Bisphenol A in hazardous waste landfill leachates

The levels of bisphenol A in hazardous waste landfill leachates collected in Japan in 1996 were determined by gas chromatograph/mass spectrometer (GC/MS). Bisphenol A was found in seven of 10 sites investigated. All the hazardous waste landfills with leachates contaminated by bisphenol A were controlled. The concentrations of bisphenol A ranged from 1.3 to 17,200 microg/l with a median concentration of 269 microg/l. The source of bisphenol A in landfill leachates may be the waste plastics in waste landfill. The concentrations of bisphenol A in some samples exceeded the EC50 or LC50 levels for aquatic biota. Landfill leachates may be a significant source of bisphenol A found in the environment.     

Glycosylation of bisphenol A by freshwater microalgae

The endocrine disruptor bisphenol A (BPA, 4,4'-isopropylidenediphenol) is used to manufacture polycarbonate plastic and epoxy resin linings of food and beverage cans, and the residues from these products are then sometimes discharged into rivers and lakes in waste leachates. However, the fate of BPA in the environment has not yet been thoroughly elucidated. Considering the effect of BPA on aquatic organisms, it is important that we estimate the concentration of BPA and its metabolites in the aquatic environment, but there are few data on the metabolites of BPA. Here, we focused on freshwater microalgae as organisms that contribute to the biodegradation or biotransformation of BPA in aquatic environments. When we added BPA to cultures of eight species of freshwater microalgae, a reduction in the concentration of BPA in the culture medium was observed in all cultures. BPA was metabolized to BPA glycosides by Pseudokirchneriella subcapitata, Scenedesmus acutus, Scenedesmus quadricauda, and Coelastrum reticulatum, and these metabolites were then released into the culture medium. The metabolite from P. subcapitata, S. acutus, and C. reticulatum was identified by FAB-MS and (1)H-NMR as bisphenol A-mono-O-beta-d-glucopyranoside (BPAGlc), and another metabolite, from S. quadricauda, was identified as bisphenol A-mono-O-beta-d-galactopyranoside (BPAGal). These results demonstrate that freshwater microalgae that inhabit universal environments can metabolize BPA to its glycosides. Because BPA glycosides accumulate in plants and algae, and may be digested to BPA by beta-glycosidase in animal intestines, more attention should be given to levels of BPA glycosides in the environment to estimate the ecological impact of discharged BPA.     

Xenoestrogens in the River Elbe and its tributaries

4-Alkylphenols, 4-alkylphenol ethoxylates, 4-alkylphenoxy carboxylates, bisphenol A, bisphenol F, 4-hydroxyacetophenon, 4-hydroxybenzoic acid and steroid hormones were analyzed in water samples of the River Elbe and its tributaries Schwarze Elster, Mulde, Saale, Havel and Schwinge. Additionally, freshly deposited sediments (FDS, composite samples) of the River Elbe and its tributaries were analyzed. The concentrations in water samples ranged from (in ng/l): bisphenol A 4 to 92, branched nonylphenol 13 to 87, branched nonylphenol ethoxylates <0.5 to 120, 4-tert. nonylphenoxy carboxylates <10 to 940 and 4-hydroxybenzoic acid 4 to 12. Steroid hormones were only detected in the Czech tributaries Jizera and Vltava in concentrations near the limit of quantification. In FDS samples the concentrations amounted to (in g/kg d.w.): bisphenol A 10-380, branched nonylphenol 27-430, branched nonylphenol ethoxylates 24-3700, nonylphenoxy carboxylates <50 and 4-hydroxybenzoic acid 23-4400. Increased bisphenol A concentrations were found in water and FDS samples taken from the Czech-German border at Schmilka and the mouth of the Schwinge (only water sample). According to studies conducted in the Elbe Estuary and the German Bight, the River Elbe must be considered as a major source of pollution for the North Sea in respect of the compounds analyzed. A comparison of bisphenol A concentrations, 4-alkylphenols and the corresponding ethoxylates analyzed in the River Elbe and its tributaries with those found in other German surface waters indicated a low level of contamination. The evaluation of the data based on LOEC-values indicated that the concentrations were well below the effectivity threshold for some 4-alkylphenols. According to recent ecotoxicological investigations, for example, with prosobranch snails, bisphenol A concentrations found in water samples of the River Elbe and its tributaries may well be detrimental to aquatic organisms. On the basis of the monitoring data and its implications for estrogenic potency the inclusion of bisphenol A in the list of priority substances (European Union Directive 2000/60/EC, Annex X) should be considered.     

Increased urinary 8-hydroxy-2��-deoxyguanosine levels in workers exposed to di-(2-ethylhexyl) phthalate in a waste plastic recycling site in China

Background

Di-(2-ethylhexyl) phthalate (DEHP) is a common plasticizer used in industrial and diverse consumer products. Animal studies indicate DEHP caused developmental, reproductive, and hepatic toxicities. However, human studies of the potential effects of DEHP are limited.

Methods

The exposed site with a history of over 20 years of waste plastic recycling was located in Hunan Province, China. The reference site without known DEHP pollution source was about 50 km far away from the exposed site. In this study, 181 workers working in plastic waste recycling and 160 gender?Cage matched farmers were recruited. DEHP concentrations in water and cultivated soil samples, serum thyroid-stimulating hormone, malondialdehyde (MDA), superoxide dismutase (SOD), urinary 8-hydroxy-2??-deoxyguanosine (8-OHdG), and micronuclei frequency in human capillary blood lymphocytes were analyzed.

Results

Mean levels of DEHP were greater in environment at the recycling site than at reference site (industry wastewater for the exposed: 42.43 ??g/l; well water: 14.20 vs. 0.79 ??g/l, pond water: 135.68 vs. 0.37 ??g/l, cultivated soil: 13.07 vs. 0.81 mg/kg, p?p?p?Conclusions The occupational DEHP exposure might contribute to oxidative deoxyribonucleic acid damage in the male workers.     

Estrogenic and dioxin-like potency in each step of a controlled landfill leachate treatment plant in Japan

The estrogenic activity (by E-screen bioassay), the concentrations of PCBs, PCDDs/PCDFs (and their resulting toxicity equivalents, TEQ) and several endocrine disrupting chemicals (EDCs: e.g., bisphenol A, nonylphenol, Butyl benzylpthalate (BBP), di-n-butylphthalate (DBP), 17alpha-ethynyl-estradiol or 4-octylphenol) have been analyzed from leachates of each step (before treatment, after biodegradation/sedimentation and after charcoal treatment) of a controlled landfill leachate treatment plant. The comparison of the effluent of the examined landfill leachate treatment plant with water from a nearby river in this study indicated no additional dioxin-like (e.g., TEQ: 0.027 compared to 1.01 pg TEQ/l; PCBs: 1.2 compared to 3.9 ng/l) or estrogenic impact (2.8 compared to 3.5 ng estradiol equivalents EE/l; analyzed by E-screen bioassay) from the leachate treatment plant into the surrounding water environment. The impact of dioxin-like compounds from uncleaned leachates into the final cleaned effluents could be sufficiently reduced by the leachate treatment plant for PCDDs (75%), PCDFs (62%), dioxin-like PCBs (97%), and the sum of TEQ (78%). The leachate treatment plant also achieved a reduction of the estrogenic activity as determined by E-screen (from 4.8 to 2.8 ng EE/l = 42%), by GC/MS for bisphenol A (>96% and nonylphenol (>98%) or by ELISA for estradiol (>80%). Additionally, for the validation of the E-screen, five known endocrine disrupting chemicals (EDCs: bisphenol A, BBP, DBP, 17 alpha-ethynyl-estradiol, 4-octylphenol) were analyzed. The EC50 values and estradiol equivalents factors (EEFs) for the five EDCs determined in this study were comparable to previously published data. The combined biological and chemical trace analysis data have provided valuable information on the relative contribution of natural, synthetic, and non-steroidal anthropogenic chemicals to the estrogenic and dioxin-like activity in leachates from a wastewater treatment plant, and water from a nearby river.     

Hexabromocyclododecanes in soils and plants from a plastic waste treatment area in North China: occurrence,diastereomer- and enantiomer-specific profiles,and metabolization

Plastic waste is a source of organic contaminants such as hexabromocyclododecanes (HBCDs). HBCDs have been found to cause developmental and reproductive toxicity; it is important to investigate the occurrence and metabolization of HBCDs in the soil environments with plastic waste contamination. This work analyzed HBCDs and their metabolites in soil and plant samples collected from Xinle and Dingzhou—the major plastic waste recycling centers in North China. Results showed that total HBCD concentrations in soils followed the order: plastic waste treatment site (11.0–624 ng/g) > roadside (2.96–85.4 ng/g) ≥ farmland (8.69–55.5 ng/g). HBCDs were detected in all the plant samples with total concentrations ranging from 3.47 to 23.4 ng/g. γ-HBCD was the dominant congener in soils, while α-HBCD was preferentially accumulated in plants. Compositions of HBCD isomers in soils and plants were significantly different (P < 0.05) among sampling sites and among plant species. HBCDs in farmland soil and all plant samples exhibited high enantio-selectivity based on the enantiomeric fractions (EFs). Furthermore, metabolites of pentabromocyclododecenes (PBCDEs) were frequently identified in soils, and mono-OH-HBCDs were the most common ones in plants. This study for the first time provides evidences of HBCD contamination in the soil-plant system caused by plastic waste, their stereo-selectivity, and metabolization behavior, improving our understanding of the environmental behavior and fate of HBCDs.     

Dioxin mass balance in a municipal waste incinerator

A dioxin mass balance in an Spanish municipal waste incinerator (MWI) is presented. Input and output inventories from two sampling collection episodes including the analysis of PCDD/PCDF in urban solid waste (USW), stack gas emissions, fly ash and slag are reported. In one collection the levels of USW were around 8 pg I-TEQ/g and non-thermal destruction was observed overall. In the other collection the levels of USW were higher (around 64 pg I-TEQ/g) and the dioxin balance revealed a thermal destruction. Analysis of the different waste materials (textile, organic, plastic, wood and paper) was performed separately and the textile samples presented the highest levels.     

Alkaline hydrothermal treatment of brominated high impact polystyrene (HIPS-Br) for bromine and bromine-free plastic recovery

A method to recover both Br and Br-free plastic from brominated flame retardant high impact polystyrene (HIPS-Br) was proposed. HIPS-Br containing 15% Br was treated in autoclave at 280 degrees C using water or KOH solution of various amounts and concentrations. Hydrothermal treatment (30 ml water) leads to 90% debromination of 1g HIPS-Br but plastic is strongly degraded and could not be recovered. Alkaline hydrothermal treatment (45 ml or 60 ml KOH 1M) showed similar debromination for up to 12 g HIPS-Br and plastic was recovered as pellets with molecular weight distribution close to that of the initial material. Debromination occurs at melt plastic/KOH solution interface when liquid/vapour equilibrium is attained inside autoclave (280 degrees C and 7 MPa in our experimental conditions) and depends on the plastic amount/KOH volume ratio. The antimony oxide synergist from HIPS-Br remains in recovered plastic during treatment. A pictorial imagination of the proposed debromination process is presented.     

Bisphenol A and Bisphenol S release in milk under household conditions from baby bottles marketed in Italy

A simple and sensitive validated analytical method based on liquid chromatography coupled to tandem fluorescence (FD) and ultraviolet (UV) spectrophotometry was applied to monitor the presence of bisphenol A and bisphenol S in plastic baby bottles marketed in Italy. The limits of detection (LOD) were 3.75 ng mL^?1 and 80.00 ng mL^?1, and those of quantification (LOQ) were 12.51 ng mL^?1 and 260.00 ng mL^?1 for BPA (FD detection) and for BPS (UV detection), respectively. BPA was found in only four samples, two samples undergone to microwave heating and two samples undergone to bottle warmer heating either at 40°C or at 80°C. Although the quantities of leached BPA were well below the reference dose for daily intake established by the European Food Safety Authority (EFSA) (4.0 µg kg^?1 bw/day), the release of BPA and BPS from these plastic materials should be carefully considered by the government authorities to increase people's awareness on this issue and to protect the most vulnerable population group.     

A novel one-step synthesis for carbon-based nanomaterials from polyethylene terephthalate (PET) bottles waste

Nowadays our planet suffers from an accumulation of plastic products that have the potential to cause great harm to the environment in the form of air, water, and land pollution. Plastic water bottles have become a great problem in the environment because of the large numbers consumed throughout the world. Certain types of plastic bottles can be recycled but most of them are not. This paper describes an economical solvent-free process that converts polyethylene terephthalate (PET) bottles waste into carbon nanostructure materials via thermal dissociation in a closed system under autogenic pressure together with additives and/or catalyst, which can act as cluster nuclei for carbon nanostructure materials such as fullerenes and carbon nanotubes. This research succeeded in producing and controlling the microstructure of various forms of carbon nanoparticles from the PET waste by optimizing the preparation parameters in terms of time, additives, and amounts of catalyst.

Implications: Plastic water bottles are becoming a growing segment of the municipal solid waste stream in the world; some are recycled but many are left in landfill sites. Recycling PET bottles waste can positively impact the environment in several ways: for instance, reduced waste, resource conservation, energy conservation, reduced greenhouse gas emissions, and decreasing the amount of pollution in air and water sources. The main novelty of the present work is based on the acquisition of high-value carbon-based nanomaterials from PET waste by a simple solvent-free chemical technique. Thus, the prepared materials are considered to be promising, cheap, eco-friendly materials that may find use in different applications.     

Survey of phthalates, alkylphenols, bisphenol A and herbicides in Spanish source waters intended for bottling

Background, aim and scope

Groundwaters and source waters are exposed to environmental pollution due to agricultural and industrial activities that can enhance the leaching of organic contaminants. Pesticides are among the most widely studied compounds in groundwater, but little information is available on the presence of phthalates, alkylphenols and bisphenol A. These compounds are used in pesticide formulations and represent an emerging family of contaminants due to their widespread environmental presence and endocrine-disrupting properties. Knowledge on the occurrence of contaminants in source waters intended for bottling is important for sanitary and regulatory purposes. So the aim of the present study was to evaluate the presence of phthalates, alkylphenols, triazines, chloroacetamides and bisphenol A throughout 131 Spanish water sources intended for bottling. Waters studied were spring waters and boreholes which have a protection diameter to minimize environmental contamination.

Materials and methods

Waters were solid-phase extracted (SPE) and analysed by gas chromatography coupled to mass spectrometry (GC-MS). Quality control analysis comprising recovery studies, blank analysis and limits of detection were performed.

Results and discussion

Using SPE and GC-MS, the 21 target compounds were satisfactorily recovered (77?C124?%) and limits of quantification were between 0.0004 and 0.029???g/L for pesticides, while for alkylphenols, bisphenol A and phthalates the limits of quantification were from 0.0018???g/L for octylphenol to 0.970???g/L for bis(2-ethylhexyl) phthalate. Among the 21 compounds analysed, only 9 were detected at levels between 0.002 and 1.115???g/L. Compounds identified were triazine herbicides, alkylphenols, bisphenol A and two phthalates. Spring waters or shallow boreholes were the sites more vulnerable to contaminants. Eighty-five percent of the samples did not contain any of the target compounds.

Conclusions

Target compounds were detected in a very low concentration and only in very few samples. This indicates the good quality of source waters intended for bottling and the effectiveness of the protection measures adopted in Spain. None of the samples analysed exceeded the maximum legislated levels for drinking water both in Spain and in the European Union.     

Identification and quantification of chlorinated bisphenol A in wastewater from wastepaper recycling plants

Chlorinated derivatives of bisphenol A were detected in the final effluents of eight paper manufacturing plants in Shizuoka, Japan, where thermal paper and/or other printed paper is used as the raw material. Their amounts were determined by gas chromatography/mass spectrometry (GC/MS) after treatment with N, O-bis(trimethylsilyl)trifluoroacetamide, and ranged from traces to 2.0 microg/l. They are likely produced by chlorination of bisphenol A, which was released into the effluents from the pulping process of wastepaper, during or after bleaching with chlorine.     

新型无机高分子絮凝剂在制革废水处理中的应用研究

介绍了一种新型无机高分子絮凝剂－硅钙复合型聚合氯化铝铁（ＳＣＰＡＦＣ）在制革废水处理中的应用。结果表明，该产品对废水的浊度去除率为９９％，ＳＳ去除率为９５％，ＣＯＤ去除率为９０％，Ｃｒ＾３＋的去除率为８５％左右。最佳使用ｐＨ值为６．０￣９．０，最佳投药量为０．３５￣０．４０ｇ／Ｌ，最佳混凝时间为１５￣２０ｍｉｎ，在同样条件下各项性能均优于ＰＡＣ２倍以上。同时该絮凝剂还可用于生活饮水、生产用水及其他     

Gaseous ammonia uptake in compost biofilters as related to compost water content

Sewage sludge and yard waste compost were used as biofilter materials and tested with respect to their capacity for removing ammonia from air at different water contents. Ammonia removal was measured in biofilters containing compost wetted to different moisture contents ranging from air dry to field capacity (maximum water holding capacity). Filters were operated for 15 days and subsequently analyzed for NH3/NH4+, NO2-, and NO3-. The measured nitrogen species concentration profiles inside the filters were used to calculate ammonia removal rates. The results showed that ammonia removal is strongly dependent on the water content in the filter material. At gravimetric water contents below 0.25 g H2O g solids(-1) for the yard waste compost and 0.5 g H2O g solids(-1) ammonia removal rates were very low but increased rapidly above these values. The sewage sludge compost filters yielded more than twice the ammonia removal rate observed for yard waste compost likely because of a high initial concentration of nitrifying bacteria originating from the wastewater treatment process and a high airwater interphase surface area that facilitates effective ammonia dissolution and transport to the biofilm.     

Interactive analysis of waste recycling and energy recovery program in a small-scale incinerator

Conflicting goals affecting solid waste management are explored in this paper to find the best implementation of resource recovery with a small-scale waste-to-energy process. Recycling paper and plastic material often leaves a shortage of thermal energy to support incineration that forces operators to supplement the process with auxiliary fuels. Although there are considerable profits to be made from material recovery, the increase of fuel usage causes conflict given that it is cost prohibitive. A series of trials performed on a small-scale 1.5-t/day incineration plant with a cyclone heat recovery system found that material recycling can impede performance. Experimental results are expressed as empirical regression formulas with regard to combustion temperature, energy transfer, and heat recovery. Process optimization is possible if the waste moisture content remains <30%. To test the robustness of the optimization analysis, a series of sensitivity analyses clarify the extent of material recycling needed with regard to plastic, paper, and metal. The experiments also test whether the moisture in the waste would decrease when recycling paper because of its exceptional capacity to absorb moisture. Results show that recycling paper is strongly recommended when the moisture content is >20%, whereas plastic recycling is not necessary at that moisture condition. Notably, plastic recovery reduces the heat needed to vaporize the water content of the solid waste, thus it is recommended only when the moisture content is <10%. For above-normal incineration temperatures, plastic recycling is encouraged, because it removes excess energy. Metal is confirmed as an overall priority in material recycling regardless of the moisture content of the incoming waste.     

An experimental study on usage of plastic oil and B20 algae biodiesel blend as substitute fuel to diesel engine

Usage of plastics has been ever increasing and now poses a tremendous threat to the environment. Millions of tons of plastics are produced annually worldwide, and the waste products have become a common feature at overflowing bins and landfills. The process of converting waste plastic into value-added fuels finds a feasible solution for recycling of plastics. Thus, two universal problems such as problems of waste plastic management and problems of fuel shortage are being tackled simultaneously. Converting waste plastics into fuel holds great promise for both the environmental and economic scenarios. In order to carry out the study on plastic wastes, the pyrolysis process was used. Pyrolysis runs without oxygen and in high temperature of about 250–300 °C. The fuel obtained from plastics is blended with B20 algae oil, which is a biodiesel obtained from microalgae. For conducting the various experiments, a 10-HP single-cylinder four-stroke direct-injection water-cooled diesel engine is employed. The engine is made to run at 1500 rpm and the load is varied gradually from 0 to 100 %. The performance, emission and combustion characteristics are observed. The BTE was observed to be higher with respect to diesel for plastic-biodiesel blend and biodiesel blend by 15.7 and 12.9 %, respectively, at full load. For plastic-biodiesel blend, the emission of UBHC and CO decreases with a slight increase in NO _x as compared to diesel. It reveals that fuel properties are comparable with petroleum products. Also, the process of converting plastic waste to fuel has now turned the problems into an opportunity to make wealth from waste.     

Mobility of dimethoate residues from spring broccoli field

Dimethoate [O, O-dimethyl-S-(N-methylcarbamoyl-methyl) phosphorodithioate] is a broad-spectrum systemic insecticide currently used worldwide and on many vegetables in Kentucky. Dimethoate is a hydrophilic compound (log KOW = 0.7) and has the potential of offsite movement from the application site into runoff and infiltration water. The dissipation patterns of dimethoate residues were studied on spring broccoli leaves and heads under field conditions. Following foliar application of Dimethoate 4E on broccoli foliage at the rate of 0.47 L acre(-1), dimethoate residues were monitored in soil, runoff water collected down the land slope, and in infiltration water collected from the vadose zone. The study was conducted on a Lowell silty loam soil (pH 6.9) planted with broccoli under three soil management practices: (i) soil mixed with municipal sewage sludge, (ii) soil mixed with yard waste compost, and (iii) no-mulch rototilled bare soil. The main objective of this investigation was to study the effect of mixing native soil with municipal sewage sludge or yard waste compost, having considerable amounts of organic matter, on off-site movement of dimethoate residues into runoff and infiltration water following spring rainfall. The initial deposits of dimethoate were 6.2 and 21.4 micro g g(-1) on broccoli heads and leaves, respectively. These residues dissipated rapidly and fell below the maximum residue limit of 2 micro g g(-1) on the heads and leaves after 10 and 14 d, respectively, with half-lives of 5.7 d on broccoli heads and 3.9 d on the leaves. Dimethoate residues detected in top 15 cm of soil (due to droplet drift and wash off residues from broccoli foliage) one day (d) following spraying, were 30.5 ng g(-1) dry soil in the sewage sludge treatment, and 46.1 and 134.5 ng g(-1) dry soil in the yard waste and no mulch treatments, respectively. Water infiltration was greater from yard waste compost treatment than from no mulch treatment, however concentrations of dimethoate in the vadose zone of the three soil treatments did not differ.     

白洋淀水中白腐真菌对双酚A的降解规律及途径研究

研究白洋淀表层水(白洋淀原水)、无机盐培养基、无机盐培养基强化的白洋淀原水中双酚A在白腐真菌作用下的生物降解规律,同时考察了细菌及pH等因素对降解率的影响.实验结果表明,白洋淀原水中双酚A在白腐真菌作用下的降解率很高.甚至高于最适营养条件(无机盐培养基)下双酚A的降解率.在6 d达到完全降解.但是无机盐培养基强化的白洋淀原水抑制了白腐真菌对双酚A的降解;当细菌存在时.白腐真菌与细菌对碳源和能源等形成了竞争关系,抑制了白腐真菌的生长.不利于白腐真菌对双酚A的降解;无机盐培养基强化的白洋淀原水在初始pH-6.00时双酚A的降解率高于初始pH=7.00时双酚A的降解率.通过气相色谱/质谱(GC/MS)分析.白腐真菌降解双酚A的中间产物包括2-对羟苯基-2-酮基-1-乙醇、2-羟基苯乙酸和丙二酸等小分子酸.     

Interactive Analysis of Waste Recycling and Energy Recovery Program in a Small-Scale Incinerator

Abstract

Conflicting goals affecting solid waste management are explored in this paper to find the best implementation of resource recovery with a small-scale waste-to-energy process. Recycling paper and plastic material often leaves a shortage of thermal energy to support incineration that forces operators to supplement the process with auxiliary fuels. Although there are considerable profits to be made from material recovery, the increase of fuel usage causes conflict given that it is cost prohibitive. A series of trials performed on a small-scale 1.5-t/day incineration plant with a cyclone heat recovery system found that material recycling can impede performance. Experimental results are expressed as empirical regression formulas with regard to combustion temperature, energy transfer, and heat recovery. Process optimization is possible if the waste moisture content remains <30%. To test the robustness of the optimization analysis, a series of sensitivity analyses clarify the extent of material recycling needed with regard to plastic, paper, and metal. The experiments also test whether the moisture in the waste would decrease when recycling paper because of its exceptional capacity to absorb moisture. Results show that recycling paper is strongly recommended when the moisture content is >20%, whereas plastic recycling is not necessary at that moisture condition. Notably, plastic recovery reduces the heat needed to vaporize the water content of the solid waste, thus it is recommended only when the moisture content is <10%. For above-normal incineration temperatures, plastic recycling is encouraged, because it removes excess energy. Metal is confirmed as an overall priority in material recycling regardless of the moisture content of the incoming waste.     

Occurrence and temporal variations of the xenoestrogens bisphenol A, 4-<Emphasis Type="Italic">tert</Emphasis>-octylphenol,and tech. 4-nonylphenol in two German wastewater treatment plants

GOAL, SCOPE, AND BACKGROUND: The xenoestrogens bisphenol A, 4-tert-octylphenol, and the technical isomer mixture of 4-nonylphenol (tech. 4-nonylphenol) belong to the group of chemicals which are called endocrine disrupters due to their property of causing hormonal dysfunctions in the endocrine system of organisms at very low concentrations. Bisphenol A, 4-tert-octylphenol, and the tech. 4-nonylphenol (mixture of isomers) were determined in water samples collected from the influent and effluent of two German wastewater treatment plants (WWTP) during a long-time sampling period from February 2003 till August 2005 to assess their occurrence and temporal variations in WWTPs. METHODS: The compounds were extracted and concentrated from water by solid-phase extraction (SPE) using Bond Elut PPL cartridges and quantified by use of gas chromatography-mass spectrometry (GC-MS). RESULTS: The influent concentrations were as follows: Bisphenol A < limit of detection of the method (< ldm)--12,205 ng L(-1), tech. 4-nonylphenol < ldm--10,186 ng L(-1), and 4-tert-octylphenol 39-1,495 ng L(-1). The measured effluent concentrations were lower with values in the range of < ldm--7,625 ng L(-1) for bisphenol A, < ldm--14,444 ng L(-1) for tech. 4-nonylphenol, and < ldm--392 ng L(-1) for 4-tert-octylphenol. All target compounds were largely eliminated during the wastewater treatment process. The elimination efficiency varied between 73% and 93%. DISCUSSION: All analytes show highly fluctuating influent concentrations with very high peak concentrations at particular sampling times. The variation of effluent concentrations is by far lower than the variation of influent concentrations. For tech. 4-nonylphenol, a significant temporal concentration variation has been detected with very high concentrations up to the microgram-per-liter level in the time from February 2003 till July 2003 and clearly decreasing concentrations in the time from June 2004 till August 2005. This corresponds well with the implementation of Directive 2003/53/EC (nonylphenol and nonylphenol ethoxylates in the European Union "may not be placed on the marked or used as a substance or constituent of preparations in concentrations equal or higher than 0.1% by mass") from January 2005 on. Bisphenol A is present in the effluent samples in a wide range of concentrations from below the detection limit to high concentrations up to the microgram-per-liter level. For 4-tert-octylphenol, no particular trend of concentration development has been observed. CONCLUSIONS: Combined SPE and GC-MS proved to be an efficient method to identify and quantify polar organic compounds in environmental samples. With respect to the concentrations measured in the present study, bisphenol A sometimes is the prominent compound in influent samples. Neither bisphenol A nor 4-tert-octylphenol or tech. 4-nonylphenol show seasonal variations. However, there was a significant general trend of decreasing concentrations of tech. 4-nonylphenol in influent and effluent samples from both WWTPs which probably reflects the implementing Directive 2003/53/EC. RECOMMENDATIONS AND PERSPECTIVES: Further research is needed to investigate whether the observed decrease of tech. 4-nonylphenol concentrations in German WWTPs since June 2004 will continue further on. The reason for the high effluent concentrations of bisphenol A in only a few samples has to be clarified in further research. The results from this study provide insight into the concentration development of the xenoestrogens bisphenol A, tech. 4-nonylphenol, and 4-tert-octylphenol in WWTPs in the time span between 2003 and 2005.