Effect of dissolved organic matter from sludge and sludge compost on soil copper sorption

Interaction of Cu with dissolved organic matter (DOM) is an important physicochemical process affecting Cu mobility in soils. The aim of this study was to investigate the effects of DOM from anaerobically digested dewatered sludge and sludge compost on the sorption of Cu on an acidic sandy loam and a calcareous clay loam. In the presence of DOM, Cu sorption capacity decreased markedly for both soils, especially for the calcareous soil. The Cu sorption isotherms could be well described by the Freundlich equation (r2 = 0.99), and the binding intensity parameter of soils in the presence of sludge DOM was lower than compost DOM. An increase in DOM concentration significantly reduced the sorption of Cu by both soils. Within the Cu and DOM concentration range studied, the decrease in Cu sorption caused by sludge DOM was consistently greater than that of compost DOM. This might be attributed to the greater amount of hydrophobic fraction of DOM in the compost. Moreover, the reduction of Cu sorption caused by DOM was more obvious in the soil with higher pH. In addition, the sorption of Cu increased with an increase in pH for both soils without the addition of DOM, while Cu sorption in the presence of DOM was unexpectedly decreased with an increase in pH at a pH >6.8. This implied that DOM produced by sludge or other C-enriched organic wastes heavily applied on calcareous soils might facilitate the leaching loss of Cu because of the formation of soluble DOM-metal complexes.     

Sorption and transport behavior of naphthalene in an aggregated soil

Soil solution chemistry influences the sorption and transport behavior of hydrophobic organic compounds (HOCs) in soil. We used both batch and column studies to investigate the influence of ionic strengths (0.03 and 1.5 M) and flow velocities (12 and 24 cm h-1) on sorption and transport of naphthalene (NAP) in aggregated soil. Sorption parameters such as the Freundlich coefficient (Kf) and exponent (n) calculated from batch studies and column experiments were also compared. Retardation of NAP transport was greater at higher solution ionic strength, which may be attributed to greater sorption affinity due to enhanced aggregation of the sorbent. The effect of ionic strength on sorption of NAP observed in the batch study was consistent with the results from the column study. The Kf and n values obtained from the batch study for the two ionic strengths ranged from 7.8 to 13.7 and 0.68 to 0.80, respectively, whereas the Kf and n values obtained from the column study ranged from 7.9 to 9.9 and 0.73 to 0.85, respectively. The effluent breakthrough curve (BTC) of NAP at a flow rate of 24 cm h-1 showed significant chemical and physical nonequilibrium behavior, implying that a considerable amount of sorption in aggregated soil was time dependent when flow was relatively fast. The BTCs calculated with the parameters determined from batch studies compared poorly with the measured BTCs. The potential for nonequilibrium transport should be incorporated in models used for predicting the fate and transport of HOCs. Furthermore, caution is required when extrapolating the results from batch studies, especially for aggregated soils.     

Sorption of the veterinary antimicrobials sulfadimethoxine and ormetoprim in soil

Currently, limited research on the fate of antimicrobials in the environment exists, once they are discharged in human and animal wastes. Sorption of two antimicrobials, sulfadimethoxine (SDM) and ormetoprim (OMP), was investigated in two soils and sand using a series of batch experiments. Because OMP and SDM are often administered in combination, their sorption was also investigated in combination as co-solutes. The rate of SDM and OMP sorption was rapid over the first few hours of the experiments, which then slowed considerably after 16 to 68 h. OMP sorption was enhanced at high concentrations when in combination with SDM, with linear sorption coefficients ranging from 1.3 to 58.3 L.kg(-1) in the single solute experiments and 4.96 to 89.7 L.kg(-1) in the co-solute experiments. Sorption of OMP as a single solute seems to provide a better fit with the Freundlich equation, which became more linear (n approached 1) when SDM was present. Overall, SDM sorbed less than OMP in the two soils and sand. SDM linear sorption coefficients ranged from 0.4 to 25.8 L.kg(-1) as a single solute and 2.5 to 22.1 L.kg(-1) as a co-solute. Sorption of SDM becomes more nonlinear (n < 1) when SDM is present in combination with OMP. Overall, sorption of both antimicrobials increased in the selected soils and sand as the organic matter, clay content, and cation exchange capacity increased. These experiments indicate relatively low sorption of SDM and OMP in natural soils, making them a potential threat to surface and ground water.     

Sorption dynamics of organic and inorganic phosphorus compounds in soil

Phosphorus retention in soils is influenced by the form of P added. The potential impact of one P compound on the sorption of other P compounds in soils has not been widely reported. Sorption isotherms were utilized to quantify P retention by benchmark soils from Indiana, Missouri, and North Carolina when P was added as inorganic P (Pi) or organic P (beta-D-glucose-6-phosphate, G6P; adenosine 5'-triphosphate, ATP; and myoinositol hexaphosphate, IP6) and to determine whether soil P sorption by these organic P compounds and Pi was competitive. Isotherm supernatants were analyzed for pH and total P using standard protocols, while Pi and organic P compounds were assayed using ion chromatography. Under the controlled conditions of this study, the affinity of all soils for P sources followed the order IP6 > G6P > ATP > Pi. Each organic P source had a different potential to desorb Pi from soils, and the order of greatest to least Pi desorption was G6P > ATP > IP6. Glucose-6-phosphate and ATP competed more directly with Pi for sorption sites than IP6 at greater rates of P addition, but at the lesser rates of P addition, IP6 actually desorbed more Pi. Inositol hexaphosphate was strongly sorbed by all three soils and was relatively unaffected by the presence of other P sources. Decreased total P sorption due to desorption of Pi can be caused by relatively small additions of organic P, which may help explain vertical P movement in manured soils. Sorption isotherms performed using Pi alone did not accurately predict total P sorption in soils.     

Sorption and transport of 17beta-estradiol and testosterone in undisturbed soil columns

Land-applied domestic animal wastes contain appreciable amounts of 17beta-estradiol (henceforth, estradiol) and testosterone. These sex hormones may be transported through soil to groundwater and streams, where they may adversely affect the environment. Previous column transport studies with these hormones used repacked soil and did not consider preferential flow. We, therefore, determined the sorption and transport characteristics of estradiol and testosterone in undisturbed soil columns (15-cm i.d. by 32-cm height). In the sorption experiment, isotherms for estradiol and testosterone were nonlinear with Freundlich exponents (n) less than one. Sorption of both hormones decreased with soil depth, and estradiol sorbed more strongly than testosterone. Average estradiol Freundlich sorption coefficients (K(f)) values were 36.9 microg(1 - n) mL(n) g(-1) for the 0- to 10-cm soil depth and 25.7 microg(1 - n) mL(n) g(-1) for the 20- to 30-cm soil depth. Average testosterone K(f) values were 26.7 microg(1 - n) mL(n) g(-1) for the 0- to 10-cm soil depth and 14.0 microg(1 - n) mL(n) g(-1) for the 20- to 30-cm soil depth. In the transport experiment, 27% of the estradiol and 42% of the testosterone leached through the soil columns. Approximately 50% of the remaining soil-bound hormones were sorbed in the top 10 cm of soil. In almost all instances, breakthrough concentrations of estradiol, testosterone, and a chloride tracer peaked simultaneously. Simultaneous breakthrough and HYDRUS-1D transport parameters indicated both chemical and physical nonequilibrium processes affected hormone transport. This suggests hormones placed on soil surfaces may contaminate groundwater under conditions of preferential flow.     

Sorption and stability of the polycyclic nitramine explosive CL-20 in soil

The polycyclic nitramine CL-20 (2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane) is being considered for use as a munition, but its environmental fate and impact are unknown. The present study consisted of two main elements. First, sorption-desorption data were measured with soils and minerals to evaluate the respective contributions of organic matter and minerals to CL-20 immobilization. Second, since CL-20 hydrolyzes at a pH of >7, the effect of sorption on CL-20 degradation was examined in alkaline soils. Sorption-desorption isotherms measured using five slightly acidic soils (5.1 < pH < 6.9) containing various amounts of total organic carbon (TOC) revealed a nonlinear sorption that increased with TOC [K(d) (0.33% TOC) = 2.4 L kg(-1); K(d) (20% TOC) = 311 L kg(-1)]. Sorption to minerals (Fe(2)O(3), silica, kaolinite, montmorillonite, illite) was very low (0 < K(d) < 0.6 L kg(-1)), suggesting that mineral phases do not contribute significantly to CL-20 sorption. Degradation of CL-20 in sterile soils having different pH values increased as follows: sandy agricultural topsoil from Varennes, QC, Canada (VT) (pH = 5.6; K(d) = 15 L kg(-1); 8% loss) < clay soil from St. Sulpice, QC, Canada (CSS) (pH = 8.1; K(d) = 1 L kg(-1); 82% loss) < sandy soil provided by Agriculture Canada (SAC) (pH = 8.1, K(d) = approximately 0 L kg(-1); 100% loss). The faster degradation in SAC soil compared with CSS soil was attributed to the absence of sorption in the former. In summary, CL-20 is highly immobilized by soils rich in organic matter. Although sorption retards abiotic degradation, CL-20 still decomposes in soils where pH is >7.5, suggesting that it will not persist in even slightly alkaline soils.     

Sorption, mobility, and transformation of estrogenic hormones in natural soil

Potent estrogenic hormones are consistently detected in the environment at low concentration, yet these chemicals are strongly sorbed to soil and are labile. The objective of this research was to improve the understanding of the processes of sorption, mobility, and transformation for estrogens in natural soils, and their interaction. Equilibrium and kinetic batch sorption experiments, and a long-term column study were used to study the fate and transport of 17beta-estradiol and its primary metabolite, estrone, in natural soil. Kinetic and equilibrium batch experiments were done using radiolabeled 17beta-estradiol and estrone. At the concentrations used, it appeared that equilibrium sorption for both estrogens was achieved between 5 and 24 h, and that the equilibrium sorption isotherms were linear. The log K(oc) values for 17beta-estradiol (2.94) and estrone (2.99) were consistent with previously reported values. Additionally, it was found that there was rate-limited sorption for both 17beta-estradiol (0.178 h(-1)) and estrone (0.210 h(-1)). An approximately 42 h long, steady-flow, saturated column experiment was used to study the transport of radiolabeled 17beta-estradiol, which was applied in a 5.00 mg L(-1) solution pulse for 44 pore volumes. 17beta-estradiol and estrone were the predominant compounds detected in the effluent. The effluent breakthrough curves were asymmetric and the transport modeling indicated that sorption was rate-limited. Sorption rates and distributions of the estrogens were in agreement between column and batch experiments. This research can provide a better link between the laboratory results and observations in the natural environment.     

Sorption and fractionation of dissolved organic matter and associated phosphorus in agricultural soil

Mobility of dissolved organic matter (DOM) strongly affects the export of nitrogen (N) and phosphorus (P) from soils to surface waters. To study the sorption and mobility of dissolved organic C and P (DOC, DOP) in soil, the pH-dependent sorption of DOM to samples from Ap, EB, and Bt horizons from a Danish agricultural Humic Hapludult was investigated and a kinetic model applicable in field-scale models tested. Sorption experiments of 1 to 72 h duration were conducted at two pH levels (pH 5.0 and 7.0) and six initial DOC concentrations (0-4.7 mmol L(-1)). Most sorption/desorption occurred during the first few hours. Dissolved organic carbon and DOP sorption decreased strongly with increased pH and desorption dominated at pH 7, especially for DOC. Due to fractionation during DOM sorption/desorption at DOC concentrations up to 2 mmol L(-1), the solution fraction of DOM was enriched in P indicating preferred leaching of DOP. The kinetics of sorption was expressed as a function of how far the solution DOC or DOP concentrations deviate from "equilibrium." The model was able to simulate the kinetics of DOC and DOP sorption/desorption at all concentrations investigated and at both pH levels making it useful for incorporation in field-scale models for quantifying DOC and DOP dynamics.     

Sorption of inorganic and total phosphorus from dairy and swine slurries to soil

Understanding P sorption from animal manures is essential to formulate best management practices with regard to land application of manure from the standpoint of crop production and environmental quality. Little research has focused on the construction of P sorption isotherms where the P source is manure. The objectives of this study were to: (i) develop a procedure to characterize how inorganic P (P(i)) and total P (P(t)) from dairy slurry and swine slurry sorbs to soil; and (ii) compare the sorption characteristics of P(i) and P(t) where the P source was dairy slurry, swine slurry, or potassium phosphate (KH2PO4). Sorption solutions were prepared in 0.1 M KCl at pH 6 and equilibrated with soils at a 1:25 (w/v) soil/solution ratio for 24 h. Inorganic P, P(t), Al, and Fe in the equilibrated solutions were measured. For all soils, P(i) and P(t) sorption capacity of dairy slurry was greater than KH2PO4. Total P sorption capacity of swine slurry was greater than KH2PO4, while P(i) sorption capacity was less than KH2PO4. Overall, P(i) and P(t) sorption strengths of the manure slurries were less than or equal to KH2PO4. Increased P(i) sorption from dairy slurry was correlated with Fe and Al desorption. Reduction of P(i) sorption capacity from swine slurry was related to preferential sorption of organic P. Additional studies need to be conducted to determine how differences in P sorption between manures and fertilizer impact in-field P availability to a crop and potential for losses in runoff water.     

Time and moisture effects on total and bioavailable copper in soil water extracts

Environmental risk assessment of heavy metals in soil frequently involves testing of freshly spiked soils kept under stable humidity conditions, but it has been questioned whether these assessments are representative of the field situation. Furthermore, the poor correspondence that is often found between total metal content and metal toxicity calls for integrated chemical and biological analysis. The aim of this work was to determine time- and moisture-dependent changes in total water-extractable Cu as well as bioavailable Cu in soil water extracts. Measurements of total water-extractable copper ([Cu]tot) were performed using furnace atomic absorption spectrometry. An in vitro assay employing a Cu-specific Pseudomonas fluorescens reporter strain was used to estimate Cu that was biologically available to the reporter strain. We refer to this copper fraction as "bioavailable," [Cu]bio. We found a time-dependent decrease in [Cu]tot and [Cu]bio during incubation for up to 220 d at field capacity. Hence the [Cu]bio was reduced to between 32 and 40% of the initial values. Furthermore, the [Cu]bio to [Cu]tot ratio correlated positively with the amount of added Cu and tended to increase with time. The moisture content of the soil was important for Cu retention. Dry soil had higher [Cu]tot concentrations than humid soil, but the [Cu]bio to [Cu]tot, ratio was lower in the dry soil. Alternating drying and wetting did not lead to a more rapid Cu retention than observed under constant humid conditions. Our observations underline the need for considering both time and moisture effects when interpreting short-term toxicity studies and when making predictions concerning possible long-term effects of Cu in the soil environment.     

Challenges of soil erosion and sludge management for sustainable development in Indonesia

Most developing countries, particularly Indonesia, will be facing problems of sludge pressure in the next decades due to the increase in practices of legal and illegal logging as well as land and water demands. Consequently, they will also be facing the challenges of soil erosion and sludge management due to increased quantities of sludge coming from several potential sources, such as activated sludge, chemical sludge, fecal sludge and solid wastes as well as erosion and sedimentation. Although the government of Indonesia has enacted laws and policies to speed up the implementation of the programs and activities related to sludge management, the detailed practice concepts in implementing the programs need to be identified. Discussion of role-sharing amongst the related government agencies, private institutions and other stakeholders is urgent for clarifying the participation of each party in the next years to come. This paper proposes a management approach and level of responsibilities in sludge management. Implementation of zero ΔQ, zero ΔS and zero ΔP policies needs to be adopted by local and central governments. Application of sludge on the agricultural lands and other uses will promote sustainable development.     

钻井液化学剂可生物降解性研究

实验测定了16种钻井液化学剂的BOD_5和COD_cr，并计算其BOD_5／COD_cr比值。提出了以BOD_5／COD_cr的比值划分钻井液化学剂可生物降解性的分级标准，并对16种钻井液化学剂的可生物降解性进行分级，为其应用提供依据。     

Influence of organic waste type and soil structure on the bacterial filtration rates in unsaturated intact soil columns

Organic wastes are considered to be a source for the potentially pathogenic microorganisms found in surface and sub-surface water resources. Following their release from the organic waste matrix, bacteria often infiltrate into soil and may be transported to significant depths contaminating aquifers. We investigated the influence of soil texture and structure and most importantly the organic waste properties on the transport and filtration coefficients of Escherichia coli and total bacteria in undisturbed soil columns. Intact soil columns (diameter 16 cm and height 25 cm) were collected from two soils: sandy clay loam (SCL) and loamy sand (LS) in Hamadan, western Iran. The cores were amended with cow manure, poultry manure and sewage sludge at a rate of 10 Mg ha(-1) (dry basis). The amended soil cores were leached at a steady-state flux of 4.8 cm h(-1) (i.e. 0.12 of saturated hydraulic conductivity of the SCL) to a total volume of up to 4 times the pore volume of the columns. The influent (C(0)) and effluent (C) were sampled at similar time intervals during the experiments and bacterial concentrations were measured by the plate count method. Cumulative numbers of the leached bacteria, filtration coefficient (lambda(f)), and relative adsorption index (S(R)) were calculated. The preferential pathways and stable structure of the SCL facilitated the rapid transport and early appearance of the bacteria in the effluent. The LS filtered more bacteria when compared with the SCL. The effluent contamination of poultry manure-treated columns was greater than the cow manure- and sewage sludge-treated ones. The difference between cow manure and sewage sludge was negligible. The lambda(f) and S(R) values for E. coli and total bacteria were greater in the LS than in the SCL. This indicates a predominant role for the physical pore-obstruction filtration mechanisms as present in the poorly structured LS vs. the retention at adsorptive sites (chemical filtration) more likely in the better structured SCL. While the results confirmed the significant role of soil structure and preferential (macroporous) pathways, manure type was proven to have a major role in determining the maximum penetration risk of bacteria by governing filtration of bacteria. Thus while the numbers of bacteria in waste may be of significance for shallow aquifers, the type of waste may determine the risk for microbial contamination of deep aquifers.     

Relationships between bacterial tolerance levels and forms of copper and zinc in soils

The effects of various fractions of copper (Cu) and zinc (Zn) on soil bacteria were evaluated by the heavy metal tolerance level of the bacterial community (IC50) in soil samples collected near a mine. The IC50 values had no relationship with the total concentrations of Zn and Cu in the soils, but were weakly correlated with the 0.05 M CaCl2-extractable form of each metal in the soils (Cu: R2 = 0.670, p < 0.01; Zn: R2 = 0.453, p < 0.05). It was found that the IC50 correlated strongly with the total concentration of each metal in the extracts from water-saturated soil samples, described below as "soil solution" (Cu: R2 = 0.789, p < 0.01; Zn: R2 = 0.617, p < 0.01). The speciation of these metals in the soil solutions was estimated using an equilibrium thermodynamic computer model, SOILCHEM. Simulated free Cu ion ranged from 18 to 98% of total Cu, and organic complexes of Cu ranged from < 1 to 56%. In all samples, Zn existing as the free ion was estimated to be more than 80% of total Zn in the soil solutions. The IC50 values were also correlated with the estimated free metal ion activities, but with slightly lower correlation coefficients than found for total concentration in the soil solutions (Cu: R2 = 0.735, p < 0.01; Zn: R2 = 0.610, p < 0.01). The results suggest that not only high metal ion activities, but also total dissolved metal concentrations in soil solutions may affect the bacterial community.     

Study on the influence of additives in an industrial calcium fluoride and waterworks sludge co-melting system

This work explores the effect of additives on the pouring temperature in a waterworks and industrial calcium fluoride sludge co-melting system. Two kinds of sludge were mixed in various ratios to find a mixing ratio at which the operating temperature for subsequent additive tests was relatively low. Various proportions of either sodium carbonate (Na2CO3) or potassium carbonate (K2CO3) reagent were added to the mixed-sludge samples to elucidate the consequent changes in pouring temperature. The experimental results revealed that the pouring temperature was lowest when calcium fluoride was mixed with waterworks sludge in a ratio of 4:6 (w/w). Adding sodium carbonate or potassium carbonate reagent to the mixed-sludge samples further reduced the pouring temperature. Increasing the amount of sodium carbonate did not significantly reduce the pouring temperature beyond that observed when 2% was added, suggesting that 2% was the optimal additional percentage of sodium carbonate. In contrast, the pouring temperature was increased when over 2% potassium carbonate was added to the mixed-sludge samples, revealing that the optimal additional percentage of potassium carbonate was also 2%. These findings indicate that both sodium carbonate and potassium carbonate can be used as additives to increase the energy efficiency of the melting process, but sodium carbonate is more operationally convenient.     

Sorption of hydrophobic pesticides on a Mediterranean soil affected by wastewater, dissolved organic matter and salts

Irrigation with treated wastewaters as an alternative in countries with severe water shortage may influence the sorption of pesticides and their environmental effects, as wastewater contains higher concentrations of suspended and dissolved organic matter and inorganic compounds than freshwater. We have examined the sorption behaviour of three highly hydrophobic pesticides (the herbicide pendimethalin and the insecticides α-cypermethrin and deltamethrin) on a Mediterranean agricultural soil using the batch equilibration method. We considered wastewater, extracts from urban sewage sludge with different dissolved organic carbon contents, and inorganic salt solutions, using Milli Q water as a control. All pesticides were strongly retained by soil although some sorption occurred on the walls of the laboratory containers, especially when wastewater and inorganic salt solutions were used. The calculation of distribution constants by measuring pesticide concentrations in soil and solution indicated that pendimethalin sorption was not affected whereas α-cypermethrin and deltamethrin retention were significantly enhanced (ca. 5 and 2 times, respectively) when wastewater or salt solutions were employed. We therefore conclude that the increased sorption of the two pesticides caused by wastewater cannot be only the result of its dissolved organic carbon content, but also of the simultaneous presence of inorganic salts in the solution.     

Fractionation and mobility of copper, lead, and zinc in soil profiles in the vicinity of a copper smelter

Four soil profiles located near a copper smelter in Poland were investigated for the distribution and chemical fractions of Cu, Pb, and Zn and their mobility in relation to soil properties. Contamination with heavy metals was primarily restricted to surface horizons and the extent of contamination was 7- to 115-fold for Cu, 30-fold for Pb, and 6-fold for Zn as compared with subsurface horizons. In the less-contaminated fine-textured soil, the metals were distributed in the order: residual > Fe-Mn oxides occluded > organically complexed > exchangeable and specifically adsorbed, while the order for sandy soils was: residual > organically complexed > Fe-Mn oxides occluded > exchangeable and specifically adsorbed. The contaminated surface horizons of these profiles showed no consistent pattern of metal distribution. However, the common features of highly contaminated soils were very low percentage of residual fraction and the dominance of the NH4OAc extractable fraction. The sum of mobile metal fractions was generally < 10% in subsurface horizons, while in the contaminated surface horizons these fractions made up 50% of the total metal contents. Soil properties contributed more to the relative distribution of the metal fractions in the studied profiles than did the distance and direction to the source of pollution. The amounts of metal extracted by 0.01 M CaCl2 accounted for only a small part of the same metals extracted by NH4OAc. The mobility indexes of metals correlated positively and significantly with the total content of metals and negatively with the clay content.     

Effect of formulation on the behavior of 1,3-dichloropropene in soil

The fumigant 1,3-dichloropropene (1,3-D) has been identified as a partial replacement for methyl bromide (CH3Br) in soil fumigation. 1,3-Dichloropropene is formulated for soil fumigation as Telone II (Dow AgroSciences, Indianapolis, IN) for shank application and as an emulsifiable concentrate (EC) (Telone EC or InLine; Dow AgroSciences) for drip application. This study investigated the effect of formulation on the phase partitioning, transformation rate, and volatilization of 1,3-D isomers. Air-water partitioning coefficients (K(H)) were slightly higher for Telone II than for Telone EC, presumably due to the higher apparent water solubility of the EC formulation. Sorption of 1,3-D isomers in two soils was not affected by formulation. Formulation had no significant effect on the rate of 1,3-D transformation in water or soil. In general, differences in the rate of 1,3-D transformation and phase partitioning due to formulation as Telone II or Telone EC were very small. Thus, the effect of formulation on 1,3-D fate may be ignored in transformation and phase partition of 1,3-D in water and soil. Packed soil columns without plastic tarp indicated that with relatively shallow subsurface (10 cm) drip application of Telone EC, emission of 1,3-D isomers was more rapid and produced greater maximum instantaneous flux than deeper (30 cm) shank injection of Telone II. Both application methods resulted in the same cumulative emissions for both isomers, 45% for (E)-1,3-D and approximately 50% for (Z)-1,3-D. These results suggest that for drip application of fumigants to be effective in reducing emissions, the fumigant must be applied at sufficient depths to prevent rapid volatilization from the soil surface if the water application rate does not sufficiently restrict vapor diffusion.     

The availability of copper in soils historically amended with sewage sludge, manure, and compost

Metals in soils amended with sewage sludge are typically less available compared with those in soils spiked with soluble metal salts. However, it is unclear if this difference remains in the long term. A survey of copper (Cu) availability was made in soils amended with sewage sludge, manure, and compost, collectively named organic amendments. Paired sets of amended and control soils were collected from 22 field trials where the organic amendments had aged up to 112 yr. Amended soils had higher total Cu concentrations (range, 2-220 mg Cu kg; median, 15 mg Cu kg) and organic C (range, 1-16 g kg; median, 4 g kg) than control soils. All samples were freshly spiked with CuCl, and the toxicity of added Cu to barley was compared between amended and control soils. The toxicity of added Cu was significantly lower in amended soils than in control soil in 15 sets by, on average, a factor of 1.4, suggesting that aged amendments do not largely increase Cu binding sites. The fraction of added Cu that is isotopic exchangeable Cu (labile Cu) was compared between control soils freshly spiked with CuCl and amended soils with both soils at identical total Cu concentrations. Copper derived from amendments was significantly less labile (on average 5.9-fold) than freshly added Cu in 18 sets of soils. This study shows that Cu availability after long-term applications of organic amendments is lower than that of freshly added Cu salts, mainly because of its lower availability in the original matrix and ageing reactions than because of increased metal binding sites in soil.     

Biosorption of heavy metals by activated sludge and their desorption characteristics

The biosorption of different metals (Cu2+, Cd2+, Zn2+, Ni2+ and Pb2+) was investigated using activated sludge. The optimum pH was 4 for Cd, Cu and Pb sorption and 5 for Ni and Zn. Biomass metal uptake clearly competed with protons present in the aqueous medium, making pH an important variable in the process. Protons consumed by biomass in control tests versus protons exchange in biosorption tests confirmed a maximum exchange between metal cations and protons at pH 2. The study of the influence of biomass concentration revealed that the amount of protons released from biomass increased with biomass concentration. This would confirm the hypothesis of ion exchange between both types of ions. The application of the Langmuir and Freundlich models showed a better fitting of experimental data to the first model. The maximum sorption uptake of the studied metals by the activated sludge showed the following decreasing order: Pb>Cu>CdZn>Ni. Desorption experiments showed that HCl was a good eluent for the five metals tested, particularly at low pH values (1 and 2). At pH 3 or 4 the desorption yield was significantly lower. However, its use did not allow the reuse of biomass in subsequent loading and unloading cycles. EDTA was also a good desorption agent, achieving the total recovery for the five metals tested at a concentration of 1mM, with the advantage that biomass could be reused for three sorption-desorption cycles.