Comparison of Accelerated Solvent Extraction, Soxhlet and Sonication Techniques for the Extraction of Estrogens, Androgens and Progestogens from Soils

Leaching of hormones from manure amended fields to receive surface water can lead to endocrine disruption in resident fish populations. In order to determine the concentrations of hormones present in manure amended soils, and thus the potential for soils to release hormones to aquatic environments, efficient extraction methods are needed. In this study, the efficacy of three techniques (accelerated solvent extraction [ASE], Soxhlet and sonication) for the extraction of estrogens, androgens and progestogens, as well as their metabolites, from various soil types were evaluated. The stability of hormones spiked into these soils and stored for 30, 90 and 210 days at -20°C was also investigated. Four experimental soil matrices (reagent sand, silt loam, clay and high organic) were spiked with 50 μL of 10 μg·mL-1 (in methanol;final conc. 100 ng·g-1) of a stock mix of hormones and isotopically-labeled standards (ISTDs). After equilibration, triplicate samples of the spiked soils were extracted by ASE, Soxhlet and sonication techniques and analysed, without post extraction cleanup, using HPLC-MS/MS. Sonication and ASE were effective at extracting hormones from all matrices with overall average apparent recoveries, for all 19 extracted analytes, of 71% ± 23% and 73% ± 16%, respectively. Soxhlet was significantly less efficient (p < 0.05) with overall average apparent recoveries of 58% ± 34%. Incorporation of ISTDs resulted in overall average process efficiencies of 108% ± 24%, 102% ± 24% and 180% ± 310% for ASE, Soxhlet and sonication, respectively. The hormones had variable stability in soils stored for at least 30 days, and therefore it recommended that soil samples be analysed within 30 days of sampling.

Impact of Beijing’s“Coal to Electricity”program on ambient PM_(2.5) and the associated reactive oxygen species(ROS)

The Beijing“Coal to Electricity”program provides a unique opportunity to explore air quality impacts by replacing residential coal burning with electrical appliances.In this study,the atmospheric ROS(Gas-phase ROS and Particle-phase ROS,abbreviated to G-ROS and P-ROS)were measured by an online instrument in parallel with concurrent PM_(2.5) sample collections analyzed for chemical composition and cellular ROS in a baseline year(Coal Use Year-CUY)and the first year following implementation of the“Coal to Electricity”program(Coal Ban Year-CBY).The results showed PM_(2.5) concentrations had no significant difference between the two sampling periods,but the activities of G-ROS,P-ROS,and cellular ROS in CBY were 8.72 nmol H_(2)O_(2)/m^(3),9.82 nmol H 2 O 2/m 3,and 2045.75μg UD/mg PM higher than in CUY.Six sources were identified by factor-analysis from the chemical components of PM_(2.5).Secondary sources(SECs)were the dominant source of PM_(2.5) in the two periods,with 15.90%higher contribution in CBY than in CUY.Industrial Emission&Coal Combustion sources(Ind.&CCs),mainly from regional transport,also increased significantly in CBY.The contributions of Aged Sea Salt&Residential Burning sources to PM_(2.5) decreased 5.31% from CUY to CBY.The correlation results illustrated that Ind.&CCs had significant positive correlations with atmospheric ROS,and SECs significantly associated with cellular ROS,especially nitrates(r=0.626,p=0.000).Therefore,the implementation of the“Coal to Electricity”program reduced PM_(2.5) contributions from coal and biomass combustion,but had little effect on the improvement of atmospheric and cellular ROS.

Understanding the sources and composition of the incremental excess of fine particles across multiple sampling locations in one air shed

Well-designed health studies and the development of effective regulatory policies need to rely on an understanding of the incremental differences in particulate matter concentrations and their sources. Although only a limited number of studies have been conducted to examine spatial differences in sources to particulate matter within an air shed, routine monitoring data can be used to better understand these differences. Measurements from the US EPA Chemical Speciation Network （CSN） collected between 2002-2008 were analyzed to demonstrate the utility of regulatory data across three sites located within 100 km of each other. Trends in concentrations, source contribution, and incremental excesses across three sites were investigated using the Positive Matrix Factorization model. Similar yearly trends in chemical composition were observed across all sites, however, excesses of organic matter and elemental carbon were observed in the urban center that originated from local emissions of mobile sources and biomass buming. Secondary sulfate and secondary nitrate constituted over half of the PM2.5 with no spatial differences observed across sites. For these components, the excess of emissions from industrial sources could be directly quantified. This study demonstrates that CSN data from multiple sites can be successfully used to derive consistent source profiles and source contributions for regional pollution, and that CSN data can be used to quantify incremental differences in source contributions of across these sites. The analysis strategy can be used in other regions of the world to take advantage of existing ambient particulate matter monitoring data to better the understanding of spatial differences in source contributions within a given air shed.