Surface-enhanced Raman spectroscopy for emerging contaminant analysis in drinking water

● Definition of emerging contaminants in drinking water is introduced. ● SERS and standard methods for emerging contaminant analysis are compared. ● Enhancement factor and accessibility of SERS hot spots are equally important. ● SERS sensors should be tailored according to emerging contaminant properties. ● Challenges to meet drinking water regulatory guidelines are discussed. Emerging contaminants (ECs) in drinking water pose threats to public health due to their environmental prevalence and potential toxicity. The occurrence of ECs in our drinking water supplies depends on their physicochemical properties, discharging rate, and susceptibility to removal by water treatment processes. Uncertain health effects of long-term exposure to ECs justify their regular monitoring in drinking water supplies. In this review article, we will summarize the current status and future opportunities of surface-enhanced Raman spectroscopy (SERS) for EC analysis in drinking water. Working principles of SERS are first introduced and a comparison of SERS and liquid chromatography-tandem mass spectrometry in terms of cost, time, sensitivity, and availability is made. Subsequently, we discuss the strategies for designing effective SERS sensors for EC analysis based on five categories—per- and polyfluoroalkyl substances, novel pesticides, pharmaceuticals, endocrine-disrupting chemicals, and microplastics. In addition to maximizing the intrinsic enhancement factors of SERS substrates, strategies to improve hot spot accessibilities to the targeting ECs are equally important. This is a review article focusing on SERS analysis of ECs in drinking water. The discussions are not only guided by numerous endeavors to advance SERS technology but also by the drinking water regulatory policy.     

我国地表水中药物与个人护理品污染现状及其繁殖毒性筛查

根据文献报道,我国地表水中已检出至少144种药物及个人护理用品(pharmaceuticals and personal care products,PPCPs),包括抗生素、激素、其他药物、个人护理品(personal care products,PCPs)4大类,其中检出浓度最高的达到了μg·L~(-1)量级,在长期的污染下有可能对水生生物产生内分泌干扰效应或繁殖毒性,进而影响到整个水生生物种群的繁衍变化。因此,有必要根据我国地表水中PPCPs的污染水平,筛查出具有潜在生态风险的PPCPs。由于目前缺乏针对PPCPs类污染物的筛选体系,以国内外优先控制污染物筛选体系为基础,借鉴基于风险的欧洲兽药分级方法,利用风险指数(risk index,RI),筛选得出目前我国的地表水中有16种具有繁殖毒性的PPCPs的RI1,包括1种抗生素,5种激素类药物,3种其他药物和7种PCPs,其中乙炔雌二醇(ethinylestradiol,EE2)的RI最高(115 730),其次是壬基酚(nonylphenol,NP)(1 796)、邻苯二甲酸二丁酯(dibutyl phthalate,DBP)(255.31),对水生态环境有较高的风险的PPCPs需进一步进行较高层次的风险评价。     

Monitoring,mapping and health risk assessment of fluoride in drinking water supplies in rural areas of Maku and Poldasht,Iran

The aim of this study was to investigate and determine fluoride concentrations in drinking water supplies in rural areas of Maku and Poldasht in West Azerbaijan Province, the northwest of Iran. Fluorosis risk assessment and characterization was also investigated. Fluoride concentrations mapping was accomplished by using the GIS system. Totally, 356 water samples, including one sample in each season, were collected from 89 water supplies providing water for 95 and 61 rural areas of Maku and Poldasht, respectively. According to the results, in Maku and Poldasht, 25 and 30 rural areas had contaminated water sources, respectively. Average annual fluoride concentrations ranged from 3.04 to 7.31 mg/l in the contaminated villages of Maku, which is about 2–4.8 times higher than the maximum standard level of the Iranian drinking water standard, and 4.52–8.21 mg/l in the contaminated areas of Poldasht, which is about 3–5.47 times higher than the maximum standard level. The maximum fluoride level was determined 11.12 mg/l and 10.98 mg/l in one of villages of Maku and Poldasht Counties in summer, respectively. Neither in Maku nor in Poldasht, water resources showed dental cavity risk, while dental fluorosis risk and skeletal fluorosis risk were very significant in some villages of both cities. Children were at most risk of fluorosis. New alternative water supplies for the contaminated villages if possible, consumption of bottled water and application of reverse osmosis are recommended as remedial actions in the contaminated areas.

     

Humanpharmakawirkstoffe in der Umwelt: Einträge, Vorkommen und der Versuch einer Bestandsaufnahme

Background

The presence of a large spectrum of pharmaceutical agents has been reported for aquatic environments (surface—and groundwater) and other aquatic media (influents and effluents of sewage treatment plants) in Germany and beyond, including their occurrence in drinking water. Considering the large number of pharmaceuticals produced for human use and released into the environment, various authors (Sattelberger 1999, Hanisch et al. 2004, Castiglioni et al. 2006, IWW 2006, Stockholm County Council 2006) tried to compile ‘priority lists’ focusing on those substances with environmental relevance. The following agents are included in all lists: ciprofloxacine, clarythromycine (antibiotics), carbamazepine (anti-epileptic agent), bezafibrate (lipid reducer), clofibric acid (lipid reducer metabolite), ethinylestradiol (sex hormone) and cylophosfamide (cytostatic agent). The agents erythromycine and sulfamethoxazole (antibiotics), ibuprofen, indometacine, propyphenazone (analgesics), atenolol (beta-blocker) and ifosfamide (cytostatic agent) can be found in three of four priority lists.

Results

Pharmaceuticals mainly enter the aquatic environment via effluent water, coming from wastewater treatment plants (including hospital and household sewerage), untreated discharges (e.g, secondary transfer of active agents into ground- and surface waters via sewage sludge application in agriculture and via landfill leachate) and leakages in the municipal sewer network.

Discussion

Potential activities towards a reduced release of pharmaceuticals into the environment should consider primarily the origin of the exposure to allow a separation of drug containing flows already at the source. Following the latter it would be possible to minimize the contamination of spring-, ground- and surface waters which serve as raw water resources for drinking water supply. However, considering the actual water pollution with pharmaceuticals and other substances, ‘end-of pipe’ techniques in the sewage and drinking water treatment are absolutely essential.

Conclusions

Sustainability criteria (e.g. protection of drinking water resources, habitats and biocoenoses, recycling and economizing use of resources) and economic aspects of modern sewage disposal concepts require a useful choice and combination of technical measures as components of centralized and decentralized sewage and drinking water treatment methods. It is though not realistic to cover and eliminate all pharmaceutical agents of environmental relevance equally effective even if a catalogue of potential technical treatment methods is elaborated thoroughly. Therefore, a concentration of efforts on selected drug agents, at least following initially some of the priority lists, is recommended.

Recommendations and Perspectives

The contamination of the water cycle with pharmaceuticals is nevertheless not exclusively to be solved via the application of technical methods. The BMBF (Federal Ministry for Education and Research) funded project start (Management Strategies for Pharmaceuticals in Drinking Water, www.start-project.de) therefore tries by implementation of a transdisciplinary approach to integrate technical-, behavioral-, and agent-orientated management strategies towards a more comprehensive and sustainable problem solution.     

Bewertung der Umweltrelevanz von Arzneistoffen

Aim The aim of this work was to investigate, which human and veterinary pharmaceuticals are of high ecological relevance due to the input into the environment as well as with regard to the effects and behaviour in the environment. Furthermore, the state of knowledge concerning the ecologically relevant substances and the need of research was evaluated. Methods A two-step approach considering the criteria quantity of sold pharmaceuticals, concentrations, effects and fate in the environment was developed to identify the pharmaceuticals of potential ecological relevance. In a second step the identified individual substances and groups of substances were considered in more detail concerning metabolism, environmental behaviour and ecological effects. Results In a first step 29 out of approximate 2,700 licensed human pharmaceuticals and seven substances as well as three substance groups used in veterinary medicine were identified as potentially ecologically relevant. The detailed assessment in a second step lead to the conclusion, that of the human pharmaceuticals 9 substances as well as two substance groups concerning the environmental behaviour and seven substances concerning the effects are of high environmental relevance. Concerning the environmental behaviour six out of seven veterinary pharmaceuticals as well as three substance groups and only three substances concerning the ecological effects were classified as relevant for the environment. Discussion By means of the presented method it was possible to limit the scope of a wide spectrum of pharmaceuticals, so that a detailed assessment of only relevant active agents was possible. Nevertheless, it is a precondition that investigations concerning the occurrence, fate and effects of the individual compounds in the environment have been already carried out and published in the literature. Conclusions The method is suitable for a comprehensive assessment of the ecological relevance of pharmaceuticals, but for a lot of human and veterinary pharmaceuticals the data available in the literature are insufficient. Recommendations For a final extensive assessment of the environmental relevance for some of the human and veterinary pharmaceuticals more studies are necessary. Especially data concerning the environmental behaviour in water and soils, data from long-term-studies for the assessment of ecological effects and data concerning metabolites and mixtures of pharmaceutical compounds are lacking.     

Persistence of gemfibrozil, naproxen and mefenamic acid in natural waters

The occurrence of pharmaceuticals in natural waters is a potential threat to human nutrition and ecosystem quality. The persistence of the acidic pharmaceuticals gemfibrozil, naproxen and mefenamic acid was studied in surface waters of Maracaibo Lake and Tule reservoir (Venezuela) under laboratory conditions. A quick and easy analytical method was developed for the determination of the acidic drugs at microgram per liter levels using aqueous derivatization, liquid–liquid extraction and gas chromatography–mass spectrometry. Pharmaceuticals degradation followed a pseudo first-order kinetic and their half-lives were calculated for every experimental condition. Under sunlight, naproxen and mefenamic acid were degraded at moderate rates with half-lives from 9.6 ± 0.5 to 27.0 ± 6.6 days, while gemfibrozil had a higher persistence (t _1/2 = 119.5 ± 15.6 − 288.8 ± 61.3 days).     

Aluminium and heavy metals in potable waters of the north Ceredigion area,mid-Wales

Routine monitoring of the public water supply in Aberystwyth revealed high levels of aluminium during November 1989. These levels were twelve times the EEC recommended level and three times the maximum permitted level. While the reservoirs supplying the region and the streams draining their upland peaty catchment areas generally contain moderate levels of Al, Al salts added as coagulating agents are a major source. There is also considerable variation of the Al in potable waters through the month of November 1989 for an Aberystwyth supply. Private supplies, from groundwaters, in the region generally contain low Al.While most drinking waters in the region contain low Pb, values close to the EEC limit have been recorded for some samples from older houses with Pb pipes, while a sample from a well supply in an old lead mining area contained three times the EEC limit. Despite the wide use of Cu piping for water supplies in the area, most values for this element in mains-water are low, with occasional higher values. However, many private supplies from spring sources are extremely Cu-rich and again levels of this element in a private supply showed a marked temporal variation during November 1989. Zinc levels in potable waters of the area are very variable. That most of the Zn in potable waters is derived from the dissolution of Cu pipes is evidenced by a strong correlation between Cu and Zn in these waters. A few Cd values of over 2 g L^–1 have also been recorded.     

Arsenic in drinking water and mortality in the Southern Great Plain,Hungary

Arsenic distribution has been found in drinking waters. A connection between arsenic and other constituents of water was determined. Close positive correlation was found between arsenic and humic substances over most of the study area. In two smaller areas, there was no correlation between arsenic and humic substances. In these waters, the arsenic distribution is not controlled by organic matter, but by other factors which need further investigations.Examination of mortality in the populations consuming water containing levels of arsenic above and below that permitted did not show any significant differences in standardised mortality ratio (SMR) from all causes of death for both male and female. The SMR from the main causes of death — diseases of the circulatory system and neoplasms — shows controversial results for males and females.     

Variability in the chemistry of private drinking water supplies and the impact of domestic treatment systems on water quality

Tap water from 497 properties using private water supplies, in an area of metalliferous and arsenic mineralisation (Cornwall, UK), was measured to assess the extent of compliance with chemical drinking water quality standards, and how this is influenced by householder water treatment decisions. The proportion of analyses exceeding water quality standards were high, with 65 % of tap water samples exceeding one or more chemical standards. The highest exceedances for health-based standards were nitrate (11 %) and arsenic (5 %). Arsenic had a maximum observed concentration of 440 µg/L. Exceedances were also high for pH (47 %), manganese (12 %) and aluminium (7 %), for which standards are set primarily on aesthetic grounds. However, the highest observed concentrations of manganese and aluminium also exceeded relevant health-based guidelines. Significant reductions in concentrations of aluminium, cadmium, copper, lead and/or nickel were found in tap waters where households were successfully treating low-pH groundwaters, and similar adventitious results were found for arsenic and nickel where treatment was installed for iron and/or manganese removal, and successful treatment specifically to decrease tap water arsenic concentrations was observed at two properties where it was installed. However, 31 % of samples where pH treatment was reported had pH < 6.5 (the minimum value in the drinking water regulations), suggesting widespread problems with system maintenance. Other examples of ineffectual treatment are seen in failed responses post-treatment, including for nitrate. This demonstrates that even where the tap waters are considered to be treated, they may still fail one or more drinking water quality standards. We find that the degree of drinking water standard exceedances warrant further work to understand environmental controls and the location of high concentrations. We also found that residents were more willing to accept drinking water with high metal (iron and manganese) concentrations than international guidelines assume. These findings point to the need for regulators to reinforce the guidance on drinking water quality standards to private water supply users, and the benefits to long-term health of complying with these, even in areas where treated mains water is widely available.     

Perfluorierte Tenside (PFT) in der aquatischen Umwelt und im Trinkwasser

Recent scientific research on perfluorinated surfactants (PS) revealed their ocurrence in German surface and drinking waters (Skutlarek, Exner, Färber 2006). Since several years, PS have been found in the global environment, especially in animal and human tissues. PS possess extreme persistence against microbiological and chemical degradation and are able to bioaccumulate in animals and humans (Houde et al. 2006). PS concentrations (sum of 12 components) in the Rhine river and its main tributaries were determined below 100 ng/L, but the rivers Ruhr (tributary of the Rhine) and Möhne (tributary of the Ruhr) showed remarkable high concentrations (Ruhr: up to 446 ng/L, Möhne: up to 4385 ng/L). The maximum concentration in drinking waters was 598 ng/L with the major component perfluorooctanoic acid (PFOA). The PS concentrations decreased similarly to the PS concentrations of the raw waters along the flow direction of the Ruhr river. Therefore it seems to be necessary to install legal regulations for these compounds.     

An efficient resin for solid-phase extraction and determination by UPLCMS/MS of 44 pharmaceutical personal care products in environmental waters

• A hydrophilic resin (GCHM) was facile synthesis and characterized. • Average absolute recovery of GCHM (75.6%) performs better than Oasis^® HLB. • Detection limits of method (SPE-UPLC-MS/MS) ranged between 0.03 and 0.6 ng/L. • 22 PPCPs were determined in environmental waters ranging from 0.5 to 1590 ng/L. In this study, a hydrophilic resin named GCHM was fabricated based on poly(N-vinyl pyrrolidone-co-divinylbenzene), characterized, and applied as a solid-phase extraction (SPE) material. Up to 44 pharmaceuticals and personal care products (PPCPs) belonging to 10 classes were recovered in environmental water samples. Different variables affecting extraction, such as adsorbent amount, sample pH, and loading speed, were optimized. Under optimal conditions, the average absolute recovery of 44 PPCPs was 75.6% using GCHM, indicating a better performance than the commercial Oasis^® HLB. SPE with home-made hydrophilic polymeric sorbent followed by ultra-performance liquid chromatography and tandem mass spectrometry was validated, and the method achieved good linearity (r²>0.991, for all analytes). In addition, the method detection limits of target compounds ranged from 0.03 to 0.6 ng/L. The developed method was applied to determine PPCPs in 10 environmental water samples taken from the Yangtze River, Huaihe River, and Taihu Lake, 1 groundwater sample from Changzhou in Jiangsu Province, 1 wastewater sample from Xiamen and 2 seawater samples from the Jiulong River in Fujian Province, China. In these samples, 22 compounds were determined at levels ranging from 0.5 to 1590 ng/L.     

Yolk androgens in great tit eggs are related to male attractiveness,breeding density and territory quality

Females can adaptively adjust phenotype of their offspring via deposition of various compounds into eggs, including androgens and other hormones. Here, I investigated how egg yolk androgens (testosterone and androstenedione) related to environmental conditions and parental traits in the great tit (Parus major) across three breeding seasons. Male and female traits studied included age, condition and multiple feather ornaments, both carotenoid- and melanin-based (carotenoid and UV chroma of yellow breast feathers, area of black breast band and white cheek immaculateness). Yolk mass increased with laying temperature, laying date and area of male black breast band. Concentration of androgens increased with breeding density, territory quality and carotenoid chroma of male yellow breast feathers and was higher in mates of 1 year old as compared to older males. Yolk androgens were not related to any of the female traits analysed. These patterns were thus consistent with (1) social and environmental effects on yolk mass and composition and (2) both positive and negative differential allocation strategies of resource allocation in females. Overall, male traits were the most important predictors of egg yolk characteristics in this socially monogamous songbird.     

Health Impact Evaluation of Boron in Drinking Water: A Geographical Risk Assessment in Northern France

Objective: To evaluate health impact of boron in drinking water. Methods: A regional scale geographical study in Northern France was conducted. Assessment of boron blood levels in a group of 180 healthy individuals and correlation with boron content in drinking water were followed by an assessment of health indicators such as birth rates, mortality rates, and sex ratios in zones of different boron content in drinking water. Results: After necessary adjustments, men living in municipalities with more than 0.30 mg/L of boron in drinking water had elevated but not significant boron blood levels compared with those living in municipalities with boron water levels of less than 0.30 mg/L (159.1 versus 123.0 ng/g; p > 0.05). The standardized birth ratio adjusted for the reference geographic zone and calendar time period was 1.07 and 1.28 in the low and high (>0.3 mg/L) boron content municipalities, respectively. The birth rate in municipalities with high boron content in drinking water was higher than that of the reference geographic zone and of the French general population (p < 10^-4). The standardized mortality ratio adjusted for the reference geographic zone and calendar time period was 0.94 and 0.92 in the low and high boron content municipalities, respectively. The mortality rate in municipalities with high boron content in drinking water was less than that of the reference geographic zone and of the French general population (p < 10^-3). No statistical difference was noted in the male–female sex ratios between the different municipality zones (p = 0.45). Conclusions: The results of this study do not support the idea of a deleterious effect of boron on human health, at the boron water level contents found in this specific region. In fact, there is a tendency toward a beneficial effect with low-dose environmental exposure (less than 1 mg/L of boron) in drinking water.     

Removal of carbamazepine from urban wastewater by sulfate radical oxidation

The occurrence of bioactive trace pollutants such as pharmaceuticals in natural waters is an emerging issue. Numerous pharmaceuticals are not completely removed in conventional wastewater treatment plants. Advanced oxidation processes may represent an interesting alternative to completely mineralize organic trace pollutants. In this article, we show that sulfate radicals generated from peroxymonosulfate/Co^II are more efficient than hydroxyl radicals generated from the Fenton’s reagent (H₂O₂/Fe^II) for the degradation of the pharmaceutical compound, carbamazepine. The second-order rate constant for the reaction of SO₄ ^·− with carbamazepine is 1.92·10⁹ M⁻¹ s⁻¹. In laboratory grade water and in real urban wastewater, SO₄ ^·− yielded a faster degradation of carbamazepine compared to HO^· . Under strongly oxidizing conditions, a nearly complete mineralization of carbamazepine was achieved, while under mildly oxidizing conditions, several intermediates were identified by LC–MS. These results show for the first time in real urban wastewater that sulfate radicals are more selective than hydroxyl radicals for the oxidation of an organic pollutant and may represent an interesting alternative in advanced oxidation processes.     

Pesticide Residues in Water From River Kaveri,South India

The residue levels of presistent chlorinated pesticides such as HCH (hexachlorocyclo-hexane) isomers and DDT (dichlorodiphenyl trichloroethane) compounds were quantified in water samples collected from the River Kaveri and its distributor River Coleroon in Tamil Nadu, South India. HCH showed higher levels in River Kaveri during premonsoon (July to September) and monsoon (October to December) months, reflecting the HCH usage during that season for paddy crops. But in the case of DDT no clear trend in residue level was observed. the α-HCH was detected as the dominant isomer in all the three sampling sites. Among DDT compounds, p,p'-DDT and p,p'-DDE showed higher percentage of the total. International comparison of residue levels revealed that the present values are comparable to the waters from Asian and South East Asian nations, but lower than some samples from other parts of India. the value of DDT is well below the EEC's maximum acceptable concentration for surface waters and lower than the recommended limit of 2000ng 1^-1 in USA water for protection of aquatic life (Water Quality Criteria, 1972).     

Toxicity of tri- and penta-valent arsenic, alone and in combination, to the cladoceran Daphnia carinata: the influence of microbial transformation in natural waters

The acute toxicity of arsenic(III) and arsenic(V) alone and in combination to a cladoceran, Daphnia carinata, was studied in both cladoceran culture medium and natural water collected from a local suburban stream. As(III) was found to be more toxic than As(V) to Daphnia survival. The LC₅₀ values for As(III), As(V), and As(III) + As(V) were 0.554, 1.499, and 0.692 mg l⁻¹, respectively. Although various species of As, particularly As(III) and As(V) co-exist together in natural waters, the existing guidelines for water quality are based on individual As species. The results of this investigation suggest that As(III) and As(V) can interact either synergistically or additively resulting in an increase in the overall toxicity of the mixture compared to individual As species. Also, indigenous microorganisms in natural water may play a significant role in the transformation of As, thereby influencing the toxicity of As in receiving waters. This study clearly suggests that the joint action of As species should be considered in the development of water quality guidelines. To our knowledge this is the first study on the interactive effect of As(III) and As(V) to a cladoceran. Thus, this study suggests that these two species of As, when present together above 0.1 mg l⁻¹ concentration, are toxic to fresh water invertebrates; therefore, pollution with these compounds may adversely affect natural ecosystems.     

Maternal provisioning for larvae and larval provisioning for juveniles in the toxopneustid sea urchin <Emphasis Type="Italic">Tripneustes gratilla</Emphasis>

Lipid and protein biochemistry of eggs (84 μm in diameter), embryos and early larvae of the tropical echinoid Tripneustes gratilla (Linnaeus 1758) were quantified to determine how maternal provisions are used to fuel development of the echinopluteus. The eggs contained a mean of 30.82 ng lipid and 87.32 ng protein. Energetic lipids were the major lipid component (55.52% of total lipid) with the major class being triglyceride (TG: mean 15.9 ng, 51.58% of total). Structural lipid was dominated by phospholipid (PL: mean 11.18 ng, 36.26% of total). Early embryogenesis was not a major drain on egg energetic lipid and protein. Development of the functional feeding larva used ca. 50% of initial egg energetic lipid and most of this was TG. Maternal TG was still present in the 8-day echinoplutei and it was estimated that this energetic lipid would be depleted in unfed larvae by day 10. There was no change in PL. In a separate experiment lipid biochemistry of rudiment stage larvae and early developing juveniles were quantified to determine how lipids are used during metamorphosis. Fed larvae accumulated lipid (mean 275.49 ng) with TG and PL being the major energetic and structural lipids, respectively. Larval lipid stores were not appreciably depleted by metamorphosis and so were available for the early benthic stage juvenile. Juveniles started their benthic existence with 314 ng total lipid (TG: mean 46.84 ng, 14.9% of total, PL: mean 137.51 ng, 43.67% of total). Nile Red histochemistry and histology showed that the stomach serves as a nutrient storage organ and, that lipid stores accrued by larvae sustain developing juveniles for up to 4 days post settlement. Triglyceride supported both non-feeding stages of development and the prefeeding larval and perimetamorphic benthic stage. In this first study of lipid stores in settlement stage echinoderm larvae, we show that T. gratilla larvae sequester the same major energetic lipid (TG) to support the early juvenile that the female parent provided them to fuel early development.     

Improved source,improved quality? Demand for drinking water quality in rural India

This paper tests the hypothesis that the expansion of improved drinking water supplies in rural India reduced household expenditure on water quality, offsetting some of the quality benefits from source protection. I estimate demand for in-home treatment using geological characteristics to predict a household's drinking water source. The probability of treatment and in particular boiling reduces by 18–27 percentage points in response to source protection, offsetting 4% of the water quality gains and saving households 0.5–1% in monthly expenditure. Behavioral choices partly counteract the water quality gains from source protection.