Linking the use of reclaimed water to indicators of crop stress by metabolomic and transcriptomic analyses. A tool to compare water irrigation quality.

The occurrence of contaminants of emerging concern (CECs) or heavy metals in reclaimed water used for agricultural irrigation may affect crop morphology and physiology. Here, we analyzed lettuce (Lactuca sativa) grown in outdoor lysimeters and irrigated with either tap water, used as a control, or reclaimed water: CAS-reclaimed water, an effluent from a conventional activated sludge system (CAS) followed by chlorination and sand filtration, or MBR-reclaimed water, an effluent from a membrane biological reactor (MBR). Chemical analyses identified seven CECs in the reclaimed waters, but only two of them were detected in lettuce (carbamazepine and azithromycin). Metabolomic and transcriptomic analyses revealed that irrigation with reclaimed water increased the concentrations of several crop metabolites (5-oxoproline, leucine, isoleucine, and fumarate) and of transcripts codifying for the plant stress-related genes Heat-Shock Protein 70 (HSP70) and Manganese Superoxide Dismutase (MnSOD). In both cases, MBR-water elicited the strongest response in lettuce, perhaps related to its comparatively high sodium adsorption ratio (4.5), rather than to its content in CECs or heavy metals. Our study indicates that crop metabolomic and transcriptomic profiles depend on the composition of irrigating water and that they could be used for testing the impact of water quality in agriculture.

Impact of organic soil amendments in antibiotic levels, antibiotic resistance gene loads, and microbiome composition in corn fields and crops.

The potential spreading of antibiotic resistance genes (ARG) into agricultural fields and crops represent a fundamental limitation on the use of organic fertilization in food production systems. We present here a study of the effect of spreading four types of organic soil amendments (raw pig slurry, liquid and solid fractions, and a digested derivative) on demonstrative plots in two consecutive productive cycles of corn harvest (Zea mays), using a mineral fertilizer as a control, following the application of organic amendments at 32-62 T per ha (150 kg total N/ha) and allowing 5-8 months between fertilization and harvest. A combination of qPCR and high-throughput 16S rDNA sequencing methods showed a small, but significant impact of the fertilizers in both ARG loads and microbiomes in soil samples, particularly after the second harvesting cycle. The slurry solid fraction showed the largest impact on both ARG loads and microbiome variation, whereas its digestion derivatives showed a much smaller impact. Soil samples with the highest ARG loads also presented increased levels of tetracyclines, indicating a potential dual hazard by ARG and antibiotic residues linked to some organic amendments. Unlike soils, no accumulation of ARG or antibiotics was observed in corn leaves (used as fodder) or grains, and no grain sample reached detection limits for neither parameter. These results support the use of organic soil amendments in corn crops, while proposing the reduction of the loads of ARGs and antibiotics from the fertilizers to greatly reduce their potential risk.

Assessment of a novel microalgae-cork based technology for removing antibiotics, pesticides and nitrates from groundwater.

Groundwater pollution has increased in recent years due to the intensification of agricultural and livestock activities. This results in a significant reduction in available freshwater resources. Here, we have studied the long term assessment of a green technology (1-4 L/day) based on a photobioreactor (PBR) containing immobilised microalgae-bacteria in polyurethane foam (PF) followed by a cork filter (CF) for removing nitrates, pesticides (atrazine and bromacil), and antibiotics (sulfamethoxazole and sulfacetamide) from groundwater. The prototype was moderately effective for removing nitrates (58%) at an HRT of 8 days, while its efficiency decreased at a HRT of 4 and 2 days (<20% removal). The combined use of PBR-CF enabled antibiotics and pesticides to be attenuated by up to 95% at an HRT of 8 days, but their attenuation decreased with shorter HRT, with pesticides being the compounds most affected (reducing from 97 to 98% at an HRT of 8 days to 23-45% at an HRT of 2 days). Pesticide transformation products were identified after the CF, supporting biodegradation as the main attenuation process. A gene-based metataxonomic assessment linked the attenuation of micropollutants to the presence of specific pesticide biodegradation species (e.g. genus Phenylobacterium, Sphingomonadaceae, and Caulobacteraceae). Therefore, the results highlighted the potential use of microalgae and cork to treat polluted groundwater.

Local and downstream cumulative effects of traditional meadow management on stream-water quality and multiple riparian taxa.

Water quality and riparian communities are among the most affected stream components by agriculture. However, little is known about the effects of riparian management for both aquatic and terrestrial taxa at different spatial scales. Here, we surveyed aquatic (diatoms) and terrestrial taxa (bryophytes, vascular plants, litter-dwelling snails, and ground and volant arthropods), to compare the abundance and richness of riparian taxa and chemical quality between reference and exposed sites in two stream reaches each of c. 3.5 km in northwestern Spain. Impacts in exposed sites were mainly due to traditional farming practices (TFPs), which included traditional meadow management, weirs built for now-unused water mills and sporadic timber harvesting. Therefore, we measured ten covariates and predictors related to the intensification of TFPs at local and within-stream scales and explored associations with riparian and water-quality measures to study the potential effects of TFPs in more detail. Reference and exposed sites did not differ significantly in water properties (diatom-biotic indices, conductivity, total organic carbon and nitrates), but exposed sites had less concentrations of soil metals Cd, Cu, Ni and Zn and less cover and richness of riparian trees, as inferred by the index QBR. Exposed sites had more volant insect decomposers and reference sites a greater abundance or richness of snails, ground predators and decomposers. Bryophyte richness was greater in reference sites. Our inferences may inform the joint cumulative downstream effects of weirs, meadow uses and riparian alterations but were generally consistent with most riparian taxa benefiting from having larger forested areas. Given the contrasting responses among taxa, we argue that land snails, terrestrial flies, and centipedes may be valuable additions to current riparian assessments mostly based on plants, beetles and spiders as indicator taxa. Our study also suggests caution when inferring farming impacts on streams from the surface area of pastoral land.

Dose effect of Zn and Cu in sludge-amended soils on vegetable uptake of trace elements, antibiotics, and antibiotic resistance genes: Human health implications.

The application of sewage sludge to agricultural fields reduces the need for mineral fertilizers by increasing soil organic matter, but may also increase soil pollution. Previous studies indicate that zinc and copper, as the most abundant elements in sewage sludge, affect plant uptake of other contaminants. This paper aims to investigate and compare the effect of increasing amounts of Zn and Cu in sludge-amended soils on the accumulation of trace elements (TEs), antibiotics (ABs), and antibiotic resistance genes (ARGs) in lettuce and radish. The vegetables were grown under controlled conditions, and the influence on plant physiology and human health were also evaluated. The results show that the addition of Zn and Cu significantly increased the concentration of TEs in the edible tissue of both vegetables. According to the hazard quotient (HQ) of the TEs, the human health risk increased 2 to 3 times and was 3-4 times greater in lettuce than in radish. In contrast to the TEs, the occurrence of ABs and most of the ARGs was higher in radish roots than lettuce leaves. ABs were not detected in lettuce leaves, and the amount of all ARGs except blaTEM was 10 times lower than in radish roots. On the other hand, the addition of Zn and Cu had no significant effect on the occurrence of ABs and ARGs in the edible part of the vegetables, and no damage was found to plant productivity or physiology. The results show that the consumption of lettuce and radish grown in sewage-sludge-amended soils under tested doses of Cu and Zn does not pose an adverse human health effect, as the total HQ value was always less than 1, and the presence of ABs and ARGs was not found to have any potential impact. Nevertheless, further studies are needed to estimate the long-term effect on human health of crops grown under frequent application of biosolids in arable soil.

Occurrence and human health risk assessment of antibiotics and trace elements in Lactuca sativa amended with different organic fertilizers.

Soil amendment with organic fertilizers is an effective approach to improve soil fertility. However, organic fertilizers may contain pollutants such as trace elements (TEs) and antibiotics (ABs), which, once deployed in arable soil, can be taken up by vegetables and have adverse effects on crops and human health. This study assesses the presence of 15 TEs and 16 ABs in lettuce grown in a greenhouse facility and amended with 3 different organic fertilizers (sewage sludge (SS), organic fraction of municipal solid waste (OFMSW), and swine manure (SM)) at 3 different fertilization doses. The results show that lettuces amended with SS resulted in the lowest content of TEs. Although 11 ABs were detected in the SM and SS fertilizers, only 3 ABs were detected in lettuce leaves. The concentrations of detected ABs in lettuce ranged from 0.67 ng/g fw (lincomycin) to 14.2 ng/g fw (ciprofloxacin) in SS. The organic fertilization dose did not affect the lettuce uptake of TEs or ABs. Moreover, the use of SS resulted in the highest lettuce yield of the organic amendments. The total hazard quotients (THQs) obtained for TEs and ABs were less than 1 for all the studied fertilization treatments. The highest THQs for TEs were observed in lettuce amended with SM (0.11-0.16), whereas the highest THQs for ABs were observed in SS treatments (0.06-0.09). The results thus suggest that consumption of lettuces amended with organic fertilizers would not pose a risk to human health due to the presence of studied TEs or ABs, but potentially harmful combined effects cannot ruled out.

Does the application of human waste as a fertilization material in agricultural production pose adverse effects on human health attributable to contaminants of emerging concern?

The QuEChERS (quick, easy, cheap, effective, rugged, and safe) ultrasound-assisted method was successfully used to determine the presence of contaminants of emerging concern (CECs) in both the growing medium (i.e. soil) and vegetable samples (i.e. potato, onion, celery, parsnip and carrot) cultivated in household gardens under field conditions impacted by the application of livestock manure mixed with human waste. CECs with a broad range of physico-chemical properties including pharmaceuticals, plasticizers, herbicides, personal care products, and biocides were investigated. Among all studied CECs, diclofenac (DCL), carbamazepine, bisphenol A (BPA) and estrogenic hormones (estrone (E1), 17α-ethinyl estradiol (EE2)) were detected and quantified in vegetable samples with a concentration range from 0.114 to 13.3 ng/g fresh weight (f.w.), while BPA, E1, and EE2 were detected in soil samples with concentration ranges from 0.526 to 0.830 ng/g f.w., 0.121-0.199 ng/g f.w. and 0.118-0.333 ng/g f.w., respectively. DCL was only quantified above the limit of quantification in one soil sample (0.151 ng/g f.w.). The human health risk was estimated using the threshold of toxicological concern approach and a standard diet for two segments of the population (i.e. adult and child). The consumption of investigated vegetables contaminated with CECs poses no risk for the Serbian population.

Organic micropollutants in sewage sludge: influence of thermal and ultrasound hydrolysis processes prior to anaerobic stabilization.

Organic micropollutants (OMP) in the household and industrial wastewater are not efficiently removed by conventional treatment processes and a significant fraction ends in sludge. Proper valorization technologies become fundamental to attain sustainable sewage sludge management, with anaerobic digestion (AD) as one of the preferred strategies. However, it exhibits some limitations that can be overcome with pre-treatment processes. In this study, the influence of different pre-treatment configurations over OMP concentration and removal during AD was assessed. The incorporation of a sequential US - TT-PT resulted in decreased concentrations of 7 of the 9 detected compounds in biosolids compared to conventional AD digestate, with bisphenol-A and ter-octylphenol showing the opposite effect. The results suggest that the assessed PT could improve the removal of sequestered or highly hydrophobic compounds through their solubilization and increased bioavailability.

Chemical characterization and phytotoxicity assessment of peri-urban soils using seed germination and root elongation tests.

The peri-urban soil is exposed to pollutants because of its proximity to the city, which may influence the quality of agricultural products. In this study, the occurrence of 16 trace elements (TEs), 16 polycyclic aromatic hydrocarbons (PAHs), and 33 contaminants of emerging concern (CECs) was analyzed in two soil sites of the peri-urban area of Barcelona (Spain) (S2 and S3) and a pristine site (S1). Levels of Pb (S2 164 and S3 150 mg kg-1) are around 2.5 times higher than the guideline values. Values for Cu (178 mg kg-1) in S2 are 1.8-fold higher, whereas for Zn, levels are slightly above the threshold in S2 (208 mg kg-1) and S3 (217 mg kg-1). The total concentrations of PAHs are significantly below the limits: 24 ng g-1 dw (S1), 38 ng g-1 dw (S2), 49 ng g-1 dw (S3), whereas only some CECs are detected with low concentrations. We also developed a simple and rapid method to assess soil pollution. Here, we use two plant growth indexes (seed germination rate and root elongation at the initial stage) of three seeds (lettuce, tomato, and cauliflower) to assess soil chemical contamination on agriculture. In the peri-urban soil, the concentration of Pb was 2.5 times higher than the guideline values, whereas for Cu and Zn, values were slightly above their limits, while only few PAHs and CECs were detected. Results for principal component analysis suggest that root elongation is a more sensitive measurement endpoint than germination rate, especially for lettuce. The germination rate of tomato relied on the nitrate in the soil and decreased sharply in the site with pollution of Cu and As. Under the specific conditions of this study, cauliflower should not be recommended to assess environmental pollution due to its low sensitivity to pollutants. In conclusion, this is a low-cost, simple, and rapid method for evaluating the effects of chemical pollution of agriculture soils on seed growth.

Antibiotic resistance gene distribution in agricultural fields and crops. A soil-to-food analysis.

Despite the social concern about the generalization of antibiotic resistance hotspots worldwide, very little is known about the contribution of different potential sources to the global risk. Here we present a quantitative analysis of the distribution of Antibiotic Resistance Genes (ARGs) in soil, rhizospheric soil, roots, leaves and beans in tomato, lettuce and broad beans crops (165 samples in total), grown in nine commercial plots distributed in four geographical zones in the vicinity of Barcelona (North East Spain). We also analyzed five soil samples from a nearby forest, with no record of agricultural activities. DNA samples were analyzed for their content in the ARGs sul1, tetM, qnrS1, blaCTX-M-32, blaOXA-58, mecA, and blaTEM, plus the integron intI1, using qPCR methods. In addition, soil microbiomes from the different plots were analyzed by amplicon-targeted 16S rRNA gene sequencing. Our data show a decreasing gradient of ARG loads from soil to fruits and beans, the latter showing only from 0.1 to 0.01% of the abundance values in soil. The type of crop was the main determinant for both ARG distribution and microbiome composition among the different plots, with minor contributions of geographic location and irrigation water source. We propose that soil amendment and/or fertilization, more than irrigation water, are the main drivers of ARG loads on the edible parts of the crop, and that they should therefore be specifically controlled.

Simultaneous determination of multiclass antibiotics and their metabolites in four types of field-grown vegetables.

The developed method was evaluated for the determination of 10 antibiotics belonging to four chemical classes (fluoroquinolones, sulfonamides, lincosamides, and metoxybenzylpyrimidines) and six of their metabolites in four vegetable matrices (lettuce, tomato, cauliflower, and broad beans). The reported method detection limits were sufficiently low (0.1-5.8 ng/g dry weight) to detect target compounds in vegetables under real agricultural practices. Absolute and relative recovery values ranged from 40 to 118% and from 70 to 118%, respectively, for all targeted compounds at the spike level of 100 ng/g dry weight. Regarding method precision, the highest relative standard deviation (RSD) was obtained for enrofloxacin in lettuce (20%), while for the rest of the compounds in all matrices, the RSD values were below 20% for the same spike level. Matrix effects, due to electrospray ionization, ranged from - 26 to 29% for 85% of all estimated values. In a field study, four of the 10 targeted antibiotics were detected in tested vegetables. For the first time, antibiotic metabolites were quantified in vegetables grown under real field conditions. More specifically, decarboxyl ofloxacin and TMP304 were detected in tomato fruits (1.5 ng/g dry weight) and lettuce leaves (21.0-23.1 ng/g dry weight), respectively. It is important to remark that the concentration of TMP304 was five times higher than that from the parental compound, emphasizing the importance of metabolite analysis in monitoring studies. Therefore, the method provided a robust, reliable, and simple-to-use tool that could prove useful for routine multiclass analysis of antibiotics and their metabolites in vegetable samples. Graphical abstract.

Occurrence and human health implications of chemical contaminants in vegetables grown in peri-urban agriculture.

Recent studies have proven that vegetables cultivated in peri-urban areas are exposed to a greater concentration of organic microcontaminants (OMCs) and trace elements (TEs) than those grown in rural areas. In this study, the occurrence and human health risk of chemical contaminants (16 TEs and 33 OMCs) in edible parts of lettuce, tomato, cauliflower, and broad beans from two farm fields in the peri-urban area of the city of Barcelona and one rural site outside the peri-urban area were assessed. The concentration of TEs and OMCs (on fresh weight basis) ranged from non-detectable to 17.4 mg/kg and from non-detectable to 256 µg/kg, respectively. Tomato fruits showed the highest concentration of TEs and OMCs. Principal component analysis indicated that the occurrence of chemical contaminants in vegetables depended on the commodity rather than the location (peri-urban vs rural). Risk assessment using hazardous quotient (HQ) and threshold of toxicological concern (TTC) approaches showed that the risk for the consumption of target vegetables in the peri-urban area was low and similar to that observed for the rural site. Total HQ values for TEs were always below 1, and a minimum consumption of 150 g/day for children and 380 g/day for adults is required to reach the TTC due to the presence of pesticides. Further studies are needed to estimate the combined effect of TEs and OMCs on human health.

Determination of the ß-glycosylate fraction of contaminants of emerging concern in lettuce (Lactuca sativa L.) grown under controlled conditions.

The uptake of a large variety of contaminants of emerging concern (CECs) by crops has already been reported, and the occurrence of phase II metabolites or conjugates has only been detected in plant cell cultures. However, the extent of their formation under cropping conditions is largely unknown. In this study, an analytical strategy to assess the conjugation of 11 CECs in lettuce (Lactuca sativa L.) irrigated with different concentrations (0, 0.05, 0.5, 5, and 50 µg L-1) of CECs was developed. The methodology involved enzymatic digestion with ß-glucosidase to obtain the total fraction (free form + conjugates) of CECs. The conjugation fraction was then obtained based on the difference. The highest extent of conjugation (i.e., 27 to 83%) was found with the most hydrophobic compounds, such as bisphenol A, carbamazepine, methyl paraben, and triclosan. So, the CEC conjugate fraction cannot be neglected in the estimate of human daily intake.

Occurrence and bioaccumulation of chemical contaminants in lettuce grown in peri-urban horticulture.

Peri-urban horticulture performs environmental and socio-economic functions and provides ecological services to nearby urban areas. Nevertheless, industrialization and water pollution have led to an increase in the exposure of peri-urban vegetables to contaminants such as trace elements (TEs) and organic microcontaminants (OMCs). In this study, the occurrence of chemical contaminants (i.e., 16 TEs, 33 OMCs) in soil and lettuce leaves from 4 farm fields in the peri-urban area of the city of Barcelona was assessed. A rural site, outside the peri-urban area of influence, was selected for comparison. The concentration of TEs and OMCs ranged from non-detectable to 803 mg/kg dw and from non-detectable to 397 µg/kg dw respectively in the peri-urban soil, and from 6 ·â€¯10-5 to 4.91 mg/kg fw and from non-detectable to 193 µg/kg fw respectively in lettuce leaves. Although the concentration of Mo, Ni, Pb, and As in the soil of the peri-urban area exceeded the environmental quality guidelines, their occurrence in lettuce complied with human food standards (except for Pb). The many fungicides (carbendazim, dimetomorph, and methylparaben) and chemicals released by plastic pipelines (tris(1-chloro-2-propyl)phosphate, bisphenol F, and 2-mercaptobenzothiazole) used in agriculture were prevalent in the soil and the edible parts of the lettuce. The occurrence of these chemical pollutants in the peri-urban area did not affect the chlorophyll, lipid, or carbohydrate content of the lettuce leaves. PCA (Principal Component Analysis) showed that soil pollution, fungicide application, and irrigation water quality are the most relevant factors determining the presence of contaminants in crops.

Linking the morphological and metabolomic response of Lactuca sativa L exposed to emerging contaminants using GC × GC-MS and chemometric tools.

The occurrence of contaminants of emerging concern (CECs) in irrigation waters (up to low µg L-1) and irrigated crops (ng g-1 in dry weight) has been reported, but the linkage between plant morphological changes and plant metabolomic response has not yet been addressed. In this study, a non-targeted metabolomic analysis was performed on lettuce (Lactuca sativa L) exposed to 11 CECs (pharmaceuticals, personal care products, anticorrosive agents and surfactants) by irrigation. The plants were watered with different CEC concentrations (0-50 µg L-1) for 34 days under controlled conditions and then harvested, extracted, derivatised and analysed by comprehensive two-dimensional gas chromatography coupled to a time-of-flight mass spectrometer (GC × GC-TOFMS). The resulting raw data were analysed using multivariate curve resolution (MCR) and partial least squares (PLS) methods. The metabolic response indicates that exposure to CECs at environmentally relevant concentrations (0.05 µg L-1) can cause significant metabolic alterations in plants (carbohydrate metabolism, the citric acid cycle, pentose phosphate pathway and glutathione pathway) linked to changes in morphological parameters (leaf height, stem width) and chlorophyll content.

Occurrence of chemical contaminants in peri-urban agricultural irrigation waters and assessment of their phytotoxicity and crop productivity.

Water scarcity and water pollution have increased the pressure on water resources worldwide. This pressure is particularly important in highly populated areas where water demand exceeds the available natural resources. In this regard, water reuse has emerged as an excellent water source alternative for peri-urban agriculture. Nevertheless, it must cope with the occurrence of chemical contaminants, ranging from trace elements (TEs) to organic microcontaminants. In this study, chemical contaminants (i.e., 15 TEs, 34 contaminants of emerging concern (CECs)), bulk parameters, and nutrients from irrigation waters and crop productivity (Lycopersicon esculentum Mill. cv. Bodar and Lactuca sativa L. cv. Batavia) were seasonally surveyed in 4 farm plots in the peri-urban area of the city of Barcelona. A pristine site, where rain-groundwater is used for irrigation, was selected for background concentrations. The average concentration levels of TEs and CECs in the irrigation water impacted by treated wastewater (TWW) were 3 (35±75µgL-1) and 13 (553±1050ngL-1) times higher than at the pristine site respectively. Principal component analysis was used to classify the irrigation waters by chemical composition. To assess the impact of the occurrence of these contaminants on agriculture, a seed germination assay (Lactuca sativa L) and real field-scale study of crop productivity (i.e., lettuce and tomato) were used. Although irrigation waters from the peri-urban area exhibited a higher frequency of detection and concentration of the assessed chemical contaminants than those of the pristine site (P1), no significant differences were found in seed phytotoxicity or crop productivity. In fact, the crops impacted by TWW showed higher productivity than the other farm plots studied, which was associated with the higher nutrient availability for plants.

Effect of soil biochar concentration on the mitigation of emerging organic contaminant uptake in lettuce.

Although crop uptake of emerging organic contaminants (EOC) from irrigation water and soils has been previously reported, successful mitigation strategies have not yet been established. In this study, soil was amended with a wood-based biochar (BC) at two rates (0, 2.5 and 5% w/w) to evaluate the effect on mitigation of EOC uptake (i.e. bisphenol A, caffeine, carbamazepine, clofibric acid, furosemide, ibuprofen, methyl dihydrojasmonate, tris(2-chloroethyl)phosphate, triclosan, and tonalide) in lettuce (Lactuca sativa L.). After 28 days of irrigation with water containing EOCs at 15µgL-1, the average EOC concentration in roots and leaves decreased by 20-76% in biochar amended soil relative to non BC-amended soil. In addition, the enantiomeric fractions (EF) of ibuprofen (IBU) in biochar amended soils (EF=0.58) and unamended soils (EF=0.76) suggest that the IBU sorbed fraction in BC is more recalcitrant to its biodegradation.

Inverse modeling of the biodegradation of emerging organic contaminants in the soil-plant system.

Understanding the processes involved in the uptake and accumulation of organic contaminants into plants is very important to assess the possible human risk associated with. Biodegradation of emerging contaminants in plants has been observed, but kinetical studies are rare. In this study, we analyse experimental data on the uptake of emerging organic contaminants into lettuce derived in a greenhouse experiment. Measured soil, root and leaf concentrations from four contaminants were selected within the applicability domain of a steady-state two-compartment standard plant uptake model: bisphenol A (BPA), carbamazepine (CBZ), triclosan (TCS) and caffeine (CAF). The model overestimated concentrations in most cases, when no degradation rates in plants were entered. Subsequently, biodegradation rates were fitted so that the measured concentrations were met. Obtained degradation kinetics are in the order, BPA < CAF ≈ TCS < CBZ in roots, and BPA ≈ TCS < CBZ << CAF in leaves. Kinetics determined by inverse modeling are, despite the inherent uncertainty, indicative of the dissipation rates. The advantage of the procedure that is additional knowledge can be gained from existing experimental data. Dissipation kinetics found via inverse modeling is not a conclusive proof for biodegradation and confirmation by experimental studies is needed.

Behaviour of pharmaceuticals and personal care products in constructed wetland compartments: Influent, effluent, pore water, substrate and plant roots.

Seven mesocosm-scale constructed wetlands (CWs) with different design configurations, dealing with primary-treated urban wastewater, were assessed for the concentration, distribution and fate of ten pharmaceutical and personal care products (PPCPs) [ibuprofen, ketoprofen, naproxen, diclofenac, salicylic acid, caffeine, carbamazepine, methyl dihydrojasmonate, galaxolide and tonalide] and eight of their transformation products (TPs). Apart from influent and effluent, various CW compartments were analysed, namely, substrate, plant roots and pore water. PPCP content in pore water depended on the specific CW configuration. Macrophytes can take up PPCPs through their roots. Ibuprofen, salicylic acid, caffeine, methyl dihydrojasmonate, galaxolide and tonalide were present on the root surface with a predominance of galaxolide and caffeine in all the planted systems. Naproxen, ibuprofen, salicylic acid, methyl dihydrojasmonate, galaxolide and tonalide were uptaken by the roots. In order to better understand the removal processes, biomass measurement and biodegradability studies through the characterization of internal-external isomeric linear alkylbenzenes present on the gravel bed were performed. Three TPs namely, ibuprofen-amide, 3-ethylbenzophenone and 4-hydroxy-diclofenac were identified for the first time in wetland pore water and effluent water, which suggests de novo formation (they were not present in the influent). Conversely, O-desmethyl-naproxen was degraded through the wetland passage since it was detected in the influent but not in the subsequent treatment stages. Biodegradation pathways are therefore suggested for most of the studied PPCPs in the assessed CWs.

Distribution and Sources of Petroleum Hydrocarbons in Recent Sediments of the Imo River, SE Nigeria.

The distribution of aliphatic and aromatic hydrocarbons in surface sediments of the lower course of the Imo River (Nigeria) was investigated to determine the sources and fate of these compounds. The aliphatic fraction is characterized by a widespread contribution of highly weathered/biodegraded hydrocarbon residues (reflected in the absence of prominent n-alkane peaks coupled with the presence of 17α(H),21ß(H)-25-norhopane, an indicator of heavy hydrocarbon biodegradation) of Nigerian crude oils (confirmed by the occurrence of 18α(H)-oleanane, a compound characteristic of oils of deltaic origin). The concentrations of polycyclic aromatic hydrocarbons (PAHs) ranging from 48 to 117 ng/g dry weight (dw; ∑13PAHs) indicate a moderate pollution, possibly lowered by the sandy lithology and low organic carbon (OC) content of the sediments. Concentrations slightly decrease towards the estuary of the river, probably due to the fact that these stations are affected by tidal flushing of pollutants adsorbed on sediment particles and carried away by occasional storm to the Atlantic Ocean. A number of PAH ratios, including parent/alkylated and isomeric compounds, indicates a predominance of petrogenic sources, with a low contribution of pyrolytic inputs, particularly of fossil fuel combustion. On the basis of OC/ON (>10) and Per/ΣPAHpenta- (>10) values, a diagenetic terrigenous OC was proposed as a source of perylene to the river.