Endocrine disrupting chemicals in wastewater treatment plants in Kenya, East Africa: Concentrations, removal efficiency, mass loading rates and ecological impacts.

This study investigated the levels, mass loadings, removal efficiency, and associated ecotoxicological risks of selected endocrine disrupting chemicals (EDCs), namely, dibutylphthalate (DBP), diethylhexylphthalate (DEHP), dimethylphthalate (DMP), linuron (LNR) and progesterone (PGT) in wastewater, sludge, and untreated dry biosolid (UDBS) samples from twelve wastewater treatment plants (WWTPs) in nine major towns in Kenya. Analysis was done using high-performance liquid chromatography coupled with triple quadrupole mass spectrometry (LC-MS/MS). All the wastewater influents had quantifiable levels of EDCs with DBP being the most abundant (37.49%) with a range of 4.33 ± 0.63 to 19.68 ± 1.24 µg L-1. DEHP was the most abundant in sludge and accounted for 48.2% ranging between 278.67 and 9243.49 ng g-1 dry weight (dw). In the UDBS samples, DEHP was also the most abundant (40%) of the total EDCs detected with levels ranging from 78.77 to 3938.54 ng g-1 dw. The average removal efficiency per pollutant was as follows: DMP (98.7%) > DEHP (91.7%) > PGT (83.4%) > DBP (77.9%) > LNR (72.2%) which can be attributed to sorption onto the biosolid, biological degradation, photolysis, and phytoremediation. The pH was negatively correlated to the EDC concentrations while total dissolved solids (TDS), chemical oxygen demand (COD), biochemical oxygen demand (BOD5), and electrical conductivity (EC) were positively correlated. The mass loadings were as high as 373.33 g day-1 of DBP in the treatment plants located in densely populated cities. DEHP and PGT had their Risk Quotients (RQs) > 1, posing a high risk to biota. DMP, DBP, and LNR posed medium risks as their RQ values were between 0.1 and 1. EDCs are therefore loaded to environmental compartments through either the effluent that loads these pollutants into the receiving aquatic ecosystem or through the UDBS, which are used as fertilizers in agricultural farmlands causing potential toxicological risks to aquatic and terrestrial life.

Insights on adsorption of carbamazepine onto iron oxide modified diatomaceous earth: Kinetics, isotherms, thermodynamics, and mechanisms.

To ameliorate adsorbent recovery by an external magnetic field, naturally occurring diatomaceous earth (DE) was modified with iron-oxide, characterized and applied for adsorption of carbamazepine (CBZ) from synthetic wastewater using batch equilibration method. The fabricated adsorbent was characterized using XRF, XRD, SEM-EDX, FT-IR, BET surface area analysis, VSM and pH of point of zero charge (pHpzc) determination. The adsorption rate was described by the pseudo-first-order (PFO) model suggesting a physisorption controlled rate-determining step. Equilibrium adsorption data were fitted to linear and nonlinear isotherm models, viz Langmuir and Freundlich models, and were best described by Freundlich nonlinear equations implying heterogeneous multilayer adsorption. The best-fitting kinetic and isotherm model was determined using four mathematical error functions. The thermodynamic parameters, namely enthalpy (ΔH = -26.4 kJ mol-1), Gibbs free energy (ΔG = -2.22 kJ mol-1 at 298 K), entropy (ΔS = -34.0 kJ mol-1), indicated that the adsorption was a spontaneous, exothermic, and physical process. The adsorption mechanism is postulated to involve cation-π interactions. Modified diatomaceous earth is a potentially excellent, low-cost, and novel sorbent for CBZ adsorption with 88% removal in 180 min and provides a possible alternative adsorbent for wastewater treatment.

Biodegradation of carbofuran in soils within Nzoia River Basin, Kenya.

Carbofuran (2,3-dihydro-2,2-dimethylbenzofuran-7-yl methylcarbamate) has been used within the Nzoia River Basin (NRB), especially in Bunyala Rice Irrigation Schemes, in Kenya for the control of pests. In this study, the capacity of native bacteria to degrade carbofuran in soils from NRB was investigated. A gram positive, rod-shaped bacteria capable of degrading carbofuran was isolated through liquid cultures with carbofuran as the only carbon and nitrogen source. The isolate degraded 98% of 100-µg mL(-1) carbofuran within 10 days with the formation of carbofuran phenol as the only detectable metabolite. The degradation of carbofuran was followed by measuring its residues in liquid cultures using high performance liquid chromatography (HPLC). Physical and morphological characteristics as well as molecular characterization confirmed the bacterial isolate to be a member of Bacillus species. The results indicate that this strain of Bacillus sp. could be considered as Bacillus cereus or Bacillus thuringiensis with a bootstrap value of 100% similar to the 16S rRNA gene sequences. The biodegradation capability of the native strains in this study indicates that they have great potential for application in bioremediation of carbofuran-contaminated soil sites.

Chlorpyrifos degradation in soils with different treatment regimes within Nzoia River Drainage Basin, Kenya.

Two organic amendments, filter mud compost and Tithonia diversifolia leaves generated within a sugarcane growing area were used to enhance the degradation of chlorpyrifos in soil. Filter mud compost and T. diversifolia leaves significantly enhanced degradation of chlorpyrifos in soils (p < 0.05) with DT50 values of 21 and 24 days, respectively. Furthermore, field degradation of chlorpyrifos in soil with prior exposure to chlorpyrifos was significantly enhanced (p = 0.034) with DT50 of 21 days compared to 30 days in soil with no previous exposure. Degradation of chlorpyrifos in sterile and non-sterile soils were significantly different (p = 0.023) with DT50 values of 161 and 27 days, respectively. Results show enhanced degradation of chlorpyrifos in organically amended soils and soils with prior exposure to the pesticide. These amendments show promise in a continuing effort to reduce chlorpyrifos concentrations in soils.

Isolation and identification of hexazinone-degrading bacterium from sugarcane-cultivated soil in Kenya.

The s-triazine herbicide hexazinone [3-cyclohexyl-6-dimethylamino-1-methyl-1,3,5-triazine-2,4(1H,3H)-dione], is widely used in agriculture for weed control. Laboratory biodegradation experiments for hexazinone in liquid cultures were carried out using sugarcane-cultivated soils in Kenya. Liquid culture experiments with hexazinone as the only carbon source led to the isolation of a bacterial strain capable of its degradation. Through morphological, biochemical and molecular characterization by 16S rRNA, the isolate was identified as Enterobacter cloacae. The isolate degraded hexazinone up to 27.3% of the initially applied concentration of 40 µg mL(-1) after 37 days of incubation in a liquid culture medium. The study reports the degradation of hexazinone and characterization of the isolated bacterial strain.

The dissipation of carbofuran in two soils with different pesticide application histories within Nzoia River Drainage Basin, Kenya.

The dissipation of carbofuran from soils within the Nzoia River Drainage Basin in Kenya was studied under real field conditions for 112 days. Results showed significantly enhanced dissipation of carbofuran with half life (DT50) values of 8 days (p = 0.038) in soils with prior exposure to carbofuran compared to 19 days in soils with no application history. At the end of the experiment, residues of 2.57% and 9.36% of the initial carbofuran applied were recorded in the two types of soil, respectively. Carbofuran metabolites identified in the study were 3-keto carbofuran and carbofuran phenol with 5.84% and 15.0% remaining in soils with prior exposure, respectively. Soils with no application history recorded 16.05% and 12.82% of 3-keto carbofuran and carbofuran phenol metabolites, respectively.

Effects of carbon amendment on in situ atrazine degradation and total microbial biomass.

This study elucidates the effects of carbon amendment on metabolic degradation of atrazine (6-chloro-N(2)-ethyl-N(4)-isopropyl-1,3,5-triazine-2,4-diamine) and total microbial biomass in soil. Degradation of (14)C-ring-labelled atrazine was monitored in laboratory incubations of soils supplemented with 0, 10, 100 and 1000 µg g(-1) sucrose concentrations. An experiment to determine the effect of carbon amendment on total microbial biomass and soil respiration was carried out with different concentrations of sucrose and non-labelled atrazine. The soils were incubated at a constant temperature and constant soil moisture at water potential of -15 kPa and a soil density of 1.3 g cm(-3). Mineralization of (14)C-ring-labelled atrazine was monitored continuously over a period of 59 d in the first experiment. The CO(2) production was monitored for 62 d in the second experiment and microbial biomass determined at the end of the incubation period. The addition of 1000 µg g(-1) sucrose reduced atrazine mineralization to 43.5% compared to 51.7% of the applied amount for the treatment without sucrose. The addition of 1000 µg g(-1) sucrose modified the transformation products to 1.08 µg g(-1) deisopropylatrazine (DIA), 0.32 µg g(-1) desethylatrazine (DEA) and 0.18 µg g(-1) deisopropyl-2-hydroxyatrazine (OH-DIA). Treatment without sucrose resulted in formation of 0.64 µg g(-1) hydroxyatrazine (HA), 0.28 µg g(-1) DIA and 0.20 µg g(-1) OH-DIA. Atrazine dealkylation was enhanced in treatments with 100 and 1000 µg g(-1) of sucrose added. HA metabolite was formed in the control (no sucrose) and in the presence of 10 µg g(-1) of sucrose, whereas DEA was only detected in treatment with 1000 µg g(-1) sucrose. Results indicate that total microbial biomass increased significantly (P < 0.001) with the addition of 1000 µg g(-1) sucrose.

Biodegradation of s-triazine herbicide atrazine by Enterobacter cloacae and Burkholderia cepacia sp. from long-term treated sugarcane-cultivated soils in Kenya.

In this study soils from sugarcane-cultivated fields were screened for bacterial species capable of atrazine (6-chloro-N²-ethyl-N4-isopropyl-1,3,5-triazine-2,4-diamine) degradation due to long exposure of the soils to this herbicide. To enrich for atrazine degraders, Minimal Salt Medium containing atrazine as the sole N source and glucose as the C source was inoculated with soils impacted with this herbicide and incubated. Bacterial growth was monitored by measuring optical density. The degradation of atrazine was followed by measuring residual atrazine in liquid cultures over a given time period by high performance liquid chromatography. Bacterial strains isolated from the enrichment cultures were characterized by biochemical tests and identified by 16S rRNA gene sequencing. Two bacterial strains coded ISL 8 and ISL 15 isolated from two different fields were shown to have 94 and 96% 16S rRNA gene sequence similarity to Burkholderia cepacia respectively. Another bacterial sp., ISL 14 was closely related to Enterobacter cloacae with a 96% 16S rRNA gene sequence similarity. There was not much difference between the extents of atrazine degradation by the enrichment cultures with communities (79-82% applied amount) from which pure strains were isolated and the pure strains themselves in liquid cultures that showed a degradation of 53-83% of applied amount. The study showed existence of bacterial strains in different sugarcane-cultivated fields which can use atrazine as a nitrogen source. The bacterial strains isolated can be used to enhance the degradation of atrazine in contaminated soils where atrazine is still considered to be recalcitrant.

The influence of filter mud compost and Tithonia diversifolia leaves on the dissipation of diuron in soils within the Nzoia River Drainage Basin, Kenya.

The aim of the study was to evaluate the environmental impact of filter mud compost and Tithonia diversifoila amendments on the dissipation of diuron in sugarcane cultivated soils. Filter mud compost is the by-product of sugarcane processing, while T. diversifoila is a common local plant that grows within the study region. The dissipation of diuron was significantly enhanced with DT(50) of 15 and 16 days (p < 0.05) in soils amended with filter mud compost and T. diversifoila, respectively compared to 26 days in non-amended soils. Residues of 0.93 %, 1.83 % and 5.40 % of the initial applied diuron were recorded at the end of the experiment in the three treatments, respectively. The residues of 3,4-dichlorophenylmethylurea metabolite were 22.93 %, 25.92 % and 30.93 %, while 10.19 %, 12.19 % and 15.46 % of 3,4-dichloroaniline metabolite remained in soil after 112 days in the three treatments, respectively.

Adsorption-desorption and leaching behavior of diuron on selected Kenyan agricultural soils.

In this work, the adsorption-desorption dynamics of diuron in three typical Kenyan agricultural soils, Nzoia (NZ), Thika (TH) and Machakos (MK) was investigated. The equilibrium adsorption data, tested against three classical nonlinear adsorption isotherms, was best described by the Freundlich model. The Freundlich adsorption constant, (KF), increased in the order MK > TH > NZ soil. Additionally, the negative Gibb's free energy values indicate the adsorption processes were thermodynamically spontaneous and physical. Multiple linear regression analysis indicated that the adsorption-desorption behavior was controlled by the clay and phosphorus contents of the soil. Phosphorus negatively affected the adsorption of diuron and promoted desorption. The groundwater ubiquity score (GUS) indicated that diuron movement rating in MK soil was 'moderate' while the movement in TH and NZ soils was 'high'.

The dissipation of hexazinone in tropical soils under semi-controlled field conditions in Kenya.

The dissipation of hexazinone (Velpar) in two tropical soil types in Kenya was studied under field and semi-controlled conditions for a period of 84 days. The dissipation was found to be very rapid and this could be attributed to adverse weather conditions including high initial rainfall as well as to low soil-organic-matter content, volatilization, surface run-off and biodegradation. The DT(50) values of dissipation obtained by first order kinetics were 20 days and 21.3 days in clay and loam soil types, respectively. The influence of bargasse compost (1000 microg/g dry soil) was also studied and was found to enhance dissipation to some extent, giving DT(50) values of 18 days and 18.3 days in clay and loam soil types, respectively.

First comprehensive study on total contents and hot water extractable fraction of selected elements in 19 medicinal plants from various locations in Nyamira County, Kenya.

A large number of medicinal plants is traditionally known in Kenya and used for treatment of various diseases, for example diabetes, where metals are supposed to be involved in pathogenesis and therapy. Therefore, detailed investigation of the concentration of a large number of metals in medicinal plants is required for improved understanding and optimisation of the therapeutic role of metals and also to exclude potentially toxic effects. Our study focused on the determination of 30 selected elements in 19 medicinal plant species each collected from 3 sampling locations in Nyamira County, Kenya. The obtained comprehensive data set showed large variability and multivariate data analysis revealed that the differences in the elemental composition were stronger dependent on the plant species than on the sampling location. In addition, hot water extractions were performed to mimic the traditional preparation of medicine from the plants. It was found that the mean extraction efficiencies were below 20% except for B, Mg, P, K, Mn, Co, Ni, Cu, Zn, Rb, Mo, Cd and Tl, which are mostly essential elements apart from Cd and Tl. Sequential (ultra)filtration of the extracts was applied as novel approach for molecular size-fractionation of the extracted elemental species. The results indicate more than 50% low molecular weight species (<3kDa) for Mg, Mn, Co, Ni and Zn while predominantly larger size-fractions (>3kDa up to<5µm) were detected for V, Cu, Al and Fe.

Effect of fluctuating soil humidity on in situ bioavailability and degradation of atrazine.

This study elucidates the effect of fluctuating soil moisture on the co-metabolic degradation of atrazine (6-chloro-N(2)-ethyl-N(4)-isopropyl-1,3,5-triazine-2,4-diamine) in soil. Degradation experiments with (14)C-ring-labelled atrazine were carried out at (i) constant (CH) and (ii) fluctuating soil humidity (FH). Temperature was kept constant in all experiments. Experiments under constant soil moisture conditions were conducted at a water potential of -15 kPa and the sets which were run under fluctuating soil moisture conditions were subjected to eight drying-rewetting cycles where they were dried to a water potential of around -200 kPa and rewetted to -15 kPa. Mineralization was monitored continuously over a period of 56d. Every two weeks the pesticide residues in soil pore water (PW), the methanol-extractable pesticide residues, the non-extractable residues (NER), and the total cell counts were determined. In the soil with FH conditions, mineralization of atrazine as well as the formation of the intermediate product deisopropyl-2-hydroxyatrazine was increased compared to the soil with constant humidity. In general, we found a significant correlation between the formation of this metabolite and atrazine mineralization. The cell counts were not different in the two experimental variants. These results indicate that the microbial activity was not a limiting factor but the mineralization of atrazine was essentially controlled by the bioavailability of the parent compound and the degradation product deisopropyl-2-hydroxyatrazine.

Atrazine and terbuthylazine mineralization by an Arthrobacter sp. isolated from a sugarcane-cultivated soil in Kenya.

A tropical soil from a Kenyan sugarcane-cultivated field showed a very high capability to mineralize (14)C-ring-labeled atrazine. In laboratory experiments this soil mineralized about 90% of the applied atrazine within 98 d. The atrazine-degrading microbial community was enriched in liquid cultures containing atrazine as the sole N source and 100 mgL(-1) glucose as additional C source. From the enrichment culture a bacterial strain was isolated and identified by comparative sequence analysis of the 16S-rDNA as member of the genus Arthrobacter. The enriched mixed culture as well as the isolated strain, designated as Arthrobacter sp. strain GZK-1, could grow on atrazine and terbuthylazine as sole N-sources; Arthrobacter sp. GZK-1 mineralized (14)C-ring-labeled atrazine up to 88% to (14)CO(2) and (14)C-ring-labeled terbuthylazine up to 65% to (14)CO(2) in a liquid culture within 14 d. The enriched microbial consortium as well as the isolated strain could be a potential solution for the remediation of s-triazine polluted agricultural soils.