Determination of total and available fractions of PAHs by SPME in oily wastewaters: overcoming interference from NAPL and NOM

Background, aim, and scope  

Polycyclic aromatic hydrocarbons (PAHs) are often found in oily wastewaters. Their presence is usually the result of human activities and has a negative effect on the environment. One important step in addressing this problem is to evaluate the effectiveness of PAH removal by biological processes since these are the most cost-effective treatments known today. Many techniques are presently available for PAH determination in wastewaters. Solid phase microextracion (SPME) is known to be one of the most effective techniques for this purpose. When analyzing complex matrices with substances such as natural organic matter (NOM) and non-aqueous phase liquids (NAPL), it is important to differentiate the free dissolved PAH from matrix-bonded PAH. PAHs associated with the bonded fraction are less susceptible to biological treatment. The present study concerns the development of a simple and suitable methodology for the determination of the freely dissolved and the total fraction of PAHs present in oily wastewaters. The methodology was then applied to an oily wastewater from a fuel station retention basin.     

Effects of low concentrations of the phenylurea herbicide diuron on biofilm algae and bacteria

A system of recirculating channels was used in this study to examine the long-term effects (29 d) of environmentally realistic concentrations of the herbicide diuron (from 0.07 to 7 μg L⁻¹) on biofilm communities. The autotrophic activity of biofilms was affected by this herbicide, as reflected by a marked decrease in the photosynthetic efficiency. Diuron exposure also increased chlorophyll-a content and reduced the biovolume of diatom taxa at low concentrations. The effects on bacteria were also remarkable. Bacterial abundance was reduced after a week of exposure to the herbicide at a range of concentrations. Effects were on the number of live bacteria and on the increase in the leucine-aminopeptidase activity. It is suggested that inputs of herbicides to the river ecosystem at low concentrations may cause a chain of effects in the biofilm, which include inhibitory effects on algae but also indirect effects on the relationships between biofilm components.     

Multi-causal and integrated assessment of sustainability: the case of agriculturization in the Argentine Pampas

Assessing the sustainability of complex development processes requires multi-causal and integrated analyses. We develop a system-based methodology, rooted in interdisciplinary discussion and consensus building between 15 experts, to construct a multi-causal diagram which examines the sustainability of the Argentine Pampas′ process of agriculturization. The resulting diagram includes 25 factors and provides a big-picture of the multiple dimensions and interrelations affecting sustainability. According to this examination, the increasing concentration of production and the incorporation of technological innovations, triggered by economic and institutional factors, are the cause of environmental distresses and social changes, whose consequences for sustainability are still highly disputed. Nevertheless, the symptoms of both environmental and social unsustainability are more evident in the case of the extra-Pampean regions than in the Pampas. This suggests that the Pampean agriculture model should not be transferred to these regions without substantial modifications. The experts did not reach consensus on whether the agriculturization process is overall sustainable or unsustainable. Lack of consensus revolved mainly around opposing perspectives regarding the significance of the threats to environmental sustainability. The magnitude of socio-distributive unbalance and loss of rural jobs were also contentious. Yet, the paper shows how the exercise of building a joint causal diagram was undoubtedly helpful for linking piece-meal disciplinary facts, brought in from all fronts, into a comprehensive and coherent picture. Readers should send their comments on this paper to: BhaskarNath@aol.com within 3 months of publication of this issue.     

Failure to confirm previous identification of two putative museum specimens of the Atlantic sturgeon, Acipenser sturio, as the Adriatic sturgeon, A. naccarii

MtDNA analyses were employed to examine the species identification of three preserved museum sturgeon specimens from the River Guadalquivir, two of which were originally described as Acipenser sturio L., 1758 by Hernando (1975; Doñana, Acta Vertd 2: 263–264). Later the same two specimens were identified as A. naccarii Bonaparte, 1836 by Garrido-Ramos et?al. (1997; Mar Biol 129: 33–39) on the basis of morphometric and nuclear DNA analyses. Three different laboratories using independent techniques were unsuccessful in extracting authentic DNA from tissue samples from the three specimens and in obtaining any verifiable PCR product. We cannot confirm the previous molecular identification of two of these specimens by Garrido-Ramos et?al. as A. naccarii. We suggest that these specimens are indeed A. sturio.     

Identification of Anthropogenic Organic Contamination Associated with the Sediments of a Hypereutropic Tropical Lake, Venezuela

The concentrations of organic carbon (Corg), inorganic carbon (Cinorg), organic nitrogen (Norg) and total aromatic (Arom_T) were determined in 25 samples of bottom sediments from the Lake Valencia, Venezuela, as a contribution to the knowledge about pollution by organic compounds in tropical lakes. Results demonstrate that the Corg and Norg concentrations do not show the pollution indexes by themselves. This is a consequence of the masking effect of naturally derived organic matter from the decay of algae and organisms in the water column and terrestrial plants, which are transported to the lake. Nevertheless, the Arom_T concentrations and the normalised Arom_T (normalized to organic carbon) make it possible to detect organic matter of anthropogenic origin, in the Arom_T levels are about nine times higher than those natural. The variation in the band intensity of the IRFT spectra for some functional groups present in the saturate and aromatic hydrocarbon fractions gives an indication of anthropogenic contribution for some zones of the lake. With the ¹H NMR spectra it was not possible to differentiate a natural source from an anthropogenic one in the lake. Naturally occurring organic compounds (eicosane, pentacosane, and hexacosane) were detected with GC technique in the saturated hydrocarbon fraction. The presence of an unresolved complex mixture (UCM) in the GC chromatograms indicates pollution by branched and cyclic hydrocarbons. These compounds are probably produced by the incomplete combustion of oil products. Potentially toxic organic compounds such as anthracene, phenanthrene and chrysene were found in the aromatic hydrocarbon fraction, which despite presenting low concentrations (ppb order) accumulate in the lake sediments along with the natural source organic matter. The main access paths of organic pollutants to the lake are the rivers which cross the two urban and industrial areas (Maracay and Valencia cities). The mixture of polluted sediments with bottom natural sediments and the autochthonous contribution of organic matter mitigate the pollution levels progressively towards the center of the lake.     

Trace metals in sediments of Southeast Pacific Fjords, north region (42.5 degrees to 46.5 degrees S)

Analyses of trace metals in benthic sediments from selected fjords and channels between 41 degrees 30' and 46 degrees 50'S, 75 degrees -72.3 degrees W were made after the CIMAR 1 Fjords expedition co-ordinated by CONA-Chile in 1995; the metals analyzed include Ba, Cd, Co, Cr, Cu, Ni, Pb, Sr, V and Zn. The objective of this study was to establish baseline values for these metals and to compare them with similar studies made in comparable, but geographically distinct, environments. Box core samples were collected at 35 stations and metal analysis was by inductively coupled plasma-atomic emission spectroscopy (ICP-AES) using the MESS-2 reference standard. The ranked abundance by metal was Ba > Sr > V > Zn > Cr > Cu approximately Ni approximately Pb > Co > Cd; these metals were not homogenous across the region and coefficients of variation were >10%. There were distinct groupings by metal and geographical area including the fjords, basins and channels. Depth profiles of the metal concentrations also varied spatially, e.g. Guafo, Laguna San Rafael, Moraleda, Corcovado, Quitralco, and Jacaf were predominantly homogeneous with depth profiles indicative of pristine systems experiencing few human impacts. In contrast, Aysen, Cupquelan and Puyuguapi Fjords had higher concentrations towards the surface, indicating elevated inputs in recent years. No major differences in metal content of the sediments were observed when compared with values from comparable natural systems in the northern hemisphere. Principal component analysis (PCA) grouped several seemingly isolated locations as having the same metal signature and indicated the pattern of dispersion across the region.     

Spatial and temporal variations in inhalable CuZnPb aerosols within the Mexico City pollution plume

We report on the CuPbZn content of PM10 and PM2.5 samples collected from three sites (urban T0, suburban T1 and rural T2) during the Mexico City MILAGRO campaign of March 2006. Daytime city centre concentrations of summation operator CuZnPb(PM10) were much higher (T0 > 450 ng m(-3)) than at the suburban site (T1 < 200 ng m(-3)). Rural site (T2) summation operator CuZnPb(PM10) concentrations exceeded 50 ng m(-3) when influenced by the megacity plume but dropped to 10 ng m(-3) during clean northerly winds. Nocturnal metal concentrations more than doubled at T0, as pollutants became trapped in the nightly inversion layer, but decreased at the rural site. Transient spikes in concentrations of different metals, e.g. a "copper event" at T0 (CuPM10 281 ng m(-3)) and "zinc event" at T1 (ZnPM10 1481 ng m(-3)) on the night of March 7-8, demonstrate how industrial pollution sources produce localised chemical inhomogeneities in the city atmosphere. Most metal aerosols are <2.5 microm and SEM study demonstrates the dominance of Fe, Ti, Ba, Cu, Pb and Zn (and lesser Sn, Mo, Sb, W, Ni, V, As, Bi) in metalliferous particles that have shapes including spherical condensates, efflorescent CuZnClS particles, cindery Zn, and Cu wire. Metal aerosol concentrations do not change in concert with PM10 mass, which is more influenced by wind resuspension than industrial emissions. Metalliferous particles can induce cell damage, and PM composition is probably more important than PM mass, with respect to negative health effects, so that better monitoring and control of industrial emissions would likely produce significant improvements in air quality.     

Effect of the organic loading rate on the performance of anaerobic acidogenic fermentation of two-phase olive mill solid residue

A study of the effect of the organic loading rate (OLR) on the anaerobic acidogenic fermentation of two-phase olive mill solid residue (OMSR) derived from fruits with a low ripening index was carried out in a laboratory-scale completely stirred tank reactor at mesophilic temperature (35 degrees C). Eight experimental runs were carried out at OLRs of 3.2, 5.6, 7.4, 9.6, 11.0, 12.9, 14.0 and 15.1g T-COD/ld, which were equivalent to hydraulic retention times of 50.0, 28.8, 21.8, 16.9, 14.7, 12.4, 11.5 and 10.7d, respectively. The experimental results obtained demonstrated that the optimum value of OLR for the acidogenic fermentation process was 12.9 g T-COD/ld, for which a maximum production of acetic acid was achieved. It was found that inhibition of the process occurred at OLRs higher than 12.9 g T-COD/ld. This was characterized by a significant decrease in the acetic acid concentration in the effluent and an increase in the concentration of other volatile acids that may affect the methanogenic step. The process inhibition was also characterized by the plateau in the curves of the effluent substrate concentration versus the OLR applied. It was found that a first-order kinetics satisfactorily described the influence of non-acetic acid soluble organic matter concentration (S-COD( *)) on the rate of soluble organic matter conversion to acetic acid (R(S-COD)( *)), and the influence of acetic acid concentration (AcH) on the rate of acetic acid production (R(AcH)), while a potential equation type adequately described the influence of acetic acid concentration on the volumetric hydrogen production (R(ACH) ). The kinetic constant for soluble organic matter removal was 0.145 d(-1), while the constant for acetic acid formation was found to be 0.075 d(-1).     

High-impact conservation: invasive mammal eradications from the islands of western México

Islands harbor a disproportionate amount of the earth's biodiversity, but a significant portion has been lost due in large part to the impacts of invasive mammals. Fortunately, invasive mammals can be routinely removed from islands, providing a powerful tool to prevent extinctions and restore ecosystems. Given that invasive mammals are still present on more than 80% of the world's major islands groups and remain a premier threat to the earth's biodiversity, it is important to disseminate replicable, scaleable models to eradicate invasive mammals from islands. We report on a successful model from western México during the past decade. A collaborative effort between nongovernmental organizations, academic biologists, Mexican government agencies, and local individuals has resulted in major restoration efforts in three island archipelagos. Forty-two populations of invasive mammals have been eradicated from 26 islands. For a cost of USD 21,615 per colony and USD 49,370 per taxon, 201 seabird colonies and 88 endemic terrestrial taxa have been protected, respectively. These conservation successes are a result of an operational model with three main components: i) a tri-national collaboration that integrates research, prioritization, financing, public education, policy work, capacity building, conservation action, monitoring, and evaluation; ii) proactive and dedicated natural resource management agencies; and iii) effective partnerships with academic researchers in Mexico and the United States. What is now needed is a detailed plan to eradicate invasive mammals from the remaining islands in the region that integrates the needed additional financing, capacity, technical advances, and policy issues. Island conservation in western Mexico provides an effective approach that can be readily applied to other archipelagos where conservation efforts have been limited.