Arsenic speciation in human hair: a new perspective for epidemiological assessment in chronic arsenicism

The analysis for arsenic in hair is commonly used in epidemiological studies to assess exposure to this toxic element. However, poor correlation between total arsenic concentration in hair and water sources have been found in previous studies. Exclusive determination of endogenous arsenic in the hair, excluding external contamination has become an analytical challenge. Arsenic speciation in hair appears as a new possibility for analytical assessing in As-exposure studies. This study applied a relative simple method for arsenic speciation in human hair based on water extraction and HPLC-HG-ICP-MS. The concentration of arsenic species in human hair was assessed in chronically As(V)-exposed populations from two villages (Esqui?a and Illapata) of the Atacama Desert, Chile. The arsenic concentrations in drinking water are 0.075 and 1.25 mg L(-1), respectively, where As(V) represented between 92 and 99.5% of the total arsenic of the consumed waters. On average, the total arsenic concentrations in hair from individuals of Esqui?a and Illapata were 0.7 and 6.1 microg g(-1), respectively. Four arsenic species, As(III), DMA(V), MMA(V) and As(V), were detected and quantified in the hair extracts. Assuming the found species in extracts represent the species in hair, more than 98% of the total arsenic in hair corresponded to inorganic As. On average, As(III) concentrations in hair were 0.25 and 3.75 microg g(-1) in Esqui?a and Illapata, respectively; while, the As(V) average concentrations were 0.15 and 0.45 microg g(-1) in Esqui?a and Illapata, respectively. Methylated species represent less than 2% of the extracted As (DMA(V)+ MMA(V)) in both populations. As(III) in hair shows the best correlation with chronic exposure to As(V) in comparison to other species and total arsenic. In fact, concentrations of As(total), As(III) and As(V) in hair samples are correlated with the age of the exposed individuals from Illapata (R= 0.65, 0.69, 0.57, respectively) and with the time of residence in this village (R= 0.54, 0.71 and 0.58, respectively).     

Valorisation of used cooking oil sludge by codigestion with swine manure

The addition of lipid wastes to the digestion of swine manure was studied as a means of increasing biogas production. Lipid waste was obtained from a biodiesel plant where used cooking oil is the feedstock. Digestion of this co-substrate was proposed as a way of valorising residual streams from the process of biodiesel production and to integrate the digestion process into the biorefinery concept.Batch digestion tests were performed at different co-digesting proportions obtaining as a result an increase in biogas production with the increase in the amount of co-substrate added to the mixture. Semi-continuous digestion was studied at a 7% (w/w) mass fraction of total solids. Co-digestion was successful at a hydraulic retention time (HRT) of 50 d but a decrease to 30 d resulted in a decrease in specific gas production and accumulation of volatile and long chain fatty acids. The CH₄ yield obtained was 326 ± 46 l/kg VS_feed at an HRT of 50 d, while this value was reduced to 274 ± 43 l/kg VS_feed when evaluated at an HRT of 30 d. However these values were higher than the one obtained under batch conditions (266 ± 40 l/kg VS_feed), thus indicating the need of acclimation to the co-substrate. Despite of operating at low organic loading rate (OLR), measurements from respirometry assays of digestate samples (at an HRT of 50 d) suggested that the effluent could not be directly applied to the soil as fertiliser and might have a negative effect over soil or crops.     

Differential responses of the freshwater wetland species Juncus effusus L. and Caltha palustris L. to iron supply in sulfidic environments

Sulfur pollution can lead to serious problems in freshwater wetlands, including phosphorus eutrophication and sulfide toxicity. We tested the effects of anaerobic iron-rich groundwater discharge in fens, simulated by iron injection, on two characteristic species (Juncus effusus and Caltha palustris) in a sulfidic environment. Biomass production of C. palustris roots showed an optimum response to the combined addition of iron and sulfide, with highest values at intermediate concentrations of both substances. Iron deficiency apparently occurred at low iron concentrations, while at high iron concentrations, growth was decreased. For J. effusus, in contrast, no toxic effects were found of both iron and sulfide. This could be explained by larger radial oxygen loss (ROL) of J. effusus and could not be explained by differences in phosphorous concentrations. The results of our experiments confirm that iron-rich groundwater discharge has the potential to affect vegetation composition through toxicity modification in sulfidic environments.     

Effect of coumaphos on cholinesterase activity, hematology, and biochemical blood parameters of bovines in tropical regions of Mexico

To assess the effect of coumaphos [O-(3-chloro-4-methyl-2-oxo-2H-1-benzopyran-7-yl) O,O-diethyl phosphorothioate] exposure on physiological responses during bovine production, acetylcolinesterase (AChE) and butyrylcholinesterase (BuChE) activities were measured in whole blood, erythrocytes, and plasma of healthy male steers (Bos Taurus x Bos indicus) sprayed with coumaphos at a non-lethal dose of 1 mg kg(- 1) body weight per day once every 14 (in vivo group) or 21 days (southern and central groups). Coumaphos topically administered at 1 mg/kg body weight per day to cattle under normal management practices in tropical areas produced a significant inhibition in erythrocyte (RBC) AChE and BuAChE activities when compared to baseline levels. RBC-AChE activity for the in vivo group decreased 71.3% (P < 0.05) and BuChE activity 59.1% (P < 0.05); RBC-AChE activity decreased 55.1% (P < 0.05) (southern group) and 43.4% (P < 0.05) (central group). Compared to the control specimens, steers from in vivo, southern, and central groups after 150 days of exposure had lower (P < 0.05) leukocyte count, absolute lymphocyte, erythrocyte, and platelet counts. Decreases in RBC-AChE activities correlated with decreased lymphocyte (r = 1.000, p = 0.01), erythrocyte (r = 1.000, p = 0.003), and platelet counts (r = 0.841, p = 0.036). Significantly increased BUN levels (P < 0.05) correlated with the decrease in RBC-AChE activities (r = - 0.997, p = 0.047) and with the decrease in absolute red blood cell (r = - 0.883, p = 0.020) and lymphocyte (r = - 0.825, p = 0.043) counts; increased (P < 0.05) total plasma protein levels correlated with the decrease in RBC-AChE activities (r = -0.998, p = 0.043), absolute red blood cell (r = - 0.998, p = 0.040), lymphocyte (r = - 0.893, p = 0.017), and platelet (r = -0.855, p = 0.030) counts. The physiological responses correlated with the erythrocyte acetylcholinesterase inhibition could be considered as early indicators or warning responses of bovine exposures to organophosphorus pesticides (OPs).     

Silver near municipal wastewater discharges into western Lake Ontario,Canada

Because of the widespread use of silver nanoparticles in commercial products, discharges of municipal wastewater may be a point source of silver in the aquatic environment. We monitored two sites in western Lake Ontario impacted by discharges from wastewater treatment plants serving the City of Toronto. Concentrations of silver were elevated in bottom sediments and suspended sediments collected at the two sites. We also deployed two types of passive samplers in the water column at the two sites, the newly developed Carbon Nanotube Integrative Samplers for monitoring “CNIS-labile” silver and Diffusive Gradient in Thin Film samplers for monitoring “DGT-labile” silver. Results from these passive samplers indicated that the concentrations of silver at the two sites were either below detection limits or were in the ng/L range. In laboratory experiments where the sediments were re-suspended in Milli-Q water, a small proportion of the silver (i.e., <?25%) was labile and partitioned as colloidal or dissolved silver into the liquid phase after agitation. Nanoparticles tentatively identified as silver nanoparticles were detected by single-particle ICP-MS in suspension after agitation of both suspended and bottom sediments. Therefore, there is a need to assess whether silver species, including silver nanoparticles are transported from wastewater treatment plants into sediments in the aquatic environment. This study is unique in focusing on the in situ distribution of silver in natural waters and in sediments that are potentially impacted by urban sources of nanoparticles.     

An urban emissions inventory for South America and its application in numerical modeling of atmospheric chemical composition at local and regional scales

This work describes the development of an urban vehicle emissions inventory for South America, based on the analysis and aggregation of available inventories for major cities, with emphasis on its application in regional atmospheric chemistry modeling. Due to the limited number of available local inventories, urban emissions were extrapolated based on the correlation between city vehicle density and mobile source emissions of carbon monoxide (CO) and nitrogen oxides (NOx). Emissions were geographically distributed using a methodology that delimits urban areas using high spatial resolution remote sensing products. This numerical algorithm enabled a more precise representation of urban centers. The derived regional inventory was evaluated by analyzing the performance of a chemical weather forecast model in relation to observations of CO, NOx and O₃ in two different urban areas, São Paulo and Belo Horizonte. The gas mixing ratios simulated using the proposed regional inventory show good agreement with observations, consistently representing their hourly and daily variability. These results show that the integration of municipal inventories in a regional emissions map and their precise distribution in fine scale resolutions are important tools in regional atmospheric chemistry modeling.     

Assessing seasonal and spatial trends of persistent organic pollutants (POPs) in Indian agricultural regions using PUF disk passive air samplers

The first survey of persistent organic pollutant (POP) concentrations in air across several Indian agricultural regions was conducted in 2006-2007. Passive samplers comprising polyurethane foam (PUF) disks were deployed on a quarterly basis at seven stations in agricultural regions, one urban site and one background site. The project was conducted as a sub-project of the Global Atmospheric Passive Sampling (GAPS) Network. In addition to revealing new information on air concentrations of several organochlorine pesticides (OCPs) and polychlorinated biphenyls (PCBs), the study has demonstrated the feasibility of conducting regional-scale monitoring for POPs in India using PUF disk samplers. The following analytes were detected with relatively high concentrations in air (mean for 2006 and 2007, pg/m³): α- and γ-hexachlorocyclohexane (HCH) (292 and 812, respectively); endosulfan I and II (2770 and 902, respectively); p,p′-DDE and p,p′-DDT (247 and 931, respectively); and for the sum of 48 PCBs, 12,100 (including a site with extremely high air concentrations in 2007) and 972 (when excluding data for this site).     

Foaming in Pachycondyla: A new defense mechanism in ants

Summary When disturbed, two species of Malayan Pachycondyla release foam threads more than 10 cm in length or foam piles. The source of the proteinaceous foam is the enlarged venom gland, which is probably frothed up by air from the spiracles of the spiracular plates. The Dufour's gland normally producing hydrocarbons in stinging ants is atrophied. Therefore, absence of the Dufour's gland could be essential to the foaming ability, since the lipophilic hydrocarbons inhibit froth production in protein solutions. The release of foam is a mechanically acting defense mechanism, which is very effective against small mass-attacking ants. Pachycondyla species are also able to sting effectively.     

Sulfate pollution: evidence for electrochemical production of persulfate by oxidizing sulfate released by the surfactant sodium dodecyl sulfate

Environmental Chemistry Letters - There is increasing concern about contamination by surfactants that are used to extract organic pollutants during remediation of polluted soils and aquifers. For...