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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Sensitive determination of cadmium using solidified floating organic drop microextraction-slotted quartz tube-flame atomic absorption spectroscopy

In this study, solidified floating organic drop microextraction (SFODME) by 1-undecanol was combined with slotted quartz tube flame atomic absorption spectrometry (SQT-FAAS) for the determination of cadmium at trace levels. Formation of a complex with 4,4′-dimethyl-2,2′-bipyridine facilitated the extraction of cadmium from aqueous solutions. Several chemical variables were optimized in order to obtain high extraction outputs. Parameters such as concentration of the ligand, pH, and amount of buffer solution were optimized to enhance the formation of cadmium complex. The SFODME method was assisted by dispersion of extractor solvent into aqueous solutions using 2-propanol. Under the optimum extraction and instrumental conditions, the limit of detection and limit of quantitation values obtained for cadmium using the combined methods (SFODME-SQT-FAAS) were found to be 0.4 and 1.3 μg L^?1, respectively. Matrix effects on the method were also examined for tap water and wastewater, and spiked recovery results were found to be very satisfactory.

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Graphical Abstract SFODME-SQT-FAAS system for sensitive determination of cadmium

     

Health risk assessment of heavy metal intake due to fish consumption in the Sistan region,Iran

The heavy metal (Pb, Cd, Cr, and Ni) content of a fish species consumed by the Sistan population and its associated health risk factors were investigated. The mean concentrations of Pb, Cd, and Cr were slightly higher than the standard levels. The Ni content of fish was below the maximum guideline proposed by the US Food and Drug Administration (USFDA). The average estimated weekly intake was significantly below the provisional tolerable intake based on the FAO and WHO standards for all studied metals. The target hazard quotients (THQ) of all metals were below 1, showing an absence of health hazard for the population of Sistan. The combined target hazard quotient for the considered metals was 26.94 × 10^?3. The cancer risk factor for Pb (1.57 × 10^?7) was below the acceptable lifetime carcinogenic risk (10^?5). The results of this study reveal an almost safe level of Pb, Cd, Cr, and Ni contents in the fish consumed by the Sistan population.

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Evaluation of the effectiveness of red mud-supported catalysts in combination with ozone and TiO<Subscript>2</Subscript> in the treatment of solution containing benzene,toluene, and xylene

Ozone and a Fe²⁺/TiO₂-based catalyst were examined in the degradation of a synthetic solution of benzene toluene and xylene (BTX) in an advanced oxidation process (AOP). The catalyst beads were made from the slurry waste of aluminum production process, by inserting the TiO₂ content and subsequent calcination. The reduction of the BTX concentration load was monitored by the reduction of chemical oxygen demand (COD) and BTX concentration. Different levels were used on factors: pH, time of treatment, initial concentration of BTX, and percentage of TiO₂. The process was conducted in a bubble column reactor with the insertion of catalyst beads. A response surface methodology technique (CCD) was used to build a model based on COD reduction results. The model was optimized using the normal-boundary intersection (NBI) algorithm to maximize COD reduction and minimize the variance attributed to the process. Optimization led to COD reductions of 80% in 2 h of experiment. Correlation analysis of coefficient models from experimental data R²_adj was 0.9966, showing a good fit of model data. In the optimized conditions, the possible increase of the biodegradability ratio of the BTX solution, through the biochemical oxygen demand (BOD) and COD, was also analyzed. Under pre-treatment conditions, the BOD/COD ratio was 0.13. After the treatment, it increased to 0.56.

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PAHs in water and surface sediments from Douro River estuary and Porto Atlantic coast (Portugal)—impacts on human health

This study investigated the presence of 16 priority polycyclic aromatic compounds (PAHs) in waters from the Douro River estuary and nearby Atlantic seacoast, which both bath the Porto metropolis. In the area, there is an oil refinery, an important harbour, an intense maritime traffic, small marinas and highly inhabited cities. For the analysis of PAHs, water samples were taken from four sampling sites, at six different times of the year (2011), and extracted by solid-phase extraction (dissolved fraction) and by ultrasound technique (suspended fraction), before their quantification by gas chromatography–mass spectrometry. Results not only proved the ubiquitous distribution of all analysed PAHs in the present habitat, but also that their global amounts (∑₁₆PAHs) were extremely high at all sampling sites. Their average concentrations attained ≈ 55 ng/L and ≈ 52 μg/g dry weight (dw), respectively, in water and surface sediments. Accordingly, the surveyed area was classified as highly polluted by these organics and so, in view of the concentrations, mutagenic/carcinogenic responses in both humans and aquatic animals are possible to occur. The percentages of carcinogenic PAHs for humans (group 1) dissolved in water and in surface sediments were ca. 5 and 6%, respectively. These results are the first reported in the area and can be used as a baseline for future control of the PAHs levels locally while serving the building of global scenarios of PAHs pollution in Europe.

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Graphical abstract Percentage of PAHs, from different categories acordingly to WHO (2016), in both surface sediments and surface waters from Douro River estuary and Porto Atlantic seacoast; group 1 - carcinogenic, group 2A - probably carcinogenic, group 2B - possibly carcinogenic, and group 3 - not classifiable as carcinogenic to humans

     

Assessment of environmentally friendly fuel emissions from in-use vehicle exhaust: low-blend iso-stoichiometric GEM mixture as example

Gasoline–ethanol–methanol fuel blends were formulated with the same stoichiometric air-to-fuel ratio and volumetric energy concentration as any binary ethanol–gasoline blend. When the stoichiometric blends operated in a vehicle, the time period, injector voltage, and pressure for each fuel injection event in the engine corresponded to a given stoichiometric air-to-fuel ratio, and the load was essentially constant. Three low oxygen content iso-stoichiometric ternary gasoline–ethanol–methanol fuel blends were prepared, and the properties were compared with regular-type fuel without added oxygen. One of the ternary fuels was tested using a fleet of in-use vehicles for15 weeks and compared to neat gasoline without oxygenated compounds as a reference. Only a small number of publications have compared these ternary fuels in the same engine, and little data exist on the performance and emissions of in-use spark-ignition engines. The total hydrocarbon emissions observed was similar in both fuels, in addition to the calculated ozone forming potential of the tailpipe and evaporative emissions. In ozone non-attainment areas, the original purpose for oxygenate gasolines was to decrease carbon monoxide emissions. The results suggest that the strategy is less effective than expected because there still exist a great number of vehicles that have suffered the progressive deterioration of emissions and do not react to oxygenation, while new vehicles are equipped with sophisticated air/fuel control systems, and oxygenation does not improve combustion because the systems adjust the stoichiometric point, making it insensitive to the origin of the added excess oxygen (fuel or excess air).

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Graphical abstract Low level ternary blend of gasoline–ethanol–methanol were prepared with the same stoichiometric air–fuel ratio and volumetric energy concentration, based on the volumetric energy density of the pre-blended components. Exhaust and evaporative emissions was compared with a blend having no oxygen in a fleet of 12 in-use vehicles. Vehicles that had suffer a normal deterioration of emissions and do not react to oxygenation, and new vehicles with more sophisticated air/fuel control systems do not improve combustion

     

Multivariate statistical and GIS-based approaches for toxic metals in tropical mangrove ecosystem,southeast coast of India

The heavy metal concentrations in water and sediment samples were investigated in the tropical Muthupet mangrove ecosystem, southeast coast of India. The results demonstrated that, ranges of metals in water comprise of Cd—0.05 to 3.72; Cu—0.5 to 4.43; Pb—6.31 to 17.87; Zn—0.0 to12.91 ppm and sediment comprises of Cd—0.06 to 0.57; Cu—4.46 to 20.59; Pb—2.90 to 21.35; Zn—4.41 to 39.18 ppm. In all the three sites, heavy metals in sediment exhibited significant higher concentrations compared to water, except Cd. The spatial distribution of metals in water and sediment samples followed a similar pattern except Cd with the preponderance of Zn (75% of total metals) followed by Cu and Pb. Muller’s Geoaccumulation indexes (Igeo) showed Cd is a potent pollutant in the ecosystem and moderately contaminated the study area. The aquaculture and agricultural culture practices follow improper disposal of municipal wastages, and idol immersion activities are the potent metallic sources for heavy metal pollution were identified by performing principle component analysis. In order to protect the ecosystem from further contamination, regular monitoring is needed to in order to control the anthropogenic discharges.

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Modified APHA closed-tube reflux colorimetric method for TOC determination in water and wastewater

The analysis of total organic carbon (TOC) by the American Public Health Association (APHA) closed-tube reflux colorimetric method requires potassium dichromate (K₂Cr₂O₇), silver sulfate (AgSO₄), and mercury (HgSO₄) sulfate in addition to large volumes of both reagents and samples. The method relies on the release of oxygen from dichromate on heating which is consumed by carbon associated with organic compounds. The method risks environmental pollution by discharging large amounts of chromium (VI) and silver and mercury sulfates. The present method used potassium monochromate (K₂CrO₄) to generate the K₂Cr₂O₇ on demand in the first phase. In addition, miniaturizing the procedure to semi microanalysis decreased the consumption of reagents and samples. In the second phase, mercury sulfate was eliminated as part of the digestion mixture through the introduction of sodium bismuthate (NaBiO₃) for the removal of chlorides from the sample. The modified method, the potassium monochromate closed-tube colorimetry with sodium bismuthate chloride removal (KMCC-Bi), generates the potassium dichromate on demand and eliminates mercury sulfate. The semi microanalysis procedure leads to a 60% reduction in sample volume and ≈?33.33 and 60% reduction in monochromate and silver sulfate consumption respectively. The LOD and LOQ were 10.17 and 33.90 mg L^?1 for APHA, and 4.95 and 16.95 mg L^?1 for KMCC-Bi. Recovery was between 83 to 98% APHA and 92 to 104% KMCC-Bi, while the RSD (%) ranged between 0.8 to 5.0% APHA and 0.00 to 0.62% KMCC-Bi. The method was applied for the UV-Vis spectrometry determination of COD in water and wastewater. Statistics was done by MINITAB 17 or MS Excel 2016.

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Sulfate exports from multiple catchments in a glaciated forested watershed in western New York, USA

Sulfate () concentrations and fluxes were studied for multiple storm events in the Point Peter Brook watershed, a glaciated, forested watershed located in Western New York, USA. Investigations were performed across one large (696 ha) and three small (1.6–3.4 ha) catchments with varying extent of riparian and wetland areas. Concentrations of in groundwater sources (mean values: 238–910 μmol_c L⁻¹) were considerably greater than concentrations recorded for rainfall (60 μmol_c L⁻¹) and throughfall (72–129 μmol_c L⁻¹). Seasonality in concentrations was most pronounced for valley-bottom riparian waters with maximum concentrations in late winter–spring (February–March) and a minimum in late summer (August). Concentrations of in wetland water were considerably less than riparian water indicating the likelihood of reduction in anoxic wetland conditions. Storm events displayed a dilution pattern in concentrations with a minimum coinciding with the maximum in throughfall contributions. End member mixing analysis (EMMA) was able to predict the storm event concentrations of for four of the six comparisons. Concentrations of at the outlet of the large (696 ha) catchment were much greater than values recorded for the smaller catchments. Exports of in streamflow exceeded the inputs from atmospheric deposition suggesting that watersheds like Point Peter Brook may not show any immediate response to decreases in atmospheric deposition.     

Exports of dissolved ammonium (NH4 +) during storm events across multiple catchments in a glaciated forested watershed

Storm event exports of dissolved were explored for multiple events in the Point Peter Brook watershed (PPBW), a glaciated, forested watershed located in Western New York, USA. Investigations were performed across four catchments (1.6–696 ha) with varying topography and the extent of surface-saturated areas. While wetland and riparian waters were important sources of during non-storm periods, throughfall and litter leachate were the dominant contributors of during storm events. Ammonium concentrations in catchment discharge displayed a sinusoidal seasonal pattern with a maximum during early spring (March) and a minimum in late summer (August–September). Storm event concentrations of in streamflow were much greater than baseflow values and showed a consistent temporal pattern with an increase in concentrations on the hydrograph rising limb, a peak at or before the discharge peak, followed by a decline in concentrations. Storm event patterns of DON were similar to while the patterns of differed from for the summer and fall events. The storm event expression of was attributed to throughfall and throughfall-mediated leaching of the litter layer. The reactive behavior of precluded its use in an end member mixing model (EMMA) for predicting streamflow concentrations. While concentrations of in precipitation and streamflow were high for the spring events, exports of in streamflow were highest for the large and intense storm events. Baseflow concentrations increased with the percent wetland/saturated area in the catchment but the same trend did not hold for storm-event concentrations.     

The Influence of a Coal-Fired Power Plant in Turkey on the Chemical Composition of Rain Water in a Certain Region

In this study, the chemical composition of the rainwater in Yatağan, which is a region surrounding a coal power plant was investigated from February to April 2002. Rainwater samples were obtained from Yatağan, located northwest of Muğla City in Turkey. pH values and concentrations of major ions (Ca²⁺, Na⁺, K⁺, , , ) in the rainwater samples were analyzed. The pH varied from 5.1 to 7.9 with an average of 6.7 which was in alkaline range considering 5.6 as the neutral pH of cloud water in equilibrium with atmospheric CO₂. In the total of 30 rain events, only three events were observed with water in the acidic range (<5.6), which occurred after continuous rains. The equivalent concentration of components followed the order: Ca²⁺ > > Na⁺ > > > K⁺ > H⁺. The anion and cation concentrations in the rainwater samples showed a high sulphate concentration (131 μEq/l), as well as high sodium (40 μEq/l) and calcium (298 μEq/l) concentrations. These values indicate that one probable source of the high sodium concentration is fly ash, after the coal burning process and the power plant can be effective on level concentrations in rainwater. In addition, the dust-rich local and surrounding limestone environment might have caused the high concentration of Ca²⁺ in rainwater of the Yatağan Basin. Due to a large contribution of these cations to the sulphate neutralization action, the rainwater of this region displays only a moderate acidity, which does not cause significant environmental impact.     

Hydrochemistry of Wet Atmospheric Precipitation Over an Urban Area in Northern Indo-Gangetic Plains

Rain water samples were collected to study the chemical composition of wet atmospheric precipitation (first event) over the Lucknow city in the northern Indo-gangetic alluvial plains. The samples were collected in the month of July, 2005 from different sites. The wet precipitation samples were analyzed for pH, EC, major ions (, Cl⁻, , , , F⁻, Na⁺, K⁺, Ca²⁺, Mg²⁺, ) and heavy metals (As, Cd, Al, Co, Cr, Cu, Fe, Mn, Mo, Ni, Hg, Pb, Se, Sn, Ti, V, Zn). The pH values of wet precipitation samples ranged between 6.5 and 8.7. The analysis of linear regression applied to the set of studied variables and computation of neutralization factors showed that neutralization occurred in precipitation samples and Ca²⁺ had the maximum neutralization capacity. It was found that Cl⁻, , Ca²⁺, Mg²⁺, Na⁺ and K⁺ in the precipitation samples originated mainly from crustal/anthropogenic sources in the region. On an average Fe, and Al accounted for >72% of the total concentration of trace metals in the wet precipitation samples followed by Zn (>10%). Enrichment factors calculated for heavy metals over reference background level in seawater and Earth’s crust showed relatively higher enrichment of Zn. The principal component analysis (PCA) identified the possible sources of ionic species and heavy metals in the wet precipitation samples.     

Atmospheric concentrations of nitric acid, sulfur dioxide, particulate nitrate and particulate sulfate, and estimation of their dry deposition on the urban- and mountain-facing sides of Mt. Gokurakuji, Western Japan

Atmospheric concentrations of nitric acid (HNO₃), sulfur dioxide (SO₂), particulate nitrate and particulate sulfate on the urban- and mountain-facing sides of Mt. Gokurakuji were measured from November 2002 to October 2003, in order to evaluate the effects of anthropogenic activity on air quality and dry deposited nitrate and sulfate on the surfaces of pine foliage. The results showed that HNO₃, SO₂ and concentrations were significantly higher (P < 0.05) on the urban-facing side (1.54, 2.48 and 0.65 μg m⁻³, respectively) than the mountain-facing side (0.67, 1.19 and 0.37 μg m⁻³, respectively), while concentrations did not differ significantly between the two sides (urban-facing: 2.80 μg m⁻³; mountain−facing: 2.05 μg m⁻³). Indirect estimates of dry deposition rates of nitrate and sulfate to the surfaces of pine foliage based on the measured concentrations approximately agreed with the measured values determined by the foliar rinsing technique in a previous study. It was found that HNO₃ was the major source (approximately 80%) of dry deposited nitrate on pine foliage, while the contribution from was about equal to that from SO₂. In conclusion, HNO₃ and SO₂ appear to be dominant species reflecting higher dry deposition rates of nitrate and sulfate on the urban-facing side compared to the mountain-facing side of Mt. Gokurakuji.     

Indoor and outdoor PM mass and number concentrations at schools in the Athens area

Simultaneous indoor and outdoor PM₁₀ and PM_2.5 concentration measurements were conducted in seven primary schools in the Athens area. Both gravimetric samplers and continuous monitors were used. Filters were subsequently analyzed for anion species. Moreover ultrafine particles number concentration was monitored continuously indoors and outdoors. Mean 8-hr PM₁₀ concentration was measured equal to 229 ± 182 μg/m³ indoors and 166 ± 133 μg/m³ outdoors. The respective PM_2.5 concentrations were 82 ± 56 μg/m³ indoors and 56 ± 26 μg/m³ outdoors. Ultrafine particles 8-h mean number concentration was measured equal to 24,000 ± 17,900 particles/cm³ indoors and 32,000 ± 14,200 particles/cm³ outdoors. PM₁₀ outdoor concentrations exhibited a greater spatial variability than the corresponding PM_2.5 ones. I/O ratios were close or above 1.00 for PM₁₀ and PM_2.5 and smaller than 1.00 for ultrafine particles. Very high I/O ratios were observed when intense activities took place. The initial results of the chemical analysis showed that accounts for the 6.6 ± 3.5% of the PM₁₀ and for the 3.1 ± 1.4%.The corresponding results for PM_2.5 are 12.0 ± 7.7% for and 3.1 ± 1.9% for . PM_2.5 indoor concentrations were highly correlated with outdoor ones and the regression line had the largest slope and a very low intercept, indicative of no indoor sources of fine particulate . The results of the statistical analysis of indoor and outdoor concentration data support the use of as a proper surrogate for indoor PM of outdoor origin.     

Factors controlling the salinity in groundwater in parts of Guntur district, Andhra Pradesh, India

Groundwater chemistry has been studied to examine the associated hydrogeochemical processes operating for the development of salinity in the groundwater in parts of Guntur district, Andhra Pradesh, India. The study area is underlain by charnockites and granitic gneisses associated with schists of the Precambrian Eastern Ghats. Groundwater is the main resource for irrigation besides drinking. Chemical parameters, pH, EC, TDS, Ca²⁺, Mg²⁺, Na⁺, K⁺, , , Cl⁻, , , F⁻ and SiO₂, are taken into account. Groundwater is of brackish type. Na⁺−Cl⁻ facies dominates the groundwater. Examination of compositional relations and mineral saturation states shows that the ion exchange of Ca²⁺ for adsorbed Na⁺, evapotranspiration, dissolution of soil salts, dissolution of NaCl and CaSO₄, and precipitation of CaCO₃ are the dominant hydrogeochemical processes associated with the groundwater composition in the area. Evapotranspiration causes accumulation of salts in the soil/weathered zone. These salts reach the water table by leaching through infiltrating recharge water. A positive relation between depth to water table and TDS with season supports this inference. The effects of human activities, such as intensive and long-term irrigation, irrigation-return-flow, application of unlimited agricultural fertilizers and recycling of saline groundwater, act to further increase the salinity in the groundwater. Therefore, the groundwater quality increases towards the flow path, while the post-monsoon groundwater shows higher concentrations of TDS, Na⁺, Mg²⁺, Cl⁻, , , F⁻ and SiO₂ ions. The study could help to understand the hydrogeochemical characteristics of the aquifer system for taking effective management measures to mitigate the inferior groundwater quality for sustainable development.     

Leaching of nitrogen, phosphorus, TOC and COD from the biosolids of the municipal wastewater treatment plant of Thessaloniki

Biosolids from the WWTP of Thessaloniki were examined for the leaching of phosphorus (as ), nitrogen (as and ), and organic matter (as TOC and COD), using two tests: (1) a pH static leaching test and (2) a characterization test, relating contaminant release to the liquid to solid (L/S) ratio. Moreover, a Microtox toxicity test was conducted, to examine the pH dependency of the toxicity of the sludge leachate on the Vibrio fischeri bacterium. Maximum phosphorus release was observed at pH < 3 and at pH > 10. Ammonium nitrogen exhibited maximum leachability at near neutral pH conditions, while nitrate nitrogen exhibited a mild increase in the leachate, as the leachant pH increased from 2 to 12. Both TOC and COD exhibited an increase in the leachate concentration, as the leachant pH was increased from 2 to 12. Ecotoxicological analysis showed that maximum toxicity occurred at very low and very high pH-conditions. As liquid-to-solid ratio increased, the leachate concentration (in mg/l) of all parameters studied decreased. The results of the study were used to conduct a release assessment estimate for the case of Thessaloniki.     

Optical Resilience of the Paraíba do Sul River (Brazil) during a Toxic Spill of a Wood-Pulping Factory: The Cataguazes Accident

This study investigates the inherent optical properties (IOP) of a Brazilian river during a non-natural, anthropogenically mediated, toxic spill of a wood-pulping factory (the ‘Cataguazes accident’). The results indicated an outstanding transformation in the river water chromophoric dissolved organic matter (CDOM) pools. For instance, increases in CDOM absorption coefficients, a _CDOM (λ), which were averaged at specific spectral intervals, , ranged from 58-fold at the UV-B and UV-A ranges to 95-fold at the PAR range. As a result, the water color expressed as CDOM absorption at 440 nm, a _CDOM (440), varied from 4.16 to 365.03 m^-1. For S-coefficient, the variations ranged from ∼1.1 to 5.6-fold, respectively, at the 300–650 nm and UV-B range. The variability of S as a proxy of dissolved chromophores was thus clearly influenced by the spectral range used. Optical proportions were also investigated through the use of and S ratios at the UV-B, UV-A, and PAR ranges and, in the case of , also at the NIR range. This approach also showed clear variations between the water samples, likely reflecting changes in the composition of optically active substances in the river system. As a whole, the findings obtained here indicated that both the quantity and quality of the chromophoric material dissolved in the river water were greatly altered by the toxic spill. The changes in the optical properties of the river water, although extreme and likely with no parallel in the literature, were quite rapid as indicated by the optical resilience of the system. Overall, this study indicates that IOP might be thought, and possibly used, as a metric tool for monitoring the state of waters and aquatic ecosystems.     

Novelty Detection – Recognition and Evaluation of Exceptional Water Reflectance Spectra

The aim of environmental surveillance is to monitor known phenomena as well as to detect exceptional situations. Synoptic monitoring of large areas in coastal waters can be performed by remote sensing using multispectral sensors onboard satellites. Many methods are in use which enable the detection and quantification of ‘standard algae’ or specific algae blooms using their known spectral response. The present study focusses on the detection of spectra outside the known range and which are referred to as exceptional spectra. In a first step observations from a one-year period were used to establish the parameterisation of what is defined as ‘normal.’ In a second step observations from a different period were used to test the novelty detection application, i.e. to look for features not occurring in the first period.      

Assessment of water quality of Manchar Lake in Sindh (Pakistan)

Manchar Lake is the largest natural freshwater lake in Pakistan. The Lake has received less fresh water in past few years. In addition, drainage water is being discharged in the Lake through Main Nara Valley Drain (MNVD) since many years. Consequently, concern has grown regarding the water quality of the Lake. The aim of this study was to assess the water quality of Manchar Lake and MNVD and the objectives were to determine physiochemical properties and the concentrations of common cations and anions as well as seven trace metals i.e. Cu, Ni, Zn, Co, Fe, Pb and Cd. The concentration of the trace metals were determined by simultaneous preconcentration and solvent extraction using flame atomic absorption spectrometer. Results of physicochemical parameters of Manchar Lake water samples showed mean pH 8.4 (±0.2), conductivity 2,310.3 (±581.3) μS cm⁻¹ and hardness (as CaCO₃) 213.1 (±62.3) mg l⁻¹. Mean concentrations of cations and anions were Na 521.5 (±49.7), Cl⁻ 413.6 (±225.7), Ca 70.7 (±12.9), Mg 56.2 (±28.9), K 17.6 (±6.5), 0.34 (±0.2) and 0.02 (±0.01) mg l⁻¹. Mean concentrations of trace metals were Zn 15.7 (±1), Fe 12 (±3.5), Pb 9 (±2.7), Cu 8.9 (±7.7), Ni 4.3 (±3.4), Co 4 (±3.4) and Cd 1.1 (±1) μg l⁻¹. MNVD water samples showed mean pH 8.9 (±0.8), conductivity 1,735.7 (±567.8) μS cm⁻¹ and hardness (as CaCO₃) 184.8 (±32.4) mg l⁻¹. In MNWD, the mean concentrations of cations and anions were Na 482.7 (±11.7), Cl⁻ 395.7 (±271.5), Ca 79.1 (±23.5), Mg 54.2 (±28.1), K 26.2 (±21.3), NO⁻³ 0.5 (±0.3) and 0.1 (±0.1) mg l⁻¹. Mean concentrations of trace metals observed in MNWD water were Fe 14.9(±3.5), Cd 8.3 (±9.4), Pb 6.9 (±2.4), Cu 6.6 (±3.1), Zn 6.2 (±1.8), Co 4.5 (±2.7), and Ni 3.5 (±2.9) μg l⁻¹. The pH of both Manchar Lake and MNVD waters and concentration of Pb in Manchar Lake and concentration of Cd in MNVD water were higher than the World Health Organisation’s guideline values for the drinking water quality. The water quality of Manchar Lake was found degraded.     

Chemical speciation in mining affected waters: the case study of Asarel-Medet mine

The inorganic chemical species in Maresh and Luda Yana rivers affected by the Cu– Mo Asarel-Medet mine, Bulgaria were determined during a low-flow and a high-flow period. The mining activities, the weathering and the oxidation processes strongly influenced the physicochemical processes in the whole water system. The main pollution source was a small lake receiving the acid effluents of the mining activities. High levels of SO₄ ^2???, Cu, Mg, Al, Mn and Fe were determined at the mining polluted and affected stations. Cu^2?+? and CuCO₃ ⁰ species (1:1) were present in the reference waters and Cu^2?+? and CuSO₄ ⁰ species (1:1) in the polluted and affected waters; Cu^2?+? species was dominating downstream. Me^2?+? followed by $\rm{MeSO}_{4}^{\kern3pt{0}}$ (Me = Mn, Zn, Cd and Pb), $\rm{PbCO}_{3}^{\kern3pt{0}}$ and $\rm{PbHCO}_{3}^{\kern3pt{+}}$ species as well as $\rm{Fe(OH)}_{2}^{\kern3pt{+}}$ , $\rm{Al(OH)}_{4}^{\kern3pt{-}}$ , $\rm{Al(OH)}_{2}^{\kern3pt{+}}$ , $\rm{Al(OH)}_{3}^{\kern3pt{0}}$ were prevailing in the system. $\rm{MeSO}_{4}^{\kern3pt{+}}$ and $\rm{Me(SO}_{4})_{2}^{\kern3pt{-}}$ (Me = Fe, Al), $\rm{Me(SO}_{4})_{2}^{\kern3pt{2-}}$ (Me = Zn, Cd and Pb), $\rm{Me(SO}_{4})_{3}^{\kern3pt{4-}}$ (Me = Zn, Cd) and $\rm{Cd(SO}_{4})_{4}^{\kern3pt{6-}}$ species polluted and affected waters. The major elements K and Na were mainly Me^?+? species, whereas Ca and Mg were Me^2?+? and $\rm{MeSO}_{4}^{\kern3pt{0}}$ species in different ratios. The concentration of concentration of $\rm{NO}_{2}^{\kern3pt{-}}$ , $\rm{NO}_{3}^{\kern3pt{-}}$ and $\rm{NH}_{4}^{\kern3pt{+}}$ species as well as complex phosphorous species such as H₂ $\rm{PO}_{4}^{\kern3pt{-}}$ , $\rm{FeHPO}_{4}^{\kern3pt{+}}$ , $\rm{HPO}_{4}^{\kern4pt{2-}}$ , $\rm{CaPO}_{4}^{\kern3pt{-}}$ , $\rm{CaHPO}_{4}^{\kern3pt{0}}$ and $\rm{MgHPO}_{4}^{\kern3pt{0}}$ were also calculated. The trace element concentrations decreased downstream due to dilution, sorption processes and precipitation, but the percentage of free metal species, which are more toxic, increased. An exception was iron and aluminum of which the dominant hydroxy colloidal and sulphate species were easily incorporated into the suspended phase.