Gas–particle partitioning of persistent organic pollutants in the Western Balkan countries affected by war conflicts

Background, aim, and scope  

Bombing and destruction of the industrial and military targets accompanied by complete or incomplete combustion during the war conflict and NATO operation in former Yugoslavia caused the emission of persistent organic pollutants into the atmosphere, water, and soil. A total of 129 ambient air samples from 24 background, urban, and industrial sites, including hot spots, were collected to assess a gas–particle partitioning behavior of various persistent organic pollutants.     

Chemical composition of atmospheric precipitation in Czechoslovakia, 1976–1984—I. Monthly samples

The results of chemical analyses of monthly atmospheric precipitation samples from 12 stations within Czechoslovakia are presented. The sampling at the station with the longest record (Hrádek u Pacova, 80 km SE from Prague) covers 9 years. There is no clear regional pattern within the sampled territory, but a spring maximum was observed for most components. For SO₄⁻² and acidity a downward trend was indicated. Statistical analyses show that the important sources of mineralization of precipitation water are (in order of importance): coal combustion; sea spray; terrigenous dust; car exhaust; cement production; “European background” sulphur.     

The photochemical formation and gas–particle partitioning of oxidation products of decamethyl cyclopentasiloxane and decamethyl tetrasiloxane in the atmosphere

Decamethyl cyclopentasiloxane (D₅) and decamethyl tetrasiloxane (MD₂M) were injected into a smog chamber containing fine Arizona road dust particles (95% surface area <2.6 μM) and an urban smog atmosphere in the daytime. A photochemical reaction – gas–particle partitioning reaction scheme, was implemented to simulate the formation and gas–particle partitioning of hydroxyl oxidation products of D₅ and MD₂M. This scheme incorporated the reactions of D₅ and MD₂M into an existing urban smog chemical mechanism carbon bond IV and partitioned the products between gas and particle phase by treating gas–particle partitioning as a kinetic process and specifying an uptake and off-gassing rate. A photochemical model PKSS was used to simulate this set of reactions. A Langmuirian partitioning model was used to convert the measured and estimated mass-based partitioning coefficients (K_P) to a molar or volume-based form. The model simulations indicated that >99% of all product silanol formed in the gas-phase partition immediately to particle phase and the experimental data agreed with model predictions. One product, D₄TOH was observed and confirmed for the D₅ reaction and this system was modeled successfully. Experimental data was inadequate for MD₂M reaction products and it is likely that more than one product formed. The model set up a framework into which more reaction and partitioning steps can be easily added.     

Review of advances in the thin layer chromatography of pesticides: 2004–2006

Applications of thin layer chromatography and high performance thin layer chromatography for the separation, detection, and qualitative and quantitative determination of pesticides, other agrochemicals, and related compounds are reviewed for the period from July 1, 2004 to November 1, 2006. Analyses are covered for a variety of samples, such as food, crops, biological, environmental, pharmaceuticals, and formulations, and for residues of pesticides of various types, including insecticides, herbicides, and fungicides, belonging to different chemical classes. In addition to references on residue analysis, studies such as pesticide-structure relationships, metabolism, degradation, and lipophilicity are covered, many of which make use of thin layer radiochromatography.     

Review of advances in the thin layer chromatography of pesticides: 2008–2010

Techniques and applications of thin layer chromatography (planar chromatography) for the separation, detection, qualitative and quantitative determination, and preparative isolation of pesticides and their metabolites and other related compounds are reviewed for the period from November 1, 2008 to November 1, 2010. Analyses are described for a variety of samples types and pesticide classes. In addition to references on residue analysis, studies such as pesticide structure-retention relationships, identification and characterization of plant pesticides and synthesized pesticides, metabolism, degradation, mobility, identification of biomarkers for detection of herbicide effects in plants, and lipophilicity are covered.     

Review of advances in the thin layer chromatography of pesticides: 2012–2014

Publications reporting techniques and applications of thin layer chromatography (planar chromatography) for the separation, detection, qualitative, and quantitative determination, and preparative isolation of pesticides and their metabolites are reviewed for the period from November 1, 2012 to November 1, 2014. Analyses are described for a variety of sample types and pesticide classes. In addition to references on residue analysis, studies such as pesticide structure – retention relationships, identification and characterization of natural and synthesized pesticides, metabolism, bioactivity, degradation, soil mobility, and lipophilicity are covered.     

Review of advances in the thin layer chromatography of pesticides: 2006–2008

Applications of thin layer chromatography and high performance thin layer chromatography for the separation, detection, qualitative and quantitative determination, and preparatire isolation of pesticides and their metabolites are reviewed for the period from July 1, 2006 to November 1, 2008. Analyses are described for a variety of sample types and pesticide classes. In addition to references on residue and formulation analysis, studies such as pesticide-structure relationships, identification and characterization of plant pesticides, metabolism, degradation, mobility, and lipophilicity are covered. Future prospects for pesticide thin layer chromatography are also considered.     

The effect of water on gas–particle partitioning of secondary organic aerosol. Part I: α-pinene/ozone system

The effect of relative humidity (RH) on aerosol formation by the semi-volatile oxidation products of the α-pinene/O₃ system has been comprehensively studied. Experiments were performed in the presence of ammonium sulfate (aqueous, dry), ammonium bisulfate seed (aqueous, dry), and aqueous calcium chloride seed aerosols to ascertain their effect on the partitioning of the oxidation products. The yield of organic aerosol varies little with RH, and is not affected by the presence of dry inorganic salt aerosols. Aqueous salt aerosols reduce the yield of organic aerosol compared to that under seed-free or dry seed conditions. The degree of reduction is electrolyte dependent, with aqueous ammonium sulfate leading to the largest reduction and aqueous calcium chloride the smallest. Hygroscopic growth of the organic aerosol from <2% to 85% RH was also monitored, and could be satisfactorily represented as the sum of the individual contributions of the organic and inorganic fractions. The implications of the growth factor measurements for concentration/activity relationships of the condensed phase organic material (assuming a liquid solution) was explored. The formation of the organic aerosol was investigated using a simple two component model, and also one including the 12 product compounds identified in a previous study. The experimental results for <2% and 50% RH (without salt seed aerosols) could be satisfactorily predicted. However, the aqueous salt seed aerosols are predicted to increase the overall yield due to the dissolution of the organic compounds into the water associated with the seed aerosol—the opposite effect to that observed. The implications of two distinct phases existing the aerosol phase were investigated.     

Influence of usage and chemical–physical properties on the atmospheric transport and deposition of pesticides to agricultural regions of Manitoba,Canada

This study quantified the masses of 14 pesticides deposited as wet (precipitation) versus dry (gaseous and particle) atmospheric deposition at a research farm in southwestern Manitoba, Canada. The concentration in air of these pesticides was also measured. Total bulk deposition amounts (wet + dry) ranged from 0.009 to 2.3 μg m^?2 for the 12 pesticides detected, and for the six pesticides with both wet and dry deposition detections, dry deposition contributed 12–51% of the total deposition over the crop growing season. Although not applied at the site, eight herbicides registered for use in Canada, as well as lindane (γ-HCH), were all frequently detected (92–100%) in the 12 air samples analyzed during the crop growing season, with by-product isomer α-HCH (75%), clopyralid (50%) and atrazine (8%) detected to a lesser extent. The chemical’s physicochemical properties and the relative mean mass of each agricultural pesticide applied in the province of Manitoba and in a 13 km radius were significant parameters in explaining the trends in the concentrations of pesticides detected in our samples. The important contribution of dry deposition to total pesticide deposition warrants greater attention in arid and semi-arid areas such as the Prairie Region of Canada, also because under a changing climate this region is estimated to experience more severe droughts while the more favorable conditions predicted for pest infestations could lead to increased pesticide applications in agricultural and urban areas.     

Urban–rural differences in atmospheric mercury speciation

Measurements of gaseous elemental mercury (GEM), particulate mercury (Hg_p), and reactive gaseous mercury (RGM) were concurrently recorded at an urban site in Detroit and a rural site in Dexter, both in Michigan for the calendar year 2004. Their average concentrations (±standard deviation) for the urban area were 2.5 ± 1.4 ng m^?3, 18.1 ± 61.0 pg m^?3, and 15.5 ± 54.9 pg m^?3, respectively, while their rural counterparts were 1.6 ± 0.6 ng m^?3, 6.1 ± 5.5 pg m^?3, and 3.8 ± 6.6 pg m^?3, respectively. The medians of urban-to-rural ratios of Hg concentrations indicate approximately 1-fold, 2-fold, and 3-fold gradients between Detroit and Dexter for GEM, Hg_p, and RGM, respectively. The urban–rural differences in Hg also varied considerably on different temporal scales and with wind flow patterns, which was most evident in RGM. Our results show that while Hg at both sites was impacted by regional sources, meteorological conditions, and photochemical transformations, the extent of variations in the observed urban-to-rural gradients, particularly in RGM, cannot be fully accounted for by these processes. Both analyses of the annual data and case studies indicate that the more variable and episodic nature of Hg, particularly RGM, seen in Detroit compared with Dexter, was the result of direct impact from local anthropogenic sources.     

The effect of water on gas–particle partitioning of secondary organic aerosol: II. m-xylene and 1,3,5-trimethylbenzene photooxidation systems

An investigation of the effect of relative humidity on aerosol formation from m-xylene and 1,3,5-trimethylbenzene photooxidation is reported. Experiments were performed in the presence and absence of ammonium sulfate seed particles (both aqueous and dry) to ascertain the effect of partitioning of oxidation products into a strong electrolytic solution or onto dry crystalline seed particles. In marked contrast to the α-pinene/ozone system, the final measured secondary organic aerosol yield was unaffected by the presence of gas-phase or liquid-phase water at relative humidities (RH) up to 50%. The hygroscopic nature of the aerosol generated upon photooxidation of m-xylene and 1,3,5-trimethylbenzene was examined; the hygroscopicity of the aerosol at 85% RH for both parent organics increased with the extent of the reaction, indicating that the first-generation oxidation products undergo further oxidation. Limited identification of the gas- and aerosol-phase products of m-xylene and 1,3,5-trimethylbenzene photooxidation is reported. It is evident that a more complete molecular identification of aromatic photooxidation aerosol awaits analytical techniques not yet brought to bear on this problem.     

The spatial–temporal chemical footprint of pesticides in China from 1999 to 2018

Environmental Science and Pollution Research - The massive use of pesticides brings considerable environmental and human health impacts. This study conducted an overall assessment of the ecological...     

Assessment of GC–MS response of selected pesticides in apple matrices related to matrix concentration

A uniform analyte response is required for GC–MS analysis in order to obtain acceptable quantitative results. The response of pesticides in complex matrices is susceptible to variation due to the interactions of co-extractives, both with pesticides or with GC–MS system. This study was conducted to determine the magnitude of the interactions, called matrix effect, and their behavior with the matrix dilution. The response of pyrimethanil (4,6-dimethyl-N-phenylpyrimidin-2-amine), cyprodinil (4-cyclopropyl-6-methyl-N-phenylpyrimidin-2-amine), trifloxystrobin (methyl-(2Z)-2-methoxyimino-2-[2-[[(E)-1-[3(trifluoromethyl)phenyl]ethylidene amino]oxymethyl]phenyl]acetate) and bifenthrin(2-methyl-3-phenylphenyl)methyl-3-[(Z)-2-chloro-3,3,3-trifluoroprop-1-enyl]-2,2-dimethylcyclopropane-1-carboxylate), used in apple crops protection, was evaluated in different concentrations of peel and flesh extracts of Granny Smith, Golden Delicious and Demi Rouge, selected as representatives of different matrix types. The matrix effect ranged from ?0.05 to 146.14%, depending on matrix type and pesticide. The highest response variation was observed in extracts of Granny Smith—an enhancement in flesh and suppression in peel extract. With the dilution, the matrix effect decreased with different magnitudes, but for Granny Smith peel extract an inverted effect was observed. The presence of the matrix effect in GC–MS pesticides analysis was obvious, requiring the application of matrix-matched calibration in quantification procedures for each variety, with calibration standards matched by the matrix concentration.     

Determination of aliphatic and polycyclic aromatic hydrocarbons in atmospheric particulate samples of a coruña city (Spain)

The hydrocarbon composition of atmospheric particulate matter from A Coruña city (Northwest Spain) has been studied. TSP (total suspended particulate) and PM₁₀ (particulate matter with aerodynamic diameter <10 µm) samples were taken over 7 and 4 months at two stations located in residential and industrial sectors of A Coruña city, respectively. The levels of hydrocarbons found in atmospheric particulate samples of A Coruña city are higher than the ones found in other cities over the world. Ratios between the analysed compounds and their sources were established. Both anthropogenic and biogenic origins were found.     

Determination of picogram quantities of chlortoluron in soil samples by luminol–chitosan chemiluminescence system

Based on the enhancing effect of chitosan (CS) on luminol-dissolved oxygen chemiluminescence (CL) reaction, a flow injection (FI) luminol–CS CL system was established. It was found that the increase of CL intensity was proportional to the concentrations of CS ranging from 0.7 to 10.0 μmol l^?1. In the presence of chlortoluron (CTU), the CL intensity of luminol–CS system could be obviously inhibited and the decrements of CL intensity were linearly proportional to the logarithm of CTU concentrations ranging from 0.01 to 70.0 ng ml^?1, giving the limit of detection 3.0 pg ml^?1 (3σ). At a flow rate of 2.0 ml min^?1, the whole process including sampling and washing could be accomplished within 36 s, offering a sample throughput of 100 h^?1. The proposed FI–CL method was successfully applied to the determination of CTU in soil samples with recoveries ranging from 95.0 % to 105.3 % and the relative standard deviations (RSDs) of less than 4.0 %.     

Organochlorine pesticides and polychlorinated biphenyls in soil and water samples in the Northeastern part of São Paulo State,Brazil

Detailed analyses of persistent organic pollutants (POPs) such as organochlorine pesticides (OCPs), hexachlorocyclohexane (HCH) isomers (HCHs), dichlorodiphenyltrichloro ethane (DDT) and its metabolites (DDTs) and congeners of polychlorinated biphenyls (PCBs) in soil and surface water from the northeastern São Paulo, Brazil allowed the evaluation of the contamination status, distribution and possible pollution sources. The pesticides and PCBs demonstrated markedly different distributions, reflecting different agricultural, domestic and industrial usage in each region studied. The ranges of HCH, DDT, and PCBs concentrations in the soil samples were 0.05–0.92, 0.12–11.01, 0.02–0.25 ng g⁻¹ dry wt, respectively, and in the surface water samples were 0.02–0.6, 0.02–0.58 and 0.02–0.5 ng l⁻¹, respectively. Overall elevated levels of DDT and PCB were recorded in region 2, a site very close to melting, automotive batteries industries, and agricultural practice regions. High ratios of metabolites of DDT to DDT isomers revealed the recent use of DDT in this environment. The sources of contamination are closely related to human activities, such as domestic and industrial discharge, street runoff, agricultural pesticides and soil erosion, due to deforestation as well as atmospheric transport.     

Organochlorine pesticides and polychlorinated biphenyls in soil and water samples in the Northeastern part of São Paulo State, Brazil

Detailed analyses of persistent organic pollutants (POPs) such as organochlorine pesticides (OCPs), hexachlorocyclohexane (HCH) isomers (HCHs), dichlorodiphenyltrichloro ethane (DDT) and its metabolites (DDTs) and congeners of polychlorinated biphenyls (PCBs) in soil and surface water from the northeastern São Paulo, Brazil allowed the evaluation of the contamination status, distribution and possible pollution sources. The pesticides and PCBs demonstrated markedly different distributions, reflecting different agricultural, domestic and industrial usage in each region studied. The ranges of HCH, DDT, and PCBs concentrations in the soil samples were 0.05–0.92, 0.12–11.01, 0.02–0.25 ng g⁻¹ dry wt, respectively, and in the surface water samples were 0.02–0.6, 0.02–0.58 and 0.02–0.5 ng l⁻¹, respectively. Overall elevated levels of DDT and PCB were recorded in region 2, a site very close to melting, automotive batteries industries, and agricultural practice regions. High ratios of metabolites of DDT to DDT isomers revealed the recent use of DDT in this environment. The sources of contamination are closely related to human activities, such as domestic and industrial discharge, street runoff, agricultural pesticides and soil erosion, due to deforestation as well as atmospheric transport.