine when full chemical kinetic calculations are required for a reliable prediction, and when equilibrium may be assumed, or when the reactions are sufficiently slow that they may be ignored completely.     

Higher Cd adsorption on biogenic elemental selenium nanoparticles

Cadmium (Cd) is a carcinogenic metal contaminating the environment and ending up in wastewaters. There is therefore a need for improved methods to remove Cd by adsorption. Biogenic elemental selenium nanoparticles have been shown to adsorb Zn, Cu and Hg, but these nanoparticles have not been tested for Cd removal. Here we studied the time-dependency and adsorption isotherm of Cd onto biogenic elemental selenium nanoparticles using batch adsorption experiments. We measured ζ-potential values to assess the stability of nanoparticles loaded with Cd. Results show that the maximum Cd adsorption capacity amounts to 176.8 mg of Cd adsorbed per g of biogenic elemental selenium nanoparticles. The ζ-potential of Cd-loaded nanoparticles became less negative from ?32.7 to ?11.7 mV when exposing nanoparticles to an initial Cd concentration of 92.7 mg L^?1. This is the first study that demonstrates the high Cd uptake capacity of biogenic elemental selenium nanoparticles, of 176.8 mg g^?1, when compared to that of traditional adsorbents such as carboxyl-functionalized activated carbon, of 13.5 mg g^?1. An additional benefit is the easy solid–liquid separation by gravity settling due to coagulation of Cd-loaded biogenic elemental selenium nanoparticles.     

Plant responses to a phytomanaged urban technosol contaminated by trace elements and polycyclic aromatic hydrocarbons

Medicago sativa was cultivated at a former harbor facility near Bordeaux (France) to phytomanage a soil contaminated by trace elements (TE) and polycyclic aromatic hydrocarbons (PAH). In parallel, a biotest with Phaseolus vulgaris was carried out on potted soils from 18 sub-sites to assess their phytotoxicity. Total soil TE and PAH concentrations, TE concentrations in the soil pore water, the foliar ionome of M. sativa (at the end of the first growth season) and of Populus nigra growing in situ, the root and shoot biomass and the foliar ionome of P. vulgaris were determined. Despite high total soil TE, soluble TE concentrations were generally low, mainly due to alkaline soil pH (7.8–8.6). Shoot dry weight (DW) yield and foliar ionome of P. vulgaris did not reflect the soil contamination, but its root DW yield decreased at highest soil TE and/or PAH concentrations. Foliar ionomes of M. sativa and P. nigra growing in situ were generally similar to the ones at uncontaminated sites. M. sativa contributed to bioavailable TE stripping by shoot removal (in g ha^?1 harvest^?1): As 0.9, Cd 0.3, Cr 0.4, Cu 16.1, Ni 2.6, Pb 4, and Zn 134. After 1 year, 72 plant species were identified in the plant community across three subsets: (I) plant community developed on bare soil sowed with M. sativa; (II) plant community developed in unharvested plots dominated by grasses; and (III) plant community developed on unsowed bare soil. The shoot DW yield (in mg ha^?1 harvest^?1) varied from 1.1 (subset I) to 6.9 (subset II). For subset III, the specific richness was the lowest in plots with the highest phytotoxicity for P. vulgaris.     

Exploring the potential of otolith microchemistry to enhance diet analysis in pinnipeds

Increasing the scope and accuracy of information about pinniped diets obtainable from non-invasive techniques is increasingly important, particularly in cases where pinniped species are threatened or endangered. This study is the first to explore the potential for using elemental analysis of the otoliths found in scat to enhance the information available for diet analyses. We investigated the effects of pinniped digestion on otolith microchemistry using laser ablation inductively coupled plasma mass spectrometry (LA-ICPMS). We compared the elements contained in the edges (adult stage) and cores (larval/juvenile stage) of otoliths from Pacific herring (Clupea pallasii), Atka mackerel (Pleurogrammus monopterygius), and Walleye pollock (Theragra chalcogramma) recovered from the scat of captive Steller sea lions (Eumetopias jubatus) to elements in a sample of pristine (undigested) otoliths. We found that digestion had a significant effect on four of the six sampled combinations of species and otolith region (herring edges and cores, mackerel edges, and pollock cores), and that Rb most frequently showed significant differences in concentration after digestion. We could significantly discriminate among species of both pristine and digested otoliths using either otolith edges or cores with the elements Ba, Rb, Sr, Y, and Mg. When compared to previously identified digested otoliths, unknown samples of the three species of digested otoliths could be discriminated with 55–100% accuracy depending on species and otolith region. When compared to a library of previously identified pristine and digested otoliths, unknown samples of digested otoliths could be discriminated to species with 65–88% accuracy. When the group of unknown digested otoliths was compared to known pristine otoliths, discrimination ranged from 45 to 65%. These results indicate that elemental analysis could be used to supplement visual identification of otoliths from scat. However, further research is required to determine whether elemental analysis of digested otoliths could be useful for prey fish population studies.     

The potential role of compost in reducing greenhouse gases.

The contribution of the agricultural sector to emissions of climate change gases is becoming better understood. At the same time, the potential role of the sector as a means through which to tackle climate change, widely neglected in the past, is becoming more widely acknowledged. The absorption potential of agricultural soils could contribute significantly to constraining growth in greenhouse gas emissions, while also contributing to improvements in soil quality in some areas. In addition to the measures listed above, other benefits of compost application may have some relevance. Some of these measures include replacement of chemical fertilizers (implying avoidance of greenhouse gases related to their production) reduced use of pesticides (avoiding emissions associated with their production), improved tilth and workability (less consumption of fuels). Typically, life-cycle analyses (LCAs) exhibit limitations related to assessing the effects of 'time-limited' carbon sequestration in soils. This has tended to obscure the potentially important effect of composting, in which biogenic carbon is held in soils for a period of time before the carbon is released. The paper seeks to understand these effects and offers comments on the contribution of biological treatments to tackling climate change issues. Key issues include the replacement of fertilizers, reduction of N2O emissions, and peat replacement.