Pablo A. Lara-Martín

Sources, transport and reactivity of anionic and non-ionic surfactants in several aquatic ecosystems in SW Spain: a comparative study.

Presence, distribution and transport mechanisms of the four major synthetic surfactants--linear alkylbenzene sulfonates (LAS), alkyl ethoxysulfates (AES), nonylphenol ethoxylates (NPEOs) and alcohol ethoxylates (AEOs)--have been simultaneously studied in different aquatic ecosystems. Urban wastewater discharges and industrial activities were identified as the main sources for these compounds and their metabolites. LAS, AES and carboxylic metabolites remained in the dissolved form (87-99%). However, NPEOs and AEOs were mostly associated with particulate matter (65-86%), so their degradation in the water column was limited due to their lower bioavailability. It was also observed that sorption to the particulate phase was more intense for longer homologs/ethoxymers for all surfactants. With respect to surface sediments, AES levels were considerably below (<0.25 mg/kg) the values detected for LAS and NPEOs. Concentrations of AEOs, however, were occasionally higher (several tens of ppm) than those found for the rest of the target compounds in several sampling stations.

Anaerobic degradation pathway of linear Alkylbenzene sulfonates (LAS) in sulfate-reducing marine sediments.

Linear alkylbenzene sulfonates (LAS) are among the principal synthetic surfactants used worldwide. Their presence in the environment has been reported in a significant number of studies, and it has been generally assumed that LAS are not biotransformed in the absence of oxygen. However, laboratory experiments performed by our group using anoxic marine sediments have reported LAS degradation percentages that can reach up to 79% in 165 days. Here, we show for the first time the initial reaction metabolites (generated via fumarate addition to the LAS molecules), their biotransformation into sulfophenyl carboxylic acids (SPC), and the progressive degradation of these by successive beta-oxidation reactions. Advanced mass spectrometry has been used to carry out the identification of these compounds. This is the first time that an anaerobic degradation pathway for LAS is described, and these results represent a significant advance in understanding the final fate of these and other similar compounds in anoxic environments.

Determining the distribution of triclosan and methyl triclosan in estuarine settings.

We have developed a method for the analysis of two sewage-derived contaminants: triclosan (TCS), an antibacterial agent, and methyl triclosan (MTCS), a TCS metabolite. For solid samples (4 g), extraction and cleanup were integrated into the same step using pressurized liquid extraction (PLE) with in-cell-clean-up (1g of florisil). The extraction was performed using dichloromethane at 100 °C, 1500 psi and 3 static extraction cycles of 5 min each. For water samples (100mL), stir bar sorptive extraction-liquid desorption (SBSE-LD) was used. Bars were stirred for 10h and analytes were later desorbed using acetonitrile. Finally, MTCS and a silylated derivative of TCS were determined by gas chromatography-mass spectrometry (GC-MS). Recovery experiments in water and sediments were performed and the results ranged from 67% to 78%. Limits of detection (LODs) were 5 ng L(-1) for TCS and 1 ng L(-1) for MTCS, in water samples, and 0.1 ng g(-1) for TCS and MTCS in solid samples. The method was applied then to determine the levels of these compounds in the estuary of Guadalete River (SW Spain). TCS and MTCS concentrations up to 9.6 ng g(-1) in sediments and 310 ng L(-1) in water were measured. Their distribution was strongly influenced by the presence of wastewater sources, treated and untreated, along the sampling area, where maximum concentrations were detected. Highest values were reached in the water column during low tides as the water volume in the estuary becomes lower.

Atmospheric pressure gas chromatography-time-of-flight-mass spectrometry (APGC-ToF-MS) for the determination of regulated and emerging contaminants in aqueous samples after stir bar sorptive extraction (SBSE).

This work presents the development, optimization and validation of a multi-residue method for the simultaneous determination of 102 contaminants, including fragrances, UV filters, repellents, endocrine disruptors, biocides, polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), and several types of pesticides in aqueous matrices. Water samples were processed using stir bar sorptive extraction (SBSE) after the optimization of several parameters: agitation time, ionic strength, presence of organic modifiers, pH, and volume of the derivatizing agent. Target compounds were extracted from the bars by liquid desorption (LD). Separation, identification and quantification of analytes were carried out by gas chromatography (GC) coupled to time-of-flight (ToF-MS) mass spectrometry. A new ionization source, atmospheric pressure gas chromatography (APGC), was tested. The optimized protocol showed acceptable recovery percentages (50-100%) and limits of detection below 1ngL(-1) for most of the compounds. Occurrence of 21 out of 102 analytes was confirmed in several environmental aquatic matrices, including seawater, sewage effluent, river water and groundwater. Non-target compounds such as organophosphorus flame retardants were also identified in real samples by accurate mass measurement of their molecular ions using GC-APGC-ToF-MS. To the best of our knowledge, this is the first time that this technique has been applied for the analysis of contaminants in aquatic systems. By employing lower energy than the more widely used electron impact ionization (EI), AGPC provides significant advantages over EI for those substances very susceptible to high fragmentation (e.g., fragrances, pyrethroids).

Occurrence of Alkyltrimethylammonium Compounds in Urban Estuarine Sediments: Behentrimonium As a New Emerging Contaminant

The distribution of alkyltrimethylammonium compounds (ATMAC), cationic surfactants used in a wide variety of applications, has been determined in sediments from Jamaica Bay (NY). Total concentrations in surficial sediments collected between 1998 and 2008 ranged from 361 to 6750 ng/g. The highest values were found in samples from a deeper basin directly affected by treated wastewater discharges. Behentrimonium, a mixture dominated by a homologue having 22 carbon atoms in its alkyl chain (ATMAC 22), was identified for the first time using time-of-flight mass spectrometry and accounted for approximately 80% of the total ATMAC in recent sediment samples. Analyses of a dated sediment core and subsequent surface grab samples revealed an exponential increase in concentration over the last three decades with a doubling time of 3.9 years. Similar temporal trends were seen in surface samples from other sites in Jamaica Bay and Newton Creek (NY), another site greatly influenced by wastewater discharges. This dramatic increase in ATMAC 22 reflects greater use of behentrimonium and likely replacement of other products containing other ATMAC homologues in personal care products. Further monitoring is recommended to assess the environmental risk and fate of this persistent emerging contaminant.

Determination and distribution of alkyl ethoxysulfates and linear alkylbenzene sulfonates in coastal marine sediments from the Bay of Cadiz (southwest of Spain)

The distribution of the two main anionic surfactants manufactured and used in the world, alkyl ethoxysulfates (AES) and linear alkylbenzene sulfonates (LAS), has been studied in sediments from a salt marsh and an estuary of the Bay of Cadiz (southwest of Spain). The identification and quantification of AES and LAS was carried out after automated Soxhlet extraction with methanol, followed by solid-phase extraction and liquid chromatography coupled to electrospray mass spectrometry. The latter procedure permitted the unequivocal identification of every LAS homologue as well as the AES homologues of up to 16 carbon atoms in their alkyl chain and of up to 12 ethylene oxide groups. Recoveries were in the range of 51% to 84% and limits of detection from 1 to 5 microg/kg. We have focused our attention particularly on AES because, in spite of their great use, these compounds have received less attention than LAS and their occurrence has not been described in marine environmental samples. Alkyl ethoxysulfates concentration values range between 100 and 400 microg/kg in the topmost layer of sediments at the sampling areas. The relative distribution of AES homologues shows higher percentages for the longer alkyl chain homologues in sediments as well as for the shorter ethoxymers. A decrease in LAS concentrations has been found relative to past studies in one of the sampling areas as a consequence of the reduction of urban wastewater discharges.

Distribution, mass inventories, and ecological risk assessment of legacy and emerging contaminants in sediments from the Pearl River Estuary in China

This study focused on comparing the occurrences and environmental toxic risks for diverse priority and emerging contaminants (>100 chemicals) in the sediments from the Pearl River Estuary (PRE, China). The most predominant compounds were cationic surfactants, organophosphate flame retardants (e.g., triisobutylphosphate), and polycyclic aromatic hydrocarbons (PAHs), accounting for >75% of the total mass inventory (∼330 metric tons). Wastewater discharges seem to be one of the main sources of pollution in the area, as the highest concentrations (>1000ngg-1 for some chemicals) were reported in the upper part of the PRE (near Guangzhou city) and Macau. Highest levels of ultraviolet (UV) filters, however, were observed in recreational areas, revealing the importance of direct sources (e.g., outdoor activities). An environmental risk assessment showed that PAHs and dichlorodiphenyl dichloroethylene had the highest hazard quotient (HQ) values (up to 233). Nonylphenol, a metabolite from nonionic surfactant, and two UV filters (2-ethyl-hexyl-4-trimethoxycinnamate and 4-methylbenzylidene camphor) also posed a significant threat to benthic species (HQ>1). Further research through the realization of monitoring campaigns and toxicity tests is encouraged, as the exposure of the resident aquatic organisms and human population to these and other emerging chemicals is expected to increase over the years.

In-cell clean-up pressurized liquid extraction and gas chromatography-tandem mass spectrometry determination of hydrophobic persistent and emerging organic pollutants in coastal sediments.

The main goal of this work was to develop, optimize and validate a multi-residue method for the simultaneous determination of 97 contaminants, including fragrances, UV filters, repellents, endocrine disruptors, biocides, polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), organophosphorus flame retardants, and several types of pesticides in marine sediment samples. Extraction and cleanup were integrated into the same step using pressurized liquid extraction (PLE) with in-cell clean-up (1g of alumina). The extraction was performed using dichloromethane at 100 °C, 1500 psi and 3 extraction cycles (5 min per cycle). Extracts were derivatized with N-(tert-butyldimethylsilyl)-N-methyltrifluoroacetamide (MTBSTFA) to improve the signal and sensitivity of some target compounds (i.e., triclosan, 2-hydroxybenzophenone). Separation, identification and quantification of analytes were carried out by gas chromatography (GC) coupled to tandem mass spectrometry. Under optimal conditions, the optimized protocol showed good recovery percentages (70-100%), linearity (>0.99) and limits of detection below 1 ng g(-1) for all compounds. Finally, the method was applied to the analysis of sediment samples from different coastal areas from Andalusia (Spain), where occurrence and distribution of emerging contaminants in sediments is very scarce. Twenty five compounds out of 98 were detected in all samples, with the endocrine disruptor nonylphenol and the fragrance galaxolide showing the highest concentrations, up to 377.6 ng g(-1) and 237.4 ng g(-1), respectively.

Occurrence and spatial distribution of emerging contaminants in the unsaturated zone. Case study: Guadalete River basin (Cadiz, Spain)

Irrigation with reclaimed water is becoming a common practice in arid- and semi-arid regions as a consequence of structural water resource scarcity. This practice can lead to contamination of the vadose zone if sewage-derived contaminants are not removed properly. In the current work, we have characterized soils from the Guadalete River basin (SW Spain), which are often irrigated with reclaimed water from a nearby wastewater treatment plant and amended using sludge. Physico-chemical, mineralogical and hydraulic properties were measured in soil samples from this area (from surface up to 2 m depth). Emerging contaminants (synthetic surfactants and pharmaceutically active compounds, or PhACs) were also determined. Synthetic surfactants, widely used in personal care products (PCPs), were found in a wide range of concentrations: 73-1300 μg kg(-1) for linear alkylbenzene sulfonates (LAS), 120-496 μg kg(-1) for alkyl ethoxysulfates (AES), 19-1090 μg kg(-1) for alcohol polyethoxylates (AEOs), and 155-280 μg kg(-1) for nonylphenol polyethoxylates (NPEOs). The presence of surfactant homologues with longer alkyl chains was predominant due to their sorption capacity. A positive correlation was found between LAS and AEOs and soil organic carbon and clay content, respectively. Out of 64 PhACs analyzed, only 7 were detected occasionally (diclofenac, metoprolol, fenofibrate, carbamazepine, clarithromycin, famotidine and hydrochlorothiazide), always at very low concentrations (from 0.1 to 1.3 μg kg(-1)).

Degradation kinetics of pharmaceuticals and personal care products in surface waters: photolysis vs biodegradation

Poor removal of many pharmaceuticals and personal care products (PPCPs) in sewage treatment leads to their discharge into the receiving waters, where they may cause negative effects. Their elimination from the water column depends of several processes, including photochemical and biological degradation. We have focused this research on comparing the degradation kinetics of a wide number (n=33) of frequently detected PPCPs considering different types of water, pH and solar irradiation. For those compounds that were susceptible of photodegradation, their rates (k) varied from 0.02 to 30.48h-1 at pH7, with the lowest values for antihypertensive and psychiatric drugs (t1/2>1000h). Modification of the pH turned into faster disappearance of most of the PPCPs (e.g., k=0.072 and 0.066h-1 for atenolol and carbamazepine at pH4, respectively). On the other hand, biodegradation was enhanced by marine bacteria in many cases, for example for mefenamic acid, caffeine and triclosan (k=0.019, 0.01 and 0.04h-1, respectively), and was faster for anionic surfactants. Comparing photodegradation and biodegradation processes, hydrochlorothiazide and diclofenac, both not biodegradable, were eliminated exclusively by irradiation (t1/2=0.15-0.43h and t1/2=0.14-0.17h, respectively). Salicylic acid and phenylbutazone were efficiently photo (t1/2<3h) and biodegraded (t1/2=116-158h), whereas some compounds such as ibuprofen, carbamazepine and atenolol had low degradation rates by any of the processes tested (t1/2=23-2310h), making then susceptible to persist in the aquatic media.