Multivariate cluster analysis as a versatile tool for the quality assessment of short chain chloroparaffin quantification in environmental samples

The compositions of commercially available solutions of short chain chlorinated paraffins (SCCP) and technical mixtures were determined by high resolution gas chromatography (HRGC) electron capture negative ionisation (ECNI) combined with low resolution mass spectrometry (LRMS). Differences and similarities in the relative distribution of congeners and homologues were investigated by cluster analysis. Samples could be separated into two groups/clusters with similar molecular mass, chlorination degree and congener pattern. With the exception of one sample, the use of CH4-ECNI-MS led to an overestimation of the chlorine content. Moreover, the influence of different SCCP mixtures on the quantification was studied. The results showed that small differences in the chlorine content could sometimes cause substantial systematic errors of up to 119% despite similar homologue and congener patterns. Errors of quantification corresponded to the deviations between response factors of sample and standard. As a consequence SCCPs should be quantified with a standard matching the overall response factor of the sample.     

PCDDs, PCDFs and dioxin-like PCBs in food of animal origin (Slovakia)

The levels of 17 toxic polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and 12 non-ortho and mono-ortho polychlorinated biphenyls (PCBs) in 73 foodstuff samples of animal origin collected from shops and small farms in selected districts of Slovak Republic are presented in this paper. The concentrations expressed as WHO-TEQ in analysed samples ranged for PCDDs/PCDFs from 0.25 pg/g fat in pork to 75 pg/g fat in cod liver. The TEQ concentrations of non-ortho PCBs were between 0.007 and 181 pg/g fat and mono-ortho PCBs between 0.0083 and 66.5 pg/g fat. The mean concentrations in freshwater fish and imported species of marine fish were 0.089 pg TEQ/g fresh weight for PCDDs/PCDFs, 0.17 pg TEQ/g fresh weight for non-ortho PCBs and 0.034 pg TEQ/g fresh weight for mono-ortho PCBs. The mean total concentration of PCDDs/PCDFs and dioxin-like PCBs in samples of infant milk formula imported from EU countries was 0.98 pg TEQ/g fat.     

A worldwide survey of polychlorinated dibenzo-p-dioxins, dibenzofurans, and related contaminants in butter

The main source of human exposure to persistent organic pollutants (POPs) is, in general, food. In this study, 64 butter samples from 37 countries were analyzed to assess the global contamination of polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs), biphenyls (PCBs), hexachlorobenzene (HCB), and 2,2-bis (4-chlorophenyl)-1,1,1-trichloroethane (DDT) together with its major metabolites. The objectives of the study were to assess the presence of major organohalogen contaminants in butter, to trace geographical differences, and to determine toxic equivalents (TEQs) of PCDDs/Fs and dioxin-like PCBs in butter. The highest PCDD/F concentrations were found in butter from Korea with an average of 1.4 pg TEQ g(-1) lipid weight (l.w.). from PCDD/F and an additional contribution from the non- and mono-ortho-PCBs of 0.55 pg TEQ g(-1) l.w. Belgian butter showed average levels of 0.53 and 1.2 pg TEQ g(-1) l.w. for PCDDs/Fs and PCBs, respectively, but one sample of Belgium butter had a total TEQ level as high as 4.0 pg TEQ g(-1) l.w. Three out of five butter samples from Portugal showed similarly high PCDD/F TEQ levels. The sigmaPCB levels in European butter appeared to be somewhat higher than in the samples from the rest of the world. The average contribution of CB-153 to the total PCB concentration was 22% (SD 6.4, coefficient of variation 29%). Generally, the PCBs contributed around 60% of the total TEQ value, with CB-126 contributing approximately half of this value. This shows the important TEQ contribution from dioxinlike PCBs to the total TEQs. The highest HCB levels were found in butter samples from Russia, Ukraine, Belgium, and Slovenia. Low levels of HCB in butter were generally found in the Southern Hemisphere. Butter samples from countries from Eastern Europe had elevated sigmaDDT concentrations, with a particularly high concentration in Ukraine butter, followed by some Russian samples, Brazil, and the U.S.     

Influence of benomyl and prometryn on the soil microbial activities and community structures in pasture grasslands of Slovakia

The effects of pesticides (a herbicide and a fungicide) on the microbial community structure and their activity were analyzed in soil from four alpine pasture grasslands in Slovakia. Specifically, the effects of the herbicide, Gesagard (prometryn active ingredient), and fungicide, Fundazol 50 WP (benomyl active ingredient), on the microbial respiration activity (CO₂ production), the numbers of selective microbial physiological groups (CFU.g^?1) and the structure (relative abundance) of soil microbial communities [(phospholipid fatty acid (PLFA)] were analyzed under controlled laboratory conditions. All treatments including the treatments with pesticides increased (statistically significantly) the production of CO₂ in all fields during 21 days of incubation and posed a statistically insignificant negative influence on the numbers of the observed physiological groups of microorganisms. The significantly negative influence was evaluated only in the numbers of two physiological groups; spores of bacteria utilizing organic nitrogen and bacteria, and their spores utilizing inorganic nitrogen. A shift in the microbial composition was evident when the PLFA patterns of samples from different sites and treatments were compared by the Principal Component Analysis (PCA). According to the second component PCA 2 (15.95 %) the locations were grouped into two clusters. The first one involved the Donovaly and Dubakovo sites and the second one contained the Velka Fatra and Mala Fatra locations. The PLFA composition of the soils showed important changes after the treatment with pesticides according to PCA 1 (66.06 %). Other treatments had not had a significant effect on the soil microbial community with the exception of the population of fungi. The lower relative abundance (significant effect) of Gram-positive bacteria, actinomycetes and general group of bacteria were determined in samples treated by the herbicide Gesagard. The application of fungicide Fundazol decreased (statistically significantly) the relative abundance of actinomycetes and general group of bacteria and paradoxically increased the population of fungi.     

Influence of H2SO4 and ferric iron on Cd bioleaching from spent Ni–Cd batteries

The paper is concerned with biohydrometallurgical methods of cadmium recovery from spent Ni–Cd batteries. Cd leaching efficiency from electrode material in different media (H₂SO₄ and Fe₂(SO₄)₃ solutions), at different Fe(III) concentrations and using the bacteria Acidithiobacillus ferrooxidans were investigated. The main aim of this study was to understand which from the bioleaching products (sulphuric acid or ferric sulphate) play a main role in the bioleaching process of Cd recovery. The influence of Fe ions on Cd leachability was confirmed. The best leaching efficiency of Cd (100%) was reached by bioleaching and also by leaching in Fe₂(SO₄)₃ solution. The results of X-ray diffraction confirmed that no cadmium was present in solid residuum obtained after the Cd bioleaching as well as Cd leaching using solely ferric iron. The use of H₂SO₄ solution resulted in the lowest efficiency of Cd leachability, the presence of hydroxides in electrode materials caused neutralization of the leaching solution and inhibition of Cd leaching.     

Impact of market constraints on the development of small-scale biogas technology in Sub-Saharan Africa: a systematic review

The sustainable production and use of small-scale biogas energy are required to ensure clean household energy access in developing countries, including the Sub-Saharan Africa (SSA) region. This is influenced by market risks, which can be identified as political, economic, social, technical, legal, and environmental (PESTLE). This study examines peer-reviewed and grey literature for the period from 2000 to 2020 to identify the PESTLE constraints and assess their impact on the sustainable development of the technology in the SSA region. The production of biogas with small-scale plants is commonly done by rural and peri-urban households. Results show that economic constraints are the most dominant and reducing at a slow pace. This is followed by political constraints, which have received much attention in the last two decades. Despite the policy improvements, broader national bioenergy policies and interventions are still to make significant gains, especially in the Central African region. In order of significance, the Southern, East, and West Africa regions have made greater progress in reducing the constraints. To achieve the sustainable development of the technology, there is a need to further address the PESTLE constraints at national and regional levels. This study partly deduces that the unsustainable production, use, and inadequate regulation of the small-scale biogas sector are delaying its transition in the SSA region.

     

Determination of trichloroacetic acid in environmental studies using carbon 14 and chlorine 36

Radioisotopes carbon 14 and chlorine 36 were used to elucidate the environmental role of trichloroacetic acid (TCA) formerly taken to be a herbicide and a secondary air pollutant with phytotoxic effects. However, use of ¹⁴C-labeling posed again known analytical problems, especially in TCA extraction from the sample matrix. Therefore—after evaluation of available methods—a new procedure using decarboxylation of [1,2-¹⁴C]TCA combined with extraction of the resultant ¹⁴C-chloroform with a non-polar solvent and its subsequent radiometric measurement was developed. The method solves previous difficulties and permits an easy determination of amounts between 0.4 and 20 kBq (10–500 ng g⁻¹) of carrier-less [1,2-¹⁴C]TCA in samples from environmental investigations. The procedure is, however, not suitable for direct [³⁶Cl]TCA determination in chlorination studies with ³⁶Cl. Because TCA might be microbially degraded in soil during extraction and sample storage and its extraction from soil or needles is never complete, the decarboxylation method—i.e. 2 h TCA decomposition to chloroform and CO₂ in aqueous solution or suspension in closed vial at 90 °C and pH 4.6 with subsequent CHCl₃ extraction—is recommended here, estimated V < 7%. Moreover, the influence of pH and temperature on the decarboxylation of TCA in aqueous solution was studied in a broad range and its environmental relevance is shown in the case of TCA decarboxylation in spruce needles which takes place also at ambient temperatures and might amount more than 10–20% after a growing season. A study of TCA distribution in spruce needles after below-ground uptake shows the highest uptake rate into current needles which have, however, a lower TCA content than older needle-year classes, TCA biodegradation in forest soil leads predominatingly to CO₂.     

Salt additions alter short-term nitrogen and carbon mobilization in a coastal Oregon Andisol

Deposition of sea salts is commonly elevated along the coast relative to inland areas, yet little is known about the effects on terrestrial ecosystem biogeochemistry. We examined the influence of NaCl concentrations on N, C, and P leaching from a coastal Oregon forest Andisol in two laboratory studies: a rapid batch extraction (approximately 1 d) and a month-long incubation using microlysimeters. In the rapid extractions, salt additions immediately mobilized significant amounts of ammonium and phosphate but not nitrate. In the month-long incubations, salt additions at concentrations in the range of coastal precipitation increased nitrate leaching from the microcosms by nearly 50% and reduced the mobility of dissolved organic carbon. Our findings suggest that coupled abiotic-biotic effects increase nitrate mobility in these soils: exchange of sodium for ammonium, then net nitrification. Changes in sea salt deposition to land and the interactions with coastal soils could alter the delivery of N and C to sensitive coastal waters.