Total suspended particulate matter (TSP) was collected during the summer and winter in five Japanese cities spanning Hokkaido to Kyushu (Sapporo, Kanazawa, Tokyo, Sagamihara and Kitakyushu) from 1997 to 2014. Nine polycyclic aromatic hydrocarbons (PAHs) with four to six rings, including pyrene (Pyr) and benzo[a]pyrene (BaP), were identified using high-performance liquid chromatography (HPLC) with fluorescence detection. Two nitropolycyclic aromatic hydrocarbons (NPAHs), 1-nitropyrene (1-NP) and 6-nitrobenzo[a]pyrene (6-NBaP), were identified by HPLC with chemiluminescence detection. A comparison of PAH and NPAH concentrations and [NPAH]/[PAH] ratios such as [1-NP]/[Pyr] and [6-NBaP]/[BaP] revealed the following characteristics in the five cities: (1) In Sapporo, Kanazawa, Tokyo and Sagamihara, the concentrations of PAHs and NPAHs were high at the beginning of the sampling period and then steadily decreased, with NPAHs decreasing faster than PAHs. The large initial [1-NP]/[Pyr] ratios suggest that the major contributor was automobiles but subsequent decreases in this ratio suggest decreased automobile contributions. (2) By contrast, PAH concentrations in Kitakyushu did not decrease during the sampling period, though concentrations of NPAHs decreased. The consistently smaller [1-NP]/[Pyr] ratio and larger [6-NBaP]/[BaP] ratio in Kitakyushu suggests that the major contributor of PAHs was not automobiles but iron manufacturing which uses a large amount of coal. The sudden increase in atmospheric PAH concentrations in the winter of 2014 may also be due to iron manufacturing.

Nonylphenol is considered an endocrine disruptor and has been reported to affect male reproductive functions. In our in vitro study, we evaluated the effects of 4-nonylphenol (4-NP) on cholesterol levels, hormone formation and viability in cultured Leydig cells from adult ICR male mice. We also determined the potential impact of 4-NP on generation of reactive oxygen species (ROS) after 44 h of cultivation. The cells were cultured with addition of 0.04; 0.2; 1.0; 2.5 and 5.0 μg/mL of 4-NP in the present of 1 IU/mL human chorionic gonadotropin (hCG) and compared to the control. The quantity of cholesterol was determined from culture medium using photometry. Determination of hormone production was performed by enzyme-linked immunosorbent assay. Metabolic activity assay was used for quantification of cell viability. The chemiluminescence technique, which uses a luminometer to measure reactive oxygen species, was employed. Applied doses of 4-NP (0.04–5.0 μg/mL) slight increase cholesterol levels and decrease production of dehydroepiandrosterone after 44 h of cultivation, but not significantly. Incubation of 4-NP treated cells with hCG significantly (P < 0.001) inhibited androstenedione, but not testosterone, formation at the highest concentration (5.0 μg/mL). The viability was significantly (P < 0.05); (P < 0.001) increased at 1.0; 2.5 and 5.0 μg/mL of 4-NP after 44 h treatment. Furthermore, 44 h treatment of 4-NP (0.04–5.0 μg/mL) caused significant (P < 0.001) intracellular accumulation of ROS in exposed cells. Taken together, the results of our in vitro study reported herein is consistent with the conclusion that 4-nonylphenol is able to influence hormonal profile, cell viability and generate ROS.

In the Athabasca oil sands region of northern Alberta, mining companies are evaluating reclamation using constructed wetlands for integration of tailings. From May to July 2008, reproductive performance of 40 breeding pairs of tree swallows (Tachycineta bicolor), plus growth and survival of nestlings, was measured on three reclaimed wetlands on two oil sands leases. A subset of nestlings was examined for i) feather corticosterone levels, ii) delayed-type hypersensitivity response, and iii) innate immune function. Nestlings on one of two wetlands created with oil sands process affected material (OSPM) were heavier and had greater wing-lengths, and mounted a stronger delayed-type hypersensitivity response compared those on the reference wetland. Corticosterone was significantly higher in male nestlings on one of two OSPM-containing wetland compared to the reference wetland. Body condition of 12-day-old female nestlings was inversely related to feather corticosterone. Under ideal weather conditions, reclaimed wetlands can support healthy populations of aerially-insectivorous birds. Under ideal weather conditions, tree swallow nestlings on reclaimed OSPM-affected wetlands are in good body condition and mount strong cell-mediated immune responses.

The redox speciation of iron was determined during the iron fertilization LOHAFEX and for the first time, the chemiluminescence assay of filtered and unfiltered samples was systematically compared. We hypothesize that higher chemiluminescence in unfiltered samples was caused by Fe(II) adsorbed onto biological particles. Dissolved and particulate Fe(II) increased in the mixed layer steadily 6-fold during the first two weeks and decreased back to initial levels by the end of LOHAFEX. Both Fe(II) forms did not show diel cycles downplaying the role of photoreduction. The chemiluminescence of unfiltered samples across the patch boundaries showed strong gradients, correlated significantly to biomass and the photosynthetic efficiency and were higher at night, indicative of a biological control. At 150 m deep, a secondary maximum of dissolved Fe(II) was associated with maxima of nitrite and ammonium despite high oxygen concentrations. We hypothesize that during LOHAFEX, iron redox speciation was mostly regulated by trophic interactions.

Formaldehyde (HCHO) is an important component in tropospheric chemistry, but the study of HCHO in rainwater is limited. This is the first report of continuous measurement of HCHO in rainwater. HCHO in rainwater was continuously measured using a modified chemiluminescence method at Sakai City, Osaka, Japan. The continuous measurement was conducted in the 2018 rainy season (Baiu) of Japan. A total of 20 rain events have been observed, and the averaged HCHO concentration of each rain event was 0.13–2.75 μM. The maximum concentration was 9.91 μM. Diurnal variation of HCHO in rainwater showed the distinctively high concentration in nighttime and no correlation with local ambient gaseous HCHO, implying another source such as aqueous photoproduction and transportation rather than scavenging. The photo-irradiation experiment revealed that photoproduction of HCHO is one of the important sources of HCHO in rainwater with the maximum production rate of 2.43 μM h⁻¹. Besides, the backward trajectory indicated that there could have a link with the air mass original location. Furthermore, microorganism activity can play a role as a sink of HCHO in rainwater that could consume HCHO with digestion rate up to 3.2 μM h⁻¹.

Ozone (O₃) decomposition in the troposphere is a very important process which prevents excessive O₃ accumulation in the air. It is particularly significant on warm summer days which are marked by a high risk of photochemical smog. We used Spearman’s rank correlation test to determine relationships between the drop in O₃ concentrations over time (-ΔO₃), nitrogen oxide (NO), nitrogen dioxide (NO₂), and total nitrogen oxide (NOₓ) concentrations and meteorological factors (1-h average) in low-polluted urban area in Olsztyn (north-eastern Poland). Nitrogen oxide concentrations were measured continuously by the chemiluminescence method, and O₃ concentrations were determined by the UV photometric method. The obtained results suggest that the rate of decomposition of tropospheric O₃ is affected mostly by the presence of NOₓ, high temperature, and air humidity (positive correlation) as well as by wind speed (negative correlation). Maximum correlation coefficient values were reported between –ΔO₃ and air temperature, –ΔO₃ and absolute air humidity when NOₓ concentrations were low (below 1.0 microgram per cubic meter), reaching 0.271 and 0.243, respectively. These results indicate that O₃ also reacted with air components other than NO and NO₂. Precipitation at average temperature of < 0 °C did not significantly contribute to a drop in O₃ concentrations at night-time. In the warm season, precipitation slowed down the rate of O₃ decomposition, mostly because NOₓ were scrubbed by rain. An analysis of seasonal and daily –ΔO₃ fluctuations revealed that –ΔO₃ values were highest in the summer and shortly after sunset in the diurnal cycle.

A highly sensitive, specific, simple, and rapid chemiluminescence enzyme immunoassay (CLEIA) was developed for the determination of microcystin-LR (MC-LR) by using strategies for oriented immobilization of functionally intact polyclonal antibodies on chitosan surface. Several physicochemical parameters such as metal ion adsorption, hexahistidine-tagged Protein G sorption, the dilution ratio polyclonal antibody concentration, and peroxidase-labeled MC-LR concentration were studied and optimized. The sorption in batch system of G-histidine and G-proteins was studied on a novel sorbent consisting of chitosan/divalent metal ions. Transition metals as Ni⁺⁺ and Zn⁺⁺ were immobilized through interaction with –NH₂ groups of chitosan in order to supply a material capable to efficiently remove the proteins from aqueous solutions. The maximum uptake of divalent metals onto the chitosan material was found to be 230 mg g⁻¹ for Zn⁺⁺ and 62 mg g⁻¹ for Ni⁺⁺. Experimental data were evaluated using the Langmuir and Freundlich models; the results were well fitted with the Langmuir model; chitosan/Ni⁺⁺ foam was found to be the best sorbent for G-protein, maximum sorption capacity obtained was 17 mg g⁻¹, and chitosan/Zn⁺⁺ was found to be the best for G-histidine with a maximum sorption capacity of 44 mg g⁻¹. Kinetic data was evaluated with pseudo-first- and pseudo-second-order models; the sorption kinetics were in all cases better represented by a pseudo-second-order model. Under optimum conditions, the calibration curve obtained for MC-LR gave detection limits of 0.5 ± 0.06 μg L⁻¹, the 50 % inhibition concentration (IC50) was 2.75 ± 0.03 μg L⁻¹, and the quantitative detection range was 0.5–25 μg L⁻¹. The limit of detection (LOD) attained from the calibration curves and the results obtained demonstrate the potential use of CLEIA with chitosan support as a screening tool for the analysis of pollutants in environmental samples.

Based on the enhancing effect of chitosan (CS) on luminol-dissolved oxygen chemiluminescence (CL) reaction, a flow injection (FI) luminol–CS CL system was established. It was found that the increase of CL intensity was proportional to the concentrations of CS ranging from 0.7 to 10.0 μmol l⁻¹. In the presence of chlortoluron (CTU), the CL intensity of luminol–CS system could be obviously inhibited and the decrements of CL intensity were linearly proportional to the logarithm of CTU concentrations ranging from 0.01 to 70.0 ng ml⁻¹, giving the limit of detection 3.0 pg ml⁻¹ (3σ). At a flow rate of 2.0 ml min⁻¹, the whole process including sampling and washing could be accomplished within 36 s, offering a sample throughput of 100 h⁻¹. The proposed FI–CL method was successfully applied to the determination of CTU in soil samples with recoveries ranging from 95.0 % to 105.3 % and the relative standard deviations (RSDs) of less than 4.0 %.

A battery of biochemical and immunological biomarkers used for pollution assessment were measured for first time in the clams Venus verrucosa and Callista chione and were compared with those of the mussel Mytilus galloprovincialis, a well-established indicator organism utilized in numerous environmental monitoring programs. Clams and mussel were transplanted at a polluted and a reference site or maintained at the laboratory. Among biochemical biomarkers, acetylcholinesterase did not differ at the polluted site in all species, but there was a significant difference between the mussel and the clams, glutathione S-transferase showed a clear inhibition at the polluted site in all species and a significant difference between the two clams was also indicated, while catalase activities were increased only in V. verrucosa at the polluted site and not in mussel or the other clam. Immunological biomarkers responses were also pronounced at the polluted site. Lysozyme activity was species-dependent whereas respiratory burst activity measured as luminol-dependent chemiluminescence (CL) was site and stimulus dependent, and it was evident in M. galloprovincialis and V. verrucosa and not in C. chione. Further investigation focused on biochemical and immunological biomarkers related with the oxidative mechanisms in clams will strengthen and expand their use as bioindicators for pollution assessment.

Introduction The change in light intensity that takes place when an ambient air sample is drawn into the detection chamber of a chemiluminescence monitor generates changes in the concentrations of several species, such as NO₂, NO and O₃. Although this phenomenon has been known for several decades, there is still no commonly accepted approach on when or how to correct for it in NO₂ and O₃ readings. Discussion In this work, we have assessed the expanded uncertainty of two chemiluminescence NO x analysers commercially available according to EN 14211:2005, with the aim of establishing the maximum allowable standard uncertainty due to the reaction between NO and O₃ in the sampling system. Conclusion Although this maximum allowable uncertainty cannot be a universal value--as it will depend on the performance of each analyser--our results have led us to propose the conservative value of 2%. We have also proposed a methodology for improving data quality which could be easily implemented by those responsible for air quality data validation.