In this study we examined 6080 data gathered by our research group during more than 20 years of research on the moss biomonitoring technique, in order to quantify the variability generated by different aspects of the protocol and to calculate the overall measurement uncertainty associated with the technique. The median variance of the concentrations of different pollutants measured in moss tissues attributed to the different methodological aspects was high, reaching values of 2851 (ng·g⁻¹)² for Cd (sample treatment), 35.1 (μg·g⁻¹)² for Cu (sample treatment), 861.7 (ng·g⁻¹)² and for Hg (material selection). These variances correspond to standard deviations that constitute 67, 126 and 59% the regional background levels of these elements in the study region. The overall measurement uncertainty associated with the worst experimental protocol (5 subsamples, refrigerated, washed, 5 × 5 m size of the sampling area and once a year sampling) was between 2 and 6 times higher than that associated with the optimal protocol (30 subsamples, dried, unwashed, 20 × 20 m size of the sampling area and once a week sampling), and between 1.5 and 7 times higher than that associated with the standardized protocol (30 subsamples and once a year sampling). The overall measurement uncertainty associated with the standardized protocol could generate variations of between 14 and 47% in the regional background levels of Cd, Cu, Hg, Pb and Zn in the study area and much higher levels of variation in polluted sampling sites. We demonstrated that although the overall measurement uncertainty of the technique is still high, it can be reduced by using already well defined aspects of the protocol. Further standardization of the protocol together with application of the information on the overall measurement uncertainty would improve the reliability and comparability of the results of different biomonitoring studies, thus extending use of the technique beyond the context of scientific research.

Mainly due to automobile traffic, but also due to other sources, the platinum group elements (PGE) platinum (Pt), palladium (Pd) and rhodium (Rh) are introduced into aquatic biotopes where they accumulate in sediments of lakes and rivers. However, the toxicity of these noble metals to aquatic organisms is not well understood and especially toxicity studies under standardized condition are lacking. Thus, the toxicity of Pt, Pd and Rh to Daphnia magna was tested in single metal exposure experiments according to OECD guideline 202. Immobility and lethality was recorded after 24 h and 48 h of exposure and EC50 and LC50, respectively, were determined. As the nominal exposure concentration of Pd differed significantly from the quantified concentration, the control of the real exposure concentration by chemical analysis is mandatory, especially for Pd.The toxicity decreased in the order Pd > Pt ≫ Rh with e.g. LC50(48 h) values of 14 μg/L for Pd, 157 μg/L for Pt and 56,800 μg/L for Rh. The exposure period had a clear effect on the toxicity of Pt, Pd and Rh. For Pt and Rh the endpoint immobility was more sensitive than the endpoint lethality whereas Pd toxicity was similar for both endpoints. The Hill slopes, which are a measure for the steepness of the concentration-response curves, showed no significant discrepancies between the different metals.The binary metal exposure to Pt and Pd revealed a more-than-additive, i.e. a synergistic toxicity using the toxic unit approach. The present study is a start to understand the toxicity of interacting PGE. The modes of action behind the synergistic effect are unclear.

Quantitative identification of nitrate (NO3−-N) sources is critical to the control of nonpoint source nitrogen pollution in an agricultural watershed. Combined with water quality monitoring, we adopted the environmental isotope (δD-H2O, δ18O-H2O, δ15N-NO3−, and δ18O-NO3−) analysis and the Markov Chain Monte Carlo (MCMC) mixing model to determine the proportions of riverine NO3−-N inputs from four potential NO3−-N sources, namely, atmospheric deposition (AD), chemical nitrogen fertilizer (NF), soil nitrogen (SN), and manure and sewage (M&S), in the ChangLe River watershed of eastern China. Results showed that NO3−-N was the main form of nitrogen in this watershed, accounting for approximately 74% of the total nitrogen concentration. A strong hydraulic interaction existed between the surface and groundwater for NO3−-N pollution. The variations of the isotopic composition in NO3−-N suggested that microbial nitrification was the dominant nitrogen transformation process in surface water, whereas significant denitrification was observed in groundwater. MCMC mixing model outputs revealed that M&S was the predominant contributor to riverine NO3−-N pollution (contributing 41.8% on average), followed by SN (34.0%), NF (21.9%), and AD (2.3%) sources. Finally, we constructed an uncertainty index, UI90, to quantitatively characterize the uncertainties inherent in NO3−-N source apportionment and discussed the reasons behind the uncertainties.

In this study, we aimed to identify the toxic effects of chlorpyrifos exposure on the tissues of common carp. For this purpose, we evaluated histopathological changes in the brain, gills, liver, kidney, testis, and ovaries after 21 days of chlorpyrifos exposure. Activation of 8-OHdG, cleaved caspase-3, and iNOS were assesed by immunofluorescence assay in chlorpyrifos-exposed brain and liver tissue. Additionally, we measured the expression levels of caspase-3, caspase-8, iNOS, MT1, CYP1A, and CYP3A genes in chlorpyrifos-exposed brain tissue, as well as the expression levels of FSH and LH genes in chlorpyrifos-exposed ovaries, using qRT-PCR. We observed severe histopathological lesions, including inflammation, degeneration, necrosis, and hemorrhage, in the evaluated tissues of common carp after both high and low levels of exposure to chlorpyrifos. We detected strong and diffuse signs of immunofluorescence reaction for 8-OHdG, iNOS, and cleaved caspase-3 in the chlorpyrifos-exposed brain and liver tissues. Furthermore, we found that chlorpyrifos exposure significantly upregulated the expressions of caspase-3, caspase-8, iNOS, and MT1, and also moderately upregulated CYP1A and CYP3A in the brain tissue of exposed carp. We also noted downregulation of FSH and LH gene expressions in chlorpyrifos-exposed ovary tissues. Based on our results, chlorpyrifos toxication caused crucial histopathological lesions in vital organs, induced oxidative stress, inflammation, and apoptosis in liver and brain tissues, and triggered reproductive sterility in common carp. Therefore, we can propose that chlorpyrifos toxication is highly dangerous to the health of common carp. Moreover, chlorpyrifos pollution in the water could threaten the common carp population. Use of chlorpyrifos should be restricted, and aquatic systems should be monitored for chlorpyrifos pollution.

Organophosphate flame retardants (PFRs) can be rapidly metabolized in the body, and recent studies have shown that the di-alkyl phosphates (DAPs) are important metabolites. The accumulation and distribution of 8 PFRs and their 4 DAPs metabolites were first investigated in whole-body samples and various tissues of three freshwater fish species (topmouth gudgeon, crucian carp and loach) with different feeding habits from locations around Beijing, China. Concentrations of ΣPFRs in whole-body samples across all sampling locations ranged from 264.7 to 1973 ng g−1 lipid weight (lw), while all the paired DAP metabolites were detected in the total range from 35.3 to 510 ng g−1 lw. The calculated log bioconcentration factors (BCFs) of PFRs in whole fish were correlated with their log KOW (P < 0.05). The metabolite/parent ratios (MPRs) of ΣDAPs were calculated and ranged from 0.10 to 1.12 in whole-fish of all species. The MPRs of BBOEP/TBOEP were the highest. With respect to their distribution in different tissues, both the parent PFRs and metabolites were found at relatively higher levels in the liver than in other tissues (muscle, intestine, kidney and ovary), which was markedly different from those observed in avian species in previous studies. The accumulation of PFRs and DAPs in various tissues was not significantly correlated with the lipid content. The highest PFRs level in the liver may be related to the active hepatic accumulation processes. Meanwhile, the MPRs for all 4 pairs were the highest in the kidney relative to the other tissues. To the best of our knowledge, this is the first study of DAPs in the wild animals, and our study may improve the understanding of the accumulation and metabolism of PFRs in the body.

In this paper, a poultry slaughterhouse wastewater (PSW) was treated in terms of chemical oxygen demand (COD) and color reduction using electro-Fenton (EF) technique under response surface methodology (RSM). The effects of five significant independent variables such as reaction time, pH, H2O2/Fe2+ molar ratio, current density, volume ratio of H2O2/PSW (ml/l) were investigated on the COD and color removal. Experimental data were optimized by Box-Behnken design (BBD) and RSM. The optimum conditions were experimentally found at pH of 4.38, reaction time of 55.60 min, H2O2/Fe2+ molar ratio of 3.73, current density of 74.07 mA/cm2, volume ratio of H2O2/PSW of 1.63 ml/l for 92.37%COD removal and at pH of 3.39, reaction time of 49.22 min, H2O2/Fe2+ molar ratio of 3.62, current density of 67.90 mA/cm2, volume ratio of H2O2/PSW of 1.44 ml/l for 88.06% color removal.

Understanding the sources, occurrence and sinks of perfluoroalkyl and polyfluoroalkyl substances (PFASs) in the urban water cycle is important to protect and utilize local water resources. Concentrations of 22 target PFASs and general water quality parameters were determined monthly for a year in filtered water samples from five tributaries and three sampling stations of an urban water body. Of the 22 target PFASs, 17 PFASs were detected with a frequency >93% including PFCAs: C4-C12 perfluoroalkyl carboxylates, C4, C6, C8, and C10 perfluoroalkane sulfonates, perfluorooctane sulfonamides and perfluorooctane sulfonamide substances (FOSAMs), C10 perfluoroalkyl phosphonic acid (C10 PFPA), 6:2 fluorotelomer sulfonic acid (6:2 FTSA) and C8/C8 perfluoroalkyl phosphinic acid (C8/C8-PFPIA). The most abundant PFASs in water were PFBS (1.4–55 ng/L), PFBA (1.0–23 ng/L), PFOS (1.5–24 ng/L) and PFOA (2.0–21 ng/L). In the tributaries, PFNA concentrations ranged from 1.2 to 87.1 ng/L except in the May 2013 samples of two tributaries, which reached 520 and 260 ng/L. Total PFAS concentrations in the sediment samples ranged from 1.6 to 15 ng/g d.w. with EtFOSAA, PFDoA, PFOS and PFDA being the dominant species. Based on water and sediment data, two types of sources were inferred: one-time or intermittent point sources and continuous non-point sources. FOSAMs and PFOS released continually from non-point sources, C8/C8 PFPIA, PFDoA and PFUnA was released from point sources. The highly water soluble short-chain PFASs including PFBA, PFPeA and PFBS remained predominantly in the water column. The factors governing solution phase concentrations appear to be compound hydrophobicity and sorption to suspended particles. Correlation of the dissolved phase concentrations with precipitation data suggested stormwater was a significant source of PFBA, PFBS, PFUnA and PFDoA. Negative correlations with precipitation indicated sources feeding FOSAA and FOSA directly into the tributaries.

Recently, portable monitors have been increasingly used to quantify air pollutant concentrations at high spatiotemporal resolution. A sampling campaign was conducted to measure the fine particulate matter (PM2.5) and carbon monoxide (CO) exposure concentrations in transport microenvironments (TMEs) in Hong Kong in January and June 2015 using TSI DustTrak and Q-Trak portable monitors. The objectives were to: (1) calibrate DustTrak and Q-Trak; (2) evaluate variability between seasons and microenvironments; (3) estimate indoor/outdoor relationships; and (4) determine minimum sample size. Calibration equations, obtained through side-by-side measurement against stationary reference methods in winter and summer, were applied to correct the measured PM2.5 data set. In general, PM2.5 concentrations in all TMEs were significantly higher in winter than in summer. The mean PM2.5 concentration in winter was lower for underground sections of the Mass Transit Railway (MTR) metro system (31 μg/m3) than for other TMEs, whereas in summer TMEs had mean PM2.5 concentrations in the range of 10–15 μg/m3, with above-ground MTR train as an exception, at 23 μg/m3. PM2.5 concentrations measured in TMEs were strongly correlated with nearby air quality monitoring stations (AQMSs) measurements in winter, but in summer there was little correlation. The minimum sample size estimates varied more among TMEs in summer versus winter because of the differences in PM2.5 concentration distributions related to changes in ambient PM2.5 concentrations and ventilation practices. This study provides a feasible protocol on the calibration and application of portable monitors in TME air quality measurement and develops a method for estimating minimum sample size.

Phytate is abundant in soils, which is stable and unavailable for plant uptake. However, it occurs in root exudates of As-hyperaccumulator Pteris vittata (PV). To elucidate its effect on As uptake and growth, P. vittata was examined on agar media (63 μM P) containing 50 μM As and/or 50 or 500 μM phytate with non As-hyperaccumulator Pteris ensiformis (PE) as a congeneric control. Phytate induced efficient As and P uptake, and enhanced growth in PV, but had little effects on PE. The As concentrations in PV fronds and roots were 157 and 31 mg kg−1 in As50+phytate50, 2.2- and 3.1-fold that of As50 treatment. Phosphorus uptake by PV was reduced by 27% in As treatment than the control (P vs. P + As) but increased by 73% comparing phytate500 to phytate500+As, indicating that PV effectively took up P from phytate. Neither As nor phytate affected Fe accumulation in PV, but phytate reduced root Fe concentration in PE (46–56%). As such, the increased As and P and the unsuppressed Fe uptake in PV probably promoted PV growth. Thus, supplying phytate to As-contaminated soils may promote As uptake and growth in PV and its phytoremediation ability.

Microbial methylation and demethylation are central to arsenic's (As) biogeochemical cycling. Here, the transformations of monomethylarsonic acid (MMA(V)) (50 mg L−1) for 15 days in cells of As-methylating fungi, Fusarium oxysporum CZ-8F1, Penicillium janthinellum SM-12F4, and Trichoderma asperellum SM-12F1, were evaluated, and trace concentrations of As(III) and As(V) were observed in fungal cell extracts. Trace amounts of DMA(V) were also detected in MMA(V) and P. janthinellum SM-12F4 incubations. In situ X-ray absorption near edge structure (XANES) indicated that after exposure to MMA(V) (500 mg L−1) for 15 days, 28.6–48.6% of accumulated As in fungal cells was DMA(V), followed by 18.4–30.3% from As(V), 0–28.1% from As(III), and 4.8–28.9% from MMA(V). The concurrent methylation and demethylation of As occurs in fungal cells. Furthermore, a majority of proteins involved in metabolism, transport, ATP activity, biosynthesis, signal transduction, DNA activity, translation, and oxidative stress were upregulated in T. asperellum SM-12F1 cells after MMA(V) exposure compared to As(III), As(V), and DMA(V). The detoxification process of T. asperellum SM-12F1 was As species-specific. Methylenetetrahydrofolate reductase (R7YMH0) donation of a methyl group for S-adenosylmethionine (SAM) generation significantly increased following MMA(V) exposure.