Unveiling Chemical Cues of Insect-Tree and Insect-Insect Interactions for the Eucalyptus Weevil and Its Egg Parasitoid by Multidimensional Gas Chromatographic Methods.

Multidimensional gas chromatography is, presently, an established and powerful analytical tool, due to higher resolving power than the classical 1D chromatographic approaches. Applied to multiple areas, it allows to isolate, detect and identify a larger number of compounds present in complex matrices, even in trace amounts. Research was conducted to determine which compounds, emitted by host plants of the eucalyptus weevil, Gonipterus platensis, might mediate host selection behavior. The identification of a pheromone blend of G. platensis is presented, revealing to be more attractive to weevils of both sexes, than the individual compounds. The volatile organic compounds (VOCs) were collected by headspace solid phase microextraction (HS-SPME), MonoTrapTM disks, and simultaneous distillation-extraction (SDE). Combining one dimensional (1D) and two-dimensional (2D) chromatographic systems-comprehensive and heart-cut two-dimensional gas chromatography (GC×GC and H/C-MD-GC, respectively) with mass spectrometry (MS) and electroantennographic (EAD) detection, enabled the selection and identification of pertinent semiochemicals which were detected by the insect antennal olfactory system. The behavioral effect of a selected blend of compounds was assessed in a two-arm olfactometer with ten parallel walking chambers, coupled to video tracking and data analysis software. An active blend, composed by cis and trans-verbenol, verbenene, myrtenol and trans-pinocarveol was achieved.

Irrigation of soil with reclaimed wastewater acts as a buffer of microbial taxonomic and functional biodiversity.

The usage of reclaimed wastewater (RWW) for irrigation of agricultural soils is increasingly being acknowledged for reducing water consumption by promoting reuse of treated wastewater, and for the delivery of extant nutrients in the soil. The downside is that RWW may be a vector for contamination of soils with contaminants of emerging concern (CECs), if left uncontrolled. Its usage is anticipated to alter the soil properties, consequently also the soil microbial community. In the present study, soil microcosms were set to monitor how short periods (up to fourteen days) of RWW irrigation influence the soil ecosystem, namely its physicochemical properties, functioning, and colonising microbiota (differentiating fungi from bacteria). Two scenarios were studied: clean soil and soil contaminated (spiked) with 9 CECs, at conditions that limit any abiotic decay processes, monitoring along time fluctuations in the taxonomic and functional microbiota diversity. As shortly as fourteen days, the irrigation of either soil with RWW did not significantly (p > 0.05) alter its physicochemical properties and scarcely impacted the bioremediation processes of the CECs that showed decay levels ranging from 24% to 100%. Bacillus spp. dominance was enhanced along time in all the soil microcosms (reaching over 70% of the total abundance on the 7th day) but the RWW help to preserve, to some extent, high bacterial diversity. Besides, irrigation with RWW acted as a buffer of the soil mycobiota, limiting alterations in its composition caused either along time (to a minor degree) or due to contamination with CECs (to a great degree). This includes limiting the rise of Rhizopus sp. relative abundance. Collectively, our data support the utility of short-term periods of RWW irrigation for preserving the soil microbial diversity and functioning, especially when fungi are considered.

Electro-bioremediation of a mixture of structurally different contaminants of emerging concern: Uncovering electrokinetic contribution.

This study analyses the electrokinetic (EK) contribution to the removal from a clay soil of a mixture of 10 different contaminants of emerging concern (CECs; 17ß-estradiol, E2; sulfamethoxazole, SMX; bisphenol A, BPA; ibuprofen, IBU; 17α-ethinylestradiol, EE2; oxybenzone, OXY; diclofenac, DCF; triclosan, TCS; caffeine, CAF; carbamazepine, CBZ). After 4 days, the CECs natural attenuation was between 0% (CBZ) and 90% (E2) yet increasing with the application of EK (20 mA, 12 h ON/OFF) to 14% (CBZ) and 100% (E2). When EK was applied, the CECs more recalcitrant to biodegradation (i.e. ≤ 13% biotic decay) mostly underwent electro-chemical induced degradation (OXY, DCF, TCS, CAF, CBZ). Daily irrigation enhanced the rates of the electro-oxidation -osmosis and -migration, increasing the CECs decay. After 8 days of EK treatment, the CECs decay increased, surpassing the decay lag phase of some compounds (OXY, TCS, and CBZ). Yet after 16 days, most CECs showed similar removals with and without EK, with EK only acting positively on SMX, OXY, TCS and CBZ (ca. +10%). Our results support that EK application can improve the removal of CECs from soil, however, under the conditions tested, 16-day treatment lead to pH alterations that decreased the bioremediation efficiency and inhibited electro-degradation near the cathode.

Emerging organic contaminants in soil irrigated with effluent: electrochemical technology as a remediation strategy.

The effluent reuse for soil irrigation is foreseen as a possible strategy to mitigate the pressure on water resources. However, there is the risk of potential accumulation in soil of emerging organic contaminants (EOCs). In the present work the electrokinetic remediation (EKR) technology, use of direct current, was applied for the removal of EOCs from a soil irrigated with effluent. For this, a soil collected from a rice field (located in Portugal) was mixed with spiked effluent to simulate flood irrigation in one time-period. The experiments were carried out for 6 days applying a low current intensity of 2.5 mA. Different current strategies were tested: continuous mode, reversed electrode polarization (REP), On/Off time periods, and the combination of the last two. The target EOCs comprises a list of six pharmaceuticals and personal care products widely detected in treated wastewater. This study showed that once introduced in soil through effluent irrigation, 20-100% of the EOCs were still present in the soil after 6 days. EKR enhanced up to 20% of the EOCs removal when comparing with control (without current). The EOC removals showed to be related to the microcosm location (anode, central or cathode sections) and dependent of EOCs characteristics. Soil characteristics did not change when On/Off system was combined with REP as a current strategy, and a more homogenous removal of the studied EOCs was achieved in the tested conditions. EKR showed to be a promising technology to be applied in EOCs contaminated soils, not only for removal purposes, but also to avoid possible dispersion in the environment.

Emerging organic contaminants in wastewater: Understanding electrochemical reactors for triclosan and its by-products degradation.

Degradation technologies applied to emerging organic contaminants from human activities are one of the major water challenges in the contamination legacy. Triclosan is an emerging contaminant, commonly used as antibacterial agent in personal care products. Triclosan is stable, lipophilic and it is proved to have ecotoxicologic effects in organics. This induces great concern since its elimination in wastewater treatment plants is not efficient and its by-products (e.g. methyl-triclosan, 2,4-dichlorophenol or 2,4,6-trichlorophenol) are even more hazardous to several environmental compartments. This work provides understanding of two different electrochemical reactors for the degradation of triclosan and its derivative by-products in effluent. A batch reactor and a flow reactor (mimicking a secondary settling tank in a wastewater treatment plant) were tested with two different working anodes: Ti/MMO and Nb/BDD. The degradation efficiency and kinetics were evaluated to find the best combination of current density, electrodes and set-up design. For both reactors the best electrode combination was achieved with Ti/MMO as anode. The batch reactor at 7 mA/cm2 during 4 h attained degradation rates below the detection limit for triclosan and 2,4,6-trichlorophenol and, 94% and 43% for 2,4-dichlorophenol and methyl triclosan, respectively. The flow reactor obtained, in approximately 1 h, degradation efficiencies between 41% and 87% for the four contaminants. This study suggests an alternative technology for emerging organic contaminants degradation, since the combination of a low current density with the flow and matrix induced disturbance increases and speeds up the compounds' elimination in a real environmental matrix.

Electronic Tongue Coupled to an Electrochemical Flow Reactor for Emerging Organic Contaminants Real Time Monitoring.

Triclosan, which is a bacteriostatic used in household items, has raised health concerns, because it might lead to antimicrobial resistance and endocrine disorders in organisms. The detection, identification, and monitoring of triclosan and its by-products (methyl triclosan, 2,4-Dichlorophenol and 2,4,6-Trichlorophenol) are a growing need in order to update current water treatments and enable the continuous supervision of the contamination plume. This work presents a customized electronic tongue prototype coupled to an electrochemical flow reactor, which aims to access the monitoring of triclosan and its derivative by-products in a real secondary effluent. An electronic tongue device, based on impedance measurements and polyethylenimine/poly(sodium 4-styrenesulfonate) layer-by-layer and TiO2, ZnO and TiO2/ZnO sputtering thin films, was developed and tested to track analyte degradation and allow for analyte detection and semi-quantification. A degradation pathway trend was observable by means of principal component analysis, being the sample separation, according to sampling time, explained by 77% the total variance in the first two components. A semi-quantitative electronic tongue was attained for triclosan and methyl-triclosan. For 2,4-Dichlorophenol and 2,4,6-Trichlorophenol, the best results were achieved with only a single sensor. Finally, working as multi-analyte quantification devices, the electronic tongues could provide information regarding the degradation kinetic and concentrations ranges in a dynamic removal treatment.

Electrokinetic remediation of contaminants of emergent concern in clay soil: Effect of operating parameters.

The potential of electrokinetic (EK) remediation to remove from soils one particular group of contaminants - contaminants of emergent concern (CECs), remains largely overlooked. The present study aimed to evaluate the efficiency of the EK process for the remediation of an agricultural clay soil containing CECs. The soil was spiked with four CECs - sulfamethoxazole, ibuprofen, triclosan and caffeine - and their status (i.e. residual amounts and spatial distribution) evaluated at the seventh day of EK treatment at a defined current intensity, directionality and duration of void period. The characterization of the soil physicochemical properties was also undertaken. The results showed similar degradation trends in all applied EK strategies, which were suchlike to that of the natural attenuation (biotic control): sulfamethoxazole > ibuprofen ≥ triclosan ≥ caffeine. The removal of the CECs was higher under a 10 mA constant current application than in the natural attenuation (up to 2.8 times higher; from 13 to 85%). Caffeine was the exception with its best removal efficiency being achieved when the ON/OFF switch mode with a void period duration of 12 h was used (36%). The use of electro-polarization reversal mode did not favour the remediation. The soil pH variations resulting from EK application were determinant for triclosan remediation, which increased with soil pH increase. The only EK condition that promoted the removal of all CECs was the ON/OFF switch mode of 12 h (removals between 36 and 72%), in which only minor physicochemical disturbances of the soil were observed. This is in accordance with a potential application of EK in-situ. The last is reinforced by the low estimated electrical cost of the best EK technology - 2.33 €/m3 for the 7 days. Overall the EK remediation processes are a promising technology to stimulate in situ the removal of CECs from agricultural soils.

Electrodialytic 2-compartment cells for emerging organic contaminants removal from effluent.

The present work discusses the efficiency of the electrodialytic (ED) process to remove emerging organic contaminants (EOCs) from effluent. The ED process was carried out in a cell of two-compartments (2 C-cell) with effluent in either the anode or cathode compartment, separated from the electrolyte compartment through an anion or a cation exchange membrane (AEM and CEM, respectively). As effluent destination might be soil irrigation, and having in mind the nutrient recycling, phosphorus was also monitored in the process. The ED removals showed to be dependent of EOCs characteristics and cell design. Removals were higher when using an AEM (60-72%) than a CEM (8-63%), except for caffeine when the effluent was placed in the cathode, that did not show any removal. When using an AEM with the effluent placed in the anode compartment, all the EOCs (including caffeine) were removed between 57-72%, mainly through electrodegradation phenomena. Regarding phosphorus, a polarity switch may be done to a 2 C-cell with a AEM, depending on the effluent final use. This technology is still in its first steps and, in both cases, further optimization of ED parameters is needed. Still, this technological innovation and cross-cutting research envisages the promotion of economic, social and environmental benefits.

Comparative assessment of LECA and Spartina maritima to remove emerging organic contaminants from wastewater.

The present work aimed to evaluate the capacity of constructed wetlands (CWs) to remove three emerging organic contaminants with different physicochemical properties: caffeine (CAF), oxybenzone (MBPh), and triclosan (TCS). The simulated CWs were set up with a matrix of light expanded clay aggregates (LECA) and planted with Spartina maritima, a salt marsh plant. Controlled experiments were carried out in microcosms using deionized water and wastewater collected at a wastewater treatment plant (WWTP), with different contaminant mass ranges, for 3, 7, and 14 days. The effects of variables were tested isolatedly and together (LECA and/or S. maritima). The presence of LECA and/or S. maritima has shown higher removal (around 61-97%) of lipophilic compounds (MBPh and TCS) than the hydrophilic compound (CAF; around 19-85%). This was attributed to the fact that hydrophilic compounds are dissolved in the water column, whereas the lipophilic ones suffer sorption processes promoting their removal by plant roots and/or LECA. In the control (only wastewater), a decrease in the three contaminant levels was observed. Adsorption and bio/rhizoremediation are the strongest hypothesis to explain the decrease in contaminants in the tested conditions.

Electrically induced displacement transport of immiscible oil in saline sediments.

Electrically assisted mitigation of coastal sediment oil pollution was simulated in floor-scale laboratory experiments using light crude oil and saline water at approximately 1/10 oil/water (O/W) mass ratio in pore fluid. The mass transport of the immiscible liquid phases was induced under constant direct current density of 2A/m(2), without water flooding. The transient pore water pressures (PWP) and the voltage differences (V) at and in between consecutive ports lined along the test specimen cell were measured over 90days. The oil phase transport occurred towards the anode half of the test specimen where the O/W volume ratio increased by 50% over its initial value within that half-length of the specimen. In contrast, the O/W ratio decreased within the cathode side half of the specimen. During this time, the PWP decreased systematically at the anode side with oil bank accumulation. PWP increased at the cathode side of the specimen, signaling increased concentration of water there as it replaced oil in the pore space. Electrically induced transport of the non-polar, non-conductive oil was accomplished in the opposing direction of flow by displacement in absence of viscous coupling of oil-water phases.

Electrokinetic remediation of six emerging organic contaminants from soil.

Some organic contaminants can accumulate in organisms and cause irreversible damages in biological systems through direct or indirect toxic effects. In this study the feasibility of the electrokinetic (EK) process for the remediation of 17ß-oestradiol (E2), 17α-ethinyloestradiol (EE2), bisphenol A (BPA), nonylphenol (NP), octylphenol (OP) and triclosan (TCS) in soils was studied in a stationary laboratory cell. The experiments were conducted using a silty loam soil (S2) at 0, 10 and 20mA and a sandy soil (S3) at 0 and 10 mA. A pH control in the anolyte reservoir (pH>13) at 10 mA was carried out using S2, too. Photo and electrodegradation experiments were also fulfilled. Results showed that EK is a viable method for the remediation of these contaminants, both through mobilization by electroosmotic flow (EOF) and electrodegradation. As EOF is very sensible to soil pH, the control in the anolyte increased EOF rate, consequently enhancing contaminants mobilization towards the cathode end. The extent of the mobilization towards the electrode end was mainly dependent on compounds solubility and octanol-water partition coefficient. In the last 24h of experiments, BPA presented the highest mobilization rate (ca. 4 µg min(-1)) with NP not being detected in the catholyte. At the end of all experiments the percentage of contaminants that remained in the soil ranged between 17 and 50 for S2, and between 27 and 48 for S3, with no statistical differences between treatments. The mass balance performed showed that the amount of contaminant not detected in the cell is similar to the quantity that potentially may suffer photo and electrodegradation.

Assessment of combined electro-nanoremediation of molinate contaminated soil.

Molinate is a pesticide widely used, both in space and time, for weed control in rice paddies. Due to its water solubility and affinity to organic matter, it is a contaminant of concern in ground and surface waters, soils and sediments. Previous works have showed that molinate can be removed from soils through electrokinetic (EK) remediation. In this work, molinate degradation by zero valent iron nanoparticles (nZVI) was tested in soils for the first time. Soil is a highly complex matrix, and pollutant partitioning between soil and water and its degradation rates in different matrices is quite challenging. A system combining nZVI and EK was also set up in order to study the nanoparticles and molinate transport, as well as molinate degradation. Results showed that molinate could be degraded by nZVI in soils, even though the process is more time demanding and degradation percentages are lower than in an aqueous solution. This shows the importance of testing contaminant degradation, not only in aqueous solutions, but also in the soil-sorbed fraction. It was also found that soil type was the most significant factor influencing iron and molinate transport. The main advantage of the simultaneous use of both methods is the molinate degradation instead of its accumulation in the catholyte.

Qualitative mass spectrometric analysis of the volatile fraction of creosote-treated railway wood sleepers by using comprehensive two-dimensional gas chromatography.

The volatile composition of 20-year-old out-of-service creosote-treated railway wood sleepers was studied. The emitted volatile fraction was collected by means of dynamic purge-and-trap concentration at ambient temperature, and analyzed by comprehensive two-dimensional gas chromatography (GC x GC) hyphenated with mass spectrometric detection systems, using quadrupole (GC x GC/qMS) and time-of-flight (GC x GC/ToF-MS) mass analyzers and selective nitrogen-phosphorus detection (GC x GC-NPD). The analysis of mass spectrometry data and GC x GC retention time allowed the tentative identification of about 300 compounds based on spectrometric data and positioning of each compound in the GC x GC plot. Major important headspace components are polyaromatic hydrocarbons, phenols and benzene derivatives, hydrocarbons and heterocyclic compounds containing nitrogen, sulphur or oxygen atoms. Many of the reported compounds are listed as belonging to toxicological substance classes which have been related to harmful health effects. GC x GC provides greater speciation and evidence of composition heterogenicity of the sample than one-dimensional GC analysis, thus allowing to better demonstrate its potential toxicity. Data obtained by specific detection systems for N-heterocycles assisted mass data interpretation assignments. The enhanced separation power obtained after GC x GC compared to one-dimensional gas chromatography (1D-GC) together with spectral deconvolution and correlation with physical-chemical data, allowed the identification of complex isomer clusters, as demonstrated for alkylquinolines, and applied also to alkylphenols, alkylbenzenes and alkylnaphthalenes.