Isotope dilution analysis of polychlorinated biphenyls (PCBs) in transformer oil and global commercial PCB formulations by high resolution gas chromatography-high resolution mass spectrometry

Special polychlorinated biphenyls (PCBs) standards (native and isotope labeled) were analyzed by isotope dilution method using HRGC-HRMS. Multiple analysis of special PCBs standards by three different laboratories produced the relative response factors (RRFs) and relative standard deviations (RSDs %) was in the average of 0.979 and 3.86, respectively. Additionally, inter-laboratory analysis of various forms of transformer oil revealed the PCBs concentrations were in the following order; PCBs fortified transformer oil (940-1300 ng/g)>PCB polluted transformer oil (490-680 ng/g)>chemically degraded-transformer oil (480-490 ng/g) and PCBs free oil (ND-17 ng/g). Chemical degradation resulted in an order of magnitude decrease in the PCB concentrations. Specifically, higher chlorinated PCBs degraded into lower chlorinated PCBs. Also, composition of PCBs have been determined in PCB formulations from Japan (Kanechlor), Germany (Clophen), USA (Aroclor), Russia (Sovol) and Poland (Chlorofen). Major PCBs (24-PCB congeners) contributed 54-67%, 55-68%, 16-69%, 71% and 72% in Kanechlor, Clophen, Aroclor, Sovol and Chlorofen, respectively to total PCBs. The homologue pattern of Kanechlor, Aroclor and Clophen in technical fromulation was similar (e.g., Kanechlor-300 resembled to those of Clophen A-30 and Aroclor-1242). Furthermore, congener-specific distributions of major PCBs/dioxin-like PCBs and toxic equivalency quantities (TEQ) were calculated. Based on our tentative assumption calculations, cumulative production of five different technical PCB formulations, WHO-TEQ emission was estimated to be approximately 16.05 tons.     

The effect of oils on PAH, PCDD, PCDF, and PCB emissions from a spark engine fueled with leaded gasoline

The effect of synthetic and mineral oils on the formation of polyaromatic hydrocarbons (PAHs), polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs), and biphenyls (PCBs) in emissions from a spark ignition engine was studied on a Skoda Favorit engine fueled with leaded gasoline. The test cycle simulated urban traffic conditions on a chassis dynamometer, in accordance with the ECC 83.00 test. The data for selected PAHs as well as PCDDs, PCDFs, and PCBs congener profiles are presented. PCDD/Fs emissions for an unused oil and the oil after 10000-km operation varied from 300 to 2000 fmol/m3, PCBs emissions from 75 to 178 pmol/m3, and PAHs emissions from 150 to 420 microg/m3. The content of PCBs in oils varied from 2 to 920 mg/kg.     

Dechlorination of PCBs in the simulative transformer oil by microwave-hydrothermal reaction with zero-valent iron involved

The conventional hydrothermal reaction with iron powder, NaOH and H₂O as reactants was reported to occur at temperature above 423 K, and iron oxides (Fe₃O₄ and NaFeO₂) and hydrogen were produced. In this study, microwave heating was adopted to take the place of conventional heating to induce the hydrothermal reaction. Under microwave irradiation, NaOH and H₂O absorbed microwave energy by space charge polarization and dipolar polarization and instantly converted it into thermal energy, which initiated the hydrothermal reaction that involved with zero-valent iron. X-ray diffraction (XRD) analysis found Fe₃O₄/NaFeO₂ and confirmed the occurrence of microwave-induced hydrothermal reaction. The developed microwave-hydrothermal reaction was employed for the dechlorination of PCBs. Hexadecane containing 100 mg L⁻¹ of Aroclor1254 was used as simulative transformer oil, and the dechlorination of PCBs was evaluated by GC/ECD, GC/MS and ion chromatography. For PCBs in 10 mL simulative transformer oil, almost complete dechlorination was achieved by 750 W microwave irradiation for 10 min, with 0.3 g iron powder, 0.3 g NaOH and 0.6 mL H₂O added. The effects of important factors including microwave power and the amounts of reactants added, on the dechlorination degree were investigated, moreover, the dechlorination mechanism was suggested. Microwave irradiation combined with the common and cheap materials, iron powder, NaOH and H₂O, might provide a fast and cost-effective method for the treatment of PCBs-containing wastes.     

Effect of temperature and particle size on the thermal desorption of PCBs from contaminated soil

Thermal desorption is widely used for remediation of soil contaminated with volatiles, such as solvents and distillates. In this study, a soil contaminated with semivolatile polychlorinated biphenyls (PCBs) was sampled at an interim storage point for waste PCB transformers and heated to temperatures from 300 to 600 °C in a flow of nitrogen to investigate the effect of temperature and particle size on thermal desorption. Two size fractions were tested: coarse soil of 420–841 μm and fine soil with particles <250 μm. A PCB removal efficiency of 98.0 % was attained after 1 h of thermal treatment at 600 °C. The residual amount of PCBs in this soil decreased with rising thermal treatment temperature while the amount transferred to the gas phase increased up to 550 °C; at 600 °C, destruction of PCBs became more obvious. At low temperature, the thermally treated soil still had a similar PCB homologue distribution as raw soil, indicating thermal desorption as a main mechanism in removal. Dechlorination and decomposition increasingly occurred at high temperature, since shifts in average chlorination level were observed, from 3.34 in the raw soil to 2.75 in soil treated at 600 °C. Fine soil particles showed higher removal efficiency and destruction efficiency than coarse particles, suggesting that desorption from coarse particles is influenced by mass transfer.     

Occurrence,spatial distribution,sources, and risks of polychlorinated biphenyls and heavy metals in surface sediments from a large eutrophic Chinese lake (Lake Chaohu)

Surface sediment from large and eutrophic Lake Chaohu was investigated to determine the occurrence, spatial distribution, sources, and risks of polychlorinated biphenyls (PCBs) and heavy metals in one of the five biggest freshwater lakes in China. Total concentration of PCBs (Σ₃₄PCBs) in Lake Chaohu was 672 pg g^?1 dry weight (dw), with a range of 7 to 3999 pg g^?1 dw, which was lower than other water bodies worldwide. The majority of heavy metals were detected at all sampling locations, except for Sr, B, and In. Concentrations of Al, Fe, Ca, Mn, Sr, Co, Zn, Cd, Pb, and Hg were similar to that reported for other lakes globally. Concentrations of K, Mg, Na, Li, Ga, and Ag were greater than the average, whereas those of Cr, Ni, and Cu were lower. Cluster analysis (CA) and positive matrix factorization (PMF) yielded accordant results for the source apportionment of PCBs. The technical PCBs and microbial degradation accounted for 34.2 % and 65.8 % of total PCBs using PMF, and PMF revealed that natural and anthropogenic sources of heavy metals accounted for 38.1 % and 61.8 %, respectively. CA indicated that some toxic heavy metals (e.g., Cd, In, Tl, and Hg) were associated with Ca–Na–Mg minerals rather than Fe–Mn minerals. The uncorrelated results between organic matter revealed by pyrolysis technology and heavy metals might be caused by the existence of competitive adsorption between organic matter and minerals. PCBs and heavy metals were coupling discharge without organochlorine pesticides (OCPs), but with polycyclic aromatic hydrocarbons (PAHs) and polybrominated diphenyl ethers (PBDEs). No sediment sample exceeded the toxic threshold for dioxin-like PCBs (dl-PCBs) set at 20 pg toxicity equivalency quantity (TEQ)?g^?1, (max dl-PCBs, 10.9 pg TEQ g^?1). However, concentrations of Ag, Cd, and Hg were at levels of environmental concern. The sediment in the drinking water source area (DWSA) was threatened by heavy metals from other areas, and some fundamental solutions were proposed to protect the DWSA.     

Uptake of microcontaminants by crops irrigated with reclaimed water and groundwater under real field greenhouse conditions

The use of reclaimed water for agricultural irrigation has emerged as a new strategy for coping with water scarcity in semiarid countries. However, the incorporation of the organic microcontaminants in such water into the diet through crop uptake poses a potential risk to human health. This paper aims to assess the presence of organic microcontaminants in different crops irrigated with groundwater and reclaimed water (secondary or tertiary effluents) in a greenhouse experiment. The determination of microcontaminants in water and vegetation samples was performed by solid-phase extraction and matrix solid-phase dispersion procedure with GC–MS/MS, respectively. The presence of nitrates in the groundwater used for irrigation increased biomass production by a higher proportion than the harvest index. The concentration of microcontaminants in lettuce, carrots, and green beans ranged from less than the limit of quantitation to 571 ng?g^?1 (fresh weight). Tributyl phosphate and butylated hydroxyanisole exhibited the highest concentration levels in crops. The concentration and frequency of detection of microcontaminants were lower in green bean pods than in green bean roots and leaves. Although the concentrations were generally low, the simultaneous presence of a variety of microcontaminants should be taken into consideration when assessing the risk to human health.     

Development and validation of LC-MS/MS method for the determination of Ochratoxin A and its metabolite Ochratoxin α in poultry tissues and eggs

The objective of this study was to develop a liquid chromatography tandem mass spectrometry (LC-MS/MS) method for the determination of Ochratoxin A (OTA) and Ochratoxin α (OTα) in poultry tissues and eggs. The two toxins were extracted by a mixture of acetonitrile/water, purified with a reversed phase C18 solid phase extraction column (SPE) and determined by LC-MS/MS. The LC-MS/MS method performances were evaluated in terms of linearity in solvent and in matrix (ranged from 0.5 to 15.10 µg L^?1 for OTA and from 0.60 to 17.85 µg L^?1 for OTα), limit of detection (LOD), limit of quantitation (LOQ), specificity, accuracy and precision in repeatability conditions. Recovery experiments were performed by spiking poultry liver, kidney, muscle and eggs around 1 µg kg^?1 and 10 µg kg^?1. LODs were 0.27 and 0.26 µg kg^?1 while LOQs were fixed at 1.0 and 1.2 µg kg^?1 for OTA and OTα, respectively. Main recoveries for OTA ranged from 82 to 109% and for OTα ranged from 55 to 89%. The values of within-laboratory relative standard deviation (RSD_r) were equal to or below 20%. Considering the results obtained and that all analytical performance criteria were fulfilled, the new extraction and purification method developed for OTA and OTα determination in animal tissues and eggs was found appropriate for control laboratories and research activities designed to ensure food safety.     

Development of a new polyclonal antibody for the determination of polychlorinated biphenyls in indoor air by ic-ELISA

A new polyclonal antibody (pAb) was prepared and used for the determination of polychlorinated biphenyls (PCBs) in air samples to promote the application of immunoassay technology in the determination of PCBs. Three PCB congeners immunogen mixture was used to stimulate immune responses in rabbits. The specific pAb to PCBs was obtained and used to develop an indirect competitive enzyme-linked immunosorbent assay (ic-ELISA). A standard curve for Aroclor 1248 was prepared using concentrations ranging from 0.1 to 100 μg L^?1. The average IC₅₀ value was 16.21 μg L^?1 and the limit of detection at 10 % inhibition (IC₉₀) was 0.069 μg L^?1. The entire procedure was then evaluated using spiked air samples. The recoveries of Aroclor 1248 at various spiking levels in the air samples ranged from 84 to 113 %, with relative standard deviations of 3 to 6 %. Under optimum conditions, the cross-reactivity profiles of the assays were obtained using three selected congeners, four Aroclor products, and other structurally related compounds of PCBs. The assays were found to be highly specific for PCB congeners and Aroclors 1248 and 1242. The air samples were then analyzed using gas chromatography coupled with high-resolution mass spectrometry to confirm the ic-ELISA results. The attained results demonstrated that the proposed method was an effective and inexpensive technique for the PCBs determination in air samples.     

Spontaneous revegetation vs. forestry reclamation in post-mining sand pits

Vegetation development of sites restored by two different methods, spontaneous revegetation and forestry reclamation, was compared in four sand pit mining complexes located in the southern part of the Czech Republic, central Europe. The space-for-time substitution method was applied to collect vegetation records in 13 differently aged and sufficiently large sites with known history. The restoration method, age (time since site abandonment/reclamation), groundwater table, slope, and aspect in all sampled plots were recorded in addition to the visual estimation of percentage cover of all present vascular plant species. Multivariate methods and GLM were used for the data elaboration. Restoration method was the major factor influencing species pattern. Both spontaneously revegetated and forestry reclaimed sites developed towards forest on a comparable timescale. Although the sites did not significantly differ in species richness (160 species in spontaneously revegetated vs. 111 in forestry reclaimed sites), spontaneously revegetated sites tended to be more diverse with more species of conservation potential (10 Red List species in spontaneous sites vs. 4 Red List species in forestry reclaimed sites). These results support the use of spontaneous revegetation as an effective and low-cost method of sand pit restoration and may contribute to implementation of this method in practice.     

Synthesis of novel polymer type sulfoxide solid phase combined with the porogen imprinting for enabling selective separation of polychlorinated biphenyls

We developed a novel polymer type sulfoxide-modified solid phase enabling to achieve selective separation of polychlorinated biphenyls (PCBs) from insulation oil. In this study, firstly we prepared base-polymer based on the concept of the molecular imprinting to capture PCBs in selectively, then, the sulfoxide groups were modified on the pore surface of base-polymers by changing preparation methods. As results of liquid chromatographic analyses for the polymers as columns, the base-polymer prepared by xylene as a porogenic solvent showed selective retention ability for chlorinated aromatic compounds by the porogen imprinting effect. Additionally, the polymer-type sulfoxide solid phases showed highly retention ability for PCBs by increasing amount of introduced sulfoxide groups. Consequently, the results of separation of PCBs comparing to insulation oil suggested that the prepared solid phase can be used for the selective separation of PCBs at the same level as a commercially available media utilized for the regulated method.     

A rapid method for screening of the Stockholm Convention POPs in small amounts of human plasma using SPE and HRGC/HRMS

A rapid analytical screening method allowing simultaneous analysis of 23 persistent organic pollutants (POPs) in human plasma was developed. Sample preparation based on solid-phase extraction (SPE) with additional clean-up using small multilayer silica gel columns. SPE was performed using a custom made polystyrene-divinylbenzene sorbent for the extraction of chlorinated and brominated POPs. Special efforts to reduce sample volume and improve speed and efficiency of the analytical procedure were made. Determination of 16 polychlorinated biphenyls (PCBs), 5 organochlorine (OC) pesticides, octachlorinated dibenzo-p-dioxin (OCDD) and polybrominated diphenyl ether (BDE #47) in 0.5 mL human plasma was performed by using high resolution gas chromatography coupled to high resolution mass spectrometry (HRGC/HRMS). Recovery of POPs ranged between 46% and 110%, and reproducibility was below 25% relative standard deviation (RSD) for all target compounds, except for trans-nonachlor and OCDD, which were present only at low levels. Limits of detection (LOD) were for the PCBs between 0.8 and 117.7 pg mL⁻¹ plasma and for the OC pesticides between 5.9 and 89.1 pg mL⁻¹ plasma. The LOD for OCDD and BDE #47 were 1.4 pg mL⁻¹ plasma, and 9.2 pg mL⁻¹ plasma, respectively. The presented method was successfully applied to 1016 human plasma samples from an epidemiological study on cardiovascular disease.     

Fast determination of phenoxy acid herbicides in carrots and apples using liquid chromatography coupled triple quadrupole mass spectrometry

A fast, simple and inexpensive method has been developed for the analysis of phenoxy acid herbicides: 2,4-dichlorophenoxyacetic acid (2,4-D), 4-chloro-2-methylphenoxyacetic acid (MCPA), 2-(4-chloro-o-tolyloxy)propionic acid (MCPP), 2-(4-aryloxyphenoxy)propionic acid (Fluazifop) and 2-(4-aryloxyphenoxy)propionic acid (Haloxyfop) in carrots and apples by liquid chromatography coupled to triple quadrupole mass spectrometry (LC/MS/MS). The compounds were analyzed by QuEChERS (quick, easy, cheap, effective, rugged, safe) methodology without cleanup.

The recoveries were performed at two spiked levels (0.05 and 0.5 mg/kg) for both matrices with six replicates for each level. The mean recoveries ranged from 70–92% for both apples and carrots. The precision of the method expressed as relative standard deviation (RSD%) was found to be in the range 3–15%. For all compounds, good linearity (r² > 0.99) was obtained over the range of concentration from 0.05 μ g/mL to 0.5 μ g/mL, corresponding to the pesticide concentrations of 0.05 mg/kg and 0.5 mg/kg, respectively. The determination limits (LOQs) ranged from 0.01 ng/mL to 1.3 ng/mL in solvent, whereas, the LOQs calculated in matrix ranged from 0.05 ng/g to 21.0 ng/g for apples and from 0.06 ng/g to 10.2 ng/g for carrots. The developed methodology combines the advantages of both QuEChERS and LC/MS/MS producing a very rapid, sensitive and cheap method useful for the routine analytical laboratories.     

Intervention to reduce PCBs: learnings from a controlled study of Anniston residents

Nonabsorbable dietary lipid reduces the absorption of dietary PCBs and increases the excretion of previously absorbed stored PCBs. Absorption of all PCB congeners will presumably be interrupted by nonabsorbable lipid; however excretion will be enhanced only for PCBs that have not been metabolized and also for their lipophilic metabolites. Our study with the nonabsorbable lipid, olestra, in a controlled trial in Anniston residents with elevated PCB levels demonstrated that it is possible to enhance removal of PCBs from the body in the clinically meaningful time frame of 1 year. The rate of disappearance of PCBs in participants who ate 15 g/day of olestra was significantly faster than the rate determined during the 5 years prior to intervention. The rate of disappearance was not changed from the pretrial rate in participants who ingested vegetable oil. Consideration of the role of body weight and fat is an important factor in the design of intervention trials of this kind, and the results of this trial suggest that the level of body fat in individuals will influence the rate of removal from the body. Previously reported data from animals and from a case report indicate that weight loss combined with nonabsorbable dietary lipid will maximize removal of PCBs and presumably other stored organochlorine compounds. The design of future intervention trials should include a focus on body fat levels and changes. Future trials should also include the testing of dietary compounds other than olestra that have affinity for PCBs, such as plant-derived polyphenols.     

Simultaneous Determination of Imidacloprid,Thiacloprid, and Thiamethoxam in Soil and Water by High-performance Liquid Chromatography with Diode-array Detection

Abstract

A high-performance liquid chromatography method with diode-array detection (HPLC-DAD) is described for the determination of three neonicotinoid insecticides imidacloprid, thiacloprid, and thiamethoxam in soil and water. The soil samples were extracted with acetonitrile, while the water samples were extracted using C₁₈ cartridges. The mean recoveries plus standard deviations for spiked soil samples were 82 ± 4.2% for thiamethoxam, 99 ± 4.2% for imidacloprid and 94 ± 1.4% for thiacloprid. The recoveries for water samples ranged from 87 ± 3.4% for thiamethoxam to 97 ± 3.9% for imidacloprid and 97 ± 2.6% for thiacloprid. The limits of quantitation (LOQ) were 0.1, 0.1, 0.01 mg/kg in soil (5 g), and 2, 2, 0.5 µg/L in water (50 mL) for thiamethoxam, imidacloprid, and thiacloprid, respectively.     

Effect of metal and glycol on mechanochemical dechlorination of polychlorinated biphenyls (PCBs)

This paper assesses the potential of mechanochemical method with fine metal powder, glycol and alkali for polychlorinated biphenyls (PCBs) removal from waste insulating oil. The effects of relevant parameters, such as kinds of chemicals, rate and time of milling were examined. After each run, the total PCBs content in waste insulating oil was measured. Polyethylene glycol 200, long chain-glycol was more effective than triethylene glycol and ethylene glycol, short chain-glycol as hydrogen donor in mechanochemical dechlorination of PCBs. A maximum of 99.9% PCBs removal (below 2ppm) and 94% total chlorine removal were achieved with the mechanochemical process for 2h.     

Tea bag filter paper as a novel protective membrane for micro-solid phase extraction of butachlor in aqueous samples

An innovative, cost-effective, simple, and environmental friendly tea bag filter paper protected micro-solid phase extraction (μ-SPE) technique was developed for the first time with the aim to miniaturize and minimize the use of organic solvents for the extraction and determination of butachlor in aqueous samples. The μ-SPE device was produced by packing 3.0 mg of an easily synthesized new sorbent, hydroxyl-functionalized polypyrrole (OH-PPY), inside a small tea bag filter paper sachet (1.0 cm × 0.5 cm) that served as a protective envelope. Both the extraction and desorption procedures were facilitated by sonication. Due to the high porosity and the fast water absorption of the tea bag filter paper, the analyte could easily diffuse through and enhance the interaction with the sorbent. Under the optimized conditions for the GC-ECD and the μ-SPE, the limit of detection (S/N ≥ 3) was 2.0 μg L^?1 while the limit of quantitation (S/N ≥ 10) was 10.0 μg L^?1. The recoveries of the butachlor spiked at 0.050, 0.10, and 0.50 μg mL^?1 ranged from 77.9 ± 3.0 to 112.5 ± 2.9%. The proposed method was successfully applied for the determination of butachlor in water samples from paddy cultivation sites. The levels found were from non-detectable to 24.71 ± 0.37 μg L^?1.     

Biomonitoring of polychlorinated biphenyls in Bavaria/Germany—long-term observations and standardization

In the 1980s, it was demonstrated that semi-volatile organic compounds (SVOCs) like polychlorinated biphenyls (PCBs) accumulate in plant leaves. Plants are at the base of the food chain, and therefore a starting point for transfer of PCBs to animals and related human exposure. For two decades, the Environment Agency of the German federal state of Bavaria (LfU) has been operating long-term monitoring stations to measure the impact of organic air pollutants. Standardized ryegrass, curly kale, and spruce needles are used as bioindicators for the atmospheric entries of PCBs into vegetation. From the end of 1990s to 2009, there was a marked decline in the concentrations of indicator PCBs (i-PCBs) and a minor decline in PCB-TEQ levels. After 2009, the concentrations leveled off. In rural areas, the median concentrations of Σ6 i-PCB in ryegrass and curly kale were about 3 and 4 μg/kg dm in 2000, and have been about 0.5 and 1 μg/kg dm since 2009, respectively. Concentrations in spruce needles fell from 0.9 to 0.4 μg/kg dm. Median PCB-TEQ concentrations in the bioindicator plants ranged from 0.05 to 0.23 ng/kg dm between 2002 and 2009 and from 0.15 to 0.05 ng/kg dm after 2009. Indicator PCB and PCB-TEQ concentrations were several times higher at the urban station in Munich than at the rural areas, reflecting the emissions from in-use PCB stocks in the building sector. The likely reason of the slower decrease of PCB-TEQ compared to i-PCBs is the formation of PCB-126 by dechlorination of industrial PCBs in open applications.     

Environmental PCBs in Guánica Bay,Puerto Rico: implications for community health

Guánica Bay, located in southwestern Puerto Rico, has suffered oil spills and other pollution discharges since the 1960s. Previous research showed elevated concentrations of polychlorinated biphenyls (PCBs) in coral reef and sediment. This research examined PCB concentrations in sediment and fish. Sediment and fish sampling in the bay was facilitated by community members. This study identified the second highest reported PCB level (129,300 ng/g) in sediment in the USA. Fish samples also showed elevated concentrations (1623 to 3768 ng/g), which were higher than the thresholds of safe levels of PCBs in fish for human consumption. The alarmingly high concentration of PCBs calls for proactive community engagement to bring awareness about contamination of the bay and more extensive sampling to test for the concentration of PCBs in seafood and the people of Guánica. This study also underscores the value of the involvement of local communities during sampling design aimed at identifying hot spots of contaminants.     

Determination of glyphosate residue in maize and rice using a fast and easy method involving liquid chromatography–mass spectrometry (LC/MS/MS)

A fast and easy method was developed for the determination of glyphosate in maize and rice by using liquid chromatography triple quadrupole mass spectrometry with a Dionex Ion Pack column and phosphate buffer mobile phase. Samples were extracted with an acidified methanol solution. An isotope-labeled internal standard was added to the sample before extraction to ensure accurate tracking and quantification. The method’s performance was evaluated through a series of assessments to determine the accuracy, precision, linearity, matrix effect, limit of detection (LOD), and limit of quantification (LOQ). The mean recoveries for both matrices were within 70–105% at three fortification levels, including the LOQ. The precision for replicates was <20% (RSD%) for both matrices. Good linearity (R²=0.9982) was obtained over the concentration range of 0.01–1.5?mg kg^?1. The LOD was determined to be 0.002?mg kg^?1 for rice and 0.004?mg kg^?1 for maize. The LOQ was 0.01?mg kg^?1 for both maize and rice. Due to its versatility, the proposed method could be considered useful for the determination of glyphosate in cereals in routine analysis.     

Rapid resolution liquid chromatography-tandem mass spectrometry method for the determination of endocrine disrupting chemicals (EDCs), pharmaceuticals and personal care products (PPCPs) in wastewater irrigated soils

A multiresidue analytical method was developed for the determination of 9 endocrine disrupting chemicals (EDCs) and 19 pharmaceuticals and personal care products (PPCPs) including acidic and neutral pharmaceuticals in water and soil samples using rapid resolution liquid chromatography-tandem mass spectrometry (RRLC-MS/MS). Solid phase extraction (SPE), and ultrasonic extraction combined with silica gel purification were applied as pretreatment methods for water and soil samples, respectively. The extracts of the EDCs and PPCPs in water and soil samples were then analyzed by RRLC-MS/MS in electrospray ionization (ESI) mode in three independent runs. The chromatographic mobile phases consisted of Milli-Q water and acetonitrile for EDCs and neutral pharmaceuticals, and Milli-Q water containing 0.01 % acetic acid (v/v) and acetonitrile: methanol (1:1, v/v) for acidic pharmaceuticals at a flow rate of 0.3 mL/min. Most of the target compounds exhibited signal suppression due to matrix effects. Measures taken to reduce matrix effects included use of isotope-labeled internal standards, and application of matrix-match calibration curves in the RRLC-MS/MS analyses. The limits of quantitation ranged between 0.15 and 14.08 ng/L for water samples and between 0.06 and 10.64 ng/g for solid samples. The recoveries for the target analytes ranged from 62 to 208 % in water samples and 43 to 177 % in solid samples, with majority of the target compounds having recoveries ranging between 70–120 %. Precision, expressed as the relative standard deviation (RSD), was obtained less than 7.6 and 20.5 % for repeatability and reproducibility, respectively. The established method was successfully applied to the water and soil samples from four irrigated plots in Guangzhou. Six compounds namely bisphenol-A, 4-nonylphenol, triclosan, triclocarban, salicylic acid and clofibric acid were detected in the soils.