Micropollutants in urban stormwater: occurrence,concentrations, and atmospheric contributions for a wide range of contaminants in three French catchments

This study aimed at: (a) providing information on the occurrence and concentration ranges in urban stormwater for a wide array of pollutants (n?=?77); (b) assessing whether despite the differences between various catchments (land use, climatic conditions, etc.), the trends in terms of contamination level are similar; and (c) analyzing the contribution of total atmospheric fallout (TAF) with respect to sources endogenous to this contamination. The studied contaminants include conventional stormwater contaminants (polycyclic aromatic hydrocarbons (PAHs), Zn, Cu, Pb, etc.), in addition to poorly or undocumented pollutants such as nonylphenol and octylphenol ethoxylates (NPnEO and OPnEO), bisphenol A (BPA), polybrominated diphenyl ethers (PBDEs), a wide variety of pesticides, and various metals of relevance (As, Ti, Sr, V). Sampling and analysis were performed using homogeneous methods on three urban catchments with different land use patterns located in three distinct French towns. For many of these pollutants, the results do not allow highlighting a significant difference in stormwater quality at the scale of the three urban catchments considered. Significant differences were, however, observed for several metals (As, Cr, Cu, Ni, Sr and Zn), PAHs, and PBDEs, though this assessment would need to be confirmed by further experiments. The pollutant distributions between dissolved and particulate phases were found to be similar across the three experimental sites, thus suggesting no site dependence. Lastly, the contributions of TAF to stormwater contamination for micropollutants were quite low. This finding held true not only for PAHs, as previously demonstrated in the literature, but also for a broader range of molecules such as BPA, NPnEO, OPnEO, and PBDEs, whose high local production is correlated with the leaching of urban surfaces, buildings, and vehicles.     

Investigation of pharmaceutical metabolites in environmental waters by LC-MS/MS

Pharmaceuticals, once ingested, are commonly metabolized in the body into more polar and soluble forms. These compounds might not be completely removed in the wastewater treatment plants and consequently being discharged into the aquatic ecosystem. In this work, a multi-class sensitive method for the analysis of 21 compounds, including 7 widely consumed pharmaceuticals and 14 relevant metabolites, has been developed based on the use of UHPLC-MS/MS in selected reaction monitoring (SRM) mode. The method was validated in six surface waters (SW) and six effluent wastewaters (EWW) at realistic concentration levels that can be found in waters. The optimized method was applied to the analysis of different types of water samples (rivers, lakes and effluent wastewater), detecting nearly all the parent compounds and metabolites investigated in this work. This fact illustrates that not only pharmaceuticals but also their metabolites are commonly present in these types of waters. Analytical research and monitoring programs should be directed not only towards parent pharmaceuticals but also towards relevant metabolites to have a realistic overview of the impact of pharmaceuticals in the aquatic environment.     

Frequency of micronuclei and of other nuclear abnormalities in erythrocytes of the grey mullet from the Mondego,Douro and Ave estuaries—Portugal

Fish are bioindicators of water pollution, and an increased rate of their erythrocyte nuclear morphological abnormalities (ENMAs)—and particularly of erythrocyte micronuclei (EMN)—is used as a genotoxicity biomarker. Despite the potential value of ENMAs and MN, there is scarce information about fish captured in Iberian estuaries. This is the case of the Portuguese estuaries of the Mondego, Douro and Ave, suffering from different levels of environmental stress and where chemical surveys have been disclosing significant amounts of certain pollutants. So, the aim of this study was to evaluate genotoxicants impacts and infer about the exposure at those ecosystems, using the grey mullet (Mugil cephalus) as bioindicator and considering the type and frequency of nuclear abnormalities of erythrocytes as proxies of genotoxicity. Sampling of mullets was done throughout the year in the important Mondego, Douro and Ave River estuaries (centre and north-western Portugal). The fish (total n?=?242) were caught in campaigns made in spring–summer and autumn–winter, using nets or fishing rods. The sampled mullets were comparable between locations in terms of the basic biometric parameters. Blood smears were stained with Diff-Quik to assess the frequencies of six types of ENMAs and MN (given per 1,000 erythrocytes). Some basic water physicochemical parameters were recorded to search for fluctuations matching the ENMAs. Overall, the most frequent nucleus abnormality was the polymorphic type, sequentially followed by the blebbed/lobed/notched, segmented, kidney shaped, vacuolated, MN and binucleated. The total average frequency of the ENMAs ranged from 73?‰ in the Mondego to 108?‰ in the Ave. The polymorphic type was typically ≥50 % of the total ENMAs, averaging about 51?‰, when considering all three estuaries. The most serious lesion—the MN—in fish from Mondego and Douro had a similar frequency (≈0.38?‰), which was significantly lower than that in the Ave (0.75?‰). No significant seasonal differences existed as to the MN rates and seasonal differences existed almost only in the Douro, with the higher values in AW. In general, the pattern of ENMAs frequencies was unrelated with the water physicochemical parameters. Considering the data for both the total ENMAs and for each specific abnormality, and bearing in mind that values of MN in fish erythrocytes >0.3?‰ usually reflect pollution by genotoxicants, it is suggested that mullets were likely being chronically exposed to such compounds, even in the allegedly less polluted ecosystem (Mondego). Moreover, data supported the following pollution exposure gradient: Mondego?<?Douro?<?Ave. The scenario and inferences nicely agree with the published data from chemical monitoring.     

Impacts on effluent contaminants from mine sites: risk assessment,fate, and distribution of pollution at basin scale

The environmental implications of mining activities are of worldwide concern. An environmental evaluation at the basin level was conducted because of widespread mining in Cajamarca in Northern Peru. A sediment monitoring program was developed at the Jequetepeque basin, located in Cajamarca. A total of 16 sites were monitored at three different times between June 2009 and July 2010, and a total of 42 samples were collected. All samples were analyzed by microwave digestion and by a sequential extraction scheme following the three-stage European Community Bureau of Reference (three-stage BCR) protocol. Trace element mobilization from the sediments to the water column was assessed by the risk assessment code (RAC). Spatial and temporal distribution of trace elements was evaluated by principal component analysis and hierarchical cluster analysis. Cd, Zn, As, and Pb showed the highest concentrations independent of season. Notably, Cu concentration and mobility increased during the wet season for all samples. Additionally, Hg concentration and mobility increased during the wet season near the mine sites. According to the enrichment factor, the highest enrichments of Cd, Zn, Pb, and As were related to mine runoff. The effect of trace elements near the mine sites at the Jequetepeque basin was considered a significant threat to the environment due to Cd, Zn, Pb, and As, and the concentrations of Cu and Hg were also considered a concern. This work establishes a baseline for the environmental quality status of the Jequetepeque basin that may support water quality management in Peru.     

Mass loads of dissolved and particulate mercury and other trace elements in the Mt. Amiata mining district,Southern Tuscany (Italy)

Total dissolved and particulate mercury (Hg), arsenic (As), and antimony (Sb) mass loads were estimated in different seasons (March and September 2011 and March 2012) in the Paglia River basin (PRB) (central Italy). The Paglia River drains the Mt. Amiata Hg district, one of the largest Hg-rich regions worldwide. Quantification of Hg, As, and Sb mass loads in this watershed allowed (1) identification of the contamination sources, (2) evaluation of the effects of Hg on the environment, and (3) determination of processes affecting Hg transport. The dominant source of Hg in the Paglia River is runoff from Hg mines in the Mt. Amiata region. The maximum Hg mass load was found to be related to runoff from the inactive Abbadia San Salvatore Mine (ASSM), and up to 30 g day^?1 of Hg, dominantly in the particulate form, was transported both in high and low flow conditions in 2011. In addition, enrichment factors (EFs) calculated for suspended particulate matter (SPM) were similar in different seasons indicating that water discharge controls the quantities of Hg transported in the PRB, and considerable Hg was transported in all seasons studied. Overall, as much as 11 kg of Hg are discharged annually in the PRB and this Hg is transported downstream to the Tiber River, and eventually to the Mediterranean Sea. Similar to Hg, maximum mass loads for As and Sb were found in March 2011, when as much as 190 g day^?1 each of As and Sb were measured from sites downstream from the ASSM. Therefore, the Paglia River represents a significant source of Hg, Sb, and As to the Mediterranean Sea.     

Evaluating the degradation of the herbicides picloram and 2,4-D in a compartmentalized reactive biobarrier with internal liquid recirculation

Tordon is a widely used herbicide formulation of 2,4-dichlorophenoxyacetic acid (2,4-D) and 4-amino-3,5,6-trichloropicolinic acid (picloram), and it is considered a toxic herbicide. The purposes of this work were to assess the feasibility of a microbial consortium inoculated in a lab-scale compartmentalized biobarrier, to remove these herbicides, and isolate, identify, and evaluate their predominant microbial constituents. Volumetric loading rates of herbicides ranging from 31.2 to 143.9 g m^?3 day^?1, for 2,4-D, and 12.8 to 59.3 g m^?3 day^?1 for picloram were probed; however, the top operational limit of the biobarrier, detected by a decay in the removal efficiency, was not reached. At the highest loading rates probed, high average removal efficiencies of 2,4-D, 99.56?±?0.44; picloram, 94.58?±?2.62; and chemical oxygen demand (COD), 89.42?±?3.68, were obtained. It was found that the lab-scale biofilm reactor efficiently removed both herbicides at dilution rates ranging from 0.92 to 4.23 day^?1, corresponding to hydraulic retention times from 1.087 to 0.236 days. On the other hand, few microbial strains able to degrade picloram are reported in the literature. In this work, three of the nine bacterial strains isolated cometabolically degrade picloram. They were identified as Hydrocarboniphaga sp., Tsukamurella sp., and Cupriavidus sp.     

Electrochemical advanced oxidation processes: today and tomorrow. A review

In recent years, new advanced oxidation processes based on the electrochemical technology, the so-called electrochemical advanced oxidation processes (EAOPs), have been developed for the prevention and remediation of environmental pollution, especially focusing on water streams. These methods are based on the electrochemical generation of a very powerful oxidizing agent, such as the hydroxyl radical (^?OH) in solution, which is then able to destroy organics up to their mineralization. EAOPs include heterogeneous processes like anodic oxidation and photoelectrocatalysis methods, in which ^?OH are generated at the anode surface either electrochemically or photochemically, and homogeneous processes like electro-Fenton, photoelectro-Fenton, and sonoelectrolysis, in which ^?OH are produced in the bulk solution. This paper presents a general overview of the application of EAOPs on the removal of aqueous organic pollutants, first reviewing the most recent works and then looking to the future. A global perspective on the fundamentals and experimental setups is offered, and laboratory-scale and pilot-scale experiments are examined and discussed.     

Distribution of PAHs and trace metals in urban stormwater sediments: combination of density fractionation,mineralogy and microanalysis

Sediment management from stormwater infiltration basins represents a real environmental and economic issue for stakeholders due to the pollution load and important tonnages of these by-products. To reduce the sediment volumes to treat, organic and metal micropollutant-bearing phases should be identified. A combination of density fractionation procedure and microanalysis techniques was used to evaluate the distribution of polycyclic aromatic hydrocarbons (PAHs) and trace metals (Cd, Cr, Cu, Ni, Pb, and Zn) within variable density fractions for three urban stormwater basin sediments. The results confirm that PAHs are found in the lightest fractions (d?d??3) whereas trace metals are equally distributed within the light, intermediary, and highest fractions (d?d?d?d?>?2.8 g cm^?3) and are mostly in the 2.3?d??3 fraction. The characterization of the five fractions by global analyses and microanalysis techniques (XRD and MEB-EDX) allowed us to identify pollutant-bearing phases. PAHs are bound to the organic matter (OM) and trace metals to OM, clays, carbonates and dense particles. Moreover, the microanalysis study underlines that OM is the main constituent responsible for the aggregation, particularly for microaggregation. In terms of sediment management, it was shown that density fractionation is not suitable for trace metals but could be adapted to separate PAH-enriched phases.     

Effect of organic amendments on the mobility of trace elements in phytoremediated techno-soils: role of the humic substances

The efficiency of aided phytostabilization using organic amendments such as ramial chipped wood (RCW) and composted sewage sludge (CSS) was studied on contaminated techno-soils, on nine experimental plots. The objective was to characterize the role of fulvic (FA) and humic acids (HA) on the mobilization of trace elements, specifically As, Cu, Mo, Pb and Zn. Results showed that the addition of CSS increased the total organic carbon and nitrogen content more than with RCW and as a result, the C/N ratio in the CSS soil was higher than in the RCW and non-amended (NE) soil, reflecting the high decomposition of soil organic matter in the CSS soil compared with the other soils. The RCW and CSS amendments increased the hydrogen index (HI) values and the oxygen index (OI) values compared with the NE soil, especially for the soil treated with CSS which contained more aliphatic than aromatic compounds. The addition of CSS to the techno-soil significantly increased the percentage of C _org associated with the HA fractions compared with the RCW and NE soils. The soil amended with CSS showed the highest E ₄/E ₆ ratio and the lowest E ₂/E ₃ ratio of FA. Zn and As were more abundant in the FA fraction than in the HA fraction, whereas Pb, Cu and Mo were more associated to HA than to FA in the treated and untreated soils, which may explain the difference in their mobility and availability.     

A new bioseed for determination of wastewater biodegradability: analysis of the experimental procedure

A new bioassay proposed in the patent P201300029 was applied to a pre-treated wastewater containing a mixture of commercial pesticides to simulate a recalcitrant industrial wastewater in order to determine its biodegradability. The test uses a mixture of standardized inoculum of the lyophilized bacteria Pseudomonas putida with the proper proportion of salts and minerals. The results highlight that biodegradation efficiency can be calculated using a gross parameter (chemical oxygen demand (COD)) which facilitates the biodegradability determination for routine water biodegradability analysis. The same trend was observed throughout the assay with the dehydrated and fresh inoculums, and only a difference of 5 % in biodegradation efficiency (E _f) was observed. The obtained results showed that the P. putida biodegradability assay can be used as a commercial test with a lyophilized inoculum in order to monitor the ready biodegradability of an organic pollutant or a WWTP influent. Moreover, a combination of the BOD₅/COD ratio and the P. putida biodegradability test is an attractive alternative in order to evaluate the biodegradability enhancement in water pre-treated with advanced oxidation processes (AOPs).