Environmental exposure of pharmaceuticals and musk fragrances in the Somes River before and after upgrading the municipal wastewater treatment plant Cluj-Napoca,Romania

Background, aim, and scope

Pharmaceutically active substances are a class of emerging contaminants, which has led to increasing concern about potential environmental risks. After excretion, substantial amounts of unchanged pharmaceuticals and their metabolites are discharged into domestic wastewaters. The absence of data on the environmental exposure in Eastern Europe is significant, since use patterns and volumes differ from country to country. In Romania, the majority of wastewater, from highly populated cities and industrial complex zones, is still discharged into surface waters without proper treatment or after inefficient treatment. In respect to this, it is important to determine the environmental occurrence and behavior of pharmaceuticals and personal care products (PPCPs) in wastewaters and surface waters. The objective of the present study was to investigate the occurrence of selected PPCPs during the transport in the Somes River by mass flow analysis before and after upgrading a municipal wastewater treatment plant (WWTP) in Cluj-Napoca, which serves 350,000 inhabitants and is the largest plant discharging into the Somes River. The concentrations of PPCPs at Cluj-Napoca can be correlated with the high population and a high number of hospitals located in the catchment area leading to higher mass flows. The results of this study are expected to provide information, with respect to the Romanian conditions, for environmental scientists, WWTP operators, and legal authorities. The data should support the improvement of existing WWTPs and implementation of new ones where necessary and, therefore, minimize the input of contaminants into ambient waters.

Materials and methods

The PPCPs were selected on the basis of consumption at the regional scale, reported aquatic toxicity, and the suitability of the gas chromatography/mass spectrometry (GC/MS) method for the determination of the compounds at trace levels. The studied PPCPs, caffeine (stimulant), carbamazepine (antiepileptic), pentoxifylline (anticoagulant), cyclophosphamide (cytostatic), ibuprofen (analgesic), and galaxolide (musk fragrance), were determined in samples of the Somes River. The analytes were enriched by solid-phase extraction and subsequently determined by GC/MS. Caffeine, pentoxifylline, and galaxolide were determined underivatized, whereas the acidic pharmaceuticals carbamazepine, cyclophosphamide, and ibuprofen were determined after derivatization with N-methyl-N-(trimethylsilyl)-trifluoroacetamide.

Results and discussion

The concentrations in the Somes River varied from below 10 ng/L up to 10 μg/L. A substantial decrease of the exposure in the Somes River could be observed due to the upgrade of the municipal WWTP in Cluj-Napoca. The loads in the river stretch between Cluj-Napoca and Dej (Somes Mic) varied strongly: caffeine (400–2,000 g/day), carbamazepine (78–213 g/day), galaxolide (140–684 g/day), ibuprofen (84–108 g/day). After the upgrade of the WWTP Cluj-Napoca, the concentrations in the Somes of caffeine, pentoxifylline, cyclophosphamide, galaxolide, and tonalide were significantly reduced (over 75%). One might be cautious comparing both studies because the relative efficiency of the WWTP’s removal of PPCP was not evaluated. However, the significantly lower concentrations of most compounds after the upgrade of the WWTP Cluj-Napoca allow one to infer that the technical measures at the source substantially reduced inputs of contaminants to the receiving river. Dej loads of the poorly biodegradable substance carbamazepine increased by a factor of 2–3 as a result of wastewater discharges into the river. The disproportionate increase in caffeine loads by a factor of 4 below Cluj-Napoca indicates inputs of untreated wastewater from the Somes Mare due to the discharge of untreated wastewater derived from Bistrita, Nasaud, and Beclean (115,000 inhabitants).

Conclusions

The relative contribution of treated and untreated wastewater in surface water might be assessed by measuring chemical markers. Recalcitrant pharmaceuticals like carbamazepine are suitable as chemical markers for estimating the relative contribution of wastewater in surface water. The easily degradable caffeine might be a good indicator for raw sewage and hardly treated wastewaters.

Recommendations and perspectives

Municipal WWTPs have the potential of a significant contribution in reducing the load of contaminants to ambient waters. The efficiency of the wastewater treatment in Cluj-Napoca improved considerably after the upgrade of the WWTP. Therefore, it is crucial that several WWTPs must be implemented or improved in the Somes Valley Watershed in order to reduce the discharge of contaminants in the Somes River from these point sources.

     

Environmental exposure of pharmaceuticals and musk fragrances in the Somes River before and after upgrading the municipal wastewater treatment plant Cluj-Napoca, Romania

Background, aim, and scope  

Pharmaceutically active substances are a class of emerging contaminants, which has led to increasing concern about potential environmental risks. After excretion, substantial amounts of unchanged pharmaceuticals and their metabolites are discharged into domestic wastewaters. The absence of data on the environmental exposure in Eastern Europe is significant, since use patterns and volumes differ from country to country. In Romania, the majority of wastewater, from highly populated cities and industrial complex zones, is still discharged into surface waters without proper treatment or after inefficient treatment. In respect to this, it is important to determine the environmental occurrence and behavior of pharmaceuticals and personal care products (PPCPs) in wastewaters and surface waters. The objective of the present study was to investigate the occurrence of selected PPCPs during the transport in the Somes River by mass flow analysis before and after upgrading a municipal wastewater treatment plant (WWTP) in Cluj-Napoca, which serves 350,000 inhabitants and is the largest plant discharging into the Somes River. The concentrations of PPCPs at Cluj-Napoca can be correlated with the high population and a high number of hospitals located in the catchment area leading to higher mass flows. The results of this study are expected to provide information, with respect to the Romanian conditions, for environmental scientists, WWTP operators, and legal authorities. The data should support the improvement of existing WWTPs and implementation of new ones where necessary and, therefore, minimize the input of contaminants into ambient waters.     

Evaluating pharmaceuticals and caffeine as indicators of fecal contamination in drinking water sources of the Greater Montreal region

We surveyed four different river systems in the Greater Montreal region, upstream and downstream of entry points of contamination, from April 2007 to January 2009. The studied compounds belong to three different groups: PPCPs (caffeine, carbamazepine, naproxen, gemfibrozil, and trimethoprim), hormones (progesterone, estrone, and estradiol), and triazine herbicides and their metabolites (atrazine, deethylatrazine, deisopropylatrazine, simazine, and cyanazine). In the system A, B, and C having low flow rate and high TOC, we observed the highest detection frequencies and mass flows of PPCPs compared to the other compounds, reflecting discharge of urban contaminations through WWTPs and CSOs. However, in River D, having high flow rate and low TOC, comparable frequency of detection of triazine and their by-products and PPCPs, reflecting cumulative loads of these compounds from the Great Lakes as well as persistency against natural attenuation processes. Considering large differences in the removal efficiencies of caffeine and carbamazepine, a high ratio of caffeine/carbamazepine might be an indicative of a greater proportion of raw sewage versus treated wastewater in surface waters. In addition, caffeine appeared to be a promising indicator of recent urban fecal contaminations, as shown by the significant correlation with FC (R² = 0.45), while carbamazepine is a good indicator of cumulative persistence compounds.     

Occurrence of cyclophosphamide and epirubicin in wastewaters by direct injection analysis–liquid chromatography–high-resolution mass spectrometry

Background, aim, and scope

According to the high incidence of cancer worldwide, the amount of cytostatic drugs administered to patients has increased. These compounds are excreted to wastewaters, and therefore become potential water contaminants. At this stage, very little is known on the presence and elimination of cytostatic compounds in wastewater treatment plants (WWTP). The aim of this study was to develop a liquid chromatography?Chigh-resolution mass spectrometry (LC?COrbitrap?CMS) method for the determination of cyclophosphamide and epirubicin in wastewaters. These compounds represent two outmost used cytostatic agents.

Materials and methods

Extraction and analytical conditions were optimized for cyclophosphamide and epirubicin in wastewater. Both solid-phase extraction using Oasis 200?mg hydrophilic?Clipophilic balanced (HLB) cartridges and direct injection analysis were evaluated. Mass spectral characterization and fragmentation conditions were optimized at 50,000 resolving power (full width at half maximum, m/z 200) to obtain maximum sensitivity and identification performance. Quality parameters (recoveries, limits of detection, and repetitivity) of the methods developed were determined, and best performance was obtained with direct water analysis of the centrifuged wastewater. Finally, this method was applied to determine the presence of cyclophosphamide and epirubicin in wastewaters from a hospital effluent, an urban effluent, and influents and effluents from three WWTP.

Results and discussion

Cyclophosphamide and epirubicin were recovered after 50?mL preconcentration on solid-phase extraction 200?mg Oasis HLB cartridges (87% and 37%, respectively), and no breakthrough was observed by extracting 500?mL of water. Limits of detection were of 0.35 and 2.77?ng/L for cyclophosphamide and epirubicin, respectively. On the other hand, direct injection of water spiked at 1???g/L provided recoveries of 107% for cyclophosphamide and 44% for epirubicin and limits of detection from 3.1 to 85?ng?L^?1, respectively. The analysis of wastewaters using direct injection analysis revealed the presence of cyclophosphamide and epirubicin in WWTP influents and hospital and urban effluents at levels ranging from 5.73 to 24.8???g?L^?1.

Conclusions

The results obtained in this study demonstrate the capability of LC?COrbitrap?CMS for accurate trace analysis of these very polar contaminants. This method permitted to identify cyclophosphamide and epirubicin in wastewaters and influents of WWTP, but no traces were detected in WWTP effluents. The methodology herein developed is sensitive and robust and applicable for screening of a large number of samples since no preconcentration is needed.     

Occurrence and removal of six pharmaceuticals and personal care products in a wastewater treatment plant employing anaerobic/anoxic/aerobic and UV processes in Shanghai,China

The occurrence and removal of six pharmaceuticals and personal care products (PPCPs) including caffeine (CF), N, N-diethyl-meta-toluamide (DEET), carbamazepine, metoprolol, trimethoprim (TMP), and sulpiride in a municipal wastewater treatment plant (WWTP) in Shanghai, China were studied in January 2013; besides, grab samples of the influent were also taken every 6 h, to investigate the daily fluctuation of the wastewater influent. The results showed the concentrations of the investigated PPCPs ranged from 17 to 11,400 ng/L in the WWTP. A low variability of the PPCP concentrations in the wastewater influent throughout the day was observed, with the relative standard deviations less than 25 % for most samples. However, for TMP and CF, the slight daily fluctuation still reflected their consumption patterns. All the target compounds except CF and DEET, exhibited poor removal efficiencies (<40 %) by biological treatment process, probably due to the low temperature in the bioreactor, which was unfavorable for activated sludge. While for the two biodegradable PPCPs, CF, and DEET, the anaerobic and oxic tank made contributions to their removal while the anoxic tank had a negative effect to their elimination. The tertiary UV treatment removed the investigated PPCPs by 5–38 %, representing a crucial polishing step to compensate for the poor removal by the biologic treatment process in winter.     

Occurrence and distribution of selected pharmaceuticals and personal care products in aquatic environments: a comparative study of regions in China with different urbanization levels

Purpose

We analyzed and compared the distributions of 13 target pharmaceuticals in different water samples from the Hangzhou metropolitan area and Linan County, Southeast China.

Methods

Sampling was conducted in five hospitals, two wastewater treatment plants (WWTPs), and Qiantang River. Samples were concentrated by solid-phase extraction and PPCP concentrations were determined by UPLC-MS/MS.

Results and discussion

Trimethoprim, erythromycin A dihydrate, norfloxacin, ofloxacin, diclofenac sodium, and atenolol were the most frequently detected pharmaceuticals in hospital effluents. Most of the pharmaceutical concentrations in hospital effluents were higher than those in the WWTP influents. Although both WWTPs adopt the anaerobic?Caerobic?Canoxic treatment process, the removal rates for pharmaceuticals, such as trimethoprim and diclofenac sodium, were completely different. Meanwhile, erythromycin A dihydrate, ofloxacin, penicillin-G, cephalexin, cefazolin, ibuprofen, and diclofenac sodium were detected in Qiantang River.

Conclusions

These results indicate that hospitals are more concentrated sources of pharmaceuticals than WWTPs, and the WWTPs are not the only route of entry of pharmaceuticals into aquatic environments in these two regions.     

Evaluation of PPCPs removal in a combined anaerobic digester-constructed wetland pilot plant treating urban wastewater

The removal efficiency of 16 pharmaceuticals and personal care products (PPCPs) from urban wastewater (dissolved and particulate phases) was evaluated for the first time in a hybrid pilot plant consisting of an upflow anaerobic sludge blanket reactor followed by two sequentially connected horizontal flow constructed wetlands: a surface flow wetland (SF CW) and a subsurface flow wetland (SSF CW). Whereas the PPCP removal associated with the dissolved phase exhibited a seasonal pattern, the fraction associated with the suspended solids showed less seasonality. In the dissolved phase, the overall removal efficiency in summer ranged from 70% to 85% for salicylic acid (SAL), methyl dihydrojasmonate, caffeine (CAF), ketoprofen and triclosan, whereas in winter it declined for most of the PPCPs to between 30% and 50%, except for CAF and SAL (>80%) and carbamazepine and butylated hydroxyl toluene (11-18%). In the suspended solids, the removal exceeded 80% for most of the target PPCPs. The efficiency of the different treatment steps was also compound-dependent, but the SF CW generally exhibited the highest removal efficiency for most of the contaminants analyzed. The characterization of the organic matter retained in the wetland gravel beds revealed the occurrence of hydrophobic contaminants such as phthalate esters and fragrances at moderate concentrations (i.e., up to 3.5 μg kg⁻¹), which declined strongly over the course of the different treatment steps. In the SF CW, the net mass accumulation rates of tonalide and galaxolide were 4 and 23 g y⁻¹ respectively, whereas in the SSF CW they were 0.3 and 1.8 g y⁻¹ respectively.     

Assessing the removal of pharmaceuticals and personal care products in a full-scale activated sludge plant

Purpose

This study aimed to investigate the removal mechanisms of pharmaceutical active compounds (PhACs) and musks in a wastewater treatment plant (WWTP). Biological removal and adsorption in the activated sludge tank as well as the effect of UV radiation used for disinfection purposes were considered when performing a mass balance on the WWTP throughout a 2-week sampling campaign.

Methods

Solid-phase extraction (SPE) was carried out to analyse the PhACs in the influent and effluent samples. Ultrasonic solvent extraction was used before SPE for PhACs analysis in sludge samples. PhAC extracts were analysed by LC-MS. Solid-phase microextraction of liquid and sludge samples was used for the analysis of musks, which were detected by GC-MS. The fluxes of the most abundant compounds (13 PhACs and 5 musks) out of 79 compounds studied were used to perform the mass balance on the WWTP.

Results

Results show that incomplete removal of diclofenac, the compound that was found in the highest abundance, was observed via biodegradation and adsorption, and that UV photolysis was the main removal mechanism for this compound. The effect of adsorption to the secondary sludge was often negligible for the PhACs, with the exceptions of diclofenac, etofenamate, hydroxyzine and indapamide. However, the musks showed a high level of adsorption to the sludge. UV radiation had an important role in reducing the concentration of some of the target compounds (e.g. diclofenac, ibuprofen, clorazepate, indapamide, enalapril and atenolol) not removed in the activated sludge tank.

Conclusions

The main removal mechanism of PhACs and musks studied in the WWTP was most often biological (45%), followed by adsorption (33%) and by UV radiation (22%). In the majority of the cases, the WWTP achieved >75% removal of the most detected PhACs and musks, with the exception of diclofenac.     

Photolysis of pharmaceuticals and personal care products in the marine environment under simulated sunlight conditions: irradiation and identification

The photochemical fate of 16 pharmaceuticals and personal care products (PPCPs) found in the environment has been studied under controlled laboratory conditions applying a sunlight simulator. Aqueous samples containing PPCPs at environmentally relevant concentrations were extracted by solid-phase extraction (SPE) after irradiation. The exposed extracts were subsequently analysed by liquid chromatography combined with triple quadrupole mass spectrometry (HPLC-MS/MS) for studying the kinetics of photolytic transformations. Almost all exposed PPCPs appeared to react with a half-life time (τ _1/2) of less than 30 min. For ranitidine, sulfamethoxazole, diclofenac, warfarin, sulfamethoxazole and ciprofloxacin, τ_1/2 was found to be even less than 5 min. The structures of major photolysis products were determined using quadrupole-time-of-flight mass spectrometry (QToF) and spectroscopic data reported in the literature. For diclofenac, the transformation products carbazol-1-yl-acidic acid and 8-chloro-9H-carbazol-1-yl-acetic acid were identified based on the mass/charge ratio of protonated ions and their fragmentation pattern in negative electrospray ionization (ESI^?-QTOF). Irradiation of carbamazepine resulted in three known products: acridine, carbamazepine-10,11-epoxide, and 10,11-dihydro-10,11-dihydroxy-carbamazepine, whereas acetaminophen was photolytically transformed to 1-(2-amino-5 hydroxyphenyl) ethenone. These photochemical products were subsequently identified in seawater or fish samples collected at sites exposed to wastewater effluents on the Saudi Arabian coast of the Red Sea.     

Occurrences of pharmaceutical and personal care products as micropollutants in rivers from Romania

The occurrence of pharmaceutical and personal care products (PPCPs) was investigated in the Somes River. The aim of this study was to obtain a first overview about the contamination of Somes River (Transylvania) with PPCPs. The samples were preconcentrated by Solid Phase Extraction (SPE) procedures and analysed by GC/MS. A number of 15 compounds including pharmaceutics, metabolites, intermediates and musk fragrances were detected in concentration ranging from 30 ng/l to 10 μg/l. The detected pharmaceuticals are included in following therapeutic groups: analgesics, antiepileptics, psychiatric, stimulants, anticoagulants, antineoplastic and disinfectants.     

Remediation potential of caffeine,oxybenzone, and triclosan by the salt marsh plants <Emphasis Type="Italic">Spartina maritima</Emphasis> and <Emphasis Type="Italic">Halimione portulacoides</Emphasis>

Pharmaceuticals and personal care products (PPCPs) have attracted increasing concern during the last decade because of their widespread uses and continuous release to the aquatic environment. This work aimed to study the distribution of caffeine (CAF), oxybenzone (MBPh), and triclosan (TCS) when they arrive in salt marsh areas and to assess their remediation potential by two different species of salt marsh plants: Spartina maritima and Halimione portulacoides. Experiments were carried out in the laboratory either in hydroponics (sediment elutriate) or in sediment soaked in elutriate, for 10 days. Controls without plants were also carried out. CAF, MBPh, and TCS were added to the media. In unvegetated sediment soaked in elutriate, CAF was mainly in the liquid phase (83%), whereas MBPh and TCS were in the solid phase (90% and 56%, respectively); the highest remediation was achieved for TCS (40%) and mainly attributed to bioremediation. The presence of plants in sediment soaked in elutriate-enhanced PPCPs remediation, decreasing CAF and TCS levels between approximately 20-30% and MBPh by 40%.. Plant uptake, adsorption to plant roots/sediments, and bio/rhizoremediation are strong hypothesis to explain the decrease of contaminants either in water or sediment fractions, according to PPCPs characteristics.     

Photosensitized degradation of caffeine: role of fulvic acids and nitrate

The photolysis of caffeine was studied in solutions of fulvic acid isolated from Suwannee River, GA (SRFA) and Old Woman Creek Natural Estuarine Research Reserve, OH (OWCFA) with different chemical amendments (nitrate and iron). Caffeine degrades slowly by direct photolysis (>170 h in artificial sunlight), but we observed enhanced photodegradation in waters containing the fulvic acids. At higher initial concentrations (10 μM) the indirect photolysis of caffeine occurs predominantly through reaction with the hydroxyl radical (OH) generated by irradiated fulvic acids. Both rate constant estimates based upon measured OH steady-state concentrations and quenching studies using isopropanol corroborate the importance of this pathway. Further, OH generated by irradiated nitrate at concentrations present in wastewater effluent plays an important role as a photosensitizer even in the presence of fulvic acids, while the photo-Fenton pathway does not at neutral or higher pH. At lower initial concentrations (0.1 μM) caffeine photolysis reactions proceed even more quickly in fulvic acid solutions and are influenced by both short- and long-lived reactive species. Studies conducted under suboxic conditions suggest that an oxygen dependent long-lived radical e.g., peroxyl radicals plays an important role in the degradation of caffeine at lower initial concentration.     

Perfluorooctanoic acid and perfluorooctane sulfonate released from a waste water treatment plant in Bavaria, Germany

Purpose

Perfluorooctanoate (PFOA), perfluorooctane sulfonate (PFOS), and precursors and derivatives thereof have been employed as surfactants and anti-adhesives. PFOA and PFOS are environmentally persistent and the discharge of municipal waste waters is one of the principal routes of these compounds into the aquatic environment. In a previous study, the concentrations of PFOA and PFOS in grab samples collected from the waste water treatment plant (WWTP) of Bayreuth, a city of 72,000 inhabitants in Bavaria, Germany, during two periods showed considerable variability. For a better estimate of average mass flows, the surfactants were monitored (five samplings) from 16 March to 18 May 2007. In a second campaign, river water receiving the WWTP effluent was sampled twice a day for five consecutive days.

Methods

Quantitative analysis was done by stable-isotope dilution, pre-cleaning, and pre-concentration by solid-phase extraction, and liquid chromatography followed by electrospray ionization/tandem mass spectrometry.

Results

The mass flows of PFOA and PFOS through the WWTP were determined. PFOA is fully discharged into the river, while about half of PFOS is retained in the sewage sludge. The average daily mass load of the river Roter Main by the WWTP of Bayreuth is about 1.2?±?0.5 g PFOA and 5?±?2 g PFOS, with variations of up to 140% within one day.

Conclusion

Overall, the total annual release to the rivers of Germany may be in the range of several hundred kilograms of PFOA and several tons of PFOS.     

Heavy metals in untreated/treated urban effluent and sludge from a biological wastewater treatment plant

Background, Aim and Scope

The presence of heavy metals in wastewater is one of the main causes of water and soil pollution. The aim of the present study was to investigate the removal of Cd, Cu, Pb, Hg, Mn, Cr and Zn in urban effluent by a biological wastewater treatment, as well as to quantify the levels of As, Be, Cd, Cr, Cu, Fe, Hg, Mn, Ni, Pb, Sn, Tl, V and Zn in dewatering sludge from the Biological Wastewater Treatment Plant to Ribeirão Preto (RP-BWTP), Brazil.

Materials and Methods

Concentrations of Cd, Cr, Cu, Mn and Pb in wastewater and those of Ni in sludge were determined by atomic absorption spectrophotometry with graphite furnace atomization. Mercury concentrations in wastewater were measured by hydride generation atomic spectrophotometry, and Zn levels were determined by atomic absorption spectrophotometry using acetylene flame. In sludge, the levels of As, Be, Cd, Cr, Cu, Fe, Hg, Mn, Pb, Sn, Tl, V and Zn were determined by inductively coupled plasma-mass spectrometry.

Results

The percentages of removal efficiency (RE) were the following: Hg 61.5%, Cd 60.0%, Zn 44.9%, Cu 44.2%, PB 39.7%, Cr 16,5% and Mn 10.4%. In turn, the mean concentrations (mg/kg) of metals in dewatering sludge followed this increasing order: Tl (<0.03), Hg (0.31), Be (0.43), As (1.14), Cd (1.34), V (59.2), Pb (132.1), Sn (166.1), Cr (195.0), Mn (208.1), Ni (239.4), Cu (391.7), Zn (864.4) and Fe (20537).

Discussion

The relationship between metal levels in untreated wastewater, as well as the removal efficiency are in agreement with previous data from various investigators, It is important to note that metal removal efficiency is not only affected by metal ion species and concentration, but also by other conditions such as operating parameters, physical, chemical, and biological factors.

Conclusions

Metal values recorded for treated wastewater and sludge were within the maximum permitted levels established by the Environmental Sanitation Company (CETESB), São Paulo, Brazil.

Recommendations

There is an urgent need for the authorities who are responsible for legislation on sludge uses in agriculture of establishing safety levels for As, Be, Hg, Sn, Tl and V.

Perspectives

According to the current metal levels, RP-BWTP sludge might be used for agriculture purposes. However, for an environmentally safe use of sewage sludge, further studies including systematic monitoring are recommended. Annual metal concentrations and predicted variations of those elements in the sludge should be monitored.

     

Occurrence and fate of PPCPs and correlations with water quality parameters in urban riverine waters of the Pearl River Delta, South China

The occurrence and fate of eight PPCPs was studied in river waters from upstream to downstream of the three rivers in the Pearl River Delta, China. The correlations of PPCP levels and water quality parameters were also investigated. The analytes of the highest concentrations were caffeine, acetaminophen, and ciprofloxacin. Carbamazepine and erythromycin-H₂O were detected at the lowest concentrations. The highest concentrations of PPCPs were found in the Shijing River, with 865 ng/L caffeine, 339 ng/L acetaminophen, and 304 ng/L ciprofloxacin. In general, the levels of PPCPs in the Zhujiang River were higher at sites where the metropolitan city Guangzhou is located and decreased from the epicenter along the river. Low levels of PPCPs were generally found in the Beijiang River. Positive correlations were found between PPCP levels, total nitrogen, ammonium nitrogen, and cumulative fluorescence excitation-emission matrix (EEM) volume. Among the four PPCPs evaluated (caffeine, acetaminophen, ciprofloxacin, and sulfamethoxazole), caffeine had the best correlations with the correlation coefficients ranging from 0.62 to 0.98. The prediction of PPCP concentrations at specified locations can be substantially simplified.     

Behavioural ecotoxicology,an “early warning” signal to assess environmental quality

Background

In this review, the position of behavioural ecotoxicology within the available means to assess the status of marine environments is described as filling the gap for the needed “early warning” signals. A few examples of studies performed since the 1960s are discussed to highlight the sensitivity of these approaches in investigating the effects of chemicals, including priority pollutants and emerging contaminants, relative to conventional toxicity tests measuring survival.

Discussion

The advantage of the behavioural response is due to the integration of biochemical and physiological processes that reflect changes at higher levels of organisation with ecological relevance. Avoidance often represents a behavioural symptom easily detected in many animals exposed to contaminants and would be a useful test to explore more widely. This rapid response would reflect a defence mechanism protective against further exposure and the potential development of more pronounced deleterious effects, whilst in some cases, escape could lead to the relocation of a species with negative consequences. An investigation of the avoidance behaviour of mud shrimp, Corophium volutator, along with the chemical analyses of sediments and amphipods to assess the quality of harbour sediments is summarised. The body burden of the amphipods was 1,000 times lower than the one associated with narcosis, emphasizing the sensitivity of this endpoint. The application of this acute toxicity test is briefly compared to additional work that involved intertidal mussels collected in the field.

Conclusions

Recent research undertaken with mud snails, Ilyanassa obsoleta, and harbour sediments confirmed the usefulness of the escape behaviour as an assessment tool. However, the limits of the state of knowledge regarding the fate of contaminants in species with the ability to metabolise contaminants is further discussed along with directions to be pursued to address questions arising from the reviewed literature.

     

The International Association for Danube Research (IAD)—portrait of a transboundary scientific NGO

Introduction

The International Association for Danube Research (IAD), a legal association (Verein) according to Austrian law, presently consists of 13 member countries and 12 expert groups covering all water-relevant scientific disciplines. IAD, founded in 1956, represents a traditional and significant stakeholder in the Danube River Basin, fulfilling an important task towards an integrative water and river basin management requested by the EU Water Framework Directive.

Discussion

IAD, stretching between basic and applied research, adapted its strategy after the major political changes in 1989. IAD fosters transdisciplinary and transboundary projects to support integrative Danube River protection in line with the governmental International Commission for the Protection of the Danube River (ICPDR) in which IAD has had observer status since 1998. Recent scientific outputs of IAD encompass, amongst others, a water quality map of the Danube and major tributaries, the Sturgeon Action Plan, hydromorphological mapping of the Drava, a macrophyte inventory, and a Mures River study. Further information about IAD can be found on our website http://www.iad.gs.

     

Evaluation of the giant reed (<Emphasis Type="Italic">Arundo donax</Emphasis>) in horizontal subsurface flow wetlands for the treatment of recirculating aquaculture system effluent

Introduction

Two emergent macrophytes, Arundo donax and Phragmites australis, were established in experimental subsurface flow, gravel-based constructed wetlands (CWs) receiving untreated recirculating aquaculture system wastewater.

Materials and methods

The hydraulic loading rate was 3.75 cm day^?1. Many of the monitored water quality parameters (biological oxygen demand [BOD], total suspended solids [TSS], total phosphorus [TP], total nitrogen [TN], total ammoniacal nitrogen [TAN], nitrate nitrogen [NO₃], and Escherichia coli) were removed efficiently by the CWs, to the extent that the CW effluent was suitable for use on human food crops grown for raw produce consumption under Victorian state regulations and also suitable for reuse within aquaculture systems.

Results and discussion

The BOD, TSS, TP, TN, TAN, and E. coli removal in the A. donax and P. australis beds was 94%, 67%, 96%, 97%, 99.6%, and effectively 100% and 95%, 87%, 95%, 98%, 99.7%, and effectively 100%, respectively, with no significant difference (p?>?0.007) in performance between the A. donax and P. australis CWs. In this study, as expected, the aboveground yield of A. donax top growth (stems + leaves) (15.0?±?3.4 kg wet weight) was considerably more than the P. australis beds (7.4?±?2.8 kg wet weight). The standing crop produced in this short (14-week) trial equates to an estimated 125 and 77 t ?ha^?1 year^?1 biomass (dry weight) for A. donax and P. australis, respectively (assuming that plant growth is similar across a 250-day (September–April) growing season and a single-cut, annual harvest).

Conclusion

The similarity of the performance of the A. donax- and P. australis-planted beds indicates that either may be used in horizontal subsurface flow wetlands treating aquaculture wastewater, although the planting of A. donax provides additional opportunities for secondary income streams through utilization of the energy-rich biomass produced.

     

Improvement of biodegradability of PVA-containing wastewater by ionizing radiation pretreatment

Background

Polyvinyl alcohol (PVA) has been widely used as sizing agents in textile and manufacturing industry, and it is a refractory compound with low biodegradability.

Objective

The objective of this paper was to treat the PVA-containing wastewater using gamma irradiation as a pretreatment strategy to improve its biodegradability and to determine the roles of different kinds of radical species played during pretreatment.

Methods

Gamma radiation was carried out in a ⁶⁰Cobalt source station, PVA concentration was analyzed by using a visible spectrophotometer and specific oxygen uptake rate (SOUR, milligram of O₂ per gram of mixed liquor volatile suspended solids (MLVSS) per hour) was measured by a microrespirometer.

Results

The results showed that the biodegradability of PVA-containing wastewater with low initial concentration (e.g., 327.8?mg/l) could be improved greatly with increasing irradiation dose. However, PVA gel formation was observed at higher initial PVA concentration (e.g., 3,341.6?mg/l) and higher irradiation dose, which inhibited PVA degradation by aerobic microorganisms. However, the formed gel could be separated by microfiltration, which led to more than 90% total organic carbon (TOC) removal.

Conclusion

Ionizing radiation could be used as a pretreatment technology for PVA-containing wastewater, and its combination with biological process is feasible.     

Occurrence and suitability of pharmaceuticals and personal care products as molecular markers for raw wastewater contamination in surface water and groundwater

This study aimed to provide the first and comprehensive data on the occurrence of 17 target pharmaceuticals and personal care products (PPCPs) in urban water environment in Singapore. Meanwhile, this study also verified the suitability of these PPCPs as specific markers of raw wastewater contamination in receiving water bodies in highly urbanized areas where both surface water and groundwater are not impacted by the discharge of treated wastewater effluents. Analytical results of wastewater showed that among 17 target PPCPs examined, only 5 PPCPs were detected in 100 % of raw wastewater samples, including acetaminophen (ACT), carbamazepine (CBZ), caffeine (CF), diethyltoluamide (DEET), and salicylic acid (SA). Similarly, these PPCPs were found in most surface water and groundwater. Interestingly, the three PPCPs (ACT, CBZ, and SA) were only detected in surface water and groundwater in the sampling sites close to relatively older sewer systems, while they were absent in background samples that were collected from the catchment with no known wastewater sources. This suggests that ACT, CBZ, and SA can be used as specific molecular markers of raw wastewater in surface water and groundwater. This study also confirmed that CF and DEET were not really associated with wastewater sources, thus cannot serve well as specific molecular markers of wastewater contamination in receiving water bodies. To the best knowledge of the authors, the use of ACT and SA as specific molecular markers of raw wastewater contamination in urban surface waters and groundwater was first reported. Further studies on the use of ACT, CBZ, and SA along with other chemical/microbial markers are recommended to identify and differentiate contamination sources of surface waters/groundwater.