| ObjectiveIn this paper,we tested the pesticide residues of three triazine herbicides(TRZHs)including prometryn,propazine and atrazine residues in multi-media environment samples including vegetables from four administrative districts and surrounding areas of Haikou City,water,and soil.The pollution level of herbicide residues was discussed.Risk of pesticide residues to ecology and human health was estimated.This work will provide theoretical basis for the development of pesticide residue separation and detection technology and risk assessment methods.MethodsA Salting-out assisted liquid-liquid extraction combined with self-assembled monolithic spin columns-solid phase micro extraction(SALLE-MSC-SPME)-UPLC-MS/MS method was develop to determine TRZHs pesticide residues in multi-media environment samples.Coconut shell biochar,an environmentally friendly solid phase adsorbent,was used as the adsorbent for MSC-SPME.Orthogonal design assisted the optimization of SALLE-MSC-SPME extraction conditions;Multiple risk assessment methods such as index of food safety(IFS),Risk(R),chronic dietary intake risk(%ADI)and risk quotient(RQ)were used to evaluate the exposure risk of pesticide residues in the population.Results1.Under the optimal extraction and determination conditions,three TRZHs obtained good linearity in the range of 0.10 ng/m L-200.00 ng/m L,and the linear coefficient(R~2)was greater than 0.999.Limits of detections(LODs)and limits of quantification(LOQs)for all the three TRZHs,calculated as the analyte concentration for which the peak height was three and ten times the background noise(3S/N and 10S/N),were attained in the range of 0.007 ng/m L~0.011 ng/m L and 0.023 ng/m L~0.036ng/m L,respectively.The recovery of the three TRZHs in multi-media environmental samples ranged from 69.00%to 124.72%with the standard deviation ranged from 0.09%to 0.43%.2.A total of 207 batches of commercially available vegetables in five categories were measured in four administrative districts of Haikou City,including leafy vegetables,fruit vegetables,aquatic cauliflower,fungus vegetables and bulbous vegetables.Among them,net concentration of prometryn detected in 7 batches and atrazine detected in 2 batches exceeded the national standard maximum residue limit,with the over standard rates of 3.38%and 0.97%,respectively.The risk assessment of9 batches of vegetables exceeding the national standard maximum residue limit showed that the IFS of male and female were 0.17 and 0.20(≤1),indicating that the overall status of TRZHs in vegetables were safe and the index of food safety of vegetables were acceptable.Risk factor of propazine was 1.10(<1.5),indicating low risk,while prometryn was 4.48(R>2.5),indicating high risk and atrazine was 2.07(1.5<R<2.5),indicating moderate risk.The%ADI of prometryn was 11.69%for men and 13.79%for women,while atrazine 24.14%for men and 28.47%for women,The value of%ADI was under 100%indicating acceptable risk.3.The TRZHs concentration in seawater and farmland soil samples around Haikou City was under the national standard maximum residue limit.The ecological risk assessment of 21 batches of samples were carried out based on risk quotient(RQ).The RQ of propazine,prometryn and atrazine in seawater samples were 0.03,0.01 and0.01,respectively,while in farmland soil samples were 0.00(RQ<0.01),indicating risk-free.Conclusions1.SALLE-MSC-SPME-UPLC-MS/MS method was novel and accurate.The method can be successfully applied to the determination of TRZHs in environmental and food samples,and has the advantages of high efficiency,sensitivity,low cost and environmental friendliness.2.In addition,the risk coefficient of prometryn,atriazine and propazine in vegetables of Haikou City was high,middle and low risk,respectively.Relevant departments need to focus on strengthening the supervision and management of prometryn in vegetables to reduce the health risks caused by pesticide residues in vegetables.3.At present,the seawater and farmland soil in the surrounding areas of Haikou city are at low risk.Relevant departments should continue to strengthen supervision to ensure that the health risk of pesticide residues in the environment remains low risk. |