Optimization and Comparison of Microwave-Assisted Extraction, Supercritical Fluid Extraction, and Eucalyptus Oil-Assisted Extraction of Polycyclic Aromatic Hydrocarbons from Soil and Sediment.

Polycyclic aromatic hydrocarbons (PAHs) are persistent organic compounds of major concern that mainly accumulate in soils and sediments, and their extraction from environmental matrices remains a crucial step when determining the extent of contamination in soils and sediments. The objective of the present study was to compare the extraction of PAHs (phenanthrene, pyrene, chrysene, and benzo[a]pyrene) from spiked soil and sediment using supercritical fluid extraction (SFE) with ethanol as the modifier, microwave-assisted extraction (MAE), and eucalyptus oil-assisted extraction (EuAE). Recoveries of PAHs were comparable between the three methods, and >80% of applied pyrene, chrysene and benzo[a]pyrene were recovered. The most efficient method of extracting PAHs from naturally incurred soils with different levels of contamination was SFE. A longer extraction time was required for the EuAE method compared with SFE and MAE under optimized conditions. However, EuAE required lower extraction temperatures (15-20 °C) compared with SFE (80 °C) and MAE (110-120 °C), and consumed less solvent than SFE and MAE. Compared with hexane/acetone used in MAE, the use of ethanol in SFE and eucalyptus oil in EuAE can be considered as more sustainable approaches to efficiently extract PAHs from spiked/naturally contaminated soils and sediments. And, although less efficient for matrices containing higher carbon content, EuAE offered a cheap, low-tech approach to extracting PAHs. Environ Toxicol Chem 2023;42:982-994. © 2023 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC.

Eucalyptus saponin- and sophorolipid-mediated desorption of polycyclic aromatic hydrocarbons from contaminated soil and sediment.

The potential for biosurfactant-mediated desorption of polyaromatic hydrocarbons (PAHs) was evaluated using PAH-spiked soil and sediment. PAH desorption behaviors and toxicity of novel saponin biosurfactant extracted from Eucalyptus camaldulensis leaves and sophoro-lipid biosurfactant were investigated. Their PAH desorption efficiencies were compared with rhamnolipid biosurfactant and the industrial-chemical surfactant, Tween 20. Based on the emulsification indices, the salt tolerance of surfactants up to 30 g/L NaCl followed the order of saponin > Tween 20 > sophorolipid > rhamnolipid, while the thermal stability over the range of 15 to 50 °C was in the order of sophorolipid > rhamnolipid > saponin > Tween 20. The saponin biosurfactant emulsion demonstrated the highest stability under a wide range of acidic to basic pHs. PAH extraction percentages of saponin and sophorolipid under the optimized surfactant concentration, volume, and incubation time were 30-50% and 30-70%, respectively. PAH desorption capacities of saponin and sophorolipid were comparable to that of rhamnolipid and Tween 20 for all matrices. Sophorolipid more efficiently desorbed low molecular weight PAHs in soil and sediment compared to the other three surfactants. Microbial respiration was used to determine biosurfactant toxicity to the soil/sediment microbiome and indicated no inhibition of respiration during 60 days of incubation, suggesting that sophorolipid- and saponin-mediated remediation may be sustainable approaches to remove PAHs from contaminated soils and sediments.

Polycyclic aromatic hydrocarbon contamination in soils and sediments: Sustainable approaches for extraction and remediation.

Polycyclic aromatic hydrocarbons (PAHs) are carcinogenic environmental pollutants that are extremely hydrophobic in nature and resistant to biological degradation. Extraction of PAHs from environmental matrices is the first and most crucial step in PAH quantification. Extraction followed by quantification is essential to understand the extent of contamination prior to the application of remediation approaches. Due to their non-polar structures, PAHs can be adsorbed tightly to the organic matter in soils and sediments, making them more difficult to be extracted. Extraction of PAHs can be achieved by a variety of methods. Techniques such as supercritical and subcritical fluid extraction, microwave-assisted solvent extraction, plant oil-assisted extraction and some microextraction techniques provide faster PAH extraction using less organic solvents, while providing a more environmentally friendly and safer process with minimum matrix interferences. More recently, more environmentally friendly methods for soil and sediment remediation have been explored. This often involves using natural chemicals, such as biosurfactants, to solubilize PAHs in contaminated soils and sediments to allow subsequent microbial degradation. Vermiremediation and microbial enzyme-mediated remediation are emerging approaches, which require further development. The following summarises the existing literature on traditional PAH extraction and bioremediation methods and contrasts them to newer, more environmentally friendly ways.

Cross-continental importance of CH4 emissions from dry inland-waters.

Despite substantial advances in quantifying greenhouse gas (GHG) emissions from dry inland waters, existing estimates mainly consist of carbon dioxide (CO2) emissions. However, methane (CH4) may also be relevant due to its higher Global Warming Potential (GWP). We report CH4 emissions from dry inland water sediments to i) provide a cross-continental estimate of such emissions for different types of aquatic systems (i.e., lakes, ponds, reservoirs, and streams) and climate zones (i.e., tropical, continental, and temperate); and ii) determine the environmental factors that control these emissions. CH4 emissions from dry inland waters were consistently higher than emissions observed in adjacent uphill soils, across climate zones and in all aquatic systems except for streams. However, the CH4 contribution (normalized to CO2 equivalents; CO2-eq) to the total GHG emissions of dry inland waters was similar for all types of aquatic systems and varied from 10 to 21%. Although we discuss multiple controlling factors, dry inland water CH4 emissions were most strongly related to sediment organic matter content and moisture. Summing CO2 and CH4 emissions revealed a cross-continental average emission of 9.6 ± 17.4 g CO2-eq m-2 d-1 from dry inland waters. We argue that increasing droughts likely expand the worldwide surface area of atmosphere-exposed aquatic sediments, thereby increasing global dry inland water CH4 emissions. Hence, CH4 cannot be ignored if we want to fully understand the carbon (C) cycle of dry sediments.

Bioaccessibility of Drug Residues on Common Police Station Work Surfaces.

The fraction of any surface-adsorbed contaminant available for absorption is considered the bioaccessible fraction. Applied previously to contaminants such as pesticides and heavy metals on surfaces such as soil, food and cosmetics, the term may also be used to describe the fraction of drug residue bound to work surfaces which may be mobilized via contact transfer with human skin. Police station work surfaces have been shown to commonly contain low levels of drug residues as thin films; however, no information is available on how readily these residues may be transferred to human skin during direct or glancing contact. A bioaccessibility study was undertaken in which jojoba oil and artificial sebum were used to mimic human sebum to identify how readily a mix of six licit and illicit drugs were transferred from three commonly used police station work surfaces. Transfer from surfaces was slightly greater for jojoba oil than sebum when using a direct pressure contact or a wiping motion. Generally, less than 5% of applied residues were recovered via direct contact, and up to 10% when a wiping motion was used to simulate a glancing contact. While swabbing of work surfaces with methanol provides a suitable environmental audit of drug residues present, it does not represent the bioaccessible fraction of residues available for contact transfer, and hence, absorption via skin or unintentional ingestion. The current study indicates that the ability of sebum to mobilize drug residues from thin films on work surfaces via casual contact is limited, and sebum may potentially assist in the preservation of residues on pitted work surfaces and on skin.

Air Quality Inside Police Drug Safes and Drug Storage Areas.

Storage of drug-based evidence inside sealed safes may allow chemical vapors to accumulate, creating concerns of drug exposure by inhalation, or the possibility of cross-contamination of drug evidence. Air samples were taken from inside eight drug safes and one small storage room at nine city and country police stations, as well as a large centralized drug evidence storage vault, in New South Wales (NSW), Australia. Sorbent tubes containing charcoal were used to determine whether any drug residues could be detected in the air, and to identify the types of chemicals present. Carbon traps were extracted and analyzed by LC-MS-MS for a suite of 22 licit and illicit drug residues and 2 metabolites. Carbon traps and SPME fibers were also analyzed by GC-MS for general volatile organic compound (VOC) residues. No detectable drug residues, either as airborne dust or vapor, were found in the safes, the storage room or the large central repository vault. No drugs were detected in any of the 34 urine samples collected at 8 of the 10 sampling locations, while only one of the five hair samples was positive for cocaine (9 pg/mg) provided by police exhibit officers at 3 of the 10 sampling locations. VOC analysis identified a variety of solvents associated with drug manufacture, plasticisers, personal care products and volatiles associated with plants such as cannabis. The results indicate that strong chemical odours emanating from drug safes are unlikely to be drug residues due to low volatility of drugs, and are more likely VOCs associated with their manufacture or from plant growing operations. Consideration should be given to the quality of air flow in rooms in which safes are housed and the use of air filtering inside safes to reduce the likelihood of VOC accumulation, and therefore the risk of human exposure.

Adaptive Management of Environmental Flows: Using Irrigation Infrastructure to Deliver Environmental Benefits During a Large Hypoxic Blackwater Event in the Southern Murray-Darling Basin, Australia.

Widespread flooding in south-eastern Australia in 2010 resulted in a hypoxic (low dissolved oxygen, DO) blackwater (high dissolved carbon) event affecting 1800 kilometres of the Murray-Darling Basin. There was concern that prolonged low DO would result in death of aquatic biota. Australian federal and state governments and local stakeholders collaborated to create refuge areas by releasing water with higher DO from irrigation canals via regulating structures (known as 'irrigation canal escapes') into rivers in the Edward-Wakool system. To determine if these environmental flows resulted in good environmental outcomes in rivers affected by hypoxic blackwater, we evaluated (1) water chemistry data collected before, during and after the intervention, from river reaches upstream and downstream of the three irrigation canal escapes used to deliver the environmental flows, (2) fish assemblage surveys undertaken before and after the blackwater event, and (3) reports of fish kills from fisheries officers and local citizens. The environmental flows had positive outcomes; mean DO increased by 1-2 mg L-1 for at least 40 km downstream of two escapes, and there were fewer days when DO was below the sub-lethal threshold of 4 mg L-1 and the lethal threshold of 2 mg L-1 at which fish are known to become stressed or die, respectively. There were no fish deaths in reaches receiving environmental flows, whereas fish deaths were reported elsewhere throughout the system. This study demonstrates that adaptive management of environmental flows can occur through collaboration and the timely provision of monitoring results and local knowledge.

The presence of licit and illicit drugs in police stations and their implications for workplace drug testing.

The presence of licit and illicit drug residues on surfaces was studied in 10 police stations and a central drug evidence store in New South Wales, Australia, with the results compared to similar surfaces in four public buildings (to establish a community baseline). The results of almost 850 workplace surface swabs were also compared to the outcome of drug analysis in urine and hair samples volunteered by police officers. Surfaces were swabbed with alcohol and the swabs were extracted and analysed by LC-MS/MS. Low level concentrations of the more commonly used drugs were detected at four public sites and one restricted access police office facility. Surface swabs taken in 10 city and country police stations yielded positive results for a broader suite of drugs than at background sites however 75-93% of the positive drug results detected in police stations were below 40ng, which is only slightly greater than the largest background result measured in the current study. This study indicates that contamination issues are more likely to be focussed in higher risk areas in police stations, such as counters and balances in charge areas, and surfaces within drug safes although front reception counters also returned surface contamination. All 64 urine samples collected in this study were negative, while only 2 of the 11 hair samples collected from donors resulted in trace concentrations for cocaine, but not its metabolite benzoylecgonine. Positive hair samples were only obtained from police donors in very high risk jobs, indicating that the exposure risk is low. Minor changes to the materials used as work surfaces, and some procedural changes in police stations and large evidence stores are suggested to decrease the likelihood of drugs contaminating work surfaces, thereby reducing the potential exposure of police officers to drugs in the workplace.

Work place drug testing of police officers after THC exposure during large volume cannabis seizures.

Police officers responsible for the seizure and removal of illegally grown cannabis plants from indoor and outdoor growing operations face the prospect of THC exposure while performing their work duties. As a result, a study investigating the amount of THC on hands and uniforms of officers during raids on cannabis growing houses (CGHs) and forest cannabis plantations (FCPs) and in the air at these sites was conducted. Swabs of gloves/hands, chests, and heads/necks were collected and analysed for THC. Results of hand swabs indicated that officers removing plants from FCPs were exposed to THC concentrations up to 20 times those involved in raids at CGHs, which was mainly associated with the number and size of plants seized. Air samples collected inside cannabis houses showed no detectable THC. Air samples collected inside the cargo area of the storage trucks used during FCP raids indicated that THC can be volatilised when lush plants are compressed by other seized plants loaded on top of them in the truck over a period of several days, allowing composting of plants at the bottom of the load to commence. The elevated temperature and humidity inside the truck may assist the decarboxylation of THCA to THC, as well as increasing the rate of volatilisation of THC. More than 100 urine samples were collected from officers in raids on both CGHs and FCPs and all tested negative for THC. Removal of cannabis plants by officers often resulted in cuts, abrasions and ruptured blisters on exposed skin surfaces, particularly at FCPs. The results in this study suggest that even when small areas of damaged skin are directly exposed to THC by contact transfer, the likelihood of showing a positive THC urine test is low.

A rapid method for the simultaneous quantification of the major tocopherols, carotenoids, free and esterified sterols in canola (Brassica napus) oil using normal phase liquid chromatography.

A normal phase high performance liquid chromatography (HPLC) method was developed to simultaneously quantify several prominent bioactive compounds in canola oil vis. α-tocopherol, γ-tocopherol, δ-tocopherol, ß-carotene, lutein, ß-sitosterol, campesterol and brassicasterol. The use of sequential diode array detection (DAD) and tandem mass spectrometry (MS/MS) allowed direct injection of oils, diluted in hexane without derivatisation or saponification, greatly reducing sample preparation time, and permitting the quantification of both free sterols and intact sterol esters. Further advantages over existing methods included increased analytical selectivity, and a chromatographic run time substantially less than other reported normal phase methods. The HPLC-DAD-MS/MS method was applied to freshly extracted canola oil samples as well as commercially available canola, palm fruit, sunflower and olive oils.

Pore Mn²âº dynamics of the rhizosphere of flooded and non-flooded rice during a long wet and drying phase in two rice growing soils.

Flooded rice soils produce elevated concentrations of soluble manganous manganese (Mn(2+)) that could be potentially toxic to subsequent crops. To provide insight into how soil pore Mn(2+) changes its concentration in a rice and post rice drying soil, we used an artificial microcosm system to follow Mn(2+) concentrations in two different soil types (red sodosol and grey vertosol) and under two irrigation regimes (flooded and saturated). Soil pore water was collected from four different depths of soil (2.5 cm, 7.5 cm, 15 cm and 25 cm) and Mn(2+) concentrations were analysed during and after the rice phase over a one year cycle. Mn(2+) increased with the advancement of anaerobic conditions at all soil depths, but the concentration was higher in flooded soil compared to saturated soil. Initially, the highest concentration of Mn(2+) was found at a depth of 7.5 cm, while at the later stage of rice growth, more Mn(2+) was found in the deepest sampling depth (25 cm). Plants grown in saturated soils showed a delay in flowering of approximately 3 weeks compared to flooded cultures. Moreover, plants grown in flooded soil produced more tillers and leaf area than those grown in saturated soil. Peak concentrations of soil Mn(2+) were associated with the reproductive stage of rice growth. Mn(2+) concentrations decreased after drainage of water. In post rice soils, Mn(2+) remained elevated for some time (lag phase), and then rapidly declined. Regression analysis revealed that the process of oxidation of Mn(2+) to Mn(4+) following water drainage decreased with soil depth.

Urban stormwater inputs to an adapted coastal wetland: role in water treatment and impacts on wetland biota.

The Lake Pertobe wetland system is a semi-natural wetland that has been modified primarily for recreational use. However, this lake system receives stormwater from much of the central business district of Warrnambool City (Victoria, Australia) and serves as a buffer zone between the stormwater system and the Merri River and Merri Marine Sanctuary. This work considers the impact of stormwater inputs on Lake Pertobe and the effectiveness of the lake in protecting the associated marine sanctuary. Sediment contaminants (including heavy metals and polycyclic aromatic hydrocarbons (PAHs)) and water quality parameters within the lake, groundwater and stormwater system were measured. Water quality parameters were highly variable between stormwater drains and rain events. Suspended solids rapidly settled along open drains and shortly after entering the lake. Groundwater inputs increased both salinity and dissolved nitrogen in some stormwater drains. Some evidence of bioaccumulation of metals in the food chain was identified and sediment concentrations of several PAHs were very high. The lake acted as a sink for PAHs and some metals and reductions in Escherichia coli, biological oxygen demand and total phosphorus were observed, affording some protection to the associated marine sanctuary. Nutrient retention was inadequate overall and it was identified that managing the lake primarily as a recreational facility impacted on the effectiveness of stormwater treatment in the system.

Hypoxia, blackwater and fish kills: experimental lethal oxygen thresholds in juvenile predatory lowland river fishes.

Hypoxia represents a growing threat to biodiversity in freshwater ecosystems. Here, aquatic surface respiration (ASR) and oxygen thresholds required for survival in freshwater and simulated blackwater are evaluated for four lowland river fishes native to the Murray-Darling Basin (MDB), Australia. Juvenile stages of predatory species including golden perch Macquaria ambigua, silver perch Bidyanus bidyanus, Murray cod Maccullochella peelii, and eel-tailed catfish Tandanus tandanus were exposed to experimental conditions of nitrogen-induced hypoxia in freshwater and hypoxic blackwater simulations using dried river red gum Eucalyptus camaldulensis leaf litter. Australia's largest freshwater fish, M. peelii, was the most sensitive to hypoxia but given that we evaluated tolerances of juveniles (0.99 ± 0.04 g; mean mass ±SE), the low tolerance of this species could not be attributed to its large maximum attainable body mass (>100,000 g). Concentrations of dissolved oxygen causing 50% mortality (LC50) in freshwater ranged from 0.25 ± 0.06 mg l(-1) in T. tandanus to 1.58 ± 0.01 mg l(-1) in M. peelii over 48 h at 25-26 °C. Logistic models predicted that first mortalities may start at oxygen concentrations ranging from 2.4 mg l(-1) to 3.1 mg l(-1) in T. tandanus and M. peelii respectively within blackwater simulations. Aquatic surface respiration preceded mortality and this behaviour is documented here for the first time in juveniles of all four species. Despite the natural occurrence of hypoxia and blackwater events in lowland rivers of the MDB, juvenile stages of these large-bodied predators are vulnerable to mortality induced by low oxygen concentration and water chemistry changes associated with the decomposition of organic material. Given the extent of natural flow regime alteration and climate change predictions of rising temperatures and more severe drought and flooding, acute episodes of hypoxia may represent an underappreciated risk to riverine fish communities.

Deployment of DGT units in marine waters to assess the environmental risk from a deep sea tailings outfall.

Measurements of total, filterable and DGT-labile concentrations of nine metals (Al, Cd, Cr, Cu, Fe, Pb, Mn, Ni and Zn) have been made at five sites up to 4.2km from a deep sea tailings outfall operated by Lihir Gold Ltd. at Lihir Island, Papua New Guinea. At each site, pairs of DGT units (one containing a 0.4mm and the other a 0.8mm diffusive gel layer) were deployed at three depths (50-70; 105-130; 135-155m) for 4-7 days. Comparison of predicted water column DGT-labile metal concentrations in field deployments showed the 0.8mm DGT units were relatively enriched in metals, with the effect being greatest closer to the outfall for Pb and Mn and least for Fe, Cr, Ni and Zn. The most likely explanation for this is that in addition to simple ion diffusion, kinetic factors associated with ageing or desorption processes govern release of metals from iron and aluminium oxyhydroxide colloids which diffuse through the gels. The thicker gels have a longer residence time over which metals can be released for adsorption. This model explains why enrichment is most pronounced near the outfall; more distant sites have lower colloid concentrations because of the longer time for coagulation to increase particle sizes to the extent they cannot enter the gels. Total and filterable metal (FM) concentrations were frequently below the limits of detection (LOD) achievable by conventional ICP-AES (1-52microgL(-1)) and this limited their usefulness for assessing environmental risk and for metal speciation determination. Because of its pre-concentration step DGT gave metal concentrations above their LODs and these decreased exponentially with distance from the outfall. Concentrations of DGT-labile metal fell below Australian water quality guidelines for protection of 99% of marine organisms within 0.13km of the outfall for Cd, Cr and Ni and below that for protection of 95% of marine organisms within 0.4, 0.7 and 3.6km for lead, zinc and copper, respectively.