Halogenated polycyclic aromatic hydrocarbon (HPAH) concentrations in tissues from three tuna species Thunnus albacares (yellowfin tuna), Katsuwonus pelamis (skipjack tuna), and Auxis thazard (frigate tuna) were determined by high-resolution gas chromatography Orbitrap mass spectrometry. The tuna samples were collected from the Indian Ocean. The instrument conditions gave high mass accuracy at 0.9 m/z isolation width of the mass filter and a mass error of <±1.0 ppm for many HPAHs. A total of 29 of the 30 targets chlorinated PAHs (ClPAHs) and 20 of the 21 targets brominated PAHs (BrPAHs) were detected in the tuna muscle samples. The mean total ClPAH, BrPAH and PAH concentrations for tuna were 127.2, 156.6 and 682.8 ng/g lipid weight, respectively. The mean total ClPAH and BrPAH concentrations (ng/g lipid weight) in the tuna were considerably lower than that of PAH concentrations. The mean total ClPAH, BrPAH and PAH concentrations in T. albacares respectively were 185.8, 249.2 and 784.1 ng/g lipid weight, irrespective of the body sizes. The mean total ClPAH, BrPAH and PAH concentrations in K. pelamis respectively were 45.1, 24.8 and 555.6 ng/g lipid weight. The mean total ClPAH, BrPAH and PAH concentrations in A. thazard respectively were 34.09, 4.73 and 433.24 ng/g lipid weight. The total ClPAH concentrations and body weights significantly positively correlated for T. albacares. The mean total ClPAH concentration in white muscles was significantly higher (p < 0.05) for large than for small T. albacares. This suggests ClPAHs could bioaccumulate in T. albacares, possibly because they are poorly metabolized. The chlorinated phenanthrene and pyrene concentrations indicated tuna accumulate these compounds increasingly effectively as the tuna grow. This was the first time large numbers of HPAHs were found in biological samples. HPAHs may adversely affect the health of humans consuming tuna.

Particulate matter (PM) released from the processes of livestock production has a negative impact on the health of animals and workers. Herein, the concentration, major chemical components, morphology and microbiological compositions of particulate matter 2.5 (PM2.5, particles with aerodynamic diameter less than 2.5 μm) in a broiler breeding house were investigated. The results showed that the PM2.5 distribution in the chicken house was affected by the illumination, draught fans, chicken frame structure and activity of the chickens in the broiler breeding house. Component analysis showed that organic carbon (OC) accounted for the largest proportion, and followed by element carbon (EC), SO42−, NO3−, NH4+, Na+, K+ and Ca2+. Ultrastructural observations revealed that the shape of PM2.5 had a round, rectangular, chain-like and irregular shape. The concentration of endotoxin was approximately 0.3 EU/m3. Microbiological analysis showed that at the genus level, the pathogenic bacteria included Staphylococcus, Corynebacterium, Enterococcus, Parabacteroides, Escherichia and Megamonas. The abundant harmful fungi were Aspergillus, Scopulariopsis, Wallemia, and Fusarium. Through redundancy analysis (RDA) analysis, we determined that OC, EC, Na+, K+, and NH4+ had strong correlations with Brachybacterium, Brevibacterium, Corynebacterium, Escherichia, Scopulariopsis and Microascus. SO42− was closely related to Scopulariopsis and Salinicoccus. Salinicoccus was also strongly correlated with NO3−. Our results indicated that feed, faeces, and outside soot are contributed to the increase in PM2.5 concentration in the chicken house, while the sources of the dominant bacterial and fungi might be feed, faeces, suspended outside soil and cereal crops.

The removal of antibiotics has attracted much attention due to their extremely high adverse impacts on the environment. However, the potential risks of degradation intermediates are seldom reported. In this work, the influence of different factors on the electro-catalytic degradation efficiency of tetracycline hydrochloride (TCH) by the prepared carbon nanotubes/agarose/indium tin oxide (CNTs/AG/ITO) electrode was investigated. Under optimal conditions (10 wt% CNTs dosage, pH = 7), the maximum degradation efficiency for TCH (10 mg L⁻¹) reached up to 96% within 30 min treatment with 4 V potential. Superoxide anions (•O₂⁻) played an important role in the electro-catalytic degradation. Totally 10 degradation intermediates were identified using HPLC-MS/MS, and the degradation pathway was proposed. Toxicities of the parent antibiotic and the identified intermediates were calculated using the ECOSAR (Ecological Structure Activity Relationship) program in EPISuite, and results showed that more toxic intermediates were generated. The maximal chronic toxicity for green algae of the intermediate increased 1439.92 times. Furthermore, antimicrobial activity was further verified by disk agar biocidal tests with Escherichia coli ATCC25922 and higher biotoxicity intermediates compared with parent compounds were confirmed to be formed. Therefore, more attention should be paid on the potential risk of degradation intermediates in the treatment of wastewater containing antibiotics.

In health-oriented air pollution control, it is vital to rank the contributions of different emission sources to the health risks posed by hazardous components in airborne fine particulate matters (PM₂.₅), such as trace metals. Towards this end, we investigated the PM₂.₅-associated metals in two densely populated regions of China, the Yangtze River Delta (YRD) and Pearl River Delta (PRD) regions, across land-use gradients. Using the positive matrix factorization (PMF) model, we performed an integrated source apportionment to quantify the contributions of the major source categories underlying metal-induced health risks with information on the bioaccessibility (using simulated lung fluid) and speciation (using synchrotron-based techniques) of metals. The results showed that the particulate trace metal profiles reflected the land-use gradient within each region, with the highest concentrations of anthropogenically enriched metals at the industrial sites in the study regions. The resulting carcinogenic risk that these elements posed was higher in the YRD than in the PRD. Chromium was the dominant contributor to the total excessive cancer risks posed by metals while manganese accounted for a large proportion of non-carcinogenic risks. An elevated contribution from industrial emissions was found in the YRD, while traffic emissions and non-traffic combustion (the burning of coal/waste/biomass) were the common dominant sources of cancer and non-cancer risks posed by metals in both regions. Moreover, the risk-oriented source apportionment of metals did not mirror the mass concentration-based one, suggesting the insufficiency of the latter to inform emission mitigation in favor of public health. While providing region-specific insights into the quantitative contribution of major source categories to the health risks of PM₂.₅-associated trace metals, our study highlighted the need to consider the health protection goal-based source apportionment and emission mitigation in supplement to the current mass concentration-based framework.

There has been a growing concern with the environmental influences of nanomaterials due to recent developments in nanotechnology. This study investigates the impact and fate of hematite nanoparticles (α-Fe₂O₃ NPs) (∼14 nm in size) on a crop species, barley (Hordeum vulgare L.). For this purpose, hematite NPs (50, 100, 200, and 400 mg/L) were hydroponically applied to barley at germination and seedling stages (three weeks). Inductively coupled plasma mass spectrophotometry (ICP-MS) along with vibrating sample magnetometer (VSM) techniques were used to track the NPs in plant tissues. The effects of NPs on the root cells were observed by scanning electron microscopy (SEM) and confocal microscopy. Results revealed that α-Fe₂O₃ NPs significantly reduced the germination rate (from 80% in control to 30% in 400 mg/L), as well as chlorophyll (36–39%) and carotenoid (37%) contents. Moreover, the treatment led to a significant decline in the quantum yield of photosystem II (Fv/Fm). Leaf VSM analysis indicated a change in magnetic signal for NPs-treated samples compared with untreated ones, which is mostly attributed to the iron (Fe) ions incorporated within the leaf tissue. Besides, Fe content in the roots and leaf had gradually increased by the increasing doses of NPs, which was confirming NPs’ translocation to the aerial parts. Microscopic observations revealed that α-Fe₂O₃ NPs altered root cell morphology and led to the injury of cell membranes. This study, in the light of our findings, shows that α-Fe₂O₃ NPs (∼14 nm in size) are taken up by the roots of the barley plants, and migrate to the plant leaves. Besides, NPs are phytotoxic for barley as they inhibit germination and pigment biosynthesis. This inhibition is probably due to the injury of the cell membranes in the roots. Therefore, the use of hematite NPs in agriculture and thereby their environmental diffusion must be addressed carefully.

Contamination by polycyclic aromatic hydrocarbons (PAHs) has been observed at high elevation environments; however, the occurrence and spatial variation of PAHs in alpine lakes of China is not well understood. We measured 15 priority PAHs in the sediments of Lake Qinghai in the Qinghai-Tibet Plateau, and assessed their distribution, source, and ecological risks. The total PAH concentration ranged from 30.4 to 125.2 ng g⁻¹. Low molecular weight PAHs were dominant in the sediments, suggesting a local source for the emissions. Sediment sites closer to local settlements and rivers had higher concentration of PAHs. The concentration of PAHs was significantly correlated with pH, probably as a result of the high salinity of the lake, while it was not significantly correlated with organic matter content. Molecular diagnostic ratio analysis indicated that PAHs were derived mainly from coal and biomass combustion. Specifically, the positive matrix factorization model showed that petrogenic sources, vehicular emissions, biomass combustion, and coal combustion contributed for 11.6, 16.3, 23.6, and 48.5% of the PAHs, respectively. The risk quotient method was used to assess ecological risk of PAHs individually. The results indicate that indeno[1,2,3-cd]pyrene, benzo[b]fluoranthene, benzo[a]pyrene, phenanthrene, and anthracene would produce moderate ecological risks in 5, 20, 65, 100, and 100% of the sediment sites, respectively, while the other 10 PAH homologues would scarcely produce any serious ecological risk. We used the hierarchical Archimedean copula integral assessment model to evaluate the integral risk of PAHs. The result showed that 10, 40, and 50% of the sediment sites belong to mid-high, low, and mid-low risk levels, respectively. The current concentration and risk levels of PAHs in this study might be used as a baseline to assess the influence of future anthropogenic activities.

Arsenic (As) has been recognized as one of the most toxic metalloids present in the surface soil contaminating food chain and posing threat to human life. Sulfur (S) fertilizer is often supplied in paddy soil for rice growth, but its impact on As mobility and related bacteria remains poorly understood. In this study, a pot experiment was set up with two different types of sulfur treatments (element sulfur and Na₂SO₄) to evaluate the effect of sulfur fertilizers on As speciation in porewater, As fractions in soil, As accumulation in rice plants. Besides, rhizosphere bacterial composition and functional genes that might influence As mobility were also studied. The results revealed that the addition of 150 mg/kg Na₂SO₄ decreased As(III) and As(V) concentrations in soil porewater at maturation stage by 77% and 64%, respectively. With the same sulfur content, Na₂SO₄ was more effective than element sulfur. The addition of sulfur fertilizers promoted rice growth and reduced As accumulation in shoots, further reduced As translocation from root to above-ground parts by 39–59%. The addition of sulfur fertilizers had little effect on genes involved in As metabolism. However, the relative abundance of Fe(III) and sulfate reduction related genera increased with the addition of 150 mg/kg Na₂SO₄, consistent with the increase of Fe(III) reducing bacteria Geobacteraceae and sulfate reducing gene dsrA. The phenomenon likely influenced the decrease of As concentrations in soil porewater and rice uptake. The outcomes indicate that promoting Fe- and S- reducing bacteria in the rhizosphere by sulfur fertilizers may be one way to reduce As risk in the soil-rice system.

Condensed organic matters (COM) with black carbon-like structures are considered as long-term carbon sinks because of their high stability. It is difficult to distinguish COM from general organic matter by conventional chemical analysis, thus the contribution by and interaction mechanisms of organo-mineral complexes in COM stabilization are unclear and generally neglected. Molecular markers related to black carbon-like structures, such as benzene polycarboxylic acids (BPCAs), are promising tools for the qualitative and quantitative analysis of COM. In this study, one natural soil and two cultivated soils with 25 y- or 55 y-tillage activities were collected and the distribution characteristics of BPCAs were detected. All the investigated soils showed similar BPCA distribution pattern, and over 60% of BPCAs were detected in clay fraction. The extractable BPCA contents were substantially increased after mineral removal. The ratios of BPCA contents before and after mineral removal indicate the extent of COM-mineral particle interactions, and our results suggested that up to 73% COM were protected by mineral particles, and more stronger interactions were noted on clay than on silt. The initial cultivation dramatically decreased COM-clay interactions, and this interaction was recovered only slowly after 55-y cultivation. Kaolinite and muscovite are important for COM protection. But a possible negative correlation between BPCAs and reactive iron oxides of the cultivated soils suggested that iron may promote COM degradation when disturbed by tillage activities. This study provided a new angle to study the stabilization of COM and emphasized the importance of organo-mineral complexes for COM stabilization.

Aquatic organisms are usually exposed to various co-existing pollutants. However, toxic effects of pesticide mixtures on aquatic organisms and its potential underlying mechanism still remain unclear. The joint effects of fenpropathrin (FEN) and paclobutrazol (PAC) on zebrafish (Danio rerio) using diverse toxicological endpoints were investigated in the current work. Our data exhibited that the 96-h LC₅₀ values of FEN to zebrafish at multiple life phases ranged from 0.0029 (0.0013–0.0042) to 0.16 (0.082–0.23) mg a.i. L⁻¹, which were lower by comparison to PAC ranging from 13.16 (8.564–21.03) to 23.43 (17.94–29.91) mg a.i. L⁻¹. Combination of FEN and PAC displayed synergistic effect on embryonic zebrafish. Activities of T-SOD, Cu/Zn-SOD and CYP450 were remarkably changed in the majority of single and mixture treatments by comparison to the untreated group. The mRNA levels of 17 genes related to oxidative stress, cellular apoptosis, immune system and endocrine system were assessed, and the data suggested that embryonic zebrafish were affected by both single pesticides and their mixtures. Five genes (P53, tsh, ERα, crh and cxcl-clc) showed greater alterations when exposed to pesticide mixtures by comparison to their individual chemicals. Therefore, it is urgently necessary to conduct more studies on mixture toxicities of different pesticides to explore the chemical mixtures with synergistic interactions.

Chromium (Cr) is a toxic element among which hexavalent chromium [Cr(VI)] is more toxic than trivalent chromium [Cr(III)]. Chromium can be reduced or oxidized in soil because soil is a complex medium and various soil components affect redox reaction of Cr in soil. Therefore, Cr speciation in hydroponics and soil was compared and Cr uptake and speciation by lettuce grown in the media were evaluated. Higher phytotoxicity was found in Cr(III) spiked soil than in Cr(VI) spiked soil, while Cr toxicity was higher in Cr(VI) treated hydroponics than Cr(III) treated hydroponics. Chromium was mainly accumulated in lettuce roots as Cr(III), and more Cr was translocated from roots to shoots grown in Cr(VI) treated hydroponics than Cr(III) treated hydroponics. Accumulation of Cr in roots grown in Cr(III) treated nutrient solution reduced Fe, K, Ca, Mg, and P uptake in lettuce. Chromium valence state was Cr(III) in lettuce leaves and roots grown in both Cr(III) and Cr(VI) treated hydroponics and soil. Chromium speciation in hydroponically grown lettuce roots was Cr(III) coordinated with 6 oxygens in the first shell and 2 or 4 carbons in the second shell as analyzed by X-ray absorption spectroscopy (XAS), which was similar to chromium acetate. The valence state of Cr in Cr(III) and Cr(VI) treated nutrient solution was not changed, while Cr(VI) was reduced to Cr(III) in Cr(VI) spiked soil by soil organic matter. Spiking of Cr(III) induced reduction of Mn in soil, which resulted in an increase of bioavailable Mn concentration in the Cr(III) spiked soil. Therefore, the increased phytotoxic effect for lettuce in Cr(III) spiked soil can be attributed to the reduction of Mn and subsequent release of Mn(II). For Cr(III) contaminated soil, Mn speciation should be considered, and bioavailable Mn concentration should be monitored although Cr existed as Cr(III) in soil.