Relevance of BFRs and thermal conditions on the formation pathways of brominated and brominated-chlorinated dibenzodioxins and dibenzofurans

The widespread use of brominated flame-retarded products in the last two decades has resulted in an increasing presence of bromine in thermal processes such as waste combustion and accidental fires. Brominated and brominated-chlorinated dibenzodioxins and dibenzofurans (PBDDs/PBDFs, PXDDs/PXDFs) are micropollutants of concern arising from such processes. The present review aims to evaluate the relevance of these compound classes in actual thermal processes. Four categories of thermal processes are discussed in this respect according to their potential for PBDD/PBDF and PXDD/PXDF generation: thermal stress, pyrolysis/gasification, insufficient combustion conditions and controlled combustion conditions. Under thermal stress situations, as they may occur in production or recycling processes, PBDDs/PBDFs precursors like polybrominated diphenylethers (PBDE) can have a relevant potential for PBDD/PBDF formation via a simple elimination. Under insufficient combustion conditions as they are present in, e.g. accidental fires and uncontrolled burning as well as gasification/pyrolysis processes, considerable amounts of PBDDs/PBDFs can be formed from BFRs, preferably via the precursor pathway. In contrast, under controlled combustion conditions, BFRs and PBDDs/PBDFs can be destroyed with high efficiency. The relevance of de novo synthesis of PXDDs/PXDFs is discussed for this condition.Providing a basis for the understanding of PXDD/PXDF formation in actual thermal processes, the present paper also summarises the formation pathways of brominated and brominated-chlorinated PXDDs/PXDFs from brominated flame retardants (BFRs) investigated during laboratory thermolysis experiments. Relevant mechanistic steps for PBDD/PBDF formation from brominated precursors are discussed including elimination reactions, condensation steps and debromination/hydrogenation reactions.In addition, chlorination/bromination and halogen exchange reactions are briefly discussed with respect for their relevance on the final distribution of PBDDs/PBDFs, mixed chlorinated PXDDs/PXDFs and PCDDs/PCDFs resulting from thermal processes.     

Ultraviolet irradiation of municipal wastewater: Evaluation of effects on organic constituents

A comparison of chromatograms derived from the UV-absorbing and oxidizable constituents present in primary and secondary municipal wastewater effluents indicates that exposure to UV irradiation at disinfection levels results in only slight chemical changes. The most pronounced chemical effects to nonvolatile organic constituents in wastewater effluents have been observed at irradiation levels in excess of those necessary for disinfection. Aliquots of effluents before and after exposure to varying levels of UV irradiation were concentrated by lyophilization prior to liquid chromatographic (LC) analysis. Anion-exchange chromatographic techniques utilizing a modified ultraviolet detector coupled in series with a cerate oxidative monitor provided excellent resolution and sensitivity in the determination of chemical changes occurring in the effluents as a result of exposure to different irradiation levels. The total coliform counts for each irradiated effluent were determined by the membrane-filter technique to evaluate the effectiveness of UV irradiation as a disinfection process for municipal wastewaters. Changes in biochemical oxygen demand (BOD), chemical oxygen demand (COD), total organic carbon (TOC), and total Kjeldahl nitrogen (TKN) at different levels of exposure to UV irradiation are presented. The results of these determinations and the gas chromatography/mass spectrometry data characterizing the observed chemical changes are discussed.     

Health effects of polybrominated dibenzo-p-dioxins (PBDDs) and dibenzofurans (PBDFs)

This article reviews the state of the science regarding the health effects of polybrominated dibenzo-p-dioxins (PBDDs) and dibenzofurans (PBDFs). While thousands of articles have been published on the health effects of 2,3,7,8-tetrachlorodibenzo-p-dioxin and related polychlorinated dibenzodioxins (PCDDs) and dibenzofurans (PCDFs), little is know about the brominated and mixed chloro/bromo homologs. Available literature suggests that brominated compounds have similar toxicity profiles to their chlorinated homologs. However, further research investigating health effects will only be useful if exposure scenarios truly exist. Current exposure data is extremely limited, posing a major data gap in assessing potential risk of these chemicals. The rapid increase in the use of brominated flame retardants has raised the level of environmental concern regarding PBDDs/PBDFs as it is likely that human, as well as wildlife, exposure to brominated dioxins and furans will increase with their use.     

Occurrence,fate and ecological risk of five typical azole fungicides as therapeutic and personal care products in the environment: A review

Azole fungicides are widely used to treat fungal infection in human. After application, these chemicals may reach to the receiving environment via direct or indirect discharge of wastewaters, thus posing potential risks to non-target organisms. We aimed to review the occurrence, fate and toxicological effects of some representative household azole fungicides in the environment. Azole fungicides were widely detected in surface water and sediment of the aquatic environment due to their incomplete removal in wastewater treatment plants. These chemicals are found resistant to microbial degradation, but can undergo photolysis under UV irradiation. Due to different physiochemical properties, azole fungicides showed different environmental behaviors. The residues of azole fungicides could cause toxic effects on aquatic organisms such as algae and fish. The reported effects include regulation changes in expression of cytochrome P450-related genes and alteration in CYP450-regulated steroidogenesis causing endocrine disruption in fish. Further studies are essential to investigate the removal of azole fungicides by advanced treatment technologies, environmental fate such as natural photolysis, and toxic pathways in aquatic organisms.     

Effect of UV radiation and artificial acid rain on productivity of wheat

Responses of physiological parameters to UV irradiation of seeds and acid spraying of plants grown from them have been studied in several wheat species. It has been shown that, in a given species, presowing UV irradiation alone and combined UV and acid treatment generally produce a similar effect. Moreover, they have no significant influence on the yielding capacity of most species and, in some cases, even improve this parameter. All the species studied may be regarded as tolerant of these stress factors.     

Photodegradation characteristics of PPCPs in water with UV treatment

The degradation characteristics of PPCPs commonly found in surface water under UV treatment were examined for 30 kinds of PPCPs using a UV/Lamp1 that emits light at a wavelength of 254 nm and a UV/Lamp2 that emits light at 254 nm and 185 nm in pure water. When a UV dose of some 230 mJ/cm² was introduced to the 30 PPCPs, photodegradation rates of about > 3% (theophylline) to 100% (diclofenac) and about > 15% (clarithromycin) to 100% (diclofenac) were observed for UV/Lamp1 and UV/Lamp2, respectively. This study also showed that UV/Lamp2, which photolyzes water molecules and generates OH radicals, is more effective for PPCP removal than UV/lamp1. It was postulated that the degradation rates of sulfamethoxazole, sulfamonomethoxine, sulfadimethoxine and sulfadimidine, all, including sulfamethoxazole, derived from sulfanilamide, under UV/Lamp1 resulted mainly from the bond-breaking reactions occurring between –SO₂– and its side atoms, the C–S bond and the N–H bond. Some PPCPs with amide bonds, such as cyclophosphamide and DEET, were highly resistant to photodegradation by UV/Lamp1. AOPs (Advanced oxidation processes) such as the UV/H₂O₂ or UV/O₃ processes should therefore be considered for their potential to remove these substances effectively.     

A code to simulate nuclear reactor inventories and associated gamma-ray spectra

A computer code has been developed to simulate the gamma-ray spectra that would be measured by airborne gamma spectrometry (AGS) systems from sources containing short-lived fission products. The code uses simple numerical methods to simulate the production and decay of fission products and generates spectra for sodium iodide (NaI) detectors using Monte Carlo codes. A new Monte Carlo code using a virtual array of detectors to reduce simulation times for airborne geometries is described. Spectra generated for a short irradiation and laboratory geometry have been compared with an experimental data set. The agreement is good. Spectra have also been generated for airborne geometries and longer irradiation periods. The application of this code to generate AGS spectra for accident scenarios and their uses in the development and evaluation of spectral analysis methods for such situations are discussed.     

Critical factors in assessing exposure to PBDEs via house dust

Assessment of indoor exposure to polybrominated diphenyl ethers (PBDEs) requires a critical examination of methods that may influence exposure estimates and comparisons between studies. We measured PBDEs in residential dust collected from 20 homes in Boston, MA, to examine 5 key questions: 1) Does the choice of dust exposure metric-e.g., concentration (ng/g) or dust loading (ng/m2)-affect analysis and results? 2) To what degree do dust concentrations change over time? 3) Do dust concentrations vary between rooms? 4) Is the home vacuum bag an acceptable surrogate for researcher-collected dust? 5) Are air and dust concentrations correlated for the same room? We used linear mixed-effects models to analyze the data while accounting for within-home and within-room correlations. We found that PBDE dust concentration and surface loading were highly correlated (r=0.86-0.95, p<0.001). Average dust concentrations did not significantly differ over an 8-month period, possibly because home furnishings changed little over this time. We observed significant differences between rooms in the same home: PBDE concentrations in the main living area were 97% higher than the bedroom for decaBDE (p=0.02) and 72% higher for pentaBDE (p=0.05). Home vacuum bag dust concentrations were significantly lower than researcher-collected dust and not strongly correlated. Air (vapor and particulate phase) and dust concentrations were correlated for pentaBDE (p=0.62, p<0.01), but not for decaBDE (p=0.25). In addition, potential markers of BDE 209 debromination (BDE 202 and the BDE197:BDE201 ratio) were also observed in household dust samples. One vacuum bag sample contained the highest concentrations of BDE 209 (527,000 ng/g) and total PBDEs (544,000 ng/g) that have been reported in house dust.     

Basic characterization of Norwegian NOM samples — Similarities and differences

NOM (natural organic matter) samples, isolated by reverse osmosis (RO), and nine NOM samples, concentrated by low-pressure, low-temperature evaporation (EVA) from various origin in Norway, were characterized by different methods. The methods included elemental content of the freeze-dried samples (C, H, N, and O), elemental content of the redissolved samples (DOC, Na, Ca, Cu, Fe, and Mn), specific spectral absorbance at λ = 254 nm (A(254 nm)/DOC) and at λ = 436 nm (A(436 nm)/DOC), UV/Vis-spectra, specific fluorescence (excitation and emission spectra), proton capacity, Cu-complexation capacity, and content of hydrolysable amino acids and carbohydrates. In addition, chromatographic characterization by gel chromatography and reversed-phase chromatography was done. Studies on adsorption and flocculation abilities and the formation of trihalomethanes (THM) and organic halogens adsorbable on activated carbon (AOX) upon chlorination were also investigated. Comparison of the results showed that the samples were different according to the origin of the sample, isolation procedure, and time of sampling. The differences are not the same for all parameters used. Standardized procedures have to be applied to redissolve the organic material in water in order to compare data. For the samples investigated, it was shown that parameters like elemental analysis (H/C ratio), the specific spectral absorption in the UV range, proton capacity, complexation capacity and anionic particle charge, amount of hydrolysable amino acids and carbohydrates, adsorption behaviour on activated carbon, and the THM-FP are sensitive parameters to show differences concerning origin and isolation procedure.     

Organoarsenicals in poultry litter: Detection,fate, and toxicity

Arsenic contamination in groundwater has endangered the health and safety of millions of people around the world. One less studied mechanism for arsenic introduction into the environment is the use of organoarsenicals in animal feed. Four organoarsenicals are commonly employed as feed additives: arsanilic acid, carbarsone, nitarsone, and roxarsone. Organoarsenicals are composed of a phenylarsonic acid molecule with substituted functional groups. This review documents the use of organoarsenicals in the poultry industry, reports analytical methods available for quantifying organic arsenic, discusses the fate and transport of organoarsenicals in environmental systems, and identifies toxicological concerns associated with these chemicals. In reviewing the literature on organoarsenicals, several research needs were highlighted: advanced analytical instrumentation that allows for identification and quantification of organoarsenical degradation products; a greater research emphasis on arsanilic acid, carbarsone, and nitarsone; identification of degradation pathways, products, and kinetics; and testing/development of agricultural wastewater and solid treatment technologies for organoarsenical-laden waste.     

An aggregate analysis of personal care products in the environment: Identifying the distribution of environmentally-relevant concentrations

Over the past 3–4 decades, per capita consumption of personal care products (PCPs) has steadily risen, resulting in increased discharge of the active and inactive ingredients present in these products into wastewater collection systems. PCPs comprise a long list of compounds employed in toothpaste, sunscreen, lotions, soaps, body washes, and insect repellants, among others. While comprehensive toxicological studies are not yet available, an increasing body of literature has shown that PCPs of all classes can impact aquatic wildlife, bacteria, and/or mammalian cells at low concentrations. Ongoing research efforts have identified PCPs in a variety of environmental compartments, including raw wastewater, wastewater effluent, surface water, wastewater solids, sediment, groundwater, and drinking water. Here, an aggregate analysis of over 5000 reported detections was conducted to better understand the distribution of environmentally-relevant PCP concentrations in, and between, these compartments. The distributions were used to identify whether aggregated environmentally-relevant concentration ranges intersected with available toxicity data. For raw wastewater, wastewater effluent, and surface water, a clear overlap was present between the 25th–75th percentiles and identified toxicity levels. This analysis suggests that improved wastewater treatment of antimicrobials, UV filters, and polycyclic musks is required to prevent negative impacts on aquatic species.     

Linking health and ecology in the medical curriculum

Human health vulnerabilities to ecosystem degradation are well documented. Destabilization of natural ecosystems and the biosphere have posed an entirely new set of risks to human health and preclude any simple extrapolations from the past. Newly emerging diseases, increasing prevalence of many vector borne diseases, increased exposure to harmful UV radiation and a number of other transformations in the natural environment, have decidedly negative implications for the sustainability of human health. Curricula in medical schools are responding to these new realities by exposing the connections between health and ecology. The program in Ecosystem Health at the University of Western Ontario serves as one model for connecting these disciplines. This program has resulted in a perceptible shift in values and professional responsibilities of emerging physicians.     

Determination of parabens and benzophenone-type UV filters in human placenta. First description of the existence of benzyl paraben and benzophenone-4

UV filters and parabens (PBs) are chemicals used in daily personal care and hygiene products to protect materials and humans from the adverse effects of UV radiation and to preserve the integrity of the formulation, respectively. Several studies highlight their widespread environmental occurrence and endocrine disrupting effects. However, little is known about human exposure to these compounds. The objective of this study was to investigate the exposure of human embryos and foetuses to endocrine disrupting UV filters and PBs.Placentas from volunteer mothers in Barcelona were collected at delivery after informed, written consent by the pregnant women. UV filters and parabens were analysed by liquid chromatography-tandem mass spectrometry. The excellent performance of the method allowed measuring the target compounds in human placental tissue at low ng/g fresh weight level. The detection frequency of the selected compounds was in the range 17–100%. Benzophenone-1, methyl paraben, butyl paraben and benzyl paraben were detected in all samples. The highest measured concentration corresponded to methyl paraben, 11.77 ng/g fresh weight. Reported concentrations of benzophenone-4 and benzyl paraben constitute the first evidence about their accumulation in placenta. The results obtained corroborate that foetuses are exposed to a wide diversity of UV filters and PBs via the placenta.     

Recent advances in aerial gamma-ray surveying

Aerial gamma-ray surveying uses NaI(Tl) detectors mounted in small aircraft to measure gamma radiation, emitted from the earth's surface. The data are collected as gamma-ray spectra, typically with 1 s counting times, from which are derived K, U and Th concentrations in the ground. Applications of aerial surveying include geological mapping for mineral exploration, soil mapping for agriculture, pollution studies and location of lost sources. Recent advances in applying statistical methods to the spectral data have resulted in large reductions in the noise levels in the surveys. Some of the methods available to do this include noise adjusted singular value decomposition (NASVD) [Proceedings of Exploration 97: Fourth Decennial International Conference on Mineral Exploration (1997) 753] and maximum noise fraction (MNF) and enhanced MNF (eMNF) [Explor. Geophys. 31 (2000) 73]. These methods, in general, apply normalization for variance to the spectra, use a principal component method to obtain the "significant" components of the data and reconstruct cleaned spectra, which are then processed in a standard manner to get radionuclide concentrations. However, they differ in the detail of the application and thus give slightly different results. In this paper, the application of noise reduction methods to various synthetic surveys is used to examine the strengths and weaknesses of the methods. In tests where there are high correlations between U and Th, the eMNF method performs best although the results are improved by prior clustering of the data by the Th/U ratio. If the data show no correlations, then the effectiveness of all the noise removal methods is reduced. If a data set is small (<1500 spectra), then MNF appears to be the better method. Consideration of the various tests suggests an optimum process whereby spectra are sorted into groups by the Th/U ratio of areas identified in a standard processing and then cleaned by eMNF or MNF, depending on the number of spectra in each group.     

Effect of soil texture on surfactant-based remediation of hydrophobic organic-contaminated soil

Surfactants may be used in remediation of subsoil and aquifer contaminated with hydrophobic compounds. The objectives of this study were to examine the effect of soil texture on hydrophobic organic contaminant (HOC; toluene, or 1,2,4-trichlorobenzene [TCB]) removal from six soils and to evaluate the optimal composition of soil texture for maximum HOC removal using aqueous surfactant solution. Selected surfactants were 4% (vol/vol) sodium diphenyl oxide disulfonate (DOSL) and 4% (wt/vol) sodium lauryl sulfate (LS). Toluene and TCB were selected as the lighter-than-water nonaqueous phase liquid (LNAPL) and denser-than-water nonaqueous phase liquid (DNAPL) model substances, respectively. Soil types used for this study were Ottawa sand and five Iowa soils (Fruitfield, Keomah, Crippin, Webster, and Galvar). The greatest recovery of toluene and TCB in batch tests was 73% and 84%, respectively, which was obtained with DOSL surfactant in Ottawa sand. The toluene removal of 95% in column tests has been achieved in the Ottawa sand and three Iowa soils (Fruitfield, Keomah, Crippin) with DOSL after effluent volume of 3750 ml (about 32 pore volume) passed. TCB removal of 98% in column tests has been achieved in Ottawa sand and three Iowa soils (Fruitfield, Keomah, Crippin) with DOSL after effluent volume of 2500 ml (about 21 pore volume) passed. These results were related with soil texture (clay content 30%), clay mineralogy (kaolinite and smectite), as a function of transported pore volume.     

Photochemistry of a major commercial polybrominated diphenyl ether flame retardant congener: 2,2',4,4',5,5'-hexabromodiphenyl ether (BDE153)

The photochemistry of a major commercial polybrominated diphenyl ether (PBDE) flame retardant congener, 2,2',4,4',5,5'-hexabromodiphenyl ether (BDE153), was investigated in acetonitrile, distilled water, and seawater. After a short irradiation period in acetonitrile at 302 nm, the major photoproducts of BDE153 included 2,2',4,4',5-(BDE99), 2,2',4,5,5'-(BDE101), and 2,4,4',5,5'-(BDE118) substituted penta-BDEs as primary photohydrodebromination products, 2,2',4,4'-(BDE47), 3,3',4,4'-(BDE77), 2,3',4,4'-(BDE66), and 2,2',4,5'-(BDE49) substituted tetra-BDEs as secondary photohydrodebromination products, a suite of non-2,3,7,8-substituted mono- through penta-brominated dibenzofurans, and three tetrabrominated 2-hydroxybiphenyl congeners. By comparison, irradiation in distilled water and seawater gave increased relative photohydrodebromination contributions and no evidence for the formation of brominated dibenzofurans or 2-hydroxybiphenyls. In all solvent systems, subsequent degradation of primary and secondary photoproducts under continuing irradiation led to a steadily decreasing reaction mass balance. The results suggest a short photochemical half-life for BDE153 in aquatic systems, with rapid photohydrodebromination to some of the most prevalent penta- and tetra-brominated diphenyl ether congeners typically observed in environmental matrices.     

Environmental risk assessment and the intrusion of bias

The concept of managing the environment and any associated human health impacts by means of such science-based tools as toxicological evaluation, risk assessment, and economic appraisal has become widely accepted in professional circles. These increasingly complex methodologies have not won universal support, however, even among the technically minded, and the wider public has in many cases remained sceptical. The public's seeming lack of enthusiasm has frequently been assigned to ignorance of science, irrationality even, and some attempts have been made to ameliorate the situation by means of education, though with little evidence of success. However, this review advances an alternative explanation, namely, that the disenchantment has more to do with procedural than technical matters. Many issues, although treated with technical risk assessment appear to have forced themselves onto the agenda because of factors only passingly connected with risk, and which are more related to the intrusion of disputed values and other sources of bias. This paper also notes that the intervention of bias in decision making is rife, and is found as much in professional as in public approaches. This need not itself be a problem, providing it is recognised and openly expressed. However, there remains a need for much greater circumspection and frankness by professions about the status of their art, and a determined effort if the full social benefits of environmental risk assessment (ERA) are to be realised.     

河流渗滤系统中苯系物污染去除机理实验模拟研究

河流渗滤是一种自然净化过程,污染河水通过该过程在河流沉积层中发生各种物理、化学和生物作用,使得污染物浓度降低,河水水质得到净化,从而达到增加地下水开采量的目的。通过静态吸附实验和淋滤实验模拟了苯系物（BTEX）在河流渗滤系统中的吸附行为和降解行为。两种环境行为中吸附作用对于BTEX的净化效果较为有限,当吸附达到饱和之后,并存在电子受体的情况下,BTEX能够发生厌氧微生物降解,降解作用能够更有效的去除BTEX污染物。其中去除效率最高的是间二甲苯,其次是乙苯、甲苯,去除率最差的是苯。微生物降解作用相对于BTEX浓度变化存在一个滞后期。BTEX各组分的土壤 水吸附分配系数Kd越大,总的降解效率也就越低。通过河流渗滤系统这一自然净化过程,可以有效地去除浓度较高的BTEX混合污染,在两种电子受体的情况下各组分平均去除效率都超过了60%,最高去除率均超过了80%。对于持续不断入渗的污染河水,当土壤吸附达到饱和、微生物活性受到抑制情况下,去除效率会大大降低,从而使BTEX穿透包气带进入含水层,对地下水产生危害     

Life cycle assessment part 2: current impact assessment practice

Providing our society with goods and services contributes to a wide range of environmental impacts. Waste generation, emissions and the consumption of resources occur at many stages in a product's life cycle-from raw material extraction, energy acquisition, production and manufacturing, use, reuse, recycling, through to ultimate disposal. These all contribute to impacts such as climate change, stratospheric ozone depletion, photooxidant formation (smog), eutrophication, acidification, toxicological stress on human health and ecosystems, the depletion of resources and noise-among others. The need exists to address these product-related contributions more holistically and in an integrated manner, providing complimentary insights to those of regulatory/process-oriented methodologies. A previous article (Part 1, Rebitzer et al., 2004) outlined how to define and model a product's life cycle in current practice, as well as the methods and tools that are available for compiling the associated waste, emissions and resource consumption data into a life cycle inventory. This article highlights how practitioners and researchers from many domains have come together to provide indicators for the different impacts attributable to products in the life cycle impact assessment (LCIA) phase of life cycle assessment (LCA).