Water quality requirements for sustaining aquifer storage and recovery operations in a low permeability fractured rock aquifer

A changing climate and increasing urbanisation has driven interest in the use of aquifer storage and recovery (ASR) schemes as an environmental management tool to supplement conventional water resources. This study focuses on ASR with stormwater in a low permeability fractured rock aquifer and the selection of water treatment methods to prevent well clogging. In this study two different injection and recovery phases were trialed. In the first phase ~1380 m(3) of potable water was injected and recovered over four cycles. In the second phase ~3300 m(3) of treated stormwater was injected and ~2410 m(3) were subsequently recovered over three cycles. Due to the success of the potable water injection cycles, its water quality was used to set pre-treatment targets for harvested urban stormwater of ≤ 0.6 NTU turbidity, ≤ 1.7 mg/L dissolved organic carbon and ≤ 0.2 mg/L biodegradable dissolved organic carbon. A range of potential ASR pre-treatment options were subsequently evaluated resulting in the adoption of an ultrafiltration/granular activated carbon system to remove suspended solids and nutrients which cause physical and biological clogging. ASR cycle testing with potable water and treated stormwater demonstrated that urban stormwater containing variable turbidity (mean 5.5 NTU) and organic carbon (mean 8.3 mg/L) concentrations before treatment could be injected into a low transmissivity fractured rock aquifer and recovered for irrigation supplies. A small decline in permeability of the formation in the vicinity of the injection well was apparent even with high quality water that met turbidity and DOC but could not consistently achieve the BDOC criteria.     

Medikamentenentsorgung in privaten Haushalten: Ein Faktor bei der Gewässerbelastung mit Arzneimittelwirkstoffen?

Background

Residues of pharmaceuticals are meanwhile detected widely in the aquatic environment. Waste water treatment plants are the main route of entry: after intake the agents or their metabolites are excreted predominantly via urine into the sewage. Largely unknown is, however, if the improper disposal of unused medicines via domestic sanitary devices (toilet or sink) contributes to the measured concentrations in the environment. Aim of this investigation was to clarify to what extent consumers in Germany dispose of unused medicines directly via domestic sewage. In July and August 2006 a representative survey of the population with 2.000 interviewees was performed for this purpose.

Results

The analysis of the survey shows that the disposal of unused medicines via domestic sewage takes place on relevant scales: approx. 16% of the population dispose at least occasionally of unused or expired tablets in the toilet whereas 43% proceed alike with liquid drugs (toilet or sink).

Discussion

A possible reason for this disposal behaviour is the widely inconsistent waste disposal communication by the municipalities and the federal states. The resulting uncertainty about the correct way to dispose of unused medicines gains in importance in the context of the high recycling willingness of the (German) population: appropriate disposal options for drug residues (tablets or liquids) arising from waste separation are often not realised.

Conclusions

Quantitative assessments on the basis of the collected data demonstrate that the established frequency of direct disposal of unused medicines via domestic sewage can partly contribute significantly to the occurrence of pharmaceuticals in the aquatic environment. Crucial parameters are here the excretion rate of the active pharmaceutical ingredient considered and the actual amount of medication waste.

Recommendations

Based on the inquiry results, measures that lead to a more adequate handling of pharmaceutical waste disposal are demanded. The establishment of a consistent and binding disposal standard for unused medicines via return in pharmacies is recommended. This measure needs to be accompanied by a simplification of the established take back systems which partly cause high time and effort for pharmacies.     

Synthesis of [13C]- and [14C]-labeled phenolic humus and lignin monomers

Natural phenolic monomers are ubiquitous in the environment and are involved in the stabilization of atmospheric carbon and the transformation of xenobiotics. Investigations on the stabilization of phenolic carbons and their environmental fate are hampered by the unavailability of commercial [13C]- and [14C]-labeled phenols. Here we report the complete chemical synthesis of the lignin and humus structural monomers p-coumaric, ferulic, and caffeic acids, p-hydroxybenzaldehyde, protocatechualdehyde, vanillin, catechol, and guaiacol, uniformly [13C]- or [14C]-labeled in the aromatic ring, starting from commercially available [U-ring-13C]- or [U-ring-14C]-labeled phenol. The synthesis of these compounds involved selective ortho-hydroxylation of the aromatic ring, Friedel-Crafts alkylation, and Knoevenagel condensation. [U-ring-13C]- or [U-ring-14C]-p-coumaric acid was synthesized via p-hydroxybenzaldehyde with a 75% yield with respect to phenol. Synthesis of [U-ring-13C]- or [U-ring-14C]-ferulic acid, consisting of six single steps via guaiacol and vanillin, had an overall yield of up to 45%. Uniformly ring-labeled caffeic acid was synthesized either via catechol and protocatechualdehyde in five single steps, yielding [U-ring-14C]-caffeic acid with a 37% yield, or via guaiacol, vanillin, and ferulic acid in seven steps, yielding [U-ring-13C]-caffeic acid with an 18% yield. Ferulic acid, [14C]-labeled at beta-C of the propenoic side chain, was synthesized from [2-14C]-malonic acid under Knoevenagel conditions with a 67% yield with respect to malonic acid. Demethylation of the [beta-14C]-ferulic acid with BBr3 in CH3CN resulted in [beta-14C]-caffeic acid with a 62% yield. All [U-ring-13C]-labeled phenolic products were analyzed by 13C nuclear magnetic resonance (13C-NMR) spectroscopy and gas chromatography-mass spectrometry (GC-MS).     

Probabilistic approaches in the effect assessment of toxic chemicals. What are the benefits and limitations?

There is an ongoing discussion whether in the environmental risk assessment for chemicals the so called 'deterministic' approach using point estimates of exposure and effect concentrations is still appropriate. Instead, the more detailed and scientifically sounder probabilistic methods that have been developed over the last years are widely recommended. Here, we present the results of a probabilistic effect assessment for the aquatic environment performed for the pesticide methyl parathion and compare them with the results obtained with the common deterministic approach as described in the EU Technical Guidance Document. Methyl parathion was chosen because a sufficient data set (acute toxicity data for about 70 species) was available. The assumptions underlying the probabilistic effect assessment are discussed in the light of the results obtained for methyl parathion. Two important assumptions made by many studies are: (i) a sufficient number of ecologically relevant toxicity data is available, (ii) the toxicity data follow a certain distribution such as log-normal. Considering the scarcity of data for many industrial chemicals, we conclude that these assumptions would not be fulfilled in many cases if the probabilistic assessment was applied to the majority of industrial chemicals. Therefore, despite the well-known limitations of the deterministic approach, it should not be replaced by probabilistic methods unless the assumptions of these methods are carefully checked in each individual case, which would significantly increase the effort for the assessment procedure.     

Release of substituents from phenolic compounds during oxidative coupling reactions

Phenolic compounds originating from plant residue decomposition or microbial metabolism form humic-like polymers during oxidative coupling reactions mediated by various phenoloxidases or metal oxides. Xenobiotic phenols participating in these reactions undergo either polymerization or binding to soil organic matter. Another effect of oxidative coupling is dehalogenation, decarboxylation or demethoxylation of the substrates. To investigate these phenomena, several naturally occurring and xenobiotic phenols were incubated with various phenoloxidases (peroxidase, laccase, tyrosinase) or with birnessite (delta-MnO(2)), and monitored for chloride release, CO(2) evolution, and methanol or methane production. The release of chloride ions during polymerization and binding ranged between 0.2% and 41.4%. Using the test compounds labeled with 14C in three different locations (carboxyl group, aromatic ring, or aliphatic chain), it was demonstrated that 14CO(2) evolution was mainly associated with the release of carboxyl groups (17.8-54.8% of the initial radioactivity). Little mineralization of 14C-labeled aromatic rings or aliphatic carbons occurred in catechol, ferulic or p-coumaric acids (0.1-0.7%). Demethoxylation ranged from 0.5% to 13.9% for 2,6-dimethoxyphenol and syringic acid, respectively. Methylphenols showed no demethylation. In conclusion, dehalogenation, decarboxylation and demethoxylation of phenolic substrates appear to be controlled by a common mechanism, in which various substituents are released if they are attached to carbon atoms involved in coupling. Electron-withdrawing substituents, such as -COOH and -Cl, are more susceptible to release than electron-donating ones, such as -OCH(3) and -CH(3). The release of organic substituents during polymerization and binding of phenols may add to CO(2) production in soil.