Isotherms and sequential extraction procedures for evaluating sorption and distribution of heavy metals in soils

Heavy metals are potentially toxic to human life and the environment. Their contaminating effect in soils depends on chemical associations. Hence, determining the chemical form of a metal in soils is important to evaluate its mobility and bioavailability. We utilized a sequential extraction procedure and sorption isotherms (monometal and competitive) to evaluate the mobility and distribution of Cd, Cu, Ni, Pb, and Zn in four soils differing in their physicochemical properties: Calcixerollic Xerochrepts (Cx1 and Cx2), Paralithic Xerorthent (Px) and Lithic Haplumbrept (Lh). Most of the metals retained under point B conditions of sorption isotherms were extracted from the more mobile fractions: exchangeable and carbonates, in contrast with the profiles of the original soils where metals were preferently associated with the residual fraction. In soils having carbonate concentration under 6% (Cx1 and Lh), the exchangeable fraction was predominant, whereas in calcareous soils (Cx2 and Px) metals extracted from carbonates predominated. Partitioning profiles were in accordance with the affinity sequences deduced from the initial slope of isotherms and showed that the soils had a greater number of surface sites and higher affinity for Pb and Cu than for Cd, Ni, or Zn. In general, the simultaneous presence of the cations under study increased the percentages of metals released in the exchangeable fraction. The tendency towards less specific forms was more noticeable in Cx2 and Px soils and for Ni, Zn, and Cd. The affinity of inorganic surfaces was larger for Zn than for Cd or Ni, but the affinity of organic surfaces was larger for Cd or Ni than for Zn.     

Solar photocatalysis as strategy for on-site reclamation of agro-wastewater polluted with pesticide residues on farms using a modular facility

Environmental Science and Pollution Research - One of the consequences of phytosanitary treatments applied to crops is the generation of a great volume of agro-wastewater having pesticide residues....     

Competitive sorption of heavy metal by soils. Isotherms and fractional factorial experiments

Competing ions strongly affect heavy metal sorption onto the solid surfaces of soil. This study evaluated competitive sorption of Cd, Cu, Ni, Pb and Zn on three soils: Calcixerollic Xerochrept, Paralithic Xerorthent and Lithic Haplumbrept. Monometal and competitive sorption isotherms were obtained at 25 degrees C. The individual effect of ions on retention of the others was ascertained by a fractional factorial analysis design. Most of the sorption isotherms belonged to type L subtype 2 in the classification of Giles. In competitive sorption the initial linear part was shorter and the knee sharper when compared with monometal sorption isotherms. Parameters related to sorptive capacity, such as Point B, Langmuir monolayer and Freundlich distribution coefficient, were higher in monometal than in competitive sorption, and in basic soils than in acidic soil. Calcium desorbed at different points of the sorption isotherms indicated that cationic exchange with Ca was the main retention mechanism in calcareous soils. For Pb, the ratio Ca desorbed/Pb sorbed was close to one; for Cu, Ni and Zn the ratio ranged from 1.20 to 1.37, probably due to partial dissolution of calcium carbonates by hydrolytic processes during retention. On the other hand, Cd had a ratio around 0.6 reflecting another additional retention mechanism, probably surface complexation. Fractional factorial design confirmed that the presence of the cations investigated reduced the amount of the five metals retained, but the presence of Cu and Pb in the system depressed Ni, Cd and Zn sorption more than the inverse. Cation mobility was enhanced when equilibrium concentration increased and the effect was higher in Ca-saturated soils.     

In situ bioassays with Chironomus riparius larvae to biomonitor metal pollution in rivers and to evaluate the efficiency of restoration measures in mine areas

In this study we evaluate the ability of an in situ bioassay with Chironomus riparius larvae, using larval development and growth as endpoints, to biomonitor water quality and to assess the biological recovery of metal contaminated freshwater ecosystems of mine areas that are subject of restoration measures. The bioassay was carried out in streams located near an abandoned goldmine in North Portugal, throughout an environmental rehabilitation of the mine (2002-2004). During this period, a decrease in the inhibition of larval growth in the metal contaminated stream was observed. The bioassay was also performed in streams located near an active tungsten mine in Central Portugal. Larval growth and development were highly inhibited in the stream that receives acid drainage from the tungsten mine and treated water from the AMD treatment station. The results indicate that the bioassay can be used to evaluate the efficiency of environmental restoration measures in mining areas.     

Application of water quality indices and analysis of the surface water quality monitoring network in semiarid North-Central Chile

Surface water quality has increasing importance worldwide and is particularly relevant in the semiarid North-Central Chile, where agriculture and mining activities are imposing heavy pressure on limited water resources. The current study presents the application of a water quality index in four watersheds of the 29°-33°S realm for the period 1999-2008, based on the Canadian Council of Ministers for the Environment approach and the Chilean regulation for irrigation water quality. In addition, two modifications to the index are tested and a comprehensive characterization of the existing monitoring network is performed through cluster analysis. The basins studied show fairly good water quality in the overall, specially the Limarí basin. On the other hand, the lower index values were obtained for the headwaters of Elqui, associated with the El Indio mining district. The first modification of the indicator (i.e., to consider parameters differentially according to their effect on human health or the environment) did not produce major differences with respect to the original index, given the generally good water quality. The second modification (i.e., to consider as threshold values the more restrictive figures derived from a set of regulations) yielded important differences in the indicator values. Finally, an adequate characterization of the monitoring network was obtained. The results presented spatial coherence and the information can be used as a basis for the optimization of the monitoring network if required.     

<Emphasis Type="Italic">Cylindrospermopsis raciborskii</Emphasis> exudate–Cu complexes: impact on copper dynamics and bioavailability in an aquatic food chain

INTRODUCTION: The increasing contamination of aquatic environments motivates studies on the interactions among natural dissolved organic matter, metals, and the biota. This investigation focused on the organic exudates of the toxic cyanobacteria Cylindrospermopsis raciborskii as a Cu carrier through a three-level aquatic trophic chain (bacteria, protozoa, and copepod). DISCUSSION: The effects of bacteria activity and growth on the metal-organic complexes were evaluated through changes in free Cu(2+) ions, total dissolved, and total particulate Cu. To be sure that the added copper would be complexed to the exudates, its complexing properties were previously determined. The cyanobacteria exudate-Cu complexes were furnished to bacteria that were further used as a food source to the protozoan Paramercium caudatum. This was then furnished as food to the copepod Mesocyclops sp. The results showed that, in general, the cyanobacterial exudates decreased Cu bioavailability and toxicity to the first trophic level (bacteria), but because the heterotrophic bacteria accumulated Cu, they were responsible for the transference for the otherwise low availability metal form. Both the bacteria and protozoan organisms accumulated Cu, but no metal accumulation was detected in the copepods.     

Water quality supply in a Portuguese teaching hospital: monitoring and studies on detection of critical points

Surveillance of drinking water quality is extremely important to human health, assuming greater relevance in hospital environments, especially to those individuals who are immunocompromised. This study is aimed to determine the effect of increasing free chlorine (Cl) concentration in a hospital water network in regard to water quality monitoring and microbial growth control, between 2010 and 2013 in Porto. The average of free Cl concentration in the period under analysis showed some heterogeneity per floor, varying between 0.84 and 1.25 mg/L. In addition, there was a rise in proportion of samples that exceeded WHO guidelines (free Cl ≥ 0.5 mg/L), particularly in the last two years of the same period. With respect to microbial analysis, 22.4% of the samples were positive for Legionella spp., 6.4% for Pseudomonas aeruginosa, 15% and 30.4% for aerobic plate counts at 36 and 22 ºC, respectively. The proportion of positive samples decreased throughout the period under analysis, in particular for Legionella spp. (41.7% in 2010 vs. non-detectable in 2013) and P. aeruginosa (10.8% in 2010 vs. 3.3% in 2013). These results are in accordance with the gradual rise in free Cl concentration (0.78 ± 0.94 mg/L in 2010 vs. 1.16 ± 0.51 mg/L in 2013). In conclusion, a suitable plan for drinking water quality was instituted which resulted in reducing microbiological growth in the waterwork network, improving public health protection. However, the detection of critical points associated with lower levels of free Cl were found on certain floors/points-of-use, requiring the need to improve the monitoring water treatment system and/or implementation of additional technologies.