Investigation of alkyl, aryl, and chlorinated OPFRs in sediments from estuarine systems: Seasonal variation, spatial distribution and ecological risks assessment.

Estuaries in South Africa are very important for biodiversity conservation and serve as focal points for leisure and tourism activities. The organophosphate flame retardants (OPFRs) levels in these aquatic systems haven't been documented in any studies as of yet. Due to the negative effects of persistent organic pollutants in South African estuaries, we examined the occurrence of eight OPFRs in sediments of two estuaries by studying their spatiotemporal distribution, season variation, and ecological risks. The Sundays Estuary (SDE), a semi-urbanized agricultural surrounding system, recorded an ∑8OPFR concentration in sediments that ranged from 0.71 to 22.5 ng/g dw, whereas Swartkops Estuary, a largely urbanized system, recorded a concentration that ranged from 0.61 to 119 ng/g dw. Alkyl-OPFRs were the prevalent homologue in both estuaries compared to the chlorinated and aryl groups. While TBP, TCPP, and TCrP were the most abundant compounds among the homologue groups. There was no distinct seasonal trend of ∑8OPFR concentration in either estuary, with summer and autumn seasons recording the highest concentrations in SDE and SWE, respectively. Ecological risks in the majority of the study sites for the detected compounds were at low (RQ < 0.1) and medium levels (0.1 ≤ RQ < 1) for certain species of fish, Daphnia magna and algae. However, the cumulative RQs for all the compounds had ∑RQs ≥1 for most sites in both estuaries, indicating that these organisms, if present in both estuaries, may be exposed to potential ecological concerns due to accumulated OPFR chemicals. The scope of future studies should be broadened to include research areas that are not only focus on the bioaccumulation patterns of these compounds but also find sustainable ways to reduce them from these estuarine environments.

Organophosphate pesticides sequestered in tissues of a seagrass species - Zostera capensis from a polluted watershed.

Organophosphate pesticides (OPPs) are persistent in the environment, but little information is available on their bioaccumulation in seagrass. In this study, the seagrass - Zostera capensis was collected from Swartkops Estuary in South Africa to investigate the bioaccumulation of OPPs from contaminated sediments and the water column. This plant was chosen because it grows abundantly in the estuary's intertidal zone, making it a viable phytoremediator in the urban environment. Extraction was performed by the QuEChERS method followed by GC-MS analysis. The mean concentration of ∑OPPs ranged from 0.01 to 0.03 µg/L for surface water; 6.20-13.35 µg/kg dw for deep-rooted sediments; 18.79-37.75 µg/kg dw for leaf tissues and 12.14-39.80 µg/kg dw for root tissues of Z. capensis. The biota-sediment accumulation factors (BSAFs) were greater than one, indicating the potential for Z. capensis to bioaccumulate and intercept the targeted pesticides. A weak insignificant correlation observed between log BSAFs and log Kow indicates that the bioaccumulation of OPPs in tissues of Z. capensis were not dependent on the Kow. Eight of the selected pesticides had root-leaf translocation factors (TFr-l) greater than 1, indicating that Z. capensis can transport these chemicals from roots to leaves. The results from this study implies that this plant species can clean up OPP contamination in the environment.

Creation of an international laboratory network towards global microplastics monitoring harmonisation.

Infrastructure is often a limiting factor in microplastics research impacting the production of scientific outputs and monitoring data. International projects are therefore required to promote collaboration and development of national and regional scientific hubs. The Commonwealth Litter Programme and the Ocean Country Partnership Programme were developed to support Global South countries to take actions on plastics entering the oceans. An international laboratory network was developed to provide the infrastructure and in country capacity to conduct the collection and processing of microplastics in environmental samples. The laboratory network was also extended to include a network developed by the University of East Anglia, UK. All the laboratories were provided with similar equipment for the collection, processing and analysis of microplastics in environmental samples. Harmonised protocols and training were also provided in country during laboratory setup to ensure comparability of quality-controlled outputs between laboratories. Such large networks are needed to produce comparable baseline and monitoring assessments.

Heavy metal compartmentalisation in salt marsh and seagrass of the urbanised Swartkops estuary, South Africa.

Wetland plants are naturally exposed to high metal concentrations, and often have mechanisms to prevent metal toxicity. This study compared metal concentrations in seagrass (Zostera capensis) and salt marsh (Spartina maritima, Salicornia tegetaria) - to determine their niche as metal sinks. Samples were collected in each season over a year at five sites in the estuary and analysed using a Total X-Ray Fluorescence (TXRF) spectrometer. Spartina maritima and S. tegetaria accumulated in their roots, and displayed little translocation to leaves (BCF = 1-14; TF[leaf/root] < 1). Contrastingly, Z. capensis showed high uptake to its leaves (TF[leaf/root] = 1-8; Mn, Zn, Cr, Pb, Ni, Cu). Spartina maritima and S. tegetaria were identified as good phytostabilisers (BCF > 1, TF[leaf/root] < 1). Compartmentalization was unique to each species, and considering their ecosystem service importance, more plant species should be analysed to estimate their ecological value for management purposes.

Tissue distribution, dietary intake and human health risk assessment of organophosphate pesticides in common fish species from South African estuaries.

This study assessed the tissue distribution, dietary intake, and potential health risks of eight OPPs in Pomadasys commersonnii (Spotted grunter) and Mugil cephalus (Flathead mullet) from the Sundays and Swartkops estuaries in South Africa. The highest concentration in fish tissues was found in muscles of M. cephalus (178 ± 80.4 ng/g ww) and P. commersonnii (591 ± 280 ng/g ww) from Sundays Estuary. The ∑6OPPs concentration in muscles from both fish species was higher in muscles than in the gills with fenitrothion dominating the distribution profile. Results from the path analysis indicate that lipid, weights, and length of the fish species do not influence the concentration of OPPs in the studied fish species. The calculated hazard ratios, which represent the non-carcinogenic risks, were less than one for all OPPs, indicating that the concentration of OPPs detected in fish muscles had negligible consequences on human health.

Ecological risk assessment of metal pollutants in two agriculturally impacted estuaries.

A focused diagnosis of ecosystem health in two South African estuaries (Kromme and Gamtoos) was conducted. Four pollution indices were used, i.e., geoaccumulation (Igeo), ecological risk (RI), contamination factor (CF) and pollution load index (PLI), to assess toxicity levels of metal contaminants in relation to background values. The Igeo results (11.1 %) can be classified as contaminated, with Cd, the only element with high values in both estuaries. Likely sources (herbicides, pesticides) of Cd are used in the agricultural dominated catchments. There was a high concentration of Mn (13.4 ± 2.51 and 12.3 ± 1.13 µg·g-1) and Fe (1289 ± 243 and 1291 ± 130 µg·g-1) at site 4 for Gamtoos and Kromme estuary respectively compared to the other metal elements. Although results indicate low metal contamination, with increasing global anthropogenic pressure, continuous monitoring should be prioritised to assist in managing estuarine systems that support a wide range of socio-economic and ecosystem services.

Organophosphate pesticides in South African eutrophic estuaries: Spatial distribution, seasonal variation, and ecological risk assessment.

The seasonal variation, spatial distribution, and ecological risks of thirteen organophosphate pesticides (OPPs) were studied in the Sundays and Swartkops estuaries in South Africa. Ten pesticides were detected in surface water samples from both estuaries, while all OPPs were detected in sediments. The highest concentration of OPPs (18.8 µg pyrazophos L-1) was detected in surface water samples from Swartkops Estuary, while 48.7 µg phosalone kg-1 dw was the highest in sediments collected from Sundays Estuary. There was no clear seasonal pattern in OPPs occurrence in surface water from both systems. However, their occurrence in sediments was in the following order: winter > autumn > summer > spring, perhaps indicating major pesticide input in the winter seasons. Results from ecological risk assessment showed that pyraclofos and chlorpyrifos (CHL) in surface water from both systems are respectively likely to cause high acute and chronic toxicity to fish (risk quotient - RQ > 1). For sediments of both estuaries, the highest acute and chronic RQs for fish were calculated for isazophos and CHL respectively. The majority of the detected OPPs in sediments posed potential high risks to Daphnia magna from both systems. These results suggest that these aquatic organisms (fish, and Daphnia), if present in the studied estuaries, can develop certain forms of abnormalities due to OPP exposure. To this end, proper measures should be taken to reduce OPP input into the estuarine systems.

Blue carbon and nutrient stocks in salt marsh and seagrass from an urban African estuary.

Halophytes in estuaries are effective sinks of carbon, nitrogen, and phosphorus. Blue carbon (BC) is carbon stored in coastal habitats such as mangroves, salt marshes and seagrass. The objectives of this study were to firstly assess the biomass and sediment C stocks in salt marsh (Spartina maritima and Salicornia tegetaria) and seagrass (Zostera capensis) habitats of the Swartkops Estuary, South Africa. Secondly, we applied the nutrient pollutant indicator (NPI) to assess the nutrient status of the estuary. Six replicate sediment cores of 1 m (summer) and 0.5 m (winter) per plant species were collected at six sites. Six replicates for biomass of each species were harvested at each site during summer and winter. Biomass and nutrient dynamics showed that there were distinct seasonal differences in the magnitude of C, N, and P stored in the plants. The sediment was the dominant C pool and differed spatially with creek sites storing more C. Out of the three species, S. maritima stored the most C (224 ± 19.1 Mg C ha-1 in sediment, 16.7 ± 1.2 Mg C ha-1 in biomass), followed by S. tegetaria (207 ± 3.5 Mg C ha-1 in sediment, 4.3 ± 0.4 Mg C ha-1 in biomass) and Z. capensis (180 ± 18.4 Mg C ha-1 in sediment, 2.1 ± 0.7 Mg C ha-1 in biomass). The N:biomass ratios were low in both seasons for Z. capensis, S. maritima and S. tegetaria (0.08, 0.02 and 0.04, respectively) indicating consistent eutrophic conditions in the estuary. Resultantly, the plants displayed a significantly lower below-ground standing biomass highlighting the potential variations of BC storage in eutrophic estuaries.

A translocation analysis of organophosphate pesticides between surface water, sediments and tissues of common reed Phragmites australis.

This study investigated the ability of common reed, Phragmites australis to take up organophosphate pesticides (OPPs). The study site was the agriculturally polluted Sundays Estuary in South Africa. Surface water, leaves, roots, and deep-rooted-sediments of P. australis were collected along the length of the estuary and analysed for 13 different OPPS. The extraction of OPPs in plant tissues was performed by QuEChERS method followed by GC-MS analysis. The highest concentration of OPPs was found in leaves (16.41-31.39 µg kg-1 dw), followed by roots (13.92-30.88 µg kg-1 dw), and sediments (3.30-8.07 µg kg-1 dw). Of the 13 targeted OPPs, only one compound was not detected across the four sample matrices, thus reflecting widespread contamination in the Sundays Estuary. The biota sediment accumulation factor (BSAF) values of pyraclofos, quinalphos, fenitrothion, phosalone, EPN, diazinon, chlorpyrifos, pyrazophos, and isazophos were higher than one implying that P. australis possesses the ability to bioaccumulate these compounds. The root-leaf translocation factors (TFr-l) of these pesticides were higher than 1, suggesting that P. australis possesses the capacity to move these pesticides from roots to leaves. The insignificant correlation observed between log BSAF and log Kow and log TFr-l and log Kow implies that OPPs uptake by P. australis tissues were not dependent on log Kow. Our study demonstrates that P. australis possesses the potential to effectively remove OPPs from contaminated water and sediment.

Microphytobenthos diversity and community structure across different micro-estuaries and micro-outlets: Effects of environmental variables on community structure.

This study forms the first basic assessment of microphytobenthos (MPB) dynamics in micro-estuaries and micro-outlets in southern Africa. It examines MPB community responses to environmental variables and further investigates MPB composition qualitatively across different micro-estuaries and micro-outlets over four seasons in a warm temperate region of the subcontinent. Combinations of multivariate analyses were used to explore similarities and differences in MPB communities between systems. Human-induced catchment changes between microsystems ranged from no alteration (rating 0; mostly micro-outlets) to extreme modification (rating 5; mostly micro-estuaries). Two hundred and sixty-seven MPB taxa were identified within all the microsystems, with 247 and 230 MPB taxa being observed in the micro-estuaries and micro-outlets, respectively. The MPB communities differed slightly in terms of microsystem types and seasons, but no significant differences were observed. Multivariate analyses (i.e. Boosted Regression Trees, Canonical Correspondence Analysis) showed that water column variables were significant and important in structuring MPB communities, with soluble reactive phosphorus, sediment pH, turbidity, ammonium and temperature being documented as key drivers. The MPB community composition clearly reflected the influence of catchment anthropogenic activities on species composition and structure. Moderately modified catchments resulted in MPB community structure variation among water bodies in relationship to land use and salinity gradients. The study found that; (i) by virtue of their size, microsystems and their catchments are likely to be particularly vulnerable to anthropogenic pressures when compared to systems of larger size; (ii) a typical impacted state may reflect reduced environmental heterogeneity which, compared to larger systems, may be achieved over much shorter time periods (following a particular event) or under much less intensive impacts; and (iii) the response in terms of MPB structure may predictably reflect a concomitant change from a complex community dynamic (structure and spatio-temporal attributes) to one that approaches a homogeneous structure (poor spatial zonation, strong taxonomic dominance, low species diversity).