Effect of bone meal (calcium phosphate) amendments on metal release from contaminated soils--a leaching column study

Metal-contaminated soil may be remediated in situ by the formation of highly insoluble metal phosphates if an appropriate phosphorus (P) source can be found. Leaching column experiments have been carried out to assess the suitability of bone meal as such a source. Bone meal additions reduced metal release from a contaminated soil, increased soil and leachate pH and decreased soil leachate toxicity. Minimal P leaching occurred from the soil. The data are consistent with a proton consuming bone meal (calcium phosphate) dissolution reaction followed by the formation of metal phosphates. Although, no metal phosphates were observed to form using X-ray diffraction of scanning electron microscopy this could be due to their low concentration. Relatively low (1:50 bone meal:soil) concentrations of fine (90-500 microns) bone meal would appear to be an effective treatment for metal-contaminated soils.     

Performance of secondary P-fertilizers in pot experiments analyzed by phosphorus X-ray absorption near-edge structure (XANES) spectroscopy

A pot experiment was carried out with maize to determine the phosphorus (P) plant-availability of different secondary P-fertilizers derived from wastewater. We analyzed the respective soils by P K-edge X-ray absorption near-edge structure (XANES) spectroscopy to determine the P chemical forms that were present and determine the transformation processes. Macro- and micro-XANES spectroscopy were used to determine the chemical state of the overall soil P and identify P compounds in P-rich spots. Mainly organic P and/or P adsorbed on organic matter or other substrates were detected in unfertilized and fertilized soils. In addition, there were indications for the formation of ammonium phosphates in some fertilized soils. However, this effect was not seen in the maize yield of all P-fertilizers. The observed reactions between phosphate from secondary P-fertilizers and co-fertilized nitrogen compounds should be further investigated. Formation of highly plant-available compounds such as ammonium phosphates could make secondary P-fertilizers more competitive to commercial phosphate rock-based fertilizers with positive effects on resources conservation.     

Improved daily precipitation nitrate and ammonium concentration models for the Chesapeake Bay Watershed

Daily precipitation nitrate and ammonium concentration models were developed for the Chesapeake Bay Watershed (USA) using a linear least-squares regression approach and precipitation chemistry data from 29 National Atmospheric Deposition Program/National Trends Network (NADP/NTN) sites. Only weekly samples that comprised a single precipitation event were used in model development. The most significant variables in both ammonium and nitrate models included: precipitation volume, the number of days since the last event, a measure of seasonality, latitude, and the proportion of land within 8km covered by forest or devoted to industry and transportation. Additional variables included in the nitrate model were the proportion of land within 0.8km covered by water and/or forest. Local and regional ammonia and nitrogen oxide emissions were not as well correlated as land cover. Modeled concentrations compared very well with event chemistry data collected at six NADP/AirMoN sites within the Chesapeake Bay Watershed. Wet deposition estimates were also consistent with observed deposition at selected sites. Accurately describing the spatial distribution of precipitation volume throughout the watershed is important in providing critical estimates of wet-fall deposition of ammonium and nitrate.     

The equilibrium of ammonium chloride aerosol with gaseous hydrochloric acid and ammonia under tropospheric conditions

Using thermodynamic data, the equilibrium constant for dissociation of solid ammonium chloride aerosol into gaseous hydrogen chloride and ammonia has been calculated. The existence of solid ammonium chloride aerosols is thermodynamically possible at temperatures and concentrations observed in the troposphere, but significant gas phase concentrations of hydrogen chloride and ammonia will also be present.     

Investigation on gene transfer from genetically modified corn (Zea mays L.) plants to soil bacteria

Knowledge about the prevalence and diversity of antibiotic resistance genes in soil bacteria communities is required to evaluate the possibility and ecological consequences of the transfer of these genes carried by genetically modified (GM) plants to soil bacteria. The neomycin phosphotransferase gene (nptII) conferring resistance to kanamycin and neomycin is one of the antibiotic resistance genes commonly present in GM plants. In this study, we investigated kanamycin-resistant (Km(R)) and neomycin-resistant (Nm(R)) soil bacterial populations in a 3-year field trial using a commercial GM corn (Zea mays L.) carrying the nptII gene and its near isogenic line. The results showed that a portion (2.3 - 15.6 %) of cultivable soil bacteria was naturally resistant to kanamycin or neomycin. However, no significant difference in the population level of Km(R) or Nm(R) soil bacteria was observed between the GM and non-GM corn fields. The nptII gene was not detected in any of the total 3000 Km(R) or Nm(R) isolates screened by PCR. Further, total soil bacterial cells were collected through Nycodenz gradient centrifugation and bacterial community DNA was subjected to PCR. Detection limit was about 500 cells per gram of fresh soil. Our study suggests that the nptII gene was relatively rare in the soil bacterial populations and there was no evidence of gene transfer from a GM corn plant to soil bacteria based on the data from total soil bacterial communities.     

Effects of sorption on biodegradation rates of 2,4-D: Improvement of Rao''s model

In the presence of sorbents, the biodegradation rates of organic compounds can be decreased or increased. Four kinds of interactions have to be considered as follows: (1) chemicals in solution reacted with bacteria in solution; (2) sorbed chemicals reacted with bacteria in solution; (3) chemicals in solution reacted with sorbed bacteria and (4) sorbed chemicals reacted with sorbed bacteria. The corresponding rate constants K can be solved in our improved model. Some special situations are discussed.

The biodegradation of 2,4-D, as an example, reacted with a pure strain (Pseudomanos sp.) which was isolated from soil polluted by 2,4-D then labeled by radioactive ³²P were performed in the presence of sediment (or soil). The results showed that 2,4-D sorbed on sediment (or soil) were available to neither bacteria in solution nor bacteria on sediment (or soil), but 2,4-D in solution can be degraded by both bacteria in solution and bacteria on sediment (or soil). Biodegradation of 2,4-D in the presence of sediment (or soil) agreed with results of Rao's model.     

Anaerobic degradation and toxicity of commercial cationic surfactants in anaerobic screening tests

Anaerobic biodegradability and toxicity on anaerobic bacteria of di(hydrogenated tallow) dimethyl ammonium chloride (DHTDMAC) and two esterquats have been investigated. A batch test system containing municipal digester solids as a source of anaerobic bacteria, based on the method proposed by the ECETOC, has been applied. To evaluate the potential toxicity of such surfactants on anaerobic sludge, a co-substrate, an easily biodegradable compound in anaerobic conditions, has been added to the samples to test and the effects on biogas production have been determined. For the esterquats studied high biodegradation levels were obtained and no toxic effects on anaerobic bacteria were observed even at the highest concentrations tested, 100 and 200 mg C/l, respectively. On the contrary, DHTDMAC was not degradated at the same test conditions. However, no inhibitory effects on the biogas production were detected for this surfactant at concentrations <100 mg C/l.     

Application of 16S rDNA-PCR amplification and DGGE fingerprinting for detection of shift in microbial community diversity in Cu-, Zn-, and Cd-contaminated paddy soils

Seven soils were sampled from farmland at different distances (0.01-5 km) from a copper and zinc smelter. The total contents of heavy metals in these soils ranged from 46 to 4895 mg Cu kg-1, 96 to 1133 mg Zn kg-1, and 6.9 to 28.8 mg Cd kg-1, respectively. The available fractions were highly correlated with total contents of the metals. In order to assess the impact of combined contamination of heavy metals on soil bacterial communities, denaturing gradient gel electrophoresis (DGGE) of polymerase chain reaction (PCR) amplicons of 16S rDNA sequence of bacteria in soil was used. Bacterial community structure was affected to some extent by heavy metals. The number of DGGE bands in soils increased with increasing distance from the copper and zinc smelter. Clustering analysis of the DGGE profiles showed that bacteria in the seven soils belonged to three clusters. Bacterial communities in three soils sampled at 0.01-0.60 km from the smelter belonged to one cluster, and those in three soils sampled at 0.8-1.2 km from the smelter belong to another cluster. Bacterial community in soil farthest from the smelter belonged to a single cluster. This study demonstrated that heavy metal contamination decreased both biomass and diversity of bacterial community in the soil.     

Bioaugmentation of a 4-chloronitrobenzene contaminated soil with Pseudomonas putida ZWL73

The strain Pseudomonas putida ZWL73, which metabolizes 4-chloronitrobenzene (4CNB) by a partial-reductive pathway, was inoculated into lab-scale 4CNB-contaminated soil for bioaugmentation purposes in this study. The degradation of 4CNB was clearly stimulated, as indicated with the gradual accumulation of ammonium and chloride. Simultaneously, the diversity and quantity of cultivable heterotrophic bacteria decreased due to 4CNB contamination, while the quantity of 4CNB-resistant bacteria increased. During the bioaugmentation, denaturing gradient gel electrophoresis analysis showed the changes of diversity in dominant populations of intrinsic soil microbiota. The results showed that Alphaproteobacteria and Betaproteobacteria were not distinctly affected, but Actinobacteria were apparently stimulated. In addition, an interesting dynamic within Acidobacteria was observed, as well as an influence on ammonia-oxidizing bacteria population. These combined findings demonstrate that the removal of 4CNB in soils by inoculating strain ZWL73 is feasible, and that specific populations in soils rapidly changed in response to 4CNB contamination and subsequent bioaugmentation.     

Effects of alfalfa and organic fertilizer on benzo[a]pyrene dissipation in an aged contaminated soil

BACKGROUND: A climate-controlled pot experiment was conducted to investigate the effects of planting alfalfa and applying organic fertilizer on the dissipation of benzo[a]pyrene from an aged contaminated agricultural soil. RESULTS: Short-term planting of alfalfa inhibited the dissipation of benzo[a]pyrene from the soil by 8.9%, and organic fertilizer enhanced benzo[a]pyrene removal from the soil by 11.6% compared with the unplanted and unfertilized treatments, respectively. No significant interaction was observed between alfalfa and organic fertilizer on benzo[a]pyrene dissipation. Sterilization completely inhibited the removal of benzo[a]pyrene from the soil indicating that its degradation by indigenous microorganisms may have been the main mechanism of dissipation. Furthermore, significant positive relationships were observed between benzo[a]pyrene removal and the contents of soil ammonium nitrogen, nitrate nitrogen, and total mineral nitrogen at the end of the experiment, suggesting that competition between plants and microorganisms for nitrogen may have inhibited benzo[a]pyrene dissipation in the rhizosphere of alfalfa and the addition of organic fertilizer may facilitate microbial degradation of benzo[a]pyrene in the soil.     

Effect of some heavy metals and soil humic substances on the phytochelatin production in wild plants from silver mine areas of Guanajuato, Mexico

Phytochelatins (PCs) were determined in the wild plants, focusing on their relationship with the levels of heavy metals and humic substances (HS) in soil. Ricinus communis and Tithonia diversifolia were collected from several sites in Guanajuato city (Mexico), which had long been the silver and gold mining center. The analysis of PCs in root extracts was carried out by liquid chromatography (derivatization with monobromobimane). Total Ag, Cd, Cu and Pb in plant roots and in soil samples, as well as soil HS were determined. The association of metals with HS in soils was evaluated by size exclusion chromatography (SEC) with UV and ICP-MS detection. The results obtained revealed the induction of PCs in R. communis but not in T. diversifolia. The levels of Cd and Pb in plant roots presented strong positive correlation with PC-2 (r = 0.9395, p = 0.005; r = 0.9573, p = 0.003, respectively), indicating that these two metals promote PCs induction in R. communis. On the other hand, the inverse correlation was found between soil HS and metal levels in roots of R. communis (Cu > Pb > Cd > Ag), in agreement with the decreasing affinity of these metals to HS. Importantly, the inverse correlation between soil HS and plant PC-2 was observed (r = −0.7825, p = 0.066). These results suggest that metals strongly bound to HS could be less bioavailable to plants, which in turn would limit their role in the induction of PCs. Indeed, the SEC elution profiles showed Pb but not Cd association with HS and the correlation between metal in soil and PC-2 in plant was statistically significant only for Cd (r = 0.7857, p = 0.064). Based on these results it is proposed that the role of heavy metals in PCs induction would depend on their uptake by R. communis, which apparently is controlled by the association of metals with soil HS. This work provides further evidence on the role of environmental conditions in the accumulation of heavy metals and phytochelatin production in plants.     

Particle analysis of an urban aerosol using high spatial resolution techniques

A single-particle scintillation counter-analyser mounted in a light aircraft has been used to obtain information on the Na and K content of the particulates in the atmosphere of Sydney, Australia. A spatial resolution of 1 km is obtained along a 250-km flight path. Total mass loadings and loadings as a function of particle size for Na and K agree with published data for filter samples collected on the ground. Na/K ratios for individual plumes indicate soil dust and combustion are the principal contributors to urban haze detected by this method. The large sea-salt contribution is readily identified and significant sources of non-marine Na exist, particularly in the smaller size ranges. The results suggest that sea-salt contribution to the Na measured in coastal city aerosols may be overestimated.     

Different decay patterns observed in a nineteenth-century building (Palma,Spain)

The effects of atmospheric pollutants and climatic conditions were studied in a decayed column in the Seminary of Sant Pere. This nineteenth-century building is situated in the historic centre of Palma (Mallorca, Spain), less than 0.5 km from the sea. Samples were collected from the internal and external part of the crusts formed in the four sides of the column. The samples were analysed by means of thermal analysis, X-ray diffractometry, scanning electron microscopy, Fourier transform infrared spectroscopy and ion chromatography. Results show significant differences in the four sides of the column. A high degree of carbonate stone sulfation is observed in all of the samples analysed. A synergistic effect between atmospheric factors and micropollutants on the deterioration of stone is observed. A high uptake of atmospheric particulate matter is found in the external part of the black crusts.     

Crown condition of Norway spruce in relation to sulphur and nitrogen deposition and soil properties in southeast Norway

Atmospheric deposition of sulphur and nitrogen compounds may lead to enhanced leaching of base cations, accumulation of nitrogen in organic matter, lowered pH and increased concentration of toxic aluminium in soil, which in turn may affect the vitality of forest trees. A general monitoring of forest condition has been initiated in many European countries, partly in order to reveal stresses caused by acidification. However, forest condition is also affected by many other factors. This paper examines a seven-year series of crown-condition data from Local County Monitoring Plots in Norway spruce stands in Norway. Average, time trend and lability variables were calculated for crown density and crown colour for each plot. Wet deposition of sulphate, ammonium and nitrate for each plot were estimated using data from the national air and precipitation monitoring programmes. Soil data are based on soil sampling within the plots. The analysis gave no evident support for the hypothesized negative effect on crown condition from sulphur and nitrogen deposition and related alterations in soil.     

Assessment of pesticide contamination in three Mississippi Delta oxbow lakes using Hyalella azteca

Three oxbow lakes in northwestern Mississippi, USA, an area of intensive agriculture, were assessed for biological impairment from historic and current-use pesticide contamination using the amphipod, Hyalella azteca. Surface water and sediment samples from three sites in each lake were collected from Deep Hollow, Beasley, and Thighman Lakes from September 2000 to February 2001. Samples were analyzed for 17 historic and current-use pesticides and selected metabolites. Ten-day H. azteca survival and growth (as length and dry weight) were measured to determine the degree of biological impairment. Maximum number of detectable pesticides in surface water from Deep Hollow, Beasley and Thighman Lakes was 10, 11, and 17, respectively. Maximum number of detectable pesticides in lake sediments was 17, 17, and 15, respectively. Bioassay results indicated no observable survival effects on H. azteca exposed to surface water or sediment from any lake examined and no growth impairment in animals exposed to lake sediments. However, growth was significantly impaired in surface water exposures from Deep Hollow Lake (2 sites) and Beasley Lake (1 site). Statistically significant relationships between growth impairment (length) and cyanazine, methyl parathion, λ-cyhalothrin, chlorfenapyr, and pp′DDE surface water concentrations in Deep Hollow Lake as well as trifluralin, atrazine, and methyl parathion in Beasley Lake were observed. Although pesticide frequency and concentrations were typically greater in sediment than surface water, bioassay results indicated decreased availability of these pesticides in sediment due to the presence of clay and organic carbon. Growth impairment observed in surface water exposures was likely due to complex interaction of pesticide mixtures that were present.     

Estimating catchment nutrient flow with the HBV-NP model: sensitivity to input data

The dynamic catchment model HBV-N has been further developed by adding routines for phosphorus transport and is now called the HBV-NP model. The model was shown to satisfactorily simulate nutrient dynamics in the R?nne? catchment (1,900 km2). Its sensitivity to input data was tested, and results demonstrated the increased sensitivity to the selection of input data on a subcatchment scale when compared with the catchment scale. Selection of soil and land use databases was found to be critical in some subcatchments but did not have a significant impact on a catchment scale. Although acceptable on a catchment scale, using templates and generalization, with regards to emissions from point sources and rural households, significantly decreased model performance in certain subcatchments when compared with using more detailed local information. A division into 64 subcatchments resulted in similar model performance at the catchment outlet when compared with a lumped approach. Adjusting the imported matrixes of the regional leaching of nitrogen, from agricultural land, against mean subcatchment water percolation did not have a significant impact on the model performance.     

Influence of the DMPP (3,4-dimethyl pyrazole phosphate) on nitrogen transformation and leaching in multi-layer soil columns

The application of nitrogen fertilizers leads to various ecological problems such as nitrate leaching. The use of nitrification inhibitors as nitrate leaching retardants is a proposal that has been suggested for inclusion in regulations in many countries. In this study, using a multi-layer soil column device, the influence of new nitrification inhibitor DMPP (3,4-dimethyl pyrazole phosphate) was studied for understanding the nitrogen vertical transformation and lowering the nitrate leaching at different soil profile depths. The results indicated that, within 60 d of experiment, the regular urea added 1.0% DMPP can effectively inhibit the ammonium oxidation in the soil, and improve the ammonium concentration in soil solution over the 20cm depths of soil profile, while decline the concentrations of nitrate and nitrite. No obvious difference was found on ammonium concentrations in soil solution collected from deep profile under 20cm depths between regular urea and the urea added 1.0% DMPP. There was also no significant difference for the nitrate, ammonium and nitrite concentrations in the soil solution under 40cm depths of soil profile with the increasing nitrogen application level, among the treatments of urea added 1.0% DMPP within 60 d. It is proposed that DMPP could be used as an effective nitrification inhibitor in some region to control ammonium oxidation and decline the ion-nitrogen leaching, minimizing the shallow groundwater pollution risk and being beneficial for the ecological environment.     

Impacts of swine manure pits on groundwater quality

Manure deep-pits are commonly used to store manure at confined animal feeding operations. However, previous to this study little information had been collected on the impacts of deep-pits on groundwater quality to provide science-based guidance in formulating regulations and waste management strategies that address risks to human health and the environment. Groundwater quality has been monitored since January 1999 at two hog finishing facilities in Illinois that use deep-pit systems for manure storage. Groundwater samples were collected on a monthly basis and analyzed for inorganic and bacteriological constituent concentrations. The two sites are located in areas with geologic environments representing different vulnerabilities for local groundwater contamination. One site is underlain by more than 6 m of clayey silt, and 7-36 m of shale. Concentrations of chloride, ammonium, phosphate, and potassium indicated that local groundwater quality had not been significantly impacted by pit leakage from this facility. Nitrate concentrations were elevated near the pit, often exceeding the 10 mg N/l drinking water standard. Isotopic nitrate signatures suggested that the nitrate was likely derived from soil organic matter and fertilizer applied to adjacent crop fields. At the other site, sandstone is located 4.6-6.1 m below land surface. Chloride concentrations and delta15N and delta15O values of dissolved nitrate indicated that this facility may have limited and localized impacts on groundwater. Other constituents, including ammonia, potassium, phosphate, and sodium were generally at or less than background concentrations. Trace- and heavy-metal concentrations in groundwater samples collected from both facilities were at concentrations less than drinking water standards. The concentration of inorganic constituents in the groundwater would not likely impact human health. Fecal streptococcus bacteria were detected at least once in groundwater from all monitoring wells at both sites. Fecal streptococcus was more common and at greater concentrations than fecal coliform. The microbiological data suggest that filtration of bacteria by soils may not be as effective as commonly assumed. The presence of fecal bacteria in the shallow groundwater may pose a significant threat to human health if the ground water is used for drinking. Both facilities are less than 4 years old and the short-term impacts of these manure storage facilities on groundwater quality have been limited. Continued monitoring of these facilities will determine if they have a long-term impact on groundwater resources.     

Chemical and biological characterization of non-extractable sulfonamide residues in soil

For sulfonamides, the formation of non-extractable residues has been identified by laboratory testing as the most relevant concentration determining process in manured soil. Therefore, the present study has been focused on the chemical and biological characterization of non-extractable residues of ¹⁴C-labeled sulfadiazine or sulfamethoxazole. In laboratory batch experiments, the test substances were spiked via standard solution or test slurry to microbially active soil samples. After incubation periods of up to 102 d, a sequential extraction technique was applied. Despite the exhaustive extraction procedure, sulfadiazine residues mainly remained non-extractable, indicating the high affinity to the soil matrix. The remobilization of non-extractable ¹⁴C-sulfadiazine residues was monitored in the activated sludge test and the Brassica rapa test. Only small amounts (<3%) were transferred into the extractable fractions and 0.1% was taken up by the plants. In the Lumbricus terrestris test A, the release of non-extractable ¹⁴C-sulfamethoxazole residues by the burrowing activity of the earthworms was investigated. The residues mainly remained non-extractable (96%). The L. terrestris test B was designed to study the immobilization of ¹⁴C-sulfamethoxazole in soil directly after the test slurry application. The mean uptake by earthworms was 1%. Extractable and non-extractable residues amounted to 5% and 93%, respectively. Consequently, the results of all tests confirmed the high affinity of the non-extractable sulfonamide residues to the soil matrix.     

Evidence of enhanced atmospheric ammoniacal nitrogen in Hells Canyon national recreation area: implications for natural and cultural resources

Agriculture releases copious fertilizing pollutants to air sheds and waterways of the northwestern United States. To evaluate threats to natural resources and historic rock paintings in remote Hells Canyon, Oregon and Idaho, deposition of ammonia (NH3), nitrogen oxides (NOx), sulfur dioxide (SO2), and hydrogen sulfide (H2S) at five stations along 60 km of the Snake River valley floor were passively sampled from July 2002 through June 2003, and ozone data and particulate chemistry were obtained from the Interagency Monitoring of Protected Visual Environments (IMPROVE) station at Hells Canyon. NH3 concentrations were high; biweekly averages peaked at 5-19 ppb in spring and summer and the nutrient-laden Snake River is a likely source. Fine particulate ammonium nitrate (NH4NO3) averaged 2.6 microg/m3 during the 20% of worst visibility days with winter drainage of air masses from the Snake River Basin and possibly long distance transport from southern California. Other pollutants were within background ranges. NH3 is corrosive to clay-based pictographs; nitrogen deposition can alter natural biotic communities and terrestrial ecosystem processes at levels reported here.