Heavy metal contamination from mining sites in South Morocco: Monitoring metal content and toxicity of soil runoff and groundwater

The aim of the present work is the assessment of metal toxicity in runoff, in their contaminated soils and in the groundwater sampled from two mining areas in the region of Marrakech using a microbial bioassay MetPLATE™. This bioassay is based on the specific inhibition of the β-galactosidase enzyme of a mutant strain of Escherichia coli, by the metallic pollutants. The stream waters from all sampling stations in the two mines were all very toxic and displayed percent enzyme inhibition exceeding 87% except SWA₄ and SWB₁ stations in mine C. Their high concentrations of copper (Cu) and zinc (Zn) confirm the acute toxicity shown by MetPLATE. The pH of stream waters from mine B and C varied between 2.1 and 6.2 and was probably responsible for metal mobilization, suggesting a problem of acid mine drainage in these mining areas. The bioassay MetPLATE™ was also applied to mine tailings and to soils contaminated by the acidic waters. The results show that the high toxicity of these soils and tailings was mainly due to the relatively concentration of soluble Zn and Cu. The use of MetPLATE™ in groundwater toxicity testing shows that, most of the samples exhibited low metal toxicity (2.7–45.5% inhibition) except GW3 of the mine B (95.3% inhibition during the wet season and 82.9% inhibition during the dry season). This high toxicity is attributed to the higher than usual concentrations of Cu (189 μg Cu l⁻¹) and Zn (1505 μg Zn l⁻¹). These results show the potential risk of the contamination of different ecosystems situated to the vicinity of these two metalliferous sites. The general trend observed was an increase in metal toxicity measured by the MetPLATE with increasing total and mobile metal concentrations in the studied matrices. Therefore, the MetPLATE bioassay is a reliable and fast bioassay to estimate the metals toxicity in the aquatic and solids samples.     

Method for automatic determination of soybean actual evapotranspiration under open top chambers (OTC) subjected to effects of water stress and air ozone concentration

The present study describes an operational method, based on the Katerji et al. (Eur J Agron 33:218-230, 2010) model, for determining the daily evapotranspiration (ET) for soybean inside open top chambers (OTCs). It includes two functions, calculated day par day, making it possible to separately take into account the effects of concentrations of air ozone and plant water stress. This last function was calibrated in function of the daily values of actual water reserve in the soil. The input variables of the method are (a) the diurnal values of global radiation and temperature, usually measured routinely in a standard weather station; (b) the daily values of the AOT40 index accumulated (accumulated ozone over a threshold of 40 ppb during daylight hours, when global radiation exceeds 50 Wm(-2)) determined inside the OTC; and (c) the actual water reserve in the soil, at the beginning of the trial. The ensemble of these input variables can be automatable; thus, the proposed method could be applied in routine. The ability of the method to take into account contrasting conditions of ozone air concentration and water stress was evaluated over three successive years, for 513 days, in ten crop growth cycles, excluding the days employed to calibrate the method. Tests were carried out in several chambers for each year and take into account the intra- and inter-year variability of ET measured inside the OTCs. On the daily scale, the slope of the linear regression between the ET measured by the soil water balance and that calculated by the proposed method, under different water conditions, are 0.98 and 1.05 for the filtered and unfiltered (or enriched) OTCs with root mean square error (RMSE) equal to 0.77 and 1.07 mm, respectively. On the seasonal scale, the mean difference between measured and calculated ET is equal to +5% and +11% for the filtered and unfiltered OTCs, respectively. The ability of the proposed method to estimate the daily and seasonal ET inside the OTCs is therefore satisfactory following inter- and intra-annual tests. Finally, suggestions about the applications of the proposed method for other species, different from soybean, were also discussed.     

Determination of polychlorinated biphenyls and total mercury in two fish species (<Emphasis Type="Italic">Esox lucius</Emphasis> and <Emphasis Type="Italic">Carassius auratus</Emphasis>) in Anzali Wetland,Iran

The Anzali Wetland is one of the most important ecosystems in the north of Iran, and parts of it were registered as a Ramsar site in 1975. However, even though, due to many problems, including eutrophication produced by inflow of excess nutrients and organic materials, the wetland was also listed on the Montreux Record indicating the need to take urgent remedial action. This study was conducted to study the levels of polychlorinated biphenyls (PCBs) and total mercury (THg) in two fish species (Esox lucius and Carassius auratus) as bio-indicators of the ecosystem condition in eastern part of Anzali Wetland. The sampling was carried out in six different periods between years 2009 and 2010. The results showed that the amounts of PCBs in the muscle of northern pike were below the detection limit of gas chromatography, whereas the average concentration in goldfish was 0.449 mg/kg wet weight. Some possible reasons for the higher levels of PCBs in goldfish in comparison with pike have been discussed. No significant (p < 0.05) correlation was observed between PCBs and biological factors (weight, length, lipid content) for both species. On the other hand, the mean concentration of THg in the muscle of pike and goldfish were 182.22 and 75.27 ng/g dry weight, respectively. Although these concentrations were below US-EPA criterion for human consumption (0.3 mg/kg), it pointed up a significant deterioration of the ecosystem condition during the past years. Finally, statistical analysis revealed a significant correlation between THg with weight and an insignificant correlation with length for pike specimens.     

Preparation and Fundamental Characterization of Cellulose Nanocrystal from Oil Palm Fronds Biomass

The objective of this work was to isolate cellulose nanocrystal (CNC) from oil palm fronds (Elaeis guineensis) and its subsequent characterization. Isolation involves sodium hydroxide/anthraquinone pulping with mechanical refining followed by total chlorine free bleaching (includes oxygen delignification, hydrogen peroxide oxidation and peracetic acid treatment) before acid hydrolysis. Bleaching significantly decreased kappa number and increased α-cellulose percentage of fibers as confirmed by Technical Association of the Pulp and Paper Industry standards. Transmission electron microscopy (TEM), X-ray diffraction, Fourier transform infrared spectroscopy and thermogravimetric analysis revealed that acid hydrolysis along with bleaching improved crystallinity index and thermal stability of the extracted nanocrystals. It was observed that CNC maintained its cellulose 1 polymorph despite hydrolysis treatment. Mean diameter as observed by TEM and average fiber aspect ratio of obtained CNC was 7.44 ± 0.17 nm and 16.53 ± 3.52, respectively making it suitable as a reinforcing material for nanocomposite.     

Application of chemical oxidation to remediate HCH-contaminated soil under batch and flow through conditions

This is the first study describing the chemical oxidation of hexachlorocyclohexanes (HCHs) in contaminated soil under water saturated and unsaturated flow through conditions. Soil contaminated with β-HCH (45 mg kg^?1) and γ-HCH (lindane, 25 mg kg^?1) was sampled from former lindane waste storage site. Efficiency of following treatments was tested at circumneutral pH: H₂O₂ alone, H₂O₂/Fe^II, Na₂S₂O₈ alone, Na₂S₂O₈/Fe^II, and KMnO₄. Experimental conditions (oxidant dose, liquid/solid ratio, and soil granulometry) were first optimized in batch experiments. Obtained results revealed that increasing dose of H₂O₂ improved the oxidation efficiency while in Na₂S₂O₈ system, maximum HCHs were removed at 300 mM. However, oxidation efficiency was slightly improved by Fe^II-activation. Increasing the solid/liquid ratio decreased HCH removal in soil samples crushed to 500 μm while an opposite trend was observed for 2-mm samples. Dynamic column experiments showed that oxidation efficiency followed the order KMnO₄ > Na₂S₂O₈/Fe^II > Na₂S₂O₈ whatever the flow condition, whereas the removal extent declined at higher flow rate (e.g., ~50% by KMnO₄ at 0.5 mL/min as compared to ~30% at 2 mL/min). Both HCH removal and oxidant decomposition extents were found higher in saturated columns than the unsaturated ones. While no significant change in relative abundance of soil mineral constituents was observed before and after chemical oxidation, more than 60% of extractable organic matter was lost after chemical oxidation, thereby underscoring the non-selective behavior of chemical oxidation in soil. Due to the complexity of soil system, chemical oxidation has rarely been reported under flow through conditions, and therefore our findings will have promising implications in developing remediation techniques under dynamic conditions closer to field applications.     

Annual and weekly patterns of ozone and particulate matter in Jeddah,Saudi Arabia

Air pollution has been an increasing concern within the Kingdom of Saudi Arabia and other Middle Eastern countries. In this work the authors present an analysis of daily ozone (O₃), nitrogen oxide (NO_x), and particulate matter (<10 μm aerodynamic diameter; PM₁₀) concentrations for two years (2010 and 2011) at sites in and around the coastal city of Jeddah, as well as a remote background site for comparison. Monthly and weekly variations, along with their implications and consequences, were also examined. O₃ within Jeddah was remarkably low, and exhibited the so-called weekend effect—elevated O₃ levels on the weekends, despite reduced emissions of O₃ precursors on those days. Weekend O₃ increases averaged between 12% and 14% in the city, suggesting that NO_x/volatile organic compound (VOC) ratios within cities such as Jeddah may be exceptionally high. Sites upwind or far removed from Jeddah did not display this weekend effect. Based on these results, emission control strategies in and around Jeddah must carefully address NO_x/VOC ratios so as to reduce O₃ at downwind locations without increasing it within urban locations themselves. PM₁₀ concentrations within Jeddah were elevated compared with North American cites of similar climatology, though comparable to other large cities within the Middle East.

Implications:Daily concentrations of O₃, PM₁₀, and NO_x in and around the city of Jeddah, Saudi Arabia, are analyzed and compared with those of other reference cities. Extremely low O₃ levels, along with a significant urban weekend effect (higher weekend O₃, despite reduced NO_x concentrations), is apparent, along with high levels of PM₁₀ within the city. Urban O₃ in Jeddah was found to be lower than that of other comparable cities, but the strong weekend effect suggests that care must be taken to reduce downwind O₃ levels without increasing them within the city itself. Further research into the emissions and chemistry contributing to the reduced O₃ levels within the city is warranted.     

Sisal/Carbon Fibre Reinforced Hybrid Composites: Tensile, Flexural and Chemical Resistance Properties

The variation of mechanical properties such as tensile and flexural properties of randomly oriented unsaturated polyester based sisal/carbon fibre reinforced hybrid composites with different fibre weight ratios have been studied. The chemical resistance test of these hybrid composites to various solvents, acids and alkalies were studied. The effect of NaOH treatment of sisal fibres on the tensile, flexural and chemical resistance properties of these sisal/carbon hybrid composites has also been studied. The hybrid composites showed an increase in tensile and flexural properties with increase in the carbon fibre loading. The tensile properties and flexural properties of these hybrid composites have been found to be higher than that of the matrix. Significant improvement in tensile properties and flexural properties of the sisal/carbon hybrid composites has been observed by alkali treatment. The chemical resistance test results showed that these untreated and alkali treated hybrid composites are résistance to all chemicals except carbon tetra chloride. Hand lay-up technique was used for making the composites and tests are carried out by using ASTM methods.     

Evaluation of the gene expression changes in Nile tilapia (<Emphasis Type="Italic">Oreochromis niloticus</Emphasis>) as affected by the bio-removal of toxic textile dyes from aqueous solution in small-scale bioreactor

A laboratory-scale bioremediation unit was designed, built and tested for the bio-removal of several Direct textile dyes. Four experiments were carried out to assess the efficiency of the bioremediation unit using Aspergillus niger fungal strain. Three commonly used Direct dyes and textile dyes mixture (simulated effluent: Direct brown, Direct violet, Direct green) were tested in this study. The strain of A. niger was efficient in the removal of the three Direct dyes. The decolorization percentages of the dyes after 24 h of incubation were 56.2, 51.7, and 95.4% for Direct brown, Direct green, Direct violet dyes, respectively. The percentages increased up to 79.4, 86.4, and 96.7% after 72 h of incubation for the same dyes, respectively. The results also showed that the fungal strain reduced the chemical oxygen demand values of simulated dye effluents from 165 to 564 mg/l with most of the dyes. The assessment of bioremediation products on biomodel was conducted using a fresh water fish. The liver and brain of Nile tilapia were tested to evaluate the expression of genes coding for several proteins related to stress such as metallothioneins (MTs), cytochrome P450 (CYP450), and heat shock proteins (HSPs). To assess the alterations in the gene expression, ten animals from each group were killed after 4 weeks of treatment. The results revealed significant increases in the brain and hepatic mRNA levels of all stress protein genes MT, CYP450, Hsp70a, b, and Hsp47 in the fish groups treated with industrial Direct violet, green, and brown dye water. Exposure of tilapia to bioremediation products after treatment with A. niger fungi reduced the over-expression of the stress protein genes in the brain and liver tissues.     

Workshop on Primary Sulfate Emissions

This article is a summary report on a workshop, Measurement Technology and Characterization of Primary Sulfur Oxides Emission from Combustion Sources, sponsored by the EPA Environmental Sciences Research Laboratory at Research Triangle Park, NC, held in Southern Pines, NC. The objectives of the workshop were: to review and discuss current measurement methods and problem areas for sulfur oxides emission with attention focused on sulfuric acid, sulfates, and sulfur-bearing particulate matter; to review and discuss emission data from various combustion sources operating under different conditions, which include various pollutant controls, fuel composition, excess boiler oxygen, etc.; to delineate and recommend areas in need of research and development effort. Scientists were invited to present the results of their studies on primary sulfate emissions. The 3-day workshop devoted one day to measurement technology, a second to characterization, and a third to critical assessment of the presented papers and development of summary working group reports on each half-day session of the initial 2 days. Thirty-one papers were presented by 29 participants on measurements and characterization. Four working group reports were developed and summarized in the last day. Highlights of the papers and reports are briefly reviewed. Workshop proceedings are available as an EPA publication.