Pharmaceutical compounds in the wastewater process stream in Northwest Ohio

In order to add to the current state of knowledge regarding occurrence and fate of Pharmaceutical and Personal Care Products (PPCP's) in the environment, influent, effluent and biosolids from three wastewater treatment facilities in Northwest Ohio, USA, and a stream containing effluent discharge from a rural treatment facility were analyzed. The three WWTP facilities vary in size and in community served, but are all Class B facilities. One facility was sampled multiple times in order to assess temporal variability. Twenty compounds including several classes of antibiotics, acidic pharmaceuticals, and prescribed medications were analyzed using ultrasonication extraction, SPE cleanup and liquid chromatography-electrospray ionization tandem mass spectrometry. The highest number of compounds and the greatest concentrations were found in the influent from the largest and most industrial WWTP facility. Short-term temporal variability was minimal at this facility. Many compounds, such as clarithromycin, salicylic acid and gemfibrizol were found at concentrations more than one order of magnitude higher than found in the effluent samples. Effluent waters contained elevated levels of carbamazepine, clindamycin and sulfamethoxazole. Differences in composition and concentration of effluent waters between facilities existed. Biosolid samples from two different facilities were very similar in PPCP composition, although concentrations varied. Ciprofloxacin was found in biosolids at concentrations (up to 46 mug/kg dry mass) lower than values reported elsewhere. Diclofenac survived the WWTP process and was found to persist in stream water incorporating effluent discharge. The low variability within one plant, as compared to the variability found among different wastewater treatment plants locally and in the literature is likely due to differences in population, PPCP usage, plant operations and/or local environment. These data are presented here for comparison with this emerging set of environmental compounds of concern.     

Material odor-odoractive compounds identified in different materials--the surprising similarities with certain foods, possible sources and hypotheses on their formation

Increased efforts have been undertaken by manufacturers to reveal the secrets of material odors, the structure of the odorants responsible, with regard to finding out the source(s) of odor and possible starting points for odor reduction, and therewith product improvement, increased consumer satisfaction and improved indoor air quality. The identification of odor-active compounds in materials by means of gas chromatography-olfactometry (GC-O, also called GC-sniffing), performed at the Fraunhofer Institute for Building Physics (IBP) during the previous years, showed surprising similarities between certain odorants found in materials and those previously identified in certain kinds of food. Examples of important odorants found in different material samples and similarities with food odorants were analyzed. Odorant sources are indicated as regards materials, and possible conditions and mechanisms of formation suggested to show starting points for odor reduction and odor improvement in material development. PRACTICAL IMPLICATIONS: If technical materials are planned to be used indoors and if they spread a distinct odor, the analysis of the compounds contained and emitted by this material using gas chromatography-olfactometry is a means to help reveal the compounds being responsible for that odor. The exact knowledge of the structure of the odorants is the prerequisite for drawing conclusions on possible sources and formation mechanisms and to reveal starting points for odor reduction and product improvement, e.g. by changing ingredients or production conditions. This contributes to an improvement of indoor air quality. Furthermore, quite often the concentrations of certain single odorants found in materials can be very low and the same odorants can be part of other well-known food flavors. This information might be useful to reduce consumers' fears of a possible impairment of their health in the future.     

Using filtrate of waste biosolids to effectively produce bio-hydrogen by anaerobic fermentation

Waste biosolids collected from sewage works is a biomass containing a vast amount of polysaccharides and proteins, and thus is considered a potential substrate for producing hydrogen using anaerobic fermentation. This work demonstrated, contrary to the common assumption, that the solids phase in waste activated biosolids presents extra nutrients for anaerobes; it in fact prohibits effective bio-hydrogen production. Using filtrate after removal of solids from biosolids produces more hydrogen than using the whole biosolids, with the former reaching a level an order of magnitude higher than the literature results.     

"Weak" ultrasonic pre-treatment on anaerobic digestion of flocculated activated biosolids

This study examined how "weak" ultrasonic pre-treatment affects anaerobic digestion of waste biosolids, treated with a cationic polyelectrolyte flocculant. In relation to pre-treatment, the term "weak" used refers to the fact that the total ultrasonic energy input to biosolids is insufficient to fully disrupt its floc structure or the cell walls, as described in the literature. Methane production potential, floc characteristics (size, morphology and zeta-potential) and process parameters (chemical oxygen demands and oxidative-reductive potentials) were monitored, as the digestion was tested. The presence of polyelectrolyte flocculants enhanced methane production within 6 days of digestion (phase I), but inhibited the digestion thereafter (phase II). Following pre-treatment by sonication (0.33 W/mL, 20 min), the methane productions of both original and flocculated biosolids significantly increased. The underlying mechanisms of weak ultrasonic pre-treatment are discussed.     

Nitrogen Release and Fertiliser Value of Thermally-Dried Biosolids

Nitrogen production from five thermally-dried biosolids plants was measured in two contrasting soil types and compared with samples of undried digested sludge cake from the same treatment works, using a controlled laboratory incubation-extraction procedure. Inorganic-N was lost from the digested biosolids during high-temperature drying by ammonia volatilisation. Nevertheless, the production of nitrate-N in soil amended with thermally-dried biosolids was similar to, or greater than, conventionally-treated dewatered sludge. The results indicate that thermal conditioning significantly increases the mineralisable organic-N content in digested biosolids. Soil properties had subtle effects on the patterns of nitrogen release, but did not significantly affect the overall accumulation of mineral-N from the biosolids. The results showed that thermally-dried anaerobically-digested biosolids are potentially highly-consistent products and effective replacements for inorganic-N fertiliser in agricultural production.     

Optimising the production of energy from coblended food waste and biosolids using batch reactor studies

Energy production from a coblended mixture of biosolids and food waste was optimised for hydrogen and methane production. Four different blends were prepared by varying the carbohydrate : protein (carb : pro) ratios. The biosolids contained a low carbohydrate fraction and so was not suitable for hydrogen production when used alone. However coblending this waste with a carbohydrate‐enriched food waste produced a greater hydrogen yield, making this option viable. Batch studies showed that the optimised mix had a biosolids concentration of 25.7% (w/w). The largest hydrogen yield of 198.5 mL/gVS_removed was observed when the carb : pro was 2.78, and this was threefold higher than the other carb : pro ratios evaluated in this study. The digestate recovered after hydrogen recovery had a C : N of 17.5, which is in the ideal range for methane production. The biochemical methane potential test showed a methane yield of 239 mL/gVS_removed, and the total volatile solids destruction following two‐phase hydrogen and methane production was 93%.     

Sorption of phenols to dissolved organic matter investigated by solid phase microextraction

The sorption of phenol and different halogenated phenols to natural organic matter of a brown water lake (HO14), of a compost extract, of Aldrich humic acid (Aldrich-HA), and to the protein bovine serum albumin (BSA) was investigated using solid phase microextraction (SPME). The limit of determination for the SPME analysis was < 15 microg/l for all phenols investigated. The extraction coefficients K(F) were calculated according to a first-order extraction kinetics. In general, the extraction equilibrium was established faster due to the presence of dissolved organic matter (DOM). The highest sorption capacity of phenols was observed for BSA with log K(OC) values in the range between 2 and 6. For the compost extract and HO14 only a small sorption of the investigated phenols was determined. On the other hand, Aldrich humic acid showed a reasonable sorption of phenols with log K(OC) values between 2 and 3. The sorption to DOM decreased when the pH of the solution was increased.     

粉末炭去除饮用水中土霉味物质的影响因素研究

采用粉末活性炭（PAC）去除饮用水中2-甲基异莰醇（MIB）、2,4,6-三氯茴萫醚（TCA）、2-异丙基-3-甲氧基吡嗪（IPMP）和2-异丁基-3-甲氧基吡嗪（IBMP）等4种常见的土霉味物质,研究了PAC种类、PAC投加量、嗅味物质的初始浓度、余氯、水质等因素对PAC去除土霉味物质的影响。结果表明,PAC吸附对嗅味物质的去除主要发生在前1 h内;煤质PAC对MIB有更高的去除率;在一定的吸附时间和活性炭投加量下,PAC对痕量嗅味物质的去除率与其初始浓度无关;余氯和有机物的存在降低了PAC对嗅味物质的吸附容量,水质对去除嗅味物质也有很大的影响。     

Selected personal care products and endocrine disruptors in biosolids: an Australia-wide survey

Personal care products (PCPs) and endocrine disrupting compounds (EDCs) are groups of organic contaminants that have been detected in biosolids around the world. There is a shortage of data on these types on compounds in Australian biosolids, making it difficult to gain an understanding of their potential risks in the environment following land application. In this study, 14 biosolids samples were collected from 13 Australian wastewater treatment plants (WWTPs) to determine concentrations of eight compounds that are PCPs and/or EDCs: 4-t-octylphenol (4tOP), 4-nonylphenol (4NP), triclosan (TCS), bisphenol A (BPA), estrone (E1), 17β-estradiol (E2), estriol (E3) and 17α-ethinylestradiol (EE2). Concentration data were evaluated to determine if there were any differences between samples that had undergone anaerobic or aerobic treatment. The concentration data were also compared to other Australian and international data. Only 4tOP, 4NP, TCS, and BPA were detected in all samples and E1 was detected in four of the 14 samples. Their concentrations ranged from 0.05 to 3.08 mg/kg, 0.35 to 513 mg/kg, < 0.01 to 11.2 mg/kg, < 0.01 to 1.47 mg/kg and < 45 to 370 μg/kg, respectively. The samples that were obtained from WWTPs that used predominantly anaerobic treatment showed significantly higher concentrations of the compounds than those obtained from WWTPs that used aerobic treatment. Overall, 4NP, TCS and BPA concentrations in Australian biosolids were lower than global averages (by 42%, 12% and 62%, respectively) and 4tOP concentrations were higher (by 25%), however, of these differences only that for BPA was statistically significant. The European Union limit value for NP in biosolids is 50 mg/kg, which 4 of the 14 samples in this study exceeded.     

Emission of volatile organic compounds during composting of municipal solid wastes

The objective of this study was to identify and quantify volatile and semi-volatile organic compounds (VOCs) produced during composting of the organic fraction of municipal solid wastes (MSW). A laboratory experiment was conducted using organic components of MSW that were decomposed under controlled aerobic conditions. Mixed paper primarily produced alkylated benzenes, alcohols and alkanes. Yard wastes primarily produced terpenes, alkylated benzenes, ketones and alkanes, while food wastes primarily produced sulfides, acids and alcohols. Among 13 aromatic VOCs found in MSW composting facilities, toluene, ethylbenzene, 1,4-dichlorobenzene, p-isopropyl toluene, and naphthalene were in the largest amounts. Unseeded mixed paper, seeded mixed paper, seeded yard wastes, unseeded yard wastes, seeded food wastes and unseeded food wastes produced approximately 6.5, 6.1, 2.1, 0.83, 2.5 and 0.33 mg of 13 volatile and semi-volatile aromatic organic compounds combined, respectively, per dry kg. All VOCs were emitted early during the composting process and their production rates decreased with time at thermophilic temperatures.     

Molecular background of the undesired odor of polypropylene materials and insights into the sources of key odorants

Screening the volatiles isolated from a standard polypropylene material consisting of a polypropylene homopolymer, the filler talcum, and a mixture of antioxidants, for odor-active compounds by application of an aroma extract dilution analysis revealed 30 odorants with flavor dilution factors ranging from 1 to 64. Eighteen odor-active compounds were subsequently quantitated by gas chromatography-mass spectrometry using stable isotopically substituted odorants as internal standards, and their odor activity values (OAVs) were calculated as ratios of the concentrations to the odor threshold values. Five odorants showed OAVs ≥1, among which were hex-1-en-3-one (OAV 12), butanoic acid (OAV 3), as well as 4-methylphenol, butan-1-ol, and 2-tert-butylphenol (all OAV 1). A comparative analysis of polypropylene materials with different additives suggested plastic-like, pungent smelling hex-1-en-3-one as an ubiquitous key odorant. Odor-active amounts of alkylphenols, in particular plastic-like, phenolic smelling 2-tert-butylphenol, were additionally formed in the presence of talcum and phenolic antioxidants. Whereas the precursors of the phenols were thus obvious, the origin of hex-1-en-3-one was unknown. Injection molding showed only little influence on odorant concentrations.     

Life-cycle flow of mercury and recycling scenario of fluorescent lamps in Japan

A greenhouse pot experiment was conducted to evaluate the feasibility of using biosolids and Lolium perenne for the phytostabilization of copper mine tailings and to evaluate the patterns of metal accumulation and translocation in plants. Biosolids were applied either on the surface or mixed with the tailings at rates of 0, 6, and 12% w/w. All pots were seeded with L. perenne and after six months, the plants were harvested and separated into roots and shoots for metal concentrations analyses as well as some physiological characteristics of the plants. In order to correlate the metal content in plant tissues with some chemical properties, the pore-water of the substrates was analyzed for metals, pH and dissolved organic carbon. Results showed that biosolids application increased the dry biomass production of L. perenne and the shoot concentrations of N and chlorophyll. On the other hand, biosolids increased the concentration of Cu and Zn in the pore-water and in plant tissues. Despite this, there were no evident symptoms of phytotoxicity and the concentration of metals was within the normal ranges described for plants and below the maximum tolerable level for animals. In addition, plant tissue analysis showed that the application of biosolids could significantly reduce Mo uptake and shoot accumulation in plants. The metals were taken up by plants in the following order: Cu>Zn>Mo>Cd. The distribution patterns of metals in plants showed that metals were mainly accumulated in the roots and only a small amount of them were transported to the shoots. These results suggest that mixed application of biosolids (6%) and the use of L. perenne could be appropriate for use in programs of phytostabilization of copper mine tailings. However, these results should be tested under field conditions in order to confirm their efficacy under semi-arid Mediterranean climate conditions.     

Fate of synthetic musks in a domestic wastewater treatment plant and in an agricultural field amended with biosolids

Synthetic musks are widely used as fragrance ingredients in personal care products, and they enter domestic wastewater treatment plants (WWTPs) through discharges into municipal sewage systems. Samples of aqueous sewage and biosolids collected from the Peterborough Wastewater Treatment Plant (WWTP), Ontario, Canada were analyzed for 11 synthetic musk compounds using GC/MS. The results showed that 1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethyl-cyclopenta[g]-2-benzopyrane (HHCB, 173.1+/-43.4 ng/L) and 7-acetyl-1,1,3,4,4,6-hexamethyl-tetrahydronaphthalene (AHTN, 41.6+/-15.8 ng/L) were the dominant fragrances in sewage, but other polycyclic musks and nitro musks were present at lower concentrations. The concentrations of HHCB and AHTN in the aqueous phase of the sewage were highly correlated with both BOD5 and TOC. The overall removal efficiency of synthetic musks from the aqueous sewage in the WWTP ranged from 43.3% to 56.9%, but removal occurred mainly by partitioning into the biosolids. Based on a mass balance model, the daily input and output of HHCB and AHTN in the Peterborough WWTP were 47 g and 46 g, respectively. In an agricultural field amended with biosolids from the Peterborough WWTP, HHCB and AHTN were detected in soil immediately after application at mean concentrations of 1.0 and 1.3 mug/kg, respectively, but concentrations declined relatively rapidly over the next 6 weeks, post-application.     

Measured physicochemical characteristics and biosolids-borne concentrations of the antimicrobial Triclocarban (TCC)

Triclocarban (TCC) is an active ingredient in antibacterial bar soaps, a common constituent of domestic wastewater, and the subject of recent criticism by consumer advocate groups and academic researchers alike. Activated sludge treatment readily removes TCC from the liquid waste stream and concentrates the antimicrobial in the solid fraction, which is often processed to produce biosolids intended for land application. Greater than half of the biosolids generated in the US are land-applied, resulting in a systematic release of biosolids-borne TCC into the terrestrial and, potentially, the aquatic environment. Multiple data gaps in the TCC literature (including basic physicochemical properties and biosolids concentrations) prevent an accurate, quantitative risk assessment of biosolids-borne TCC. We utilized the USEPA Office of Prevention, Pesticides, and Toxic Substances (OPPTS) harmonized test guidelines to measure TCC solubility and log K_ow values as 0.045 mg L⁻¹ and 3.5, respectively. The measured physicochemical 2 properties differed from computer model predictions. The mean concentration of TCC in 23 biosolids representative of multiple sludge processing methods was 19 ± 11 mg kg⁻¹.     

Variations in amounts and potential sources of volatile organic chemicals in new cars

This study examines inter-brand, intra-brand and intra-model variations in volatile organic chemical (VOC) levels inside new cars. The effect of temperature on interior VOC levels was examined using model automobiles with and without the air-conditioning running. Potential sources of VOC were assessed by comparing VOC levels with two interior trims (leather and fabric) and by analyzing VOC emissions from various interior components. Five brands of new car, both domestic and imported, were tested. Twelve targeted VOCs were collected on solid sorbents and analyzed using thermal desorption and GC/FID. VOCs from interior parts and adhesives were identified using solid phase micro-extraction (SPME) coupled with GC/MS. The VOC concentrations varied markedly among brands and within models, and individual VOC levels ranged from below the detection limit (a few mug per cubic meter) to thousands of mug per cubic meter. The intra-model variability (mean, 47%) in the VOC levels was approximately 50% that within each brand (mean, 95%). Although interior trim levels affected VOC levels, the effects differed among brands. Reduction of the cabin temperature reduced most VOC levels, but the impact was not statistically significant. Screening tests for VOCs from interior parts revealed that butylated hydroxytoluene (BHT), a common anti-oxidant, was the most common chemical. Long-chain aliphatic hydrocarbons, particularly C14-C17, were identified in most grease (lubricant) samples, and toluene and xylenes were ubiquitously present in adhesive samples. Process-related compounds, such as plasticizer, were also identified in interior parts. In-cabin VOC levels varied significantly among makes/models and interior trims. Concerned consumers should purchase older new cars from manufacturers since VOC levels inside car cabins normally declines over time. Improved processes or materials with lower VOC emission potential should be used to minimize in-cabin VOC sources for new cars.     

Effect of residual chlorine on the analysis of geosmin, 2-MIB and MTBE in drinking water using the SPME technique

The effect of chlorine on the analysis of three organic compounds (geosmin, 2-methylisoborneol (2-MIB) and methyl tert-butyl ether (MTBE)) in drinking water is elucidated. Three fibers for solid-phase microextraction (SPME) were employed for the extraction of the organic compounds from drinking water samples with and without free residual chlorine present. A gas chromatograph coupled with a mass spectrometer was used to analyze the compounds trapped by the fibers. The presence of chlorine substantially reduces the observed geosmin, 2-MIB, and MTBE concentrations. Depending on the analyte and chlorine concentrations, an experimental error of 10-70% may be observed due to the presence of free residual chlorine. The impact is larger for lower organic compound concentrations, and under higher residual chlorine conditions. To counteract the effect from residual chlorine, sodium thiosulfate was used to dechlorinate the water. After dechlorination the experimental error was less than 10%, suggesting that dechlorination is necessary when applying SPME for the extraction of organic compounds from chlorinated drinking water.     

The effect of thermal hydrolysis pretreatment on the anaerobic degradation of nonylphenol and short-chain nonylphenol ethoxylates in digested biosolids

The presence of micropollutants can be a concern for land application of biosolids. Of particular interest are nonylphenol diethoxylate (NP₂EO), nonylphenol monoethoxylate (NP₁EO), and nonylphenol (NP), collectively referred to as NPE, which accumulate in anaerobically digested biosolids and are subject to regulation based on the environmental risks associated with them. Because biosolids are a valuable nutrient resource, it is essential that we understand how various treatment processes impact the fate of NPE in biosolids. Thermal hydrolysis (TH) coupled with mesophilic anaerobic digestion (MAD) is an advanced digestion process that destroys pathogens in biosolids and increases methane yields and volatile solids destruction. We investigated the impact of thermal hydrolysis pretreatment on the subsequent biodegradation of NPE in digested biosolids. Biosolids were treated with TH, anaerobic digestion, and aerobic digestion in laboratory-scale reactors, and NPE were analyzed in the influent and effluent of the digesters. NP₂EO and NP₁EO have been observed to degrade to the more estrogenic NP under anaerobic conditions; therefore, changes in the ratio of NP:NPE were of interest. The increase in NP:NPE following MAD was 56%; the average increase of this ratio in four sets of TH-MAD samples, however, was only 24.6 ± 3.1%. In addition, TH experiments performed in pure water verified that, during TH, the high temperature and pressure alone did not directly destroy NPE; TH experiments with NP added to sludge also showed that NP was not destroyed by the high temperature and pressure of TH when in a more complex sludge matrix. The post-aerobic digestion phases removed NPE, regardless of whether TH pretreatment occurred. This research indicates that changes in biosolids processing can have impacts beyond just gas production and solids destruction.     

固相微萃取/气质联用测定水中五种异味有机物

采用固相微萃取（SPME）法富集、气相色谱/质谱定量测定水体中的五种痕量异味有机物：2-异丙基-3-甲氧基吡嗪（IPMP）、2-异丁基-3-甲氧基吡嗪（IBMP）、2-甲基异冰片（2-MIB）、2,4,6-三氯苯甲醚（2,4,6-TCA）、土味素（Geosmin）.对五种物质的检出限均在5.0ng/L以下,加标回收率为86.7%～96.2%,相对标准偏差为3.9%～7.1%.     

Determination of polycyclic aromatic hydrocarbons in sea water using solid‐phase microextraction

Solid‐phase microextraction (SPME) technique with poly(dimethylsiloxane)‐coated fiber has been employed for the rapid determination of sixteen polycyclic aromatic hydrocarbons (PAHs) present in natural water. The method is solvent‐less with the analytes being adsorbed and then desorbed thermally at the injector port of a gas chromato‐graph (GC) prior to mass spectrometric (MS) analysis in selective ion monitoring (SIM) mode. The influences of the injector port temperature, desorption time and initial oven temperature on the thermal desorption of PAHs from the fiber were investigated. Then the optimum SPME conditions were applied for the qualitative and quantitative determination of PAHs in environmental samples. The recoveries of the 16 PAHs being spiked into sea water at 50 ng/mL level were 75.3%. The levels of PAHs in the Singapore coastal sea water are between 0.02–8.50 ng/mL using SPME(PDMS).     

Ecological impact of application of wastewater biosolids to agricultural soil

There has been little investigation of the ecological interactions between major organisms brought about by the application of wastewater biosolids to agricultural soil. This paper provides an overview of the possible effects of biosolids application on these ecosystems by using what is known about the ecology and diversity of microbial populations in soil and biosolids. Areas considered include interactions between indigenous and introduced bacterial populations, impacts of biosolids application on soil protozoa and the role of phages in bacterial population dynamics. These ecological processes are particularly relevant, for instance, to increase an understanding of the fundamental mechanisms responsible for inactivation of potentially infectious enteric microorganisms in biosolids‐amended agricultural soil.