Do contaminants originating from state-of-the-art treated wastewater impact the ecological quality of surface waters?

Since the 1980s, advances in wastewater treatment technology have led to considerably improved surface water quality in the urban areas of many high income countries. However, trace concentrations of organic wastewater-associated contaminants may still pose a key environmental hazard impairing the ecological quality of surface waters. To identify key impact factors, we analyzed the effects of a wide range of anthropogenic and environmental variables on the aquatic macroinvertebrate community. We assessed ecological water quality at 26 sampling sites in four urban German lowland river systems with a 0–100% load of state-of-the-art biological activated sludge treated wastewater. The chemical analysis suite comprised 12 organic contaminants (five phosphor organic flame retardants, two musk fragrances, bisphenol A, nonylphenol, octylphenol, diethyltoluamide, terbutryn), 16 polycyclic aromatic hydrocarbons, and 12 heavy metals. Non-metric multidimensional scaling identified organic contaminants that are mainly wastewater-associated (i.e., phosphor organic flame retardants, musk fragrances, and diethyltoluamide) as a major impact variable on macroinvertebrate species composition. The structural degradation of streams was also identified as a significant factor. Multiple linear regression models revealed a significant impact of organic contaminants on invertebrate populations, in particular on Ephemeroptera, Plecoptera, and Trichoptera species. Spearman rank correlation analyses confirmed wastewater-associated organic contaminants as the most significant variable negatively impacting the biodiversity of sensitive macroinvertebrate species. In addition to increased aquatic pollution with organic contaminants, a greater wastewater fraction was accompanied by a slight decrease in oxygen concentration and an increase in salinity. This study highlights the importance of reducing the wastewater-associated impact on surface waters. For aquatic ecosystems in urban areas this would lead to: (i) improvement of the ecological integrity, (ii) reduction of biodiversity loss, and (iii) faster achievement of objectives of legislative requirements, e.g., the European Water Framework Directive

Identification strategy for unknown pollutants using high-resolution mass spectrometry: Androgen-disrupting compounds identified through effect-directed analysis

Effect-directed analysis has been applied to a river sediment sample of concern to identify the compounds responsible for the observed effects in an in vitro (anti-)androgenicity assay. For identification after non-target analysis performed on a high-resolution LTQ-Orbitrap, we developed a de novo identification strategy including physico-chemical parameters derived from the effect-directed analysis approach. With this identification strategy, we were able to handle the immense amount of data produced by non-target accurate mass analysis. The effect-directed analysis approach, together with the identification strategy, led to the successful identification of eight androgen-disrupting compounds belonging to very diverse compound classes: an oxygenated polyaromatic hydrocarbon, organophosphates, musks, and steroids. This is one of the first studies in the field of environmental analysis dealing with the difficult task of handling the large amount of data produced from non-target analysis. The combination of bioassay activity assessment, accurate mass measurement, and the identification and confirmation strategy is a promising approach for future identification of environmental key toxicants that are not included as priority pollutants in monitoring programs

FI on-line chemiluminescence reaction for determination of MCPA in water samples

This paper reports an economic, simple, and rapid FI-CL method for the determination of MCPA. This method requires simple instrumentation and it is fast enough to be used in routine analyses. A chemiluminescence signal is generated by reaction between photodegraded MCPA and ferricyanide solution in alkaline medium. All physical and chemical parameters in the flow injection chemiluminescence system were optimized in the experimental setting. To eliminate interference, a solid-phase extraction stage with SDB-1 cartridges and ethanol elution is applied. The signal-MCPA concentration relation is linear in concentration intervals between 0.0015 and 0.6 ¿g¿mL -1. The calibration lines are statistically similar in different working conditions: standards with ethanol without extraction and standards with ethanol and extraction, allowing standards to be excluded from the extraction step, which simplifies the process. The detection limit (DL) is 0.5 ng¿mL -1, which is the same order as the maximum limit established in legislation regarding pesticide limits in water destined for human consumption. A DL of 0.13 ng¿mL -1 can be reached if a sample of 100 mL is preconcentrated. The interday variance coefficient is 3% and the sample throughput is 90 h -1. The water analysis method is efficient with relative error percentages lower than 5% with respect to the added concentration. © 2011 Springer-Verlag.Authors acknowledge to the "Ministerio de Educacion y Ciencia" of Spain and FEDER funds for financial support (Project CTM2006-11991)Torres Cartas, S.; Gómez Benito, C.; Meseguer-Lloret, S. (2012). FI on-line chemiluminescence reaction for determination of MCPA in water samples. Analytical and Bioanalytical Chemistry. 402:1289-1296. https://doi.org/10.1007/s00216-011-5567-1S12891296402Navarro JS (2008) Utilización de plaguicidas en las asociaciones de tratamientos integrados en agricultura en la región de Murcia. Consejería de Sanidad Región de MurciaBarceló D, Hennion MC (1997) Trace determination of pesticide and their degradation products in water. Elsevier, AmsterdamKöck M, Farré M, Martínez E, Gajda-Schrantz K, Ginebreda A, Navarro A, López de Alda M, Barceló D (2010) J Hydrol 383(1–2):73–82Woudneh MB, Sekela M, Tuominen T, Gledhill M (2007) J Chromatogr A 1139(1):121–129Laganà A, Bacaloni A, De-Leva I, Faberi A, Fago G, Marino A (2002) Anal Chim Acta 462:187–198Comoretto L, Arfib B, Chiron S (2007) Sci Total Environ 380(1–3):124–132Kuster M, de Alda MJL, Barata C, Raldá D, Barceló D (2008) Talanta 75(2):390–401Kuster M, de Alda MJL, Hernando MD, Petrovic M, Martín-Alonso J, Barceló D (2008) J Hydrol 358(1–2):112–123Gervais G, Brosillon S, Laplanche A, Helen C (2008) J Chromatogr A 1202(2):163–172Housari F, Höhener P, Chiron S (2011) Sci Total Environ 409(3):582–587Delhomme O, Raeppel C, Briand O, Millet M (2011) Anal Bioanal Chem 399:1325–1334Royal decree 140/2003, 7th of February that establishes the health criteria for the water quality for human consumption. (BOE 21 February 2003)von-der-Ohe PC, Dulio V, Slobodnik J, de-Deckere E, Köhne R, Ebert RU, Ginebreda A, de-Cooman de-Cooman W, Schüürmann G, Brack W (2011) Sci Total Environ 409(11):2064–2077Horwitz W (ed) (2000) Official methods of analysis of AOAC International, 17th edn. AOAC International, GaithersburgMoret S, Sánchez JM, Salvadó V, Hidalgo M (2005) J Chromatogr A 1099(1–2):55–63Tran ATK, Hyne RV, Doble P (2007) Chemosphere 67(5):944–953Long F, Shi HC, He M, Zhu AN (2008) Biosens Bioelectron 23:1361–1366Meulenberg EP, Stoks PG (1995) Anal Chim Acta 311:407–413Chuang JC, Van Emon JM, Durnford J, Thomas K (2005) Talanta 67:658–666Boro RC, Kaushal J, Nangia Y, Wangoo N, Bhashi A, Suri CR (2011) Analyst 136(10):2125–2130Eremin SA, Laassis P, Aaron JJ (1996) Talanta 43:295–301Almansa-López EM, García-Campaña AM, Aaron JJ, Cuadros-Rodriguez L (2003) Talanta 60:355–367García LF, Eremin S, Aaron JJ (1996) Anal Lett 29(8):1447–1461García-Campaña AM, Aaron JJ, Bosque-Sendra JM (2002) Luminescence 17:285–287Lara FJ, García-Campaña AM, Aaron JJ (2010) Anal Chim Acta 679:17–30López-Paz J, Catalá-Icardo M (2011) Anal Lett 44(1–3):146–175Mbaye M, Gaye-Seye M, Aaron JJ, Coly A, Tine A (2011) Anal Bioanal Chem 400(2):403–410López-Paz JL, Catalá-Icardo M, Antón-Garrido B (2009) Anal Bioanal Chem 394:1073–1079López-Paz J, Catalá-Icardo M (2008) Anal Chim Acta 625(2):173–179Chen X, Lin Z, Cai Z, Chen X, Wang X (2008) Talanta 76(5):1083–1087Meseguer-Lloret S, Torres-Cartas S, Gómez-Benito M (2010) Anal Bioanal Chem 398:3175–3182Catalá-Icardo M, Martínez-Calatayud J (2008) Crit Rev Anal Chem 38(2):118–13

Assessing the ecological impact of banana farms on water quality using aquatic macroinvertebrate community composition

In Costa Rica, considerable effort goes to conservation and protection of biodiversity, while at the same time agricultural pesticide use is among the highest in the world. Several protected areas, some being wetlands or marine reserves, are situated downstream large-scale banana farms, with an average of 57 pesticide applications per year. The banana industry is increasingly aware of the need to reduce their negative environmental impact, but few ecological field studies have been made to evaluate the efficiency of proposed mitigation strategies. This study compared the composition of benthic macroinvertebrate communities up- and downstream effluent water from banana farms in order to assess whether benthic invertebrate community structure can be used to detect environmental impact of banana farming, and thereby usable to assess improvements in management practises. Aquatic invertebrate samples were collected at 13 sites, using kick-net sampling, both up- and downstream banana farms in fast flowing streams in the Caribbean zone of Costa Rica. In total, 2888 invertebrate specimens were collected, belonging to 15 orders and 48 families or taxa. The change in community composition was analysed using multivariate statistics. Additionally, a biodiversity index and the Biological Monitoring Working Party (BMWP) score system was applied along with a number of community composition descriptors. Multivariate analyses indicated that surface waters immediately up- and downstream large-scale banana farms have different macroinvertebrate community compositions with the most evident differences being higher dominance by a single taxa and a much higher total abundance, mostly of that same taxon. Assessment of macroinvertebrate community composition thus appears to be a viable approach to detect negative impact from chemical-intensive agriculture and could become an effective means to monitor the efficacy of changes/proposed improvements in farming practises in Costa Rica and similar systems

Unexpected removal of the most neutral cationic pharmaceutical in river waters

Contamination of surface waters by pharmaceuticals is now widespread. There are few data on their environmental behaviour, particularly for those which are cationic at typical surface water pH. As the external surfaces of bacterio-plankton cells are hydrophilic with a net negative charge, it was anticipated that bacterio-plankton in surface-waters would preferentially remove the most extensively-ionised cation at a given pH. To test this hypothesis, the persistence of four, widely-used, cationic pharmaceuticals, chloroquine, quinine, fluphenazine and levamisole, was assessed in batch microcosms, comprising water and bacterio-plankton, to which pharmaceuticals were added and incubated for 21 days. Results show that levamisole concentrations decreased by 19 % in microcosms containing bacterio-plankton, and by 13 % in a parallel microcosm containing tripeptide as a priming agent. In contrast to levamisole, concentrations of quinine, chloroquine and fluphenazine were unchanged over 21 days in microcosms containing bacterio-plankton. At the river-water pH, levamisole is 28 % cationic, while quinine is 91–98 % cationic, chloroquine 99 % cationic and fluphenazine 72–86 % cationic. Thus, the most neutral compound, levamisole, showed greatest removal, contradicting the expected bacterio-plankton preference for ionised molecules. However, levamisole was the most hydrophilic molecule, based on its octanol–water solubility coefficient (K ow). Overall, the pattern of pharmaceutical behaviour within the incubations did not reflect the relative hydrophilicity of the pharmaceuticals predicted by the octanol–water distribution coefficient, D ow, suggesting that improved predictive power, with respect to modelling bioaccumulation, may be needed to develop robust environmental risk assessments for cationic pharmaceuticals

Effects of pesticides monitored with three sampling methods in 24 sites on macroinvertebrates and microorganisms.

Grab water samples, sediment samples, and 2,2,4-trimethylpentane passive samplers (TRIMPS) were used to determine the exposure to 97 pesticides in 24 southeast Australian stream sites over 5 months. Macroinvertebrate communities and selected microorganisms (bacteria, flagellates, ciliates, amoebas, nematodes, and gastrotrichs) were sampled to detect relationships with pesticide toxicity. Sediment samples had the highest estimated toxicities in terms of toxic units (TU) for Daphnia magna (TUDM) and for Selenastrum capricornutum (TUSC). The pesticide-selective SPEARpesticides and the general SIGNAL index for macroinvertebrates exhibited negative linear relationships (r(2) = 0.67 and 0.36, respectively) with pesticide contamination in terms of log maximum TUDM (log mTUDM), suggesting macroinvertebrate community change due to pesticide exposure. Pesticide contamination was the only measured variable explaining variation in ecological quality. Variation in the densities of several microbial groups was best explained by environmental variables other than log TUs. The log mTUDM values derived from sediment concentrations were most important to establish a link with effects on macroinvertebrates, whereas log mTUDM of grab water samples had only minor contribution. Current-use insecticides and fungicides can affect macroinvertebrate communities and monitoring of sediment and continuous water sampling is needed to detect these effects