Characterization of spatial and temporal patterns in surface water quality: a case study of four major Lebanese rivers

In this work, four major Lebanese rivers were investigated, the Damour, Ibrahim, Kadisha, and Orontes, which are located in South, Central, and North Lebanon and Bekaa Valley, respectively. Five sampling sites were considered from upstream to downstream, and 12 sampling campaigns over four seasons were conducted during 2010–2011. Thirty-seven physicochemical parameters and five microbial tests were evaluated. A principal component analysis (PCA) was used for data evaluation. The first PCA, applied to the matrix-containing data that was acquired on all four rivers, showed that each river was distinct in terms of trophic state and pollution sources. The Ibrahim River was more likely to be polluted with industrial and human discharges, while the Kadisha River was severely polluted with anthropogenic human wastes. The Orontes and Damour rivers seemed to have the lowest rates of water pollution, especially the Orontes, which had the best water quality. PCA was also performed on individual data matrices for each river. In all cases, the results showed that the springs of each river have good water quality and are free from severe contamination. The other monitoring sites on each river were likely exposed to human activities and showed important spatial evolution. Through this work, a spatiotemporal fingerprint was obtained for each studied river, defining a “water mass reference” for each one. This model could be used as a monitoring tool for subsequent water quality surveys to highlight any temporal evolution of water quality.

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Linking Excess Nutrients,Light, and Fine Bedded Sediments to Impacts on Faunal Assemblages in Headwater Agricultural Streams1

Griffith, Michael B., F. Bernard Daniel, Matthew A. Morrison, Michael E. Troyer, James M. Lazorchak, and Joseph P. Schubauer‐Berigan, 2009. Linking Excess Nutrients, Light, and Fine Bedded Sediments to Impacts on Faunal Assemblages in Headwater Agricultural Streams. Journal of the American Water Resources Association (JAWRA) 45(6):1475‐1492. Abstract: Biological impairments in streams are typically defined by regulatory agencies in terms of altered invertebrate or fish assemblages. While nutrients, canopy cover, and sediment fines contribute to these impairments, these stressors are often defined, at least in part, by their impacts on periphyton. Path analysis can extend these assessments to impacts on invertebrates and fish by characterizing the direct and indirect relationships among variables along defined model pathways. With data from headwater tributaries in the Little Miami River, Ohio, we tested models of the impacts of nutrients [total nitrogen (TN), total phosphorus (TP), and the nitrogen to phosphorus (N/P) ratio], the percentage of (%) open canopy, and the % sand and fines on three periphyton metrics [periphytic ash‐free dry mass (AFDM), the percent abundance of cyanobacteria (% cyanobacteria), and the percent abundance of Chlorophyta (% Chlorophyta)] and, in turn, on selected invertebrate or fish metrics. Our objective was to develop and evaluate a statistical model that assesses the direct and indirect impacts of excess nutrients on macroinvertebrate and fish in these streams and demonstrate how this approach might be applicable elsewhere. The results suggest indirect pathways for the influences of nutrients, canopy cover, and fine bedded sediments on invertebrates or fish that are mediated by their influences on periphyton. This is in addition to any direct impacts of these stressors on the invertebrate and fish metrics. In most models, all three periphyton metrics increased with % open canopy. Periphytic AFDM increased with TN, while % cyanobacteria decreased. The % cyanobacteria also decreased with % sand and fines, but % Chlorophyta increased. The metrics, percent abundance of (%) three most dominant (macroinvertebrate) taxa, % Trichoptera, and % herbivorous fish all increased with periphytic AFDM, while % climbers, % swimmers, and %Lepomis cyanellus Rafinesque decreased. Lepomis cyanellus is an indicator species, because it is generally common in these streams and relatively tolerant to various common environmental stressors. The % three most dominant macroinvertebrate taxa increased while % Hydropsychidae (Trichoptera) and %L. cyanellus decreased with % cyanobacteria. The % Trichoptera and %L. cyanellus increased with % Chlorophyta. Some macroinvertebrate metrics, such as the % burrowers and number of burrower taxa, did not have any statistically significant relationships with the periphyton metrics but did exhibit a direct pathway with % sand and fines. These analyses illustrate how path analysis can be used to estimate the relationships among the variables in a conceptual model, modify the model, assess the relative importance of different paths, and explore responses resulting from stressors with interacting and indirect impacts.     

Photolysis of beta-blockers in environmental waters

Many drugs such as beta-blockers have been shown to occur in aquatic environments. Even if adequate ecotoxicity data are not available, it is of primary importance to get informations about their fate in environmental waters, particularly about their photofate in sewage treatment plant effluents (STP). The main difficulties when studying pharmaceutical photochemical behaviour in environmental waters, are linked to the very low environmentally relevant concentrations (ng L(-1) to microg L(-1)) which can generate problems in terms of analytical sensitivity. Moreover, the complexity of environmental matrices can modify micropollutants degradation kinetics. The photodegradation of beta-blockers has been compared at two concentration levels (10 microg L(-1) and 10 mg L(-1)) and in two different matrices (pure water and STP effluent). It has been shown that the concentration does not influence beta-blockers degradation pathways, thus allowing the identification of degradation compounds using the 10 mg L(-1) solutions. Although environmental waters speed up the degradation process, the same photoproducts were appeared in both matrices. Using LC-MS/MS, hydroxyl radical additions have been identified as an important degradation pathway for especially pindolol, propranolol and timolol, leading to several positional isomers, corresponding to mono-, di- or tri-hydroxylations. Kinetics of appearance/disappearance of these photoproducts have been studied in STP effluents.     

Determination of soil content in chlordecone (organochlorine pesticide) using near infrared reflectance spectroscopy (NIRS)

Chlordecone is a toxic organochlorine insecticide that was used in banana plantations until 1993 in the French West Indies. This study aimed at assessing the potential of near infrared reflectance spectroscopy (NIRS) for determining chlordecone content in Andosols, Nitisols and Ferralsols from Martinique. Using partial least square regression, chlordecone content conventionally determined through gas chromatography–mass spectrometry could be correctly predicted by NIRS (Q² = 0.75, R² = 0.82 for the total set), especially for samples with chlordecone content <12 mg kg⁻¹ or when the sample set was rather homogeneous (Q² = 0.91, R² = 0.82 for the Andosols). Conventional measures and NIRS predictions were poorly correlated for chlordecone content >12 mg kg⁻¹, nevertheless ca. 80% samples were correctly predicted when the set was divided into three or four classes of chlordecone content. Thus NIRS could be considered a time- and cost-effective method for characterising soil contamination by chlordecone.     

Zn isotope study of atmospheric emissions and dry depositions within a 5 km radius of a Pb–Zn refinery

The present paper examines the use of zinc isotopes as tracers of atmospheric sources and focuses on the potential fractionation of Zn isotopes through anthropogenic processes. In order to do so, Zn isotopic ratios are measured in enriched ores and airborne particles associated with pyrometallurgical activities of one of the major Pb–Zn refineries in France. Supporting the isotopic investigation, this paper also compares morphological and chemical characteristics of Zn particles collected on dry deposition plates (“environmental samples”) placed within a 5 km radius of the smelter, with those of Zn particles collected inside the plant (“process samples”), i.e. dust collected from the main exhaust system of the plant. To ensure a constant isotopic “supply”, the refinery processed a specific set of ores during the sampling campaigns, as agreed with the executive staff of the plant. Enriched ores and dust produced by the successive Zn extraction steps show strong isotope fractionation (from ?0.66 to +0.22‰) mainly related to evaporation processes within the blast furnaces. Dust from the main chimney displays a δ⁶⁶Zn value of ?0.67‰. Application of the Rayleigh equation to evaluate the fractionation factor associated with the Zn vapor produced after a free evaporation gives a range of α_ore/vapor from 1.0004 to 1.0008. The dry deposits, collected on plates downwind of the refinery, display δ⁶⁶Zn variations of up to +0.7‰. However, it is to be noted that between 190 and 1250 m from the main chimney of the refinery, the dry deposits show a high level of large (>10 μm) Zn, S, Fe and O bearing aggregates characterized by positive δ⁶⁶Zn values (+0.02 to +0.19‰). These airborne particles probably derive from the re-suspension of slag heaps and local emissions from the working-units. In contrast, from 1720 to 4560 m, the dry deposits are comprised of small (PM10) particles, including spherical Zn-bearing aggregates, showing negative δ⁶⁶Zn values (?0.52 to ?0.02‰). Our results suggest that the source of the distal dry fallouts is the main chimney plume, whose light Zn isotopic signature they preserve. Based on Zn isotopic analysis in combination with morphological and chemical characteristics of airborne particles, the present study suggests the traceability of smelter dusts by Zn isotopes.     

Multidimensional validation of a numerical model for simulating a DNAPL release in heterogeneous porous media

A fixed-volume release of 1,2-DCE, tracked in space and time with a light transmission/image analysis system, provided a data set for the infiltration, redistribution, and immobilisation of a dense non-aqueous phase liquid (DNAPL) in a heterogeneous porous medium. The two-dimensional bench scale flow cell was packed with a spatially correlated, random heterogeneous distribution of six sand types. In order to provide the necessary modelling parameters, detailed constitutive relationships were measured at the local scale for the six sands. These experiments revealed that nonwetting phase (NWP) relative permeability-saturation (k(rN)-S(W)) relationships are strongly correlated to sand type. Trends in the best-fit k(rN)-S(W) parameters reflected a positive correlation between mean grain diameter and the maximum NWP relative permeability, k(rN)(max). Multiphase flow simulations of the bench scale experiment best reproduced the experimental observations, producing excellent matches in both time and space, when the measured, correlated local scale k(rN)-S(W) relationships were employed.     

High relatedness and inbreeding in two species of haplodiploid eusocial thrips (Insecta: Thysanoptera) revealed by microsatellite analysis

Relatedness and inbreeding coefficients were estimated for Oncothrips tepperi and O. habrus, two species of eusocial gall-forming thrips, using data from two microsatellite loci. Relatedness between sets of individuals (sexes and castes) for O. tepperi ranged from 0.5 to 0.85 and for O. habrus estimates were centered around 0.5. Multiple mating in O. habrus was implicated in lowering relatedness within a gall. We estimated the inbreeding coefficient to be 0.38 for both species, the highest estimates known for eusocial insects. Our findings imply that high relatedness and inbreeding are important for the evolution and form of social behavior in Australian gall-forming Thysanoptera. Received: 14 November 1997 / Accepted after revision: 14 March 1998     

Combined Non-Catalytic Reduction of NOx and SO2 by Ammonia Liquor during Staged Fluidized-Bed Combustion

Emissions of NOx and SO2 were monitored in the presence of ammonia liquor in a 0.09 m2 and 2 m high stainless-steel fluidized-bed combustor. Experiments were carried out at 2 m/s fluidizing velocity, 40% excess air, and 870 °C bed temperature. Ammonia liquor with 7% ammonia by weight was injected into the freeboard of the combustor 52 cm above the distributor through a water-cooled injector. A 65 : 34 primary/secondary air ratio was maintained throughout the investigation. Approximately 70% of NO and 20% of SO2 was reduced at an NH3/NO molar ratio of 2 : 1, respectively. However, a higher reduction in SO2 emissions (62%) was achieved at a very high NH3/NO molar ratio of 7 : 1. These experiments showed that ammonia addition did have a significant effect in SO2 reduction if injected in an excess amount. The injection of ammonia liquor combined with staged combustion was found to be very effective in reducing NOx emissions. A reduction of about 50% was achieved at an NH3/NO molar ratio of 0.6 : 1 which is also coupled with a very low level of ammonia in the flue.     

Combining polar organic chemical integrative samplers (POCIS) with toxicity testing to evaluate pesticide mixture effects on natural phototrophic biofilms

Polar organic chemical integrative samplers (POCIS) are valuable tools in passive sampling methods for monitoring polar organic pesticides in freshwaters. Pesticides extracted from the environment using such methods can be used to toxicity tests. This study evaluated the acute effects of POCIS extracts on natural phototrophic biofilm communities. Our results demonstrate an effect of POCIS pesticide mixtures on chlorophyll a fluorescence, photosynthetic efficiency and community structure. Nevertheless, the range of biofilm responses differs according to origin of the biofilms tested, revealing spatial variations in the sensitivity of natural communities in the studied stream. Combining passive sampler extracts with community-level toxicity tests offers promising perspectives for ecological risk assessment.     

Organochlorine pesticide in fresh and pasteurized cow's milk from Kampala markets

Fresh and pasteurized milk samples from Kampala markets were analyzed for organochlorine pesticides using a gas chromatograph equipped with an electron capture detector. Five organochlorine pesticides, namely; aldrin, dieldrin, endosulfan, lindane, DDT and its metabolites were detected in the milk samples and confirmed with a gas chromatograph equipped with a mass spectrometer [GC-MS]. The mean values are expressed in mg kg⁻¹ milk fat (mf) basis. The mean concentration in the fresh milk (n = 54) were: 0.026 ± 0.003 mg kg⁻¹ mf; 0.002 ± 0.0003 mg kg⁻¹, below the detection limit; 0.007 ± 0.003 mg kg⁻¹, 0.009 ± 0.002 mg kg⁻¹ milk fat for lindane, endosulfan dieldrin and aldrin, respectively. The mean concentrations of p,p′-DDE; p,p′-DDT and o,p′-DDT were 0.009 ± 0.002 mg kg⁻¹; 0.033 ± 0.007 mg kg⁻¹ and 0.008 ± 0.001 mg kg⁻¹ mf, respectively in the fresh milk samples.In the pasteurized milk samples (n = 47), the mean concentrations recorded were: 0.008 ± 0.003 mg kg⁻¹, 0.025 ± 0.004 mg kg⁻¹, and 0.007 ± 0.001 mg kg⁻¹, respectively for p,p′-DDE; p,p′-DDT and o,p′-DDT.Alpha and beta-endosulfan recorded the concentration below the detection limit and the mean of 0.022 ± 0.001 mg kg⁻¹ mf, 0.005 ± 0.002 mg kg⁻¹ mf, and 0.006 ± 0.0002 mg kg⁻¹ mf, respectively for lindane, dieldrin and aldrin. Although, most of the residues detected were above the residue limits set by the FAO/WHO (2008), bioaccumulation of these residues is likely to pose health risks to the consumers of milk in Uganda.