Screening level risk assessment model for chemical fate and effects in the environment

A screening level risk assessment model is developed and described to assess and prioritize chemicals by estimating environmental fate and transport, bioaccumulation, and exposure to humans and wildlife for a unit emission rate. The most sensitive risk endpoint is identified and a critical emission rate is then calculated as a result of that endpoint being reached. Finally, this estimated critical emission rate is compared with the estimated actual emission rate as a risk assessment factor. This "back-tracking" process avoids the use of highly uncertain emission rate data as model input. The application of the model is demonstrated in detail for three diverse chemicals and in less detail for a group of 70 chemicals drawn from the Canadian Domestic Substances List. The simple Level II and the more complex Level III fate calculations are used to "bin" substances into categories of similar probable risk. The essential role of the model is to synthesize information on chemical and environmental properties within a consistent mass balance framework to yield an overall estimate of screening level risk with respect to the defined endpoint. The approach may be useful to identify and prioritize those chemicals of commerce that are of greatest potential concern and require more comprehensive modeling and monitoring evaluations in actual regional environments and food webs.     

Triclosan: occurrence and fate of a widely used biocide in the aquatic environment: field measurements in wastewater treatment plants,surface waters,and lake sediments

Triclosan is used as an antimicrobial agent in a wide range of medical and consumer care products. To investigate the occurrence and fate of triclosan in the aquatic environment, analytical methods for the quantification of triclosan in surface water and wastewater, sludge, and sediment were developed. Furthermore, the fate of triclosan in a wastewater treatment plant (biological degradation, 79%; sorption to sludge, 15%; input into the receiving surface water, 6%) was measured during a field study. Despite the high overall removal rate, the concentration in the wastewater effluents were in the range of 42-213 ng/L leading to concentrations of 11-98 ng/L in the receiving rivers. Moreover, a high removal rate of 0.03 d(-1) for triclosan in the epilimnion of the lake Greifensee was observed. This is due to photochemical degradation. The measured vertical concentration profile of triclosan in a lake sediment core of lake Greifensee reflects its increased use over 30 years. As the measured concentrations in surface waters are in the range of the predicted no effect concentration of 50 ng/L, more measurements and a detailed investigation of the degradation processes are needed.     

植物精油化学成分的研究进展

真菌毒素是真菌生长过程中产生的有毒代谢产物,是危害农产品质量安全的重要因子。植物精油是真菌生长和真菌毒素累积的天然抑制剂,但易挥发、稳定性和水溶性差等弊端限制了其应用,近年来植物精油纳米制剂的开发和利用可解决植物精油上述弊端,提升其生物利用度。本文总结了植物精油可通过抑制真菌毒素产生和降解真菌毒素的方式降低农产品中真菌毒素的污染水平,探讨了植物精油抑制真菌生长产毒的机制,综述了植物精油及其纳米制剂防控农产品中真菌毒素污染的研究现状,并对存在问题进行了讨论,以期为进一步开发和利用植物精油防控真菌毒素提供有益参考。     

Photochemical fate of pharmaceuticals in the environment: cimetidine and ranitidine

The photochemical fates of the histamine H2-receptor antagonists cimetidine and ranitidine were studied. Each of the two environmentally relevant pharmaceuticals displayed high rates of reaction with both singlet oxygen (1O2, O2(1delta(g))) and hydroxyl radical (*OH), two transient oxidants formed in sunlit natural waters. For cimetidine, the bimolecular rate constant for reaction with *OH in water is 6.5 +/- 0.5 x 10(9) M(-1) s(-1). Over the pH range 4-10, cimetidine reacts with 1O2 with bimolecular rate constants ranging from 3.3 +/- 0.3 x 10(6) M(-1) s(-1) at low pH to 2.5 +/- 0.2 x 10(8) M(-1) s(-1) in alkaline solutions. The bimolecular rate constants for ranitidine reacting with 1O2 in water ranges from 1.6 +/- 0.2 x 10(7) M(-1) s(-1) at pH 6-6.4 +/- 0.2 x 10(7) M(-1) s(-1) at pH 10. Reaction of ranitidine hydrochloride with *OH proceeds with a rate constant of 1.5 +/- 0.2 x 10(10) M(-1) s(-1). Ranitidine was also degraded in direct photolysis experiments with a half-life of 35 min under noon summertime sunlight at 45 degrees latitude, while cimetidine was shown to be resistant to direct photolysis. The results of these experiments, combined with the expected steady-state near surface concentrations of 1O2 and *OH, indicate that photooxidation mediated by 1O2 is the likely degradation pathway for cimetidine in most natural waters, and photodegradation by direct photolysis is expected to be the major pathway for ranitidine, with some degradation caused by 1O2. These predictions were verified in studies using Mississippi River water. Model compounds were analyzed by laser flash photolysis experiments to assess which functionalities within ranitidine and cimetidine are most susceptible to singlet-oxygenation and direct photolysis. The heterocyclic moieties of the pharmaceuticals were clearly implicated as the sites of reaction with 1O2, as evidenced by the high relative rate constants of the furan and imidazole models. The nitroacetamidine portion of ranitidine has been shown to be the moiety active in direct photolysis.     

Azole fungicides: occurrence and fate in wastewater and surface waters

The mode of action of azole compounds implies a potential to affect endocrine systems of different organisms and is reason for environmental concern. The occurrence and fate of nine agricultural azole fungicides, some of them also used as biocides, and four azole pharmaceuticals were studied in wastewater treatment plants (WWTPs) and lakes in Switzerland. Two pharmaceuticals (fluconazole, clotrimazole, 10-110 ng L(-1)) and two biocides (propiconazole, tebuconazole, 1-30 ng L(-1)) were consistently observed in WWTP influents. Loads determined in untreated and treated wastewater indicated thatfluconazole, propiconazole, and tebuconazole were largely unaffected by wastewater treatment, but clotrimazole was effectively eliminated (> 80%). Incubation studies with activated sludge showed no degradation for fluconazole and clotrimazole within 24 h, but strong sorption of clotrimazole to activated sludge. Slow degradation and some sorption were observed for tebuconazole and propiconazole (degradation half-lives, 2-3 d). In lakes, fluconazole, propiconazole, and tebuconazole were detected at low nanogram-per-liter levels. Concentrations of the pharmaceutical fluconazole correlated with the expected contamination by domestic wastewater, but not those of the biocides. Per capita loads of propiconazole and tebuconazole in lakes suggested additional inputs; for example, from agricultural use or urban runoff rainwater.     

Polybrominated diphenyl ethers in watershed soils of the Pearl River Delta, China: occurrence, inventory, and fate

Soils play an important role in the distribution and biogeochemical cycling of polybrominated diphenyl ethers (PBDEs) as they are a major reservoir and sink for PBDEs due to their large sorption capacity. In this study, concentrations, compositional profiles, mass inventories, and fate of sigma9PBDEs (28, 47, 66, 100, 99, 154, 153, 138, 183) and BDE 209 were investigated in 33 surface soils, six profile soils, and three point-source polluted soils (close to e-waste dismantling sites) from the Pearl River Delta (PRD), China. The concentrations of sigma9PBDEs and BDE 209 in the surface soils ranged from 0.13 to 3.81 ng/g with an average of 1.02 ng/g and from 2.38 to 66.6 ng/g with an average of 13.8 ng/g, respectively, and ranged from 1.93 to 19.5 ng/g and from 25.7 to 102 ng/g, respectively, in the point-source contaminated soils. The PBDE compositional patterns in the surface soils indicated deca-BDE, penta-BDE, and octa-BDE products as the main sources, but those in the point-source samples suggested deca-BDE and octa-BDE technical mixtures as the dominant sources. The mass inventories of PBDEs in soils of the PRD were estimated at 3.98 and 44.4 t for sigma9PBDEs and BDE 209, respectively. The average loading of PBDEs in the soils was comparable to that in the sediments of the Pearl River Estuary, suggesting that soil erosion and surface runoff are an important mode to transport PBDEs from terrestrial sources to oceans in the PRD. Individual BDE congeners, sigma9PBDEs, and PBDE 209, were significantly correlated with total organic carbon (TOC), and a good regression (except for BDE 47) between the logarithms of TOC-normalized BDE average concentrations and their log K(ow) was also obtained, indicating that sorption of PBDEs on soil organic matter governed their spatial distribution, transportation, and fate in the soils. Predicted aqueous and gaseous concentrations of PBDEs were derived from the soil-water and soil-air partitioning models, respectively, and good agreements were obtained between the predicted and previously reported values. BDE 47 and/or 28 did not appear to follow the same trend for these models, an indication that an portion of them was likely the biodegradation byproducts in soils.     

Occurrence and fate of barbiturates in the aquatic environment

Barbiturates have been widely used as sedative hypnotics in the mid-1960s and since then mainly as veterinary drugs. To monitor their presence and fate in the aquatic environment, a method based on gas chromatography-mass spectrometry (GC-MS) has been developed to quantify butalbital, secobarbital, hexobarbital, aprobarbital, phenobarbital, and pentobarbital, all with a limit of detection (LOD) down to 1 ng/L. From the various investigated waste and surface water samples, barbiturates were only, but regularly detected in the Mulde, a tributary of the river Elbe in Germany at relevant concentrations up to several microg/L. Investigations of groundwater being affected with wastewater infiltration several decades ago also revealed a barbiturate pattern, indicating a strong recalcitrance of these drugs. To confirm this hypothesis, studies were carried out on biotic and abiotic degradation. Both, the biodegradability under aerobic conditions and hydrolysis did not show any degradation, implementing, that the investigated barbiturates, once released into the aquatic environment, show high stability over a long period of time.     

Food-grade nanoemulsions: formulation, fabrication, properties, performance, biological fate, and potential toxicity

Nanoemulsions fabricated from food-grade ingredients are being increasingly utilized in the food industry to encapsulate, protect, and deliver lipophilic functional components, such as biologically-active lipids (e.g., ω-3 fatty acids, conjugated linoleic acid) and oil-soluble flavors, vitamins, preservatives, and nutraceuticals. The small size of the particles in nanoemulsions (r<100 nm) means that they have a number of potential advantages over conventional emulsions-higher stability to droplet aggregation and gravitational separation, high optical clarity, ability to modulate product texture, and, increased bioavailability of lipophilic components. On the other hand, there may also be some risks associated with the oral ingestion of nanoemulsions, such as their ability to change the biological fate of bioactive components within the gastrointestinal tract and the potential toxicity of some of the components used in their fabrication. This review article provides an overview of the current status of nanoemulsion formulation, fabrication, properties, applications, biological fate, and potential toxicity with emphasis on systems suitable for utilization within the food and beverage industry.     

Alkaloids in food: a review of toxicity,analytical methods,occurrence and risk assessments

Food Science and Biotechnology - Alkaloids have been utilized by humans for years. They have diverse applications in pharmaceuticals. They have been proven to be effective in treating a number of...     

Analytical screening of marine algal toxins for seafood safety assessment in a protected Mediterranean shallow water environment

Microalgal species growing in marine and aquaculture environments can be responsible for harmful events because of their ability to produce potent natural toxins that can accumulate in edible mollusc species. Their consumption can cause severe illness and even be lethal. The European Union provides comprehensive regulations covering various general food safety aspects to manage the risk of contamination in shellfish farms. Many analytical methods have been proposed to evaluate algal toxins presence in the environment and in food products, for conducting surveillance studies of the main molluscs production sites and, where necessary, immediate monitoring of possible contamination of shellfish. In this work, a one-year analytical surveillance study was carried out to verify the possible presence of algal biotoxins in molluscs from a Mediterranean breeding area. Water and molluscs were sampled from a district of the North-East coast of Sicily, consisting of a unique brackish ecosystem of two lakes connected to each other and to the sea by narrow canals. Water samples were collected to investigate phytoplankton i by microscope analysis to assess the presence of potentially toxin-producing species, such as Pseudo-nitzschia spp, Alexandrium spp and Gonyaulax spinifera, although the presence of toxic phytoplankton has never reached alert levels. Mussels and clams samples were submitted to analysis of paralytic shellfish poisoning toxins, amnesic shellfish poisoning toxins and lipophilic toxins by liquid chromatography-based methods Only a few yessotoxins were detected, having concentrations always below the regulation limits. An existing liquid chromatography-tandem mass spectrometry-based multiresidue method for lipophilic biotoxins was adopted and extended to cover emerging biotoxins such as cyclic imines. The performance of the analytical method for Gymnodimine A and Spirolide 13-desMeC was assessed, obtaining respective quantitation limits of 20 and 10 µg kg^?1, a precision always lower than 13% and trueness in the 81–120% range. Method applicability was confirmed using certified materials and a naturally contaminated sample.     

Emission, fate and effects of soluble silicates (waterglass) in the aquatic environment

Soluble silicates, commercially known as waterglass, are among the largest volume synthetic chemicals in the world. Silicon from waterglass is rapidly transformed to the biologically active orthosilicic acid (referred to as dissolved silicate). This paper aims to assess the impact of waterglass on the aquatic environment in Western Europe. The emission to surface waters from the four most relevant application areas, household detergents, pulp and paper production, water and wastewater treatment, and soil stabilization, is estimated to be ca. 88-121 kton of SiO2 per year. This is a small fraction (<2%) of the estimated total amount of dissolved silicate transported by rivers to the oceans. Locally, increases in dissolved silicate concentration will decrease the ratios of N:Si and P:Si, which could influence phytoplankton species composition and favor the growth of diatoms over other groups of algae. Significant adverse effects in aquatic ecosystems are not expected.     

Patulin in fruit juices: occurrence,bioaccessibility, and risk assessment for Serbian population

This paper reports the first study of patulin occurrence in fruit juices and risk assessment related to patulin intake by children, adolescents and adults in Serbia. During 3 consecutive years (2013–2015), 142 fruit (apple or multi-fruit) juices were collected from the market and analysed using HPLC-UV. Patulin was found in 51.4% of juices with 0.7% of the samples in excess of the legal limit of 50 μg kg^?1 (mean 4.3 μg kg^?1). Apple juices showed significantly higher percentage of contaminated samples (74.0% vs 27.5%), as well as higher mean patulin content (6.4 vs 2.1 μg kg^?1) when compared with the multi-fruit ones. Bioaccessibility of patulin in fruit juices was studied using the standardised in vitro digestion method. A mean of 21.6% of the initial patulin amount reached the end of the intestinal phase showing a significant reduction of this toxin during the human digestion process. Risk assessment of patulin intake by Serbian children, adolescents and adults, conducted by deterministic and probabilistic approaches and including the bioaccessibility results, revealed no health concern. Although patulin alone does not represent risk, further research should consider its co-occurrence with other toxic substances in food and potential adverse effects of their mixtures.     

Acrylamide and 5-hydroxymethylfurfural (HMF): A review on metabolism, toxicity, occurrence in food and mitigation strategies

Neo-formed contaminants (NFCs) are compounds forming during heating or preservation processes and exhibiting possible harmful effects to humans. Among the several NFCs described in literature, Acrylamide and 5-hydroxymethylfurfural (HMF) have attracted the attention of the scientific community in recent years. Both acrylamide and HMF are considered as probably or potentially carcinogenic to humans or might be metabolized by humans to potentially carcinogenic compounds. Acrylamide and HMF are mainly formed through Maillard Reaction and can be regarded as the most important heat-induced contaminants occurring in bread and bakery products. Acrylamide is carcinogen in rodent and some recent epidemiological studies have highlighted the association between dietary acrylamide and an increased risk of some types of cancer. HMF has been recently shown to be converted in vivo to 5-sulfoxymethylfurfural (SMF) which is a genotoxic compound. Dietary intake of HMF is in the order of mg/kg far above that of other food toxicants. In this paper, the latest available data on acrylamide and HMF have been reviewed focusing on available mitigation strategies, metabolism, dietary exposure, and toxicity. The results from the epidemiological studies about acrylamide and cancer risk and their relevance have been discussed, the major gaps of knowledge have been identified and the perspective of ongoing and future research was established.     

Determination of nitrates by a novel ion chromatographic method: occurrence in leafy vegetables (organic and conventional) and exposure assessment for Italian consumers

A novel ion chromatographic method to detect nitrates in vegetables was developed, and the nitrate contents in green salad (a mixture of endive and prickly lettuce), lettuce, chicory, rocket and spinach were determined from Italian markets in 1996 -2002. These leaf vegetables were included because they are currently supposed to provide most of the nitrate intake in the typical Italian diet. The highest content of nitrate was detected in chicory (6250 mg kg -1 ) and rocket (6120 mg kg -1 ), which are consumed in large quantities in some regions of Italy. Green salad and lettuce contained less nitrate (highest values = 4200 and 3300 mg kg -1 , respectively), but because they are consumed more generally, they provided 60% of the total intake of nitrates. Only a few samples were above the legal limits, with seasonal variation. A significantly higher nitrate content was found in organically grown green salad and rocket than in those conventionally produced. These data indicate that the average intake of nitrates from leafy vegetables is below the acceptable daily intake, i.e. 3.7 mg nitrate ion kg -1 body weight day -1 , but the total intake should be monitored to protect groups at risk, such as children and vegetarians.     

The occurrence of methicillin-resistant non-aureus staphylococci in samples from cows,young stock,and the environment on German dairy farms

This study aimed to determine the occurrence of methicillin-resistant (MR) non-aureus staphylococci (NAS) on 20 preselected German dairy farms. Farms were selected based on the detection of methicillin-resistant Staphylococcus aureus (MRSA) during previous diagnostic investigations. Bacterial culture of presumptive MR-NAS was based on a 2-step enrichment method that has been recommended for MRSA detection. Quarter milk samples (QMS), bulk tank milk, swab samples from young stock, and environmental samples were collected for bacterial culture. Methicillin-resistant NAS were detected on all study farms. The MR-NAS positive test rate was 3.3% (77/2,347) in QMS, 42.1% (8/19) in bulk tank milk, 29.1% (59/203) in nasal swabs from milk-fed calves, 18.3% (35/191) in postweaning calves, and 7.3% (14/191) in nasal swabs from prefresh heifers. In the environment, MR-NAS were detected in dust samples on 25% (5/20) of the dairy farms as well as in teat liners and suckers from automatic calf feeders. The geometric mean somatic cell count in QMS affected by MR-NAS (183,000 cells/mL) was slightly higher compared with all QMS (114,000 cells/mL). Nine MR-NAS species were identified; Staph. sciuri, Staph. lentus, Staph. fleurettii, Staph. epidermidis, and Staph. haemolyticus were the most common species. In addition, 170 NAS isolates were identified that showed reduced cefoxitin susceptibility (4 mg/L) but did not harbor the mecA or mecC genes. On some farms, similar mobile genetic elements were detected in MR-NAS and MRSA. It was suggested that resistance genes may be transferred between NAS and Staph. aureus on the respective farms.     

Toxic elements in eggs and egg-based products: occurrence,exposure assessment and risk characterisation for the Serbian population

This study aimed to assess the exposure of the Serbian adult population to As, Cd, Pb and Hg through the consumption of eggs and egg-based products and to assess health risks. Coccidiostat residues were also examined, and their contribution to acceptable daily intake was calculated. Egg samples were collected from 2018 to 2020. The consumption survey was conducted during 2020. A Monte Carlo simulation was performed to estimate the intake of toxic elements based on one-day and seven-day recalls of egg consumption. The results obtained showed that the adult population in Serbia is not exposed to health risks from the studied toxic elements when consuming eggs and egg-based products. The presence of anticoccidial agents was detected in 22% of egg samples at concentrations above the limits prescribed by current regulations in Serbia (which do not allow detectable levels of coccidiostats in eggs), with the main risk of exposure being to coccidiostat residues associated with maduramycin.     

Furan in heat‐treated foods: Formation,exposure, toxicity,and aspects of risk assessment

Furan is formed in a variety of heat‐treated foods through thermal degradation of natural food constituents. Relatively high levels of furan contamination are found in ground roasted coffee, instant coffee, and processed baby foods. European exposure estimates suggest that mean dietary exposure to furan may be as high as 1.23 and 1.01 μg/kg bw/day for adults and 3‐ to 12‐month‐old infants, respectively. Furan is a potent hepatotoxin and hepatocarcinogen in rodents, causing hepatocellular adenomas and carcinomas in rats and mice, and high incidences of cholangiocarcinomas in rats at doses ≥2 mg/kg bw. There is therefore a relatively low margin of exposure between estimated human exposure and doses that cause a high tumor incidence in rodents. Since a genotoxic mode of action cannot be excluded for furan‐induced tumor formation, the present exposures may indicate a risk to human health and need for mitigation. This review summarizes the current knowledge on mechanisms of furan formation in food, human dietary exposure to furan, and furan toxicity, and highlights the need to establish the risk resulting from the genotoxic and carcinogenic properties of furan at doses lower than 2 mg/kg bw.     

Photochemical fate of sulfa drugs in the aquatic environment: sulfa drugs containing five-membered heterocyclic groups

The photochemical fate of five sulfa drugs with varying five-membered heterocyclic substituents (sulfamethoxazole, sulfisoxazole, sulfamethizole, sulfathiazole, and sulfamoxole) was investigated in aqueous solution. The rate of direct photolysis of these compounds is dependent upon the identity of the heterocyclic R group as well as the pH of the solution. Matrix deconvolution methods were employed to determine the absorption spectrum and photolysis rate of each protonation state (cationic, neutral, and anionic). From these data, quantum yields for direct photodegradation were calculated for each protonation state of the sulfa drugs. The quantum yields calculated range from <0.005 for the neutral state of sulfamethizole to 0.7 +/- 0.3 for the protonated state of sulfisoxazole. The protonation state that is most photoreactive varies among the sulfa drugs and cannot be attributed to the rate of photon absorption. Products arising from the direct photolysis of the sulfa drugs were also investigated. For all the compounds, sulfanilic acid was observed as a common product. The singlet oxygen quenching rates of the sulfa drugs were determined by laser flash photolysis and range from (2 +/- 1) x 10(4) M(-1) s(-1) for sulfamethoxazole to (3.0 +/- 0.7) x 10(8) M(-1) s(-1) for sulfamoxole. Reaction of the sulfa drugs with hydroxyl radical is not modulated by the R group, and the rate constants are all near the bimolecular diffusion-controlled limit of 10(10) M(-1) s(-1). The photodegradation of the sulfa drugs in natural water samples of Lake Josephine (St. Paul, MN) and Lake Superior was attributed solely to direct photolysis. This study indicates thatthese similarly structured antibiotics will be subject to a wide range of photodegradation rates with sulfathiazole degrading relatively quickly, sulfisoxazole and sulfamethizole degrading moderately, and sulfamethoxazole degrading much more slowly.