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.     

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.     

Determination of potentially bioaccumulating complex mixtures of organochlorine compounds in wastewater: a review

Organic chlorine compounds can be persistent environmental contaminants and may be accumulated through the food chain to the aquatic organisms, to fish and humans, depending basically on their hydrophobic properties. Consequently, there is an interest to measure these organic compounds from both the scientific and regulatory communities. The analytical essays have been improved for measuring specific organic chlorine compounds that present the most toxicological potential (polychlorinated biphenyls [PCBs], certain pesticides and dioxins), although they are tedious and time-consuming procedures. The existing tests to measure adsorbable organic halogens (AOX) or extractable organic halogens (EOX) do not distinguish the more hydrophobic organic chlorine matter. The intention of this paper is to make a review of the existing methods to measure the potentially bioaccumulating organochlorine compounds (OCs) from wastewater and propose a methodology to a standardisation procedure for complex mixtures of OCs in wastewater, such as pulp mill effluents. A new method has been proposed for determining the most hydrophobic part of the extractable organic halogens (EOX(fob)), the lowest reported value is 0.6 microg/l, expressed as chloride, and the relative standard deviation at 20 microg/l is 7% on laboratory samples and 30% on real effluents. This new procedure could be a valuable tool to complement environmental risk assessment studies of wastewater discharges.     

Polar organic pollutants in air: A review of collection and analysis

Pollutants which are capable of being extracted into nonpolar solvent such as hexane have received the greatest attention in environmental monitoring. However, the polar fraction, inherently more difficult to analyze, is currently undergoing closer scrutiny. Sampling methods specifically designed to entrap polar particles and vapors are compared. Ion-exchange and reversed-phase liquid chromatography columns are examples of such specific sampling techniques. Various extraction schemes are presented with their individual problems and capabilities. Although there are numerous papers on the analysis of polar organic pollutants, few report actual measurements of ambient air samples. Current reports on polar organic pollutants measured in air samples are summarized. Polar organics are generally divided into three categories: acidic, basic, and neutral. Analytical methods relating to the following categories of polar organic compounds are reviewed: (1) phenols, mono- and dicarboxylic acids, and sulfonic acids, (2) aliphatic and aromatic amines, and (3) alcohols, aldehydes and ketones, phthalate esters, isocyanates and N-nitrosamines. Derivatization techniques, such as ester formation, are compared to the analysis of the unsubstituted compound. The formation of such derivatives is often the best way to trace specific compounds at very low levels.     

Ecological effects of sulfur dioxide,fluorides, and minor air pollutants: recent trends and research needs

The regulation of the emissions of 'traditional' primary air pollutants (fluorides, sulfur dioxide) has changed the pattern of exposure of ecological systems, with greatly reduced exposure close to sources, but with a smaller effect in some remote areas. Measurements show that recovery is occurring at some sites, in fresh water chemistry (reduced acidity) and in sensitive biota (sustainable fish populations). However, the pattern of change in exposure has not always been simply related to emission reductions. An understanding of responses to recent changes will improve our predictions of the response to future emission changes, both locally and globally. As exposure to 'traditional' pollutants is reduced, the potential for other pollutants to have effects becomes more evident. In the aqueous phase, we need to understand the role of soluble and suspended organics, but this also means explicit recognition of the possibility of phase exchange, and the role of photolytic reactions on plant, soil, and water surfaces. Do highly reactive free radicals in the atmosphere, formed by the action of sunlight on volatile organic compounds, have direct effects on plants? Organic compounds and heavy metals may be bioactive as gases and particles, but for many potentially toxic compounds, the experimental evidence for biotic response is very limited. To evaluate the potential effects of pollutants, we need to understand the pathways by which airborne pollutants enter and react within ecosystems. For vegetation, we have to consider bidirectional fluxes, and distinguish among uptake through stomata, through leaf surfaces, or through roots. There are several challenges for the future. (1) Can we devise experiments that permit exposure of vegetation to gases, particles, and/or aqueous pollutants at 'realistic' concentrations? (2) Can we include the potential interactions with photolytically derived free radicals, and the dynamics of exchange? (3) How do we allow for responses to pollutant mixtures, or the simultaneous exposure to pollutants in gas, particle, and aqueous phases? The recognition of the importance of the dynamic exchange of pollutants between phases will be the key to the development of effective experimental approaches to evaluating cause-effect relationships between pollutant mixtures and ecosystem responses.     

Comparison of VOC and ammonia emissions from individual PVC materials, adhesives and from complete structures

Emission rates of volatile organic compounds (VOCs) and ammonia measured from six PVC materials and four adhesives in the laboratory were compared to the emission rates measured on site from complete structures. Significantly higher specific emission rates (SERs) were generally measured from the complete structures than from individual materials. There were large differences between different PVC materials in their permeability for VOCs originating from the underlying structure. Glycol ethers and esters from adhesives used in the installation contributed to the emissions from the PVC covered structure. Emissions of 2-ethylhexanol and TXIB (2,2,4-trimethyl-1,3-pentanediol diisobutyrate) were common. High ammonia SERs were measured from single adhesives but their contribution to the emissions from the complete structure did not appear as obvious as for VOCs. The results indicate that three factors affected the VOC emissions from the PVC flooring on a structure: 1) the permeability of the PVC product for VOCs, 2) the VOC emission from the adhesive used, and 3) the VOC emission from the backside of the PVC product.     

Polychlorinated diphenyl ethers (PCDEs): environmental levels, toxicity and human exposure: a review of the published literature

This paper reviews the state of the science regarding polychlorinated diphenyl ethers (PCDEs), a group of halogenated aromatic compounds, which are structurally related to polychlorinated biphenyls (PCBs) and polychlorinated dibenzofurans (PCDFs). Special attention is paid to the environmental levels, toxicity, and human exposure. PCDEs have been detected in a number of environmental samples, and their widespread occurrence in the environment is mainly the result of their presence as impurities in chlorophenol preparations. In humans, PCDE congeners have been detected in adipose tissue. As for other persistent organic pollutants (POPs), dietary intake is very probably the main route of exposure to PCDEs for the general population. However, data concerning PCDE levels in foodstuffs are very limited. It is concluded that investigations on experimental toxicity, dietary intake, and potential human health effects of PCDEs are clearly necessary.     

The effects of FeCl3 on the distribution of the heavy metals Cd, Cu, Cr, and Zn in a simulated multimetal incineration system

Recognizing that waste-derived chlorine can enhance heavy metal emissions by forming volatile metallic chlorides during municipal solid waste (MSW) combustion, and that in Taiwan, FeCl3-containing sewage sludge may either be landfilled or coincinerated with other MSW, this study thus investigated the effects of FeCl3 on the speciation and partitioning of heavy metals in a multimetal incineration system by using a tubular furnace and FeCl3-spiked simulated wastes. The molar ratio of chlorine content to heavy metal content (referred to as the Cl/ M ratio), ranging from 3 to 200, was used as a parameter to evaluate the effects of chlorine on the movement of heavy metals between the incinerator discharges. Results indicate that speciation and partitioning were related to the affinity between the chlorine and the heavy metals and between chlorine and hydrogen in the combustion system. The effectiveness of increasing the Cl/M ratio to the formation potential of metallic chlorides and on the shift of heavy metals from the bottom ash to the fly ash and/or the flue gases was found to have in increasing order as follows: Zn>Cu>Cr, a phenomenon basically reflecting the volatility of the heavy metals and their chlorides formed during combustion.     

A review of airborne polycyclic aromatic hydrocarbons (PAHs) and their human health effects

Polycyclic aromatic hydrocarbons (PAHs) are a large group of organic compounds comprised of two or more fused benzene rings arranged in various configurations. PAHs are widespread environmental contaminants formed as a result of incomplete combustion of organic materials such as fossil fuels. The occurrence of PAHs in ambient air is an increasing concern because of their carcinogenicity and mutagenicity. Although emissions and allowable concentrations of PAHs in air are now regulated, the health risk posed by PAH exposure suggests a continuing need for their control through air quality management. In light of the environmental significance of PAH exposure, this review offers an overview of PAH properties, fates, transformations, human exposure, and health effects (acute and chronic) associated with their emission to the atmosphere. Biomarkers of PAH exposure and their significance are also discussed.     

Measurement of organic compound emission using small test chambers

Organic compounds emitted from a variety of indoor materials have been measured using small (166 L) environmental test chambers. The paper discusses: a) factors to be considered in small chamber testing; b) parameters to be controlled; c) the types of results obtained. The following types of materials have been tested: adhesives, caulks, pressed wood products, floor waxes, paints, and solid insecticides. Selected data are presented. For each material, chamber concentrations of organic compounds have been determined for a range of environmental conditions (e.g., air exchange rate, temperature and relative humidity). Emission rates for individual organic compounds, as well as total measured organics, were calculated. The effects of environmental variables on emission rates have been evaluated. Models are used to evaluate the effect of chamber walls and concentration on emission rates.     

Chemical dusts, vapours, and fumes causing asthma

Allergic respiratory disease due to common allergens of organic origin is wwell known. Less familiar, but of increasing importance, are chemicals of organic and inorganic nature, met as dusts, vapours, and fumes. Their relevance is shown in occupational respiratory allergic disorders. Confirmation is given by “real life,” simulated, occupational-type provocation tests. Controlled exposure with minute amounts for brief periods, thus closely simulating allergic sensitivity, can precisely identify etiological causes in often complex exposures. The capacity of these widely different agents in different forms to elicit the different patterns of asthmatic reactions, is a pointed example of their potential role, as well as the role of chemical agents in general. The introduction into indoor environments of such materials demands consideration of their possible allergenic ffects and of the need to recognise the various forms of allergic respiratory reaction they may cause.     

Quantifying summed fullerene nC60 and related transformation products in water using LC LTQ Orbitrap MS and application to environmental samples

The application of engineered nanomaterials increases strongly. Development of analytical techniques and their application to environmental samples is essential for human and environmental risk assessment of the nanoparticles. The objective of this study was to develop a sensitive analytical method to quantify nC(60) in water, using accurate mass screening liquid chromatography-hybrid linear ion trap Orbitrap mass spectrometry. nC(60) can be transformed by oxidation, reduction and photochemical reaction. Therefore, the formation of some transformation products of nC(60) was studied as well. Finally, the developed analytical method was applied to surface water samples from several locations in the Netherlands. The developed method enabled to detect and quantify aqueous concentrations of the summed nC(60) and its transformation products as low as 5 ng/L. It was observed that nC(60) transformation products exceed quantities of the parent C(60). Despite the high sensitivity of the developed method, no nC(60) or transformation products were detected in an array of Dutch surface waters. This might be due to low emissions, losses in the aqueous phase by sedimentation, sorption or further transformation processes.     

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.     

Bioremediation of PAHs and VOCs: Advances in clay mineral–microbial interaction

Bioremediation is an effective strategy for cleaning up organic contaminants, such as polycyclic aromatic hydrocarbons (PAHs) and volatile organic compounds (VOCs). Advanced bioremediation implies that biotic agents are more efficient in degrading the contaminants completely. Bioremediation by microbial degradation is often employed and to make this process efficient, natural and cost-effective materials can serve as supportive matrices. Clay/modified clay minerals are effective adsorbents of PAHs/VOCs, and readily available substrate and habitat for microorganisms in the natural soil and sediment. However, the mechanism underpinning clay-mediated biodegradation of organic compounds is often unclear, and this requires critical investigation. This review describes the role of clay/modified clay minerals in hydrocarbon bioremediation through interaction with microbial agents in specific scenarios. The vision is on a faster, more efficient and cost-effective bioremediation technique using clay-based products. This review also proposes future research directions in the field of clay modulated microbial degradation of hydrocarbons.     

A case study on identification of airborne organic compounds and time courses of their concentrations in the cabin of a new car for private use

The cabin of an automobile can be considered to be a part of the living environment because many people spend long periods of time during business, shopping, recreation or travel activities. However, little is known about the interior air contamination due to organic compounds diffusing from the interior materials used in the interior of automobiles. In the present study, the compounds in the interior air of a new car were identified, and the time courses of their concentrations were examined for over 3 years after the delivery (July, 1999). A total of 162 organic compounds, involving many aliphatic hydrocarbons and aromatic hydrocarbons, were identified. High concentrations of n-nonane (458 microg/m(3) on the day following delivery), n-decane (1301 microg/m(3)), n-undecane (1616 microg/m(3)), n-dodecane (716 microg/m(3)), n-tridecane (320 microg/m(3)), 1-hexadecene (768 microg/m(3)), ethylbenzene (361 microg/m(3)), xylene (4003 microg/m(3)) and 2,2'-azobis(isobutyronitrile) (429 microg/m(3)) were detected, and the sum of the concentrations determined for all compounds excluding formaldehyde (TVOC) was approximately 14 mg/m(3) on the day after the delivery. The concentrations of most compounds decreased with time, but increased with a rise of the interior temperature. The TVOC concentration in the next summer (July, 2000) was approximately one-tenth of the initial concentration. During the 3-year study period, the TVOC concentrations in summer exceeded the indoor guideline value (300 mug/m(3)) proposed by [Seifert B. Volatile organic compounds. In: Maroni M, Seifert B, Lindvall T, editors. Indoor air quality. A comprehensive reference book. Air quality monographs, vol. 3. Netherlands: Elsevier Science; 1995. p. 819-21]. The interior temperature and days lapsed after delivery were the main factors affecting the interior concentrations of most compounds according to multiple linear regression analysis. The results of this study offer useful fundamental data for investigations on air pollution in automotive cabins due to the organic compounds diffusing from the interior materials.     

河流型水源地源水有机物种类分布特性及其与消毒副产物关系

研究了不同水文期条件下长三角某典型河流型水源地源水有机物种类分布特性及其与消毒副产物关系。结果表明，该水源地源水有机污染特性呈现出丰水期>平水期>枯水期的特点，水体腐殖化程度依次降低。经树脂富集分离后水样溶解性有机物(DOM)各组分占总有机碳(DOC)的比例有所不同。丰水期：疏水性有机酸(HPO A,38%)>亲水性有机物(HPI,26%)>过渡亲水性有机酸(TPI A,16%)>疏水性有机中性物质(HPO N,12%)>过渡亲水性中性物质(TPI N,8%)；平水期：HPO A(32%)>HPO N(22%)>TPI A(20%)>HPI(18%)>TPI N(8%)；枯水期：HPO A(28%)>TPI A(24%)>HPO N(20%)>HPI(19%)>TPI N(9%)。DOM中仅HPI组分比紫外吸光度值(SUVA)低于原水，其余均高于原水，其中HPO A组分SUVA值最高，是原水的177倍。各水文期条件下，疏水性有机物（疏水性有机酸和疏水性中性物质）对三卤甲烷和卤乙酸生成的贡献，分别超过全部有机物氯化后消毒副产物生成量的60%和65%，表明疏水性有机物是最主要的消毒副产物前体物，应当作为水处理工艺重点去除的有机物组分。各水文期源水有机物特性与消毒副产物生成潜能的关系变化不大，三卤甲烷生成潜能(STHMFP)与SUVA的线性相关度较高，卤乙酸生成潜能(SHAAFP)与SUVA的线性相关度一般。因此，可用水样SUVA值间接反映三卤甲烷生成潜能，以利于在实际生产中快速监控水中消毒副产物前体物的变化趋势     

An overview of commercially used brominated flame retardants,their applications,their use patterns in different countries/regions and possible modes of release

Brominated flame retardants (BFRs) are used in a variety of consumer products and several of those are produced in large quantities. These compounds have been detected in environmental samples, which can be attributed to the anthropogenic uses of these compounds. Brominated flame retardants are produced via direct bromination of organic molecules or via addition of bromine to alkenes; hence, an overview of the production and usage of bromine over the past three decades is covered. Production, application, and environmental occurrence of high production brominated flame retardants including Tetrabromobisphenol A, polybrominated biphenyls, Penta-, Octa-, Deca-brominated diphenyl ether (oxide) formulation and hexabromocyclododecane are discussed.     

Environmental levels, toxicity and human exposure to tributyltin (TBT)-contaminated marine environment. a review. b_antizar@hotmail.com

Tributyltin (TBT) is a toxic chemical used for various industrial purposes such as slime control in paper mills, disinfection of circulating industrial cooling waters, antifouling agents, and the preservation of wood. Due to its widespread use as an antifouling agent in boat paints, TBT is a common contaminant of marine and freshwater ecosystems exceeding acute and chronic toxicity levels. TBT is the most significant pesticide in marine and freshwaters in Europe and consequently its environmental level, fate, toxicity and human exposure are of current concern. Thus, the European Union has decided to specifically include TBT compounds in its list of priority compounds in water in order to control its fate in natural systems, due to their toxic, persistent, bioaccumulative and endocrine disruptive characteristics. Additionally, the International Maritime Organization has called for a global treaty that bans the application of TBT-based paints starting 1 of January 2003, and total prohibition by 1 of January 2008. This paper reviews the state of the science regarding TBT, with special attention paid to the environmental levels, toxicity, and human exposure. TBT compounds have been detected in a number of environmental samples. In humans, organotin compounds have been detected in blood and in the liver. As for other persistent organic pollutants, dietary intake is most probably the main route of exposure to TBT compounds for the general population. However, data concerning TBT levels in foodstuffs are scarce. It is concluded that investigations on experimental toxicity, dietary intake, potential human health effects and development of new sustainable technologies to remove TBT compounds are clearly necessary.     

Toxicological effects of disinfections using sodium hypochlorite on aquatic organisms and its contribution to AOX formation in hospital wastewater

Sodium hypochlorite (NaOCl) is often used for disinfecting hospital wastewater in order to prevent the spread of pathogenic microorganisms, causal agents of nosocomial infectious diseases. Chlorine disinfectants in wastewater react with organic matters, giving rise to organic chlorine compounds such as AOX (halogenated organic compounds adsorbable on activated carbon), which are toxic for aquatic organisms and are persistent environmental contaminants. The aim of this study was to evaluate the toxicity on aquatic organisms of hospital wastewater from services using NaOCl in pre-chlorination. Wastewater samples from the infectious and tropical diseases department of a hospital of a large city in southeast of France were collected. Three samples per day were collected in the connecting well department at 9 a.m., 1 p.m. and 5 p.m. during 8 days from 13 March to 22 March 2001, and a mixture was made at 6 p.m. with the three samples in order to obtain a representative sample for the day. The toxicity test comprised the 24-h EC50 on Daphnia magna and a bioluminescence assay using Vibrio fischeri photobacteria. Fecal coliforms and physicochemical analyses such as total organic carbon (TOC), chloride, AOX, total suspended solids (TSS) and chemical oxygen demand (COD) were carried out. Wastewater samples highlighted considerable acute toxicity on D. magna and V. fischeri photobacteria. However, low most probable numbers (MPN), ranging from <3 to 2400 for 100 ml, were detected for fecal coliforms. Statistical analysis, with a confidence interval of 95%, gave a strong linear regression assessed with r=0.98 between AOX concentrations and EC50 (TU) on daphnia. The identification of an ideal concentration of NaOCl in disinfecting hospital wastewater, i.e. its non-observed effect concentration (NOEC) on algae and D. magna, seems to be a research issue that could facilitate the control of AOX toxicity effects on aquatic organisms. Therefore, it would be necessary to monitor the biocide properties of NaOCl on fecal coliforms at various doses and its toxicity effects on aquatic organisms.     

Mechanistic aspects regarding the direct aqueous environmental photochemistry of phenol and its simple halogenated derivatives. A review

We have reviewed the mechanistic aspects regarding the direct aqueous phase environmental photochemistry of phenol and its simple halogenated derivatives. These compounds are important industrial and natural products, are ubiquitous in aquatic systems, and their acute and chronic toxicity makes their environmental fate of interest. Work over the past two decades has unified the photochemistry of phenol and its simple halogenated derivatives. In general, three photochemical pathways dominate in aqueous solution depending on the nature of the substrate: (1) photoionization, (2) photochemical aryl-halogen bond homolysis, and (3) photochemical aryl-halogen bond heterolysis. Photoionization typically results in an array of biaryl radical coupling products which are only relevant for highly concentrated waste streams. Photolytic aryl-halogen bond homolysis will primarily give photoreduction products where reducing agents such as dissolved organic matter or reduced metal cations are present, and radical coupling products in highly concentrated waste streams. The 2- and 4-substituted halophenols may undergo photochemical aryl-halogen bond heterolysis upon irradiation to give an aryl cation. The aryl cation can be attacked by water to give the corresponding hydroxylated derivative, or may deprotonate to generate alpha- and gamma-ketocarbenes, respectively. Following their formation, the singlet alpha-ketocarbenes may undergo Wolff rearrangements to cyclopentadiene-ketenes that are subsequently hydrolyzed to cyclopentadiene carboxylic acids. The triplet alpha- and gamma-ketocarbenes are attacked by oxygen and hydrolyzed to give benzoquinones, directly hydrolyzed to yield hydroquinones, reduced to give phenols, or could take part in coupling reactions in highly concentrated waste streams to give dimers and hydroxybiaryl complexes. Additional studies in natural water samples are required to assess the relative importance of these direct irradiation mechanisms relative to indirect photolysis and other abiotic and biotic degradation and environmental partitioning pathways across the continuum of marine, freshwater, and wastewater biogeochemical signatures.