Bioaccessibility and health risk assessment of hydrophobic organic pollutants in soils from four typical industrial contaminated sites in China.

There have been reports of potential health risks for people from hydrophobic organic pollutants, such as polycyclic aromatic hydrocarbons (PAHs), polychlorinated hydrocarbons (PCHs), and organophosphate flame retardants (OPFRs). When a contaminated site is used for residential housing or public utility and recreation areas, the soil-bound organic pollutants might pose a threat to human health. In this study, we investigated the contamination profiles and potential risks to human health of 15 PAHs, 6 PCHs, and 12 OPFRs in soils from four contaminated sites in China. We used an in vitro method to determine the oral bioaccessibility of soil pollutants. Total PAHs were found at concentrations ranging from 26.4 ng/g to 987 ng/g. PCHs (0.27‒14.3 ng/g) and OPFRs (6.30‒310 ng/g) were detected, but at low levels compared to earlier reports. The levels of PAHs, PCHs, and OPFRs released from contaminated soils into simulated gastrointestinal fluids ranged from 1.74% to 91.0%, 2.51% to 39.6%, and 1.37% to 96.9%, respectively. Based on both spiked and unspiked samples, we found that the oral bioaccessibility of pollutants was correlated with their logKow and molecular weight, and the total organic carbon content and pH of soils. PAHs in 13 out of 38 contaminated soil samples posed potential high risks to children. When considering oral bioaccessibility, nine soils still posed potential risks, while the risks in the remaining soils became negligible. The contribution of this paper is that it corrects the health risk of soil-bound organic pollutants by detecting bioaccessibility in actual soils from different contaminated sites.

Human bare and clothing-covered skin exposure to chlorinated paraffins for the general populations: Exposure pattern differential and significance of indirect dermal exposure via clothing-to-skin transport.

To investigate human exposure to short-chain chlorinated paraffins (SCCPs) and medium-chain chlorinated paraffins (MCCPs) through dermal and oral intake via hand-to-mouth contact, wipes from the face, forearm, hand, and foot of 30 volunteers were sampled. The concentration of ∑SCCPs and ∑MCCPs ranged from 0.66 to 119 and 0.71 to 565 µg/m2, respectively. Hands exhibited significantly higher ∑CPs concentrations than other skin areas, indicating that direct contact with indoor surfaces contributed considerable CP levels on this bare skin area. Gender differences in CP levels were observed in wipes from all locations, except for the hands, possibly because of the significant variability in residuals on the hands. A significant positive relationship was found between CP levels on the hands and faces, and the CP ratios of the hands/faces were related to log KOA. Bare skin showed more significant variations in CP partitioning among related congeners and between genders than skin covered by clothing, as elucidated by the linear analysis of RSD and log KOA. Although concentrations on clothing-covered areas were relatively lower than on bare skin, the median estimated dermal absorption doses of ∑SCCPs and ∑MCCPs (152 and 737 ng/kg bw/day, respectively) for the entire body were approximately 1-2 orders of magnitude higher than those for oral ingestion (1.62 and 7.94 ng/kg bw/day, respectively), emphasizing indirect dermal uptake as a significant exposure pathway for humans.

Aromatic Structures Govern the Formation of Chlorinated Byproducts in Dichlorine Radical Reactions.

Radical-induced disinfection byproduct (DBP) formation is drawing attention with increasing applications of advanced oxidation processes (AOPs). Cl2•- represents one of the extensively generated radicals in AOPs, whose behavior in DBP formation remains unknown. In this study, we found that aromatic structures serve as the main DBP precursors in Cl2•- reactions by employing diverse groups of model compounds. At a typical Cl2•- exposure of 1.2 × 10-9 M·s, the sum concentrations of 7 regulated aliphatic DBPs (e.g., trichloromethane, chloroacetic acids) are ∼0.10 to 0.48 µM for aromatic precursors and <0.05 µM for aliphatic ones. The DBP formation mechanisms from Cl2•- reactions involved the formation of chlorinated aromatics, radical-induced oxygen incorporation followed by ring cleavage, and the interactions of Cl2•- with ring-cleavage intermediates. In reacting with DOM, Cl2•- reactions produced much fewer aliphatic DBPs (5% of the total organochlorine vs 40% for chlorination) and chloroacetic acids dominated the aliphatic DBPs (usually trihalomethane for chlorination), which can be well interpreted by the precursors and mechanisms proposed. This work comprehensively reveals the precursors, formation patterns, and mechanisms of DBPs during the less-studied Cl2•- reactions, highlighting the importance of eliminating the aromatic structures of DOM before the AOPs.

Spatiotemporal distribution of organochlorine pesticides in the upper La Antigua watershed, Veracruz Mexico.

Even though the use of organochlorine pesticides has been prohibited since the last century their presence is still being recorded around the world. In the upper La Antigua watershed, Veracruz, Mexico we have reported concentrations of these contaminants in different compartments of the riverine ecosystems. This is of relevance due to their potential disruptive endocrine effect on the vertebrates drinking the water or feeding in the riverine area. In this study we evaluated concentrations of organochlorine pesticides (OCPs) in streams running throughout mountain cloud forest and two different types of land use, pasture lands and coffee plantations. Water and periphyton samples were collected during the wet and the dry seasons from streams located in independent micro-basins. Spatial explicit analyzes show that the concentrations measured are independent of the distribution of the streams in the geographical area sampled. However seasonal differences were found during the dry season in the water and during the rainy season in periphyton. While OCPs in water support the idea that micro-basins can be used as independent monitoring units, OCPs in periphyton can be indicators of the effect of different land use. Some concentrations of all the OCPs registered had values above the limits for tap water.

[Validation of an Analytical Method for Organochlorine Pesticide Residues in Beef Products by GC-MS Using Sampling with Increment Reduction].

We developed a simultaneous determination method for the environmentally persistent organochlorine pesticides aldrin/dieldrin, γ-BHC, DDT, endrin, and heptachlor in beef products. In the method, we adopted incremental reduction for sample collection in order to improve the uniformity of the samples. In incremental reduction, a sample was ground and spread to an even thickness, divided into sections, and collected in an equal amount from each section. After extraction with an acetonitrile/ethanol mixture (1 : 1 v/v), sample clean-up was performed by refrigerated centrifu-gation and solid-phase extraction. This process was easy and did not require gel permeation chromatography. The sample was analyzed by GC-MS. A validation study of the development method showed that the tested pesticides met the target values indicated in the validity evaluation guideline.

[Three cases of occupational chronic chloropropene poisoning].

Chronic chloropropene poisoning is a disease mainly caused by peripheral nerve damage due to close contact with chloropropene in industrial production, its clinical manifestations include varying degrees of sensory, motor, or tendon reflex disorders in the distal limbs, and neuromyography can show neurogenic damage. This article analyzed and summarized the clinical characteristics, diagnosis and treatment methods of three patients with occupational chronic chloropropene poisoning, in order to enhance the clinical understanding of occupational chronic chloropropene poisoning and provide reference for clinical diagnosis and treatment.

[A case of oral chloropicrin poisoning].

Chloropicrin is a commonly used pesticide in agricultural production. The clinical manifestations of oral poisoning patients are complex, and the lesions involve multiple organs. At present, the specific pathogenic mechanism of such poisoning is not clear, and the treatment experience is insufficient, so there are certain difficulties in clinical diagnosis, treatment and treatment. In this paper, the data of a patient with oral chloropicrin poisoning treated in Yidu Central Hospital of Weifang City in April 2023 were summarized. The patient was admitted to our hospital for treatment in time, and his condition improved after Hemopurification, methylene blue reduction, organ support, infection prevention as well as other symptomatic support. Oral chlorophenol can cause lung damage, skin and mucous membrane damage, and may have certain effects on the nervous system and kidney. Early intervention, especially blood purification, is effective.

Development of a Novel SPME Coating for Efficient Extraction of Organochlorine Pesticides in Liquid Dairy Products.

A sensitive and accurate analysis of organochlorine pesticide (OCP) residues in dairy products poses a significant challenge. Herein, a novel covalent organic polymer, Azo-COP-1, was synthesized for the enhanced extraction of OCPs in dairy products. The solid phase microextraction fiber coated with Azo-COP-1 demonstrated excellent extraction performance for the OCPs via hydrogen bonding, halogen bonding, π-π stacking, and electrostatic interactions. Coupled with gas chromatography-electron capture detection, we developed a facile and reliable method for detecting OCPs in six types of dairy products with low limits of detection (2.0-400 pg g-1) and high method recoveries (82.6-113%). Azo-COP-1 coatings exhibited good stability and durability. The results verified the feasibility of using Azo-COP-1-based SPME to extract OCP residues in dairy product samples, highlighting its potential for routine monitoring of pesticide residues and food safety assessments.

Mapping pesticide residues in soil for China: Characteristics and risks.

The widespread application of pesticides in China has led to the accumulation of residues in soil. However, few regional studies have fully elucidated the characteristics of pesticide residues in soil (PRS) and the associated risks to the ecosystem and human health on a national level. Therefore, this study aims to compile a dataset on PRS in China from 2006 to 2020 and analyze the interactions and impacts between PRS and the environment. The average concentration of PRS in China was 243.96 µg/kg which was lower than the levels reported in Euro-Americans and other nations. This study revealed PRS in China predominantly originates from organochlorine pesticide residues, with DDTs and HCHs being significant contributors. Despite the high intensity of pesticide application in the Southeast China, PRS concentrations were comparable to those in the Northeast, due to environmental factors that favor pesticide degradation in the Southeast. Both legacy and in-use pesticides were transported by surface runoff or air current, resulting in their accumulation in soil of the lower Yangtze River basin or the piedmont soil of Qinling Mountains, respectively. The average soil environment carrying capacity of PRS in China was -69.5 kg. The ecological risk contributed by PRS in China was mainly at a negligible level. Carcinogenic risks of PRS to adults (4.6 ×10-4) and children (6 ×10-4) exceeded the tolerable thresholds (10-5) by a small margin.

Review on analytical methods and occurrence of organic contaminants in continental water sediments.

Various industries produce a myriad of synthetic molecules used to satisfy our needs, but all these molecules are likely to reach aquatic environments. The number of organic contaminants found in rivers and lakes continues to rise, and part of this contamination gets transferred into sediments. Analytical methods to detect problematic substances in the environment often use mass spectrometry coupled with chromatography. Here we reviewed a set of 163 articles and compiled the relevant information into a comprehensive database for analysing organic contaminants in continental sediments including suspended particulate matter and surface and bottom sediments in lakes, rivers and estuaries. We found 1204 compounds detected at least once in sediments, and classified them into 11 categories, i.e. hydrocarbons, flame retardants, polychlorinated biphenyls (PCB), plasticizers, per- and poly-fluoroalkyl substances (PFAS), organochlorines (OCP) and other pesticides, pharmaceuticals, hormones, personal care products (PCP), and other contaminants. Concentrations of these compounds varied from a few ng to several mg/kg of dry sediment. Even hydrophilic compounds were detected in high concentrations. Well-known hydrophobic and persistent contaminants tend to be analysed with mass spectrometry coupled to gas chromatography (GC-MS) whereas contaminants of emerging concern (CEC) are usually analysed with liquid chromatography- mass spectrometry (LC-MS). Suspect screening and non-target analysis (NTA), which use high-resolution mass spectrometry, are still scarcely used on sediment but hold promise for gaining deeper knowledge of organic contamination in aquatic environments.

[Screening of Characteristic Pollutants and Risk Pollutants in Different Media in the Yangtze River Basin Using Comprehensive Evaluation and Risk Quotient Methods].

A variety of pollutants have frequently been detected in the Yangtze River Basin with the rapid economic development, the population increase, and the acceleration of urbanization, which threaten the aquatic ecosystem and human health. A multi-criteria comprehensive evaluation method was developed to identify the characteristic pollutants, and the risk quotient method was used to derive the risk pollutants in water and sediment samples in this article. A total of 155 pollutants from 11 categories were detected in the Yangtze River Basin according to the literature research. Then, the K-means method was used to analyze the cluster of pollutant comprehensive scores. All pollutants were graded based on their scores and recorded as Ⅰ-Ⅵ according to the number of cases in each cluster. A total of 43 pollutants with high scores of Ⅰ and Ⅱ were listed as the characteristic pollutants, which included 11 polycyclic aromatic hydrocarbons, 11 organochlorine pesticides, 10 polychlorinated biphenyls, eight dioxins, two heavy metals, and one phthalate ester. The top five median concentrations of contaminants in water and sediment samples were heavy metals, polycyclic aromatic hydrocarbons, phthalates esters, bisphenols, and pharmaceuticals and personal care products. According to the principle of risk maximization, the risk entropy value （RQ） was calculated based on the highest pollutant concentration. A total of 38 risky pollutants were screened in the water samples （RQ ≥ 0.1）. There were eight high-risk pollutants with RQ ≥ 1, which included benzo[a,h]-anthracene, anthracene, benzo[a]anthracene, pyrene, methoxychlor, aldrin, 2,4'-dichlorodiphenyl, and cadmium. There were 15 high-risk contaminants in the sediment, which included benzo[b]fluoranthene, anthracene, acenaphthene, fluoranthene, cadmium, lead, chromium, arsenic, selenium, dibutyl phthalate, dimethyl phthalate, diisobutyl phthalate, norfloxacin, perfluorobutyric acid, and bisphenol A. The risk pollutants contained emerging pollutants, which included ten pollutants in water samples and nine pollutants in sediments. Antibiotic pollutants accounted for the largest proportion of these emerging pollutants. The information provided in this article may be useful for the relevant departments to monitor the pollutants and propose management programs for the Yangtze River Basin. Additionally, it is of great significance for the ecological environmental protection and management of the Yangtze River Basin.

Spatial distribution and air-soil exchange of short and medium chain chlorinated paraffins in Lahore, Pakistan.

This study provides the first systematic data on the distribution of short- (SCCPs) and medium chlorinated paraffins (MCCPs) in the atmosphere and surface soils of Lahore, Pakistan. The spatial distribution of SCCPs and MCCPs in air (n = 12) and soil (n = 15) was investigated from industrial, residential, commercial, conventional e-waste burning and background areas of Lahore. The concentrations ranged from below the limit of detection (

Persistent Organic Pollutants (POPs), Current Use Pesticides (CUPs) and Polycyclic Aromatic Hydrocarbons (PAHs) in edible marine invertebrates from a Patagonian harbor.

Despite their global ban in 2001, persistent organic pollutants (POPs) remain detectable in marine species, posing ongoing environmental and health risks. Current use pesticides (CUPs) like chlorpyrifos and chlorothalonil, along with polycyclic aromatic hydrocarbons (PAHs), also contaminate coastal areas, affecting human health. This study assessed POPs, CUPs and PAHs in bivalves, gastropods, polychaetes, crustaceans, and echinoderms from an Atlantic Patagonian harbor. Concentrations of organochlorine pesticides (OCPs), polychlorinated biphenyls (PCBs), and polybrominated diphenyl ethers (PBDEs) ranged from

Detection of Short-Chain Chlorinated Aliphatic Hydrocarbons through an Engineered Biosensor with Tailored Ligand Specificity.

Short-chain chlorinated aliphatic hydrocarbons (SCAHs), commonly used as industrial reagents and solvents, pose a significant threat to ecosystems and human health as they infiltrate aquatic environments due to extensive usage and accidental spills. Whole-cell biosensors have emerged as cost-effective, rapid, and real-time analytical tools for environmental monitoring and remediation. While the broad ligand specificity of transcriptional factors (TFs) often prohibits the application of such biosensors. Herein, we exploited a semirational transition ligand approach in conjunction with a positive/negative fluorescence-activated cell sorting (FACS) strategy to develop a biosensor based on the TF AlkS, which is highly specific for SCAHs. Furthermore, through promoter-directed evolution, the performance of the biosensor was further enhanced. Mutation in the -10 region of constitutive promoter PalkS resulted in reduced AlkS leakage expression, while mutation in the -10 region of inducible promoter PalkB increased its accessibility to the AlkS-SCAHs complex. This led to an 89% reduction in background fluorescence leakage of the optimized biosensor, M2-463, further enhancing its response to SCAHs. The optimized biosensor was highly sensitive and exhibited a broader dynamic response range with a 150-fold increase in fluorescence output after 1 h of induction. The detection limit (LOD) reached 0.03 ppm, and the average recovery rate of SCAHs in actual water samples ranged from 95.87 to 101.20%. The accuracy and precision of the proposed biosensor were validated using gas chromatography-mass spectrometry (GC-MS), demonstrating the promising application for SCAH detection in an actual environment sample.

Assessment of persistent and emerging pollutants levels in marine bivalves in the Gulf of Suez, Egypt.

Bivalves possess important ecological and economic values. They have been extensively used as bioindicators for both emerging and classical pollutants in the aquatic environment. This study investigates the levels of trace metals, polycyclic aromatic hydrocarbons (PAHs), and organochlorine pesticides (OCPs), alongside microplastic (MPs), in Tridacna maxima, Paphia textile, and Paratapes undulatus, collected from the Gulf of Suez. This work represents the first investigation of MPs in marine bivalves from the Gulf of Suez. MPs were detected in 72% of the specimens examined and four types of MPs were identified. The metal pollution index indicated that bivalves may have long-term toxic effects on human consumers. The results showed minimal hydrocarbon pollution. Diagnostic ratios indicated a combination of pyrolytic and petrogenic sources, with a notable influence from pyrolytic origins. The risk assessment reflected that the levels of certain trace metals, PAHs, and OCP contaminants could present a low risk to human health.

The effects of estuarine outflows on coastal marine ecosystems in New South Wales, Australia.

In the state of New South Wales (NSW), Australia, recent legislative action has focused on identifying key threats to the marine estate. We used a systematic literature review to evaluate the knowledge status of the effects of estuarine outflows on coastal marine ecosystems, within the environmental, hydrological, and physicochemical context of NSW waters. Results focussed on studies that measured outcomes for marine biota (n = 56). Trace elements and organochlorines were the most frequently studied contaminant types, with reported biological concentrations often below guideline values but detected at the highest concentrations adjacent to urban sources. Few studies measured the impacts of legacy and emerging contaminants to animal health, or the flow on effects to marine ecosystems in NSW. Our review highlights key biological and geographical data gaps in estuarine outflow research in NSW, particularly of the impact on ecosystems of exported carbon and nutrients to the oligotrophic waters of NSW.

Organochlorine pesticides and polychlorinated biphenyls in sediments of the Lanzhou reach of Yellow River (China): Spatial distribution, sources and risk assessment.

Knowledge about sediment levels and sources of persistent organic pollutants (POPs) in Lanzhou section Yellow River remains limited. Organochlorine pesticides (OCPs) and polychlorinated biphenyls (PCBs) levels in 12 sediment samples from this region were measured by GC/MS. OCPs concentrations ranged from 85.6 to 202 ng/g, while PCBs levels varied between 3.08 and 32.3 ng/g. Our findings demonstrated a significant correlation between these pollutants and total organic matter (TOC), highlighting TOC's role in pollutants distribution. Notably, OCPs and PCBs levels were higher in the eastern section, following the water flow direction. The primary OCPs components were hexachlorocyclohexane (HCH) and dichlorodiphenyltrichloroethane (DDT), whereas PCBs were dominated by perchlorinated compound. Source identification indicated that OCPs primarily originated from historical residues and recent applications, while industrial activities as significant PCBs sources. Sediment quality guidelines and health risk assessments indicated negligible environmental risk. This study providing valuable insights on sediment pollution control and management strategies.

Pesticides under the category of persistent organic pollutants and emerging contaminants in surface sediments of an Arctic Fjord and nearby lakes.

This study focuses on the distribution of some selected organochlorine pesticides and emerging contaminants within the surface sediments of an Arctic fjord, Kongsfjorden and nearby lakes. Organochlorine pesticides (OCPs) such as dicloran, p,p'-DDT, p,p'-DDE, p,p'-DDD were studied along with five emerging contaminants namely diuron, chlorpyrifos, dicofol, pendimethalin and bifenthrin. The highest values of OCPs recorded among the fjord and lake environments during the time of study was 0.3355 ng/g (dicloran), 0.0152 ng/g (p,p'-DDT), 0.0117 ng/g (p,p'-DDE), and 0.0137 ng/g (p,p'-DDD). Except dicofol, all other pesticides were found in both the years (2018 & 2019) with an elevated concentration during 2019. The presence of fresh as well as past input of contaminants was obtained from the values of DDTs ratio. The sediment quality guidelines of DDTs confirm that the fjord and lakes are clean to marginally polluted in which the adverse effects can rarely occur at this present juncture.

Polychlorinated alkanes in indoor environment: A review of levels, sources, exposure, and health implications for chlorinated paraffin mixtures.

Polychlorinated n-alkanes (PCAs) are the main components of chlorinated paraffins (CPs) mixtures, that have been commonly grouped into short-chain (SCCPs, C10-13), medium-chain (MCCPs, C14-17), and long-chain (LCCPs, C18-30) CPs. PCAs pose a significant risk to human health as they are broadly present in indoor environments and are potentially persistent, bioaccumulative, and toxic. The lack of specific terminology and harmonization in analytical methodologies for PCA analysis complicates direct comparisons between studies. The present work summarizes the different methodologies applied for the analysis of PCAs in indoor dust, air, and organic films. The large variability between the reviewed studies points to the difficulties to assess PCA contamination in these matrices and to mitigate risks associated with indoor exposure. Based on our review of physicochemical properties of PCAs and previously reported sum of measurable S/M/LCCPs levels, the homologue groups PCAs-C10-13 are found to be mostly present in the gas phase, PCAs-C14-17 in particulate matter and organic films, and PCAs-C≥18 in settled dust. However, we emphasized that mapping PCA sources and distribution in the indoors is highly dependent on the individual homologues. To further comprehend indoor PCA distribution, we described the uses of PCA in building materials and household products to apportion important indoor sources of emissions and pathways for human exposure. The greatest risk for indoor PCAs were estimated to arise from dermal absorption and ingestion through contact with dust and CP containing products. In addition, there are several factors affecting indoor PCA levels and exposure in different regions, including legislation, presence of specific products, cleaning routines, and ventilation frequency. This review provides comprehensive analysis of available indoor PCA data, the physicochemical properties, applied analytical methods, possible interior sources, variables affecting the levels, human exposure to PCAs, as well as need for more information, thereby providing perspectives for future research studies.

The ototoxicity of chlorinated paraffins via inducing apoptosis, oxidative stress and endoplasmic reticulum stress in cochlea hair cells.

Hearing loss is a common chronic sensory deficit that affects millions of people worldwide and has emerged as a significant public health concern. The association between environmental exposure to chemicals and the prevalence of hearing impairment has recently attracted increased attention. Chlorinated paraffins (CPs) are a type of chemical compound that has been widely used and commonly detected in samples of both environmental and human origin. The knowledge of the toxicological effects of CPs, particularly its ototoxicity, remains limited at present. In this study, six commercial CPs were selected and evaluated using cochlea hair HEI-OC1 cells for their cytotoxicity, apoptosis, DNA damage, reactive oxygen species (ROS) accumulation and oxidative response. The cytotoxicity was observed after CPs exposure at high concentrations except for C-40 and was positively related to the chlorine content (Cl-content) in both CCK-8 and trypan blue assays. All 6 CPs induced cells apoptosis through caspase-dependent apoptotic pathway. CPs exposure induced DNA damage and stimulated ROS overproduction. Antioxidant N-acetyl-L-cysteine (NAC) could reverse the cytotoxicity and ROS accumulation caused by CPs exposure. The overexpression of ATF4 and CHOP indicated that endoplasmic reticulum (ER) stress was involved in the CPs induced cytotoxicity. Thus, CPs induced cytotoxicity and apoptosis via ROS accumulation, ER stress and DNA damage and positively related to the Cl-content and our findings indicate that CPs may pose a risk of ototoxicity at environmental relevant exposure levels.