Adsorption of mono- and di-butyltin by a wheat charcoal: pH effects and modeling

Understanding adsorption processes of butyltins (BTs) such as monobutyltin (MBT) and dibutyltin (DBT) by black carbons is important for the evaluation of BT exposure risks to organisms and humans. However, relevant knowledge is scarce. In this study, the acidity constants pK_a,1 = 2.3, pK_a,2 = 3.5 and pK_a,3 = 5.9 for MBT and pK_a,1 = 3.0 and pK_a,2 = 5.1 for DBT are estimated via potentiometric titration. Additionally, adsorption isotherms of BTs to a wheat charcoal were determined. The adsorption behavior was observed to be pH-dependent due to BT speciation and the pH-dependent surface charge of the charcoal. MBT adsorption to the charcoal decreases with increasing pH from 4 to 8, while the highest adsorption occurs at pH 6 for DBT. Adsorption of the BTs is successfully described in the pH range of 3-10 by using a newly developed pH-dependent Dual Langmuir model. The model has the potential to predict the interaction of BT species with charcoal, which can contribute to the risk assessments of BTs in the environment.     

The pH-dependent adsorption of tributyltin to charcoals and soot

Widespread use of tributyltin (TBT) poses a serious environmental problem. Adsorption by black carbon (BC) may strongly affect its behavior. The adsorption of TBT to well characterized soot and two charcoals with specific surface area in the range of 62-111 m² g⁻¹ have been investigated with main focus on pH effects. The charcoals but not soot possess acidic functional groups. TBT adsorption reaches maximum at pH 6-7 for charcoals, and at pH > 6 for soot. Soot has between 1.5 and 15 times higher adsorption density (0.09-1.77 μmol m⁻²) than charcoals, but charcoals show up to 17 times higher sorption affinities than soot. TBT adsorption is successfully described by a new pH-dependent dual Langmuir model considering electrostatic and hydrophobic adsorption, and pH effects on TBT speciation and BC surface charge. It is inferred that strong sorption of the TBTOH species to BC may affect TBT toxicity.     

Regulatory risk control through mandatory occupational safety and health (OSH) certification and testing regimes (CTRs)

Governments make increasing use of private certification and testing infrastructures as an alternative for traditional regulatory arrangements in several areas including occupational safety and health (OSH).This research, commissioned by the Dutch Inspectorate for Work and Income (IWI), concerns an analysis of risk control of four certification and testing regimes (CTRs) in the Netherlands, three mandatory regimes and one non-mandatory regime. The aim was to create a better understanding of problems that may arise in the risk control through such regimes and to identify critical processes and factors that can affect the risk control process.The results of this research are reported in two papers in this special issue (see also Zwetsloot et al., this issue). This one presents an analysis of the risk control at the regulatory level, and its associated critical factors and processes. These critical factors are clustered in four essential processes: the regulatory choice for a CTR, the definition of requirements for the auditing or inspection regime, the certification and testing processes as such, and the processes needed for the self-correcting or learning capability of the CTR. Jointly, these factors and processes form a framework for both the design and the evaluation of such regimes. The case studies clearly demonstrate that these critical factors may undermine the effectiveness of such regulatory practices. We propose that a further development of our framework should be used in the (re)design process for proposed and existing CTRs, and in the process of independent evaluation of such regimes.     

昔日丹麦的家畜管理方式对景观中植物种子散布的影响

目前,北欧自然(半自然)生境中物种丰富度的降低很大程度上归咎于生境破坏以及由此而导致的植物种子在破碎化生境之间扩散的局限性.尽管一些生境可能早已从以往的景观中分割出去,但是那些分割部分的隔离程度可能不及目前的状态.本文试图从三个空间尺度上寻求家畜在昔日农业景观中充当植物繁殖体载体的证据.家畜充当植物种子散布者主要在以下三个尺度具有重要意义:在景观中自由活动(1～10 km);驱使动物摄食坚果以及将动物赶到庄园(10～50km):将活的牲畜输送出去(数百公里).对于大多数植物物种来说,在现代景观中扩散的机会大为减少了,其结果可能导致诸如草原、草地和荒野等自然(半自然)植物群落物种丰富度的减少.     

Time and moisture effects on total and bioavailable copper in soil water extracts

Environmental risk assessment of heavy metals in soil frequently involves testing of freshly spiked soils kept under stable humidity conditions, but it has been questioned whether these assessments are representative of the field situation. Furthermore, the poor correspondence that is often found between total metal content and metal toxicity calls for integrated chemical and biological analysis. The aim of this work was to determine time- and moisture-dependent changes in total water-extractable Cu as well as bioavailable Cu in soil water extracts. Measurements of total water-extractable copper ([Cu]tot) were performed using furnace atomic absorption spectrometry. An in vitro assay employing a Cu-specific Pseudomonas fluorescens reporter strain was used to estimate Cu that was biologically available to the reporter strain. We refer to this copper fraction as "bioavailable," [Cu]bio. We found a time-dependent decrease in [Cu]tot and [Cu]bio during incubation for up to 220 d at field capacity. Hence the [Cu]bio was reduced to between 32 and 40% of the initial values. Furthermore, the [Cu]bio to [Cu]tot ratio correlated positively with the amount of added Cu and tended to increase with time. The moisture content of the soil was important for Cu retention. Dry soil had higher [Cu]tot concentrations than humid soil, but the [Cu]bio to [Cu]tot, ratio was lower in the dry soil. Alternating drying and wetting did not lead to a more rapid Cu retention than observed under constant humid conditions. Our observations underline the need for considering both time and moisture effects when interpreting short-term toxicity studies and when making predictions concerning possible long-term effects of Cu in the soil environment.     

AN EX POST ANALYSIS OF THE UNCOMPAHGRE PROJECT1

ABSTRACT: The national and regional economic impact of the Bureau of Reclamation's Uncompahgre Project which was authorized in 1903 is assessed. Benefit-cost ratios for the project are calculated for a range of production cost estimates and discount rates. An economic base approach is used to estimate the project's regional economic impact. Although the project has been marginal in terms of an economic efficiency rationale it has been an important impetus to regional economic growth in the Uncompahgre Region over time.     

Inherent mineralization of 2,6-dichlorobenzamide (BAM) in unsaturated zone and aquifers--effect of initial concentrations and adaptation

The dichlobenil metabolite BAM (2,6-dichlorobenzamide) is frequently detected in aquifers e.g. in Denmark despite the mother compound dichlobenil was banned here since 1997. BAM mineralization was investigated at environmentally relevant concentrations in sediment samples. Undisturbed sediment cores with known dichlobenil application were collected from topsoil to 8.5 m below surface resulting in 57 samples hereof 4 aquifer samples. Mineralization was only substantial (>10%) in the uppermost meter of the unsaturated zone. Microbial adaptation, observed as faster mineralization in pre-exposed than in pristine sediments from the same location, was only evident in sandy sediment where dichlobenil was still present, but not in clayey sediments. Higher initial concentrations (1-5000 μg/kg) did not stimulate mineralization in pristine clayey or sandy sediments, or in pre-exposed sand. However, in pre-exposed clay mineralization was stimulated at high concentrations. Furthermore BAM was for the first time mineralized in aerobic aquifer sediments from different BAM-contaminated groundwater locations.     

Effects of eutrophication on reef-building corals

Seven fringing reef complexes were chosen along the leeward coast (west) of Barbados to study the effects of eutrophication processes upon the scleractinian coral assemblages. The structure of scleractinian coral communities was studied along an eutrophication gradient with a quantitative sampling method (line transect) in terms of species composition, zonation and diversity patterns. On the basis of these data the fringing reefs were divided into three ecological zones: back reef, reef flat, and spur and groove. Statistically discernible and biologically significant differences in scleractinian coral community structure, benthic algal cover and Diadema antillarum Philippi densities were recorded among the seven fringing reefs. High correlations between environmental variables and biotic patterns indicate that the effects of eutrophication processes (nutrient enrichment, sedimentation, turbidity, toxicity and bacterial activity) were directly and/or indirectly affecting the community structure of scleractinian coral assemblages. In general, species diversity was most sensitive in delineating among-reef, and among-zone, differences, which were attributed to intensification of eutrophication processes. Porites astreoides Lamarck, P. porites (Pallas), Siderastrea radians (Pallas), and Agaricia agaricites (Linnaeus) were the most abundant coral species in the polluted southern reefs. The absence and/or low abundance of coral species previously characterized as well adapted to high turbidity and sedimentation [i.e. Montastrea cavernosa Linnaeus, Meandrina meandrites (Linnaeus)] indicate that eutrophication processes may adversely affect these species. It is suggested that sediment rejection abilities, combined with feeding and reproductive strategies, are the primary biological processes of scleractinian corals through which eutrophication processes directly and/or indirectly affect the structure of coral communities.     

Exposure to metals (Ca,K, Mn) and road salt (NaCl) differentially affect development and survival in two model amphibians

ABSTRACT

Human activity has led to widespread chemical alteration of natural environments. Aquatic ecosystems are especially susceptible to chemical changes, including those caused by runoff and invasive species. Here, we examined the effects of water chemistry, specifically sodium chloride as well as three metals (Ca, K, and Mn) known to differ between native and invasive wetland plant species’ leaf tissues, on the development of two model amphibians: the native Northern leopard frog, Lithobates pipiens, and the non-native African clawed frog, Xenopus laevis. We exposed frog eggs to metal treatment solutions and measured time to hatching (TTH), and following hatching, we exposed tadpoles to a lethal concentration of sodium chloride and recorded time to death (TTD). We found that increasing metal concentrations generally resulted in acceleration of TTH for Xenopus tadpoles, but had no effect on leopard frogs. However, increasing metal concentrations (Ca, Mn) increased leopard frog tadpole susceptibility to NaCl (decreased TTD), while increasing metal concentrations (Ca, K) generally resulted in decreased Xenopus tadpole susceptibility to NaCl. Overall, our data suggest that invasive amphibians may be more tolerant to chemical changes than native amphibians, including those driven by the introduction of invasive plant species.