The fate and risk of selected pharmaceutical and personal care products in wastewater treatment plants and a pilot-scale multistage constructed wetland system

The removal of 12 pharmaceuticals and personal care products (PPCPs) in two full-scale wastewater treatment plants (WWTPs) and a tertiary treatment system was studied. The ecological risks of effluents from both secondary and tertiary treatment systems as well as excess sludge were evaluated. Primary treatment and ultraviolet light disinfection showed limited ability to remove most selected PPCPs. The combination of an anaerobic process and triple-oxidation ditches can eliminate DEET better than the anaerobic/anoxic/oxic process. Adsorption to sludge played a key role in the removal of triclocarban. Multistage constructed wetlands as a tertiary treatment efficiently removed caffeine and ibuprofen from wastewater and could decrease the risk of partial selected PPCPs. Selected PPCPs residues in excess sludge generally produced higher risks to the ecological environment than effluents from WWTPs.     

Phosphorus removal from municipal wastewater by hydrous ferric oxide reactive filtration and coupled chemically enhanced secondary treatment: part I--performance.

This work examines the performance of a hydrous ferric oxide (HFO) reactive filtration (RF) process with coupled chemically enhanced secondary treatment (RECYCLE) for phosphorus removal from municipal wastewater (HFO-RF-RECYCLE). A 3-month, 0.95-ML/d (0.25-mgd) demonstration of HFO-RF-RECYCLE was performed at a municipal wastewater treatment plant equipped with oxidation ditches and secondary clarifiers. Influent to the plant averaged 6.0 mg/L phosphorus, with a tertiary effluent average of 0.011 mg/L phosphorus. Iron doses to the plant were low, at 5 mg/L. Inline recycling of HFO solution rejects to the plant influent resulted in a maximum 90.3%, dose-dependent reduction of phosphorus in the secondary effluent at 4.5 ML/d (1.2 mgd). Other results included reduction of total suspended solids and turbidity. A mass balance analysis was performed. We conclude that HFO-RF-RECYCLE may allow very low levels of phosphorus discharge from municipal wastewater treatment plants with a ferric-iron-based tertiary filtration process and residual recycling.     

Phosphorus removal from municipal wastewater by hydrous ferric oxide reactive filtration and coupled chemically enhanced secondary treatment: part II--mechanism.

The removal mechanism of a hydrous ferric oxide (HFO) reactive filtration (RF) process with coupled chemically enhanced secondary treatment (RECYCLE) for phosphorus removal from municipal wastewater (HFO-RF-RECYCLE) was examined. A 0.95-ML/d (0.25-mgd) demonstration of HFO-RF-RECYCLE was performed at a municipal wastewater treatment plant equipped with oxidation ditches and secondary clarifiers. Influent to the plant averaged 6.0 mg/L phosphorus, with a 3-month tertiary effluent average of 0.011 mg/L phosphorus. In addition to aqueous geochemical modeling, experiments with surface charge, scanning electron microscopy, adsorptive capacity, thermal desorption, and most probable number of iron(III)-reducing bacteria were performed on samples from the system, to determine the major phosphorus-removal pathways. Results suggest that, in addition to filtration of particulate phosphorus, the low tertiary effluent total phosphorus result was achieved by adsorption.     

Modeling oil price uncertainty effects on economic growth in Mexico: a sector-level analysis

This paper analyzes the impact of international oil price uncertainty on the different economic sectors (primary, secondary, and tertiary) in Mexico in the period 1993:1–2020:4 through a bivariate structural vector autoregressive (VAR) model with a generalized autoregressive conditional heteroskedasticity (GARCH) in mean to capture the impact of oil volatility on economic growth at the sectoral level of economic activity. The results show that the uncertainty of the international price of oil has a differentiated effect on the different sectors of economic activity in Mexico since it does not influence the primary sector; it negatively impacts the secondary sector, and there is mixed evidence in the tertiary sector. Additionally, evidence is provided that both positive and negative shocks to the international oil price have asymmetric effects at the sectoral level in Mexico. The results highlight the need to implement public policies, at the country level, that help mitigate the effect of uncertainty in the oil market and promote economic stability at the sector level.

     

Trace metal speciation and fluxes within a major French wastewater treatment plant: impact of the successive treatments stages

Seven metals (Cd, Co, Cr, Cu, Fe, Ni and Pb) were monitored at the Seine-Aval wastewater treatment plant during 6 sampling campaigns in April 2004. Particulate and dissolved metals have been measured in 24 h composite samples at each treatment stage (primary settling, secondary activated sludge and tertiary flocculation by FeCl₃). In addition, the diffusive gradient in thin film technique (DGT) was used to determine the dissolved inert and labile metal fraction. Although all treatment stages were able to decrease particulate metals concentrations in wastewater, most dissolved metals concentrations were mainly affected during primary settling. This unexpected result was attributed to tertiary sludge filtrate recirculation. Metals added via the FeCl₃ reagent at the tertiary treatment were shown to lower the overall Cr removal from wastewater and to enrich Ni in effluents. The plant operating conditions (recirculation and reagent addition) appear therefore as important as treatment processes for the metals removal. Total metal fluxes were highly decreased by the whole treatment plant for Cd, Cr, Cu and Pb and to a lesser extend for Co and Ni. However, the labile metal fluxes were poorly decreased for Cu (18%), not significantly decreased for Ni and increased for Fe. The labile fraction of Cd, Co and Cr was not detectable at any stage of the plant. Discharged labile fluxes, at least for Ni, were potentially significant compared to the labile metal fluxes in the river measured downstream the plant. Treated urban wastewater discharges should be carefully considered as a possible source of bioavailable trace metals.     

Aerobic and anaerobic abiotic oxidation of squalene in the presence of hydroperoxides

Abiotic oxidation of squalene in the presence of hydroperoxysterols was studied in seawater under aerobic and anaerobic conditions. This ubiquitous isoprenoid alkene is quickly degraded in the presence of oxygen and its oxidation results mainly in the production of tertiary alcohols and to a lesser extent of epoxides and secondary alcohols. Although the degradation of squalene logically slows down under anaerobic conditions, a significant oxidation affording similar products than in the case of aerobic degradation has been observed. These results show that hydroperoxysterols, which seem to be well preserved in Recent sediments, could contribute to the oxidation of unsaturated lipids (such as squalene) in sedimentary environments under oxic and anoxic conditions.     

制浆造纸废水生化出水的混凝处理研究

研究了硫酸铝和三氯化铁对制浆造纸废水生化出水的处理效果.研究发现,不调节原水pH值,硫酸铝投加量为600 mg/L或三氯化铁投加量为300mg/L时,混凝后废水的COD＜150 mg/L,色度＜50倍,出水均符合现阶段排放标准.混凝剂比较发现,在最佳反应条件下,2种混凝剂的处理效果相当,但硫酸铝混凝的成本低于三氯化铁....     

Biodegradability of ethylenediamine-based complexing agents and related compounds

The biological degradability (Zahn-Wellens test) of ethylenediamine derivatives with carboxymethyl and 2-hydroxyethyl groups was investigated. Mixed bacterial culture (activated sludge) was used as inoculum (non-adapted sludge and sludge adapted at different mean biomass retention time, the so-called sludge age). Biodegradability of ethylene(propylene)di(tri)amine-based complexing agents depends on the character and number of substituents and nitrogen atoms in the molecule. Tetra(penta)substituted derivatives with two or more tertiary nitrogen atoms and carboxymethyl or 2-hydroxyethyl groups in the molecule (EDTA, DTPA, PDTA, HEDTA) are very stable from an environmental point of view. On the contrary, disubstituted derivatives with two secondary nitrogen atoms in the molecule (e.g., EDDA) are potentially degradable.     

Evaluating China’s regional energy and environmental efficiency by considering three internal parallel industries

With the rapid development of China’s economy, high energy consumption and high pollution emission have become serious problems. To solve these problems, many studies have been done to evaluate energy and environmental efficiency, as the results can provide valuable information to improve performance. However, the previous research mainly evaluates China’s regional energy and environmental efficiency by considering each region’s industry as a whole system, ignoring the internal structure. In reality, each region mainly includes three parallel types of industry: primary, secondary, and tertiary. Therefore, this paper provides a parallel data envelopment analysis (DEA) approach to evaluate China’s regional energy and environment efficiency by considering these parallel industrial systems. The following findings can be obtained based on the empirical results: (1) the overall energy efficiency of China is low, and the inefficiency of the economic system is mainly sourced from the lower energy and environmental performance of the primary industry and the tertiary industry. (2) the introduction of the environmental variable (CO₂) leads to the increase of some backward areas’ efficiencies. (3) the energy efficiency of each provincial region is different, and most of them have their own inefficient industries. (4) the total factor productivity of China is declining, mainly because of the decline of technical efficiency.

     

Effects of tertiary treatment by fungi on organic compounds in a kraft pulp mill effluent

Background, aim and scope  

Pulp and paper mills generate a plethora of pollutants depending upon the type of pulping process. Efforts to mitigate the environmental impact of such effluents have been made by developing more effective biological treatment systems in terms of biochemical oxygen demand, chemical oxygen demand, colour and lignin content. This study is the first that reports an evaluation of the effects of a tertiary treatment by fungi (Pleurotus sajor caju, Trametes versicolor and Phanerochaete chrysosporium and Rhizopus oryzae) on individual organic compounds of a Eucalyptus globulus bleached kraft pulp and paper mill final effluent after secondary treatment (final effluent).     

An analysis of the chemical safety of secondary effluent for reuse purposes and the requirement for advanced treatment

This paper presents a study on the chemical safety of the secondary effluent for reuse purposes and the requirement of advanced treatment. Water quality analysis was conducted regarding conventional chemical items, hazardous metals, trace organics and endocrine disrupting chemicals (EDCs). Generally speaking, the turbidity, COD, BOD, TN and TP of the secondary effluent can meet the Chinese standards for urban miscellaneous water reuse but higher colour is a problem. Further removal of BOD and TP may still be required if the water is reused for landscape and environmental purposes especially relating to recreation. In addition, Hazardous metals, trace organics and endocrine disrupting chemicals (EDCs) are not the main problems for water reuse. At the same time, several tertiary treatment processes were evaluated. The coagulation–filtration process is effective process for further improvement of the conventional water quality items and removal of hazardous metals but less effective in dealing with dissolved organic matter. The ultrafiltration (UF) can achieve almost complete removal of turbid matter while its ability to remove dissolved substances is limited. The ozone–biofiltration is the most effective for colour and organic removal but it can hardly remove the residual hazardous metals. Therefore, the selection of suitable process for different water quality is important for water use.     

Antimicrobial activity of metal oxide nanoparticles supported onto natural clinoptilolite

The antimicrobial activity of Cu₂O, ZnO and NiO nanoparticles supported onto natural clinoptilolite was investigated in the secondary effluent under dark conditions. After 24 h of contact the Cu₂O and ZnO nanoparticles reduced the numbers of viable bacterial cells of Escherichia coli and Staphylococcus aureus in pure culture for four to six orders of magnitude and showed consistent 100% of antibacterial activity against native E. coli after 1 h of contact during 48 exposures. The antibacterial activity of NiO nanoparticles was less efficient. The Cu₂O and NiO nanoparticles showed 100% of antiprotozoan activity against Paramecium caudatum and Euplotes affinis after 1 h of contact, while ZnO nanoparticles were less efficient. The morphology and crystallinity of the nanoparticles were not affected by microorganisms. The metal oxide nanoparticles could find a novel application in the disinfection of secondary effluent and removal of pathogenic microorganisms in the tertiary stage of wastewater treatment.     

城市第三产业环境行为信息公开化研究初探

产业结构调整和城市化进程加速了中国第三产业的发展，但同时也给环境造成了影响和破坏。分析了中国第三产业环境污染特点，第三产业发展对环境管理的挑战。同时结合污染控制信息手段和环境信息公开的特点和优势，对开展第三产业环境行为信息公开化研究提出了建议。     

Personal reactive clouds: Introducing the concept of near-head chemistry

The “personal cloud” effect and its impact on human exposure to airborne pollutants are well documented. A great deal is also known regarding indoor air chemistry, particularly as related to ozone reactions with mono-terpenes. In this paper we hypothesize the presence of personal reactive clouds that result from ozone reactions with terpenes and terpenoids emitted from personal care products. A proof of concept assessment was completed based on reaction rates between ozone and five reactive organic compounds that are found in personal care products. Screening experiments were also completed with three perfumes and two hairsprays to determine the extent of secondary organic aerosol formation in the breathing zone of a subject who had applied these products. The results of screening calculations and preliminary experiments confirm that chemistry occurs in the near-head region of individuals who apply scented personal care products to their hair or facial skin. Additional research is needed to characterize reaction products and health consequences associated with near-head chemistry and associated personal reactive clouds.     

Biotic and abiotic transformations of methyl tertiary butyl ether (MTBE)

Background Methyl tertiary butyl ether (MTBE) is a fuel additive which is used all over the world. In recent years it has often been found in groundwater, mainly in the USA, but also in Europe. Although MTBE seems to be a minor toxic, it affects the taste and odour of water at concentrations of < 30 μg/L. Although MTBE is often a recalcitrant compound, it is known that many ethers can be degraded by abiotic means. The aim of this study was to examine biotic and abiotic transformations of MTBE with respect to the particular conditions of a contaminated site (former refinery) in Leuna, Germany. Methods Groundwater samples from wells of a contaminated site were used for aerobic and anaerobic degradation experiments. The abiotic degradation experiment (hydrolysis) was conducted employing an ion-exchange resin and MTBE solutions in distilled water. MTBE, tertiary butyl formate (TBF) and tertiary butyl alcohol (TBA) were measured by a gas chromatograph with flame ionisation detector (FID). Aldehydes and organic acids were respectively analysed by a gas chromatograph with electron capture detector (ECD) and high-performance ion chromatography (HPIC). Results and Discussion Under aerobic conditions, MTBE was degraded in laboratory experiments. Only 4 of a total of 30 anaerobic experiments exhibited degradation, and the process was very slow. In no cases were metabolites detected, but a few degradation products (TBF, TBA and formic acid) were found on the site, possibly due to the lower temperatures in groundwater. The abiotic degradation of MTBE with an ion-exchange resin as a catalyst at pH 3.5 was much faster than hydrolysis in diluted hydrochloric acid (pH 1.0). Conclusion Although the aerobic degradation of MTBE in the environment seems to be possible, the specific conditions responsible are widely unknown. Successful aerobic degradation only seems to take place if there is a lack of other utilisable compounds. However, MTBE is often accompanied by other fuel compounds on contaminated sites and anaerobic conditions prevail. MTBE is often recalcitrant under anaerobic conditions, at least in the presence of other carbon sources. The abiotic hydrolysis of MTBE seems to be of secondary importance (on site), but it might be possible to enhance it with catalysts. Recommendation and Outlook MTBE only seems to be recalcitrant under particular conditions. In some cases, the degradation of MTBE on contaminated sites could be supported by oxygen. Enhanced hydrolysis could also be an alternative. - * The basis of this peer-reviewed paper is a presentation at the 9th FECS Conference on 'Chemistry and Environment', 29 August to 1 September 2004, Bordeaux, France.     

Effects of pH and feeding regime on methylmercury accumulation within aquatic microcosms

The effect of pH (pH 5, 6 or 7) on accumulation of radiolabelled methylmercury was examined using a laboratory microcosm system. Accumulation of labelled mercury at three trophic levels, primary consumers (Daphnia magna), secondary consumers (rainbow trout, Salmo gairdneri) and tertiary consumers (walleye, Stizostedion vitreum) was not significantly affected by pH. Our results are in direct contrast with field observations of elevated methylmercury concentrations in fish from low pH water and indicate that the elevated mercury residues observed in the field result from factors other than the direct effects of pH on accumulation of methylmercury by aquatic organisms. Both water and diet were important as sources of the labelled mercury which was accumulated by walleye. Walleye which were fed rainbow trout, that had accumulated labelled mercury from within the experimental microcosms, accumulated almost twice as much labelled mercury as walleye fed non-labelled prey, or walleye which were not fed. Walleye fed non-labelled rainbow trout accumulated slightly more labelled mercury than walleye which were not fed, presumably as a result of the higher metabolic rate of the fish which were fed.     

Combinations of Azadirachta indica and Cedrus deodara oil with piperonyl butoxide, MGK-264 and Embelia ribes against Lymnaea acuminata

The binary and tertiary combinations of plant-derived molluscicides Azadirachta indica and Cedrus deodara oil with synergists MGK-264, piperonyl butoxide (PB) and fruit powder of Embelia ribes were used against the Lymnaea acuminata. It was observed that the toxic effects of these mixtures were time- and dose-dependent. The binary and tertiary mixtures of plant-derived molluscicides with synergists were more toxic with respect to the single treatment of the plant-derived molluscicides. Maximum synergistic action in binary and tertiary combinations was found in A. indica + C. deodara oil and A. indica + PB + C. deodara in 1:7 and 1:5:7 ratio, respectively.     

Structure elucidation of four possible biogenic organohalogens using isotope exchange mass spectrometry

The molecular structures of four unknown bioaccumulating halogenated compounds, C10H6N2Br3Cl3, C10H6N2Br4Cl2, C10H6N2Br5Cl, and C10H6N2Br6 were characterized using isotope exchange positive chemical ionization (IE-PCI) mass spectrometry (MS) and identified by comparison to synthesized standards. NH3 and ND3 were used as reagent gases for the IE-PCI-MS experiment. The shift in mass of the quasimolecular ion between the NH3 and ND3 PCI obtained spectra indicated the number of exchangeable hydrogens attached to the two nitrogen atoms in C10H6N2Br4Cl2, and thus the type of amines present (primary, secondary, or tertiary). 19 compounds (13 amines of varying degree of substitution; six containing no nitrogen) were used as reference compounds and controls in the experiment to validate the IE-PCI technique. The results of the IE-PCI-MS indicated the presence of two tertiary amine functional groups. The molecular structures of the four hexahalogenated compounds were then proposed to be 1,1'-dimethyl-3,3',4,-tribromo-4',5,5'-trichloro-2,2'-bipyrrole, 1,1'-dimethyl-3,3',4,4'-tetrabromo-5,5'-dichloro-2,2'-bipyrrole, 1,1'-dimethyl-3,3',4,4',5-pentabromo-5'-chloro-2,2'-bipyrrole, and 1,1'-dimethyl-3,3',4,4',5,5'-hexabromo-2,2'-bipyrrole and subsequently synthesized. Comparison of retention times and electron capture negative ionization (ECNI) full scans on various gas chromatography (GC) columns between the synthesized bipyrroles and the corresponding unknown compounds in biota indicated that three of the unknown compounds--possible marine natural products--were the proposed halogenated dimethyl bipyrroles. The placement of the halogen atoms on the fourth compound, C10H6N2Br3Cl3 could not be unequivocally determined since the synthesized standard could not be fully characterized.     

Uptake of microcontaminants by crops irrigated with reclaimed water and groundwater under real field greenhouse conditions

The use of reclaimed water for agricultural irrigation has emerged as a new strategy for coping with water scarcity in semiarid countries. However, the incorporation of the organic microcontaminants in such water into the diet through crop uptake poses a potential risk to human health. This paper aims to assess the presence of organic microcontaminants in different crops irrigated with groundwater and reclaimed water (secondary or tertiary effluents) in a greenhouse experiment. The determination of microcontaminants in water and vegetation samples was performed by solid-phase extraction and matrix solid-phase dispersion procedure with GC–MS/MS, respectively. The presence of nitrates in the groundwater used for irrigation increased biomass production by a higher proportion than the harvest index. The concentration of microcontaminants in lettuce, carrots, and green beans ranged from less than the limit of quantitation to 571 ng?g^?1 (fresh weight). Tributyl phosphate and butylated hydroxyanisole exhibited the highest concentration levels in crops. The concentration and frequency of detection of microcontaminants were lower in green bean pods than in green bean roots and leaves. Although the concentrations were generally low, the simultaneous presence of a variety of microcontaminants should be taken into consideration when assessing the risk to human health.     

Wastewater nutrient removal by Chlorella pyrenoidosa and Scenedesmus sp

Two different species of photosynthetic microalgae, Chlorella pyrenoidosa and Scenedesmus sp., were grown in settled and activated sewage filtrates at two different inoculum sizes, aimed to reduce nutrient load from wastewater. Higher growth rates were recorded in cultures with higher inoculum size, and algal cells usually grew better in settled sewage than in activated sewage. As algae started to grow and multiply, both nitrogen and phosphorus content in wastewater decreased significantly. The removal rate was rapid during the first week of growth and more than 2/3 of wastewater N and P was reduced. After the initial period, the removal rate slowed down. At the end of this study, more than 80% of total-P and inorganic N present in settled sewage were reduced but such removal efficiency was lower in activated sewage. In general, high inoculum size of algal cells provided more N and P removal than low inoculum, and Chlorella cells performed better than Scenedesmus. These results suggest that cultivation of Chlorella seems to be one of the feasible methods to reduce the amount of nitrogen and phosphorus entering the nearby coastal water, thus preventing the eutrophication problem. It is also clear that algal ponds with high inoculum size might be more suitable to be installed as a secondary rather than a tertiary treatment process.