A review of occurrences and treatment of polynuclear aromatic hydrocarbons in water

The scope of PAH contamination of raw, finished, and distributed waters is reviewed. The concentrations of PAHs in drinking water sources range from nanogram to microgram-per-liter quantities. Conventional treatment (flocculation, sedimentation, chlorination, and filtration) appears to substantially reduce total PAH concentrations present at higher concentrations in source waters. A major factor in this reduction is the removal of PAHs adsorbed onto particulate matter. The role of chlorination is not clear and reactions of PAHs with chlorine may in fact produce products which themselves are deleterious. Activated carbon can further assist in PAH removal. However, it may be inappropriate for treatment of PAHs present at low concentrations. Water entering the distribution system can become recontaminated via contact with reservoirs and pipes coated with coal-tar or asphalt based products.     

Environmental degradation by mud in tropical estuaries

In wet tropical countries, the intense rainfall and the lack of effective restrictions on human activities in the river catchment leads to increased rates of soil erosion. This has increased the sediment loads many times over from the natural level. As a result, estuarine and coastal waters are becoming increasingly muddy with associated losses for society in terms of increased flooding and a degradation of the environment, the fisheries and the economic use of these waters. It is suggested that science-based models be used to predict the fate of mud in estuaries and coastal waters when planning development in river catchments, particularly in wet tropical countries. This would help integrate land and water management. Modelling technology is demonstrated by a combination of field and model studies in four turbid tropical estuaries, namely the Fly River in Papua New Guinea, the Mekong River in Vietnam, the Cimanuk River in Indonesia, and Hinchinbrook Channel in Australia. The final model is adapted to local conditions and extensively uses data assimilation especially for open boundary conditions. There can be a feedback between the hydrodynamics and the mud dynamics when the system silts; in wet tropical countries this can occur rapidly, sometimes in only 30 years. Electronic Publication     

Anion mobility in soils: Relevance to nutrient transport from forest ecosystems

Nutrient transport from forest ecosystems is strongly regulated by the availability of anions in soil solution. Each of the major anions in forest soil solutions has some unique properties which affect its production and mobility. The production of bicarbonate, one of the most common anions, is regulated by soil CO₂ pressure and pH. The mobility of phosphate is most strongly affected by adsorption reactions. The mobility of nitrate is regulated almost solely by biological processes, whereas chloride is relatively uninvolved in either biological or inorganic chemical reactions. Sulfate is intermediate, being involved in both biological and inorganic chemical reactions.Knowing these properties of the major anions, it is possible to assess and to predict the effects of several diverse site manipulations on soil leaching rates. Case studies from a site in Washington State consistently demonstrate the importance of accounting for bicarbonate transformations following site manipulations.Although organic anions are frequently dominant in cold-region soil solutions, very little information on the complex factors affecting their mobilities is available. Further research into organic anion mobility and futher attention to bicarbonate mobility should add greatly to the body of knowledge on nutrient transport processes in forest soils.     

The analysis of free chlorine in the presence of nitrogenous organic compounds

Comparative analyses for aqueous chlorine using Standard Methods indicated that in chlorinated solutions containing nitrogenous organic compounds, none of these methods gave a reliable measurement of free available chlorine. Examination of the cyanuric acid-aqueous chlorine system showed that combined chlorine reacted as if it were free chlorine in all the Standard Methods. The implication of these studies for water and wastewater chlorination is that in waters containing nitrogenous organic compounds, N-Chloro compounds form which may result in an overestimation of the disinfecting potential of the added chlorine, when free chlorine is measured by Standard Methods.     

Chemical contaminants in swimming pools: Occurrence,implications and control

A range of trace chemical contaminants have been reported to occur in swimming pools. Current disinfection practices and monitoring of swimming pool water quality are aimed at preventing the spread of microbial infections and diseases. However, disinfection by-products (DBPs) are formed when the disinfectants used react with organic and inorganic matter in the pool. Additional chemicals may be present in swimming pools originating from anthropogenic sources (bodily excretions, lotions, cosmetics, etc.) or from the source water used where trace chemicals may already be present. DBPs have been the most widely investigated trace chemical contaminants, including trihalomethanes (THMs), haloacetic acids (HAAs), halobenzoquinones (HBQs), haloacetonitriles (HANs), halonitromethanes (HNMs), N-nitrosamines, nitrite, nitrates and chloramines. The presence and concentrations of these chemical contaminants are dependent upon several factors including the types of pools, types of disinfectants used, disinfectant dosages, bather loads, temperature and pH of swimming pool waters. Chemical constituents of personal care products (PCPs) such as parabens and ultraviolet (UV) filters from sunscreens have also been reported. By-products from reactions of these chemicals with disinfectants and UV irradiation have been reported and some may be more toxic than their parent compounds. There is evidence to suggest that exposure to some of these chemicals may lead to health risks. This paper provides a detailed review of various chemical contaminants reported in swimming pools. The concentrations of chemicals present in swimming pools may also provide an alternative indicator to swimming pool water quality, providing insights to contamination sources. Alternative treatment methods such as activated carbon filtration and advanced oxidation processes may be beneficial in improving swimming pool water quality.     

A novel abbreviation standard for organobromine,organochlorine and organophosphorus flame retardants and some characteristics of the chemicals

Ever since the interest in organic environmental contaminants first emerged 50 years ago, there has been a need to present discussion of such chemicals and their transformation products using simple abbreviations so as to avoid the repetitive use of long chemical names. As the number of chemicals of concern has increased, the number of abbreviations has also increased dramatically, sometimes resulting in the use of different abbreviations for the same chemical. In this article, we propose abbreviations for flame retardants (FRs) substituted with bromine or chlorine atoms or including a functional group containing phosphorus, i.e. BFRs, CFRs and PFRs, respectively. Due to the large number of halogenated and organophosphorus FRs, it has become increasingly important to develop a strategy for abbreviating the chemical names of FRs. In this paper, a two step procedure is proposed for deriving practical abbreviations (PRABs) for the chemicals discussed. In the first step, structural abbreviations (STABs) are developed using specific STAB criteria based on the FR structure. However, since several of the derived STABs are complicated and long, we propose instead the use of PRABs. These are, commonly, an extract of the most essential part of the STAB, while also considering abbreviations previously used in the literature. We indicate how these can be used to develop an abbreviation that can be generally accepted by scientists and other professionals involved in FR related work. Tables with PRABs and STABs for BFRs, CFRs and PFRs are presented, including CAS (Chemical Abstract Service) numbers, notes of abbreviations that have been used previously, CA (Chemical Abstract) name, common names and trade names, as well as some fundamental physico-chemical constants.     

Numerical modeling of tracer transport in a contact tank

Chlorine is extensively used to disinfect the drinking water supply. However, the inefficient use of chlorine as a disinfectant can result in the formation of chemical compounds which can have adverse health effects. Numerical models are increasingly being used in the design of efficient chlorine contact tanks. In this paper, details are given of the application of a two-dimensional semi-time-centred implicit QUICK scheme to model the transport of a tracer in a scaled physical model of a serpentine chlorine contact disinfection tank. The model is shown to give good agreement with laboratory measurements in the compartments of the tank where the flow is relatively uniform over the depth.     

Radionuclide and chemical concentrations in mineral waters at Saratoga Springs, New York

A project to characterize the radionuclide and chemical components in natural spring waters in the vicinity of Saratoga Springs, New York (USA) has been completed. As a result of the measured radionuclide and chemical content, eight springs were labeled as mineral waters, whereas three springs contained very low concentrations of these components. The mineral waters were highly enriched in alkaline and alkaline-earth elements, as well as chloride ions. Three isotopes of radium ((224)Ra, (226)Ra, (228)Ra) were detected in the mineral waters and reached concentrations of 1, 20, and 2 Bq/L, respectively. Overall, the (226)Ra isotope constituted about 80% of the total radioactivity measured in the water samples. Dissolved uranium concentrations in the mineral waters were very low (mean approximately 50 mBq/L).     

Natural and man-made organobromine compounds in marine biota from Central Norway

Brominated organic pollutants were found in selected samples of mollusk tissue, fish liver, as well as in the eggs and livers of shag from three sites in Central Norway. More than 80 organobromines were identified owing to the defined isotope ratio acquired by GC/ECNI-MS. However, only a few peaks could be assigned to anthropogenic brominated flame retardants (polybrominated diphenyl ethers). Most of the organobromine compounds detected were unknown or halogenated natural products. The known halogenated natural products MHC-1 and TBA were abundant in all samples and usually between equally abundant, and up to 50 fold more concentrated than the major polybrominated diphenyl ether congener BDE 47. The halogenated natural products BC-2 (2-MeO-BDE 68) and BC-3 (6'-MeO-BDE 47), were on level with BDE 100 which was the second most abundant BDE congener in many samples. The previously identified natural polybrominated hexahydroxanthene derivatives (PBHDs) were detected for the first time in bird eggs. Being major contaminants in bird eggs, PBHDs were only present at low levels in bird liver from nestlings originating from the same clutch. Such differences were detected for several other major contaminants. One unknown tetrabromo compound particularly abundant in mussels from Munkholmen was studied by GC/MS and the molecular ion was detected at m/z 446. The abundance of the most important unknown compounds did not correlate with BDEs and they most likely represent halogenated natural products. This study supports that halogenated natural products have to be treated as serious contaminants of marine coastal waters. Our data suggest that their abundance is highest in habitats along the shoreline. Thorough examination of these compounds in environmental samples is an important task.     

Avoidance and toxicity responses of fish to intermittent chlorination

The ability of fish to actively avoid concentrations of chlorine in a steep, horizontal, laboratory-controlled gradient was found to be species-specific and dependent upon the acclimation temperature, water quality conditions, and the type of chlorine residual tested. Comparison of behavioral avoidances with the results from bioassays using some form of intermittent chlorination, as reported in the literature, indicated that LC₅₀ concentrations (levels that cause the mortality of half the test individuals in a designated time period) usually exceeded avoidance threshold concentrations.This chlorine avoidance study, which was carried out in a field laboratory that utilized New River water for holding and testing procedures, was located at the Glen Lyn power plant in southwestern Virginia. Two basic types of avoidance trials were employed, TRC (total residual chlorine) and chloramine (CRC) exposures. The TRC trials contained variable amounts of free (FRC) and combined residual chlorine (CRC) depending upon water quality, while in chloramine trials, the TRC exposure was mainly comprised of monochloramine with little or no FRC. The first significant avoidance in TRC trials for several fish species tested, varied from 0.05 mg/1 for coho salmon (Oncorhynchus kisutch) to 0.40 for channel catfish (Ictalurus punctatus). Low levels of hypochlorous acid (HOCl), which are considered to be a potentially toxic constituent of FRC, appeared to consistently influence the avoidance response. Initial avoidance concentrations to HOCl ranged from 0.01–0.02 mg/1 for coho salmon to 0.04–0.12 mg/1 for channel catfish, depending upon acclimation temperatures tested. The pH in river water was more influential than temperature in controlling the amount of HOCl present within the FRC at each TRC exposure. Avoidance responses by fish to CRC concentrations were either equal to or greater than TRC exposures and were dependent upon the ammonia-N content. Chloramine and FRC (specifically the HOCl fraction) have been reported to have different mechanisms of toxicity, which offered possible explanations for the differences observed in avoidance behavior. Chlorine residuals discharged from the Glen Lyn power plant in previous years have exceeded the LC₅₀ values reported for many species, although no major fish kills from chlorine have been documented. Behavioral avoidance responses by fish to potentially lethal chlorinated discharges in aquatic receiving systems may be a major mechanism of these populations in adapting to or interacting within these industrially influenced environments.     

Assessing and managing sediment contamination in transitional waters

Sediment contamination remains a global problem, particularly in transitional waters such as estuaries and coastal lagoons, which are the recipients of chemicals from multiple near- and far-field sources. Although transitional waters are highly productive ecosystems, approaches for assessing and managing their sediment contamination are not as well developed as in marine and fresh waters. Further, although transitional waters remain defined by their variable and unique natural water quality characteristics, particularly salinity, the biota inhabiting such ecosystems, once thought to be defined by Remane's “paradox of brackish water”, are being redefined. The purpose of the present paper is to build on an earlier but now dated (> 12 years old) review of methods to assess sediment contamination in estuaries, extending this to all transitional waters, including information on integrative assessments and on management decision-making. The following are specifically discussed: chemical assessments; bioindicators; biomarkers; and, biological surveys. Assessment and management of sediment contamination in transitional waters need to be focused on ecosystem services and, where appropriate and possible, be proactive rather than reactive when uncertainty has been suitably reduced.     

Predicting the transfer of 137Cs to rice plants by a dynamic compartment model with a consideration of the soil properties

The factors governing chlorine transfer from Phaeozem and Greyzem soils to various important crop species (foodstuff and forage) were determined in natural conditions in the Kiev region of Ukraine. The stable chlorine concentration ratio (CR) values were the lowest in apple (0.5+/-0.3) and strawberry (2+/-1), higher in vegetables (5+/-3), seeds (15+/-7) and reached a maximum in straw (187+/-90). The average CR values of 36Cl were estimated for the most important crops using all experimental data on 36Cl and stable chlorine transfer into plants from various soils. It was experimentally shown that boiling potatoes in water leads to an equilibrium between 36Cl specific content in the water and moisture in the cooked potato. The 36Cl processing factor (PF) for boiling various foodstuffs is equal to the ratio of water mass in the cooked foodstuff to the total water mass (in the food and the decoction). 36Cl PF for cereal flour can be estimated as 1. The 36Cl processing factor for dairy products is equal to the ratio of residual water mass in the product to initial water mass in milk. At a 36Cl specific activity in soil of 1 Bq kg-1, the estimated annual dietary 36Cl intake into human organism (adult man) is about 10 kBq. Sixty to seventy percent of the above amount will be taken in via milk and dairy products, 7-16% via meat, 14-16% via bread and bakery items and 8-12% via vegetables. The highest annual 36Cl intake, 10.7 kBq, is predicted for 1-year-old children. The expected effective doses from annual 36Cl intake are higher for younger age groups, increasing from 0.008 mSv in adults to 0.12 mSv in 1-year-old children.     

Environmental significance of nitrogenous organic compounds in aquatic sources

The presence of nitrogenous organic compounds in raw water sources for municipal supplies is of environmental concern because many of them exert significant chlorine demand, while some produce complex stable mutagenic products upon chlorination or are precursors to haloform formation. Seven N-organic compounds have been identified in municipal water concentrates (adenine, 5-chlorouracil, cytosine, guanine, purine, thymine, and uracil) at concentrations ranging from 20 to 860 μg/L. Eight compounds (adenine, cytosine, purine, pyrrole, thymine, tryptophan, tyrosine, and uracil) have been found in filtrates from cultures of either Anabaena flos aquae or Oscillatoria tenuis. Calculated CHCl₃ levels which might have formed at pH 7 in the water supplies were well below the maximum contaminant level (MCL) of 0.1 mg/L proposed by the U.S. Environmental Protection Agency (USEPA) for total trihalogenated methanes. Calculated levels of CHCl₃ which might have been formed under more alkaline conditions, however, were more than 10% of the MCL and were therefore significant. Calculated levels of combined forms of chlorine yielding falsely positive tests for free chlorine in some samples were slightly less or exceeded the 0.5 mg/L free chlorine residual generally taken as an acceptable level of disinfection. The demonstration of a parallel increase in organic nitrogen content with population density in two laboratory grown blue-green algal cultures, and the finding of elevated organic nitrogen values in a water supply sample collected during the occurrence of a blue-green algal bloom, suggested that summer algal bloom occurrence can add considerably to the organic nitrogen content and the trihalomethane potential of water supplies.     

Remediation of water pollution caused by pharmaceutical residues based on electrochemical separation and degradation technologies: A review

In the last years, the decontamination and disinfection of waters by means of direct or integrated electrochemical processes are being considered as a very appealing alternative due to the significant improvement of the electrode materials and the coupling with low-cost renewable energy sources. Many electrochemical technologies are currently available for the remediation of waters contaminated by refractory organic pollutants such as pharmaceutical micropollutants, whose presence in the environment has become a matter of major concern. Recent reviews have focused on the removal of pharmaceutical residues upon the application of other important methods like ozonation and advanced oxidation processes. Here, we present an overview on the electrochemical methods devised for the treatment of pharmaceutical residues from both, synthetic solutions and real pharmaceutical wastewaters. Electrochemical separation technologies such as membrane technologies, electrocoagulation and internal micro-electrolysis, which only isolate the pollutants from water, are firstly introduced. The fundamentals and experimental set-ups involved in technologies that allow the degradation of pharmaceuticals, like anodic oxidation, electro-oxidation with active chlorine, electro-Fenton, photoelectro-Fenton and photoelectrocatalysis among others, are further discussed. Progress on the promising solar photoelectro-Fenton process devised and further developed in our laboratory is especially highlighted and documented. The abatement of total organic carbon or reduction of chemical oxygen demand from contaminated waters allows the comparison between the different methods and materials. The routes for the degradation of the some pharmaceuticals are also presented.     

Use of geochemical data banks in monitoring the natural environment — a case study from Sri Lanka

A survey carried out on the incidence of dental diseases and the distribution of fluoride in drinking water wells and also copper in such waters in Sri Lanka showed the influence of the natural environmental factors on the prevalence of certain geographical diseases. In the case of the geographical variation of dental fluorosis and dental caries it was found that in Sri Lanka, more than any artificially created causes, the natural environmental factors such as mineral occurrences containing the elements concerned, climate, topography, geology, structure, soil, etc. play a very significant role in the geographic variations of elements and hence incidence of diseases. The same was found to be true in the case of copper in potable waters.Two cities in the dry zone of Sri Lanka namely Anuradhapura and Polonnaruwa had a natural fluoride concentration ranging from 0.34 to 4.55 ppm. In some of these regions dental fluorosis was as high as 77.5%. Kandy, situated in the wet zone on the other hand, had in its well waters a low fluoride concentration of less than 0.2 ppm and hence only 13% dental fluorosis. Similarly copper in the well waters of Sri Lanka showed a range of concentrations depending on many natural environmental factors and in some areas far removed from any effects of industrialization still had high copper concentrations of the order of 1–3 ppm, due to the occurrence of copper bearing mineral deposits.It is the aim of this paper to illustrate the use of establishing natural geochemical data banks in monitoring the environment as they would provide useful background values. Any attempt at erecting national or international acceptable levels for the chemical elements must necessarily consider those which are natural to defined environments.     

Influence of air-sea fluxes on chlorine isotopic composition of ocean water: implications for constancy in delta37Cl--a statistical inference

The behaviors of chlorine isotopes in relation to air-sea flux variables have been investigated through multivariate statistical analyses (MSA). The MSA technique provides an approach to reduce the data set and was applied to a set of 7 air-sea flux variables to supplement and describe the variation in chlorine isotopic compositions (delta37Cl) of ocean water. The variation in delta37Cl values of surface ocean water from 51 stations in 4 major world oceans--the Pacific, Atlantic, Indian and the Southern Ocean has been observed from -0.76 to +0.74 per thousand (av. 0.039+/-0.04 per thousand). The observed delta37Cl values show basic homogeneity and indicate that the air-sea fluxes act differently in different oceanic regions and help to maintain the balance between delta37Cl values of the world oceans. The study showed that it is possible to model the behavior of chlorine isotopes to the extent of 38-73% for different geographical regions. The models offered here are purely statistical in nature; however, the relationships uncovered by these models extend our understanding of the constancy in delta37Cl of ocean water in relation to air-sea flux variables.     

GIS-based statistical model for the prediction of flood hazard susceptibility

At present, flood is the most significant environmental problem in the entire world. In this work, flood susceptibility (FS) analysis has been done in the Dwarkeswar River basin of Bengal basin, India. Fourteen flood causative factors extracted from different datasets like DEM, satellite images, geology, soil and rainfall data have been considered to predict FS. Three heuristic models and one statistical model fuzzy Logic (FL), frequency ratio (FR), multi-criteria decision analysis (MCDA) and logistic regression (LR) have been used. The validating datasets are used to validate these models. The result shows that 68.71%, 68.7%, 60.56% and 48.51% area of the basin is under the moderate to very high FS by the MCDA, FR, FL and LR, respectively. The ROC curve with AUC analysis has shown that the accuracy level of the LR model (AUC?=?0.916) is very much successful to predict the flood. The rest of the models like FL, MCDA and FR (AUC?=?0.893, 0.857 and 0.835, respectively) have lesser accuracy than the LR model. The elevation was the most dominating factor with coefficient value of 19.078 in preparation of the FS according to the LR model. The outcome of this study can be implemented by local and state authority to minimize the flood hazard.

     

Abnormal high natural radium concentration in surface waters

Unexpected high 228Ra concentrations, up to 2 Bq 1(-1), were found in waters of a coastal lagoon close to a monazite sand separation plant. Due to their use as process waters in this plant, the initial supposition was a contamination related to its operation. However, it was concluded that these abnormal radium concentrations had a natural origin, springs at the lagoon head area with high 228Ra and 226Ra concentrations. The strong relationship among radium and light rare-earth elements (LREEs), the observed 228Ra/226Ra activity ratio and the rare-earth element pattern in the spring waters suggested that monazite is the main source of nuclides for water, indicating the disturbance of monazite chemical stability by the combined effects of low pH and high salinity. Both factors combined allow relatively low mobility of thorium, but, on the other hand, a relatively high mobility of radium and LREEs.     

Partitioning of metals in sediments from the Odiel River (Spain)

The Odiel River runs through an area known as the Iberian pyrite belt in the province of Huelva in the southwestern corner of the Iberian Peninsula. Its waters are acidic and contain large amounts of heavy metals from erosion and mining activity. In addition, the Odiel River estuary is one of the most industrialized areas in southern Spain and, consequently, receives the discharge of industrial and urban waste. Seventeen sediment samples from the Odiel and its main tributaries were analyzed for this study. The chemical partitioning of metals (Cu, Zn, Cd, Pb, Fe, Ni, Cr and Co) in each sample was determined in four fractions (acid-soluble, reducible, oxidizable and residual). The total content of each of the metals was also determined. The results showed high concentrations of Fe, Cu, Zn, Pb and Cd, undoubtedly as a result of contamination from the mining and industrial activity mentioned above. However, the concentrations of the other metals analyzed were low since there are no sources of pollution by them in the Odiel River. Based on the chemical distribution of metals, we found that Cd, Zn and Cu are the most mobile metals (i.e., metals that can pass easily into the water under changing environmental conditions). Cd is the metal that showed the highest percentages in the acid-soluble fraction (the most labile) and the lowest in the residual fraction. However, Pb, Fe, Cr and Ni are present in the greatest percentages in the residual fraction, which implies that these metals are strongly linked to the sediments.     

Phytoestrogens and mycoestrogens in surface waters — Their sources,occurrence, and potential contribution to estrogenic activity

This review discusses the potential contribution of phytoestrogens and mycoestrogens to in vitro estrogenic activities occurring in surface waters and in vivo estrogenic effects in fish. Main types, sources, and pathways of entry into aquatic environment of these detected compounds were summarized. Reviewed concentrations of phyto/mycoestrogens in surface waters were mostly undetectable or in low ng/L ranges, but exceeded tens of μg/L for the flavonoids biochanin A, daidzein and genistein at some sites. While a few phytosterols were reported to occur at relatively high concentrations in surface waters, information about their potencies in in vitro systems is very limited, and contradictory in some cases. The relative estrogenic activities of compounds (compared to standard estrogen 17β-estradiol) by various in vitro assays were included, and found to differ by orders of magnitude. These potencies were used to estimate total potential estrogenic activities based on chemical analyses of phyto/mycoestrogens. In vivo effective concentrations of waterborne phyto/mycoestrogens were available only for biochanin A, daidzein, formononetin, genistein, equol, sitosterol, and zearalenone. The lowest observable effect concentrations in vivo were reported for the mycoestrogen zearalenone. This compound and especially its metabolites also elicited the highest in vitro estrogenic potencies. Despite the limited information available, the review documents low contribution of phyto/mycoestrogens to estrogenic activity in vast majority of surface waters, but significant contribution to in vitro responses and potentially also to in vivo effects in areas with high concentrations.