Four fluoroquinolone antibiotics (norfloxacin, ciprofloxacin, lomefloxacin, and enrofloxacin) in tap water in Guangzhou and Macao were analyzed using high performance liquid chromatography fluorescence detection. The results showed that all target antibiotics were detected in high rate both in Guangzhou (77.5%) and Macao (100%), ranging from 1.0 to 679.7 ng/L (SD ≤ 37.6) in Guangzhou, and from 2.0 to 37.0 ng/L (SD ≤ 2.5) in Macao. The fluoroquinolone antibiotics pollution in tap water widely distributes in Guangzhou and Macao. In addition, the effect of rainfall on concentration of fluoroquinolone antibiotics in south China was also investigated. Our result indicates that the antibiotic concentration in tap water in Guangzhou tends to obviously reduce at the beginning of rainy season, even decreases below the limit of quantification immediately. Thus, it was clarified that the heavy rain in south China has the function of reducing the fluoroquinolone antibiotics concentrations in tap water.

Eels are an ideal biomonitor for persistent organic pollutants (POPs) because of their high lipid content, longevity and tendency to remain within a defined range during their freshwater life phase. This study investigated concentrations of POPs in eels (Anguilla anguilla) from 30 sites across Scotland, including polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (BDEs), DDT (and metabolites), hexachlorocyclohexanes (α, β, γ-HCH), hexachlorobenzene (HCB), hexachlorobutadiene (HCBD) and pentachlorobenzene. Despite its EU-wide ban ∼30 years ago, DDT and its derivatives were detected in almost all samples. PCB 153 and 138 were the most widely detected PCB congeners, while BDE 47 was the dominant BDE. Pentachlorobenzene was not detected, while HCBD was detected once only. α-HCH, β-HCH and HCB concentrations were very low (generally <3 μg/kg or below detection). When compared with 1986 and 1995 data, the results revealed considerable decreases in p,p′-DDE concentrations. More drastic reductions were evident for γ-HCH, reflecting the tightening restrictions on pesticide use imposed over the previous decades.

Microcystins are cyanobacterial hepatotoxins capable of accumulation into animal tissues. The toxins act by inhibiting specific protein phosphatases and both non-covalent and covalent interactions occur. The 2-methyl-3-methoxy-4-phenylbutyric acid (MMPB) method determines the total, i.e. the sum of free and protein-bound microcystin in tissues. The aim of the method development in this paper was to tackle the problems with the MMPB methodology: the rather laborious workflow and the loss of material during different steps of the method. In the optimised workflow the oxidation recovery was of acceptable level (29–40%), the extraction efficiency good (62–97%), but the signal suppression effect from the matrix remained severe in our system (16–37% signal left). The extraction efficiency for the determination of the free, extractable microcystins, was found to be good, 52–100%, depending on the sample and the toxin variant and concentration. The study concerns method development for the LC–MS–MS analysis of both free and protein-bound microcystin in tissue materials.

Element load, conventional biomarkers and altered protein expression profiles were studied in Carcinus maenas crabs, to assess contamination of “Domingo Rubio” stream, an aquatic ecosystem that receives pyritic metals, industrial contaminants, and pesticides. Lower antioxidative activities – glucose-6-phosphate and 6-phosphogluconate dehydrogenases, catalase – were found in parallel to higher levels of damaged biomolecules – malondialdehyde, oxidized glutathione –, due to oxidative lesions promoted by contaminants, as the increased levels of essential – Zn, Cu, Co – and nonessential – Cr, Ni, Cd – elements. Utility of Proteomics to assess environmental quality was confirmed, especially after considering the six proteins identified by de novo sequencing through capLC-μESI-ITMS/MS and homology search on databases. They include tripartite motif-containing protein 11 and ATF7 transcription factor (upregulated), plus CBR-NHR-218 nuclear hormone receptor, two components of the ABC transporters and aldehyde dehydrogenase (downregulated). These proteins could be used as novel potential biomarkers of the deleterious effects of pollutants present in the area.

The aim of this study was to validate lichens as biomonitors of PAH atmospheric deposition; for that, an inter-comparison between the PAH profile and concentrations intercepted in lichens with those of air, soil and pine needles was performed. The study was conducted in a petro-industrial area and the results showed that PAH profiles in lichens were similar to those of the air and pine needles, but completely different from those of soils. Lichens accumulated higher PAH concentrations when compared to the other environmental compartments and its concentrations were significantly and linearly correlated with concentrations of PAHs in soil; we showed that a translation of the lichen PAHs concentrations into regulatory standards is possible, fulfilling one of the most important requirements of using lichens as biomonitors. With lichens we were then able to characterize the air PAHs profile of urban, petro-industrial and background areas. Lichen PAH concentrations can identify geographic areas that may be out of compliance with regulatory standards.

The impact of residual PAHs (2250 ± 71 μg total PAHs g−1) following enhanced natural attenuation (ENA) of creosote-contaminated soil (7767 ± 1286 μg total PAHs g−1) was assessed using a variety of ecological assays. Microtox™ results for aqueous soil extracts indicated that there was no significant difference in EC50 values for uncontaminated, pre- and post-remediated soil. However, in studies conducted with Eisenia fetida, PAH bioaccumulation was reduced by up to 6.5-fold as a result of ENA. Similarly, Beta vulgaris L. biomass yields were increased 2.1-fold following ENA of creosote-contaminated soil. While earthworm and plant assays indicated that PAH bioavailability was reduced following ENA, the residual PAH fraction still exerted toxicological impacts on both receptors. Results from this study highlight that residual PAHs following ENA (presumably non-bioavailable to bioremediation) may still be bioavailable to important receptor organisms such as earthworms and plants. Residual PAHs in creosote-contaminated soil following enhanced natural attenuation impacted negatively on ecological receptors.

One-step immunochromatographic assay (ICA) has been developed using colloidal gold-labeled monoclonal antibody probe for the rapid detection of lead ions in water samples. The ICA was based on the theory of competitive reactivity, and the results can be easily judged based on the presence or absence of a red colored test line with visual detection. Under optimal conditions, this method shows high detecting sensitivity with a LOD (limit of detection) of 50 ng/ml. Stability test indicates that the immunochromatographic strips are stable for 8 weeks at room temperature. During practical application, nanometer TiO2 is used to enrich the lead ions in water samples. The ICA is successfully applied in the measurement of lead ion concentrations in local water samples, and the results are highly consistent with that of ICP-MS. Detecting lead ions with ICA can be done within 4 min and is very useful for the rapid onsite testing.

We modified an analytical method to determine polybrominated diphenyl ethers (PBDEs) in urban soils of Bratislava (Slovakia). Gel permeation chromatography (GPC) introduced as a clean-up step for soil extracts substantially reduced matrix enhancements when PBDEs were measured with gas chromatography-negative chemical ionization-mass spectrometry (GC-NCI-MS). The resulting method proved to be accurate, precise, and showed low detection limits. The sum of 15 PBDE concentrations in surface horizons of Bratislava soils ranged from 87 to 627 pg g-1. PBDE concentrations were mostly higher in surface than deeper horizons probably because of atmospheric deposition and lack of substantial vertical transport. Lower brominated PBDEs undergo more soil-atmosphere exchanges or are more scavenged and transferred with litter fall to the soil organic matter than higher brominated ones as suggested by the correlation between lower brominated PBDEs and soil organic C (Corg) concentrations.

Background, aim, and scope Organoarsenical-containing animal feeds that promote growth and resistance to parasites are mostly excreted unchanged, ending up in nearby wastewater storage lagoons. Earlier work documented the partial transformation of organoarsenicals, such as, 3-nitro-4-hydroxyphenylarsonic acid (roxarsone) to the more toxic inorganic arsenate [As(V)] and 3-amino-4-hydroxyphenylarsonic acid (3-AHPAA). Unidentified roxarsone metabolites using liquid chromatography coupled to inductively coupled plasma mass spectrometry (LC/ICP-MS) were also inferred from the corresponding As mass balance. Earlier batch experiments in our laboratory suggested the presence of organometallic (Cu) complexes during relevant roxarsone degradation experiments. We hypothesized that organocopper compounds were complexed to roxarsone, mediating its degradation in field-collected swine wastewater samples from storage lagoons. The objective of this study was to investigate the role of organometallic (Cu) complexes during roxarsone degradation under aerobic conditions in swine wastewater suspensions, using electrospray ionization mass spectrometry (ES-MS). Materials and methods Two swine wastewater samples differing in % solids content and total recoverable Cu concentrations were reacted with 500 ppb of roxarsone under aerobic conditions for 16 days. LC/ICP-MS and ES-MS were used for As speciation analyses, and characterization of metal-organoarsenical complexes in swine wastewater subsamples, respectively. Results and discussion An organocopper roxarsone metabolite was found only in the high-Cu wastewater sample, suggesting the role of Cu in roxarsone degradation under aerobic conditions. The organocopper metabolite was not found in the low-Cu wastewater sample, because roxarsone did not undergo degradation under aerobic conditions even after 16 days. Conclusions Aerobic degradation of organoarsenicals (roxarsone) has not been documented before. Preliminary dataset from this study illustrates the direct and/or indirect association of particulate Cu in catalyzing roxarsone degradation under aerobic conditions in samples with high % solids content. Recommendations and perspectives Concerns regarding the degradation of roxarsone in wastewater to the more toxic inorganic As may be partially linked to the presence of particulate Cu. The presence of Cu in wastewater-suspended particle surfaces has never been coupled before to organoarsenicals degradation reactions, thus, further studies are needed to elucidate the related reaction mechanisms and pathways. Water depth-dependent solid particle distribution profiles in wastewater storage lagoons could provide empirical evidence towards the design of effective degradation practices for nitrophenol-containing compounds, such as, organoarsenical-containing antibiotics, or explosive munitions compounds.

Background, aim and scope Photochemical processes can decontaminate the aqueous environment from xenobiotics, but they also produce secondary pollutants. This paper presents field and laboratory evidence of the transformation of 4-chlorophenol (4CP) into 2-nitro-4-chlorophenol (2N4CP). Materials and methods Field monitoring of 4CP and 2N4CP was carried out by solid phase extraction coupled with liquid chromatography-multiple reaction monitoring mass spectrometry. Laboratory irradiation experiments were carried out under a UV-Vis lamp, and the time evolution of the compounds of interest was followed by liquid chromatography. Purpose The purpose of this study was elucidating the pathways leading to 2N4CP from 4CP in paddy field water. Results and discussion The field monitoring results suggest that 4CP can be transformed into 2N4CP in the paddy field water of the Rhône delta (Southern France). The laboratory study indicates that the transformation can take place via photonitration by •NO₂. The nitration process is inhibited by bicarbonate, possibly due to basification that favours the occurrence of the 4-chlorophenolate. The latter could consume •NO₂ without being nitrated. Photonitration in the presence of bicarbonate could account for the observed transformation in the field. Conclusions Photonitration of 4CP to 2N4CP by •NO₂ could account for the observed interconversion of the two compounds in paddy fields. The results are of concern because 2N4CP is biorecalcitrant and toxic. Recommendations and perspectives Bicarbonate can modulate the photonitration of 4CP into 2N4CP, which can be very significant in bicarbonate-poor waters.