Organocopper complexes during roxarsone degradation in wastewater lagoons

Background, aim, and scope  

Organoarsenical-containing animal feeds that promote growth and resistance to parasites are mostly excreted unchanged, ending up in nearby wastewater storage lagoons. Earlier work documented the partial transformation of organoarsenicals, such as, 3-nitro-4-hydroxyphenylarsonic acid (roxarsone) to the more toxic inorganic arsenate [As(V)] and 3-amino-4-hydroxyphenylarsonic acid (3-AHPAA). Unidentified roxarsone metabolites using liquid chromatography coupled to inductively coupled plasma mass spectrometry (LC/ICP-MS) were also inferred from the corresponding As mass balance. Earlier batch experiments in our laboratory suggested the presence of organometallic (Cu) complexes during relevant roxarsone degradation experiments. We hypothesized that organocopper compounds were complexed to roxarsone, mediating its degradation in field-collected swine wastewater samples from storage lagoons. The objective of this study was to investigate the role of organometallic (Cu) complexes during roxarsone degradation under aerobic conditions in swine wastewater suspensions, using electrospray ionization mass spectrometry (ES-MS).     

Analysis of phytochelatin complexes in the lead tolerant vetiver grass [Vetiveria zizanioides (L.)] using liquid chromatography and mass spectrometry

Ethylenediamene tetraacetic acid (EDTA) has been used to mobilize soil lead (Pb) and enhance plant uptake for phytoremediation. Chelant bound Pb is considered less toxic compared to free Pb ions and hence might induce less stress on plants. Characterization of possible Pb complexes with phytochelatins (PC_n, metal-binding peptides) and EDTA in plant tissues will enhance our understanding of Pb tolerance mechanisms. In a previous study, we showed that vetiver grass (Vetiveria zizanioides L.) can accumulate up to 19,800 and 3350 mg Pb kg⁻¹ dry weight in root and shoot tissues, respectively; in a hydroponics set-up. Following the basic incubation study, a greenhouse experiment was conducted to elucidate the efficiency of vetiver grass (with or without EDTA) in remediating Pb-contaminated soils from actual residential sites where Pb-based paints were used. The levels of total thiols, PC_n, and catalase (an antioxidant enzyme) were measured in vetiver root and shoot following chelant-assisted phytostabilization. In the presence of 15 mM kg ⁻¹ EDTA, vetiver accumulated 4460 and 480 mg Pb kg⁻¹ dry root and shoot tissue, respectively; that are 15- and 24-fold higher compared to those in untreated controls. Despite higher Pb concentrations in the plant tissues, the amount of total thiols and catalase activity in EDTA treated vetiver tissues was comparable to chelant unamended controls, indicating lowered Pb toxicity by chelation with EDTA. The identification of glutathione (referred as PC₁) (m/z 308.2), along with chelated complexes like Pb-EDTA (m/z 498.8) and PC₁-Pb-EDTA (m/z 805.3) in vetiver root tissue using electrospray tandem mass spectrometry (ES-MS) highlights the possible role of such species towards Pb tolerance in vetiver grass.     

Different habitats, different habits? Response to foraging information in the parasitic wasp Venturia canescens

The parasitic wasp, Venturia canescens (Gravenhorst) (Hymenoptera: Ichneumonidae), has two reproductive modes, namely, thelytoky or arrhenotoky, and occurs in habitats with highly variable or relatively stable host abundances, respectively. Since information processing is costly, we expected that information indicating resource availability would be mainly used by the thelytokous wasps and less so by the arrhenotokous type. This idea was explored by two different approaches. In a study on patch-time allocation, we used females from ten populations and measured patch-residence times of individuals that visited multiple patches at different encounter rates. In a more detailed approach, thelytokous and arrhenotokous females from a single location were observed continuously while foraging, and all behaviors were recorded. Wasps of both reproductive modes (i.e., both habitat types) used information for the assessment of habitat quality. However, the way that the information was used differed between them. Whereas thelytokous females used foraging information to maximize their efficiency at high patch-encounter rates, arrhenotokous females merely reduced the number of offspring produced without changing patch times. The behavior of the arrhenotokous females should result in a spreading of offspring across the habitat and, thus, reduced sib-mating. The foraging strategy of these wasps might therefore be an adaptation to reduce costs associated with inbreeding.     

Exchangeable lead from prediction models relates to vetiver lead uptake in different soil types

Prediction models for exchangeable soil lead, published earlier in this journal (Andra et al. 2010a), were developed using a suite of native lead (Pb) paint-contaminated residential soils from two US cities heavily populated with homes constructed prior to Pb ban in paints. In this study, we tested the feasibility and practical applications of these prediction models for developing a phytoremediation design using vetiver grass (Vetiveria zizanioides), a Pb-tolerant plant. The models were used to estimate the exchangeable fraction of Pb available for vetiver uptake in four lead-spiked soil types, both acidic and alkaline, with varying physico-chemical properties and that are different from those used to build the prediction models. Results indicate a strong correlation for predictable exchangeable Pb with the observed fraction and as well with total Pb accumulated by vetiver grass grown in these soils. The correlation coefficient for the predicted vs. observed exchangeable Pb with p < 0.001 was 0.999, 0.996, 0.949, and 0.998 in the Immokalee, Millhopper, Pahokee Muck, and Tobosa soil type, respectively. Similarly, the correlation coefficient for the predicted exchangeable Pb vs. accumulated Pb in vetiver grass with p?< 0.001 was 0.948, 0.983, 0.929, and 0.969 for each soil type, respectively. This study suggests that the success of a phytoremediation design could be assessed upfront by predicting the exchangeable Pb fraction in a given soil type based on its properties. This helps in modifying the soil conditions to enhance phytoextraction of Pb from contaminated soils.     

Social factors mediating human–carnivore coexistence: Understanding thematic strands influencing coexistence in Central Romania

Facilitating human–carnivore coexistence depends on the biophysical environment but also on social factors. Focusing on Central Romania, we conducted 71 semi-structured interviews to explore human–bear (Ursus arctos) coexistence. Qualitative content and discourse analysis identified three socially mediated thematic strands, which showed different ways in which perceived interactions between people, bears and the environment shape coexistence. The “landscape-bear strand” described perceptions of the way in which the landscape offers resources for the bear, while the “landscape-human strand” related to ways in which humans experience the landscape. The “management strand” related to the way bears was managed. All three strands highlight both threats and opportunities for the peaceful coexistence of people and bears. Management and policy interventions could be improved by systematically considering the possible effects of interventions on each of the three strands shaping coexistence. Future research should explore the relevance of the identified thematic strands in other settings worldwide.

Electronic supplementary material

The online version of this article (doi:10.1007/s13280-015-0760-7) contains supplementary material, which is available to authorized users.     

Nitrous oxide supersaturation at the liquid/air interface of animal waste

Concentrated animal feeding operations around the globe generate large amounts of nitrous oxide (N₂O) in the surrounding atmosphere. Liquid animal waste systems have received little attention with respect to N₂O emissions. We hypothesized that the solution chemistry of animal waste aqueous suspensions would promote conditions that lead to N₂O supersaturation at the liquid/air interface. The concentration of dissolved N₂O in poultry litter (PL) aqueous suspensions at 25 °C was 0.36 μg N₂O mL⁻¹, at least an order of magnitude greater than that measured in water in equilibrium with ambient air, suggesting N₂O supersaturation. There was a nonlinear increase in the N₂O Henry constants of PL from 2810 atm/mole fraction at 35 °C to 17 300 atm/mole fraction at 41 °C. The extremely high N₂O Henry constants were partially ascribed to N₂O complexation with aromatic moieties. Complexed N₂O structures were unstable at temperatures > 35 °C, supplying the headspace with additional free N₂O concentrations.     

Controlling the fate of roxarsone and inorganic arsenic in poultry litter

A growing body of literature reports 3-nitro-4-hydroxyphenylarsonic acid (roxarsone) degradation in poultry litter (PL) to the more toxic inorganic arsenic (As). Aluminum-based drinking-water treatment residuals (WTR) present a low-cost amendment technology to reduce As availability in PL, similar to the use of alum to reduce phosphorus availability. Batch experiments investigated the effectiveness of WTR in removing roxarsone and inorganic As species from PL aqueous suspensions. Incubation experiments with WTR-amended PL evaluated the effects of WTR application rates (2.5-15% by weight) and incubation time (up to 32 d) at two incubation temperatures (23 and 35 degrees C) on As availability in PL. Batch PL aqueous experiments showed the high affinity of As(V), As(III), dimethylarsinic acid (DMA), monomethylarsonic acid (MMA), and roxarsone for the WTR. The 10% WTR amendment rate decreased As availability in PL by half of that of the unamended (no WTR) PL-incubated samples. The reduction in dissolved As concentrations during incubation of WTR-amended PL samples was kinetically limited, being complete within 13 d. Parallel reductions in roxarsone, As(V), and DMA concentrations were observed with liquid chromatography-inductively coupled plasma mass spectrometry, whereas As(III) and MMA concentrations were always <5% of dissolved As. Incubation temperature did not significantly (p > 0.05) influence dissolved As concentrations in the WTR-amended PL. Potential formation of a copper-containing roxarsone metabolite was considered in PL aqueous suspensions with the aid of electrospray mass spectrometry. Further experiments in the field are necessary to ensure that sorbed As is stable in WTR-amended PL.     

Predicting potentially plant-available lead in contaminated residential sites

Lead (Pb)-based paints pose a serious health problem to people living in residential settings constructed prior to 1978. Children are at a greater risk to Pb exposure resulting from hand-to-mouth activity in Pb-contaminated residential soils. For soil Pb, the most environmentally friendly, potentially cheap, and visually unobtrusive in situ technology is phytoremediation. However, the limiting factor in a successful phytoremediation strategy is the availability of Pb for plant uptake. The purpose of this study was to establish a relationship between soil properties and the plant-available/exchangeable Pb fraction in the selected Pb-based paint-contaminated residential sites. We selected 20 such sites from two different locations (San Antonio, Texas and Baltimore, Maryland) with varying soil properties and total soil Pb concentrations ranging between 256 and 4,182 mg kg^?1. Despite higher Pb levels in these soils that exceeds US EPA permissible limit of 400 mg kg^???1, it is known that the plant-available Pb pools are significantly lower because of their sorption to soil components such as organic matter, Fe?CMn oxides, and clays, and their precipitation in the form of carbonates, hydroxides, and phosphates. Principal component analysis and hierarchical clustering showed that the potentially plant-available Pb fraction is controlled by soil pH in the case of acidic Baltimore soils, while soil organic matter plays a major role in alkaline San Antonio soils. Statistical models developed suggest that Pb is likely to be more available for plant uptake in Baltimore soils and a chelant-assisted phytoextraction strategy will be potentially necessary for San Antonio soils in mobilizing Pb from complexed pool to the plant-available pool. A thorough knowledge of site-specific factors is therefore essential in developing a suitable and successful phytoremediation model.