34 research outputs found
Active Intra-Abdominal Drainage Following Abdominal Digestive System Surgery: A Meta-Analysis and Systematic Review
Our objective is to compare the early outcomes associated with passive (gravity) drainage (PG) and active drainage (AD) after surgery. Studies published until April 28, 2022 were retrieved from the PubMed, Cochrane Central Register of Controlled Trials (CENTRAL), EMBASE, Web of Science databases. Nine studies with 14,169 patients were identified. Two groups had the same intra-abdominal infection rate (RR: 0.55; P = 0.13); In subgroup analysis of pancreaticoduodenectomy, active drainage had no significant effect on postoperative pancreatic fistula (POPF) rate (RR: 1.21; P = 0.26) and clinically relevant POPF (CR-POPF) (RR: 1.05; P = 0.72); Active drainage was not associated with lower percutaneous drainage rate (RR: 1.00; P = 0.96), incidence of sepsis (RR: 1.00; P = 0.99) and overall morbidity (RR: 1.02; P = 0.73). Both groups had the same POPF rate (RR: 1.20; P = 0.18) and CR-POPF rate (RR: 1.20; P = 0.18) after distal pancreatectomy. There was no difference between two groups on the day of drain removal after pancreaticoduodenectomy (Mean difference: −0.16; P = 0.81) and liver surgery (Mean difference: 0.03; P = 0.99). Active drainage is not superior to passive drainage and both drainage methods can be considered.</p
Identifying Iron Foundries as a New Source of Unintentional Polychlorinated Naphthalenes and Characterizing Their Emission Profiles
Iron
foundries have been identified as dioxin sources in previous
field investigations. Similar formation mechanisms between dioxins
and unintentional polychlorinated naphthalenes (PCNs) have led us
to speculate that iron foundries are also potential PCN sources. In
this study, PCNs in stack gas and fly ash samples representing atmospheric
and residue emissions from 13 typical iron foundry plants were analyzed.
The average emission factor of ∑<sub>2–8</sub>PCNs to
residue was calculated to be 61 μg t<sup>–1</sup>, with
a range of 10–107 μg t<sup>–1</sup>. The emission
factors of ∑<sub>2–8</sub>PCNs to air in two case plants
were 267 and 1472 μg t<sup>–1</sup>. The derived emission
factors might be useful for estimating annual emissions and understanding
the contribution of PCNs from iron foundries. The possible formation
mechanisms of PCNs, based on the PCN profiles, are discussed. Successive
reductions in the abundance of homologues were observed to occur with
the increase in chlorine substituted numbers. Abundances of congeners
containing more β-position chlorines in the naphthalene skeleton
were much higher than those of congeners containing more α-position
chlorines for penta-, hexa-, and hepta- homologues, which suggests
that the β-positions are favored for chlorination. Potential
chlorination pathways from tetra- to octa- homologues are proposed
A Novel Method for Profiling and Quantifying Short- and Medium-Chain Chlorinated Paraffins in Environmental Samples Using Comprehensive Two-Dimensional Gas Chromatography–Electron Capture Negative Ionization High-Resolution Time-of-Flight Mass Spectrometry
Chlorinated paraffins
(CPs) are complex technical mixtures containing
thousands of isomers. Analyzing CPs in environmental matrices is extremely
challenging. CPs have broad, unresolved profiles when analyzed by
one-dimensional gas chromatography (GC). Comprehensive two-dimensional
GC (GC×GC) can separate CPs with a high degree of orthogonality.
A novel method for simultaneously profiling and quantifying short-
and medium-chain CPs, using GC×GC coupled with electron capture
negative ionization high-resolution time-of-flight mass spectrometry,
was developed. The method allowed 48 CP formula congener groups to
be analyzed highly selectively in one injection through accurate mass
measurements of the [M – Cl]<sup>−</sup> ions in full
scan mode. The correlation coefficients (<i>R</i><sup>2</sup>) for the linear calibration curves for different chlorine contents
were 0.982 for short-chain CPs and 0.945 for medium-chain CPs. The
method was successfully used to determine CPs in sediment and fish
samples. By using this method, with enhanced chromatographic separation
and high mass resolution, interferences between CP congeners and other
organohalogen compounds, such as toxaphene, are minimized. New compounds,
with the formulas C<sub>9</sub>H<sub>14</sub>Cl<sub>6</sub> and C<sub>9</sub>H<sub>13</sub>Cl<sub>7</sub>, were found in sediment and biological
samples for the first time. The method was shown to be a powerful
tool for the analysis of CPs in environmental samples
Molecular Mechanism of Dioxin Formation from Chlorophenol based on Electron Paramagnetic Resonance Spectroscopy
Few studies have investigated the
free radical intermediates involved
in the formation of polychlorinated dibenzo-<i>p</i>-dioxins
and dibenzofurans (PCDD/Fs) from chlorophenol. This study clarified
the reaction pathways during thermochemical formation of PCDDs from
2,3,6-trichlorophenol (TCP) over a Cu(II)O/silica matrix, which was
used to simulate fly ash, at 298–523 K. The reaction was studied
using electron paramagnetic resonance (EPR) spectroscopy and theoretical
calculations. In situ EPR indicated the TCP radical (TCPR) formed
by hydrogen abstraction of TCP. Five elementary processes including
dimerization of TCPR, <i>ortho</i>-chloride abstraction,
Smiles rearrangement, ring closure, and intra-annular elimination
of Cl were proposed to occur during formation of PCDDs. The proposed
mechanism was further confirmed by the detection of PCDD products
from thermochemical experiments in a tube furnace. Several dominant
congeners, including 1,2,6,9-tetrachlorodibenzo-<i>p</i>-dioxin (TeCDD), 1,2,6,7-TeCDD, 1,2,8,9-TeCDD, and 1,4,6,9-TeCDD
were detected by gas chromatography/quadrupole time-of-flight mass
spectrometry, and further confirmed by gas chromatography/high resolution
mass spectrometry. The detected PCDD products agree with the proposed
PCDD formation mechanism. Relatively high temperatures were found
to lead to dechlorination of TCPR to form phenoxy radicals in addition
to PCDD/Fs. These radicals will be attached to particles, which will
increase their lifetimes. These reactions were further verified by
molecular orbital theory calculations. The discovery of persistent
phenoxy radicals is of environmental significance because of their
potential toxicity. The details of this mechanism could be used for
controlling PCDD/F formation during industrial thermal processes
Long-Term Temporal Trends of Polychlorinated Biphenyls and Their Controlling Sources in China
Polychlorinated biphenyls (PCBs)
are industrial organic contaminants
identified as persistent, bioaccumulative, toxic (PBT), and subject
to long-range transport (LRT) with global scale significance. This
study focuses on a reconstruction and prediction for China of long-term
emission trends of intentionally and unintentionally produced (UP)
∑<sub>7</sub>PCBs (UP-PCBs, from the manufacture of steel,
cement and sinter iron) and their re-emissions from secondary sources
(e.g., soils and vegetation) using a dynamic fate model (BETR-Global).
Contemporary emission estimates combined with predictions from the
multimedia fate model suggest that primary sources still dominate,
although unintentional sources are predicted to become a main contributor
from 2035 for PCB-28. Imported e-waste is predicted to play an increasing
role until 2020–2030 on a national scale due to the decline
of intentionally produced (IP) emissions. Hypothetical emission scenarios
suggest that China could become a potential source to neighboring
regions with a net output of ∼0.4 t year<sup>–1</sup> by around 2050. However, future emission scenarios and hence model
results will be dictated by the efficiency of control measures
Metal-Catalyzed Formation of Organic Pollutants Intermediated by Organic Free Radicals
Metal compounds play important roles in the formation
of organic
pollutants during thermal-related processes. However, the metal-catalyzed
predominant organic pollutants have not previously been characterized
nor have any detailed catalytic mechanisms been clarified. Here, we
preciously distinguished the multiple organic free radical intermediates
on metal catalyst surfaces during the organic pollutant formation
through laboratory and theoretical studies. Differences between the
organic free radical intermediate species, concentrations, and formation
mechanisms under the catalysis of different metal compounds were investigated.
The results were verified mutually with the differed characteristics
of organic pollutant products. CuO predominantly catalyzed the formation
of highly chlorinated phenoxy radical intermediates and dioxins. High
proportions of semiquinone radicals and oxygen-containing derivatives
were found on ZnO surfaces. Differently, methyl-substituted phenoxy
radicals and long-chain products formed on Al2O3 surfaces. The results will be instructive for the target emission
control of priority organic pollutants during thermal-related processes
rich in different metal compounds
Secondary Copper Smelters as Sources of Chlorinated and Brominated Polycyclic Aromatic Hydrocarbons
The generation of and extent to which
chlorinated and brominated
polycyclic aromatic hydrocarbons (Cl/Br-PAHs) are formed and released
from secondary copper smelters remain unknown. This field study, to
our knowledge, is the first to identify secondary copper smelters
as new sources of Cl/Br-PAHs. Mass concentrations of ∑<sub>19</sub>Cl-PAHs and ∑<sub>19</sub>Br-PAHs ranged from 5.8
to 271 ng Nm<sup>–3</sup> and 0.59 to 52.4 ng Nm<sup>–3</sup>, respectively. A comparison of Cl/Br-PAH concentrations in stack
gas and fly ash from secondary copper smelters indicated that the
use of scrap copper as raw material or the addition of coal or heavy
oil as reductant may contribute to the elevated formation and emission
of Cl/Br-PAHs. Congener profiles of Cl/Br-PAHs in stack gas and fly
ash from secondary copper smelters were different with those of Cl/Br-PAHs
from waste incinerations and other previously reported sources, thus
could be used as possible fingerprints and source apportionments of
environmental Cl/Br-PAHs. Atmospheric levels of Cl/Br-PAHs in the
workplace or smelter surroundings were determined and potential exposures
were assessed. Although chlorination of PAHs was previously recognized
as an important formation pathway of Cl/Br-PAHs, it was not verified
to be the major formation pathway for Cl/Br-PAHs from secondary copper
smelters in this study
Pivotal Roles of Metal Oxides in the Formation of Environmentally Persistent Free Radicals
Environmentally
persistent free radicals (EPFRs) are emerging pollutants
that can adversely affect human health. Although the pivotal roles
of metal oxides in EPFR formation have been identified, few studies
have investigated the influence of the metal oxide species, size,
or concentration on the formation of EPFRs. In this study, EPFR formation
from a polyaromatic hydrocarbon with chlorine and hydroxyl substituents
(2,4-dichloro-1-naphthol) was investigated using electron paramagnetic
resonance spectroscopy. The effect of the metal oxide on the EPFR
species and its lifetime and yield were evaluated. The spectra obtained
with catalysis by CuO, Al<sub>2</sub>O<sub>3</sub>, ZnO, and NiO were
obviously different, indicating that different EPFRs formed. The abilities
of the metal oxides to promote EPFR formation were in the order Al<sub>2</sub>O<sub>3</sub> > ZnO > CuO > NiO, which were in accordance
with the oxidizing strengths of the metal cations. A decay study showed
that the generated radicals were persistent, with a maximum 1/<i>e</i> lifetime of 108 days on the surface of Al<sub>2</sub>O<sub>3</sub>. The radical yields were dependent on the concentration and
particle size of the metal oxide. Metal oxide nanoparticles increased
the EPFR concentrations more than micrometer-sized particles
Thermochemical Formation of Polybrominated Dibenzo‑<i>p</i>‑Dioxins and Dibenzofurans Mediated by Secondary Copper Smelter Fly Ash, and Implications for Emission Reduction
Heterogeneous reactions
mediated by fly ash are important to polychlorinated
dibenzo-<i>p</i>-dioxin and dibenzofuran (PCDD/Fs) formation.
However, the formation of polybrominated dibenzo-<i>p</i>-dioxins and dibenzofurans (PBDD/Fs) through heterogeneous reactions
is not yet well understood. Experiments were performed to investigate
the thermochemical formation of PBDD/Fs at 150–450 °C
through heterogeneous reactions on fly ash from a secondary copper
smelter. The maximum PBDD/F concentration was 325 times higher than
the initial PBDD/F concentration in the fly ash. The PBDD/F concentration
after the experiment at 150 °C was five times higher than the
initial concentration. PBDD/Fs have not previously been found to form
at such a low temperature. Secondary-copper-smelter fly ash clearly
promoted PBDD/F formation, and this conclusion was supported by the
low activation energies that were found in Arrhenius’s law
calculations. Thermochemical formation of PBDD/Fs mediated by fly
ash deposited in industrial facilities could explain “memory
effects” that have been found for PCDD/Fs and similar compounds
released from industrial facilities. Abundant polybrominated diphenyl
ethers (PBDEs) that were formed through fly ash-mediated reactions
could be important precursors for PBDD/Fs also formed through fly
ash-mediated reactions. The amounts of PBDEs that formed through fly
ash-mediated reactions suggested that secondary copper smelters could
be important sources of reformed PBDEs
Thermal Oxidation Degradation of 2,2′,4,4′-Tetrabromodiphenyl Ether over Li<sub>α</sub>TiO<sub><i>x</i></sub> Micro/Nanostructures with Dozens of Oxidative Product Analyses and Reaction Mechanisms
Flowerlike Li<sub>α</sub>TiO<sub><i>x</i></sub> micro/nanostructures
were successfully synthesized to degrade 2,2′,4,4′-tetrabromodiphenyl
ether (BDE-47) at 250–350 °C. The pseudo-first-order kinetics
rate constant of the reaction at 300 °C was in the range of 0.034–0.055
min<sup>–1</sup>. The activation energy was as low as 39.9–48.1
kJ/mol. The excellent performance attained over Li<sub>α</sub>TiO<sub><i>x</i></sub> was attributed to Li dopant having
the electron-donating effect, which enhanced the oxygen species mobility.
The oxidative reaction was believed to be the dominant degradation
pathway following the Mars–van Krevelen mechanism, being accompanied
by the weak hydrodebromination occurrence generating the trace mono-
to tri-BDEs. More than 70 types of oxidation products containing diphenyl
ether backbone, single-benzene rings, and ring-opened products were
detected by GC-MS with derivatization, ESI-FT-ICR-MS, and ion chromatography.
An increase in the number of ring-cracked oxidative products under
prolonged reaction was observed by ESI-FT-ICR-MS analysis according
to the van Krevelen diagram. In the oxidative reaction, a series of
oxidative products, such as OH-tri-BDEs and OH-tetra-BDEs, first formed
via the nucleophilic O<sup>2–</sup> attack and subsequently
transformed into dibromophenol, tribromophenol, and benzenedicarboxylic
and benzoic acids, etc. They could be further attacked by electrophilic
O<sub>2</sub><sup>–</sup> and O<sup>–</sup> and completely
cracked to small molecules such as formic, acetic, propionic, and
butyric acids