Structure of Mn-Zr mixed oxides catalysts and their catalytic performance in the gas-phase oxidation of chlorocarbons

The catalytic activity and selectivity of manganese zirconia mixed oxides were evaluated for the oxidation of two common chlorinated pollutants found in waste streams, namely 1,2-dichloroethane (DCE) and trichloroethylene (TCE). Mixed oxides with varying Mn-Zr content were prepared by coprecipitation via nitrates, and subsequent calcination at 600 degrees C for 4 h in air. These catalysts were characterised by means of several techniques such as atomic emission spectrometry, N2 adsorption-desorption, powder X-ray diffraction, temperature-programmed desorption of ammonia, pyridine adsorption followed by diffuse reflectance infrared spectroscopy and temperature-programmed reduction with hydrogen. The active catalytic behaviour of Mn-Zr mixed oxides was ascribed to a substantial surface acidity combined with readily accessible active oxygen species. Hence, the mixed oxide with 40 mol% manganese content was found to be an optimum catalyst for the combustion of both chlorocarbons with a T50 value around 305 and 315 degrees C for DCE and TCE oxidation, respectively. The major oxidation products were carbon dioxide, hydrogen chloride and chlorine. It was observed that the formation of both CO2 and Cl2 was promoted with Mn loading.     

Combined effect of diuron and simazine on photosystem II photochemistry in a sandy soil and soil amended with solid olive-mill waste

Diuron (3-(3,4-dichlorophenyl)- = 1,1-dimethylurea) and simazine (6-chloro-N(2), N(4)-diethyl-1,3,5-triazine-2,4-diamine) are soil-applied herbicides used in olive crops. The objective of this study is to investigate the effect of these herbicides on Photosystem II photochemistry of Olea europaea L., and whether the amendment of soil with an organic waste (OW) from olive oil production industry modifies this effect. For this purpose, herbicide soil adsorption studies, with unamended and OW-amended soil, and chlorophyll fluorescence measurements in adult olive leaves, after one, two and three weeks of soil herbicide treatment and/or OW amendment, were performed. Soil application of these herbicides reduced the efficiency of Photosystem II photochemistry of olive trees due to chronic photoinhibition, and this effect is counterbalanced by the addition of OW to the soil. OW reduces herbicide uptake by the plant due to an increase in herbicide adsorption.     

Heavy metals in untreated/treated urban effluent and sludge from a biological wastewater treatment plant

Background, Aim and Scope

The presence of heavy metals in wastewater is one of the main causes of water and soil pollution. The aim of the present study was to investigate the removal of Cd, Cu, Pb, Hg, Mn, Cr and Zn in urban effluent by a biological wastewater treatment, as well as to quantify the levels of As, Be, Cd, Cr, Cu, Fe, Hg, Mn, Ni, Pb, Sn, Tl, V and Zn in dewatering sludge from the Biological Wastewater Treatment Plant to Ribeirão Preto (RP-BWTP), Brazil.

Materials and Methods

Concentrations of Cd, Cr, Cu, Mn and Pb in wastewater and those of Ni in sludge were determined by atomic absorption spectrophotometry with graphite furnace atomization. Mercury concentrations in wastewater were measured by hydride generation atomic spectrophotometry, and Zn levels were determined by atomic absorption spectrophotometry using acetylene flame. In sludge, the levels of As, Be, Cd, Cr, Cu, Fe, Hg, Mn, Pb, Sn, Tl, V and Zn were determined by inductively coupled plasma-mass spectrometry.

Results

The percentages of removal efficiency (RE) were the following: Hg 61.5%, Cd 60.0%, Zn 44.9%, Cu 44.2%, PB 39.7%, Cr 16,5% and Mn 10.4%. In turn, the mean concentrations (mg/kg) of metals in dewatering sludge followed this increasing order: Tl (<0.03), Hg (0.31), Be (0.43), As (1.14), Cd (1.34), V (59.2), Pb (132.1), Sn (166.1), Cr (195.0), Mn (208.1), Ni (239.4), Cu (391.7), Zn (864.4) and Fe (20537).

Discussion

The relationship between metal levels in untreated wastewater, as well as the removal efficiency are in agreement with previous data from various investigators, It is important to note that metal removal efficiency is not only affected by metal ion species and concentration, but also by other conditions such as operating parameters, physical, chemical, and biological factors.

Conclusions

Metal values recorded for treated wastewater and sludge were within the maximum permitted levels established by the Environmental Sanitation Company (CETESB), São Paulo, Brazil.

Recommendations

There is an urgent need for the authorities who are responsible for legislation on sludge uses in agriculture of establishing safety levels for As, Be, Hg, Sn, Tl and V.

Perspectives

According to the current metal levels, RP-BWTP sludge might be used for agriculture purposes. However, for an environmentally safe use of sewage sludge, further studies including systematic monitoring are recommended. Annual metal concentrations and predicted variations of those elements in the sludge should be monitored.

     

Validation and global uncertainty of a gas chromatographic with mass spectrometry method for fenamidone analysis in grapes and wines

Fenamidone is an imidazolinone fungicide recently introduced in viticulture practices. This work reports the validation and assessment of global uncertainty of a gas chromatographic with mass spectrometry method to analyze fenamidone in grapes and wines. This method consists in a simple and fast liquid-liquid extraction step followed by chromatographic determination. Limits of detection for fenamidone in grapes and wines were, respectively, 0.05 mg/kg and 0.06 mg/L, precision was below 9.4% and average recovery was 89 +/- 5%. In the concentration range from 0.05 to 1.00 mg/kg (or mg/L) of fenamidone, global uncertainty calculated following the EURACHEM/CITAC rules, and also by the Horwitz function, was below 25%. The EURACHEM/CITAC global uncertainty budget used gave lower estimates than those obtained from the Horwitz function.     

Seasonal baseline of nutrients and stable isotopes in a saline lake of Argentina: biogeochemical processes and river runoff effects

The seasonal variability of inorganic and organic nutrients and stable isotopes and their relations with plankton and environmental conditions were monitored in Lake Chasicó. Principal component analysis evidenced the strong influence of the river runoff on several biogeochemical variables. Silicate concentrations were controlled by diatom biomass and river discharge. Higher values of nitrate and soluble reactive phosphorus (SRP) indicated agricultural uses in the river basin. Elevated pH values (～9) inhibiting nitrification in the lake explained partially the dominance of ammonium: ～83 % of dissolved inorganic nitrogen (DIN). The low DIN/SRP ratio inferred nitrogen limitation, although the hypotheses of iron and CO₂ limitation are relevant in alkaline lakes. Particulate organic matter (POM) and dissolved organic matter (DOM) were mainly of autochthonous origin. The main allochthonous input was imported by the river as POM owning to the arid conditions. Dissolved organic carbon was likely top-down regulated by the bacterioplankton grazer Brachionus plicatilis. The δ¹³C signature was a good indicator of primary production and its values were influenced probably by CO₂ limitation. The δ¹⁵N did not evidence nitrogen fixation and suggested the effects of anthropogenic activities. The preservation of a good water quality in the lake is crucial for resource management.     

Assessment of microcystins in lake water and fish (Mugilidae, <Emphasis Type="Italic">Liza</Emphasis> sp.) in the largest Spanish coastal lake

Cyanobacteria dominance and cyanotoxin production can become major threats to humans and aquatic life, especially in warm shallow lakes, which are often dominated by cyanobacteria. This study investigates the occurrence and distribution of microcystins (MCYST) in water, cell-bound and in the tissues of the commercial mugilid Liza sp. in the largest, coastal, Spanish Mediterranean lake (Albufera of Valencia). This is the first report concerning microcystin accumulation in tissues of mugilid fish species. Considerable amounts of microcystins were found in the water and seston, which correlated with development of Microcystis aeruginosa populations in the lake. The MCYST concentrations found in Lake Albufera (mean 1.7 and 17 μg/L and maximum 16 and 120 μg/L in water and seston, respectively) exceeded by one to two orders of magnitude the guideline levels proposed by the World Health Organization and were higher than that reported in other lakes of the Mediterranean zone. The presence of MCYST was found in all the fishes studied and accumulated differently among tissues of the commercial species Liza sp. Toxin accumulation in fish tissues showed that although the target organ for MCYST was the liver, high concentrations of microcystins were also found in other analysed tissues (liver>intestine>gills>muscle). Human tolerable daily intake for microcystins is assessed relative to the WHO guidelines, and potential toxicological risks for humans, wildlife and related ecosystems of the lake are discussed.     

Metal-contaminated potato crops and potential human health risk in Bolivian mining highlands

This study assessed metals in irrigation water, soil and potato crops impacted by mining discharges, as well as potential human health risk in the high desert near the historic mining center of Potosí, Bolivia. Metal concentrations were compared with international concentration limit guidelines. In addition, an ingested average daily dose and minimum risk level were used to determine the hazard quotient from potato consumption for adults and children. Irrigation water maximum concentrations of Cd, Pb and Zn in mining-impacted sites were elevated 20- to 1100-fold above international concentration limit guidelines. Agricultural soils contained total metal concentrations of As, Cd, Pb and Zn that exceeded concentration limits in agricultural soil guidelines by 22-, 9-, 3- and 12-fold, respectively. Potato tubers in mining-impacted sites had maximum concentrations of As, Cd, Pb and Zn that exceeded concentration limits in commercially sold vegetables by 9-, 10-, 16- and fourfold, respectively. Using conservative assumptions, hazard quotients (HQ) for potatoes alone were elevated for As, Cd and Pb among children (range 1.1–71.8), in nearly all of the mining-impacted areas; and for As and Cd among adults (range 1.2–34.2) in nearly all of the mining-impacted areas. Only one mining-impacted area had a Pb adult HQ for potatoes above 1 for adults. Toxic trace elements in a major regional dietary staple may be a greater concern than previously appreciated. Considering the multitude of other metal exposure routes in this region, it is likely that total HQ values for these metals may be substantially higher than our estimates.     

Contamination levels of polychlorinated biphenyls in wild versus cultivated samples of female and male mussels (Mytilus sp.) from the Northwest Coast of Iberian Peninsula—new application for QuEChERS (Quick, Easy, Cheap, Effective, Rugged, and Safe) methodology

A newly analytical method based on QuEChERS extraction followed by gas chromatography with mass spectrometry (GC-MS) analysis was developed and validated for the quantification of 18 PCBs in wild (from Matosinhos Beach, Portugal) and cultivated (from Ria de Arousa, Spain) mussel samples, pooled by sex. Wild animals showed higher PCB levels than cultivated mussels, with males from both origins, presenting an upper contamination profile comparing with females. This fact seems to be correlated with few biometric parameters, but other interdependencies, not addressed herein, such as distinct lipid contents between sexes, as a consequence of the gametogenic stage, may also explain this data. Overall, data reiterate the importance of investigating the presence of PCBs in marine biological samples, which can act both as bioindicators of environmental contamination, either as food quality controls for human health.     

Combined effect of diuron and simazine on photosystem II photochemistry in a sandy soil and soil amended with solid olive-mill waste

Diuron (3-(3,4-dichlorophenyl)- = 1,1-dimethylurea) and simazine (6-chloro-N ², N ⁴-diethyl-1,3,5-triazine-2,4-diamine) are soil-applied herbicides used in olive crops. The objective of this study is to investigate the effect of these herbicides on Photosystem II photochemistry of Olea europaea L., and whether the amendment of soil with an organic waste (OW) from olive oil production industry modifies this effect. For this purpose, herbicide soil adsorption studies, with unamended and OW-amended soil, and chlorophyll fluorescence measurements in adult olive leaves, after one, two and three weeks of soil herbicide treatment and/or OW amendment, were performed. Soil application of these herbicides reduced the efficiency of Photosystem II photochemistry of olive trees due to chronic photoinhibition, and this effect is counterbalanced by the addition of OW to the soil. OW reduces herbicide uptake by the plant due to an increase in herbicide adsorption.     

Decolouration of azo dyes by <Emphasis Type="Italic">Phanerochaete chrysosporium</Emphasis> immobilised into alginate beads

Background, aim and scope  

Because of high discharged volumes and effluent composition, wastewater from the textile industry can be considered as the most polluting amongst all industrial sectors, thus greatly requiring appropriate treatment technologies. Although some abiotic methods for the reduction of several dyes exist, these require highly expensive catalysts and reagents. Biotechnological approaches were proven to be potentially effective in the treatment of this pollution source in an eco-efficient manner. The white-rot fungi are, so far, the most efficient microorganisms in degrading synthetic dyes. This white-rot fungi’s property is due to the production of extracellular lignin-modifying enzymes, which are able to degrade a wide range of xenobiotic compounds because of their low substrate specificity. In this paper, we studied the ability of the white-rot fungus Phanerochaete chrysosporium immobilised into Ca-alginate beads to decolourise different recalcitrant azo dyes such as Direct Violet 51 (DV), Reactive Black 5 (RB), Ponceau Xylidine (PX) and Bismark Brown R (BB) in successive batch cultures. To the best of our knowledge, this is the first study on the immobilisation of P. chrysosporium into Ca-alginate beads for its application in dye decolouration.