A review on the fate of micro and nano plastics (MNPs) and their implication in regulating nutrient cycling in constructed wetland systems.

This review discusses the micro-nano plastics (MNPs) and their interaction with physical, chemical and biological processes in a constructed wetland (CW) system that is typically used as a nature-based tertiary wastewater treatment for municipal as well as industrial applications. Individual components of the CW system such as substrate, microorganisms and plants were considered to assess how MNPs influence the CW processes. One of the main functions of a CW system is removal of nutrients like nitrogen (N) and phosphorus (P) and here we highlight the pathways through which the MNPs influence CW's efficacy of nutrient removal. The presence of morphologically (size and shape) and chemically different MNPs influence the growth rate of microorganisms important in N and P cycling, invertebrates, decomposers, and the plants which affect the overall efficiency of a CW treatment system. Certain plant species take up the MNPs, and some toxicity has been observed. This review focuses on two significant aspects: (1) the presence of MNPs in a significant concentration affects the efficiency of N and P removal, and (2) the removal of MNPs. Because MNPs reduce the enzyme activities in abundance and overproduction of ROS oxidizes the enzyme active sites, resulting in the depletion of proteins, ultimately inhibiting nitrogen and phosphorus removal within the substrate layer. The review found that the majority of the studies used sand-activated carbon (SAC), granular-activated carbon (GAC), rice straw, granular limestone, and calcium carbonate, as a substrate for CW treatment systems. Common plant species used in the CW include Phragmites, Arabidopsis thaliana, Lepidium sativum, Thalia dealbata, and Canna indica, which were also found to be dominant in the uptake of the MNPs in the CWs. The MNPs were found to affect earthworms such as Eisenia fetida, Caenorhabditis elegans, and, Enchytraeus crypticus, whereas Metaphire vulgaris were found unaffected. Though various mechanisms take place during the removal process, adsorption and uptake mechanism effectively emphasize the removal of MNPs and nitrogen and phosphorus in CW. The MNPs characteristics (type, size, and concentration) play a crucial role in the removal efficiency of nano-plastics (NPs) and micro-plastics (MPs). The enhanced removal efficiency of NPs compared to MPs can be attributed to their smaller size, resulting in a faster reaction rate. However, NPs dose variation showed fluctuating removal efficiency, whereas MPs dose increment reduces removal efficiency. MP and NPs dose variation also affected toxicity to plants and earthworms as observed from data. Understanding the fate and removal of microplastics in wetland systems will help determine the reuse potential of wastewater and restrict the release of microplastics. This study provides information on various aspects and highlights future gaps and needs for MNP fate study in CW systems.

Trends and patterns of polycyclic aromatic hydrocarbons (PAHs) in forest fire-affected soils and water mediums with implications on human health risk assessment.

Forest fires are extreme natural/artificial events releasing polycyclic aromatic hydrocarbons (PAHs), which are carcinogenic. Most of the released PAHs are trapped in burnt ash, a part of which is transported and settle on different mediums like soil and water. After strong rainfall events, PAHs enter into surface water bodies through surface runoff, thereby deteriorating water quality. Changes in PAHs levels during the post-fire duration and human health risks due to PAHs released from forest fires need attention. This study aim to explain the trends and patterns of PAHs and health risks due to exposure to soil and water contaminated with PAHs. Forest fires release a higher percentage of low molecular weight PAHs (LMW PAHs) than high molecular weight PAHs (HMW PAHs). Ash and burnt soils contain a higher percentage of LMW PAHs since biomass burning releases huge amounts of LMW PAHs. Whereas, sediments contain a higher percentage of HMW PAHs since most of the LMW PAHs are already degraded. HMW PAHs were causing higher risk to humans (both cancer and non-cancer) due to their higher oxidation potential. Exposure to water contaminated by PAHs resulted in higher health risks for both BaP equivalent and a mixture of PAHs. Exposure to sediment produced the highest health risk due to a higher percentage of HMW PAHs, followed by surface water, burnt soil, ash, and unburnt soil. Cancer and non-cancer risk due to dermal exposure was more elevated than oral exposure. The mixture of PAHs in sediment produced a higher average dermal risk for children (2.21E+00 for cancer and 7.69E+03 for non-cancer risk) and oral cancer risk for adults (7.11E-03). However, exposure to BaP equivalent in sediment produced higher oral non-cancer risk (7.01E+02) for children. Thus, effective PAHs monitoring is required in both soil and surface water mediums for ensuring proper treatment in water supply systems.

A comprehensive review on the decentralized composting systems for household biodegradable waste management.

Municipal solid waste primarily consists of household biodegradable waste (HBW). HBW treatment is a crucial step in many countries due to rapid urbanization. Composting is an effective technique to treat HBW. However, conventional composting systems are unable to produce matured compost (MC), as well as releasing huge amounts of greenhouse and odorous gases. Therefore, this review attempts to suggest suitable composting system to manage HBW, role of additives and bulking agents in composting process, identify knowledge gaps and recommend future research directions. Centralized composting systems are unable to produce MC due to improper sorting and inadequate aeration for composting substrate. Recently, decentralized compost systems (DCS) are becoming more popular due to effective solid waste reduction at the household and/or community level itself, thereby reducing the burden on municipalities. Solid waste sorting and aeration for the composting substrate is easy at DCS, thereby producing MC. However, Mono-composting of HBW in DCS leads to production of immature compost and release greenhouse and odorous gases due to lower free air space and carbon-to-nitrogen ratios, and higher moisture content. Mixing HBW with additives and bulking agents in DCS resulted in a proper initial substrate for composting, allowing rapid degradation of substrate due to longer duration of thermophilic phase and produce MC within a shorter duration. However, people have lack of awareness about solid waste management is the biggest challenge. More studies are needed to eliminate greenhouse and odorous gases emissions by mixing different combinations of bulking agents and additives (mainly microbial additives) to HBW in DCS.

Implication of microplastic toxicity on functioning of microalgae in aquatic system.

Microplastics (MPs) released from both primary and secondary sources affect the functioning of aquatic system. These MPs and components leached, can interact with aquatic organisms of all trophic levels, including the primary producers, such as microalgae. Considering the ecological value of microalgae and the toxicological effects of MPs towards them, this review provides: (1) a detailed understanding of the interactions between MPs and microalgae in the complex natural environment; (2) a discussion about the toxic effects of single type and mixtures of plastic particles on the microalgae cells, and (3) a discussion about the impacts of MPs on various features of microalgae -based bioremediation technology. For this purpose, toxic effects of MPs on various microalgal species were compiled and plastic components of MPs were ranked on the basis of their toxic effects. Based on available data, ranking for various plastic components was found to be: Polystyrene (PS) (rank 1) > Polyvinyl Chloride (PVC) > Polypropylene (PP) > Polyethylene (PE) (rank 4). Furthermore, the review suggested the need to understand joint toxicity of MPs along with co-contaminants on microalgae as the presence of other pollutants along with MPs might affect microalgae differently. In-depth investigations are required to check the impact of MPs on microalgae-based wastewater treatment technology and controlling factors.

Effect of seawater acidification and plasticizer (Bisphenol-A) on aggregation of nanoparticles.

This study investigated the effect of an organic pollutant (Bisphenol- A, an endocrine-disrupting chemical) on the stability of a mixture of nanoparticles (NPs). Experiments were conducted in seawater chemistry condition with TiO2/ZnO NP concentration ratio: 0.01, 0.1, 1, 10,100; pH: 7.4 and 8.1; BPA concentration: 1 and 10 µg/L. The presence of BPA was found to increase the size of NP. Lower pH of 7.4 increased size of NPs from 3 to 297% (at 1 µg/L BPA; NP ratio = 0.1 to 100). Aggregation rate constant values ranged between 0.17 and 1.81 nm/s in pH 7.4 suspension and between 0.48 and 56 nm/s in pH 8.1 suspension. Factors, such as pH and NP mass concentration had major effects on size change for suspension having the same ratio of TiO2/ZnO. NP aggregate was comprised of 97% ZnO NP, 3% TiO2 NP and had 1.39 mg/kg BPA. Overall, this study found dominance of van der Waals forces of attraction in mixture suspension of NPs and BPA. The obtained result on NP persistence in seawater can now be used in estimating exposure doses of a mixture of nanoparticles during inadvertent exposure.

Setting guidelines for co-occurring nanoparticles in water medium.

This study developed a framework termed as "mixNanohealthrisk" hereafter, for the first time as per literature review, to provide exposure limit or reference dose for co-occurring nanoparticles (NPs) in water for different regions of the world. The effect of interaction of NPs on (i) NP occurrence in environment and (ii) toxic effects were incorporated for estimating NP exposure dose and associated risks (in terms of risk quotient (RQ) and hazard index (HI). Reference dose (RfD) values for SiO2, CeO2, TiO2, Al2O3, Fe2O3, CNT, C60, ZnO and CuO NPs were calculated for the first time in this study based on toxicity studies. RfD values for top three risk-posing nanoparticles when co-occurring together were found to be 0.1 mg/kg/d (CuO), 0.12 mg/kg/d (ZnO) and 0.19 mg/kg/d (TiO2). Calculated maximum allowable concentration values for these nanoparticles were found to be 70.8, 84.4 and 136 mg/L for CuO, ZnO and TiO2 NPs. Exposures to nanoparticles aggregate (ZnO NP + CuO NP) in mixture suspension was found to have allowable ZnO and CuO concentration values of 24.7 mg/L and 175.2 mg/L respectively when present as aggregate. Top three regions identified with highest risk quotient were found to be USA followed by Switzerland and whole of Europe. During use of NP-interaction data for estimating risks, Ag, TiO2 and CuO NPs were found to have lowest maximum allowable concentration values. The identified top three risk-posing NPs can be used for conducting toxicity studies for mixture of NPs and long-term monitoring so that it can be used for setting up guideline concentration values for NPs in mixture for water environment.

Weight-of-evidence process for assessing human health risk of mixture of metal oxide nanoparticles and corresponding ions in aquatic matrices.

This study proposed a framework to estimate health risks due to exposure of mixture of nanoparticles (NPs) from surface water, for the first time, as per authors' best knowledge. The framework consisted of hazard identification, exposure assessment, dose-response assessment, risk characterization and risk management steps. Concentrations of mixture of NPs and associated ions were compiled and range of values were used for exposure estimation. The resulting concentrations of nanoparticle and metal ions in simulated digestive fluid were calculated and used to estimate exposure dose to digestive system organs during a hypothetical exposure of water during recreational activity. Exposure doses of different possible combinations of ZnO NP, CuO NP, Zn2+ and Cu2+ ions were considered. The ECHA weight-of- evidence framework was used for formulating hypotheses and collecting evidence for determining reference dose (RfD) and interaction parameter for estimating hazard interaction value (an index for risk) as per the USEPA modified weight-of-evidence method for estimating risks of binary NPs and ions. RfD values of CuO (0.0262 mg/kg/d) and ZnO NP (0.0315 mg/kg/d) were derived using information from rat-based oral toxicity studies and assumed values of uncertainty factors. The results showed that mixture of NPs under environmentally-relevant conditions do not pose any health risk. The uncertainty analysis indicated that ZnO + CuO + Zn + Cu ion suspension posed the highest risk. The switchover analysis indicated that NP concentration >0.207 mg/L resulted in risk estimate greater than 1 and pose risk. Although risk estimate was found to be smaller than 1 under the studied natural water condition, efforts should be made to continue monitoring mixture of NPs as a precautionary approach. More efforts are required to obtain data on (i)toxicity of mixture of NPs, (ii)their interaction effects, (iii)fractions of NPs reaching target organ in order to accurately predict risk. Potential benefit of this framework is in its usage for development of structure for estimating exposure risks due to mixture of NPs and ions from surface water. This can also be used to adopt methodology for gathering information on evidence required in different steps of risk assessment process, like obtaining RfD/uncertainty factor -related parameters in dose-response assessment step, deriving interaction and mixture toxicity-related parameters in risk estimation step.

Stability and characterization of mixture of three particle system containing ZnO-CuO nanoparticles and clay.

The aim of this study was to understand heteroaggregation of mixture of ZnO and CuO nanoparticles (NPs) with clay, for the first time as per the authors' knowledge. Aggregation studies of mixture of ZnO and CuO nanoparticles with clay was done (ionic strength =5 mM; pH 7; nanoparticles concentration = 0.1 mg/L, 1 mg/L, 10 mg/L; Clay concentration = 1, 10, and 100 mg/L and HA concentration = 0.1,1, and 10 mg/L as total organic carbon). Critical coagulation concentration (CCC) and attachment efficiency values of suspensions with ZnO: CuO ratio = 0.1, 1, 10 were also determined. Aggregation and liquid portions of mixture suspension at equal mass ratio were characterized for size, zeta potential (ZP), metal and ion contents, pH and conductivity. Results indicated that CCC was found to be 120.7 mM for ZnO: CuO ratio 10 and 1144 mM for ZnO: CuO ratio 1. Values of attachment efficiency were obtained to be 0.9 and 0.8 for these two ZnO:CuO ratio. At natural water ionic strength (IS) condition, aggregate rate constant of mixture of particles ranged from 0.281 to 8.63 nm/min for 10 mg/L NP concentration. Aggregation in suspension containing mixture of particles was found to be affected by NP concentration, clay concentration, and humic acid (p < 0.05). During a 1-h aggregation study, 2.67 mg Cu metal/g aggregate and 0.38 mg Zn/g aggregate were found in aggregates of 5 mM suspension. Overall, this study provided information on aggregation characterization of mixture of metal oxide nanoparticles (ZnO and CuO) in HA and clay presence, which is useful in understanding aggregation formation and in characterizing exposure dose for environmental risk assessment. More detailed information on a three -particle system with natural colloids is required for predicting their fate in aquatic system and defining risk.

Tradeoff between risks through ingestion of nanoparticle contaminated water or fish: Human health perspective.

This study proposed a framework (termed as "nanoHealthRisk" hereafter) for incorporating i) interaction of nanoparticles (NPs) with fishes, ii) availability of NPs to the human digestive system, and iii) estimation of health risk due to fish consumption and inadvertent ingestion of NP-contaminated surface water, for the first time as per the literature review. The framework was applied for estimating health risks due to hypothetical exposures of pristine ZnO, CuO, and TiO2 NPs (without any surface functionalization) from fish tissues. Values of bio- concentration factors (BCF) of ZnO, CuO, and TiO2 NPs in fish and model distributions of bio-assimilation factor of ZnO, CuO and TiO2 NPs in the human digestive system were incorporated explicitly in the risk assessment of NPs for the first time. ZnO NP was observed to be transferred more to the human digestive system from aqueous matrix than the other two NPs. Maximum allowable values of NP posing no risk were found to be 0.115 mg/L, 0.152 mg/L, and 1.77 × 107 mg/L for pristine ZnO, CuO and TiO2 NP, respectively. At the environmental concentration range, exposures of studied NPs from aquatic environment under the assumptions used did not pose any health risk under the conditions studied in this study. More work is required to (1) Estimate bio-concentration factors of a mixture of NPs with other constituents in fish tissues, (2) Estimate dissolution of NP from fish tissue in human digestive media, (3) Generate new data to develop reference dose of NP for human health risk assessment, and (4) Study effect of NP fate in the water on health risk through fish consumption pathway. Until all above-mentioned aspects are not explicitly incorporated in the risk assessment framework, risk estimates do not represent the risk from environment completely. Thus, continuous monitoring of these NPs in the environment is required to protect health due to chronic exposure of small concentrations of NPs from an aqueous matrix.

Understanding effect of solution chemistry on heteroaggregation of zinc oxide and copper oxide nanoparticles.

The reported presence of mixture of nanoparticles in environmental water warrants developing understanding on their aggregation and fate. This study tried to address this question and focused on understanding effects of pH (3,7 and 10), background electrolyte concentration (1 mM and 10 mM as NaCl) and nanoparticle (NP) concentration (1 and 10 mg/L) on stability of suspension containing mixture of two commonly-found metal oxide-based NP (i.e., ZnO and CuO NPs) in a 6-h study (output variables: aggregation rate constant, settling rate constant, difference in zeta potential, change of metal content in suspension and on aggregates). Two iso-electric point values were obtained: pH 3.08 and 8.33 for mixture suspension in DI (De-ionized) water and pH 5.69 and 8.65 for mixture suspension with 10 mM electrolyte concentration. Settling rate constant and aggregation rate constant values of suspension containing mixture of NPs varied between 0.02 and 0.23 NTU/(NTU-hour) and 0.0002 and 0.03 nm/s, respectively. At natural pH condition, settling rate constant and aggregation rate constant values were obtained to be 0.05 NTU/(NTU- hour) and 0.012 nm/s. The Derjaguin-Landau-Verway-Overbeek (DLVO) analyses indicated that aggregation of mixture of NPs might be happening due to combined effects of ionic layer compression, charge neutralization and van der Waals attraction. Dissolution of nanoparticles was found to be significantly affected by change in pH of suspension. Stability of mixture of nanoparticles was observed to decrease with increasing pH, ionic strength and nanoparticle concentration values. For ZnO and CuO nanoparticles, model equations were developed for predicting their (i) aggregation rate constant, (ii) settling rate constant, (iii) difference in zeta potential, (iv) percentage change of metal in suspension and (v) solid Zn fractions of mixture of nanoparticles as a function of pH, ionic strength and NP concentration. These information are useful in understanding fate of mixture of NPs in suspension as well as in settled solids in natural water bodies and in water treatment systems.