Short-and medium-chain chlorinated paraffins in imported commercial dry cat and dog food in China:Concentrations,distributions and risk assessment

Chlorinated paraffins(CPs)are produced in large amounts and used worldwide.Dietary intake is the primary pathway for the exposure of pets to CPs,but limited information is available concerning the potential contamination of pet food by CPs.In the present study,the concentrations and congener group profiles of short-chain CPs(SCCPs)and medium-chain CPs(MCCPs)were assessed in 35 imported commercial dry cat and dog foods collected in China,and the estimated daily intakes of SCCPs and MCCPs for cats and dogs through the consumption of such foods was calculated.The concentrations of SCCPs and MCCPs in the cat and dog foods were determined to be in the ranges of 108e45,300 ng/g(median:1340 ng/g)and 3.8e52,700 ng/g(median:11 ng/g),respectively.The predominant congener groups were C10Cl6 for SCCPs and C14Cl7-8 for MCCPs.The high levels of CPs found in certain pet foods suggest the potential for adverse health effects.

Development of matrix solid-phase dispersion method for the extraction of short-chain chlorinated paraffins in human placenta

Chlorinated paraffins（SCCPs） are widely used worldwide, and they can be released into the environment during their production, transport, usage and disposal, which pose potential risks for human health. In this work, an efficient, reliable and rapid pretreatment method based on matrix solid-phase dispersion（MSPD） was developed for the analysis of short-chain CPs（SCCPs） in human placenta by gas chromatograph-electron capture negative ion low-resolution mass spectrometry（GC-ECNI-LRMS） and gas chromatography–quadrupole time-of-flight mass spectrometry（GC–QTOF-HRMS）. The MSPD-relevant parameters including dispersing sorbent,sample-to-sorbent mass ratio, and elution solvent were optimized using the orthogonal test.Silica gel was found to be the optimal dispersing sorbent among the selected matrices. Under the optimal conditions, 44% acidic silica gel can be used as the co-sorbent to remove lipid and eluted by the mixture of hexane and dichloromethane（7：3, V/V）. The spiked recoveries of the optimized method were 77.4% and 91.4% for analyzing SCCPs in human placenta by GC-ECNI-LRMS and GC–QTOF-HRMS, and the corresponding relative standard deviations were10.2% and 5.6%, respectively. The method detection limit for the total SCCPs was 36.8 ng/g（dry weight, dw） and 19.2 ng/g（dw） as measured by GC-ECNI-LRMS and GC–QTOF-HRMS,respectively. The concentrations of SCCPs in four human placentas were in the range of

Long-range atmospheric transport and alpine condensation of short-chain chlorinated paraffins on the southeastern Tibetan Plateau

Pristine alpine regions are ideal regions for investigating the long-range atmospheric transport and cold trapping effects of short chain chlorinated paraffins(SCCPs).The concentrations and alpine condensation of SCCPs were investigated in lichen samples collected from the southeastern Tibetan Plateau.The concentrations of SCCPs ranged from 3098 to 6999 ng/g lipid weight(lw)and appeared to have an increasing trend with altitude.For congeners,C10 dominated among all the congener groups.The different environmental behavior for different congener groups was closely related to their octanol-air partition coefficient(Koa).C10 congeners showed an increasing trend with altitude,whereas C13 congeners were negatively correlated with altitude.Volumetric bioconcentration factors(BCF)of SCCPs reached 8.71 in lichens,which were higher than other semivolatile organic compounds(SVOCs)such as organochlorine pesticides(OCPs),polybrominated diphenyl ethers(PBDEs),polychlorinated biphenyls(PCBs),and hexabromocyclododecane(HBCD).These results suggested that SCCPs were prone to accumulate in the lichen from the air and provided evidence for the role of lichens as a suitable atmospheric indicator in the Tibetan Plateau.

Predicting Chromatographic Retention Time of C10-Chlorinated Paraffins in Gas Chromatography-Mass Spectrometry Using Quantitative Structure Retention Relationship

Chlorinated paraffins（CPs） are potential persistent organic pollutants（POPs）, which threat the safety of environment and organisms. However, the analysis of CPs is a difficult task due to their complex composition containing thousands of congeners. In the present work, quantitative structure retention relationship（QSRR） of CPs was studied. A total of 470 molecular descriptors were generated, for describing the structures of 28 CPs and 12 descriptors relevant to retention time of the CPs were selected by stepwise regression. Then, QSRR models between retention time on the one hand and the selected descriptors on the other hand were established by multiple linear regres- sion（MLR）, partial least squares（PLS） and least square support vector regression（LS-SVR）. The result shows that PLS model is better than MLR and LS-SVR, obtaining a squared correlation coefficient（r2） of 0.9996 and a root mean squared error（RMSE） of 0.015. The PLS model was then used to predict the retention time of 49 C10-CPs. Three of them were investigated by gas chromatography coupled with mass spectrometry（GC-MS）. A well-defined correlation was found between the measured retention time and the predicted value.

Novel biomonitoring method for determining five classes of legacy and alternative flame retardants in human serum samples

Flame retardants(FRs)are ubiquitous in environment and biota and may pose harm to human health.In recent years,concern regarding legacy and alternative FRs has been intensified due to their widespread production and increasing contamination in environmental and human matrices.In this study,we developed and validated a novel analytical method for simultaneous determination of legacy and alternative FRs,including polychlorinated naphthalenes(PCNs),short-and middle-chain chlorinated paraffins(SCCPs and MCCPs),novel brominated flame retardants(NBFRs),and organophosphate esters(OPEs)in human serum.Serum samples were prepared by liquid-liquid extraction using ethyl acetate,and purified with Oasis®HLB cartridge and Florisil–silica gel columns.Instrumental analyses were carried out using gas chromatography-triple quadrupole mass spectrometry,highresolution gas chromatography coupled with high-resolution mass spectrometry,and gas chromatography coupled with quadrupole time-of-flight mass spectrometry,respectively.The proposed method was validated for linearity,sensitivity,precision,accuracy,and matrix effects.Method detection limits for NBFRs,OPEs,PCNs,SCCPs,and MCCPs were 4.6×10^(–4)–8.6×10^(–2),4.3×10^(–3)–1.3,1.1×10^(–5)–1.0×10^(–4),1.5,and 9.0×10–1 ng/mL,respectively.Matrix spike recoveries ranged from 73%–122%,71%–124%,75%–129%,92%–126%,and 94%–126%for NBFRs,OPEs,PCNs,SCCPs,and MCCPs,respectively.The analytical method was applied for detection of real human serum.CPs were the dominant FRs in serum,indicating CPs were widely presented in human serum and should be pay more attention for their health risk.

Chlorination pattern effect on thermodynamic parameters and environmental degradability for C_(10)-SCCPs: Quantum chemical calculation based on virtual combinational library

Short-chain chlorinated paraffins（SCCPs） are still controversial candidates for inclusion in the Stockholm Convention.The inherent mixture nature of SCCPs makes it rather difficult to explore their environmental behaviors.A virtual molecule library of 42,720 C10-SCCP congeners covering the full structure spectrum was constructed.We explored the structural effects on the thermodynamic parameters and environmental degradability of C10-SCCPs through semi-empirical quantum chemical calculations.The thermodynamic properties were acquired using the AM1 method,and frontier molecular orbital analysis was carried out to obtain the EHOMO,ELUMO and ELUMO-EHOMO for degradability exploration at the same level.The influence of the chlorination degree（NCl on the relative stability and environmental degradation was elucidated.A novel structural descriptor,μ,was proposed to measure the dispersion of the chlorine atoms within a molecule.There were significant correlations between thermodynamic values and NCl,while the reported NCl-dependent pollution profile of C10-SCCPs in environmental samples was basically consistent with the predicted order of formation stability of C10-SCCP congeners.In addition,isomers with largeμ showed higher relative stability than those with small μ.This could be further verified by the relationship between μ and the reactivity of nucleophilic substitution and · OH attack respectively.The C10-SCCP congeners with less Cl substitution and lower dispersion degree are susceptible to environmental degradation via nucleophilic substitution and hydroxyl radical attack,while direct photolysis of C10-SCCP congeners cannot readily occur due to the large ELUMO-EHOMO values.The chlorination effect and the conclusions were further checked with appropriate density functional theory（DFT） calculations.