[Prediction Spatial Distribution of Soil Organic Matter Based on Improved BP Neural Network with Optimized Sparrow Search Algorithm].

Soil organic matter is an important indicator of soil fertility, and it is necessary to improve the accuracy of regional organic matter spatial distribution prediction. In this study, we analyzed the organic matter content of 1 690 soil surface layers (0-20 cm) and collected data on the natural environment and human activities in the Weining Plain of the Yellow River Basin. The SOM spatial distribution prediction model was established with 1 348 points using classical statistics, deterministic interpolation, geostatistical interpolation, and machine learning, respectively, and 342 sample points data were used as the test set to test and analyze the prediction accuracy of different models. The results showed that the average SOM content of the surface soil of the Weining Plain was 14.34 g·kg-1, and the average soil organic matter variation across 1 690 sampling points was 34.81%, indicating a medium degree of variability. The results also revealed a spatial distribution trend, with low soil organic matter content in the northeast and southwest, high soil organic matter on the left and right banks of the Yellow River in the middle, and relatively high soil organic matter in the sloping terrain of the Weining Plain. The four types of methods in order of high to low prediction accuracy were the machine learning method, geostatistical interpolation method, deterministic interpolation method, and classical statistical method. Through comparison, the BP neural network that was improved based on the optimized sparrow search algorithm had the best prediction accuracy, and the optimized sparrow search algorithm had better convergence accuracy, avoided falling into local optimization, prevented data overfitting, and had better prediction ability. This optimization algorithm can improve the accuracy of SOM prediction and has good application prospects in soil attribute prediction.

Fate of Cd during mineral transformation by sulfate-reducing bacteria in clay-size fractions from soils with high geochemical background.

Sulfate-reducing bacteria (SRB) can immobilize heavy metals in soils through biomineralization, and the parent rock and minerals in the soil are critical to the immobilization efficiency of SRB. To date, there is little knowledge about the fate of Cd associated with the parent rocks and minerals of soil during Cd immobilized by SRB. In this study, we created a model system using clay-size fraction of soil and SRB to explore the role of SRB in immobilizing Cd in soils from stratigraphic successions with high geochemical background. In the system, clay-size fractions (particle size < 2 µm) with concentration of Cd (0.24-2.84 mg/kg) were extracted from soils for bacteria inoculation. After SRB reaction for 10 days, the Cd fraction tended to transform into iron-manganese bound. Further, two clay-size fractions, i.e., the non-crystalline iron oxide (Fe-OX) and the crystalline iron oxide (Fe-CBD), were separated by extraction. The reaction of SRB with them verified the transformation of primary iron-bearing minerals into secondary iron-bearing minerals, which contributed to Cd redistribution. This study shows that SRB could exploit the composition and structure of minerals to induce mineral recrystallization, thereby aggravating Cd redistribution and immobilization in clay-size fractions from stratigraphic successions with high geochemical background.

Environmental implication of geochemical record in the Arctic Ny-Ålesund glacial sediment, Svalbard (Norway).

Glacial sediments as an important end member of the global dust system, could indicate changes in global climate, aerosols sources, ocean elements, and productivity. With global warming, ice caps shrinking and glaciers retreat at high latitudes have attracted concern. To understand the response of glacier to environment and climate in modern high latitude ice-marginal environments, this paper investigated glacial sediments in the Ny-Ålesund region of the Arctic and clarified the response of polar environmental to global changes through geochemical characteristics of glacial sediments. The results showed that: 1) main factors affecting the elements distribution of the Ny-Ålesund glacial sediments were thought as soil formation, bedrock and weathering, and biological activity; 2) variations of SiO2/Al2O3 and SiO2/Al2O3 + Fe2O3, indicating low weathering of the soil. The ratio of Na2O/K2O indicating a weak chemical weathering, was negatively correlated to the CIA. With the average CIA of Ny-Ålesund glacial sediments for main minerals of quartz, feldspar, and muscovite as well as dolomite and calcite 50.13, which implied glacial sediments at the early stage of chemical weathering and depletion of Ca and Na; 3) the separating effect of stones and soils by stone circle formation due to thermal conductivity and frost heave makes sediments in stone circle have lower chemical weathering with only two main minerals, albite and quartz; 4) changes of carbonate content in sediments with glacier front retreating in different period implied that weathering rate of calcite averagely reached an estimate of 0.0792%wt/year in glacier A. The succession of vegetation made biological weathering become an important driving force for carbonate leaching from glacial sediments. These results and data provide scientifically significant archive for future global change studies.

Assessing the fractionation and bioavailability of heavy metals in soil-rice system and the associated health risk.

This study developed a method to build relationships between chemical fractionations of heavy metals in soils and their accumulations in rice and estimate the respective contribution of each geochemical speciation in the soils from the Yangtze River Delta, China. In contaminated areas, residue and humic acid-bound fractions in soils were the main phases for most heavy metals. The mobility of heavy metals was in this following order: Cd > Pb ≈ Zn > Ni > As ≈ Cr > Hg. Transfer factors calculated by the ratios of specific fractionations of heavy metals in the soil-rice system were used to assess the capability of different metal speciation transfer from soil to rice. The carbonate and Fe/Mn oxyhydroxides bound phase had significant positive correlations with total metal concentrations in rice. Hg uptake by rice might be related to the exchangeable and carbonate-bound fractions of soil Hg. Results of PCA analysis of transfer factors estimated that the labile fractions (i.e. water soluble, exchangeable and carbonate bound) contributed more than 40% of the heavy metal accumulations in rice. Effect of organic matter and residue fraction on metals transfer was estimated to be ~ 25 to ~ 30% while contribution of humic acid and Fe/Mn oxyhydroxides-bound fractions was estimated to be ~ 20 to ~ 30%. Modified risk assessment code (mRAC) and ecological contamination index (ECI) confirmed that the soil samples were polluted by heavy metals. Soil Cd contributed more than 80% of mRAC. Contrarily, the main contributors to ECI were identified as As, Hg, Pb and Zn. The average values of total target hazard quotient (TTHQ) and Risktotal were above 1 and 10-4 respectively, implying people living in the study area were exposed to both non-carcinogenic and carcinogenic risk. As and Pb were the main contributor to high TTHQ value while As, Cd and Cr in rice contributed mostly to Risktotal value. Spatial changes of ecological risk indexes and human health risk indexes showed that the samples with high TTHQ values distributed in the area with high values of mRAC. Likewise, the area with high ECI values and with high carcinogenic risk overlapped.

Chemical speciation of phosphorus in surface sediments from the Jiangsu Coast, East China: Influences, provenances and bioavailabilities.

Sixty-one surface sediment samples collected from the Jiangsu Coast (JSC), East China were investigated to explore the influences, provenances and bioavailabilities of P species. Authigenic and detrital P fractions were the dominant species, accounting for 28.53% and 44.04% of the total P content, respectively. Exchangeable, Fe-bound and organic P fractions were biologically available, with an average total of 5.94 µmol/g; this value was governed by grain sizes and the organic matter and carbonate contents. Exchangeable and organic P fractions were transformed between each other, while contributing to the formation of Fe-bound and authigenic P. Phosphorus in the JSC sediments originated mainly from the Yellow River. The unique distribution pattern of P species in the JSC depends on P sources and local environments. These findings improve our understanding of the P cycle and eutrophication in the Jiangsu Coastal Zone.

Evolution of groundwater chemistry in coastal aquifers of the Jiangsu, east China: Insights from a multi-isotope (δ2H, δ18O, 87Sr/86Sr, and δ11B) approach.

Groundwater salinization is currently a very serious and challenging issue in many parts of the world. With an increasing demographic pressure and remarkable changes of water and land uses over the last decades, the multilayer coastal aquifer system of Jiangsu province, east China, was affected by increasing salinization. In this study, we investigate the groundwater salinization process and the salinity sources of the aquifer system in Nantong area (southern part of the Jiangsu coastal plain) using a multi-isotope (δ2H, δ18O, 87Sr/86Sr, and δ11B) approach. The results show that the TDS (total dissolved solids) values in most deep groundwater samples are generally lower than those of the shallow groundwater samples. The TDS of both shallow and deep groundwater increase from western Nantong (inland) to the eastern coastal region of the Yellow Sea. The chemical types transform from Ca-Mg-HCO3 or Mg-Ca-HCO3 to NaCl. The stable hydrogen and oxygen isotopes signatures of the groundwater samples indicate that local precipitation likely acts as the main recharge source of both the shallow and deep confined groundwater systems. The deep groundwater shows more depleted isotopes, suggesting recharging by the precipitation under a cold climate before the Holocene period. The shallow groundwater features heavier water isotopes, indicating recharging source from recent precipitation under a warm climate. The variations in δ11B and 87Sr/86Sr of groundwater samples can be explained by the changes of solute sources. In the inland region (western Nantong), shallow groundwater with higher TDS is mainly caused by evaporation-induced concentration, whereas in coastal areas, seawater intrusion exerts a major influence on the chemical composition of the shallow groundwater. Our results show that that seawater intrusion mainly occurs in eastern and southeastern Nantong area. We also find that hydraulic connection between shallow and deep groundwater is strengthened by continuous overexploitation, and deep groundwater is mixed with shallow groundwater at some points. The mixing between upper saline water and deep freshwater, together with water-rock interactions, likely explain the observed low salinity in deep groundwater in coastal areas. Overall, with growing observations of salty seawater intrusion in the estuary region of the Yangtze River, future efforts are needed to prevent further seawater intrusion as sea level rises and groundwater table declines. In this context, our findings provide key information for groundwater management in other coastal aquifers, east China.

Evaluation of various approaches to predict cadmium bioavailability to rice grown in soils with high geochemical background in the karst region, Southwestern China.

Evaluating the bioavailability of Cd to rice (Oryza sativa L.) was essential in the karst region, Southwestern China, where the soils have previously been shown to be anomalously enriched in Cd through geogenic processes. In this research, we examined the bioavailability of Cd to rice samples collected from 278 sites in Guangxi province, where rice is the most widely cultivated cereal crop that is responsible for the largest human dietary exposure to Cd. Both soil chemical extraction and soil-plant transfer modelling approaches were used to predict the bioavailability to rice. Some of the soil types were highly enriched in Cd, but their bioavailability was low, since the soil carbonates raised soil pH and remarkably reduced Cd bioavailability. In contrast, acidic soils (Ca was largely leached) with relatively low total Cd, the grown rice plants accumulated higher Cd in their grains. Results from CaCl2 extraction experiments provided good predictions for Cd in rice grain grown in soils of different types. Stepwise multiple regressions revealed soil pH and soil Ca content were the dominant factors that control the transfer of Cd from soil to rice. An extended Freundlich-type model and a polynomial surface model provided good prediction for Cd in rice grains. The diffusive gradients in thin films (DGT) technique gave the best estimation of soil Cd bioavailability, whereas water-extracted soil solution Cd provided relatively poor fits. Regional soil threshold that derived using the models, can avoid exceedance of Cd in rice and thereby enable local agricultural practitioners or authorities to develop appropriate management for croplands with high Cd background.

Multivariate linear regression model for source apportionment and health risk assessment of heavy metals from different environmental media.

The study evaluated source apportionment of heavy metals in vegetable samples from the potential sources of fertilizer, water and soil samples collected along the Changjiang River delta in China. The results showed that 25.72% of vegetable samples (Brassica chinensis L.) containing Pb, and Cd, Cu, Hg and Zn at relatively serious levels were from soil. Combined with principle component analysis (PCA) and cluster analysis (CA), the results of the spatial distribution of heavy metals in different environmental media indicated that fertilizer, water and soil were the main sources of heavy metals in vegetables. The results of multivariate linear regression (MLR) using partition indexes (P) showed that fertilizer contributed to 38.5%, 40.56%, 46.01%, 53.34% and 65.25% of As, Cd, Cu, Pb and Zn contents in vegetables, respectively. In contrast, 44.58% of As, 32.57% of Hg and 32.83% of Pb in vegetables came from soil and 42.78% of Cd and 66.97% of Hg contents in vegetables came from the irrigation water. The results of PCA and CA verified that MLR using P was suitable for determining source apportionment in a vegetable. A health risk assessment was performed; As, Cd and Pb contributed to more than 75% of the total hazard quotient (THQ) values and total carcinogenic risk values (Risktotal) for adults and children through oral ingestion. More than 70% of the estimated THQ and Risktotal is contributed by water and fertilizer. Therefore, it is necessary to increase efforts in screening limits/levels of heavy metals in fertilizer and irrigation water and prioritize appropriate pollution management strategies.

Incorporating Bioaccessibility into Human Health Risk Assessment of Heavy Metals in Rice ( Oryza sativa L.): A Probabilistic-Based Analysis.

A systematic investigation into total and bioaccessible heavy metal concentrations in rice grains harvested from heavy metal-contaminated regions was carried out to assess the potential health risk to local residents. Arsenic, Cr, Cu, Pb, and Zn concentrations were within acceptable levels while Cd and Ni concentrations appeared to be much higher than in other studies. The bioaccessibity of As, Cd, and Ni was high (>25%) and could be well predicted from their total concentrations. The noncarcinogenic risk posed by As and Cd was significant. The carcinogenic risk posed by all bioaccessible heavy metals at the fifth percentile was 10-fold higher than the acceptable level, and Cd and Ni were the major contributors. The contribution of each metal to the combined carcinogenic risk indicates that taking pertinent precautions for different types of cancer, aimed at individuals with different levels of exposure to heavy metals, will greatly reduce morbidity and mortality rates.

Coral trace metal of natural and anthropogenic influences in the northern South China Sea.

The composition and concentrations of trace metals in coastal seawater have changed in parallel with variations in geochemical processes, climate and anthropogenic activities. To evaluate the response of trace metals in coastal seawater to climatic changes and human disturbances, we report annual-resolution trace element data for a Porites coral core covering ~100years of continuous growth from a fringing reef in Xiaodonghai Bay in the northern South China Sea. The results suggested that the trace metal contents in the coral skeleton demonstrated decadal to interdecadal fluctuations with several large or small peaks in certain years with remarkable environmental significances. All of the trace metals in coastal surface seawater, especially Cr and Pb (related to industrial or traffic emissions), were impacted by terrestrial inputs, except for Sr and U, which were impacted by the surface seawater temperature (SST). Moreover, Mn, Ni, Fe and Co were also contributed by weapons and military supplies during wars, and Cu, Cd and Zn were further impacted by upwelling associated with their biogeochemical cycles. Ba and rare earth element (REE) in coastal surface seawater were dominated by runoff and groundwater discharge associated with precipitation. This study provided the potential for some trace metals (e.g., REE, Ba, Cu, Cd, and Zn) in coral skeletons to be used as proxies of natural (e.g., upwelling and precipitation) and anthropogenic (e.g., war and coastal construction) variability of seawater chemistry to enable the reconstruction of environmental and climatic changes through time.

Cadmium transfer from contaminated soils to the human body through rice consumption in southern Jiangsu Province, China.

Consumption of crops grown in cadmium-contaminated soils is an important Cd exposure route to humans. The present study utilizes statistical analysis and in vitro digestion experiments to uncover the transfer processes of Cd from soils to the human body through rice consumption. Here, a model was created to predict the levels of bioaccessible Cd in rice grains using phytoavailable Cd quantities in the soil. During the in vitro digestion, a relatively constant ratio between the total and bioaccessible Cd in rice was observed. About 14.89% of Cd in soils was found to be transferred into rice grains and up to 3.19% could be transferred from rice grains to the human body. This model was able to sufficiently predict rice grain cadmium concentrations based on CaCl2 extracted zinc and cadmium concentrations in soils (R2 = 0.862). The bioaccessible Cd concentration in rice grains was also able to be predicted using CaCl2 extracted cadmium from soil (R2 = 0.892). The models established in this study demonstrated that CaCl2 is a suitable indicator of total rice Cd concentrations and bioaccessible rice grain Cd concentrations. The chain model approach proposed in this study can be used for the fast and accurate evaluation of human Cd exposure through rice consumption based on the soil conditions in contaminated regions.

Vibrational spectroscopic characterization of mudstones in a hydrocarbon-bearing depression, South China Sea: Implications for thermal maturity evaluation.

A better understanding of mineral transformations in sedimentary rocks and the controls on thermal maturity have become essential in the petroleum exploration industry in recent years. The Fushan Depression is an important hydrocarbon-bearing depression in South China Sea, which can be subdivided into three structural zones: the western, central and eastern zones. In this study, a series of mudstone samples selected from 13 drilling cores with depths ranging from 2100 to 3800 m were studied using infrared reflectance spectroscopy and X-Ray Powder Diffraction (XRD) methods. And another 10 samples have been chosen for vitrinite reflectance measurement so as to investigate the ability of using infrared spectroscopy for thermal maturity evaluations. The infrared spectra results show that quartz and silicates (e.g. illite, kaolinite, smectite) are the dominant minerals in all samples. The semi-quantitative XRD analysis reveals a clear trend in illite content as the eastern zone (mean 80.81%)>the western zone (mean 73.52%)>the central zone (mean 55.04%) as well as a contrary trend in kaolinite content. This study documents that the peak height and position of Si-O antisymmetric stretching bands at ~1025 cm(-1) and ~1000 cm(-1) have a significant correlation with the degree of kaolinite illitization, suggesting that the utility of infrared spectroscopy is a valuable tool for the study of thermal maturity in sedimentary basins. The infrared spectra and XRD results together with vitrinite reflectance data indicate that the thermal maturity in the eastern zone is anomalously high, followed by the western zone, and that in the central zone is lowest. The igneous intrusion in the eastern zone has a significant impact on thermal maturation, resulting in high degree of kaolinite illitization. By contrast, the abundance in kaolinite in the central zone represents relatively low degree of kaolinite illitization, which should be attributed to shallow burial depth.

Past 140-year environmental record in the northern South China Sea: evidence from coral skeletal trace metal variations.

About 140-year changes in the trace metals in Porites coral samples from two locations in the northern South China Sea were investigated. Results of PCA analyses suggest that near the coast, terrestrial input impacted behavior of trace metals by 28.4%, impact of Sea Surface Temperature (SST) was 19.0%, contribution of war and infrastructure were 14.4% and 15.6% respectively. But for a location in the open sea, contribution of War and SST reached 33.2% and 16.5%, while activities of infrastructure and guano exploration reached 13.2% and 14.7%. While the spatiotemporal change model of Cu, Cd and Pb in seawater of the north area of South China Sea during 1986-1997 were reconstructed. It was found that in the sea area Cu and Cd contaminations were distributed near the coast while areas around Sanya, Hainan had high Pb levels because of the well-developed tourism related activities.

Vibrational spectroscopic characterization of growth bands in Porites coral from South China Sea.

A series of samples from different growth bands of Porites coral skeleton were studied using Raman, infrared reflectance methods. The Raman spectra proved that skeleton samples from different growth bands have the same mineral phase as aragonite, but a band at 133 cm(-1) for the top layer shows a transition from ~120 cm(-1) for vaterite to ~141 cm(-1) for aragonite. It is inferred that the vaterite should be the precursor of aragonite of coral skeleton. The positional shift in the infrared spectra of the skeleton samples from growth bands correlate significantly to their minor elements (Li, Mg, Sr, Mn, Fe and U) contents. Mg, Sr and U especially have significant negative correlations with the positions of the antisymmetric stretching band ν3 at ~1469 cm(-1). And Li shows a high negative correlation with ν2 band (~855 cm(-1)), while Sr and Mn show similar negative correlation with ν4 band (~712 cm(-1)). And Mn also shows a negative correlation with ν1 band (~1082 cm(-1)). A significantly negative correlation is observed for U with ν1+ν4 band (~1786 cm(-1)). However, Fe shows positive correlation with ν1, ν2, ν3, ν4 and ν1+ν4 bands shifts, especially a significant correlation with ν1 band (~1082 cm(-1)). New insights into the characteristics of coral at different growth bands of skeleton are given in present work.