Metal accumulation risks in regularly flooded and non-flooded parts of floodplains of the River Rhine: Extractability and exposure through the food chain

Ecotoxicological risks of sediment contamination in floodplains are supposed to be highest in the regularly flooded parts. Therefore, in risk assessments, the non-flooded parts are neglected or considered to be reference areas. We investigated the metal extractability and levels in important food sources for vertebrates, viz. grass shoots and earthworms, in flooded as well as non-flooded parts and compared these with total metal concentrations. A comparison of these areas in the moderately polluted 'Afferdensche en Deestsche Waarden' floodplains along the River Rhine showed that total Zn, Pb, and Cd concentrations were highest in the regularly flooded parts. However, CaCl₂-extractable Zn concentrations were highest in non-flooded areas, and those of Pb and Cd were equal in both areas. Total Cu concentrations were not significantly different between the two areas, but CaCl₂-extractable Cu concentrations were highest in the regularly flooded areas. The metal concentrations in grass shoots of non-flooded areas were equal to (Zn, Cu, Cd) or higher than (Pb) those in regularly flooded areas. Zn concentrations in earthworms in regularly flooded areas were higher, but concentrations of Cu, Pb, and Cd were not. Ecotoxicological risk assessments require analysis of the total and potentially bioavailable metal concentrations in soils as well as concentrations in biota. This study shows that the less contaminated non-flooded areas in moderately polluted floodplains cannot be neglected in metal accumulation studies and cannot be used as pristine reference areas.     

The effects of oil sands wetlands on wood frogs (Rana sylvatica)

Extraction of crude oil from oil sand produces solid (sand) and liquid (water with suspended fine particles) tailings materials, called oil sands process-affected materials (OSPM). These waste materials are stored on the mine site due to a “zero discharge” policy and must be reclaimed when operations end. The liquid tailings materials are known to contain naphthenic acids and polycyclic aromatic hydrocarbons and have high pH and salinity. One method of reclamation is the “wet landscape” approach, which involves using oil sands tailings materials to form wetlands that would mimic natural wetland ecological function. This study investigated the effects of wetlands formed with oil sands tailings materials on the survival and growth of wood frog (Rana sylvatica) larvae. In spring 2007, in-situ caging studies were completed in 14 wetlands that were of four different classes; young or old, reference or reclaimed. Tadpole survival was different between types of wetlands, with young tailings-affected wetlands (≤7 years old) having 41.5%, 62.6%, and 54.7% higher tadpole mortality than old tailings-affected (>7 years old), young reference, and old reference wetlands, respectively. Since old wetlands created from OSPM showed effects on tadpoles similar to those of reference wetlands, which had markedly lower toxicity than young tailings-affected wetlands, we provide evidence that wetlands, at least 7 years old, can sustain amphibian life.     

Disrupted bone metabolism in contaminant-exposed white storks (Ciconia ciconia) in southwestern Spain

In 1998, the Aznalcóllar mine tailings dyke in southwestern Spain broke, flooding the Agrio-Guadiamar river system with acid tailings up to the borders of one of the largest breeding colonies of white storks in the western Palearctic, Dehesa de Abajo. Over the following years, a high proportion of nestlings developed leg defects not seen before the spill, prompting this study. Nestlings with deformed legs had significantly lower plasma phosphorous (P) and higher Ca:P ratios than non-deformed cohorts in the first two years, but in the third year, when more, younger birds were studied, plasma P ranged from much higher to much lower in the affected colony compared with reference birds. Coefficients of variation for phosphorous were 19% and 60%, in reference and contaminated colonies, respectively. Storks from the contaminated colony were unable to control P levels and Ca:P ratios within the narrow limits necessary for normal bone development.     

Fate of metal-associated POM in a soil under arable land use contaminated by metallurgical fallout in northern France

Organic matter is a major metal-retaining constituent in soils. Among the diversity of organic components in soils, particulate organic matter (POM) accumulates large amounts of metals, but the fate of such metal-associated POM is unknown. We studied different POM size fractions and their corresponding mineral size-fractions isolated from the surface horizon of a soil affected by metallurgical fallout. Analyses of total and EDTA extractible metal contents performed on all size fractions demonstrated that with decreasing POM size, larger metal concentrations were observed but they were less extractable. Micromorphological study revealed the occurrence of opaque parts in decaying POM fragments and their individualization as fine, irregularly shaped opaque fragments in the soil matrix. This work suggested a mutual sequestration of metal pollutants and organic carbon as micro-meter sized, metal-enriched organic particles derived from POM, representing an original pathway for natural attenuation of risk related to metal contaminated soils.     

淡水水体底泥中厌氧氨氧化菌的原位鉴别

采用16S rRNA方法对江苏省新沂河的底泥样品进行了厌氧氨氧化菌的原位检测,建立了样品的16S rRNA克隆文库,共包括6个16S rRNA克隆序列.对文库中克隆序列利用ARB软件包进行了排队分析及系统发育树的绘制.分析结果表明,新沂河底泥样品中含有与已知厌氧氨氧化菌Candidatus“Brocadia anammoxidans”相似性为91%的16S rRNA基因,经鉴定为厌氧氨氧化菌Brocadia分支的新种类.样品中还含有组成Planctomycetes新分支的16S rRNA基因,它们与已知厌氧氨氧化菌序列的遗传距离较远,其微生物特性还有待进一步研究.厌氧氨氧化菌在淡水环境中的发现将有助于进一步研究厌氧氨氧化过程在受损淡水生态系统修复重建中的作用,重新认识其中的氮循环过程.     

The effect of turbation on zinc relocation in a vertical floodplain soil profile

Turbation is hypothesized to affect the redistribution of heavy metals in polluted floodplain soils by effects on mobility. This hypothesis was tested in microcosms by turbation of zinc-spiked sediment top layers. Manual turbation caused a fast decrease of the zinc content in the upper 15 cm of the soil, even though turbation was only applied to the upper two centimetres. It was especially zinc attached to colloid and organic matter particles that was redistributed from the top layer. Percolation processes resulted in the attached zinc being drained to depths of more than 15 cm. The decrease in zinc content of the topsoil was even stronger in combination with inundation. No indications were found for the redistribution of zinc as a result of an increase of the extractability with 0.01 M CaCl2 or changes in pH. The findings suggest that mechanical turbation and bioturbation may redistribute heavy metals from topsoils in polluted floodplains just after inundation as observed in these turbation experiments.     

Morphology, chemistry and distribution of neoformed spherulites in agricultural land affected by metallurgical point-source pollution

Metal distribution patterns in superficial soil horizons of agricultural land affected by metallurgical point-source pollution were studied using optical and electron microscopy, synchrotron radiation and spectroscopy analyses. The site is located in northern France, at the center of a former entry lane to a bunker of World War II, temporarily paved with coarse industrial waste fragments and removed at the end of the war. Thin sections made from undisturbed soil samples from A and B horizons were studied. Optical microscopy revealed the occurrence of yellow micrometer-sized (Ap horizon) and red decamicrometer-sized spherulites (AB, B(1)g horizons) as well as distinct distribution patterns. The chemical composition of the spherulites was dominated by Fe, Mn, Zn, Pb, Ca, and P. Comparison of calculated Zn stocks, both in the groundmass and in spherulites, showed a quasi-exclusive Zn accumulation in these neoformed features. Their formation was related to several factors: (i) liberation of metal elements due to weathering of waste products, (ii) Ca and P supply from fertilizing practices, (iii) co-precipitation of metal elements and Ca and P in a porous soil environment, after slow exudation of a supersaturated soil solution in more confined mineral media.     

Aryl hydrocarbon receptor (AhR) inducers and estrogen receptor (ER) activities in surface sediments of Three Gorges Reservoir,China evaluated with in vitro cell bioassays

Two types of biological tests were employed for monitoring the toxicological profile of sediment cores in the Three Gorges Reservoir (TGR), China. In the present study, sediments collected in June 2010 from TGR were analyzed for estrogen receptor (ER)- and aryl hydrocarbon receptor (AhR)-mediated activities. The estrogenic activity was assessed using a rapid yeast estrogen bioassay, based on the expression of a green fluorescent reporter protein. Weak anti-estrogenic activity was detected in sediments from an area close to the dam of the reservoir, and weak estrogenic activities ranging from 0.3 to 1 ng 17β-estradiol (E2) equivalents (EQ) g^?1 dry weight sediment (dw) were detected in sediments from the Wanzhou to Guojiaba areas. In the upstream areas Wanzhou and Wushan, sediments demonstrated additive effects in co-administration of 1 nM E2 in the yeast test system, while sediments from the downstream Badong and Guojiaba areas showed estrogenic activities which seemed to be more than additive (synergistic activity). There was an increasing tendency in estrogenic activity from upstream of TGR to downstream, while this tendency terminated and converted into anti-estrogenic activity in the area close to the dam. The AhR activity was detected employing rat hepatoma cell line (H4IIE). EROD activities were found homogenously distributed in sediments in TGR ranging from 200 to 311 pg 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) EQ g^?1 dw for total AhR agonists and from 45 to 76 pg TCDD EQ g^?1 dw for more persistent AhR agonists. The known AhR agonists polycyclic aromatic hydrocarbon, polychlorinated biphenyl, and PCDD/F only explained up to 8 % of the more persistent AhR agonist activity in the samples, which suggests that unidentified AhR-active compounds represented a great proportion of the TCDD EQ in sediments from TGR. These findings of estrogenic potential and dioxin-like activity in TGR sediments provide possible weight-of-evidence of potential ecotoxicological causes for the declines in fish populations which have been observed during the past decades in TGR.     

Compromised metamorphosis and thyroid hormone changes in wood frogs (Lithobates sylvaticus) raised on reclaimed wetlands on the Athabasca oil sands

The wet landscape approach to oil sands tailings reclamation in the Athabasca Oil Sands region involves creating wetlands from fluid tailings in mined-out pits. We measured time to metamorphosis, thyroid hormone status, and detoxification enzyme (EROD) induction in Wood frog (Lithobates sylvaticus) tadpoles raised on reclaimed oil sands wetlands of different ages [young (≤7 yr) vs. old (>7 yr)] and compared data with tadpoles raised on reference (control) wetlands. Metamorphosis was delayed or never occurred in tadpoles raised in young tailings; those exposed to older tailings developed similarly to those in reference wetlands. Thyroid hormone disruption likely played an important role in the metamorphosis delay as the T3:T4 ratio was lowest in tadpoles raised in young, tailings-affected wetlands. Our findings suggest tailings wetlands become less toxic with age, and that these amphibians will be able to complete their life cycle in tailing wetlands that have sufficiently detoxified with age.