Phthalates and other organic chemicals in agricultural soils after use of different types of conventional and biodegradable plastics.

Various plastic materials are used in contact with agricultural soil, like mulching films, crop covers, weed controlling fabrics and nets. Polyethylene (PE) mulches have already been recognized as a significant source of plastic in soil and they have been shown to contain additives like phthalates, known as endocrine disruptors. However, other agricultural plastics are less studied, and little is known on the substances potentially released from them endangering biodiversity and the human health. This research aims to assess whether different agricultural plastics release additives into soil and to compare the release among various materials. We collected soil samples from 38 agricultural fields where conventional mulching films (PE), weed controlling fabrics (PP), biodegradable mulches based on polybutylene adipate terephthalate (PBAT), frost covers (PP), and oxo-degradable films (at least OXO-PE) were used. We analyzed the soils for phthalates and acetyl tributyl citrate (ATBC), used as plastic additives, and for polycyclic aromatic hydrocarbons (PAH) and dodecane that have high affinity for plastics. In comparison to the control soils, dibutylphthalate (DBP) and ATBC concentrations were significantly higher in soils mulched with PE and, partly, with biodegradable films. DBP concentration found in soil samples ranged between below the limit of quantification at a control site (1.5 µg kg-1) to 135 µg kg-1 at a site mulched with OXO-PE. The highest ATBC concentration, 22 ± 6 µg kg-1, was registered in a site mulched with PE, showing a statistically significant difference not only in comparison to the controls but also when compared to sites mulched with OXO-PE (p = 0.029) and PBAT (p < 0.009). On the contrary, the use of agricultural plastics did not influence the concentration of PAHs and dodecane. Our results indicate that agricultural plastics are a source of some organic chemicals to agricultural soils, including phthalates that are known for posing threat to soil ecosystem and human health.

Human papillomavirus self-sampling with mRNA testing benefits routine screening.

High risk human papillomavirus (hrHPV) based screening provides the possibility of vaginal self-sampling as a tool to increase screening attendance. In order to evaluate the impact and feasibility of opt-in self-sampling in the Finnish setting, we invited a randomized population of 5350 women not attending screening after age group invitation or after reminder, to attend HPV self-sampling-based screening in the autumn of 2018 in Helsinki. Out of those, 1282 (24.0%) expressed their interest and ordered the sampling package. Eventually 787 women (14.7% of the total invited population) took part in screening, 770 women by providing a vaginal sample within 2 months from invitation and 17 by providing a pap smear in the laboratory. Self-taken samples were collected in Aptima Multitest vials and tested using the Aptima HPV mRNA assay. A high proportion, 158/770 (20.5%) of the samples were positive in the Aptima HPV assay. One hundred and forty-one samples were further submitted to Aptima HPV Genotyping and extended genotyping by a Luminex based assay. Of those, 23 samples (16.3%) were HPV 16 positive and 7 (5.0%) were positive for HPV 18/45; extended genotyping revealed multiple high-risk and low-risk HPV genotypes. At follow-up seven cases of high-grade squamous intraepithelial lesion (HSIL) were diagnosed, which represents 4.4% of HPV positive women and 0.9% of screened women, whereas the rate was 0.5% in routine screening. Our findings suggest that self-sampling with HPV mRNA testing is a feasible approach to improve screening efficacy in a high-risk population among original nonattendees.

Hazardous contaminants in plastics contained in compost and agricultural soil.

Macro-, meso- and microplastic (MAP, MEP, MP) occurrence in compost is an environmental issue whose extent and effects are not yet understood. Here, we studied the occurrence of MAPs, MEPs and MPs in compost samples, and the transfer of hazardous contaminants from plastics to compost and soil. MAPs/MEPs and MPs concentrations in compost were 6.5 g/kg and 6.6 ± 1.5 pieces/kg; from common recommendations for compost application, we estimated ∼4-23 × 107 pieces MPs and 4-29 × 104 g MAPs/MEPs ha-1 per year ending into agricultural soils fertilized with such compost. Regarding contaminants, bis(ethylhexyl) phthalate, acetyl tributyl citrate, dodecane and nonanal were extracted in higher concentrations from plastics and plastic-contaminated compost than from compost where MAPs/MEPs had been removed prior to extraction and analysis. However, some contaminants were present even after MAPs/MEPs removal, ascribable to short- and long-term release by MAPs/MEPs, and to the presence of MPs. DEHP concentration was higher in soils where compost was applied than in fields where it was not used. These results, along with estimations of plastic load to soil from the use of compost, show that compost application is a source of plastic pollution into agricultural fields, and that plastic might transfer hazardous contaminants to soil.

Occurrence and characterization of microplastic and mesoplastic pollution in the Migliarino San Rossore, Massaciuccoli Nature Park (Italy).

Microplastics pollution is progressively threatening natural parks across the world. In the framework of monitoring this concerning trend, the present study focuses on the occurrence and identification of mesoplastics (MEPs) and microplastics (MPs) in sand samples collected before and after the summer season from the beach of the Nature Park of Migliarino San Rossore Massaciuccoli (Pisa, Italy). Meso- and microplastics were identified using Fourier transform infrared spectroscopy 2D Imaging, and detected in all samples with average concentrations of 207 ± 30 MPs/kg d.w., and 100 ± 44 MEPs/kg d.w., respectively. Seasonal changes of flow of the Arno River, industrial activities, and urban footprint were considered as the major sources of plastic pollution. Our results showed the occurrence of both natural and synthetic polymers including cellulose, polyethylene, polypropylene, polyamides, polyethylene terephthalate, and acrylonitrile.

Olive oil-based method for the extraction, quantification and identification of microplastics in soil and compost samples.

Microplastics (MPs) have become a pressing environmental concern over the past few years and their extraction from solid samples is a scientific challenge that needs to be faced and solved. Standardized and validated protocols for MPs extraction are lacking and the existing methodology, such as density separation, is often unable to separate high density polymers. The aim of our research was to develop a non-density based, inexpensive, simple and safe method to extract MPs from soil and compost samples. We tested an oil-based extracting technique exploiting the oleophilic properties of plastics. For validating the method, soil and compost samples were spiked with six different micro-polymers: polyethylene, polystyrene, polyvinyl chloride, polycarbonate, polyethylene terephthalate and polyurethane. The obtained results are promising, and the polymer density had only a small role in the recovery rate: low, medium and high density polymers reached a mean recovery rate of 90% ±2%, 97% ± 5% and 95% ± 4%, respectively.

Monitoring cell-specific neutral lipid accumulation in Phaeodactylum tricornutum (Bacillariophyceae) with Nile Red staining - a new method for FlowCAM.

With the fluorescent stain Nile Red (NR), phytoplankton lipid accumulation can be monitored quickly and in situ. In the light of recent results in phytoplankton diversity research, there is also a need for cell- and species-specific lipid measurement techniques. The objective of this work was to investigate whether cell-specific phytoplankton lipid accumulation could be monitored with the image-based particle analyzer FlowCAM™ and NR staining. Applying Phaeodactylum tricornutum as a model species, we compared the FlowCAM method to two established lipid quantification methods: spectrofluorometric NR fluorescence measurement and total lipid analysis by gas chromatography. The experiment was carried out in batch cultures under nitrogen limitation to induce lipid accumulation. We showed significant correlation between the three different lipid quantification methods confirming the applicability of the novel FlowCAM method in cell-specific and near real-time lipid quantification. Furthermore, with the method described here, the lipid content of taxonomically distinguished cells can eventually be measured from multispecies cultures, opening several new possibilities to study species-specific responses to stress conditions and the complementarity effect.

Challenge of paediatric compounding to solid dosage forms sachets and hard capsules - Finnish perspective.

OBJECTIVES: The study evaluated the quality of compounded sachets and hard gelatine capsules and their feasibility in paediatric drug administration. METHODS: Commercial tablets were compounded to sachets and capsules in hospital environment, and the uniformity of content and simulated drug dose were determined. KEY FINDINGS: Compounded formulations were successfully obtained for a range of drug substances; dipyridamole, spironolactone, warfarin and sotalol formulations were within acceptable limits for uniformity of content, in most cases. However, some loss of drug was seen. The type and amount of excipients were found to affect uniformity of content; good conformity of capsules was obtained using lactose monohydrate as filler, whereas microcrystalline cellulose was a better choice in sachets. In capsules, content uniformity was obtained for a range of drug doses. If the drug is aimed to be administered through a nasogastric tube, solubility of the drug and excipients should be considered, as they were found to affect the simulated drug dose in administration. CONCLUSIONS: Compounded sachets and capsules fulfilled the quality requirements in most cases. In compounding, the choice of excipients should be considered as they can affect conformity of the dosage form or its usability in practice. Quality assurance of compounded formulations should be taken into consideration in hospital pharmacies.

Identification of organic xenobiotics in urban aquatic environments using time-of-flight mass spectrometry.

Qualitative non-target and post-target analysis methods using gas chromatography-time-of-flight mass spectrometry were applied for analysing neutral and acidic organic xenobiotics in urban and suburban water samples. Ten water samples representing wastewater, stormwater and surface water matrices were collected and concentrated using solid phase extraction. Compound identification was performed using a spectral deconvolution program, accurate mass measurements and comparisons with library spectra. The non-target and post-target analyses identified 36 and 18 compounds, respectively. The identification of 10 compounds was afterwards confirmed with standard compounds. Organophosphate esters were the most abundant compound group detected. The combination of non-target and post-target analyses proved a useful tool in the tentative identification of xenobiotics in water samples. Post-target analysis can complement non-target analysis results at low analyte concentrations. Results showed that several organic xenobiotics originate in urban areas and accumulate in the environment. The wastewater sample produced the highest number of identified compounds, but most of these compounds were also found in stormwater samples from the city centre. Nearly all the compounds present in wastewater were additionally detected in the surface water sample taken 3 km downstream from the wastewater effluent discharge point. Only a few xenobiotics were otherwise detected in the surface water samples.

Qualitative nontarget analysis of landfill leachate using gas chromatography time-of-flight mass spectrometry.

Nontarget analysis means that a sample is analysed without preselection of the studied analytes. While target analysis attempts to determine whether certain selected compounds are present in the sample, nontarget analysis is performed to explore what unknown compounds can be found. We developed a nontarget method using a landfill leachate sample as a complex test sample. The method was based on the use of a gas chromatograph-time-of-flight mass spectrometer (GC-TOF-MS) for final analysis and a deconvolution computer application for data processing. This nontarget analysis method was tested and validated by applying it to a landfill leachate sample spiked with 11 organic pollutants that were treated as unknowns. Sensitivity was found to be the most critical parameter affecting the success of nontarget analysis. The limit of identification (LOI) was 2500 ng L(-1) for four of the 11 compounds, 500 ng L(-1) for three compounds and 100 ng L(-1) for one compound. Three compounds were not detected in any of the spiked samples. A six-stage identification process was developed based on the spiking experiments. The process was based on the forward fit value of the library hit, the number of deconvoluted ions and the accurate mass scoring of the measured ions. The process was applied to an unspiked leachate water sample. Altogether, 44 compounds were tentatively identified in the sample. Elemental compositions of 36 components were additionally determined for which an unequivocal compound identification could not be given. Nontarget analysis with GC-TOF-MS is a promising method for the qualitative analysis of complex water samples. However, we conclude that the computer application for nontarget analysis needs improvement to decrease the amount of manual work needed in the identification process.

Critical evaluation of screening techniques for emerging environmental contaminants based on accurate mass measurements with time-of-flight mass spectrometry.

Emerging contaminants from wastewater effluent samples were analysed, using posttarget and nontarget analysis techniques. The samples were analysed with an ultra performance liquid chromatograph-time-of-flight mass spectrometer (UPLC-TOF-MS), and the resulting data were processed with commercial deconvolution software. The method works well for posttarget analysis with prior information about the retention times of the compounds of interest. With positive polarity, 63 of 66 compounds and with negative polarity, 18 of 20 compounds were correctly identified in a spiked sample, while two compounds of a total of 88 fell out of the mass range. Furthermore, a four-stage process for identification was developed for the posttarget analysis lacking the retention time data. In the process, the number of candidate compounds was reduced by using the accurate mass of selected compounds in two steps (stages 1 and 2), structure-property relationships (stage 3) and isotope patterns of the analytes (stage 4). The process developed was validated by analysing wastewater samples spiked with 88 compounds. This procedure can be used to gain a preliminary indication of the presence of certain analytes in the samples. Nontarget analysis was tested by applying a theoretical mass spectra library for a wastewater sample spiked with six pharmaceuticals. The results showed a high number of false identifications. In addition, manual processing of the data was considered laborious and ineffective. Finally, the posttarget analysis was applied to a real wastewater sample. The analysis revealed the presence of six compounds that were afterwards confirmed with standard compounds as being correct. Three psycholeptics (nordiazepam, oxazepam and temazepam) could be tentatively identified, using the identification process developed. Posttarget analysis with UPLC-TOF-MS proved to be a promising method for analysing wastewater samples, while we concluded that the software for nontarget analysis will need improvement before it can be used in environmental analytical work with LC-TOF-MS systems.

Multiresidue method for the analysis of emerging contaminants in wastewater by ultra performance liquid chromatography-time-of-flight mass spectrometry.

A multiresidue method for screening of emerging contaminants in aquatic environments was developed. The method was based on sample pretreatment with solid phase extraction (SPE) and analysis with an ultra performance liquid chromatograph-time-of-flight mass spectrometer (UPLC-TOF-MS). The method was optimized and tested with standard solutions of model compounds containing 84 pesticides and pharmaceuticals. Four different SPE sorbents were evaluated to gain maximum recovery for the analytes. For the final procedure a combination of two different sorbents was chosen. In spite of high matrix suppression, the method quantification limits (MQLs) were acceptable. Therefore, the method can be used for screening known target compounds. The applicability of the method for posttarget and nontarget screening will be reported later. To preliminarily assess the quantitative performance of the method, some compounds in wastewater effluent were quantified using the standard addition method. Three pesticides and eight pharmaceuticals were found in concentrations up to ∼2200 ng/L.

Organochlorine concentrations in the Saimaa ringed seal (Phoca hispida saimensis) from Lake Haukivesi, Finland, 1981 to 2000, and in its diet today.

Organochlorine and mercury (Hg) pollution has been one possible reason for a decline in the size of the population of the Saimaa ringed seal (Phoca hispida saimensis) in Lake Haukivesi, Finland. In this study, we analyzed changes in the concentrations of organochlorine compounds (OCls) and extractable organic halogen (EOX) in the blubber of Saimaa ringed seals that died from 1981 to 2000. In addition, the present concentrations and biomagnification factors of OCls and Hg from the main prey fish of ringed seal and pike (Esox lucius) were determined. Concentrations of pollutants in bream (Abramis brama) also were analyzed. The decline in the OCl concentrations in blubber was, on average, 25% during the two decades since polychlorinated biphenyls and DDT compounds were banned. Today, concentrations in blubber of Saimaa ringed seals are similar of those in ringed seals from the Arctic. Correspondingly in fish, the OCl and Hg concentrations were, on average, similar to those found in other studies on Finnish and Arctic areas. The low diet concentrations and metabolism of OCls also reflect the lower age correlation of OCls in the male ringed seals in the 1990s than in the 1980s. Biomagnification was considerably higher from fish to the ringed seal than from prey fish to pike because of higher feeding rate of ringed seals and differences in the metabolisms of these animals.

Diagnostic accuracy of acute maxillary sinusitis in adults in primary care.

OBJECTIVE: To evaluate the diagnostic value of symptoms and signs used in diagnosing acute community-acquired maxillary sinusitis (ACAMS), and to find useful clinical predictors for diagnosing it in adults in primary care. DESIGN: Prospective study in the study group and retrospective study in the reference group. SETTING: One primary care centre in the study group and another in the reference group. SUBJECTS: 50 adults with prolonged upper respiratory tract infection > or = 7 days) or self-suspected maxillary sinusitis. As a reference group, an analysis of records and diagnoses made by GP of 45 adult patients with the same inclusion criteria from another primary care clinic. MAIN OUTCOME MEASURES: The signs and symptoms associated with the diagnosis of ACAMS by GP and otorhinolaryngologist. The value of CRP, ultrasound and peak nasal expiratory flow in the diagnosis. RESULTS: Neither ultrasound nor any of the clinical signs increased the accuracy of diagnosis. Peak nasal expiratory flow below the normal range was associated with the diagnosis of ACAMS (p = 0.03). The presence of an otorhinolaryngologist had an influence on GP practice when compared with the reference group. CONCLUSION: The diagnosis of ACAMS is difficult with the available clinical methods. Peak nasal expiratory flow needs further study. New diagnostic means are needed.