The increased use of pesticides during recent years necessitates a reevaluation of the effect of those compounds by extending the range of nontarget species commonly used in risk assessment. In the present work, we thus determined the impact of the pesticides glyphosate, carbendazim, and malathion on the parasite Chordodes nobilii in both natural and reconstituted freshwater as the assay medium and tested the sensitivity of three of this species's ecologically relevant parameters—e. g., embryo nonviablity and the infective capability of larvae exposed for 48 or 96 h either in ovo or after hatching via the infection index mean abundance—to compare those parameters to data from previous trials with reconstituted freshwater. In natural-freshwater assays, at environmentally relevant concentrations, all three pesticides inhibited the preparasitic-stage endpoints; with carbendazim being the most toxic pesticide and the subsequent infectivity of larvae exposed in ovo the most sensitive endpoint. In general, the 50%-inhibitory concentrations assayed in reconstituted freshwater were higher than those obtained in natural freshwater, indicating a certain protective effect; whereas the maximal toxicity of the three pesticides in both aqueous environments was essentially similar. The sensitivity of C. nobilii to these agents demonstrated that this species is one of the most susceptible to toxicity by all three pesticides. These findings with the assay methodology provide relevant information for a future assessment of the risk of toxicity to aquatic ecosystems and furthermore underscore the need to include parasitic organisms among the nontarget species canvassed. We also recommend that in the bioassays in which the risk assessment is carried out, water from a nontarget species's natural environment be used in parallel in order to obtain more conclusive results.

This study systematically explored the effect of humic acid (HA) (as model of natural organic matter) on the kinetics, products and transformation pathway of triclosan (TCS) by laccase-catalyzed oxidation. It was found that TCS could be effectively transformed by laccase-catalysis, with the apparent second-order rate constant being 0.056 U⁻¹ mL min⁻¹. HA inhibited the removal rate of TCS. HA-induced inhibition was negatively correlated with HA concentration in the range of 0–10 mg L⁻¹ and pH-dependent from 3.5 to 9.5. FT-IR and ¹³C NMR spectra showed a decrease of aromatic hydroxyl (phenolic) groups and an increase of aromatic ether groups, indicating the cross-linking of HA via C-O-C and C-N-C bonds during enzyme-catalyzed oxidation. Ten principle oxidative products, including two quinone-like products (2-chlorohydroquinone, 2-chloro-5-(2,4-dichlodichlorophenoxy)-(1,4)benzoquinone), one chlorinated phenol (2,4-dichlorophenol (2,4-DCP)), three dimers, two trimmers and two tetramers, were detected by gas chromatograghy/mass spectrometry (GC-MS) and high performance liquid chromatography/quadrupole time-of-flight/mass spectrometry (HPLC/Q-TOF/MS). The presence of HA induced significantly lesser generation of self-polymers and enhanced cross-coupling between HA and self-polymers via C-O-C, C-N-C and C-C coupling pathways. A plausible transformation pathway was proposed as follows: TCS was initially oxidized to form reactive phenoxyl radicals, which self-coupled to each other subsequently by C-C and C-O pathway, yielding self-polymers. In addition, the scission of ether bond was also observed. The presence of HA can promote scission of ether bond and further oxidation of phenoxyl radicals, forming hydroxylated or quinone-like TCS. This study shed light on the behavior of TCS in natural environment and engineered processes, as well provided a perspective for the water/wastewater treatment using enzyme-catalyzed oxidation techniques.

Ostrava in the Moravian-Silesian region (Czech Republic) is a European air pollution hot spot for airborne particulate matter (PM), polycyclic aromatic hydrocarbons (PAHs), and ultrafine particles (UFPs). Air pollution source apportionment is essential for implementation of successful abatement strategies. UFPs or nanoparticles of diameter <100 nm exhibit the highest deposition efficiency in human lungs. To permit apportionment of PM sources at the hot-spot including nanoparticles, Positive Matrix Factorization (PMF) was applied to highly time resolved particle number size distributions (NSD, 14 nm-10 μm) and PM₀.₀₉₋₁.₁₅ chemical composition. Diurnal patterns, meteorological variables, gaseous pollutants, organic markers, and associations between the NSD factors and chemical composition factors were used to identify the pollution sources. The PMF on the NSD reveals two factors in the ultrafine size range: industrial UFPs (28%, number mode diameter - NMD 45 nm), industrial/fresh road traffic nanoparticles (26%, NMD 26 nm); three factors in the accumulation size range: urban background (24%, NMD 93 nm), coal burning (14%, volume mode diameter - VMD 0.5 μm), regional pollution (3%, VMD 0.8 μm) and one factor in the coarse size range: industrial coarse particles/road dust (2%, VMD 5 μm). The PMF analysis of PM₀.₀₉₋₁.₁₅ revealed four factors: SIA/CC/BB (52%), road dust (18%), sinter/steel (16%), iron production (16%). The factors in the ultrafine size range resolved with NSD have a positive correlation with sinter/steel production and iron production factors resolved with chemical composition. Coal combustion factor resolved with NSD has moderate correlation with SIA/CC/BB factor. The organic markers homohopanes correlate with coal combustion and the levoglucosan correlates with urban background. The PMF applications to NSD and chemical composition datasets are complementary. PAHs in PM₁ were found to be associated with coal combustion factor.

Silver barb Barbodes gonionotus fry were exposed to polyvinyl chloride (PVC) fragments at increasing concentrations of 0.2, 0.5 and 1.0 mg/L for 96 h, following which whole body histological evaluation and analysis of the digestive enzymes trypsin and chymotrypsin were performed. Whole body trypsin and chymotrypsin activities increased significantly in fish exposed to 0.5 and 1.0 mg/L PVC as compared those exposed to zero or 0.2 mg/L PVC. In fish exposed to all tested concentrations, PVCs were observed in both the proximal and distal intestine, and fish exposed to 0.5–1.0 and 1.0 mg/L PVC, respectively, and these particles were associated with localized thickening of the mucosal epithelium. No tissue damage was evident in any other internal organs or gills. This lack of damage may be attributed to the absence of contaminants associated with the PVC fragments and their relatively smooth surface. The increased whole body trypsin and chymotrypsin activities may indicate an attempt to enhance digestion to compensate for epithelial thickening of the intestine and/or to digest the plastics.

Antibiotics can effectively protect livestock from pathogen infection, but residual antibiotics in manure bring risks to ecosystems and public health. Here, we demonstrated that black soldier fly larvae (BSFL) could provide an environmentally friendly manure treatment based on their ability to effectively and rapidly degrade tetracycline (TC). Investigation of the biological mechanisms and degradation pathways of TC by BSFL indicated that nearly 97% of TC was degraded within 12 days in a non-sterile BSFL treatment system, which is up to 1.6-fold faster than that achieved by normal composting. Our results showed that rapid TC-degradation was largely carried out by the intestinal microbiota of the larvae, which doubled the TC-degradation rates compared to those achieved in sterile BSFL systems. This conclusion was further supported by highly-efficient TC-biodegradation both in vivo and in vitro by four larval intestinal isolates. Moreover, detailed microbiome analysis indicated that intestinal bacterial and fungal communities were modified along with significantly increased tet gene copy number in the gut, providing the means to tolerate and degrade TC. Through analysis of TC degradation in vitro, four possible biodegradation products, two hydrolysis products and three conceivable inactivation products were identified, which suggested TC degradation reactions including hydrolysis, oxygenation, deamination, demethylation, ring-cleavage, modification, etc. In conclusion, our studies suggested an estimation of the fate of TC antibiotics in manure treatment by BSFL colonized by gut microbes. These results may provide a strategy for accelerating the degradation of antibiotics by adjusting the intestinal microbiota of BSFL.

Analysis of the disruptive effects of chemicals on lipids in invertebrates is limited by our poor knowledge of the lipid metabolic pathways and the complete lipidome. Recent studies shown that juvenoids and bisphenol A disrupted the dynamics of lipid droplets in the crustacean Daphnia magna. This study used ultra-high performance liquid chromatography/time-of-flight mass spectrometry (UHPLC/TOFMS) to study how juvenoids (pyriproxyfen and methyl farnesoate) and bisphenol A disrupt the dynamics of glycerophospholipids and glycerolipids in Daphnia adults and their allocation to eggs. Lipidomic analysis identified 234 individual lipids corresponding to three classes of glycerolipids, seven of glycerophospholipids, and one of sphingolipids, of which 194 changed according to the chemical treatments and time. Adult females in the control and bisphenol A treatment groups had low levels of triacylglycerols but high levels of glycerophospholipids, whereas those in the juvenoid treatment groups had high levels of triacylglycerols and low levels of glycerophospholipids. The opposite trend was observed for the lipid contents in the eggs produced. Because the juvenoids reduced reproduction dramatically, the females allocated less triacylglycerols to their eggs than the controls did. Interestingly, females exposed to bisphenol A allocated less triacylglycerols to their eggs despite producing a similar number of eggs as that of the controls. Thin-layer chromatography analyses confirmed the UHPLC/TOFMS results and allowed qualitative determination of cholesterol, which was also accumulated in females exposed to the juvenoids.

The aim of this study was to assess, for the first time, the concentrations, sources, dry deposition and human health risks of polycyclic aromatic hydrocarbons (PAHs), aliphatic hydrocarbons (AHs), polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs) in total suspended particle (TSP) samples collected in Bizerte city, Tunisia (North Africa), during one year (March 2015–January 2016). Concentrations of PAHs, AHs, PCBs and OCPs ranged 0.5–17.8 ng m−3, 6.7–126.5 ng m−3, 0.3–11 pg m−3 and 0.2–3.6 pg m−3, respectively, with higher levels of all contaminants measured in winter. A combined analysis revealed AHs originating from both biogenic and petrogenic sources, while diesel vehicle emissions were identified as dominant sources for PAHs. PCB potential sources included electronic, iron, cement, lubricant factories located within or outside Bizerte city. The dominant OCP congeners were p,p′-DDT and p,p′-DDE, reflecting a current or past use in agriculture. Health risk assessment showed that the lifetime excess cancer risk from exposure to airborne BaP was negligible in Bizerte, except in winter, where a potential risk to the local population may occur.

Glyphosate (GLY) is one of the most used herbicide worldwide. Considering that information concerning the impact of GLY on bivalves is scarce, in this study we evaluated for the first time the effects of environmentally realistic concentrations of GLY (10, 100 and 1000 μg/L) to the mussel Mytilus galloprovincialis. Mussels were exposed for 7, 14 and 21 days and several biomarkers were measured in haemocytes/haemolymph (total haemocyte counts, haemocyte diameter and volume, haemolymph pH, haemolymph lactate dehydrogenase activity, haemocyte lysate lysozyme and acid phosphatase activities), as well as in gills and digestive gland (antioxidant enzyme and acetylcholinesterase activities). The concentrations of GLY and its main metabolite aminomethylphosphonic acid in the experimental tanks were also measured. The MANOVA analysis demonstrated that the experimental variables considered (exposure concentration, exposure duration, and their interaction) affected significantly biomarker responses. In addition, the two-way ANOVA analysis indicated that GLY was able to affect most of the cellular parameters measured, whereas antioxidant enzyme activities resulted to be influenced moderately. Interestingly, exposure to GLY reduced significantly acetylcholinesterase activity in gills. Although preliminary, the results of this study demonstrated that GLY can affect both cellular and biochemical parameters in mussels, highlighting a potential risk for aquatic invertebrates.

Cometabolism mechanisms of organic pollutants in environmental microbes have not been fully understood. In this study, a global analysis of Mycobacterium sp. strain A1-PYR transcriptomes on different PAH substrates (single or binary of pyrene (PYR) and phenanthrene (PHE)) was conducted. Comparative results demonstrated that expression levels of 23 PAH degradation enzymes were significantly higher in the binary substrate than in the PYR-only one. These enzymes constituted an integrated enzymatic system to actualize all transformation steps of PYR, and most of their encoded genes formed a novel gene cascade in the genome of strain A1-PYR. The roles of different genotypes of enzymes in PYR cometabolism were also discriminated even though all of their gene sequences were presented in the genome of this strain. NidAB and PdoA2B2 instead of NidA3B3 served the initial oxidization of PAHs, and PcaL replaced PcaCD to catalyze the formation of 3-oxoadipate. Novel genes associated with PYR cometabolism was also predicted by the relationships between their transcription profiles and PYR removal. The results showed that ABC-type transporters probably played important roles in the transport of PAHs and their metabolites through cell membrane, and [4Fe-4S] ferredoxin might be essential for dioxygenases (NidAB and PdoA2B2) to achieve oxidative activities. This study provided molecular insight in that microbial degrader subtly cometabolized recalcitrant PAHs with relatively more degradable ones.

Nitrogen runoff from fertiliser intensive land uses has become an issue worldwide, contributing to algal blooms, hypoxic waters and aquatic biodiversity losses. This study assessed potential nutrient pollution from blueberry farms in subtropical Australia and examines whether nutrient loads were driven by groundwater discharge and/or surface water runoff. Streams downstream of eight blueberry farms were compared to eight nearby control sites without any blueberry activity. In the 90 day sample period, there were three rain events >90 mm day⁻¹ that produced runoff sufficient to create flooding. Overall, the results revealed a clear link between blueberry farming and nitrogen runoff in headwater streams. While NOX (nitrate + nitrite) was the dominant nitrogen species downstream of blueberry farms, dissolved organic nitrogen (DON) was the dominant species in control sites. The concentrations and loads of NOₓ were one order of magnitude lower in the eight non-blueberry (6.3 ± 2.0 μmol L⁻¹; 1.6 ± 1.2 kg N-NOX ha⁻¹ yr⁻¹) than the eight blueberry (56.9 ± 14.2 μmol L⁻¹; 21.8 ± 8.0 kg N-NOX ha⁻¹ yr⁻¹) sites. NOX concentrations and loads were highest following rain events. Radon (²²²Rn, a natural groundwater tracer) observations and low nitrogen concentration in groundwater samples further suggest that surface runoff dominates the delivery of nitrogen to the creeks investigated. NOX concentrations and loads in creeks correlated with blueberry farm density. At >15% of blueberry land use in a catchment, there was a detectable influence in NOX concentrations and loads in the headwater streams. Assuming that our load estimates can be up-scaled to annual nitrogen creek exports, and that local farmers use the recommended amount of fertiliser (121 kg N ha⁻¹ yr⁻¹), between 18 and 25% of the used fertiliser was lost to the creeks. This implies that there are opportunities for decreasing the use of fertilisers in this catchment and managing any nitrogen that escapes to the creeks.