UV irradiation enhanced removal of colloidal phosphorus in agricultural runoff.

Colloidal phosphorus (P) is an important P form in agricultural runoff and can threaten water quality. However, up to date, there are few effective approaches to mitigate colloidal P pollution. This study investigated the effect of ultraviolet (UV) irradiation on medium-colloidal (MC; 220 nm-450 nm) and fine-colloidal (FC; 3 kDa-220 nm) P in agricultural runoff. Under 24 h of UV irradiation, as the most abundant colloidal P fraction, concentration of total P (TP) in FC consistently decreased by 81.0%, while TP concentration in MC first increased by 74.4% after 3 h and then decreased with irradiation time. At the same time, particulate TP (>450 nm) concentration was found to be increased from 0 to 14.7 µM. However, there were no obvious variations in TP concentrations in FC and MC fractions under dark conditions. In FC fraction, with the decrease of TP, the corresponding concentrations of iron (Fe), aluminum (Al), silicon (Si) declined synchronously, and ferric iron/ferrous iron (Fe(III)/Fe(II)) ratio and organic matter (OM) concentration were reduced as well. These results suggested that P in FC fraction was gradually transformed into particulate P during photoreduction of Fe(III) and photodegradation of OM under UV irradiation. Our study helps to understand the mechanism of the phototransformation of colloidal P, and propose an UV irradiation-based approach to remove colloidal P in agricultural runoff.

Contribution of Biogas Slurry-Derived Colloids to Plant P Uptake and Phosphatase Activities: Spatiotemporal Response.

The bioavailability for varied-size phosphorus (P)-binding colloids (Pcoll) especially from external P sources in soil terrestrial ecosystems remains unclear. This study evaluated the differential contribution of various-sized biogas slurry (BS)-derived colloids to plant available P uptake in the rhizosphere and the corresponding patterns of phosphatase response. Keeping the same content of total P input (15 mg kg-1), we applied different size-fractioned BS-derived colloids including nanosized colloids (NCs, 1-20 nm), fine-sized colloids (FCs, 20-220 nm), and medium-sized colloids (MCs, 220-450 nm) respectively to conduct a 45-day rice (Oryza sativa L.) rhizotron experiment. During the whole cultivation period, the dynamics of chemical characteristics and P fractions in each experimental rhizosphere soil solution were analyzed. The spatial and temporal dynamics examination of P-transforming enzymes (acid phosphatases) in the rice rhizosphere was visualized by a soil zymography technique after 5, 25, and 45 days of rice transplantation. The results indicated that the acid phosphatase activities and its hot spot areas were significantly 1) correlated with the relative bioavailability of colloidal P (RBAcoll), 2) increased with the colloid-free (truly dissolved P) and BS-derived NC addition, and 3) affected by the plant growth stage. With the nanosized BS colloid addition, the RBAcoll and plant biomass were respectively found to be the highest (64% and 1.22 g plant-1), in which the acid phosphatase-catalyzed hydrolysis of organic Pcoll played an important role. All of the above suggested that nanosized BS-derived colloids are an effective alternative to conventional phosphorus fertilizer for promoting plant P uptake and P bioavailability.

Biochar-coupled organic fertilizer reduced soil water-dispersible colloidal phosphorus contents in agricultural fields.

Soil water-dispersible colloidal phosphorus (WCP) presents high mobility, however, the regulatory effect of biochar-coupled organic fertilizer is rarely known, especially under different cropping patterns. This study investigated the P adsorption, soil aggregate stability, and WCP in three paddy and three vegetable fields. These soils were amended with different fertilizers (chemical fertilizer, CF; substitution of solid-sheep manure or liquid-biogas slurry organic fertilizer, SOF/LOF; substitution of biochar-coupled organic fertilizers, BSOF/BLOF). Results presented that the LOF averagely increased the WCP contents by 50.2% across the sites, but the SOF and BSOF/BLOF averagely decreased their contents by 38.5% and 50.7% in comparison with the CF. The WCP decline in the BSOF/BLOF-amended soils was mainly attributed to the intensive P adsorption capacity and soil aggregate stability. The BSOF/BLOF increased the amorphous Fe and Al contents in the fields in comparison with the CF, which improved the adsorption capacity of soil particles, further improving the maximum absorbed P (Qmax) and reducing the dissolved organic matter (DOC), leading to the improvement of > 2 mm water-stable aggregate (WSA>2mm) and subsequent WCP decrease. This was proved by the remarkable negative associations between the WCP and Qmax (R2 = 0.78, p < 0.01) and WSA>2mm (R2 = 0.74, p < 0.01). This study manifests that biochar-coupled organic fertilizer could effectively reduce soil WCP content via the improvement of P adsorption and aggregate stability.

Prediction of nano, fine, and medium colloidal phosphorus in agricultural soils with machine learning.

Soil colloids have been shown to play a critical role in soil phosphorus (P) mobility and transport. However, identifying the potential mechanisms behind colloidal P (Pcoll) release and the key influencing factors remains a blind spot. Herein, a machine learning approach (random forest (RF) coupled with partial dependence plot analyses) was applied to determine the effects of different soil physicochemical parameters on Pcoll content in three colloidal subfractions (i.e., nano- (NC): 1-20 nm, fine- (FC): 20-220 nm and medium-sized colloids (MC): 220-450 nm) based on a regional dataset of 12 farmlands in Zhejiang Province, China. RF successfully predicted Pcoll content (R2 = 0.98). Results showed that colloidal- organic carbon (OCcoll) and minerals were the major determinants of total Pcoll content (1-450 nm); their critical values for increasing Pcoll release were 87.0 mg L-1 for OCcoll, 11.0 mg L-1 for iron (Fecoll) or aluminium (Alcoll), 2.6 mg L-1 for calcium (Cacoll), 9.0 mg L-1 for magnesium (Mgcoll), 2.5 mg L-1 for silicon (Sicoll), and 1.4 mg L-1 for manganese (Mncoll). Among three colloidal subfractions, the major factors determining Pcoll were soil Olsen-P (POlsen; 125.0 mg kg-1), Cacoll (2.5 mg L-1), and colloidal P saturation (21.0%) in NC; Mncoll (1.5 mg L-1), Mgcoll (6.8 mg L-1), and POlsen (135.0 mg kg-1) in FC; while Mncoll (1.5 mg L-1), Alcoll (2.5 mg L-1), and Fecoll (3.8 mg L-1) in MC, respectively. OCcoll had a considerable effect in the three fractions, with critical values of 80.0 mg L-1 in NC or FC, and 50.0 mg L-1 in MC. Our study concluded that the information gleaned using the RF model can be used as crucial evidence to identify the key determinants of different size fractionated Pcoll contents. However, we still need to discover one or more easy-to-measure parameters that can help us better predict Pcoll.

Nano and fine colloids suspended in the soil solution regulate phosphorus desorption and lability in organic fertiliser-amended soils.

Mobile colloids impact phosphorus (P) binding and transport in agroecosystems. However, their relationship to P-lability and their relative importance to P-bioavailability is unclear. In soils amended with organic fertilisers, we investigated the effects of nano (NC; 1-20 nm), fine (FC; 20-220 nm), and medium (MC; 220-450 nm) colloids suspended in soil solution on soil P-desorption and lability. The underlying hypothesis is that mobile colloids of different sizes, i.e., NC, FC, and MC, may contribute differently to P-lability in soils enriched with organic fertiliser. NC- and FC-bound Pcoll were positively correlated with P-lability parameters from diffusive gradient in thin films (DGTA-labile P concentration, r ≥ 0.88; and DGTA-effective P concentration, r ≥ 0.87). The corresponding relations with MC-bound Pcoll are weaker (r values of 0.50 and 0.51). NC- and FC-bound Pcoll were also strongly correlated with soil P-resupply (r ≥ 0.64) and desorption (r ≥ 0.79) parameters during DGTA deployment, and the mobility of these colloids was corroborated by electron microscopy of DGTA gels. MC-bound Pcoll was negatively correlated with the solid-to-solution distribution coefficient (r = -0.42), indicating this fraction is unlikely to be the source of P-release from the solid phase after P-depletion from the soil solution. We conclude that NC and FC mainly contribute to regulating soil desorbable-P supply to the soil solution in the DGTA depletion zone (in vitro proxy for plant rhizosphere), and consequently may act as critical conditioners of P-bioavailability, whereas MC tends to form complexes that lead to P-occlusion rather than lability.

Biochar reduces colloidal phosphorus in soil aggregates: The role of microbial communities.

Colloidal phosphorus (Pcoll) in paddy soils can pose a serious threat to the water environment. Biochar amendment not only directly absorb Pcoll to reduce the runoff loss, but also create hotspots for microbial communities which simultaneously affects soil Pcoll. However, despite the crucial role of microorganisms, it remains elusive regarding how biochar and its feedstock types affect the relationships of soil microbial communities and Pcoll in soil matrix (such as at soil aggregate level). To address the knowledge gap, we explored the (in)direct effects of biochar on the soil Pcoll in physically separated fractions including micro- (53-250 µm) and macroaggregates (250-2000 µm). Results showed that straw and manure biochars decreased the soil Pcoll content by 55.2-56.7% in microaggregates and 41.2-48.4% in macroaggregates after 120 days of incubation, compared to the respective control. The fungal communities showed a significantly correlation (0.34, p < 0.05) with Pcoll content in the macroaggregates, whereas the bacterial communities were extremely significantly correlated (0.66, p < 0.001) with Pcoll content in the microaggregates. Furthermore, the partial least squares path model analysis indicated that biochar amendments directly increased Pcoll content (0.76 and 0.61) in micro- and macroaggregates, but the reduced Pcoll content by biochar was mainly derived from indirect effects, such as changed soil biological characteristics carbon (C)/P (-0.69), microbial biomass C (-0.63), microbial biomass P (-0.68), keystone taxa Proteobacteria (-0.63), and Ascomycota (-0.59), particularly for the macroaggregates. This study highlights that to some extent, biochar addition can reduce soil Pcoll content by affecting microbial communities (some keystone taxa), and soil biological characteristics at soil aggregate level.

Nano and micro manure amendments decrease degree of phosphorus saturation and colloidal phosphorus release from agriculture soils.

The manure fertilizer increases the phosphorus (P) saturation of soils and the colloidal P release to water bodies. Manure of different particle-sizes may have different effects on colloidal P release by soil, and to date there is limited knowledge on colloidal P release from soils amended with different size manures. We produced sheep micro- (SMicro) and nano-manure (SNano), and poultry micro- (PMicro), nano-manure (PNano) from bulk samples by wet fractionation method. The fractionation reduced the P contents of micro- and nano-manures, and enriched them in ash and calcium, iron (Fe), magnesium, and aluminum (Al) phosphate minerals compared with the bulk manures. The degree of P saturation (DPS) in Anthorsol and Cambisol was decreased (SMicro, 17.6 and 17.2 %; SNano, 14.5 and 13.3 % and PMicro, 19.0 and 19.7 mg kg-1; PNano, 17.0 and 14.3 mg kg-1) and released less colloidal P (SMicro, 3.12 and 3.78 mg kg-1; SNano, 3.01 and 3.56 mg kg-1 and PMicro, 3.34 and 3.92 mg kg-1; PNano, 3.21 and 3.65 mg kg-1) than the soils receiving the bulk manures. The decrease in colloidal P was correlated with less DPS in both soils amended with micro and nano manures. That is, the only measurable effect of manure particle size on colloidal P release from the amended soils was due to chemical fractionation during separation of the size fractions. It was suggested that nano and micro manures were the effective approach to reduce colloidal P release from manure amended soils.

Organic Carbon Linkage with Soil Colloidal Phosphorus at Regional and Field Scales: Insights from Size Fractionation of Fine Particles.

Nano and colloidal particles (1-1000 nm) play important roles in phosphorus (P) migration and loss from agricultural soils; however, little is known about their relative distribution in arable crop soils under varying agricultural geolandscapes at the regional scale. Surface soils (0-20 cm depth) were collected from 15 agricultural fields, including two sites with different carbon input strategies, in Zhejiang Province, China, and water-dispersible nanocolloids (0.6-25 nm), fine colloids (25-160 nm), and medium colloids (160-500 nm) were separated and analyzed using the asymmetrical flow field flow fractionation technique. Three levels of fine-colloidal P content (3583-6142, 859-2612, and 514-653 µg kg-1) were identified at the regional scale. The nanocolloidal fraction correlated with organic carbon (Corg) and calcium (Ca), and the fine colloidal fraction with Corg, silicon (Si), aluminum (Al), and iron (Fe). Significant linear relationships existed between colloidal P and Corg, Si, Al, Fe, and Ca and for nanocolloidal P with Ca. The organic carbon controlled colloidal P saturation, which in turn affected the P carrier ability of colloids. Field-scale organic carbon inputs did not change the overall morphological trends in size fractions of water-dispersible colloids. However, they significantly affected the peak concentration in each of the nano-, fine-, and medium-colloidal P fractions. Application of chemical fertilizer with carbon-based solid manure and/or modified biochar reduced the soil nano-, fine-, and medium-colloidal P content by 30-40%; however,the application of chemical fertilizer with biogas slurry boosted colloidal P formation. This study provides a deep and novel understanding of the forms and composition of colloidal P in agricultural soils and highlights their spatial regulation by soil characteristics and carbon inputs.

The influence of alum based nutrient removal process on the physical, chemical and biological characteristics of phosphorus in the paper processing facility effluent.

This study examined the physical, chemical and biological characteristics of the phosphorus (P) in the effluents from a paper processing facility before and after an alum based P removal process. The alum based treatment process reduced effluent total P concentrations from an average of 230 ± 103 (±1 SD) µg L-1 to an average of 36 ± 10 µg L-1. Ultra-filtration showed the treatment process shifted the P in these effluents from being 75 ± 9% particulate pre-removal to being 52 ± 0% dissolved and 27 ± 1% colloidal after the Trident P removal process. The alum removal process also reduced the fraction of reactive P in the dissolved and colloidal pools from 55% to 14%, respectively. Algal phosphorus bioavailability (BAP) bioassays showed the BAP of these effluents averaged 12 ± 9% of total P. Algal dissolved P uptake experiments indicated ≈ 30% of the dissolved P was converted to particulate P (which usually indicates algal uptake) during 21-day bioassays. However, treatments without algae indicated >80% of the apparent algal uptake may have been due to colloidal P forming flocs via physical-chemical processes. These analyses indicate the phosphorus contained in this paper processing facility's effluents had much lower bioavailability than the P in typical municipal wastewater treatment plant effluents.

Effect of sheep manure-derived biochar on colloidal phosphorus release in soils from various land uses.

Colloidal phosphorus (CP) as an additional route of P mobilization in soil solution has gained much attention. A batch experiment was conducted to investigate the effect of sheep manure-derived biochar (SMB) on CP release from various land uses (paddy, vegetable, tea, and citrus) at a rate of 0% as a control treatment (CK), 1% as a low (L) level, 2% as a middle (M) level, and 4% as a high (H) level of SMB application. The CP and MRPcoll in the solution increased from 30.58 to 88.97% and from 2.45 to 55.54% of total P (TP), respectively. The SMB enhanced CP release in all the soils and all the treatments (except CK and L levels in tea soil; CK, L, and M levels in vegetable soil; and L and M levels in citrus soil). Multiple linear regression revealed a significant correlation between CP and MRPcoll and between colloidal iron, aluminum, calcium, and total organic carbon (Fecoll, Alcoll, Cacoll, and TOCcoll) and pH, which may play an important role as CP carriers that could depend on the pH. This study suggests that the application of SMB in the soil at an appropriate rate of 1 and 2% for tea and vegetable soils, respectively, could be beneficial to avoid the risk of CP release in water bodies.

Transport of colloidal phosphorus in runoff and sediment on sloping farmland in the purple soil area of south-western China.

Colloidal particles in runoff could play an important role in phosphorus (P) transfer from sloped farmland to waterbodies. We investigated the distribution of P in different-size particles from a purple soil and colloidal phosphorus (CP) loss in runoff and sediment from sloped farmland in south-western China. The profile distribution of P showed obvious surface accumulation. The risk of P loss in topsoil was greater than those of the other soil layers on sloping farmland of purple soil. The concentration of soil particles of < 0.002 mm in purple soil profiles was low, but the total phosphorus (TP) and available phosphorus (AP) concentrations of soil particles of < 0.002 mm were high. During a rainfall event, CP loss is significantly power function related to the runoff yield rate, and is linearly related to the sediment yield rate. The majority of P in runoff was CP. The total loss of CP in runoff was 139.52 g ha-1, in which surface runoff accounted for 64.3%. CP loss can be controlled by controlling runoff from sloping farmland, especially surface runoff. Our results suggest that CP loss should be valued in the process of nutrient loss, as well as CP transfer should be given greater consideration in the mechanistic studies of the P transfer process.

Iron colloids reduce the bioavailability of phosphorus to the green alga Raphidocelis subcapitata.

Phosphorus (P) is a limiting nutrient in many aquatic systems. The bioavailability of P in natural waters strongly depends on its speciation. In this study, structural properties of iron colloids were determined and related to their effect on P sorption and P bioavailability. The freshwater green alga Raphidocelis subcapitata was exposed to media spiked with radiolabelled (33)PO4, and the uptake of (33)P was monitored for 1 h. The media contained various concentrations of synthetic iron colloids with a size between 10 kDa and 0.45 µm. The iron colloids were stabilised by natural organic matter. EXAFS spectroscopy showed that these colloids predominantly consisted of ferrihydrite with small amounts of organically complexed Fe. In colloid-free treatments, the P uptake flux by the algae obeyed Michaelis-Menten kinetics. In the presence of iron colloids at 9 or 90 µM Fe, corresponding to molar P:Fe ratios between 0.02 and 0.17, the truly dissolved P (<10 kDa) was between 4 and 60% of the total dissolved P (<0.45 µm). These colloids reduced the P uptake flux by R. subcapitata compared to colloid-free treatments at the same total dissolved P concentration. However, the P uptake flux from colloid containing solutions equalled that from colloid-free ones when expressed as truly dissolved P. This demonstrates that colloidal P did not contribute to the P uptake flux. It is concluded that, on the short term, phosphate adsorbed to ferrihydrite colloids is not available to the green alga R. subcapitata.