Spatial and temporal trends in water quality in a Mediterranean temporary river impacted by sewage effluents

This paper analyzes how changes in hydrological conditions can affect the water quality of a temporary river that receives direct inputs of sewage effluents. Data from 12 spatial surveys of the Vène river were examined. Physico-chemical parameters, major ion, and nutrient concentrations were measured. Analyses of variance (ANOVA) and multivariate analyses were performed. ANOVA revealed significant spatial differences for conductivity and major ion but no significant spatial differences for nutrient concentrations even if higher average concentrations were observed at stations located downstream from sewage effluent discharge points. Significant temporal differences were observed among all the parameters. Karstic springs had a marked dilution effect on the direct disposal of sewage effluents. During high-flow periods, nutrient concentrations were high to moderate whereas nutrient concentrations ranged from moderate to bad at stations located downstream from the direct inputs of sewage effluents during low-flow periods. Principal component analysis showed that water quality parameters that explained the water quality of the Vène river were highly dependent on hydrological conditions. Cluster analysis showed that when the karstic springs were flowing, water quality was homogeneous all along the river, whereas when karstic springs were dry, water quality at the monitoring stations was more fragmented. These results underline the importance of considering hydrological conditions when monitoring the water quality of temporary rivers. In view of the pollution observed in the Vène river, “good water chemical status” can probably only be achieved by improving the management of sewage effluents during low-flow periods.     

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.     

Estimating the aquatic emissions and fate of perfluorooctane sulfonate (PFOS) into the river Rhine

The sources, distribution, levels and sinks of perfluorooctane sulfonate (PFOS) estimated to be released from areas of high population density, have been explored using the river Rhine as a case study. A comparison between modelled and measured data is presented, along with analysis of the importance of PFOS sorption in riverine systems. PFOS releases into the Rhine were estimated to be 325-690 kg/yr based on per capita emission rates of 27-57 μg day(-1) from a population of 33 million living within a 50 km zone either side of the river. Sorption of PFOS to suspended particles and sediments may alter its fate in the aquatic environment. Therefore available measured and modelled partitioning data was assessed, and K(d) values (sorption coefficient) of 7.5 and 20 were selected. This resulted in sediment-water ratios of 23-76 : 1, which are similar to ratios reported in the literature, and resulted in modelled estimates that <20% of the total PFOS entering the Rhine binds to sediments or suspended particles. The calculated discharge from the Rhine to the North Sea based on measured data was 420-2200 kg/yr; our model predictions are in good agreement with these estimates. Emission trends were accurately predicted, suggesting population density can be effectively used as a surrogate for diffuse PFOS emissions from product use, while predicted concentrations were a factor of 2-4 below measured data showing the importance of other sources. Transfer of PFOS to sediment is estimated to be minimal, and consequently discharges to the North Sea are roughly equal to PFOS releases to river water.     

Occurrence and fate of pharmaceutical and personal care products in a sewage treatment works

The occurrence and fate of eight pharmaceutical and personal care products (PPCPs) during sewage treatment has been studied in a pilot-scale treatment plant, comprising a primary settler (2.85 m(3)), an aeration tank (1.845 m(3)) and a secondary clarifier (0.5 m(3)), placed on site at a wastewater treatment works in the north west of the UK. It was fed both with raw sewage and the return liquor produced after sludge centrifugation, thus representing the most common configuration for a municipal sewage treatment plant based on the activated sludge process. Samples were taken at six different locations, including the return liquor stream, and analysed for musk fragrances and pharmaceutically active compounds belonging to various therapeutic groups such as anti-inflammatory drugs, tranquillisers and antiepileptics. Mass balances were conducted for those PPCPs that were quantifiable. The fate of the PPCPs was found to differ according to their physical-chemical characteristics. Anti-inflammatories underwent a degradation process and were almost completely removed from sewage during the biological treatment step. Musk fragrances were only partially removed, through adsorption onto the primary suspended solids and the biomass in the aerobic process, due to their strong lipophilic characteristics. The results of this study provide increasing evidence that the partial removal of these substances through the sewage treatment process contribute to the environmental occurrence of PPCPs. Consequently, existing STPs should be upgraded in order to attenuate the release of these substances into the aquatic environment.     

Occurrences and fate of selected human antibiotics in influents and effluents of sewage treatment plant and effluent-receiving river Yamuna in Delhi (India)

Antibiotics consumption has increased worldwide, and their residues are frequently reported in aquatic environments. It is believed that antibiotics reach aquatic water bodies through sewage. Medicine consumed for healthcare practices are often released into sewage, and after sewage treatment plant, it reaches the receiving water bodies of lakes or rivers. In the present study, we determined the fate of some commonly used antibiotics in a sewage treatment plant (STP) located in Delhi and the environmental concentration of these antibiotics in the Yamuna River, which receives the sewage and industrial effluent of Delhi. There are many reports on antibiotics occurrences in STP and river water worldwide, but monitoring data from the Indian subcontinent is sparse. Samples were taken from a STP and from six sampling sites on the Yamuna River. Several antibiotics were tested for using offline solid-phase extraction followed by high-performance liquid chromatography equipped with photodiode array analysis. Recoveries varied from 25.5–108.8 %. Ampicillin had the maximum concentration in wastewater influents (104.2?±?98.11 μg l^?1) and effluents (12.68?±?8.38 μg l^?1). The fluoroquinolones and cephalosporins had the lower concentrations. Treatment efficiencies varied between 55 and 99 %. Significant amounts of antibiotics were discharged in effluents and were detected in the receiving water body. The concentration of antibiotics in the Yamuna River varied from not detected to 13.75 μg l^?1 (ampicillin) for the compounds investigated.     

Evaluation of Clostridium perfringens as a tracer of sewage contamination in sediments by two enumeration methods

A traditional method of enumerating Clostridium perfringens using membrane filtration (MF) as an indicator of fecal contamination was compared to recently developed rapid method using Rapid Fung Double Tube (RFDT) in an evaluation to characterize the extent of sewage contamination in sediments of the Great Lakes. Evaluation of these two methods included determining C. perfringens concentrations and recovery efficiencies from sewage, sewage-spiked sediments, and water (surface and bottom) and sediment samples collected from two Great Lakes. The RFDT method proved to be a superior method for identifying C. perfringens in lake sediments compared to MF, as it had higher recovery efficiency and was more rapid, reliable, simple, and effective. This study provides biological evidence of the long-term deposition and movement of sewage particulates in the Great Lakes environment and demonstrates the potential usefulness of C. perfringens as a tracer for sewage contamination using a reliable enumeration method.     

Statistical analysis of trends in organic pollution and pollution by nutrients at selected Danube river stations

The paper describes an application of a statistical analysis for estimating long-term trends in pollutant concentrations of selected pollutants in the Danube river. The results show the changes of concentrations of NH(4)(+)-N, NO(3)(-)-N, PO(4)(3-)-P, total P, BOD(5) and COD(Cr) in a ten year period with the aim to find how the concentrations vary in the whole stretch of this river. The study was based on the data collected in the frame of Transnational Monitoring Network of the ICPDR. To obtain plausible results we have chosen statistical methods, such as tests based on the Spearman correlation coefficient and median regression, which are not sensitive to departures from normality as high skewness or outliers.     

Partition of heavy metals in a tropical river system impacted by municipal waste

A research program was established to identify the governing factors for the partition coefficient (K _D ) of heavy metals between suspended particulate and dissolved phases in the Day River system a tropical, highly alluvial aquatic system, in Vietnam. The targeted river system, draining an urbanized–industrialized catchment where discharged wastewater is mostly untreated, could be separated into the least impacted, pristine area, and the most impacted, polluted area. Organic matter degradation was shown to govern the variation of parameters like total organic carbon, biochemical oxygen demand, chemical oxygen demand, nutrients, conductivity, or redox potential. Heavy metals in both dissolved and particulate phases were enriched in severely polluted area because of wastewater inflow that contains concentrated metals and intensification of metal influx from sediment. Results show log K _D in the order Mn?<?As?<?Zn?<?Hg?<?Ni?<?Cu?<?Cd?<?Co?<?Pb?<?Cr?<?Fe and As?<?Zn?<?Ni?<?Mn?<?Cr?<?Cu?<?Co?<?Fe in the polluted zone and the pristine zone, respectively. A decreasing tendency of partition coefficients of 11 heavy metals considered from the pristine to the impacted zones was observed. Three explanations for the difference are: (1) increase of solubility of most heavy metals in low redox potential, (2) competition for the binding sites with major and minor cations, and (3) complexation with dissolved organic matter concentrated in municipal waste impacted water. Apart from domestic waste impact, statistical analysis has contributed to identify the influence of climate condition and hydrological regime to the partition of heavy metals in the area.     

Study of phytopigments in river bed sediments: effects of the organic matter, nutrients and metal composition

Phytopigment estimation has a considerable interest in the evaluation of freshwater bodies' quality, because it takes into account the synergistic effect of nutrients like phosphorus or nitrogen on algal growth producing eutrophication. Furthermore, their increasing concentration constitutes the first step in the formation of biofilms on the surface sediments, adding a new and very important element to the dynamic nature of the surface sediments. In this study the distribution of phytoplankton--in terms of chlorophyll-a, chlorophyll-b, phaeophytin-a, phaeophytin-b, total carotenoids, total chlorophyll, and total phaeophytin--was evaluated in river bed sediments. Samples collected at sites with low levels of nutrients (P,N) and metal concentrations showed lower phytopigment concentrations than those collected at the sampling sites affected by sources of pollution. Phytoplankton concentrations were directly and highly related to the organic matter concentrations--in particular to the humic fraction--as well as to the total nitrogen (N), total phosphorus (P(T)) and available phosphorus (P(A)) concentrations in sediments. In addition, phytoplankton also correlates positively with Cu, Zn, Fe and Al extracted in oxalate, being Cu the variable that most influences the phytopigment growth. These are essential metals for the metabolism of the phytoplankton, so therefore the increase in metal concentrations can increase algal growth, unless they reach toxic levels.     

Multi-objective, decision-based assessment of a water quality monitoring network in a river system

Water quality monitoring network design has historically tended to use experience, intuition and subjective judgement in locating monitoring stations. Better design procedures to optimize monitoring systems need to simultaneously identify significant planning objectives and consider a number of social, economic and environmental constraints. The consideration of multiple objectives may require further decision analysis to determine the preference weights associated with the objectives to aid in the decision-making process. This may require the application of an optimization study to extract such information from decision makers or experts and to evaluate the overall effectiveness of locating strategies. This paper assesses the optimal expansion and relocation strategies of a water quality monitoring network using a two-stage analysis. The first stage focuses on the information retrieval of preference weights with respect to the designated planning objectives. With the aid of a pre-emptive goal programming model, data analysis is applied to obtain the essential information from the questionnaire outputs. The second stage then utilizes a weighted multi-objective optimization approach to search for the optimal locating strategies of the monitoring stations in the river basin. Practical implementation is illustrated by a case study in the Kao-Ping River Basin, south Taiwan.     

Expres: An expert system for assessing the fate of pesticides in the subsurface

The expert system described here is designed to aid regulatory personnel in their assessment of the potential for pesticides to contaminate the soil and groundwater environment. The expert system, known as EXPRES (EXpert system for Pesticide Regulatory Evaluation Simulations), consists of existing numerical models which are used to simulate the transport and transformation of pesticides in the unsaturated zone, coupled with a knowledge-based system that guides the user through the choice of all the necessary information for characterizing the physical, meteorological, hydrogeological, pedological and agricultural settings of typical agricultural regions across Canada, as required by the pesticide model. The expert system is designed to be used as a management tool to aid in policy decisions. Thus, its purpose is to provide an assessment of the potential hazards and to identify if further study is warranted.     

Mercury fate in ageing and melting snow: development and testing of a controlled laboratory system

A snow cover can modify when, to what extent, and in what form atmospherically deposited mercury is released to the underlying surface media and/or back to the atmosphere. Investigations of mercury transport and transformation processes in snow packs are hampered by the difficulty in controlling experimental and melt conditions and due to the huge variability in the composition and physical structure of environmental snow packs. A method was developed that allows the detailed mechanistic investigation of mercury fate in snow that is made, aged and melted under controlled laboratory conditions. A number of control samples established that mercury in indoor air, scavenged during the snow making process, constitutes the dominant source of mercury in the artificial snow. No addition of mercury is required. The amount of mercury in fresh snow was quantitatively (102 and 106% in two experiments) recovered in the dissolved and particulate fractions of the melt water and the vessel head space, confirming a mass balance for mercury and the absence of unquantifiable mercury sources and sinks in the experimental system. In snow made from unmodified tap water, more than half of the mercury present in the snowpack was recovered from the bottom of the snow vessel after all of the snow had melted. Such late elution is indicative of mercury being mostly associated with particles that are filtered by, and retained in, the shrinking snowpack. Addition of salt to the snow-making water at an environmentally realistic pH notably shifted the distribution of mercury in the snowpack from the particulate to the dissolved phase, resulting in more than 60% of the mercury eluting in the dissolved phase of early melt water fractions.     

Spatial and temporal distribution of butyltin compounds in a Northern Chesapeake Bay Marina and river system

This study was designed to: determine dibutyltin (DBT), tributyltin (TBT) and tetrabutyltin (TTBT) bi-weekly for a four month period (June-September 1986) in the Port Annapolis Marina, Mears Marina, Back Creek and Severn River area of Northern Chesapeake Bay; measure DBT, TBT and TTBT for five successive days (Thursday-Monday) to determine possible daily effects (weekday versus weekend) and determine DBT, TBT and TTBT every two hours for one full tidal cycle in the study area. Maximum concentrations of TBT were reported at both Port Annapolis Marina (1801 ng L^–1) and Mears Marina (1171 ng L^–1) during early June followed by significant reductions in TBT during late summer and early fall. All 4 Back Creek Stations also had highest concentrations of TBT in early June; significant reductions occurred during the next three months. The highest concentration of TBT reported in the Severn River (48 ng L^–1) occurred in September. The lowest TBT value (5 ng L^-1) at this station occurred in June. TTBT was not detected in any of the samples. The day of week sampled (Thursday-Monday) during the daily experiments was not found to significantly affect TBT concentrations. TBT evaluations every two hours during the tidal cycle demonstrated that values peaked at 1400 and 1600 hr time intervals. Peak concentrations of TBT occurred during a rising tide. The possible consequence of the measured TBT concentrations for aquatic biota are discussed.     

Assessment of contamination and biomarker responses in two species of herons on the St. Lawrence river

This study was undertaken to validate potential biomarkers of exposure and effects due to chemical contaminants in breedingcolonies of the Great Blue Heron and the Black-crowned Night-Heron on the St. Lawrence River. Eggs and fledglings from both species were collected from many colonies along theRiver. The fledglings from colonies in freshwater and brackishwater were more contaminated by mercury and PCBs than those from estuarine and gulf colonies. With respect to fledglings ofthe two heron species, some morphometric and blood biochemicalmeasurements, including plasma thyroid hormones and retinol, were significantly different among colonies. Significant differences were also observed in liver retinoids, EROD and porphyrins among colonies. The results of this study suggestthat plasma retinoids and thyroid hormones are good biomarkersof exposure and effects, and are sufficiently sensitive to reflect local and regional variations in contamination. Along with the measure of contaminants in egg and plasma, they constitute non-invasive biomarkers which represent an importantcriteria for long term monitoring of wildlife species. It is concluded that the Great Blue Heron is an appropriate sentinelspecies in the surveillance network for the St. Lawrence River.     

Dynamics and quantification of dissolved heavy metals in the Mahanadi river estuarine system,India

Dynamics of heavy metals such as Fe, Mn, Zn, Cr, Cu, Co, Ni, Pb, and Cd in surface water of Mahanadi River estuarine systems were studied taking 31 different stations and three different seasons. This study demonstrates that the elemental concentrations are extremely variable and most of them are higher than the World river average. Among the heavy metals, iron is present at highest concentration while cadmium is at the least. The spatial pattern of heavy metals suggests that their anthropogenic sources are possibly from two major fertilizer plants and municipal sewage from three major towns as well as agricultural runoff. The temporal variations for metals like Fe, Cu, and Pb exhibit higher values during the monsoon season, which are related to agricultural runoff. Concentrations of Ni, Pb, and Cd exceed the maximum permissible limits of surface water quality in some polluted stations and pose health risks. Dissolved heavy metals like Fe, Mn, Cr, Ni, and Pb exhibit a non-conservative behavior during estuarine mixing, while Zn, Cu, and Co distribution is conservative. Distribution of cadmium in the estuarine region indicates some mobilization which may be due to desorption. The enrichment ratio data suggest that various industrial wastes and municipal wastes contribute most of the dissolved metals in the Mahanadi River. The Mahanadi River transports 18.216 × 10³ t of total heavy metals into the Bay of Bengal and the calculated rate of erosion in the basin is 128.645 kg km^− 2 year^− 1.     

Pharmaceutical residues in the river Rhine--results of a one-decade monitoring programme

In this paper, results of an extensive monitoring programme for pharmaceutical residues in the river Rhine are presented. For one decade (1997 until 2006), the occurrence of widely used human pharmaceuticals like analgesics, lipid regulators, antiepileptics and others has been studied at four locations along the river Rhine. The results of more than 500 analyses clearly prove that compounds such as carbamazepine or diclofenac are regularly found in the river Rhine in concentrations up to several hundred ng per litre. Combining concentration levels with data on water flow enables the calculation of transports, which e.g. for carbamazepine or diclofenac were in the range of several tons per year. The evaluation of the long-term monitoring data shows that only a slight decrease in concentration levels as well as in annual transports can be observed and thus the contamination of the river Rhine by pharmaceutical residues during the last decade has to be regarded as almost constant. Seasonal variations can be detected for bezafibrate, diclofenac and ibuprofen, for which the concentrations are much lower in the summer months. A more effective removal during wastewater treatment in the warmer periods of the year seems to be the major reason for those variations. For carbamazepine, no comparable seasonal effect can be found.     

Seasonal ecology of hydrocarbon-utilizing microbes in the surface Waters of a river

Seasonal changes in the microbial communities of the New Calabar Riverwater have been investigated. Analyses of the BOD, pH, salinity, oil and grease levels of effluents of industries sited along the river were also conducted. High hydrocarbon-utilizing microbial populations were found. The percentage of hydrocarbon-utilizing heterotrophic bacteria ranged between 0–98% and 0–68% in the rainy and dry months, respectively. Counts of hydrocarbon-utilizing actinomycetes in the rainy months ranged between 0–95% and 2–55% in the dry months. The hydrocarbon-utilizing yeast population ranged between 1–95% and 2–85% for the rainy and dry months, respectively. Rainy month values for hydrocarbon-utilizing mould population ranged from 0–17% while dry month values ranged from 0–47%. The hydrocarbon-utilizing cyanobacterial population ranged between 0–95% and 0–33% in the rainy and dry months, respectively. Our results suggest that the heterotrophic bacterial and cyanobacterial populations are higher in the rainy months than in the dry months. However, the hydrocarbon-utilizing yeast, mould and actinomycete populations did not show seasonal variation.     

Distributions of lead and cadmium in dust in the vicinity of a sewage sludge incinerator

The content of lead and cadmium in surface dust within a 4 km radius of a sewage sludge incinerator has been investigated. Particular attention was given to Pb and Cd in different size fractions of dust, an aspect not explored in previous studies, and the differences between expressions of contamination as concentration or loading were examined. Despite suggestions from reports that sludge incinerators may have difficulty in complying with emission standards, the present investigation found little evidence for a major contribution to local pollution by the incinerator. Certainly, the highest Cd level was found some 2.2 km downwind of the prevailing wind direction from the incinerator, suggesting some resultant contamination, although the levels do not appear to be excessive. Similar observations apply to Pb contamination of the area. While data of the type produced in this study contribute to an understanding of environmental quality, both loadings and levels need to be considered, as the implications of only consideration one of these may be limited and even misleading.     

Polyfluoroalkyl compounds in the aquatic environment: a review of their occurrence and fate

The occurrence and fate of polyfluoroalkyl compounds (PFCs) in the aquatic environment has been recognized as one of the emerging issues in environmental chemistry. PFCs comprise a diverse group of chemicals that are widely used as processing additives during fluoropolymer production and as surfactants in consumer applications for over 50 years. PFCs are known to be persistent, bioaccumulative and have possible adverse effects on humans and wildlife. As a result, perfluorooctane sulfonate (PFOS) has been added to the persistent organic pollutants (POPs) list of the Stockholm Convention in May 2009. However, their homologues, neutral precursor compounds and new PFCs classes continue to be produced. In general, several PFCs from different classes have been detected ubiquitously in the aqueous environment while the concentrations usually range between pg and ng per litre for individual compounds. Sources of PFCs into the aqueous environment are both point sources (e.g., wastewater treatment plant effluents) and nonpoint sources (e.g., surface runoff). The detected congener composition in environmental samples depends on their physicochemical characteristics and may provide information to their sources and transport pathways. However, the dominant transport pathways of individual PFCs to remote regions have not been conclusively characterised to date. The objective of this article is to give an overview on existing knowledge of the occurrence, fate and processes of PFCs in the aquatic environment. Finally, this article identifies knowledge gaps, presents conclusions and recommendations for future work.     

Water and sediment quality of dry season pools in a dryland river system: the upper Leichhardt River, Queensland, Australia

This article presents the geochemical characteristics and physicochemical properties of water and sediment from twelve semi-permanent, dryland pools in the upper Leichhardt River catchment, north-west Queensland, Australia. The pools were examined to better understand the quality of sediments and temporary waters in a dryland system with a well-established metal contamination problem. Water and sediment sampling was conducted at the beginning of the hydroperiod in May and September 2007. Water samples were analyzed for major solute compositions (Ca, Na, K, Mg, Cl, SO(4), HCO(3)) and water-soluble (operationally defined as the <0.45 μm fraction) metals (Cd, Cu, Pb, Zn). Sediment samples were analyzed for total extractable and bioaccessible metals (As, Cd, Cu, Pb, Zn), elemental composition and grain morphology. At the time of sampling a number of pools contained water and sediment with elevated concentrations, compared to Australian regulatory guidelines, of Cu (maximum: water 28 μg L(-1); sediment 770 mg kg(-1)), Pb (maximum: water 3.4 μg L(-1); sediment 630 mg kg(-1)) and Zn (maximum: water 150 μg L(-1); sediment 780 mg kg(-1)). Concentrations of Cd and As in pools were relatively low and generally within Australian regulatory guideline values. Localized factors, such as the interaction of waters with anthropogenic contaminants from modern and historic mine wastes (i.e. residual smelter and slag materials), exert influence on the quality of pool waters. Although the pools of the upper Leichhardt River catchment are contaminated, they do not appear to be the primary repository of water and sediment associated metals when compared to materials in the remainder channel and floodplain. Nevertheless, a precautionary approach should be adopted to mitigating human exposure to contaminated environments, which might include the installation of appropriate warning signs by local health and environmental authorities.