Evaluation of various chemical extraction methods to estimate plant-available arsenic in mine soils

Elevated levels of bioavailable As in mining soils, agricultural areas and human habitats may cause potential toxicity to human health, plants and microbe. Therefore, it is essential to determine proper soil chemical extraction method in order to estimate plant-available As in mining soils and protect agricultural and environmental ecosystems by evaluation of environmental risk and implementation of remediation measures. In this study, six single soil chemical extraction processes and four-step sequential chemical extraction protocol were used to determine the relative distribution of As in different chemical forms of soils and their correlations with total As in plants grown in mining areas and greenhouse experiments. The strongest relationship between As determined by single soil chemical extraction and As in plant biomass was found for sodium acetate and mixed acid extractant. The mean percent of total As extracted was: ammonium oxalate (41%)>hydroxylamine hydrochloride (32%)>mixed acid (16%)>phosphate (6%)>sodium acetate (1.2%)>water (0.13%). This trend suggests that most of the As in these soils is inside the soil mineral matrix and can only be released when iron oxides and other minerals are dissolved by the stronger chemical extractant. Single soil chemical extraction methods using sodium acetate and mixed acids, that extract As fractions complexed to soil particles or on the surface of mineral matrix of hydrous oxides of Fe, Mn and Al (exchangeable+sorbed forms) can be employed to estimate and predict the bioavailable As fraction for plant uptake in mining affected soils. In sequential chemical extraction methods, ammonium nitrate and hydroxylamine hydrochloride may be used to provide closer estimates of plant-available As in mining soils.     

X-ray absorption and photoelectron spectroscopy investigation of selenite reduction by FeII-bearing minerals

The long-lived radionuclide 79Se is one of the elements of concern for the safe storage of high-level nuclear waste, since clay minerals in engineered barriers and natural aquifer sediments strongly adsorb cationic species, but to lesser extent anions like selenate (SeVIO4(2-)) and selenite (SeIVO3(2-)). Previous investigations have demonstrated, however, that SeIV and SeVI are reduced by surface-associated FeII, thereby forming insoluble Se0 and Fe selenides. Here we show that the mixed FeII/III (hydr)oxides green rust and magnetite, and the FeII sulfide mackinawite reduce selenite rapidly (< 1 day) to FeSe, while the slightly slower reduction by the FeII carbonate siderite produces elemental Se. In the case of mackinawite, both S(-II) and FeII surface atoms are oxidized at a ratio of one to four by producing a defective mackinawite surface. Comparison of these spectroscopic results with thermodynamic equilibrium modeling provides evidence that the nature of reduction end product in these FeII systems is controlled by the concentration of HSe(-); Se0 forms only at lower HSe(-) concentrations related to slower HSeO3(-) reduction kinetics. Even under thermodynamically unstable conditions, the initially formed Se solid phases may remain stable for longer periods since their low solubility prevents the dissolution required for a phase transformation into more stable solids. The reduction by Fe2+-montmorillonite is generally much slower and restricted to a pH range, where selenite is adsorbed (pH < 7), stressing the importance of a heterogeneous, surface-enhanced electron transfer reaction. Although the solids precipitated by the redox reaction are nanocrystalline, their solubility remains below 6.3 x 10(-8) M. No evidence for aqueous metal selenide colloids nor for Se sorption to colloidal phases was found. Since FeII phases like the ones investigated here should be ubiquitous in the near field of nuclear waste disposals as well as in the surrounding aquifers, mobility of the fission product 79Se may be much lower than previously assumed.     

Survey of mercury,cadmium and lead content of household batteries

The objective of this work was to provide updated information on the development of the potential impact of heavy metal containing batteries on municipal waste and battery recycling processes following transposition of the new EU Batteries Directive 2006/66/EC. A representative sample of 146 different types of commercially available dry and button cells as well as lithium-ion accumulators for mobile phones were analysed for their mercury (Hg)-, cadmium (Cd)- and lead (Pb)-contents. The methods used for preparing the cells and analysing the heavy metals Hg, Cd, and Pb were either developed during a former study or newly developed. Several batteries contained higher mass fractions of mercury or cadmium than the EU limits. Only half of the batteries with mercury and/or lead fractions above the marking thresholds were labelled. Alkaline–manganese mono-cells and Li-ion accumulators, on average, contained the lowest heavy metal concentrations, while zinc–carbon batteries, on average, contained the highest levels.     

Surveillance of Enteric Viruses and Thermotolerant Coliforms in Surface Water and Bivalves from a Mangrove Estuary in Southeastern Brazil

This study was conducted to evaluate the microbiological quality of a mangrove estuary in the Vitória Bay region, Espírito Santo, Brazil. We analyzed the presence and concentration of enteric viruses and thermotolerant coliforms in water, mussels (Mytella charruana and Mytella guyanensis), and oysters (Crassostrea rhizophorae), collected over a 13-month period. Human adenovirus, rotavirus A (RVA), and norovirus genogroup II were analyzed by quantitative PCR. The highest viral load was found in RVA-positive samples with a concentration of 3.0 × 10⁴ genome copies (GC) L⁻¹ in water samples and 1.3 × 10⁵ GC g⁻¹ in bivalves. RVA was the most prevalent virus in all matrices. Thermotolerant coliforms were quantified as colony-forming units (CFU) by the membrane filtration method. The concentration of these bacteria in water was in accordance with the Brazilian standard for recreational waters (< 250 CFU 100 mL⁻¹) during most of the monitoring period (12 out of 13 months). However, thermotolerant coliform concentrations of 3.0, 3.1, and 2.6 log CFU 100 g⁻¹ were detected in M. charruana, M. guyanensis, and C. rhizophorae, respectively. The presence of human-specific viruses in water and bivalves reflects the strong anthropogenic impact on the mangrove and serves as an early warning of waterborne and foodborne disease outbreaks resulting from the consumption of shellfish and the practice of water recreational activities in the region.

     

Comparative study of polyhydroxyalkanoates production from acidified and anaerobically treated brewery wastewater using enriched mixed microbial culture

The production of polyhydroxyalkanoates(PHA) from wastewaters using microbial mixed cultures(MMC) has been attracting increased interest because of PHA's biodegradability characteristics. Production of PHA by an MMC enriched with PHA-accumulating bacteria was compared using anaerobically treated and acidified brewery wastewaters under various feeding strategies, namely pulse and batch feed addition. To obtain an enriched MMC, a sequencing batch reactor was inoculated with activated sludge fed with acetate and subjected to aerobic dynamic feeding. The enriched MMC was able to accumulate PHA up to 72.6% of cell dry weight(CDW) with pulse addition of acetate controlled by the dissolved oxygen(DO) concentration in the reactor. In a batch accumulation experiment with acetate,the PHA content achieved(28.5% CDW) was less than that of the pulse feeding strategy with the same amount of acetate(～2000 mg C/L). Using anaerobically treated and acidified brewery wastewater fed in pulses, the maximum PHA accumulated by the enriched MMC was similar for both wastewaters(45% CDW), in spite of the higher volatile fatty acid concentration in acidified brewery wastewater. The pulse feed addition controlled by the DO concentration was difficult to implement for wastewater as compared to acetate because the difference in DO concentration between substrate availability and depletion was low. For the batch addition of acidified wastewater, a slightly lower PHA content(39%CDW) was obtained. These results show that both brewery wastewaters can be utilized for PHA production with a similar maximum PHA storage capacity.     

3-to-1: unraveling structural transitions in ureases

Ureases are nickel-dependent enzymes which catalyze the hydrolysis of urea to ammonia and carbamate. Despite the apparent wealth of data on ureases, many crucial aspects regarding these enzymes are still unknown, or constitute matter for ongoing debates. One of these is most certainly their structural organization: ureases from plants and fungi have a single unit, while bacterial and archaean ones have three-chained structures. However, the primitive state of these proteins — single- or three-chained — is yet unknown, despite many efforts in the field. Through phylogenetic inference using three different datasets and two different algorithms, we were able to observe chain number transitions displayed in a 3-to-1 fashion. Our results imply that the ancestral state for ureases is the three-chained organization, with single-chained ureases deriving from them. The two-chained variants are not evolutionary intermediates. A fusion process, different from those already studied, may explain this structural transition.     

The effect of multiple mating on genetic relatedness in larval aggregations of the imported willow leaf beetle (Plagiodera versicolora,Coleoptera: Chrysomelidae)

Summary The effect of multiple mating on the average genetic relatedness within socially interacting sib groups was studied in the imported willow leaf beetle. Using an electrophoretically determined genetic marker, it was demonstrated that between 49 and 96% of wild caught females produce egg clutches expressing multiple sires. Following theoretical predictions of Wade (1982), this information was used to estimate the harmonic mean number of sires per family and then the average relatedness within families. Average relatedness was estimated to be 0.38. An alternate form of data analysis suggested by Pamilo and Crozier (1982) did not require any knowledge of paternity and resulted in a slightly higher estimate of relatedness, 0.44.     

Umweltmonitoring von Herbiziden in aquatischen Systemen

Herbicides of the chlorinated phenoxyalkanoic acid group like 2,4-D, 2,4-DP and MCPP, belong to the most commonly used pesticides. This is also true for the Land Brandenburg. Therefore, this substance group was integrated in the current state monitoring programme for ground and surface water quality. Starting in 2001, the analysis was carried out complying with DIN 38407-20 by gas chromatography and mass spectrometric detection after enrichment with solid phase extraction and following derivatization with diazomethane-forming methyl esters. Quantifying 2,4-D considering selected ions in a surface water sample from the river Oder, a remarkable peak pattern was observed. A second peak with identical spectrum was found about 0.7 minutes earlier than the 2,4-D calibrated peak. Its intensity suggested a concentration 10–20 fold higher than the 2,4-D level. This unknown peak was identified as 2,6-D which is a structure isomer of the herbicide 2,4-D. This substance has not been described in literature or chemical substance databases known to us yet. Structure isomers have been found in other samples too. We suppose that the chlorinated phenoxyalkanoic acids chlorinated in the 6-position of the phenyl ring are formed as a technical by-product and show a higher persistance than the commonly known agents.     

A recursive ecological indicator system for the supply chain of a company

This paper proposes the concept of cumulative eco-intensity with which environmental or sustainability indicators are related to the added value of economic activities. The intensities are passed on recursively from supplier to supplier and thus make it possible to include upstream and downstream effects along the supply and waste disposal chain. The process is applied to whole companies and (by contrast with LCA) not to individual products. At comparatively low expenditure for the individual companies, it allows vertical comparisons along the value-adding chain and horizontal comparisons among companies or production locations. This provides a decision-making aid for a company seeking to fulfil its ecological or sustainability responsibility in the entire production and supply chains.