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).     

Indoor Air Quality at Rural and Urban Sites in Pakistan

In the developing world, the vast majority of people rely on solid biomass fuels for cooking and heating which results in poor indoor air quality. The present study determined indoor air quality in some rural and urban areas of Pakistan. Measurements were made of particulate mass (PM10, PM2.5 and PM1), number concentration and bioaerosols in different micro environments. PM10 concentrations of up to 8,555 μg/m³ were observed inside the kitchens where biofuels were used as energy source. Cleaning and smoking was identified as a major source of indoor particulate pollution and concentrations of more than more than 2,000 μg/m³ were recorded in the living room during these activities. Indoor number concentrations in Lahore were typically greater than those observed outdoors in European cites. At a rural site the highest Colony Forming Units (CFUs) were in the 0.5 μm–2 μm size fraction, while at the urban location CFUs were dominant for 2 μm–16 μm. It was observed that CFUs(Colony Forming Units) counts were higher inside living rooms than kitchens. It is important to note that women and children were exposed to extremely high levels of particulates during cooking. Overall, indoor air quality in Pakistan was poor and there is a dire need to take a serious step to combat with it.     

Fate of arsenic in swine waste from concentrated animal feeding operations

Swine diets are often supplemented by organoarsenicals, such as 3-nitro-4-hydroxyphenylarsonic acid (roxarsone) to treat animal diseases and promote growth. Recent work reported roxarsone degradation under anaerobic conditions in poultry litter, but no such data exist for swine wastes typically stored in lagoons nearby concentrated animal feeding operations (CAFOs). The objectives of this study were to: (i) characterize a suite of swine wastes collected from 19 randomly selected CAFOs for soluble arsenate [As(V)], arsenite [As(III)], dimethylarsenic acid (DMA), monomethylarsonic acid (MMA), 3-amino-4-hydroxyphenylarsonic acid (3-HPPA), p-arsanilic acid, and roxarsone, and (ii) determine the geochemical fate of roxarsone in storage lagoons nearby CAFOs. Swine waste suspensions were spiked with roxarsone and incubated under dark/light and aerobic/anaerobic conditions to monitor roxarsone degradation kinetics. Arsenic speciation analysis using liquid chromatography and inductively coupled plasma mass spectrometry (LC-ICPMS) illustrated the prevalence of As(V) in swine waste suspensions. Roxarsone underwent degradation to either organoarsenicals (3-HPPA) or As(V) and a number of unidentified metabolites. Roxarsone degradation occurred under anaerobic conditions for suspensions low in solids content, but suspensions higher in solids content facilitated roxarsone degradation under both anaerobic and aerobic conditions. Increased solids content enhanced roxarsone degradation kinetics under aerobic conditions. According to current waste storage and sampling practices, arsenic in swine wastes stored in lagoons has been overlooked as a possible environmental health issue.     

Separation and identification of heterocyclic nitrogen compounds in biooil derived by fast pyrolysis of chicken manure

N-heterocyclics were separated from a biooil, generated by the pyrolysis of chicken manures by column chromatography over neutral alumina and silica, and identified by Pyrolysis Field Ionization Mass Spectrometry (Py-FIMS) and Electrospray Ionization Mass Spectrometry (ESI-MS). Identities of chemical structures, whose presence was indicated by ESI-MS, were confirmed by comparing the Collision-Induced Dissociations (CID's) mass spectra of unknown and standards. The following seven base structures were identified: pyrazine, benzoquinoline, carbazole, phenylpyridine, indole, pyrazole and pyridine. Available hydrogens bonded to ring carbons and nitrogens on the seven N-heterocyclics were increasingly substituted by alkyl groups, mainly methylene groups (m/z 14) to yield mono-, di-, tri- methyl N-heterocyclics. In some instances, longer alkyl chains, such as ethyl, propyl, up to heptyl groups were the substituents.     

Health risks associated with heavy metals in the drinking water of Swat, northern Pakistan

The concentrations of heavy metals such as Cd, Cr, Cu, Mn, Ni, Pb and Zn were investigated in drinking water sources （surface and groundwater） collected from Swat valley, Khyber Pakhtunkhwa, Pakistan. The potential health risks of heavy metals to the local population and their possible source apportionment were also studied. Heavy metal concentrations were analysed using atomic absorption spectrometer and compared with permissible limits set by Pakistan Environmental Protection Agency and World Health Organization. The concentrations of Cd, Cr, Ni and Pb were higher than their respective permissible limits, while Cu, Mn and Zn concentrations were observed within their respective limits. Health risk indicators such as chronic daily intake （CDI） and health risk index （HRI） were calculated for adults and children separately. CDIs and HRIs of heavy metals were found in the order of Cr 〉 Mn 〉 Ni 〉 Zn 〉 Cd 〉 Cu 〉 Pb and Cd 〉 Ni 〉 Mn 〉 Cr 〉 Cu 〉 Pb 〉 Zn, respectively. HRIs of selected heavy metals in the drinking water were less than 1, indicating no health risk to the local people. Multivariate and univariate statistical analyses showed that geologic and anthropogenic activities were the possible sources of water contamination with heavy metals in the study area.     

Production and growth of microalgae in urine and wastewater: A review

Environmental Chemistry Letters - Issues of climate change, energy demand, and natural resources depletion are calling for circular methods to produce value-added products such as biomass, biofuel,...     

Adaptation to climate change as resilience for urban extreme poor: lessons learned from targeted asset transfers programmes in Dhaka city of Bangladesh

This paper aims to identify how targeted asset transfers help to build adaptive capacity and adaptive actions of the urban extreme poor to climate change phenomena. This paper explores the theoretical debates of community-based adaptation approach and failure of such approach to address urban extreme poor. The empirical evidence of these theoretical debates will be drawn from two informal settlements of Dhaka city, where a targeted asset transfer project has been implementing since 2009. This paper explains that urban extreme poor usually work as unskilled labour and lack different livelihood capitals; and climate change is an increasingly important influence exacerbating an already vulnerable livelihood context. There is growing recognition in the literature that poor urban people and communities are adapting to climate change in physical and behavioural terms. But, in the case of urban extreme poor these adaptation approaches are delivering short-term survival strategies disregarding the notion of wellbeing in the medium to long-term perspectives. It is also evident that community level initiatives structurally reproduce the exclusion of the urban extreme poor. However, poverty literatures acknowledge that poverty-centred approaches could help to reduce vulnerability. As urban extreme poor are significantly more resource constrained, it is reasonable to assert that targeted asset transfers could be a poverty-centred adaptation approach in a changing climate. Targeted asset transfers approaches are the outcomes of recent social protection revolution that especially consider accumulation of physical, financial, human, and social capital in order to build adaptive capacity of the urban extreme poor. This adaptive capacity of the extreme poor may facilitate adjustments in assets, livelihoods, behaviours, and technologies in order to reduce future climate vulnerability. In this context, this paper seeks to answer whether targeted asset transfer approaches can be considered as effective poverty-centred adaptation approaches for the urban extreme poor or not.     

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.     

ESTIMATES OF THE ECONOMIC VALUE PRODUCTIVITY OF IRRIGATION WATER IN PAKISTAN FROM FARM SURVEYS1

Data from two cross-sectional surveys totaling over 2000 farmers in Pakistan are analyzed with regression techniques to estimate the value productivity of irrigation water and related resources. Returns to irrigation water vary by province, but in general are found to be high relative to estimated costs of obtaining water. Salinity of water supplies is an important productivity depressant. The results will be useful in determining the economic feasibility of various means for augmenting supplies and for improving delivery and application efficiencies.