Sorption of hazardous metals from single and multi-element solutions by saltbush biomass in batch and continuous mode: interference of calcium and magnesium in batch mode

Batch studies were performed to determine the interference of calcium (Ca) and magnesium (Mg) on the sorption of Cu(II), Cd(II), Cr(III), Cr(VI), Pb(II), and Zn(II) [from CuSO(4), K(2)Cr(2)O(7), Pb(NO(3))(2), Cr(NO(3))(3), ZnCl(2), and Cd(NO(3))(2)] by saltbush (Atriplex canescens) biomass. The results demonstrated that Ca and Mg at concentrations of at least 20 times higher than the concentration of most of the target metals did not interfere with the metal binding. The data show that the batch binding capacity from a multimetal solution at pH 5.0 was (micromol/g) about 260 for Cr(III) and Pb, and about 117, 54, and 49 for Cu, Zn, and Cd, respectively. The use of 0.1M HCl allowed the recovery of 85-100% of the bound Cu, Cr(III), and Pb, and more than 37% of the bound Cd and Zn. The column binding capacity for Pb was about 49 micromol/g from both the single and multimetal solutions, while it was, respectively about 35 and 23 micromol/g for Cr(III). The binding capacity for Cu and Zn from the single and multimetal column experiments was 35 micromol/g and less than 10 micromol/g, respectively. The stripping data from the single column experiment showed that 0.1M HCl allowed the recovery of all the bound Cu and Zn, 90% and 74% of the bound Pb and Cr(VI), respectively, and less than 25% of the bound Cd and Cr(III), while the stripping from the multimetal experiment showed that 0.1M HCl allowed the recovery of all the bound Cu and about 74%, 54%, 43%, and 40% of the bound Pb, Zn, Cd, and Cr(III), respectively.     

Relationship between occupational social class and exposure to organochlorine pesticides during pregnancy

Background

Little evidence is available on the influence of socioeconomic factors on exposure to persistent organic pollutants, especially during vulnerable periods such as pregnancy and early life.

Objective

To investigate the relationship of maternal social class with placental concentrations of organochlorine pesticides (OCPs) and their combined estrogenic activity measured with a biomarker of exposure.

Methods

Exposure to 16 OCPs (DDTs, endosulfans, and seven other compounds) and the total effective xenoestrogenic burden (TEXB) were analyzed in placentas from a mother-child cohort. OCP concentrations were quantified by gas chromatography and mass spectrometry, and TEXB was assessed with the E-Screen bioassay. Social class was classified according to maternal occupation. Multivariate regression analysis was conducted to examine variations in pesticide exposure and TEXB as a function of maternal social class in 257 subjects.

Results

Placental p,p′-DDT concentrations were higher in social classes III and IV than in classes I-II (the most affluent); concentrations of the sum of DDTs were higher in class IV; and exposure to the sum of endosulfans was greater in class III. HCB concentrations were higher among women in class IV than in classes I-II and among manual (classes III-V) than non-manual workers. However, the trend across social classes was only statistically significant for HCB. Social class significantly explained 10% of the variability in concentrations of the sum of endosulfans.

Conclusion

There is a need to explore whether more disadvantaged populations suffer higher levels of exposure to pesticides or other environmental chemicals and how different social processes contribute to this exposure.     

Leachable 226Ra in Philippine phosphogypsum and its implication in groundwater contamination in Isabel, Leyte, Philippines

Phosphogypsum (PG), the major waste material in phosphate fertilizer processing, has been known to contain enhanced levels of naturally-occurring radionuclides especially (226)Ra.The lack of radioactivity data regarding Philippine phosphogypsum and its environmental behavior in the Philippine setting has brought concern on possible contamination of groundwater beneath the phosphogypsum ponds in Isabel, Leyte, Philippines. The radioactivity of Philippine phosphogypsum was determined and the leaching of (226)Ra from phosphogypsum and through local soil was quantified. Level of (226)Ra in groundwater samples in Isabel, Leyte, Philippines was also quantified to address the primary concern. It was found that the (226)Ra activity in Philippine phosphogypsum is distributed in a wide range from 91.5 to 935 Bq/kg. As much as 5% of (226)Ra can be leached from Philippine PG with deionized water. In vitro soil leach experiments suggest that the soil in the phosphate fertilizer plant area would be able to deter the intrusion of (226)Ra into the water table. Compared to reported values of natural groundwater levels of (226)Ra, the concentration of this radionuclide in Isabel, Leyte groundwater suggest that there is no (226)Ra intrusion brought about by the presence of phosphogypsum ponds in the area.     

Identification of heavy metal sources by multivariable analysis in a typical Mediterranean city (SE Spain)

Problems associated with heavy metal characterization in the majority of sites are often due to multiple sources of pollution. This work presents the results through the use of advanced statistical techniques to identify sources of soil heavy metals in a typical Mediterranean city. The multivariable analysis performed on seven metals identified four sources controlling their variability. Cr, Mn, and Ni contents were associated to soil parent materials; Cd and Pb contents were related to anthropogenic activities, specifically industrial activities and traffic; Cu content is controlled by long-term application of inorganic fertilizers in agricultural areas. Finally, zinc concentration is associated to commercial and outdoor activities in the area. These results were supported by the fact that metals associated to parent material (Cr, Mn, and Ni) were better correlated with soil lithogenic properties, while anthropogenic metals were correlated with more variable soil constituents.     

Real-world emissions of in-use off-road vehicles in Mexico

Off-road vehicles used in construction and agricultural activities can contribute substantially to emissions of gaseous pollutants and can be a major source of submicrometer carbonaceous particles in many parts of the world. However, there have been relatively few efforts in quantifying the emission factors (EFs) and for estimating the potential emission reduction benefits using emission control technologies for these vehicles. This study characterized the black carbon (BC) component of particulate matter and NOx, CO, and CO₂ EFs of selected diesel-powered off-road mobile sources in Mexico under real-world operating conditions using on-board portable emissions measurements systems (PEMS). The vehicles sampled included two backhoes, one tractor, a crane, an excavator, two front loaders, two bulldozers, an air compressor, and a power generator used in the construction and agricultural activities. For a selected number of these vehicles the emissions were further characterized with wall-flow diesel particle filters (DPFs) and partial-flow DPFs (p-DPFs) installed. Fuel-based EFs presented less variability than time-based emission rates, particularly for the BC. Average baseline EFs in working conditions for BC, NOx, and CO ranged from 0.04 to 5.7, from 12.6 to 81.8, and from 7.9 to 285.7 g/kg-fuel, respectively, and a high dependency by operation mode and by vehicle type was observed. Measurement-base frequency distributions of EFs by operation mode are proposed as an alternative method for characterizing the variability of off-road vehicles emissions under real-world conditions. Mass-based reductions for black carbon EFs were substantially large (above 99%) when DPFs were installed and the vehicles were idling, and the reductions were moderate (in the 20–60% range) for p-DPFs in working operating conditions. The observed high variability in measured EFs also indicates the need for detailed vehicle operation data for accurately estimating emissions from off-road vehicles in emissions inventories.

Implications: Measurements of off-road vehicles used in construction and agricultural activities in Mexico using on-board portable emissions measurements systems (PEMS) showed that these vehicles can be major sources of black carbon and NO_X. Emission factors varied significantly under real-world operating conditions, suggesting the need for detailed vehicle operation data for accurately estimating emissions inventories. Tests conducted in a selected number of sampled vehicles indicated that diesel particle filters (DPFs) are an effective technology for control of diesel particulate emissions and can provide potentially large emissions reduction in Mexico if widely implemented.     

Carbon mineralization,microbial activity and metal dynamics in tailing ponds amended with pig slurry and marble waste

A field experiment was set up in Cartagena-La Unión Mining District, SE Spain, aimed at evaluating the short-term effects of pig slurry (PS) amendment alone and together with marble waste (MW) on organic matter mineralization, microbial activity and stabilization of heavy metals in two tailing ponds. These structures pose environmental risk owing to high metals contents, low organic matter and nutrients, and null vegetation. Carbon mineralization, exchangeable metals and microbiological properties were monitored during 67 d. The application of amendments led to a rapid decrease of exchangeable metals concentrations, except for Cu, with decreases up to 98%, 75% and 97% for Cd, Pb and Zn, respectively. The combined addition of MW + PS was the treatment with greater reduction in metals concentrations. The addition of PS caused a significant increase in respiration rates, although in MW + PS plots respiration was lower than in PS plots. The mineralized C from the pig slurry was low, approximately 25–30% and 4–12% for PS and MW + PS treatments, respectively. Soluble carbon (Csol), microbial biomass carbon (MBC) and β-galactosidase and β-glucosidase activities increased after the application of the organic amendment. However, after 3 d these parameters started a decreasing trend reaching similar values than control from approximately day 25 for Csol and MBC. The PS treatment promoted highest values in enzyme activities, which remained high upon time. Arylesterase activity increased in the MW + PS treatment. Thus, the remediation techniques used improved soil microbiological status and reduced metal availability. The combined application of PS + MW reduced the degradability of the organic compounds.     

Kinetic studies of endosulfan photochemical degradations by ultraviolet light irradiation in aqueous medium

Kinetic studies of endosulfan photochemical degradation in controlled aqueous systems were carried out by ultraviolet light irradiation at λ = 254 nm. The photolysis of (α + β: 2 + 1) endosulfan, α-endosulfan and β-endosulfan were first-order kinetics. The observed rate constants obtained from linear least-squares analysis of the data were 1 × 10^?4 s^?1; 1 × 10^?4 s^?1; and 2 × 10^?5 s^?1, respectively, and the calculated quantum yields (φ) were 1, 1 and 1.6, respectively. Preliminary differential pulse polarographic (DPP) analysis allowed to observe the possible endosulfan photochemical degradation pathway. This degradation route involves the formation of the endosulfan diol, its transformation to endosulfan ether and finally the ether's complete degradation by observing the potential shifts.     

Residues levels of organochlorine pesticide in cow's milk from industrial farms in Hidalgo,Mexico

A survey was carried out from 2008 to 2010 to determine the concentrations of 16 organochlorine pesticide residues (OPRs) from Tizayuca, Hidalgo, Mexico. Organochlorine residue determinations were made from milk fat, using chromatographic cleanup and analysis by gas chromatography with an electron capture detector. The OPR concentrations found were from below the detection limit (DL) to 0.91 ng g^?1 in 2008, DL to 0.38 ng g^?1 in 2009 and DL to 0.59 ng g^?1 in 2010. In general concentrations of organochlorine pesticides were higher in the wet season (3.37 ng g^?1 and 4.79 ng g^?1) than the dry season (1.92 ng g^?1 and 2.71 ng g^?1) for 2009 and 2010, due to control of pests in the pasture and sheds. According to Codex Alimentarius regulations, individual pesticides did not exceed the permissible limits, which for example were 10 μg kg^?1 for alpha hexachlorocyclohexane (HCH) and endosulfan I, 20 μg kg^?1 for p,p’-DDT, and 6 μg kg^?1 for dieldrin, endrin and heptachlor. A reduction of organochlorine pesticide concentrations in cow's milk was noted, indicating that the Mexican government has achieved reduction or elimination of some organochlorine pesticides in response to global agreements on persistent organic pollutants.