Manganese and zinc in acidic agricultural soils from Central Spain: Distribution and phytoavailability prediction with chemical extraction tests

The extractability and distribution of manganese (Mn) and zinc (Zn) were evaluated in acidic agricultural soils from Central Spain. Both single (0.1 M hydrochloride [HCl] and 0.05 M ethylenediaminetetraacetate [EDTA]) and sequential extraction procedures (SEP) (modified Tessier procedure and Community Bureau of Reference [BCR] protocol) were applied to 29 representative soils that belong to the Alfisol, Inceptisol, and Entisol orders. Average relative Mn extractabilities with respect to the total content (16.6% for HCl and 31.9% for EDTA) were higher than those of Zn (7.7% for HCl and 6.5% for EDTA). Manganese was mainly released in the oxide-bound phase of both SEP (33.1% for modified Tessier and 48.9% for BCR), whereas Zn was predominantly found in the residual fraction (49.1% for modified Tessier and 31.4% for BCR). Significant correlations were only found between the amounts of extractable Zn and the oxide-bound fraction in both SEP. Few relationships were established between Zn fractions extracted by the BCR procedure and those obtained with the Tessier method. Both metal concentrations in spring barley (Hordeum vulgare L., cv Beka) grown in 11 selected soils and the calculated soil/plant transfer coefficients (soil/plant concentration factor (CF), mean values of 31.2 for Mn and 196 for Zn) were poorly (or not at all) correlated with the different extracted soil fractions (single and sequential). A number of empirical equations have been obtained by regression analyses to predict the Mn and Zn uptake by barley, with soil metal forms and some soil characteristics as components (pH for Mn and organic matter for Zn). Values of R2 in the equations were relatively low (<68%). Single-extraction techniques produced worse results than SEP for the evaluation of Mn phytoavailability. The modified Tessier procedure provided better predictions of Zn uptake by plants than BCR, but not better than those obtained with the HCl extraction method

Assessment of trace element pollution and its environmental risk to freshwater sediments influenced by anthropogenic contributions: The case study of Alqueva reservoir (Guadiana Basin)

The Guadiana Basin.(SW Iberian Peninsula) is affected by acid mine drainage (AMD), a consequence of ancient mining activities in the Iberian Pyrite Belt (IPB). Consequently, the sedimerits at the Alqueva reservoir (SE Portugal) in the Guadiana Basin are potentially contaminated by trace elements, which make important: (i) to characterize the status of trace element pollution of the sediments; (ii) to evaluate the mobility and the bioavailability of As, Cd, Cu, Cr, Pb and Zn; and (iii) to assess the environmental risk associated with the total and bioavailable concentrations of trace elements, using the sediment quality guidelines (SQGs) and the risk assessment code (RAC). Metal enrichment factors (EF) and geoaccumulation indexes (I-geo), determined taking into account the regional background levels, revealed that, among the metals analyzed, Cd contributed the highest to pollution levels followed by Pb and As. Despite the trace element contamination of the Alqueva sediments, the sequential extraction showed that Most of them are found in the oxidizable and residual fractions, which indicates that they are sparingly bioavailable, with exception of Cd (acid-labile fraction) and Pb (reducible fraction). Based on the RAC, Cd was the only metal that presented a high risk, while Pb, As and Zn showed a medium risk. Moreover, the SQGs revealed the existence of certain areas of extremely high risk, particularly related to high concentrations of total As and, in less extent, of Pb and Cd, associated with AMD, wastewater discharges and runoff of plant protection products from agricultural fields located near the reservoir. (C) 2015 Elsevier By. All rights reserved.FCT (Fundacao para a Ciencia e Tecnologia) [PTDC/AAC-AMB/103547/2008]; FEDER, through POFC (Eixo I - Programa Operacional Fatores de Competitividade) from QREN [COMPETE Re: FCOMP-01-0124-FEDER-008582]info:eu-repo/semantics/publishedVersio

Heavy metal bioavailability and bioaccessibility in soil

This chapter considers the use of a variety of approaches to assess either the bioavailability or the bioaccessibility of metals in soil. The bioavailability of metals from soils is considered with respect to a series of single-extraction methods, including the use of ethylenediaminetetraacetic acid (EDTA), acetic acid, diethylenetriaminepentaacetic acid (DTPA), ammonium nitrate, calcium chloride and sodium nitrate. Then, a procedure for the recovery of metals using a three-stage sequential extraction protocol is described. Two alternate approaches for assessing the environmental health risk to humans by undertaking in vitro gastrointestinal extraction (also known as the physiologically based extraction test, PBET) are considered. Finally, two acid digestion protocols that allow the pseudo-total metal content of samples to be assessed are provided. In all cases details of how the different approaches can be performed are provided, including the specific reagents required (and their preparation), details of the different extraction and acid digestion protocols to be followed and suitable analytical details to allow the measurement of metals by inductively coupled plasma mass spectrometry (ICP-MS) with/without a collision/reaction cell. A detailed Notes section provides experimental details to guide the reader through some of the practical aspects of the procedures. Finally, some experimental results are provided as evidence of the suitability of the approaches described including single-extraction data, using EDTA and acetic acid, for metals in CRM BCR 700. In addition, in vitro gastrointestinal extraction data are provided for metals in CRM SRM 1570A (spinach leaves). The influence of time on the intestinal fluid phase on the recovery of metals in CRM SRM 1570A (spinach leaves) and CRM INCT-TL-1 (tea leaves) is investigated, as well as the repeatability in terms of recovery of metals from soil over a 3-week period by in vitro gastrointestinal extraction

Mobility of antimony, arsenic and lead at a former mine, Glendinning, Scotland

Elevated concentrations of antimony (Sb), arsenic (As) and lead (Pb) in upland organic-rich soils have resulted from past Sb mining activities at Glendinning, southern Scotland. Transfer of these elements into soil porewaters was linked to the production and leaching of dissolved organic matter and to leaching of spoil material. Sb was predominantly present in truly dissolved (&lt; 3 kDa) forms whilst As and Pb were more commonly associated with large Fe-rich/organic colloids. The distinctive porewater behaviour of Sb accounts for its loss from deeper sections of certain cores and its transport over greater distances down steeper sections of the catchment. Although Sb and As concentrations decreased with increasing distance down a steep gully from the main spoil heap, elevated concentrations (~ 6-8 and 13-20 μg L− 1, respectively) were detected in receiving streamwaters. Thus, only partial attenuation occurs in steeply sloping sections of mining-impacted upland organic-rich soils and so spoil-derived contamination of surface waters may continue over time periods of decades to centuries

Fractionation and ecotoxicological implication of potentially toxic metals in sediments of three urban rivers and the Lagos Lagoon, Nigeria, West Africa

The potential environmental impact of sediment-bound Cd, Cr, Cu, Pb and Zn in three trans-urban rivers in Lagos state and in the Lagos Lagoon was assessed by use of the modified Community Bureau of Reference (BCR) sequential extraction. The quality of the data was checked using BCR CRM 143R and BCR CRM 701. Good agreement was obtained between found and certified/indicative values. Of the rivers, the Odo-Iyaalaro, was generally the most contaminated and the Ibeshe the least. Higher concentrations of metals were generally found in the dry season compared to the wet season. Cadmium and Zn were released mostly in the acid exchangeable step of the sequential extraction, indicating that they have the greatest potential mobility and bioavailability of the analytes studied. Chromium and Cu were associated mainly with the reducible and oxidisable fractions, and Pb predominantly with the reducible and residual fractions. Sediments with the highest pseudototal analyte concentrations also released higher proportions of analytes earlier in the sequential extraction procedure. The study suggests that, during the dry season, potentially toxic metals (PTM) may accumulate in sediments in relatively labile forms that are released and can potentially be transported or bioaccumulate in the rainy season. Application of risk assessment codes and Hankanson potential risk indices indicated that Cd was the element of greatest concern in the Lagos Lagoon system. The study indicated that there is a need to strengthen environmental management and pollution control measures to reduce risk from PTM, but that even relatively simple strategies, such as seasonal restrictions on dredging and fishing, could be beneficial

(Per)chlorate-reducing bacteria can utilize aerobic and anaerobic pathways of aromatic degradation with (per)chlorate as an electron acceptor.

UnlabelledThe pathways involved in aromatic compound oxidation under perchlorate and chlorate [collectively known as (per)chlorate]-reducing conditions are poorly understood. Previous studies suggest that these are oxygenase-dependent pathways involving O2 biogenically produced during (per)chlorate respiration. Recently, we described Sedimenticola selenatireducens CUZ and Dechloromarinus chlorophilus NSS, which oxidized phenylacetate and benzoate, two key intermediates in aromatic compound catabolism, coupled to the reduction of perchlorate or chlorate, respectively, and nitrate. While strain CUZ also oxidized benzoate and phenylacetate with oxygen as an electron acceptor, strain NSS oxidized only the latter, even at a very low oxygen concentration (1%, vol/vol). Strains CUZ and NSS contain similar genes for both the anaerobic and aerobic-hybrid pathways of benzoate and phenylacetate degradation; however, the key genes (paaABCD) encoding the epoxidase of the aerobic-hybrid phenylacetate pathway were not found in either genome. By using transcriptomics and proteomics, as well as by monitoring metabolic intermediates, we investigated the utilization of the anaerobic and aerobic-hybrid pathways on different electron acceptors. For strain CUZ, the results indicated utilization of the anaerobic pathways with perchlorate and nitrate as electron acceptors and of the aerobic-hybrid pathways in the presence of oxygen. In contrast, proteomic results suggest that strain NSS may use a combination of the anaerobic and aerobic-hybrid pathways when growing on phenylacetate with chlorate. Though microbial (per)chlorate reduction produces molecular oxygen through the dismutation of chlorite (ClO2(-)), this study demonstrates that anaerobic pathways for the degradation of aromatics can still be utilized by these novel organisms.ImportanceS. selenatireducens CUZ and D. chlorophilus NSS are (per)chlorate- and chlorate-reducing bacteria, respectively, whose genomes encode both anaerobic and aerobic-hybrid pathways for the degradation of phenylacetate and benzoate. Previous studies have shown that (per)chlorate-reducing bacteria and chlorate-reducing bacteria (CRB) can use aerobic pathways to oxidize aromatic compounds in otherwise anoxic environments by capturing the oxygen produced from chlorite dismutation. In contrast, we demonstrate that S. selenatireducens CUZ is the first perchlorate reducer known to utilize anaerobic aromatic degradation pathways with perchlorate as an electron acceptor and that it does so in preference over the aerobic-hybrid pathways, regardless of any oxygen produced from chlorite dismutation. D. chlorophilus NSS, on the other hand, may be carrying out anaerobic and aerobic-hybrid processes simultaneously. Concurrent use of anaerobic and aerobic pathways has not been previously reported for other CRB or any microorganisms that encode similar pathways of phenylacetate or benzoate degradation and may be advantageous in low-oxygen environments

Multi-Elemental Inductively Coupled Plasma-Optical Emission Spectroscopic Calibration Problems of the Sequential Extraction Procedure for the Fractionation of the Heavy Metal Content From Aquatic Sediments

For the characterisation of the environmental mobility of heavy metal contamination in aquatic sediments, the EU Bureau of Reference has proposed a fractionation by sequential extraction procedure. For its validation, the CRM-701 sample is available containing Cd, Cr, Cu, Ni, Pb, and Zn. In this paper, the matrix-matched calibration problems are presented. A multi-elemental inductively coupled plasma-optical emission technique is employed for the detection of heavy metals in the extracts. It was established that the sensitivities are strongly influenced by the extractants, which causes significant matrix effects: the sensitivities are strongly influenced by the solvents applied in extraction steps; the summarised recoveries show an acceptable agreement with the certified values; however, in the individual extraction steps for certain elements significant differences may occur due to the neglected interferences. Therefore, further optimisation is required utilising the flexible line selection possibility offered by the HORIBA Jobin Yvon ACTIVA-M instrument

Fractionation of soil phosphorus in a long-term phosphate fertilization

The changes in inorganic and organic phosphorus (P) fractions of soil resulting from long-term fertilization (40 years) were investigated. In order to improve understanding of the sink and sources of phosphorus, P-fractions were extracted from soil samples of 0-30 and 30-60 cm depth with different amounts of monoammonium-phosphate (MAP) and then determined. Stagnosol was the type of the studied soil. Phosphate fertilizer was applied in 26, 39 and 52 kgP/ha amounts during the period of 40 years. Samples were subjected to sequential extraction according to the modified Chang and Jackson method and BCR (Community Bureau of Reference) sequential extraction procedure in order to extract different forms of phosphorus. The Certified Reference material CRM 684 (River Sediment Extractable Phosphorus) was used to provide accuracy of the instrument and both used methods. Furthermore, the association of phosphorus with substrates was provided by comparison of the results of sequential methods of phosphorus species with the sequential extraction of metals (Fe, Al, Mn and Ca). Results of continuous fertilization during 40 years indicated the increase of all the phosphorus forms in the soil except of phosphorus bound to calcium and organic phosphorus. Application of higher amounts of P-fertilizer resulted in dominance of Al-P fraction in studied soil which indicated that this fraction was the most responsible for the migration of phosphorus along the soil profile