Pollution of soils with organophosphorus flame retardants and plasticizers

The detection of the three organophosphate esters TCEP, TCPP and TBEP in soil samples indicates that pollution of soils from diffuse atmospheric sources has to be considered in risk assessments.     

Organophosphorus flame retardants and plasticizers in air from various indoor environments

Eleven organophosphorus compounds (OPs) that are used as plasticizers and flame retardants were analysed in duplicate samples of indoor air from 17 domestic and occupational environments. Solid-phase extraction (SPE) columns were used as adsorbents and analysis was performed using GC with a nitrogen phosphorus selective detector. The total amounts of OPs in the air samples ranged between 36 and 950 ng m(-3); tris(chloropropyl) phosphate (TCPP) and tris(2-chloroethyl) phosphate (TCEP) being the most abundant (0.4 to 730 ng m(-3)), followed by tributyl phosphate (0.5-120 ng m(-3)). Public buildings tended to have about 3-4 times higher levels of OPs than domestic buildings. The relative amounts of individual OPs varied between the sites and generally reflected the building materials, furniture and consumer products used in the sampled environments. Potential sources of these compounds include, inter alia, acoustic ceilings, upholstered furniture, wall coverings, floor polish and polyvinylchloride floor coverings. A correlation was observed between the TCEP concentrations in the air in the sampled environments and previously reported concentrations in dust, but no such correlation was seen for the heavier and less volatile tris(2-butoxyethyl) phosphate (TBEP). Based on estimated amounts of indoor air inhaled and dust ingested, adults and children in the sampled environments would be exposed to up to 5.8 microg kg(-1) day(-1) and 57 microg kg(-1) day(-1) total OPs, respectively.     

Occurrence and distribution of organophosphorus flame retardants and plasticizers in anthropogenically affected groundwater

Occurrence and distribution of chlorinated and non-chlorinated organophosphates in 72 groundwater samples from Germany under different recharge/infiltration conditions were investigated. Tris(2-chloro-1-methylethyl) phosphate (TCPP) and tris(2-chloroethyl) phosphate (TCEP) were the most frequently detected organophosphates in groundwater samples. Highest individual organophosphate concentrations (>0.1 μg L(-1)) were determined in groundwater polluted by infiltrating leachate and groundwater recharged via riverbank filtration of organophosphate-loaded recipients. In samples from springs and deep groundwater monitoring wells that are not affected by surface waters, organophosphate concentrations were mostly below the limit of detection. The occurrence (3-9 ng L(-1)) of TCPP and TCEP in samples from aquifers with groundwater ages between 20 and 45 years indicates the persistence of both compounds within the aquifer. At urban sites organophosphate-loaded precipitation, surface runoff, and leakage of wastewater influenced groundwater quality. For rural sites, where groundwater recharge is only influenced by precipitation, organophosphates were very rarely detectable in groundwater.     

Concentrations of organophosphate esters and brominated flame retardants in German indoor dust samples

While it is known that the ingestion of indoor dust contributes substantially to human exposure to the recently restricted polybrominated diphenyl ethers (PBDEs), the situation for one class of potential replacements, i.e. organophosphate esters (OPEs), used in a variety of applications including as flame retardants has yet to be fully characterised. In this study, surface dust from twelve different cars from various locations throughout Germany were analysed for eight OPEs, decabromodiphenyl ethane (DBDPE), and eight PBDEs. In five cars, tris-(1,3-dichloro-2-propyl) phosphate (TDCPP) was the dominant compound with concentrations up to 620 μg g(-1) dust. High concentrations of tri-cresyl phosphate (TCP) (up to 150 μg g(-1)) were also detected in two samples of car dust. Dust from ten offices in the same building in Ludwigsburg, Germany was also analysed. In these samples, tri (2-butoxyethyl) phosphate (TBEP) predominated with an average concentration of 7.0 μg g(-1) dust, followed by tris (1-chloro-2-propyl) phosphate (TCPP) at 3.0 μg g(-1) and triphenyl phosphate (TPhP) at 2.5 μg g(-1) dust. Although caution must be exercised given the relatively small database reported here; this study provides evidence that cars and offices from Germany are significantly more contaminated with OPEs than PBDEs. Average concentrations of ΣOPEs were ten times higher in car than in office dust. This is the first study to provide data on a wide range of OPE concentrations in German indoor dust samples.     

Brominated flame retardants in plasma samples from three different occupational groups in Norway

Brominated flame retardants (BFRs) are widely used in plastics, textile coatings, electrical appliances and printed circuit boards to prohibit the development of fires. In order to investigate how exposure to BFRs is related to specific occupations, samples were obtained from Norwegian individuals working at an electronics dismantling facility, in the production of printed circuit boards, or as laboratory personnel. Nine BFRs were quantified in the plasma samples: 2,4,4'-tribromodiphenyl ether (BDE-28), 2,2',4,4'-tetrabromodiphenyl ether (BDE-47), 2,2',4,4',5-pentabromodiphenyl ether (BDE-99), 2,2',4,4',6-pentabromodiphenyl ether (BDE-100), 2,2',4,4',5,5'-hexabromodiphenyl ether (BDE-153), 2,2',4,4',5,6'-hexabromodiphenyl ether (BDE-154), 2,2',3,4,4',5',6-heptabromodiphenyl ether (BDE-183), 2,4,6-tribromophenol (TriBP) and tetrabromobisphenol A (TBBP-A). The BFRs were extracted from plasma using solid-phase extraction (SPE). The plasma lipids were decomposed by treatment with concentrated sulfuric acid directly on the SPE column, prior to the elution of the BFRs. Following diazomethane derivatization, the samples were analysed by gas chromatography-electron capture mass spectrometry. The subjects working at the electronics dismantling plant had significantly higher plasma levels of TBBP-A and BDE-153 compared to the other groups, and the heptabrominated congener BDE-183 was only detected in plasma from this group. TriBP was generally the most abundant BFR present, and the plasma concentrations were in the range 0.17-81 ng g-1 lipids. BDE-47 was the dominant BDE congener in all the individual samples and the levels were in the range 0.43-14.6 ng g-1 lipids. The total amounts of the seven BDEs were 8.8, 3.9 and 3.0 ng g-1 lipids for the group of electronics dismantlers, circuit board producers and laboratory personnel, respectively. Generally, large variations in the individual concentration levels were found within the groups, especially in the group of electronics dismantlers, where the relative standard deviations for BDE concentrations were in the range 23-164%. The levels of BFRs were not correlated to age or the level of 2,2',4,4',5,5'-hexachlorobiphenyl (CB-153). The present work indicates that the population in Norway is exposed to several BFRs, probably with food as a major source. The elevated level of higher brominated BDEs and TBBP-A in the plasma from the workers at the dismantling plant suggests an additional occupational exposure for these individuals. Thus, human exposure to BFRs seems to originate from a combination of different sources; however, further studies investigating plasma samples from a larger number of individuals are necessary for a more complete assessment of human exposure pathways to these environmental contaminants.     

Evaluation of phosphorus loads from Ontario municipal wastewater treatment plants

Results are presented from an evaluation of the nature and accuracy of phosphorus loads discharged by Ontario municipal wastewater treatment plants into the Great Lakes. Data were examined for the 96 plants treating flows in excess of 4546 m³d^-1 for the period 1981 to 1985. For the Lake Erie, Lake Ontario/St. Lawrence River and Upper Great Lakes basins, total basin phosphorus loads were classified according to type of wastewater treatment system, the type of chemical added for phosphorus removal, plant capacity, and sampling frequency. Load estimation techniques were compared using the 1985 daily data from three representative treatment plants. Annual phosphorus loads were compared using the complete data records for the plants and using Monte Carlo techniques to simulate an incomplete data record typical of once per week effluent phosphorus sampling. Potential sources of bias were identified in annual phosphorus load estimates from municipal treatment plants.     

Characteristic occurrence patterns of micropollutants and their removal efficiencies in industrial wastewater treatment plants

The concentrations and removal efficiencies of various kinds of micropollutants were investigated and the relationships between the input sources of industrial wastewater and occurrence patterns of each micropollutant were identified at nine on-site industrial wastewater treatment plants (WWTPs). The distribution pattern of each compound varied according to the WWTP type and several micropollutants were significantly related with specific industries: chlorinated phenols (ClPhs) with paper and metal industries, polycyclic aromatic hydrocarbons (PAHs) with petrogenic- and pyrogenic-related industries, polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) with the paper industry, and chlorinated benzenes (ClBzs) with dye-related industries. The activated sludge (AS) process was very efficient in the removal of ClPhs and PAHs, and the filtration process in the removal of PCDD/Fs and 1,4-dioxane. Generally, the removal efficiencies of each micropollutant varied according to the WWTP type.     

Brominated flame retardants in the environment of Asia-Pacific: an overview of spatial and temporal trends

In this paper, we summarize spatial and temporal trends of polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecanes (HBCDs) in coastal and marine biota, and further assess human exposure to these brominated flame retardants (BFRs) in Asia-Pacific. The review is based mainly on the studies that were conducted in our laboratory and utilized samples archived in the environmental specimen bank (es-BANK) of Ehime University, Japan. The studies suggest that the target BFRs are ubiquitous in the environment of Asia-Pacific. Examination of spatial trends reveals that concentrations of these contaminants are relatively high in samples from Korea, South China and Japan. In general, the magnitude of environmental contamination by PBDEs in Asia-Pacific, as well as human exposure to these contaminants, seem to be comparable to or slightly higher than in Europe, but lower than in North America. Evaluation of temporal trends in concentrations of BFRs in marine mammals from the coastal waters of Japan and China showed drastic increase during the last 30 years. These changes in BFR levels in samples from Japan were in line with trends in production/use of the commercial formulations. Since the withdrawal of some PBDE products from the Japanese market in the 1990s, concentrations of HBCDs appear to exceed those of PBDEs, reflecting increasing usage of HBCDs over PBDEs. The increasing environmental contamination by BFRs in Chinese coastal waters indicates that contamination by BFRs has already become evident, even in developing countries. In view of the rising environmental levels and the high consumption volume of BFRs in Asia, further efforts should be made to monitor environmental contamination by these chemicals in order to identify sources and reduce emissions.     

Polycyclic aromatic hydrocarbons in effluents from wastewater treatment plants and receiving streams in Tianjin, China

Surface water, suspended particulate matter, pore water, and sediment samples were collected and analyzed for polycyclic aromatic hydrocarbons (PAHs) in Yongding New River, South Drainage Canal and North Drainage Canal, which receive most of wastewater from industrial city of Tianjin. PAH concentrations in effluent samples of wastewater treatment plants (WTP) discharging into the South Drainage Canal and North Drainage Canal were quantified for the first time. The results showed that the discharge of the WTPs recently only contributed to the PAH contamination in the canals near the outlets of the WTPs. PAH levels in sediments of the streams were greatly higher than those in soils by riverbank probably due to receiving large amounts of untreated wastewater. Unusually high benz[a] anthracene concentration strongly influenced the seasonal and spatial variation of total PAH concentrations in South Drainage Canal. Paired samples t test of ??Nap, Fl, Phe, Fluo and ??Nap, Phe, Fluo, Chry concentrations, which were dominant components in the air samples from non-heating and heating season, respectively, in the suspended particulate matters from the streams showed that PAH source from air deposition was more important for Yongding New River than that for South Drainage Canal and North Drainage Canal. Source apportionment based on PAH profiles indicated that coal combustion was the major PAH contamination source, and coke oven sources and wood combustion also contributed to the PAH contamination of the streams. This was further indicated by organic petrography analysis.     

The antibacterial effects of engineered nanomaterials: implications for wastewater treatment plants

Nanotechnology is currently at the forefront of scientific research and technological developments that have resulted in the manufacture of novel consumer products and numerous industrial applications using engineered nanomaterials (ENMs). With the increasing number of applications and uses of ENMs comes an increasing likelihood of nanoscale materials posing potential risks to the environment and engineered technical systems such as wastewater treatment plants (WWTPs). Recent scientific data suggests that ENMs that are useful in, for example, medical applications due to their novel physicochemical properties, may also cause adverse effects to the bacterial populations used in wastewater treatment systems. In this review, the toxicological effects of titanium nanoparticles (nTiO(2)), zinc oxide (nZnO), carbon nanotubes (CNTs), fullerenes (C(60)) and silver nanoparticles (AgNPs) to bacteria were examined. The results suggest that the potential ENMs risks to bacteria are non-uniform (need to be assessed case-by-case), and are dependent on numerous factors (e.g. size, pH, surface area, natural organic matter). Currently available data are therefore insufficient for evaluating the risks that ENMs pose in WWTPs. To fill these knowledge gaps, we recommend scenario specific studies aimed at improving our understanding on: (i) estimated volumes of ENMs in effluents, (ii) the antibacterial sensitivity of cultures within WWTPs towards selected ENMs, and (iii) processes improving the stability of ENMs in solutions. Two factors that merit consideration for elucidating the potential risks systematically are the toxicity mechanisms of ENMs to bacteria, and the influencing factors based on inherent physicochemical properties and environmental factors. Furthermore, the complexity of behaviour and fate of ENMs in real WWTPs requires case studies for assessing the ENMs risks to bacteria in vivo. The current laboratory results derived using simplified exposure media do not reflect actual environmental conditions.     

Occurrence and distribution of polycyclic aromatic carbons in sludges from wastewater treatment plants in Guangdong, China

In this study, the occurrence and distribution of polycyclic aromatic hydrocarbons (PAHs) were investigated in six sludge samples collected from Guangdong Province, China. Concentrations of PAHs varying from 2,534.1 to 6,926.6 μg kg^???1 (dry sludge) were observed in three municipal wastewater treatment plants with phenanthrene (Phe), fluoranthene, and pyrene being the main compounds. In addition, 682.6 μg kg^???1 PAHs were detected in one sludge sample from a food processing plant, with fluorene, Phe, and chrysene being the main components. No PAHs were detected in sludge samples obtained from two cosmetic plants. The levels and distributional characteristics of PAHs, polychlorinated biphenyls (PCBs), and polycyclic musks (PMs) from the samples were also compared. The results of this comparison indicated that petrochemical refineries and road traffic played important roles in the PAH loads in sludge, while PMs primarily originated from domestic wastewater and industrial wastewater from cosmetic plants. Finally, the presence of 98.8 μg kg^???1 PCBs in sludge suggested diffusional emission sources from electrical components containing PCBs.     

Determination of organophosphorus fire retardants and plasticizers in wastewater samples using MAE-SPME with GC-ICPMS and GC-TOFMS detection

Determination of organophosphorus fire retardants and plasticizers at trace levels in wastewater is described. In this work, microwave assisted extraction (MAE) and solid-phase microextraction (SPME) are used for sample preparation to extract and preconcentrate the analytes, followed by analysis by gas chromatography coupled to inductively coupled plasma mass spectrometry (GC-ICP-MS) for phosphorus-specific detection. Gas chromatography coupled to time of flight mass spectrometry (GC-TOF-MS) was used to confirm the organphosphorus fire retardants in wastewater. The detection limits of organophosphorus fire retardants (OPFRs) were 29 ng L(-1) for tri-n-butyl phosphate (TnBP), 45 ng for L(-1) for tris(2-butoxyethyl)phosphate (TBEP), and 50 ng L(-1) for tris(2-ethylhexyl)phosphate (TEHP). Optimized extraction conditions were performed at 65 degrees C for 30 min and with 10% NaCl. Application of MAE during the sample preparation prior to the SPME allowed the detection of tris(2-ethylhexyl) phosphate, which has been difficult to determine in previous work. Application of the method to wastewater samples resulted in detecting 3.1 microg L(-1) P from TnBP, 5.0 microg L(-1) P from TBEP, and 4.0 microg L(-1) P from TEHP. The presence of these compounds were also confirmed by SPME-GC-TOF-MS.     

Presence and partitioning properties of the flame retardants pentabromotoluene, pentabromoethylbenzene and hexabromobenzene near suspected source zones in Norway

The brominated flame retardants (BFRs), pentabromotoluene (PBT), pentabromoethylbenzene (PBEB) and hexabromobenzene (HBB), exhibit physical-chemical properties similar to other persistent organic pollutants, and have been in use as flame retardants for several decades. Data on these BFRs in diverse environmental samples can be found in studies from the 1970s and 1980s, as well as in recent years, though very little in the years in between. Due to a lack of data, the cause for the apparent re-emergence of these BFRs in recent studies is unclear, and could reflect changes in production volumes, accumulation of transformation products from BFR precursors, improved analytical techniques or simply a re-emergence in concern. Very little data are available on their environmentally relevant partitioning properties, which could help to explain the occurrence and fate of these BFRs. In this study we analysed for the presence of HBB, PBT, and PBEB in diverse environmental samples from potential Norwegian BFR source zones. Additionally, environmental partitioning properties of these BFRs as well as brominated benzenes were estimated and validated using experimental data for brominated benzenes. Of the three BFRs, HBB was identified in detectable quantities at most source zones, PBEB only near a metal recycling factory, and PBT only in a few additional locations from where PBEB was detected. Data from this study show that HBB is likely widely distributed, as verified both by chemical analysis and estimated properties. Measured HBB levels in wastewater treatment plants indicate that the treatment practices used in the study locations are not effective at lowering HBB levels, perhaps due to association with low density suspended solids (e.g. microplastics).     

Heavy metal concentration and speciation of seven representative municipal sludges from wastewater treatment plants in Northeast China

The analysis of heavy metals is very important for assessing the feasibility of the agricultural utilization for the municipal sludge. In this paper, a four-step sequential extraction method was applied to extract heavy metals (Cu, Zn, Mn, Cr, and Ni) in municipal sludges from seven individual wastewater treatment plants located in Jilin and Heilongjiang Province, China, for estimating the mobility and bioavailability of the metal ions in the agricultural application. The total concentrations of heavy metals and their chemical fractions after the sequential extraction were determined. Principal component analysis (PCA) was applied to analyze the relations of heavy metals fractions in the municipal sludges. Experimental results indicated that the total concentrations of Cu, Zn, Cr, and Ni in all sludge samples were below the threshold values set out by the Chinese legislation (GB18918-2002). Specially, Zn had a high bioavailability and mobility, Cu and Cr had potential bioavailability, while Mn mainly existed in the residual fraction of municipal sludge. On the other hand, Ni had different mobility in different municipal sludge. PCA results were confirmed by the environmental behavior of heavy metals.     

Analysis and occurrence of emerging chlorinated and brominated flame retardants in surficial sediment of the Dalian coastal area in China

The concentrations and distributions of some typical chlorinated flame retardants (Dechlorane or Mirex, Dechlorane 602 (Dec 602), Dechlorane 603 (Dec 603), Dechlorane 604 (Dec 604) and Dechlorane Plus (DP)) and brominated FRs (polybrominated diphenyl ethers (PBDEs), pentabromoethylbenzene (PBEB) and 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE)) were analyzed in surficial sediment collected from the Dalian coastal area in northeast China. Dec 603, Dec 604, and BTBPE were below their respective limits of detection (LOD) in all sediment samples, while Dechlorane, Dec 602, DP, Σ13BDE (tri- to hepta-BDEs), BDE 209, and PBEB were identified in the ranges <0.015-39.9 ng g(-1) dry weight (dw), <0.011-0.156 ng g(-1) dw, 0.69-7.00 ng g(-1) dw, 0.017-1.33 ng g(-1) dw, 3.94-103 ng g(-1) dw, and <0.073-1.9 ng g(-1) dw, respectively. Relationships between these chlorinated and brominated FRs were analyzed using Pearson's correlation and principal component analysis (PCA). DP, Dechlorane, Σ13BDE, and BDE 209 showed significantly positive correlation (p<0.05), and these relationships showed excellent agreement with PCA results. The spatial trends for Dechlorane, DP, BDE 209, and Σ13BDE showed that high concentrations were found in the industrial zone and lower concentrations in residential and garden zones. The results imply that these FRs are originating from a common source, and support the view that direct input from the effluent of sewage outlets is a major source of these compounds in Dalian sediment.     

Speciation of heavy metals in biosolids of wastewater treatment plants at Mysore,Karnataka, India

Urban wastewater treatment leads to the generation of large quantities of biosolids. Accumulation of biosolids is a problem of environmental relevance due to the existence of heavy metals in the biosolids. Determination of total metal in biosolid provides information relating pollution levels. Determination of their mobilization capacity and behaviour in the environment is an important task. An experimental approach commonly used for studying the mobility, transport and bioavailability of metal in biosolids is the use of selective sequential extraction procedure. In the present study an attempt has been made to study the heavy metal properties in biosolid samples collected from urban wastewater treatment plants located at Mysore, Karnataka. Few heavy metals selected for the present study are cadmium, chromium, copper, iron, nickel and zinc. The concentration of these metals in biosolids and their partition in different fractions are studied. The speciation of metals based on the sequential extraction scheme was carried out. The concentration of heavy metals is lower than that established by European legislation. The residual fraction has the maximum percentage of heavy metals whereas, only a small fraction of heavy metals (Fe, Zn and Cd) are extracted in the most soluble fractions, exchangeable and carbonate fractions.     

Quantitative assessment of polycyclic aromatic hydrocarbons in sewage sludge from wastewater treatment plants in Qingdao, China

In this study, 16 polycyclic aromatic hydrocarbons (PAHs) were detected in sewage sludge samples from four wastewater treatment plants (WWTPs) in Qingdao, China. These WWTPs differ in the type of treatment used and in the origin of the wastewater. The total amounts of PAHs in digested sludges ranged from 1.9645 to 6.5752 mg/kg, which did not exceed the projected European Union cut-off limits (6 mg/kg) for sludge found in farmland, except for the Haibohe WWTP. Significant differences were observed in overall PAH values between WWTPs receiving domestic effluents and those receiving industrial effluents. The total amounts of PAHs in digested sludge from the Licunhe and Haibohe WWTPs, which mainly received industrial effluents, were markedly higher than those of the Tuandao and Huangdao WWTPs, which received only domestic effluents. The distribution of PAH compounds in digested sludges were analysed. At the Tuandao, Huangdao and Licunhe WWTPs, 2-, 3-, 4-benzene rings were predominant, accounting for 100%, 99.8% and 99.0% of the sum concentration of 16 PAHs (∑PAHs), respectively. At the Haibohe WWTP, a large number of high molecular weight PAHs (5-, 6-benzene rings) were observed, accounting for 30% of the ∑PAHs. The sum of seven carcinogenic PAHs (∑PAHs-c) ranged from 0.8694 to 3.0389 mg/kg in four WWTPs. The highest value was found in the Haibohe WWTP. Moreover, the PAH concentrations in sludges from the different treatment processes in the Licunhe and Tuandao WWTPs are discussed.     

Techno-economical efficiency and productivity change of wastewater treatment plants: the role of internal and external factors

Efficiency and productivity are important measures for identifying best practice in businesses and optimising resource-use. This study analyses how these two measures change across the period 2003-2008 for 196 wastewater treatment plants (WWTPs) in Spain, by using the benchmarking methods of Data Envelopment Analysis and the Malmquist Productivity Index. To identify which variables contribute to the sustainability of the WWTPs, differences in efficiency scores and productivity indices for external factors are also investigated. Our results indicate that both efficiency and productivity decreased over the five years. We verify that the productivity drop is primarily explained by technical change. Furthermore, certain external variables affected WWTP efficiency, including plant size, treatment technology and energy consumption. However, plants with low energy consumption are the only ones which improve their productivity. Finally, the benchmarking analyses proved to be useful as management tools in the wastewater sector, by providing vital information for improving the sustainability of plants.     

Assessing the feasibility of wastewater recycling and treatment efficiency of wastewater treatment units

Wastewater reuse can significantly reduce environmental pollution and save the water sources. The study selected Cheng-Ching Lake water treatment plant in southern Taiwan to discuss the feasibility of wastewater recycling and treatment efficiency of wastewater treatment units. The treatment units of this plant include wastewater basin, sedimentation basin, sludge thickener and sludge dewatering facility. In this study, the treatment efficiency of SS and turbidity were 48.35–99.68% and 24.15–99.36%, respectively, showing the significant removal efficiency of the wastewater process. However, the removal efficiencies of NH₃–N, total organic carbon (TOC) and chemical oxygen demand (COD) are limited by wastewater treatment processes. Because NH₃–N, TOC and COD of the mixing supernatant and raw water are regulated raw water quality standards, supernatant reuse is feasible and workable during wastewater processes at this plant. Overall, analytical results indicated that supernatant reuse is feasible.