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Characterization and source identification of organic phosphorus in sediments of a hypereutrophic lake Full text
2020
Yuan, Hezhong | Tai, Ziqiu | Li, Qiang | Zhang, Fengmin
High phosphorus (P) load and consequent algal bloom are critical issues because of their harmful effects to aquatic ecosystems. The organic phosphorus (Po) cycling and hydrolyzation pathway in the sediments of a hypereutrophic lake area with high algae biomass were investigated using stable isotopes (δ¹³C and δ¹⁵N) along with C/N ratios, a sequential extraction procedure, ³¹P NMR spectrum, and alkaline phosphatase activity (APA) was measured simultaneously. C/N ratios lower than 10 combined with lighter δ¹³C (−23.5 to −25.2‰) and δ¹⁵N values (3.7–9.5‰) indicated that endogenous algal debris contributed to the predominant proportions of P-containing organic matter in the sediments. Sequential extraction results showed that Po fractions decreased as nonlabile Po > moderately labile Po > biomass-Po. Decreasing humic-associated Po (HA-Po) in sediments downward suggested the degradation of high-molecular-weight Po compounds on the geological time scale to low-molecular-weight Po including fulvic-associated Po (FA-Po), which is an important source of labile Po in the sediment. An analysis of the solution ³¹P NMR spectrum analysis showed that important Po compound groups decreased in the order of orthophosphate monoesters > DNA-Po > phospholipids. The significant correlation indicated that orthophosphate monoesters were the predominant components of HA-Po. Rapid hydrolysis of labile orthophosphate diesters further facilitated the accumulation of orthophosphate monoesters in the sediments. Additionally, the simultaneously upward increasing trend demonstrated that APA accelerated the mineralization of Po into dissolved reactive phosphorus (DRP), which might feed back to eutrophication in algae-dominant lakes. The significantly low half-life time (T₁/₂) for important Po compound groups indicated faster metabolism processes, including hydrolysis and mineralization, in hypereutrophic lakes with high algae biomass. These findings provided improved insights for better understanding of the origin and cycling processes as well as management of Po in hypereutrophic lakes.
Show more [+] Less [-]Occurrence, phase distribution, and bioaccumulation of organophosphate esters (OPEs) in mariculture farms of the Beibu Gulf, China: A health risk assessment through seafood consumption Full text
2020
Zhang, Ruijie | Yu, Kefu | Li, An | Zeng, Weibin | Lin, Tian | Wang, Yinghui
As emerging pollutants, the occurrence and risks of organophosphate esters (OPEs) in mariculture farms should be concerned; however, information is limited. Beibu Gulf is one of the essential mariculture zones in China. This study aimed to investigate the occurrence of OPEs in mariculture farms of the Beibu Gulf, their phase distribution and bioaccumulation among sediment, organisms (shrimp, crab, and oyster), water, and feed. Human exposure to OPEs through seafood consumption was also assessed. The total concentrations of the 11 target OPEs (∑₁₁OPEs) in the water samples ranged 32.9–227 ng L⁻¹. It was significantly higher in water from the culture ponds (mean 122 ng L⁻¹) than in water from the estuaries and nearshore areas (mean 51.1 ng L⁻¹) (nonparametric test, p < 0.05). ∑₁₁OPEs in the feeds averaged 46.0 (range 21.7–84.5) ng g⁻¹ dw, which is similar to the level in the organism samples (mean 55.5, range 21.3–138 ng g⁻¹ dw) and 4.4 times higher than that in the sediment (mean 10.9, range 35–22.1 ng g⁻¹ dw). The ∑₁₁OPEs released from the feeds to the culture ponds was estimated to be 49 μg m⁻² per three-month period. In the aquaculture ponds, the sediment-water distribution coefficient (log KOC), and the bioaccumulation factors from the water (log BWAFs) or the feed (log BFAFs) to the organisms, depend linearly on the hydrophobicity (log KOW) of OPEs. The log BWAFs and log BFAFs increased with increasing log KOW within the log KOW range of 1–7. The human exposure to OPEs through consumption of shrimp, crab, and oysters from the mariculture farms does not pose a health risk at present.
Show more [+] Less [-]Respirable inorganic fibers dispersed in air and settled in human lung samples: Assessment of their nature, source, and concentration in a NW Italy large city Full text
2020
Capella, Silvana | Bellis, Donata | Fioretti, Elena | Marinelli, Roberto | Belluso, Elena
The present investigation represents a new approach useful to evaluate the general population risk correlated with environmental exposure to air dispersed inorganic fibers. The used method is based on the evaluation of the respirable inorganic fibers both air dispersed in a big city and contained in lungs of the general population following their respiration. Moreover, these data allow to identify the sources of dispersion (anthropogenic or natural) in air of the inorganic fibers and therefore to apply strategies to improve air quality. To describe this approach, we investigated air samples from a big city in NW Italy and lung inorganic burden of people here lived. This paper reports the data of the airborne inorganic fibers detected in two sampling campaign (2014 and 2016), in 24 districts of Torino (Piemonte - NW Italy), and in some autoptic lungs of general population lived here. The airborne fibers (collected on mixed-cellulose esters membrane) were characterized by SEMEDS. The identified inorganic fiber species were assigned to 5 classes, one of these including 2 types of asbestos. These last are grouped as tremolite/actinolite asbestos. They are dispersed from natural sources (i.e. certain kinds of rocks outcropping in the city surrounding areas). In no-one of the 24 districts of Torino their concentration highlighted a situation of asbestos pollution in place.A correlation with inorganic fibers (collected on mixed-cellulose esters membrane and characterized by SEM-EDS) detected in lung tissue samples of 10 subjects lived in Torino all their life and without professional exposure to asbestos were attempted. The only types of fibers identified as asbestos are tremolite/actinolite asbestos, and they match those detected in air sampling. The number of fibers per 1 g of tissue dry weight is lower than the quantities reported as indicative of significant asbestos exposure. We observed interesting gender differences.
Show more [+] Less [-]Missed atmospheric organic phosphorus emitted by terrestrial plants, part 2: Experiment of volatile phosphorus Full text
2020
Li, Wei | Li, Bengang | Tao, Shu | Ciais, Philippe | Piao, Shilong | Shen, Guofeng | Peng, Shushi | Wang, Rong | Gasser, Thomas | Balkanski, Yves | Li, Laurent | Fu, Bo | Yin, Tianya | Li, Xinyue | An, Jie | Han, Yunman
The emission and deposition of global atmospheric phosphorus (P) have long been considered unbalanced, and primary biogenic aerosol particles (PBAP) and phosphine (PH₃) are considered to be the only atmospheric P sources from the ecosystem. In this work, we found and quantified volatile organic phosphorus (VOP) emissions from plants unaccounted for in previous studies. In a greenhouse in which lemons were cultivated, the atmospheric total phosphorus (TP) concentration of particulate matter (PM) was 41.8% higher than that in a greenhouse containing only soil, and the proportion of organic phosphorus (OP) in TP was doubled. ³¹P nuclear magnetic resonance tests (³¹P-NMR) of PM showed that phosphate monoesters were the main components contributed by plants in both the greenhouse and at an outside observation site. Atmospheric gaseous P was directly measured to be 1–2 orders of magnitude lower than P in PM but appeared to double during plant growing seasons relative to other months. Bag-sampling and gas chromatography mass spectrometry (GCMS) tests showed that the gaseous P emitted by plants in the greenhouse was triethyl phosphate. VOP might be an important component of atmospheric P that has been underestimated in previous studies.
Show more [+] Less [-]Occurrence and distribution of organophosphate esters in the air and soils of Ny-Ålesund and London Island, Svalbard, Arctic Full text
2020
Han, Xu | Hao, Yanfen | Li, Yingming | Yang, Ruiqiang | Wang, Pu | Zhang, Gaoxin | Zhang, Qinghua | Jiang, Guibin
The levels of eight organophosphate esters (OPEs) were analyzed in air and soil samples collected at Ny-Ålesund and London Island, Svalbard during the Chinese Scientific Research Expedition to the Arctic during 2014–2015. The concentrations of total OPEs (∑OPEs) ranged from 357 pg/m³ to 852 pg/m³ in the air and from 1.33 ng/g to 17.5 ng/g dry weight (dw) in the soils. Non-Cl OPEs accounted for 56 ± 13% and 62 ± 16% of ∑OPEs for the air and soil, respectively. Tris(2-chloroethyl) phosphate (TCEP) was the dominant compound in the air, with an average concentration of 180 ± 122 pg/m³. Triphenyl phosphate, tri(1-chloro-2-propyl) phosphate, and TCEP were the most abundant OPEs in the soils, with mean values of 1.77, 2.13, and 1.02 ng/g dw, respectively. Compared with the levels of polybrominated diphenyl ethers found in Arctic regions in previous studies, OPEs showed significantly higher concentrations, thereby indicating the large production and wide usage of OPEs globally. In addition, the fugacity fraction results indicated that net deposition from air to soil was dominated in the area. Overall, the occurrence and distribution of OPEs in the air and soils in the Arctic region indicated that OPEs can undergo long-range atmospheric transport and accumulate in remote regions.
Show more [+] Less [-]A comprehensive risk assessment of human inhalation exposure to atmospheric halogenated flame retardants and organophosphate esters in an urban zone Full text
2019
Hu, Yuan-Jie | Bao, Lian-Jun | Huang, Chun-Li | Li, Shao-Meng | Zeng, E. Y. (Eddy Y.)
Inhalation exposure to flame retardants used as additives to minimize fire risk and plasticizers is ubiquitous in human daily activities, but has not been adequately assessed. To address this research gap, the present study conducted an assessment of human health risk for four age groups through inhalation exposure to size fractionated particle-bound and gaseous halogenated flame retardants (polybrominated diphenyl ethers (PBDEs) and alternative halogenated flame retardants (AHFRs)) and organophosphate esters (OPEs) at indoor and outdoor environments (school, office, and residence) in three districts of a megacity (Guangzhou, China). Results demonstrated that OPEs were the dominant components among all targets. Indoor daily intakes of PBDEs and OPEs were 13–16 times greater than outdoor levels for all age groups. Gaseous OPEs contributed significantly greater than particle-bound compounds to daily intakes of all target compounds. Based on the different life scenarios, hazard quotient (HQ) and incremental life cancer risk (ILCR) from adults exposure to PBDEs and OPEs in indoor and outdoor settings were the greatest, followed by adolescents, children, and seniors. The estimated HQ and ILCR for all age groups both indoors and outdoors were lower than the safe level (HQ = 1 and ILCR = 10−6), indicating that the potential health risk for local residents in Guangzhou via inhalation exposure to atmospheric halogenated flame retardants and OPEs was low.
Show more [+] Less [-]The potential role of sediment organic phosphorus in algal growth in a low nutrient lake Full text
2019
Ni, Zhaokui | Wang, Shengrui | Cai, Jingjing | Li, Hong | Jenkins, Alan | Maberly, Stephen C. | May, Linda
The role of sediment–bound organic phosphorus (Pₒ) as an additional nutrient source is a component of internal P budgets in lake system that is usually neglected. Here we examined the relative importance of sediment Pₒ to internal P load and the role of bioavailable Pₒ in algal growth in Lake Erhai, China. Lake Erhai sediment extractable Pₒ accounted for 11–43% (27% average) of extractable total P, and bioavailable Pₒ accounted for 21–66% (40%) of Pₒ. The massive storage of bioavailable Pₒ represents an important form of available P, essential to internal loads. The bioavailable Pₒ includes mainnly labile monoester P and diester P was identified in the sequential extractions by H₂O, NaHCO₃, NaOH, and HCl. 40% of H₂O−Pₒ, 39% of NaHCO₃−Pₒ, 43% of NaOH−Pₒ, and 56% of HCl−Pₒ can be hydrolyzed to labile monoester and diester P, suggesting that the bioavailability of Pₒ fractions was in decreasing order as follows: HCl−Pₒ > NaOH−Pₒ > H₂O−Pₒ > NaHCO₃−Pₒ. It is implied that traditional sequential fractionation of Pₒ might overestimate the availability of labile Pₒ in sediments. Furthermore, analysis of the environmental processes of bioavailable Pₒ showed that the stabler structure of dissloved organic matter (DOM) alleviated the degradation and release of diester P, abundant alkaline phosphatase due to higher algal biomass promoted the degradation of diester P. The stability of DOM structure and the degradation of diester P might responsible for the spatial differences of labile monoester P. The biogeochemical cycle of bioavailable Pₒ replenishs available P pools in overlying water and further facilitate algal growth during the algal blooms. Therefore, to control the algal blooms in Lake Erhai, an effective action is urgently required to reduce the accumulation of Pₒ in sediments and interrupt the supply cycle of bioavailable Pₒ to algal growth.
Show more [+] Less [-]Residuals of organophosphate esters in foodstuffs and implication for human exposure Full text
2018
Ding, Jinjian | Deng, Tongqing | Xu, Mengmeng | Wang, Shen | Yang, Fangxing
Foodstuffs may be contaminated by organophosphate esters (OPEs) and become an important source of human exposure since OPEs are ubiquitous in the environment. In the present study, 10 OPEs were analyzed in various food matrices collected from a city in Eastern China including chicken, pork, fishes, vegetables, tofu, eggs, milk and cereals. The concentrations of Σ₁₀OPEs ranged from 1.1 to 9.6 ng g⁻¹ fresh weight (fw) in the foodstuffs. Cereals had the highest residual level of total OPEs with a mean value of 5.7 ng g⁻¹ fw. Tris(2-ethylhexyl) phosphate was detected in all foodstuff samples and showed the highest median residual concentration of 1.3 ng g⁻¹ fw among the OPE analogs. The daily dietary intake of OPEs was calculated as 3.6 and 2.4 μg d⁻¹ for adults and children. Cereals were identified as the major contributor to the total OPEs among different types of foodstuffs. Preliminary exposure assessment revealed that the current non-cancer health risks of OPEs via dietary intake were in the range of 10⁻⁵-10⁻³, indicating low risk levels. Moreover, the hazard index of OPEs indicated that the risk for children (3 × 10⁻³) was higher than adults (2 × 10⁻³).
Show more [+] Less [-]A multi-year study of VOC emissions at a chemical waste disposal facility using mobile APCI-MS and LPCI-MS instruments Full text
2018
Healy, Robert M. | Chen, Qingfeng | Bennett, Julie | Karellas, Nicholas S.
Real-time analysis of volatile organic compounds (VOCs) in air is useful both for source identification and emissions compliance applications. In this work, two complementary triple quadrupole mass spectrometers, fitted with an atmospheric pressure chemical ionization (APCI) and a low pressure chemical ionization (LPCI) source, respectively, were deployed simultaneously to investigate emissions of VOCs associated with an Ontario-based chemical waste disposal facility. Mobile measurements performed upwind and downwind of the facility enabled selection of the best locations for stationary sampling. Seven separate field studies were undertaken between 2000 and 2016 to assess how emissions of VOCs have changed at the site as a function of time. Up to twenty-nine VOCs were successfully identified and quantified using MS/MS in each study. Simultaneous deployment of the two mass spectrometers enabled the detection of polar VOCs including alcohols, esters, amines and ketones as well as non-polar aromatic VOCs including benzene and naphthalene in real time. Concentrations of VOCs were found to decrease significantly in the vicinity of the facility over the sixteen year period, in particular since 2007. Concentration values for each year are compared with odour thresholds and provincial guidelines and implications of future expansion of on-site solid waste landfill volumes are also discussed.
Show more [+] Less [-]Occurrence, distribution and risk of organophosphate esters in urban road dust in Beijing, China Full text
2018
Li, Wenhui | Shi, Yali | Gao, Lihong | Wu, Chuandong | Liu, Jiemin | Cai, Yaqi
As a major group of plasticizers and flame-retardants, organophosphate esters (OPEs) have attracted particular attention due to their wide occurrence and potential impacts on human health and ecosystems. In the present study, the occurrence and distribution of 14 OPEs, including seven Alkyl-OPEs, three Cl-OPEs, and four Aryl-OPEs, were investigated in 65 road dust samples collected from November to December 2014 in Beijing, China. Cl-OPEs were the predominant compounds in the road dust samples, with the median concentration of 646 μg/kg, followed by the Alkyl-OPEs (median 135 μg/kg) and Aryl-OPEs (median 129 μg/kg). Tris(2-chloro-1-methylethyl) phosphate (TCPP) was the most abundant OPE with the median concentration of 384 μg/kg. In addition, OPEs levels showed significant difference (p < 0.05) in the spatial distribution. Markedly higher levels of OPEs were observed in 2nd and 3rd ring road with heavy traffic and high population density, indicating that the traffic and population were important factors for this distribution pattern. It was further supported by the analysis of OPEs in roadside soil and indoor dust in the vicinity of road dust sample sites. Finally, the average daily dose (ADD) for OPEs via inhalation, dermal absorption, and ingestion was calculated to evaluate the carcinogenic and non-carcinogenic risks to residents exposed to OPEs in the road dust. Risk assessment revealed that the risk originating from exposure to OPEs of road dust is currently low in Beijing, China.
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